JPS63233913A - Perfume composition - Google Patents

Abstract

PURPOSE:To obtain a perfume composition, containing (7Z,10Z)-hexadecadienal and useful for aromatizing or flavoring foods, cosmetics, etc., or improving and enhancing aroma or flavor thereof. CONSTITUTION:A perfume composition obtained by containing a compound, expressed by the formula and having strong oily aroma and flavor common with cheese, chicken, dried small sardines and shellfishes as well as aroma and flavor suggesting citrus of orange. For example, 0.1-1% compound can be added to a perfume composition for conventional cheese oil to provide a perfume composition capable of strongly impressing fat. 0.05-1% compound can be added to a perfume composition for soap or shampoo to emphasize naturalness of floral odor extracted from natural products.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is represented by the following formula (A). A fragrance composition characterized by containing (7Z, 10Z)-hexadecadienal (I).

The above compound 1 is a known substance isolated from cucumber and reported by Kemp (J, Am, Oi IChe
(SOC, 1975, 11t 300), however, the aroma and flavor of ■ and its use as a flavoring agent have never been described, and there are no articles suggesting this.

And ■ has never been synthesized before.

The analysis group (Kajiwara et al.) of the present inventors.

We studied the volatile components of Ulva (Algae algae), which belongs to the green algae in seaweed, and isolated L as one of the major components. Then, I was synthesized for the first time and its structure was confirmed.

On the other hand, the application group discovered that ■ is a substance that greatly contributes to the aroma of Ulva. As a result of a detailed investigation of the aroma and flavor of ■, it was found that ■ is not limited to the aroma and flavor of Ulva.

It was discovered that this compound is very useful as a fragrance that can be used for many purposes.

According to the conventional understanding, when the number of carbon atoms in the unsaturated aldehyde of the higher linear fatty layer increases from 14 to 15 or more, the number of carbon atoms increases.

Each has been replaced with a characteristic aroma and flavor whose intensity gradually decreases. However, surprisingly, a chemical compound with 16 carbon atoms and two cis-type unsaturated bonds,
The reason for the stronger-than-expected aroma and flavor is probably due to two cis-unsaturated bonds.Until now, there has been no research on the sensory properties of cis-unsaturated higher aldehydes with 14 to 15 or more carbon atoms. This is an area that has received little attention in the fragrance field.

According to the research of the present inventor, ■ is common to cheese, chicken, dried sardines, and shellfish. Oil-like aroma and flavor (f
Atty note) Furthermore, it also has an aroma and flavor reminiscent of citrus or orange.

Incorporated into fragrance compositions of cosmetic fragrances limited to food fragrances,
It has been found that it can be widely used as an aroma and flavor imparting agent or as an improved reinforcing agent.

For example, in the case of two food flavorings, it is preferable to take advantage of the characteristics of I to add 0.1 to 1% of I to a conventional flavoring composition for cheese, thereby creating a flavoring composition that is strongly associated with fat. Can be done. In addition, in perfumery for cosmetics, by adding 0.05 to 1% to perfume compositions for soaps and shampoos, the naturalness of the floral smell extracted from natural products can be emphasized. In this way, by incorporating (2), it is possible to create a fragrance composition that has never existed before.

The usefulness of the present invention will be clarified by describing the production example of 1 by 9 synthesis, followed by the examples of perfume compositions.

Production example of compound (2) The production example of (2) can be divided into steps 1 to 3, and each can be shown by the reaction formula as follows.Step 1: x Step 2: Step 3: ■ Description of step 1 : Metallic sodium was dissolved in liquid ammonium, acetylene gas was blown into the solution, and ethylene oxide was added dropwise to obtain 3-butynol (n).

This was reacted with 2,3-dihydropyran to form pyranyl ether (m), and then further reacted with pentyl bromide to produce 9-(2-tetrahydrobyranyloxy)-6
-nonine (IV, 9-THPΦ0-6-nonine) was synthesized.

After depyranyl etherification in a mixture of 30% phosphoric acid and methanol, Lindlar
) Hydrogenation is carried out in the presence of a catalyst and quinoline, (3
Z)-nonenol (VI) was obtained. This was tosylated in lysine, then reacted with sodium iodide in the dark to form an iodine derivative (■), and then reacted with triphenylphosphine (Pφ3) to form a phosphonium salt (
■), obtained.

Description of step 2; 1,6-hexanediol (X), 4
After monobromination with 7% hydrobromic acid to form pyranyl ether (X■), a reaction between Grignard reagent prepared using metallic magnesium in tetrahydrofuran (THF) and triethyl-orthoformate was carried out. Acetal (Xm) was synthesized by reaction, and aldehyde (XIV) was obtained by deacetalization reaction in a mixture of water and acetone.

Explanation of Step 3; Phosphonium salt (IX) and aldehyde (
XIV) with THF and hexamethylphosphoramide (H
n-butyllithium (BuLi
) and Wittig reaction was carried out at -78°C. The product (XV) was depyranyl-etherified with a mixture of 30% phosphoric acid and methanol, and further subjected to Coltins oxidation to obtain the desired product (7Z, 1
0Z)-hexadecadienal (1) was obtained.

The above is an outline of the synthesis method, and next, a specific example will be described.

Specific manufacturing example〉 Processes 1 to 3 are further subdivided into 2 steps A to G.
Each of the five stages will be explained in detail below.

Process 1: From stage a to ri.

7. Process for producing 3-butynol (II).

Sodium metal (32 g, 1.4 mol) was dissolved in liquid ammonia (700 ml) at -40°C.

Acetylene gas was blown into the mixture, and ethylene oxide (51 g, 1.2 mol) was added dropwise thereto, followed by stirring at -33°C for 24 hours. It was cooled again to -40°C, ammonium chloride (75g, 1.4mol) was added, and the mixture was allowed to warm to room temperature to evaporate the ammonia.

Water was added to the residue and extracted with ether. After washing with 2N-hydrochloric acid and saturated saline, it was dried over sodium sulfate and distilled under reduced pressure to obtain ■ (18 g, yield 44%), bp7
7℃/80mm.

A. A method for producing 4-(2-tetrahydrobyranyloxy)-1-butyne (m).

The above II (20 g, 0.29 mol) was reacted with 2,3-dihydrobyran (36 g, 0.43 mol) and a catalytic amount of concentrated sulfuric acid at room temperature. Ether was added, washed with saturated brine and then saturated sodium bicarbonate, dried over 8 sodium chloride, and distilled under reduced pressure to obtain (39.1 g, yield 88%), bplO6°C/24 mm.

A method for producing 9-(2-tetrahydrobyranyloxy)-6-nonine (IV).

= liquid ammonia (700 ml) at 40°C.

Dissolve metallic sodium (9.0g) and add the above ■
was dripped. Furthermore, pentyl bromide (67.3 g, 0.
44 mol) was added dropwise and stirred at -33°C for 24 hours.

Cool again to -40°C and add ammonium chloride (31g
, 0.58 mol) was added thereto, and the temperature was returned to room temperature to vaporize ammonia. Water was added to the residue and extracted with ether. 2N
- Washed with hydrochloric acid and saturated saline, dried over sodium sulfate, and distilled under reduced pressure to obtain ■ (44.1 g, yield 77
%), bpH 7°C/1mm.

Process for producing 3-noninol (V).

Rin! (108 ml) and methanol (325 ml) was added dropwise to the mixture and stirred at room temperature.While adding saturated brine, methanol was distilled off under reduced pressure and extracted with ether.The ether layer was extracted with ether. After washing with saturated brine and saturated sodium bicarbonate water, it was dried over sodium sulfate and distilled under reduced pressure to obtain v (25.2 g, yield 91%).
, bp98℃15mm.

E. A method for producing (3Z)-nonenol (VI).

Hydrogen gas (1, SL) was blown into n-hexane (IL), quinoline (2,5 rnl), Lindlar catalyst (2 g) and V (7 g, 50 mmol). 1 After the reaction was completed, it was filtered through a glass filter. 2 Washed with 3N-hydrochloric acid saturated with sodium chloride and saturated saline, and distilled under reduced pressure to obtain (5)
．． 6 g, yield 78%), bp 84°C/1 mm.

force, (3Z)-(nonen-l-yl)-tosylate (■
) manufacturing method.

VI (3,95 ml) in pyridine (100 ml) at 0 °C.
g, 27.8 mmol) and p-toluenesulfonyl chloride (p-TsCl, 10.5 g, 55 mmol)
was added and stirred for 24 hours. The mixture was poured into 1.3 L of cold 2N hydrochloric acid and extracted with ether. After washing with saturated brine and saturated sodium bicarbonate water, it was dried over sodium sulfate and concentrated under reduced pressure to obtain (7.6 g, yield 92%).

Method for producing (3Z)-1-iodononene (■) In a dark place, add (7.6 g) and sodium iodide (7.5 g, 50 mmol) to acetone (50 ml), and add 6 g at room temperature.
Stirred for 7 hours. The reaction mixture was poured into cold water in a cool dark place, extracted with ether, washed with 12% aqueous sodium bisulfite and saturated brine, dried over sodium sulfate, and concentrated under reduced pressure to obtain (5.5 g, yield 85%).

A method for producing (3Z)-(nonen-1-yl)-triphenylphosphonium-iodite (IX).

In the dark under a nitrogen stream, triphenylphosphine (6.3 g, 24 mmol) was dissolved in benzene (100 ml), and after refluxing for 1 hour, (5.5 g) was added to give 43.
The mixture was stirred at 80°C for an hour. The temperature was returned to room temperature, benzene was distilled off, and the mixture was washed with ether. The remaining oil was dissolved in dichloromethane and concentrated under reduced pressure. Furthermore, it was dried at 55° C. under reduced pressure to obtain crude crystals. Recrystallize from methyl acetate■
(8.7 g, yield 77%), mp 86°C.

Process 2: From stage ke to shi.

K. Method for producing 6-promohexanol (XI).

In toluene (500 ml), 1,6-hexanedio-k (X, 59 g, 0.50 mol) and 47% hydrogen bromide @ (105 ml, 0, 9 mol) were added, and 9
The reaction was carried out at 0°C for 14 hours. The organic layer was washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by adsorption on calcium chloride (67.8 g
, yield 75%).

A method for producing 6-(2-tetrahydrobyranyloxy)-1-bromohexane (XI).

Ether was added to the reaction product of XI (46.4 g, 0.26 mol) and 2,3-dihydrobyran (32.8 g, 0.39 mol) stirred at room temperature in the presence of a catalytic amount of concentrated sulfuric acid. The mixture was washed with saturated brine and saturated sodium bicarbonate, dried over sodium sulfate, and concentrated under reduced pressure to obtain
(67.5 g, yield 99%).

A method for producing 7-(2-tetrahydrobyranyloxy)-hebutane diethyl acetal (Xm).

In a nitrogen stream, THF (70 (111)) was mixed with the metal magnesium (5.5 g, 0.22 mol) and iodine (a small amount).
xn (54g) dissolved in THF (70ml)
, 0.2 mol) was added dropwise and stirred at 40°C for 1 hour.
triethyl-orthoforme) (50 g, 0.
34 mol) was added thereto and stirred for 48 hours. water at room temperature (16
After stirring for a while, the mixture was extracted with hexane. After washing this with saturated saline and sodium bicarbonate water.

It was dried over sodium sulfate and concentrated under reduced pressure to obtain x■ (5
8g, yield 99%).

A method for producing 7-(2-tetrahydrobyranyloxy)-heptanal (XrV).

Add oxalic acid (31.0 g, 0.25 mol) to a mixed solvent of acetone (210 ml) and water (140 ml),
Further, add XIII (24 g, 83 mmol) and
Stirred at 0°C for 35 minutes. Sodium bicarbonate (25g
), the acetone was distilled off under reduced pressure, the residue was extracted with ether, washed with saturated brine and saturated sodium bicarbonate, dried over sodium sulfate, concentrated under reduced pressure, and extracted with X.
IV was obtained (9"4gl 53% yield).

Process 3: From step S to step S.

s, 1-(2-tetrahydrobyranyloxy)-(7Z
, 10Z)-hexadecadiene (XV).

IX (17.0 g, 33 mmol) was dissolved in THF (500
n-Bu dissolved in n-Bu
After adding Li (28ml 1.42 mmol) and stirring for 20 minutes, HMPA (43ml) 7XIV (7,
0 g, 33 mmol) was added thereto, and the mixture was stirred at 0° C. or lower for 1 hour. After adding water, THE was distilled off under reduced pressure, the aqueous layer was saturated with di-salt, and extracted with ether. After concentration under reduced pressure, n
-Dissolved in hexane, washed with saturated saline and dried over sodium sulfate. After concentrating under reduced pressure, it was treated with a silica gel column (eluent: n-hexane) to obtain x■ (
4.4 g, yield 41%).

Se, (7Z, 10Z)-hexadecadienal (XVI
) manufacturing method.

The above XV (4.4 g) was added to a mixture of phosphoric acid (80 ml) and methanol (200 ml), and the mixture was stirred at room temperature. Methanol was distilled off under reduced pressure, and the residue was extracted with ether. This was washed with aqueous sodium hydroxide solution and saturated brine, dried over sodium sulfate, and then treated with a silica gel column to obtain XVI (2.8 g, yield 86%).

Method for producing (7Z, 10Z)-hexadecadienal (I).

Pyridine (9,2
g) and stirred at room temperature, chromium dioxide (5,8
g, 58 mmol) and stirred for 15 minutes. XV
After stirring for another 15 minutes, filter the mixture through a Florisil column, wash the residue with ether, collect the organic layer, wash with dilute acid and saturated brine, and dry over sodium sulfate. This was treated with a silica gel column to obtain I (1.65 g, yield 77%).

The analytical data of I, which was first synthesized as described in Section 2, are shown below.

Synthetic ■ exhibited the same aroma and flavor as I isolated from the +ilI alga Ulva.

H-NMR: -CLO(δ 9.67, IH, t, J
=1.7Hz), 2 (-CL=CL-)(δ5.30
,4H,m), -CH=CH-CJiJ.

-CH=CH-(δ 2.80.2H,t, J=5.5
Hz), -CH2-C1-CHO(δ2.45.2H+
m) + 2 (=]-1-C Dannie) (81,98,
4Ht m) I-C Dannie (δ1.30.12H, m)
, CL, (δ 0.90.3H, t, J=7Hz)
.

IR (cm-1): 2725 (CHO), 1730 (
C=O), 1660 (C=C).

MS: m/z 23B (6.5%, M+), 15
1 (3,5), 137 (4,7), 123 (5°7
), 109 (15,7), 98 (4,4,
9).

81 (69,4), 67 (100), 55
(40,8), 41 (14,9).

Note that among the compounds shown in the above steps, x■ and XVI are new compounds.

As mentioned at the beginning, Compound I has a characteristic aroma and flavor. Examples of producing a fragrance composition utilizing this organoleptic property will be specifically described in the following Examples. It is not limited.

<Example> Example 1゜ A cheese flavor was prepared using the following ingredients (weight ratio).

Butyl butyryl lactate 2.0 3-methylbutanoate 0.5 ethyl
Butyrate 1.5 Butanoic acid
4.0 Decanoic acid
1.02-hebutanone
1.02-undecanone
0.5 lactic acid 1.0
Ethanol 8.0 Propylene glycol 80.5 total
100.0 The above composition and 1 g of ■ added to 100 g of the above composition were subjected to sensory evaluation by 6 skilled perfumers. As a result, it was pointed out that the composition containing ■ had a stronger cheddar cheese-like aroma and flavor, and the addition of ■ enhanced the brightness and naturalness characteristic of cheddar.

Example 2 A citrus type fragrance was prepared by mixing the following components.

Jasmine base 4.0 Rose base 1.0 α-amylcinnamaldehyde 1.0 Dimethyl anthranilate 2.0 Terpineol
5.0 Linalool 15
．． 0 linalyl acetate 5.0 octanal 10% 2.0 nonanal 10% 1.0 decanal 5
0%*2.0 Lemon oil 5.0 Lime oil 5. Od-limonene
52.0 total
ioo,.

The above composition in wood ethanol and 2 g of a 10% ethanol solution of I added to 100 g of the above composition were subjected to sensory evaluation by six experienced perfumers. The composition in which everyone added summer is better.
Rich in natural citrus and fresh aroma,
Furthermore, he pointed out that the strength and diffusion of the odor were better.

Example 3 A rose type fragrance was prepared by mixing each component as follows.

Rhodinol 10 Phenylethyl Alcohol 20 Cinnamyl Alcohol 6 Geraniol
20 citronellol
14 linalool
6 Hydroxycitronellal 5 Linalyl Acetate 4 Eugenol 4 Geranium Oil (African) 10 Phenylethyl Acetate
1 total
100 The above composition and 6 g of a 1% ethanol solution of I added to 100 g of the above composition were subjected to sensory evaluation by six experienced perfumers. As a result, it was pointed out that the composition to which ■ was added had a stronger brilliance and naturalness peculiar to rose, and had better odor and diffusivity.

Claims (1)

[Claims] A fragrance composition characterized by containing (7Z,10Z)-hexadecadienal.