JPH07247474A - Gelling agent for organic solvent or oil and fat - Google Patents

Abstract

PURPOSE:To obtain a gelling agent for organic solvent or oil and fat, containing a specific cyclic dipeptide as an active component, forming a uniform and smooth gel, having excellent feeling and gelling performance and useful as a waste-oil treating agent, etc. CONSTITUTION:This gelling agent for organic solvent or oil and fat contains glutamic acid or its alkyl ester, a compound selected from glycine, alanine, valine, leucine, isoleucine and phenylalanine and preferably 50-100wt.% of a cyclic dipeptide expressed by formula I [A is H, CH3, (CH3)2CH, (CH3)2CHCH2, (C2H5)(CH2)CH or group of formula II; R is H or a 1-22C alkyl] as active components. The gelling agent is preferably added to an organic solvent or oil and fat in an amount of 0.1-5W/V%.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a gelling agent for organic solvents or fats and oils containing a cyclic dipeptide consisting of a specific amino acid as an active ingredient.

[0002]

2. Description of the Related Art Heretofore, many studies and reports concerning oil-based gelling agents have not been found as compared with aqueous gelling agents. However, in recent years, among oily gelling agents, 12-hydroxystearic acid obtained from castor oil as a raw material has been marketed as a waste oil treatment agent, and the development in this field has been progressing recently. However, 12-hydroxystearic acid has limited types of oily substances to be gelled, and the obtained gel tends to have a dull feel, and its application range is narrow.

On the other hand, in order to solve these problems, gelling agents utilizing various amino acids (for example, N-lauroyl-L-glutamic acid-α, γ-di-n-butylamide) have been developed. This is a compound that can gel various organic solvents and fats and oils by chemically modifying the amino acid itself or by selecting a substance that reacts with a functional group such as an amino group or a carboxyl group. Is. Also, the gel strength can be adjusted by preparing the amino acid derivative by carrying out the same treatment as described above, and therefore, many studies have been conducted. However, these amino acid-based oily gelling agents were mainly linear peptide derivatives as described in, for example, JP-A-51-91884. Further, these peptide derivatives were not always satisfactory in gelling ability and feel of the resulting gel.

[0004]

SUMMARY OF THE INVENTION The present inventors have completed the present invention as a result of preparing various amino acid compounds based on the present situation and comparing and examining the gel forming ability and the like in detail. Is. That is, it is an object of the present invention to provide a gelling agent which is excellent in gelling ability as compared with a conventional oily gelling agent and forms a gel having a good feel.

[0005]

In order to achieve the above object, the present invention provides a glutamic acid or an alkyl ester thereof and one of the following selected from the group consisting of glycine, alanine, valine, leucine, isoleucine and phenylalanine. The gist of the invention is a gelling agent for organic solvents or fats and oils containing the cyclic dipeptide represented by the general formula (1) as an active ingredient.

[Chemical 4] [However, in formula (1), A is H, CH ₃ , (CH ₃ ) ₂ C
_{H, (CH 3) 2 CHCH} 2, (C 2 H 5) (CH 3)
CH or

[Chemical 5] And R is H or a linear or side chain alkyl group having 1 to 22 carbon atoms. ]

The essential components in the gelling agent of the present invention are glutamic acid, which is an aliphatic acidic amino acid, and glycine and alanine, which are neutral aliphatic amino acids.
1 type selected from the group consisting of valine, leucine, isoleucine and phenylalanine is a cyclic dipeptide in which a 6-membered ring structure is formed by two amide bonds,
The carboxyl group based on the glutamic acid is free or is converted to a linear or side chain alkyl ester having 1 to 22 carbon atoms. Such a cyclic dipeptide is represented by the above general formula (1).

The starting amino acid of the cyclic dipeptide of the present invention is obtained by extracting a hydrolyzate of a protein derived from a natural product with an acid, an alkali or an enzyme, a product isolated from a fermentation or culture product of a microorganism, or a chemical product. Any of those obtained by a synthetic method may be used. Further, the optical isomer can be used regardless of the difference between D-form, L-form and DL-form (racemic form), but the L-form or DL-form commercially available as an industrial raw material can be obtained at low cost, It is convenient.

The cyclic dipeptide of the present invention can be synthesized by a known method by appropriately selecting the above amino acids. For example, first, glutamic acid, which is the acidic amino acid, and any lower alcohol such as methanol, ethanol, n-propanol, isopropanol, n-butanol, and isobutanol are mixed with hydrogen chloride, sulfuric acid, paratoluenesulfonic acid, zinc, tin, and the like. Is used as a catalyst or in the absence of a catalyst to heat at reduced pressure or normal pressure to cause an esterification reaction to prepare a lower alcohol diester of glutamic acid.

On the other hand, the neutral amino acid, after protecting the α-amino group which is one of the functional groups, undergoes an amidation reaction with the lower alcohol diester of glutamic acid to form a cyclic dipeptide, The protecting group for the α-amino group is removed. As a protecting group for this purpose, a benzyloxycarbonyl group (Z group), a t-butoxycarbonyl group (Boc group), a 9-fluorenylmethoxycarbonyl group (Fmoc group), a 3-nitro-2-pyridinesulfenyl group ( Npys group) exists in large numbers, but it is common to introduce a Z group that is easily eliminated. Benzyloxycarbonyl chloride (Z-Cl) was used to introduce the Z group, and Sc
By the hotten-Baumann reaction, the reaction is carried out by dropping simultaneously with an aqueous solution of sodium hydroxide.

Then, the lower alcohol diester of glutamic acid and the neutral amino acid having the Z group introduced therein are subjected to an amidation reaction at 40 ° C. for about half a day using dicyclohexylcarbodiimide (DCC) to give a linear dipeptide derivative. It is prepared and deprotected by using a lower alcohol or a hydrocarbon having about 5 to 10 carbon atoms as a solvent in the presence of a catalyst such as palladium carbon, nickel or platinum for several hours at room temperature by blowing hydrogen gas. To do. As a method for such a deprotecting group, other methods such as acid treatment with trifluoroacetic acid or anhydrous hydrogen fluoride are generally used. However, in the case of elimination from a short-chain peptide, a mild catalytic reduction method is often used. Used. After removing the catalyst from the reaction,
The cyclic dipeptide of the present invention (a cyclized product of a lower alcohol ester of glutamic acid and a neutral amino acid) can be obtained as crystals by dissolving in mesitylene, dioxane, dichloromethane, tetrahydrofuran or the like and refluxing for several hours.

The cyclic dipeptide can be further purified by recrystallization using a lower alcohol such as methanol or ethanol as a solvent. Further, if the hydrolysis is carried out in the presence of the acidic catalyst, or the ester bond is saponified with an alkali such as sodium hydroxide or potassium hydroxide and then neutralized with hydrochloric acid or the like, the carboxyl group derived from the raw material glutamic acid is released. A cyclic dipeptide (a cyclized product of glutamic acid and a neutral amino acid) can be prepared.

Furthermore, the above-mentioned two kinds of cyclic dipeptides (one in which the carboxyl group derived from glutamic acid is lower alcohol esterified and one in which it is free) are used,
A cyclic dipeptide of a lower alcohol ester of glutamic acid and a neutral amino acid together with an alcohol having a linear or side chain alkyl group having 1 to 22 carbon atoms, more preferably 1 to 18 carbon atoms, and most preferably 2 to 10 carbon atoms. In the case of, a transesterification reaction is carried out using a metal alcoholate such as sodium methylate or lithium ethylate, lipase, sulfuric acid, p-toluenesulfonic acid, etc. as a catalyst, or in the case of a cyclic dipeptide of glutamic acid and a neutral amino acid, sulfuric acid, para Toluene sulfonic acid, zinc, tin,
The esterification reaction is carried out using titanium oxide as a catalyst, and in any case, the carboxyl group derived from the starting glutamic acid is esterified with a linear or side chain alcohol having 1 to 22 carbon atoms (a cyclic dipeptide (the alcohol of glutamic acid. A cyclized product of an ester and a neutral amino acid) can be synthesized.

The linear or side chain alcohols having 1 to 22 carbon atoms are methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, n-pentanol, n-hexanol. , Cyclohexanol, n-heptanol, n-
Octanol, 2,4,4-trimethylpentanol,
2-ethylhexanol, n-nonanol, n-decanol, 3,7-dimethyloctanol, lauryl alcohol, tridecanol, neotridecanol, myristyl alcohol, pentadecanol, 2-methyltetradecanol, 5-methyltetradecanol , Palmityl alcohol, 2,2-dimethyltetradecanol, heptadecanol, stearyl alcohol, oleyl alcohol, methyl side chain isostearyl alcohol, 2-heptylundecanol, hevenyl alcohol, 2-octyldodecanol, etc. it can. In the case of alcohols having 22 or more carbon atoms, cyclic dipeptides are not preferable because they are crystallized when mixed with organic solvents or fats and oils.

In the present invention, various combinations of the above-mentioned neutral amino acids and alcohols are effective, but especially for halogen-based and aromatic organic solvents, neutral amino acids are preferable, and glycine and alanine are preferable. , Valine, leucine, phenylalanine, more preferably a combination of glycine, valine, leucine, phenylalanine and alcohols having 1 to 12 carbon atoms, and neutral amino acids for oils and fats, preferably glycine, alanine, Valine, leucine, isoleucine, phenylalanine, and more preferably a combination of glycine, alanine, valine, leucine, phenylalanine and an alcohol having 1 to 18 carbon atoms is desirable.

The various cyclic dipeptides thus obtained are
The gelling agent of the present invention can be prepared by appropriately using one kind or two or more kinds. Further, the gelling agent of the present invention may contain known gelling agents, thickeners, waxes and the like in addition to the cyclic dipeptide. Known gelling agents include aqueous gelling agents such as pectin, sodium alginate, carrageenan, sodium polyacrylic acid or sodium polymethacrylate, and also mokuro, 12-hydroxystearic acid, N-lauroyl-L-glutamic acid- N-acyl-, such as α, γ-di-n-butylamide
There are oil-based gelling agents such as amino acid-alkylamides, new oily sucrose fatty acid esters, dextrin fatty acid esters, starch fatty acid esters, dibenzylidene sorbitol, dibenzylidene xylitol, acrylic acid or methacrylic acid based polymers.

Examples of known thickeners include gum arabic, xanthan gum, guar gum, tragacanth gum, locust bean gum, curdlan, gellan gum, flax seed mucilage, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose and the like. Examples of known waxes include carnauba wax, candelilla wax, shellac wax, beeswax, sugar wax, rice wax, cottonseed wax, sunflower wax, paraffin wax, montan wax, bayberry wax and the like. be able to.

The gelling agent of the present invention contains the cyclic dipeptide in an amount of 20 to 100% by weight, preferably 50 to 100% by weight.
It is a mixture. When it is less than 20% by weight, it is not possible to exhibit an effective gelling ability as compared with the conventional oil-based gelling agent, or it is difficult to obtain a gel having a good feel. The gelling agent of the present invention can be applied to organic solvents or fats and oils in an amount of 0.
1 to 10% by weight / volume (percentage of addition amount of gelling agent of the present invention: g per unit volume of organic solvent or oil / fat: ml, the same applies hereinafter), preferably 0.1 to 5% by weight / volume % To have a good gelling ability. If it is less than 0.1% by weight / volume, the desired gel cannot be obtained.

In the present invention, various organic solvents can be used, but halogen-based solvents and aromatic solvents, especially benzene-based solvents are preferable, and specific examples thereof include carbon tetrachloride, benzene, toluene, xylene and methoxybenzene. There are chlorobenzene and nitrobenzene. The oils and fats are preferably liquid or semi-solid at room temperature, more preferably those that are liquid, soybean oil, rapeseed oil, corn oil, safflower oil, sunflower oil, cottonseed oil, olive oil, palm oil, Examples include linseed oil, castor oil, fish oil, lard, beef tallow, and processed fats and oils obtained by mixing, fractionating, or transesterifying these, and triglycerides composed of mixed fatty acids of triacetin, tributyrin, tricaprylin, caprylic acid, and capric acid. The glycerides (which may include diglycerides and monoglycerides) having a single or mixed fatty acid having 2 to 10 carbon atoms as a constituent fatty acid can be targeted.

A predetermined amount of the gelling agent of the present invention is added to the organic solvent or fats and oils, and if necessary, heated to about 40 to 80 ° C., stirred and mixed to dissolve, and then around room temperature (20 to 20 ° C.).
A gelled product can be prepared by allowing it to stand at 25 ° C. The gel-like product obtained is in a uniform and smooth state, unlike agar or gelatin, and has no liquid part even when stored at room temperature for a long time. It does not become liquid.

[0020]

EXAMPLES In the following synthesis examples, examples and comparative examples,% is by weight unless otherwise specified. Synthesis Example 1 73.5 g of L-glutamic acid was suspended in 1 liter of absolute ethanol, and dry hydrogen chloride gas was introduced. The mixture was occasionally shaken to dissolve L-glutamic acid, cooled with ice water, and further introduced with hydrogen chloride until saturated. Keep the mixture dry for 4 hours at room temperature and again at 0-5 ° C.
It was cooled to and left overnight. The obtained hydrochloride salt was collected by filtration, washed successively with cold ethanol and anhydrous ether, dried under reduced pressure in a desiccator containing sodium hydroxide, and recrystallized from ethanol and ether to give diethyl L-glutamate. [Hereinafter, abbreviated as L-Glu (O-Et) ₂ ] 86.5 g was obtained.

On the other hand, 65.6 g of L-leucine was dissolved in 250 ml of 2N aqueous sodium hydroxide solution, and 50 ml of ether was added.
Was added as a solvent, and the mixture was stirred at ice temperature for 10 minutes, and then 85.3 g of benzyloxycarbonyl chloride and 250 ml of a 2N sodium hydroxide aqueous solution were simultaneously added in 10 batches. The solution was transferred to a separating funnel and the aqueous layer was separated while washing with ether. Add 250 ml of ethyl acetate to this
About 1 ml of hydrochloric acid was added, and the mixture was stirred. The washing with water was repeated 3 times, magnesium sulfate was added to the ethyl acetate layer to remove water, and this was filtered off with a filter paper. Then, the filtrate was put into an eggplant-shaped flask, and ethyl acetate was distilled off under reduced pressure at about 50 ° C. About 150 ml of new ethyl acetate was added to this while warming, and petroleum ether was added little by little and shaken. Petroleum ether was added until the liquid became cloudy, and this was left in a refrigerator for recrystallization to obtain 75.0 g of Z-leucine (hereinafter abbreviated as Z-L-Leu).

Next, L-Glu (O-Et)₂And Z-L-
Reaction with Leu was performed. Z-L-Le in an eggplant flask
Add 26.5 g of u and 400 ml of ethyl acetate and stir in an ice bath.
I stirred. Dicyclohexylcarbodiimide (DC
C) By adding 22.7 g and stirring at room temperature for 1 hour,
The system became cloudy. In this state, L-Glu (O-Et) ₂
Add 17.5g and stir for 1 hour.
After warming, stirring was continued overnight. Ethyl acetate 8 in this solution
After adding 00 ml and heating and stirring, the generated precipitate was removed.
It was recrystallized by distilling off ethyl acetate under reduced pressure.
Let After cooling, this was filtered to obtain crystals, and the filtrate was ethyl acetate.
After dissolving in 800 ml of chill, the same treatment is performed to form crystals.
Then, both crystals were combined. By vacuum drying this,
L-Glu (O-Et)₂And Z-L-Leu straight chain
Dipeptide derivative [hereinafter referred to as ZL-Leu-L-Glu
(O-Et)₂20.8 g was obtained.

ZL-Leu-L-Glu (O-Et)
₂ 20 g was dissolved in 500 ml of methanol and used as a catalyst 1
2% of 0% palladium-supported carbon was added, and hydrogen gas was injected at room temperature for 6 hours to deZ-group. After the catalyst was filtered off and the filtrate was concentrated, the obtained L-Leu-L-Gl was obtained.
u (O-Et) ₂ was dissolved in 400 ml of mesitylene (2,4,6-trimethylbenzene) and refluxed for 5 hours to carry out a cyclization reaction. After the reaction, mesitylene was concentrated to 100 ml, and the precipitated crystals were separated by filtration with filter paper, washed with petroleum ether and dried under reduced pressure to obtain a crude product, which was recrystallized with 100 ml of ethanol to give L-glutamic acid monohydrate. A cyclic dipeptide in which ethyl ester and L-leucine have a six-membered ring structure through two amide bonds [hereinafter, referred to as cyclo
Abbreviated as (L-Leu-L-Glu (O-Et))] (Sample No. 1), 11.6 g was obtained.

The outline of the reaction step is represented by the reaction formulas, which are represented by the formulas (2) and (3).

[Chemical 6]

[Chemical 7]

Synthesis Examples 2 and 3 L-Glu (O-Et) ₂ obtained by the method described in Synthesis Example 1
17.5 g and Z-obtained according to the method described in Synthesis Example 1.
L-Val 25.1 g was used and treated in a similar manner to give a cyclic dipeptide of L-glutamic acid monoethyl ester and L-valine [hereinafter referred to as cyclo (L-Val-L-
Glu (O-Et))] (Sample No. 2) 25.6
g was obtained. Furthermore, a cyclic dipeptide of L-glutamic acid monoethyl ester and L-glycine [hereinafter referred to as cyclo (L-Gly-L-Glu was prepared by the same method as in Synthesis Example 1.
(O-Et))] (Sample No. 3) was obtained.

Synthesis Example 4 The cyclo (L-Leu-L-Glu obtained in Synthesis Example 1 was used.
To 10 g of (O-Et) (Sample No. 1) was added 50 ml of methanol containing 1N-hydrochloric acid, and the mixture was refluxed for 1 hour to cause the hydrolysis reaction of ethyl ester. After the reaction, methanol was distilled off under reduced pressure, washed with 50 ml of petroleum ether, and dried under reduced pressure to obtain a crude product, which was recrystallized with 20 ml of ethanol to obtain two L-glutamic acid and L-leucine. A cyclic dipeptide having a six-membered ring structure through an amide bond of [(hereinafter, cyclo (L-Leu-L-Glu (O
H))] (Sample No. 4) (6.4 g) was obtained.

Synthesis Examples 5 to 10 The cyclo (L-Leu-L-Glu obtained in Synthesis Example 1 was used.
8.3 g of lauryl alcohol was added to 10 g of (O-Et)) (sample No. 1), and 30 mg of p-toluenesulfonic acid was used as a catalyst and heated at 120 ° C. for 4 hours under reduced pressure of 100 mmHg and stirred. Then, it melt | dissolved in chloroform 2 times weight and it used for the silica gel chromatography. As a result, the unreacted alcohol fraction was removed to obtain a fraction containing a transesterification (alcoholsis) reaction product. Further, chloroform was distilled off under reduced pressure to remove a cyclic dipeptide of L-glutamic acid monolauryl ester and L-leucine [hereinafter, c
abbreviated as yclo (L-Leu-L-Glu (O-La))] (Sample No. 5) was obtained. In the same manner, the sample No. L- from 1 and 3,7-dimethyloctanol
Cyclic dipeptide of glutamic acid mono 3,7-dimethyloctyl ester and L-leucine [hereinafter referred to as cyclo
(Abbreviated as L-Leu-L-Glu (O-Mo))] (Sample No. 6) was obtained.

Further, the cyclo (LV) obtained in Synthesis Example 2 was used.
al-L-Glu (O-Et)) (Sample No. 2), lauryl alcohol, stearyl alcohol, 3,
A cyclic dipeptide of L-glutamic acid monolauryl ester and L-valine [hereinafter, referred to as cyclo (L-Val-
L-Glu (O-La))] (Sample No. 7), L
-A cyclic dipeptide of glutamic acid monostearyl ester and L-valine [hereinafter referred to as cyclo (L-Val-L
-Glu (O-St))] (Sample No. 8), L-
Cyclic dipeptide of glutamic acid mono 3,7-dimethyloctyl ester and L-valine [hereinafter referred to as cyclo (L
-Val-L-Glu (O-Mo))] (Sample N
o. 9), a cyclic dipeptide of L-glutamic acid mono-2-ethylhexyl ester and L-valine [hereinafter referred to as cyc
abbreviated as lo (L-Val-L-Glu (O-Eh))]
(Sample No. 10) was obtained.

Example 1 cyclo (L-Leu-L-Glu (O-Et))
The gelation ability of (Sample No. 1) with respect to various organic solvents or fats and oils was examined. That is, in a test tube with a lid, 300 mg of the cyclic dipeptide, 10 ml of an organic solvent or oils and fats
After collecting, heating and melting, the state when cooled to 25 ° C. was observed. A gel is used when the entire contents are in the form of gel, and the liquid does not exude when the test tube is tilted and does not fluidize.For gelled substances, the critical gelling concentration (organic solvent or oil or fat) The minimum weight of cyclic dipeptide required for gelling 1 ml of the class: percentage of g, unit: weight / volume%, hereinafter referred to as CGC) was determined.

As a result, the sample No. CGC of 1 is 2.0% by weight / volume% for carbon tetrachloride and 0.1% for benzene.
6 wt / vol%, 0.2 wt / vol% for toluene, 0.7 wt / vol% for methoxybenzene, 1.0 wt / vol% for chlorobenzene, 1 for tricaprylin 0.0 wt / vol%, 0.9 wt / vol% with respect to triolein, and 0.5 wt / vol% with soybean oil, the cyclic dipeptide of sample No. 1 was found in organic solvents and oils and fats. On the other hand, it was confirmed that it has gelling ability and is suitable as the gelling agent of the present invention. All the gels obtained had a uniform and smooth feel.

Example 2 cyclo (L-Val-L-Glu (O-Et))
The gelation ability of (Sample No. 2) with respect to various organic solvents or fats and oils was examined by the same method as in Example 1. As a result, the sample No. CGC of 2 was 0.2, 1.1, 2.1, 2.3 and 0.3 for toluene, chlorobenzene, tricaprylin, triolein and soybean oil, respectively.
5 is each weight / volume%, and sample No. It was revealed that the cyclic dipeptide of No. 2 has gelling ability with respect to organic solvents and oils and fats and is suitable as the gelling agent of the present invention.
All the gels obtained had a uniform and smooth feel.

Example 3 cyclo (L-Gly-L-Glu (O-Et))
The gelling ability of (Sample No. 3) with respect to various organic solvents or fats and oils was examined by the same method as in Example 1. As a result, the sample No. CGC of 3 is chloroform, benzene,
2.0, 2.0, 2.0, 1.0 for toluene, methoxybenzene, chlorobenzene, nitrobenzene, tricaprylin, triolein and soybean oil, respectively.
1.0, 1.0, 0.4, 0.3 and 0.3 each weight /
Volume%, sample No. It was confirmed that the cyclic dipeptide of 3 has a gelling ability with respect to organic solvents and oils and fats and is suitable as the gelling agent of the present invention. All the gels obtained had a uniform and smooth feel.

Example 4 cyclo (L-Leu-L-Glu (OH)) (Sample
The gelling ability of No. 4) against various organic solvents or oils and fats was examined by the same method as in Example 1. as a result,
The CGC of sample No. 4 was 0.6% by weight / volume with respect to soybean oil, and the cyclic dipeptide of sample No. 4 had gelation ability with respect to fats and oils and was suitable as the gelling agent of the present invention. I understood. The obtained gel had a uniform and smooth feel.

Examples 5-10 Cyclo (L-Leu-L-G) obtained in Synthesis Examples 5-10
lu (O-La)) (Sample No. 5), cyclo (L-
Leu-L-Glu (O-Mo)) (Sample No. 6), c
yclo (L-Val-L-Glu (O-La)) (Sample No. 7), cyclo (L-Val-L-Glu (O
-St)) (Sample No. 8), cyclo (L-Val-
L-Glu (O-Mo)) (Sample No. 9) and cyc
lo (L-Val-L-Glu (O-Eh)) (Sample N
o. The gelling ability of 10) against various organic solvents or oils and fats was examined by the same method as in Example 1. As a result, the sample No. CGC of 5 was 2.0, 1.8 and 1.6 for carbon tetrachloride, benzene, toluene and soybean oil, respectively.
And 0.8% by weight / volume%, respectively. 6 CG
C was 2.0% by weight / volume% with respect to carbon tetrachloride, benzene and toluene, respectively.

Sample No. The CGC of No. 7 was 1.3% by weight / volume% with respect to carbon tetrachloride. CGC of 8 was 0.8 and 0.8 for tricaprylin and soybean oil.
5% by weight / volume%, and sample No. CGC of 9 was 0.6, 2.5, 1.9 and 1.4% by weight / volume for carbon tetrachloride, toluene, triolein and soybean oil, respectively. CGC of 10 is 2.0, 0.9, respectively for carbon tetrachloride, benzene, toluene, chlorobenzene, tricaprylin, triolein and soybean oil,
0.9, 1.5, 1.4, 2.0 and 2.0 each weight /
It was% by volume. From these things, sample No. 5 to No.
It was found that the 10 cyclic dipeptides have a gelling ability to organic solvents and / or oils and fats and are suitable as the gelling agent of the present invention. All the gels obtained had a uniform and smooth feel.

Example 11 cyclo (L-Leu-L-Glu (O-Et))
(Sample No. 1): 40%, cyclo (L-Val-L
A mixture of -Glu (O-Mo)) (Sample No. 9): 40% and 12-hydroxystearic acid: 20% was heated to 80 ° C to uniformly mix, and cooled to room temperature.
By the same method as in Example 1, an organic solvent or fats and oils containing 3% by weight and 8% by weight of this was prepared, and the presence or absence of gel forming ability was examined. Carbon tetrachloride, benzene, toluene, It was found that methoxybenzene, chlorobenzene, tricaprylin, triolein and soybean oil all gave a gel having a uniform and smooth feel.

Example 2 cyclo (L-Gly-L-Glu (O-Et))
(Sample No. 3): A mixture consisting of 50%, 12-hydroxystearic acid: 30%, sunflower wax: 10% and beeswax: 10% was heated to 80 ° C. and uniformly mixed, and cooled to room temperature. By the same method as in Example 1,
Organic solvents or fats and oils containing 1 wt / vol%, 7 wt / vol% and 10 wt / vol% were prepared, and the presence or absence of gel-forming ability was examined. Chloroform, carbon tetrachloride,
It was found that benzene, toluene, methoxybenzene, chlorobenzene, nitrobenzene, tricaprylin, triolein and soybean oil all gave a uniform and smooth-feeling gel.

Comparative Example 1 Ethanol, acetone, ethyl acetate, chloroform, carbon tetrachloride, benzene, toluene, cyclohexane, methoxybenzene, chlorobenzene and nitrobenzene as organic solvents, and tricaprylin, triolein and soybean oil as fats and oils. Then, 1.0% by weight / volume% of 12-hydroxystearic acid was added to each of them, and Example 1 was used.
When the gelling ability was examined in the same manner as in (1), it was insoluble in the organic solvent and soluble in fats and oils, but showed a viscous flow state, and no uniform gel was obtained. Furthermore, when 2.0% by weight / volume% of 12-hydroxystearic acid was added to the above oils and fats and the gelling ability was examined in the same manner, a gel was obtained, but it was a fragile gel with a nap.

Comparative Example 2 Sample No. 1 [cyclo (L-Leu-L-Glu (O
-Et))], sample no. 8 [cyclo (L-Gly-
L-Glu (O-Me))], sample no. 14 [cycl
o (L-Val-L-Glu (O-Et))] and sample no. 20 [cyclo (L-Phe-L-Glu (O
-Et))] was subjected to transesterification using octacosanol according to the method described in Synthesis Example 4 and subjected to silica gel column chromatography to obtain the transesterification product of the cyclic dipeptide. None of these formed a gel with the various organic solvents and fats and oils described in Comparative Example 1.

[0040]

EFFECTS OF THE INVENTION According to the present invention, a gel having excellent gelling ability to various organic solvents, particularly halogen-based and aromatic-based solvents, especially benzene-based solvents, or fats and oils, and forming a uniform and smooth gel. An agent can be provided.

Claims (3)

[Claims] 1. An organic compound comprising a cyclic dipeptide represented by the following general formula (1) as an active ingredient: glutamic acid or an alkyl ester thereof and one kind selected from the group consisting of glycine, alanine, valine, leucine, isoleucine and phenylalanine. Gelling agent for solvents or oils and fats. [Chemical 1] [However, in formula (1), A is H, CH ₃ , (CH ₃ ) ₂ C
_{H, (CH 3) 2 CHCH} 2, (C 2 H 5) (CH 3)
CH or And R is H or a linear or side chain alkyl group having 1 to 22 carbon atoms. ] 2. In the general formula (1), A is H and (CH
₃ ) ₂ CH, (CH ₃ ) ₂ CHCH ₂ or The gelling agent according to claim 1, wherein R is any one of a linear or side chain alkyl group having 1 to 12 carbon atoms. 3. The gelling agent according to claim 1, wherein the organic solvent is a halogen-based solvent or a benzene-based solvent.