JP2002097175A - Method for producing betaine ester - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a betaine ester, capable of industrially easily producing the highly qualified betaine ester of a high-molecular weight alcohol, a polyhydric alcohol, an alcohol which occurres easily side reactions such as dehydration and rearrangement, of which the all are difficult to be produced by conventional methods. SOLUTION: This method for producing the betaine ester comprises a process where a halogenated fatty acid ester of a 1-4C saturated or unsaturated monohydric alcohol [hereinafter, referred to as an alcohol (a)] is reacted with a tertiary amine, then the unreacted halogenated fatty acid ester is removed to obtain a betaine ester of the alcohol (a) [hereinafter, referred to a betaine ester (A)], and another process where the obtained betaine ester (A) is reacted with an alcohol having two or more carbon atoms [hereinafter, referred to as an alcohol (b)] which is different from the alcohol (a) in the presence of a basic catalyst to be subjected to transesterification so that the betain ester of the alcohol (b) is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a process for producing betaine ester, which is a compound having an alcohol releasing function and useful as a fabric softening agent, a hair surface modifier and the like.

[0002]

2. Description of the Related Art Conventionally, betaine esters are produced by the following methods: (1) quaternization reaction of a tertiary amine with a halogenated fatty acid ester of a functional alcohol (Menschutkin reaction);
Acid-catalyzed esterification reaction of the corresponding betaine and functional alcohol (JP-B-51-36732), (3) Reaction of betaine acid chloride with higher alcohol (US Pat.
No. 383) and (4) N-methylation of an ω-amino acid alkyl ester with an alkylating agent such as diazomethane. However, these production methods have a problem that side reactions are likely to occur and a large amount of waste is produced as a by-product, making purification difficult.

[0003]

An object of the present invention is to provide high-quality betaines such as high molecular weight alcohols, polyhydric alcohols and alcohols which are liable to cause side reactions such as dehydration and rearrangement, which have been difficult to produce by conventional methods. It is to obtain the ester industrially easily.

[0004]

According to the present invention, there is provided a compound having 1 to 4 carbon atoms.
Reacting a halogenated fatty acid ester of a saturated or unsaturated monohydric alcohol (hereinafter referred to as alcohol (a)) with a tertiary amine, and removing the unreacted halogenated fatty acid ester to obtain a betaine of alcohol (a). A step of obtaining an ester (hereinafter referred to as a betaine ester (A)), and subjecting the betaine ester (A) to an alcohol having 2 or more carbon atoms (hereinafter referred to as an alcohol (b)) excluding the alcohol (a) in the presence of a basic catalyst There is provided a process for producing a betaine ester, comprising a step of obtaining a betaine ester of an alcohol (b) by transesterification (hereinafter referred to as a betaine ester (B)).

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a betaine ester has a structure in which a carboxyl group, which is an acid form of betaine, and an alcohol are esterified.

[Production process of betaine ester (A)] Reaction of halogenated fatty acid ester of alcohol (a) (hereinafter simply referred to as halogenated fatty acid ester) with tertiary amine to obtain betaine ester (A) In the step, the halogenated fatty acid ester is preferably 1 to 10 equivalents, more preferably 1 to 3 equivalents, more preferably 1.
0-1.2 equivalents are particularly preferred.

The tertiary amine and the halogenated fatty acid ester may be added simultaneously, or the tertiary amine may be dropped into the halogenated fatty acid ester. When adding a solvent,
In the case of simultaneous addition, when the tertiary amine is dropped simultaneously, the tertiary amine may be mixed with the tertiary amine, or may be mixed with both the halogenated fatty acid ester and the tertiary amine. When the tertiary amine is a low boiling amine, it may be introduced as a gas into the halogenated fatty acid ester in the reaction vessel, or may be liquefied and cooled and introduced into the pressure-resistant closed reaction vessel at the same time as the halogenated fatty acid ester. Alternatively, it may be dissolved in a solvent and introduced into the reaction tank as a solution.

The reaction temperature is preferably from 0 to 150 ° C.,
-100 ° C is more preferable in terms of suppressing a side reaction, and particularly preferably 40-80 ° C. If the viscosity rises below 80 ° C. and hinders operations such as stirring and transfer, it is preferable to dilute with a solvent described below.

In the present invention, the above betaine ester (A)
It is preferable to add a solvent selected from alcohols, ethers or esters having no hydroxyl group, and hydrocarbons from the reaction step for obtaining the unreacted halogenated fatty acid esters under reduced pressure distillation described below. At this time, the amount of the solvent to be added is preferably 10 to 1000% by weight, more preferably 20 to 100% by weight, based on the whole charged amount.

The alcohol used as the solvent is preferably methanol, ethanol, allyl alcohol, 1-propanol and 2-propanol or a mixed alcohol thereof, and more preferably the same alcohol as the alcohol (a) constituting the halogenated fatty acid ester.

In the ether used as a solvent,
Dimethyl ether, diethyl ether and tert-butyl methyl ether are esters; methyl acetate and ethyl acetate are esters; and hydrocarbons are pentane, hexane, heptane, petroleum ether, cyclohexane, toluene and limonene. It is preferable from the viewpoint of properties.

After completion of the reaction, unreacted halogenated fatty acid esters are removed by a method such as distillation under reduced pressure. For distillation under reduced pressure, it is preferable to use a distillation column or a thin-film distillation apparatus attached to the reaction tank. The pressure in the tank is preferably 3.99 to 0.00133 kPa, and 1.
33-0.133 kPa is more preferable. The tank temperature is 20-100
C is preferable, 20-80 C is more preferable, and 40-8
0 ° C. is particularly preferred in terms of suppressing side reactions.

In order to suppress a rise in viscosity due to the progress of distillation under reduced pressure, a new solvent can be added. The solvent to be added is not particularly limited as long as it has a higher boiling point than the halogenated fatty acid ester to be distilled off, but those capable of maintaining a viscosity of less than 0.5 Pas at a temperature of 20 to 80 ° C. under reduced pressure conditions. It is more preferable to select from ether, hydrocarbon and alcohol (b) described below.

Examples of preferred ethers include dipropyl ether, dibutyl ether, dipentyl ether,
Dihexyl ether, diheptyl ether, dioctyl ether, ethylene glycol dialkyl ether, diethylene glycol dialkyl ether, propylene glycol dialkyl ether, trialkyl glyceryl ether, polyoxyethylene dimethyl ether, polyoxyethylene diethyl ether, polyoxyethylene dibutyl ether, polyoxypropylene dialkyl Ether, polyoxyethylene-polyoxypropylene copolymer alcohol dialkyl ether, polyoxybutylene dialkyl ether, and the like.

Examples of preferred hydrocarbons are octane,
Nonane, decane, dodecane, liquid paraffin, methylcyclohexane, toluene, xylene, limonene and the like can be mentioned.

[Halogenated fatty acid ester] The halogenated fatty acid ester of the present invention has the general formula (I)

[0017]

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(Wherein X is a chlorine atom or a bromine atom, A is a linear or branched alkylene group having 1 to 3 carbon atoms, and R is an alkyl or alkenyl group having 1 to 4 carbon atoms.) Are preferred. Specifically, methyl chloroacetate, ethyl chloroacetate, propyl chloroacetate, butyl chloroacetate, ethyl bromoacetate, methyl bromoacetate, methyl 2-chloropropionate, ethyl 2-chloropropionate, propyl 2-chloropropionate, Butyl 2-chloropropionate, methyl 2-bromopropionate, ethyl 2-bromopropionate, 2-
Propyl bromopropionate, butyl 2-bromopropionate, and the like are preferable, and ethyl chloroacetate, methyl chloroacetate, and methyl 2-chloropropionate are more preferable. Ethyl chloroacetate is particularly preferable because it can be easily distilled under reduced pressure.

[Tertiary amine] The tertiary amine of the present invention preferably has at least one tertiary amino group, and at least one of the substituents on the nitrogen atom of the tertiary amino group is a methyl group. Or an ethyl group, and primary or secondary
Those having no primary amino group are more preferred. These three
Among the secondary amines, the general formula (II), (III) or (IV)

[0020]

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Wherein R ¹ represents a monovalent saturated or unsaturated aliphatic hydrocarbon group having 1 to 30 carbon atoms, an aromatic hydrocarbon group or an alicyclic hydrocarbon group, and R ² and R ³ represent Each represents a methyl group or an ethyl group, and R ⁴ CO— has 1 to 3 carbon atoms.
An acyl group of 0, R ⁵ represents an alkylene group having 1 to 3 carbon atoms, and R ⁶ and R ⁷ represent a methyl group or an ethyl group, respectively. . In particular, tertiary amines represented by the following formulas, in particular, dimethylalkylamine (C1 to C30 of alkyl group), alkanoylaminopropyldimethylamine (C2 to C30 of alkanoyl group), N, N, N ', N'- Tetraalkyl-1,3-diaminopropane (alkyl group having 1 to 2 carbon atoms) is preferred.

Specific examples of these preferred tertiary amines include trimethylamine, ethyldimethylamine, propyldimethylamine, butyldimethylamine, hexyldimethylamine, octyldimethylamine, decyldimethylamine, dodecyldimethylamine, tetradecyldimethylamine, Hexadecyldimethylamine, octadecyldimethylamine, eicosanyldimethylamine, docosanyldimethylamine, acetylaminopropyldimethylamine, propanoylaminopropyldimethylamine, butanoylaminopropyldimethylamine, hexanoylaminopropyldimethylamine, octanoylamino Propyldimethylamine, decanoylaminopropyldimethylamine, dodecanoylaminopropyldimethylamine, tetra Kano yl aminopropyl dimethyl amine, hexadecanoylamino-dimethylamine, octadecanoylamino dimethylamine,
Eicosanoylaminopropyldimethylamine, docosanoylaminopropyldimethylamine, N, N, N ', N'-tetramethyl-1,3-diaminopropane and the like.

[Transesterification Step] The amount of the alcohol (b) charged in the transesterification reaction between the betaine ester (A) and the alcohol (b) is preferably 1 to 10 equivalents to the betaine ester (A). 22 equivalents is more preferable in that unreacted substances can be reduced. When the alcohol (b) remains as a solvent in the previous step, it is preferable that the total is within the above range.

In the transesterification reaction, the temperature in the tank is:
15 to 120 ° C is preferable, and more preferably 30 to 80 ° C.
° C, and particularly preferably from 40 to 60 ° C, because alcohol (a) generated after the reaction can be easily distilled off. The pressure in the tank depends on the boiling points of the alcohols (a) and (b) to be produced, but is preferably from 0.00133 to 13.3 kPa, more preferably from 0.133 to 5.33 kPa.

In the transesterification reaction, if necessary, a solvent which is generally stable to alkali, such as ether or hydrocarbon, can be used. For example, a solvent that can be used when the above-mentioned halogenated fatty acid ester is distilled off under reduced pressure is exemplified.

In the transesterification, a basic catalyst is used as a catalyst. As the basic catalyst, a metal alkoxide or the like having excellent compatibility with a reactant is preferable. Is more preferable.
As the alkali metal alkoxide, sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, potassium tert-butoxide and the like are preferable, and sodium methoxide and sodium or potassium alkoxide of alcohol (b) are preferable.

The amount of the basic catalyst to be added at the time of transesterification is preferably 0.1 to 20 times, more preferably 1 to 10 times, and more preferably 5 to 10 times the mol of the betaine ester (A).
10 moles are preferred. The method of adding the basic catalyst is preferably a method in which the basic catalyst is added dropwise under reduced pressure and stirring.

The transesterification is usually completed within 1 to 5 hours after the addition of the basic catalyst. The obtained betaine ester (B) may be subjected to purification such as solvent distillation or crystallization depending on the use, but the reaction-terminated product may be used as it is.

[Alcohol (b)] The alcohol (b) used in the present invention has 2 carbon atoms excluding the alcohol (a).
Alcohol having at least 5 carbon atoms, especially 5 to 15 carbon atoms.
Aliphatic monohydric alcohols having 2 or more carbon atoms, especially 2 to 15
Aliphatic polyhydric alcohols having 2 or more carbon atoms, especially 2-28
Preferred are fluorinated alcohols having 5 or more carbon atoms, especially alicyclic alcohols having 5 to 15 carbon atoms, aromatic alcohols having 6 or more carbon atoms, particularly 6 to 20 carbon atoms, and heterocyclic alcohols having 5 or more carbon atoms, particularly 5 to 9 carbon atoms. . Further, it is preferable that the alcohol (b) has a function that can be imparted to various toiletry products when it is released alone. In particular, the aromatic alcohol (1), which is a compounded fragrance component, has antibacterial and antifungal properties. Antimicrobial alcohol (2), moisturizing alcohol (3) having moisturizing properties, bioactive alcohol having bioactivity and coloring alcohol having coloring property (4), surface modifying properties having general surface activity Alcohol (5) is preferred,
Fragrant alcohol (1), antimicrobial alcohol (2)
Is more preferred.

(1) Aroma alcohols are alcohols and the like used for fragrances described in Synthetic fragrances (Chemical Industry Daily), and include the following.

A saturated or unsaturated straight-chain or branched-chain alcohol having 5 to 15 carbon atoms, green leaf alcohol (cis-3-hexenol), 3-octenol, 9-decenol, geraniol, nerol, citronellol, rosinol, farnesol, hydroxy Citronellol and the like.

An aromatic alcohol having 6 to 12 carbon atoms, benzyl alcohol, β-phenylethyl alcohol,
Cinnamic alcohol, γ-phenylpropyl alcohol, anis alcohol, phenoxyethyl alcohol, styryl alcohol, 3-methyl-5-phenylpentanol, 2,2-dimethyl-3- (3-methylphenyl) -propanol and the like.

A saturated or unsaturated cyclic alcohol having 8 to 15 carbon atoms 2,4-dimethyl-3-cyclohexene-1-methanol, 4-isopropylcyclohexylmethanol, 1- (4-isopropylcyclohexyl) ethanol, p- tert-butylcyclohexanol, o-tert-butylcyclohexanol, L-
Menthol, 1- (2-t-butylcyclohexyloxy) -2
-Butanol, pentamethylcyclohexylpropanol, 1- (2,2,6-trimethylcyclohexyl) -3-hexanol, Santalol, vetiverol and the like.

(2) The antimicrobial alcohol is an alcohol or the like used for antibacterial and fungicide described in the Japanese Antibacterial and Fungicide Dictionary (published by the Japan Society of Antifungal and Fungicide), and includes the following.

A fatty acid polyhydric alcohol having 3 to 15 carbon atoms such as glycerol monolaurate, tri (hydroxymethyl) nitromethane, and 2-bromo-2-nitropropane-1,3-diol;

C7-9 heterocyclic alcohols 1,3-bis (hydroxymethyl) -5,5'-dimethylhydantoin, hexahydro-1,3,5-tris (hydroxyethyl) -S-triazine, etc. .

(3) The moisturizing alcohol is an alcohol generally having a moisturizing effect, and examples thereof include the following.

An aliphatic polyhydric alcohol having 2 to 6 carbon atoms, such as glycerin, propylene glycol, ethylene glycol, pentaerythritol, and glucose;

(4) The physiologically active alcohol and the coloring alcohol are vitamins having a hydroxyl group, adrenocorticotropic hormone, pheromone, carotenoid and the like, and the following are preferable.

An unsaturated linear or cyclic monohydric or polyhydric alcohol having 16 to 40 carbon atoms, vitamin A ₁ , vitamin A ₂ , riboflavin, L-ascorbic acid, vitamin D ₂ , vitamin D ₃ , and vitamin D ₄ , Corticosterone, dehydrocorticosterone, deoxycorticosterone, bombicol, violaxanthin,
Cryptoxanthin, zeaxanthin, lutein, rubixanthin and the like.

C20 aromatic alcohols such as quinine and quinidine.

(5) Examples of the surface-modifying alcohol include the following.

A polyalkylene alkyl ether represented by the formula (V) R ¹¹ -O- (R ¹² O) _p -H (V) (wherein R ¹¹ has 1 to 24 carbon atoms, preferably 1 to 24 carbon atoms) 18
R ¹² is an alkyl or alkenyl group of 2 to 3 carbon atoms
Represents a linear or branched alkylene group, and p represents a number of 1 to 20, preferably 1 to 10. ) Specifically, ethylene glycol monoalkyl ether, diethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, polyoxyethylene monomethyl ether, polyoxyethylene monoethyl ether, polyoxyethylene monooleyl ether, polyoxypropylene monoalkyl ether, Polyoxyethylene-polyoxypropylene copolymer alcohol monoalkyl ether, polyoxybutylene monoalkyl ether and the like.

Glyceryl ether represented by the formula (VI) R ¹³ -O-CH ₂ -CH (OR ¹⁴ ) -CH ₂ -OR ¹⁵ (VI) wherein R ¹³ , R ¹⁴ and R ¹⁵ Are the same or different and are each a hydrogen atom or a group represented by the formula (VII) R ¹¹ -O- (R ¹² O) _q- (VII) (R ¹¹ and R ¹² have the same meanings as described above;
Indicates the number of ) Represents a group represented by R ¹³ , R ¹⁴ , R ¹⁵
At least one is a hydrogen atom, and not all of them are hydrogen atoms at the same time. Specific examples include monoalkyl glyceryl ether, dialkyl glyceryl ether, and methyltriethylene glyceryl ether. Alkyl glycosides having an alkyl chain of 1 to 18 carbon atoms. Specifically, α-methyl glycoside, β-dodecyl glycoside, and the like.

A fluorine-containing alcohol represented by the formula (VIII) R ^f- (CH ₂ ) _n -OH (VIII) (wherein R ^f is a linear or branched alkyl group having 1 to 20 carbon atoms) A fluoroalkyl group in which at least one of the hydrogen atoms is substituted by a fluorine atom, and n represents an integer of 1 to 8.) Specific examples include 2,2,3,3,3-pentafluoropropanol and 2- (perfluoro Octyl) ethanol, 2- (perfluorodecyl) ethanol, 6- (perfluoroethyl) hexanol, 6- (perfluorobutyl) hexanol, 6- (perfluorohexyl) hexanol, 6-
(Perfluorooctyl) hexanol, 6- (perfluoroisopropyl) hexanol, 4,4,4-trifluorobutanol, 2,2,3,4,4,4-hexafluorobutanol,
2,2,3,3-tetrafluoropropanol, 1H, 1H, 5H-octafluoropentanol, 1H, 1H, 7H-dodecafluoroheptanol, 1H, 1H, 9H-hexadecafluorononanol, 2- (per Fluoro-3-methylbutyl) ethanol, 2
-(Perfluoro-5-methylhexyl) ethanol, 2-
(Perfluoro-7-methyloctyl) ethanol, 2-
(Perfluoro-9-methyldodecyl) ethanol, 6-
(Perfluoro-1-methylethyl) hexanol, 2-
(Perfluoro-3-methylbutyl) hexanol, 6-
(Perfluoro-5-methylhexyl) hexanol, 6-
(Perfluoro-7-methyloctyl) hexanol, 4,
4,4-trifluoro-2-buten-1-ol, 1H, 1H, 2H, 2H, 3
H, 3H-perfluorononanol and the like.

[0046]

EXAMPLES In the examples, parts and percentages are by weight unless otherwise specified.

Example 1: Production of N, N-dimethyl-N-geranyloxycarbonylmethyl-N- (3- (octadecanoylamino) propyl) ammonium chloride 3.69 kg (10 mol) of decanoyl-1,3-diaminopropane and 2 L of 99.5% ethanol (2.5
kg), heat and dissolve in a dry nitrogen atmosphere, keep warm and stir at 45 ° C, and add 1.35 kg of ethyl chloroacetate to this.
(11 mol) at a dropping rate of 60 mL / min, and the temperature in the tank is 45 ± 3 ° C.
For 10 hours. ¹ H-NMR spectrum of the reaction mixture (F
T, 200 MHz), and confirm that the absorption peak derived from the raw material amine has disappeared.
The remaining ethyl chloroacetate and ethanol were distilled off under reduced pressure while blowing at 0.2 m ³ / h. 2.3L of distillate in fraction receiver
At the time of accumulation, when dry nitrogen was introduced into the tank and the pressure was adjusted to normal pressure, and the viscosity of the reaction mixture in the tank was measured, it was 485 mPas.
A tendency to increase the viscosity was observed, and the residual amount of ethyl chloroacetate in the reaction product was measured by gas chromatography to be 1.6%. Geraniol 3.1k at this point
g (20 mol) was charged and stirred at 45 ° C. for 10 minutes. After confirming that the viscosity of the reaction product was 250 mPa · s, the contents in the tank were transferred to a thin-film distillation apparatus (Smith type). The wall temperature of the still was set at 49 ° C. and the pressure was set at 0.133 kPa, and the distillation was performed under reduced pressure for further 8 hours. The residual amount of ethyl chloroacetate in the mixture of the intermediate betaine ester and geraniol remaining in the still was measured by gas chromatography and found to be less than the lower detection limit (15 mg / kg). The obtained pale yellow oily mixture was transferred to a reaction tank, the temperature in the tank was 43 ± 2 ° C., and the pressure in the tank was 1.33 to
At 2.67 kPa, 408 mL of a 28% sodium methoxide methanol solution was added 5 times at 40-minute intervals for a total of 5 transesterification reactions. The total amount of sodium methoxide added to the reaction product was 54 g (1 mol). The ¹ H-NMR spectrum was measured 40 minutes after the addition of the fifth sodium methoxide.When the ¹ H-NMR spectrum was measured, the absorption peak derived from the ethyl ester disappeared, and N, N-dimethyl-N-chloride containing 18% of geraniol was contained. Geranyloxycarbonylmethyl-N- (3- (octadecanoylamino) propyl) ammonium has a viscosity of 21 at 40 ° C.
0mPa · s light brown liquid (light brown wax at 25 ° C)
7.31 kg (10 mol; 100% yield) was obtained. The amounts of ethyl chloroacetate and geranyl chloroacetate contained therein were less than 10 mg / kg by GC and GC / MASS quantification.

Example 2 1,3-bis (N, N-dimethyl chloride)
Production of N-geranyloxycarbonylmethylammonium) propane N, N, N ', N'-tetramethyl-1,3-diaminopropane 2.6kg (20mol) and 99.5% ethanol 5L (4kg) are charged into a reaction tank and dried. Heat and dissolve in a nitrogen atmosphere, keep warm and stir at 45 ° C, and add 2.69 kg (22 mol) of ethyl chloroacetate to the mixture at a dropping rate of 6
The mixture was charged at 0 L / min and stirred at a tank temperature of 45 ± 3 ° C. for 5 hours.
Measure the ¹ H-NMR spectrum (FT, 200 MHz) of the reaction mixture,
After confirming that the absorption peak derived from the starting amine had disappeared, the pressure in the tank was reduced, and the remaining ethyl chloroacetate and ethanol were distilled off under reduced pressure while blowing dry nitrogen at 0.2 m ³ / h. When the distillate was collected up to 5 L in the fraction receiver, dry nitrogen was introduced into the tank and the pressure of the reaction mixture in the tank was measured at normal pressure, and the viscosity was 630 mPas. Was found, and the residual amount of ethyl chloroacetate in the reaction product was measured by gas chromatography to be 2.8%. At this point 7.7 kg (50 mol) of geraniol was charged,
After stirring at 45 ° C for 10 minutes and confirming that the viscosity of the reaction product is 490 mPa · s, the contents in the tank are thin-film distillation apparatus (Smith type)
Transferred to. The wall temperature of the still was set to 49 ° C., the pressure was set to 0.133 kPa, and the distillation under reduced pressure was performed for another 10 hours. The residual amount of ethyl chloroacetate in the mixture of the intermediate betaine ester and geraniol remaining in the still was measured by gas chromatography and found to be less than the lower detection limit (15 mg / kg). The obtained pale yellow oily mixture was transferred to a reaction vessel, and after stabilizing at a vessel temperature of 43 ± 2 ° C. and a vessel pressure of 1.33 to 2.66 kPa, 81.6 mL of a 28% sodium methoxide methanol solution was added.
Each of them was added 5 times at intervals of 40 minutes to carry out a transesterification reaction. The total amount of the active component of sodium methoxide added to the reaction product was 108 g (2 mol). 40 minutes after the addition of the fifth sodium methoxide, ¹ H-NMR spectrum was measured. The absorption peak derived from the ethyl ester disappeared, and 1,3-bis (germanol) containing 11.5% of geraniol (N, N
-Dimethyl-N-geranyloxycarbonylmethylammonium) propane at 40 ° C has a viscosity of 490 mPa · s.
13.4 kg (20 mol;
Yield 100%). The amount of ethyl chloroacetate and geranyl chloroacetate contained in this was determined by GC / MASS quantification.
Both were less than 10 mg / kg.

Example 3: Production of N, N-dimethyl-N-menthyloxycarbonylmethyl-N- (3- (octadecanoylamino) propyl) ammonium chloride 3.69 kg (10 mol) of decanoyl-1,3-diaminopropane and 2 L of 99.5% ethanol (2.5
kg), heat and dissolve in a dry nitrogen atmosphere, keep warm and stir at 45 ° C, and add 1.35 kg of ethyl chloroacetate to this.
(11 mol) at a dropping rate of 60 mL / min, and the temperature in the tank is 45 ± 3 ° C.
For 10 hours. ¹ H-NMR spectrum of the reaction mixture (F
T, 200 MHz), and confirm that the absorption peak derived from the raw material amine has disappeared.
The remaining ethyl chloroacetate and ethanol were distilled off under reduced pressure while blowing at 0.2 m ³ / h. 2.3L of distillate in fraction receiver
At the time of accumulation, when dry nitrogen was introduced into the tank and the pressure was adjusted to normal pressure, and the viscosity of the reaction mixture in the tank was measured, the result was 500 mPas
The tendency to increase the viscosity was observed, and the residual amount of ethyl chloroacetate in the reaction product was measured by gas chromatography to be 1.5%. Menthol 3.14k at this point
g (20 mol) was charged and stirred at 45 ° C. for 10 minutes. After confirming that the viscosity of the reaction product was 250 mPa · s, the contents in the tank were transferred to a thin-film distillation apparatus (Smith type). The wall temperature of the still was set at 49 ° C. and the pressure was set at 0.133 kPa, and the distillation was performed under reduced pressure for further 8 hours. The residual amount of ethyl chloroacetate in the mixture of the intermediate betaine ester and menthol remaining in the still was measured by gas chromatography and found to be less than the lower detection limit (15 mg / kg). The obtained pale yellow oily mixture was transferred to a reaction vessel, 10 L of limonene was added to the reaction vessel, and at a vessel temperature of 70 ± 2 ° C. and a vessel pressure of 1.33 to 2.67 kPa, 81.6 mL of a 28% sodium methoxide methanol solution was added. A total of 5 additions were made at 40-minute intervals to carry out a transesterification reaction. The total amount of the effective amount of sodium methoxide added to the reaction product is 108 g (2 mol
l). Add 5th sodium methoxide and add 4
When the ¹ H-NMR spectrum was measured 0 minutes later, the absorption peak derived from the ethyl ester disappeared. 50 ° C ± 2 in the tank
At 100 ° C., 100 L of acetone was added, and the mixture was stirred at 50 ° C. ± 2 ° C. for 1 hour to form a homogeneous solution. The reaction solution was cooled to room temperature and crystallized to remove most of menthol and limonene. The crystals were dried under reduced pressure, and N, N-dimethyl-N-menthyloxycarbonylmethyl-N- (3- (octadecanoylamino) propyl) ammonium chloride containing 18% of menthol was converted into yellow crystals to give 4.15 kg (7.5 mol ; Yield 75%). The amounts of ethyl chloroacetate and menthyl chloroacetate contained therein were less than 10 mg / kg by GC and GC / MASS quantification.

Example 4 Production of N, N, N-trimethyl-N-geranyloxycarbonylmethylammonium chloride 400 g of 99.5% ethanol and ethyl chloroacetate 42 were placed in a reaction vessel.
g (0.34 mol) was charged and cooled to 0 ° C. 90 g (1.52 mol) of trimethylamine was introduced from a bomb and 0 ° C.
For 10 hours. The reaction mixture was heated to 45 ° C. and
The remaining trimethylamine, ethyl chloroacetate, and ethanol were removed under reduced pressure of 33 kPa under reduced pressure. 79 g (0.5 mol) of geraniol was charged and stirred at 45 ° C. for 10 minutes. After confirming that the viscosity of the reaction product was 250 mPa · s, the contents in the tank were transferred to a thin-film distillation apparatus (Smith type). The wall temperature of the still was set at 49 ° C. and the pressure was set at 0.133 kPa, and the distillation was performed under reduced pressure for further 8 hours. The residual amount of ethyl chloroacetate in the mixture of the intermediate betaine ester and geraniol remaining in the still was measured by gas chromatography and found to be less than the lower detection limit (15 mg / kg). The obtained pale yellow oily mixture was transferred to a reaction vessel, and at a vessel temperature of 43 ± 2 ° C. and a vessel pressure of 1.33 to 2.67 kPa, 13 g (0.07 mol) of a 28% sodium methoxide methanol solution was added at 40 minute intervals. A total of 5 additions were performed to perform a transesterification reaction. The total amount of the active component of sodium methoxide added to the reaction product was 18.4 g (0.
34 mol). 40 minutes after the addition of the fifth sodium methoxide, ¹ H-NMR spectrum was measured.The absorption peak derived from the ethyl ester disappeared, and N, N, N-trimethyl chloride containing about 18% of geraniol was found. -N-geranyloxycarbonylmethylammonium viscosity at 40 ℃
127 g (0.34 mol; 100% yield) was obtained as a light brown liquid (light brown wax at 25 ° C.) of 210 mPa · s. The amounts of ethyl chloroacetate and geranyl chloroacetate contained in this product were both 1 by GC and GC / MASS quantification.
It was less than 0 mg / kg.

Example 5 N, N-dimethyl-N-dodecyl chloride
Production of -N-geranyloxycarbonylmethylammonium The same procedure as in Example 4 was carried out except that 66 g (0.31 mol) of dodecyldimethylamine was used instead of 90 g (1.52 mol) of trimethylamine to carry out the reaction at 45 ° C. N, N-dimethyl-N-dodecyl-N- chloride containing about 12% geraniol
Geranyloxycarbonylmethylammonium as a light brown wax-like substance, 162 g (0.31 mol; yield 100%)
Obtained. The amounts of ethyl chloroacetate and geranyl chloroacetate contained therein were less than 10 mg / kg by GC and GC / MASS quantification.

[0052]

According to the present invention, betaine esters such as high molecular weight alcohols, polyhydric alcohols and alcohols which are liable to cause side reactions such as dehydration and rearrangement, which have been difficult to produce industrially, can be produced at high quality and at low cost. And can be manufactured efficiently.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // C07B 61/00 300 C07B 61/00 300 (72) Inventor Sakuya Tanaka 1334 Minato 1334 Minato, Wakayama-shi, Wakayama Kao 4H006 AA02 AC48 AC52 BA69 BJ20 BT12 BU32 BU50 BV22 4H039 CA66 CD10 CD40 CE10

Claims (2)

[Claims] An unreacted halogenated fatty acid ester obtained by reacting a tertiary amine with a halogenated fatty acid ester of a saturated or unsaturated monohydric alcohol having 1 to 4 carbon atoms (hereinafter referred to as alcohol (a)). To obtain a betaine ester of an alcohol (a) (hereinafter referred to as a betaine ester (A)), and an alcohol having 2 or more carbon atoms excluding the betaine ester (A) and the alcohol (a) (hereinafter an alcohol (b) ) In the presence of a basic catalyst to obtain a betaine ester of the alcohol (b). 2. The halogenated fatty acid ester of the alcohol (a) is a compound represented by the general formula (I).
A method for producing the betaine ester described in the above. Embedded image (In the formula, X is a chlorine atom or a bromine atom, A is a linear or branched alkylene group having 1 to 3 carbon atoms, and R is an alkyl group or an alkenyl group having 1 to 4 carbon atoms.)