JP3266308B2 - 1- (2,2,6-trimethylcyclohexyl) -5-hexen-3-ol and a fragrance composition containing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel 1- (2,2,6)
-Trimethylcyclohexyl) -5-hexene-3-ol and a fragrance composition containing the same.

[0002]

2. Description of the Related Art Conventionally, 1- (2,2,6-trimethylcyclohexyl) -5-hexane-3-ol has been known as amber.
It is known as a very useful fragrance composition having a similar odor (Japanese Patent Application Laid-Open No. Sho 54-117439), and its geometric isomers and optically active isomers have been reported in detail (Japanese Patent Application Laid-Open No. 59-176207). No., JP-A-60-66
No. 75, JP-A-61-191636, JP-A-62-70314, JP-A-4-21642, EP-A-457022, HELV
ETICA CHIMICA ACTA 68 (19
85) 1961-1985).

However, 1- (2,2,6-trimethylcyclohexyl)-having a double bond at the terminal of the alkyl chain.
5-Hexen-3-ol is a novel compound, and its odor is not known at all.

[0004]

It is known that the fragrance of a fragrance composition is totally different due to a difference in functional groups and a slight difference in structure, or a fragrance is a new fragrance having a different fragrance. Therefore, studying the aroma of various compounds is very important in providing a new perfume material corresponding to various uses and tastes.

[0005] Recently, in addition to the fragrance, those having stability and safety have been demanded. Therefore, an object of the present invention is to provide a new fragrance material to meet the above demand.

[0006]

Under such circumstances, the present inventors have conducted intensive studies and as a result, the following formula (1) which has not been synthesized before has been obtained.

[0007]

Embedded image Found that the novel compound 1- (2,2,6-trimethylcyclohexyl) -5-hexen-3-ol represented by the formula (1) has a useful aroma and is excellent in stability and safety. Completed the invention.

That is, the present invention provides a novel compound 1- (2,2,
6-trimethylcyclohexyl) -5-hexene-3-
An object of the present invention is to provide an ole and a fragrance composition containing the same.

Further, the present inventors have the following formula (2)

[0010]

Embedded image (6S) of a novel compound 1- (2,2,6-trimethylcyclohexyl) -5-hexen-3-ol represented by
It has also been found that the body is a useful fragrance material having a different odor and a stronger odor from its (6R) -form or racemic body.

The 1- (2,2,6-trimethylcyclohexyl) -5-hexen-3-ol of the present invention can be synthesized according to the following reaction formula 1.

[0012]

Embedded image (In the formula, X represents a halogen atom.)

That is, by reacting 3- (2,2,6-trimethylcyclohexyl) propanal (3) with allyl magnesium halide (4), 1
-(2,2,6-Trimethylcyclohexyl) -5-hexen-3-ol (1) can be obtained.

The use of the (6S) -form or the (6R) -form of 3- (2,2,6-trimethylcyclohexyl) propanal as a starting material provides an optically active (6) -form.
S)-or (6R) -1- (2,2,6-trimethylcyclohexyl) -5-hexen-3-ol can be obtained.

The starting material 3- (2,2,6-trimethylcyclohexyl) propanal (3) is disclosed in JP-A-4-21.
As disclosed in JP-A-649, for example, it can be synthesized according to the following reaction route 1.

[0016]

Embedded image (In the formula, R ¹ represents a hydrogen atom or a methyl group, Ac represents an acetyl group, Et represents an ethyl group, and wavy lines represent trans and / or cis positions.)

That is, the compound (5) typified by citronellal is reacted with acetic anhydride to form an enol acetate (6), which is then cyclized with a phosphoric acid catalyst to obtain dihydrocyclocitrate. (7).

The dihydrocyclocitral (7) is reacted with phosphonoacetic acid triethyl ester (8) to give 3- (2,2,6-trimethylcyclohexyl).
Ethyl acrylate (9) was obtained and reduced with a reducing agent such as sodium borohydride to give 3- (2,2,6-
Trimethylcyclohexyl) -2-propene-1-o-
Then, hydrogenation was carried out using palladium carbon as a catalyst to obtain 3- (2,2,6-trimethylcyclohexyl) propanal (3).

When an optically active compound such as l-citronellal or d-citronellal is used as the starting compound (5), (6S)-or (6R)-
1- (2,2,6-trimethylcyclohexyl) -5-
Hexen-3-ol can be obtained.

As described above, 1- (2, 2,
6-trimethylcyclohexyl) -5-hexene-3-
Racemic and optically active forms of all are obtained. Further, the ratio of the trans-form / cis-form of the racemic form and the optically active form thus obtained can be obtained at about 95/5, and the optical purity of the optically active form can be obtained at about 98% ee. .

The thus obtained 1- (2,2,6)
-Trimethylcyclohexyl) -5-hexen-3-ol is an amber-like odor of 1- (2,2,6-trimethylcyclohexyl) -5-hexane-3-ol having no double bond. In comparison, it was found to be a useful fragrance material having a stronger musk-like aroma.

Further, the optically active substance (6S)-
1- (2,2,6-trimethylcyclohexyl) -5-
Hexen-3-ol was also found to have a different odor and a sharper and stronger odor than its (6R)-or racemic form. In other words, the (6S) -body has a sweet musk-like, sharp amber-like fragrance, while the (6R)-
The body was found to have essentially no musk, amber odor, but a slightly woody odor with a slight moldiness.

The racemic aroma prepared by mixing both enantiomers at a ratio of 1: 1 has a weaker aroma intensity than that of the (6S) -form, and is slightly less sharp in woody and musky. −,
It was found to have an amber aroma.

Further, the (6S) -form is like a different compound from the (6R) -form, sharply lifts the top note of the fragrance composition, is fresher, and has an excellent fragrance imparting effect. It was also found to be a very useful fragrance material having a remarkably strong retention property and a much stronger masking power such as a base odor such as soap, a bleach odor or an ozone odor. Moreover, it turned out that it is excellent also in stability and safety.

The racemic or (6S) -form of 1- (2,2,6-trimethylcyclohexyl) -5-hexen-3-ol of the present invention is used in a perfume composition in an amount of 0.001.
-50% by weight, preferably 0.01-20% by weight.

Thus, the present invention containing 1- (2,2,6-trimethylcyclohexyl) -5-hexene-3-ol has a high diffusibility and aroma-retaining property, and is fresh and highly palatable. The present invention can provide a fragrance imparting or fragrance improving reinforcing agent, and can also provide cosmetics, health and hygiene materials, pharmaceuticals, and the like containing fragrance components.

That is, shampoos, rinses, perfumes,
Colons, hair tonics, hair creams, poma
And other cosmetic bases for hair, white powder, lipstick, other cosmetic bases and cosmetic detergents, soaps, dishwashing detergents, laundry detergents,
Softeners, disinfecting detergents, deodorant detergents, indoor fragrances, furniture care, disinfectants, insecticides, bleaching agents, various other sanitary detergents, toothpaste, mouthwash, toilet paper -It is possible to increase the commercial value by blending an appropriate amount capable of imparting a unique fragrance to a fragrance or the like for facilitating ingestion of a drug.

[0028]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Synthesis Examples, Examples, Test Examples, and Comparative Examples, but the present invention is not limited to these Examples. The analytical instruments and analytical conditions in the present example are shown below.

GC equipment: HEWLETT PA
CKARD 5890 Column: Carbowax 20M 0.2 mm x 25
m Temperature rise: 80 ° C. to 220 ° C., 5 ° C./min NMR equipment: BRUKER AM × 400 GC-MS equipment: Hitachi M-2000A Hitachi M-80B Optical rotation equipment: JASCO DIP-360 Cell: 3φ × 100 mm

Synthesis Example 1 Synthesis of (6S) -1- (2,2,6-trimethylcyclohexyl) -5-hexen-3-ol; with stirrer, thermometer, dropping funnel and condenser 150 ml (1 mol / l diethyl ether solution) and 90 ml of diethyl ether were placed in a 1-liter four-neck flask under a nitrogen atmosphere, and (6S) -3- (2,
2,6-trimethylcyclohexyl) propanal 13
g in diethyl ether (90 ml) at 20-25 ° C.
, And the mixture was stirred at the same temperature for 4 hours to complete the reaction. The reaction solution was treated in a conventional manner, and 21 g of the obtained concentrated oil was purified by silica gel column chromatography to give (6S) -1- (2,2,6-trimethylcyclohexyl) -5-hexene-3-o-. 9
g was obtained. [Α] ²⁵ _D + 14.34 ° The purity by gas chromatography was such that the ratio of the trans-form and the cis-form shown by the following formula was 95/5.

[0031]

Embedded image

The obtained (6S) -1- (2,2,6-trimethylcyclohexyl) -5-hexen-3-ol was separated and purified by gas chromatography to have a purity of 99.5.
% Is shown below. Transformer IR (νmax, cm ^-1 ); 3350,3070,2920,2870,2840,1640,14
75, 1460, 1440, 1385, 1365 ¹ H-NMR (400 MHz, CDCl _3, δ); 0.55 (m, 1 H), 0.79 (s, 3 H), 0.
87 to 0.95 (7H), 1.18 (m, 1H), 1.31 to 1.47 (6H), 1.54 to 1.59
(4H), 2.15 (m, 1H), 1.94 (m, 1H), 3.60 (m, 1H), 5.12 to 5.17 (2
H), 5.82 (m, 1H) MS (m / z); 206 (M-18,2), 191 (2), 183 (40), 149 (5), 123 (1
9), 109 (54), 83 (82), 69 (100), 41 (98)

Synthesis Example 2 Synthesis of (6R) -1- (2,2,6-trimethylcyclohexyl) -5-hexen-3-ol; (6S) -3
According to Synthesis Example 1, except that 12 g of (6R) -3- (2,2,6-trimethylcyclohexyl) propanal was used instead of-(2,2,6-trimethylcyclohexyl) propanal. ) -1- (2,2,6-trimethylcyclohexyl) -5-hexen-3-ol
g was obtained. [Α] ²⁵ _D -14.33 ° The purity by gas chromatography was such that the ratio of the trans-form and the cis-form shown by the following formula was 95.3 / 4.7.

[0034]

Embedded image

Example 1 Fragrance composition for fusere-like fiber softener; (6S) -1- (2,2,6-trimethylcyclohexyl) -5-hexene-3-ol synthesized in Synthesis Example 1 And (6R) -3- (2,2,6-trimethylcyclohexyl) propanal synthesized in Synthesis Example 2 at a ratio of 1: 1 to prepare a racemic 1- (2,2,6) -Trimethylcyclohexyl) -5-hexene-3-ol was used to prepare a highly palatable fusere-like fiber softener perfume composition according to the formulation shown in Table 1.

[0036]

TABLE 1 Formulation (parts by weight) Coumarin 50 Ethylene brassate 200 Patchouli oil 30 Dimethylbenzyl methanol 100 n-Tetradecylaldehyde 10 2,4-Di-tert-butylcyclohexanone 100 Benzyl salicylate 200 Lavandin oil 50 Amylcinamic aldehyde 100 Cyclamenaldehyde 100 Acetylcedrene 40 Racemic 1- (2,2,6-trimethylcyclohexyl) -5-hexen-3-ol 20 1000

Example 2 Fluoral-Bouquet perfume; synthesized in Synthesis Example 1 (6S)
-1- (2,2,6-trimethylcyclohexyl) -5
-Floralrub having violet-like characteristics with high palatability according to the formulation of Table 2 using hexene-3-ol
A perfume-like perfume was prepared.

[0038]

Table 2 Formulation (parts by weight) undecanal 50 ylang-ylang oil 20 linalool 10 ethyl linalyl acetate 5 phenylethyl phenylacetate 10 β-phenylethyl alcohol 150 l-citronellol 50 benzyl salicylate 250 salicylic acid Cis-3-hexenyl 50 dihydrojasmine 120 geranyl acetate 15 musk ketone 10 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-γ-2- Benzopyran 30 p-tert-butyl-α-methylhydrocinnamic aldehyde 45 4- (4-hydroxy-4-methylpentyl) -3-cyclohexene-10-carbaldehyde 15 2-acetyl-2,3,8,8 -Tetramethyloctalin 130 α-Damascon 10 (6S) -1- (2,2,6-trimethylcyclohexyl) -5-hexen-3-ol 30 1000

Test Example 1 Stability test with soap; (6S) -1 synthesized in Synthesis Example 1
-(2,2,6-Trimethylcyclohexyl) -5-hexene-3-ol is perfumed with soap, sealed in a glass container and placed in a 50 ° C. thermostat for 2 months for stability test Was done. As a result of examining the change of the fragrance by five panelists, it was found that there was no decomposition odor and no change or deterioration of the fragrance was observed, and the odor was stable with time. Further, in order to examine the stability to sunlight, the above soap was placed under sunlight at room temperature for one month, and a color burn test was performed. As a result, no color burn was recognized.

Test Example 2 Stability test in an acidic solution; (6S) -1- (2,2,6-trimethylcyclohexyl) -5-hexene-3-ol synthesized in Synthesis Example 1 having the following formulation. Of acetic acid (pH 3) was prepared. Preparation (g) Acetic acid 1 Triethyl citrate 50 (6S) -1- (2,2,6-trimethylcyclohexyl) -5-hexen-3-ol 10 n-dodecane (internal standard) 1

This solution was placed in a 100 ml glass container and stored in a constant temperature room at 50 ° C. for 2 months, and the composition change was examined by gas chromatography. As a result, no change was observed, indicating that (6S) -1- (2,2,6-trimethylcyclohexyl) -5-hexen-3-ol was stable under acetic acid acidity (pH 3).

Test Example 3 Stability test in a basic solution; (6S) -1- (2,2,6-trimethylcyclohexyl) -5-hexene-3-o-synthesized in Synthesis Example 1 having the following formulation. A basic solution (pH 10) was prepared. Treatment (g) triethylamine 1 triethylcitrate 50 (6S) -1- (2,2,6-trimethylcyclohexyl) -5-hexen-3-ol 5 water 0.5 methanol 10 n-dodecane (Inner mark) 1

This solution was placed in a 100 ml glass container and stored in a constant temperature room at 50 ° C. for 2 months, and the composition change was examined by gas chromatography. As a result, no change was observed, indicating that (6S) -1- (2,2,6-trimethylcyclohexyl) -5-hexen-3-ol was stable under amine basicity (pH 10). .

Test Example 4 Masking and stability test using an enzyme-containing bleach; an enzyme-containing bleach composition was prepared according to the following formulation. Preparation (parts by weight) Sodium percarbonate 93.7 Enzyme (Alcalase 29T: manufactured by Noving Trees) 1.0 Calcium sulfate anhydrous 5.0 (6S) -1- (2,2,6-trimethylcyclohexyl) ) -5-Hexen-3-ol 50% ethanol solution 0.3 100

Further, based on the above formula, (6)
S) -1- (2,2,6-trimethylcyclohexyl)
Instead of a 50% solution of -5-hexene-3-ol in 50% ethanol, 50% ethanol of (6R) -1- (2,2,6-trimethylcyclohexyl) -5-hexen-3-ol was used. -Containing bleaching agent prepared according to each of the formulas using a 1: 1 mixture of the (6S) -form obtained in Synthetic Example 1 and the (6R) -form obtained in Synthetic Example 2). A comparative test was performed on the composition. That is, the bleaching composition was sealed in a plastic container bottle, placed in a thermostatic chamber, stored at 40 ° C. for 30 days, and examined for changes in enzyme odor. Table 3 shows the results determined by 10 expert panelists. From the above results, the bleach using the (6S) -form completely masked the enzyme odor, and almost satisfactory results were also obtained with the bleach using the racemic form. In both cases, there was no change in flavor.

[0046]

Table 3 1- (2,2,6-trimethyl) Enzyme odor Enzyme odor Enzyme odor Cyclohexyl) -5- Absolutely quite hexene-3-ol Not felt Felt (6S) -body 10 0 people 0 people (6R)-body 0 people 4 people 6 racemic body 8 people 2 people 0 people

Test Example 5 Safety test: (6S) -1- (2,2, obtained in Synthesis Example 1)
6-trimethylcyclohexyl) -5-hexene-3-
Regarding the safety of all, a sensitization test, a primary skin irritation test, a phototoxicity test and a mutagenicity test were conducted.
All were negative, indicating that the safety was very high.

Comparative Study Example 1 A green floral-like shampoo perfume composition was prepared according to the formulation shown in Table 4 below.

[0049]

Table 4 Formulation A Formulation B (parts by weight) Musk ketone 50 50 Ethylene brassate 250 250 Methyl dihydrojasmonate 70 70 p-Isobutyl-α-methyldihydrocinnamic aldehyde 200 200 1-citronellol 100 100 Eugenol 20 20 Phenylacetaldehyde (50% dipropylene glycol solution) 10 10 2-Methyl-4-phenylbutan-2-yl acetate 50 50 2,4-Dimethyl-3-cyclohexene carbaldehyde 10 10 Undecylenaldehyde 55 Lime oil 20 20 cis-3-hexenyl propionate 55 5-p-hydroxyphenylbutan-2-one (50% dipropylene glycol solution) 20 20 Lemon oil 40 40 Tetrahydro linalool 50 50 Salicyl Benzyl 80 80 Dipropylene glycol 10 10 (6S) -1- (2,2,6-trimethylcyclohexyl) -5-hexene-3-ol 10- (6S) -1- (2,2,6 -Trimethylcyclohexyl) hexane-3-ol-10 1000 1000 Formulation A of the compound of the present invention containing (6S) -1- (2,2,6-trimethylcyclohexyl) -5-hexen-3-ol And Formulation B containing (6S) -1- (2,2,6-trimethylcyclohexyl) hexane-3-ol, which is a known fragrance that is similar to the compound of the present invention. A shampoo using the formula A and the formula B was subjected to a palatability test by a specialized panel of 20 persons. As a result, 18 persons answered that the one using the prescription A had a better fragrance, was fresher and warmer, and the whole was better than the one using the prescription B. Regarding the residual scent of hair after shampooing, 19 people answered that they liked it because it had a strong scent, was warm and had a good scent balance.

[0050]

Industrial Applicability The present invention provides an industrially useful racemic or optically active (6S) -1- (2,2,6-trimethylcyclohexyl) -5-hexen-3-ol and a fragrance containing the same as an active ingredient Is provided. That is, racemic or optically active (6S) -1- (2,2,6-trimethylcyclohexyl) -5-hexen-3-ol is excellent in properties as a fragrance, whereby racemic or optically active (6S) -1- (2,2,6-trimethylcyclohexyl) -5-hexen-3-ol is excellent.
S) -1- (2,2,6-trimethylcyclohexyl)
-5-Hexen-3-ol and fragrances containing it as an active ingredient are used in various fields of cosmetics and health and hygiene materials.

────────────────────────────────────────────────── ─── Continued on the front page (58) Fields investigated (Int. Cl. ⁷ , DB name) C07C 33/14 A61K 7/46 C11B 9/00 CA (STN) CAOLD (STN) MARPAT (STN) REGISTRY (STN )

Claims (4)

(57) [Claims] (1) Formula (1) 1- (2,2,6-trimethylcyclohexyl) -5-hexen-3-ol represented by the formula: (2) Formula (2) (6S) -1- (2,2,6-trimethylcyclohexyl) -5-hexen-3-ol represented by the formula: 3. A fragrance composition comprising 1- (2,2,6-trimethylcyclohexyl) -5-hexen-3-ol according to claim 1. 4. The optical activity (6S) -1- according to claim 2.
A fragrance composition comprising (2,2,6-trimethylcyclohexyl) -5-hexene-3-ol.