JP2759546B2 - (3S) -3,7-dimethyl-2-methylene-6-octen-1-al, a process for producing the same, and a fragrance composition containing the same - Google Patents

Description

The present invention relates to an optically active compound represented by the following formula (1): (In the formula, * means an asymmetric carbon atom.) (3S) -3,7-dimethyl-2-methylene-
The present invention relates to 6-octen-1-al and a method for producing the same, and a fragrance composition containing the compound of the formula (1). (3S)
-3,7-dimethyl-2-methylene-6-octene-1-
Earl is a compound having an excellent citrus scent, and the fragrance composition of the present invention containing the compound can be effectively used for various cosmetics, fragrances, other health and hygiene materials and the like.

[Conventional technology]

In general, useful biologically active substances having an asymmetric structure are often specific enantiomers, and this is particularly the case in the fields of pharmaceuticals, agricultural chemicals, pheromones, food additives and the like. There are no exceptions in the field of perfumery. For example, (-)-menthol is useful for the smell of peppermint, (+)-carvone is useful for the smell of Himewikyo, and (+)-nootkatone is useful for the smell of grapefruit. Each of them has a different odor from other optical enantiomers or has a stronger odor than other optical enantiomers. Recent examples of such phenomena include α-yonone, linalool, hydroxycitronellal, and rose oxide [for example, edited by The Chemical Society of Japan; “Review of Chemistry (Vol. 14) Chemistry "p.170-172 (1976)]. in this way,
The development of optically active perfume compounds has received particular attention in recent years.

By the way, 3,7-dimethyl-2-methylene-6-octen-1-al is known to have a sweet and fresh citrus-like and grass-like aroma [S. Arctander, Perfum
e and Flavor Chemicals, Montclair, Monograph No. 2009
(1969)], for example, by reacting citronellal [3,7-dimethyl-6-octen-1-al] with formaldehyde and water in the presence of a catalytic amount or a larger amount of diethylamine [US Patent No. 3,463,818]. The compound thus obtained is
Since there is one asymmetric carbon atom in the molecule, the existence of two enantiomers, a (+)-form and a (-)-form, is expected, but there is no description about this in the above specification. However, citronellal used as a raw material can be obtained for the first time by the method described in Japanese Patent Publication No. Sho 58-17747 filed by the present applicant and Japanese Patent Publication No. Sho 62-51945 which has been further studied (+ )-And (-)-forms have been individually and industrially synthesized, and those which have hitherto been commercially available before have been obtained from racemic synthetic products or natural citranera oil. Since the optical purity obtained is of the (+) form with about 80-85% ee, the compound obtained by the above synthesis method is a racemic form or a (+) form (3S)-
3,7-dimethyl-2-methylene-6-octen-1-al.

Also, (3S) -3,7-dimethyl-2-methylene-6-
For octen-1-al, other synthetic methods, for example, according to the following reaction formula, As an example of synthesizing 2-methylenealdehyde from a primary alcohol, (+)-citronellol [(3S) -3,7
-Dimethyl-6-octen-1-ol] [S. TAKANO et al .; CHEMISTRY LETTERS., (7), p.1283-128]
4 (1989)], in the process of synthesizing certain alkaloid intermediates, (+)-citronellal derived from (R)-(+)-pulegone was converted to N, N-dimethylmethylene ammonium iodide [H ₂ C ^{_{= N (CH 3) 2 +}} I - ] at alkylated amine obtained as a quaternary ammonium salt with methyl iodide, a method that may be treated with a base [JDWhite al; Tetr
ahedron Letters, 29 , (18), p.2139-2142 (1988)]
Have been reported. However, the (+)-form (3S) -3,7-dimethyl-2-methylene-6-octen-1-al has been isolated or synthesized, and its aroma and properties have been confirmed. No examples are found, and no report has been made on its perfume properties.

3,7-dimethyl-2-methylene-6-octene-1-
As a method for producing 2-methylenealdehyde which is the skeleton of Earl, a reaction between ammonia or a hydrochloride of a primary or secondary amine with formaldehyde and a compound containing a reactive hydrogen atom, which is known by the name of Mannich reaction, is known. A method of reacting a mixture of an aldehyde having a CH ₂ group at the α-position to the carbonyl group and formaldehyde with a strong acid salt of a primary or secondary amine [US Pat.
518,416], a method of condensing an aliphatic aldehyde with formaldehyde in the presence of an ammonium salt (U.S. Pat.No. 2,639,295) is known, but all of these methods use an amine salt or an ammonium salt. . Furthermore, a method has been proposed in which a specific aldehyde and formaldehyde are reacted at a molar ratio of 1: 1 in the presence of a catalytic amount of a specific enamine (Japanese Patent Application Laid-Open No. 55-87735). Here, enamine is used as a catalyst, and as for the reaction between enamine and formaldehyde, the transition state of the bond between vinylamine and formaldehyde has been studied, and it has been reported that a stable imino alcohol can be obtained (A. Sevin et al .; Journal of Organic Chemistry, 52 ,
(25), p.5611-5615 (1987)].

[Problems to be solved by the invention]

In recent years, along with the diversification of various cosmetics, fragrances, and other health and hygiene materials, unprecedented new demands have been raised for fragrances used in these, and fragrance substances having a unique fragrance with high diffusivity and high palatability Development is required. In particular, with respect to citrus-based fragrance compositions that are most in demand among fragrances, development of new fragrance materials that can be differentiated has been desired.

Accordingly, an object of the present invention is to provide a compound that can be a new material of a citrus-based flavor that satisfies the above demand, and to provide a flavor composition containing the compound.

[Means for solving the problem]

In view of the above-mentioned circumstances, the present inventors have heretofore been known to have a citrus-like, grass-like aroma, 3,7-dimethyl-
As a result of diligent research on the optically active form of 2-methylene-6-octen-1-al, the form is (+)-form (3S).
-3,7-dimethyl-2-methylene-6-octene-1-
Earl was successfully obtained in a pure form, and the (-) form of (3S) -3,7-dimethyl-
The odor of 2-methylene-6-octen-1-al and a slightly coarse citronellal-like fragrance are mediocre as a fragrance, whereas the fragrance of the (+) body is very fresh and clean bergamot-like citrus. The present invention was found to be odorous and very useful as an active ingredient of a citrus-based fragrance composition or as a modulator, and completed the present invention.

(3S) -3,7-dimethyl-2-methylene-6 of the present invention
-Octene-1-al (1) is prepared, for example, according to the following reaction formula, using (3S) -N, N-diethyl-3,7-dimethyl-1,6.
-Produced by reacting octadienylamine (2) with formaldehyde or a formaldehyde-forming compound.

(In the formula, * means an asymmetric carbon atom.) The starting compound (3S) -N, N-diethyl-3,7-dimethyl-1,6-octadienylamine (1 )
Can be obtained in high optical purity by isomerizing geranyldiethylamine using a rhodium complex catalyst according to the method of Yunbayashi et al., Which is an intermediate in the synthesis of (−)-citronellal and (−)-citronellol. H.Kumobayashi is produced in large quantities industrially as a body.
Et al; Journal of the American Chemical Society, 100 ,
(12), p. 1949-3950 (1978), K. Tan et al .; Angewandte Ch.
emie International Edition in English, 24 , (3),
p.217-249 (1985), JP-B-62-51945].

In the method of the present invention, the amount of formaldehyde to enamine (2) may be at least 1 equivalent to enamine, but it is particularly preferable to use 1.1 to 1.5 equivalent. Although formaldehyde is preferably used as an aqueous solution, the reaction proceeds if its concentration is in the range of 5 to 65%,
Economically, the concentration is preferably 30 to 40%. Also,
Compounds that form formaldehyde under certain conditions can be used in place of formaldehyde, such as condensation products of formaldehyde,
For example, paraformaldehyde and the like can be mentioned.

Regarding the reaction temperature of enamine (2) with formaldehyde or a formaldehyde-forming compound, 20 to 100 ° C.
The reaction proceeds, but from the viewpoint of yield, the reaction temperature is particularly preferably 65 to 90 ° C. The reaction time may be appropriately determined according to the reaction temperature, but is preferably 2 to 8 hours.

Under the above conditions, the enamine (2) is reacted with formaldehyde or a formaldehyde-forming compound, preferably under stirring, and after completion of the reaction, purified by means such as washing, concentration, and distillation to obtain the desired (3S) -3 , 7-dimethyl-
2-methylene-6-octen-1-al can be obtained.

The reaction of the method of the present invention is carried out by using (3R) -N, N
By using diethyl-3,7-dimethyl-1,6-octadienylamine, the compound of the present invention and the optical antipode of (3R) -3,7-dimethyl-2-methylene-6 are obtained.
-It can also be applied to the production of octene-1-al.

(3S) -3,7-dimethyl-2-methylene-6 of the present invention
-Octen-1-al has a surprisingly different odor than the conventional (-)-form (3R) -3,7-dimethyl-2-methylene-6-octen-1-al. ing. That is, the (-) form and the racemic form are somewhat coarse citronellal-like fragrances, which are ordinary as a fragrance, whereas the (+) form is (3S) -3,7-dimethyl-2-methylene-6. -Octene-1-al is a very fresh and clean bergamot-like citrus odor, which has a high diffusibility and retention property, and is a fresh and highly palatable fragrance imparting agent or fragrance-improving reinforcement. A perfume composition of the agent can be provided. The amount of (3S) -3,7-dimethyl-2-methylene-6-octen-1-al in the perfume composition of the present invention is not particularly limited, but is not particularly limited.
Preferred is 1 to 50% by weight, especially 1 to 20% by weight.

In addition, the flavoring composition of the present invention may be blended with a compounded flavoring which is generally used.

The fragrance composition thus obtained can provide various cosmetics, fragrances, other health and hygiene materials, etc. containing the fragrance composition as a fragrance component. Shampoos, rinses, hair tonics,
Cosmetic base for hair such as hair cream and pomade;
Lipsticks and other cosmetic bases; cosmetic detergent bases, soaps, dishwashing detergents, laundry detergents, disinfecting detergents, detergents such as deodorant detergents; oral compositions such as toothpastes, mouthwashes; softeners; Room air freshener, furniture care, disinfectant, insecticide, bleach, toilet paper, solvent, perfume for facilitating the taking of pharmaceuticals, etc. Can increase value.

〔Example〕

Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.

Example 1 Production of (3S) -3,7-dimethyl-2-methylene-6-octen-1-al In a 500 ml four-necked flask equipped with a condenser, a thermometer, a dropping funnel, a sieve tube and a stirrer, (3S) -N, N
-Diethyl-3,7-dimethyl-1,6-octadienylamine 500 g (2.4 mol) [manufactured by Takasago International Corporation, ▲
[Α] ²⁵ _D ▼ = + 47.46 ゜, optical purity = 98% ee, purity in gas chromatography = 99.9%], and heat
The temperature was adjusted to 85 ° C., and 286 g of a commercially available 35% aqueous formaldehyde solution (3.3 mol of formaldehyde) was added dropwise over 1 hour while stirring at the same temperature. Thereafter, stirring was continued at the same temperature for 6 hours to complete the reaction. After cooling the reaction solution to 5 ° C, 10%
1170 g of a sulfuric acid solution and 100 g of toluene were added, washed with water, and separated.
After washing once each with 0 g and saturated saline solution 440 g, the liquid was separated. The organic layer was concentrated under reduced pressure using an evaporator to obtain 379 g of a colorless concentrated oil. 379 g of the concentrated oil was precision-distilled into a 40 cm repacked evaporator to obtain 302 g of the desired (3S) -3,7-dimethyl-2-methylene-6-octene-1-al (yield 76%) [boiling point = 44 ℃ / 1mmHg, ▲ [α] ²⁵ _D ▼ = +11.44
純度, purity in gas chromatography = 99.8%]. The physical properties of this product were as follows.

¹ H-NMR (CDCl ₃ ) δ ppm: 1.06 (d, 3H), 1.39 (m, 1H),
1.53 (m, 1H), 1.56 (s, 3H), 1.67 (s, 3H), 1.93 (m, 2
H), 2.70 (m, 1H), 5.07 (m, 1H), 5.98 (s, 1H), 6.22
(S, 1H), 9.53 (s, 1H) MS (m / e value); 166 (M ⁺ , 22), 151 (21), 133 (10), 124
(21), 109 (100), 95 (34), 81 (36), 70 (65), 55 (8
8), 41 (81), 29 (6) Reference Example 1 (3R) -N, N-dimethyl-1,6-octadienylamine [manufactured by Takasago International Corporation. Synthetic intermediate of (+)-citronellal and (-)-menthol. ▲ [α] ²⁵ _D ▼ =
(3R) -3,7-dimethyl-2-methylene-6-octene-1 in the same manner as in Example 1 using -47.46 °, optical purity = 98% ee, purity in gas chromatography = 99.9%]. -[[[Α] ²⁵ _D ▼ = -11.44 ゜, purity by gas chromatography = 99.8%].

Example 2 Fragrance composition (3S) -3,7-dimethyl-2- produced in Example 1
Methylene-6-octene-1-al [hereinafter “(3S)
A body composition] was used to prepare a highly palatable fusea-type male fragrance perfume composition having the following formulation. Similarly, as a comparative example, the (3R) -3,7 obtained in Reference Example 1 was used.
-Dimethyl-2-methylene-6-octene-1-al [hereinafter referred to as "(3R) form"] (Comparative Example 1), and (3S)
Body: A perfume composition containing a mixture of (3R) bodies = 1: 1 [hereinafter referred to as “racemic body”] (Comparative Example 2) was prepared. A taste test was conducted on the obtained three kinds of fragrance compositions by 10 expert panelists. As a result, all 10 persons answered that the perfume composition containing (3S) -3,7-dimethyl-2-methylene-6-octen-1-al of the present invention was fresh, natural, and liked. . The amounts are shown in parts by weight.

Example 3 Fragrance composition (3S) -3,7-dimethyl-2- produced in Example 1
Using methylene-6-octene-1-al, a lavender-type soap fragrance composition having a high palatability having the following formulation was prepared.

Formulation Parts by weight 1,3,4,6,7,8-Hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-γ-2-benzopyran 200 Allyl salicylate 40 Anisaldehyde 10 Coumarin 130 Geranium oil 60 (-) - citronellol 30 lavandin oil 160 linalyl acetate 50 linalool 30 patchouli oil 80 phenylethyl alcohol 30 isobornyl cyclohexanol 40 (3S)-3,7-dimethyl-2-methylene-6-octen-1 are According to 100 total 1000 [effect of the invention the present invention is industrially useful optically active compound (3S)-3,7-dimethyl-2-methylene-6-octene-1-al, easily Using available raw materials,
It can be obtained with a simple process and at high yield and low cost. The perfume composition of the present invention containing (3S) -3,7-dimethyl-2-methylene-6-octen-1-al has excellent diffusibility and retention properties, and is excellent in freshness and high palatability. Since it has a fragrance, it can be effectively used in a wide range of fields such as various cosmetics, fragrances, and other health and hygiene materials.

Claims (3)

(57) [Claims] 1. The following equation (1): (In the formula, * means an asymmetric carbon atom.) (3S) -3,7-dimethyl-2-methylene-
6-octene-1-al. (2) (3S) -N, N-diethyl-3,7-dimethyl-
The following formula (1) characterized in that formaldehyde or a formaldehyde-forming compound is reacted with 1,6-octadienylamine. (In the formula, * means an asymmetric carbon atom.) (3S) -3,7-dimethyl-2-methylene-
Production method of 6-octene-1-al. 3. The following equation (1): (In the formula, * means an asymmetric carbon atom.) (3S) -3,7-dimethyl-2-methylene-
A fragrance composition comprising 6-octene-1-al.