JP2022111433A - Novel compound and gelling agent - Google Patents

Abstract

To provide a compound capable of forming an organogel.SOLUTION: The compound is represented by the structural formula in the figure, where A represents hydrogen or OR, and each R is independently selected from the group consisting of hydrogen, a C10-22 linear alkyl group, an acyl group derived from a C10-22 linear saturated fatty acid, and an acyl group derived from a γ-amino butyric acid derivative.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to novel compounds, and more particularly to novel compounds having the ability to gel liquids other than water. The present invention also relates to gelling agents, particularly liquid gelling agents other than water.

Gelling agents are used to thicken or solidify liquids, and examples of gels that can be formed by such gelling agents include aqueous hydrogels and liquids other than water (so-called organic solvents) as dispersion media. Organogel is known. Many gelling agents are known for preparing water-based gels, but there are various liquids other than water (organic solvent-based gels). The types of gelling agents for this purpose are limited. For example, Patent Document 1 and Non-Patent Document 1 describe that a compound in which a straight-chain fatty acid is ester-bonded to a certain monosaccharide skeleton can gel various organic solvents. In addition, Non-Patent Document 2 describes that 4-(N-tetradecanoyl)aminohydroxybutanoic acid has the ability to gel organic solvents.

JP 2019-89719 A

ChemPlus Chem 2020, 85, 701-710. J. Physical Chem., B 2014, 118, 12112-12120.

On the other hand, the compounds described in Patent Document 1 and Non-Patent Document 1 have the drawback that the gel formed has low transparency, and the hardness and viscosity of the gel are also low. Therefore, there is still a need for compounds that have excellent properties in terms of the nature of the gels formed and the types of organic solvents that can be gelled. Accordingly, an object of the present invention is to provide a compound capable of forming an organogel.

（１）
（Ａは、水素又はＯＲを表し、
各Ｒは、それぞれ独立して、水素、炭素数１０～２２の直鎖アルキル基、炭素数１０～２２の直鎖飽和脂肪酸に由来するアシル基、及び、以下の式：

で示されるγ－アミノ酪酸誘導体に由来するアシル基からなる群から選択され、ｎは８～１８であり、Ｒの少なくとも１つは前記γ－アミノ酪酸誘導体に由来するアシル基である）
の化合物。
〔２〕式（２）又は（３）：

（２）

（３）
（各Ｒの定義は、前記〔１〕に記載のとおり）
で表される、前記〔１〕に記載の化合物。
〔３〕Ｒとして１つ以下の水素を有する、前記〔１〕又は〔２〕に記載の化合物。
〔４〕Ｒのすべてが同時に、前記γ－アミノ酪酸に由来するアシル基である、前記〔１〕～〔３〕のいずれか１項に記載の化合物。
〔５〕ｎが１０～１６である、前記〔１〕～〔４〕のいずれか１項に記載の化合物。
〔６〕前記〔１〕～〔５〕のいずれか１項に記載の化合物を含む、組成物。
〔７〕式（１）：

（１）
（Ａは、水素又はＯＲを表し、
各Ｒは、それぞれ独立して、水素、炭素数１０～２２の直鎖アルキル基、炭素数１０～２２の直鎖飽和脂肪酸に由来するアシル基、及び、以下の式：

で示されるγ－アミノ酪酸誘導体に由来するアシル基からなる群から選択され、ｎは８～１８であり、Ｒの少なくとも１つは前記γ－アミノ酪酸誘導体に由来するアシル基である）
の化合物を含むか、又は、
式（４）：

（４）
（ｎは８～１１又は１３～１８である）
の化合物を含む、ゲル化剤。
〔８〕前記〔７〕に記載のゲル化剤と、少なくとも１種の水以外の液体とを含む、ゲル状組成物。
〔９〕前記〔１〕～〔５〕のいずれか１項に記載の化合物の製造方法であって、
式（５）：

（５）
（Ａ’は、水素又はＯＨを表す）
の化合物を、以下の式：

（ｎは８～１８である）
で示されるＧＡＢＡ誘導体又はその酸ハロゲン化物、酸無水物若しくはエステル体と反応させて、前記式（５）の化合物の水酸基の少なくとも１つをエステル化する工程を含む、製造方法。
〔１０〕前記式（５）の化合物の水酸基の一部をエーテル化して、炭素数１０～２２の直鎖アルキル基を備えるエーテル構造を形成する工程、及び／又は、前記式（５）の化合物の水酸基の一部をエステル化して、炭素数１０～２２の直鎖飽和脂肪酸に由来するアシル基を備えるエステル構造を形成する工程をさらに含む、前記〔９〕に記載の製造方法。 The present inventors have made intensive studies to solve the above problems, and found that the compound of the following formula (1) and the compound of the formula (4) containing a partial structure thereof have the ability to gel liquids other than water. and completed the present invention. That is, the present invention provides compounds and gelling agents shown below.
[1] Formula (1):

(1)
(A represents hydrogen or OR,
Each R is independently hydrogen, a linear alkyl group having 10 to 22 carbon atoms, an acyl group derived from a linear saturated fatty acid having 10 to 22 carbon atoms, and the following formula:

wherein n is 8 to 18, and at least one of R is an acyl group derived from the γ-aminobutyric acid derivative)
compound.
[2] Formula (2) or (3):

(2)

(3)
(The definition of each R is as described in [1] above)
The compound according to [1] above, represented by
[3] The compound according to [1] or [2] above, which has one or less hydrogen as R.
[4] The compound according to any one of [1] to [3], wherein all of R are simultaneously acyl groups derived from γ-aminobutyric acid.
[5] The compound according to any one of [1] to [4] above, wherein n is 10 to 16.
[6] A composition comprising the compound according to any one of [1] to [5].
[7] Formula (1):

(1)
(A represents hydrogen or OR,
Each R is independently hydrogen, a linear alkyl group having 10 to 22 carbon atoms, an acyl group derived from a linear saturated fatty acid having 10 to 22 carbon atoms, and the following formula:

wherein n is 8 to 18, and at least one of R is an acyl group derived from the γ-aminobutyric acid derivative)
or
Formula (4):

(4)
(n is 8-11 or 13-18)
A gelling agent comprising a compound of
[8] A gel composition comprising the gelling agent according to [7] above and at least one liquid other than water.
[9] A method for producing the compound according to any one of [1] to [5],
Formula (5):

(5)
(A' represents hydrogen or OH)
the compound of the following formula:

(n is 8-18)
A production method comprising the step of reacting with a GABA derivative represented by or an acid halide, acid anhydride or ester thereof to esterify at least one of the hydroxyl groups of the compound of formula (5).
[10] A step of etherifying a portion of the hydroxyl groups of the compound of formula (5) to form an ether structure comprising a linear alkyl group having 10 to 22 carbon atoms, and/or the compound of formula (5). The production method according to [9] above, further comprising the step of esterifying a portion of the hydroxyl groups of to form an ester structure having an acyl group derived from a linear saturated fatty acid having 10 to 22 carbon atoms.

According to the present invention, novel compounds and novel gelling agents are provided that have the ability to gel liquids other than water. Therefore, the choice of compounds capable of forming organogels can be increased.

Figure 2 shows a scanning electron microscope (SEM) image of a gel formed by a compound of the invention (magnification 45,000). SEM images of gels formed by conventional compounds are shown (magnification 40,000).

（１）
の化合物に関している。式（１）中、Ａは、水素又はＯＲを表しており、本発明の化合物は、１，５－アンヒドログルシトール若しくはグルコピラノースの誘導体又はその立体異性体である。 The present invention will now be described in more detail.
The present invention provides the formula (1):

(1)
is concerned with the compound of In formula (1), A represents hydrogen or OR, and the compounds of the present invention are derivatives of 1,5-anhydroglucitol or glucopyranose, or stereoisomers thereof.

で示されるγ－アミノ酪酸（ＧＡＢＡ）誘導体に由来するアシル基からなる群から選択され、ｎは８～１８であり、Ｒの少なくとも１つは前記ＧＡＢＡ誘導体に由来するアシル基である。前記ＧＡＢＡ誘導体に由来するアシル基について、好ましくは、ｎは１０～１６である。ｎがこのような範囲であると、本発明の化合物は、より多くの種類の有機溶媒において、より高い硬度を有し、かつより高い透明性を有するゲルを形成することができる。 Each R is independently hydrogen, a linear alkyl group having 10 to 22 carbon atoms or 12 to 18 carbon atoms, an acyl group derived from a linear saturated fatty acid having 10 to 22 carbon atoms or 12 to 18 carbon atoms, and the following formula:

is selected from the group consisting of acyl groups derived from γ-aminobutyric acid (GABA) derivatives represented by n is 8 to 18, and at least one of R is an acyl group derived from the GABA derivative. For acyl groups derived from said GABA derivatives, n is preferably 10-16. When n is in such a range, the compound of the present invention can form gels with higher hardness and higher transparency in more kinds of organic solvents.

As noted above, the compounds of the invention have an amide linking moiety and a linear alkyl moiety at R. Although not bound by any particular theory, the compound can be fibrous by hydrogen bonds formed between molecules by the amide bond portion, and has lipophilicity by the straight-chain alkyl portion. , can form a network structure of the fibers in various organic solvents to form an organogel.

（２）

（３）
で表される、１，５－アンヒドロ－Ｄ－グルシトール（１，５－ＡＧ）若しくはＤ－グルコピラノース（Ｇｌｃ）の誘導体又はその立体異性体である。特に、１，５－ＡＧは、還元性を有さず化学的に安定な構造であるため、その合成中に不要な反応が引き起こされにくく、意図せず生成物が着色するという問題が生じにくい。 In some embodiments, the compounds of the invention have formula (2) or (3):

(2)

(3)
is a derivative of 1,5-anhydro-D-glucitol (1,5-AG) or D-glucopyranose (Glc) or a stereoisomer thereof. In particular, 1,5-AG does not have reducibility and has a chemically stable structure, so unnecessary reactions are less likely to occur during its synthesis, and the problem of unintentional coloring of the product is less likely to occur. .

In some embodiments, the compounds of the invention have up to one hydrogen as R. Preferably, the compound does not have hydrogen as R, that is, each R is independently derived from a linear alkyl group having 10 to 22 carbon atoms, a linear saturated fatty acid having 10 to 22 carbon atoms. It is selected from the group consisting of an acyl group and an acyl group derived from the GABA derivative, wherein at least one of R is an acyl group derived from the GABA derivative. In a particular embodiment, all of R are simultaneously acyl groups derived from said GABA derivative. Compounds with less hydrogen as R have higher hydrophobicity and are easier to crystallize, so the target compound can be easily isolated simply by crystallization and filtration, and the purification load is reduced.

In another aspect, the invention also relates to a composition comprising a compound of formula (1) above. Since the compound of formula (1) has gelling ability, the composition of the present invention is useful as a gelling agent.

（１）
（Ａは、水素又はＯＲを表し、
各Ｒは、それぞれ独立して、水素、炭素数１０～２２の直鎖アルキル基、炭素数１０～２２の直鎖飽和脂肪酸に由来するアシル基、及び、以下の式：

で示されるγ－アミノ酪酸誘導体に由来するアシル基からなる群から選択され、ｎは８～１８であり、Ｒの少なくとも１つは前記γ－アミノ酪酸誘導体に由来するアシル基である）
の化合物を含むか、又は、
式（４）：

（４）
（ｎは８～１１又は１３～１８である）
の化合物を含んでいる。本発明のゲル化剤は、水以外の液体をゲル化することができる。前記式（１）の化合物又は前記式（４）の化合物の使用量は、特に限定されないが、例えば、ゲル化の対象となる液体の全質量に対して、約０．５～約２０質量％であってもよい。 In another aspect, the invention also relates to gelling agents. The gelling agent of the present invention has the formula (1):

(1)
(A represents hydrogen or OR,
Each R is independently hydrogen, a linear alkyl group having 10 to 22 carbon atoms, an acyl group derived from a linear saturated fatty acid having 10 to 22 carbon atoms, and the following formula:

wherein n is 8 to 18, and at least one of R is an acyl group derived from the γ-aminobutyric acid derivative)
or
Formula (4):

(4)
(n is 8-11 or 13-18)
contains a compound of The gelling agent of the present invention can gel liquids other than water. The amount of the compound of formula (1) or the compound of formula (4) used is not particularly limited, but for example, about 0.5 to about 20% by mass with respect to the total mass of the liquid to be gelled. may be

The liquid to be gelled is not particularly limited as long as it is a liquid other than water, and may be an organic solvent (oil) that phase separates from water or an organic solvent that does not phase separate from water. Hydrocarbon organic solvents such as liquid paraffin, squalane, hydrogenated polyisobutene, and petrolatum; , diisostearyl malate, polyglyceryl-2 triisostearate, etc.; higher fatty acids such as capric acid, lauric acid; oils and fats such as olive oil, canola oil, soybean oil, castor oil; candelilla wax, jojoba oil, etc. alcohols such as octyldodecanol and hydrous ethanol; silicone oils such as diphenylsiloxyphenyl trimethicone; ester organic solvents such as ethyl acetate; aromatic hydrocarbon organic solvents such as toluene; A halogen-based organic solvent or the like may also be used.

Since the compound of formula (1) and the compound of formula (4) can gel various liquids other than water, the composition or gelling agent of the present invention can be used in various fields. can be done. For example, in the food field, the composition or gelling agent of the present invention can be used to prepare swallowing food, solidify liquid oil, suppress separation of liquid oil from food (peanut butter, etc.), and food (chocolate, whipped cream, etc.) ), and in the cosmetics field, it can be used for pencil-like cosmetics such as lipsticks, lip glosses, concealers, antiperspirant sticks, ointments, lipliners, and eyeliners. In the pharmaceutical field, it can be used for ointments and percutaneous absorbents.

In another aspect, the invention also relates to a gel composition comprising said gelling agent and at least one liquid other than water. That is, the gel composition of the present invention is formed from the gelling agent and has good hardness and transparency.

The composition, gelling agent, or gel composition of the present invention may further contain any excipients and/or additives commonly used in the art as long as they do not impair the purpose of the present invention, It may further contain other components having gelling ability.

（５）
（Ａ’は、水素又はＯＨを表す）
の化合物を、以下の式：

（ｎは８～１８である）
で示されるＧＡＢＡ誘導体又はその酸ハロゲン化物、酸無水物若しくはエステル体と反応させて、前記式（５）の化合物の水酸基の少なくとも１つをエステル化する工程を含む。このエステル化反応を完全に進めると、すべてのＲが前記ＧＡＢＡ誘導体に由来するアシル基である前記式（１）の化合物が得られるが、このエステル化反応を不完全に進めて未反応の水酸基を残したり、前記式（５）の化合物の一部の水酸基を予め保護基などで保護したりすると、一部のＲが水素である前記式（１）の化合物が得られる。 In another aspect, the present invention also relates to a process for preparing compounds of formula (1) above. As the means employed in the production method of the present invention, those commonly used in the art can be employed without particular limitation.

(5)
(A' represents hydrogen or OH)
the compound of the following formula:

(n is 8-18)
and a step of esterifying at least one hydroxyl group of the compound of formula (5) by reacting with a GABA derivative represented by or its acid halide, acid anhydride or ester. If this esterification reaction proceeds completely, the compound of the formula (1) in which all Rs are acyl groups derived from the GABA derivative is obtained. or protecting a portion of the hydroxyl groups of the compound of the formula (5) with a protecting group or the like in advance, the compound of the formula (1) can be obtained in which a portion of R is hydrogen.

The compound of formula (5) can be 1,5-anhydroglucitol or glucopyranose or a stereoisomer thereof. Examples of the GABA derivative include 4-[(1-oxodecyl)amino]butanoic acid (4-[(1-oxodecyl)amino]butanoic acid), 4-[(1-oxoundecyl)amino]butanoic acid (4- [(1-oxoundecyl)amino]butanoic acid), 4-[(1-oxododecyl)amino]butanoic acid, 4-[(1-oxotridecyl) Amino]butanoic acid (4-[(1-oxotetradecyl)amino]butanoic acid), 4-[(1-oxotetradecyl)amino]butanoic acid (4-[(1-oxotetradecyl)amino]butanoic acid), 4- [(1-oxopentadecyl)amino]butanoic acid (4-[(1-oxopentadecyl)amino]butanoic acid), 4-[(1-oxohexadecyl)amino]butanoic acid (4-[(1-oxohexadecyl) amino]butanoic acid), 4-[(1-oxoheptadecyl)amino]butanoic acid), 4-[(1-oxoheptadecyl)amino]butanoic acid (4 -[(1-oxooctadecyl)amino]butanoic acid), 4-[(1-oxononadecyl)amino]butanoic acid), and 4-[(1-oxoeicosyl) ) amino]butanoic acid (4-[(1-oxoeicosyl)amino]butanoic acid) and the like. The acid halide of the GABA derivative is not particularly limited, and may be, for example, a chloride, bromide, or iodide. The ester of the GABA derivative is not particularly limited, but may be, for example, an ester with a lower alcohol (having 1 to 5 carbon atoms) such as methanol and ethanol.

The reaction conditions of the compound of the formula (5) and the GABA derivative or its acid halide, acid anhydride or ester are not particularly limited, but for example, in an organic solvent, the compound of the formula (5) and the A GABA derivative or an acid halide, acid anhydride or ester thereof is mixed at a molar ratio of about 1:3 or more, preferably about 1:4 to about 1:10, and heated at a temperature of room temperature to 100 ° C. may be reacted by holding at . As the organic solvent, those commonly used in the art can be employed without particular limitation, and examples thereof include dichloroethane, N,N-dimethylformamide, toluene, N-methyl-2-pyrrolidone, Alternatively, it may be dichloromethane or the like.

The step of reacting the compound of formula (5) with the GABA derivative or its acid halide, acid anhydride or ester may be carried out, for example, in the presence of a basic compound and/or a condensing agent. As the basic compound and the condensing agent, those commonly used in the art can be employed without particular limitation. Examples of the basic compound include 4-dimethylaminopyridine, pyridine, Alternatively, it may be triethylamine or the like. Further, the condensing agent may be diisopropylcarbodiimide, dicyclohexylcarbodiimide, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, or the like.

The reaction between the compound of formula (5) and the GABA derivative or its acid halide, acid anhydride or ester is known as an acylation reaction. The compound of formula (1) can also be produced by other known reactions. For example, a method in which the compound of formula (5) and the GABA derivative are directly reacted at a high temperature using an acidic compound as a catalyst; using as a catalyst, a method of reacting in an organic solvent such as N,N-dimethylformamide; A method of adding soap to obtain a microemulsion, adding a small amount of catalyst thereto, and subjecting it to transesterification under reduced pressure; It can also be produced by reaction.

In one aspect, the production method of the present invention further comprises the step of preparing the GABA derivative or its acid halide, acid anhydride or ester. The GABA derivative or its acid halide, acid anhydride or ester can be appropriately prepared by a conventional acylation reaction or amidation reaction. For example, GABA may be reacted with linear saturated fatty acids having 10 to 20 carbon atoms or their acid halides, acid anhydrides or esters. The reaction conditions are not particularly limited. The reaction may be carried out by mixing in a molar ratio of 1:1 to about 1:3 and maintaining the temperature between 0°C and 80°C. As the aqueous solution, those commonly used in the art can be employed without particular limitation, and for example, the aqueous solution may be a basic aqueous solution such as an aqueous potassium hydroxide solution.

In one aspect, the production method of the present invention includes a step of etherifying a portion of the hydroxyl groups of the compound of formula (5) to form an ether structure having a linear alkyl group having 10 to 22 carbon atoms, and/or , esterifying a portion of the hydroxyl groups of the compound of formula (5) to form an ester structure having an acyl group derived from a linear saturated fatty acid having 10 to 22 carbon atoms. At this time, hydroxyl groups that do not participate in etherification or esterification may be appropriately protected with a protecting group or the like.

EXAMPLES The present invention will be specifically described below with reference to Examples, but the scope of the present invention is not limited to these Examples.

〔Method〕
Compounds were prepared according to the Preparation Examples described below, and their chemical structures and properties were confirmed by nuclear magnetic resonance (NMR), mass spectrometry (MS), optical rotation measurements, and melting point measurements. Specifically, the prepared compound was dissolved in deuterated chloroform or a mixture of deuterated chloroform and deuterated methanol, and subjected to ¹ H NMR (400.13 MHz) and ¹³ C NMR at 300 K using an Avance 400 spectrometer (Bruker BioSpin). (100.61 MHz) was measured. Tetramethylsilane was used as internal standard (0 ppm) (s=singlet, d=doublet, t=triplet, m=multiplet). Accurate mass measurements were also performed using ESI-Orbitrap-MS (Thermo Fisher Scientific Inc. VELOS PRO). Optical rotation was measured by dissolving each compound in chloroform:methanol=10:1 and using P-1020-GT (JASCO) at room temperature. The melting point was measured while observing the sample on a temperature controller (Mettler FP82 hot stage, coupled with Mettler FP90, accuracy of 0.4° C.) with a microscope (OLYMPUS BX51).

The gelling ability of the compound was confirmed by gel hardness measurement and turbidity measurement. Specifically, the hardness of a gel composition (thickness of about 10 mm) to which a test compound was added and allowed to stand overnight was measured using RHEONER II (YAMADEN RE2-33005C). A spherical plunger with a diameter of 5 mm was inserted at a speed of 60 mm/min, and the maximum stress until the plunger was inserted by 2.5 mm was taken as the gel hardness. Turbidity measurement was performed by placing the above preparation in a glass container and measuring the absorbance at 660 nm with a spectrophotometer (Beckman DU650). Water was measured and set to 0 as a blank. Further, for some gels, the surface was coated with osmium by an osmium deposition apparatus, and SEM images were observed using JSM-7600F (JEOL, SEM).

[Preparation Example 1] 4-[(1-oxododecyl)amino]butanoic acid (Compound 1; C ₁₂ GABA), 4-[(1-oxotetradecyl)amino]butanoic acid (Compound 2; C ₁₄ GABA), Synthesis of 4-[(1-oxohexadecyl)amino]butanoic acid (Compound 3; C ₁₆ GABA) and 4-[(1-oxooctadecyl)amino]butanoic acid (Compound 4; C ₁₈ GABA)

GABA and various fatty acid chlorides (dodecanoic acid chloride, tetradecanoic acid chloride, palmitic acid chloride, or stearic acid chloride) are reacted by a conventional method (see International Publication No. 2013/148991 if necessary) to obtain C ₁₂ GABA. (yield 76%), C ₁₄ GABA (yield 17%), C ₁₆ GABA (yield 37%), and C ₁₈ GABA (yield 80%) were synthesized respectively. The NMR of the synthesized compound was measured and confirmed to match the known NMR chart.

[Preparation Example 2] Synthesis of 1,5-AG bound with linear saturated fatty acid-containing GABA

(2-1) 1,5-anhydro-2,3,4,6-tetra-O-{4-[(1-oxododecyl)amino]butanoyl}-D-glucitol (1,5-anhydro-2, Synthesis of 3,4,6-tetra-O-{4-[(1-oxododecyl)amino]butanoyl}-D-glucitol, Compound 5; C ₁₂ GABA-AG) 1,5-AG crystals (24 mg, 0.5 mg) 146 mmol) was dissolved in 100 μL of water and dried with a vacuum pump to make it amorphous. Compound 1 (250 mg, 0.876 mmol) and 4-(dimethylamino)pyridine (DMAP; 214 mg, 1.75 mmol) were added thereto and suspended in 1,2-dichloroethane (20 mL). After heating to 60° C. to dissolve, N,N′-diisopropylcarbodiimide (DIC; 275 μL, 1.76 mmol) was added and reacted at 60° C. for 1.5 hours. After confirming the completion of the reaction, 60 mL of methanol was added, and the mixture was stirred at room temperature for 1.5 hours. The reaction mixture was concentrated under reduced pressure and purified by silica gel column chromatography (chloroform:methanol=20:1). It was crystallized with 80% methanol to give pure compound 5 (63.81 mg, yield 35%). The results of optical rotation measurement, melting point measurement, NMR method and MS measurement results are shown below.

(2-2) 1,5-anhydro-2,3,4,6-tetra-O-{4-[(1-oxotetradecyl)amino]butanoyl}-D-glucitol (1,5-anhydro-2 ,3,4,6-tetra-O-{4-[(1-oxotetradecyl)amino]butanoyl}-D-glucitol, Compound 6; C ₁₄ GABA-AG) Compound 2 (275 mg, 0.877 mmol) was used, and since crystals were generated when methanol was added after the reaction was completed, the crystals were filtered with filter paper without performing silica gel column chromatography. to give pure compound 6 (94.20 mg, 48% yield). The results of optical rotation measurement, melting point measurement, NMR method and MS measurement results are shown below.

(2-3) 1,5-anhydro-2,3,4,6-tetra-O-{4-[(1-oxohexadecyl)amino]butanoyl}-D-glucitol (1,5-anhydro-2 ,3,4,6-tetra-O-{4-[(1-oxohexadecyl)amino]butanoyl}-D-glucitol, Compound 7; C ₁₆ GABA-AG) Compound 3 (300 mg, Highly pure compound 7 (193.10 mg, yield 91%) was obtained in the same manner as in (2-2) above except that 0.878 mmol) was used. The results of optical rotation measurement, melting point measurement, NMR method and MS measurement results are shown below.

(2-4) 1,5-anhydro-2,3,4,6-tetra-O-{4-[(1-oxooctadecyl)amino]butanoyl}-D-glucitol (1,5-anhydro-2, Synthesis of 3,4,6-tetra-O-{4-[(1-oxooctadecyl)amino]butanoyl}-D-glucitol, Compound 8; C ₁₈ GABA-AG) Compound 4 (324 mg, 0 .877 mmol) was used in the same manner as in (2-2) above to obtain highly pure compound 8 (154.86 mg, yield 67%). The results of optical rotation measurement, melting point measurement, NMR method and MS measurement results are shown below.

（＊反応温度を室温に変更すると化合物９の収率は４４％になった。） [Preparation Example 3] Synthesis of D-glucopyranose (Glc) bound with linear saturated fatty acid-containing GABA

(*When the reaction temperature was changed to room temperature, the yield of compound 9 became 44%.)

(3-1) 1,2,3,4,6-penta-O-{4-[(1-oxododecyl)amino]butanoyl}-D-glucopyranoside (1,2,3,4,6-penta- Synthesis of O-{4-[(1-oxododecyl)amino]butanoyl}-D-glucopyranoside, Compound 9; C ₁₂ GABA-Glc) Glc crystals (20 mg, 0.111 mmol) were dissolved in 100 μL of water and dried with a vacuum pump. to form an amorphous state. Compound 1 (238 mg, 0.834 mmol) and DMAP (203 mg, 1.66 mmol) were added thereto and suspended in 1,2-dichloroethane (20 mL). After heating to 60° C. to dissolve, DIC (261 μL, 1.67 mmol) was added and reacted at 60° C. for 1.5 hours. After confirming the completion of the reaction, 30 mL of methanol was added, and the mixture was stirred at room temperature for 1.5 hours. The reaction mixture was concentrated under reduced pressure and purified by silica gel column chromatography (chloroform:methanol=20:1). It was crystallized with 80% methanol to obtain highly pure compound 9 (12.08 mg, yield 7%, α:β=0.13:0.87). The yield was 44% (α:β=0.13:0.87) when the reaction was performed at room temperature instead of 60°C. The results of melting point measurement, NMR method and MS measurement results are shown below.

(3-2) 1,2,3,4,6-penta-O-{4-[(1-oxotetradecyl)amino]butanoyl}-D-glucopyranoside (1,2,3,4,6-penta -O-{4-[(1-oxotetradecyl)amino]butanoyl}-D-glucopyranoside, Compound 10; C ₁₄ GABA-Glc) Compound 2 (261 mg, 0.833 mmol) was used instead of Compound 1. , And, since crystals were generated when methanol and water were added after the completion of the reaction, the crystals were filtered with filter paper without performing silica gel column chromatography. Compound 10 (28.66 mg, 16% yield, α:β=0.15:0.85) was obtained. The results of melting point measurement, NMR method and MS measurement results are shown below.

(3-3) 1,2,3,4,6-penta-O-{4-[(1-oxohexadecyl)amino]butanoyl}-D-glucopyranoside (1,2,3,4,6-penta Synthesis of -O-{4-[(1-oxohexadecyl)amino]butanoyl}-D-glucopyranoside, compound 11; C ₁₆ GABA-Glc) Using compound 3 (284 mg, 0.832 mmol) instead of compound 2 A highly pure compound 11 (87.67 mg, yield 44%, α:β=0.48:0.52) was obtained in the same manner as in (3-2) above. The results of melting point measurement, NMR method and MS measurement results are shown below.

(3-4) 1,2,3,4,6-penta-O-{4-[(1-oxooctadecyl)amino]butanoyl}-D-glucopyranoside (1,2,3,4,6-penta- Synthesis of O-{4-[ ₍ 1-oxooctadecyl)amino]butanoyl}-D-glucopyranoside, compound 12; Highly pure compound 12 (103.48 mg, yield 48%, α:β=0.51:0.49) was obtained in the same manner as in (3-2) above. The results of melting point measurement, NMR method and MS measurement results are shown below.

[Test Example 1]
Put liquid paraffin #350 (LP#350) or triethylhexanoin (TIO) in a screw tube bottle, add any of compounds 1 to 12 to a concentration of 1% by mass, and heat at 100 to 150 ° C. melted on a hot plate. Then, the resulting solution was allowed to stand at room temperature for 12 hours or longer, and gel formation was observed. When the fluidity of the solution was lost and the contents did not run off even when the screw-type vial was turned upside down, it was determined that a gel had been formed, and the hardness of the formed gel was measured. Table 1 shows the results.

Most of compounds 1-12 were able to gel both LP#350 and TIO at a concentration of 1% by weight. Compound 6, in particular, was able to form a hard gel on both LP#350 and TIO. An increase in viscosity was observed even with compounds that failed to form a gel at a concentration of 1% by mass, and a gel can be formed by increasing the concentration to about 5% by mass. 1,5-AG cannot be dissolved in liquid paraffin and TIO and cannot form a gel.

[Test Example 2]
Various organic solvents were placed in a screw tube bottle, and compound 6 or a known compound (1,5-anhydro-2,3,4,6-tetrapalmitoyl-D-glucitol; C ₁₆ AG) was added thereto at a concentration of 1 mass%. and dissolved on a hot plate at 100-150°C. Then, the resulting solution was allowed to stand at room temperature for 12 hours or longer, and gel formation was observed. When the fluidity of the solution was lost and the contents did not run off even when the screw-type vial was turned upside down, it was determined that a gel had been formed, and the hardness of the formed gel was measured. The turbidity of the contents of the screw vial was also measured. Table 2 shows the results.

C ₁₆ AG was unable to form a gel with isopropyl myristate and 80% ethanol aqueous solution. Compound 6, on the other hand, was able to form gels in all organic solvents tested and in most of them exhibited higher hardness than gels formed by C ₁₆ AG. In olive squalane and 2-octyl-1-dodecanol, the hardness of the gel formed by compound 6 was comparable to that formed by C ₁₆ AG, but the gel formed by compound 6 was Turbidity was low and transparency was high.

[Test Example 3]
Liquid paraffin #350 (LP#350) was placed in a screw vial, compound 6 or C ₁₆ AG was added thereto to a concentration of 1% by mass, and dissolved on a hot plate at 100-150°C. The resulting solution was allowed to stand at room temperature for 12 hours or longer to form a gel. The gel was placed in hexane and allowed to stand for 2 days to deoil and then observed with a scanning electron microscope.

Comparing the SEM image of the gel formed by Compound 6 (Fig. 1) and the SEM image of the gel formed by C ₁₆ AG (Fig. 2), it was found that the former formed a finer fibrous structure. rice field. The gel formed by compound 6 is considered to have higher transparency than the gel formed by C ₁₆ AG, because the fibers constituting the gel are thin. According to Non-Patent Document 1, C ₁₆ AG forms a fibrous structure due to weak hydrogen bonding between the oxygen atom of the carbonyl group and the hydrogen atom of the alkyl group, but this fibrous structure is not so stable. , a plurality of fibers gather together to form a thick fiber structure, which is considered to be in a stable state. On the other hand, the compound of the present invention forms a stable fibrous structure due to the strong hydrogen bond formed by the amide bond portion, so that it can be dispersed in the entire organic solvent while maintaining the thin fibrous structure and form a highly transparent gel. it is conceivable that.

From the above, it was found that the compounds and gelling agents of the present invention can form gels with high hardness and transparency, and can gel various organic solvents. Therefore, it was possible to increase the selection of compounds capable of forming organogels.

Claims (10)

Formula (1):

(1)
(A represents hydrogen or OR,
Each R is independently hydrogen, a linear alkyl group having 10 to 22 carbon atoms, an acyl group derived from a linear saturated fatty acid having 10 to 22 carbon atoms, and the following formula:

wherein n is 8 to 18, and at least one of R is an acyl group derived from the γ-aminobutyric acid derivative)
compound. Formula (2) or (3):

(2)

(3)
(The definition of each R is as described in claim 1)
2. The compound of claim 1, represented by: 3. A compound according to claim 1 or 2, having up to one hydrogen as R. A compound according to any one of claims 1 to 3, wherein all of R are simultaneously acyl groups derived from said γ-aminobutyric acid. A compound according to any one of claims 1-4, wherein n is 10-16. A composition comprising a compound according to any one of claims 1-5. Formula (1):

(1)
(A represents hydrogen or OR,
Each R is independently hydrogen, a linear alkyl group having 10 to 22 carbon atoms, an acyl group derived from a linear saturated fatty acid having 10 to 22 carbon atoms, and the following formula:

wherein n is 8 to 18, and at least one of R is an acyl group derived from the γ-aminobutyric acid derivative)
or
Formula (4):

(4)
(n is 8-11 or 13-18)
A gelling agent comprising a compound of A gel composition comprising the gelling agent according to claim 7 and at least one liquid other than water. A method for producing the compound according to any one of claims 1 to 5,
Formula (5):

(5)
(A' represents hydrogen or OH)
the compound of the following formula:

(n is 8-18)
A production method comprising the step of reacting with a GABA derivative represented by or an acid halide, acid anhydride or ester thereof to esterify at least one of the hydroxyl groups of the compound of formula (5). A step of etherifying a portion of the hydroxyl groups of the compound of formula (5) to form an ether structure comprising a linear alkyl group having 10 to 22 carbon atoms, and/or of hydroxyl groups of the compound of formula (5). The production method according to claim 9, further comprising the step of partially esterifying to form an ester structure having an acyl group derived from a linear saturated fatty acid having 10 to 22 carbon atoms.

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