JP4358082B2 - PROPANON DERIVATIVE, PROCESS FOR PRODUCING THE SAME AND PERFUME COMPOSITION CONTAINING THE SAME - Google Patents

Description

  The present invention relates to a novel propanone derivative, a process for producing the same, and a fragrance composition containing the same.

A compound of the present invention, 1- (2,5,6,6- tetramethyl-1-cyclohexen-1-yl) propan-2-one (hereinafter referred to as β body.), 1- ( 2,5,6,6-tetramethyl-2-cyclohexen-1-yl) propan-2-one (hereinafter referred to as α form ) has not been reported to have been isolated or synthesized so far. The fragrance and flavor characteristics were not known at all. Further , 1- (6-methylene-2,2,3-trimethylcyclohexane-1-yl) propan-2-one (hereinafter referred to as γ-form) has been already synthesized in Non-Patent Document 1. However, there has been no report on the aroma and flavor characteristics of this compound so far, and it has never been known that it has utility as a fragrance.

  On the other hand, as a compound having the same skeleton as the compound of the present invention, 1- (2,6,6-trimethyl-2-cyclohexen-1-yl) propan-2-one is described in Patent Document 1, and floral. , Fruity-like, woody-like, iris-like, and violet-like fragrance-flavoring characteristics. In addition, 1- (6,6-dimethyl-2-methylenecyclohexane-1-yl) propan-2-one is described in Patent Document 2, and herbal-like, green-like, and floral-like with a fresh pine needle tone. , Fruity-like, woody-like, iris-like, and violet-like fragrance-flavoring characteristics, which are described as being useful.

JP-A-10-195014 Japanese Patent Laid-Open No. 10-226664 Julia, S .; , Julia, M .; Linares, H .; , And Blondel, J. et al. C. Bull. Soc. Chim. France, 1952-1959 (1962).

  In recent years, consumer preferences have been diversified, and accordingly, foods and cosmetics having various flavors have been manufactured. In response to these diversifications, the development of a new and unique type of unique fragrance material that has not been able to meet the demand for food fragrances and cosmetic fragrances with various fragrances using conventional fragrance compounds alone. Is strongly demanded.

Therefore, the present inventors have intensively studied to solve the above-mentioned problems. As a result, a novel compound of claim 1 and a compound of claim 3 of the present invention has a unique aroma flavor characteristics unprecedented that can resolve requests problems described above, found to be very useful as perfume compounds The present invention has been completed.
Thus, the present invention relates to 1- (2,5,6,6-tetramethyl-1-cyclohexen-1-yl) propan-2-one or 1- (2,5,6,6-tetramethyl-2-cyclohexene -1-yl) propan-2-one .
The present invention also provides the following formula (1a)

In represented by cis-1- (2,5,6,6- tetramethyl-2-cyclohexen-1-yl) propan-2-on-or formula (1b)

Trans-1- (2,5,6,6-tetramethyl-2-cyclohexen-1-yl) propan-2-one represented by the formula:
Furthermore, the present invention relates to 1- (2,5,6,6-tetramethyl-1-cyclohexen-1-yl) propan-2-one, 1- (2,5,6,6-tetramethyl-2-cyclohexene A propanone derivative selected from -1-yl) propan-2-one and 1- (6-methylene-2,2,3-trimethylcyclohexane-1-yl) propan-2-one as an active ingredient. A featured fragrance composition can be provided.
The present invention also provides the cis-1- (2,5,6,6-tetramethyl-2-cyclohexen-1-yl) propan-2-one (1a) and / or trans-1- (2,5 , 6,6-tetramethyl-2-cyclohexen-1-yl) propan-2-one (1b) as an active ingredient can be provided.

Help Ropanon derivatives provided by the present invention, each has a characteristic aroma flavor characteristics, by using these one or two or more in suitably food flavor or fragrance or cosmetic fragrance, a conventional It is possible to provide a characteristic fragrance composition imparted with no preferred natural feeling.

The γ- form of the present invention is obtained by subjecting an allyl vinyl ether type compound synthesized from 3,3,4-trimethyl-1-cyclohexenemethanol and isopropenyl methyl ether to a Claisen rearrangement reaction to give a geometry having a cis / trans ratio of about 1/9. It can be synthesized as a mixture of isomers. The 3,3,4-trimethyl-1-cyclohexene methanol used here is a commercially available 2,3-dimethylphenol as a raw material (Kawanobe. T., Kogami. K., Hayashi. K., Matsui). M., Agric. Biol. Chem., 51, 791 (1987)).

Further, the prior SL γ body when isomerized in the presence of an acid, can be obtained propanone derivative according to claim 1. Here, the acid to be used is not particularly limited. For example, inorganic acids such as phosphoric acid, sulfuric acid and hydrochloric acid; organic acids such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, acetic acid and oxalic acid; aluminum chloride, Examples include Lewis acids such as trifluoroborane ether complexes and zinc chloride; acidic ion exchange resins and the like. As usage-amount of an acid, 0.001-20 mol% is good with respect to (gamma) body which is a raw material, and 0.1-10 mol% is more preferable. In this reaction, a solvent may or may not be used. When a solvent is used, water, alcohols, ethers, ketones, esters, hydrocarbons, halogen compounds, etc. are used as the solvent. The amount used thereof is preferably 0.5 to 10 times by weight, particularly preferably 1 to 5 times by weight based on the raw material. Moreover, the above-mentioned acid can also be used as a solvent, and the amount used in this case is preferably 0.5 to 10 times by weight, particularly preferably 1 to 5 times by weight based on the raw material. Further, the temperature at the time of carrying out this reaction is not particularly limited, but it is preferably −20 to 60 ° C. in view of slow progress under low temperature and side reactions such as polymerization under high temperature. ° C is more preferred. The propanone derivative thus obtained is a mixture of a β-form having a double bond at the 1-position in the cyclohexane ring and an α-form having a double bond at the 2-position in the cyclohexane ring. When the raw material γ-form used is a geometric isomer mixture, the obtained α-form is also obtained as a mixture of geometric isomers. The isomers can be isolated by treating the resulting isomer mixture with a method such as column chromatography or preparative gas chromatography, if desired. In addition, a hydrogenated product can be obtained by performing a catalytic hydrogenation reaction using one or more of the α-form, β-form, and γ-form described above as raw materials.

  The α-form, β-form, γ-form, and hydrogenated form that can be prepared in this way can be used as they are after the reaction, but can be used after purification by a method such as distillation or column chromatography, if desired. it can. Moreover, although these compounds can also be used independently, they can also be used as a mixture.

  The aroma characteristics of the α-form, β-form, γ-form and hydrogenated form of the product of the present invention are as shown in the following table.

  The compound of the present invention has its own unique fragrance, but by adding the compound of the present invention to a fragrance composition comprising a known fragrance component, while maintaining harmony with the fragrance composition, It is extremely effective for improvement and enhancement.

The blending amount of one kind or a mixture of two or more of the α-form, β-form, γ-form and hydrogenated form of claim 1 and claim 3 used in the perfume composition of the present invention, Although it varies depending on the use of the blended fragrance, it is generally 0.01 to 50% by weight, preferably 0.01 to 30% by weight in the fragrance composition.

  The ratio of geometric isomers for each of the α-form and the γ-form used in the fragrance composition of the present invention varies depending on the intended fragrance, the use of the blended fragrance, etc., but cis / trans = 0/100 to 50/50 is preferable, and cis / trans = 0/100 to 20/80 is particularly preferable.

  Other examples of the fragrance compound used when preparing the fragrance composition using the compound of the present invention include, for example, Perfume Chemical Directory, 1, 2, 3 [Osamu Okuda, Yodogawa Shoten Publishing], Perfume and flavor Chemicals, 1, 2 [Steffen Arctander], synthetic fragrances [Genji Motoichi, Kagaku Kogyo Nippo Publishing] and the like.

  By using the fragrance composition of the present invention in food and drink products, it is possible to provide a unique product that gives the product a characteristic fragrance characteristic and can satisfy diversifying consumer needs. Examples of the food and drink include beverages, frozen confectionery, desserts, confectionery, seasonings and the like. By using the fragrance composition of the present invention in cosmetics, it is possible to provide a unique product that can impart the characteristic fragrance characteristics to the product and satisfy diversifying consumer needs. Examples of the cosmetics include perfume, eau de cologne, lotion, hair dye, soap, body soap, shampoo, rinse, treatment, shaving cream, detergent, bleach, fragrance, perfume oil and incense.

  Hereinafter, the present invention will be described in detail with reference to Examples, Reference Examples and Comparative Examples, but the present invention is not limited thereto.

Reference Example 1: Synthesis of 1- (6-methylene-2,2,3-trimethylcyclohexane-1-yl) propan-2-one 3,3,4-trimethyl-1-cyclohexenemethanol in a 1 L pressure vessel (46.2 g, 0.30 mol), isopropenyl methyl ether (216.0 g, 3.0 mol), and pivalic acid (6.1 g, 0.06 mol) are reacted at 180 ° C. for 5 hours in a nitrogen atmosphere. The reaction solution was concentrated with an evaporator, and the resulting crude product (88.0 g) was distilled under reduced pressure to give 1- (6-methylene-2,2,3-trimethylcyclohexane-1-yl) propane-2. -On (38.5 g) was obtained. Yield 66%.
As a result of analysis, the obtained compound was a geometric isomer mixture of cis / trans = 10/90.
(Physical property data)
1- (6-methylene-2,2,3-trimethylcyclohexane-1-yl) propan-2-one <br/> aroma: woody, scent ^NMR (1 H with freshness in camphor-like, 400 MHz, CDCl ₃ ): 0.81 (s, 3H); 0.82 (d, 3H, J = 6.8 Hz); 0.88 (s, 3H); 1.20-1.27 (m, 1H); 50-1.58 (m, 2H); 2.10 (s, 3H); 2.10-2. 21 (m, 2H); 2.42-2.60 (m, 3H); 4.58 ( s, 1H); 4.69 (s, 1H) δ ppm
NMR ( ¹³ C, 100 MHz, CDCl ₃ ): 15.59; 21.46; 26.40; 30.23; 30.84; 31.61; 35.29; 36.64; 43.01; 109.96; 148.42; 208.89 δ ppm
MS: 194 (M ⁺ , 1), 179 (17), 161 (6), 151 (13), 136 (66), 121 (89), 109 (39), 95 (57), 83 (54), 77 (13), 67 (24), 55 (44), 43 (100), 27 (6).
* Spectral data are for the major isomers.

Example 1: 1- (2,5,6,6-tetramethyl-2-cyclohexen-1-yl) propan-2-one and 1- (2,5,6,6-tetramethyl-1-cyclohexene- Synthesis of 1-yl) propan-2-one mixture A 30 mL reaction flask is charged with 85% phosphoric acid (9.7 g) and stirred under ice-water cooling. Here, 1- (6-methylene-2,2,3-trimethylcyclohexane-1-yl) propan-2-one (9.7 g, 50.0 mmol) obtained in Reference Example 1 was added at 10 ± 5 ° C. / Add dropwise at 0.5 hr and stir for 6 hr. After water addition, ether extraction, sodium bicarbonate washing and brine washing are performed, followed by drying and concentration to obtain a residue (9.7 g). The fraction (6.8 g) obtained by distillation was purified by silica gel column chromatography to obtain the desired isomer mixture (4.7 g). Yield 48%.

  As a result of analysis, the obtained mixture was found to be 39% 1- (2,5,6,6-tetramethyl-2-cyclohexen-1-yl) propan-2-one, 1- (2,5,6,6 -Tetramethyl-1-cyclohexen-1-yl) propan-2-one is a mixture of 56% and 1- (2,5,6,6-tetramethyl-2-cyclohexen-1-yl) propan-2 For -one, it was a geometric isomer mixture of cis / trans = 12/88.

  The obtained mixture was further fractionated by silica gel column chromatography to give regioisomer 1- (2,5,6,6-tetramethyl-2-cyclohexen-1-yl) propan-2-one. And 1- (2,5,6,6-tetramethyl-1-cyclohexen-1-yl) propan-2-one were isolated. Furthermore, 1- (2,5,6,6-tetramethyl-2-cyclohexen-1-yl) propan-2-one is fractionated by preparative gas chromatography to obtain a cis isomer that is a geometric isomer. And the trans isomer was isolated.

(Physical property data)
Trans-1- (2,5,6,6-tetramethyl-2-cyclohexen-1-yl) propan-2-one Odor: Damascon-like fruity, floral and fresh scent NMR ( ¹ H, 400 MHz, CDCl ₃ ): 0.76 (s, 3H); 0.79 (s, 3H); 0.82 (d, 3H, J = 6.8 Hz); 1.42-1.56 (m 1.59 (d, 3H, J = 1.5 Hz); 1.56-1.66 (m, 1H); 1.92-2.02 (m, 1H); 2.17 (s) , 3H); 2.23 (dd, J = 17.7, 4.0 Hz, 1H); 2.32-2.34 (m, 1H); 2.62 (dd, J = 17.7, 6. 5 Hz, 1 H); 5.27 (brs, 1 H) δ ppm
_{^{NMR (13 C, 100MHz, CDCl}} 3): 15.31; 20.94; 22.87; 25.23; 30.30; 31.90; 32.48; 34.91; 45.63; 45.82 121.20; 136.34; 208.82 δ ppm
MS: 194 (M ⁺ , 2), 136 (63), 121 (100), 109 (10), 95 (9), 81 (23), 70 (10), 55 (13), 43 (54).
Cis-1- (2,5,6,6-tetramethyl-2-cyclohexen-1-yl) propan-2-one Odor: Methyl ionone-like aroma NMR (< ¹ > H, 400 MHz with slight ozone note ) , CDCl ₃ ): 0.62 (s, 3H); 0.85 (d, 3H, J = 6.6 Hz) 0.88 (s, 3H); 1.47-1.48 (m, 3H); 1.49-1.58 (m, 1H); 1.58-1.65 (m, 1H); 1.84-1.93 (m, 1H); 2.21 (s, 3H); 45 (d, J = 6.0 Hz, 2H); 2.59-2.65 (m, 1H); 5.36 (brs, 1H) δppm
_{^{NMR (13 C, 100MHz, CDCl}} 3): 14.62; 15.92; 22.19; 26.11; 30.14; 31.84; 35.12; 38.17; 43.27; 44.68 122.26; 134.73; 208.93 δ ppm
MS: 194 (M ^<+> , 2), 136 (70), 121 (72), 109 (21), 95 (16), 81 (39), 70 (18), 55 (25), 43 (100).
1- (2,5,6,6- tetramethyl-1-cyclohexen-1-yl) propan-2-one <br/> aroma: camphor, fragrant ^NMR (1 H with herbal sense borneol-like, 400 MHz, CDCl ₃ ): 0.79 (s, 3H); 0.90 (d, 3H, J = 6.8 Hz); 0.92 (s, 3H); 1.35 to 1.45 (m, 1H); 1.5-1.60 (m, 2H); 1.52 (s, 3H); 1.90-2.00 (m, 1H); 2.05-2.25 (m, 1H); 15 (s, 3H); 3.12 (s, 2H) δppm
_{^{NMR (13 C, 100MHz, CDCl}} 3): 16.65; 20.67; 21.53; 26.54; 27.15; 29.23; 31.61; 37.86; 39.00; 44.37 130.74; 131.40; 207.87 δppm
MS: 194 (M ⁺ , 14), 179 (18), 161 (5), 151 (15), 137 (29), 121 (100), 109 (49), 95 (47), 81 (18), 67 (17), 55 (14), 43 (50). .

Example 2: Synthesis of 1- (2,5,6,6-tetramethylcyclohexane-1-yl) propan-2-one 1- (6-methylene-2 obtained in Reference Example 1 in a 50 mL pressure vessel , 2,3-trimethylcyclohexane-1-yl) propan-2-one (2.9 g, 15.0 mmol), 95% ethanol (15 mL) and 5% Pd-C (0.3 g), and after nitrogen substitution The reaction was conducted at 100 ° C. under a hydrogen pressure of 0.5 MPa, the catalyst was filtered, concentrated and distilled under reduced pressure to obtain a fraction (2.6 g) containing about 85% hydride. Yield 87%.
(Physical property data)
1- (2,5,6,6-tetramethylcyclohexane-1-yl) propan-2-one Odor: Woody, camphor-like amber, scented with NMR undertone ( ¹ H, 400 MHz, CDCl ₃ ): 0.52 to 1.00 (m, 12H); 1.20 to 1.65 (m, 6H); 1.55 to 2.02 (m, 1H); 2.02-2 .50 (m, 2H); 2.16 (s, 3H) δ ppm
_{^{NMR (13 C, 100MHz, CDCl}} 3): 14.86; 20.90; 23.33; 27.90; 28.77; 29.85; 30.04; 34.60; 35.78; 39.97 40.80; 44.72; 121.03 δppm
MS: 196 (M ⁺ , 5), 138 (59), 123 (92), 111 (30), 95 (23), 83 (22), 69 (27), 55 (47), 43 (100), 29 (6).
* Spectral data are for the major isomers.

Example 3 Preparation of Fresh Citrus Type Perfume Using 1- (2,5,6,6-tetramethyl-2-cyclohexen-1-yl) propan-2-one produced in Example 1, described below A fresh citrus type fragrance composition was prepared according to the following formula. Similarly, as Comparative Example 1, a fragrance composition using α-damascon instead of 1- (2,5,6,6-tetramethyl-2-cyclohexen-1-yl) propan-2-one was prepared.

About Example 3 and the comparative example 1, the fragrance evaluation by 10 expert panelists was performed. The evaluation method is as follows.
(Evaluation methods)
Strength (5) Strong, (4) Slightly strong, (3) Neither, (2) Slightly weak, (1) Weak, 5 levels, Diffusivity, (5) Good, (4) Slightly good , (3) General, (2) Slightly bad, (1) Bad, evaluated in five stages, and the arithmetic average of the scores of each panel was taken as the overall score, and the evaluation results are shown in Table 3.

  As described above, the evaluation result that Example 3 using the product of the present invention is more diffusive and has a fresh citrus-like aroma is preferred, which is preferable.

Examples 4, 5, 6: Preparation of herbal floral type fragrance 1- (6-methylene-2,2,3-trimethylcyclohexane-1-yl) propan-2-one produced in Reference Example 1, Example 1 1- (2,5,6,6-tetramethyl-1-cyclohexen-1-yl) propan-2-one prepared in 1 and 1- (2,5,6,6-tetramethyl prepared in Example 2 A herbal floral type fragrance composition was prepared with the following formulation using cyclohexane-1-yl) propan-2-one. Similarly, a fragrance composition using camphor instead of the product of the present invention used in Examples 4, 5 and 6 as Comparative Example 2 was prepared.

For Examples 4, 5, and 6 and Comparative Example 2, fragrance evaluation was performed by 10 expert panelists in the same manner as in the previous period, and the evaluation results are shown in Table 5.

  As described above, all of Examples 4, 5, and 6 using the product of the present invention were evaluated to be preferable because the fresh herbal floral-like fragrance having a higher diffusibility than Comparative Example 2 was enhanced.

Example 7: Perfume Example to Shampoo Each of the perfume compositions of Examples 3, 4, 5, 6 and Comparative Examples 1 and 2 was perfume 0.3% each to a shampoo base having the following prescription to give a shampoo composition. Was prepared.

Each of the obtained shampoo compositions was subjected to fragrance evaluation by 10 professional panelists, and shampoo fragrance evaluations using the fragrance compositions of Example 3 and Comparative Example 1 are shown in Table 7, and Examples 4, 5, Table 8 shows the fragrance evaluation of shampoos using the fragrance compositions of No. 6 and Comparative Example 2. The evaluation method is as follows.
(Evaluation methods)
Strength, (5) Strong, (4) Slightly strong, (3) Neither, (2) Slightly weak, (1) Slightly weak, (5) Good, (4) Slightly good , (3) General, (2) Slightly bad, (1) Bad, and the arithmetic average of the scores of each panel was used as the overall score.

  As described above, the evaluation result that Example 3 using the product of the present invention is preferable because it has a higher palatability and a fresh citrus-like aroma is preferred.

  As described above, all of Examples 4, 5, and 6 using the product of the present invention had an evaluation result that a fresh herbal floral-like aroma having higher palatability than Comparative Example 2 was enhanced and preferable.

Claims (4)

1- (2,5,6,6-tetramethyl-1-cyclohexen-1-yl) propan-2-one or 1- (2,5,6,6-tetramethyl-2-cyclohexen-1-yl) Propan-2-one. The following formula (1a)

In represented by cis-1- (2,5,6,6- tetramethyl-2-cyclohexen-1-yl) propan-2-on-or formula (1b)

Trans-1- (2,5,6,6-tetramethyl-2-cyclohexen-1-yl) propan-2-one represented by: 1- (2,5,6,6-tetramethyl-1-cyclohexen-1-yl) propan-2-one, 1- (2,5,6,6-tetramethyl-2-cyclohexen-1-yl) A fragrance composition comprising a propanone derivative selected from propan-2-one and 1- (6-methylene-2,2,3-trimethylcyclohexane-1-yl) propan-2-one as an active ingredient object. The cis-1- (2,5,6,6-tetramethyl-2-cyclohexen-1-yl) propan-2-one (1a) and / or trans-1- (2,5,6) according to claim 2. , 6-tetramethyl-2-cyclohexen-1-yl) propan-2-one (1b) as an active ingredient.