JPH0539260A - 6-cyclohexyl-2-methyl-4-or-5-hepten-3-one and perfume composition containing the same compound - Google Patents

Abstract

PURPOSE:To obtain a new readily producible 6-cyclohexyl-2-methyl-4-or-5- heptene-3-one extremely important as perfume, having a citrus, fruity or lactone- like fragrance. CONSTITUTION:6-Cyclohexyl-2-methyl-4-or-5-hepten-3-one shown by formula I (broken line is double bond at either 4-position or 5-position). The compound shown by formula I, for example, is obtained by condensing 2-cyclohexylpropanal with 3-methyl-2-butanone.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel aromatic compound and a fragrance composition containing the compound.

[0002]

2. Description of the Related Art Conventionally, the problems to be solved by the invention
Many useful perfume compounds are known for derivatives such as acetals of aromatic aldehydes. Less well known are those having a corresponding saturated cyclohexyl group. For example, Okuda Osamu, "Perfume Chemistry Guide II", Hirokawa Shoten, page 1019, the acetal part describes an acetal compound having about 50 phenyl groups, whereas an acetal having a cyclohexyl group is described. Only one is listed. On the other hand, the present inventors have found that a 2-cyclohexylpropanal derivative, which is a compound having a cyclohexyl group, is useful as a fragrance, and previously reported it (JP-A-2-67241).
Publication).

By the way, the fragrance of a compound is completely different due to a slight difference in structure, and its properties such as retention and volatility are generally changed.
It is extremely important to synthesize various compounds and investigate their odors in order to obtain new fragrances.

[0004]

Means for Solving the Problems The present inventors
Focusing on the ease of producing a cyclohexylpropanal derivative, the present inventors have conducted intensive studies to obtain a compound useful as a fragrance from the compound as a raw material. As a result, the compound 6-cyclohexyl-2-methyl-4 or 5-to be described later is obtained.
The present invention has been completed by finding that hepten-3-one has a citrus-like, fruit-like, lactone-like odor and is extremely important as a fragrance.

That is, the present invention provides 6-cyclohexyl-2-methyl-4 or 5-hepten-3-one represented by the following formula (1).

[0006]

[Chemical 3]

(In the formula, the broken line indicates that there is a double bond at either the 4-position or the 5-position.)

Further, the present invention provides a fragrance composition characterized by containing 6-cyclohexyl-2-methyl-4 or 5-hepten-3-one represented by the above formula (1). is there.

The compound (1) of the present invention is produced, for example, by condensing 2-cyclohexylpropanal with 3-methyl-2-butanone according to the following reaction formula.

[0010]

[Chemical 4]

(In the formula, the broken line indicates that there is a double bond at either the 4-position or the 5-position.)

[0012] The conditions for this reaction are RL, published in 1979. Elle. Augustin, "Carbon-Carbon Bond Formation", Volume 1, Marcel Decker, RL Augustine, "Car
Bon-Carbon Bond Formatio
n "Vol.1, Mercel Dekker In
c. ,) On page 1-84 can be used.

As an example, water or an alcoholic solvent such as methanol or ethanol or a mixture thereof is used as a solvent, and an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or sodium methylate is used as a catalyst. The reaction is carried out using an alkali metal alcoholate such as sodium ethylate or potassium methylate. Here, the catalyst amount is 0.01 to 1.0 equivalent, preferably 0.1 to 0.5 equivalent.
It is equivalent.

The reaction time and reaction temperature vary depending on the solvent used, but are preferably room temperature to 100 ° C. and 5 to 10 hours.

In the above reaction, the compound (1) of the present invention is usually obtained as a mixture of plural kinds of isomers due to its double bond portion (position 4 or 5).
In use, they can be separated or used as a mixture as they are.

The compound (1) of the present invention itself has a citrus-like, fruit-like, lactone-like aroma, so that it can be used as it is. Furthermore, depending on the purpose,
Various fragrance base materials can be combined as a fragrance preparation material to prepare various fragrance compositions by a conventional method.

[0017]

The 6-cyclohexyl-2-methyl-4 or 5-hepten-3-one obtained according to the present invention has a citrus-like, fruit-like, lactone-like odor and is suitable for use as a fragrance alone. Suitable. Further, the compound (1) is also excellent as a material for blending various fragrances, and is a high-grade fragrance composition, perfume, soap, shampoo, hair rinse, detergent,
It can be widely used for cosmetics, hair sprays, fragrances, and other products that require perfume.

[0018]

EXAMPLES The present invention will be specifically described below with reference to Examples, but it goes without saying that the present invention is not limited thereto.

Example 1 40 g of 3-methyl-2-butanone (465 mmo) was placed in a 500 ml round bottom flask equipped with a Dimroth and a dropping funnel.
l), 2-cyclohexylpropanal 61.5g (465m
mol), 300 ml of methanol and 5 g of sodium hydroxide
(125 mmol) was added. Then heat the reaction mixture,
The mixture was stirred at reflux temperature for 6 hours. After the solvent methanol was distilled under reduced pressure, 100 ml of water was added and the organic layer was extracted with hexane.

As a result of purifying the reaction mixture by distillation,
(E) -6-Cyclohexyl-2-methyl-4-hepten-3-one, (Z) -6-cyclohexyl-2-methyl-4-hepten-3-one and trans-6-cyclohexyl-2-methyl-. A mixture of 5-hepten-3-one (isomer ratio 5: 1: 4, boiling point (bp) 97 ° C./5 mmHg,
A yield of 68%) was obtained. The isomer ratio and its structure were determined by the results of capillary gas chromatography (Carbowax 20M 25 m, column temperature 150 ° C. and temperature was raised to 200 ° C. at 2 ° C./minute) and NMR analysis.

The above compound was a colorless and transparent liquid having a citrus-like, fruit-like, lactone-like aroma.

The IR of the above isomer mixture is as follows:
NMR and GC-MS data are shown.

IR (film); 1452, 1629, 1677, 17
16, 2860, 2932, 2968cm ^-1 NMR (CDCl ₃ ); 0.9-1.5 (m, 6.8H), 1.03 (d, J = 7Hz, 1.2
H), 1.09 (d, J = 7Hz, 3.6H), 1.11 (d, J = 7Hz, 2.4H), 1.60 (d, J = 1.1Hz, 1.5H), 1.6-1.8 (m, 1.5H), 1.89 (m, 0.5H), 2.13 (sex, J = 7Hz, 0.4H), 2.30 (m, 0.1H), 2.66 (sep, J = 7Hz, 0.4H), 2.84 (sep, J = 7Hz, 0.4H ), 3.16 (d, J = 7Hz, 1.0H), 3.19 (dd, J = 1.4Hz and J = 7Hz, 0.2H), 5.25 (dt, J = 1.4Hz and J = 7Hz, 0.1H), 5.33 ( tm, J = 7Hz, 0.4H), 6.09 (d, J = 15Hz, 0.4H), 6.79 (dd, J = 7Hz and J = 15Hz, 0.4H) ppm GC-MS (M ⁺ ); any of the above isomerism Also about the body 2
10

Example 2 (Orchid-type compounded fragrance) To 800 parts by weight of a compounded fragrance having the following composition, 200 parts by weight of the mixture obtained in Example 1 was added.

(Parts by Weight) Linalool 80 Terpineol 60 Phenylacetaldehyde Dimethylacetal 20 9-Decen-1-ol 10 Ethyltricyclo [5.2.1.0 ^2,6 ] decane-2-oleate 20 Trimethylundecenal 10 Heliotropin 60 Hexyl salicylate 140 Methyl dihydrojasmonate 400 800

As a result, an orchid type mixed fragrance having a floral sweet scent added to the base note was obtained.

Claims (2)

[Claims] 1. 6-Cyclohexyl-2-methyl-4 or 5-hepten-3-one represented by the following formula (1). [Chemical 1] (In the formula, the broken line indicates that there is a double bond at either the 4-position or the 5-position.) 2. A fragrance composition comprising 6-cyclohexyl-2-methyl-4 or 5-hepten-3-one represented by the following formula (1). [Chemical 2] (In the formula, the broken line indicates that there is a double bond at either the 4-position or the 5-position.)