JP2006521285A - New sesquiterpene oxides as perfumes and flavors - Google Patents

Abstract

The present invention relates to novel sesquiterpene oxides 3S, 3aR, 7aR, -6 isopropyl-1,1,3, of formula (I) by reaction of elemol with peracid at temperatures in the range of 20-30 ° C. A method for preparing 3a-tetramethyl 1,3,3a, 4,7,7a-hexahydro-isobenzofuran is described. The present invention also discusses the use of compounds of formula (1) as perfumes and flavoring agents.

Description

  The present invention relates to novel sesquiterpene oxides of formula (I) 3S, 3aR, 7aR, -6 isopropyl-1,1,3,3a-tetramethyl 1,3,3a, 4,7,7a -Hexahydro-isobenzofuran and process for its preparation. In addition, a mixture of diastereoisomers in a 75:25 ratio of the compound of formula (1) has a multiodorant that is a combination of Diou, Laurel, Thyme and Florex.

  The compounds defined in Formula 1 have been detected among other reaction products during the course of research on peracid dehydration of sesquiterpene elemol.

  JP 54-84551 published on July 5, 1979 by Nagakura et al. (Patent Document 1) consists of substances, in particular, α-elementene and δ-elementene resulting from the heat dehydration reaction of β-elemol. Mention the use of oily and multicomponent oxidation products obtained by peracid treatment of mixtures or α-elemene mixtures separated from said dehydration reaction products as perfumes for cosmetic and food flavors Yes.

  It is important to point out that this prior art document does not specify any structure or configuration of any of the components of the mixture other than providing infrared absorption and NMR spectra of the mixture. Indeed, for the preparation of diastereomeric mixtures of elemental oxides derived from α- and δ-elementenes, respectively, theoretically in Scheme I The sesquiterpene alcohols 2 and 3 shown can be predicted.

  The compound of formula (1) has not been artificially synthesized and has not been isolated or reported from natural products. Its use as a perfume or flavor component was also not known in the prior art.

During the synthesis of the reference compound, elemol dehydration reaction was performed. A novel sesquiterpene oxide with a pleasant scent, which is a compound of the present invention, was obtained as a by-product of the reaction.
JP-A-54-84551

Objects of the present invention The main object of the present invention is to provide a novel sesquiterpene oxide 3S, 3aR, 7aR, -6 isopropyl-1,1,3,3a-tetramethyl 1,3,3a 4,7,7a-Hexahydro-isobenzofuran and process for its preparation.

  The object of the present invention is to provide compounds of formula (1) having perfume and flavor properties.

  Another object of the present invention is to provide a stereoisomer mixture of compounds of formula (1) having multiple odorants that are a combination of Diou, Laurel, Thyme and Florex.

  It is a further object of the present invention to provide stereoisomers of compounds of formula (1) that have significant differences in their aromatic properties. A further object of the present invention is to utilize the compounds of formula (1) in high purity fragrances, eau de cologne, hygiene products, hair care products, body deodorants, fragrances and cosmetics.

  A further object of the present invention is to provide the use of a compound of formula (1) alone or in combination with other perfume ingredients, solvents or additives in order to obtain the desired olfactory effect.

  A further object of the present invention is to provide incorporation of different proportions of compounds of formula (1) into various products depending on the nature of the product used and to obtain the desired olfactory effect. .

SUMMARY OF THE INVENTION Accordingly, the present invention provides a novel sesquiterpene oxide of formula (I) 3S, 3aR, 7aR, -6 isopropyl- A method for preparing 1,1,3,3a-tetramethyl 1,3,3a, 4,7,7a-hexahydro-isobenzofuran is described. The present invention also discusses the use of compounds of formula (1) as perfumes and flavoring agents.

BRIEF DESCRIPTION OF THE DRAWINGS Formula 1 shows the basic structure of a novel sesquiterpene oxide.

  Scheme 1 shows the formation of elemental alcohols 2 and 3, which are products predicted from the reaction of the element with the reaction conditions given in JP 54-084551.

DETAILED DESCRIPTION OF THE INVENTION According to the purpose, the invention relates to 3S, 3aR, 7aR-6-isopropyl-1,1,3,3a-tetramethyl-1,3,3,9,4,7,7a-hexa There is provided a compound of formula (1) designated hydroisobenzofuran.

Embodiments of the present invention provide compounds having the following properties:
Pale yellow oil, [α] _D -57.2 (EtOH)
Infrared absorption: 2964,1377,1184,950,808,777cm ^-1
1 H NMR (CDCl ₃ ): δ5.36 (1H, d, J = 6.12Hz); 3.55 (1H, q, J = 7.2Hz); 2.26 (1H, m); 1.24 (3H, s); 1.16 ( 3H, s); 0.77 (3H, s); 1.03 (6H, d, J = 7.92Hz); 1.13 (3H, d, J = 7.2Hz); 1.9,1.72,1.89,1.75,
¹³ C NMR: 78.7; 81.2; 42.7; 37.7; 117.0; 143.4; 23.9; 54.3; 14.4; 12.6; 24.8; 30.6; 35.2; 21.4; 21.9 ppm,
MS: 222 (14), 207 (30), 178 (14), 163 (32), 149 (10), 135 (75), 93 (100), 79 (18)

  A further aspect of the present invention provides compounds having an isobenzofuran ring responsible for olfactory properties.

  Another further aspect of the invention provides compounds for use in high purity fragrances, eau de cologne, hygiene products, batch gels, hair care products, deodorants, fragrances or cosmetics.

  Another aspect of the invention provides compounds that can be used to impart fragrance to consumer products, either alone or as a mixture of isomers.

Yet another aspect of the present invention provides a method for preparing compound (1) comprising the following steps.
a) A step of obtaining a solution by dissolving elemol in glacial acetic acid,
b) obtaining a reaction mixture by adding perchlorid acid to the solution of step (a) in the temperature range of 20-30 ° C.,
c) stirring the reaction mixture of step (b) at ambient temperature for 60-80 hours;
d) a step of diluting the reaction mixture of the step (d) with water, extracting an organic solvent with an aqueous solution, and separating the organic layer and the aqueous layer;
e) a step of washing the organic layer of the step (d) with an aqueous sodium hydrogen carbonate solution followed by water;
f) drying the washed organic layer with anhydrous sodium sulfate, performing filtration, and removing the solvent from the filtrate to obtain a crude product; and
g) A step of obtaining the compound of the formula (1) by purifying the crude product of the step (f) by eluting with a silica gel column with a mixture of organic solvents.

  Yet another aspect of the present invention provides a method wherein the peracid used in step (b) is selected from the group consisting of peracetic acid, perchloric acid or perbenzoic acid.

  Yet another aspect of the present invention provides a method wherein the organic solvent used in step (d) is selected from diethyl ether, methylene chloride, chloroform or ethyl acetate.

  Yet another aspect of the invention provides a method wherein the mixture of organic solvents used in step (g) is ethyl acetate and petroleum ether (4:96).

  Yet another aspect of the invention provides a method having an isobenzofuran ring responsible for olfactory properties.

  Yet another aspect of the present invention provides a method wherein the compound is used in a high purity perfume, eau de cologne, hygiene product, batch gel, hair care product, deodorant, fragrance or cosmetic. This compound can be used as an additive and when used in applications, the product is accepted by the user and it does not show any adverse reactions.

  Yet another aspect of the present invention provides a synergistic composition comprising an effective amount of Compound (I) or an isomer mixture thereof, said composition comprising a soap, shower or bath gel, hygiene product Useful in filling fragrances, hair care products such as shampoos, body deodorants, fragrances or cosmetics.

  Yet another aspect of the invention provides compositions that are used alone or in combination with other perfumes, solvents or additives.

  Yet another aspect of the present invention provides a composition wherein the isomer mixture of said compound (I) in a 75:25 ratio is a multiple odorant that is a combination of Diou, Laurel, Thyme and Florex.

  Although the invention is illustrated with reference to examples, the examples should not be construed to limit the scope of the invention.

Preparation of the compound of formula 1 To a solution of elemol (3.5 gm) in glacial acetic acid (42 ml) was added perchloric acid (0.7 ml, 60%). The reaction mixture was kept stirring at room temperature (25-27 ° C.) for 72 hours. The reaction product was diluted with water and extracted with ether. The ethereal extract was washed with sodium bicarbonate followed by water and dried over anhydrous sodium sulfate. Removal of the solvent gave a crude product containing all the stereoisomers of sesquiterpene oxide in addition to the element (the main product of the reaction). Preferred compounds are the main components of stereoisomeric mixtures.

Purification of the preferred compound 3S, 3aR, 7aR-6 isopropyl-1,1,3,3a-tetramethyl 1,3,3a, 4,7,7a, hexahydroisobenzofuran Flash column chromatography was performed on silica gel using the solution (4:96) to obtain the preferred compound. The Rf of the compound in the same solvent system as the developing solvent was 0.6. Yield: 0.28 g.

Analytical data:
Pale yellow oil, [α] _D -57.2 (EtOH)
Infrared absorption: 2964,1377,1184,950,808,777cm ^-1
1 H NMR (CDCl ₃ ): δ 5.36 (1H, d, J = 6.12Hz); 3.55 (1H, q, J = 7.2Hz); 2.26 (1H, m); 1.24 (3H, s); 1.16 ( 3H, s); 0.77 (3H, s); 1.03 (6H, d, J = 7.92Hz); 1.13 (3H, d, J = 7.2Hz); 1.9,1.72,1.89,1.75,
¹³ C NMR: 78.7; 81.2; 42.7; 37.7; 117.0; 143.4; 23.9; 54.3; 14.4; 12.6; 24.8; 30.6; 35.2; 21.4; 21.9 ppm,
MS: 222 (14), 207 (30), 178 (14), 163 (32), 149 (10), 135 (75), 93 (100), 79 (18)

Advantages of the present invention
1. The molecule is a novel one used for new applications.
2. It is a multi-odorant substance with the properties of Diau, Laurel, Thyme and Florex.
3. This compound can be used as an additive and when used in the above applications, the product is accepted by the user and it does not show any adverse reaction.

Formula 1 shows the basic structure of a novel sesquiterpene oxide. Scheme 1 shows the formation of elemental alcohols 2 and 3, which are the products predicted from the reaction of elements with the reaction conditions given in JP 54-84551.

Claims (14)

3S, 3aR, 7aR-6-isopropyl-1,1,3,3a-tetramethyl-1,3,3,9,4,7,7a-hexahydroisobenzofuran compound represented by the formula (1).

The compound according to claim 1, which exhibits the following properties.
Pale yellow oil, [α] _D -57.2 (EtOH)
Infrared absorption: 2964,1377,1184,950,808,777cm ^-1
1 H NMR (CDCl ₃ ): δ 5.36 (1H, d, J = 6.12Hz); 3.55 (1H, q, J = 7.2Hz); 2.26 (1H, m); 1.24 (3H, s); 1.16 ( 3H, s); 0.77 (3H, s); 1.03 (6H, d, J = 7.92Hz); 1.13 (3H, d, J = 7.2Hz); 1.9,1.72,1.89,1.75,
¹³ C NMR: 78.7; 81.2; 42.7; 37.7; 117.0; 143.4; 23.9; 54.3; 14.4; 12.6; 24.8; 30.6; 35.2; 21.4; 21.9 ppm,
MS: 222 (14), 207 (30), 178 (14), 163 (32), 149 (10), 135 (75), 93 (100), 79 (18)   The compound according to claim 1, wherein the compound has an isobenzofuran ring that causes olfactory properties.   The compound according to claim 1, wherein the compound is used in a highly pure fragrance, eau de cologne, hygiene product, batch gel, hair care product, deodorant, fragrance or cosmetic.   2. A compound according to claim 1 which can be used as a single substance or as a mixture of isomers to impart a fragrance to a consumer product. The method for preparing compound (1) according to claim 1, comprising the following steps.
a) A step of obtaining a solution by dissolving elemol in glacial acetic acid,
b) obtaining a reaction mixture by adding perchlorid acid to the solution of step (a) in the temperature range of 20-30 ° C.,
c) stirring the reaction mixture of step (b) at ambient temperature for 60-80 hours;
d) a step of diluting the reaction mixture of the step (d) with water, extracting an organic solvent with an aqueous solution, and separating the organic layer and the aqueous layer;
e) a step of washing the organic layer of the step (d) with an aqueous sodium hydrogen carbonate solution followed by water;
f) drying the washed organic layer with anhydrous sodium sulfate, performing filtration, and removing the solvent from the filtrate to obtain a crude product; and
g) A step of obtaining the compound of the formula (1) by purifying the crude product of the step (f) by eluting with a silica gel column with a mixture of organic solvents.   7. The method of claim 6, wherein the peracid used in step (b) is selected from the group consisting of peracetic acid, perchloric acid or perbenzoic acid.   The method of claim 6, wherein the organic solvent used in step (d) is selected from diethyl ether, methylene chloride, chloroform or ethyl acetate.   The method of claim 6, wherein the mixture of organic solvents used in step (g) is ethyl acetate and petroleum ether (4:96).   7. The method according to claim 6, wherein the compound obtained in the step (g) has an isobenzofuran ring that causes olfactory characteristics.   7. The method according to claim 6, wherein the resulting compound is used in a high-perfume fragrance, eau de cologne, hygiene product, batch gel, hair care product, deodorant, fragrance or cosmetic.   A synergistic composition comprising an effective amount of Compound (I) or a mixture of isomers thereof, soap, shower or bath gel, hygiene products, hair care products such as shampoos, body deodorants, fragrances Or a composition that is useful for filling cosmetics with fragrances.   13. A composition according to claim 12, wherein the composition is used alone or in combination with other perfumes, solvents or additives. 9. A composition according to claim 8, wherein the mixture of isomers of compound (I) in a 75:25 ratio is a multiodorant which is a combination of diau, laurel, thyme and florex.

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