Title of Invention	PROCESS FOR THE PREPARATION OF ACYLPHOSPHANES OR BISACYLPHOSPHANES
Abstract	The invention relates to a process for the preparation of (bis)acylphosphanes of formula I n and m are each independently of the other 1 or 2; Ri if n = 1, is e.g. unsubstituted or substituted CrC18alkyl or C2-C18alkenyl, or phenyl, Ri if n = 2, is e.g. a divalent radical of the monovalent radical defined above; R2 is e.g. C^-C^alky!, C3-Ci2cycloalkyl, C2-Ci8alkenyl, mesityl, phenyl, naphthyl; R3 is one of the radicals defined under FV, the process comprises the steps a) contacting e.g. elemental phosphorous [P]«, P(Hal)3 with a reducing metal optionally in the presence of a catalyst or an activator in a solvent to obtain metal phosphides Me3P or Me'3P2, wherein Me is an alkali metal and Me' is an earth alkali metal or to obtain metal polyphosphides b) optionally adding a proton source, optionally in the presence of a catalyst or an activator to obtain metal dihydrogen phosphides MePH2; c) subsequent acylation reaction with m acid halides of formula III or m carboxylic acid esters of formula IV or, in case that in formula I m = 1, with one carboxylic ester of formula IV followed by one acid halide of formula III or vice versa .wherein R is the residue of an alcohol and R2 is as defined above; d) alkylation reaction subsequent reaction with an electrophilic agent RiHal or other electrophilic agents to obtain the compounds of formula I. An oxidation step may follow to obtain mono- and bisacylphosphane oxides or mono-and bisacylphosphane sulfides, which are used as photoinitiators.

Title of Invention

PROCESS FOR THE PREPARATION OF ACYLPHOSPHANES OR BISACYLPHOSPHANES

Abstract

The invention relates to a process for the preparation of (bis)acylphosphanes of formula I n and m are each independently of the other 1 or 2; Ri if n = 1, is e.g. unsubstituted or substituted CrC18alkyl or C2-C18alkenyl, or phenyl, Ri if n = 2, is e.g. a divalent radical of the monovalent radical defined above; R2 is e.g. C^-C^alky!, C3-Ci2cycloalkyl, C2-Ci8alkenyl, mesityl, phenyl, naphthyl; R3 is one of the radicals defined under FV, the process comprises the steps a) contacting e.g. elemental phosphorous [P]«, P(Hal)3 with a reducing metal optionally in the presence of a catalyst or an activator in a solvent to obtain metal phosphides Me3P or Me'3P2, wherein Me is an alkali metal and Me' is an earth alkali metal or to obtain metal polyphosphides b) optionally adding a proton source, optionally in the presence of a catalyst or an activator to obtain metal dihydrogen phosphides MePH2; c) subsequent acylation reaction with m acid halides of formula III or m carboxylic acid esters of formula IV or, in case that in formula I m = 1, with one carboxylic ester of formula IV followed by one acid halide of formula III or vice versa .wherein R is the residue of an alcohol and R2 is as defined above; d) alkylation reaction subsequent reaction with an electrophilic agent RiHal or other electrophilic agents to obtain the compounds of formula I. An oxidation step may follow to obtain mono- and bisacylphosphane oxides or mono-and bisacylphosphane sulfides, which are used as photoinitiators.

Full Text	Process for preparing acvlphosphanes and derivatives thereof The present invention relates to a new, selective process for the preparation of mono- and bisacylphosphanes, mono- and bisacylphosphane oxides or mono- and bisacylphosphane sulfides starting from elemental phosphorous [P], or phosphorous reagents with a formal oxidation state of phosphorous > -3, such as for example phosphorous trihalogenide P(Hal)3 or, phosphorous oxides without isolation of the intermediates. As the technology of the mono- and bisacylphosphine oxides is becoming increasingly important owing to the excellent photoinitiator properties of these compounds there is also a need for highly practicable processes involving as little elaboration for the preparation of the required intermediates, especially of the corresponding mono- and bisacylphosphanes, but also of the oxide and sulfide end products. There still remains a need for a process which allows a high variability and flexibility for the introduction of all three substituents at the phosphorous atom of mono- and bisacylphosphane structures. The European Patent Publication EP1 135 399 B1 describes a process for the preparation of mono- and bisacylphosphanes, of mono- and bisacylphosphane oxides and of mono- and bisacylphosphane sulfides, which process comprises first reacting organic P-monohalogeno-phosphanes (R2-PCI) or P,P-dihalogenophosphanes (R-PCI2) or mixtures thereof, with an alkali metal or magnesium in combination with lithium, where appropriate in the presence of a catalyst, and then carrying out the reaction with acid halides and, in the case of the process for the preparation of oxides, carrying out an oxidation step and, in the case of the preparation of sulfides, reacting the phosphanes so obtained with sulfur. The reaction is usefully carried out in a solvent. The solvent used may be, in particular, ethers which are liquid at normal pressure and room temperature. Examples thereof are dimethyl ether, diethyl ether, methylpropyl ether, 1,2-dimethoxyethane, bis(2-methoxyethyl)ether, dioxane or tetrahydro-furan. Tetrahydrofuran is preferably used. The International Application PCT/EP 04/51427 describes a process to prepare mono- and bisacylphosphanes, which process comprises first reacting organic P-monohalogeno-phosphanes (R2-PCI) or P,P-dihalogenophosphanes (R-PCI2), or phosphorous halide oxide or phosphorous halide sulfide with an alkali metal (metallation) in a solvent in the presence of a proton source (reduction), and where appropriate in the presence of a catalyst, and then carrying out the reaction with acid halides. Brandsma and coworkers describe the preparation of dihydrogen metal phosphides, represented by the formula MePH2, by the reaction of Me3P with a proton source (tert-butanol) in an organic solvent, preferably THF or DME (M.C.J.M. van Hoijdonk, G. Gerritsen, L. Brandsma, Phosphorous, Sulfur, Silicon 2000, 162, 39-49). Addition of an alkyl halide RHal leads to the formation of a monoalkyl phosphine RPH2. It is known that monoalkyl phosphines can be further reacted with an acid halide, as described in the International Application PCT/EP 04/51427, filed July 9, 2004. A. Steinicke and coworkers describe the reduction of red phosphorous with strongly reducing metals, giving metal phosphides MenPm. Addition of an alkyl halide leads to the formation of alkylcyclophosphanes cyclo-(RP)n (A. Steinicke, K.-H. Thiele, A. Haaland, V.I. Sokolov, H.V. Volden, Z. anorg. allg. Chem. 1997, 623, 1925-1930). Reductive cleavage of alkylcyclophosphanes with a metal in the presence of a proton source (e.g. tert-butanol) gives a monoalkyl phosphine RPH2, which can be further reacted with an acid halide, as described in the International Application PCT/EP 04/51427. The above referenced patent publications describe a process wherein the alkyl or aryl substituent at the phosphorous atom of the mono- or bisacylphosphane was part of the starting material R2-PCI or R-PCI2. As only a limited number of P-monohalogenophosphanes (R2-PCI) or P,P-dihalogenophosphanes (R-PCI2) are readily available, accessible, or processible, there is a need to develop a process enabling the preparation of mono- and bisacylphosphanes which process provides a higher variance for the substituents at the phosphorous atom. Furthermore, it should be avoided to use toxic, pyrophoric and difficult to handle phosphorous starting materials, like phosphine gas (PH3), or primary and secondary alkyl and aryl phosphines R-PH2. R2-PH, respectively. Photoinitiators bearing suitable functional groups that allow a chemical reaction with suitable functional groups on low molecular, oligomeric or polymeric compounds are highly demanded for the development of compositions containing low volatile and non-migrating photoinitiators, as they are for examples required for printing inks used in direct food contact applications. Furthermore, photoinitiators bearing suitable functional groups can be linked to other additives, such as sensitizers, stabilizers, surface active agents and so on, in order to provide an additional functionality to the photoinitiator. Hence an easy access to such functionalized photoinitiators, especially mono- or bisacylphosphine oxides, is highly desirable In the above mentioned patent publications, the acylation of the intermediate primary or secondary alkyl and aryl phosphines R-PH2 and R2-PH, respectively, is performed in the presence of strong bases, such as butyl lithium, or alkali metals such as lithium or sodium. Many functional groups do not tolerate such reaction conditions. Hence the type of functional groups that can be introduced on the residue R by the processes claimed in the afore mentioned patents is limited to those that tolerate these harsh reaction conditions. Therefore, there is a need for a synthetic access that allows the easy introduction of a broader variety of functional groups on the substituents on the phosphorous atom. It has now been found that in the process according to the invention a reactive intermediate is generated, which can selectively be alkylated/arylated using any alkylating/arylating agent (e.g. RHal), or reacted with typical electrophiles. The substituent R at the phosphorous atom is thus introduced via a reaction with an electrophile within the said process. The possibility of using any electrophile provides a higher variance for the substituents at the phosphorous atom. Furthermore, said substituent R is introduced after the acylation step that requires the use of strong bases, such as butyl lithium, or of alkali metals, such as lithium or sodium. Thus even substituents bearing functional groups that would not tolerate such conditions can be introduced, thereby considerably enlarging the variance of functional groups. Starting with the reduction of elemental phosphorous [P],, phosphorous trihalogenide P(Hal)3, or other phosphorous compounds possessing a phosphorous atom with a formal oxidation state > -3, followed by the acylation of the obtained metal phosphides MenPm [e.g-trialkali metal phosphide (Me3P)], or the acylation of dihydrogen metal phosphide (MePH2), it is possible to avoid the use, the isolation, the generation, or the handling of a toxic gas like PH3, or alkyl and aryl phosphines. The whole process may optionally be performed in the same reactor ("one-pot" reaction). The invention relates to a process for the preparation of acylphosphanes or bisacylphosphanes of formula I n and m are each independently of the other 1 or 2; Ri if n = 1, is unsubstituted linear or branched CrCi8alkyl or C2-C18alkenyl; or linear or branched d-Ci8alkyl or C2-C18alkenyl substituted once or more than once by groups selected from: -OR10, -SR10, -OCO-R10, -COO-R10> -CH=CH-CO-OR10 or -C(C1-C4alkyl)=C(C1-C4alkyl)-CO-OR10; wherein Rio is hydrogen, d-dsalkyl, or C2-C18alkyl which is interrupted by one or several non-successive -O-atoms, a di,-tri,-tetra-or polyethylene glycol residue, C3-C12-cycloalkyl, tetrahydropyran-2-yl, phenyl-d-d-alkylene, phenyl-CrC4-alkenylene, d-C6alkyl substituted by halogen or substituted by cyclohexyl or cyclopentyl, or substituted by tetrahydrofuranyl, furanyl, isopropyl-4-methyl-coclohexyl, C2-C18-alkenyl, unsubstituted phenyl, naphthyl or biphenyl being unsubstituted or phenyl, naphthyl or biphenyl substituted by one to five d-Cs-alkyl, d-C8-aikoxy, d-C8-alkylthio and/or halogen; or Ri is linear or branched d-d8alkyl or C2-C18alkenyl substituted by -CO-Rn; wherein Rn is d-C18alkyI, or C2-C18alkyl which is interrupted by one or several non-successive -O-atoms, C3-Ci2-cycloalkylf phenyl-d-C4-aIkylene, unsubstituted phenyl, naphthyl or biphenyl being unsubstituted or phenyl, naphthyl or biphenyl substituted by one to five d-Cs-alkyl, d-C8-alkoxy, d-C8-alkylthio and/or halogen or Ri is linear or branched d-d8alkyl or C2-C18alkenyl substituted by -CO-(CH)2-CO-d-C6alkyl, CO-(CH)2-CO-phenyl, or by CO-(CH)2-COO-d-Ci8alkyl; or Ri is linear or branched d-dsalkyl or C2-C18alkenyl substituted by ~NR12R13, -N(R12)-CO-R10, -N(R12)-CO.OR10, -N(R12)-CO-NR12R13, -N(R12)-CO-Hal, -CO-NR12R13) wherein R10 is as defined above and R12 and R13 independently of one another are is hydrogen, d-dsalkyl, C2-C18alkyl which is interrupted by one or several non-successive O atoms, C3-C2-cycloalkyl, C2-C18-alkenyl, phenyl-d-d-alkyl, phenyl, naphthyl, pyridyl, the radicals phenyl, naphthyl or pyridyl being unsubstituted or substituted by one to five C1-C8-alkyl, C1-C8-alkoxy, Ci-C8-alkylthio and/or halogen; or R12 and R13 forms a 5- or 6-membered 0-, S- or N-containing heterocyclic ring; that may be further annelated by an aliphatic or aromatic ring; or -SO2-R10, -SO2-OR10, -S02-NR12Ri3, wherein R10,R12and R13 are as defined above; or -PO(OCi-Caalkyl)2. or -SiR14Ri5Ri6, wherein R14, R15 and Ri6 independently of one another are H( C1-C8alkyl, C2-C8alkenyl, phenyl, C7-C9phenylalkyl, -OC1-C8alkyl, -0-SiR17R18R19, wherein R17, R18 and R19 are independently of each other H, C1-C8alkyl, C2-C8alkenyl, phenyl, C7- C9phenylalkyl, -OC1-C8alkyl; or -CH=CH-phenyl or -C(C1-C4alkyl)=C(C1-C4alkyl)-phenylI phenyl-CrC4alkyl, phenyl, naphthyl, biphenyl, C5-C12cycloalkyl or a 5- or 6-membered 0-, S- or N-containing heterocyclic, ring; benzophenonyl, thioxanthonyl; or Ri is C2-C18alkyl or C2-Ci8alkenyl which is interrupted by one or several non-successive -0-, -NH-, -NR12- or -S- atoms, and may additionally be substituted once or more than once by groups selected from: halogen or CN, or -OR10, -SR10, -OCO-R10, -COO-R10j wherein R10 is as defined above; or -NR12Ri3, -N(R12)-CO-R10, -N(R12)-CO-OR10, -N(R12)-CO-NR12R13, -N(R12)-CO-Hal, -CO-NR12Ri3, wherein R10 and R12 and R13 are as defined above; or -SO2-R10, -SO2-OR10, -S02-NR12R13, wherein R10l R12and Ri3 are as defined above;or -PO(OC1-C8alkyl)2> or -SiR14Ri5Ri6, wherein R14l R15 and R16 are as defined above; or phenyl-CrC^alkyl, phenyl or C5-C12cycloalkyl; or Ri is C2-C18alkyl or C2-C18alkenyl which is interrupted by -CO-, -COO-, -OCO-, -OCOO-, -CO-N(R12)-, -N(R12)-CO-, -N(R12)-CO-N(R12)-, -N(R12)-COO-, -COO-CrCiaalkylene, -COS-CrC18alkylene, -SOs-, -S02-0-, -S02-N(R12)-, -(CH3)2Si-[OSi(CH3)2 ]m- with m = 1-6, phenyl-Ci-C4alkylene, phenylene, naphthylene, biphenylene, C5-C12cycloalkylene or a 5- or 6-membered 0-, S- or N-containing heterocyclic ring; wherein R12 is as defined above; or Ri is trimethylsilyl or Hal-(CH3)2Si-[OSi(CH3)2 ]m- or (CH3)3Si-[OSi(CH3)2 ]m- with m = 1-6 ;or Ri is -COOH, -COO-R10, -CO-NR12R13, -CO-vinyl, -CO-phenyl which is unsubstituted or substituted by one or more -CH3, -OCH3, -CI; wherein R10, R12 and Ri3 are as defined above;or Ri is phenyl-CrC4alkyl, phenyl, naphthyl, biphenyl, C5-C12cycloalkyl or a 5- or 6-membered 0-, S- or N-containing heterocyclic ring; all of the radicals phenyl, naphthyl, biphenyl, C5-C12cycloalkyl or the 5- or 6-membered -0-, S- or N-containing heterocyclic ring being unsubstituted or substituted by one to five halogen, d-Csalkyl, C1-C8alkylthio, CrCsalkoxy and/or -NR12R13; wherein R12and R13 are as defined above; R2 is C\|-C18alkyl or C2-C18alkeny ; C1-C18alkyl or C2-C18alkenyl substituted once or more than once by halogen; or -OR10, -OCO-R10, -OCO-Hal, -COO-R10, -CH=CH-CO-OR10 -N(R12)-CO-R10, -N(R12)-CO-Hal, ; -C(CrC4alkyl)=C(CrC4alkyl)-CO-OR10, -CO-NR12R13, wherein R10l R12and R13 are as defined above; or -CH=CH-phenyl or -C(CrC4alkyl)=C(C1-C4alkyl)-phenyl; C3-C12cycloalkyl, C2-C18alkenyl, phenyl-d^alkyl, phenyl, naphthyl, anthryl. biphenyl or a 5- or 6-membered -0-, S- or N-containing heterocyclic ring, the radicals phenyl, naphthyl, biphenyl or the 5- or 6-membered -0-, S- or N-containing heterocyclic ring being unsubstituted or substituted by one to five halogen, C1-C8alkyl, C13 C8alkoxy and/or C1-C8alkylthio; R3 is one of the radicals defined under R13 the process comprises the steps a) contacting elemental phosphorous [P]« P(Hal)3 or other phosphorous compounds in which the formal oxidation state of the phosphorous atom is higher than (-3) with a reducing metal optionally in the presence of a catalyst or an activator in a solvent to obtain metal phosphides Me3P or Me'3P2, wherein Me is an alkali metal and Me' is an earth alkali metal or to obtain metal polyphosphides, b) optionally adding a proton source, optionally in the presence of a catalyst or an activator to obtain metal dihydrogen phosphides MePH2; c) subsequent acylation reaction with m acid halides of formula III or m carboxylic acid c defined above, R2o is CpCs-alkyl,, C1-C8.perfluoroalkyl, aryl or CrC4-alkylaryl, R2i is H or C1-C8alkyl; R22 is (Vdealkyl or C2-Ci6alkenyl substituted once or more than once by halogen -OR10, -NR12Ri3, -SR10, -OCO-R10, -OCO-Hal, -COO-R10, -N(R12)-CO-R10, -N(R12)-CO-OR10, -N(R12)-CO-NR12R13, -N(R12)-CO-Hal, -CO-NRi2Ri3l -SO2-R10, -SO2-OR10, -S02-NRi2R13, -CH=CH-CO-OR10, -CH=CH-phenyl, -C(Ci-C4alkyl)=C(CrC4alkyl)-CO-OR10 or -C(CrC4alkyI)=C(C1-C4alkyl)-phenyl, phenyl-CrC4alkyl, phenyl, naphthyl, biphenyl, C5-C12cycloalkyl or a 5-or 6-membered 0-, S- or N-containing heterocyclic ring; R23 is H or CH3, and n = 1-5 and R10, R12and R13 is as defined above; The subsequent reaction of the intermediate obtained according to c) can also be performed under typical conditions known in the art for enolates such as radical or metal-promoted addition reactions, such as a palladium-catalyzed reaction with RiHal, in which Ri is an unsubstituted or substituted aryl group. The subsequent reaction can also include first a protonation reaction of the enolate, followed by a subsequent radical or metal-promoted addition reaction with RiHal, where Ri is an unsubstituted or substituted aryl group. wherein R1( R2 and R3 are as defined in claim 1, which process comprises the steps a), b) and c) as defined in claim 1; and d) reaction with an electrophilic agent RiHal or other electrophilic agents containing the residue Ri as defined in claim 1 step d for m = 1 followed by the reaction with an electrophilic agent R3Hal or other electrophilic agents containing the residue R3 as defined in claim 1 step d for m=1 to obtain the compounds of formula P. In another of its aspect, this invention relates to a process for the preparation of symmetric bisacylphosphanes of the formula I" (compounds of the formula I with n = 1 and m = 2) wherein fy and R2 are as defined in claim 1, which process comprises the steps a), b) and c) as defined in claim 1 for m = 2; and d) reaction with an electrophilic agent RiHal or other electrophilic agents containing the residue Ri as defined in claim 1 step d for m = 2 to obtain the compounds of formula I". In another of its aspect, this invention relates to a process for the preparation of un-symmetric bisacylphosphanes of the formula P (compounds of the formula I with n = 1 and m = 2) wherein R^ is as defined in claim 1 and R2 and R2' independently of one another are as defined in claim 1 under R2 with the proviso that R2 is not equal R2\ which process comprises the steps a) and b) as defined in claim 1; and c) subsequent reaction with an acid halide of formula III or a carboxylic acid ester of formula IV wherein R is the residue of an alcohol and R2 is as defined in claim 1; subsequent reaction with a second acid halide III' or a second carboxylic acid ester of the formula IV, wherein R2' and Hal are as defined above. d) reaction with an electrophilic agent RiHal or other electrophilic agents containing the residue fy as defined in claim 1 step d for m = 2 to obtain the compounds of formula I"'. In another of its aspect, this invention also relates to a process for the preparation of symmetric metal bisacylphosphides of the formula (V) or (Va) wherein R2 is as defined in claim 1 and the metal is Li, Na, K, Mg, which process comprises the steps a) b) and c) as defined in claim 1 for m = 2. In another of its aspect, this invention also relates to a process for the preparation of unsymmetric metal bisacylphosphides of the formula (V) or (Va') wherein R2and R2' are as defined in claim 4 and the metal is Li, Na, K, Mg, which process comprises the steps a) b) and c) as defined in claim 4. In another of its aspects, this invention relates to a process for the preparation of (bis)acyl-phosphane oxides and (bis)acylphosphane sulfides of formula VI Ri. R2, R3, n and m are as defined above, and Z is O or S, by oxidation or reaction with sulfur of the acylphosphane of formula I, l\ I" or I'". Definitions: C1-C18Alkyl is linear or branched and is, for example, C\|-C12-, C1-C8-, CrC6- or CrC4alkyl. Examples are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, 2,4,4-trimethylpentyl, 2-ethylhexyl, octyl, nonyl, decyl, undecyl, dodecyl, tetra-decyl, pentadecyl, hexadecyl, heptadecyl or octadecyl. C2-C18Alkyl or C2-C18alkenyl which is interrupted once or several times by non-successive -0-, -NH-, -NR9-, -S-atoms is interrupted, for example, 1-9, e.g. 1-7, 1-5, 1-3 or 1 or 2, times by -0-, -NH-, -NR12-,-S- atoms , the -0-, -NH-, -NR12-, -S-atoms always being interrupted by at least one methylene group. The alkyl groups or alkenyl groups may be linear or branched. The structural units obtained are thus, for example, -CH2-X-CH3, -CH2CH2-X-CH2CH3, -[CH2CH2X]y-CH3l where y = 1-8, -(CH2CH2X)7CH2CH3, -CH2-CH(CH3)-X-CH2-CH2CH3 or -CH2-CH(CH3)-X-CH2-CH3 with X= -0-, -S-, -NH-, -NR12- and the corresponding alkenyl structures. Examples for C2-C18alkyl or C2-C18alkenyl which is interrupted by -CO-, -COO-, -OCO-, -OCOO-, -CO-N(R12)-, -N(R12)-CO-, -N(R12)-CO-N(R12)-, -N(Ri2)-COO-, -COO-Ci-C18alkylene, -COS-Ci-Ci8alkylene, -S02-, -S02-0-, -S02-N(R12)-, -(CH3)2Si-[OSi(CH3)2 ]m-, phenyl-d-C4alkylene, phenylene, naphthylene, biphenylene, C5-C12cycloalkylene or a 5- or 6-membered O-, S- or N-containing heterocyclic ring are the following structures -CH2-W-CH3, -CH2CH2-W-CH2CH3, -[CH2CH2W]y-CH3, where y = 1-8, -(CH2CH2W)7CH2CH3, -CH2-CH(CH3)-W-CH2-CH2CH3, -CH2-W-CH2-CH3, -CH2-W-CH3, -CH2-W-C(CH3)3, -CH(CH3)-W-CH2-CH3, -CH2-CH2-CH2-W-CH3, -(CH2)8-W-CH3, -CH2-CH2-W-CH=CH2, -CH2-CH2-W-C(CH3)=CH2 or -CH2-CH(CH3)-W-CH2-CH3 with W= -CO-, -COO-, -OCO-, -OCOO-, -CO-N(R12)-, -N(R12)-CO-, -N(Ri2)-CO-N(R12)-, -N(R12)-COO-, -COO-CrCisalkylene, -COS-Ci-Ci8alkylene, -S02-, -S02-O-, -S02-N(R12)-, -(CH3)2Si-[OSi(CH3)2 ]m, -(CH2)3-Si-(0-CH2-CH3)3, -CH2-CH2-P0-(0-CH2-CH3)2, phenyl-Ci^alkylene, phenylene, naphthylene, biphenylene, C5-C12cycloalkylene or a 5- or 6-membered 0-, S- or N-containing heterocyclic divalent ring, N-phthalimidyl C2-Ci8Alkenyl radicals may be mono- or polyunsaturated, linear or branched, cyclic or bicyclic and are, for example, vinyl, allyl, methallyl, 1,1-dimethylallyl, propenyl, butenyl, pentadienyl, hexenyl octenyl or exo or endo (bicyclo[2.2.1]hept-2-en-5-yl)-methyl preferably vinyl , allyl, 3-buten-1-yl (unser Ex) or exo and endo (bicyclo[2.2.1]hept-2-en-5-yl)-methyl. C5-Ci2Cycloalkyl is, for example, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, preferably cyclopentyl and cyclohexyl, more preferably cyclohexyl. Ci-C8Alkoxy is linear or branched radicals and is typically methoxy, ethoxy, propoxy, isopro-poxy, n-butyloxy, sec-butyloxy, isobutyloxy, tert-butyloxy, pentyloxy, hexyloxy, heptyloxy, 2,4,4-trimethylpentyloxy, 2-ethylhexyloxy or octyloxy, preferably methoxy, ethoxy, propoxy, isopropoxy, n-butyloxy, sec-butyloxy, isobutyloxy, tert-butyloxy, most preferably methoxy. Phenyl-Ci-C4alkyl is e.g., benzyl, phenylethyl, a-methylbenzyl or a,a-dimethylbenzyl, preferably benzyl. Halogen (= Hal) is fluoro, chloro, bromo and iodo, preferably chloro and bromo, most preferably chloro. Examples of -0-, S- or N-containing 5- or 6-membered heterocyclic rings are furyl, thienyl, pyrrolyl, oxinyl, dioxinyl or pyridyl. The cited heterocyclic radicals may be substituted by one to five, e.g. by one or two, linear or branched C^Csalkyl, halogen and/or d-C8alkoxy. Examples of such compounds are dimethylpyridyl, dimethylpyrrolyl or methylfuryl. Substituted phenyl, naphthyl or biphenyl is substituted by one to five, e.g. by one, two, three or four, preferably by one, two or three, for example linear or branched C1-C8alkylf linear or branched C1-C8alkoxy or by halogen. Preferred substituents for phenyl, naphthyl and biphenyl are d-C4alkyl, e.g. methyl, C1-C4alkoxy, e.g. methoxy or ethoxy, and chloro. Particularly preferred substituents are, for example, 2,4,6-trimethyIphenyl, 2,6-dichlorophenyl, 2,6-dimethylphenyl or 2,6-dimethoxy-phenyl, 2-ethoxynapht-1-yl, 2-methylnaphth-1-yl. R2 is, for example, Ci-C18alkyl or phenyl, preferably 2,4,6-trimethylphenyl, 2,6-dimethylphenyl or 2,6-dimethoxyphenyl, tert-butyl, 1,1 -diphenylethyl, 2-phenylpropyl, 2-methylbutyl, 2-methylpentyl, most preferably 2,4,6-trimethylphenyl. The residue of an alcohol is a group RO wherein R is CrCe branched or linear, alkyl, alkenyl, benzyl. R is, for example, ethyl, iso-propyl, n-propyl, t-butyl or n-butyl, 2-ethyl hexyl or other branched octyl species such as 2,4,4-trimethyloctyl. The compound of formula I, wherein R, is -CO-phenyl which is substituted by one or more -CH3, -OCH3, -CI is a triacylphosphane. These triacylphosphanes are preferably ortho-mono substituted. The reducing metal (= Me) is selected from the group consisting of lithium, potassium, sodium, magnesium in combination with lithium preferably lithium, potassium, sodium, more preferably lithium or sodium, most preferably sodium. MePH2 may have the form of a cluster as shown in Example 11. The common forms of elemental phosphorous (= [P]«) include the white phosphorous, the red phosphorous which is high melting and less reactive than the white phosphorous, and the black phosphorous which is even less reactive. For the purposes of the process of this invention, the red phosphorous is preferred. Other sources of reducible phosphorous are also suitable for use in this process. Suitable phosphorous compounds are those in which the formal oxidation state of the phosphorous atom is higher than (-3). Examples are phosphorous oxides such as P4On (n = 6-10), (P205)0 ( o = 1-oo), phosphorous trihalides PX3 (X = halogen), including phosphorous trifluoride, phosphorous trichloride, phosphorous tribromide or phosphorous triiodide; phosphorous sulfides P4Sp(p = 2-10) and (PS)q (q = 0.25-8); phosphorous oxohalides or thiohalides such as POX3. and PSX3 (X = halogen); mixtures of the before mentioned compounds with metal oxides (MekH\|PmOn phosphates, phosphonates, phosphinates), metal sulfides or metal halides, preferentially phosphorous containing minerals. Further useful phosphorous compounds are phosphazanes (R2PNR2), phosphazenes ((RPNR)X (R2PN)X, R3PNR)) and phosphonitrides (PN or P3N5), as well as mixtures of these compounds with the reducible phosphorous compound mentioned before. Still another class of useful phosphorous compounds are phosphates (P=0(OR)3); phosphonates (RP=0(OR)2) and phosphites (R2P=0(OR)), thiophosphates (P=S(OR)3); thiophosphonates (RP=S(OR)2) and thiophosphites (R2P=S(OR)), with R being any organic radical. For the purpose of the process of the invention, phosphorous trichloride is preferred. Useful catalysts in step a) and b) are aromatic polycyclic hydrocarbon catalysts, with or without heteroatoms, such as naphthalene, anthracene, phenanthrene, biphenyl, terphenyl, quaterphenyl, triphenylene, trans-1,2-diphenylethane, pyrene, perylene, acenapthalene, decacyclene, quinoline, N-ethylcarbazole, dibenzothiophene or dibenzofuran. It is preferred that a catalyst is present, which is preferably naphthalene and biphenyl, most preferably napththalene. Other catalysts in step a) and b) are alkali or earth alkali hydroxides or Na, K, or Li alcoholates or alcohols. Other catalysts in step a) and b) are combinations of alkali and/or earth alkali metals and/or alcohols. Activators in step a) and b) are amines (triethylamine, tributylamine, piperidine, morpholine, N-methylpiperidine, N-methyl morpholine) or polyamines such as, for example TMEDA = NX^N'-tetramethylethylenediamine, PMDTA = pentamethyldiethylenetriamine, or sparteine. Other activators in step a) and b) are polyethers, such as crown ethers, for example 12-crown-6. As solvent there are used ethers such as dimethyl ether, diethyl ether, methylpropyl ether, 1,2-dimethoxyethane (DME), bis(2-methoxyethyl)ether (diglyme), dioxane, or tetrahydro-furan, or in mixtures thereof, or arene solvents such as benzene, toluene, o-, m- or p-xylene, mesitylene, ethylbenzene, diphenylethane, 1,2,3,4-tetrahydronaphthalene (tetraline), iso-propylbenzene (cumol), or in mixtures thereof. Preferred solvents are ethers or mixtures of ethers and arene solvents, most preferred are ethers. A suitable solvent for step a) and b) is liquid ammonia, a mixture of liquid ammonia and an ether such as tetrahydrofuran, a mixture of liquid ammonia and a tertiary alcohol or a tertiary alcohol alone. Preferred is liquid ammonia and tetrahydrofuran. The proton source is a CH-, NH-, SH-, or OH-acid compound. CH-acid compounds have an active methylene group, such as, for example, malonic esters, cyanoacetic esters, acetylacetone, acetoacetic esters, succinic acid esters, N- methylpyrrolidone and the like. Furthermore an enol, an enol ether may be a CH-acid compound. NH-acid compounds are, for example, lactams or pyrrolidone or salts such as ammonium salts or amidinium salts. OH-acid, SH-acid compounds are alcohols or thioalcohols. Preferred the proton source are sterically hindered alcohols, trialkylamine hydrohalogenes, bisarylamines, malono nitrile, malonic acid esters, amidine hydrohalogene R-C(=NH)-NH2HCI and carboxylic acids. The sterically hindered alcohol is selected from the group consisting of secondary or tertiary C3-Ci8alcohols, preferably of tert-butanol, tert-amyl-alcohol, 3-methyl-3-pentanol, 3-ethyl-3-pentanol, triphenylmethanol, 3,7-dimethyl-3-octanol, 2-methyl-1-phenyl-2-propanol, 2-methyl-4-phenyl-2-butanol, fenchyl alcohol, 2,4-dimethyl-3-pentanol, 1-dimethylamino-2-propanol or hexylene glycol, especially preferred tert-butanol, tert-amylalcohol or 3-methyl-3-pentanol. The trialkylamine hydrohalogene is selected from tert-fCrCshN-HCI, preferably trimethyl-amine hydrochloride, triethylamine hydrochloride ortributylamine hydrochloride. Preferred substituents: In the above-described processes m = 2 is preferred and R1( if n = 1, is phenyl or unsubstituted linear or branched d-C^alkyl or C2-Ci8alkenyl; or linear or branched d-dsalkyl or C2-C18alkenyl substituted once or more than once by groups selected from: ^o O halogen or CN, or - o -OR10) -SR10, -OCO-R10, -COO-R10> -CH=CH-CO-OR10 or -C(C1-C4alkyl)=C(C1-C4alkyl)-CO-OR10; wherein R10 is hydrogen, C1-C18alkyl, or C2-C18alkyl which is interrupted by one or several non-successive -O-atoms, a di,-tri,-tetra-or polyethylene glycol residue, C3-C12-cycloalkyl, tetrahydropyran-2-yl, phenyl-Ci-C4-alkylene, phenyl-d-d-alkenylene, C1-C6alkyl substituted by halogen or substituted by cyclohexyl or cyclopentyl, or substituted by tetrahydrofuranyl, furanyl, isopropyl-4-methyl-coclohexyl, C2-C18-alkenyl, unsubstituted phenyl, naphthyl or biphenyl being unsubstituted or phenyl, naphthyl or biphenyl substituted by one to five d-d-alkyl, d-d-alkoxy, d-Cs-alkylthio and/or halogen; and R2 is phenyl or phenyl which is substituted by halogen, d-dalkoxy or d-dalkyl. Especially preferred are n=1 and RT is phenyl linear or branched d-dalkyl or C2-d8alkenyl or is linear or branched d-dalkyl or C2-d8alkenyl substituted by CN, trifluormethyl, oxiranyl, isoindole-1,3-dione, -O-d-dsalkyl, -O-benzyl, -CO-phenyl, -CO-C1-C18alkyl, -OCO-d-dsalkylj-OCO-Crdsalkenyl; -COO-Crdsalkyl; -COO-d-dsalkylene-phenyl, -COO-d-dsalkylene-cycloalkyl, -COO-C1-C18alkylene-tetrahydrofuranyl, -COO-C1-C8alkylene-furanyl, -COO-cycloalkyl, -COO-C1-C18alkenyl;-COO-C1-C18alkenylene«phenyl;-COO-(CH2)2-3-CI, -COO-[(CH2)2-3-0]1.1o-Crdalkyl;-COO-[(CH2)2-3-0]1.10-C1-C4-OH, -CO-CH2-CO-C1-C18alkyl; -CO-CH2-COO-d-C18alkyl, -O-tetrahydropyranyl, bicyclo[2.2.1]hept»2»en-5-yl)-methyl, PO(Od-dalkyl)2 and wherein R2 is phenyl which is substituted in 2,6- or 2,4,6-position by d-C4alkyl and/or d-dalkoxy, and/or chlorine; 2-ethoxy-naphth-1-yl, 2-methyl-naphth-1-yl or anthr-9-yl. Especially preferred for n=2 R1( if n = 2, is d-doalkylene, or biphenylene or -CH2-COO-Z-OCO-CH2- wherein Z is C1-C8 alkylene or a bridge derived from a di,-tri,-tetra-or polyethylene glycol. R3 is CrC12alkyl, cyclohexyl, phenyl or biphenyl, the radicals phenyl and biphenyl being unsubstituted or substituted by one to four d-dalkyl and/or d-C8alkoxy. Compounds of formula I which are particularly preferably used in the above process are those wherein n is 1. The residue "Hal" is preferably chloro. Other preferred compounds of formula I in the above process are those, wherein m is defined as the number two, i.e. bisacylphosphane or bisacylphosphane oxides or bisacyl-phosphane sulfides. The process is especially suitable to prepare alkyl bisacyl phosphanes (R Using the inventive process it is possible to prepare new (bis)acylphosphanes which are also part of the invention. wherein n =1 and Ri is linear or branched C1-C8alkyl or C2-C18alkenyl substituted by CN, trifluormethyl, oxiranyl, isoindole-1,3-dione, -0-Ci-Ci8alkyl, -O-benzyl, -CO-phenyl, -CO-Ci-Cisalkyl, -OCO-C1-C18alkyl;-OCO-C1-C18alkenyl; -COO-GrC18alkyl; -COO-C1-C18alkylene-phenyl, -COO-CVdsalkylene-cycloalkyl, -COO-C1-C18alkylene-tetrahydrofuranyl, -COO-C1-C18alkylene-furanyl, -COO-cycloalkyl, -COO-C1-C18alkenyl;-COO-C1-C18alkenylene-phenyl;-COO-(CH2)2-3-CI, -COO-[(CH2)r3-0]i-io-C1-C6alkyl;-COO-[(CH2)2-3-0]Mo-CrC6-OHI -CO-CH2-CO-C1-C18alkyl; -CO-CH2-COO-C1-Ci8alkyl, -O-tetrahydropyranyl, bicyclo[2.2.1]hept-2-en-5-yl)-methyl, PO(OC1-C6alkyl)2 and wherein m R2 and R3 are as defined in claim 1. Process parameters Step a) The elemental phosphorous may be employed as a finely divided solid or as a melt, or it may be dissolved or dispersed in an inert organic solvent. As elemental phosphorous is spontaneously flammable in moist air, it is preferred that the reaction be carried out in an inert gas atmosphere. PCI3 is preferentially dissolved in an inert organic solvent; Other suitable phosphorous compounds with a formal oxidation state of the phosphorous atom higher than -3 are employed as solids, in suspension or dissolved in an inert organic solvent. As solvents, ethers such as dimethoxyethane, liquid ammonia or a mixture of liquid ammonia and tetrahydrofuran are preferred. Step a) is preferably carried out in the presence of a hydrocarbon catalyst. Advantageously, the reaction of the reducing metal, dispersed in a solvent, and phosphorous may be effected at temperatures ranging from -70°C to +160°C, e.g. from room temperature to 80°C. Step b) In the inventive process step b) is optionally. Thus, metal phosphides MenPm [e.g. trialkali metal phosphide (Me3P)] may react directly with the acylating agent. However, because of an improved yield, step b) is preferably carried out. The reaction temperature is preferably in the range from -20°C to +160°C, e.g. from room temperature to 80°C. Catalysts and activators in step a) and b) are used in a molar ratio of catalyst to the reducing metal of for example 1:2 to 1:1000. Catalysts and activators in step a) and b) may be added prior or during the reduction of elemental phosphorous. It is possible to optionally isolate the product of step b) as an alcoholate cluster of the phosphide before using it in step c). It is possible to add polar or dipolar co-solvents to the reaction mixture during or after step a) and b). Such solvents may be linear or cyclic amides like dimethylacetamide (DMA), n-methyl pyrrolidone (NMP), cyclic ureas like 1,3-dimethypropylene urea (DMPU), linear and cyclic glycols like diglyme and dimethoxyethane (DME). Step c) The reaction temperature for the reaction with the acid halide is usefully in the range from -20° to +80°C. A bisacylphosphide intermediate is formed which may form an O-coordinated bisacylphosphaenolate chelate complex of the formula (V) or (Va') The bisacylphosphide intermediate is stabilized due to the formation of an O-coordinated bisacylphosphaenolate chelate complex in the case of alkali metals. The complex might be further stabilized by metal-metal exchange. Suitable exchange metals are: boron, aluminium, chromium, nickel. Step d) The enolate may be isolated or may easily be further reacted with an electrophilic agent. The choice of the electrophilic agent is not limited. Non limiting examples are: straight-chain or branched d-CisalkyI halides, C2-C8alkenyl halides, substituted alkylhalides such as fluoro, or hydroxy, or carbonyl, or sulfonyl, or vinyl, or siloxanyl, or alkoxycarbonyl, or acyloxy or by heterocyclic groups substituted alkylhalides, C5-C12cycloalkyl halides, benzyl halides and aryl halides such as phenyl halide, naphthyl halide or biphenyl halide. Other electophilic agents are alkyl sulfates, alkyltosylates, alkylmethylsulfonates, epoxides, episulfide or acrylate or methacrylate esters.. It is likewise possible to use alkylating reagents giving ionic functions, e.g., monobromoacetic acid, monobromopropionic acid, sodium 3-bromopropanesulfonate and N-(2-bromoethyl)diethylamine. Silyl or siloxanyl groups may be implemented via chlorosilane or chlorosiloxane, or by the use of a-halo-co-silanyl or siloxanylalkanes. The reaction temperature in step d) is usefully in the range from room temperature to 100°. The bisacylphosphane of formula I can be isolated by the customary technological methods which are known to the skilled person, for example by filtration, evaporation or distillation. Likewise, the customary methods of purification may be used, for example crystallisation, distillation or chromatography. However, the phosphanes can also be reacted without isolation to the corresponding mono-or bisacylphosphane oxides or mono- or bisacylphosphane sulfides. Using the process of this invention it is also possible to prepare mono- and bisacyl-phosphanes together in one reaction step. Depending on the substituents used, unsymmetric compounds may be formed by the novel process. Monoacylphosphane oxides are compounds of the formula I' corresponding to compounds of the formula I wherein n=1 and m=1. The residues RT and R3 may be the same or may be different. Bisacylphosphane oxides are compounds of the formula H corresponding to compounds of the formula I wherein n=1 and m=2. The residues R2 and R2* may be the same or may be different. By means of the novel process it is furthermore also possible to prepare mixtures of aliphatic and aromatic monoacylphosphanes or mixtures of aliphatic and aromatic bisacylphosphanes. If required, all of the mixtures may be separated by the processes customarily used in the technology or they may be further used as they are. This invention also relates to a process for the preparation of mono- and bisacylphosphane oxides or mono- and bisacylphosphane sulfides. This process is first carried out as described above and a mono- or bisacylphosphane (I) is prepared. The crude reaction product (I) can then be further processed without purification and an additional reaction step may be carried out without isolation of the phosphane (I) using the solution of the crude product. If required, the solvent may be changed, for example, by concentrating the solution containing the mono-or bisacylphosphane and taking up the residue in a new solvent. Of course it is also possible to further react above-described unseparated mixtures of compounds of formula (I) to the corresponding oxide or sulfide. It is recommended to adjust the pH of the reaction mixture prior to the oxidation step to a pH of 2-8, preferably to a pH of 3-6 by addition of typical inorganic and/or organic acids or buffer systems. When preparing the respective oxide (Via), the oxidation of the phosphane (I) is carried out using the oxidant conventionally used in the technology Suitable oxidants are in particular hydrogen peroxide and organic peroxy compounds, for example peracetic acid or t-butylhydroperoxide, air or pure oxygen. The oxidation is usefully carried out in solution. Suitable solvents are aromatic hydrocarbons, such as benzene, toluene, m-xylene, p-xylene, ethylbenzene or mesitylene, or aliphatic hydrocarbons, such as alkanes and alkane mixtures, e.g. petroleum ether, hexane or cyclo-hexane.During oxidation, the reaction temperature is preferably kept in the range from 0° to 120°C, preferably from 20° and 80°C. The reaction products (Via) can be isolated and purified by conventional processing methods known to the skilled person. The mono- or bisacylphosphanes (I) are in this case reacted in substance or, where appropriate, in a suitable inert organic solvent with an equimolar to 2-fold molar amount of elementary sulfur. Suitable solvents are for example those described for the oxidation reaction. However, it is also possible to use e.g. aliphatic or aromatic ethers, such as dibutyl ether, dioxane, diethylene glycol dimethyl ether or diphenyl ether, in the temperature range from 20° to 250°C, preferably from 60° to 120°C. The resulting mono- or bisacylphosphane sulfide, or its solution, is usefully freed from any remaining elementary sulfur by filtration. After the solvent is removed, the mono- or bisacylphosphane sulfide can be isolated by distillation, chromatography or recrystallisation in pure form. As mentioned above, it is also possible to use mixtures of compounds of formula I for the oxidation or reaction to the sulfide. The correspondingly obtained oxide or sulfide mixtures can either be separated by processes customarily used in the technology or may be used as mixtures. All of the above reactions are usefully carried out with exclusion of air in an inert gas atmosphere, e.g. under nitrogen or argon gas. The respective reaction mixture is usefully also stirred. The acid halides (III, III'), the carboxylic acid esters (IV, IV) or the electrophilic compounds RT-Hal or R3-Hal used as starting materials are known substances, some of which are commercially available, or may be prepared in analogy to known compounds. It is characteristic of the novel process that the individual processing steps can be carried out directly one after the other without the need for isolating and purifying the respective intermediates. Mixtures such as those described in the process for the preparation of the corresponding phosphanes may also be formed, or may also be specifically produced, in the above-described process for the preparation of mono- or bisacylphosphane oxides or mono- or bisacylphosphane sulfides. Such mixtures can be separated by methods known in the technology or may be further used in the form of mixtures. The phosphanes which are accessible by the novel process are important educts for the preparation of the corresponding phosphane oxides and phosphane sulfides. The phosphane oxides and phosphane sulfides are used in the art as initiators in photopolymerisation reactions. The oxidation is usefully carried out in solution. Suitable solvents are aromatic hydrocarbons, such as benzene, toluene, m-xylene, p-xylene, ethylbenzene or mesitylene, or aliphatic hydrocarbons, such as alkanes and alkane mixtures, e.g. petroleum ether, hexane or cyclo-hexane. During oxidation, the reaction temperature is preferably kept in the range from 0° to 120°C, preferably from 20° and 80°C. The reaction products can be isolated and purified by conventional processing methods known to the skilled person. Using the process of this invention it is possible to prepare bisacylphosphanes or bisacyl-phospane oxides or sulfides without isolating any intermediate ("one-pot" reaction). If two different acid halides or two different carboxylic acid esters are used, unsymmetric compounds may be formed by the novel process. Preferred is a process wherein a carboxylic acid ester followed by an acid chloride of a different acid may be used for the synthesis of unsymmetric compounds. The phosphanes which are accessible by the novel process are important educts for the preparation of the corresponding phosphane oxides and phosphane sulfides. The phosphane oxides and phosphane sulfides are used in the art as initiators in photopolymerisation reactions. Preferences A process for the preparation of (bis)acylphosphanes or (bis)acylphosphane oxides of formula I or VI the process comprising the steps of: a) contacting red phosphorous or PCI3 with an alkali metal in the presence of a solvent and optionally in the presence of polycyclic hydrocarbon catalyst b) adding a sterically hindered alcohol; c) subsequent reaction with two equivalents of an acid halide Hal-CO-R2 to obtain a metal bisacylphosphide [R2-CO-P=C(OMe)R2], wherein Me is Na or Li; or with one equivalent of a caboxylic acid ester RO-CO-R2, followed by one equivalent of an acid halide Hal-CO-R2" to obtain a metal bisacylphosphide [R2-CO-P=C(OMe)R2'], wherein Me is an alkali metal d) subsequent reaction with an electrophilic agent R-jHal or RiOSC^ORi to obtain the compounds of formula I. Preferred is a step a) whereby sodium in liquid ammonia is contacted with red phosphorus in tetrahydrofuran. The following examples illustrate the invention in more detail, although it is not intended that the invention be limited to the examples. As in the remaining description and in the patent claims, parts or percentages are by weight, unless otherwise stated. General: Solvents are used as received (without any treatment) or dried over molecular sieves or by azeotropic distillation. The course of the reaction is monitored by 31P-NMR spectroscopy. Example 1 Preparation of [isobutyl-(2,4,6-trimethyl-benzoyl)-phosphinoyl]-(2,4,6-tri-methyl-phenyl) -methanone using sodium and tert-butanol as proton source. formula I Ri = iso-butyl, R2 = mesityl, m=2 a) Preparation of Na3P 3.45 g of sodium sand (150 mmol, 3 eq., M = 22.99 g/mol), 1.55 g of purified red phosphorous (50.0 mmol, 1 eq., M = 30.97 g/mol) and 125 mg of naphthalene (1.0 mmol, M = 128.17 g/mol) are suspended in 120 ml of dimethoxyethane (DME). The suspension is heated up to 75°C and kept at this temperature for 20 h under stirring. A color change from green over red-brown into black takes place. b) Preparation of NaPH2 The reaction mixture of step a) is cooled down to -10 to -15°C. 10 ml of tert-butanol (0.1 mol, 2 eq., M = 74.12 g/mol) in 10 ml DME is added within 20 min under stirring. A nearly clear brown solution is obtained, containing a small amount of unreacted sodium. Stirring is continued for another 20 min. 16.8 ml of 2,4,6-trimethylbenzoyl chloride (TMBCI) (0.1 mol, 2 eq., M = 182.65 g/mol) are quickly added to the reaction mixture of step b), resulting in a color change to yellow. The reaction mixture is left stirring for another 20 min under ice cooling, followed by stirring for one hour at room temperature. The 31P NMR spectra shows a signal for sodium bis(mesitoyl)phosphideDME {Na[P(COMes)2]DME} at 82 ppm (>95%). c-1) Isolation of {Na[P(COMes)2]DME} The reaction mixture of step c) is concentrated under high vacuum. The resulting orange-yellow foam is taken up in 100 ml of toluene and then filtered through G4/Celite. The filter cake is twice washed with toluene providing a clear orange-yellow filtrate solution. The filtrate solution is concentrated under vacuum to a volume of about 70 ml, and then carefully overlayed with hexane (30 ml). Yellow cubic crystals separate from the solution and are identified as sodium bis(mesitoyI)phosphidexDME {Na[P(COMes)2]xDME} (C24H32Na04P, M = 438.47 g/mol) by 31P-, 1H- and 13C-NMR spectroscopy. Furthermore, single-crystal X-ray structural analysis shows that the crystals are composed of an ion pair complex of the formula [Na3[P(COMes)2]4] [Na(DME)3]. The yellow crystals are soluble in toluene, THF and DME, however little soluble in hexane. M.p. = 208°C. 1H-NMR (250.13 MHz, C6D6, 25°C): 5 = 6.60 (s, 4 H, Mes CH), 2.94 (s, 4 H, DME CH2), 2.87 (s, 6 H, DME CH3), 2.61 (s, 12 H, Mes o-CH3), 2.08 (s, 6 H, Mes p-CH3). 13C{H}-NMR (75.47 MHz, C6D6, 25°C): 6 = 236.2 (d, 1JCp = 94.0 Hz, CO), 145.5 (d, 2JCP = 38.3 Hz, Mes C1), 136.3 (d, 5JCP = 0.9 Hz, Mes C4), 133.9 (d, 3JCP = 2.7 Hz, Mes C2'6), 128.3 (s, Mes C3'5), 71.0 (s, DME CH2), 58.4 (s, DME CH3), 21.1 (s, Mes p~CH3), 20.1 (d, 4JCP = 2.5 Hz, Mes o-CH3). 31P{H}-NMR (101.25 MHz, C6D6, 25°C): 6 = 84.1 (br.). c-2) A DME-free product is obtained if the toluene filtrate solution from step c-1) is completely concentrated under vacuum first. The residue is suspended in n-hexane (80 ml), the resulting yellow solid filtered off and then dried under high vacuum. According to NMR spectroscopy measurements, the product consists of DME-free {Na[P(COMes)2} (C20H22NaO2P, M=348.35 g/mol). d) Alkylation to iso-BuP(COMes)2 The solution obtained in step c) is concentrated to 80 ml. 9.6 g of isobutyl bromide (0.07 mol, 1.4 eq., M = 137.02 g/mol) are added. The yellow-orange suspension is heated up to 60°C and kept at this temperature for 96 h under stirring. The 31P NMR spectra of the reaction solution shows a signal for iso-BuP(COMes)2 at 48 ppm (>91%). The light-yellow suspension is filtered through G4/Celite and the filter cake washed once with DME (10 ml). All volatile compounds are removed under high vacuum giving iso-BuP(COMes)2 as a yellow oil. e) Oxidation to iso-BuP(=0)(COMes)2 iso-BuP(COMes)2 obtained in step d) is first taken up in 50 ml of toluene. Water (25 ml) and 2-3 drops of cone. H2S04 are slowly added at room temperature, such that the pH of the aqueous phase is below a value of four. 6.0 ml of hydrogen peroxide (30% solution in H20, 0.053 mol, 1.05 eqM M = 34.02 g/mol) are added at such a rate that the temperature does not rise above 70°C. The resulting suspension is heated up to 60°C and kept at this temperature for two hours. The 31P NMR spectra of the toluene phase shows a new signal at 27 ppm (>83%), identified as iso-BuP(=0)(COMes)2. 20 ml of water are added and the aqueous phase saturated with NaCI. The organic phase is separated, first washed with 20 ml of a 1% aqueous NaHC03 solution, and then with water (3x15 ml). Drying of the organic phase over MgS04, filtration and concentration under vacuum gives a yellow oil which is further purified via column chromatography (Si02, n-hexane/ethyl acetate 4:1). 7.56 g (38%, related to red phosphorous) of iso-BuP(=0)(COMes)2 (C24H31P03, M = 398.47 g/mol) are obtained as a light yellow solid with Rf = 0.35 (n-hexane/ethyl acetate 4:1). 1H-NMR (300.13 MHz, CDCI3, 25°C): 5 = 6.85 (s, 4 H, Mes CH), 2.28 (s, 6 H, Mes p-CH3), 2.25 (s, 12 H, Mes o-CH3), 2.13 (m, 1 H, PCH2CH), 2.11 (m, 2 H, PCH2), 1.05 (d, 3JHH = 5.9 Hz, 6 H, CHCH3). 13C{H}-NMR (75.47 MHz, CDCI3, 25°C): 6 = 216.6 (d, 1JCP = 52.8 Hz, CO), 141.3 (d, 5JCP = 0.5 Hz, Mes C4), 136.1 (d, 2JCP = 40.1 Hz, Mes C1), 135.8 (d, 3JCP = 0.7 Hz, Mes C26), 129.4 (d, 4JCP = 0.8 Hz, Mes C3'5), 34.4 (d, 1JCP = 52.5 Hz, PCH2), 24.6 (d, 3JCP = 8.5 Hz, CHCH3), 23.9 (d, 2JCP = 4.5 Hz, PCH2CH), 21.4 (s, Mes p-CH3), 19.9 (d, 4JCP = 0.5 Hz, Mes o-CH3). 31P{H}-NMR (121.49 MHz, CDCI3) 25°C): 6 = 28.2. EA: calculated: [C] 72.34%, [H] 7.84%, [P] 7.77%; found [C] 72.19%, [H] 7.79%, [P] 7.81%. MS (El): m/z = 398 (M+, 0.33%), 251 (M+ - MesCO, 1%), 147 (MesCO+, 100%), 119 (Mes+, 7.5%). formula I, Ri = iso-butyl, R2 = mesityl, m=2 a) Preparation of Li3P 0.56 g of lithium powder (81 mmol), 0.84 g of red phosphorous (27 mmol) and 610 mg of naphthalene (4.8 mmol) are suspended in 60 ml of DME. The suspension is heated up to 75°C and kept at this temperature for 20 h under stirring. b) None. c) Preparation of lithium bis(mesitoyl)phosphide> The light brown mixture of step a) is cooled down to 30 to 40°C. 10.06 g of 2,4,6-trimethylbenzoyl chloride (54 mmol) are dropwise added. The reaction mixture is left stirring for 3 h at room temperature. d) Alkylation to iso-BuP(COMes)2 5.9 g of isobutyl bromide are added portion wise under stirring to the solution obtained in step c) (Reaction temperature 70-80°C). The reaction mixture is filtered over hyflo (Hyflo Super Cel®; Fluka, Buchs, Switzerland).The filtrate is evaporated to dryness, the residual mass dissolved in toluene and extracted with water and with sodium chloride solution. The organic phase is dried over Na2S04 and concentrated. 7.43 g of iso-BuP(COMes)2 is obtained as a yellow oil. e) Oxidation to iso-BuP(=0)(COMes)2 Analogous to step e) in Example 1. The crude product has been purified via column chromatography (Si02, n-hexane/ethyl acetate 85:15). 2.36 g (22%, related to red phosphorous) of iso-BuP(=0)(COMes)2 are obtained as a yellow oil which crystallize upon standing. 1H-NMR (CDCI3): 5 = 6.87 (s; 4 H); 2.30 (s; 6 H); 2.27 (s; 12 H); 2.10-2.17 (m; 3 H); 1.07 (d; 6 H). 31P-NMR (CDCI3): 5 = 29.3 formula I, R a) Preparation of Na3P analogous to Example 1. b) Preparation of NaPH2 analogous to Example 1. c) Preparation of sodium bis(mesitoyl)phosphide> to Example 1. d) Alkylation to methyl-bis(mesitoyl)phosphane, CH3P(COMes)2 A solution of {Na[P(COMes)2]DME} in DME prepared according to step c) is concentrated to 80 ml, 7.08 g of methyl iodide (0.05 mol, 1.0 eq., M = 141.94 g/mol) are added. The orange suspension is heated up to 60°C and kept at 60°C for 2 h under stirring. The 31P NMR spectrum shows a new signal at 39 ppm (>98%) identified as MeP(COMes)2. The light yellow suspension is filtered through G4/Celite and the filter cake washed once with DME (10 ml). All volatile compounds are removed under high vacuum giving MeP(COMes)2 as a yellow oil. e) Oxidation to CH3P(=0)(COMes)2, Analogous to Example 1. The 31P NMR spectra of the toluene phase shows a new signal at 22.6 ppm (>95%), identified as CH3P(=0)(COMes)2. The crude product has been purified via column chromatography (Si02, n-hexane/ethyl acetate 4:1). 5.06 g (29%, related to red phosphorous) of CH3P(=0)(COMes)2 (C2iH2503P, M = 356.40 g/mol) are obtained as a light yellow solid with Rf = 0.2 (n-hexane/ethyl acetate 4:1). M.p. = 126°C. 1H-NMR (300.13 MHz, CDCI3, 25°C): 5 = 6.86 (s, 4 H, Mes CH), 2.29 (s, 6 H, Mes p-CH3), 2.27 (s, 12 H, Mes o-CH3), 2.11 (d, 3 H, 2JPH = 12.3 Hz, PCH3). 13C{H}-NMR (75.47 MHz, CDCI3, 25°C): 6 = 216.7 (d, 1JCP = 58.3 Hz, CO), 141.4 (d, 5JCP = 0.6 Hz, Mes C4), 135.9 (d, 2JCP = 41.4 Hz, Mes C1), 135.6 (d, 3JCP = 0.8 Hz, Mes C2,6), 129.3 (d, 4JCP = 0.9 Hz, Mes C3'5), 21.4 (s, Mes p-CH3), 19.8 (d, 4JCP = 0.5 Hz, Mes o-CH3), 12.6 (d, 1JCP = 56.8 Hz, PCH3). 31P{H}-NMR (121.49 MHz, CDCI3, 25°C): 6 = 23.7. EA: calculated: [C] 70.77%, [H] 7.07%, [P] 8.69%; found [C] 70.69%, [H] 7.14%, [P] 8.70%. Example 4 Preparation of [methyl-(2,4}6-trimethyl-benzoyl)-phosphanyl]-(2,4,6-tri-methyl-phenyl)-methanone, starting from phosphorous trichloride, using sodium and 3-methyl-3-pentanol. a) Preparation of Na3P 3.72 g of sodium (162 mmol) and 0.51 g of naphthalene (4 mmol) are suspended in 70 ml of DME. 3.82 g of phosphorous trichloride (27 mmol) in 5 ml of DME is dropwise added within 15 min at room temperature. The suspension is stirred at room temperature overnight, and then for 2 h at 50-60°C, giving a black suspension. b) Preparation of NaPH2 The reaction mixture is cooled down to 20°C and 5.52 g of 3-methyl-3-pentanol (54 mmol) are added within 20 min. Stirring is continued overnight giving a light brown suspension. c) Preparation of sodium bis(mesitoyl)phosphidexDME, {Na[P(COMes)2]DME} 10.06 g of 2,4,6-trimethylbenzoyl chloride (54 mmol) are added within 5-10 min. The reaction mixture is left stirring for 2 h at room temperature giving an orange-white suspension. d) Alkylation to methyl-bis(mesitoyl)phosphane, CH3P(COMes)2 2.74 g of methyl iodide (19 mmol) are added dropwise and left stirring for 2 h at 35-40°C. The resulting white-yellow suspension is filtered over hyflo and concentrated under vacuum. The residue is redissolved in toluene and extracted two times with water and once with saturated aqueous NaCI solution. The organic phase is dried over Na2S04 and concentrated under vacuum. 12.34 g of crude CH3P(COMes)2 are obtained as a yellow oil. e) Oxidation to CH3P(=0)(COMes)2 The crude oil is redissolved in 30 ml of toluene and treated with 3.06 g of H202 (30% in H20, 27 mmol) within 5 min at 20°C. Stirring is continued for 30 min. The reaction mixture is diluted and then extracted with water, 2% aqueous NaHC03 and saturated NaCI solution, followed by drying over Na2S04 and concentration under vacuum. 9.41 g of yellow oil are stirred in 15 ml hexane during 30 min resulting in the precipitation of a solid which is collected by filtration. Washing with cold hexane and drying under high vacuum provides 3.85 g (40%, related to red phosphorous) of a white-yellow solid. An additional 0.27 g solid (3%) has been isolated from the mother liquor. a) Preparation of Li3P analogous Example 2, with 1.04 g of naphthalene (8.1 mmol). b) Preparation of LiPH2 The mixture of step a) is cooled down to 0 to 10°C. A solution of 5.58 g of 3-methyl-3-pentanol (54 mmol) in 5 ml of DME are added within 45 min under stirring. The reaction mixture is left stirring for another 120 min without cooling. c) Preparation of lithium bis(mesitoyl)phosphidexDME, {Li[P(COMes)2]DME} 10.06 g of 2,4,6-trimethylbenzoyl chloride (54 mmol) are dropwise added to the reaction mixture of step b) at 10-20°C within 25 min. The reaction mixture is left stirring for 40 min at room temperature. d) Alkylation to CH3P(COMes)2 The resulting thin brown-red suspension from step c) is dropwise treated with 5.75 g of methyl iodide (40.5 mmol) during 10 min under stirring. The reaction mixture is left stirring for another 100 min at 40°C, then filtered and concentrated under vacuum. The residue is dissolved in toluene (150 ml) and extracted with water (4 x). The toluene phase has been further treated as described in step e). e) Oxidation to CH3P(=0)(COMes)2 Analogous to step e) in Example 1. The crude product (10.3 g) has been purified via column chromatography (Si02, heptane/ethyl acetate 1:1). 1.82 g (19%, related to red phosphorous) of CH3P(=0)(COMes)2 are obtained as a light yellow solid. 1H-NMR (CDCI3): 6 = 6.88 (s, 4 H); 2.30(s, 6 H); 2.29(s, 12 H); 1.81-1.85 (d, 3 H). 31P-NMR (CDCI3): 5 = 24.8. a) Preparation of Li3P analogous to Example 2, with 0.51 g of naphthalene (4 mmol). b) None. c) Preparation of lithium bis(mesitoyl)phosphidexDME, {Li[P(COMes)2]DME} 10.06 g of 2,4,6-trimethylbenzoyl chloride (54 mmol) are dropwise added to the light brown reaction mixture of step a) at 30-40°C within 40 min. The reaction mixture is left stirring for 2.5 h at room temperature. d) Alkylation to CH3P(COMes)2 4.22 g of methyl iodide (29.7 mmol) are added within 15 min under stirring at 25-35°C to the solution obtained in step c). The reaction mixture is left stirring for 20 h at 40°C, cooled down to room temperature and then filtered over hyflo (Hyflo Super Cel®; Fluka, Buchs, Switzerland). The resulting filtrate is concentrated under vacuum, the residue dissolved in toluene and extracted three times with water and with saturated sodium chloride solution. The organic phase is dried over Na2S04 and concentrated under vacuum. 6.76 g of crude CH3P(COMes)2 are obtained as a yellow oil. e) Oxidation to CH3P(=0)(COMes)2 Analogous to step e) in Example 2. The crude product (5.32 g) has been purified via column chromatography (Si02, heptane/ethyl acetate 1:1). 1.27 g (13%, related to red phosphorous) of CH3P(=0)(COMes)2 are obtained as a white solid. 1H-NMR (CDCI3): 6 = 6.88 (s, 4 H); 2.30(s, 6 H); 2.29(s, 12 H); 1.81-1.85 (d, 3 H). 31P-NMR (CDCI3): 5 = 24.8. formula I, R1 = benzyl, R2, = mesityl, m=2 a) Preparation of Li3P 104 mg of lithium granulate (15 mmol), 155 mg of purified red phosphorous (5 mmol) and 64 mg of naphthalene (0.5 mmol) are suspended in 20 ml of DME. The suspension is heated to 70-80°C and kept at this temperature for 16 h under stirring. b) Preparation of LiPH2 Analogous to Example 4, with 1.02 g of 3-methyl-3-pentanol (10 mmol). c) Preparation of lithium bis(mesitoyl)phosphideDME, {Li[P(COMes)2]DME} Analogous to Example 4, with 1.83 g of 2,4,6-trimethylbenzoyl chloride (10 mmol). d) Alkylation to benzyl-P(COMes)2 1.31 g of benzyl bromide (7.5 mmol) are added to the thin light brown suspension obtained in step c) within 15 min under stirring. The reaction mixture is left stirring for another 2.5 h at 50-60°C. DME is removed under vacuum and the residue taken up in toluene (40 ml). e) Oxidation to benzyl-P(=0)(COMes)2 Analogous to step e) in Example 1. The crude product (2.3 g) has been purified via column chromatography (Si02, heptane/ethyl acetate 60:40). 207 mg of benzyl-P(=0)(COMes)2 are obtained as a yellow viscous oil. 1H-NMR (CDCI3): 5 = 7.25-7.32 (m, 5 H); 6.82 (s, 4 H); 3.60-3.64 (d, 2 H); 2.28 (s, 6 H); 2.08 (s, 12 H). 31P-NMR (CDCI3): 5 = 24.1. a) 1. c) Preparation of sodium bis(mesitoyl)phosphidexDME, {Na[P(COMes)2]xDME} Analogous to Example 1. d) preparation of [CF3-CH2-CH(CH3)-CH2]P(COMes)2 2.2 g of {Na[P(COMes)2]DME} (5.0 mmol, M = 438.47 g/mol) obtained according to step 1c) are dissolved in 40 ml of toluene and 30 ml of DME. 1.7 g of 1-bromo-2-methyl-4,4,4-trifluorobutane (1,66 eq., 8.3 mmol, M = 205.02 g/mol) are added. The reaction mixture is stirred at 80°C for 72 h. The 31P-NMR spectra shows no more signal of the starting material and a new signal at 45.7 ppm. The light yellow suspension is filtered through G4/Celite. The filtrate solution is concentrated to 50 ml. e) Oxidation to [CF3-CH2-CH(Me)-CH2]P(=0)(COMes)2 Analogous to Example 1. The 31P NMR spectra of the toluene phase shows a new signal at 26.4 ppm. The crude product has been purified via column chromatography (Si02, n-hexane/ethyl acetate 7:2). 1.05 g (45%, related to red phosphorous) of [CF3-CH2-CH(CH3)-CH2]P(=0)(COMes)2 (C25H30F3O3P, M = 466.47 g/mol) are obtained as a yellow oil with Rf = 0.4 (n-hexane/ethyl acetate 7:2). The yellow oil solidifies after several days storage in the fridge. M.p. = 78°C. 1H-NMR* (250.13 MHz, CDCI3, 25°C): 5 = 6.84 (s, 4 H, Mes CH), 2.40 (m, 2 H, CH2CF3), 2.26 (s, 6 H, Mes p-CH3), 2.23 (s, 6 H, Mes o-CH3), 2.20 (s, 6 H, Mes 0-CH3), 2.18 (m, 2 H, PCH2), 2.04 (m, 1 H, PCH2CH), 1.16 (d, 3JHH = 6.3 Hz, 3 H, CHCH3). 13C{H}-NMR* (62.90 MHz, CDCI3, 25°C): 5 = 215.8 (d, 1JCP = 52.4 Hz, CO), 215.4 (d, 1JCP = 52.7 Hz, CO), 141.5 (d, 5JCP = 0.6 Hz, Mes C4), 141.5 (d, 5JCP = 0.6 Hz, Mes C4), 135.8 (d, 3JCP = 0.7 Hz, Mes C2'6), 135.7 (d, 3JCP = 0.7 Hz, Mes C2'6), 135.7 (d, 2JCP = 40.6 Hz, Mes C1), 135.6 (d, 2JCP = 40.7 Hz, Mes C1), 129.3 (s, Mes C3'5), 129.3 (s, Mes C3'5),126.5 (q, 1JCF = 277.3 Hz, CF3), 40.8 (q, 2JCF = 27.5 Hz, CH2CF3), 40.7 (q, 2JCF = 27.5 Hz, CH2CF3), 32.0 (d, 1JCP = 52.9 Hz, PCH2), 23.7 (br., PCH2CH), 21.9 (d, 3JCP = 7.3 Hz, CHCH3), 21.2 (s, Mes p- CH3). 21.2 (s, Mes p-CH3), 19.8 (d, 4JCP = 0.4 Hz, Mes o-CH3), 19.7 (d, 4JCP = 0.4 Hz, Mes o- CH3). 19F-NMR (CDCI3, 25°C): 5 = -63.1 (m, CF3). 31P{H}-NMR (101.25 MHz, CDCI3, 25°C): 6 = 26.4. MS (El): m/z = 466 (M+, 3%), 319 (M+ - MesCO, 26%), 147.5 (MesCO\ 100%), 119.2 (Mes63%). Example 9 Preparation of [{3-[bis-(2,4,6-trimethyI-benzoyl)-phosphinoyl]-propyl}-(2,4,6-trimethyl-benzoyI)-phosphinoyl]-(2,4,6-trimethyl-phenyl)-methanone using lithium and no proton source. Formula I, n =2, RT = propylene, R2 = mesityl, m=2 a) Preparation of Li3P Analogous to Example 2, with 0.51 g of naphthalene (4 mmol). b) None. c) Preparation of lithium bis(mesitoyl)phosphidexDME, {Li[P(COMes)2]DME} Analogous to Example 2. 10.06 g of 2,4,6-trimethylbenzoyl chloride (54 mmol) are dropwise added to the light brown reaction mixture of step a) at 30-40°C within 30 min. The reaction mixture is left stirring for 1.5hat40-50°C. d) Alkylation to 0.91 g of 1,3-diiodopropane (3.0 mmol) are added within 5 min under stirring at 40-50°C to the solution obtained in step c). The reaction mixture is stirred for 40 min at the same temperature, and then for 6 h at 60-70°C. An additional 0.91 g of diiodopropane (3.0 mmol) are added within 5 min and the resulting reaction mixture left stirring for another 22 h at 60-70°C. After cooling down to 30-40°C, 0.87 g of methanol (27 mmol) are added and stirring continued for one hour at the same temperature. The reaction mixture is cooled down to room temperature and filtered over hyflo (Hyflo Super Cel®; Fluka, Buchs, Switzerland). The resulting filtrate is concentrated under vacuum, the residue dissolved in toluene and extracted three times with water and with saturated sodium chloride solution. The organic phase is dried over Na2S04 and concentrated under vacuum. 7.7 g of an orange oil are obtained. e) Oxidation analogous to step e) in Example 1. The crude product (5.32 g) has been purified via column chromatography (Si02, heptane/ethyl acetate 1:1) giving 1.52 g of a white solid. The solid has been further stirred in hexane, seperated and then dried under high vacuum giving 1.24 g (13%, related to red phosphorous) of the title compound as a yellow solid. 1H-NMR (CDCI3): 6 = 6.85 (s; 8 H); 2.23-2.37 (m; 4 H); 2.28 (s; 12 H); 2.23 (s; 24 H); 1.95-2.10 (m; 2 H). 31P-NMR (CDCI3): 5 = 26.7. a) preparation of Na3P analogous to Example 1 b) preparation of NaPH2 analogous to Example 1 c) preparation of sodium bis(mesitoyl)phosphidexDME, {Na[P(COMes)2]DME} analogous to Example 1 d) preparation of phenyl-bis(mesitoyl)phosphane, phenyl-P(COMes)2 One equivalent of phenyl iodide is added together with 1 mol% of Pd(PPh3)4. The reaction mixture is left stirring for 24 h at 60°C, showing 25% conversion according to the 31P-NMR spectra. Afterwards, the reaction mixture is left stirring for an additional 48 h giving a conversion of 33%. e) Oxidation analogous to step e) in Example 1 provides [phenyl-(2,4,6-trimethyl-benzoyl)-phosphinoyl]-(2,4,6-trimethyl-phenyl)-methanone (= Irgacure 819) as yellowish solid. 0.194 g of purified red phosphorus (6.26 mmol, 1 eq., M =30.97 g/mol) and 0.5 g of sodium sand (21.75 mmol, 3.47 eq., M = 22.99 g/mol) are grinded under argon atmosphere in an agate mortar providing a dark grey, viscous mass. The mixture is then heated under argon up to 300°C during 2 min in a Schlenk-tube giving a grey-black powder. The powder is then suspended in 10 ml of dimethoxyethane followed by dropwise addition of 1.147 g tert-butanol (15.47 mmol). The reaction is accompanied by vigorous gas evolution. The grey suspension is then stirred for 4 h at room temperature and the resulting grey-brown suspension filtered over Celite. The clear beige solution is concentrated under vacuum and the resulting light beige powder suspended in 10 ml of toluene. The suspension is heated up until a clear beige solution is formed. Octahedral crystals separate which are collected by filtration and then washed with 2 ml of toluene. 0.95 g of product (13% related to NaPH2) are obtained as a colorless solid. me proauci is cnaracienzea uy x-ray sirucuire analysis anu uunespunus iu an aiuunuiaie cluster with the formula [Nai3(OtBu)12@PH2]: (C48H11oNa13012p) M = 1209.22 g/mol)]. 1H-NMR (300.13 MHz, C6D6, 25°C): 5 = 1.49 (s, 110 H, lBu), - 2.18 (d, 2 H,1Jp,H = 142.5 Hz). 31P-NMR (121.47 MHz, C6D6j 25°C): 8 = - 292.3 (t, 1JPiH = 142.5 Hz) Example 12 Preparation of alcoholate cluster of phosphide by the reaction of sodium tert-butoxide with sodium phosphide NaPH2 has been first prepared according to Brauer, "Handbuch der Praparativen Anorganischen Chemie", Bd I, p. 510. Afterwards, 1.03 g sodium tert-butoxide (10.7 mmol, 12 eq., M = 96.10 g/mol) and 50 mg NaPH2 (0.89 mmol, 1 eq., M = 55.98 g/mol) are suspended in 15 mol of toluene. The beige suspension is kept for 24 hours at room temperature. Colorless, octahedral crystals separate from the reaction mixture which are collected by filtration and further washed with 2 ml of toluene. 0.85 g of product (78% related to NaPH2) are obtained as a colorless solid. The same analytical data are obtained like the product from example 11, corresponding to the formula [Na13(OtBu)12@PH2]: (C48H11oNa13Oi2P, M = 1209.22 g/mol)]. Example 13 Preparation of sodium bis(mesitoyl)phosphide {Na[P(COMes)2]} or sodium bis(mesitoyl)phosphideDME {Na[P(COMes)2]xDME} from [Na13(OtBu)12@PH2]. 1 g of [Na^O^u)^®?^] from example 12 (0.83 mmol, 1 eq., M = 1209.22 g/mol) is dissolved in toluene (the same experiment has been also run in DME). The resulting mixture is cooled over an ice-bath. 0.3 g of 2,4,6-trimethylbenzoyl chloride (TMBCI) in 5 ml of toluene are added dropwise. Stirring is continued for 30 min at room temperature. All volatile compounds have been removed at 0.1 Torr and the yellow-orange residue taken up in toluene. Subsequent filtration and crystallization from toluene/n-hexane leads to {Na[P(COMes)2]}. Furthermore, {Na[P(COMes)2]xDME} has been isolated when DME was used instead of toluene for the same procedure. This complex can be further alkylated as e.g. in Example 1 d). Formula I, R2=mesityl, R2 = t.butyl 0.5 g of NaPH2 (8.9 mmol, 1 eq., M = 55.98 g/mol), prepared according to example 11, are suspended in 30 ml of toluene. 1.575 g of methyl 2,4,6-trimethylbenzoate (8.9 mmol, 1 eq., M = 178.23 g/mol) in 10 ml of THF are dropwise added and stirring is continued for 30 min at room temperature. The resulting yellow suspension is filtered and then concentrated under high vacuum giving a yellow oil. The oil is taken up in 20 ml of THF and dropwise treated at room temperature with 0.807 g of pivalolyl chloride (2,2-dimethylpropionyl chloride) (6.7 mmol, 0.75 eq., M = 120.58 g/mol) in 10 ml of THF. The yellow suspension is stirred for 30 min at room temperature. 0.855 g of sodium tert-butoxide (8.9 mmol, 1 eq., M = 96.10 g/mol) are added in several portions providing a yellow-orange suspension. After stirring for 30 min at room temperature 0.55 ml of methyl iodide (8.9 mmol, 1 eq., M = 141.94 g/mol) are dropwise added giving an almost colorless suspension. Stirring is continued for an additional hour at room temperature. The reaction mixture is concentrated under vacuum and then taken up in 20 ml of toluene, filtered over Celite and additional rinsing with 10 ml of toluene. 31P-NMR analysis shows one resonance at 23.7 ppm for 2,2-dimethyl-1-[methyK2,4,6-trimethyl-benzoyl)-phosphanyl]-propan-1-one. To the resulting solution is added 10 ml of water and 2.01 g of 30% H202 solution (17.8 mmol, 2 eq., M = 34.01 g/mol). The reaction mixture is stirred for 4 h at 30°C. The organic phase is washed three times with 10 ml of water and the aqueous phases washed with 20 ml of toluene. The combined organic phases are dried over MgS04 and then concentrated under vacuum. The resulting yellow oil is purified by flash chromatography (hexane/ethyl acetate 1:1, Rf = 0.45). Yield: 0.69 g yellow oil (26%, C16H2303P, M = 294,33 g/mol) 1H-NMR (300.13 MHz, CDCI3, 25°C): 5 = 6.88 (s, 2 H, Mes CH), 2.30 (s, 3 H, Mes p-CH3), 2.29 (s, 6 H, Mes o-CH3), 1.76 (d, 2JP(H = 12.6 Hz, PCH3), 1.28 (s, 9 H, lBu). 13C{H}-NMR (75.47 MHz, CDCI3, 25°C): S = 220.9 (d, 1JCP = 43.1 Hz, 'BuCO), 215.2 (d, 1JCP = 57.7 Hz, MesCO), 140.7 (d, 5JCP = 0.8 Hz, Mes C4), 136.1 (d, 2JCP = 42.3 Hz, Mes C1), 134.6 (d, 3JCP = 0.6 Hz, Mes C2'6), 129.0 (d, 4JCP = 0.7 Hz, Mes C35), 48.6 (d, 2JCP = 37.6 Hz, C(CH3)3), 24.3 (s, C(CH3)3), 21.2 (s, Mes p-CH3), 19.8 (s, Mes o-CH3), 12.9 (d, 1JCP = 57.4 Hz, PCH3).31P-NMR (121.5 MHz, CDCI3, 25°C): 5 = 28.2 (q, 2JP,H = 12.6 Hz). 3.72 g of sodium (162 mmol) and 0.51 g of naphthalene (4 mmol) are suspended in 70 ml of DME. 3.82 g of PCI3 (27 mmol) is dropwise added within 15 min at room temperature. The suspension is stirred at room temperature overnight, giving a black suspension. b) Preparation of NaPH2 To the reaction mixture 5.52 g of 3-methyl-3-pentanol (54 mmol) are added dropwise within 3 hours. Stirring is continued for an additional 5.5 hours at room temperature, giving a light brown suspension. c) Preparation of sodium bis(mesitoyl)phosphideDME, {Na[P(COMes)2]xDME} 10.06 g of 2,4,6-trimethylbenzoyl chloride (54 mmol) are added dropwise within 30 min. The reaction mixture is left stirring over night at room temperature giving an orange- yellow suspension. d) Alkyiation to acetic acid 3-[bis-(2,4,6-trimethyl-benzoyl)-phosphanyl]-propyl ester 29.7 mmol of 3-bromopropylacetate (synthesised analogue to 6-bromohexylacetate according to literature: Z. Naturforsch.55 b; 2000; p 583 ) are added dropwise within 10 min. and left stirring for 2.5 h at 50-60°C. The resulting yellow suspension is taken to dryness and resolved in 100 ml toluene (yellow suspension). 31P-NMR(d6-benzene): 53.2 ppm (bisacyl-alkylphosphine) e) Oxidation 60 ml water are added to the crude reaction mixture. The pH is adjusted with 2 molar HCI to 5-7 and treated with 4.46 g of hydrogen peroxide (30% in H20, 40.5 mmol) within 5 min at room temperature. After heating to 50-60°C stirring is continued for 2h. The reaction mixture is separated and the organic layer is extracted with 2% aqueous NaHC03 and saturated NaCI solution, followed by drying over Na2S04 and concentration under vacuum. The crude 13.86g yellow oil is purified by preparative chromatography (heptane/ethylacetat 1:1; silicagel), to give 4.34 g 3-[bis-(2,4,6-trimethyl-benzoyl)-phosphinoyl]-propyl acetate as a yellow oil (yield 36%). 31P-NMR(CDCI3):27.5ppm a> after prep-chromatographie (heptane/ethylacetat 3:7; silicagel), b) after crystallisation from petrolether c) after prep-chromatographie (heptane/ethylacetat 3:7; silicagel), d) after crystallisation from petrolether e) after crystallisation from hexane f) after prep-chromatographie (heptane/ethylacetat 6:4; silicagel), 9) after prep-chromatographie (heptane/ethylacetat 7:3; silicagel), h) after prep-chromatographie (heptane : ethylacetat 1:1; silicagel), 0 after prep-chromatographie (heptane : ethylacetat 4:6; silicagel), a. Preparation of NaPH2 1.725 g (0.075 mol, 3 equivalents) Sodium sand are dissolved in 50 ml liquid ammonium at -70°C under argon. To this solution, a suspension of 0.775 g (0.025 mol, 1 equivalent) purified red phosophorus (grounded to hours, keeping the temperature between -55 and -65°C, while a reddish-beige solid is deposited from the reaction mixture. This solid is dissolved upon the addition of 4.8 ml tert-butanol (0.05 mol, 2 equivalents) in 7 ml tetrahydrofuran at -60°C over 1.5 hours. The blue solution is stirred for 2.5 hours at -60°C, during which time the color changes to green and finally ochre. The solution is slowly warmed to room temperature over a time of 4 hours. The 31P-NMR spectrum of the solution shows a resonance line at -297 ppm (t, 1J(P, H) = 155 Hz, NaPH2). b. Preparation of sodium bis (mesitoyl)phosphidexDME, {Na[P(COMes)2]xDME} The volatile components of the reaction mixture obtained according to example 32a are evaporated in vacuum and the residual ochre solid is dissolved in 60 ml dimethoxyethane (DME). 9.15 g (0.05 mol, 2 equivalents) of 2,4,6-trimethylbenzoyl chloride are slowly added at room temperature over one hour, resulting in a color change of the suspension to yellow and a slight increase of the temperature. The reaction mixture is stirred for another hour at room temperature. A single resonance at 81.6 ppm in the 31P-NMR spectrum shows the formation of sodium bis (mesitoyl)phosphidexDME, {Na[P(COMes)2]xDME}, in high yield. c. Alkylation to [Bis-(2,4,6-trimethyl-benzoyl)-phosphanyl]-acetic acid ethyl ester 4.175 g (0.025 mol. 1 equivalent) bromacetic acid ethyl ester are added over 15 minutes to the solution obtained in step b. After stirring, the solvent and all volatile compounds are removed under vacuum. [Bis-(2,4,6-trimethyl-benzoyl)-phosphanyl]-acetic acid ethyl ester is obtained as a beige solid in 60% yield (Referent to the red phosphorus starting material). The 31P-NMR spectrum shows the formation this product in high purity by a single resonance line at 46.5 ppm. Example 33 Preparation of acetic acid 3-[bis-(2,6-dimethoxy-benzoyl)-phosphinoyi]-propyl ester, starting from phosphorus trichloride. a) Preparation of Na3P 3.72 g of sodium (162 mmol) and 0.51 g of naphthalene (4 mmol) are suspended in 70 ml of DME. 3.82 g of phosphorus trichloride (27 mmol) are dropwise added within 15 min at room temperature. The suspension is stirred at room temperature overnight, giving a black suspension. b) Preparation of NaPH2 To the reaction mixture 5.52 g of 3-methyl-3-pentanol (54 mmol) dissolved in 10 ml DME are added dropwise within 3 hours. Stirring is continued for an additional 5.5 hours at room temperature, giving a light brown suspension. c) Preparation of sodium bis(2,6-dimethoxybenzoyl)phosphideDME, 10.83 g of 2,6 Dimethoxybenzoylchloride (54 mmol) dissolved in 20 ml DME are added dropwise within 50 min. The reaction mixture is left stirring over night at room temperature giving a brown-yellow suspension. d) Alkylation to acetic acid 3-[bis-(2,6-dimethoxy-benzoyl)-phosphanyl]-propyl ester 29.7 mmol of 3-bromopropylacetate (synthesised analogously to 6-bromohexylacetate reported in Z. Naturforsch.55 b; 2000; p 583 ) are added drop wise within 10 min. and left stirring for 3 h at 50-60°C. The resulting yellow suspension is taken to dryness and resolved in 80 ml toluene (yellow suspension). 31P-NMR(C6D6): 55.4 ppm (Bisacyl-alkylphosphine) e) Oxidation 50 ml water are added to the crude reaction mixture. 4.46 g of hydrogen peroxide (30% in H20, 40.5 mmol) are added within 5 min at room temperature. After heating to 50-60°C stirring is continued for 1 h. The reaction mixture is separated and the organic layer is extracted with 2% aqueous NaHC03 and saturated NaCI solution, followed by drying over Na2S04 and concentration under vacuum. The crude 13.77g yellow oil is purified by crystallisation from hexane, resulting in 6.76 g acetic acid 3-[bis-(2,6-dimethoxy-benzoyl)-phosphinoyl]-propyl ester as white yellow crystals (yield 52%). 31P-NMR(CDCI3):27.0ppm Examples 34-36 (Table 2) are prepared using the same reaction sequence as for sample33, expect that in step d the alkylating agent listed in Table 1 is used instead of 3-bromopropylacetate. Table 2 a) Preparation of Na3P 3.72 g of sodium (162 mmol) and 0.51 g of naphthalene (4 mmol) are suspended in 65 ml of DME. 3.82 g of phosphorus trichloride (27 mmol) dissolved in 5 ml DME is dropwise added within 10 min at room temperature. The suspension is stirred at room temperature overnight, giving a black suspension. b) Preparation of NaPH2 To the reaction mixture 5.52 g of 3-methyl-3-pentanol (54 mmol) dissolved in 10 ml DME are added drop wise within 1.5 hours. Stirring is continued for an additional 5 hours at room temperature, giving a light brown suspension. c) Preparation of sodium bis(2,6-dichlorobenzoyl)phosphideDME, 11.31 g of 2,6 Dichlorobenzoylchloride (54 mmol) dissolved in 10 ml DME are added drop wise within 60 min. The reaction mixture is left stirring over night at room temperature giving a yellow-brown suspension. d) Alkylation to acetic acid 3-[bis-(2,6-dichloro-benzoyl)-phosphanyl]-propyl ester 29.7 mmol of 3-bromopropylacetate (synthesised analogously to 6-bromohexylacetate reported in Z. Naturforsch.55 b; 2000; p 583) are added drop wise within 10 min. and left stirring for 8 h at 50-60°C. The resulting yellow suspension is taken to dryness and resolved in 80 ml toluene (yellow suspension). 31P-NMR(C6D6): 48.8 ppm (Bisacyl-alkylphosphine) e) Oxidation 50 ml water are added to the crude reaction mixture. 4.46 g of hydrogen peroxide (30% in H20, 40.5 mmol) are added within 5 min at room temperature. After heating to 50-60°C stirring is continued for 2 h. The reaction mixture is separated and the organic layer is extracted with 2% aqueous NaHC03 and saturated NaCI solution, followed by drying over Na2S04 and concentration under vacuum. The crude 10.6 g yellow oil is purified by prep-chromatography (heptane/ethylacetate 20:80; silicagel), resulting in 0.87 g acetic acid 3-[bis-(2,6-dichloro-benzoyl)-phosphinoyl]-propyl ester as yellow crystals (yield 7%). 31P-NMR(CDCI3): 25.0 ppm Example 38 (Table 3) is prepared using the same reaction sequence as for sample B, expect that in step d the alkylating agent listed in Table 3 is used instead of 3-bromopropylacetate. Example 39 and 40 Examples 39 and 40 (Table 4) are prepared using the same reaction sequence as described for example 1, expect that in step d the alkylating agent listed in Table 4 is used instead of isobutyl bromide. Example 41 Preparation of [Bis-(2-ethoxy-naphthalene-1-carbonyl)-phosphinoyl]-acetic acid ethyl ester, starting from phosphorus trichloride The compound of example 41 is prepared following the reaction sequence of example 32, except that 2-ethoxy-naphthalene-1-carbonyl chloride is used for the acylation step 15c and ethyl 2-bromoacetate in the alkylation step 15d). [Bis-(2-ethoxy-naphthalene-1-carbonyi)-phosphanyl]-acetic acid ethyl ester obtained in step d) has a 31P-NMR resonance at 51.77 ppm. Examples 42-75 Preparation of 2-[bis-(2,4,6-trimethyl-benzoyl)-phosphanyl] acetic acid esters and 2-[bis-(2,4,6-trimethyl-benzoyl)-phosphinoyl] acetic acid esters The 2-[bis-(2,4,6-trimethyl-benzoyl)-phosphanyl] acetic acid esters (Formula A) and 2-[bis-(2,4,6-trimethyl-benzoyl)-phosphinoyl] acetic acid esters (Formula B) derivatives of examples 42-75 (Table 5) are prepared using the reaction sequence reported for Example 15, expect that in step d the alkylating agents listed in Table 5 are used instead of 3-bromopropylacetate. Table 5. Alternatively, the compounds collected in Table 5 can also be prepared by transesterification of the methyl ester (Example 17) or ethyl ester (Example 18) with the corresponding alcohol in the presence of a suitable catalyst using reaction conditions known to in the literature. Suitable catalyst are, for example but without limiting to these examples, tin oxide, Fascat 4200 (dibutylzinn-diacetate commercially available of the Arkema group)., aluminium(lll) acetylacetonate or zirconium(IV)propoxide. Examples 76-78 Preparation of 2-[bis-(2,4,6-trimethyl-benzoyl)-phosphanyl] acetic acid esters and 2-[bis-(2,4,6-trimethyl-benzoyl)-phosphinoyl] acetic acid esters The 2-[bis-(2,4,6-trimethyl-benzoyl)-phosphanyl] acetic acid esters (Formula A) and 2-[bis-(2,4,6-trimethyl-benzoyl)-phosphinoyl] acetic acid esters (Formula B) derivatives of examples 76-78 (Table 6) are by transesterification of the methyl ester (Example 17) using the alcohol listed in Table 6 alcohol in the presence of Fascat 4200,as catalyst. Table 6 Examples 79-80 Preparation of 1-[bis-(2,4l6-trimethyl-benzoyl)-phosphanyl]-alkanesand 1-[bis-(2,4,6-trimethyl-benzoyl)-phosphinoyl]-alkanes 1-[Bis-(2,4,6-trimethyl-benzoyl)-phosphanyl]-alkanes (Formula A) and 1-[bis-(2,4,6-trimethyl-benzoyl)-phosphinoyl]-alkanes (Formula B) of Examples 79 - 80 (Table 7) are prepared using the same reaction sequence as described for example 1, expect that in step d the alkylating agent listed in Table 4 is used instead of isobutyl bromide. Examples 81-86 Preparation of 1-[bis-(2l4,6-trimethyl-benzoyl)-phosphanyl]-pentane-2,4-dione and 1 -[bis-(2,4,6-trimethyl-benzoyl)-phosphinoyl]-pentane-2,4-dione derivatives or 4-[bis-(2,4,6-trimethyl-benzoyl)-phosphanyl]-3-oxo-butyric acid esters 4-[bis-(2,4,6-trimethyl-benzoyl)-phosphinoyl]-3-oxo-butyric acid esters The bis-(2,4,6-trimethyl-benzoyl)-phosphanyl (Formula A) and bis-(2,4,6-trimethyl-benzoyl)-phosphinoyl derivatives (Formula B) of examples 81-86 (Table 8) are prepared using the reaction sequence reported for example 15, expect that in step d the alkylating agents listed in Table 7 are used instead of 3-bromopropylacetate. Table 8. Examples 87-93: Preparation of [bis-(2-ethoxy-naphthalene-1-carbonyl)-phosphanyl]-acetic acid ester derivatives and [bis-(2-ethoxy-naphthalene-1-carbonyl)-phosphinoyl]-acetic acid ester derivatives The [bis-(2-ethoxy-naphthalene-1-carbonyl)-phosphanyl]-acetic acid ester derivatives (Formula A) and [bis-(2-ethoxy«naphthalene-1-carbonyl)-phosphinoyl]-acetic acid ester derivatives (Formula B) of examples 87-93 are prepared following the reaction sequence of example 41, except that that in step d the alkylating agents listed in Table 9 are used instead of 3-bromopropylacetate Alternatively, the compounds collected in Table 9 can also be prepared by transesterification of the ethyl ester (Example 41) with the corresponding alcohol in the presence of a suitable catalyst using reaction conditions known in the literature. Suitable catalyst are, for example but without limiting to these examples, tin oxide, Fascat 4200 (Arkema Group), aluminium(lll) acetylacetonate or zirconium(IV)propoxide. Examples 94-100: Preparation of [(2-ethoxy-naphthalene-1-carbonyl)-(2,4,6-trimethylbenzoyl)-phosphanyl]-acetic acid ester derivatives and [(2-ethoxy-naphthalene-1-carbonyl)-(2,4,6-trimethylbenzoyl)-phosphionoyl]-acetic acid ester derivatives The [(2-ethoxy-naphthalene-1-carbonylH2,4,6-trimethylbenzoyl)-phosphanyl]-acetic acid ester derivatives and [(2-ethoxy-naphthalene-1-carbonyl)-(2,4,6-trimethylbenzoyl)-phosphionoyl]-acetic acid ester derivatives of examples 94-100 are prepared following the reaction sequence of example 14, except that [(2-ethoxy-naphthalene-1-carboxylic acid chloride is used in the first acylation step instead of pivaloyl chloride and the alkylating agents listed in Table 10 are used instead of methyl iodide. Alternatively, the compounds collected in Table 10 can also be prepared by transesterification of the ethyl ester (Example 41) with the corresponding alcohol in the presence of a suitable catalyst using reaction conditions known in the literature. Suitable catalyst are, for example but without limiting to these examples, tin oxide, Fascat 4200 (Arkema Group), aluminium(lll) acetylacetonate or zirconium(IV)propoxide. Examples 101-106; Preparation of diesters of bis-(2,4,6-trimethyl-benzoyl)-phosphanoyl]-acetic acid and bis-(2,4,6-trimethyl-benzoyl)-phosphinoyl]-acetic acid The diesters of bis-(2,4,6-trimethyI-benzoyl)-phosphanoyl]-acetic acid (Formula A) and bis-(2,4,6-trimethyl-benzoyl)-phosphinoyl]-acetic acid (Formula B) derivatives of examples 101-106 (Table 11) are prepared using the reaction sequence reported for example 15, expect that in step d the 0.5 equivalents of the alkylating agents listed in Table 11 are used instead of 3-bromopropyiacetate. Alternatively, the compounds collected in Table 11 can also be prepared by transesterification of the methyl ester (Example 17) or ethyl ester (Example 18) with 0.5 equivalents of the corresponding alcohol in the presence of a suitable catalyst using reaction conditions known in the literature. Suitable catalyst are, for example but without limiting to these examples, tin oxide, Fascat 4200 (Arkema Group), aluminium(lll) acetylacetonate orzirconium(IV)propoxide. Application examples: Pendulum Hardness A UV-curable white coat is prepared by mixing 67.5 parts of polyester acrylate oligomer (RTMEBECRYL 830, UCB, Belgium) 5.0 parts of hexanediol diacrylate 2.5 parts of trimethylolpropane triacrylate 25.0 parts of rutile titanium dioxide (RTMR-TC2, Tioxide, France) 2.0 parts of the photoinitiator The coating is applied to a coil-coated aluminium sheet using a 100 nm slotted doctor knife and then cured. Curing is carried out by conveying the sample twice, on a conveyor belt which is moving at a speed of 10 m/min, beneath an 80 W/cm medium-pressure mercury lamp (Hanovia, USA). The pendulum hardness is then determined in accordance with Konig (DIN53157) in [s]. The pendulum hardness is a measure of the through-curing of the composition. The higher the values, the more effective the curing which has been carried out. After the first pendulum hardness determination, the sample is after-exposed under low-pressure mercury lamps of the type TL 40W/03 (Philips; Emission maximum of 430 nm), and after 16h the pendulum hardness is determined again. Yellow index The yellow Index b was determined in accordance with ASTMD 1925-88. The Table below shows the results. Claims 1. A process for the preparation of acylphosphanes or bisacylphosphanes of formula I n and m are each independently of the other 1 or 2; Ri if n = 1, is unsubstituted linear or branched CrCi8alkyl or C2-Ci8alkenyl; or linear or branched CrC18alkyl or C2-C18alkenyl substituted once or more than once by groups selected from: -OR10, -SRio, -OCO-R10, -COO-R10 -CH=CH-CO-ORi0 or -C(CrC4alkyl)=C(CrC4alkyl)-CO-OR10; wherein Rio is hydrogen, CrC18alkyl, or C2-C18alkyl which is interrupted by one or several non-successive -O-atoms, a di,-tri,-tetra-or polyethylene glycol residue, C3-Ci2-cycloalkyl, tetrahydropyran-2-yl, phenyl-CrC4-alkylene, phenyl-c1-C4alkenylene, CrC6alkyl substituted by halogen or substituted by cyclohexyl or cyclopentyl, or substituted by tetrahydrofuranyl, furanyl, isopropyl-4-methyl-coclohexyl, C2-C18-alkenyl, unsubstituted phenyl, naphthyl or biphenyl being unsubstituted or phenyl, naphthyl or biphenyl substituted by one to five CrCs-alkyl, d-C8-alkoxy, CrCs-alkylthio and/or halogen; or Ri is linear or branched CrC18alkyl or C2-C18alkenyl substituted by -CO-Rn; wherein Rn is CrC18alkyl, or C2"Ci8alkyl which is interrupted by one or several non-successive -O-atoms, C3-Ci2-cycloalkyl, phenyl-CrC4-alkylene, unsubstituted phenyl, naphthyl or biphenyl being unsubstituted or phenyl, naphthyl or biphenyl substituted by one to five CrC8-alkyl, CrC8-alkoxy, CrC8-alkylthio and/or halogen or Ri is linear or branched Ci-C18alkyl or C2-C18alkenyl substituted by -CO-(CH)2-CO-CrCealkyl, CO-(CH)2-CO-phenyl, or by CO-CCHJrCOO-C1-c18alkyl; or Ri is linear or branched CrC18alkyl or C2-C18alkenyl substituted by -NR12R13) -N(Ri2)-CO-R10, -N(R12)-CO-OR10, -N(R12)-CO-NR12R13, -N(R12)-CO-Hal, -CO-NR12R13, wherein R10 is as defined above and R12 and Ri3 independently of one another are is hydrogen, CrC18alkyl, C2-C18alkyl which is interrupted by one or several non-successive O atoms, C3-C12-cycloalkyl, C2-C18-alkenyl, phenyl-Ci-C4-alkyl, phenyl, naphthyl, pyridyl, the radicals phenyl, naphthyl or pyridyl being unsubstituted or substituted by one to five CrC8-alkyl, CrC8-alkoxy, CrC8-alkylthio and/or halogen; or R12 and R13 forms a 5- or 6-membered 0-, S- or N-containing heterocyclic ring; that may be further annelated by an aliphatic or aromatic ring; or -SO2-R10, -SO2-ORi0, -S02-NR12R13, wherein Ri0,Ri2 and R13 are as defined above; or -PO(OCrC8alkyl)2, or -SiRi4Ri5Ri6, wherein R14, R15 and R16 independently of one another are H, Cr C8alkyl, C2-C8alkenyl, phenyl, C7-C9phenylalkyl, -OCVQjalkyl, -0-SiRi7Ri8Ri9, wherein R17, R18 and Ri9 are independently of each other H, d-Csalkyl, C2-C8alkenyl, phenyl, C7-C9phenylalkyl, -OCrC8alkyl; or -CH=CH-phenyl or -C(CrC4alkyl)=C(CrC4alkyl)-phenyl, phenyl-CrdalkyI, phenyl, naphthyl, biphenyl, C5-C12cycloalkyl or a 5- or 6-membered 0-, S- or N-containing heterocyclic, ring; benzophenonyl, thioxanthonyl; or Ri is C2-C18alkyl or C2-Ci8alkenyl which is interrupted by one or several non-successive -0-, -NH-, -NR12- or -S- atoms, and may additionally be substituted once or more than once by groups selected from: halogen or CN, or -OR™, -SR10, -OCO-R10, -COO-Ri0j wherein Ri0 is as defined above; or -NR12R13, -N(Ri2)-CO-R10, -N(R12)-CO-OR10, -N(Ri2)-CO-NR12R13, -N(Ri2)-CO-Hal, -CO-NR12R13, wherein R10 and Ri2 and Ri3 are as defined above; or -SO2-R10, -SO2-OR10, -S02-NR12R13, wherein R10l Ri2 and R13 are as defined above;or -PO(OCrC8alkyl)2, or -SiR14Ri5Ri6. wherein R14, R15 and Ri6 are as defined above; or phenyl-CrC4alkyl, phenyl or C5-Ci2cycloalkyl; or Ri is C2-Ci8alkyl or C2-C18alkenyl which is interrupted by -CO-, -COO-, -OCO-, - OCOO-, -CO-N(R12)-, -N(R12)-CO-, -N(R12)-CO-N(Ri2)-, -N(R12)-COO-, -COO-C1- C18alkylene, -COS-Ci-C18alkylene, -S02-, -S02-0-, -S02-N(R12)-, -(CH3)2Si- [OSi(CH3)2 ]m- with m = 1-6, phenyl-CrC4alkylene, phenylene, naphthylene, biphenylene, C5-C12cycloalkylene or a 5- or 6-membered 0-, S~ or N-containing heterocyclic ring; wherein R12 is as defined above; or Ri is trimethylsilyl or Hal-(CH3)2Si-[OSi(CH3)2 ]m- or (CH3)3Si-[OSi(CH3)2 ]m- with m = 1-6 ;or R, is -COOH, -COO-R10, -CO-NRi2R13, -CO-vinyl, -CO-phenyl which is unsubstituted or substituted by one or more -CH3, -OCH3, -CI; wherein R10, Ri2 and Ri3 are as defined above;or R1 is phenyl-C1-C4alkyl, phenyl, naphthyl, biphenyl, C5-Ci2cycloalkyl or a 5- or 6- membered 0-, S- or N-containing heterocyclic ring; all of the radicals phenyl, naphthyl, biphenyl, C5-C12cycloalkyl or the 5- or 6-membered -0-, S- or N- containing heterocyclic ring being unsubstituted or substituted by one to five halogen, CrC8alkyl, CrCealkylthio, CrC8alkoxy and/or -NR12Ri3; wherein Ri2 and R13 are as defined above; R1 if n = 2, is a divalent radical of the monovalent radical defined above or is -CH2-COO-Z-OCO-CH2- wherein Q is a single bond, -CH2-, -CR6R7-, -O- or -S- ; R4 and R5 are each independently of the other hydrogen, CrC4alkyl or Ci-C4alkoxy; R6 and R7 are each independently of the other d-C4alkyl; Z is CrCis alkylene or a bridge derived from a di,-tri,-tetra-or polyethylene glycol. R1 if n = 2, is a divalent radical of the monovalent radical defined above or is wherein Q is a single bond, -CH2-, -CR6R7-, -O- or -S- ; R4 and R5 are each independently of the other hydrogen, CrC4alkyl or Ci-C4alkoxy; R6 and R7 are each independently of the other (VCalkyl; R2 is CrC18alkyl or C2-C18alkenyl ; C1C18alkyl or C2-C18alkenyl substituted once or more than once by halogen; or -OR10, -OCO-R10, -OCO-Hal, -COO-R10, -CH=CH-CO-OR10 -N(R12)-CO-R10, -N(R12)-CO-Hal, ; -C(C1-C4alkyl)=C(C1-C4alkyl)-CO-OR10, -CO-NR12R13l wherein R10, R12 and R13 are as defined above; or -CH=CH-phenyl or -C(Cr C4alkyl)=C(CrC4alkyl)-phenyl; C3-C12cycloalkyl, C2-C18alkenyl, phenyl-Crdalkyl, phenyl, naphthyl, anthryl. biphenyl or a 5- or 6-membered -O-, S- or N-containing heterocyclic ring, the radicals phenyl, naphthyl, biphenyl or the 5- or 6-membered -0-, S- or N-containing heterocyclic ring being unsubstituted or substituted by one to five halogen, Ci-C8alkyl, d-C8alkoxy and/or CrCsalkylthio; R3 is one of the radicals defined under R^ the process comprises the steps a) contacting elemental phosphorous [P]*., P(Hal)3 or other phosphorous compounds in which the formal oxidation state of the phosphorous atom is higher than (-3) with a reducing metal optionally in the presence of a catalyst or an activator in a solvent to obtain metal phosphides Me3P or Me'3P2, wherein Me is an alkali metal and Me' is an earth alkali metal or to obtain metal polyphosphides b) optionally adding a proton source, optionally in the presence of a catalyst or an activator to obtain metal dihydrogen phosphides MePH2; c) subsequent acylation reaction with m acid halides of formula III or m carboxylic acid esters of formula IV or, in case that in formula I m = 1, with one carboxylic ester of formula IV followed by one acid halide of formula III or vice versa ,wherein R is the residue of an alcohol and R2 is as defined above; d) alkylation reaction in case of m = 2, subsequent reaction with an electrophilic agent RiHal or other electrophilic agents such as RTOSCVO-R-I , (Ri-0)3POf H2C=CR23COOR10 wherein ^ and R10 are as defined above, R2o is Ci-Cs-alkyl,, C-rC8-perfluoroalkyl, aryl or CrC4-alkylaryl, R2i is H or CrC8alkyl; R22 is CrC16alkyl or C2-C16alkenyl substituted once or more than once by halogen -OR™, -NR12Ri3, -SR10, -OCO-R10, -OCO-Hal, -COO-R10, -IM(R12)-CO-R10l -N(R12)-CO-OR10, -N(R12)-CO-NRl2R13, -N(R12)-CO-Hal, -CO-NR12R13, -SO2-R10, -SO2-ORi0, -S02-NRi2Ri3, -CH=CH-CO-OR10, -CH=CH-phenyl, "C(CrC4alkyl)=C(C1-C4alkyl)-CO-OR1o or -C(CrC4alkyl)=C(Cr C4alkyl)-phenyl, phenyl-CrC4alkyl, phenyl, naphthyl, biphenyl, C5-C12cycloalkyl or a 5- or 6-membered 0-, S- or N-containing heterocyclic ring; R23 is H or CH3, and n = 1-5 and R10) R12 and Ri3 is as defined above; and in the case of m = 1 reaction with an electrophilic agent R^al or other electrophilic agents such as RrOSOrO-Ri , and R23 are as defined above followed by the reaction with an electrophilic agent R3Hal or other electrophilic O agents such as R3-OS02-OR3, R3-OS02-R2o, D„ / \ (R3-0)3POf are as defined above to obtain the compounds of formula I. 2- A process according to claim 1 for the preparation of monoacylphosphanes of the formula I' (compounds of the formula I with n = 1 and m = 1) wherein R1, R2 and R3 are as defined in claim 1 which process comprises the steps a), b) and c) as defined in claim 1; and d) reaction with an electrophilic agent R^al or other electrophilic agents containing the residue R1 as defined in claim 1 step d for m = 1 followed by the reaction with an electrophilic agent R3Hal or other electrophilic agents containing the residue R3 as defined in claim 1 step d for m=1 to obtain the compounds of formula I'. 3. A process according to claim 1 for the preparation of symmetric bisacylphosphanes of the formula I" (compounds of the formula I with n = 1 and m = 2) wherein F^ and R2 are as defined in claim 1, which process comprises the steps a), b) and c) as defined in claim 1 for m = 2; and d) reaction with an electrophilic agent RiHal or other electrophilic agents containing the residue R to obtain the compounds of formula I". 4, A process according to claim 1 for the preparation of unsymmetric bisacylphosphanes of the formula H (compounds of the formula I with n = 1 and m = 2) wherein Ri is as defined in claim 1 and R2 and R2' independently of one another are as defined in claim 1 under R2 with the proviso that R2 is not equal R2\ which process comprises the steps a) and b) as defined in claim 1; and c) subsequent reaction with an acid halide of formula III or a carboxylic acid ester of formula IV wherein R is the residue of an alcohol and R2 is as defined above; subsequent reaction with a second acid halide III' or a second carboxylic acid ester of the formula IV, wherein R2' and Hal are as defined above, d) reaction with an electrophilic agent RiHal or other electrophilic agents containing the residue R-\ as defined in claim 1 step d for m = 2 to obtain the compounds of formula I'". 5. A process for the preparation of symmetric metal bisacylphosphides of the formula (V) or (Va) wherein R2 is as defined in claim 1 and the metal is Li, Na, K, Mg, which process comprises the steps a) b) and c) as defined in claim 1 for m = 2. 6. A process according to claim 1 for the preparation of unsymmetric metal bisacylphosphides of the formula (V) or (Va') wherein R2and R2' are as defined in claim 4 and the metal is Li, Na, K, Mg, which process comprises the steps a) b) and c) as defined in claim 4. 7. A process according to claim 1, wherein are n=1 and Ri is phenyl, linear or branched d-C8alkyl or C2-C18alkenyl or is linear or branched CrC8alkyl or C2-C18alkenyl substituted by CN, trifluormethyl, oxiranyl, isoindole-1,3-dione, -O- d-Cisalkyl, -O-benzyl, -CO-phenyl, -CO-d-dsalkyl, -OCO-d-dsalkylj-OCO-d-dsalkenyl; -COO-d-C18alkyl;-COO-d-d8alkylene-phenyl,-COO-d-dsalkylene-cycloalkyl, -COO-d-d8alkylene-tetrahydrofuranyl, -COO-CrC18alkylene-furanyl, -COO-cycloalkyl.-COO-d-C^alkenylj-COO-C1-c18alkenylene-phenyl; -COO-(CH2)2-3-CI, -COO-[(CH2)2-3-0]1_1o-C1-C6alkyl;-COO-[(CH2)2-3-0]1_10-C1-C6-OH, -CO-CH^CO-CrCiaalkylj-CO-CH^COO-CrCisalkyl.-O-tetrahydropyrany!, bicyclo[2.2.1]hept-2-en-5-yl)-methyl, PO(OCrC6alkyl)2 and wherein R2 is phenyl which is substituted in 2,6- or 2,4,6-position by d-C4alkyl and/or CrC4alkoxy, and/or chlorine; 2-ethoxy-naphth-1-yl, 2-methyl-naphth-1-yl oranthr-9-yl. 8. A process according to claim 1 for the preparation of (bis)acylphosphane ox ides and (bis)acylphosphane sulfides of formula IV Ri. R2, R3, n and m are as defined in claim 1, and Z is O or S, by oxidation or reaction with sulfur of the acylphosphane of formula I, l\ I" or I"'. 9. A process according to claim 1 for the preparation of (bis)acylphosphanes of formula I, the process comprising the steps of: a) contacting red phosphorous or PCI3 with an alkali metal in the presence of a solvent and optionally in the presence of polycyclic hydrocarbon catalyst, b) adding a sterically hindered alcohol; c) subsequent reaction with two equivalents of an acid halide Hal-CO-R2 to obtain a metal bisacylphosphide [R2-CO-P=C(OMe)R2], wherein Me is Na or Li; or with one equivalent of a caboxylic acid ester RO-CO-R2, followed by one equivalent of an acid halide Hal-CO-R2" to obtain a metal bisacylphosphide [R2-CO-P=C(OMe)R2'], wherein Me is an alkali metal d) subsequent reaction with an electrophilic agent RiHal or RiOSC^ORi to obtain the compounds of formula I. 10. A process according to claim 9, wherein in step a) sodium in liquid ammonia is contacted with red phosphorus in tetrahydrofuran. 11. Acylphosphanes and bisacylphosphanes of the formula I wherein n= 1 and Ri is linear or branched CrC18alkyl or C2-C18alkenyl substituted once or more than once by groups selected from: halogen or CN, or — -OR10, -SR10, -OCO-R10, -COO-Ri0> -CH=CH-CO-OR10 or -C(CrC4alkyl)=C(Ci-C4alkyl)-CO-OR10; wherein Rio is hydrogen, CrCi8alkyl, or C2-C18alkyl which is interrupted by one or several non-successive -O-atoms, a di,-tri,-tetra-or polyethylene glycol residue, C3-Ci2-cycloalkyl, tetrahydropyran-2-yl, phenyl-Ci-C4-alkylene, phenyl-C1-c18alkenylene, CrC6alkyl substituted by halogen or substituted by cyclohexyl or cyclopentyl, or substituted by tetrahydrofuranyl, furanyl, isopropyl-4-methyl-coctohexyl, C2-C18-alkenyl, unsubstituted phenyl, naphthyl or biphenyl being unsubstituted or phenyl, naphthyl or biphenyl substituted by one to five Ci-C8-alkyl, Ci-C8-alkoxy, CrC8-alkylthio and/or halogen; or Ri is linear or branched CrC18alkyl or C2-C18alkenyl substituted by -CO-Rn; wherein Rn is Crdsalkyl, or C2-Ci8alkyl which is interrupted by one or several non-successive -O-atoms, C3-Ci2-cycloalkyl, phenyl-C^C^alkylene, unsubstituted phenyl, naphthyl or biphenyl being unsubstituted or phenyl, naphthyl or biphenyl substituted by one to five CrC8-alkyl, CrC8-alkoxy, CrC8-alkylthio and/or halogen or Ri is linear or branched CrCi8alkyl or C2-Ci8alkenyl substituted by -CO-(CH)2-CO-CrC6alkyl, CO-(CH)2-CO-phenyl, or by CO-(CH)2-COO-CrCi8alkyl; or Ri is linear or branched Ci-C18alkyl or C2-Ci8alkenyl substituted by -NR12R13, -N(R12)-CO-R10) -N(R12)-CO-OR10, -N(R12)-CO-NR12R13, -N(R12)-CO-Hal, -CO-NR12R13, wherein R10 is as defined above and Ri2 and Ri3 independently of one another are is hydrogen, CrCi8alkyl, C2-C18alkyl which is interrupted by one or several non-successive O atoms, C3-C12-cycloalkyl, C2-C18- alkenyl, phenyl-CrC4-alkyl, phenyl, naphthyl, pyridyl, the radicals phenyl, naphthyl or pyridyl being unsubstituted or substituted by one to five d-C8-alkyl, CrC8-alkoxy, CrC8-alkylthio and/or halogen; or R12 and R13 forms a 5- or 6- membered 0-, S- or N-containing heterocyclic ring; that may be further annelated by an aliphatic or aromatic ring; or -S02-Rio, -SO2-OR10, -S02-NR12Ri3, wherein Rio,Ri2 and R13 are as defined above; or -PO(OCrC8alkyl)2, or -SiRuRisRie. wherein R14, R15 and Ri6 independently of one another are H, Cr C8alkyl, C2-C8alkenyl, phenyl, C7-C9phenylalkyl, -OCrC8aIkyl, -0-SiR17R18R19, wherein R17j R18 and R19 are independently of each other H, CrC8alkyl, C2- C8alkenyl, phenyl, C7-C9phenylalkyl, -OCrC8alkyl; or -CH=CH-phenyl or -C(Cl-C4alkyl)=C(C1-C4alkyl)-phenyl, phenyl-CrC4alkyl, phenyl, naphthyl, biphenyl, C5-C12cycloalkyI or a 5- or 6-membered 0-, S- or N- containing heterocyclic, ring; benzophenonyl, thioxanthonyl; or Ri is C2-C18alkyl or C2-Ci8alkenyl which is interrupted by one or several non-successive -0-, -NH-, -NR12- or -S- atoms, and may additionally be substituted once or more than once by groups selected from: halogen or CN, or -OR10, -SR10, -OCO-R10, -COO-R10j wherein R10 is as defined above; or -NR12R13, -N(R12)-CO-R10J -N(R12)-CO-OR10) -N(R12)-CO-NR12R13, -N(R12)-CO-Hal, -CO-NRi2R13, wherein R10 and R12 and R13 are as defined above; or -SO2-R10, -SO2-OR10, -S02-NR12R13, wherein Ri0) Ri2 and Ri3 are as defined above;or -PO(OCrC8alkyl)2, or -SiR14Ri5Ri6, wherein R14, R15 and R16 are as defined above; or phenyl-Ci-C4alkyl, phenyl or C5-C12cycloalkyl; or Ri is C2-C18alkyl or C2-C18alkenyl which is interrupted by -CO-, -COO-, -OCO-, -OCOO-, -CO-N(R12)-, -N(R12)-CO-, -N(R12)-CO-N(R12)-, -N(R12)-COO-, -COO-C1- C18alkyiene, -COS-C^C^alkylene, -SOr, -S02-0-, -S02-N(R12)-, -(CH3)2Si-[OSi(CH3)2 ]m- with m = 1-6, phenyl-C1-C4alkylene, phenylene, naphthylene, biphenylene, C5-C12cycloalkylene or a 5- or 6-membered 0-, S- or N-containing heterocyclic ring; wherein R12 is as defined above; or R, is trimethylsilyl or Hal-(CH3)2Si-[OSi(CH3)2 ]m- or (CH3)3Si-[OSi(CH3)2 ]m- with m = 1-6 ;or R., is -COOH, -COO-R10, -CO-NR^R^.-CO-vinyl, -CO-phenyl which is unsubstituted or substituted by one or more ~CH3, -OCH3, -CI; wherein R10, R12 and R13 are as defined above and m, R2 and R3 are as defined in claim 1, or wherein n=2 and R1 if n=2, is -CH2-COO-Z-OCO-CH2- Z is GI-C-IB alkylene or a bridge derived from a di,-tri,-tetra-or polyethylene glycol. 12. Acylphosphanes and bisacylphosphanes of the formula I according to claim 11 wherein n = 1 and R1 is linear or branched C.,-C8alkyl or C2-C18alkenyl substituted by CN, trifluormethyl, oxiranyl, isoindole-1,3-dione, -O-C^C-isalkyi, -Q-benzyl, -CO-phenyl, -CO-C^C^alkyl, -OCO-C^C^alkyh-OCO-C1-c18alkenyl; -COO-CrC18alkyl; -COO-CrC18alkylene-phenyl,-COO-CrC18alkylene-cycloalkylf -COO-Ci-C^alkylene-tetrahydrofuranyl, -COO-CrC18alkylene-furanyl, -COO-cycloalkyl, -COO-d-C^alkenyl; -COO-CrC18alkenylene-phenyl; -COO-(CH2)2-3-CI, -COO-[(CH2)2-rO]1.10-CrC6alkyl;-COO-[(CH2)r3-O]1.1(rCrC6-OHl -CO-CH2-CO-CrC18alkyl; -CO-CtVCOO-C1-c18alkyl, -O-tetrahydropyranyl, bicyclo[2.2.1]hept-2-en-5-yl)-methyl, PO(OCrC6alkyl)2 and wherein m R2 and R3 are as defined in claim 1 or wherein n = 2 and Rn= -CH2-COO-Z-OCO-CH2-Z is CpC-jB alkylene or a bridge derived from a di,-tri,-tetra-or polyethylene glycol. 13. The use of acylphosphanes and of bisacylphosphanes of claim 11 and 12 as photoinitiators. Dated this 23 day of May 2007

Full Text

Process for preparing acvlphosphanes and derivatives thereof
The present invention relates to a new, selective process for the preparation of mono- and bisacylphosphanes, mono- and bisacylphosphane oxides or mono- and bisacylphosphane sulfides starting from elemental phosphorous [P]*, or phosphorous reagents with a formal oxidation state of phosphorous > -3, such as for example phosphorous trihalogenide P(Hal)3 or, phosphorous oxides without isolation of the intermediates.
As the technology of the mono- and bisacylphosphine oxides is becoming increasingly important owing to the excellent photoinitiator properties of these compounds there is also a need for highly practicable processes involving as little elaboration for the preparation of the required intermediates, especially of the corresponding mono- and bisacylphosphanes, but also of the oxide and sulfide end products. There still remains a need for a process which allows a high variability and flexibility for the introduction of all three substituents at the phosphorous atom of mono- and bisacylphosphane structures.
The European Patent Publication EP1 135 399 B1 describes a process for the preparation of mono- and bisacylphosphanes, of mono- and bisacylphosphane oxides and of mono- and bisacylphosphane sulfides, which process comprises first reacting organic P-monohalogeno-phosphanes (R2-PCI) or P,P-dihalogenophosphanes (R-PCI2) or mixtures thereof, with an alkali metal or magnesium in combination with lithium, where appropriate in the presence of a catalyst, and then carrying out the reaction with acid halides and, in the case of the process for the preparation of oxides, carrying out an oxidation step and, in the case of the preparation of sulfides, reacting the phosphanes so obtained with sulfur. The reaction is usefully carried out in a solvent. The solvent used may be, in particular, ethers which are liquid at normal pressure and room temperature. Examples thereof are dimethyl ether, diethyl ether, methylpropyl ether, 1,2-dimethoxyethane, bis(2-methoxyethyl)ether, dioxane or tetrahydro-furan. Tetrahydrofuran is preferably used.
The International Application PCT/EP 04/51427 describes a process to prepare mono- and bisacylphosphanes, which process comprises first reacting organic P-monohalogeno-phosphanes (R2-PCI) or P,P-dihalogenophosphanes (R-PCI2), or phosphorous halide oxide or phosphorous halide sulfide with an alkali metal (metallation) in a solvent in the presence of a proton source (reduction), and where appropriate in the presence of a catalyst, and then carrying out the reaction with acid halides.

Brandsma and coworkers describe the preparation of dihydrogen metal phosphides, represented by the formula MePH2, by the reaction of Me3P with a proton source (tert-butanol) in an organic solvent, preferably THF or DME (M.C.J.M. van Hoijdonk, G. Gerritsen, L. Brandsma, Phosphorous, Sulfur, Silicon 2000, 162, 39-49). Addition of an alkyl halide RHal leads to the formation of a monoalkyl phosphine RPH2. It is known that monoalkyl phosphines can be further reacted with an acid halide, as described in the International Application PCT/EP 04/51427, filed July 9, 2004.
A. Steinicke and coworkers describe the reduction of red phosphorous with strongly reducing metals, giving metal phosphides MenPm. Addition of an alkyl halide leads to the formation of alkylcyclophosphanes cyclo-(RP)n (A. Steinicke, K.-H. Thiele, A. Haaland, V.I. Sokolov, H.V. Volden, Z. anorg. allg. Chem. 1997, 623, 1925-1930). Reductive cleavage of alkylcyclophosphanes with a metal in the presence of a proton source (e.g. tert-butanol) gives a monoalkyl phosphine RPH2, which can be further reacted with an acid halide, as described in the International Application PCT/EP 04/51427.
The above referenced patent publications describe a process wherein the alkyl or aryl substituent at the phosphorous atom of the mono- or bisacylphosphane was part of the starting material R2-PCI or R-PCI2. As only a limited number of P-monohalogenophosphanes (R2-PCI) or P,P-dihalogenophosphanes (R-PCI2) are readily available, accessible, or processible, there is a need to develop a process enabling the preparation of mono- and bisacylphosphanes which process provides a higher variance for the substituents at the phosphorous atom. Furthermore, it should be avoided to use toxic, pyrophoric and difficult to handle phosphorous starting materials, like phosphine gas (PH3), or primary and secondary alkyl and aryl phosphines R-PH2. R2-PH, respectively.
Photoinitiators bearing suitable functional groups that allow a chemical reaction with suitable functional groups on low molecular, oligomeric or polymeric compounds are highly demanded for the development of compositions containing low volatile and non-migrating photoinitiators, as they are for examples required for printing inks used in direct food contact applications. Furthermore, photoinitiators bearing suitable functional groups can be linked to other additives, such as sensitizers, stabilizers, surface active agents and so on, in order to provide an additional functionality to the photoinitiator. Hence an easy access to such

functionalized photoinitiators, especially mono- or bisacylphosphine oxides, is highly desirable
In the above mentioned patent publications, the acylation of the intermediate primary or secondary alkyl and aryl phosphines R-PH2 and R2-PH, respectively, is performed in the presence of strong bases, such as butyl lithium, or alkali metals such as lithium or sodium. Many functional groups do not tolerate such reaction conditions. Hence the type of functional groups that can be introduced on the residue R by the processes claimed in the afore mentioned patents is limited to those that tolerate these harsh reaction conditions. Therefore, there is a need for a synthetic access that allows the easy introduction of a broader variety of functional groups on the substituents on the phosphorous atom.
It has now been found that in the process according to the invention a reactive intermediate is generated, which can selectively be alkylated/arylated using any alkylating/arylating agent (e.g. RHal), or reacted with typical electrophiles. The substituent R at the phosphorous atom is thus introduced via a reaction with an electrophile within the said process. The possibility of using any electrophile provides a higher variance for the substituents at the phosphorous atom.
Furthermore, said substituent R is introduced after the acylation step that requires the use of strong bases, such as butyl lithium, or of alkali metals, such as lithium or sodium. Thus even substituents bearing functional groups that would not tolerate such conditions can be introduced, thereby considerably enlarging the variance of functional groups.
Starting with the reduction of elemental phosphorous [P]*,, phosphorous trihalogenide P(Hal)3, or other phosphorous compounds possessing a phosphorous atom with a formal oxidation state > -3, followed by the acylation of the obtained metal phosphides MenPm [e.g-trialkali metal phosphide (Me3P)], or the acylation of dihydrogen metal phosphide (MePH2), it is possible to avoid the use, the isolation, the generation, or the handling of a toxic gas like PH3, or alkyl and aryl phosphines. The whole process may optionally be performed in the same reactor ("one-pot" reaction).
The invention relates to a process for the preparation of acylphosphanes or bisacylphosphanes of formula I

n and m are each independently of the other 1 or 2;
Ri if n = 1, is unsubstituted linear or branched CrCi8alkyl or C2-C18alkenyl; or
linear or branched d-Ci8alkyl or C2-C18alkenyl substituted once or more than once by
groups selected from:

-OR10, -SR10, -OCO-R10, -COO-R10> -CH=CH-CO-OR10 or -C(C1-C4alkyl)=C(C1-C4alkyl)-CO-OR10; wherein
Rio is hydrogen, d-dsalkyl, or C2-C18alkyl which is interrupted by one or several non-successive -O-atoms, a di,-tri,-tetra-or polyethylene glycol residue, C3-C12-cycloalkyl, tetrahydropyran-2-yl, phenyl-d-d-alkylene, phenyl-CrC4-alkenylene, d-C6alkyl substituted by halogen or substituted by cyclohexyl or cyclopentyl, or substituted by tetrahydrofuranyl, furanyl, isopropyl-4-methyl-coclohexyl, C2-C18-alkenyl, unsubstituted phenyl, naphthyl or biphenyl being unsubstituted or phenyl, naphthyl or biphenyl substituted by one to five d-Cs-alkyl, d-C8-aikoxy, d-C8-alkylthio and/or halogen; or
Ri is linear or branched d-d8alkyl or C2-C18alkenyl substituted by -CO-Rn; wherein
Rn is d-C18alkyI, or C2-C18alkyl which is interrupted by one or several non-successive -O-atoms, C3-Ci2-cycloalkylf phenyl-d-C4-aIkylene, unsubstituted phenyl, naphthyl or biphenyl being unsubstituted or phenyl, naphthyl or biphenyl substituted by one to five d-Cs-alkyl, d-C8-alkoxy, d-C8-alkylthio and/or halogen or
Ri is linear or branched d-d8alkyl or C2-C18alkenyl substituted by -CO-(CH)2-CO-d-C6alkyl, CO-(CH)2-CO-phenyl, or by CO-(CH)2-COO-d-Ci8alkyl; or
Ri is linear or branched d-dsalkyl or C2-C18alkenyl substituted by ~NR12R13, -N(R12)-CO-R10, -N(R12)-CO.OR10, -N(R12)-CO-NR12R13,
-N(R12)-CO-Hal, -CO-NR12R13) wherein R10 is as defined above and R12 and R13 independently of one another are is hydrogen, d-dsalkyl, C2-C18alkyl which is interrupted by one or several non-successive O atoms, C3-C2-cycloalkyl, C2-C18-alkenyl, phenyl-d-d-alkyl, phenyl, naphthyl, pyridyl, the radicals phenyl, naphthyl or

pyridyl being unsubstituted or substituted by one to five C1-C8-alkyl, C1-C8-alkoxy, Ci-C8-alkylthio and/or halogen; or R12 and R13 forms a 5- or 6-membered 0-, S- or N-containing heterocyclic ring; that may be further annelated by an aliphatic or aromatic ring; or
-SO2-R10, -SO2-OR10, -S02-NR12Ri3, wherein R10,R12and R13 are as defined above; or
-PO(OCi-Caalkyl)2. or
-SiR14Ri5Ri6, wherein R14, R15 and Ri6 independently of one another are H( C1-C8alkyl,
C2-C8alkenyl, phenyl, C7-C9phenylalkyl, -OC1-C8alkyl, -0-SiR17R18R19, wherein R17, R18
and R19 are independently of each other H, C1-C8alkyl, C2-C8alkenyl, phenyl, C7-
C9phenylalkyl, -OC1-C8alkyl; or
-CH=CH-phenyl or -C(C1-C4alkyl)=C(C1-C4alkyl)-phenylI phenyl-CrC4alkyl, phenyl,
naphthyl, biphenyl, C5-C12cycloalkyl or a 5- or 6-membered 0-, S- or N-containing
heterocyclic, ring; benzophenonyl, thioxanthonyl;
or
Ri is C2-C18alkyl or C2-Ci8alkenyl which is interrupted by one or several non-successive -0-, -NH-, -NR12- or -S- atoms, and may additionally be substituted once or more than once by groups selected from: halogen or CN, or
-OR10, -SR10, -OCO-R10, -COO-R10j wherein R10 is as defined above; or -NR12Ri3, -N(R12)-CO-R10, -N(R12)-CO-OR10, -N(R12)-CO-NR12R13, -N(R12)-CO-Hal, -CO-NR12Ri3, wherein R10 and R12 and R13 are as defined above; or -SO2-R10, -SO2-OR10, -S02-NR12R13, wherein R10l R12and Ri3 are as defined above;or -PO(OC1-C8alkyl)2> or
-SiR14Ri5Ri6, wherein R14l R15 and R16 are as defined above; or phenyl-CrC^alkyl, phenyl or C5-C12cycloalkyl; or
Ri is C2-C18alkyl or C2-C18alkenyl which is interrupted by -CO-, -COO-, -OCO-, -OCOO-, -CO-N(R12)-, -N(R12)-CO-, -N(R12)-CO-N(R12)-, -N(R12)-COO-, -COO-CrCiaalkylene, -COS-CrC18alkylene, -SOs-, -S02-0-, -S02-N(R12)-, -(CH3)2Si-[OSi(CH3)2 ]m- with m = 1-6, phenyl-Ci-C4alkylene, phenylene, naphthylene, biphenylene, C5-C12cycloalkylene or a 5- or 6-membered 0-, S- or N-containing heterocyclic ring; wherein R12 is as defined above; or
Ri is trimethylsilyl or Hal-(CH3)2Si-[OSi(CH3)2 ]m- or (CH3)3Si-[OSi(CH3)2 ]m- with m = 1-6 ;or

Ri is -COOH, -COO-R10, -CO-NR12R13, -CO-vinyl, -CO-phenyl which is unsubstituted or substituted by one or more -CH3, -OCH3, -CI; wherein R10, R12 and Ri3 are as defined above;or
Ri is phenyl-CrC4alkyl, phenyl, naphthyl, biphenyl, C5-C12cycloalkyl or a 5- or 6-membered 0-, S- or N-containing heterocyclic ring; all of the radicals phenyl, naphthyl, biphenyl, C5-C12cycloalkyl or the 5- or 6-membered -0-, S- or N-containing heterocyclic ring being unsubstituted or substituted by one to five halogen, d-Csalkyl, C1-C8alkylthio, CrCsalkoxy and/or -NR12R13; wherein R12and R13 are as defined above;

R2 is C|-C18alkyl or C2-C18alkeny ; C1-C18alkyl or C2-C18alkenyl substituted once or more than once by halogen; or
-OR10, -OCO-R10, -OCO-Hal, -COO-R10, -CH=CH-CO-OR10 -N(R12)-CO-R10, -N(R12)-CO-Hal, ; -C(CrC4alkyl)=C(CrC4alkyl)-CO-OR10, -CO-NR12R13, wherein R10l R12and R13 are as defined above; or -CH=CH-phenyl or -C(CrC4alkyl)=C(C1-C4alkyl)-phenyl; C3-C12cycloalkyl, C2-C18alkenyl, phenyl-d^alkyl, phenyl, naphthyl, anthryl. biphenyl or a 5- or 6-membered -0-, S- or N-containing heterocyclic ring, the radicals phenyl, naphthyl, biphenyl or the 5- or 6-membered -0-, S- or N-containing heterocyclic ring being unsubstituted or substituted by one to five halogen, C1-C8alkyl, C13 C8alkoxy and/or C1-C8alkylthio;
R3 is one of the radicals defined under R13
the process comprises the steps

a) contacting elemental phosphorous [P]« P(Hal)3 or other phosphorous compounds in
which the formal oxidation state of the phosphorous atom is higher than (-3)
with a reducing metal optionally in the presence of a catalyst or an activator in a solvent to obtain metal phosphides Me3P or Me'3P2, wherein Me is an alkali metal and Me' is an earth alkali metal or to obtain metal polyphosphides,
b) optionally adding a proton source, optionally in the presence of a catalyst or an
activator to obtain metal dihydrogen phosphides MePH2;
c) subsequent acylation reaction with m acid halides of formula III or m carboxylic acid
c

defined above, R2o is CpCs-alkyl,, C1-C8.perfluoroalkyl, aryl or CrC4-alkylaryl, R2i is H or C1-C8alkyl; R22 is (Vdealkyl or C2-Ci6alkenyl substituted once or more than once by halogen -OR10, -NR12Ri3, -SR10, -OCO-R10, -OCO-Hal, -COO-R10, -N(R12)-CO-R10, -N(R12)-CO-OR10, -N(R12)-CO-NR12R13, -N(R12)-CO-Hal, -CO-NRi2Ri3l -SO2-R10, -SO2-OR10, -S02-NRi2R13, -CH=CH-CO-OR10, -CH=CH-phenyl, -C(Ci-C4alkyl)=C(CrC4alkyl)-CO-OR10 or -C(CrC4alkyI)=C(C1-C4alkyl)-phenyl, phenyl-CrC4alkyl, phenyl, naphthyl, biphenyl, C5-C12cycloalkyl or a 5-or 6-membered 0-, S- or N-containing heterocyclic ring; R23 is H or CH3, and n = 1-5 and R10, R12and R13 is as defined above;

The subsequent reaction of the intermediate obtained according to c) can also be performed under typical conditions known in the art for enolates such as radical or metal-promoted addition reactions, such as a palladium-catalyzed reaction with RiHal, in which Ri is an unsubstituted or substituted aryl group.
The subsequent reaction can also include first a protonation reaction of the enolate, followed by a subsequent radical or metal-promoted addition reaction with RiHal, where Ri is an unsubstituted or substituted aryl group.

wherein R1( R2 and R3 are as defined in claim 1,
which process comprises the steps a), b) and c) as defined in claim 1; and
d) reaction with an electrophilic agent RiHal or other electrophilic agents containing the
residue Ri as defined in claim 1 step d for m = 1
followed by the reaction with an electrophilic agent R3Hal or other electrophilic agents
containing the residue R3 as defined in claim 1 step d for m=1
to obtain the compounds of formula P.

In another of its aspect, this invention relates to a process for the preparation of symmetric bisacylphosphanes of the formula I" (compounds of the formula I with n = 1 and m = 2)

wherein fy and R2 are as defined in claim 1,
which process comprises the steps a), b) and c) as defined in claim 1 for m = 2; and
d) reaction with an electrophilic agent RiHal or other electrophilic agents containing the
residue Ri as defined in claim 1 step d for m = 2
to obtain the compounds of formula I".
In another of its aspect, this invention relates to a process for the preparation of un-symmetric bisacylphosphanes of the formula P (compounds of the formula I with n = 1 and m = 2)
wherein R^ is as defined in claim 1 and R2 and R2' independently of one another are as defined in claim 1 under R2 with the proviso that R2 is not equal R2\ which process comprises the steps a) and b) as defined in claim 1; and c) subsequent reaction with an acid halide of formula III or a carboxylic acid ester of formula IV
wherein R is the residue of an alcohol and R2 is as defined in claim 1;
subsequent reaction with a second acid halide III' or a second carboxylic acid ester of
the formula IV,
wherein R2' and Hal are as defined above.

d) reaction with an electrophilic agent RiHal or other electrophilic agents containing the
residue fy as defined in claim 1 step d for m = 2 to obtain the compounds of formula I"'.
In another of its aspect, this invention also relates to a process for the preparation of symmetric metal bisacylphosphides of the formula (V) or (Va)

wherein R2 is as defined in claim 1 and the metal is Li, Na, K, Mg, which process comprises the steps a) b) and c) as defined in claim 1 for m = 2.
In another of its aspect, this invention also relates to a process for the preparation of unsymmetric metal bisacylphosphides of the formula (V) or (Va')

wherein R2and R2' are as defined in claim 4 and the metal is Li, Na, K, Mg, which process comprises the steps a) b) and c) as defined in claim 4.
In another of its aspects, this invention relates to a process for the preparation of (bis)acyl-phosphane oxides and (bis)acylphosphane sulfides of formula VI

Ri. R2, R3, n and m are as defined above, and Z is O or S,
by oxidation or reaction with sulfur of the acylphosphane of formula I, l\ I" or I'".
Definitions:
C1-C18Alkyl is linear or branched and is, for example, C|-C12-, C1-C8-, CrC6- or CrC4alkyl. Examples are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, 2,4,4-trimethylpentyl, 2-ethylhexyl, octyl, nonyl, decyl, undecyl, dodecyl, tetra-decyl, pentadecyl, hexadecyl, heptadecyl or octadecyl.
C2-C18Alkyl or C2-C18alkenyl which is interrupted once or several times by non-successive -0-, -NH-, -NR9-, -S-atoms is interrupted, for example, 1-9, e.g. 1-7, 1-5, 1-3 or 1 or 2, times by -0-, -NH-, -NR12-,-S- atoms , the -0-, -NH-, -NR12-, -S-atoms always being interrupted by at least one methylene group. The alkyl groups or alkenyl groups may be linear or branched. The structural units obtained are thus, for example, -CH2-X-CH3, -CH2CH2-X-CH2CH3, -[CH2CH2X]y-CH3l where y = 1-8, -(CH2CH2X)7CH2CH3, -CH2-CH(CH3)-X-CH2-CH2CH3 or -CH2-CH(CH3)-X-CH2-CH3 with X= -0-, -S-, -NH-, -NR12- and the corresponding alkenyl structures.
Examples for C2-C18alkyl or C2-C18alkenyl which is interrupted by -CO-, -COO-, -OCO-, -OCOO-, -CO-N(R12)-, -N(R12)-CO-, -N(R12)-CO-N(R12)-, -N(Ri2)-COO-, -COO-Ci-C18alkylene, -COS-Ci-Ci8alkylene, -S02-, -S02-0-, -S02-N(R12)-, -(CH3)2Si-[OSi(CH3)2 ]m-, phenyl-d-C4alkylene, phenylene, naphthylene, biphenylene, C5-C12cycloalkylene or a 5- or 6-membered O-, S- or N-containing heterocyclic ring are the following structures -CH2-W-CH3, -CH2CH2-W-CH2CH3, -[CH2CH2W]y-CH3, where y = 1-8, -(CH2CH2W)7CH2CH3, -CH2-CH(CH3)-W-CH2-CH2CH3, -CH2-W-CH2-CH3, -CH2-W-CH3, -CH2-W-C(CH3)3, -CH(CH3)-W-CH2-CH3, -CH2-CH2-CH2-W-CH3, -(CH2)8-W-CH3, -CH2-CH2-W-CH=CH2, -CH2-CH2-W-C(CH3)=CH2 or -CH2-CH(CH3)-W-CH2-CH3 with W= -CO-, -COO-, -OCO-, -OCOO-, -CO-N(R12)-, -N(R12)-CO-, -N(Ri2)-CO-N(R12)-, -N(R12)-COO-, -COO-CrCisalkylene, -COS-Ci-Ci8alkylene, -S02-, -S02-O-, -S02-N(R12)-, -(CH3)2Si-[OSi(CH3)2 ]m, -(CH2)3-Si-(0-CH2-CH3)3, -CH2-CH2-P0-(0-CH2-CH3)2, phenyl-Ci^alkylene, phenylene, naphthylene, biphenylene, C5-C12cycloalkylene or a 5- or 6-membered 0-, S- or N-containing heterocyclic divalent ring, N-phthalimidyl
C2-Ci8Alkenyl radicals may be mono- or polyunsaturated, linear or branched, cyclic or bicyclic and are, for example, vinyl, allyl, methallyl, 1,1-dimethylallyl, propenyl, butenyl, pentadienyl,

hexenyl octenyl or exo or endo (bicyclo[2.2.1]hept-2-en-5-yl)-methyl preferably vinyl , allyl, 3-buten-1-yl (unser Ex) or exo and endo (bicyclo[2.2.1]hept-2-en-5-yl)-methyl.
C5-Ci2Cycloalkyl is, for example, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, preferably cyclopentyl and cyclohexyl, more preferably cyclohexyl.
Ci-C8Alkoxy is linear or branched radicals and is typically methoxy, ethoxy, propoxy, isopro-poxy, n-butyloxy, sec-butyloxy, isobutyloxy, tert-butyloxy, pentyloxy, hexyloxy, heptyloxy, 2,4,4-trimethylpentyloxy, 2-ethylhexyloxy or octyloxy, preferably methoxy, ethoxy, propoxy, isopropoxy, n-butyloxy, sec-butyloxy, isobutyloxy, tert-butyloxy, most preferably methoxy.
Phenyl-Ci-C4alkyl is e.g., benzyl, phenylethyl, a-methylbenzyl or a,a-dimethylbenzyl, preferably benzyl.
Halogen (= Hal) is fluoro, chloro, bromo and iodo, preferably chloro and bromo, most preferably chloro.

Examples of -0-, S- or N-containing 5- or 6-membered heterocyclic rings are furyl, thienyl, pyrrolyl, oxinyl, dioxinyl or pyridyl. The cited heterocyclic radicals may be substituted by one to five, e.g. by one or two, linear or branched C^Csalkyl, halogen and/or d-C8alkoxy. Examples of such compounds are dimethylpyridyl, dimethylpyrrolyl or methylfuryl.

Substituted phenyl, naphthyl or biphenyl is substituted by one to five, e.g. by one, two, three or four, preferably by one, two or three, for example linear or branched C1-C8alkylf linear or branched C1-C8alkoxy or by halogen.
Preferred substituents for phenyl, naphthyl and biphenyl are d-C4alkyl, e.g. methyl, C1-C4alkoxy, e.g. methoxy or ethoxy, and chloro. Particularly preferred substituents are, for example, 2,4,6-trimethyIphenyl, 2,6-dichlorophenyl, 2,6-dimethylphenyl or 2,6-dimethoxy-phenyl, 2-ethoxynapht-1-yl, 2-methylnaphth-1-yl.
R2 is, for example, Ci-C18alkyl or phenyl, preferably 2,4,6-trimethylphenyl, 2,6-dimethylphenyl or 2,6-dimethoxyphenyl, tert-butyl, 1,1 -diphenylethyl, 2-phenylpropyl, 2-methylbutyl, 2-methylpentyl, most preferably 2,4,6-trimethylphenyl.
The residue of an alcohol is a group RO wherein R is CrCe branched or linear, alkyl, alkenyl, benzyl. R is, for example, ethyl, iso-propyl, n-propyl, t-butyl or n-butyl, 2-ethyl hexyl or other branched octyl species such as 2,4,4-trimethyloctyl.
The compound of formula I, wherein R, is -CO-phenyl which is substituted by one or more -CH3, -OCH3, -CI is a triacylphosphane. These triacylphosphanes are preferably ortho-mono substituted.
The reducing metal (= Me) is selected from the group consisting of lithium, potassium, sodium, magnesium in combination with lithium preferably lithium, potassium, sodium, more preferably lithium or sodium, most preferably sodium.
MePH2 may have the form of a cluster as shown in Example 11.
The common forms of elemental phosphorous (= [P]«) include the white phosphorous, the red phosphorous which is high melting and less reactive than the white phosphorous, and the black phosphorous which is even less reactive. For the purposes of the process of this invention, the red phosphorous is preferred.
Other sources of reducible phosphorous are also suitable for use in this process. Suitable phosphorous compounds are those in which the formal oxidation state of the phosphorous atom is higher than (-3). Examples are phosphorous oxides such as P4On (n = 6-10), (P205)0 ( o = 1-oo), phosphorous trihalides PX3 (X = halogen), including phosphorous trifluoride, phosphorous trichloride, phosphorous tribromide or phosphorous triiodide; phosphorous

sulfides P4Sp(p = 2-10) and (PS)q (q = 0.25-8); phosphorous oxohalides or thiohalides such as POX3. and PSX3 (X = halogen); mixtures of the before mentioned compounds with metal oxides (MekH|PmOn phosphates, phosphonates, phosphinates), metal sulfides or metal halides, preferentially phosphorous containing minerals. Further useful phosphorous compounds are phosphazanes (R2PNR2), phosphazenes ((RPNR)X (R2PN)X, R3PNR)) and phosphonitrides (PN or P3N5), as well as mixtures of these compounds with the reducible phosphorous compound mentioned before. Still another class of useful phosphorous compounds are phosphates (P=0(OR)3); phosphonates (RP=0(OR)2) and phosphites (R2P=0(OR)), thiophosphates (P=S(OR)3); thiophosphonates (RP=S(OR)2) and thiophosphites (R2P=S(OR)), with R being any organic radical. For the purpose of the process of the invention, phosphorous trichloride is preferred.
Useful catalysts in step a) and b) are aromatic polycyclic hydrocarbon catalysts, with or without heteroatoms, such as naphthalene, anthracene, phenanthrene, biphenyl, terphenyl, quaterphenyl, triphenylene, trans-1,2-diphenylethane, pyrene, perylene, acenapthalene, decacyclene, quinoline, N-ethylcarbazole, dibenzothiophene or dibenzofuran. It is preferred that a catalyst is present, which is preferably naphthalene and biphenyl, most preferably napththalene.
Other catalysts in step a) and b) are alkali or earth alkali hydroxides or Na, K, or Li alcoholates or alcohols.
Other catalysts in step a) and b) are combinations of alkali and/or earth alkali metals and/or alcohols.
Activators in step a) and b) are amines (triethylamine, tributylamine, piperidine, morpholine, N-methylpiperidine, N-methyl morpholine) or polyamines such as, for example TMEDA = NX^N'-tetramethylethylenediamine, PMDTA = pentamethyldiethylenetriamine, or sparteine.
Other activators in step a) and b) are polyethers, such as crown ethers, for example 12-crown-6.
As solvent there are used ethers such as dimethyl ether, diethyl ether, methylpropyl ether, 1,2-dimethoxyethane (DME), bis(2-methoxyethyl)ether (diglyme), dioxane, or tetrahydro-furan, or in mixtures thereof, or arene solvents such as benzene, toluene, o-, m- or p-xylene,

mesitylene, ethylbenzene, diphenylethane, 1,2,3,4-tetrahydronaphthalene (tetraline), iso-propylbenzene (cumol), or in mixtures thereof. Preferred solvents are ethers or mixtures of ethers and arene solvents, most preferred are ethers.
A suitable solvent for step a) and b) is liquid ammonia, a mixture of liquid ammonia and an ether such as tetrahydrofuran, a mixture of liquid ammonia and a tertiary alcohol or a tertiary alcohol alone. Preferred is liquid ammonia and tetrahydrofuran.
The proton source is a CH-, NH-, SH-, or OH-acid compound.
CH-acid compounds have an active methylene group, such as, for example, malonic esters,
cyanoacetic esters, acetylacetone, acetoacetic esters, succinic acid esters, N-
methylpyrrolidone and the like. Furthermore an enol, an enol ether may be a CH-acid
compound.
NH-acid compounds are, for example, lactams or pyrrolidone or salts such as ammonium salts or amidinium salts.
OH-acid, SH-acid compounds are alcohols or thioalcohols.
Preferred the proton source are sterically hindered alcohols, trialkylamine hydrohalogenes, bisarylamines, malono nitrile, malonic acid esters, amidine hydrohalogene R-C(=NH)-NH2HCI and carboxylic acids.
The sterically hindered alcohol is selected from the group consisting of secondary or tertiary C3-Ci8alcohols, preferably of tert-butanol, tert-amyl-alcohol, 3-methyl-3-pentanol, 3-ethyl-3-pentanol, triphenylmethanol, 3,7-dimethyl-3-octanol, 2-methyl-1-phenyl-2-propanol, 2-methyl-4-phenyl-2-butanol, fenchyl alcohol, 2,4-dimethyl-3-pentanol, 1-dimethylamino-2-propanol or hexylene glycol, especially preferred tert-butanol, tert-amylalcohol or 3-methyl-3-pentanol.
The trialkylamine hydrohalogene is selected from tert-fCrCshN-HCI, preferably trimethyl-amine hydrochloride, triethylamine hydrochloride ortributylamine hydrochloride.
Preferred substituents:
In the above-described processes m = 2 is preferred and R1( if n = 1, is phenyl or unsubstituted linear or branched d-C^alkyl or C2-Ci8alkenyl; or

linear or branched d-dsalkyl or C2-C18alkenyl substituted once or more than once by groups selected from:
^o
O
halogen or CN, or - o
-OR10) -SR10, -OCO-R10, -COO-R10> -CH=CH-CO-OR10 or -C(C1-C4alkyl)=C(C1-C4alkyl)-CO-OR10; wherein
R10 is hydrogen, C1-C18alkyl, or C2-C18alkyl which is interrupted by one or several non-successive -O-atoms, a di,-tri,-tetra-or polyethylene glycol residue, C3-C12-cycloalkyl, tetrahydropyran-2-yl, phenyl-Ci-C4-alkylene, phenyl-d-d-alkenylene, C1-C6alkyl substituted by halogen or substituted by cyclohexyl or cyclopentyl, or substituted by tetrahydrofuranyl, furanyl, isopropyl-4-methyl-coclohexyl, C2-C18-alkenyl, unsubstituted phenyl, naphthyl or biphenyl being unsubstituted or phenyl, naphthyl or biphenyl substituted by one to five d-d-alkyl, d-d-alkoxy, d-Cs-alkylthio and/or halogen; and R2 is phenyl or phenyl which is substituted by halogen, d-dalkoxy or d-dalkyl.
Especially preferred are n=1 and RT is phenyl linear or branched d-dalkyl or C2-d8alkenyl or is linear or branched d-dalkyl or C2-d8alkenyl substituted by CN, trifluormethyl, oxiranyl, isoindole-1,3-dione, -O-d-dsalkyl, -O-benzyl, -CO-phenyl, -CO-C1-C18alkyl,
-OCO-d-dsalkylj-OCO-Crdsalkenyl;
-COO-Crdsalkyl; -COO-d-dsalkylene-phenyl, -COO-d-dsalkylene-cycloalkyl, -COO-C1-C18alkylene-tetrahydrofuranyl, -COO-C1-C8alkylene-furanyl, -COO-cycloalkyl, -COO-C1-C18alkenyl;-COO-C1-C18alkenylene«phenyl;-COO-(CH2)2-3-CI, -COO-[(CH2)2-3-0]1.1o-Crdalkyl;-COO-[(CH2)2-3-0]1.10-C1-C4-OH,
-CO-CH2-CO-C1-C18alkyl; -CO-CH2-COO-d-C18alkyl, -O-tetrahydropyranyl,
bicyclo[2.2.1]hept»2»en-5-yl)-methyl, PO(Od-dalkyl)2 and
wherein R2 is phenyl which is substituted in 2,6- or 2,4,6-position by d-C4alkyl and/or d-dalkoxy, and/or chlorine; 2-ethoxy-naphth-1-yl, 2-methyl-naphth-1-yl or anthr-9-yl.
Especially preferred for n=2 R1( if n = 2, is d-doalkylene, or biphenylene or -CH2-COO-Z-OCO-CH2- wherein Z is C1-C8 alkylene or a bridge derived from a di,-tri,-tetra-or polyethylene glycol.
R3 is CrC12alkyl, cyclohexyl, phenyl or biphenyl, the radicals phenyl and biphenyl being unsubstituted or substituted by one to four d-dalkyl and/or d-C8alkoxy.

Compounds of formula I which are particularly preferably used in the above process are those wherein n is 1.
The residue "Hal" is preferably chloro.
Other preferred compounds of formula I in the above process are those, wherein m is defined as the number two, i.e. bisacylphosphane or bisacylphosphane oxides or bisacyl-phosphane sulfides.
The process is especially suitable to prepare alkyl bisacyl phosphanes (R Using the inventive process it is possible to prepare new (bis)acylphosphanes which are also part of the invention.

wherein n =1 and
Ri is linear or branched C1-C8alkyl or C2-C18alkenyl substituted by CN, trifluormethyl,
oxiranyl, isoindole-1,3-dione, -0-Ci-Ci8alkyl, -O-benzyl, -CO-phenyl, -CO-Ci-Cisalkyl,
-OCO-C1-C18alkyl;-OCO-C1-C18alkenyl;
-COO-GrC18alkyl; -COO-C1-C18alkylene-phenyl, -COO-CVdsalkylene-cycloalkyl, -COO-C1-C18alkylene-tetrahydrofuranyl, -COO-C1-C18alkylene-furanyl, -COO-cycloalkyl, -COO-C1-C18alkenyl;-COO-C1-C18alkenylene-phenyl;-COO-(CH2)2-3-CI, -COO-[(CH2)r3-0]i-io-C1-C6alkyl;-COO-[(CH2)2-3-0]Mo-CrC6-OHI
-CO-CH2-CO-C1-C18alkyl; -CO-CH2-COO-C1-Ci8alkyl, -O-tetrahydropyranyl,
bicyclo[2.2.1]hept-2-en-5-yl)-methyl, PO(OC1-C6alkyl)2 and wherein m R2 and R3 are as defined in claim 1.

Process parameters Step a)
The elemental phosphorous may be employed as a finely divided solid or as a melt, or it may
be dissolved or dispersed in an inert organic solvent. As elemental phosphorous is
spontaneously flammable in moist air, it is preferred that the reaction be carried out in an
inert gas atmosphere.
PCI3 is preferentially dissolved in an inert organic solvent; Other suitable phosphorous
compounds with a formal oxidation state of the phosphorous atom higher than -3 are
employed as solids, in suspension or dissolved in an inert organic solvent.
As solvents, ethers such as dimethoxyethane, liquid ammonia or a mixture of liquid ammonia
and tetrahydrofuran are preferred.
Step a) is preferably carried out in the presence of a hydrocarbon catalyst.
Advantageously, the reaction of the reducing metal, dispersed in a solvent, and phosphorous may be effected at temperatures ranging from -70°C to +160°C, e.g. from room temperature to 80°C.
Step b)
In the inventive process step b) is optionally. Thus, metal phosphides MenPm [e.g. trialkali metal phosphide (Me3P)] may react directly with the acylating agent. However, because of an improved yield, step b) is preferably carried out. The reaction temperature is preferably in the range from -20°C to +160°C, e.g. from room temperature to 80°C.
Catalysts and activators in step a) and b) are used in a molar ratio of catalyst to the reducing metal of for example 1:2 to 1:1000.
Catalysts and activators in step a) and b) may be added prior or during the reduction of elemental phosphorous.
It is possible to optionally isolate the product of step b) as an alcoholate cluster of the phosphide before using it in step c).
It is possible to add polar or dipolar co-solvents to the reaction mixture during or after step a) and b). Such solvents may be linear or cyclic amides like dimethylacetamide (DMA), n-methyl pyrrolidone (NMP), cyclic ureas like 1,3-dimethypropylene urea (DMPU), linear and cyclic glycols like diglyme and dimethoxyethane (DME).

Step c)
The reaction temperature for the reaction with the acid halide is usefully in the range from -20° to +80°C. A bisacylphosphide intermediate is formed which may form an O-coordinated bisacylphosphaenolate chelate complex of the formula (V) or (Va')

The bisacylphosphide intermediate is stabilized due to the formation of an O-coordinated bisacylphosphaenolate chelate complex in the case of alkali metals. The complex might be further stabilized by metal-metal exchange. Suitable exchange metals are: boron, aluminium, chromium, nickel.
Step d)
The enolate may be isolated or may easily be further reacted with an electrophilic agent. The choice of the electrophilic agent is not limited. Non limiting examples are: straight-chain or branched d-CisalkyI halides, C2-C8alkenyl halides, substituted alkylhalides such as fluoro, or hydroxy, or carbonyl, or sulfonyl, or vinyl, or siloxanyl, or alkoxycarbonyl, or acyloxy or by heterocyclic groups substituted alkylhalides, C5-C12cycloalkyl halides, benzyl halides and aryl halides such as phenyl halide, naphthyl halide or biphenyl halide. Other electophilic agents are alkyl sulfates, alkyltosylates, alkylmethylsulfonates, epoxides, episulfide or acrylate or methacrylate esters.. It is likewise possible to use alkylating reagents giving ionic functions, e.g., monobromoacetic acid, monobromopropionic acid, sodium 3-bromopropanesulfonate and N-(2-bromoethyl)diethylamine. Silyl or siloxanyl groups may be implemented via chlorosilane or chlorosiloxane, or by the use of a-halo-co-silanyl or siloxanylalkanes.
The reaction temperature in step d) is usefully in the range from room temperature to 100°.
The bisacylphosphane of formula I can be isolated by the customary technological methods which are known to the skilled person, for example by filtration, evaporation or distillation. Likewise, the customary methods of purification may be used, for example crystallisation, distillation or chromatography.

However, the phosphanes can also be reacted without isolation to the corresponding mono-or bisacylphosphane oxides or mono- or bisacylphosphane sulfides.
Using the process of this invention it is also possible to prepare mono- and bisacyl-phosphanes together in one reaction step.
Depending on the substituents used, unsymmetric compounds may be formed by the novel process.
Monoacylphosphane oxides are compounds of the formula I' corresponding to compounds of the formula I wherein n=1 and m=1.

The residues RT and R3 may be the same or may be different.
Bisacylphosphane oxides are compounds of the formula H corresponding to compounds of the formula I wherein n=1 and m=2.

The residues R2 and R2* may be the same or may be different.
By means of the novel process it is furthermore also possible to prepare mixtures of aliphatic and aromatic monoacylphosphanes or mixtures of aliphatic and aromatic bisacylphosphanes.
If required, all of the mixtures may be separated by the processes customarily used in the technology or they may be further used as they are.
This invention also relates to a process for the preparation of mono- and bisacylphosphane oxides or mono- and bisacylphosphane sulfides. This process is first carried out as described above and a mono- or bisacylphosphane (I) is prepared. The crude reaction product (I) can then be further processed without purification and an additional reaction step may be carried out without isolation of the phosphane (I) using the solution of the crude product. If required,

the solvent may be changed, for example, by concentrating the solution containing the mono-or bisacylphosphane and taking up the residue in a new solvent. Of course it is also possible to further react above-described unseparated mixtures of compounds of formula (I) to the corresponding oxide or sulfide.
It is recommended to adjust the pH of the reaction mixture prior to the oxidation step to a pH of 2-8, preferably to a pH of 3-6 by addition of typical inorganic and/or organic acids or buffer systems.
When preparing the respective oxide (Via), the oxidation of the phosphane (I) is carried out using the oxidant conventionally used in the technology

Suitable oxidants are in particular hydrogen peroxide and organic peroxy compounds, for example peracetic acid or t-butylhydroperoxide, air or pure oxygen.
The oxidation is usefully carried out in solution. Suitable solvents are aromatic hydrocarbons, such as benzene, toluene, m-xylene, p-xylene, ethylbenzene or mesitylene, or aliphatic hydrocarbons, such as alkanes and alkane mixtures, e.g. petroleum ether, hexane or cyclo-hexane.During oxidation, the reaction temperature is preferably kept in the range from 0° to 120°C, preferably from 20° and 80°C.
The reaction products (Via) can be isolated and purified by conventional processing methods known to the skilled person.

The mono- or bisacylphosphanes (I) are in this case reacted in substance or, where appropriate, in a suitable inert organic solvent with an equimolar to 2-fold molar amount of elementary sulfur. Suitable solvents are for example those described for the oxidation reaction. However, it is also possible to use e.g. aliphatic or aromatic ethers, such as dibutyl ether, dioxane, diethylene glycol dimethyl ether or diphenyl ether, in the temperature range from 20° to 250°C, preferably from 60° to 120°C. The resulting mono- or bisacylphosphane sulfide, or its solution, is usefully freed from any remaining elementary sulfur by filtration. After the solvent is removed, the mono- or bisacylphosphane sulfide can be isolated by distillation, chromatography or recrystallisation in pure form.
As mentioned above, it is also possible to use mixtures of compounds of formula I for the oxidation or reaction to the sulfide. The correspondingly obtained oxide or sulfide mixtures can either be separated by processes customarily used in the technology or may be used as mixtures.
All of the above reactions are usefully carried out with exclusion of air in an inert gas atmosphere, e.g. under nitrogen or argon gas. The respective reaction mixture is usefully also stirred.
The acid halides (III, III'), the carboxylic acid esters (IV, IV) or the electrophilic compounds RT-Hal or R3-Hal used as starting materials are known substances, some of which are commercially available, or may be prepared in analogy to known compounds.
It is characteristic of the novel process that the individual processing steps can be carried out directly one after the other without the need for isolating and purifying the respective intermediates.
Mixtures such as those described in the process for the preparation of the corresponding phosphanes may also be formed, or may also be specifically produced, in the above-described process for the preparation of mono- or bisacylphosphane oxides or mono- or bisacylphosphane sulfides. Such mixtures can be separated by methods known in the technology or may be further used in the form of mixtures.
The phosphanes which are accessible by the novel process are important educts for the preparation of the corresponding phosphane oxides and phosphane sulfides. The phosphane

oxides and phosphane sulfides are used in the art as initiators in photopolymerisation reactions.
The oxidation is usefully carried out in solution. Suitable solvents are aromatic hydrocarbons, such as benzene, toluene, m-xylene, p-xylene, ethylbenzene or mesitylene, or aliphatic hydrocarbons, such as alkanes and alkane mixtures, e.g. petroleum ether, hexane or cyclo-hexane. During oxidation, the reaction temperature is preferably kept in the range from 0° to 120°C, preferably from 20° and 80°C. The reaction products can be isolated and purified by conventional processing methods known to the skilled person.
Using the process of this invention it is possible to prepare bisacylphosphanes or bisacyl-phospane oxides or sulfides without isolating any intermediate ("one-pot" reaction).
If two different acid halides or two different carboxylic acid esters are used, unsymmetric compounds may be formed by the novel process. Preferred is a process wherein a carboxylic acid ester followed by an acid chloride of a different acid may be used for the synthesis of unsymmetric compounds.
The phosphanes which are accessible by the novel process are important educts for the preparation of the corresponding phosphane oxides and phosphane sulfides. The phosphane oxides and phosphane sulfides are used in the art as initiators in photopolymerisation reactions.
Preferences
A process for the preparation of (bis)acylphosphanes or (bis)acylphosphane oxides of formula I or VI the process comprising the steps of:
a) contacting red phosphorous or PCI3 with an alkali metal in the presence of a solvent and optionally in the presence of polycyclic hydrocarbon catalyst
b) adding a sterically hindered alcohol;
c) subsequent reaction with two equivalents of an acid halide Hal-CO-R2 to obtain a metal bisacylphosphide [R2-CO-P=C(OMe)R2], wherein Me is Na or Li; or with one equivalent of a caboxylic acid ester RO-CO-R2, followed by one equivalent of an acid halide Hal-CO-R2" to obtain a metal bisacylphosphide [R2-CO-P=C(OMe)R2'], wherein Me is an alkali metal

d) subsequent reaction with an electrophilic agent R-jHal or RiOSC^ORi to obtain the compounds of formula I.
Preferred is a step a) whereby sodium in liquid ammonia is contacted with red phosphorus in tetrahydrofuran.
The following examples illustrate the invention in more detail, although it is not intended that the invention be limited to the examples. As in the remaining description and in the patent claims, parts or percentages are by weight, unless otherwise stated.

General: Solvents are used as received (without any treatment) or dried over molecular sieves or by azeotropic distillation. The course of the reaction is monitored by 31P-NMR spectroscopy.
Example 1 Preparation of [isobutyl-(2,4,6-trimethyl-benzoyl)-phosphinoyl]-(2,4,6-tri-methyl-phenyl) -methanone using sodium and tert-butanol as proton source.

formula I Ri = iso-butyl, R2 = mesityl, m=2 a) Preparation of Na3P

3.45 g of sodium sand (150 mmol, 3 eq., M = 22.99 g/mol), 1.55 g of purified red phosphorous (50.0 mmol, 1 eq., M = 30.97 g/mol) and 125 mg of naphthalene (1.0 mmol, M = 128.17 g/mol) are suspended in 120 ml of dimethoxyethane (DME). The suspension is heated up to 75°C and kept at this temperature for 20 h under stirring. A color change from green over red-brown into black takes place.
b) Preparation of NaPH2
The reaction mixture of step a) is cooled down to -10 to -15°C. 10 ml of tert-butanol (0.1 mol, 2 eq., M = 74.12 g/mol) in 10 ml DME is added within 20 min under stirring. A nearly clear brown solution is obtained, containing a small amount of unreacted sodium. Stirring is continued for another 20 min.

16.8 ml of 2,4,6-trimethylbenzoyl chloride (TMBCI) (0.1 mol, 2 eq., M = 182.65 g/mol) are quickly added to the reaction mixture of step b), resulting in a color change to yellow. The reaction mixture is left stirring for another 20 min under ice cooling, followed by stirring for one hour at room temperature. The 31P NMR spectra shows a signal for sodium bis(mesitoyl)phosphide*DME {Na[P(COMes)2]*DME} at 82 ppm (>95%).
c-1) Isolation of {Na[P(COMes)2]*DME}
The reaction mixture of step c) is concentrated under high vacuum. The resulting orange-yellow foam is taken up in 100 ml of toluene and then filtered through G4/Celite. The filter cake is twice washed with toluene providing a clear orange-yellow filtrate solution. The filtrate solution is concentrated under vacuum to a volume of about 70 ml, and then carefully overlayed with hexane (30 ml). Yellow cubic crystals separate from the solution and are identified as sodium bis(mesitoyI)phosphidexDME {Na[P(COMes)2]xDME} (C24H32Na04P, M = 438.47 g/mol) by 31P-, 1H- and 13C-NMR spectroscopy. Furthermore, single-crystal X-ray structural analysis shows that the crystals are composed of an ion pair complex of the formula [Na3[P(COMes)2]4] [Na(DME)3]. The yellow crystals are soluble in toluene, THF and DME, however little soluble in hexane.

M.p. = 208°C.
1H-NMR (250.13 MHz, C6D6, 25°C): 5 = 6.60 (s, 4 H, Mes CH), 2.94 (s, 4 H, DME CH2), 2.87
(s, 6 H, DME CH3), 2.61 (s, 12 H, Mes o-CH3), 2.08 (s, 6 H, Mes p-CH3).
13C{H}-NMR (75.47 MHz, C6D6, 25°C): 6 = 236.2 (d, 1JCp = 94.0 Hz, CO), 145.5 (d, 2JCP =
38.3 Hz, Mes C1), 136.3 (d, 5JCP = 0.9 Hz, Mes C4), 133.9 (d, 3JCP = 2.7 Hz, Mes C2'6), 128.3
(s, Mes C3'5), 71.0 (s, DME CH2), 58.4 (s, DME CH3), 21.1 (s, Mes p~CH3), 20.1 (d, 4JCP = 2.5
Hz, Mes o-CH3).
31P{H}-NMR (101.25 MHz, C6D6, 25°C): 6 = 84.1 (br.).
c-2) A DME-free product is obtained if the toluene filtrate solution from step c-1) is completely concentrated under vacuum first. The residue is suspended in n-hexane (80 ml), the resulting yellow solid filtered off and then dried under high vacuum. According to NMR spectroscopy measurements, the product consists of DME-free {Na[P(COMes)2} (C20H22NaO2P, M=348.35 g/mol).
d) Alkylation to iso-BuP(COMes)2
The solution obtained in step c) is concentrated to 80 ml. 9.6 g of isobutyl bromide (0.07 mol, 1.4 eq., M = 137.02 g/mol) are added. The yellow-orange suspension is heated up to 60°C and kept at this temperature for 96 h under stirring. The 31P NMR spectra of the reaction solution shows a signal for iso-BuP(COMes)2 at 48 ppm (>91%). The light-yellow suspension is filtered through G4/Celite and the filter cake washed once with DME (10 ml). All volatile compounds are removed under high vacuum giving iso-BuP(COMes)2 as a yellow oil.
e) Oxidation to iso-BuP(=0)(COMes)2
iso-BuP(COMes)2 obtained in step d) is first taken up in 50 ml of toluene. Water (25 ml) and 2-3 drops of cone. H2S04 are slowly added at room temperature, such that the pH of the aqueous phase is below a value of four. 6.0 ml of hydrogen peroxide (30% solution in H20, 0.053 mol, 1.05 eqM M = 34.02 g/mol) are added at such a rate that the temperature does not rise above 70°C. The resulting suspension is heated up to 60°C and kept at this temperature for two hours. The 31P NMR spectra of the toluene phase shows a new signal at 27 ppm (>83%), identified as iso-BuP(=0)(COMes)2. 20 ml of water are added and the aqueous phase saturated with NaCI. The organic phase is separated, first washed with 20 ml of a 1% aqueous NaHC03 solution, and then with water (3x15 ml). Drying of the organic phase over MgS04, filtration and concentration under vacuum gives a yellow oil which is further purified via column chromatography (Si02, n-hexane/ethyl acetate 4:1). 7.56 g (38%, related to red

phosphorous) of iso-BuP(=0)(COMes)2 (C24H31P03, M = 398.47 g/mol) are obtained as a light yellow solid with Rf = 0.35 (n-hexane/ethyl acetate 4:1).
1H-NMR (300.13 MHz, CDCI3, 25°C): 5 = 6.85 (s, 4 H, Mes CH), 2.28 (s, 6 H, Mes p-CH3),
2.25 (s, 12 H, Mes o-CH3), 2.13 (m, 1 H, PCH2CH), 2.11 (m, 2 H, PCH2), 1.05 (d, 3JHH = 5.9
Hz, 6 H, CHCH3).
13C{H}-NMR (75.47 MHz, CDCI3, 25°C): 6 = 216.6 (d, 1JCP = 52.8 Hz, CO), 141.3 (d, 5JCP =
0.5 Hz, Mes C4), 136.1 (d, 2JCP = 40.1 Hz, Mes C1), 135.8 (d, 3JCP = 0.7 Hz, Mes C26), 129.4
(d, 4JCP = 0.8 Hz, Mes C3'5), 34.4 (d, 1JCP = 52.5 Hz, PCH2), 24.6 (d, 3JCP = 8.5 Hz, CHCH3),
23.9 (d, 2JCP = 4.5 Hz, PCH2CH), 21.4 (s, Mes p-CH3), 19.9 (d, 4JCP = 0.5 Hz, Mes o-CH3).
31P{H}-NMR (121.49 MHz, CDCI3) 25°C): 6 = 28.2.
EA: calculated: [C] 72.34%, [H] 7.84%, [P] 7.77%; found [C] 72.19%, [H] 7.79%, [P] 7.81%.
MS (El): m/z = 398 (M+, 0.33%), 251 (M+ - MesCO, 1%), 147 (MesCO+, 100%), 119 (Mes+,
7.5%).

formula I, Ri = iso-butyl, R2 = mesityl, m=2
a) Preparation of Li3P
0.56 g of lithium powder (81 mmol), 0.84 g of red phosphorous (27 mmol) and 610 mg of naphthalene (4.8 mmol) are suspended in 60 ml of DME. The suspension is heated up to 75°C and kept at this temperature for 20 h under stirring.
b) None.
c) Preparation of lithium bis(mesitoyl)phosphide> The light brown mixture of step a) is cooled down to 30 to 40°C. 10.06 g of 2,4,6-trimethylbenzoyl chloride (54 mmol) are dropwise added. The reaction mixture is left stirring for 3 h at room temperature.

d) Alkylation to iso-BuP(COMes)2
5.9 g of isobutyl bromide are added portion wise under stirring to the solution obtained in step c) (Reaction temperature 70-80°C). The reaction mixture is filtered over hyflo (Hyflo Super Cel®; Fluka, Buchs, Switzerland).The filtrate is evaporated to dryness, the residual mass dissolved in toluene and extracted with water and with sodium chloride solution. The organic phase is dried over Na2S04 and concentrated. 7.43 g of iso-BuP(COMes)2 is obtained as a yellow oil.
e) Oxidation to iso-BuP(=0)(COMes)2
Analogous to step e) in Example 1.
The crude product has been purified via column chromatography (Si02, n-hexane/ethyl acetate 85:15). 2.36 g (22%, related to red phosphorous) of iso-BuP(=0)(COMes)2 are obtained as a yellow oil which crystallize upon standing.
1H-NMR (CDCI3): 5 = 6.87 (s; 4 H); 2.30 (s; 6 H); 2.27 (s; 12 H); 2.10-2.17 (m; 3 H); 1.07 (d; 6 H). 31P-NMR (CDCI3): 5 = 29.3

formula I, R a) Preparation of Na3P analogous to Example 1.
b) Preparation of NaPH2 analogous to Example 1.
c) Preparation of sodium bis(mesitoyl)phosphide> to Example 1.
d) Alkylation to methyl-bis(mesitoyl)phosphane, CH3P(COMes)2
A solution of {Na[P(COMes)2]*DME} in DME prepared according to step c) is concentrated to 80 ml, 7.08 g of methyl iodide (0.05 mol, 1.0 eq., M = 141.94 g/mol) are added. The orange suspension is heated up to 60°C and kept at 60°C for 2 h under stirring. The 31P NMR spectrum shows a new signal at 39 ppm (>98%) identified as MeP(COMes)2. The light yellow

suspension is filtered through G4/Celite and the filter cake washed once with DME (10 ml). All volatile compounds are removed under high vacuum giving MeP(COMes)2 as a yellow oil.
e) Oxidation to CH3P(=0)(COMes)2, Analogous to Example 1.
The 31P NMR spectra of the toluene phase shows a new signal at 22.6 ppm (>95%), identified as CH3P(=0)(COMes)2. The crude product has been purified via column chromatography (Si02, n-hexane/ethyl acetate 4:1). 5.06 g (29%, related to red phosphorous) of CH3P(=0)(COMes)2 (C2iH2503P, M = 356.40 g/mol) are obtained as a light yellow solid with Rf = 0.2 (n-hexane/ethyl acetate 4:1).
M.p. = 126°C.
1H-NMR (300.13 MHz, CDCI3, 25°C): 5 = 6.86 (s, 4 H, Mes CH), 2.29 (s, 6 H, Mes p-CH3),
2.27 (s, 12 H, Mes o-CH3), 2.11 (d, 3 H, 2JPH = 12.3 Hz, PCH3).
13C{H}-NMR (75.47 MHz, CDCI3, 25°C): 6 = 216.7 (d, 1JCP = 58.3 Hz, CO), 141.4 (d, 5JCP =
0.6 Hz, Mes C4), 135.9 (d, 2JCP = 41.4 Hz, Mes C1), 135.6 (d, 3JCP = 0.8 Hz, Mes C2,6), 129.3
(d, 4JCP = 0.9 Hz, Mes C3'5), 21.4 (s, Mes p-CH3), 19.8 (d, 4JCP = 0.5 Hz, Mes o-CH3), 12.6 (d,
1JCP = 56.8 Hz, PCH3).
31P{H}-NMR (121.49 MHz, CDCI3, 25°C): 6 = 23.7.
EA: calculated: [C] 70.77%, [H] 7.07%, [P] 8.69%; found [C] 70.69%, [H] 7.14%, [P] 8.70%.
Example 4 Preparation of [methyl-(2,4}6-trimethyl-benzoyl)-phosphanyl]-(2,4,6-tri-methyl-phenyl)-methanone, starting from phosphorous trichloride, using sodium and 3-methyl-3-pentanol.

a) Preparation of Na3P
3.72 g of sodium (162 mmol) and 0.51 g of naphthalene (4 mmol) are suspended in 70 ml of DME. 3.82 g of phosphorous trichloride (27 mmol) in 5 ml of DME is dropwise added within 15 min at room temperature. The suspension is stirred at room temperature overnight, and then for 2 h at 50-60°C, giving a black suspension.
b) Preparation of NaPH2
The reaction mixture is cooled down to 20°C and 5.52 g of 3-methyl-3-pentanol (54 mmol) are added within 20 min. Stirring is continued overnight giving a light brown suspension.

c) Preparation of sodium bis(mesitoyl)phosphidexDME, {Na[P(COMes)2]*DME}
10.06 g of 2,4,6-trimethylbenzoyl chloride (54 mmol) are added within 5-10 min. The reaction mixture is left stirring for 2 h at room temperature giving an orange-white suspension.
d) Alkylation to methyl-bis(mesitoyl)phosphane, CH3P(COMes)2
2.74 g of methyl iodide (19 mmol) are added dropwise and left stirring for 2 h at 35-40°C. The resulting white-yellow suspension is filtered over hyflo and concentrated under vacuum. The residue is redissolved in toluene and extracted two times with water and once with saturated aqueous NaCI solution. The organic phase is dried over Na2S04 and concentrated under vacuum. 12.34 g of crude CH3P(COMes)2 are obtained as a yellow oil.
e) Oxidation to CH3P(=0)(COMes)2
The crude oil is redissolved in 30 ml of toluene and treated with 3.06 g of H202 (30% in H20, 27 mmol) within 5 min at 20°C. Stirring is continued for 30 min. The reaction mixture is diluted and then extracted with water, 2% aqueous NaHC03 and saturated NaCI solution, followed by drying over Na2S04 and concentration under vacuum. 9.41 g of yellow oil are stirred in 15 ml hexane during 30 min resulting in the precipitation of a solid which is collected by filtration. Washing with cold hexane and drying under high vacuum provides 3.85 g (40%, related to red phosphorous) of a white-yellow solid. An additional 0.27 g solid (3%) has been isolated from the mother liquor.

a) Preparation of Li3P analogous Example 2, with 1.04 g of naphthalene (8.1 mmol).
b) Preparation of LiPH2
The mixture of step a) is cooled down to 0 to 10°C. A solution of 5.58 g of 3-methyl-3-pentanol (54 mmol) in 5 ml of DME are added within 45 min under stirring. The reaction mixture is left stirring for another 120 min without cooling.

c) Preparation of lithium bis(mesitoyl)phosphidexDME, {Li[P(COMes)2]*DME}
10.06 g of 2,4,6-trimethylbenzoyl chloride (54 mmol) are dropwise added to the reaction mixture of step b) at 10-20°C within 25 min. The reaction mixture is left stirring for 40 min at room temperature.
d) Alkylation to CH3P(COMes)2
The resulting thin brown-red suspension from step c) is dropwise treated with 5.75 g of methyl iodide (40.5 mmol) during 10 min under stirring. The reaction mixture is left stirring for another 100 min at 40°C, then filtered and concentrated under vacuum. The residue is dissolved in toluene (150 ml) and extracted with water (4 x). The toluene phase has been further treated as described in step e).
e) Oxidation to CH3P(=0)(COMes)2
Analogous to step e) in Example 1.
The crude product (10.3 g) has been purified via column chromatography (Si02, heptane/ethyl acetate 1:1). 1.82 g (19%, related to red phosphorous) of CH3P(=0)(COMes)2 are obtained as a light yellow solid.
1H-NMR (CDCI3): 6 = 6.88 (s, 4 H); 2.30(s, 6 H); 2.29(s, 12 H); 1.81-1.85 (d, 3 H). 31P-NMR (CDCI3): 5 = 24.8.

a) Preparation of Li3P analogous to Example 2, with 0.51 g of naphthalene (4 mmol).
b) None.
c) Preparation of lithium bis(mesitoyl)phosphidexDME, {Li[P(COMes)2]*DME}

10.06 g of 2,4,6-trimethylbenzoyl chloride (54 mmol) are dropwise added to the light brown reaction mixture of step a) at 30-40°C within 40 min. The reaction mixture is left stirring for 2.5 h at room temperature.
d) Alkylation to CH3P(COMes)2
4.22 g of methyl iodide (29.7 mmol) are added within 15 min under stirring at 25-35°C to the solution obtained in step c). The reaction mixture is left stirring for 20 h at 40°C, cooled down to room temperature and then filtered over hyflo (Hyflo Super Cel®; Fluka, Buchs, Switzerland). The resulting filtrate is concentrated under vacuum, the residue dissolved in toluene and extracted three times with water and with saturated sodium chloride solution. The organic phase is dried over Na2S04 and concentrated under vacuum. 6.76 g of crude CH3P(COMes)2 are obtained as a yellow oil.
e) Oxidation to CH3P(=0)(COMes)2
Analogous to step e) in Example 2.
The crude product (5.32 g) has been purified via column chromatography (Si02, heptane/ethyl acetate 1:1). 1.27 g (13%, related to red phosphorous) of CH3P(=0)(COMes)2 are obtained as a white solid.
1H-NMR (CDCI3): 6 = 6.88 (s, 4 H); 2.30(s, 6 H); 2.29(s, 12 H); 1.81-1.85 (d, 3 H). 31P-NMR (CDCI3): 5 = 24.8.

formula I, R1 = benzyl, R2, = mesityl, m=2
a) Preparation of Li3P
104 mg of lithium granulate (15 mmol), 155 mg of purified red phosphorous (5 mmol) and 64 mg of naphthalene (0.5 mmol) are suspended in 20 ml of DME. The suspension is heated to 70-80°C and kept at this temperature for 16 h under stirring.

b) Preparation of LiPH2
Analogous to Example 4, with 1.02 g of 3-methyl-3-pentanol (10 mmol).
c) Preparation of lithium bis(mesitoyl)phosphide*DME, {Li[P(COMes)2]*DME} Analogous to Example 4, with 1.83 g of 2,4,6-trimethylbenzoyl chloride (10 mmol).
d) Alkylation to benzyl-P(COMes)2
1.31 g of benzyl bromide (7.5 mmol) are added to the thin light brown suspension obtained in step c) within 15 min under stirring. The reaction mixture is left stirring for another 2.5 h at 50-60°C. DME is removed under vacuum and the residue taken up in toluene (40 ml).
e) Oxidation to benzyl-P(=0)(COMes)2
Analogous to step e) in Example 1.
The crude product (2.3 g) has been purified via column chromatography (Si02, heptane/ethyl acetate 60:40). 207 mg of benzyl-P(=0)(COMes)2 are obtained as a yellow viscous oil.
1H-NMR (CDCI3): 5 = 7.25-7.32 (m, 5 H); 6.82 (s, 4 H); 3.60-3.64 (d, 2 H); 2.28 (s, 6 H); 2.08 (s, 12 H). 31P-NMR (CDCI3): 5 = 24.1.

a) 1.
c) Preparation of sodium bis(mesitoyl)phosphidexDME, {Na[P(COMes)2]xDME}

Analogous to Example 1.
d) preparation of [CF3-CH2-CH(CH3)-CH2]P(COMes)2
2.2 g of {Na[P(COMes)2]*DME} (5.0 mmol, M = 438.47 g/mol) obtained according to step 1c) are dissolved in 40 ml of toluene and 30 ml of DME. 1.7 g of 1-bromo-2-methyl-4,4,4-trifluorobutane (1,66 eq., 8.3 mmol, M = 205.02 g/mol) are added. The reaction mixture is stirred at 80°C for 72 h. The 31P-NMR spectra shows no more signal of the starting material and a new signal at 45.7 ppm. The light yellow suspension is filtered through G4/Celite. The filtrate solution is concentrated to 50 ml.
e) Oxidation to [CF3-CH2-CH(Me)-CH2]P(=0)(COMes)2
Analogous to Example 1.
The 31P NMR spectra of the toluene phase shows a new signal at 26.4 ppm. The crude product has been purified via column chromatography (Si02, n-hexane/ethyl acetate 7:2). 1.05 g (45%, related to red phosphorous) of [CF3-CH2-CH(CH3)-CH2]P(=0)(COMes)2 (C25H30F3O3P, M = 466.47 g/mol) are obtained as a yellow oil with Rf = 0.4 (n-hexane/ethyl acetate 7:2). The yellow oil solidifies after several days storage in the fridge.
M.p. = 78°C.
1H-NMR* (250.13 MHz, CDCI3, 25°C): 5 = 6.84 (s, 4 H, Mes CH), 2.40 (m, 2 H, CH2CF3),
2.26 (s, 6 H, Mes p-CH3), 2.23 (s, 6 H, Mes o-CH3), 2.20 (s, 6 H, Mes 0-CH3), 2.18 (m, 2 H,
PCH2), 2.04 (m, 1 H, PCH2CH), 1.16 (d, 3JHH = 6.3 Hz, 3 H, CHCH3).
13C{H}-NMR* (62.90 MHz, CDCI3, 25°C): 5 = 215.8 (d, 1JCP = 52.4 Hz, CO), 215.4 (d, 1JCP =
52.7 Hz, CO), 141.5 (d, 5JCP = 0.6 Hz, Mes C4), 141.5 (d, 5JCP = 0.6 Hz, Mes C4), 135.8 (d,
3JCP = 0.7 Hz, Mes C2'6), 135.7 (d, 3JCP = 0.7 Hz, Mes C2'6), 135.7 (d, 2JCP = 40.6 Hz, Mes C1),
135.6 (d, 2JCP = 40.7 Hz, Mes C1), 129.3 (s, Mes C3'5), 129.3 (s, Mes C3'5),126.5 (q, 1JCF =
277.3 Hz, CF3), 40.8 (q, 2JCF = 27.5 Hz, CH2CF3), 40.7 (q, 2JCF = 27.5 Hz, CH2CF3), 32.0 (d,
1JCP = 52.9 Hz, PCH2), 23.7 (br., PCH2CH), 21.9 (d, 3JCP = 7.3 Hz, CHCH3), 21.2 (s, Mes p-
CH3). 21.2 (s, Mes p-CH3), 19.8 (d, 4JCP = 0.4 Hz, Mes o-CH3), 19.7 (d, 4JCP = 0.4 Hz, Mes o-
CH3).
19F-NMR (CDCI3, 25°C): 5 = -63.1 (m, CF3).
31P{H}-NMR (101.25 MHz, CDCI3, 25°C): 6 = 26.4.
MS (El): m/z = 466 (M+, 3%), 319 (M+ - MesCO, 26%), 147.5 (MesCO\ 100%), 119.2 (Mes63%).

Example 9 Preparation of [{3-[bis-(2,4,6-trimethyI-benzoyl)-phosphinoyl]-propyl}-(2,4,6-trimethyl-benzoyI)-phosphinoyl]-(2,4,6-trimethyl-phenyl)-methanone using lithium and no proton source.
Formula I, n =2, RT = propylene, R2 = mesityl, m=2
a) Preparation of Li3P
Analogous to Example 2, with 0.51 g of naphthalene (4 mmol).
b) None.
c) Preparation of lithium bis(mesitoyl)phosphidexDME, {Li[P(COMes)2]*DME} Analogous to Example 2.
10.06 g of 2,4,6-trimethylbenzoyl chloride (54 mmol) are dropwise added to the light brown reaction mixture of step a) at 30-40°C within 30 min. The reaction mixture is left stirring for 1.5hat40-50°C.
d) Alkylation to
0.91 g of 1,3-diiodopropane (3.0 mmol) are added within 5 min under stirring at 40-50°C to the solution obtained in step c). The reaction mixture is stirred for 40 min at the same temperature, and then for 6 h at 60-70°C. An additional 0.91 g of diiodopropane (3.0 mmol) are added within 5 min and the resulting reaction mixture left stirring for another 22 h at 60-70°C. After cooling down to 30-40°C, 0.87 g of methanol (27 mmol) are added and stirring continued for one hour at the same temperature. The reaction mixture is cooled down to room temperature and filtered over hyflo (Hyflo Super Cel®; Fluka, Buchs, Switzerland). The

resulting filtrate is concentrated under vacuum, the residue dissolved in toluene and extracted three times with water and with saturated sodium chloride solution. The organic phase is dried over Na2S04 and concentrated under vacuum. 7.7 g of an orange oil are obtained.
e) Oxidation analogous to step e) in Example 1.
The crude product (5.32 g) has been purified via column chromatography (Si02, heptane/ethyl acetate 1:1) giving 1.52 g of a white solid. The solid has been further stirred in hexane, seperated and then dried under high vacuum giving 1.24 g (13%, related to red phosphorous) of the title compound as a yellow solid.
1H-NMR (CDCI3): 6 = 6.85 (s; 8 H); 2.23-2.37 (m; 4 H); 2.28 (s; 12 H); 2.23 (s; 24 H); 1.95-2.10 (m; 2 H). 31P-NMR (CDCI3): 5 = 26.7.

a) preparation of Na3P analogous to Example 1
b) preparation of NaPH2 analogous to Example 1
c) preparation of sodium bis(mesitoyl)phosphidexDME, {Na[P(COMes)2]*DME} analogous
to Example 1
d) preparation of phenyl-bis(mesitoyl)phosphane, phenyl-P(COMes)2
One equivalent of phenyl iodide is added together with 1 mol% of Pd(PPh3)4. The reaction mixture is left stirring for 24 h at 60°C, showing 25% conversion according to the 31P-NMR spectra. Afterwards, the reaction mixture is left stirring for an additional 48 h giving a conversion of 33%.

e) Oxidation analogous to step e) in Example 1 provides [phenyl-(2,4,6-trimethyl-benzoyl)-phosphinoyl]-(2,4,6-trimethyl-phenyl)-methanone (= Irgacure 819) as yellowish solid.

0.194 g of purified red phosphorus (6.26 mmol, 1 eq., M =30.97 g/mol) and 0.5 g of sodium sand (21.75 mmol, 3.47 eq., M = 22.99 g/mol) are grinded under argon atmosphere in an agate mortar providing a dark grey, viscous mass. The mixture is then heated under argon up to 300°C during 2 min in a Schlenk-tube giving a grey-black powder. The powder is then suspended in 10 ml of dimethoxyethane followed by dropwise addition of 1.147 g tert-butanol (15.47 mmol). The reaction is accompanied by vigorous gas evolution. The grey suspension is then stirred for 4 h at room temperature and the resulting grey-brown suspension filtered over Celite. The clear beige solution is concentrated under vacuum and the resulting light beige powder suspended in 10 ml of toluene. The suspension is heated up until a clear beige solution is formed. Octahedral crystals separate which are collected by filtration and then washed with 2 ml of toluene. 0.95 g of product (13% related to NaPH2) are obtained as a colorless solid.

me proauci is cnaracienzea uy x-ray sirucuire analysis anu uunespunus iu an aiuunuiaie cluster with the formula [Nai3(OtBu)12@PH2]: (C48H11oNa13012p) M = 1209.22 g/mol)]. 1H-NMR (300.13 MHz, C6D6, 25°C): 5 = 1.49 (s, 110 H, lBu), - 2.18 (d, 2 H,1Jp,H = 142.5 Hz). 31P-NMR (121.47 MHz, C6D6j 25°C): 8 = - 292.3 (t, 1JPiH = 142.5 Hz)
Example 12 Preparation of alcoholate cluster of phosphide by the reaction of sodium tert-butoxide with sodium phosphide
NaPH2 has been first prepared according to Brauer, "Handbuch der Praparativen Anorganischen Chemie", Bd I, p. 510.
Afterwards, 1.03 g sodium tert-butoxide (10.7 mmol, 12 eq., M = 96.10 g/mol) and 50 mg NaPH2 (0.89 mmol, 1 eq., M = 55.98 g/mol) are suspended in 15 mol of toluene. The beige suspension is kept for 24 hours at room temperature. Colorless, octahedral crystals separate from the reaction mixture which are collected by filtration and further washed with 2 ml of toluene. 0.85 g of product (78% related to NaPH2) are obtained as a colorless solid.
The same analytical data are obtained like the product from example 11, corresponding to the formula [Na13(OtBu)12@PH2]: (C48H11oNa13Oi2P, M = 1209.22 g/mol)].
Example 13 Preparation of sodium bis(mesitoyl)phosphide {Na[P(COMes)2]} or sodium bis(mesitoyl)phosphide*DME {Na[P(COMes)2]xDME} from [Na13(OtBu)12@PH2].
1 g of [Na^O^u)^®?^] from example 12 (0.83 mmol, 1 eq., M = 1209.22 g/mol) is dissolved in toluene (the same experiment has been also run in DME). The resulting mixture is cooled over an ice-bath. 0.3 g of 2,4,6-trimethylbenzoyl chloride (TMBCI) in 5 ml of toluene are added dropwise. Stirring is continued for 30 min at room temperature. All volatile compounds have been removed at 0.1 Torr and the yellow-orange residue taken up in toluene. Subsequent filtration and crystallization from toluene/n-hexane leads to {Na[P(COMes)2]}. Furthermore, {Na[P(COMes)2]xDME} has been isolated when DME was used instead of toluene for the same procedure.
This complex can be further alkylated as e.g. in Example 1 d).

Formula I, R2=mesityl, R2 = t.butyl
0.5 g of NaPH2 (8.9 mmol, 1 eq., M = 55.98 g/mol), prepared according to example 11, are suspended in 30 ml of toluene. 1.575 g of methyl 2,4,6-trimethylbenzoate (8.9 mmol, 1 eq., M = 178.23 g/mol) in 10 ml of THF are dropwise added and stirring is continued for 30 min at room temperature. The resulting yellow suspension is filtered and then concentrated under high vacuum giving a yellow oil.
The oil is taken up in 20 ml of THF and dropwise treated at room temperature with 0.807 g of pivalolyl chloride (2,2-dimethylpropionyl chloride) (6.7 mmol, 0.75 eq., M = 120.58 g/mol) in 10 ml of THF. The yellow suspension is stirred for 30 min at room temperature. 0.855 g of sodium tert-butoxide (8.9 mmol, 1 eq., M = 96.10 g/mol) are added in several portions providing a yellow-orange suspension. After stirring for 30 min at room temperature 0.55 ml of methyl iodide (8.9 mmol, 1 eq., M = 141.94 g/mol) are dropwise added giving an almost colorless suspension. Stirring is continued for an additional hour at room temperature. The reaction mixture is concentrated under vacuum and then taken up in 20 ml of toluene, filtered over Celite and additional rinsing with 10 ml of toluene. 31P-NMR analysis shows one resonance at 23.7 ppm for 2,2-dimethyl-1-[methyK2,4,6-trimethyl-benzoyl)-phosphanyl]-propan-1-one.
To the resulting solution is added 10 ml of water and 2.01 g of 30% H202 solution (17.8 mmol, 2 eq., M = 34.01 g/mol). The reaction mixture is stirred for 4 h at 30°C. The organic phase is washed three times with 10 ml of water and the aqueous phases washed with 20 ml of toluene. The combined organic phases are dried over MgS04 and then concentrated under vacuum. The resulting yellow oil is purified by flash chromatography (hexane/ethyl acetate 1:1, Rf = 0.45). Yield: 0.69 g yellow oil (26%, C16H2303P, M = 294,33 g/mol)
1H-NMR (300.13 MHz, CDCI3, 25°C): 5 = 6.88 (s, 2 H, Mes CH), 2.30 (s, 3 H, Mes p-CH3), 2.29 (s, 6 H, Mes o-CH3), 1.76 (d, 2JP(H = 12.6 Hz, PCH3), 1.28 (s, 9 H, lBu).
13C{H}-NMR (75.47 MHz, CDCI3, 25°C): S = 220.9 (d, 1JCP = 43.1 Hz, 'BuCO), 215.2 (d, 1JCP = 57.7 Hz, MesCO), 140.7 (d, 5JCP = 0.8 Hz, Mes C4), 136.1 (d, 2JCP = 42.3 Hz, Mes C1), 134.6 (d, 3JCP = 0.6 Hz, Mes C2'6), 129.0 (d, 4JCP = 0.7 Hz, Mes C35), 48.6 (d, 2JCP = 37.6 Hz, C(CH3)3), 24.3 (s, C(CH3)3), 21.2 (s, Mes p-CH3), 19.8 (s, Mes o-CH3), 12.9 (d, 1JCP = 57.4 Hz, PCH3).31P-NMR (121.5 MHz, CDCI3, 25°C): 5 = 28.2 (q, 2JP,H = 12.6 Hz).

3.72 g of sodium (162 mmol) and 0.51 g of naphthalene (4 mmol) are suspended in 70 ml of DME. 3.82 g of PCI3 (27 mmol) is dropwise added within 15 min at room temperature. The suspension is stirred at room temperature overnight, giving a black suspension.
b) Preparation of NaPH2
To the reaction mixture 5.52 g of 3-methyl-3-pentanol (54 mmol) are added dropwise within 3 hours. Stirring is continued for an additional 5.5 hours at room temperature, giving a light brown suspension.
c) Preparation of sodium bis(mesitoyl)phosphide*DME, {Na[P(COMes)2]xDME}
10.06 g of 2,4,6-trimethylbenzoyl chloride (54 mmol) are added dropwise within 30 min.
The reaction mixture is left stirring over night at room temperature giving an orange-
yellow suspension.
d) Alkyiation to acetic acid 3-[bis-(2,4,6-trimethyl-benzoyl)-phosphanyl]-propyl
ester
29.7 mmol of 3-bromopropylacetate (synthesised analogue to 6-bromohexylacetate
according to literature: Z. Naturforsch.55 b; 2000; p 583 ) are added dropwise within 10
min. and left stirring for 2.5 h at 50-60°C. The resulting yellow suspension is taken to
dryness and resolved in 100 ml toluene (yellow suspension).
31P-NMR(d6-benzene): 53.2 ppm (bisacyl-alkylphosphine)
e) Oxidation

60 ml water are added to the crude reaction mixture. The pH is adjusted with 2 molar HCI to 5-7 and treated with 4.46 g of hydrogen peroxide (30% in H20, 40.5 mmol) within 5 min at room temperature. After heating to 50-60°C stirring is continued for 2h. The reaction mixture is separated and the organic layer is extracted with 2% aqueous NaHC03 and saturated NaCI solution, followed by drying over Na2S04 and concentration under vacuum. The crude 13.86g yellow oil is purified by preparative chromatography (heptane/ethylacetat 1:1; silicagel), to give 4.34 g 3-[bis-(2,4,6-trimethyl-benzoyl)-phosphinoyl]-propyl acetate as a yellow oil (yield 36%).
31P-NMR(CDCI3):27.5ppm

a> after prep-chromatographie (heptane/ethylacetat 3:7; silicagel),
b) after crystallisation from petrolether
c) after prep-chromatographie (heptane/ethylacetat 3:7; silicagel),
d) after crystallisation from petrolether
e) after crystallisation from hexane
f) after prep-chromatographie (heptane/ethylacetat 6:4; silicagel),
9) after prep-chromatographie (heptane/ethylacetat 7:3; silicagel),
h) after prep-chromatographie (heptane : ethylacetat 1:1; silicagel),
0 after prep-chromatographie (heptane : ethylacetat 4:6; silicagel),

a. Preparation of NaPH2
1.725 g (0.075 mol, 3 equivalents) Sodium sand are dissolved in 50 ml liquid ammonium at -70°C under argon. To this solution, a suspension of 0.775 g (0.025 mol, 1 equivalent) purified red phosophorus (grounded to
hours, keeping the temperature between -55 and -65°C, while a reddish-beige solid is deposited from the reaction mixture. This solid is dissolved upon the addition of 4.8 ml tert-butanol (0.05 mol, 2 equivalents) in 7 ml tetrahydrofuran at -60°C over 1.5 hours. The blue solution is stirred for 2.5 hours at -60°C, during which time the color changes to green and finally ochre. The solution is slowly warmed to room temperature over a time of 4 hours. The 31P-NMR spectrum of the solution shows a resonance line at -297 ppm (t, 1J(P, H) = 155 Hz, NaPH2).
b. Preparation of sodium bis (mesitoyl)phosphidexDME, {Na[P(COMes)2]xDME}
The volatile components of the reaction mixture obtained according to example 32a are evaporated in vacuum and the residual ochre solid is dissolved in 60 ml dimethoxyethane (DME). 9.15 g (0.05 mol, 2 equivalents) of 2,4,6-trimethylbenzoyl chloride are slowly added at room temperature over one hour, resulting in a color change of the suspension to yellow and a slight increase of the temperature. The reaction mixture is stirred for another hour at room temperature. A single resonance at 81.6 ppm in the 31P-NMR spectrum shows the formation of sodium bis (mesitoyl)phosphidexDME, {Na[P(COMes)2]xDME}, in high yield.
c. Alkylation to [Bis-(2,4,6-trimethyl-benzoyl)-phosphanyl]-acetic acid ethyl ester
4.175 g (0.025 mol. 1 equivalent) bromacetic acid ethyl ester are added over 15 minutes to the solution obtained in step b. After stirring, the solvent and all volatile compounds are removed under vacuum. [Bis-(2,4,6-trimethyl-benzoyl)-phosphanyl]-acetic acid ethyl ester is obtained as a beige solid in 60% yield (Referent to the red phosphorus starting material). The 31P-NMR spectrum shows the formation this product in high purity by a single resonance line at 46.5 ppm.
Example 33 Preparation of acetic acid 3-[bis-(2,6-dimethoxy-benzoyl)-phosphinoyi]-propyl ester, starting from phosphorus trichloride.

a) Preparation of Na3P
3.72 g of sodium (162 mmol) and 0.51 g of naphthalene (4 mmol) are suspended in 70 ml of DME. 3.82 g of phosphorus trichloride (27 mmol) are dropwise added within 15 min at room temperature. The suspension is stirred at room temperature overnight, giving a black suspension.
b) Preparation of NaPH2
To the reaction mixture 5.52 g of 3-methyl-3-pentanol (54 mmol) dissolved in 10 ml DME are added dropwise within 3 hours. Stirring is continued for an additional 5.5 hours at room temperature, giving a light brown suspension.
c) Preparation of sodium bis(2,6-dimethoxybenzoyl)phosphide*DME,
10.83 g of 2,6 Dimethoxybenzoylchloride (54 mmol) dissolved in 20 ml DME are added dropwise within 50 min. The reaction mixture is left stirring over night at room temperature giving a brown-yellow suspension.
d) Alkylation to acetic acid 3-[bis-(2,6-dimethoxy-benzoyl)-phosphanyl]-propyl
ester
29.7 mmol of 3-bromopropylacetate (synthesised analogously to 6-bromohexylacetate reported in Z. Naturforsch.55 b; 2000; p 583 ) are added drop wise within 10 min. and left stirring for 3 h at 50-60°C. The resulting yellow suspension is taken to dryness and resolved in 80 ml toluene (yellow suspension).
31P-NMR(C6D6): 55.4 ppm (Bisacyl-alkylphosphine)
e) Oxidation
50 ml water are added to the crude reaction mixture. 4.46 g of hydrogen peroxide (30% in H20, 40.5 mmol) are added within 5 min at room temperature. After heating to 50-60°C stirring is continued for 1 h. The reaction mixture is separated and the organic layer is extracted with 2% aqueous NaHC03 and saturated NaCI solution, followed by

drying over Na2S04 and concentration under vacuum. The crude 13.77g yellow oil is purified by crystallisation from hexane, resulting in 6.76 g acetic acid 3-[bis-(2,6-dimethoxy-benzoyl)-phosphinoyl]-propyl ester as white yellow crystals (yield 52%).
31P-NMR(CDCI3):27.0ppm
Examples 34-36 (Table 2) are prepared using the same reaction sequence as for sample33, expect that in step d the alkylating agent listed in Table 1 is used instead of 3-bromopropylacetate.
Table 2

a) Preparation of Na3P
3.72 g of sodium (162 mmol) and 0.51 g of naphthalene (4 mmol) are suspended in 65 ml of DME. 3.82 g of phosphorus trichloride (27 mmol) dissolved in 5 ml DME is dropwise added within 10 min at room temperature. The suspension is stirred at room temperature overnight, giving a black suspension.
b) Preparation of NaPH2
To the reaction mixture 5.52 g of 3-methyl-3-pentanol (54 mmol) dissolved in 10 ml DME are added drop wise within 1.5 hours. Stirring is continued for an additional 5 hours at room temperature, giving a light brown suspension.
c) Preparation of sodium bis(2,6-dichlorobenzoyl)phosphide*DME,
11.31 g of 2,6 Dichlorobenzoylchloride (54 mmol) dissolved in 10 ml DME are added drop wise within 60 min. The reaction mixture is left stirring over night at room temperature giving a yellow-brown suspension.
d) Alkylation to acetic acid 3-[bis-(2,6-dichloro-benzoyl)-phosphanyl]-propyl
ester
29.7 mmol of 3-bromopropylacetate (synthesised analogously to 6-bromohexylacetate reported in Z. Naturforsch.55 b; 2000; p 583) are added drop wise within 10 min. and

left stirring for 8 h at 50-60°C. The resulting yellow suspension is taken to dryness and resolved in 80 ml toluene (yellow suspension).
31P-NMR(C6D6): 48.8 ppm (Bisacyl-alkylphosphine)
e) Oxidation
50 ml water are added to the crude reaction mixture. 4.46 g of hydrogen peroxide (30% in H20, 40.5 mmol) are added within 5 min at room temperature. After heating to 50-60°C stirring is continued for 2 h. The reaction mixture is separated and the organic layer is extracted with 2% aqueous NaHC03 and saturated NaCI solution, followed by drying over Na2S04 and concentration under vacuum. The crude 10.6 g yellow oil is purified by prep-chromatography (heptane/ethylacetate 20:80; silicagel), resulting in 0.87 g acetic acid 3-[bis-(2,6-dichloro-benzoyl)-phosphinoyl]-propyl ester as yellow crystals (yield 7%).
31P-NMR(CDCI3): 25.0 ppm
Example 38 (Table 3) is prepared using the same reaction sequence as for sample B, expect that in step d the alkylating agent listed in Table 3 is used instead of 3-bromopropylacetate.

Example 39 and 40
Examples 39 and 40 (Table 4) are prepared using the same reaction sequence as described for example 1, expect that in step d the alkylating agent listed in Table 4 is used instead of isobutyl bromide.

Example 41 Preparation of [Bis-(2-ethoxy-naphthalene-1-carbonyl)-phosphinoyl]-acetic acid ethyl ester, starting from phosphorus trichloride

The compound of example 41 is prepared following the reaction sequence of example 32, except that 2-ethoxy-naphthalene-1-carbonyl chloride is used for the acylation step 15c and ethyl 2-bromoacetate in the alkylation step 15d). [Bis-(2-ethoxy-naphthalene-1-carbonyi)-phosphanyl]-acetic acid ethyl ester obtained in step d) has a 31P-NMR resonance at 51.77 ppm.
Examples 42-75 Preparation of 2-[bis-(2,4,6-trimethyl-benzoyl)-phosphanyl] acetic acid esters and 2-[bis-(2,4,6-trimethyl-benzoyl)-phosphinoyl] acetic acid esters
The 2-[bis-(2,4,6-trimethyl-benzoyl)-phosphanyl] acetic acid esters (Formula A) and 2-[bis-(2,4,6-trimethyl-benzoyl)-phosphinoyl] acetic acid esters (Formula B) derivatives of examples 42-75 (Table 5) are prepared using the reaction sequence reported for Example 15, expect that in step d the alkylating agents listed in Table 5 are used instead of 3-bromopropylacetate. Table 5.

Alternatively, the compounds collected in Table 5 can also be prepared by transesterification of the methyl ester (Example 17) or ethyl ester (Example 18) with the corresponding alcohol in the presence of a suitable catalyst using reaction conditions known to in the literature. Suitable catalyst are, for example but without limiting to these examples, tin oxide, Fascat 4200 (dibutylzinn-diacetate commercially available of the Arkema group)., aluminium(lll) acetylacetonate or zirconium(IV)propoxide.
Examples 76-78 Preparation of 2-[bis-(2,4,6-trimethyl-benzoyl)-phosphanyl] acetic acid esters and 2-[bis-(2,4,6-trimethyl-benzoyl)-phosphinoyl] acetic acid esters
The 2-[bis-(2,4,6-trimethyl-benzoyl)-phosphanyl] acetic acid esters (Formula A) and 2-[bis-(2,4,6-trimethyl-benzoyl)-phosphinoyl] acetic acid esters (Formula B) derivatives of

examples 76-78 (Table 6) are by transesterification of the methyl ester (Example 17) using the alcohol listed in Table 6 alcohol in the presence of Fascat 4200,as catalyst. Table 6

Examples 79-80 Preparation of 1-[bis-(2,4l6-trimethyl-benzoyl)-phosphanyl]-alkanesand 1-[bis-(2,4,6-trimethyl-benzoyl)-phosphinoyl]-alkanes
1-[Bis-(2,4,6-trimethyl-benzoyl)-phosphanyl]-alkanes (Formula A) and 1-[bis-(2,4,6-trimethyl-benzoyl)-phosphinoyl]-alkanes (Formula B) of Examples 79 - 80 (Table 7) are prepared using the same reaction sequence as described for example 1, expect that in step d the alkylating agent listed in Table 4 is used instead of isobutyl bromide.

Examples 81-86 Preparation of 1-[bis-(2l4,6-trimethyl-benzoyl)-phosphanyl]-pentane-2,4-dione and 1 -[bis-(2,4,6-trimethyl-benzoyl)-phosphinoyl]-pentane-2,4-dione derivatives or 4-[bis-(2,4,6-trimethyl-benzoyl)-phosphanyl]-3-oxo-butyric acid esters 4-[bis-(2,4,6-trimethyl-benzoyl)-phosphinoyl]-3-oxo-butyric acid esters
The bis-(2,4,6-trimethyl-benzoyl)-phosphanyl (Formula A) and bis-(2,4,6-trimethyl-benzoyl)-phosphinoyl derivatives (Formula B) of examples 81-86 (Table 8) are prepared using the reaction sequence reported for example 15, expect that in step d the alkylating agents listed in Table 7 are used instead of 3-bromopropylacetate.
Table 8.

Examples 87-93: Preparation of [bis-(2-ethoxy-naphthalene-1-carbonyl)-phosphanyl]-acetic acid ester derivatives and [bis-(2-ethoxy-naphthalene-1-carbonyl)-phosphinoyl]-acetic acid ester derivatives
The [bis-(2-ethoxy-naphthalene-1-carbonyl)-phosphanyl]-acetic acid ester derivatives (Formula A) and [bis-(2-ethoxy«naphthalene-1-carbonyl)-phosphinoyl]-acetic acid ester derivatives (Formula B) of examples 87-93 are prepared following the reaction sequence of example 41, except that that in step d the alkylating agents listed in Table 9 are used instead of 3-bromopropylacetate

Alternatively, the compounds collected in Table 9 can also be prepared by transesterification of the ethyl ester (Example 41) with the corresponding alcohol in the presence of a suitable catalyst using reaction conditions known in the literature. Suitable catalyst are, for example but without limiting to these examples, tin oxide, Fascat 4200 (Arkema Group), aluminium(lll) acetylacetonate or zirconium(IV)propoxide.
Examples 94-100: Preparation of [(2-ethoxy-naphthalene-1-carbonyl)-(2,4,6-trimethylbenzoyl)-phosphanyl]-acetic acid ester derivatives and [(2-ethoxy-naphthalene-1-carbonyl)-(2,4,6-trimethylbenzoyl)-phosphionoyl]-acetic acid ester
derivatives
The [(2-ethoxy-naphthalene-1-carbonylH2,4,6-trimethylbenzoyl)-phosphanyl]-acetic
acid ester derivatives and [(2-ethoxy-naphthalene-1-carbonyl)-(2,4,6-trimethylbenzoyl)-phosphionoyl]-acetic acid ester derivatives of examples 94-100 are prepared following the reaction sequence of example 14, except that [(2-ethoxy-naphthalene-1-carboxylic acid chloride is used in the first acylation step instead of pivaloyl chloride and the alkylating agents listed in Table 10 are used instead of methyl iodide.

Alternatively, the compounds collected in Table 10 can also be prepared by transesterification of the ethyl ester (Example 41) with the corresponding alcohol in the presence of a suitable catalyst using reaction conditions known in the literature. Suitable catalyst are, for example but without limiting to these examples, tin oxide, Fascat 4200 (Arkema Group), aluminium(lll) acetylacetonate or zirconium(IV)propoxide.
Examples 101-106; Preparation of diesters of bis-(2,4,6-trimethyl-benzoyl)-phosphanoyl]-acetic acid and bis-(2,4,6-trimethyl-benzoyl)-phosphinoyl]-acetic
acid
The diesters of bis-(2,4,6-trimethyI-benzoyl)-phosphanoyl]-acetic acid (Formula A) and bis-(2,4,6-trimethyl-benzoyl)-phosphinoyl]-acetic acid (Formula B) derivatives of examples 101-106 (Table 11) are prepared using the reaction sequence reported for example 15, expect that in step d the 0.5 equivalents of the alkylating agents listed in Table 11 are used instead of 3-bromopropyiacetate.

Alternatively, the compounds collected in Table 11 can also be prepared by transesterification of the methyl ester (Example 17) or ethyl ester (Example 18) with 0.5 equivalents of the corresponding alcohol in the presence of a suitable catalyst using reaction conditions known in the literature. Suitable catalyst are, for example but without limiting to these examples, tin oxide, Fascat 4200 (Arkema Group), aluminium(lll) acetylacetonate orzirconium(IV)propoxide.

Application examples: Pendulum Hardness
A UV-curable white coat is prepared by mixing
67.5 parts of polyester acrylate oligomer (RTMEBECRYL 830, UCB, Belgium)
5.0 parts of hexanediol diacrylate
2.5 parts of trimethylolpropane triacrylate 25.0 parts of rutile titanium dioxide (RTMR-TC2, Tioxide, France)
2.0 parts of the photoinitiator The coating is applied to a coil-coated aluminium sheet using a 100 nm slotted doctor knife and then cured. Curing is carried out by conveying the sample twice, on a conveyor belt which is moving at a speed of 10 m/min, beneath an 80 W/cm medium-pressure mercury lamp (Hanovia, USA). The pendulum hardness is then determined in accordance with Konig (DIN53157) in [s]. The pendulum hardness is a measure of the through-curing of the composition. The higher the values, the more effective the curing which has been carried out. After the first pendulum hardness determination, the sample is after-exposed under low-pressure mercury lamps of the type TL 40W/03 (Philips; Emission maximum of 430 nm), and after 16h the pendulum hardness is determined again.
Yellow index
The yellow Index b was determined in accordance with ASTMD 1925-88.
The Table below shows the results.

Claims
1. A process for the preparation of acylphosphanes or bisacylphosphanes of formula I

n and m are each independently of the other 1 or 2;
Ri if n = 1, is unsubstituted linear or branched CrCi8alkyl or C2-Ci8alkenyl; or
linear or branched CrC18alkyl or C2-C18alkenyl substituted once or more than
once by groups selected from:
-OR10, -SRio, -OCO-R10, -COO-R10 -CH=CH-CO-ORi0 or -C(CrC4alkyl)=C(CrC4alkyl)-CO-OR10; wherein
Rio is hydrogen, CrC18alkyl, or C2-C18alkyl which is interrupted by one or several non-successive -O-atoms, a di,-tri,-tetra-or polyethylene glycol residue, C3-Ci2-cycloalkyl, tetrahydropyran-2-yl, phenyl-CrC4-alkylene, phenyl-c1-C4alkenylene, CrC6alkyl substituted by halogen or substituted by cyclohexyl or cyclopentyl, or substituted by tetrahydrofuranyl, furanyl, isopropyl-4-methyl-coclohexyl, C2-C18-alkenyl, unsubstituted phenyl, naphthyl or biphenyl being unsubstituted or phenyl, naphthyl or biphenyl substituted by one to five CrCs-alkyl, d-C8-alkoxy, CrCs-alkylthio and/or halogen; or Ri is linear or branched CrC18alkyl or C2-C18alkenyl substituted by -CO-Rn; wherein
Rn is CrC18alkyl, or C2"Ci8alkyl which is interrupted by one or several non-successive -O-atoms, C3-Ci2-cycloalkyl, phenyl-CrC4-alkylene, unsubstituted phenyl, naphthyl or biphenyl being unsubstituted or phenyl, naphthyl or biphenyl

substituted by one to five CrC8-alkyl, CrC8-alkoxy, CrC8-alkylthio and/or halogen or
Ri is linear or branched Ci-C18alkyl or C2-C18alkenyl substituted by -CO-(CH)2-CO-CrCealkyl, CO-(CH)2-CO-phenyl, or by CO-CCHJrCOO-C1-c18alkyl; or
Ri is linear or branched CrC18alkyl or C2-C18alkenyl substituted by -NR12R13) -N(Ri2)-CO-R10, -N(R12)-CO-OR10, -N(R12)-CO-NR12R13, -N(R12)-CO-Hal, -CO-NR12R13, wherein R10 is as defined above and R12 and Ri3 independently of one another are is hydrogen, CrC18alkyl, C2-C18alkyl which is interrupted by one or several non-successive O atoms, C3-C12-cycloalkyl, C2-C18-alkenyl, phenyl-Ci-C4-alkyl, phenyl, naphthyl, pyridyl, the radicals phenyl, naphthyl or pyridyl being unsubstituted or substituted by one to five CrC8-alkyl, CrC8-alkoxy, CrC8-alkylthio and/or halogen; or R12 and R13 forms a 5- or 6-membered 0-, S- or N-containing heterocyclic ring; that may be further annelated by an aliphatic or aromatic ring; or
-SO2-R10, -SO2-ORi0, -S02-NR12R13, wherein Ri0,Ri2 and R13 are as defined above; or
-PO(OCrC8alkyl)2, or
-SiRi4Ri5Ri6, wherein R14, R15 and R16 independently of one another are H, Cr C8alkyl, C2-C8alkenyl, phenyl, C7-C9phenylalkyl, -OCVQjalkyl, -0-SiRi7Ri8Ri9, wherein R17, R18 and Ri9 are independently of each other H, d-Csalkyl, C2-C8alkenyl, phenyl, C7-C9phenylalkyl, -OCrC8alkyl; or
-CH=CH-phenyl or -C(CrC4alkyl)=C(CrC4alkyl)-phenyl, phenyl-CrdalkyI, phenyl, naphthyl, biphenyl, C5-C12cycloalkyl or a 5- or 6-membered 0-, S- or N-containing heterocyclic, ring; benzophenonyl, thioxanthonyl; or
Ri is C2-C18alkyl or C2-Ci8alkenyl which is interrupted by one or several non-successive -0-, -NH-, -NR12- or -S- atoms, and may additionally be substituted once or more than once by groups selected from: halogen or CN, or
-OR™, -SR10, -OCO-R10, -COO-Ri0j wherein Ri0 is as defined above; or -NR12R13, -N(Ri2)-CO-R10, -N(R12)-CO-OR10, -N(Ri2)-CO-NR12R13, -N(Ri2)-CO-Hal, -CO-NR12R13, wherein R10 and Ri2 and Ri3 are as defined above; or

-SO2-R10, -SO2-OR10, -S02-NR12R13, wherein R10l Ri2 and R13 are as defined
above;or
-PO(OCrC8alkyl)2, or
-SiR14Ri5Ri6. wherein R14, R15 and Ri6 are as defined above; or
phenyl-CrC4alkyl, phenyl or C5-Ci2cycloalkyl;
or Ri is C2-Ci8alkyl or C2-C18alkenyl which is interrupted by -CO-, -COO-, -OCO-, -
OCOO-, -CO-N(R12)-, -N(R12)-CO-, -N(R12)-CO-N(Ri2)-, -N(R12)-COO-, -COO-C1-
C18alkylene, -COS-Ci-C18alkylene, -S02-, -S02-0-, -S02-N(R12)-, -(CH3)2Si-
[OSi(CH3)2 ]m- with m = 1-6, phenyl-CrC4alkylene, phenylene, naphthylene,
biphenylene, C5-C12cycloalkylene or a 5- or 6-membered 0-, S~ or N-containing
heterocyclic ring; wherein R12 is as defined above;
or Ri is trimethylsilyl or Hal-(CH3)2Si-[OSi(CH3)2 ]m- or (CH3)3Si-[OSi(CH3)2 ]m- with m =
1-6 ;or R, is -COOH, -COO-R10, -CO-NRi2R13, -CO-vinyl, -CO-phenyl which is unsubstituted
or substituted by one or more -CH3, -OCH3, -CI; wherein R10, Ri2 and Ri3 are as
defined above;or R1 is phenyl-C1-C4alkyl, phenyl, naphthyl, biphenyl, C5-Ci2cycloalkyl or a 5- or 6-
membered 0-, S- or N-containing heterocyclic ring; all of the radicals phenyl,
naphthyl, biphenyl, C5-C12cycloalkyl or the 5- or 6-membered -0-, S- or N-
containing heterocyclic ring being unsubstituted or substituted by one to five
halogen, CrC8alkyl, CrCealkylthio, CrC8alkoxy and/or -NR12Ri3; wherein Ri2
and R13 are as defined above;
R1 if n = 2, is a divalent radical of the monovalent radical defined above or is

-CH2-COO-Z-OCO-CH2- wherein
Q is a single bond, -CH2-, -CR6R7-, -O- or -S- ; R4 and R5 are each

independently of the other hydrogen, CrC4alkyl or Ci-C4alkoxy; R6 and R7 are each independently of the other d-C4alkyl;
Z is CrCis alkylene or a bridge derived from a di,-tri,-tetra-or polyethylene glycol. R1 if n = 2, is a divalent radical of the monovalent radical defined above or is

wherein
Q is a single bond, -CH2-, -CR6R7-, -O- or -S- ; R4 and R5 are each independently of the other hydrogen, CrC4alkyl or Ci-C4alkoxy; R6 and R7 are each independently of the other (VCalkyl;
R2 is CrC18alkyl or C2-C18alkenyl ; C1C18alkyl or C2-C18alkenyl substituted once or more than once by halogen; or
-OR10, -OCO-R10, -OCO-Hal, -COO-R10, -CH=CH-CO-OR10 -N(R12)-CO-R10, -N(R12)-CO-Hal, ; -C(C1-C4alkyl)=C(C1-C4alkyl)-CO-OR10, -CO-NR12R13l wherein R10, R12 and R13 are as defined above; or -CH=CH-phenyl or -C(Cr C4alkyl)=C(CrC4alkyl)-phenyl; C3-C12cycloalkyl, C2-C18alkenyl, phenyl-Crdalkyl, phenyl, naphthyl, anthryl. biphenyl or a 5- or 6-membered -O-, S- or N-containing heterocyclic ring, the radicals phenyl, naphthyl, biphenyl or the 5- or 6-membered -0-, S- or N-containing heterocyclic ring being unsubstituted or substituted by one to five halogen, Ci-C8alkyl, d-C8alkoxy and/or CrCsalkylthio;
R3 is one of the radicals defined under R^
the process comprises the steps
a) contacting elemental phosphorous [P]*., P(Hal)3 or other phosphorous
compounds in which the formal oxidation state of the phosphorous atom is higher
than (-3)

with a reducing metal optionally in the presence of a catalyst or an activator in a solvent to obtain metal phosphides Me3P or Me'3P2, wherein Me is an alkali metal and Me' is an earth alkali metal or to obtain metal polyphosphides
b) optionally adding a proton source, optionally in the presence of a catalyst or an
activator to obtain metal dihydrogen phosphides MePH2;
c) subsequent acylation reaction with m acid halides of formula III or m carboxylic
acid esters of formula IV
or, in case that in formula I m = 1, with one carboxylic ester of formula IV followed by one acid halide of formula III or vice versa ,wherein R is the residue of an alcohol and R2 is as defined above;
d) alkylation reaction
in case of m = 2, subsequent reaction with an electrophilic agent RiHal or other
electrophilic agents such as RTOSCVO-R-I ,
(Ri-0)3POf H2C=CR23COOR10 wherein ^ and R10 are as
defined above, R2o is Ci-Cs-alkyl,, C-rC8-perfluoroalkyl, aryl or CrC4-alkylaryl, R2i is H or CrC8alkyl; R22 is CrC16alkyl or C2-C16alkenyl substituted once or more than once by halogen -OR™, -NR12Ri3, -SR10, -OCO-R10, -OCO-Hal, -COO-R10, -IM(R12)-CO-R10l -N(R12)-CO-OR10, -N(R12)-CO-NRl2R13, -N(R12)-CO-Hal, -CO-NR12R13, -SO2-R10, -SO2-ORi0, -S02-NRi2Ri3, -CH=CH-CO-OR10, -CH=CH-phenyl, "C(CrC4alkyl)=C(C1-C4alkyl)-CO-OR1o or -C(CrC4alkyl)=C(Cr C4alkyl)-phenyl, phenyl-CrC4alkyl, phenyl, naphthyl, biphenyl, C5-C12cycloalkyl or a 5- or 6-membered 0-, S- or N-containing heterocyclic ring; R23 is H or CH3, and n = 1-5 and R10) R12 and Ri3 is as defined above;
and in the case of m = 1 reaction with an electrophilic agent R^al or other electrophilic agents such as RrOSOrO-Ri ,

and R23 are as defined above
followed by the reaction with an electrophilic agent R3Hal or other electrophilic
O agents such as R3-OS02-OR3, R3-OS02-R2o, D„ / \ (R3-0)3POf

are as defined above
to obtain the compounds of formula I.
2- A process according to claim 1 for the preparation of monoacylphosphanes of the formula I' (compounds of the formula I with n = 1 and m = 1)

wherein R1, R2 and R3 are as defined in claim 1
which process comprises the steps a), b) and c) as defined in claim 1; and
d) reaction with an electrophilic agent R^al or other electrophilic agents containing the
residue R1 as defined in claim 1 step d for m = 1
followed by the reaction with an electrophilic agent R3Hal or other electrophilic agents
containing the residue R3 as defined in claim 1 step d for m=1
to obtain the compounds of formula I'.
3. A process according to claim 1 for the preparation of symmetric bisacylphosphanes of the formula I" (compounds of the formula I with n = 1 and m =
2)

wherein F^ and R2 are as defined in claim 1,
which process comprises the steps a), b) and c) as defined in claim 1 for m = 2; and
d) reaction with an electrophilic agent RiHal or other electrophilic agents containing the
residue R to obtain the compounds of formula I".
4, A process according to claim 1 for the preparation of unsymmetric bisacylphosphanes of the formula H (compounds of the formula I with n = 1 and m = 2)
wherein Ri is as defined in claim 1 and R2 and R2' independently of one another are as defined in claim 1 under R2 with the proviso that R2 is not equal R2\ which process comprises the steps a) and b) as defined in claim 1; and
c) subsequent reaction with an acid halide of formula III or a carboxylic acid ester of
formula IV
wherein R is the residue of an alcohol and R2 is as defined above;
subsequent reaction with a second acid halide III' or a second carboxylic acid
ester of the formula IV,
wherein R2' and Hal are as defined above,
d) reaction with an electrophilic agent RiHal or other electrophilic agents containing
the residue R-\ as defined in claim 1 step d for m = 2
to obtain the compounds of formula I'".

5. A process for the preparation of symmetric metal bisacylphosphides of the formula
(V) or (Va)
wherein R2 is as defined in claim 1 and the metal is Li, Na, K, Mg, which process comprises the steps a) b) and c) as defined in claim 1 for m = 2.
6. A process according to claim 1 for the preparation of unsymmetric metal
bisacylphosphides of the formula (V) or (Va')

wherein R2and R2' are as defined in claim 4 and the metal is Li, Na, K, Mg, which process comprises the steps a) b) and c) as defined in claim 4.
7. A process according to claim 1, wherein are n=1 and Ri is phenyl, linear or
branched d-C8alkyl or C2-C18alkenyl or is linear or branched CrC8alkyl or
C2-C18alkenyl substituted by CN, trifluormethyl, oxiranyl, isoindole-1,3-dione, -O-
d-Cisalkyl, -O-benzyl, -CO-phenyl, -CO-d-dsalkyl,
-OCO-d-dsalkylj-OCO-d-dsalkenyl;
-COO-d-C18alkyl;-COO-d-d8alkylene-phenyl,-COO-d-dsalkylene-cycloalkyl, -COO-d-d8alkylene-tetrahydrofuranyl, -COO-CrC18alkylene-furanyl, -COO-cycloalkyl.-COO-d-C^alkenylj-COO-C1-c18alkenylene-phenyl; -COO-(CH2)2-3-CI,

-COO-[(CH2)2-3-0]1_1o-C1-C6alkyl;-COO-[(CH2)2-3-0]1_10-C1-C6-OH, -CO-CH^CO-CrCiaalkylj-CO-CH^COO-CrCisalkyl.-O-tetrahydropyrany!, bicyclo[2.2.1]hept-2-en-5-yl)-methyl, PO(OCrC6alkyl)2 and
wherein R2 is phenyl which is substituted in 2,6- or 2,4,6-position by d-C4alkyl and/or CrC4alkoxy, and/or chlorine; 2-ethoxy-naphth-1-yl, 2-methyl-naphth-1-yl oranthr-9-yl.
8. A process according to claim 1 for the preparation of (bis)acylphosphane ox
ides and (bis)acylphosphane sulfides of formula IV

Ri. R2, R3, n and m are as defined in claim 1, and Z is O or S,
by oxidation or reaction with sulfur of the acylphosphane of formula I, l\ I" or I"'.
9. A process according to claim 1 for the preparation of (bis)acylphosphanes of
formula I, the process comprising the steps of:
a) contacting red phosphorous or PCI3 with an alkali metal in the presence of a solvent and optionally in the presence of polycyclic hydrocarbon catalyst,
b) adding a sterically hindered alcohol;
c) subsequent reaction with two equivalents of an acid halide Hal-CO-R2 to obtain a metal bisacylphosphide [R2-CO-P=C(OMe)R2], wherein Me is Na or Li; or with one equivalent of a caboxylic acid ester RO-CO-R2, followed by one equivalent of an acid halide Hal-CO-R2" to obtain a metal bisacylphosphide [R2-CO-P=C(OMe)R2'], wherein Me is an alkali metal
d) subsequent reaction with an electrophilic agent RiHal or RiOSC^ORi to obtain the compounds of formula I.
10. A process according to claim 9, wherein in step a) sodium in liquid ammonia is
contacted with red phosphorus in tetrahydrofuran.

11. Acylphosphanes and bisacylphosphanes of the formula I

wherein n= 1 and
Ri is linear or branched CrC18alkyl or C2-C18alkenyl substituted once or more than
once by groups selected from:
halogen or CN, or — -OR10, -SR10, -OCO-R10, -COO-Ri0> -CH=CH-CO-OR10 or -C(CrC4alkyl)=C(Ci-C4alkyl)-CO-OR10; wherein
Rio is hydrogen, CrCi8alkyl, or C2-C18alkyl which is interrupted by one or several non-successive -O-atoms, a di,-tri,-tetra-or polyethylene glycol residue, C3-Ci2-cycloalkyl, tetrahydropyran-2-yl, phenyl-Ci-C4-alkylene, phenyl-C1-c18alkenylene, CrC6alkyl substituted by halogen or substituted by cyclohexyl or cyclopentyl, or substituted by tetrahydrofuranyl, furanyl, isopropyl-4-methyl-coctohexyl, C2-C18-alkenyl, unsubstituted phenyl, naphthyl or biphenyl being unsubstituted or phenyl, naphthyl or biphenyl substituted by one to five Ci-C8-alkyl, Ci-C8-alkoxy, CrC8-alkylthio and/or halogen; or
Ri is linear or branched CrC18alkyl or C2-C18alkenyl substituted by -CO-Rn; wherein
Rn is Crdsalkyl, or C2-Ci8alkyl which is interrupted by one or several non-successive -O-atoms, C3-Ci2-cycloalkyl, phenyl-C^C^alkylene, unsubstituted phenyl, naphthyl or biphenyl being unsubstituted or phenyl, naphthyl or biphenyl substituted by one to five CrC8-alkyl, CrC8-alkoxy, CrC8-alkylthio and/or halogen or
Ri is linear or branched CrCi8alkyl or C2-Ci8alkenyl substituted by -CO-(CH)2-CO-CrC6alkyl, CO-(CH)2-CO-phenyl, or by CO-(CH)2-COO-CrCi8alkyl; or
Ri is linear or branched Ci-C18alkyl or C2-Ci8alkenyl substituted by -NR12R13, -N(R12)-CO-R10) -N(R12)-CO-OR10, -N(R12)-CO-NR12R13, -N(R12)-CO-Hal, -CO-NR12R13, wherein R10 is as defined above and Ri2 and Ri3

independently of one another are is hydrogen, CrCi8alkyl, C2-C18alkyl which is
interrupted by one or several non-successive O atoms, C3-C12-cycloalkyl, C2-C18-
alkenyl, phenyl-CrC4-alkyl, phenyl, naphthyl, pyridyl, the radicals phenyl,
naphthyl or pyridyl being unsubstituted or substituted by one to five d-C8-alkyl,
CrC8-alkoxy, CrC8-alkylthio and/or halogen; or R12 and R13 forms a 5- or 6-
membered 0-, S- or N-containing heterocyclic ring; that may be further annelated
by an aliphatic or aromatic ring; or
-S02-Rio, -SO2-OR10, -S02-NR12Ri3, wherein Rio,Ri2 and R13 are as defined
above; or
-PO(OCrC8alkyl)2, or
-SiRuRisRie. wherein R14, R15 and Ri6 independently of one another are H, Cr
C8alkyl, C2-C8alkenyl, phenyl, C7-C9phenylalkyl, -OCrC8aIkyl, -0-SiR17R18R19,
wherein R17j R18 and R19 are independently of each other H, CrC8alkyl, C2-
C8alkenyl, phenyl, C7-C9phenylalkyl, -OCrC8alkyl; or
-CH=CH-phenyl or -C(Cl-C4alkyl)=C(C1-C4alkyl)-phenyl, phenyl-CrC4alkyl,
phenyl, naphthyl, biphenyl, C5-C12cycloalkyI or a 5- or 6-membered 0-, S- or N-
containing heterocyclic, ring; benzophenonyl, thioxanthonyl;
or
Ri is C2-C18alkyl or C2-Ci8alkenyl which is interrupted by one or several non-successive -0-, -NH-, -NR12- or -S- atoms, and may additionally be substituted once or more than once by groups selected from: halogen or CN, or
-OR10, -SR10, -OCO-R10, -COO-R10j wherein R10 is as defined above; or -NR12R13, -N(R12)-CO-R10J -N(R12)-CO-OR10) -N(R12)-CO-NR12R13, -N(R12)-CO-Hal, -CO-NRi2R13, wherein R10 and R12 and R13 are as defined above; or
-SO2-R10, -SO2-OR10, -S02-NR12R13, wherein Ri0) Ri2 and Ri3 are as defined above;or
-PO(OCrC8alkyl)2, or
-SiR14Ri5Ri6, wherein R14, R15 and R16 are as defined above; or phenyl-Ci-C4alkyl, phenyl or C5-C12cycloalkyl; or
Ri is C2-C18alkyl or C2-C18alkenyl which is interrupted by -CO-, -COO-, -OCO-, -OCOO-, -CO-N(R12)-, -N(R12)-CO-, -N(R12)-CO-N(R12)-, -N(R12)-COO-, -COO-C1-

C18alkyiene, -COS-C^C^alkylene, -SOr, -S02-0-, -S02-N(R12)-, -(CH3)2Si-[OSi(CH3)2 ]m- with m = 1-6, phenyl-C1-C4alkylene, phenylene, naphthylene, biphenylene, C5-C12cycloalkylene or a 5- or 6-membered 0-, S- or N-containing heterocyclic ring; wherein R12 is as defined above; or R, is trimethylsilyl or Hal-(CH3)2Si-[OSi(CH3)2 ]m- or (CH3)3Si-[OSi(CH3)2 ]m- with m =
1-6 ;or R., is -COOH, -COO-R10, -CO-NR^R^.-CO-vinyl, -CO-phenyl which is unsubstituted or substituted by one or more ~CH3, -OCH3, -CI; wherein R10, R12 and R13 are as defined above and m, R2 and R3 are as defined in claim 1, or wherein n=2 and R1 if n=2, is
-CH2-COO-Z-OCO-CH2-
Z is GI-C-IB alkylene or a bridge derived from a di,-tri,-tetra-or polyethylene
glycol.
12. Acylphosphanes and bisacylphosphanes of the formula I according to claim 11
wherein n = 1 and
R1 is linear or branched C.,-C8alkyl or C2-C18alkenyl substituted by CN, trifluormethyl, oxiranyl, isoindole-1,3-dione, -O-C^C-isalkyi, -Q-benzyl, -CO-phenyl, -CO-C^C^alkyl,
-OCO-C^C^alkyh-OCO-C1-c18alkenyl; -COO-CrC18alkyl; -COO-CrC18alkylene-phenyl,-COO-CrC18alkylene-cycloalkylf
-COO-Ci-C^alkylene-tetrahydrofuranyl, -COO-CrC18alkylene-furanyl, -COO-cycloalkyl, -COO-d-C^alkenyl; -COO-CrC18alkenylene-phenyl; -COO-(CH2)2-3-CI,
-COO-[(CH2)2-rO]1.10-CrC6alkyl;-COO-[(CH2)r3-O]1.1(rCrC6-OHl
-CO-CH2-CO-CrC18alkyl; -CO-CtVCOO-C1-c18alkyl, -O-tetrahydropyranyl, bicyclo[2.2.1]hept-2-en-5-yl)-methyl, PO(OCrC6alkyl)2 and wherein m R2 and R3 are as defined in claim 1 or wherein n = 2 and Rn= -CH2-COO-Z-OCO-CH2-Z is CpC-jB alkylene or a bridge derived from a di,-tri,-tetra-or polyethylene glycol.
13. The use of acylphosphanes and of bisacylphosphanes of claim 11 and 12 as
photoinitiators.
Dated this 23 day of May 2007

Documents:

2224-CHENP-2007 AMENDED CLAIMS 17-09-2013.pdf

2224-CHENP-2007 AMENDED PAGES OF SPECIFICATION 17-09-2013.pdf

2224-CHENP-2007 CORRESPONDENCE OTHERS 09-10-2013.pdf

2224-CHENP-2007 CORRESPONDENCE OTHERS 22-04-2013.pdf

2224-CHENP-2007 CORRESPONDENCE OTHERS 21-08-2013.pdf

2224-CHENP-2007 FORM-1 17-09-2013.pdf

2224-CHENP-2007 FORM-3 22-04-2013.pdf

2224-CHENP-2007 FORM-3 09-10-2013.pdf

2224-CHENP-2007 FORM-3 17-09-2013.pdf

2224-CHENP-2007 OTHER PATENT DOCUMENT 17-09-2013.pdf

2224-CHENP-2007 PRIORITY DOCUMENT 17-09-2013.pdf

2224-CHENP-2007 EXAMINATION REPORT REPLY RECEIVED 17-09-2013.pdf

2224-chenp-2007-abstract.pdf

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2224-chenp-2007-description(complete).pdf

2224-chenp-2007-form 1.pdf

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Patent Number

260962

Indian Patent Application Number

2224/CHENP/2007

PG Journal Number

22/2014

Publication Date

30-May-2014

Grant Date

29-May-2014

Date of Filing

23-May-2007

Name of Patentee

CIBA HOLDING INC

Applicant Address

KLYBECSTRASSE 141,CH-4057 BASEL , SWITZERLAND

Inventors:

#	Inventor's Name	Inventor's Address
1	MURER, PETER	HOHESTRASSE 166, CH-4104 OBERWIL, SWITZERLAND
2	WOLF, JEAN-PIERRE	CHILMETWEG 6, CH-4464 MAISPRACH, SWITZERLAND
3	BURKHARDT, STEPHAN	GANASACHERWEG 42, CH-4460 GELTERKINDEN , SWITZERLAND
4	GRUTZMACHER, HANSJORG	REBBERGASSE Id, CH-8157 DIELSDORF, SWITZERLAND
5	STEIN, DANIEL	TECHNIKUMSTRASSE 9, CH-6048 HORW, SWITZERLAND
6	DIETLIKER, KURT	BASELMATTWEG 132, CH-4123 ALLSCHWIL, SWITZERLAND

PCT International Classification Number

C07F 9/50

PCT International Application Number

PCT/EP05/55935

PCT International Filing date

2005-11-14

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	04105987.4	2004-11-23	EUROPEAN UNION