JPH03221599A - Perfume composition - Google Patents

Abstract

PURPOSE:To obtain a new safe perfume composition having sharp, MUGE-like green floral ton fragrance free from ozone-like aroma, containing optically active (-)-p-isobutyl-alpha-methyldihydrocinnamic aldehyde. CONSTITUTION:The objective composition containing about 0.1-50wt.% (especially preferably 1-20wt.%) optically active (-)-p-isobutyl-alpha- methyldihydrocinnamic aldehyde shown by the formula having >=30% ee optical purity. The compound is obtained by asymmetrically hydrogenating an unsaturated carboxylic acid in the presence of an active phosphine complex into an acid chloride and reducing the acid chloride with a reducing agent such as lithium tri-t-butoxyaluminum hydride.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel bouyo perfume composition which is free from ozone-like aroma and has a sharp, muguet-like clean 70-ral aroma.

[Conventional technology]

Generally speaking, among physiologically active substances having an asymmetric structure, those useful are often specific enantiomers, and this tendency is particularly prevalent in the fields of medicines, agricultural chemicals, pheromones, food additives, etc. The field of fragrances is no exception; for example, l-menthol is used for the scent of pepper, and (
+)-Carvone, for the smell of grapefruit (+)-
Nootkatone and the like are useful, all of which have a different or strong odor than other optical enantiomers. Recent examples of such phenomena include α-ionone, linalool, hydroxycitronellal, rose oxide, etc. (for example, Kagaku Review, 14 (1)
976), "Chemistry of Taste and Smell" Chapter 6).

By the way, (±)-p-isobutyl-α-methyldihydrocinnamaldehyde is known to have a strong cyclamen-like aroma that is very diffusive (Japanese Patent Publication No. 45-2
Publication No. 3926).

However, since this compound has one asymmetric carbon in the molecule, it is expected that there are two enantiomers, the (+) and (=) forms, but the one described in the above publication is a racemic mixture. There are no reports yet on the establishment of these isomers individually or on the properties of these isomers.

In addition, p-tert-butyl-α-methyldihydrocinnamaldehyde (which has a structure similar to p-isobutyl-α-methyldihydrocinnamaldehyde and has a Muguet-like aroma)
JP-A-55-36459), p-isopropyl-
α-Methyl dihydrocinnamaldehyde (oil chemistry, 3
0 [2] (1981) p, 1.09, JP-A-5
5-27166), the optically active substance is determined by optical resolution method.

[Problem to be solved by the invention]

On the other hand, in recent years, with the diversification of various cosmetics and health and hygiene materials, there has been an increase in new, unprecedented demand for fragrances for cosmetics and health and hygiene materials. There has been a demand for the development of fragrance substances, and in particular there has been a shortage of fragrance materials with a muguet-like floral aroma.

Therefore, an object of the present invention is to provide a fragrance composition that is made of optical isomers and can impart a muguet-like floral fragrance.

[Means to solve the problem]

The inventors of the present invention conducted extensive research in view of the above circumstances, and as a result,
We have succeeded in developing an optically active form of p-isobutyl-α-methyldihydrocinnamaldehyde, and this (-) form has a muguet-like floral aroma, but it is useful as a fragrance because it does not have the ozone-like odor that this racemic form has. The present invention was completed by discovering that this can be achieved.

That is, the present invention provides a fragrance composition containing optically active (-)-p-isobutyl α-methyl dihydrocinnamaldehyde represented by the following formula (1).

Optically active (-)-p-isobutyl-α- used in the present invention
Methyl dihydrocinnamaldehyde (hereinafter referred to as “compound (1)
)") can be produced, for example, by the method shown in the following formula, through an asymmetric hydrogenation step and a reduction step.

Asymmetric hydrogenation step> (2) (3) (1) That is, an unsaturated carboxylic acid represented by formula (2) is subjected to asymmetric hydrogenation in the presence of an active phosphine complex to form a compound (3), After converting this into acid chloride (4), if it is reduced using a reducing agent such as lithium triturgical Y xyaluminum hydride [LiAl(t-BuO) 3H], optically active (-)-p-isobutyl-
α-Methyl dihydrocinnamaldehyde (1) can be produced.

Hereinafter, this production method will be explained separately into an asymmetric hydrogenation step and a reduction step.

(i) Asymmetric hydrogenation process If compound (2) is hydrogenated using a ruthenium catalyst, an optically active form of compound (3) can be obtained.

As a ruthenium catalyst, J, Org, Chem,
, 52 [14] (1987) pJ176, the ruthenium-optically active phosphine complex described in JP-A-63-239245 and the following general formula (5) % formula % (5) [wherein R-BINAP is the formula ( 6) means a tertiary phosphine represented by R means a hydrogen atom or a methyl group, X means a halogen atom, S means benzene or acetonitrile which may have a substituent, Y is a halogen atom, Cj! 0. , P
F,, BPh, or BF, and when S is benzene which may have a substituent, I M 1m is 1, n is l
and S is acetonyl) When l is 1, m is 2 and n is 1; when l is O, m is 4 and n is 2]. Can be mentioned. Among them, [Ru1 (p-cymene) ((R)-BINAP
)]l is particularly preferred. The reaction is carried out by dissolving compound (2) in a protic solvent such as methanol, ethanol, methyl cellosolve, etc., adding a ruthenium catalyst of 1/100 to 1/1000 times the mole of compound (2), and hydrogen pressure 4.
~125 kg/crl, hydrogenation temperature -10~80℃
This is carried out by stirring for 1 to 100 hours.

(ii) Reduction Step In the reduction step, it is most important that the reduction of the optically active p-isobutyl-α-methyldihydrocinnamic acid (3) stops at the aldehyde without progressing to the alcohol and that racemization does not occur. Various reduction methods are possible for this purpose, but for example, carboxylic acid chloride is reduced by L+Aj!
(t-BuQ) A method of reduction using sH (lithium tritert-butoxyaluminum hydride) [for example, J, ^mer.

Chem, Sac, 80 (195B) p. 53
77, JP-A-55-36459, JP-A-55-2
No. 7166] is particularly preferred in terms of steric retention.

The reaction begins with optically active p-isobutyl-α-methyldihydrocinnamic acid (3) obtained by an asymmetric hydrogenation reaction.
is reacted with a chlorinating agent such as thionyl chloride to form an optically active p
-isobutyl-α-methyldihydrocinnamic acid chloride (4), and then the compound (4) was added to LiA 1 (t-Bud
) sH is added and carried out at -80 to -10°C.

Regarding the optical purity of the target compound (1), optically active compound (1) was oxidized with acidic potassium permanganate at room temperature to obtain optically active p-isobutyl-α-methyldihydrocinnamic acid. (3), which was converted to acid chloride (4) by reacting with thionyl chloride, (+)-
The 2-octyl ester was analyzed by gas chromatography using a glass capillary column, and the difference in area percentage between the two diastereomers produced was used as the optical purity (Japanese Unexamined Patent Publication No. 55-36459).

In addition, compound (2), which is a raw material for compound (1), can be prepared by, for example, a method using a π-allyl complex of palladium as shown in the following formula (Tetrahedron Lett,
27C22] (1986) p, 2483. ,y,O
rg, Chem, 52[14] (1987) p, 3
176).

Margin below (7) HC) 10/KHCO.

Ac20/PyridinePd (OAc) 2/PPh3/CH*CNP d (
OAc) 2/P P haHCOOH/Et, N That is, p-isobutylbenzyl chloride (7), which is industrially easily available as a raw material, is condensed with diallyl malonate to produce diallyl 2-(p-isobutylbenzyl)malonate. As (8), (8) is hydroxymethylated to produce 2
-(p-isobutylbenzyl)2-hydroxymethylmalonate diallyl (9) and acetylated (9) to give 2
Diallyl -(p-isobutylbenzyl)-2-acetoxymethylmalonate QO is obtained. By deaceticating Q[l with a palladium catalyst to produce allyl p-isobutyl-α-methylenedihydrocinnamate 01), and further hydrolyzing (Company) with a palladium catalyst, (2) is obtained in high yield. I can do it.

Surprisingly, the aroma qualities between the optical antipodes of p-inbutyl-α-methyl dihydrocinnamaldehyde obtained in this way are completely different, and the (+) one has a clean ozone-like aroma. On the other hand, (-) one has a sharp, muguet-like green floral fragrance. In comparison, the racemic compound has both the aroma characteristics of (+) and (-), but the ozone-like aroma becomes a problem when creating a flower-like fragrance composition. The amount used and the range of floral fragrance compositions used are limited to specific ranges. On the other hand, since (-) one does not have an ozone-like aroma, there are no restrictions on the amount or range of use when creating a fragrance with a flower-like fragrance composition, so it can be used very usefully as a new Muguet fragrance material. I can do things. (-) Regarding the optical purity of the monolith, when creating a fragrance with a flower-like fragrance composition using 30% ee or more, (+) the influence of the ozone-like aroma of the monolith will be almost eliminated, and the amount and range of use will be limited. It can be used as a new material without being destroyed.

Therefore, compound (1) [(-) form] is added to the fragrance composition of the present invention.
Although the blending amount is not particularly limited, it is preferably 0.1 to 50% by weight, particularly 1 to 20% by weight.

Further, the perfume composition of the present invention may contain commonly used mixed perfumes.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to synthesis examples, test examples, and examples, but the present invention is not limited thereto.

Synthesis Example 1 p-isobutyl-α-methylenedihydrocinnamic acid (2)
Synthesis: 88.4 g of diallyl malonate (0,4
8 mol>, 259.4 g (1.88 mol) of potassium carbonate, and 600.0 g of acetone were added, and the mixture was heated and stirred.

p-isobutylbenzyl chloride (7) 172 under reflux
．． 2 g (0.94 mol) was added dropwise over 1 hour, and an additional 60
The mixture was stirred and reacted at ℃ for 5 hours. After cooling to room temperature, 700 g of water and 200 g of toluene were added and washed, the organic layer was separated, and further washed with 400 g of saturated brine and separated. After recovering toluene under reduced pressure with an evaporator, p-isobutylbenzyl chloride 94.8
g was collected to obtain 143.4 g of crude diallyl 2-(4-isobutylbenzyl)malonate (8).

51 flask, 143.4 g of crude diallyl 2-(4-isobutylbenzyl)malonate CB), 5 g of potassium hydrogen carbonate
2.0g, allyl alcohol 700rn! , tetrahydrofuran (THF) 10100O! Then, 700 g of water was added and stirred at room temperature. 100.0 g of a 30% formaldehyde aqueous solution was added dropwise to the reaction solution over 1 hour, and the mixture was further stirred for 24 hours to react. After recovering the solvent under reduced pressure with an evaporator, it was extracted with ether and 400ml of water! After washing with water and separating the layers, the mixture was washed with 200% saturated brine and separated.

Ether was recovered using an evaporator to obtain 161.6 g of crude diallyl 2-(4isobutylbenzyl)-2-hydroxymethylmalonate (9). This stuff has pyridine 14
2.0 g was added and stirred at room temperature, 146.0 g of acetic anhydride was added dropwise at the same temperature over 1 hour, and the mixture was further stirred for 16 hours to react. The resulting reaction mixture was poured into 400 rnl of cold water and extracted with 200 ml of toluene.

This was washed with water and separated, then washed with 400ml of 5% sodium carbonate, and separated into 400ml of saturated saline. The solution was washed and separated. Next, toluene was recovered under reduced pressure using an evaporator and purified by silica gel chromatography to obtain 140.6 g of diallyl 2-(4-inbutylbenzyl)-2-acetoxymethylmalonate α0.

Diallyl 2-(4-isobutylbenzyl)-2-acetoxymethylmalonate αI) was placed in a nitrogen-substituted flask.
138. Og, 2.24 g of haladiacetate A, 10.48 g of 1-liphenylphosphine and 4 acetonitrile
80- was added thereto, and the mixture was stirred and reacted at 45° C. for 1 hour in a nitrogen stream.

After cooling to room temperature, it was concentrated under reduced pressure using an evaporator and purified by silica gel column chromatography to obtain allyl p-isobutyl-α-methylene dihydrocinnamate Ql).
85.2g was obtained. 1.94 g of palladium acetate was placed in a nitrogen-substituted flask.

Triphenylphosphine 4.4g5THP400mj
l! and stirred at room temperature under a nitrogen stream. Add to this 26.4 g of formic acid, 70.0 g ST of ethylamine
HF150mi! and then 74.4 g of allyl p-isobutyl-α-methylenedihydrocinnamate Q
A THF 400mf solution of I) was added dropwise over 1 hour, and then 3
The reaction was stirred for 0 minutes. The reaction mixture was condensed under reduced pressure using an evaporator, and separated by silica gel column chromatography using a hexane-ethyl acetate mixed solvent to obtain crude p-inbutyl-α-methylene dihydrocinnamic acid (2) 58
．． 2g was obtained. This product was recrystallized using hexane as a solvent to obtain 40.3 g of p-isobutyl-α-methylene dihydrocinnamic acid (2).

Melting point: 55.5°C 'H-NMR (δppm) 0,91 (6H,d, J=6.6Hz) 1,85
(IH, ω) 2, 44 (28, d, J=7.4) 1z) 3, 60
(2H, s) 5, 56 (ltl, s) 6.36 (1)1. s) 7,09 (4H,m) Synthesis Example 2 [Rul (p-cymene) ((R)-BINAP)
]I(iodo-π-p-cymene-C2,2'-bis(
Diphenylphosphino)-1,1'-binaphthyl]ruthenium iodo) compound I&: RuC1, -3H,D 1. Og, 90% ethanol 30- and p-mentha-1,5-diene 5mff (3
1 mmol) was stirred at 45-50°C for 5 hours, the precipitated crystals were filtered, washed with methanol, dried, and an orange solid [Ru(p-cymene) Cj! 2] 2 (μm dichloro-π-p-cymene-ruthenium) was obtained.

3.5 g of this [Ru (p-cymene)
87ml of water! A solution dissolved in was added dropwise.

■ After stirring for 6 hours, the liquid was separated, washed with 200ml of water, the solvent was distilled off, and the result was a deep purple solid [Ru
(p-cymene) 1. ]2(μm short-π-p-
4.9 g of cymene-ruthenium was obtained. Next, this [R
u(p-cymene) I2]20.25 g (0,2
6 mmol) and (R)-BINAP OJ5 g (0,
56 mmol) in ethanol 45 and methylene chloride 23
- and stirred at 50°C for 1 hour. The reaction solution was filtered on Celite and concentrated to dryness to obtain a brown solid [Ru1
(p-cymene)((R)-BINAP)]! 0.58
I got g.

Elemental analysis value: C5J4s12PJu CH Theoretical value (%) 58.34 4.17 Actual value (
%) 57,96 3.73”P-NMR(C
DCI! >δppm: 24.8 (J=60.2Hz)
41.6 (J = 60.0 Hz) Bottom example 3 (-)-p-isobutyl-α-methyldihydrocinnamic acid (3) F &: In a nitrogen-substituted autoclave No. 11, p-inbutyl-α-methyl Dihydrocinnamic acid (2) 20.0g (91.7 mmol) [
Ru1(p-cymene)((R)-BINAP)]I2
00 mg (0.18 mmol) and 400 kg of dry methanol were charged, cooled to 0°C, and the inside of the container was replaced with hydrogen until the hydrogen pressure was 100 kg/CI+! The reaction was stirred at the same temperature for 16 minutes.
I did it for an hour. After returning this to room temperature, it was concentrated under reduced pressure using an evaporator, and separated and purified by silica gel chromatography using a hexane-ethyl acetate mixed solvent.
-p-isobutyl-α-methyldihydrocinnamic acid (3N
9.7g ([α]2'=-20.60°C) ICj2
°c=2.0) was obtained. This (-)-p-isobutyl α
-The optical purity of methyldihydrocinnamic acid (3) was determined by dissolving it in a small amount of toluene and adding in sequence a toluene solution of thionyl chloride, a toluene solution of pyridine, and a toluene solution of (+)-2-octanol to 100% The optically active (+)-2-octyl ester produced by a heating reaction at ℃ for 10 minutes was analyzed using a 25 m glass capillary column, and the result was determined to be 74.7% ee from the difference in area percentage of the two diastereomers. did.

Base example 4 Synthesis of (-)-p-isobutyl-α-methyldihydrocinnamaldehyde (1): (-)-p-isobutyl-α-methyldihydrocinnamic acid (3; optical purity 74.7%ee ) 18.7g (85
mmol) was dissolved in 100 mmol of toluene and stirred for 1 hour at room temperature with 30.3 g (1), 255 mol) of thionyl chloride and 0.3 g of DMF (dimethylformamide). The solvent was removed and (-)-p-isobutyl-α-methyldihydrocinnamate chloride (4;
+) Optical purity 7 by -2-octyl ester analysis method
4.5%ee) was obtained. Dry this acid chloride in THF.
LiAj! (
t-Bun)sH21.6g (85 mmol) of TH
F100rnl solution was added dropwise over 1 hour. After stirring at the same temperature for 1 hour and at room temperature for 2 hours, water was added, the solvent was distilled off using an evaporator, 2.5N-HCA was then added, and the mixture was extracted with diethyl ether, washed with water, and further washed with 5% NaaCL. The solvent was distilled off using an evaporator, and the purified L(-)-p-isobutyl-
α-Methyldihydrocinnamaldehyde (IO2, 6g
((α)2'=-6i, 41°CHCl3C=1.
2) was obtained.

Dissolve 17 µ of this (-)-p-isobutyl-α-methyldihydrocinnamaldehyde (1) in 0.2-ml of acetone and 0.2 ml of water! and 32 mg of concentrated sulfuric acid were added thereto, and 0.4 - of an aqueous solution of 25 rng of potassium permanganate was added dropwise thereto over 1 hour with stirring at room temperature, followed by further stirring for 1 hour. Add 10 mg of sodium sulfite, extract with chloroform,
The solvent was distilled off to obtain (-)-p-isobutyl-α-methyldihydrocinnamic acid (3).

The optical purity of this product was determined to be 70.5% ee using the same (+)-2-octyl ester analysis method as in Base Example 3.

Test Example Bottom Optical purity of 70.5%ee obtained in Example 4 (-) =
p-Isobutyl-α-methyldihydrocaldehyde (1) was mixed with the racemate to obtain (−)-p with the following optical purity.
-Isobutyl-α-methyldihydrocinnamaldehyde was prepared, and its aroma quality was examined by 10 expert panelists. As shown below, the optical purity is 30%ee.
It has been found that the above compositions have almost no ozone-like odor influence and can be used as part of flower-like fragrance compositions without being limited in the scope or amount of use.

Margin below N [l Optical purity [α] = 5 Aroma properties 60.0 50.0 40.0 5.45° - 4,54° - 3,63° Same as above Same as above Same as above 7 10.0 -0.91° Same as above Example 1 A new perfume was prepared according to the following formulation using (-)-p-isobutyl-α-methyldihydrocinnamaldehyde having different optical purity of Nα1 to No. 8 prepared in the test example.

Prescription (
Weight part) Bergamotu 1
10 lemon oil 10
5 Basil Oil Galbanum Cis-3-Hexenyl Salicylate Aldehyde C-14 Ylang Ylang Oil Cassie Absolute Valmarosa Linalol Phenylethyl Alcohol Citronellol Hydroxycitronellal α-Hexyl Cinnamic Aldehyde Citro, Lylacetate Geranyl Acetate Drodinol Terpineol Methyl eugenol Cinnamic Alcohol Vetiveryl Acetate Vetiverol Sandal Wood Oil Indole Civet Apricot Ambrette Oil Oakmoss Purgarian Rose Iris Oil α-isomethylionone Methyl dihydrojasmonate Total 1000 10 people about the new perfume with the above formulation Specialist panelists and 20
As a result of conducting a preference test on 20 ordinary women aged ~30, 27 out of 30 chose sample Nα1.2.3.
．． Some answered that they liked the one using 4 the most, and 1.
They answered that they did not notice any difference in aroma between those using 2.3.4. Regarding sample Nα5, 23 out of 30 people answered that they preferred it. 30 for sample No. 6.7
14 people out of the people said that the odor was a little ozone-like. Regarding the product using Nα8 (racemic form), 18 people answered that they did not like the odor because it had a mellow smell and felt an ozone-like stimulus.

Example 2 First, jasmine synthetic essential oil was prepared according to the following formulation.

Prescription (parts by weight) Indole 13 Methyl palmitate 6 Benzyl benzoate 215 Linalool
75 Methyl dihydrodiasmonate 7 Geranyl linalool
30 Sysdiasmonbenzoin Jasmine Absolute Isophytol Methylyllinate Benzyl Acetate Benzyl Alcohol Syshexenyl Benzoate Methyl-N-acetyl Anthranil Eugenol Jasmine Lactone Methyl dihydroabietate Phytyl Acetate True Balsam Vanilla Resin Total 1000 Above Jasmine Coal Essential Oil 1000 Weight 30 parts by weight each of (-)-p-isobutyl α-methyl dihydrocinnamaldehyde of k3 prepared in the test example and No. 8 (racemic body) were added to each part to prepare a new synthetic jasmine essential oil. As a result of a palatability survey conducted by eight expert panelists, all of them answered that the new synthetic jasmine essential oil using Nα3 was mellower, more natural, and more durable. Regarding the new jasmine essential oil using N[18 (racemic form), 5 people answered that it was irritating and lacked naturalness, and that they preferred the original synthetic jasmine essential oil prepared using the above formulation. Ta.

Example 3 First, a Muguet fragrance composition was prepared according to the following formulation.

Formula (Weight B) Benzyl acetate 30 Linalool 30 Dimethylbenzyl carbinol 50 Bergamot
20 citronellyl formate 20 rhodinol
150 heliotropin
40 ylang ylang oil
10 cinnamon alcohol
150 hydroxycitronellal
500 total
1000 90 parts by weight of N(L 3 (-)-p-isobutyl-α-methyldihydrocinnamic aldehyde prepared in the test example was mixed with 1000 parts by weight of the above Muguet fragrance composition to obtain a new Muguet fragrance composition. Prepared.

As a result of a preference survey conducted by five expert panelists, all of them answered that they liked the new Muguet fragrance composition because it was fresher, had a lively natural feel, and was elegant.

〔Effect of the invention〕

The fragrance composition of the present invention has a sharp, muguet-like green floral fragrance and does not have an ozone-like fragrance, so the range and amount of use is not limited, and it can be used in various cosmetics, health and hygiene materials, pharmaceuticals, etc. Can be widely used.

that's all

Claims (1)

[Claims] 1. Contains optically active (-)-p-isobutyl-α-methyldihydrocinnamaldehyde represented by the following formula (1) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (1) Perfume composition. 2. The fragrance composition according to claim 1, wherein the optically active (-)-p-isobutyl-α-methyl dihydrocinnamaldehyde has an optical purity of 30%ee or more.