JPH05286878A - 1-@(3754/24)2,2,6-trimethylcyclohexyl)-5-hexen-3-ol and perfume composition containing the same - Google Patents

Abstract

PURPOSE:To obtain a new compound useful for perfume, etc., having sweet musk-like and keen amber-like fragrance, having excellent stability, safety, aroma retention, diffusion and palatability. CONSTITUTION:1-(2,2,6-Trimethylcyclohexyl)-5-hexen-3-ol of formula I. The compound of formula I is obtained by reacting 3-(2,2,6-trimethylcyclohexyl) propanal of formula II with an allyl magnesium halide of formula III.

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 is amber.
It is known as a very useful fragrance composition having such a fragrance (Japanese Patent Laid-Open No. 54-117439), and detailed reports have been made on its geometrical isomers and optically active isomers (Japanese Patent Laid-Open No. 59-176207). Japanese Patent Laid-Open No. 60-66
75, JP 61-191636, JP 62-70314, JP 4-21642, European Patent Application Publication No. 457022, HELV.
ETICA CHIMICA ACTA 68 (19
85) 1961-1985).

However, 1- (2,2,6-trimethylcyclohexyl) -having a double bond at the end 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 completely different due to a difference in functional groups or a slight difference in structure, or is a new fragrance having a different fragrance quality. Therefore, it is very important to study the fragrance of various compounds in order to provide a new fragrance material corresponding to various uses and tastes.

In addition, recently, those having stability and safety in addition to fragrance are required. Therefore, an object of the present invention is to provide a new fragrance material to meet the above demand.

[0006]

Under such circumstances, the inventors of the present invention have conducted diligent research and as a result, the following formula (1), which has not been synthesized conventionally, is obtained.

[0007]

[Chemical 3] It has been found that the novel compound 1- (2,2,6-trimethylcyclohexyl) -5-hexene-3-ol represented by has a useful fragrance and is excellent in stability and safety. Completed the invention.

That is, the present invention is a novel compound 1- (2,2,
6-trimethylcyclohexyl) -5-hexene-3-
The present invention provides an oil and a fragrance composition containing the same.

Further, the present inventors have the following equation (2):

[0010]

[Chemical 4] A new compound represented by 1- (2,2,6-trimethylcyclohexyl) -5-hexene-3-ol (6S)
It was also found that the-body is a useful fragrance material having an aroma quality and a stronger aroma different from that of the (6R) -body or the racemic body.

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

[0012]

[Chemical 5] (In the formula, X represents a halogen atom.)

That is, 1 is easily obtained by reacting 3- (2,2,6-trimethylcyclohexyl) propanal (3) with allylmagnesium halide (4).
It is possible to obtain-(2,2,6-trimethylcyclohexyl) -5-hexene-3-ol (1).

Further, by using the (6S) -form or (6R) -form of 3- (2,2,6-trimethylcyclohexyl) propanal as a starting material, the optically active (6
S)-or (6R) -1- (2,2,6-trimethylcyclohexyl) -5-hexene-3-ol can be obtained.

The starting material 3- (2,2,6-trimethylcyclohexyl) propanal (3) is described in JP-A-4-21.
For example, it can be synthesized according to the following reaction route 1 as disclosed in Japanese Patent No. 649.

[0016]

[Chemical 6] (In the formula, R ¹ represents a hydrogen atom or a methyl group, Ac represents an acetyl group, Et represents an ethyl group, and a wavy line represents a trans position and / or a cis position.)

That is, a compound (5) typified by citronellal is reacted with acetic anhydride to give an enol acetate (6), which is then subjected to a cyclization reaction with a phosphoric acid catalyst to give dihydrocyclocitral. Get Le (7).

By reacting this dihydrocyclocitral (7) with phosphonoacetic acid triethyl ester (8), 3- (2,2,6-trimethylcyclohexyl) is obtained.
Ethyl acrylate (9) was obtained and reduced with a reducing agent such as sodium borohydride to give 3- (2,2,6-
(Trimethylcyclohexyl) -2-propen-1-o-
To give 3- (2,2,6-trimethylcyclohexyl) propanal (3) by hydrogenating the compound (10) with palladium carbon as a catalyst.

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

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

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

Further, its optically active substance (6S)-
1- (2,2,6-trimethylcyclohexyl) -5-
It was also found that hexene-3-ol has an aroma different from its (6R) -form or racemate and a sharper and more intense aroma. In other words, the (6S) -body has a sweet musk-like and sharp umber-like aroma, whereas (6R)-
It was found that the body had basically no musk, umber-flavor, but a weak, woody odor with some mildness.

The racemic fragrance prepared by mixing both antipodes in a ratio of 1: 1 has a weaker fragrance intensity than the (6S) -form, and Woody and Musuki have a slight lack of sharpness. -,
It was found to have an amber scent.

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

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

Thus, a fresh, highly palatable and highly palatable product containing 1- (2,2,6-trimethylcyclohexyl) -5-hexene-3-ol of the present invention is provided. It is possible to provide a scent-imparting or fragrance-improving / reinforcing agent, and to provide fragrances, cosmetics, health and hygiene materials, pharmaceuticals, etc., which are contained as scent components.

That is, shampoo, rinse, perfume,
Colons, hair-tonics, hair-creams, poma-
De other hair cosmetic base, white powder, lipstick, other cosmetic base and cosmetic detergent, soap, dishwashing detergent, laundry detergent,
Softeners, disinfecting detergents, deodorant detergents, indoor air fresheners, furniture care, disinfectants, insecticides, bleaches, other various sanitary detergents, toothpaste, mouthwash, toilet paper. -The commercial value can be increased by adding an appropriate amount capable of imparting a unique aroma to a flavoring agent or the like for facilitating taking the medicine.

[0028]

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

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

Synthesis Example 1 Synthesis of (6S) -1- (2,2,6-trimethylcyclohexyl) -5-hexene-3-ol; Stirrer, thermometer, dropping funnel, condenser Into a 1-liter four-necked flask, under a nitrogen atmosphere, 150 ml of allylmagnesium bromide (1 mol / l diethyl ether solution) and 90 ml of diethyl ether were charged, and (6S) -3- (2,2)
2,6-Trimethylcyclohexyl) propanal 13
g diethyl ether (90 ml) solution at 20-25 ° C.
The mixture was added dropwise at 1 hour over 1 hour, and the mixture was stirred for 4 hours at the same temperature to complete the reaction. The reaction solution was treated by a conventional method, and 21 g of the concentrated oil obtained was purified by silica gel column chromatography to obtain (6S) -1- (2,2,6-trimethylcyclohexyl) -5-hexene-3-o-. 9
g was obtained. [Α] ²⁵ _D + 14.34 ° Gas chromatographic purity was 95/5 in terms of the ratio of trans isomer and cis isomer represented by the following formula.

[0031]

[Chemical 7]

The obtained (6S) -1- (2,2,6-trimethylcyclohexyl) -5-hexene-3-ol was separated and purified by gas chromatography to have a purity of 99.5.
The data of% are shown below. Trans IR (νmax, cm ^-1 ); 3350,3070,2920,2870,2840,1640,14
75,1460,1440,1385,1365 ¹ H-NMR (400MHz, CDCl _3, δ); 0.55 (m, 1H), 0.79 (s, 3H), 0.
87〜0.95 (7H), 1.18 (m, 1H), 1.31〜1.47 (6H), 1.54〜1.59
(4H), 2.15 (m, 1H), 1.94 (m, 1H), 3.60 (m, 1H), 5.12 ~ 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-hexene-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 (6R ) -1- (2,2,6-trimethylcyclohexyl) -5-hexene-3-ol
g was obtained. [Α] ²⁵ _D -14.33 ° Gas chromatographic purity was 95.3 / 4.7 in the ratio of trans isomer and cis isomer represented by the following formula.

[0034]

[Chemical 8]

Example 1 Fragrance composition for fuser-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 in a ratio of 1: 1 to prepare a racemic 1- (2,2,6 -Trimethylcyclohexyl) -5-hexene-3-ol was used to prepare a fuser-like fragrance composition for a fiber softener having a high palatability according to the formulation shown in Table 1.

[0036]

Table 1 Formulation (parts by weight) Coumarin 50 Ethylene brushlate 200 Patchouli oil 30 Dimethylbenzyl methanol 100 n-Tetradecylaldehyde 10 2,4-Di-tert-butylcyclohexanone 100 Benzyl salicylate 200 Lavandin oil 50 Amylcinnamic aldehyde 100 Cyclamenaldehyde 100 Acetyl cedrene 40 1- (2,2,6-trimethylcyclohexyl) -5-hexene-3-ol racemate 20 1000

Example 2 Flouralbuque tone perfume; synthesized in Synthesis Example 1 (6S)
-1- (2,2,6-trimethylcyclohexyl) -5
-Floralbue having highly palatable violet-like characteristics according to the formulation of Table 2 using hexene-3-ol-
Ketone perfume was prepared.

[0038]

Table 2 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 -Tetramethyloctaline 130 α-Damascon 10 (6S) -1- (2,2,6-Trimethylcyclohexyl) -5-hexene-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 scented to soap, sealed in a glass container and placed in a 50 ° C incubator for a stability test for 2 months. I went. As a result of investigating changes in aroma quality by five panelists, it was found that there was no decomposition odor and no change and deterioration of aroma were observed, and it was stable over time. Further, in order to examine the stability to sunlight, the above soap was placed in the sunlight at room temperature for one month, and a color burn test was conducted. As a result, no color burn was observed.

Test Example 2 Stability test in acidic solution: (6S) -1- (2,2,6-trimethylcyclohexyl) -5-hexene-3-ol synthesized in Synthesis Example 1 having the following formulation An acetic acid acid solution (pH 3) was prepared. Method (g) Acetic acid 1 Triethyl citrate 50 (6S) -1- (2,2,6-Trimethylcyclohexyl) -5-hexene-3-ol 10 n-Dodecane (internal standard) 1

This solution was placed in a 100 ml glass container and stored in a thermostatic chamber at 50 ° C. for 2 months, and then the change in composition was examined by gas chromatography. As a result, no change was observed and (6S) -1- (2,2,6-trimethylcyclohexyl) -5-hexene-3-ol was found to be stable under acidic acetic acid (pH 3).

Test Example 3 Stability test in basic solution; (6S) -1- (2,2,6-trimethylcyclohexyl) -5-hexene-3-o- synthesized in Synthesis Example 1 having the following formulation. A basic solution of pH 10 was prepared. Method (g) Triethylamine 1 Triethylcitrate 50 (6S) -1- (2,2,6-Trimethylcyclohexyl) -5-hexene-3-ol 5 Water 0.5 Methanol 10 n-dodecane (Internal standard) 1

This solution was placed in a 100 ml glass container and stored in a thermostatic chamber at 50 ° C. for 2 months, and then the change in composition was examined by gas chromatography. As a result, no change was observed and (6S) -1- (2,2,6-trimethylcyclohexyl) -5-hexene-3-ol was found to be stable under amine basicity (pH 10). ..

Test Example 4 Masking and stability test using enzyme-containing bleaching agent: An enzyme-containing bleaching agent composition was prepared according to the following formulation. Method (parts by weight) Sodium percarbonate 93.7 Enzyme (Alcalase 29T: manufactured by Novoingstry) 1.0 Anhydrous calcium sulfate 5.0 (6S) -1- (2,2,6-trimethylcyclohexyl) ) -5-Hexen-3-ol 50% ethanol solution 0.3 100

Further, based on the above prescription, (6
S) -1- (2,2,6-trimethylcyclohexyl)
50% ethanol solution of (6R) -1- (2,2,6-trimethylcyclohexyl) -5-hexene-3-ol instead of a 50% ethanol solution of 5-hexene-3-ol -Enzyme-containing bleach prepared by each formulation using a solution and a racemate (1: 1 mixture of (6S) -form obtained in Synthesis Example 1 and (6R) -form obtained in Synthesis Example 2) Comparative tests were performed on the compositions. That is, the above bleaching agent composition was sealed in a plastic container bottle, placed in a thermostatic chamber and stored at 40 ° C. for 30 days, and the change in enzymatic odor was examined. Table 3 shows the results determined by 10 specialized panelists. From the above results, the bleaching agent using the (6S) -form completely masked the enzymatic odor, and the bleaching agent using the racemic form was almost satisfactory. Also, there was no change in fragrance quality in both cases.

[0046]

[Table 3] Table 3 1- (2,2,6-trimethyl Enzymatic odor Enzymatic odor Enzymatic odor Cyclohexyl) -5- Quite slightly hexen-3-ol Not felt Feeled (6S) -body 10 0 people 0 people (6R) -body 0 people 4 6 people 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, sensitization test, primary skin irritation test, phototoxicity test and mutagenicity test were conducted.
Both were negative and were found to be extremely safe.

Comparative Examination Example 1 A green floral tone shampoo fragrance 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 Brassulate 250 250 Methyl Dihydrojasmonate 70 70 70 p-isobutyl-α-methyldihydrocinnamaldehyde 200 200 l-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-cyclohexenecarbaldehyde 10 10 Undecylenaldehyde 55 5 Lime oil 20 20 cis-3-hexenyl propionate 5 5 4-p-hydroxyphenylbutan-2-one (50% dipropylene glycol solution) 20 20 Lemon oil 40 40 Tetrahydrolinalol 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 containing (6S) -1- (2,2,6-trimethylcyclohexyl) -5-hexene-3-ol of the compound of the present invention , And a formulation B containing (6S) -1- (2,2,6-trimethylcyclohexyl) hexane-3-ol, which is a known fragrance that is a compound similar to the compound of the present invention. With respect to the shampoos using the formulations A and B, the palatability test was performed by 20 expert panelists. As a result, 18 people answered that the one using the prescription A had a better fragrance, was fresher and warmer, and had a better wholeness than the one using the prescription B. Regarding the residual scent of hair after shampooing, 19 people said that they liked the strong scent, the warmth, and the good scent balance.

[0050]

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

Claims (4)

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