JP2001206868A - Betaine compound and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hydroxyl group-containing betaine compound and a long chain alkyl group-containing betaine compound which have each excellent biodegradability and are each useful for surfactants, sterilizers, antistatics, softening and finishing agents, anti-corrosive agents, resin modifiers, raw materials for intermediates, and so on, and to provide methods for producing the compounds. SOLUTION: This hydroxyl group-containing betaine compound represented by the general formula (1) (R1 and R2 are the same of differently each H, a 1 to 8C hydrocarbon group or a hydroxyl group-having 1 to 8C hydrocarbon group, provided that a case that R1 and R2 are each H is excluded, when R1 and R2 are not each H, R1 and R2 may be bound to each other through a single bond or through at least one element selected from the group consisting of O, S and N; R3 is H, methyl or hydroxymethyl; A is a 2 to 25C hydrocarbon group).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a betaine compound containing a hydroxyl group and a betaine compound containing a long-chain alkyl group, and a method for producing them.

[0002]

BACKGROUND ART A betaine compound is a compound having a cation portion and an anion portion in one molecule, and has recently attracted attention as an amphoteric activator because of its chemical structure. Such amphoteric surfactants have various excellent properties such as extremely excellent hard water resistance and extremely low toxicity, and include surfactants, bactericides, antistatic agents, softening agents, It is suitably used for applications such as rust agents.

JP-A-5-32600 discloses that an aliphatic primary amine is reacted with a quaternary ammonium compound having a specific structure at a pH of 6 to less than 8, and the resulting reaction product is converted to a specific halogenated lower amine. Carboxylic acid and pH 6 or higher 8
A method for producing a betaine compound by reacting at less than 10 g is disclosed. Since the betaine compound produced by such a production method has foaming power, detergency, and the like, it can be used as a surfactant for cleaning hair and body. However, such betaine compounds have room for further study on related compounds in order to impart various properties other than foaming power, detergency, and the like, and to thereby broaden applications.

Japanese Patent Application Laid-Open No. 5-294905 discloses a carbobetaine compound and a method for producing the same.
This method for producing a carbobetaine compound is a method of reacting a specific amino compound with a salt having a halogen atom. Since the carbobetaine compound produced by such a production method has a moisturizing property on hair and skin, it can be used as a moisturizing agent for hair and skin cosmetics. However, such a carbobetaine compound still has room for further study on related compounds in order to impart various properties other than the moisturizing property and to thereby broaden the application.

[0005]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above situation, has excellent biodegradability, and has a surfactant, a bactericide, an antistatic agent, a softening agent, a rust inhibitor, and a resin. An object of the present invention is to provide a hydroxyl group-containing betaine compound and a long chain alkyl group-containing betaine compound useful as a modifier, an intermediate raw material, and the like, and a method for producing them.

[0006]

The present invention provides a compound represented by the following general formula (1):

[0007]

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(Wherein, R ¹ and R ² are the same or different and each represent a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, or a hydrocarbon group having 1 to 8 carbon atoms having a hydroxyl group. except when ¹ and R ² are both hydrogen atoms. Moreover, if the R ¹ and R ² are not both hydrogen atoms, R ¹ and R ² are bound to each other by a single bond,
Alternatively, they may be bonded to each other via at least one element selected from the group consisting of O, S, and N. R ³ represents a hydrogen atom, a methyl group or a hydroxymethyl group. A represents a hydrocarbon group having 2 to 25 carbon atoms. ) Is a hydroxyl group-containing betaine compound. The present invention also provides the following general formula (1):

[0009]

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(Wherein R ¹ , R ² , R ³ and A are the same as described above), which is a method for producing a hydroxyl group-containing betaine compound represented by the following general formula (2):

[0011]

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(Wherein R ¹ , R ² and R ³ are the same as described above). A process for producing a hydroxyl group-containing betaine compound, which comprises the step of reacting a β-alanine derivative represented by the formula is there. The present invention also provides the following general formula (3):

[0013]

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(Wherein R ⁶ and R ⁷ are the same or different and each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms. However, when R ⁶ and R ⁷ are both hydrogen atoms, When both R ⁶ and R ⁷ are not hydrogen atoms, R ⁶ and R ⁷ are bonded to each other by a single bond, or at least one selected from the group consisting of O, S and N. R ³ and A may be the same as described above, and R ⁴ and R ⁵ may be
One of them represents a hydrogen atom, and the other one has 5 carbon atoms.
Represents up to 30 hydrocarbon groups. X is a hydrogen atom or -CO
Represents OM. M represents a hydrogen atom, a metal atom or an ammonium group. ) Is a betaine compound containing a long-chain alkyl group. The present invention further provides the following general formula (3):

[0015]

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(Wherein R ⁶ , R ⁷ , R ³ , A, R ⁴ , R
⁵ and X are the same as above. A method for producing a betaine compound containing a long-chain alkyl group represented by the following general formula (6):

[0017]

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(Wherein R ⁶ , R ⁷ , R ³ and A are the same as those described above), and a hydroxyl group-containing betaine compound represented by the following general formula (4):

[0019]

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(Wherein R ⁴ , R ⁵ and X are the same as described above), or a carboxylic acid having a long-chain alkyl group represented by the following general formula (5):

[0021]

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(Wherein R ⁴ and R ⁵ are the same as above)
The method for producing a long chain alkyl group-containing betaine compound includes a step of reacting with a long chain alkyl group-containing carboxylic anhydride represented by the formula: Hereinafter, the present invention will be described in detail.

The hydroxyl group-containing betaine compound of the present invention is represented by the above general formula (1). In the above general formula (1), R ¹
And the hydrocarbon group having 1 to 8 carbon atoms for R ² is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, a cyclohexyl group, and an octyl group. And a hydrocarbon group having 1 to 8 carbon atoms having a hydroxyl group in R ¹ and R ² is not particularly limited. Examples thereof include a 2-hydroxyethyl group, a 3-hydroxypropyl group, Examples include a 2-hydroxypropyl group, a 2-hydroxybutyl group, a 2-hydroxyhexyl group, and a 2-hydroxyoctyl group. Also, R ¹ and R
^When both are not hydrogen atoms, the groups are particularly limited when they are bonded to each other by a single bond or bonded to each other via at least one element selected from the group consisting of O, S and N. However, for example, a tetramethylene group, a pentamethylene group, a hexamethylene group,
Examples thereof include an ethyleneoxyethylene group and an ethyleneiminoethylene group. In the general formula (1), the hydrocarbon group having 2 to 25 carbon atoms in A is not particularly limited, and examples thereof include a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group, a pentyl group,
Octyl, decyl, dodecyl, tetradecyl,
Examples include a hexadecyl group, an octadecyl group, an eicosyl group, a docosyl group, and a pentacosyl group.

The hydroxyl group-containing betaine compound of the present invention comprises 1
N ⁺ as a cation part and CO as an anion part in the molecule
O ^- and a specific hydrocarbon group or the like is bonded to N ⁺ ,
In addition, it is a betaine compound with a specific structure having a hydroxyl group, is excellent in biodegradability, surfactants, bactericides, antistatic agents, softening agents, rust inhibitors, resin modifiers, raw materials for intermediates, etc. Useful for

The method for producing the hydroxyl group-containing betaine compound of the present invention is not particularly limited. For example, a hydroxyl group including a step of reacting a β-alanine derivative represented by the above general formula (2) with a monooxirane compound. The method for producing the contained betaine compound can be suitably applied. The method for producing such a hydroxyl group-containing betaine compound is also one of the present invention. In this specification, the above step is also referred to as a monooxirane compound addition step.

The β-alanine derivative represented by the general formula (2) used in the step of adding the monooxirane compound is not particularly limited. For example, (meth) acrylic acid,
1 for acrylic acids such as 2-hydroxymethylacrylic acid
A compound easily synthesized by adding a secondary amine or a secondary amine can be used. The method for producing a hydroxyl group-containing betaine compound of the present invention may include a step of synthesizing the β-alanine derivative represented by the general formula (2). In this specification, the above step is also referred to as a β-alanine derivative synthesis step.

The primary amine is not particularly limited.
For example, octylamine, 2-ethylhexylamine,
Heptylamine, hexylamine, pentylamine, n
Linear or branched such as -butylamine, isobutylamine, n-propylamine, isopropylamine, ethylamine, methylamine, 2-hydroxyethylamine, 2-hydroxypropylamine, 2-hydroxyhexylamine, and 2-hydroxyoctylamine; Primary alkylamines and primary hydroxyalkylamines are exemplified. These may be used alone or in combination of two or more.

The secondary amine is not particularly limited.
For example, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-n-pentylamine, methylethylamine, dihexylamine, dioctylamine, ethyleneimine, pyrrolidine, piperidine,
Hexamethyleneimine, morpholine, piperazine, N-
Methyl piperazine, di- (2-hydroxy) ethylamine, di- (2-hydroxy) propylamine, di- (2
Linear, branched or cyclic secondary alkylamines such as -hydroxy) octylamine; and secondary hydroxyalkylamines. These may be used alone,
More than one species may be used in combination.

In the step of synthesizing the β-alanine derivative, the method of mixing the acrylic acid with the primary amine or the secondary amine is not particularly limited. For example, the heat of neutralization generated by the mixing is suppressed, In order to facilitate the control, it is preferable that one of them is charged in a reaction vessel and the other is added continuously or sequentially. That is, acrylic acid is charged in a reaction vessel, and a primary amine or a secondary amine may be added continuously or sequentially. Alternatively, primary or secondary amine may be charged in a reaction vessel, and acrylic acid may be continuously added. Or you may add sequentially.

In the step of synthesizing the β-alanine derivative, the reaction can be carried out without a solvent, but a solvent may be used if necessary. Also, no special catalyst is required,
A catalyst may be used for the purpose of promoting reaction or suppressing side reactions.

The solvent is not particularly limited as long as it does not react with the acid or amine as a raw material and does not inhibit the reaction. Examples thereof include aliphatic hydrocarbons such as hexane and octane; cyclohexane and the like. Alicyclic saturated hydrocarbons such as cyclohexene; aromatic hydrocarbons such as benzene, toluene and xylene; ketones such as acetone and methyl ethyl ketone; methyl acetate, ethyl acetate, butyl acetate and the like Esters; halogenated hydrocarbons such as dichloromethane, chloroform and carbon tetrachloride; ethers such as diethyl ether, dioxane, dioxolane; alcohols such as methanol, ethanol, isopropanol and butanol; and water; amides such as dimethylformamide Sulphoxides such as dimethylsulphoxide, acetonitrile Nitriles such as Le, and the like. These may be used alone or in combination of two or more.

The catalyst is not particularly restricted but includes, for example, bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium methylate, lithium methylate, sodium ethylate, tertiary amine compounds and quaternary ammonium compounds. Catalysts and the like. These may be used alone or in combination of two or more.

In the step of synthesizing the β-alanine derivative, a polymerization inhibitor may be used to prevent polymerization of acrylic acids. The polymerization inhibitor used is not particularly restricted but includes, for example, phenolic polymerization inhibitors such as hydroquinone, methoxyhydroquinone and benzoquinone, sulfur such as dilauryl-3,3'-thiodipropionate, 2-mercaptobenzimidazole and phenothiazine. And a phosphorus-based polymerization inhibitor such as tris (isodecyl) phosphite and diphenylisodecylphosphite. These may be used alone or in combination of two or more.

The reaction temperature in the step of synthesizing the β-alanine derivative is not particularly limited, and is preferably, for example, a temperature range not higher than the boiling point of the starting acid or amine. More preferably, the temperature is 0 to 250 ° C. from the viewpoint of easy control of the reaction temperature. More preferably, the temperature is from 20 to 150 ° C., since a side reaction due to excessive heating can be suppressed and the β-alanine derivative can be obtained with high selectivity. Further, the reaction pressure is not particularly limited, for example,
It is preferable to carry out at 10 atm or less.

The monooxirane compound used in the step of adding the monooxirane compound is not particularly limited. For example, ethylene oxide, propylene oxide,
Butylene oxide, 1,2-epoxyoctane, 1,2
-Epoxy decane, 1,2-epoxide decane, 1,2
-Epoxypentadecane, 1,2-epoxyoctadecane, 1,2-epoxyeicosane, 1,2-epoxypentacosane and the like. These may be used alone or in combination of two or more. In the step of adding the monooxirane compound, the method of mixing the β-alanine derivative and the monooxirane compound is not particularly limited. For example, considering the reactivity of the monooxirane compound, β
-It is preferred to determine the method of mixing the alanine derivative with the monooxirane compound. Usually, it is preferable to charge a β-alanine derivative in a reaction vessel and continuously or sequentially add a monooxirane compound. However, depending on reaction conditions, the β-alanine derivative and the monooxirane compound may be mixed at once.

In the step of adding a monooxirane compound, the reaction is preferably performed in an inert gas atmosphere because the monooxirane compound has explosive properties.
The inert gas is not particularly limited, and includes, for example, nitrogen, helium, neon, and the like. Usually, nitrogen gas is used.

In the step of adding the monooxirane compound, when the reaction is carried out under pressurized conditions, the reaction vessel may be previously pressurized with the inert gas in order to avoid the explosion range of the monooxirane compound. preferable. The state of pressurization by the inert gas is preferably determined in consideration of the reactivity and reaction temperature of the monooxirane compound used, and the pressure resistance of the reaction vessel used. In addition, the reaction pressure is not particularly limited, and for example, it is preferably performed at 10 atm or less.

The above-mentioned step of adding a monooxirane compound can be carried out without a solvent, but a solvent may be used if necessary. A catalyst is not particularly required, but a catalyst may be used for the purpose of accelerating the reaction and suppressing side reactions. The solvent is not particularly limited as long as it does not inhibit the reaction, and examples thereof include the same solvents as those described above. These may be used alone or in combination of two or more.

The catalyst is not particularly restricted but includes, for example, the above-mentioned basic catalysts; acid catalysts such as hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid and zeolite. These may be used alone or in combination of two or more.
The reaction temperature in the above-mentioned monooxirane compound addition step is not particularly limited, and for example, is preferably 0 to 200 ° C from the viewpoint of easy control of the reaction temperature.
More preferably, from 20 to 1 in terms of suppression of side reactions.
50 ° C. The method for producing a hydroxyl group-containing betaine compound of the present invention can efficiently produce the hydroxyl group-containing betaine compound represented by the general formula (1) in high yield by including the above-described monooxirane compound addition step. Things.

The long chain alkyl group-containing betaine compound of the present invention is represented by the above general formula (3). The above general formula (3)
Wherein a hydrocarbon group having 1 to 8 carbon atoms in R ⁶ and R ⁷ ;
A group in which R ⁶ and R ⁷ are not hydrogen atoms and are bonded to each other by a single bond or bonded to each other via at least one element selected from the group consisting of O, S and N; 2 to 25 carbon atoms in A
The hydrocarbon group is not particularly limited, and examples thereof include the same groups as described above.

In the general formula (3), as the hydrocarbon group having 5 to 30 carbon atoms for R ⁴ and R ^5, one or more hydrogen atoms in the hydrocarbon group are a fluorine atom or a chlorine atom. May be substituted without particular limitation, for example, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosyl group, docosyl group, tetracosyl group, triacontyl group Linear or branched alkyl groups such as, 2-ethylhexyl and the like; octenyl, decenyl, dodecenyl, tetradecenyl, hexadecenyl, octadecenyl, eicosenyl, docosenyl, tetracosenyl, triaconthenyl and the like An alkenyl group of
Examples thereof include groups in which these groups are combined.

In the general formula (3), when X is represented by —COOM, the long chain alkyl group-containing betaine compound has a structure in which when M is a carboxyl group which is a hydrogen atom,
When M is a metal atom, it becomes a metal salt type, and when M is an ammonium group, it becomes an ammonium salt type.

The long chain alkyl group-containing betaine compound of the present invention
The substance is a cation moiety N in one molecule. ⁺ And in the anion part
A certain COO^- And N⁺ Contains a specific hydrocarbon group, etc.
A long-chain alkyl group via an ester bond.
Betaine compound with a specific structure
Excellent surfactant, surfactant, bactericide, antistatic agent, soft finish
Useful as a polishing agent, rust inhibitor, resin modifier,
You.

The method for producing the long chain alkyl group-containing betaine compound of the present invention is not particularly limited. For example, a hydroxyl group-containing betaine compound represented by the above general formula (6) and a compound represented by the above general formula (4) A method for producing a long-chain alkyl group-containing betaine compound comprising a step of reacting the long-chain alkyl group-containing carboxylic acid or the long-chain alkyl group-containing carboxylic anhydride represented by the general formula (5). Can be applied to The method for producing such a long chain alkyl group-containing betaine compound is also one of the present invention.
In this specification, the above step is also referred to as a long-chain alkyl group introduction step.

The hydroxyl-containing betaine compound represented by the general formula (6) used in the long-chain alkyl group introduction step is not particularly limited, and for example, those produced by the above-described method for producing a hydroxyl-containing betaine compound may be used. Preferably, it is used. In this case, the method for producing a long chain alkyl group-containing betaine compound of the present invention preferably includes the above-mentioned monooxirane compound addition step.

The long-chain alkyl group-containing carboxylic acid represented by the general formula (4) used in the long-chain alkyl group introduction step may be a monocarboxylic acid type wherein X is a hydrogen atom, and X is -COOM. The dicarboxylic acid type represented by However, in the case of the dicarboxylic acid type, M is preferably a metal atom or an ammonium group. When X is a carboxyl group or an alkoxycarbonyl group represented by -COOR (R represents a hydrocarbon group or the like), 1 mol of a long-chain alkyl group-containing carboxylic acid represented by the general formula (4): Since 2 moles of the hydroxyl group-containing betaine compound represented by the general formula (6) may react, the desired long chain alkyl group-containing betaine compound represented by the general formula (3) can be obtained in high yield. May not be.
Further, the hydrocarbon group having 5 to 30 carbon atoms in R ⁴ and R ⁵ may be a saturated hydrocarbon group or an unsaturated hydrocarbon group.

The long-chain alkyl group-containing carboxylic acid represented by the general formula (4) is not particularly limited as long as it is as described above. For example, caprylic acid, capric acid,
Monocarboxylic acid types such as lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, linoleic acid and linolenic acid; dicarboxylic acids such as dodecenylsuccinic acid, tetradecenylsuccinic acid and octadecenylsuccinic acid Type. These may be used alone,
More than one species may be used in combination.

The reaction between the hydroxyl group-containing betaine compound represented by the general formula (6) and the long-chain alkyl group-containing carboxylic acid represented by the general formula (4) can be carried out by a dehydration condensation reaction. The catalyst used in the dehydration condensation reaction is not particularly limited as long as it is usually used in the dehydration condensation reaction, and examples thereof include sulfuric acid, hydrochloric acid, nitric acid, p-toluenesulfonic acid, methanesulfonic acid, and zeolite. Acid catalyst. These may be used alone,
More than one species may be used in combination.

The dehydration condensation reaction can be carried out without a solvent, but it is preferable to use an appropriate solvent in order to control the reaction temperature and to easily remove water as a by-product. The solvent is not particularly limited as long as it does not react with a hydroxyl group-containing betaine compound or a long-chain alkyl group-containing carboxylic acid as a raw material and does not inhibit the reaction. Is mentioned. These may be used alone or in combination of two or more. However, alcohols, water, and ester solvents are not preferred because they participate in the reaction and cannot obtain a desired long-chain alkyl group-containing betaine compound in good yield.

The reaction temperature in the dehydration-condensation reaction is not particularly limited, and is preferably, for example, a temperature range not higher than the boiling point of a hydroxyl group-containing betaine compound or a long-chain alkyl group-containing carboxylic acid. More preferably,
20 to 250 ° C. from the viewpoint of easy control of the reaction temperature
It is. More preferably, the temperature is 50 to 200 ° C., since a side reaction due to excessive heating can be suppressed, and a long chain alkyl group-containing betaine compound can be obtained with high selectivity. The reaction pressure is not particularly limited.
tm or less.

The long-chain alkyl group-containing carboxylic anhydride represented by the general formula (5) used in the above-mentioned long-chain alkyl group introduction step is characterized in that the hydrocarbon group having 5 to 30 carbon atoms in R ⁴ and R ⁵ is saturated. It may be a hydrocarbon group or an unsaturated hydrocarbon group. The long-chain alkyl group-containing carboxylic anhydride represented by the general formula (5) is not particularly limited as long as it is as described above. For example, dodecenyl succinic anhydride, tetradecenyl succinic anhydride ,
And octadecenyl succinic anhydride. These may be used alone or in combination of two or more.

In the case of a reaction between the hydroxyl group-containing betaine compound represented by the general formula (6) and the long-chain alkyl group-containing carboxylic anhydride represented by the general formula (5), The long chain alkyl group-containing betaine compound represented is in an acid form in which X is a carboxyl group.

In the above reaction, no reaction is required for the reaction between the hydroxyl group-containing compound and the carboxylic acid anhydride. The above reaction can be carried out without a solvent, but a solvent may be used if necessary. The solvent is not particularly limited as long as it does not react with the hydroxyl group-containing betaine compound or the long-chain alkyl group-containing carboxylic anhydride as a raw material, and does not inhibit the reaction. And the like. These may be used alone or in combination of two or more. However,
Alcohols and water are not preferred because they react with the long-chain alkyl group-containing carboxylic anhydride.

The reaction temperature in the above reaction is not particularly limited, and is preferably, for example, a temperature range not higher than the boiling point of the hydroxyl group-containing betaine compound and the long-chain alkyl group-containing carboxylic anhydride. More preferably,-
50-300 ° C. More preferably, a side reaction due to excessive heating can be suppressed, and a long chain alkyl group-containing betaine compound can be obtained with high selectivity.
° C. The reaction pressure is not particularly limited, and is preferably, for example, 10 atm or less.

The method for producing a long-chain alkyl group-containing betaine compound of the present invention relates to the case where X in the long-chain alkyl group-containing betaine compound produced by the above-mentioned long chain alkyl group-introducing step is represented by -COOM. , M, for example, when X is a carboxyl group in an acid form, a step of neutralizing the acid form into a metal salt form or an ammonium salt form may be included. The method for producing a long-chain alkyl group-containing betaine compound of the present invention includes the above-described long-chain alkyl group-introducing step, whereby the long-chain alkyl group-containing betaine compound represented by the general formula (3) can be efficiently produced at high yield. It can be manufactured at a high rate.

[0056]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Reference Example 1N, N-di-n-butyl-β-
Alanine synthesis  300 equipped with stirrer, cooling pipe, thermometer and dropping funnel
100 ml di-n-butylamine in a four-necked flask.
g (0.7738 mol), and the temperature in the system was reduced with an ice water bath.
While maintaining the temperature at 30 ° C. or less while stirring.
5.7 g (0.7730 mol) and phenothiazine 0.1
g was added dropwise over 30 minutes. After dropping,
The mixture was heated in an oil bath at 80 ° C. and reacted for 4 hours. End of reaction
Afterwards, acrylic acid and di
When the amount of n-butylamine was determined, the conversion of acrylic acid was determined.
Conversion is 98%, conversion of di-n-butylamine is 98%
And N, N-di-n-butyl-β-alanine 15
2.5 g (98% yield) were obtained.

Reference Example 2N, N-di-n-pentyl-β
-Synthesis of alanine  100 equipped with stirrer, cooling pipe, thermometer and dropping funnel
50 ml di-n-pentylamine in a four-necked flask.
g (0.3179 mol) and the temperature in the system in an ice water bath.
While maintaining the temperature at 30 ° C. or lower while stirring the acrylic acid 2
2.9 g (0.3178 mol) and phenothiazine 0.0
The mixture with 5 g was added dropwise over 30 minutes. Drip end
Thereafter, the mixture was heated in an oil bath at 80 ° C. and reacted for 4 hours. End of reaction
After completion, acrylic acid and
When di-n-pentylamine was quantified, acrylic acid
Is 95%, and the conversion of di-n-pentylamine is 95%.
95%, N, N-di-n-pentyl-β-alani
69.2 g (yield 95%) were obtained.

Reference Example 3N, N-di- (2-hydroxy
B) Synthesis of ethyl-β-alanine  100 equipped with stirrer, cooling pipe, thermometer and dropping funnel
ml of 4- (2-hydroxy) ethyl
Luamine (50 g, 0.4756 mol)
While maintaining the temperature inside the system with stirring at 30 ° C or less,
34.2 g (0.4751 mol) of acrylic acid and phenothi
A mixture with 0.02 g of azine was added dropwise over 1 hour.
After completion of the dropwise addition, the mixture was heated in an oil bath at 80 ° C. and reacted for 3 hours.
Was. After the completion of the reaction, gas chromatography
Determination of lylic acid and di- (2-hydroxy) ethylamine
As a result, the conversion of acrylic acid was 99%, and di- (2-
The conversion of hydroxy) ethylamine is 99%,
N, N-di- (2-hydroxy) ethyl-β-alanine
83.3 g (99% yield) was obtained.

Embodiment 13- (N, N-di-n-butyl
-N- (2-hydroxy) propyl) ammoniopropa
Synthesis of noate [hydroxyl-containing betaine compound 1]  100ml simple autoclay equipped with stirrer and thermometer
To the N, N-di-n-butyl-β obtained in Reference Example 1.
-30 g (0.1490 mol) of alanine, monooxira
8.66 g (0.149 g) of propylene oxide
1 mol), and 20 g of isopropyl alcohol as a solvent.
And 1 g of water.
Internal pressure of 3 atm is applied after 3 replacements with elemental gas
Gas was charged as described above. Then, add oil in an 80 ° C oil bath.
The reaction was carried out for 8 hours with stirring while heating. Early in the reaction
Showed an internal pressure of 3.6 atm, but after 6 hours the internal pressure
It decreased to 3.4 atm. Cool the resulting reaction solution to room temperature
After filling, the filled nitrogen gas is exhausted, and then the reaction solution
Into a 500 ml eggplant flask,
Distilling off coal and water with a rotary evaporator
Is a hydroxyl-containing betaine compound of the present invention,
-(N, N-di-n-butyl-N- (2-hydroxy)
Propyl) ammoniopropanoate [solid containing hydroxyl group]
In compound 1] about 38.5 g (yield: 99.5%) was obtained.
Was.

The obtained hydroxyl-containing betaine compound ¹
The H-nuclear magnetic resonance spectrum is shown in FIG. 1 and the infrared absorption spectrum is shown in FIG. Referring to FIG. 1, a peak of a propylene oxide-derived methine group is observed at 4.0 ppm, which is about 1.0 ppm lower than a propylene oxide methine group peak (3.0 ppm) observed in the case of unreacted propylene oxide. It was shifted by 0 ppm. In FIG. 2, the absorption (2550 to 2600 cm ⁻¹ ) derived from the amino group of N, N-di-n-butyl-β-alanine as the raw material had disappeared. Furthermore, around 840 cm ^-1, around 950 cm ^-1 ,
1140 cm ^-1 vicinity, -CH ₂ -N newly generated in the vicinity of 1200 cm ^{-1 +,} absorption from -CH-OH was observed, the 3300～3400Cm ^-1 was observed stretching vibration absorption of OH group. From these, it was confirmed that the hydroxyl group-containing betaine compound 1 represented by the following formula (7) was obtained.

[0062]

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Embodiment 23- (N, N-di-n-butyl
-N- (2-hydroxy) ethyl) ammoniopropano
Synthesis of Ethate [hydroxyl-containing betaine compound 2]  100ml simple autoclay equipped with stirrer and thermometer
To the N, N-di-n-butyl-β obtained in Reference Example 1.
-30 g of alanine (0.1490 mol), as solvent
25 g of 1,2-dimethoxyethane and 2 g of water were charged,
Place the autoclave three times with nitrogen gas at room temperature
After the replacement, fill with nitrogen gas so that an internal pressure of 5 atm is applied.
I filled it. Then, autoclave using an oil bath at 80 ° C.
The inside was heated to a constant temperature. Internal temperature becomes constant
At the time, ethylene oxa
7.5 g (0.1703 mol) of the
Over 10 minutes so that the pressure inside does not exceed 8 atm
Added sequentially. After the addition is completed, heat in an oil bath at 80 ° C.
The mixture was reacted for 6 hours while stirring. Ethylene oxide added
Immediately after application, the internal pressure showed 8 atm, but after 6 hours,
The pressure dropped to 5.1 atm. Allow the resulting reaction solution to reach room temperature.
After cooling in, filled nitrogen gas and remaining
The ethylene oxide was evacuated and then the reaction was
Transfer to a 2 ml eggplant flask and add 1,2-dimethoxyethane
And water are distilled off using a rotary evaporator.
The hydroxyl-containing betaine compound of the present invention,
(N, N-di-n-butyl-N- (2-hydroxy) e
Chill) ammoniopropanoate [hydroxyl-containing betaine
Compound 2] was obtained in an amount of about 36.2 g (yield: 99%).

[0064] The resulting hydroxy-containing betaine compound 2 ¹
The H-nuclear magnetic resonance spectrum is shown in FIG. 3, and the infrared absorption spectrum is shown in FIG. Referring to FIG. 3, a peak of a methylene group derived from ethylene oxide is observed at 4.2 ppm, which is about 1 ppm lower than the peak of a methylene group of ethylene oxide (2.5 ppm) observed in the case of no reaction. It was shifted by 7 ppm. FIG. 4 shows that the absorption (2550 to 2600 cm ⁻¹ ) derived from the amino group of the raw material N, N-di-n-butyl-β-alanine disappeared. Furthermore, around 830 cm ^-1, around 950 cm ^-1 ,
-CH ₂ -N ⁺ newly formed around 1200 cm ⁻¹ ,
-CH-OH-derived absorption was observed and 3200 to 3400
At cm ^-1 , stretching vibration absorption of OH groups was observed. From these, it was confirmed that the hydroxyl group-containing betaine compound 2 represented by the following formula (8) was obtained.

[0065]

Embedded image

Embodiment 33- (N, N-di-n-pliers
Ru-N- (2-hydroxy) propyl) ammoniopro
Synthesis of panoate [hydroxyl-containing betaine compound 3]  100ml simple autoclay equipped with stirrer and thermometer
To the N, N-di-n-pentyl- obtained in Reference Example 2.
β-alanine 25 g (0.1090 mol), monooxy
7 g of propylene oxide (0.1205 mol
), 20 g of 1,2-dimethoxyethane as a solvent and water
2 g, and the inside of the autoclave was charged with nitrogen gas at room temperature.
After 3 times replacement with internal gas, internal pressure of 3 atm is applied.
Was filled with nitrogen gas. Then heat it in an oil bath at 80 ° C
The reaction was continued for 8 hours while stirring. At the beginning of the reaction
The pressure showed 4.1 atm, but after 6 hours the internal pressure was 3.
It dropped to 4 atm. Cool the resulting reaction to room temperature.
After that, the filled nitrogen gas is exhausted, and then the reaction solution is
Transfer to a 00 ml eggplant flask and add 1,2-dimethoxyquine
And water are removed by a rotary evaporator.
The hydroxyl-containing betaine compound of the present invention,
(N, N-di-n-pentyl-N- (2-hydroxy)
Propyl) ammoniopropanoate [solid containing hydroxyl group]
In compound 3], about 31 g (yield: 99%) was obtained.

The obtained hydroxyl-containing betaine compound 3¹
The H-nuclear magnetic resonance spectrum is shown in FIG.
The torque is shown in FIG. Referring to FIG.
A peak of methine group derived from propylene oxide was observed.
And the peak is the propylene oxide
More than the peak of methine group of oxide (3.0 ppm)
It was shifted by 1.0 ppm. Also, looking at FIG.
Of N, N-di-n-pentyl-β-alanine
Absorption from mino group (2550-2600cm^-1) Disappears
Was. In addition, 840cm^-1Near, 960cm^-1Attached
Nearby, 1150cm^-1Near 1200cm^-1New near
-CH generated_Two -N⁺ And the absorption derived from -CH-OH
3300-3400cm ^-1OH group stretching vibration
Absorption was seen. From these, the following equation (9) is used.
The obtained hydroxyl-containing betaine compound 3 has been obtained.
Was confirmed.

[0068]

Embedded image

Embodiment 43- (N, N-di-n-butyl
-N- (2- (3-carboxyl-3-dodecenyl-1)
-Oxo) propoxy) propyl) ammoniopropano
Synthesis of Eate [Betaine Compound 1 Containing Long Alkyl Group]  100 equipped with stirrer, cooling pipe, thermometer and dropping funnel
in a 4-ml four-necked flask,
(N, N-di-n-butyl-N- (2-hydroxy) p
Ropyr) Ammoniopropanoate [hydroxyl-containing betai
Compound 1] 20 g (0.0771 mol)
And 30 g of toluene, while stirring, oil at 80 ° C
While heating in the bath, dodecenyl succinic anhydride 20.54
g (0.0771 mol) was added dropwise over 5 minutes. Dripping
After completion, the mixture was heated in an oil bath at 80 ° C. and reacted for 3 hours. Anti
After the reaction, transfer the reaction solution to a 500 ml eggplant flask,
Toluene is removed by rotary evaporator
The long-chain alkyl group-containing betaine compound of the present invention
3- (N, N-di-n-butyl-N- (2- (3-
(Carboxy-3-dodecenyl-1-oxo) propoxy
C) propyl) ammonium propanoate [long-chain alkyl
40.5 g (yield 99.9)
%).

FIG. 7 shows the ¹ H-nuclear magnetic resonance spectrum of the obtained betaine compound 1 having a long-chain alkyl group, and FIG. 8 shows the infrared absorption spectrum. Looking at FIG.
A peak of propylene oxide-derived methine was observed at 4.2 ppm, and the peak was shifted by about 0.1 ppm from a peak (about 4.0 ppm) observed in the case of no reaction. In addition, a peak derived from a proton of a carboxyl group generated by ring opening of dodecenyl succinic anhydride was observed at 9.6 to 9.8 ppm. Further, when looking at FIG. 8, the stretching vibration absorption of the OH group observed at 3300 to 3400 cm ^-1 disappears, and
At m ⁻¹ , absorption of stretching vibration of CO ₂ —H of a carboxyl group generated by ring opening of dodecenyl succinic anhydride was observed. From these, it was confirmed that the betaine compound 1 containing a long-chain alkyl group represented by the following formula (10) was obtained.

[0071]

Embedded image

Example 5 3- (N, N-di-n-butyl)
-N- (2-cococarboxy) propyl) ammoniop
Lopanoate [Long chain alkyl group-containing betaine compound 2]
Of the 3- (N, N-di-n-butyl-N- (2-) obtained in Example 1 was placed in a 100 ml four-necked flask equipped with a synthetic stirrer, a condenser, a thermometer and a Dien-Stark tube. (Hydroxy) propyl) ammoniopropanoate [hydroxyl-containing betaine compound 1] 15 g (0.0578 mol), cocoalkylcarboxylic acid 13 g (0.0579 mol), toluene 20 g as a solvent, and p-toluenesulfonic acid 0 as a catalyst .2 g, 140 ° C. with stirring
The reaction was carried out for 18 hours while heating in an oil bath. After completion of the reaction, the dehydration amount was 0.98 g, and the theoretical dehydration amount was 1.04 g.
g, the conversion of the dehydration reaction was found to be 94%. The obtained reaction solution was transferred to a 500 ml eggplant-shaped flask, and toluene was distilled off by a rotary evaporator to give 3- (N, N-di-n-butyl-), a betaine compound containing a long-chain alkyl group of the present invention.
About 25.2 g (yield: 94%) of N- (2-cococarboxy) propyl) ammoniopropanoate [betaine compound 2 containing a long-chain alkyl group] was obtained.

FIG. 9 shows the ¹ H-nuclear magnetic resonance spectrum of the obtained betaine compound 2 containing a long-chain alkyl group, and FIG. 10 shows the infrared absorption spectrum. Looking at FIG.
A peak of propylene oxide-derived methine was observed at 4.2 ppm, and the peak was shifted by about 0.1 ppm from a peak (about 4.0 ppm) observed in the case of no reaction. Also, looking at FIG.
The stretching vibration absorption of the OH group observed at 0 cm ^-1 disappeared. Furthermore, absorption of stretching vibrations of CO ₂ —H around 2550 to 2600 cm ⁻¹ derived from the carboxyl group of unreacted cocoalkyl carboxylic acid was not observed. From these, it was confirmed that the betaine compound 2 containing a long-chain alkyl group represented by the following formula (11) was obtained. In the formula, Rc represents a cocoalkyl group (Cococoy)
l).

[0074]

Embedded image

Embodiment 63- (N, N-di-n-butyl
-N- (2- (3-carboxyl-3-dodecenyl-1)
-Oxo) propoxy) ethyl) ammoniopropanoe
Synthesis of betaine compound 3 containing long chain alkyl group  100 equipped with stirrer, cooling pipe, thermometer and dropping funnel
in a 4-ml four-necked flask,
(N, N-di-n-butyl-N- (2-hydroxy) e
Chill) ammoniopropanoate [hydroxyl-containing betaine
Compound 2] 20 g (0.0815 mol) as a solvent
30 g of toluene is charged and an oil bath at 80 ° C. while stirring.
21.7 g of dodecenyl succinic anhydride while heating with
(0.0815 mol) was added dropwise over 5 minutes. End of dripping
After completion, the mixture was heated in an oil bath at 80 ° C. and reacted for 3 hours. reaction
After completion, transfer the reaction solution to a 500 ml eggplant flask,
Ruen is distilled off on a rotary evaporator.
The betaine compound having a long chain alkyl group of the present invention.
3- (N, N-di-n-butyl-N- (2- (3-
(Carboxy-3-dodecenyl-1-oxo) propoxy
B) Ethyl) ammoniopropanoate [long-chain alkyl
Group-containing betaine compound 3] 41.5 g (yield 99.5)
%).

FIG. 11 shows the ¹ H-nuclear magnetic resonance spectrum of the obtained betaine compound 3 containing a long-chain alkyl group, and FIG. 12 shows the infrared absorption spectrum. Looking at FIG.
A methylene peak derived from ethylene oxide is observed at 3 to 4.4 ppm, which is about 0.1 ppm higher than the peak (about 4.2 ppm) observed when unreacted.
Was shifting. In addition, a peak derived from proton of a carboxyl group generated by ring opening of dodecenyl succinic anhydride was observed at around 9.1 ppm. Further, when looking at FIG. 12, the stretching vibration absorption of the OH group observed around 3300 to 3400 cm ^-1 disappears, and
Stretching vibration absorption of CO ₂ —H was observed at around 0 cm ⁻¹ . From these, it was confirmed that the betaine compound 3 containing a long-chain alkyl group represented by the following formula (12) was obtained.

[0077]

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Embodiment 73- (N, N-di-n-butyl
-N- (2-cococarboxy) ethyl) ammoniopro
Of panoate [long chain alkyl group-containing betaine compound 4]
Synthesis  Stirrer, cooling tube, thermometer and Dien-Stark tube
In a 100 ml four-necked flask equipped with
3- (N, N-di-n-butyl-N- (2-hydro
Xy) ethyl) ammoniopropanoate [containing hydroxyl group
Betaine compound 2] 13.5 (0.0551 mol),
12.3 g of sialkylcarboxylic acid (0.0550
), 20 g of toluene as a solvent, and p as a catalyst
-0.2 g of toluenesulfonic acid is charged and stirred
The reaction was carried out for 19 hours while heating in a 140 ° C. oil bath. Anti
After completion of the reaction, the dehydration amount is 0.95 g, and the theoretical dehydration amount is
Since it is 0.99 g, the conversion rate of the dehydration reaction is 96%.
It turned out to be. 500 ml of the obtained reaction solution
Transfer to an eggplant flask and use a rotary evaporator
By distilling off toluene, the long-chain alkyl of the present invention is obtained.
3- (N, N-di-n-) which is a group-containing betaine compound
Butyl-N- (2-cococarboxy) ethyl) ammonium
Opropanoate (a betaine compound containing a long chain alkyl group)
4] About 24.8 g (yield: 96%) was obtained.

FIG. 13 shows the ¹ H-nuclear magnetic resonance spectrum of the obtained betaine compound 4 containing a long-chain alkyl group, and FIG. 14 shows the infrared absorption spectrum. Looking at FIG.
A methylene peak derived from ethylene oxide is observed at 2 to 4.4 ppm, which is about 0.2 ppm lower than the peak observed in the case of no reaction (around 4.1 to 4.2 ppm).
There was a 2 ppm shift. Referring to FIG.
The stretching vibration absorption of the OH group observed at 00 to 3400 cm ^-1 disappeared. Furthermore, 2550-2600 derived from the carboxyl group of unreacted cocoalkylcarboxylic acid
Absorption of stretching vibration of CO ₂ —H near cm ⁻¹ was not observed. From these, it was confirmed that the betaine compound 4 containing a long-chain alkyl group represented by the following formula (13) was obtained. In the formula, Rc is the same as described above.

[0080]

Embedded image

Embodiment 83- (N, N-di-n-pliers
Ru-N- (2- (3-carboxyl-3-dodecenyl-
1-oxo) propoxy) propyl) ammoniopropa
Noate (long chain alkyl group-containing betaine compound 5)
Success  100 equipped with stirrer, cooling pipe, thermometer and dropping funnel
3-ml obtained in Example 3 in a 4-ml four-necked flask.
(N, N-di-n-pentyl-N- (2-hydroxy)
Propyl) ammoniopropanoate [solid containing hydroxyl group]
In compound 3] 13 g (0.0452 mol) and a solvent
And charged with 30 g of toluene.
12 g of dodecenyl succinic anhydride while heating in an oil bath
(0.0451 mol) was added dropwise over 5 minutes. End of dripping
After completion, the mixture was heated in an oil bath at 80 ° C. and reacted for 3 hours. reaction
After completion, transfer the reaction solution to a 500 ml eggplant flask,
Ruen is distilled off on a rotary evaporator.
The betaine compound having a long chain alkyl group of the present invention.
3- (N, N-di-n-pentyl-N- (2- (3
-Carboxy-3-dodecenyl-1-oxo) propo
Xy) propyl) ammoniopropanoate [long chain al
Killed group-containing betaine compound 5] 24.8 g (yield 99.
2%).

FIG. 15 shows the ¹ H-nuclear magnetic resonance spectrum of the obtained betaine compound 5 having a long-chain alkyl group, and FIG. 16 shows the infrared absorption spectrum. Looking at FIG.
A peak of methine derived from propylene oxide is observed at 1 to 4.2 ppm, which is about 0.1 ppm higher than the peak (around 4.0 ppm) observed when unreacted.
Was shifting. In addition, a peak derived from proton of a carboxyl group generated by ring opening of dodecenyl succinic anhydride was observed at 8.4 ppm. Further, referring to FIG.
The stretching vibration absorption of the OH group observed around 3300 cm ^-1 disappeared, and instead, the stretching vibration absorption of CO ₂ -H was observed around 2500 to 2550 cm ^-1 . From these, it was confirmed that the betaine compound 5 having a long-chain alkyl group represented by the following formula (14) was obtained.

[0083]

Embedded image

Embodiment 93- (N, N-di-n-pliers
Ru-N- (2-cococarboxy) propyl) ammonio
Propanoate (a betaine compound containing a long chain alkyl group)
Synthesis of 6]  Stirrer, cooling tube, thermometer and Dien-Stark tube
In a 100 ml four-necked flask equipped with
3- (N, N-di-n-pentyl-N- (2-hydrogen)
Roxy) propyl) ammoniopropanoate [hydroxyl group
Containing betaine compound 3] 13.5 g (0.0470
), 10.5 g (0.046) of cocoalkylcarboxylic acid
9 mol), 20 g of toluene as a solvent, and a catalyst
And add 0.2 g of p-toluenesulfonic acid.
While heating in a 140 ° C oil bath, react for 16 hours.
Was. After completion of the reaction, the amount of dehydration is 0.81 g,
Since the amount is 0.85 g, the conversion of the dehydration reaction is 9
It turned out to be 5%. 500 m of the obtained reaction solution
l to an eggplant flask and put it on a rotary evaporator.
By further distilling off toluene, the long-chain alcohol of the present invention is obtained.
3- (N, N-di-), a betaine compound containing a kill group
n-pentyl-N- (2-cococarboxy) propyl)
Ammoniopropanoate (Beta containing long chain alkyl group)
Compound 6] was obtained in an amount of about 22 g (yield: 95%).

FIG. 17 shows the ¹ H-nuclear magnetic resonance spectrum of the obtained betaine compound 6 having a long-chain alkyl group, and FIG. 18 shows the infrared absorption spectrum. Looking at FIG.
A peak of methine derived from propylene oxide is observed at 1 to 4.2 ppm, which is about 0.1 ppm higher than the peak (around 4.0 ppm) observed when unreacted.
Was shifting. Also, looking at FIG.
The stretching vibration absorption of the OH group observed at 400 cm ^-1 had disappeared. Furthermore, absorption of stretching vibrations of CO ₂ —H around 2550 to 2600 cm ⁻¹ derived from the carboxyl group of unreacted cocoalkyl carboxylic acid was not observed. From these, it was confirmed that a betaine compound containing a long-chain alkyl group represented by the following formula (15) was obtained. In the formula, Rc is the same as described above.

[0086]

Embedded image

Embodiment 103- (N, N-di-n-butyl)
Ru-N- (2-hydroxy) dodecyl) ammoniopro
Synthesis of panoate [hydroxyl-containing betaine compound 4]  100ml 4-port equipped with stirrer, cooling tube and thermometer
The N, N-di-n-butyl obtained in Reference Example 1 was added to the flask.
Le-β-alanine 12 g (0.0596 mol)
As xylan, 11 g of 1,2-epoxide decane (0.
0596 mol), 30 g of toluene was charged as a solvent,
At room temperature for 10 minutes in a four-necked flask with nitrogen gas
Was replaced. Then, while heating in an oil bath at 120 ° C,
The reaction was carried out for 6 hours with stirring. Flow nitrogen gas during the reaction.
To perform a reaction under a nitrogen gas atmosphere. Got
After cooling the reaction solution to room temperature, the reaction solution was
Transfer toluene to the rotary evaporator
The hydroxyl group-containing betaine of the present invention
The compound, 3- (N, N-di-n-butyl-N-
(2-Hydroxy) dodecylammoniopropanoate
[Hydroxy group-containing betaine compound 4] about 22.7 g (yield:
98.7%).

[0088] ¹ of the obtained hydroxyl group-containing betaine compound 4
FIG. 19 shows the H-nuclear magnetic resonance spectrum and FIG. 20 shows the infrared absorption spectrum. Looking at FIG. 19, 4.2 pp
In m, a peak of a methine group derived from 1,2-epoxide dodecane is observed, and this peak is observed in the case of unreacted 1,1.
The peak of the methine group of 2-epoxide decane (3.0 pp)
m) by about 1.2 ppm. FIG.
0, the raw material N, N-di-n-butyl-β-
Absorption (2550-2600 cm ^-1 ) derived from the alanine group had disappeared. In addition, 950cm ^-1, 1090cm ^-1,
-CH ₂ -N ⁺ newly formed around 1200 cm ⁻¹ ,
-CH-OH-derived absorption was observed, and 3300 to 3500
At cm ^-1 , stretching vibration absorption of OH groups was observed. From these, it was confirmed that the hydroxyl group-containing betaine compound 4 represented by the following formula (16) was obtained.

[0089]

Embedded image

Embodiment 113- (N, N-di- (2-h
Droxy) ethyl-N- (2-hydroxy) octyl)
Ammoniopropanoate [hydroxyl-containing betaine compound
Synthesis of 5]  100 equipped with stirrer, cooling pipe, thermometer and dropping funnel
ml of the N, N-
Di- (2-hydroxy) ethyl-β-alanine 10 g
(0.0564 mol), 20 g of methanol as a solvent,
And, 0.6 g of triethylamine was charged as a catalyst,
At room temperature for 10 minutes in a four-necked flask with nitrogen gas
Was replaced. Thereafter, methanol is refluxed in an oil bath at 80 ° C.
The internal temperature was raised until After the internal temperature becomes constant,
7.24 g of 1,2-epoxyoctane as xylan
(0.0564 mol) and 10 g of methanol
It was dropped over 20 minutes. After dropping, methanol returns
The mixture was reacted for 10 hours while stirring in a flowing state. In reaction
Flow nitrogen gas and react under nitrogen gas atmosphere.
went. After cooling the obtained reaction solution to room temperature, the reaction solution
Was transferred to a 300 ml eggplant flask, and meta as a solvent was
Of ethanol and triethylamine as a catalyst
By distilling off with an evaporator, the hydroxyl group of the present invention is obtained.
3- (N, N-di- (2-
(Hydroxy) ethyl-N- (2-hydroxy) octyl
A) Ammoniopropanoate [hydroxylated betaine compound
Compound 5] about 16.4 g (yield: 95.1%) was obtained.

The obtained hydroxy-containing betaine compound 5¹
The H-nuclear magnetic resonance spectrum is shown in FIG.
The vector is shown in FIG. Looking at FIG. 21, 4.1 pp
The peak of a methine group derived from 1,2-epoxyoctane in m
Is observed, and the peak is observed when unreacted.
The peak of the methine group of 2-epoxyoctane (2.9 pp
m) by about 1.2 ppm. FIG.
2 shows that the raw material N, N-di- (2-hydroxy
B) Absorption derived from the amino group of ethyl-β-alanine (25
50-2600cm^-1) Had disappeared. In addition, 104
0cm^-1, 1080cm^-1, 1200cm^-1New near
-CH generated_Two -N⁺ , The absorption from -CH-OH is
Seen, 3300-3400cm ^-1Has an OH group
Dynamic absorption was observed. From these, the following equation (17)
That the hydroxy betaine compound 5 represented by
Was confirmed.

[0092]

Embedded image

[0093]

The hydroxyl group-containing betaine compound and the long chain alkyl group-containing betaine compound of the present invention are excellent in biodegradability and have a surfactant, a bactericide, an antistatic agent, a softening agent, It is useful as a rust inhibitor, a resin modifier, a raw material for an intermediate, and the like. ADVANTAGE OF THE INVENTION The manufacturing method of the betaine compound of this invention can manufacture a hydroxyl group containing betaine compound and a long chain alkyl group containing betaine compound efficiently and with high yield.

[Brief description of the drawings]

FIG. 1 shows a ¹ H-nuclear magnetic resonance spectrum of a hydroxy group-containing betaine compound 1 obtained in Example 1.

FIG. 2 shows an infrared absorption spectrum of a hydroxyl-containing betaine compound 1 obtained in Example 1.

FIG. 3 shows a ¹ H-nuclear magnetic resonance spectrum of a hydroxyl group-containing betaine compound 2 obtained in Example 2.

4 shows an infrared absorption spectrum of a hydroxyl group-containing betaine compound 2 obtained in Example 2. FIG.

FIG. 5 shows a ¹ H-nuclear magnetic resonance spectrum of a hydroxyl group-containing betaine compound 3 obtained in Example 3.

6 shows an infrared absorption spectrum of a hydroxyl-containing betaine compound 3 obtained in Example 3. FIG.

FIG. 7 shows the ¹ H-nuclear magnetic resonance spectrum of the betaine compound 1 having a long-chain alkyl group obtained in Example 4.

8 shows an infrared absorption spectrum of the betaine compound 1 having a long chain alkyl group obtained in Example 4. FIG.

9 shows a ¹ H-nuclear magnetic resonance spectrum of the betaine compound 2 having a long chain alkyl group obtained in Example 5. FIG.

FIG. 10 shows an infrared absorption spectrum of a betaine compound 2 having a long-chain alkyl group obtained in Example 5.

FIG. 11 shows a ¹ H-nuclear magnetic resonance spectrum of betaine compound 3 having a long-chain alkyl group obtained in Example 6.

12 shows an infrared absorption spectrum of the betaine compound 3 having a long chain alkyl group obtained in Example 6. FIG.

13 shows a ¹ H-nuclear magnetic resonance spectrum of a betaine compound 4 having a long-chain alkyl group obtained in Example 7. FIG.

14 shows an infrared absorption spectrum of betaine compound 4 having a long-chain alkyl group obtained in Example 7. FIG.

FIG. 15 shows a ¹ H-nuclear magnetic resonance spectrum of a long-chain alkyl group-containing betaine compound 5 obtained in Example 8.

16 shows an infrared absorption spectrum of a betaine compound 5 having a long-chain alkyl group obtained in Example 8. FIG.

17 shows a ¹ H-nuclear magnetic resonance spectrum of the betaine compound 6 having a long-chain alkyl group obtained in Example 9. FIG.

18 shows an infrared absorption spectrum of a betaine compound 6 having a long-chain alkyl group obtained in Example 9. FIG.

FIG. 19 shows a ¹ H-nuclear magnetic resonance spectrum of a hydroxyl group-containing betaine compound 4 obtained in Example 10.

20 shows an infrared absorption spectrum of a hydroxyl group-containing betaine compound 4 obtained in Example 10. FIG.

FIG. 21 shows a ¹ H-nuclear magnetic resonance spectrum of a hydroxyl group-containing betaine compound 5 obtained in Example 11.

FIG. 22 shows an infrared absorption spectrum of a hydroxyl group-containing betaine compound 5 obtained in Example 11.

Claims (4)

[Claims] 1. The following general formula (1): (Wherein, R ¹ and R ² are the same or different, represent a hydrocarbon group having 1 to 8 carbon atoms having a hydrocarbon group or a hydroxyl group of a hydrogen atom or a 1 to 8 carbon atoms. However, R ¹ and R ^Two
Except when both are hydrogen atoms. When both R ¹ and R ² are not hydrogen atoms, R ¹ and R ²
May be bonded to each other by a single bond, or may be bonded to each other via at least one element selected from the group consisting of O, S, and N. R ³ represents a hydrogen atom, a methyl group or a hydroxymethyl group. A represents a hydrocarbon group having 2 to 25 carbon atoms. A) a betaine compound containing a hydroxyl group; 2. The following general formula (1): (Wherein, R ¹ and R ² are the same or different, represent a hydrocarbon group having 1 to 8 carbon atoms having a hydrocarbon group or a hydroxyl group of a hydrogen atom or a 1 to 8 carbon atoms. However, R ¹ and R ^Two
Except when both are hydrogen atoms. When both R ¹ and R ² are not hydrogen atoms, R ¹ and R ²
May be bonded to each other by a single bond, or may be bonded to each other via at least one element selected from the group consisting of O, S, and N. R ³ represents a hydrogen atom, a methyl group or a hydroxymethyl group. A represents a hydrocarbon group having 2 to 25 carbon atoms. A method for producing a hydroxyl group-containing betaine compound represented by the following general formula (2): (Wherein, R ¹ , R ² and R ³ are the same as described above), which comprises a step of reacting a β-alanine derivative represented by the formula (I) with a monooxirane compound. Method. 3. The following general formula (3): (Wherein, R ⁶ and R ⁷ are the same or different and each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms.
Except when ⁶ and R ⁷ are both hydrogen atoms. When both R ⁶ and R ⁷ are not hydrogen atoms, R
⁶ and R ⁷ are linked to each other by a single bond, or
They may be bonded to each other via at least one element selected from the group consisting of O, S and N. R ³
Represents a hydrogen atom, a methyl group or a hydroxymethyl group. A represents a hydrocarbon group having 2 to 25 carbon atoms. One of R ⁴ and R ⁵ represents a hydrogen atom, and the other one represents a hydrocarbon group having 5 to 30 carbon atoms. X represents a hydrogen atom or -COOM. M represents a hydrogen atom, a metal atom or an ammonium group. A betaine compound containing a long-chain alkyl group, which is represented by the formula: 4. The following general formula (3): (Wherein, R ⁶ and R ⁷ are the same or different and each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms.
Except when ⁶ and R ⁷ are both hydrogen atoms. When both R ⁶ and R ⁷ are not hydrogen atoms, R
⁶ and R ⁷ are linked to each other by a single bond, or
They may be bonded to each other via at least one element selected from the group consisting of O, S and N. R ³
Represents a hydrogen atom, a methyl group or a hydroxymethyl group. A represents a hydrocarbon group having 2 to 25 carbon atoms. One of R ⁴ and R ⁵ represents a hydrogen atom, and the other one represents a hydrocarbon group having 5 to 30 carbon atoms. X represents a hydrogen atom or -COOM. M represents a hydrogen atom, a metal atom or an ammonium group. A method for producing a long-chain alkyl group-containing betaine compound represented by the following general formula (6): (Wherein, R ⁶ , R ⁷ , R ³ and A are the same as described above) and a betaine compound having a hydroxyl group represented by the following general formula (4): (Wherein R ⁴ , R ⁵ and X are the same as described above), or a carboxylic acid having a long-chain alkyl group represented by the following general formula (5): (Wherein R ⁴ and R ⁵ are the same as described above), which comprises reacting with a long-chain alkyl group-containing carboxylic anhydride represented by the formula: Method.