Title of Invention

PROCESS FOR MANUFACTURE OF BIS-QUATERNARY SALTS OF CINNAMIDOALKYLAMINES

Abstract

A process for the preparing novel,'to-ciimamidoalkylarriine quaternary compounds of Formula' I, Formula I Formula i' wherein; R1 represents up to four substituents, same or different, selected fromH, halo, -OH, -NH2, -N02, -OCH3, -N(CH3)2, alkyl groups containing up to 6 carbon atoms, alkoxy groups containing up to 6 carbon atoms, alkylamino or A^N-dialkylamino groups containing up to 6 carbon atoms, or, thioalkyl groups containing up to 6 carbon atoms, alkyl sulfonate groups containing up to 6 carbon atoms; R2 is selected from hydrogen, alkyl group containing up to 6 carbon atoms, hydroxyalkyl group containing up to 6 carbon atoms and R5-OH, wherein R5 is polyalkylene oxide containing up to 20 moles of alkylene oxide such as ethylene oxide or propylene oxide or mixtures thereof; R3 and R4 are independently selected from benzyl, alkyl group containing up to 6 carbon atoms, (B-hydroxyalkyl group containing up to 6 carbon atoms and R5-OH, wherein R5 is polyalkylene oxide containing up to 20 moles of alkylene oxide such as ethylene oxide or propylene oxide or mixtures thereof; n is an integer from 1 to 18; m is an integer from 1 to 10; X" is a counter anion of quaternary centres selected from halides including chloride, bromide, iodide and methane sulphonate and its derivatives such as trifluoro methane sulphonate, benzene sulphonates including itsp-bromo, nitro and methyl derivatives; comprising steps of reacting one mole of a compound of Formula II, R1 is same as that in the compound of said Formula I that is being synthesized, and R6 is H or an alkyl group with 1 to 4 carbon atoms, with 1.1 to 3.0 moles of a compound of Formula III, wherein, R2, R3, R4 and n are same as that for the compound of said Formula I that is being synthesized, with or without a basic catalyst, to obtain a compound of Formula IV, wherein, R1, R2, R3, R4 and n are same as that for the compound of said Formula I that is being synthesized, till all of the said compound of Formula II has been reacted; Formula II Formula II ii) distilling off unreacted compound of said Formula III, remaining after the amidification reaction of step (i) under vacuum to obtain said compound of Formula IV; Formula III Formula Hi' Formula IV Formula IV' -3 ^4 iii) reacting 2 moles of said compound of Formula IV obtained at the end of step (ii) with 1 mole of alkylating compound of Formula V, wherein, X" and m are same as those for the compound of said Formula I that is being synthesized, by stirring under nitrogen, in the presence of an inert solvent, from about 30 % to 80 % by weight of the reaction mass, until X" reaches the stoichiometric level forming a concentrate of said compound of said Formula I in the inert solvent.

Full Text

FORM 2 THE PATENTS ACT, 1970 (39 of 1970) COMPLETE SPECIFICATION (See Section 10 : Rule 13) TITLE Process for manufacture of few-quaternary salts of cinnamidoalkylaruines APPLICANT Galaxy Surfactants Ltd., C-49/2, TTC Industrial Area, Pawne, Navi-Mumbai 400 703, Maharashtra, India. A Public Limited Company Registered under Indian Company's Act - 1956 The following specification particularly describes the nature of this invention and the manner in. which it is to be performed :- Field of Invention This invention relates to a process for manufacture of water-soluble, cationic, few-quaternary saltsf; of cinnamidoalkylamine compounds. This invention particularly relates to synthesis of tailor made non-hydrolyzable, non-irritating compounds having substantivity to cotton, wool, skin and hair and UV-radiation absorbing properties useful in soap and toiletries formulation. Background and Prior Art US patent 5,427,773 (1995) discloses preparation of cationic substantive photofilters like dodecyl dimethyl amino benzamido propyl dimethyl ammonium tosylate. In this process, a primary amino group of N, iV-dimethyl propyl diamine is reacted with dimethyl amino benzoic acid to form an amido amine and then the tertiary amino group is quatemised with alkyl tosylate. However, the sunscreening agents described in this patent are water-insoluble. US patent 5,601,811 (1997) describes preparation of substantive UV-absorbing cinnaiTiidoarniue cationic, quaternary salts by reacting N.iV-dimethyl propyl diamine with cinnamic acid derivatives to create corresponding ciimamidoamines which are then quatemised by usual quaternising agents to yield water-soluble / water-dispersible compounds. Water-solubility of such molecules is very important for proper delivery and / or uniform distribution of these molecules on the skin and hair. That would also reduce use of many different compounds in one formulation for imparting each functional property desired. Water-solubility of such molecules can also be increased by introducing more hydrophilic centres in the structure. The quaternary ammonium moiety in the molecule increases its solubility and substantivity and also imparts anti-microbial properties to the molecule. Such a tailor-made multifunctional molecule would meet the need of cosmetics formulators. These molecules could also be expected to possess moderate surface activity by virtue of having both hydrophobic and hydrophilic portions in them. A formulation with single molecule having multifunctional activity could cater to needs of different consumers. Thus, there is a need to synthesize new molecules having high levels of substantivity to the skin and hair, having UV-absorbing property, particularly in the UV-B region, having anti-microbial property and water-solubility. Object of the invention The main object of the present invention is therefore to synthesize a molecule with cinnamido moiety preferably few-quaternary moiety to provide UV-absorption, two cationic centres to provide significant levels of substantivity and introduce oxyethylene chain between the two quaternary centres to provide additional hydrophilicity for excellent water-solubility in addition to that provided by cationic centres. Summary of the invention The present invention provides a process for the preparing fc-cirmarrndoalkylamine quaternary compounds of Formula I, wherein; Ri represents up to four substituents, same or different, selected from H, halo, -OH, -NH2, -N02, -OCH3, -N(CH3)2, alkyl groups containing up to 6 carbon atoms, alkoxy groups containing up to 6 carbon atoms, alkylamino or Af.A^dialkylamino groups containing up to 6 carbon atoms, or, thioalkyl groups containing up to 6 carbon atoms, alkyl sulfonate groups containing up to 6 carbon atoms; R2 is selected from hydrogen, alkyl group containing up to 6 carbon atoms, hydroxyalkyl group containing up to 6 carbon atoms and R5-OH, wherein R5 is polyalkylene oxide containing up to 20 moles of alkylene oxide such as ethylene oxide or propylene oxide or mixtures thereof; R3 and R4 are independently selected from benzyl, alkyl group containing up to 6 carbon atoms, (3-hydroxyalkyl group containing up to 6 carbon atoms and R5-OH, wherein R5 is polyalkylene oxide containing up to 20 moles of alkylene oxide such as ethylene oxide or propylene oxide or mixtures thereof; n is an integer from 1 to 18; m is an integer from 1 to 10; X" is a counter anion of quaternary centres selected from halides including chloride, bromide, iodide and methane sulphonate and its derivatives such as trifluoro methane sulphonate, benzene sulphonates including its p-bromo, nitro and methyl derivatives; comprising steps of i) reacting one mole of a compound of Formula II, wherein, R1 is same as that in the compound of said Formula I that is being synthesized, and R6 is H or an alkyl group with 1 to 4 carbon atoms, with 1.1 to 3.0 moles of a compound of Formula III, wherein, R2, R3, R4 and n are same as that for the compound of said Formula I that is being synthesized, with or without a basic catalyst, to obtain a compound of Formula IV, wherein, R1, R2, R3, R4 and n are same as that for the compound of said Formula I that is being synthesized, till all of the said compound of Formula II has been reacted; ii) distilling off unreacted compound of said Formula III, remaining after the amidification reaction of step (i) under vacuum to obtain said compound of Formula IV; iii) reacting 2 moles of said compound of Formula IV obtained at the end of step (ii) with 1 mole of alkylating compound of Formula V, wherein, X" and m are same as those for the compound of said Formula I that is being synthesized, by stirring under nitrogen, in the presence of an inert solvent, from about 30 % to 80 % by weight of the reaction mass, until X" reaches the stoichiometric level forming a concentrate of said compound of said Formula I in the inert solvent. Detailed description of the invention In the process, the amidification reaction between a compound of the Formula II with that of Formula III is carried out at from about 120°C to about 200°C, under pressure from about 10 psi to about 100 psi, in the presence of a basic catalyst such as sodium methoxide, sodium hydroxide from 0.25 % to 5.0 % by weight of the reaction mass, to afford the intermediate compound of Formula IV"! Alternately, this reaction is carried out in the presence of a basic catalyst such as sodium methoxide, sodium hydroxide from 0.25 % to 5.0 % by weight of the reaction mass under atmospheric pressure, under blanket of nitrogen, with an arrangement for continuous selective removal of lower alcohol formed in the reaction. In the process, the quaternisation reaction between intermediate compound of Formula IV and that of Formula V is carried out at from about 60°C to about 120°C in the presence of an inert solvent in a pressure reactor under pressures up to 50 psi. Alternately, this reaction is carried out at the boiling point or slightly below the boiling point of the solvent, in an open vessel. The inert solvent used for quaternization reaction in this process is selected from water, alcohols, glycols or mixtures thereof. The quantity of the inert solvent used in the process is from about 45 % to about 55 % by weight of the reaction mass, so that the compound formed is directly usable in the soap or cosmetic formulations, without isolating the product. The UV-absorbing compounds of the present invention are to-quaternary salts of cinnamic acid amido amines. The cinnamic acid amido amines are prepared by reacting lower alkyl esters of cinnamic acid with an amino compound having a second tertiary amino group that is subsequently quaternized. Thus, the precursors of the present invention include essentially any quaternizable reaction product of lower alkyl ester of cinnamic acid and amino compound having a second tertiary amino group, provided that both the reactants are not very hydrophobic so that on quaternizing, the quaternary compounds formed are not rendered water-insoluble. The compounds of the present invention include to-quaternary amidoamine linked through oxyethylene bridge between the two quaternary centres. The object of this invention is to obtain UV absorption through cinnamido moiety, significant levels of substantivity through two cationic centres and finally excellent water solubility from the cationic centres as well as oxyethylene chain between the two quaternary centres. The number and their nature of selected substituents should not be too hydrophobic to render the final bis-quaternary water-insoluble. For purposes of the present application, water-soluble compounds are defined as being soluble in water at levels above 15 % w/w. These water-soluble compounds of this invention are useful for making compositions for skin and hair care and fabric care. Such compositions and their preparations have been described in the accompanying patent, Indian Patent Appln. No. 904 / Mum/ 2000 filed on the same day as this application. The preferred to-quaternary compounds in accordance with the present invention form aqueous solutions at levels of at least about 15 % by weight. The more preferred quaternary compounds in accordance with the present invention have a solubility of at least about 25 % by weight. The most preferred compounds have a water-solubility of at least 50 % w/w. In another embodiment the process of the present invention relates to manufacture of compounds of Formula I, in which Ri is selected from H, -OH, -N02, -NH2, halogen, tyA^dialkylamino groups containing from 1 to 6 carbon atoms; R2 is selected from H, R5-OH, wherein, R5 is polyalkylene oxide containing from 1 to about 20 moles of alkylene oxide, R3 and R4 are independently selected from R5-OH, wherein R5 is polyalkylene oxide containing up to 1 to 20 moles of alkylene oxide such as ethylene oxide, propylene oxide or mixtures thereof, X" is CI", m is an integer having values from 1 to 10 and n is an integer having values from 1 to 18 from the compounds of Formula II, III and IV, with respective substituents R1 of Formula II, R2, R3, R4 and n of Formula III and X" and m of Formula V as defined for the compounds of Formula I in this embodiment and R6 of Formula II being H or an alkyl group containing from 1 to 4 carbon atoms. In another embodiment the process of the present invention relates to manufacture of compounds of Formula I, in which R1 is selected from H, -OH, halogen, NNialkylamino groups containing from 1 to 6 carbon atoms, alkoxy groups containing 1 to 6 carbon atoms; R2 is selected from R5-OH, wherein, R5 is polyalkylene oxide containing from 1 to about 20 moles of alkylene oxide such as ethylene oxide, propylene oxide or mixtures thereof, R3 = R4 = methyl; X" = CI", m =1 and n = 3, from the compounds of Formula II, III and IV, with respective substituents R1 of Formula II, R2, R3, R4 and n of Formula III and X" and m of Formula V as defined for the compounds of Formula I in this embodiment and R6 of Formula II being H or an alkyl group containing from 1 to 4 carbon atoms. In another embodiment the process of the present invention relates to manufacture of compounds of Formula I, in which R1 = H; R2 is selected from H, alkyl group containing carbon up to 6, R5-OH, wherein, R5 is polyalkylene oxide containing from 1 to about 20 moles of alkylene oxide, R3 and R4 are independently selected from alkyl groups containing 1 to 6 carbons, R5-OH, wherein, R5 is polyalkylene oxide containing from 1 to about 20 moles of alkylene oxide such as ethylene oxide, propylene oxide or mixtures thereof; X" = CI", m is an integer between 1 to 10 and n is an integer between 1 and 18, from the compounds of general Formula II, III and IV, with respective substituents R1 of Formula II, R2, R3, R4 and n of Formula III and X" and m of Formula V as defined for the compounds of Formula I in this embodiment and R5 of Formula II being H or an alkyl group containing from 1 to 4 carbon atoms. In another embodiment the process of the present invention relates to manufacture of a compound of Formula I', B,(B-di(p-methoxy cinnamidopropyldimethyl ammonium chloride)ethyl ether (named Bis-Quat) corresponding to general Formula I, in which R1 = -OCH3, R2 = H, R3 = R4 = -CH3, X" = CI", m = 1 and n = 3, from the compounds of Formula II' (p-methoxy ethyl cinnamate), corresponding to Formula II, Formula III' (N,Ndimethylpropyldiamine) corresponding to Formula III, forming an intermediate compound of Formula IV' (p-methoxy cinnamidopropyldimethyl amine) corresponding to general Formula IV shown in the accompanying drawing and Formula V' (bis,-2-chloroethyl ether) corresponding to general Formula V, with respective substituents R1 of Formula II, R2, R3, R4 and n of Formula III and X and m of Formula V as defined for the compounds of Formula I in this embodiment, and R6 of Formula II being ethyl. The bis-quaternary amines in accordance with the present invention have the structure of Formula I. The phenyl ring of the cinnamido moiety may contain up to four ring substituents, Rla, R1b, R1c and Rld, is selected from groups such as halo, -OH, -NH2, -N02, -OCH3, -N(CH3)2 on the phenyl ring same or different. As shown in Formula I, the ring is preferably unsubstituted (R1 is hydrogen) or contains one substituent. R1 is selected from moieties such as halo, -OH, -NH2, -N02, -OCH3, -N(CH3)2 on the phenyl ring. Referring again to Formula I, the amido nitrogen is also preferably unsubstituted (R2 is hydrogen). However, the amido nitrogen may also contain a substituent, depicted in Formula I as R2, selected from alkyl groups containing up to 6 carbon atoms or R2 is selected from R5-OH wherein R5 is polyalkylene oxide containing up to 20 moles of an alkylene oxide such as ethylene oxide, propylene oxide and mixtures thereof. The preferred alkyl chain on amido nitrogen is methyl. The polyalkylene oxide preferably contains between 1 to 10 moles of an alkylene oxide and more preferably contains 5 moles of an alkylene oxide. Ethylene oxide is preferred alkylene oxide in view of desired water solubility of final bis-quatemeries. The quaternized nitrogen of the compounds in accordance with the present invention preferably contains two substituents, R3 and R4, as depicted in Formula I, R3 and R4 are independently selected from hydrogen, (Bhydroxy alkyl, benzyl and alkyl groups containing up to 6 carbon atoms or polyalkylene oxy group containing 1 to 10 mole of alkylene oxide. The compounds of the present invention are quaternary salts of cinnamido alky lamines as shown in Formula I, in which n is an integer between 1 and 18, both inclusive. Preferred compounds in accordance with the present invention are few-quaternary salts of cinnamido alkylamines in which n is an integer between 2 and 12, both inclusive and most preferably, n of Formula I is 3. The compounds of the present invention are to-quaternary salts of cinnamidoalkylaminbs ras shown in Formula I, in which m is an integer between 1 to 18, both inclusive. The preferred value , for m is between 2 to 6. The to-quaternary salts of the present invention are formed from bifunctional alkylating agent and its homologues where m is an integer between 2 and 6, both inclusive (Formula V). It is well understood by ordinary skill in the art, that the to-quaternary salts of the present invention, will also include an anion derived from quaternisation reactions. Given the quaternizing agents described above, the quaternary salts of the present invention will contain an anion, such as X~of Formula I, selected from chloride, bromide, iodide, sulphate, alkosulphate, mesylate, triflate, tosylate and the like. The to-quaternaries (Formula I) of the present invention are synthesized as concentrated solutions by A^-alkylating cinnairudoamines (Formula IV) with bifunctional alkylating agents having Formula V. Cirmamidoalkylamine (Formula IV) are in turn synthesized by amidification of lower alkyl esters of cinnamic acid (Formula II, alkyl group (R^) may vary from Ci to C4) by appropriate diamines (Formula III) containing a tertiary amino group. Ri, R2, R3 and R4 of cinnarrMoalkylamine (Formula IV) and the diamine (Formula III) are the same as described with respect to Formula I. The amidification reaction is performed at temperatures up to 200°C and pressures up to 100 psi. Accordingly, cinnamic acid esters and amino compounds are selected that are liquid within the disclosed temperature and pressure range. This reaction generates lower alcohol that need not be distilled out. In the present invention the reaction of one mole of cinnamic acid ester is carried with 1.2 to 3 moles of diamine at 130 to 200°C, preferably at 180°C, for 12 to 36 hours. This condensation is catalysed by bases such as sodium hydroxide, sodium methoxide or ethoxide, potassium hydroxide and the like. The amines themselves can catalyse the reaction, however, the rates are found to be slower as compared with the bases like sodium methoxide and the like. From about 0.5 % to 5.0 % w/w of the basic catalyst should be employed. Preferred amount of such catalyst is 1,0 % w/w. The reaction is conveniently monitored by TLC or HPLC using UV detection. After the complete disappearance of cinnamic acid ester the excess diamine is distilled off under vacuum This amidification can also be carried out under atmospheric pressure under blanket of nitrogen with an arrangement for selective condensation of the diamine and continuous removal of lower alcohol. The same reaction can be performed using cinnamic acid in place of cinnamic acid ester at temperatures up to 200°C and pressures of 100 psi, keeping the same stoichiometry (1 : 1.2 to 3). The excess diamine serves as solvent for the reaction. The cinnamidoalkylamines (Formula IV, 1 mole) are Af-aHcylated with bifunctional quatemising agents (Fonnula V, 0.5 moles) in the presence of a suitable inert solvent that governs the temperature at which the reaction is carried out. Quaternization of cinnamidoamines is carried out in the inert solvents that include lower alkanols, glycols, water and combinations thereof. Lower alkanols having one to four carbons atoms are suitable for use with the present invention. Glycols having from three to eight carbon atoms are suitable for use with the present invention. However, water is the most suitable solvent. The inert solvents are present in the reaction mass to extent of 20 to 80 % resulting in solids content of final product from 80 to 20 %. The quaternisation reaction can be conveniently done in a pressure reactor as well as in an open system. The temperatures suitable for pressure reaction range from about 60 - 125°C with the pressures up to 50 psi. The pressures are governed by the amount of solvent and the temperature selected for the reaction. The conditions of reaction in an open vessel also get dictated by the choice of solvent. The reactions are usually carried out at boiling point or slightly below boiling point of the solvent employed. The resulting fets-quaternary salts are obtained as concentrated solutions in either water or an inert solvent. The progress of the reaction is monitored by measuring the amount of unreacted alkylating agent by chromatography or by estimation of unquaternized amidoamine or by estimation of X". On Quaternization, the alcoholic solvents or water can be easily removed from concentrated solutions of quaternary ammonium salts to obtain solvent free pure compounds. However, they are slightly tacky, hygroscopic solids and difficult to handle and hence it is convenient to market or use these products as concentrated solutions. Since most of the quaternizations are conveniently carried out in aqueous medium, the bis-quatemaries of the present invention may be marketed in this form for many end-use applications such as hair care, skin care and fabric care compositions. The invention will now be illustrated with the help of examples. The examples are by way of illustrations only and in no way restrict the scope of invention. Example I Process for preparation of S.B'-tflCp-methoxy cinnamidopropvldimethvlammonium chloride) ethyl ether: The compound of Formula I' wherein Ri = OCH3, R2 = H, R3,R4 = CH3, n = 3, m = 1, X = CI. /7-Methoxy cinnamidopropyldimethylamine was synthesised according to procedure described below. a) Preparation of p-methoxy cinnamidopropvldimethvlamine : Ethyl p-methoxy cinnamate (206.0 g, 1.0 mole), N,N-dimethylpropylamine (306.0 g, 3.0 mole) and sodium methoxide (2.0 g) were charged in a pressure reactor. The air inside the reactor was flushed out by purging of nitrogen. The reaction mixture was then stirred at 180°C (this generated pressure of 18 kg / cm2) for 36 hours. The progress of reaction was monitored by disappearance of ethyl /7-methoxy cinnamate on chromatography (TLC and HPLC). The TLC was performed on aluminium coated silica gel plates (Merck - 60-F-254) and viewed with a UV lamp at 254 nm HPLC was performed using reversed phase technique on a C-18 bonded (octadecyl silane) column and 60 % aqueous methanol as mobile phase (1.0 ml / min) and detection at 280 nm The excess amine was removed under vacuum The golden yellow solid (263.0 g) thus obtained had amine value of 245. Molar extinction coefficient, e, in methanol was found to be 24,224 at 290 nm IR in dichloromethane showed carbonyl stretching of amide at 1660 cm'1 and NH stretching at 3300 cm'1. 'H NMR (300 MHz, CDC13) : 5 1.73 (p, 2H, J = 6.6 Hz), 2.26 (s, 6H), 2.42 (t, 2H, J = 6.6 Hz), 3.45 (q, 2H, J = 6.0 Hz), 3.81 (s, 3H), 6.27 (d, 1H, J = 15.6 Hz), 6.86 (d, 2H, J = 8.7 Hz), 7.43 (d, 2H, J = 8.7 Hz), 7.53 (d, 1H, J = 15.6 Hz). This shows that the structural formula of the intermediate compound p-methoxy cinnamidopropyldimethylamine formed is as shown by Formula IV' in the accompanying drawing b) Preparation of B,B'-rfi(p-methoxy cirjnamidopropvldimethvlammonium chloride) ethyl ether (Formula V) : p-Methoxy cinnamidopropyldimethylamine (263.0 g, 1.0 mole) and to-(2-dichloroethyl)ether (71.5 g, 0.5 mole) and deionised water (334.5 ml) were charged in a pressure reactor. The air inside was flushed out by purging nitrogen. The reaction mixture was then stirred at 115°C (pressure 3 kg / cm2) for 36 hours. The progress of the reaction was followed by analysing the chloride content. The reaction yielded 669.0 g of product as light amber colored liquid with slight cinnamom like odor, pH 7.5, chloride content of 5.2 % and solids 50 %. The molar extinction coefficient in aqueous solution at 292 nm Xmax was found to be 42,729. The surface tension of 0.25 % solution was measured by DuNouy method (platinum-iridium ring method) on a Kruss tentiometer (model K 10 ST) and was found to be 41.8 dynes/cm. Hereafter, 50 % solution of the to-quaternary the compound having structural Formula i' will be referred to as Bis-Quat, although, it is possible to prepare solutions of higher concentrations. 'H NMR (300 MHz, D20) : 5 1.98 (m, 4H), 3.11 (s, 12H), 3.29 (t, 4H, J = 6.3 Hz), 3.39 (m, 4H), 3.60 (improperly resolved triplet, 4H), 3.71 (s, 6H), 3.94 (improperly resolved triplet, 4H), 6.27 (d, 2H, J = 15.6 Hz), 6.84 (d, 4H, J = 8.7 Hz), 7.29 (d, 2H, J = 15.9 Hz), 7.38 (d, 4H, J = 9.0 Hz). Bis-Quat was found to kill bacterial species E. coli (ATCC-10148), Pseudomonas aeuroginosa, Candida albicans (ATCC-10231) at dilution 1:400 (1250 ppm on 100 % active) after a contact time of 10 minutes. Example II In this example, the process of Example I was repeated with change in reaction conditions in step (a) as well as step (b) a) Preparation of p-methoxy cinnamidopropvldimethylamine : In one litre reactor fitted with a reflux condensor, a mixture of /?-methoxy ethyl cinnamate (206.0 g, 1.0 mole), N, N-dimethylpropyldiamine (306.0 g, 3.0 mole) and sodium methoxide (2.0 g) under nitrogen was stirred at 140°C for 12 hours and then at 180°C for another 12 hours. The progress of the reaction was monitored by disappearance of /j-methoxy ethyl cinnamate by chromatography. The excess amine was removed under vacuum to yield the p-methoxy cirmamodopropyldimethylamine (264.0 g) as yellow solid. The amidoamine (Formula IV') thus obtained was found to be identical with the amidoamine obtained in step (a) of Example I by HPLC and NMR. b) Preparation of B,B'-di(p-methoxy cinnamidopropyldimethvlammonium chloride) ethyl ether (Formula i'): A mixture of p -methoxy cinnamidopropyldimethylamine (264.0 g, 1.0 mole) and bis-(2-dichloroethyl)ether (71.5 g, 0.5 mole) and isopropanol (334.5 ml) was stirred under nitrogen in an open vessel at 85°C for 36 hours. The progress of the reaction was followed by analysing the chloride content. The reaction yielded 669.0 g of product as light amber colored liquid, chloride content of 5.2 % and solids 50 %. A small sample was then dried in oven at 105°C to yield the ftis-quaternary as pale yellow solid, the PMR, molar extinction coefficient, surface tension of which were found to be identical with the one obtained from the experiment described in step (b) of Example I. A process for preparing water-soluble, to-cinnamidoalkylamino quaternary compounds of general Formula I, substantially as herein described, in the text and in the examples. Advantages of the process : The process of the present invention gives few-quaternary compounds having high solubility, substantivity and sunscreen properties useful in soaps and toiletries compositions and fabric care products. The process of the present invention gives a product in solution form and is convenient to use in the formulation directly. We claim 1. A process for the preparing novel,'to-ciimamidoalkylarriine quaternary compounds of Formula' I, Formula I Formula i' wherein; R1 represents up to four substituents, same or different, selected fromH, halo, -OH, -NH2, -N02, -OCH3, -N(CH3)2, alkyl groups containing up to 6 carbon atoms, alkoxy groups containing up to 6 carbon atoms, alkylamino or A^N-dialkylamino groups containing up to 6 carbon atoms, or, thioalkyl groups containing up to 6 carbon atoms, alkyl sulfonate groups containing up to 6 carbon atoms; R2 is selected from hydrogen, alkyl group containing up to 6 carbon atoms, hydroxyalkyl group containing up to 6 carbon atoms and R5-OH, wherein R5 is polyalkylene oxide containing up to 20 moles of alkylene oxide such as ethylene oxide or propylene oxide or mixtures thereof; R3 and R4 are independently selected from benzyl, alkyl group containing up to 6 carbon atoms, (B-hydroxyalkyl group containing up to 6 carbon atoms and R5-OH, wherein R5 is polyalkylene oxide containing up to 20 moles of alkylene oxide such as ethylene oxide or propylene oxide or mixtures thereof; n is an integer from 1 to 18; m is an integer from 1 to 10; X" is a counter anion of quaternary centres selected from halides including chloride, bromide, iodide and methane sulphonate and its derivatives such as trifluoro methane sulphonate, benzene sulphonates including itsp-bromo, nitro and methyl derivatives; comprising steps of reacting one mole of a compound of Formula II, R1 is same as that in the compound of said Formula I that is being synthesized, and R6 is H or an alkyl group with 1 to 4 carbon atoms, with 1.1 to 3.0 moles of a compound of Formula III, wherein, R2, R3, R4 and n are same as that for the compound of said Formula I that is being synthesized, with or without a basic catalyst, to obtain a compound of Formula IV, wherein, R1, R2, R3, R4 and n are same as that for the compound of said Formula I that is being synthesized, till all of the said compound of Formula II has been reacted; Formula II Formula II ii) distilling off unreacted compound of said Formula III, remaining after the amidification reaction of step (i) under vacuum to obtain said compound of Formula IV; Formula III Formula Hi' Formula IV Formula IV' -3 ^4 iii) reacting 2 moles of said compound of Formula IV obtained at the end of step (ii) with 1 mole of alkylating compound of Formula V, wherein, X" and m are same as those for the compound of said Formula I that is being synthesized, by stirring under nitrogen, in the presence of an inert solvent, from about 30 % to 80 % by weight of the reaction mass, until X" reaches the stoichiometric level forming a concentrate of said compound of said Formula I in the inert solvent. 2. A process as claimed in claim 1, step (i) wherein, the said reaction of compound of said Formula II with that of said Formula III is carried out at about 120°C to about 200°C, under pressure from about 10 psi to about 100 psi, in the presence of a basic catalyst such as sodium methoxide, sodium hydroxide, from 0.25 % to 5.0 % by weight of the reaction mass. 3. A process as claimed in claim 1 step (i), wherein, the said reaction of compound of said Formula II with that of said Formula III is carried out at about 120°C to about 200°C in the presence of basic catalyst such as sodium methoxide, sodium hydroxide from 0.25 % to 5.0 % by weight of the reaction mass under atmospheric pressure, under blanket of nitrogen, with an arrangement for continuous selective removal of lower alcohols formed in the reaction. 4. A process as claimed in claim 1, wherein the inert solvent used in step (iii) is selected from water, lower alcohols with one to four carbon atoms, glycols or mixtures thereof. 5. A process as claimed in claim 1 and 4, wherein, the said inert solvent used in step (iii) is from about 45 % to 55 % by weight of reaction mass. 6. A process as claimed in any claim 1, 4 and 5, wherein, said reaction between intermediate compound of said Formula IV and that of said Formula V in step (iii) is carried out at from about 60°C to about 120 °C in a pressure reactor under pressures up to 50 psi. 7. A process as claimed in claim 1, wherein, said reaction between intermediate compound of said Formula IV and that of said Formula V in step (iii) is carried out at the boiling point or slightly below the boiling point of solvent in an open vessel. 8. A process as claimed in any claim 1 - 7, wherein, are manufactured the compounds of Formula I, in which Ri is selected from -OH, -NO2, -NH2, halogen, Af N-dialkylamino groups containing from 1 to 6 carbon atoms; R2 is selected from H, R5-OH, wherein, R5 is polyalkylene oxide containing from 1 to about 20 moles of alkylene oxide, R3 and R4 are independently selected from R5-OH, wherein R5 is polyalkylene oxide containing up to 1 to 20 moles of alkylene oxide such as ethylene oxide, propylene oxide or mixtures thereof, X" is CI", m is an integer having values from 1 to 10 and n is an integer having values from 1 to 18 from the compounds of Formula II, III and IV, with respective substituents R1 of Formula II, R2, R3, R4 and n of Formula III and X" and m of Formula V as defined for the compounds of Formula I in this claim and R6 of Formula II being H or an alkyl group containing from 1 to 4 carbon atoms. 9. A process as claimed in any claim 1-7, wherein, are manufactured in the compounds of Formula I, in which R1 is selected from H, -OH, halogen, Af,Af-dialkylarnino groups containing from 1 to 6 carbon atoms, alkoxy groups containing 1 to 6 carbon atoms; R2 is selected from R5-OH, wherein, R5 is polyalkylene oxide containing from 1 to about 20 moles of alkylene oxide such as ethylene oxide, propylene oxide or mixtures thereof, R3 = R4 = methyl; X" = CI", m =1 and n = 3, from the compounds of Formula II, III and IV, with respective substituents R1 of Formula II, R2, R3, R4 and n of Formula III and X" and m of Formula V as defined for the compounds of Formula I in this claim and R6 of Formula II being H or an alkyl group containing from 1 to 4 carbon atoms. 10. A process as claimed in any claim 1-7, wherein, are manufactured the compounds of Formula I, in which R1 = H; R2 is selected from H, alkyl group containing carbon up to 6, R5-OH, wherein, R5 is polyalkylene oxide containing from 1 to about 20 moles of alkylene oxide, R3 and R4 are independently selected from alkyl groups containing 1 to 6 carbons, R5-OH, wherein, R5 is polyalkylene oxide containing from 1 to about 20 moles of alkylene oxide such as ethylene oxide, propylene oxide or mixtures thereof; X' = CI", m is an integer between 1 to 10 and n is an integer between 1 and 18, from the compounds of general Formula II, III and IV, with respective substituents R1 of Formula II, R2, R3, R4 and n of Formula III and X" and m of Formula V as defined for the compounds of Formula I in this claim and R6 of Formula II being H or an alkyl group containing from 1 to 4 carbon atoms. 11. A process as claimed in any claim 1-7, wherein, is manufactured the compounds of Formula I' : P,|3'-di(p-methoxy cinnamidopropyldimethylainmonium chloride) ethyl ether (named as Bis-Quat) corresponding to general Formula I, in which Ri = -OCH3, R2 = H, R3 = R4 = -CH3, X" = CI', m = 1 and n = 3, from the compounds of Formula II/ (/7-methoxy ethyl cinnamate), corresponding to Formula II, Formula III' (N, N-dimethylpropyldiamine) corresponding to Formula III, forming an intermediate compound of Formula IV' (p-methoxy cinnamidopropyldimethyl amine) corresponding to general Formula IV and Formula V' (bis-2-chloroethyl ether) corresponding to general Formula V, with respective substituents R\ of Formula II, R2, R3, R4 and n of Formula III and X" and m of Formula V as defined for the compounds of Formula I in this claim, and R6 of Formula II being ethyl. 12. A process for preparing novel, to-cinnamidoalkylamino quaternary compounds of general Formula I, substantially as herein described, in the text and in the examples. Dated this 4Ul day of October, 2000. (Shanbhag Shashikant) Galaxy Surfactants Limited. C-49/2, TTC Indl. Area, Pawne, Navi Mumbai - 400 703 (Applicant) Indian Patent Application No. 903 / Mum / 2000. Galaxy Surfactants Limited. Two sheets Sheet No. 1 Formula I Indian Patent Application No. 903 / Mum / 2000. Galaxy Surfactants Limited. Two sheets Sheet No.2 Formula II Formula II Formula HI1 Formula V Formula V' 3 0 DEC 2003 For GALAXY SURFACTANT LTD Director / Authorised Signatory (Applicant)

Documents:

903-mum-2000-claim(granted)-(30-12-2003).pdf

903-mum-2000-claims (granted)-(30-12-2003).doc

903-mum-2000-claims(granted)-(30-12-2003).pdf

903-mum-2000-correspondence(1)-(27-06-2001).pdf

903-mum-2000-correspondence(30-12-2003).pdf

903-mum-2000-correspondence(ipo)-(15-02-2007).pdf

903-mum-2000-drawing-(30-12-2003).pdf

903-mum-2000-form 1(06-10-2000).pdf

903-mum-2000-form 19(24-06-2003).pdf

903-mum-2000-form 2 (granted)-(30-12-2003).doc

903-mum-2000-form 2(granted)-(30-12-2003).pdf

903-mum-2000-form 26(06-10-2000).pdf

903-mum-2000-form 3(30-12-2003).pdf