Indian Patents. 227168:ALCOHOLS & KETONES OF BI AND TRICYCLIC COMPOUNDS AND A METHOD FOR MANUFACTURING FRAGRANCE COMPOSITION COMPRISING THE SAME

Title of Invention	ALCOHOLS & KETONES OF BI AND TRICYCLIC COMPOUNDS AND A METHOD FOR MANUFACTURING FRAGRANCE COMPOSITION COMPRISING THE SAME
Abstract	The present invention relates to a compound of formulla I as descrided in the specification. The present invention also relates to a method for maufacturing fragrance composition comprising the same.

Full Text	This invention relates to novel compounds having woody, vetiver and patchouli-like odour notes. This invention relates furthermore to a method for their production and to flavour and fragrance compositions containing them. Compounds having woody, vetiver and patchouli-like odour notes are described in the literature, for example the class of sesquiterpenes that naturally occur in essential oils and which can be isolated by water-steam distillation of a plant or parts of a plant. This process is very cost intensive and the quality and the odour as well as the flavour characteristics of the isolated compounds may vary with the climate and the origin of the plant. Thus, there is an ongoing demand in the fragrance and flavour industry for new compounds imparting, enhancing, or improving woody, vetiver and patchouli-like notes. Tricyclic sesquiterpenes, in particular patchoulol and derivatives thereof have been disclosed in the U.S. Patent No. 4,011,269. The compounds described therein develop odoriferous notes the character of which is reminiscent of that of patchouli oil. We have now found a novel class of compounds having much sought after woody, vetiver and patchouli-like odour notes and which may be produced from synthetic starting materials. In a first aspect the invention provides a compound of the formula I wherein R\ R4, R6 and R7 are independently hydrogen, methyl or ethyl; R2 and R3 are independently hydrogen, or C1.5 alkyl, e.g. methyl, ethyl, or linear or branced propyl, butyl, or pentyl; or R2 and R3 together with the carbon atom to which they are attached form a 5- or 6- membered cycloylkyl ring; R5 is hydrogen, or C^ alkyl, e.g. methyl, ethyl or linear or branched propyl; R8is hydrogen, or branched lower C3.7 alkyl, e.g. isopropyl, tert. butyl; R9 is hydrogen, methyl, ethyl, or branched lower C3.7 alkyl, e.g. isopropyl, tert. butyl; R10 is ethyl or propyl; R11 is C M alkyl, e.g. methyl, ethyl, or linear or branched propyl or butyl; R12 is hydroxy; R13 is hydrogen, or C v4 alkyl, e.g. methyl ethyl, or linear or branched propyl or butyl; or R12and R13 together with the carbon atom to which they are attached form a carbonyl group; the dashed line represents either a C-C single bond or no bond; and a) when C5 and C8 are connected by single bond and C9 and C6 are connected by a single bond, C9 and C5 are not connected by a bond, n=1, R7, R8 are hydrogen, and R9 is hydrogen, methyl or ethyl; or b) when C5 and C8 are connected by a single bond and C9 and C6 are connected by a single bond, C9 and C5 are not connected, n=0, R7, R8 is hydrogen, R9 is a branched lower C3.7 alkyl; or c) when C5 and C8 are not connected by a bond, C9 and C5 are connected by a single bond, R7 is hydrogen, methyl or ethyl, R8 is a branched lower C 3.7 alkyl, or R7 and R8 together with the carbon atoms to which they are attached form a 5- or 6- membered cycloalkyl ring, n = 0, and the bond between C6 and C8 may be a single bond or a double bond. wherein R1, R4, R6, and R16 are independently hydrogen, methyl or ethyl; R7 and R14are independently hydrogen, methyl or ethyl; or, R7 and R14 together with the carbon atoms to which they are attached form a 5- or 6- membered cycloalkyl ring; R2 and R3 are independently hydrogen, or C1.5 alkyl, e.g. methyl, ethyl, or linear or branched propyl, butyl, or pentyl; or, R2 and R3 together with the carbon atom to which they are attached form a 5- or 6- membered cycloalkyl ring; R6 is hydrogen, or CM alkyl, e.g. methyl, ethyl, or linear or branched propyl; R15 is CM alkyl, e.g. methyl, ethyl, or linear or branched propyl; R12 is hydroxy; R13 is hydrogen or CM alkyl, e.g. methyl, ethyl, or linear or branched propyl; or R12 and R13 together with the carbon atom to which they are attached form a carbonyl group; and in formula Ic the bond between C6 and C8 may be a single bond, or the dotted line together with the bond between C6 and C8 may represent a double bond . The compounds according to the present invention contain one or more chiral centres and as such may exist as a mixture of stereoisomers, or they may be resolved as isomerically pure forms. Resolving stereoisomers adds to the complexity of manufacture and purification of these compounds and so it is preferred to use the compounds as mixtures of their stereoisomers simply for economic reasons. However, if it is desired to prepare individual stereoisomers, this may be achieved according to methodology known in the art, e.g. preparative HPLC and GC or by stereoselective syntheses. Particular preferred compounds of formula la are 1,5,7,8,8-Pentamethyl-tricyclo[3.3.1.027]nonan-6-one, I.SJ.S.S-Pentamethyl-tricycloia.S.I.O^^nonan-e-one, 1,3,3,5,7,8,8-Heptamethyl-tricyclo[3.3.1.027]nonan-6-one, 3,3,5,7,8,8-Hexamethyl-tricyclo[3.3.1.02'7]nonan-6-one, 3,3,5,8,8-Pentamethyl-tricyclo[3.3.1.027]nonan-6-one, 5,7,8,8-Tetramethyl-tricyclo[3.3.1,02,7]nonan-6-one, and 5,6,7,8,8-Pentamethyl-tricyclo[3.3.1.02,7]nonan-6-ol. A particular preferred compound of formula lb is 1-lsopropyl-3,3,5-trimethyl-tricyclo[3.2.1.02 7]octan-6-one. Particular preferred compounds of formula Ic are 5-lsopropyl-1,3-dimethyl-bicyclo[3.2.1]oct-3-en-2-one, 5-lsopropyl-1,3-dimethyl-bicyclo[3.2.1]octan-2-one, 5-tert-Butyl-1,3-dimethyl-bicyclo[3.2.1]oct-3-en-2-one, 5-sec-Butyl-1,3-dimethyl-bicyclo[3.2.1 ]oct-3-ene-2-one, 5-lsopropyl-3-methyl-bicyclo[3.2.1 ]oct-3-ene-2-one, 5,7-Diisopropyl-3-methyl-bicyclo[3.2.1]oct-3-en-2-one, 5-lsopropyl-3,7,7-trimethyl-bicyclo[3.2.1]oct-3-en-2-one, and I.S.S-Trimethyl-I.S.ey.S.Sa-hexahydro-l^a-ethano-naphthalen-2-one. In another aspect the invention provides flavour and fragrance compositions comprising a compound of formula I or mixtures thereof, more particularly compounds of formula la, lb, or Ic or mixtures thereof. Particular preferred are compositions that comprise at least one compound of formula la and one compound of formula Ic. In addition, the compounds may be used in combination with a basis material. As used herein, the "basis material" includes all known odourant molecules selected from the extensive range of natural and synthetic molecules currently available, such as essential oil, alcohols, aldehydes and ketones, ether and acetals, ester and lactones, macrocycles and heterocycles, and/or in admixture with one or more ingredients or excipients conventionally used in conjunction with odourants in fragrance compositions, for example carrier materials, and other auxiliary agents commonly used in the art. In one embodiment, the compounds of the present invention may be used in fragrance applications, e.g. in any field of fine and functionary perfumery. In another embodiment, the compounds of the present invention may be used in flavour applications and are particularly useful in modifying for example strawberry and raspberry flavours but also brown flavours. They may be used in herbal mixtures and teas. The compounds of the present invention are also well suited for example in mouthwash applications. In flavourant applications, the compounds of the present invention may be present in compositions in amounts ranging from 0.001 to 5 % by weight of a flavour composition, more preferably from 0.01 to 0.5 % by weight. The compounds according to the present invention may be used for herbal flavour compositions, strawberry and raspberry compositions, brown flavour compositions, or tea compositions. When used in fragrance applications, compounds of the present invention can be employed in wide ranging amounts depending upon the specific application and on the nature and quantity of other odourant ingredients, that may be for example, from about 0.001 to about 20 weight percent. In one embodiment compounds may be employed in a fabric softener comprising in amount of about 0.001 to 0.05 weight percent. In another embodiment compounds of the present invention may be in alcoholic solution in amounts of about 0.1 to 20 weight percent, more preferably between about 0.1 and 5 weight percent. However, these values should not be limiting on the present invention, since the experienced perfumer and flavourist may also achieve effects or may create novel accords with lower or higher concentrations. The compounds of the present invention may be employed into the fragrance application simply by directly mixing the fragrance composition with the fragrance application, or they may, in an earlier step be entrapped with an entrapment material, for example, polymers, capsules, microcapsules and nanocapsules, liposomes, film formers, absorbents such as carbon or zeolites, cyclic oligosaccharides and mixtures thereof, or they may be chemically bonded to substrates, which are adapted to release the fragrance molecule upon application of an external stimulus such as light, enzyme, or the like, and then mixed with the application. Thus, the invention additionally provides a method of manufacturing a fragrance application, comprising the incorporation of a compound of formula I as a fragrance ingredient, either by directly admixing the compound of formula I to the application or by admixing a fragrance composition comprising a compound of formula I, which may then be mixed to a fragrance application, using conventional techniques and methods. As used herein, "fragrance application" means any product, such as fine perfumery, e.g. perfume and Eau de Toilette; household products, e.g. detergents for dishwasher, surface cleaner; laundry products, e.g. softener, bleach, detergent; body care products, e.g. shampoo, shower gel; and cosmetics, e.g. deodorant, vanishing creme, comprising an odourant. This list of products is given by way of illustration and is not to be regarded as being in any way limiting. The compounds according to the present invention may be prepared according to a process wherein appropriately substituted cyclohexenones are reacted with ally! bromide or allyl chloride under reaction conditions well known to the person skilled in the art (Bull. Chem. Soc. Jpn., 2298 - 2303 (1993). The resulting alkylated cyclohexenones (formula II as shown below) may be converted in the presence of ethyl aluminium-dichloride or methyl aluminium-dichloride to provide compounds of formula I wherein R12 and R13 taken together represents an oxygen atom, as illustrated by compounds of formula la, lb, and Ic in scheme 1. The conditions under which such Lewis acid catalyzed reactions may proceed is described for example by Snider et al. in the Journal of Am. Chem. Soc. 1980, 102, 5872 - 5880 which is herein incorporated by reference. The resulting carbonyl group at C1 may be reduced and/or alkylated to give further compounds of formula I. Similarly, if there is a double bond at C6 and C8 this can be reduced in a known manner to give still further compounds of formula I. Compounds of formula II may also be prepared by alkylation of appropiately substituted phenols by reaction of the phenol with a metal hydride and an alkenylchloride (Greuter, H. et al. (1977) Helv. Chim. Acta, 60, 1701), followed by hydrogenation. Whether a compound of formula la, lb, Ic, or a mixture thereof is formed depends on the substituent pattern R2, R3, and R16 of the alkylated cyclohexenone (II). A compound of formula Ic is formed as a main product if R2, R3, and R18 of formula II are hydrogen. A mixture of compounds of formula la and lb as main product is performed if R2 and R3 of formula II at the same time are not hydrogen. A mixture of compounds of formula la and Ic as main product is formed if R2 and R3 of formula II are hydrogen and R16 of formula II is not hydrogen. The compounds are useful in flavour and/or fragrance compositions as mixtures, however, should one wish to use the compounds in pure form, they can be separated easily by purification processes, such as HPLC or preparative GC, according to the methodology known in the art. The term "main product", as used herein with reference to single compounds, refers to a product comprising at least 50% by weight of that compound, more preferably more than 75% by weight, most preferably more than 90% by weight. When this term is used in relation to a mixture of compounds, e.g. one compound of formula la and one compound of formula Ic, it refers to a product comprising at least 50% by weight of this mixture, more particular more than 75% by weight, most particular more than 90% by weight. The conversion of compounds of formula II for a selective preparation of compounds of formula la of the present invention may also be performed by photochemical induction. Surprisingly we found that compounds of formula la may be formed by photochemically induced intramolecular [2+2] cycloaddition of compounds of formula II. For the photochemical induction a Hg-lamp may be used for a time period of about 1 to 15 hours. However, the induction time may depend on the solvent used and on additives such as sensitisers and Lewis acids. Preferred solvents are methanol, ethanol and iso propanol. Thus, in another aspect the invention refers to a method of preparing compounds of formula la by photochemically induced cycloaddition. Further particulars as to reaction conditions are provided in the examples. There now follows a series of examples that illustrate the invention. Example 1: a)2-Methyl-6-(3-methvl-but-2-enyl)-cyclohex-2-enone To a solution of LDA (prepared from BuLi, 1.6 M in hexane, 75 ml, 0.12mol and diisopropylamine, 12.2g, 0.12mol) in THF (50ml) was added 2-methyl-cyclohex-2-enone (11.0g, 0.1 mol) at -78°C. The mixture was stirred for 1h at -78°C and prenyl bromide 17.88g, 0.12mol) was added. The mixture was stirred over night, while the temperature was allowed to rise to room temperature. MTBE (50 ml) and sat. NH4CI were added, the organic phase was separated and washed with brine, dried (MgS04) and concentrated in vacuo. The residue was distilled in a Kugelrohr oven to yield 9.8g (55%) of a slightly yellow oil. 1H-NMR (400 MHz, CDCI3): 6.82 (bs, 1H), 5.14-5.09 (m, 1H), 2.56-2.48 (m, 1H), 2.37-2.25 (m, 3H), 2.13-2.03 (m, 2H), 1.77 (s, 3H), 1.70 (s. 3H), 1.75-1.68 (m, 1H), 1.61 (s, 3H) ppm. 13C-NMR (100MHz, CDCI3): 201.6 (s), 144.3 (d), 135.1 (s), 133.0 (s), 121.8 (d), 46.9 (d), 27.8 (t), 27.7 (t), 25.7 (q), 25.0 (t), 17.6 (q), 16.0 (q) ppm. GC/MS (El): 178 (M+, 30), 168 (25), 123 (37), 110 (100), 95 (63), 83 (33), 69 (26), 53 (34), 41 (71), 39 (44). IR (ATR): 2966s, 2924s, 1672vs, 1451s, 1377s, 1181m, 1088m, 836m cm"1. b) 2.6-dimethvl-6-(3-methvl-but-2-enyl)-cvclohex-2-enone Sodium hydride (60%, 85 g, 2.13 mol) was added portionwise to a solution of 2,6-dimethylphenol (250g, 2.05 mol) in 2L of toluene at 10-15°C. The resulting suspension was stirred for 45 min. The mixture was cooled to 5°C, and prenyl chloride (262g, 2.13 mol, 85%) was added during 1.5 h keeping the temperature at 5°C. The mixture was then stirred for further 2h at 10-15°C. Methanol (1L) and palladium (2.5g, 10% on charcoal) was added and the gray suspension was hydrogenated at 0.3 bar overpressure, keeping the temperature at 20-22°C (ice bath). The suspension was then filtered through a pad of celite. The yellow filtrate was washed with water (0.5L), aqueous sodium hydroxide (0.5L) and brine (0.5L), dried (MgS04) and concentrated in vacuo. The residue was distilled over a 5cm Vigreux column to yield 318g (81%, bp 78-82°C/0.05Torr) of a colorless oil. Odor description: fruity, grapefruit, minty, bergamot 1H-NMR (400MHz, CDCI3): 6.62 (bs, 1H, 3-H), 5.06-5.11 (m, 1H, 2"-H), 2.34-2.28 (m, 2H, 4-H), 2.25-2.14 (m, 2H, 1'H), 1.91 (dt, J5a,5b * 13.6 Hz, J5a,4 - 6.1 Hz, 1H, 5a-H), 1.76 (s, 3H, 2-CH3), 1.77-1.70 (m, 1H, 5b-H), 1.70 (s, 3H, 4'-H), 1.59 (s, 3H, 3'-CH3), 1.05 (s, 3H, 6-CH3) ppm. GC/MS (El): 192 (M+, 16), 124 (100), 109 (74), 82 (31), 69 (40), 41 (57). IR (ATR): 2965s, 2922s, 1667vs, 1449m, 1376m, 1033m cm"1. Example 2: 5-lsoDropvl-1.3-dimethvl-bicvclof3.2.noct-3-en-2-one To a solution of 2,6-dimethyl-6-(3-methyl-but-2-enyl)-cyclohex-2-enone (5.00 g, 26.04 mmol) in toluene (40 ml) was added dropwise neat EtAICI2 (97%, 1.5 eq., 4.96 g, 39.06 mmol). During the addition, the temperature was kept below 10°C. The brown mixture was kept at room temperature over night and was then poured on icecold saturated NH4CI. The mixture was extracted with MTBE, washed with brine, dried (MgS04) and concentrated in vacuo. The residue was distilled bulb to bulb to yield 4.50 g (90%) of an colorless oil. Odor description: woody, patchouli, vetiver, hesperidic 'H-NMR (400MHz, CDCI3): 6.86 (bs, 1H, 4-H), 1.81 (dt, J= 11.0, 2.2 Hz, 1H, 8-Ha), 1.78-1.72 (m, 2H, 6-Ha, 7-H«). 1.75 (d, J= 1.6 Hz, 3-CH3), 1.69 (sept, J = 6.8 Hz, 1H, 5-CH(CH3)2), 1.64-1.53 (m, 2H, 6-Hb, 7-Hb), 1.37 (dd, J= 11.0, 2.2 Hz, 1H, 8-Hb), 1.24 (s, 3H, I-CH3), 100 (d, J = 6.8Hz, 3H, 5-CH(CH3)CH3), 0.93 (d, J = 6.8 Hz, 3H, CH(CH3)CH3) ppm. 13C-NMR (100MHz, CDCI3): 205.2 (s, C-2), 151.7 (d, C-4), 133.1 n this composition 1,5,7,8,8-Pentamethyl-tricyclo[3.3.1.02'7]nonan-6-one enhances and larmonizes the woody part. It underlines the patchouli aspect but gives also a new nodern woody character. The compound blends well with the floral part of the perfume ind provides volume without giving a heavy impression. WE CLAIM: 1. A compound of formula I wherein R1, R4, R6 and R7 are independently hydrogen, methyl or ethyl; R2 and R3 are independently hydrogen, or C 1.5 alkyl; or R2 and R3 together with the carbon atom to which they are attached form a 5- or 6-membered cycloyalkyl ring; R5 is hydrogen, or CM alkyl; o R is hydrogen, or branched lower C3.7 alkyl; R9 is hydrogen, methyl, ethyl, or branched lower C3.7 alkyl; R10 is ethyl or propyl; R11 is C1-4 alkyl; R is hydroxy; R13 is hydrogen, or C M alkyl; or R12 and R13 together with the carbon atom to which they are attached form a carbonyl group; the dashed line represents either a C-C single bond or no bond; and b) when C5 and C8 are connected by a single bond and C9 and C6 are connected by a single bond, C9 and C5 are not connected by a bond, n=l, R7, R8 are hydrogen, and R9 is hydrogen, methyl or ethyl; or b) when C5 and C8 are connected by a single bond and C9 and C6 are connected by a single bond, C9 and C5 are not connected, n=0, R7, R8 is hydrogen, R9 is a branched lower C3.7 alkyl; or c) when C5 and C8 are not connected by a bond, C9 and C5 are connected by a single bond, R7 is hydrogen, methyl or ethyl, R8 is a branched lower C 3.7 alkyl, or R and R together with the carbon atoms to which they are attached form a 5- or 6- membered cycloalkyl ring, n = 0, and the bond between C6 and C8 may be a single bond or a double bond. 2. The compound as claimed in claim 1 having a formula la wherein R1, R4, R6, R14 and R16 are independently hydrogen, methyl or ethyl; R2 and R3 are independently hydrogen, or Ci.5 alkyl; or, R2 and R3 together with the carbon atom to which they are attached form a 5- or 6-membered cycloalkyl ring; R5 is hydrogen, or C1-4 alkyl; R15 is C1-4 alkyl; R is hydroxy; R13 is hydrogen or C1.4 alkyl; or R and R together with the carbon atom to which they are attached form a carbonyl group. 3. The compound as claimed in claim 1 of formula lb, wherein R1, R4, R6, R14 and R16 are independently hydrogen, methyl or ethyl; R2 and R3 are independently hydrogen, or Ci.5 alkyl; or, R and R together with the carbon atom to which they are attached form a 5- or 6- * membered cycloalkyl ring; R5 is hydrogen, or CM alkyl; R15 is C1-4alkyl; R12 is hydroxy; R13 is hydrogen or CM alkyl; or R12 and R13 together with the carbon atom to which they are attached form a carbonyl group. 4. The compound as claimed in claim 1 of formula Ic, wherein R1,R4,R6,R14andR16 are independently hydrogen, methyl or ethyl; R5 is hydrogen, or C1-4alkyl; R7 and R14 are independently hydrogen, methyl or ethyl; or, R7 and R14 together with the carbon atoms to which they are attached form a 5- or 6-membered cycloalkyl ring; R15 is C1-4alkyl; R12 is hydroxy; R13 is hydrogen or C1-4 alkyl; or R and R together with the carbon atom to which they are attached form a carbonyl group; and the bond between C6 and C8 may be a single bond; or the dotted line together with the bond between C6 and C8 may represent a double bond. 5. The compound as claimed in claim 1 selected from the group consisting of l,5,7,8,8-Pentamethyl-tricyclo[3.3.1.02,7]nonan-6-one;l,5,7,8,8-Pentamethyl-tricyclo[3.3.1.02,7]nonan-6-one; l,3,3,5,7,8,8-Heptamethyl-tricyclo[3.3.1.02,7]nonan-6-one; 3,3,5,7,8,8-Hexamethyl-tricyclo[3.3.1.02,7]nonan-6-one; 3,3,5,8,8-Pentamethyl-tricyclo[3.3.1.02'7]nonan-6-one; 5,7,8,8-Tetramethyl-tricyclo[3.3.1.02'7]nonan-6-one;l-Isopropyl-3,3,5-trimethyl-tricyclo[3.2.1.02'7]octan-6-one;5-Isopropyl-l,3-dimethyl-bicyclo[3.2.1]oct-3-en-2-one; 5- Isopropyl-l,3-dimethyl-bicyclo[3.2.1]octan-2-one; 5-tert-Butyl-l,3-dimethyl-bicyclo[3.2.1]oct-3-en-2-one;5-sec-Butyl-l,3-dimethyl-bicyclo[3.2.1]oct-3-ene-2-one;5-Isopropyl-3-methyl-bicyclo[3.2.1]oct-3-ene-2-one; 5,7-Diisopropyl-3-methyl-bicyclo[3.2.1]oct-3-en-2-one; 5-Isopropyl-3,7,7-trimethyl-bicyclo[3.2.1]oct-3-en-2-one;l,3,5-Trimethyl-l,5,6,7,8»8a-hexahydro-l,4a-ethano-naphthalen-2-one; and 5,6,7,8,8-Pentamethyl-tricyclo[3.3.1.02,7]nonan-6-ol. 6. The method of manufacturing a flavour or fragrance composition, comprising the step of incorporating a compound of formula I as claimed in claim 1 to a base material. 7. The method of manufacturing a fragranced application, comprising the incorporation of a compound of formula I as claimed in claim 1. 8. The method as claimed in claim 10 wherein the fragranced application is selected from the group consisting of perfume, household product, laundry product, body care product and cosmetics. wherein R1, R4, and R6 are independently hydrogen, methyl or ethyl; R2 and R3 are independently hydrogen, or C1.5 alkyl; or R and R together with the carbon atom to which they are attached form a 5- or 6-membered cycloylkyl ring; R5 is hydrogen, or C1-4 alkyl; R7 and R14 are independently hydrogen, methyl or ethyl; or R7 and R14 together with the carbon atoms to which they are attached form a 5- or 6-membered cycloalkane ring; R16 is hydrogen, or lower branched C3.7 alkyl, and optionally followed by the step of reduction and/or alkylation of the carbonyl group at CI. wherein R2, R3, and R16 are hydrogen; R1, R4 and R6 are independently hydrogen, methyl or ethyl; R7 and R14 are independently hydrogen, methyl or ethyl; or R7 and R14 together with the carbon atoms to which they are attached form a 5- or 6- membered cycloalkane ring; R5 is hydrogen, linear or branced C1-4 alkyl; R15 is linear or branched C1-4 alkyl; and and optionally followed by the step of hydrogenation across the double bond at C6 and C8, and optionally followed by the step of reduction and/or alkylation of the carbonyl group at CI.

Full Text

This invention relates to novel compounds having woody, vetiver and patchouli-like odour notes. This invention relates furthermore to a method for their production and to flavour and fragrance compositions containing them.
Compounds having woody, vetiver and patchouli-like odour notes are described in the literature, for example the class of sesquiterpenes that naturally occur in essential oils and which can be isolated by water-steam distillation of a plant or parts of a plant. This process is very cost intensive and the quality and the odour as well as the flavour characteristics of the isolated compounds may vary with the climate and the origin of the plant. Thus, there is an ongoing demand in the fragrance and flavour industry for new compounds imparting, enhancing, or improving woody, vetiver and patchouli-like notes.
Tricyclic sesquiterpenes, in particular patchoulol and derivatives thereof have been disclosed in the U.S. Patent No. 4,011,269. The compounds described therein develop odoriferous notes the character of which is reminiscent of that of patchouli oil.
We have now found a novel class of compounds having much sought after woody, vetiver and patchouli-like odour notes and which may be produced from synthetic starting materials.
In a first aspect the invention provides a compound of the formula I
wherein
R\ R4, R6 and R7 are independently hydrogen, methyl or ethyl;

R2 and R3 are independently hydrogen, or C1.5 alkyl, e.g. methyl, ethyl, or linear or
branced propyl, butyl, or pentyl; or
R2 and R3 together with the carbon atom to which they are attached form a 5- or 6-
membered cycloylkyl ring;
R5 is hydrogen, or C^ alkyl, e.g. methyl, ethyl or linear or branched propyl;
R8is hydrogen, or branched lower C3.7 alkyl, e.g. isopropyl, tert. butyl;
R9 is hydrogen, methyl, ethyl, or branched lower C3.7 alkyl, e.g. isopropyl, tert. butyl;
R10 is ethyl or propyl;
R11 is C M alkyl, e.g. methyl, ethyl, or linear or branched propyl or butyl;
R12 is hydroxy;
R13 is hydrogen, or C v4 alkyl, e.g. methyl ethyl, or linear or branched propyl or butyl; or
R12and R13 together with the carbon atom to which they are attached form a carbonyl
group;
the dashed line represents either a C-C single bond or no bond; and
a) when C5 and C8 are connected by single bond and C9 and C6 are connected by a
single bond, C9 and C5 are not connected by a bond,
n=1,
R7, R8 are hydrogen, and
R9 is hydrogen, methyl or ethyl; or
b) when C5 and C8 are connected by a single bond and C9 and C6 are connected by
a single bond, C9 and C5 are not connected,
n=0,
R7, R8 is hydrogen,
R9 is a branched lower C3.7 alkyl; or
c) when C5 and C8 are not connected by a bond, C9 and C5 are connected by a
single bond,
R7 is hydrogen, methyl or ethyl,
R8 is a branched lower C 3.7 alkyl, or
R7 and R8 together with the carbon atoms to which they are attached form a 5- or 6-
membered cycloalkyl ring,
n = 0, and
the bond between C6 and C8 may be a single bond or a double bond.

wherein
R1, R4, R6, and R16 are independently hydrogen, methyl or ethyl;
R7 and R14are independently hydrogen, methyl or ethyl; or,
R7 and R14 together with the carbon atoms to which they are attached form a 5- or 6-
membered cycloalkyl ring;
R2 and R3 are independently hydrogen, or C1.5 alkyl, e.g. methyl, ethyl, or linear or
branched propyl, butyl, or pentyl; or,
R2 and R3 together with the carbon atom to which they are attached form a 5- or 6-
membered cycloalkyl ring;
R6 is hydrogen, or CM alkyl, e.g. methyl, ethyl, or linear or branched propyl;
R15 is CM alkyl, e.g. methyl, ethyl, or linear or branched propyl;
R12 is hydroxy;
R13 is hydrogen or CM alkyl, e.g. methyl, ethyl, or linear or branched propyl; or
R12 and R13 together with the carbon atom to which they are attached form a carbonyl
group; and
in formula Ic the bond between C6 and C8 may be a single bond, or the dotted line
together with the bond between C6 and C8 may represent a double bond .

The compounds according to the present invention contain one or more chiral centres and as such may exist as a mixture of stereoisomers, or they may be resolved as isomerically pure forms. Resolving stereoisomers adds to the complexity of manufacture and purification of these compounds and so it is preferred to use the compounds as mixtures of their stereoisomers simply for economic reasons. However, if it is desired to prepare individual stereoisomers, this may be achieved according to methodology known in the art, e.g. preparative HPLC and GC or by stereoselective syntheses.
Particular preferred compounds of formula la are 1,5,7,8,8-Pentamethyl-tricyclo[3.3.1.027]nonan-6-one, I.SJ.S.S-Pentamethyl-tricycloia.S.I.O^^nonan-e-one, 1,3,3,5,7,8,8-Heptamethyl-tricyclo[3.3.1.027]nonan-6-one, 3,3,5,7,8,8-Hexamethyl-tricyclo[3.3.1.02'7]nonan-6-one, 3,3,5,8,8-Pentamethyl-tricyclo[3.3.1.027]nonan-6-one, 5,7,8,8-Tetramethyl-tricyclo[3.3.1,02,7]nonan-6-one, and 5,6,7,8,8-Pentamethyl-tricyclo[3.3.1.02,7]nonan-6-ol.
A particular preferred compound of formula lb is 1-lsopropyl-3,3,5-trimethyl-tricyclo[3.2.1.02 7]octan-6-one.
Particular preferred compounds of formula Ic are 5-lsopropyl-1,3-dimethyl-bicyclo[3.2.1]oct-3-en-2-one, 5-lsopropyl-1,3-dimethyl-bicyclo[3.2.1]octan-2-one, 5-tert-Butyl-1,3-dimethyl-bicyclo[3.2.1]oct-3-en-2-one, 5-sec-Butyl-1,3-dimethyl-bicyclo[3.2.1 ]oct-3-ene-2-one, 5-lsopropyl-3-methyl-bicyclo[3.2.1 ]oct-3-ene-2-one, 5,7-Diisopropyl-3-methyl-bicyclo[3.2.1]oct-3-en-2-one, 5-lsopropyl-3,7,7-trimethyl-bicyclo[3.2.1]oct-3-en-2-one, and I.S.S-Trimethyl-I.S.ey.S.Sa-hexahydro-l^a-ethano-naphthalen-2-one.
In another aspect the invention provides flavour and fragrance compositions comprising a compound of formula I or mixtures thereof, more particularly compounds of formula la, lb, or Ic or mixtures thereof. Particular preferred are compositions that comprise at least one compound of formula la and one compound of formula Ic.
In addition, the compounds may be used in combination with a basis material. As used herein, the "basis material" includes all known odourant molecules selected from the extensive range of natural and synthetic molecules currently available, such as

essential oil, alcohols, aldehydes and ketones, ether and acetals, ester and lactones, macrocycles and heterocycles, and/or in admixture with one or more ingredients or excipients conventionally used in conjunction with odourants in fragrance compositions, for example carrier materials, and other auxiliary agents commonly used in the art.
In one embodiment, the compounds of the present invention may be used in fragrance applications, e.g. in any field of fine and functionary perfumery.
In another embodiment, the compounds of the present invention may be used in flavour applications and are particularly useful in modifying for example strawberry and raspberry flavours but also brown flavours. They may be used in herbal mixtures and teas. The compounds of the present invention are also well suited for example in mouthwash applications.
In flavourant applications, the compounds of the present invention may be present in compositions in amounts ranging from 0.001 to 5 % by weight of a flavour composition, more preferably from 0.01 to 0.5 % by weight. The compounds according to the present invention may be used for herbal flavour compositions, strawberry and raspberry compositions, brown flavour compositions, or tea compositions.
When used in fragrance applications, compounds of the present invention can be employed in wide ranging amounts depending upon the specific application and on the nature and quantity of other odourant ingredients, that may be for example, from about 0.001 to about 20 weight percent. In one embodiment compounds may be employed in a fabric softener comprising in amount of about 0.001 to 0.05 weight percent. In another embodiment compounds of the present invention may be in alcoholic solution in amounts of about 0.1 to 20 weight percent, more preferably between about 0.1 and 5 weight percent.
However, these values should not be limiting on the present invention, since the experienced perfumer and flavourist may also achieve effects or may create novel accords with lower or higher concentrations.
The compounds of the present invention may be employed into the fragrance application simply by directly mixing the fragrance composition with the fragrance

application, or they may, in an earlier step be entrapped with an entrapment material, for example, polymers, capsules, microcapsules and nanocapsules, liposomes, film formers, absorbents such as carbon or zeolites, cyclic oligosaccharides and mixtures thereof, or they may be chemically bonded to substrates, which are adapted to release the fragrance molecule upon application of an external stimulus such as light, enzyme, or the like, and then mixed with the application.
Thus, the invention additionally provides a method of manufacturing a fragrance application, comprising the incorporation of a compound of formula I as a fragrance ingredient, either by directly admixing the compound of formula I to the application or by admixing a fragrance composition comprising a compound of formula I, which may then be mixed to a fragrance application, using conventional techniques and methods.
As used herein, "fragrance application" means any product, such as fine perfumery, e.g. perfume and Eau de Toilette; household products, e.g. detergents for dishwasher, surface cleaner; laundry products, e.g. softener, bleach, detergent; body care products, e.g. shampoo, shower gel; and cosmetics, e.g. deodorant, vanishing creme, comprising an odourant. This list of products is given by way of illustration and is not to be regarded as being in any way limiting.
The compounds according to the present invention may be prepared according to a process wherein appropriately substituted cyclohexenones are reacted with ally! bromide or allyl chloride under reaction conditions well known to the person skilled in the art (Bull. Chem. Soc. Jpn., 2298 - 2303 (1993). The resulting alkylated cyclohexenones (formula II as shown below) may be converted in the presence of ethyl aluminium-dichloride or methyl aluminium-dichloride to provide compounds of formula I wherein R12 and R13 taken together represents an oxygen atom, as illustrated by compounds of formula la, lb, and Ic in scheme 1. The conditions under which such Lewis acid catalyzed reactions may proceed is described for example by Snider et al. in the Journal of Am. Chem. Soc. 1980, 102, 5872 - 5880 which is herein incorporated by reference.
The resulting carbonyl group at C1 may be reduced and/or alkylated to give further compounds of formula I. Similarly, if there is a double bond at C6 and C8 this can be reduced in a known manner to give still further compounds of formula I.

Compounds of formula II may also be prepared by alkylation of appropiately substituted phenols by reaction of the phenol with a metal hydride and an alkenylchloride (Greuter, H. et al. (1977) Helv. Chim. Acta, 60, 1701), followed by hydrogenation.
Whether a compound of formula la, lb, Ic, or a mixture thereof is formed depends on the substituent pattern R2, R3, and R16 of the alkylated cyclohexenone (II). A compound of formula Ic is formed as a main product if R2, R3, and R18 of formula II are hydrogen. A mixture of compounds of formula la and lb as main product is performed if R2 and R3 of formula II at the same time are not hydrogen. A mixture of compounds of formula la and Ic as main product is formed if R2 and R3 of formula II are hydrogen and R16 of formula II is not hydrogen. The compounds are useful in flavour and/or fragrance compositions as mixtures, however, should one wish to use the compounds in pure form, they can be separated easily by purification processes, such as HPLC or preparative GC, according to the methodology known in the art.
The term "main product", as used herein with reference to single compounds, refers to a product comprising at least 50% by weight of that compound, more preferably more than 75% by weight, most preferably more than 90% by weight. When this term is used in relation to a mixture of compounds, e.g. one compound of formula la and one compound of formula Ic, it refers to a product comprising at least 50% by weight of this

mixture, more particular more than 75% by weight, most particular more than 90% by weight.
The conversion of compounds of formula II for a selective preparation of compounds of formula la of the present invention may also be performed by photochemical induction. Surprisingly we found that compounds of formula la may be formed by photochemically induced intramolecular [2+2] cycloaddition of compounds of formula II. For the photochemical induction a Hg-lamp may be used for a time period of about 1 to 15 hours. However, the induction time may depend on the solvent used and on additives such as sensitisers and Lewis acids. Preferred solvents are methanol, ethanol and iso propanol.
Thus, in another aspect the invention refers to a method of preparing compounds of formula la by photochemically induced cycloaddition.
Further particulars as to reaction conditions are provided in the examples.
There now follows a series of examples that illustrate the invention.
Example 1:
a)2-Methyl-6-(3-methvl-but-2-enyl)-cyclohex-2-enone To a solution of LDA (prepared from BuLi, 1.6 M in hexane, 75 ml, 0.12mol and diisopropylamine, 12.2g, 0.12mol) in THF (50ml) was added 2-methyl-cyclohex-2-enone (11.0g, 0.1 mol) at -78°C. The mixture was stirred for 1h at -78°C and prenyl bromide 17.88g, 0.12mol) was added. The mixture was stirred over night, while the temperature was allowed to rise to room temperature. MTBE (50 ml) and sat. NH4CI were added, the organic phase was separated and washed with brine, dried (MgS04) and concentrated in vacuo. The residue was distilled in a Kugelrohr oven to yield 9.8g (55%) of a slightly yellow oil.
1H-NMR (400 MHz, CDCI3): 6.82 (bs, 1H), 5.14-5.09 (m, 1H), 2.56-2.48 (m, 1H), 2.37-2.25 (m, 3H), 2.13-2.03 (m, 2H), 1.77 (s, 3H), 1.70 (s. 3H), 1.75-1.68 (m, 1H), 1.61 (s, 3H) ppm. 13C-NMR (100MHz, CDCI3): 201.6 (s), 144.3 (d), 135.1 (s), 133.0 (s), 121.8 (d), 46.9 (d), 27.8 (t), 27.7 (t), 25.7 (q), 25.0 (t), 17.6 (q), 16.0 (q) ppm. GC/MS (El): 178 (M+, 30), 168 (25), 123 (37), 110 (100), 95 (63), 83 (33), 69 (26), 53 (34), 41 (71), 39 (44). IR (ATR): 2966s, 2924s, 1672vs, 1451s, 1377s, 1181m, 1088m, 836m cm"1.

b) 2.6-dimethvl-6-(3-methvl-but-2-enyl)-cvclohex-2-enone Sodium hydride (60%, 85 g, 2.13 mol) was added portionwise to a solution of 2,6-dimethylphenol (250g, 2.05 mol) in 2L of toluene at 10-15°C. The resulting suspension was stirred for 45 min. The mixture was cooled to 5°C, and prenyl chloride (262g, 2.13 mol, 85%) was added during 1.5 h keeping the temperature at 5°C. The mixture was then stirred for further 2h at 10-15°C. Methanol (1L) and palladium (2.5g, 10% on charcoal) was added and the gray suspension was hydrogenated at 0.3 bar overpressure, keeping the temperature at 20-22°C (ice bath). The suspension was then filtered through a pad of celite. The yellow filtrate was washed with water (0.5L), aqueous sodium hydroxide (0.5L) and brine (0.5L), dried (MgS04) and concentrated in vacuo. The residue was distilled over a 5cm Vigreux column to yield 318g (81%, bp 78-82°C/0.05Torr) of a colorless oil. Odor description: fruity, grapefruit, minty, bergamot
1H-NMR (400MHz, CDCI3): 6.62 (bs, 1H, 3-H), 5.06-5.11 (m, 1H, 2"-H), 2.34-2.28 (m, 2H, 4-H), 2.25-2.14 (m, 2H, 1'H), 1.91 (dt, J5a,5b * 13.6 Hz, J5a,4 - 6.1 Hz, 1H, 5a-H), 1.76 (s, 3H, 2-CH3), 1.77-1.70 (m, 1H, 5b-H), 1.70 (s, 3H, 4'-H), 1.59 (s, 3H, 3'-CH3), 1.05 (s, 3H, 6-CH3) ppm. GC/MS (El): 192 (M+, 16), 124 (100), 109 (74), 82 (31), 69 (40), 41 (57). IR (ATR): 2965s, 2922s, 1667vs, 1449m, 1376m, 1033m cm"1.
Example 2: 5-lsoDropvl-1.3-dimethvl-bicvclof3.2.noct-3-en-2-one To a solution of 2,6-dimethyl-6-(3-methyl-but-2-enyl)-cyclohex-2-enone (5.00 g, 26.04 mmol) in toluene (40 ml) was added dropwise neat EtAICI2 (97%, 1.5 eq., 4.96 g, 39.06 mmol). During the addition, the temperature was kept below 10°C. The brown mixture was kept at room temperature over night and was then poured on icecold saturated NH4CI. The mixture was extracted with MTBE, washed with brine, dried (MgS04) and concentrated in vacuo. The residue was distilled bulb to bulb to yield 4.50 g (90%) of an colorless oil.
Odor description: woody, patchouli, vetiver, hesperidic
'H-NMR (400MHz, CDCI3): 6.86 (bs, 1H, 4-H), 1.81 (dt, J= 11.0, 2.2 Hz, 1H, 8-Ha), 1.78-1.72 (m, 2H, 6-Ha, 7-H«). 1.75 (d, J= 1.6 Hz, 3-CH3), 1.69 (sept, J = 6.8 Hz, 1H, 5-CH(CH3)2), 1.64-1.53 (m, 2H, 6-Hb, 7-Hb), 1.37 (dd, J= 11.0, 2.2 Hz, 1H, 8-Hb), 1.24 (s, 3H, I-CH3), 100 (d, J = 6.8Hz, 3H, 5-CH(CH3)CH3), 0.93 (d, J = 6.8 Hz, 3H, CH(CH3)CH3) ppm. 13C-NMR (100MHz, CDCI3): 205.2 (s, C-2), 151.7 (d, C-4), 133.1

n this composition 1,5,7,8,8-Pentamethyl-tricyclo[3.3.1.02'7]nonan-6-one enhances and larmonizes the woody part. It underlines the patchouli aspect but gives also a new nodern woody character. The compound blends well with the floral part of the perfume ind provides volume without giving a heavy impression.

WE CLAIM:
1. A compound of formula I
wherein
R1, R4, R6 and R7 are independently hydrogen, methyl or ethyl; R2 and R3 are independently hydrogen, or C 1.5 alkyl; or
R2 and R3 together with the carbon atom to which they are attached form a 5- or 6-membered cycloyalkyl ring; R5 is hydrogen, or CM alkyl;
o
R is hydrogen, or branched lower C3.7 alkyl;
R9 is hydrogen, methyl, ethyl, or branched lower C3.7 alkyl;
R10 is ethyl or propyl;
R11 is C1-4 alkyl;
R is hydroxy;
R13 is hydrogen, or C M alkyl; or
R12 and R13 together with the carbon atom to which they are attached form a carbonyl
group;
the dashed line represents either a C-C single bond or no bond; and
b) when C5 and C8 are connected by a single bond and C9 and C6 are connected by a single bond, C9 and C5 are not connected by a bond, n=l, R7, R8 are hydrogen, and

R9 is hydrogen, methyl or ethyl; or
b) when C5 and C8 are connected by a single bond and C9 and C6 are connected
by a single bond, C9 and C5 are not connected,
n=0,
R7, R8 is hydrogen,
R9 is a branched lower C3.7 alkyl; or
c) when C5 and C8 are not connected by a bond, C9 and C5 are connected by a single
bond,
R7 is hydrogen, methyl or ethyl, R8 is a branched lower C 3.7 alkyl, or R and R together with the carbon atoms to which they are attached form a 5- or 6-
membered cycloalkyl ring,
n = 0, and
the bond between C6 and C8 may be a single bond or a double bond.
2. The compound as claimed in claim 1 having a formula la

wherein
R1, R4, R6, R14 and R16 are independently hydrogen, methyl or ethyl;
R2 and R3 are independently hydrogen, or Ci.5 alkyl; or, R2 and R3 together with the carbon atom to which they are attached form a 5- or 6-membered cycloalkyl ring;
R5 is hydrogen, or C1-4 alkyl;

R15 is C1-4 alkyl;
R is hydroxy;
R13 is hydrogen or C1.4 alkyl; or R and R together with the carbon atom to which they are attached form a carbonyl group.
3. The compound as claimed in claim 1 of formula lb,

wherein
R1, R4, R6, R14 and R16 are independently hydrogen, methyl or ethyl;
R2 and R3 are independently hydrogen, or Ci.5 alkyl; or,
R and R together with the carbon atom to which they are attached form a 5- or 6-
* membered cycloalkyl ring;
R5 is hydrogen, or CM alkyl;
R15 is C1-4alkyl;
R12 is hydroxy;
R13 is hydrogen or CM alkyl; or
R12 and R13 together with the carbon atom to which they are attached form a carbonyl group.
4. The compound as claimed in claim 1 of formula Ic,

wherein
R1,R4,R6,R14andR16 are independently hydrogen, methyl or ethyl;
R5 is hydrogen, or C1-4alkyl;
R7 and R14 are independently hydrogen, methyl or ethyl; or,
R7 and R14 together with the carbon atoms to which they are attached form a 5- or 6-membered cycloalkyl ring;
R15 is C1-4alkyl;
R12 is hydroxy;
R13 is hydrogen or C1-4 alkyl; or R and R together with the carbon atom to which they are attached form a carbonyl group; and the bond between C6 and C8 may be a single bond;
or the dotted line together with the bond between C6 and C8 may represent a double bond.
5. The compound as claimed in claim 1 selected from the group consisting of l,5,7,8,8-Pentamethyl-tricyclo[3.3.1.02,7]nonan-6-one;l,5,7,8,8-Pentamethyl-tricyclo[3.3.1.02,7]nonan-6-one; l,3,3,5,7,8,8-Heptamethyl-tricyclo[3.3.1.02,7]nonan-6-one; 3,3,5,7,8,8-Hexamethyl-tricyclo[3.3.1.02,7]nonan-6-one; 3,3,5,8,8-Pentamethyl-tricyclo[3.3.1.02'7]nonan-6-one; 5,7,8,8-Tetramethyl-tricyclo[3.3.1.02'7]nonan-6-one;l-Isopropyl-3,3,5-trimethyl-tricyclo[3.2.1.02'7]octan-6-one;5-Isopropyl-l,3-dimethyl-bicyclo[3.2.1]oct-3-en-2-one; 5- Isopropyl-l,3-dimethyl-bicyclo[3.2.1]octan-2-one; 5-tert-Butyl-l,3-dimethyl-bicyclo[3.2.1]oct-3-en-2-one;5-sec-Butyl-l,3-dimethyl-bicyclo[3.2.1]oct-3-ene-2-one;5-Isopropyl-3-methyl-bicyclo[3.2.1]oct-3-ene-2-one;

5,7-Diisopropyl-3-methyl-bicyclo[3.2.1]oct-3-en-2-one; 5-Isopropyl-3,7,7-trimethyl-bicyclo[3.2.1]oct-3-en-2-one;l,3,5-Trimethyl-l,5,6,7,8»8a-hexahydro-l,4a-ethano-naphthalen-2-one; and 5,6,7,8,8-Pentamethyl-tricyclo[3.3.1.02,7]nonan-6-ol.
6. The method of manufacturing a flavour or fragrance composition, comprising
the step of incorporating a compound of formula I as claimed in claim 1 to a base
material.
7. The method of manufacturing a fragranced application, comprising the
incorporation of a compound of formula I as claimed in claim 1.
8. The method as claimed in claim 10 wherein the fragranced application is
selected from the group consisting of perfume, household product, laundry product,
body care product and cosmetics.

wherein
R1, R4, and R6 are independently hydrogen, methyl or ethyl;
R2 and R3 are independently hydrogen, or C1.5 alkyl; or
R and R together with the carbon atom to which they are attached form a 5- or 6-membered cycloylkyl ring;
R5 is hydrogen, or C1-4 alkyl;
R7 and R14 are independently hydrogen, methyl or ethyl; or
R7 and R14 together with the carbon atoms to which they are attached form a 5- or 6-membered cycloalkane ring;
R16 is hydrogen, or lower branched C3.7 alkyl,
and optionally followed by the step of reduction and/or alkylation of the carbonyl group at CI.

wherein
R2, R3, and R16 are hydrogen;
R1, R4 and R6 are independently hydrogen, methyl or ethyl;
R7 and R14 are independently hydrogen, methyl or ethyl; or

R7 and R14 together with the carbon atoms to which they are attached form a 5- or 6-
membered cycloalkane ring;
R5 is hydrogen, linear or branced C1-4 alkyl;
R15 is linear or branched C1-4 alkyl; and
and optionally followed by the step of hydrogenation across the double bond at C6
and C8, and
optionally followed by the step of reduction and/or alkylation of the carbonyl group at
CI.

Documents:

2866-chenp-2004 abstract duplicate.pdf

2866-chenp-2004 abstract.pdf

2866-chenp-2004 claims duplicate.pdf

2866-chenp-2004 claims.pdf

2866-chenp-2004 correspondence others.pdf

2866-chenp-2004 correspondence po.pdf

2866-chenp-2004 description (complete) duplicate.pdf

2866-chenp-2004 description (complete).pdf

2866-chenp-2004 form-1.pdf

2866-chenp-2004 form-18.pdf

2866-chenp-2004 form-3.pdf

2866-chenp-2004 form-5.pdf

2866-chenp-2004 pct.pdf

2866-chenp-2004 petition.pdf

2866-chenp-2004.rtf

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Patent Number

227168

Indian Patent Application Number

2866/CHENP/2004

PG Journal Number

07/2009

Publication Date

13-Feb-2009

Grant Date

05-Jan-2009

Date of Filing

16-Dec-2004

Name of Patentee

GIVAUDAN SA

Applicant Address

CHEMIN DE LA PARFUMERIE 5, CH-1214 VERIER,

Inventors:

#	Inventor's Name	Inventor's Address
1	GOEKE, ANDREAS	GRUZENSTRASSE 21, CH-8600 DUBENDORF,

PCT International Classification Number

CO7C49/443

PCT International Application Number

PCT/CH03/00401

PCT International Filing date

2003-06-20

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	0214344.4	2002-06-21	U.K.