Flavor and fragrance formulation (III)

Abstract

The present invention relates to the use of specific organic compounds as flavor and fragrance material. Furthermore the invention relates to new specific organic compounds, as well as to flavor and fragrance formulations comprising at least one of the specific organic compounds.

Claims

1. A flavor and fragrance formulation comprising 0.0001 to 10 wt %, relative to total weight of the flavor and fragrance formulation, of at least one compound of formula (II): ##STR00012## R.sub.5 signifies CH.sub.2CH.sub.2CH.sub.3; and R6 signifies OH or O(CO)CH.sub.3.

2. The flavor and fragrance formulation according to claim 1, wherein the flavor and fragrance formulation is a solid, gel or liquid.

3. The flavor and fragrance formulation according to claim 1, wherein the flavor and fragrance formulation is selected from the group consisting of a perfumes, hair care products, household products, laundry products, body care products and cosmetic products.

4. The flavor and fragrance formulation according to claim 1, wherein the at least one compound of formula (II) is present in an amount of 0.01-5 wt-%, based on the total weight of the flavor and fragrance formulation.

5. The flavor and fragrance formulation according to claim 1, further comprising at least one auxiliary compound selected from the group consisting of solvents, adjuvants, thickeners, surface active agents, pigments, extenders, rheology modifiers, dyestuffs, antioxidants and fillers.

6. A compound of formula (X): ##STR00013##

Description

EXAMPLES

(1) All compounds were evaluated by a panel of four persons for their intensity whereby a range of 1 to 10 was used (1=very low intensity; 10=very high intensity). Furthermore these four persons also described the odor of the compounds. The tenancy was evaluated by one person after 3, 6, 8, 24, 48, 72 and 96 hours. For such evaluations a piece of paper was immersed in each single liquid compound as such.

Example 1

Manufacture and olfactory properties of the compound of formula III (7-methoxy-3,7-dimethyl-octan-3-ol)

a) Manufacture of 6-methoxy-6-methyl-2-heptanon by methoxylation of 6-methyl-5-hepten-2-on

(2) 6000.0 g of 6-methyl-5-hepten-2-on and 9480.0 g of methanol are mixed in a reactor and cooled to 0 C. 4507.8 g of H.sub.2SO.sub.4 (96 weight-%) are added within 40 minutes by keeping the temperature. The reaction mixture is then heated up to 30 C. After 5 hours the reaction mixture is poured on ice water and extracted with methyl tert-butyl ether. The combined methyl tert-butyl ether phases are washed with 20 weight-% aqueous Na.sub.2CO.sub.3 solution and concentrated NaCl solution. The solvent is removed from the organic phase and the residue distilled (10 mbar; 130 C.) to yield 6-methoxy-6-methyl-2-heptanon.

b) Manufacture of 7-methoxy-3,7-dimethyl-1-octin-3-ol by ethinylation of 6-methoxy-6-methyl-2-heptanon

(3) 2566.4 g of 6-methoxy-6-methyl-2-heptanon are put in an autoclave under nitrogen and cooled down to a temperature of 15 C. 5221.0 g of ammonia (NH.sub.3) are added. The reaction mixture is cooled again to 15 C. Then acetylene (C.sub.2H.sub.2) is added. The reaction mixture is cooled again to 15 C. Then 52.8 g of a 40 weight % aqueous potassium hydroxide (KOH) solution are added continuously. After the end of the reaction the reaction mixture is neutralized with acetic acid, extracted with water and the solvent removed. The resulting raw product is then distilled to obtain 7-methoxy-3,7-dimethyl-1-octin-3-ol.

c) Manufacture of 7-methoxy-3,7-dimethyl-octan-3-ol by hydrogenation of 7-methoxy-3,7-dimethyl-1-octin-3-ol

(4) 404.83 g of 7-methoxy-3,7-dimethyl-1-octin-3-ol and 1.00 g of 5% Pd on carbon (Pd/C) are put in an autoclave under nitrogen and heated to a temperature of 60 C. under stirring. Then the nitrogen is exchanged by hydrogen and put to an absolute pressure of 2 bar. After the calculated amount of hydrogen has been consumed the reaction mixture is filtered and distilled (2 mbar, 130 C.) to obtain the compound of formula III.

d) Olfactory Properties

(5) Odor description: very little camphor; chemical; pharmaceutical; medical; gum; herbs; swimming pool.

(6) Intensity: 4.

(7) Tenancy: 24-48 hours.

Example 2

Manufacture and Olfactory Properties of the Compound of Formula IV

(8) 7-methoxy-3,7-dimethyl-1-octin-3-ol is manufactured as already described in example 1 a) and b).

a) Manufacture of 7-methoxy-3,7-dimethyl-1-octin-3-yl acetate

(9) 560.0 g of 7-methoxy-3,7-dimethyl-1-octin-3-ol and 0.49 g of p-toluene sulfonic acid in water are mixed and heated up to a temperature of 40 C. 372.5 g of acetic acid anhydride are added within 2 hours. After ca. 20 hours the reaction mixture is cooled down and distilled to obtain 7-methoxy-3,7-dimethyl-1-octin-3-yl acetate.

b) Manufacture of the compound of formula (IV) by hydrogenation of 7-methoxy-3,7-dimethyl-1-octin-3-yl acetate

(10) 373.56 g of 7-methoxy-3,7-dimethyl-1-octin-3-yl acetate and 0.80 g of 5% Pd on carbon (Pd/C) are put in an autoclave under nitrogen and heated to a temperature of 60 C. under stirring. Then the nitrogen is exchanged by hydrogen and put to an absolute pressure of 2 bar. After the calculated amount of hydrogen has been consumed the reaction mixture is filtered and distilled (2 mbar, 135 C.) to obtain the compound of formula (IV).

c) Olfactory Properties

(11) Odor description: drugstore; pharma odor.

(12) Intensity: 2.

(13) Tenancy: 8-24 hours.

Example 3

Manufacture and Olfactory Properties of the Compound of Formula V

a) Manufacture of 6-methoxy-6-methyl-2-octanon by methoxylation of 6-methyl-5-octen-2-on

(14) 6600.0 g of 6-methyl-5-octen-2-on and 9390.0 g of methanol are mixed in a reactor and cooled to 0 C. 4462.8 g of H.sub.2SO.sub.4 (96 weight-%) are added within 40 minutes by keeping the temperature. The reaction mixture is then heated up to 30 C. After 5 hours the reaction mixture is poured on ice water and extracted with methyl tert-butyl ether. The combined methyl tert-butyl ether phases are washed with 20 weight-% aqueous Na.sub.2CO.sub.3 solution and concentrated NaCl solution. The solvent is removed from the organic phase and the residue distilled (5 mbar; 125 C.) to yield 6-methoxy-6-methyl-2-octanon.

b) Manufacture of 7-methoxy-3,7-dimethyl-1-nonin-3-ol by ethinylation of 6-methoxy-6-methyl-2-octanon

(15) 1265.0 g of 6-methoxy-6-methyl-2-octanon are put in an autoclave under nitrogen and cooled down to a temperature of 15 C. 3226.0 g of ammonia (NH.sub.3) are added. The reaction mixture is cooled again to 15 C. Then acetylene (C.sub.2H.sub.2) is added. The reaction mixture is cooled again to 15 C. Then 33.0 g of a 40 weight-% aqueous potassium hydroxide (KOH) solution are added continuously. After the end of the reaction the reaction mixture is neutralized with acetic acid, extracted with water and the solvent removed. The resulting raw product is then distilled to obtain 7-methoxy-3,7-dimethyl-1-nonin-3-ol.

c) Manufacture of 7-methoxy-3,7-dimethyl-nonan-3-ol by hydrogenation of 7-methoxy-3,7-dimethyl-1-nonin-3-ol

(16) 304.68 g of 7-methoxy-3,7-dimethyl-1-nonin-3-ol and 0.80 g of 5% Pd on carbon (Pd/C) are put in an autoclave under nitrogen and heated to a temperature of 40 C. under stirring. Then the nitrogen is exchanged by hydrogen and put to an absolute pressure of 2 bar. After the calculated amount of hydrogen has been consumed the reaction mixture is filtered and distilled (2 mbar, 140 C.) to obtain the compound of formula (V).

d) Olfactory Properties

(17) Odour description: forest soil; fir tree; pleasant.

(18) Intensity: 3.5.

(19) Tenancy: 48-72 hours.

Example 4

Manufacture and Olfactory Properties of the Compound of Formula VI

(20) 7-methoxy-3,7-dimethyl-1-nonin-3-ol is manufactured as already described in example 3 a) and b).

a) Manufacture of 7-methoxy-3,7-dimethyl-1-nonin-3-yl acetate by acylation of 7-methoxy-3,7-dimethyl-1-nonin-3-ol

(21) 707.0 g of 7-methoxy-3,7-dimethyl-1-nonin-3-ol and 0.57 g of p-toluene sulfonic acid in water are mixed and heated up to a temperature of 60 C. 437.1 g of acetic acid anhydride are added within 2 hours. After ca. 20 hours the reaction mixture is cooled down and distilled to obtain 7-methoxy-3,7-dimethyl-1-nonin-3-yl acetate.

b) Manufacture of the compound of formula (VI) by hydrogenation of 7-methoxy-3,7-dimethyl-1-nonin-3-yl acetate

(22) 292.26 g of 7-methoxy-3,7-dimethyl-1-nonin-3-yl acetate and 0.80 g of 5% Pd on carbon (Pd/C) are put in an autoclave under nitrogen and heated to a temperature of 60 C. under stirring. Then the nitrogen is exchanged by hydrogen and put to an absolute pressure of 2 bar. After the calculated amount of hydrogen has been consumed the reaction mixture is filtered and distilled (2 mbar, 140 C.) to obtain the compound of formula (VI).

c) Olfactory Properties

(23) Odor description: wet carton; metallic; chemical; pharmaceutical; very, very little natural resin; fir; new clothes.

(24) Intensity: 2.5.

(25) Tenancy: 24-48 hours.

Example 5

Manufacture and Olfactory Properties of the Compound of Formula VII

(26) 3,6,7-Trimethyl-6-octen-1-in-3-ol may be prepared by ethinylation of 5,6-dimethyl-5-hepten-2-on.

a) Manufacture of 3,6,7-trimethyl-6-octen-1-in-3-ylacetate by acylation of 3,6,7-trimethyl-6-octen-1-in-3-ol

(27) 650.0 g of 3,6,7-trimethyl-6-octen-1-in-3-ol and 0.63 g of p-toluene sulfonic acid in water are mixed and heated up to a temperature of 40 C. 479.3 g of acetic acid anhydride are added within 2 hours. After ca. 20 hours the reaction mixture is cooled down and distilled to obtain 3,6,7-trimethyl-6-octen-1-in-3-yl acetate.

b) Manufacture of the compound of formula (VII) by hydrogenation of 3,6,7-trimethyl-6-octen-1-in-3-yl acetate

(28) 444.0 g of 3,6,7-trimethyl-6-octen-1-in-3-yl acetate and 1.2 g of 5% Pd on carbon (Pd/C) are put in an autoclave under nitrogen and heated to a temperature of 60 C. under stirring. Then the nitrogen is exchanged by hydrogen and put to an absolute pressure of 2 bar. After the calculated amount of hydrogen has been consumed the reaction mixture is filtered and distilled (2 mbar, 120 C.) to obtain the compound of formula (VII).

c) Olfactory Properties

(29) Odor description: melon; light; fresh; baby powder.

(30) Intensity: 4.5.

(31) Tenancy: 6-8 hours.

Example 6

Manufacture and Olfactory Properties of the Compound of Formula VIII

a) Manufacture of 6-methyl-2-nonanon by hydrogenation of 6-methyl-5-nonen-2-on

(32) 900.0 g of 6-methyl-5-nonen-2-on and 1.60 g of 5% Pd on carbon (Pd/C) are put in an autoclave under nitrogen and heated to a temperature of 60 C. under stirring. Then the nitrogen is exchanged by hydrogen and put to an absolute pressure of 2 bar. After the calculated amount of hydrogen has been consumed the reaction mixture is filtered and distilled (10 mbar, 120 C.) to obtain 6-methyl-2-nonanon.

b) Manufacture of 3,7-dimethyl-1-decin-3-ol by ethinylation of 6-methyl-2-nonanon

(33) 760.0 g of 6-methyl-2-nonanon are put in an autoclave under nitrogen and cooled down to a temperature of 15 C. 1305.0 g of ammonia (NH.sub.3) are added. The reaction mixture is cooled again to 15 C. Then acetylene (C.sub.2H.sub.2) is added. The reaction mixture is cooled again to 15 C. Then 14.0 g of a 40 weight-% aqueous potassium hydroxide (KOH) solution are added continuously. After the end of the reaction the reaction mixture is neutralized with acetic acid, extracted with water and the solvent removed. The resulting raw product is then distilled to obtain 3,7-dimethyl-1-decin-3-ol.

c) Manufacture of 3,7-dimethyl-1-decin-3-ylacetate

(34) 472.0 g of 3,7-dimethyl-1-decin-3-ol and 0.42 g of p-toluene sulfonic acid in water are mixed and heated up to a temperature of 40 C. 317.4 g of acetic acid anhydride are added within 2 hours. After ca. 20 hours the reaction mixture is cooled down and distilled to obtain 3,7-dimethyl-1-decin-3-yl acetate.

d) Manufacture of the compound of formula (VIII) by hydrogenation of 3,7-dimethyl-1-decin-3-ylacetate

(35) 162.0 g of 3,7-dimethyl-1-decin-3-yl acetate and 0.20 g of 5% Pd on carbon (Pd/C) are put in an autoclave under nitrogen and heated to a temperature of 60 C. under stirring. Then the nitrogen is exchanged by hydrogen and put to an absolute pressure of 2 bar. After the calculated amount of hydrogen has been consumed the reaction mixture is filtered and distilled (2 mbar, 140 C.) to obtain the compound of formula (VIII).

e) Olfactory Properties

(36) Odor description: grain/cereal; flour.

(37) Intensity: 4.

(38) Tenancy: 8-24 hours.

Example 7

Manufacture and Olfactory Properties of the Compound of Formula IX

a) Manufacture of 3,7-dimethyl-6-decen-1-in-3-ol by ethinylation of 6-methyl-5-nonen-2-on

(39) 1360.0 g of 6-methyl-5-nonen-2-on are put in an autoclave under nitrogen and cooled down to a temperature of 15 C. 2548.0 g of ammonia (NH.sub.3) are added. The reaction mixture is cooled again to 15 C. Then acetylene (C.sub.2H.sub.2) is added. The reaction mixture is cooled again to 15 C. Then 26.4 g of a 40 weight-% aqueous potassium hydroxide (KOH) solution are added continuously. After the end of the reaction the reaction mixture is neutralized with acetic acid, extracted with water and the solvent removed. The resulting raw product is then distilled to obtain 3,7-dimethyl-6-decen-1-in-3-ol.

b) Manufacture of the compound of formula (IX) by hydrogenation of 3,7-dimethyl-6-decen-1-in-3-ol

(40) 220.0 g of 3,7-dimethyl-6-decen-1-in-3-ol and 0.50 g of 5% Pd on carbon (Pd/C) are put in an autoclave under nitrogen and heated to a temperature of 60 C. under stirring. Then the nitrogen is exchanged by hydrogen and put to an absolute pressure of 2 bar. After the calculated amount of hydrogen has been consumed the reaction mixture is filtered and distilled (2 mbar, 130 C.) to obtain the compound of formula (IX).

c) Olfactory Properties

(41) Odor description: dusty; green.

(42) Intensity: 4.5.

(43) Tenancy: 8-24 hours.

Example 8

Manufacture and Olfactory Properties of the Compound of Formula X

(44) 3,7-Dimethyl-6-decen-1-in-3-ol is prepared as described in example 7 a).

a) Manufacture of 3,7-dimethyl-6-decen-1-in-3-yl acetate by acylation of 3,7-dimethyl-6-decen-1-in-3-ol

(45) 609.0 g of 3,7-dimethyl-6-decen-1-in-3-ol and 0.54 g of p-toluene sulfonic acid in water are mixed and heated up to a temperature of 40 C. 414.1 g of acetic acid anhydride are added within 2 hours. After ca. 20 hours the reaction mixture is cooled down and distilled to obtain 3,7-dimethyl-6-decen-1-in-3-yl acetate.

b) Manufacture of the compound of formula (X) by hydrogenation of 3,7-dimethyl-6-decen-1-in-3-yl acetate

(46) 239.0 g of 3,7-dimethyl-6-decen-1-in-3-yl acetate, 6.5 g of Lindlar catalyst (5% Pd+3.5% Pb on CaCO.sub.3) and 0.28 g of zinc acetate are put in an autoclave and heated under nitrogen to a temperature of 40 C. Nitrogen is exchanged by hydrogen (H.sub.2) and the reaction mixture put at an absolute pressure of 2 bar. After the calculated amount of hydrogen has been consumed the reaction mixture is filtered and distilled (2 mbar, 140 C.) to obtain 3,7-dimethyl-6-decen-3-yl acetate (=compound of formula X).

c) Olfactory Properties

(47) Odor description: broad-leaved forest; green grass.

(48) Intensity: 2.5.

(49) Tenancy: 8-24 hours.

Example 9

Manufacture and Olfactory Properties of the Compound of Formula XI

a) Manufacture of 6-methoxy-6-methyl-nonan-2-on by methoxylation of 6-methyl-5-nonen-2-on

(50) 6404.0 g of 6-methyl-5-nonen-2-on, 10400.0 g of methanol and 2050.0 g of Amberlyst 15 wet are mixed in a reactor and heated up to 80 C. After 15 hours the reaction mixture is cooled and reduced in volume by distilling. The remaining residue is then distilled (2 mbar; 145 C.) to give 6-methoxy-6-methyl-nonan-2-on.

b) Manufacture of 7-methoxy-3,7-dimethyl-1-decin-3-ol by ethinylation of 6-methoxy-6-methyl-2-nonanon

(51) 1020.0 g of 6-methoxy-6-methyl-2-nonanon are put in an autoclave under nitrogen and cooled down to a temperature of 15 C. 1931.0 g of ammonia (NH.sub.3) are added. The reaction mixture is cooled again to 15 C. Then acetylene (C.sub.2H.sub.2) is added. The reaction mixture is cooled again to 15 C. Then 19.8 g of a 40 weight % aqueous potassium hydroxide (KOH) solution are added continuously. After the end of the reaction the reaction mixture is neutralized with acetic acid, extracted with water and the solvent removed. The resulting raw product is then distilled to obtain 7-methoxy-3,7-dimethyl-1-decin-3-ol.

c) Manufacture of the compound of formula (XI) by hydrogenation of 7-methoxy-3,7-dimethyl-1-decin-3-ol

(52) 220.0 g of 7-methoxy-3,7-dimethyl-1-decin-3-ol and 0.25 g of 5% Pd on carbon (Pd/C) are put in an autoclave under nitrogen and heated to a temperature of 45 C. under stirring. Then the nitrogen is exchanged by hydrogen and put to an absolute pressure of 2 bar. After the calculated amount of hydrogen has been consumed the reaction mixture is filtered and distilled (2 mbar, 140 C.) to obtain the compound of formula (XI) (=7-methoxy-3,7-dimethyl-3-decanol).

d) Olfactory Properties

(53) Odor description: melon; citrus.

(54) Intensity: 3.

(55) Tenancy: 48-72 hours.

Example 10

Manufacture and Olfactory Properties of the Compound of Formula XII

(56) 7-Methoxy-3,7-dimethyl-1-decin-3-ol is prepared as described in example 9 a) and b).

a) Manufacture of 7-methoxy-3,7-dimethyl-1-decin-3-yl acetate by acylation of 7-methoxy-3,7-dimethyl-1-decin-3-ol

(57) 430.0 g of 7-Methoxy-3,7-dimethyl-1-decin-3-ol and 0.32 g of p-toluene sulfonic acid in water are mixed and heated up to a temperature of 40 C. 248.3 g of acetic acid anhydride are added within 2 hours. After ca. 20 hours the reaction mixture is cooled down and distilled to obtain 7-methoxy-3,7-dimethyl-1-decin-3-yl acetate.

b) Manufacture of the compound of formula (XII) by hydrogenation of 7-methoxy-3,7-dimethyl-1-decin-3-yl acetate

(58) 190.0 g of 7-methoxy-3,7-dimethyl-1-decin-3-yl acetate and 1.5 g of 5% Pd on carbon (Pd/C) are put in an autoclave under nitrogen and heated to a temperature of 45 C. under stirring. Then the nitrogen is exchanged by hydrogen and put to an absolute pressure of 2 bar. After the calculated amount of hydrogen has been consumed the reaction mixture is filtered and distilled (1 mbar, 150 C.) to obtain the compound of formula (XII) (=7-methoxy-3,7-dimethyl-3-decanyl acetate).

c) Olfactory Properties

(59) Tenancy: 48-72 hours.

Example 11

Olfactory Properties of the Compound of Formula XIII

(60) Odor description: dry wood with water (sauna); warm aspect; dusty; old flannel; sweety.

(61) Intensity: 5.

(62) Tenancy: 6-8 hours.

Example 12

Olfactory Properties of the Compound of Formula XIV

(63) Odor description: flowery; citrus; fresh; washing agent; rotten wood; olibanum.

(64) Intensity: 6.5.

(65) Tenancy: 3-6 hours.

Example 13

Olfactory Properties of the Compound of Formula XV

(66) Odor description: soil; mushroom; flowery; dusty.

(67) Intensity: 4.5.

(68) Tenancy: 6-8 hours.

Example 14

Olfactory Properties of the Compound of Formula XVI

(69) Odor description: tropical fruits; pleasant.

(70) Intensity: 4.5.

(71) Tenancy: 3-6 hours.

Example 15

Olfactory Properties of the Compound of Formula XVII

(72) Odour description: dusty, dry.

(73) Intensity: 4.

(74) Tenancy: 8-24 hours.