JP2515261B2 - Methyl-4,6-0-alkylidene-D-glycoside - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION Industrial Field of the Invention The present invention is a compound substantially odorless in itself,
The present invention relates to a novel compound which has not been described in the prior art and has an extremely excellent retaining effect as a retaining agent for perfumes. The present invention also relates to the use of the compound of the above formula (1) and a method for producing the same.

More specifically, the present invention provides the following formula (1) However Shikichu, R represents an alkyl group or an alkenyl group of C ₉ of C ₅ -C _11, the wavy line of the novel compounds of the prior art documents undescribed represented in shows Axial or equatorial bond methyl 4,6
It relates to 0-alkylidene-D-glycosides.

Further, the present invention provides a novel perfume composition which is extremely useful as a retaining agent for a prepared perfume composition containing the compound of the formula (1) as an active ingredient, in which the compound of the formula (1) has an extremely excellent perfume retaining property. Also related to things.

 Furthermore, it also relates to a process for producing the compound of formula (1).

(Prior Art) Since natural fragrances and synthetic fragrances are generally highly volatile, a compounded fragrance obtained by compounding these fragrances is a compounded fragrance in which the more volatile component of the compounded fragrance evaporates over time. The component balance may be lost and the fragrance tone may change significantly.

Conventionally, in order to prevent such a change, various holding agents for adjusting the volatility or holding ability of the fragrance substance have been used by blending it as an active ingredient in the fragrance.

As the above retaining agent, for example, diethyl phthalate, benzyl benzoate, triethyl citrate, diethylene glycol monoethyl ether, isopropyl myristate, propylene glycol, dipropylene glycol, etc. are usually used.

Furthermore, in recent years, various compounds which have the effects of a diluent, a retaining agent, a stabilizer, etc., alone at the same time have been proposed as perfume conditioners. Examples of these compounds include 2-ethylhexylbenzoate, 3-phenylpropyl-2-ethylbutyrate (JP-A-55-133303), for example, benzylphenoxyacetate, benzyl-3-phenoxypropionate (special 55-133304), for example, ethylene glycol dibenzoate, diethylene glycol dibenzoate (JP-A-55-133305), such as dihexyl tertarate, trihexyl citrate (JP-A-55-133304).
55-133306) and the like have been proposed.

(Problems to be Solved by the Invention) The above-mentioned conventionally used diethyl phthalate ...
・ ・ ・ ・ ・ ・ ・ ・ The dipropylene glycols are not always satisfactory in the effect of retaining the fragrance.

In addition, the compounds described in the above-mentioned patent publications are not satisfactory as the effect of retaining the fragrance.

Furthermore, the methyl-4,6-0-benzylidene-α-D-glucopyranoside described in JP-A-60-188037, JP-A-60-188039 and JP-B-56-44055 is a synthetic intermediate for sweeteners. , Or a method for synthesizing an ether or ester derivative of the compound, the formula (1) novel compound of the present invention and a method for producing the same are mentioned at all, and further, a retaining property of a fragrance. Has not been described or suggested at all.

(Means for Solving Problems) In view of the above circumstances, the present inventors have earnestly studied to develop a new type of holding agent useful as a holding agent for perfumes and mixed perfumes, and as a result, have not been described in the conventional literature. Formula (1) above
Succeeded in synthesizing a new compound, and the compound is substantially odorless, chemically stable and excellent in skin safety,
It has been discovered that it has an extremely excellent holding effect as a holding agent for various flavors and their mixed flavors. Further, it was discovered that the compound of the above formula (1) can be easily synthesized.

Therefore, an object of the present invention is to provide a novel compound of the above formula (1) which has not been described in the prior art and a method for producing the same. or,
The present invention provides a novel perfume composition characterized by containing the compound of formula (1) as an active ingredient in a perfume and a prepared perfume composition thereof.

The following formula (1) of the present invention However, in the formula, R represents a C _{5 to} C ₁₁ alkyl group or a C ₉ alkenyl group, and a wavy line represents an axial or equatorial bond, and a methyl-4,6-0-alkylidene-D-glycoside represented by To synthesize, for example, the following formula (2) The wavy line indicates an axial or equatorial bond. The methyl-D-glycoside represented by the following formula (3) in the presence of an acid in an organic solvent However, in the formula, R represents a C _{5 to} C ₁₁ alkyl or C ₉ alkenyl group, and can be easily synthesized by contacting with an aldehyde dimethyl acetal represented by:

The method for synthesizing the compound of the above formula (1) of the present invention can be represented as follows when shown in a process diagram.

The mode for synthesizing the compound of formula (1) of the present invention will be described in detail below with reference to the example of the above process chart.

Examples of the compound included in the methyl-D-glycoside of the formula (2) necessary for synthesizing the compound of the formula (1) of the present invention include, for example, methyl-α or β-D-glucopyranoside,
Methyl-α, or D-galactopyranoside, methyl-
Methyl hexacarbon sugars such as α or β-D-mannopyranoside can be exemplified.

These pyranosides are readily available compounds on the market. Aldehyde dimethyl acetal of formula (3) is also a compound that can be easily obtained on the market, and can be easily synthesized if desired.

When synthesizing, it is possible to easily synthesize by commercially available aldehyde, for example, by reacting with aldehyde methyl orthoformate in the presence of p-toluenesulfonic acid in methanol.

To synthesize the compound of formula (1) of the present invention, for example, the compound of formula (2) can be easily and inexpensively and industrially synthesized by contacting the compound of formula (3) with the compound in the presence of an acid in an organic solvent. You can The temperature of this reaction can be appropriately selected and changed, but a temperature range of about 40 to about 150 ° C. can be preferably exemplified. Further, the reaction time can be appropriately selected and carried out, but, for example, the reaction time is usually in the range of about 1 to about 6 hours.

Preferable examples of the organic solvent used in the above reaction include dimethylformamide, dichloroethane, ethyl acetate, benzene, toluene and cyclohexane. The amount of these organic solvents used is not particularly limited and may be appropriately selected. For example, the amount may be about 1 to about 5 times the weight of the compound of the formula (2). . The amount of the compound of formula (3) used is, for example, about 0.5 to 1 mol of the compound of formula (2).
A range of about 2 mol can be exemplified. As the acid used, for example, p-toluenesulfonic acid, sulfuric acid, phosphoric acid and the like can be preferably exemplified. The amount of these acids used is, for example, about 0.1 based on the compound of the formula (2).
The amount used may be in the range of about 1 to about 5% by weight. The reaction can be carried out under reduced pressure if desired. The degree of reduced pressure can be appropriately selected and changed, but is usually, for example, about 10 to about 60.
It is performed in the range of mmHg.

After completion of the reaction, for example, an appropriate amount of sodium carbonate is added to the reaction solution, the solvent is distilled off under reduced pressure, and the residue is purified by column chromatography using silica gel to easily obtain the target compound. it can.

Thus, the compound included in the methyl-4,6-0-alkylidene-D-glycoside of the above formula (1) obtained as described above is, for example, methyl-4,6-0-hexylidene-α, or β, D-glucopyranoside, methyl-4,6-0-hexylidene-α, or β, D-galactopyranoside, methyl-4,6-0-hexylidene-α, or β, D-mannopyranoside, methyl-4 , 6-0-Heptylidene-α, or β, D-glucopyranoside, methyl-4,6-heptylidene-α, or β, D-galactopyranoside, methyl-4,6-0-heptylidene-α, or β , D-mannopyranoside, methyl-4,6-0-octylidene-α, or β, D-glucopyranoside, methyl-4,
6-0-octylidene-α, or β, D-galactopyranoside, methyl-4,6-0-octylidene-α, or β, D-mannopyranoside, methyl-4,6-0-nonylidene-α, or β-glucopyranoside, methyl-4,6
-0-nonylidene-α or β, D-galactopyranoside, methyl-4,6-0-nonylidene-α, or β, D-
Mannopyranoside, methyl-4,6-0-decylidene-
α, or β, D-glucopyranoside, methyl-4,6-0
-Decylidene-α, or β, D-galactopyranoside,
Methyl-4,6-0-decylidene-α or β, D-mannopyranoside, methyl-4,6-0-undecylidene-
α, or β, D-glucopyranoside, methyl-4,6-0
-Undecylidene-α, or β, D-galactopyranoside, methyl-4,6-0-undecylidene-α, or β,
D-mannopyranoside, methyl-4,6-0-dodecylidene-α, or β, D-glucopyranoside, methyl-4,6,-
0-dodecylidene-α or β, D-galactopyranoside, methyl-4,6-0-dodecylidene-α, or β, D
-Mannopyranoside, methyl-4,6-0- (3,7-dimethyl-6-octene-1-ylidene) -α, or β, D-
Glucopyranoside, methyl-4,6-0- (3,7-dimethyl-6-octene-1-ylidene) -α, or β, D-galactopyranoside, methyl 4,6-0- (3,7- Dimethyl
6-octene-1-ylidene) -α or β, D-mannopyranoside can be mentioned. These compounds of formula (1) have an excellent effect which has never been obtained as a holding agent for perfumes and prepared perfume compositions, and the amount used is not particularly limited and may be appropriately selected and used. However, in the case of a prepared perfume composition, for example, the range of about 5 to about 50% by weight, preferably about 10 to about
The usage amount in the range of about 30% can be exemplified.

Hereinafter, embodiments of the present invention will be described in more detail with reference to examples.

(Example) (1) Synthesis of methyl-4,6-0-hexylidene-α, D-glucopyranoside.

Add 9.7 g of methyl-α, D-glucopyranoside (0.
05 mol), hexanal dimethyl acetal 8.0 g (0.05
Mol), 50 ml of dimethylformamide and 0.5 g of p-toenesulfonic acid were charged, and the reaction was carried out under reduced pressure (30 mmHg) at 40 ° C. for 8 hours while distilling methanol off. After the reaction was completed, 1 g of sodium carbonate was added to the reaction solution, the solvent was distilled off under reduced pressure, and the residue was purified by column chromatography (chloroform / methanol = 90/10) using 500 g of silica gel to obtain 9.97 g (72.2 % Target compound was obtained. ¹ H-NMRδ (CDCl ₃ ) ppm 0.89 (3H, t, J = 4.6Hz) 1.1 to 1.9 (9H, m) 3.41 (3H, s) 3.22 to 4.53 (8H, m) 4.73 (1H, d, J = 3.5 Hz) (2) Synthesis of methyl-4,6-0-heptylidene-α, D-glucopyranoside.

In Example (1), 8.0 g of heptanal dimethyl acetal (0.
(055 mol) was used, and the same procedure was followed as in Example (1) to obtain 10.61 g of the target compound. (Yield; 73.2%) ¹ H-NMRδ (CDCl ₃ ) ppm 0.89 (3H, t, J = 4.6Hz) 1.1 to 1.9 (11H, m) 3.41 (3H, s) 3.22 to 4.53 (8H, m) 4.73 (1H, d, J = 3.5Hz) (3) Synthesis of methyl-4,6-0-octylidene-α, D-glucopyranoside.

In Example (1), instead of hexanal dimethyl acetal, 8.7 g of octanal dimethyl acetal (0.
(1 mol) was obtained in the same manner as in Example (1) except that (05 mol) was used. (Yield; 75.0%) ¹ H-NMRδ (CDCl ₃ ) ppm 0.89 (3H, t, J = 4.6Hz) 1.1 to 1.9 (13H, m) 3.41 (3H, s) 3.22 to 4.53 (8H, m) 4.73 (1H, d, J = 3.5Hz) (4) Synthesis of methyl-4,6-0-nonylidene-α, D-glucopyranoside.

In Example (1), instead of hexanal dimethyl acetal, nonanal dimethyl acetal 9.4 g (0.
(1 mol) was obtained in the same manner as in Example (1) except that (05 mol) was used. (Yield; 74.1%) ¹ H-NMRδ (CDCl ₃ ) ppm 0.89 (3H, t, J = 4.6Hz) 1.1 to 1.9 (15H, m) 3.41 (3H, s) 3.22 to 4.53 (8H, m) 4.73 (1H, d, J = 3.5Hz) (5) Synthesis of methyl-4,6-0-decylidene-α, D-glucopyranoside.

In Example (1), 10.1 g of decanal dityl acetal (0.0 g) was used instead of hexanal dimethyl acetal.
The same procedure as in Example (1) except that 5 mol) was used to obtain 12.4 g of the target compound. (Yield; 74.5%) ¹ H-NMRδ (CDCl ₃ ) ppm 0.89 (3H, t, J = 4.6Hz) 1.1 to 1.9 (17H, m) 3.41 (3H, s) 3.22 to 4.54 (8H, m) 4.73 (1H, d, J = 3.5Hz) (6) Synthesis of methyl-4,6-0-undecylidene-α, D-glucopyranoside.

In Example (1), undecanal dimethyl acetal 10.8 was used instead of hexanal dimethyl acetal.
The same procedure was followed as in Example (1) except that g (0.05 mol) was used to obtain 10.6 g of the target compound. (Yield; 72.8%) ¹ H-NMRδ (CDCl ₃ ) ppm 0.89 (3H, t, J = 4.6Hz) 1.1 to 1.9 (19H, m) 3.41 (3H, s) 3.22 to 4.54 (8H, m) 4.73 (1H, d, J = 3.5Hz) (7) Synthesis of methyl-4,6-0-dodecylidene-α, D-glucopyranoside.

In Example (1), 12.7 g of dodecanal dimethyl acetal instead of hexanal dimethyl acetal
13.35 g of the target compound was obtained in the same manner as in Example (1) except that (0.055 mol) was used. (Yield; 74.1%) ¹ H-NMRδ (CDCl ₃ ) ppm 0.88 (3H, t, J = 5.9Hz) 1.1 to 1.68 (21H, m) 3.41 (3H, s) 3.22 to 4.58 (8H, m) 4.73 (1H, d, J = 2.9Hz) (8) Methyl-4,6-0- (3,7-dimethyl-6-octene-
Synthesis of 1-ylidene) -α, D-glucopyranoside.

Citronellal dimethyl acetal 13.86 g (69.2 mol), dimethyl sulfide 110 ml, methyl-α, D-glucopyranoside 13.44 g (69.2 mol), p-toluenesulfonic acid 0.2 g were charged into a flask, and 30 mmHg at 40 ° C. under reduced pressure. The reaction was carried out for 3 hours while distilling off methanol. After completion of the reaction, 1 g of sodium carbonate was added to the reaction solution and concentrated under reduced pressure, and the residue was purified by column chromatography (chloroform / methanol = 95/5) using 500 g of silica gel to obtain the target compound 1
6.1 g was obtained. (Yield; 70.4%) ¹ H-NMRδ (CDCl ₃ ) ppm 0.91 (3H, d, J = 5.7Hz) 1.59 (3H, s) 1.67 (3H, m) 3.41 (3H, s) 4.73 (1H, d , J = 3.3 Hz) (Application Example) This application example shows the effect of retaining the fragrance of the compound of the present invention obtained in Example 1 above.

Retention effect test 90% by weight of a model compounded fragrance consisting of 12 kinds of effective substances shown in Table 1 below and 10% by weight of a compound of the present invention or a comparative compound were uniformly dissolved and mixed to prepare a compounded fragrance. A sample is prepared by adding four times as much ethyl alcohol as the fragrance.

0.5g of this sample or model blended fragrance was applied to odor paper (9cm x 9cm, 2.4g), and then a temperature of 25 ° C and a constant temperature of 50%,
In a room with constant humidity, a judge consisting of 5 fragrance technicians determined the degree of fragrance change 50 minutes, 180 minutes, and 300 minutes after the end of application (0 minutes), as shown in Table 2 below. Judgment was made according to the standard, and the results are shown by ○, △, ×, and XX.

 The test results of the holding effect are shown in Table 3.

As is evident from Table 3, the perfume retention effect of the compounds of the invention is very good and significantly better than known retention agents.

(Effect) The compound of the above formula (1) of the present invention is a novel compound which has not been described in the conventional literature and is substantially odorless per se, chemically stable, and excellent in skin safety. Then, the compound has a very excellent effect as a perfume and a retaining agent for these prepared flavoring compositions, and it is possible to provide a new prepared flavoring composition containing the compound of the formula (1) as an active ingredient. In addition, the composition is a useful compound that can be used in a wide range of fields such as cosmetics, cosmetics, foods and drinks.

Claims (1)

(57) [Claims] 1. The following formula (1) However, in the formula, R represents a C _{5 to} C ₁₁ alkyl group or a C ₉ alkenyl group, and the wavy line represents an axial or equatorial bond. Methyl-4,6-0-alkylidene-D-glycoside