JPH10158257A - Production of optical active delta-lactone and perfume containing said delta-lactone - Google Patents

Abstract

PROBLEM TO BE SOLVED: To inexpensively and simply obtain an optically active δ-lactone that can be used as a perfume by using an essential oil collected from the bark of a tree plant, Cryptocarya messoia Becc. SOLUTION: (A) An optically active δ-decenolactone and/or δ-dodeceno-lactone of formula I (R is pentyl, heptyl) is obtained by separating from the essential oil collected from the bark of Cryptopcarya massoia Becc. These lactones are catalytically reduced in the presence of, for example, a palladium on carbon catalyst to give (R)(+)-δ-decalactone and/or (R)(+)-δ-dodecalactone of formula II. The resultant compound of formula II can be used as a perfume. According to this process, these lactones can be inexpensively produced in large amounts in no need of complicated operations.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to an optically active δ- useful as a material of a flavor used in foods, cosmetics, tobacco and the like.
The present invention relates to a lactone production method and a fragrance containing the δ-lactone.

[0002]

2. Description of the Related Art Conventionally, δ-lactone has been well known as an aroma component contained in various foods such as dairy products and coconut. Among δ-lactones, δ having 10 carbon atoms
-Decalactone and δ-dodecalactone having 12 carbon atoms are contained in dairy products, coconut, and various processed foods at the contents shown in Table 1 below, and have a great influence on the aroma of the food.

[0003]

[Table 1]

However, since δ-lactone is a chiral compound, there are R-form and S-form. Then, when the R / S ratio of each food is examined, as shown in Table 2, the R-form is contained more than the S-form.

[0005]

[Table 2]

[0006]

The δ-lactone synthesized by ordinary chemical synthesis means is a racemate. Therefore, in order to obtain an R-form δ-lactone useful as a perfume material, it is necessary to optically resolve the R-form δ-lactone from the synthesized racemic body. Therefore, Japanese Patent Application Laid-Open No.
No. 9 discloses that the lipase produced by a microorganism is acted on to optically resolve racemic lactones, and the resulting hydroxycarboxylic acid is dehydrated and cyclized, whereby the abundance ratio of R / S is determined by the natural abundance ratio. A method for obtaining an optically active δ-lactone prepared in US Pat.

[0007] However, optical resolution by microorganisms and the like has a problem of low productivity, and the resulting optically active δ-lactone must be expensive. The present invention provides a method for producing an optically active δ-lactone that can easily and inexpensively obtain an optically active δ-lactone without requiring a complicated synthesis route or optical resolution, and a fragrance containing the δ-lactone. To provide.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above problems, and as a result, have found that Cryptocarya massoi, a plant mainly produced in Indonesia.
a Becc. )), About 50% (R) (−)-δ-decenolactone and about (R) (−)-δ-dodecenolactone are commonly referred to as essential oils obtained from the bark of (B). Attention was paid to the fact that the essential oil was contained at 7%, and a new finding was obtained that the R-form δ-lactone can be easily obtained by reducing the optically active compound separated from the essential oil. Was completed.

That is, since the essential oil obtained from the bark is commercially available and can be obtained at relatively low cost and in large quantities, it is relatively easy and inexpensive to obtain R-form δ-lactone. Is possible. Therefore, the method for producing an optically active δ-lactone of the present invention comprises
MASOIA BEC (Cryptocarya mass)
oia Becc. From the essential oil of the bark of the general formula (1):

[0010]

Embedded image

(Wherein, R represents a pentyl group or a heptyl group). An optically active δ-decenolactone and / or δ-dodecenolactone represented by the formula:

[0012]

Embedded image

Wherein R is the same as defined above, and (R) (+)-δ-decalactone and / or (R) (+)-δ-dodecalactone are obtained. I do. The fragrance of the present invention is characterized by containing (R) (+)-δ-decalactone and / or (R) (+)-δ-dodecalactone obtained by the above method.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The starting material used in the present invention is Cryptocary, a species belonging to the genus Cryptocarya masoaiae of the genus Lauraceae.
a massia Becc. ], Also known as Cryptocarya aromatika (Besse) costa [Cry
ptocarya aromatica (Bec.)
kosterm]. In Indonesia, the bark is used as Messui, Misui, Miso, Mas
ohi or Masoyi, spices, medicinal (cough,
Medicines for diarrhea and abdominal pain).

The essential oil of Cryptocarya masoia bech includes Indonesian p. t. Djasula W
essential oil commercially available from Angi (Massia)
Oia essential oil) can be used. In addition, Massoyalactone commercially available as a perfume raw material from Shalabo Co., Ltd.
acton) or dodecenoic delta lactone 5
0 (Dodecenoic Deltaacton)
50) can also be used as starting material. All were isolated from the essential oil of Cryptocarya masoia bec, and the masoia lactone corresponds to the optically active δ-decenolactone (that is, (R) (−)-δ-decenolactone). On the other hand, dodecenoic delta lactone 50 is a mixture (1: 1) of the optically active δ-dodecenolactone (that is, (R) (−)-δ-dodecenolactone) and benzyl benzoate. When this mixture is used in the present invention, the optically active δ-dodecenolactone may be previously separated from benzyl benzoate by distillation or the like, or the mixture may be used as a reaction raw material. This is because benzyl benzoate may be contained in the fragrance regardless of the presence or absence of reduction.

The optically active δ-decenolactone and δ
-Dodecenolactone is used which is separated by distillation from the essential oils, in particular volatile essential oils. Distillation includes steam distillation, vacuum distillation, and the like, and any of them can be employed.
Further, optically active δ-decenolactone and δ-dodecenolactone separated by other separation means can also be used.

At this time, δ-decenolactone and δ-dodecenolactone may be separated from the essential oil as a mixture, or each may be isolated by utilizing a difference in boiling point. In any case, it can be subjected to the following reduction reaction. Examples of the reduction include a hydrogenation reaction in the presence of a catalyst of a transition metal (palladium, nickel, platinum, copper, rhodium, etc.), and a reduction reaction using a usual reducing agent. Examples of the reducing agent include nonmetal ions, acids, lower oxide lower oxyacid salts, metals having a high ionization tendency or amalgam thereof, low valent metal salts, hydrides, hydrazine, diimide, formic acid, aldehydes, saccharides, L-ascorbic acid and the like. In the present invention, a catalytic reduction method using palladium carbon or the like is particularly preferably employed.

The reaction formula by the catalytic reduction method using palladium carbon is shown below. Reaction process formula (I):

Embedded image (In the formula, R is the same as described above.) Such catalytic reduction can be carried out in an organic solvent at normal pressure or under pressure, at a reaction temperature of 10 to 40 ° C. and a reaction time of 3 hours.
It is about 0 to 120 minutes.

The reaction product is subjected to column chromatography.
To obtain an optically active δ-lactone represented by the general formula (2). Reaction product (R) (+)-
δ-decalactone and (R) (+)-δ-dodecalactone may be isolated during the purification process, or may be used as a perfume raw material as a mixture.

That is, (R) (+)-δ-decalactone and (R) obtained by the method of the present invention.
(+)-Δ-dodecalactone is suitable for producing a compounded perfume to be added to foods, cosmetics, tobacco, etc. by using either one alone or by mixing both with other perfume materials.

[0021]

The present invention will be described below in detail with reference to Reference Examples, Examples and Formulation Examples. Reference Example [(R) (−)-δ-desenocton and (R) (−)
Separation of Essential Oil from δ-Dodecenolactone] Indonesian p. t. Vacuum distillation from Masoia essential oil available from Djasula Wangi (129-132 ° C)
(R) (−)-δ-decenolactone (masoyalactone) and (137-141) under the conditions of (/ 3 mmHg).
(R) (−)-δ-dodecenolactone, respectively, under the conditions of (° C./3 mmHg).

¹ H-NMR, ¹³ C-NM of the obtained (R) (−)-δ-decenolactone (masoyalactone)
R, infrared absorption spectrum and optical rotation are as follows. ¹ H-NMR (δ): 0.90 (3H), 1.27-
1.72 (8H), 2.33 (2H), 4.42 (1
H), 6.01 (1H), 6.89 (1H). ¹³ C-NMR (δ): 13.84 (q, C-10), 2
2.37 (t, C-9), 24.38 (t, C-8),
29.28 (t, C-7), 31.42 (t, C-
6), 34.73 (t, C-4), 77.94 (d, C
-5), 121.29 (d, C-2), 144.99.
(D, C-3), 164.49 (s, C-1). IR (cm ^-1 ): 2952, 2930, 2870, 17
21, 1389, 1252, 1117, 1040, 81
6. [Α] _D ²² : -98.36 ° and (R) (−)-δ-
¹ H-NMR, ¹³ C-NMR, infrared absorption spectrum and optical rotation of dodecenolactone are as follows.

¹ H-NMR (δ): 0.88 (3H),
1.20 to 2.00 (12H), 2.33 (2H),
4.42 (1H), 6.03 (1H), 6.88 (1
H). ¹³ C-NMR (δ): 14.05 (q, C-12), 2
2.60 (t, C-11), 24.79 (t, C-1)
0), 29.09 (t, C-9), 29.29 (t, C
-8), 29.38 (t, C-7), 31.71 (t,
C-6), 34.85 (t, C-4), 78.02.
(D, C-5), 121.44 (d, C-2), 14
4.98 (d, C-3), 164.59 (s, C-
1). IR (cm ^-1 ): 2952, 2930, 2870, 17
21, 1389, 1252, 1117, 1040, 81
6. [Α] _D ²² : −85.94 ° Example 1 [Synthesis of (R) (+)-δ-decalactone] In a hydrogen stream, (R) (−)-δ-decenolactone (50 g), 5
% Palladium on carbon (0.5 g), ethyl alcohol 30
0 ml were mixed and stirred vigorously at 10 atm for 1 hour. Next, the reaction solution was filtered to remove palladium carbon, the residue was washed with ethyl alcohol, and the washing solution and the filtrate were mixed. Next, the filtrate was concentrated under reduced pressure to obtain the title compound.

The ¹ H-NMR, ¹³ C-NMR, infrared absorption spectrum and optical rotation of the title compound (R) (+)-δ-decalactone are as follows. ¹ H-NMR (δ): 0.89 (t, 3H) 1.26
~ 2.00 (m, 12H) 2.50 (m, 2H) 4.2
8 (m, 1H). ¹³ C-NMR (δ): 13.85 (q, C-10) 1
8.38 (t, C-9) 22.39 (t, C-8) 2
4.49 (t, C-7) 27.69 (t, C-3) 2
9.35 (t, C-4) 31.48 (t, C-6) 3
5.69 (t, C-2) 80.51 (d, C-5) 17
1.84 (s, C-1). IR (cm ^-1 ): 2953, 2932, 2870, 17
36, 1460, 1245, 1186, 1167.10
53,1036,866. [Α] _D ²² : + 54.95 ° Example 2 [Synthesis of (R) (+)-δ-dodecalactone] Example 2 was repeated except that (R) (−)-δ-dodecenolactone was used as a starting material. The reaction was carried out in the same manner to synthesize the title compound. The ¹ H-NMR, ¹³ C-NMR, infrared absorption spectrum and optical rotation of the title compound (R) (+)-δ-dodecalactone are as follows.

¹ H-NMR (δ): 0.80 (t, 3
H) 1.20-2.00 (m, 16H) 2.52
(M, 2H) 4.28 (m, 1H). ¹³ C-NMR (δ): 14.05 (q, C-12), 1
8.48 (t, C-11), 22.60 (t, C-1)
0), 24.91 (t, C-9), 27.78 (t, C
-8), 29.12 (t, C-7), 29.36 (t,
C-3), 29.46 (t, C-4), 31.74.
(T, C-6), 35.83 (t, C-2), 80.6
2 (d, C-5), 172.05 (s, C-1). IR (cm ^-1 ): 2953, 2932, 2870, 17
36, 1460, 1245, 1186, 1167.10
53,1036,866. [Α] _D ²² : + 22.05 ° FIG. 1 shows an infrared absorption spectrum of α, β-unsaturated-δ-lactone to which optically active δ-decenolactone and δ-dodecenolactone belong. FIG. 2 shows an infrared absorption spectrum of the optically active δ-lactone represented by the general formula (1) obtained by reducing the optically active α, β-unsaturated-δ-lactone. Formulation Example 1 (Components) (parts by weight) diacetyl 2.0 butyl butyrate 2.0 acetoin 4.0 butyric acid 6.0 caproic acid 9.0 caprylic acid 4.0 2-heptanone 1.0 2-nonanone 2.0 ( R) (+)-δ-decalactone 40.0 (R) (+)-δ- dodecalactone 30.0 propylene glycol 200.0 ethyl alcohol 700.0 total 1000.0 synthesized in Examples 1 and 2 (R) (+)-δ-decalactone and (R) (+)-δ-dodecalactone were dissolved in propylene glycol and ethyl alcohol together with the various flavor materials described above to prepare a basic butter flavor. . Comparative Formulation Example 1 Instead of the compounds of (R) (+)-δ-decalactone and (R) (+)-δ-dodecalactone as δ-lactones, racemic δ-decalactone and δ-dodecalactone were used, respectively. A basic butter flavor was prepared in the same manner as in Preparation Example 1 except that the same amount was used.

Each of the fragrances obtained in Formulation Example 1 and Comparative Formulation Example 1 was subjected to a sensory test by a specialized panel of 10 persons. As a result, all of the specialized panels were (R) (+)-δ-decalactone and (R) (+)-
All of the fragrances of Formulation Example 1 in which δ-dodecalactone was incorporated were closer to the scent of natural butter and had a strong mellow and rich flavor. Formulation Example 2 (Components) (parts by weight) Ethyl maltol 0.1 Vanillin 0.1 Ethyl acetate 5.0 Ethyl myristate 8.0 Benzaldehyde 1.0 Benzyl alcohol 30.0 Linalool 8.0 2 -Methylbutyric acid 3.0 γ-decalactone 3.0 (R) (+)-δ-decalactone 5.0 γ-undecalactone 20.0 (R) (+)-δ-dodecalactone 3.8 -S NPC 10.0 Propylene glycol 200.0 Ethyl alcohol 700.0 Total 1000.0 (R) (+)-δ-decalactone synthesized in Examples 1 and 2, (R) (+)-δ -Dodecalactone was dissolved in propylene glycol and ethyl alcohol together with the various perfume materials described above to prepare a base pitch perfume. Comparative Formulation Example 2 (R) (+)-δ-decalactone and (R) (+)-
A basic pitch flavor was prepared in the same manner as in Preparation Example 2, except that racemic δ-decalactone and δ-dodecalactone were used in the same amounts, respectively, instead of the δ-dodecalactone compound.

A sensory test was performed on the fragrances obtained in Formulation Example 2 and Comparative Formulation Example 2 by a panel of 10 experts.
As a result, the fragrance of Formulation Example 2 in which (R) (+)-δ-decalactone and (R) (+)-δ-dodecalactone were incorporated compared with Comparative Formulation Example 2, was more natural and fresh. Everyone judged that the scent of the peach was good and the pulp feeling was good.

[0028]

According to the production method of the present invention, there is an effect that an R-form δ-lactone useful as a perfume material can be easily obtained by using a cheap and easily available raw material. Therefore, the fragrance containing this δ-lactone has an effect of having an excellent fragrance more natural than the conventional fragrance containing racemic-δ lactone.

[Brief description of the drawings]

FIG. 1 is a graph showing an infrared absorption spectrum of α, β-unsaturated-δ-lactone to which optically active δ-decenolactone and δ-dodecenolactone belong.

FIG. 2 shows an optically active δ- represented by the general formula (1) obtained by reducing an optically active α, β-unsaturated-δ-lactone.
It is a graph which shows the infrared absorption spectrum of a lactone.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Toshinobu Giga 2-5-8, Hirano-cho, Chuo-ku, Osaka-shi, Osaka Inside Nagaoka Inc. Osaka Research Laboratory

Claims (2)

[Claims] 1. Cryptocarya masoia bech (Cr
yptocarya massoia Becc. General formula (1) isolated from the essential oil of the bark of the formula (1): (Wherein, R represents a pentyl group or a heptyl group.) An optically active δ-decenolactone and / or δ
-Reduction of dodecenolactone to formula (2): (Wherein, R is the same as described above).
(+)-Δ-decalactone and / or (R) (+)
A method for producing optically active δ-lactone, characterized by obtaining δ-dodecalactone. 2. A fragrance containing (R) (+)-δ-decalactone and / or (R) (+)-δ-dodecalactone obtained by the production method according to claim 1.