WO2000053576A1

WO2000053576A1 - Gelling or coagulating agents for liquid organic media

Info

Publication number: WO2000053576A1
Application number: PCT/JP2000/001234
Authority: WO
Inventors: Kenji Hanabusa; Hiroko Nakayama; Mutsumi Kimura; Hirofusa Shirai
Original assignee: Ajinomoto Co., Inc.
Priority date: 1999-03-11
Filing date: 2000-03-02
Publication date: 2000-09-14
Also published as: JP2000256303A; JP4099891B2

Abstract

Novel Nα-alkyl- or alkenylcarbamoyl-Nφ-acylamino acid esters represented by general formula (1); (wherein R1 is linear or branched C¿7?-C21 alkyl or alkenyl; R?2¿ is linear, branched or cyclic C¿1?-C22 alkyl or alkenyl; R?3¿ is linear, branched or cyclic C¿8?-C22 alkyl or alkenyl; and n is an integer of 2 to 4). These esters can gel or coagulate a wide variety of liquid organic media by the addition thereof even in a small amount to give gels excellent in long-term and ordinary-temperature stability, and can be synthesized by an easy and simple process, thus being useful as excellent gelling or coagulating agents.

Description

Description Gelling or solidifying agent for liquid organic medium

(Technical field)

The present invention is an organic medium New ^alpha useful for gelling or solidifying exhibiting the liquid state at normal temperature - characterized in that it contains one with Ashiruamino acid ester compound and less of these - alkyl or Aruke carbamoylmethyl over New ^omega And a gelling or solidifying agent.

(Background technology)

By controlling the flowability of various cosmetics, pharmaceuticals, agricultural chemicals, adhesives, resins, paints, etc., which are liquid at room temperature, the method of processing these into a form that meets the diversified purpose of use is extremely industrial. This is an important technology. Also, for example, disasters and marine pollution caused by oil spills are serious social problems, but if oil can be solidified, it will be possible not only to spread the oil but also to collect it easily and efficiently. Oil gelation can be an extremely effective means of controlling oil spills. In addition, edible waste oil from households causes water pollution, but if the waste oil can be gelled by a simple method and discarded as a solid, the adverse effect on the environment can be reduced.

Examples of such a substance having a function of controlling the fluidity and viscosity of a liquid substance include alkali metal salts of long-chain fatty acids (JP-A-55-75493) and metal soaps (JP-B-59-595). 216), 12-hydroxystearic acid (Japanese Patent Publication No. 60-449968), a condensate of a polyhydric alcohol and benzaldehyde (Japanese Patent Application Laid-Open No. 59-77859), and p-acylamino Acid amide (Japanese Patent Publication No. 54-333798) was known.

Among them, metal salts of long-chain fatty acids and metallic soaps gel liquid organic media. Alternatively, a large amount of addition is required for solidification, and there are restrictions on use conditions such as pH. Also, since 12-hydroxystearic acid has few types of organic media that can be gelled and has a low gelling ability, the resulting gel is weak and brittle and easily breaks, and lacks gel stability near room temperature. On the other hand, polyvalent alcohol and benzaldehyde condensates, such as dibenzylidene sorbitol, can gel many organic media, but have a high dissolution temperature, so they can be used in combination with low boiling substances or substances that are sensitive to heat. There are restrictions when doing so. In addition, there is a disadvantage that the acetal site in the condensate is unstable and decomposed. N-Acyl amino acid amides, such as N-lauroyl L-glutamic acid and 7-di-n-butylamide, can gel or solidify many organic media with a small amount of addition. Although the obtained gel had high strength, it did not have sufficient gelling ability with respect to lower alcohols such as methanol and did not necessarily have satisfactory gelling performance.

In order to remedy the above drawbacks, gelling or solidifying agents for liquid organic media have been actively developed in recent years. Examples thereof include cyclohexanthyl carboxamide (JP-A-10-273477), bis (acylamino) cyclohexane derivative (JP-A-10-237034), and oligobutidealkylamide derivative (JP-A-10-24539). 6, JP-A-10-226614), dialkyl perylene derivatives obtained by reacting diaminocyclohexane with alkyl isocyanate (JP-A-8-231 942), cyclic peptides ( JP-A-7-247474, JP-A-7-247473) and the like. These can gel or solidify a wide variety of liquid organic media with a small amount of addition, and the resulting gel has high strength and excellent stability near room temperature. However, on the other hand, the gelling ability is greatly affected by the configuration of the compound, making it difficult to synthesize and separate the raw material having a specific configuration, making it difficult to obtain the raw material, and the production process involves many reaction steps, making the process complicated. There is a problem with productivity. (Disclosure of the Invention)

Under the background of the prior art described in the preceding paragraph, the present invention is capable of gelling or solidifying a wide variety of liquid organic media with a small amount of addition, and the gelled material has a long-term stability near room temperature. An object of the present invention is to provide a gelling or solidifying agent which is excellent and can be produced by a simpler method.

The present inventor has conducted extensive studies in order to solve the problems described above, New ^alpha represented by the following general formula (1) - alkyl or alkenyl carbamoylmethyl over New ^omega - § shea Ruamino ester compound, various They have found that they have excellent gelling ability with various liquid organic media and can be synthesized by a simple method. Based on such findings, they have completed the present invention.

That is, the present invention relates to ^a Na-alkyl or alkenylcarbamoyl-— ^ω -acyl amino acid ester compound represented by the following general formula (1) itself, and a gelling or solidifying agent containing the compound as an active ingredient.

R ^ ONH (CH ₂ ) nCHCOOR

(1)

HN C ONHR

(Wherein, R ¹ represents a linear or branched alkyl or alkenyl group having from 21 to 21 carbon atoms, and R ² represents a linear or branched and / or cyclic group having from 1 to 22 carbon atoms.) An alkyl or alkenyl group having a structure, R ³ is an alkyl or alkenyl group having a straight or branched chain having 8 to 22 carbon atoms and / or having a cyclic structure, and n is an integer of 2 to 4. Show.)

Hereinafter, the present invention will be described in detail.

Ester compound of the present invention, New ^omega - the Ashiruamino acid as a starting material, carboxy It is obtained by esterification of the W group with an alcohol and alkylation or carbamoylation by alkylation of the amino group with an alkylisocyanate or alkenylisocyanate. Incidentally, the ester compound of the present invention is a novel compound.

The Ashiruamino ^acid, Ν ^£ - - Ν ω Ashirurijin, N ^fi - Ashiruoru two Chin, N Aashiru Ichihi, include Ajiamino butyric, in this, New ^epsilon - Ashirurijin is most preferred.

—As the acyl group of the amino acid, an acyl group derived from a linear or branched saturated or unsaturated fatty acid having 8 to 22 carbon atoms is preferable. For example, octanoic acid, decanoic acid , Lauric acid, palmitic acid, stearic acid, and oleic acid. When the number of carbon atoms of the acyl group is less than 8, the gelling ability is poor, and when it is more than 22, the solubility in a liquid organic medium is poor, and a treatment at a high temperature is required for dissolution, which is not appropriate.

New ^omega - Ashiruamino acid, for example a basic amino acid and a long chain fatty acid can be easily synthesized by heating dehydration. Industrially available amino acids include "Amihob LL" (N ^£ -lauroyl-L-lysine) manufactured by Ajinomoto Co., Inc.

Ν ^ω -Acyl amino acid may be either optically active or racemic. These may be used alone or in combination of two or more.

The alcohol used for esterification of ^ω -acyl amino acid is an alcohol having a linear or branched saturated or unsaturated and / or cyclic having 1 to 22 carbon atoms, such as methanol, ethanol, η —Propanol, isopropanol, η-butanol, 2-butanol, η-pentanol, η-hexanol, cyclohexanol, η-hexanol, η-octanol, 2-ethylhexa Knoll, η-nonanol, η-decanol, lauryl alcohol, myristylua Examples thereof include alcohol, palmityl alcohol, stearyl alcohol, oleyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, and 2-octyldodecanol. If it is not esterified, the compound will crystallize and have no gelling ability.If it has more than 22 carbon atoms, its solubility in liquid organic media will be poor, and it will be difficult to dissolve it. It is not appropriate because it requires processing at

(1) Alkyl isocyanate used for alkylation of a primary amino group of ^ω -acyl amino acid, which has a linear or branched and / or cyclic structure having 8 to 18 carbon atoms. For example, octyl isocyanate, nonyl isocyanate, decyl isocyanate, pendecyl isocyanate, dodecyl isocyanate, tridecyl isocyanate, tetradecyl isocyanate, pentadecyl isocyanate, hexadecyl isocyanate Examples thereof include cyanate, heptadecyl isocyanate, octadecyl isocyanate, 2-ethylhexyl isocyanate, and 21-hexyldecyl isocyanate. If the alkylisocyanate has less than 8 carbon atoms, the organic solvent that can be gelled is limited, and if it has more than 18 carbon atoms, the solubility in the liquid organic medium is poor, and it will dissolve. This requires high temperature treatment, which is not appropriate. Examples of industrially available alkyl isocyanates include “Millionaires” (octadecyl isocyanate) manufactured by Hodogaya Chemical Industry Co., Ltd. These may be used alone or as a mixture of two or more.

As mentioned above, the ester compound of the present invention is a novel compound, which is obtained by using the above-mentioned “amino acid”, alcohol and alkyl isocyanate or alkenyl isocyanate as raw materials, and by a generally known method. Ru can be synthesized, for example, first New ^omega -. the presence of an esterification catalyst of the carboxyl groups of Ashiruamino acid, or heating with an alcohol in the absence of a catalyst (normal pressure, reduced pressure) dehydration condensation reaction, W transesterification, after carried out according to the esterification reaction, such as azeotropic dehydration condensation reaction, raw form and New ^omega - Ashiruamino ester compound and equivalent alkyl I Société § sulfonates Wakashi phrases the Aruke two Ruisoshianeto not It can be synthesized by reacting in an active solvent in the presence or absence of a catalyst. Of course, by these methods Razutomo, previously N ^a - alkyl or Aruke carbamoylmethyl over New ^omega - and Ashirua amino acid, then nothing like no problem even if a method of esterifying this. The reaction product thus obtained may contain unreacted raw materials in addition to the target ester compound, but it may be purified by a known method such as extraction, recrystallization, or chromatography. it can. This purification may be performed to such an extent that the object (effect) of the present invention is not adversely affected by the use of the gelling or solidifying agent of the present invention. The mixture may be used as it is, as long as the gelling ability is not affected.

There is no particular difficulty in gelling or solidifying the liquid organic medium of the present invention containing the ester compound of the present invention as an active ingredient. In an extreme case, only the ester compound of the present invention can be referred to as the gelling or solidifying agent of the present invention. It can be prepared by blending additives such as agents.

The ester compound of the present invention is excellent in the action of gelling or solidifying a wide variety of liquid organic media with a small amount of addition. Examples of the liquid organic medium include mineral oils such as gazolin, kerosene, light oil, and heavy oil; animal oils such as whale oil and dicin oil; soybean oil, olive oil, castor oil, linseed oil, corn oil, Vegetable oils such as castor oil, rapeseed oil, and cottonseed oil; hydrocarbons such as petroleum benzene, liquid paraffin, benzene, toluene, hexane, and cyclohexane; ethyl acetate, butyl acetate, amyl acetate, getyl sebacate, and sebacic acid Esters such as dioctyl, getyl phthalate, dioctyl phthalate, and polyoxyalkylene glycol fatty acid esters; ethers such as diglyme and polyalkylene glycol ether; cyclic esters such as THF and dioxane; Ternes; ketones and aldehydes such as acetone, methylethyl ketone, methyl isobutyl ketone, cyclohexanone and anisaldehyde; lower alcohols such as methanol, ethanol, propanol and butanol; methylpolysiloxane Silicone oils such as methylphenylpolysiloxane, octamethylcyclotetrasiloxane, and decamethylcyclopentylsiloxane; halogen-containing substances such as benzene and carbon tetrachloride; highly polar organic solvents such as DMF and DMS; It is extremely effective in the range of ^ regardless of the type of flammable and non-flammable organic medium, and is also effective for a mixture of these organic media and a medium that is the main component.

There is no particular difficulty in gelling or solidifying the liquid organic medium with the gelling or solidifying agent containing the ester compound of the present invention as an active ingredient. For example, it can be performed as follows. That is, the gelling or solidifying agent of the present invention (including, as described above, the one comprising only the ester compound of the present invention) is added to the above-mentioned liquid organic medium, and 50 The liquid organic medium can be changed to a gelled or solidified substance by heating and stirring to a uniform state of about 120 ° C. and then standing at room temperature. The amount of the ester compound used in the present invention depends on the type of the organic medium to be gelled or solidified, but it is 1 to 400 parts by weight, preferably 1 to 100 parts by weight, based on the liquid organic medium 1,000 parts by weight. The amount is from 200 to 200 parts by weight, preferably from 1 to 100 parts by weight, and more preferably from 2 to 80 parts by weight. If the amount used is less than 1 part by weight, the gelling or solidification will not be sufficient, and if it is more than 400 parts by weight, when gelling or solidifying, a part of the gelling agent will crystallize and precipitate, resulting in a non-uniform state. Appearance is poor and stable gelation or solidification strength cannot be maintained, which is not appropriate. The hardness of the gelled product or the solidified product can be freely adjusted by the amount of the ester compound of the present invention.

As described above, the ester compound of the present invention (therefore, the gelling or solidifying agent of the present invention) can be synthesized from industrially manufactured easily available raw materials by a simple method. Cosmetics, pharmaceuticals, agricultural chemicals, By adding to adhesives, resins, paints, etc., their fluidity can be controlled, and they are also useful for treating spilled oil and domestic waste oil.

(Best mode for carrying out the invention)

Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples. Production Example 1 N. Synthesis of ooctadecylcarbamoyl ー^ω —lauroyllysine methyl ester

Ν ^£ —Lauroyl—L-lysine (Amihope LL, manufactured by Ajinomoto Co., Inc.) To 107 g (0.326 mo 1) of methanol, add 800 ml of methanol, introduce dry hydrogen chloride gas while cooling in ice water, and stir. This gave a completely homogeneous solution. Further, hydrogen chloride gas was introduced until saturation. The reaction mixture was allowed to stand without moisture to leave. The reaction solution was concentrated under reduced pressure, and 200 ml of methanol was newly added to the residue, followed by concentration under reduced pressure. This operation was repeated twice, 500 ml of Jetil ether was added to the obtained residue, the mixture was gently shaken, the ether was removed by suction filtration, and the product was collected by filtration. Dissolve the hydrochloride salt in water 3 L, and stirred well by adding 450 m 1 of morpholine solution (2. 30 mo 1), then dried filtered precipitate crystals, N ^£ - Rauroiru L Riji down methyl ester 78.2 g (0.228 mo 1) were obtained. Next, 750 ml of toluene was added, and the mixture was heated to 90 ° C. and stirred to obtain a transparent homogeneous solution. Here, 67.4 g of Octadecyl isocyanate ("Millionate II", manufactured by Hodogaya Chemical Co., Ltd.)

(0.222 mol) was added dropwise, and the mixture was heated and stirred to complete the reaction. The stirring was stopped, the reaction product was cooled and the gelled reaction product was crushed, 500 ml of petroleum ether was added, and the mixture was filtered and dried under reduced pressure. The crystals were recrystallized from 2-propanol to obtain 141 g of a white powdery compound (0.221 mol, yield: 68%). Elemental analysis of this, IR, NMR and other descriptive values supported the chemical structure of the target compound. The IR measurement results are shown below.

111 measurement results (1:81: 333 1, 2 920, 285 1, 17 19, 1642, 1 527, 1467, 1 2 1 0, 1 19 1, 1 17 1 cm- ¹ . production example 2 N ^a - O Kuta dodecylcarbamoyl one N ^£ - Rauroiru L synthesis of single Rijine Chiruesuteru

In the same manner as in Preparation Example 1 except that 1.3 L of ethanol was used instead of methanol in the esterification reaction of Preparation Example 1, 11.6 g of N ^£ —lauroylu L-lysineethyl ester ( 0.3 3 3 mo 1) obtained. Here, 92.5 g (0.313mo1) of octadecyl isocyanate was added dropwise, and the same operation as in Production Example 1 was carried out to obtain 189 g (0.390 mol, Yield 89%). Its descriptive values, such as elemental analysis, IR, and NMR, supported the chemical structure of the target compound. The results of IR measurement are shown below.

IR measurement results (KB r): 3305, 2 9 1 9, 2 8 50, 1 7 26, 1 6 40, 1 557, 1 54 1, 1466, 1 1 89 cm- Comparative Example 1 N ^a - n-butyl Synthesis of Rucarbamoyl-N ^£ —Lauroyl-L-Lysineethyl Ester

N obtained by the esterification reaction of preparation 2 ^£ - Rauroiru to L one Rijinechiruesu ether, the same procedure as by changing the O Kuta decyl iso Xia sulfonate in n- heptyl iso Xia sulfonates, white powdery compound 1 22 g (82% yield). Comparative Example 2 New ^alpha - alkoxy carbamoyl over New cyclohexane ^£ - Synthesis of lauroyl one L- lysine Echiruesuteru The white powdery compound was converted to N ^£ —lauroyl—L—lysineethyl ester obtained in the esterification reaction of Production Example 2 by changing octyl decyl isocyanate to cyclohexyl isocyanate. 33.5 g (yield 85%) was obtained. Comparative inspection example 1

The ester compound of the present invention obtained in Production Examples 1 and 2 and the compounds of Comparative Examples 1 and 2, which are not included in the ester compound of the present invention, 12-hydroxystearic acid, and N-lauroylu L Glutamic acid and y-di-n-butylamide were tested for their ability to gel or solidify in representative organic media by the following test method. The results are shown in Table 1 below. Test method

The compound of the present invention and the comparative control compound were each added to a test tube with a lid in an amount of 5 mg each, and 2 ml of each organic medium was added to each, and the lid was capped and completely dissolved completely. Until heated. After dissolution, the solution was allowed to stand in a thermostat at 25 ° C for 2 hours and visually observed. Add compound if gelation is incomplete, add organic medium if gelled completely, and add the minimum amount of compound required to gel each organic medium per ml (Mg). However, the maximum amount of the compound to be added was up to 20 mg per 2 m1 of the organic medium, and in this state, a liquid or a substance that crystallized and precipitated was evaluated as “no gelation”. Note that “1” in the table indicates that measurement has not been performed. Table 1

Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Liquid Organic Medium Comparative Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 2 1 2—Human 'roxy N-acyl amino acid compound Steering compound Ethanol compound 2 6 2 5 2 0 1 5 8 0 1 5 Cyclohexa Non 4 5 5 0 3 5 5 0 No gelling 25 5 70 No gelling No gelling No gelling No gelling

1,4,1-dioxane 2 7 2 3 2 5 2 5 No gelation

Tetrahydrofuran 5 0 6 0 6 5 No gelling No gelling 30 Benzene 3 9 2 7 1 5 1 5 1 5 Tonolene 3 4 3 0 2 5 2 0 2 5 2 Black outlet benzene 2 9 3 0 1 5 3 0 11 Nitro benzene 1 5 1 7 1 5 1 0 11

D M F 3 5 4 0 Not gelled Not gelled Not gelled 8 5

DMSO 1 8 25 Gelation Not Gelated Not Gelated 955 Tetrachlorinated Carbon 6 0 8 0 3 0 5 0 2 0 3 0 Pyridin 3 8 3 5 Gelation Without gelation without gelation 90 0

1

Light oil 1 3 2 0 1 0 1 0

Silicon oil 20 3 10 5 No gelation 10

From Table 1, it is clear that the ester compound of the present invention can gel various organic media with a small amount of addition as compared with a conventional gelling agent. When the obtained gel was stored at 30 ° C for 1 month and its state was observed, the gel was uniform without any change from the initial state, and no liquid portion was generated even after long-term storage. It was confirmed to be stable.

(Industrial applicability)

According to the investigation, New ^alpha represented by the chemical formula (1) - to gel or solidify at Ashiruamino ester compound small amount of a wide variety of liquid organic medium with - alkyl or alkenyl-carbamoyl over New ^omega It is possible to provide a gelling or solidifying agent which is excellent in long-term stability at around room temperature and can be synthesized by a simpler method.

Claims

The scope of the claims

1. N ^a represented by the following general formula (1) - alkyl or alkenyl carba mode Iru New ^omega - Ashiruamino ester compound.

I (1)

HNCONHR ³

(Wherein, R ¹ represents a linear or branched alkyl or alkenyl group having 7 to 21 carbon atoms, and R ² represents a linear or branched chain having 1 to 22 carbon atoms and / or Or an alkyl or alkenyl group having a cyclic structure, R ³ is a linear or branched chain having 8 to 22 carbon atoms and / or an alkyl or alkenyl group having a cyclic structure, and n is 2 to 4 Indicates an integer.)

2. N described in claim 1. A gelling or solidifying agent for a liquid organic medium comprising at least one monoalkyl or alkenylcarbamoyl- ケ^ω -acyl amino acid ester compound as an active ingredient.