JP2000072736A - Benzenecarboxamide compound and gelling agent or solidifying agent for organic liquid - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound useful as a gelling agent or a solidifying agent in industrial fields including processing fields for coating materials, inks, lubricating oils, agricultures, fisheries, cosmetics or medicines, fibers, polymers, rubbers, metals, etc. SOLUTION: This compound is represented by formula I [X1 and X2 are each AA-NHR (AA is an amino acid acyl); R is an 8-22C alkyl; (n) is 1 or 2], e.g. N,N'-phthaloyl-bis(L-valylaminododecane). The compound represented by formula I can be produced by a method for reacting, e.g. an amino acid represented by the formula H-AA-OH with an alkylamine represented by the formula RNH2 at 0-100 deg.C for 15-30 h, then reacting the resultant amino acid alkylamide represented by the formula H-AA-NHR with a benzenecarboxylic acid chloride represented by formula II in the presence of a base in a dry solvent at 0-100 deg.C for 5-15 h and affording a benzenecarboxamide compound represented by formula III, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel benzenecarboxylic acid amide compound useful as a gelling or solidifying agent for an organic liquid, and a gelling or solidifying agent containing this compound as an active ingredient. The gelling or solidifying agent of the present invention can be used in industrial fields including coatings, inks, lubricating oils, agriculture, fisheries, cosmetics and pharmaceuticals, fibers, resins, polymers, rubbers, metals and the like.

[0002]

2. Description of the Related Art In general, 12-hydroxystearic acid, which has a function of gelling or solidifying organic liquids (animal and vegetable oils, esters, polyols, ethers, alcohols, hydrocarbons, etc.) used in the above-mentioned industrial fields, includes: Dibenzylidene sorbitol, alkali metal salts and alkaline earth metal salts of fatty acids and the like are known.

[0003] Among them, 12-hydroxystearic acid is inexpensive, but there are few kinds of organic liquids that can be gelled or solidified, and the temperature at which the obtained gel softens is low.
On the other hand, dibenzylidene sorbitol forms a strong gel with a small amount of addition, but has the disadvantage of liberating benzaldehyde, and is unsuitable for solidifying low-boiling short-chain alcohols due to its high melting point. is there. Alkali metal salts and alkaline earth metal salts of fatty acids require a large amount of addition for gelation or solidification, and have limitations such as limited usable conditions.

[0004]

As described above, the gelling or solidifying agents proposed so far do not have a sufficiently satisfactory function in any of the above points.

[0005] Accordingly, an object of the present invention is to make it easy to produce, to be able to gel or solidify various organic liquids with a small amount of addition, to be uniform and to have a long term storage and temperature change. Provided are a benzenecarboxylic acid amide compound useful as a gelling or solidifying agent for an organic liquid and a gelling or solidifying agent for an organic liquid containing the compound as an active ingredient, which can be formed into a gelled or solidified product having high stability. It is in.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, have synthesized a novel benzenecarboxylic acid amide compound, which is an excellent gel for various organic liquids. The inventors have found that the present invention has a chemical ability, and have completed the present invention.

That is, the present invention provides a compound represented by the following general formula (I):

Embedded image

(In the general formula (I), X ¹ and X ² each represent —AA-NHR, AA is an amino acid acyl group, R is an alkyl group having 8 to 22 carbon atoms, and n is 1 or 2. Benzenecarboxylic acid amide compound represented by the following formula: Further, the present invention provides a gelling or solidifying agent for an organic liquid, comprising the benzenecarboxylic acid amide compound represented by the general formula (I) as an active ingredient.

In the above general formula (I), the general formula (I)
Wherein n is 1 or 2; n is 1;
When X ² is in the ortho position relative to COX ^1, X ¹ and X ² each represent a -AA-NHR, each AA is L-
X ¹ and X ² are each -AA when n is 1 and COX ² is meta to COX ¹ , and each R may be an alkyl group having 12 carbon atoms.
Represents -NHR, each AA is L-valyl or L-isoleucyl, and each R is an alkyl group having 12 carbon atoms, or each AA is L-valyl or D, L-valyl, And each R can be an alkyl group having 18 carbon atoms, when n is 1 and COX ² is in the para position with respect to COX ¹ , X ¹ and X ² are each -AA-
Represents NHR, each AA is L-valyl, glycyl, L-leucyl or L-isoleucyl, and each R is an alkyl group having 12 carbon atoms, or each AA is L-valyl, L-leucyl, L-isoleucyl or D, L-
Valyl, and each R may be an alkyl group having 18 carbon atoms, and when n is 2, the two COX ² are both meta to COX ¹ , and X ¹ and X ² are each -A
Represents A-NHR, wherein each AA is L-valyl or L-leucyl, and each R may be an alkyl group having 12 carbon atoms.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The benzenecarboxylic acid amide compound of the present invention is represented by the above general formula (I). In the general formula (I), X ¹ and X ² each represent -AA-NHR
AA represents an amino acid acyl group, and each R has 8 to 2 carbon atoms.
2 alkyl groups, n represents 1 or 2. A bond between a carbonyl group directly bonded to a benzene ring and -AA- -COAA-
Is an amide bond.

The amino acid acyl group (AA) is specifically represented by
Examples thereof include glycyl, alanyl, valyl, leucyl, isoleucyl and the like, and among them, valyl is particularly preferred in terms of gelling ability. These amino acid acyl groups can be used in both L-form and DL-form. The amino acid acyl groups themselves may be used alone or in combination of two or more.

The alkyl group (R) has 8 to 2 carbon atoms.
2, saturated, straight-chain and / or branched alkyl groups can be used. Specifically as a linear alkyl group,
Octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, henycosyl group, docosyl group can be exemplified. . As a branched alkyl group, a 2-ethylhexyl group, a 2,4,4-trimethylpentyl group, a 3,5,5-trimethylhexyl group,
3,7-dimethyloctyl group, 6-propylnonyl group,
12-methyltridecyl, 2-methyltetradecyl, 5-methyltetradecyl, 2,2-dimethyltetradecyl, 2-hexyldecyl, 2-heptylundecyl, 2-octyldodecyl, etc. Can be illustrated. These linear alkyl groups or branched alkyl groups may be used alone or as a mixture of two or more. Preferred in terms of gelling ability are a dodecyl group (a linear alkyl group having 12 carbon atoms) and an octadecyl group (a linear alkyl group having 18 carbon atoms). Among them, an octadecyl group is particularly preferred.

[0013] Further, n is 1 or 2, and accordingly, the benzenecarboxylic acid constituting the basic skeleton is benzenedicarboxylic acid or benzenetricarboxylic acid. Specifically, phthalic acid (1, 1) is used as benzenedicarboxylic acid.
2-benzenedicarboxylic acid), isophthalic acid (1,3-
Benzenedicarboxylic acid), terephthalic acid (1,4-benzenedicarboxylic acid), and benzenetricarboxylic acid include 1,3,5-tricarboxylic acid, 1,2,4-benzenetricarboxylic acid and the like. Of these, terephthalic acid is particularly preferred for benzenedicarboxylic acid and 1,3,5-benzenetricarboxylic acid is preferred for benzenetricarboxylic acid in terms of gelling ability.

Specific examples of the benzenecarboxylic acid amide compounds of the present invention 54 compounds are listed below. Unless otherwise specified, each amino acid acyl group AA is the same, and R is also the same. When X ¹ = X ² , these are collectively displayed as X.

In the above general formula (I), the phthalic diamide compound wherein n is 1 and COX ² is ortho to COX ¹ is an amino acid acyl group (hereinafter referred to as AA) L-valyl. , and the and (or less R) alkyl group is dodecyl (X = L-Val -NH- C 12 H 25)
In a compound 1: N, N'-phthaloyl - bis (L- valyl aminododecanoic), AA is L- isoleucyl, and R is a dodecyl group (X = L-Ile -NH- C 12 H
₂₅ ) Compound 2: N, N'-phthaloyl-bis (L
-Isoleucylaminododecane), AA is L-valyl, and R is an octadecyl group (X = L-Val-NH-
Compound 3: C ₁₈ H ₃₇ ): N, N′-phthaloyl-bis (L-valylaminooctadecane), AA is L-leucyl, and R is a docosyl group (X = L-Leu-NH)
-C ₂₂ H _45), compound 4: N, N'-phthaloyl -
Bis (L-leucylaminodocosan), AA is L-alanyl, and R is a hexadecyl group (X = L-Ala −
NH-C ₁₆ H _33), Compound 5: N, N'-phthaloyl - bis (L- alanyl-amino hexadecanoic), AA is glycyl, and R is octadecyl (X = L-Gl
y—NH—C ₁₈ H ₃₇ ) Compound 6: N, N′-phthaloyl-bis (glycylaminooctadecane), AA is D, L-leucyl, and R is a tetradecyl group (X
= D, L-Leu-NH -C 14 H 29) , compound 7:
N, N'-phthaloyl-bis (D, L-leucylaminotetradecane), AA is L-valyl, and R is 2
- ethylhexyl group (X = L-Val -NH- C 8 H 17)
8: N, N′-phthaloyl-bis (L-valylamino-2-ethylhexane), AA is L-isoleucyl, and one of R is a dodecyl group and the other is an octadecyl group (X ¹ = L _{-Ile -NH-C 12 H 25,} X
^{2 = L-Ile -NH-C} 18 H 37) , compound 9, AA
Is L-isoleucyl and the other is L-leucyl, and R is a dodecyl group (X ¹ = L-Ile-NH-C
₁₂ H ₂₅ , X ² = L-Leu-NH—C ₁₂ H ₂₅ ).

In the above general formula (I), as an isophthalic diamide compound wherein n is 1 and COX ² is meta-position to COX ¹ , AA is L-valyl and R is a dodecyl group (X = L-Val -NH- C 12 H 25) , compound 11: N, N'isophthaloyl - bis (L
- valyl aminododecanoic), AA is L- isoleucyl, and R is a dodecyl group (X = L-Ile -NH- C 12
H _25), Compound 12: N, N'isophthaloyl -
Bis (L-isoleucylaminododecane), AA is L-
Valyl and R is an octadecyl group (X = L-Val
-NH-C ₁₈ H _37), Compound 13: N, N'isophthaloyl - bis (L- valyl amino octadecane),
AA is D, L-a-valyl, and the compound R is an octadecyl group (X = D, L-Val -NH-C 18 H 37) 1
4: N, N'isophthaloyl - bis (D, L- valyl amino-octadecane), AA is L- leucyl and R is Okutadokoshiru group (X = L-Leu -NH- C 22 H
₄₅ ), compound 15: N, N'-isophthaloyl-bis (L-leucylaminooctadocosan), wherein AA is L-
Alanyl, and R is a hexadecyl group (X = L-Al
a -NH-C ₁₆ H _33), Compound 16: N, N'isophthaloyl - bis (L- alanyl-amino hexadecanoic), AA is glycyl, and R is octadecyl (X = Gly -NH-C ₁₈ H ₃₇ )
N'- isophthaloyl - bis (glycyl-aminooctadecane), AA is D, an L- leucyl and R is a tetradecyl radical (X = D, L-Leu -NH-C 14 H 29) Compound 18: N , N'-isophthaloyl-bis (D,
L-leucylaminotetradecane), AA is L-valyl, and R is a 2-ethylhexyl group (X = L-Val
—NH—C ₈ H ₁₇ ) compound 19: N, N′-isophthaloyl-bis (L-valylamino-2-ethylhexane), AA is L-isoleucyl, and one of R is a dodecyl group and the other is Is an octadecyl group (X ¹ = L-
_{Ile -NH-C 12 H 25,} X 2 = L-Ile -NH-C 18 H
₃₇₎ compounds wherein 20, one of AA is L- isoleucyl other is L- leucyl and R is a dodecyl group ^{(X 1 = L-Ile -NH} -C 12 H 25, X 2 = L-Leu −
NH-C ₁₂ H _25), compound 21 can be mentioned.

In the above general formula (I), as a terephthalic acid diamide compound wherein n is 1 and COX ² is para to COX ¹ , AA is L-valyl and R is a dodecyl group (X = L-Val -NH- C 12 H 25) , compound 22: N, N'terephthaloyl - bis (L
- valyl aminododecanoic), AA is glycyl, and compounds wherein R is a dodecyl group _{(X = Gly -NH-C 12} H 25) 23: N, N'- terephthaloyl - bis (glycyl aminododecanoic), AA There L- is leucyl and compound R is a dodecyl group (X = L-Leu -NH- C 12 H 25) 24: N, N'- terephthaloyl - bis (L-
Isoleucyl aminododecanoic), AA is L- isoleucyl, and R is a dodecyl group (X = L-Ile -NH- C 12
H ₂₅ ) Compound 25: N, N′-terephthaloyl-
Bis (L-isoleucylaminododecane), AA is L-
Valyl and R is an octadecyl group (X = L-Val
-NH-C ₁₈ H _37), Compound 26: N, N'terephthaloyl - bis (L- valyl amino octadecane),
AA is L- leucyl and R is octadecyl (X = L-Leu -NH- C 18 H 37) Compound 27:
N, N'terephthaloyl - bis (L- leucyl amino-octadecane), AA is L- isoleucyl, and R is octadecyl (X = L-Ile -NH- C 18 H 37)
28: N, N′-terephthaloyl-bis (L-isoleucylaminooctadecane), wherein AA is D,
L-valyl and R is an octadecyl group (X = D,
_{L-Val -NH-C 18 H} 37) , Compound 29: N,
N'- terephthaloyl - bis (D, L- valyl amino-octadecane), AA is L- valyl, and compounds wherein R is a tetradecyl radical (X = L-Val -NH- C 14 H 29) 30: N, N'-terephthaloyl-bis (L-valylaminotetradecane), AA is L-valyl, and R is a hexadecyl group (X = L-Val-NH-C
₁₆ H _33), Compound 31: N, N'terephthaloyl - bis (L- valyl amino-hexadecane), AA is L-
Valyl and R is an icosyl group (X = L-Val-N
Compound 32 which is H—C ₂₀ H ₄₁ ): N, N′-terephthaloyl-bis (L-valylaminoicosane), and AA is L
-Valyl, and R is a docosyl group (X = L-Val-
Compound 33 which is NH—C ₂₂ H ₄₅ ): N, N′-terephthaloyl-bis (L-valylaminodocosan), AA is L-leucyl, and R is an octadocosyl group (X =
_{L-Leu -NH-C 22 H} 45) , Compound 34: N,
N'- terephthaloyl - bis (L- leucyl amino oct docosanoic), an AA is L- alanyl, and compounds wherein R is a hexadecyl group (X = L-Ala -NH- C 16 H 33) 35: N , N′-terephthaloyl-bis (L-alanylaminohexadecane), AA is glycyl,
And R is octadecyl _{(X = Gly -NH-C 18} H 37)
36: N, N′-terephthaloyl-bis (glycylaminooctadecane), AA is D, L-leucyl, and R is a tetradecyl group (X = D, L-Le)
_{u-NH-C 14 H 29} ) , Compound 37: N, N'terephthaloyl - bis (D, L- leucyl amino tetradecane), a AA is L- valyl, and wherein R is 2-ethylhexyl group (X _{= L-Val -NH-C 8} H 17) , compound 38: N, N'terephthaloyl - bis (L- Bariruamino 2-ethyl hexane), AA is L- isoleucyl, and one of R is dodecyl The other being an octadecyl group (X ¹ = L-Ile-NH—C ₁₂ H ₂₅ , X ²
_{= L-Ile -NH-C 18} H 37) , compound 39, AA
Is L-isoleucyl and the other is L-leucyl, and R is a dodecyl group (X ¹ = L-Ile-NH-C
₁₂ H ₂₅ , X ² = L-Leu-NH—C ₁₂ H ₂₅ ).

In the general formula (I), n is 2 and two COX ² are both meta-positions to COX ¹ as a 1,3,5-tricarboxylic acid triamide compound,
AA is L-valyl, and R is a dodecyl group (X = L
-Val -NH-C ₁₂ H _25), Compound 41: N,
N ', N "-1,3,5-benzenetricarbonyl-tris (L-valylaminododecane), AA is L-leucyl, and R is a dodecyl group (X = L-Leu-NH-
Compound 42 which is C ₁₂ H ₂₅ ): N, N ′, N ″ -1,
3,5-benzenetricarbonyl-tris (L-leucylaminododecane), AA is L-isoleucyl,
And R is a dodecyl group (X = L-Ile -NH- C 12 H 25)
Compound 43: N, N ′, N ″ -1,3,5-benzenetricarbonyl-tris (L-isoleucylaminododecane), AA is L-valyl, and R is an octadecyl group (X = _{L-Val -NH-C 18 H} 37) , compound 44: N, N ', N "-1,3,5- benzene tricarbonyl - tris (L- valyl amino octadecane),
AA is L- leucyl, and compound R is an Okutadokoshiru group (X = L-Leu -NH- C 22 H 45) 45:
N, N ', N "-1,3,5-benzenetricarbonyl-tris (L-leucylaminooctadocosan), AA
Is L-alanyl, and R is a hexadecyl group (X =
_{L-Ala -NH-C 16 H} 33) , Compound 46: N,
N ', N "-1,3,5-benzenetricarbonyl-tris (L-alanylaminohexadecane), AA is glycyl, and R is an octadecyl group (X = Gly-NH
-C ₁₈ H ₃₇ ), compound 47: N, N ′, N ″ -1,
3,5-benzenetricarbonyl-tris (glycylaminooctadecane), AA is D, L-leucyl,
And R is a tetradecyl group (X = D, L-Leu-NH-C
₁₄ H ₂₉ ) Compound 48: N, N ′, N ″ -1,3,
5-benzenetricarbonyl-tris (D, L-leucylaminotetradecane), AA is L-valyl, and R is a 2-ethylhexyl group (X = L-Val-NH-C
₈ H _17), Compound 49: N, N ', N "-1,3,
5-benzenetricarbonyl-tris (L-valylamino-2-ethylhexane), AA is L-isoleucyl, and one of the three Rs is a dodecyl group and the other 2
One is an octadecyl group (X ¹ = L-Ile-NH-C
^{_{12 H 25, X 2 = L}} -Ile -NH-C 18 H 37) , compound 50, AA is the L- isoleucyl, three one of R is an octadecyl group other two are dodecyl (X
^{1 = L-Ile -NH-C} 18 H 37, X 2 = L-Ile -NH
-C ₁₂ H ₂₅ ), one of the three AAs is L-isoleucyl, the other two are L-leucyl, and R is a dodecyl group (X ¹ = L-Ile-NH-C _{12).
^{H 25, X 2 = L-}} Leu -NH-C 12 H 25) one of the compounds 52,3 single AA where it is L- leucyl other 2
One is L-isoleucyl and R is a dodecyl group (X
^{1 = L-Leu -NH-C} 12 H 25, X 2 = L-Ile -NH
—C ₁₂ H ₂₅ ).

In the above general formula (I), 1,2,4-tricarboxylic acid wherein n is 2 and two COX ² are in the ortho position with respect to COX ¹ and the other is in the para position As a triamide compound, AA is L-valyl and R is an octadecyl group (X = L-Val-NH-C
₁₈ H ₃₇ ) Compound 54: N, N ′, N ″ -1,2,2
4-benzenetricarbonyl-tris (L-valylaminooctadecane).

Among these benzenecarboxylic acid amide compounds, compound 26 (N, N'-terephthaloyl-bis (L-valylaminooctadecane)) is an excellent gelling agent capable of gelling most kinds of organic solvents.

The benzenecarboxylic acid amide compound of the present invention can be easily synthesized by the following two-step reaction.

[0022]

Embedded image

First, in step (1), the amino acid HA corresponding to the amino acid acyl group AA in the general formula (I)
A-OH with an alkylamine RNH ₂ (R is the as defined) can be easily synthesized amino acid alkyl amide H-AA-NHR by a known method from. Although the method and conditions are not particularly limited, for example, the N-terminal of an amino acid is protected with a protecting group such as a benzyloxycarbonyl group, and then both materials are subjected to a dehydration reaction in a dry solvent at a predetermined reaction equivalent. The desired amino acid alkylamide can be obtained by removing the protecting group of the product. In this reaction, both reaction materials are used in approximately equimolar amounts,
The reaction can be performed at a temperature of 0 ° C. for 15 to 30 hours.

Next, in step (2), the obtained amino acid alkylamide is reacted with a benzenecarboxylic acid chloride represented by the formula (II), and the benzenecarboxylic acid amide compound ( Formula (I)). Although the method and conditions are not particularly limited, for example, an amino acid alkylamide and benzenecarboxylic acid chloride may be subjected to a condensation reaction in a dry solvent in a predetermined reaction equivalent in the presence of a base such as triethylamine. In this reaction, both reactants are used in a molar ratio of approximately (n + 1): 1 at a temperature of 0 ° C. to 100 ° C.
It can be performed for hours to 15 hours.

When unreacted raw materials and by-products (such as monoamide compounds) remain in the reaction product, they can be purified by known means such as distillation under reduced pressure and solvent separation. For example, the purification of the reactants can be performed by removing unreacted substances and the like under reduced pressure, recrystallization with a large amount of an organic solvent such as acetone, activated clay, activated carbon, silica gel, treatment with an adsorbent such as alumina, and the like. These may be applied alone or in combination as needed. When the compound of the present invention is used as a gelling agent or a solidifying agent for an organic liquid, a small amount (less than several weight%) of unreacted raw materials (benzene carboxylic acid and / or amino acid alkylamide) and by-products of monoamide compound and the like may be used. Mixing of things is not particularly noticeable.

The benzenecarboxylic acid amide compound of the present invention is useful as a gelling or solidifying agent for various organic liquids.

The organic liquids include animal and vegetable oils and fats such as soybean oil, rapeseed oil, corn oil, safflower oil, sunflower oil, cottonseed oil, olive oil, palm oil, castor oil, fish oil, lard, tallow, and isopropyl myristate. , Tri-2-
Esters such as ethylhexanoic acid glyceride and 2-octyldodecyl myristate, polyethylene glycol,
Polyols such as polypropylene glycol and polyglycerin, ethers such as ethyl cellosolve and butyl cellosolve, alcohols such as methanol and ethanol, kerosene, heavy oil, liquid oils such as liquid paraffin and isoparaffin, and organic oils such as xylene and toluene So-called waste oils such as solvents, waste edible oils, waste lubricating oils, waste metal processing oils and the like can be targeted.

The benzenedicarboxylic acid diamide compound used as a gelling or solidifying agent in the present invention is preferably a benzenedicarboxylic acid diamide compound or a mixture of a benzenedicarboxylic acid diamide compound and a benzenedicarboxylic acid monoamide compound, most preferably. It is a benzenedicarboxylic acid diamide compound. Similarly, the benzenetricarboxylic acid triamide compound used in the present invention is preferably a benzenetricarboxylic acid triamide compound, or a mixture of a benzenetricarboxylic acid triamide compound and a benzenetricarboxylic acid diamide compound, and most preferably a benzenetricarboxylic acid triamide compound. is there.

The use of the gelling or solidifying agent of the present invention is as follows:
To 1 mL of the organic liquid, 1 to 50 mg, preferably 2 to 20 mg, of the gelling or solidifying agent of the present invention is added, and if necessary, the mixture is heated to about 60 to 120 ° C., stirred until a uniform state is obtained, and then cooled to room temperature. When left to stand, a gelled or solidified product can be prepared. This is a uniform gel or solid, and does not generate a liquid portion at room temperature, and does not generate a liquid portion even during long-term storage. The gelled or solidified product thus prepared can be used as a base or formulation in the fields of paints, inks, lubricating oils, cosmetics, pharmaceuticals, and agriculture.

Although the gelling or solidifying agent of the present invention can be used alone, it may be used in combination with a conventionally known gelling agent, a solidifying agent such as a natural wax or a synthetic wax in an appropriate amount without departing from the object of the present invention. Is also good.

[0031]

EXAMPLE 1 In a four-necked flask equipped with a stirrer, thermometer, nitrogen gas inlet tube and water separator, benzyloxycarbonyl L- was added.
9.22 g of valine (Tokyo Kasei Co., Ltd. reagent)
37 mol) was dissolved in 200 mL of dry ethyl acetate, and under ice cooling, 8.33 g (0.040 mol) of dicyclohexylcarbodiimide (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. After stirring for 1 hour, dodecylamine 6.8 was added.
0 g (0.037 mol) was added and heated to 70 ° C. once,
Subsequently, it was allowed to cool to room temperature. The gel generated at this time is 50
The mixture was crushed by adding mL of acetone, and the insolubles were collected by suction filtration, washed well with acetone, and dried at room temperature. 8.17
g of a white solid were obtained. This was dissolved in 250 mL of ethanol, palladium carbon was dissolved, 50 mL of ethanol was added, and hydrogen gas was injected to perform reduction. After completion of the reduction, the catalyst was removed, the solvent was distilled off, and the residue was recrystallized from ethanol to obtain 4.16 g of L-validodecylamide. Next, 0.57 g of L-validodecylamide (0.0
02 mol) and 0.20 g (0.0%) of phthaloyl chloride.
01 mol) in dry tetrahydrofuran, and 0.70 mL (0.005 mol) of triethylamine under ice-cooling.
After stirring to room temperature, the reaction was completed by heating. After that, the solvent was distilled off and recrystallized from ethanol.
0.20 g of a phthalic diamide compound (Compound 1) was obtained.

[0032]

Example 2 An isophthalic acid diamide compound (compound 11) was prepared in the same manner as in Example 1 except that phthaloyl chloride in Example 1 was replaced with isophthaloyl chloride.
0.51 g was obtained.

[0034]

Example 3 L-isoleucyldodecylamide was prepared in the same manner as in Example 1 except that benzyloxycarbonyl L-isoleucine was used in place of benzyloxycarbonyl L-valine used in Example 1 above. Obtained. Thereafter, 0.43 g of an isophthalic acid diamide compound (Compound 12) was obtained in the same manner as in Example 1 except that phthaloyl chloride in Example 1 was replaced with isophthaloyl chloride.

[0036]

Example 4 The procedure of Example 1 was repeated, except that octadecylamine was used in place of dodecylamine of Example 1 to obtain L-
Valyl octadecylamide was obtained. Thereafter, 0.72 g of an isophthalic acid diamide compound (compound 13) was obtained in the same manner as in Example 1 except that phthaloyl chloride in Example 1 was replaced with isophthaloyl chloride.

[0038]

Example 5 The method described in Example 1 was repeated, except that benzyloxycarbonyl D, L-valine and octadecylamine were used instead of benzyloxycarbonyl D, L-valine and dodecylamine used in Example 1 above. Similarly, D, L-valyl octadecylamide was obtained. Thereafter, 0.97 g of an isophthalic acid diamide compound (Compound 14) was obtained in the same manner as in Example 1 except that phthaloyl chloride of Example 1 was replaced with isophthaloyl chloride.

[0040]

Example 6 A terephthalic acid diamide compound (compound 22) was prepared in the same manner as in Example 1 except that phthaloyl chloride in Example 1 was replaced with terephthaloyl chloride.
0.57 g was obtained.

[0042]

Example 7 Glycyl dodecylamide was obtained in the same manner as in Example 1, except that benzyloxycarbonyl glycine was used instead of benzyloxycarbonyl L-valine used in Example 1. Thereafter, 0.54 g of a terephthalic acid diamide compound (Compound 23) was obtained in the same manner as in Example 1, except that phthaloyl chloride in Example 1 was replaced with terephthaloyl chloride.

[0044]

Example 8 L-leucyldodecylamide was obtained in the same manner as in Example 1 except that benzyloxycarbonyl L-leucine was used instead of benzyloxycarbonyl L-valine used in Example 1 above. Was. Thereafter, 0.45 g of a terephthalic acid diamide compound (compound 24) was obtained in the same manner as in Example 1, except that phthaloyl chloride in Example 1 was replaced with terephthaloyl chloride.

[0046]

Example 9 L-isoleucyldodecylamide was obtained in the same manner as in Example 1 except that benzyloxycarbonyl L-isoleucine was used instead of benzyloxycarbonyl L-valine used in the above example. Was. Then, the first embodiment
Was replaced with terephthaloyl chloride to obtain 0.37 g of a terephthalic acid diamide compound (compound 25) in the same manner as in Example 1.

[0048]

Example 10 The procedure of Example 1 was repeated, except that octadecylamine was used instead of dodecylamine.
Valyl octadecylamide was obtained. Thereafter, 0.80 g of a terephthalic acid diamide compound (compound 26) was obtained in the same manner as in Example 1, except that phthaloyl chloride in Example 1 was replaced with terephthaloyl chloride.

[0050]

Example 11 In the same manner as in Example 1, except that benzyloxycarbonyl L-leucine was used instead of benzyloxycarbonyl L-valine and octadecylamine was used instead of dodecylamine used in Example 1 above. L-Leucyloctadecylamide was obtained. Thereafter, 0.53 g of a terephthalic acid diamide compound (compound 27) was obtained in the same manner as in Example 1, except that phthaloyl chloride in Example 1 was replaced with terephthaloyl chloride.

[0052]

Example 12 The procedure of Example 1 was repeated, except that benzyloxycarbonyl L-isoleucine was used in place of benzyloxycarbonyl L-valine and octadecylamine was used in place of dodecylamine. L-isoleucyl octadecylamide was obtained. Then, the first embodiment
Was replaced with terephthaloyl chloride to obtain 0.63 g of a terephthalic acid diamide compound (compound 28) in the same manner as in Example 1.

[0054]

Example 13 The same procedure as in Example 1 was repeated, except that benzyloxycarbonyl D, L-valine was used instead of benzyloxycarbonyl L-valine and octadecylamine was used instead of dodecylamine. Thus, D, L-valyloctadecylamide was obtained. Thereafter, the phthaloyl chloride of Example 1 was replaced with terephthaloyl chloride to obtain 0.88 g of a terephthalic acid diamide compound (compound 29) in the same manner as in Example 1.

[0056]

Example 14 The phthaloyl chloride of Example 1 was replaced with 1,3,5-benzenetricarbonyltrichloride and
A 3-fold molar amount of L-validodecylamide was reacted with 3,5-benzenetricarbonyltrichloride, and 1,3,5 was obtained in the same manner as in Example 1.
-Benzenetricarboxylic acid triamide compound (compound 4
1) 0.96 g was obtained.

[0058]

Example 15 L-leucyldodecylamide was obtained in the same manner as in Example 1 except that benzyloxycarbonyl L-leucine was used instead of benzyloxycarbonyl L-valine used in the above example. Was. Thereafter, the phthaloyl chloride of Example 1 was replaced with 1,3,5-benzenetricarbonyltrichloride, and L-molar amount of 3 times the amount of 1,3,5-benzenetricarbonyltrichloride was used.
Example 1 was reacted with leucyldodecylamide.
In the same manner as described, 0.99 g of a 1,3,5-benzenetricarboxylic acid triamide compound (compound 42) was obtained.

[0060]

Example 16 The ability of the benzenecarboxylic acid amide compound obtained according to the present invention and 12-hydroxystearic acid, sodium stearate and carnauba wax as controls to gel or solidify a typical organic liquid was tested. A mixture obtained by adding 3% by weight of the gelling or solidifying agent according to the present invention to various organic liquids is placed in a test tube, heated to about 60 ° C. or more, and then left to cool at room temperature (25 ° C.). At this time, the contents were examined for fluidity, and for those having no fluidity, the hardness of the gel was examined. The evaluation was performed on a four-point scale (◎: no fluidity: the gel was uniform and hard, ○:
No fluidity: The gel is uniform and soft, △: slightly fluid, ×: heterogeneous mixture or uniform but fluid
I went in.

The experimental results are shown in the following table. Table 1 shows the results of the gelation or solidification ability using the phthalic acid diamide compound, Table 2 shows the results of the isophthalic acid diamide compound, and Table 3 shows the results of the terephthalic acid diamide compound. Table 4 shows the results. * I-C8 in all tables
Is a 2-ethylhexyl group, ** the mixing ratio in the case of a mixed amine is 1: 1 (molar ratio), and the *** mixing ratio in the case of a mixed amino acid is 1: 1 (molar ratio). Table 4
The benzene tricarboxylic acid triamide compound in
Note that compounds 43-53 are 1,3,5-benzenetricarboxylic triamides and only compound 54 is 1,2,4-benzenetricarboxylic triamide. Compounds 50 and 51 and Compound 52 in Table 4
And 53 are each a mixture of two compounds (molar ratio 1:
1).

[0063]

[Table 1]

[0064]

[Table 2]

[0065]

[Table 3]

[0066]

[Table 4]

The organic liquid to which the carboxylic acid amide compound of the present invention is added as a main component forms a uniform and smooth gelled product despite the addition of a smaller amount than conventional gelling agents and waxes. It turned out to be. Further, the gelled product prepared is prepared for 10 to 30 days every month for one month.
When the temperature was changed at a temperature range of ° C., and the state was examined, all those according to the present invention maintained the initial state of preparation,
It has been confirmed that it has excellent stability against long-term temperature changes.

[0068]

According to the present invention, there is provided a carboxylic acid amide compound represented by the above general formula (I), and the gelling or solidifying agent containing the carboxylic acid amide compound as an active ingredient is an animal or vegetable oil, an ester, a polyol, an ether, For a wide range of organic liquids such as alcohols and hydrocarbon oils, or for waste cooking oil, waste lubricating oil, waste metal processing oil, etc. A gel or solid having excellent stability can be prepared.

Continued on the front page F-term (reference) 4G065 AA05 AA10 AB01Y AB02X AB02Y AB03X AB11Y AB16Y AB17Y AB18Y AB29X BA09 BA20 BB02 BB08 CA16 DA02 DA03 DA04 DA05 DA06 DA07 4G075 AA33 AA37 CA02 CA03 4H006 AA01 AA4B39 BBA90 BC90 BC DA13 DA14 EA40

Claims (4)

[Claims] 1. A compound represented by the following general formula (I) (In the general formula (I), X ¹ and X ² each represent -AA
Benzenecarboxylic acid amide compound represented by -NHR, AA represents an amino acid acyl group, each R represents an alkyl group having 8 to 22 carbon atoms, and n represents 1 or 2. 2. The following general formula (I): (In the general formula (I), X ¹ and X ² each represent -AA
AA represents an amino acid acyl group, each R represents an alkyl group having 8 to 22 carbon atoms, and n represents 1 or 2). Solidifying agent. 3. The following general formula (I): (In the general formula (I), n is 1 or 2, and when n is 1 and COX ² is ortho to COX ¹ , X ¹ and X ² are each -AA-NH
R represents each AA is L-valyl, and each R is an alkyl group having 12 carbon atoms, when n is 1 and COX ² is in the meta position to COX ¹ , X ¹ And X ² are each -AA-NH
Represents R, each AA is L-valyl or L-isoleucyl, and each R is an alkyl group having 12 carbon atoms, or each AA is L-valyl or D, L-valyl, and When each R is an alkyl group having 18 carbon atoms, n is 1 and COX ² is in the para position with respect to COX ¹ , X ¹ and X ² are each -AA-NH
Represents R, each AA is L-valyl, glycyl, L-leucyl or L-isoleucyl, and each R is an alkyl group having 12 carbon atoms, or each AA is L-valyl, L-leucyl, L-isoleucyl or D, L-valyl, and each R is an alkyl group having 18 carbon atoms. When n is 2, two COX ² are both meta-position to COX ¹ and X ¹ And X ² are each -AA-NH
Wherein each AA is L-valyl or L-leucyl, and each R is an alkyl group having 12 carbon atoms). 4. The following general formula (I): (In the general formula (I), n is 1 or 2, and when n is 1 and COX ² is ortho to COX ¹ , X ¹ and X ² are each -AA-N
HR, each AA is L-valyl, and each R is an alkyl group having 12 carbon atoms, when n is 1 and COX ² is in the meta position to COX ¹ , X ¹ And X ² are each -AA-NH
Represents R, each AA is L-valyl or L-isoleucyl, and each R is an alkyl group having 12 carbon atoms, or each AA is L-valyl or D, L-valyl, and When each R is an alkyl group having 18 carbon atoms, n is 1 and COX ² is in the para position with respect to COX ¹ , X ¹ and X ² are each -AA-NH
Represents R, each AA is L-valyl, glycyl, L-leucyl or L-isoleucyl, and each R is an alkyl group having 12 carbon atoms, or each AA is L-valyl, L-leucyl, L-isoleucyl or D, L-valyl, and each R is an alkyl group having 18 carbon atoms. When n is 2, two COX ² are both meta-position to COX ¹ and X ¹ And X ² are each -AA-NH
Wherein each AA is L-valyl or L-leucyl, and each R is an alkyl group having 12 carbon atoms, a compound selected from the group consisting of benzenecarboxylic acid amide compounds represented by the formula: A gelling or solidifying agent for an organic liquid.