JPS58157750A - Production of betain ester salt - Google Patents

Abstract

PURPOSE:The reaction of a halocarboxylic ester with trimethylamine is conducted in the presence of a dialkyl ketone to produce the titled compound through simple process operations in high yield, additionally with easy isolation of the product. CONSTITUTION:The reaction between a halocarboxylic ester of formulaI (R is 8-22C alkyl, alkenyl; R' is 2-4C alkylene; R'' is 1-3C alkylene; n is 0- about 10 where, when n is 2 or more, R' may be identical or different; X is halogen) and trimethylamine is carried out in the presence of a dialkyl ketone at 40-70 deg.C to give the objective compound of formula II. The amount of trimethylamine is 1.0-1.3mol per mole of the halocarboxylic ester and that of the dialkyl ketone is the same or more amount than the ester. beta-Chloropropionic acid or chloroacetic acid is cited as a halocarboxylic acid.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a betaine ester salt, and more particularly to a method for producing a betaine ester salt from a halocarginic acid ester and trimethylamine.

The ester reaction product of glycine betaine and an alcohol with a hydrophobic group has excellent performance as a quaternary ammonium salt type cationic surfactant, and is also expected to have many uses as it has low mobility and antibacterial activity. ing.

Recently, as a method for producing betaine ester salts using inexpensive raw materials, a method has been reported in which betaines and alcohols are reacted using a sulfonic acid catalyst (Japanese Unexamined Patent Publication No. 76818/1983). However, this method uses a stoichiometrically equivalent mole or more of an acid catalyst with respect to betaines, and it is necessary to react the betaines and the acid catalyst in advance, which has the disadvantage that the reaction time is long. However, since the product is a sulfonic acid salt, it has the disadvantage of being limited in terms of use.

The object of the present invention is to eliminate the drawbacks of the above-mentioned conventional methods and to provide a method for producing betaine ester salts with a high yield through simple reaction operations and in which the product can be easily separated.

That is, the present invention is based on the general formula (It) RO(R'0)nCOR''PP(CH3)3.P
(In the formula, R is carbon #J, an alkyl group or alkenyl group having 8 to 22 carbon atoms, R' is an alkylene group having 2 to 4 carbon atoms, and R'' is an alkylene group having 1 to 3 carbon atoms. group, n is a number from 1 to about 10, and when n is 2 or more, R' may be the same or different; , a halocarboxylic acid nistert represented by the general formula (1) % formula % () (in the formula, R, R', R", n and X are the same as in the general formula I) and trimethylamine in the presence of a dialkyl ketone. It is characterized by reacting to

The halocarmine ester represented by the general formula (1) is
It is selected from higher alcohols and alkylene oxide adducts of higher alcohols, and is easily produced by Nisdell reaction between alcohols and monohalogenated carboxylic acids.

Examples of alcohols include aliphatic alcohols having 8 to 22 carbon atoms and alkylene oxides having 2 to 4 carbon atoms;
Examples of suitable aliphatic alcohols include saturated higher alcohols such as octyl alcohol, lauryl alcohol, tsukurumithyl alcohol, myristyl alcohol, and stylyl alcohol, and oleyl alcohol. Examples include unsaturated higher alcohols. Furthermore, alkylene oxides include ethylene oxide, propylene oxide, and butylene oxide.

Examples of higher alcohol alkylene oxide adducts include polyoxyethylene ether, polyoxypropylene ether, and poly(oxyethylene-oxypropylene) ether of higher alcohols.

Specific examples of halocarboxylic acids include monochloroacetic acid, monobromoacetic acid, β-chlorozolopionic acid, β-bromopropionic acid, α-chlorozolopionic acid, α-bromopropionic acid, r-chlorobutyric acid, and γ-bromobutyric acid. etc. can be exemplified. Among these, monochloroacetic acid and β
-chloropropionic acid.

It is appropriate to use trimethylamine in an amount of about 1.0 to 1.3 mol per 1 mol of the halocarboxylic acid ester.

It is preferable to use a small amount in excess, considering the low nodal point of trimethylamine.

As the dialkyl ketone, a dialkyl ketone having 3 to 9 carbon atoms is suitable. Specific examples of dialkyl ketones include acetone, methyl ethyl ketone, diethyl ketone, methyl isodityl ketone, and diisobutyl ketone. 1” can be shown.

The amount of dialkyl ketone to be used is preferably at least the same amount as the amount of halocarline phosphate. If the amount of solvent is small, it will become a gel state during the reaction,
Unable to react smoothly.

To produce betaine Nisder salt according to the present method,
For example, trimethylamine may be added in a liquid state under pressure to a 7" dialkyl ketone solution of halocarboxylic acid varnish, and the reaction may be carried out at a reaction temperature of 40 to 70°C.
Trimethylamine can also be added gradually over time.

When the reaction is complete, cool to room temperature and separate the precipitated crystals.

! If necessary, the solution may be forcibly cooled until crystals are sufficiently precipitated.

As is clear from the above description and the examples below, according to the invention, betaine ester salts can be produced in high yield through simple operations, and the product can be easily separated.

Example 1 Lauryl alcohol monochloroacetic acid ester/L/65.677 (025 mol) and 75 J of acetone were placed in a 500° C. glass autoclave, and the temperature was raised to 50° C. while stirring. Then, 17.7 lI (0.3 (1 mol)) of trimenalamine was added to the surface over 20 minutes, and the mixture was reacted for 3 hours while maintaining the temperature at 50°C.

After cooling at room temperature, the resulting precipitate was suctioned under reduced pressure for one time, and then dried on a 3IIl-nitrogen dry bed at 40°C to obtain 76.4I (yield: 95%) as a white powder. The elemental analysis values for this material are shown (as Ct1HsaNO2Cl).

Analysis value Calculated value C: 63.61chi 63.459bH: 11.
15chi 11. Article 20N: 4.32chi 4.35chi Also, when the infrared absorption spectrum was determined for the city 1j, 1
Absorption based on ester was observed at 735 cm.

Furthermore, N-NMR of the quaternary ammonium salt was found to be 3.68 ppM by H'-NMR using summer chloroform solvent.
Absorption based on methyl and +C at 1.26 ppM
H. Absorption based on methylene was observed.

From the above, the substance obtained as a white powder in this example was glycine betaine lauryl varnish.

Confirmed to be chill salt.

For comparison, the experiment was repeated by changing the N of acetate from 75J9 to 6O, @VC, and the reaction solution started to gel after about 30 minutes of reaction after the completion of the addition of trimethylamine. One reaction had to be stopped halfway because stirring became impossible.

Example 2 The same procedure as in Example 1 was performed except that methyl isodityl ketone was used instead of acetone, and the result was 74.8. Glycine betaine lauryl ester salt fr of li+ (yield 4=93%) was obtained.

Example 3 In Example 1, instead of lauryl alcohol monochrome co-acetate ester, monochlorophric acid polyoxyethylene lauryl alcohol ether (average number of added moles of ethylene oxide 3.0) ester 98.6, P (0,2
When the same operation was performed except that 5 mol) was used, the result was 102.0. Glycine/betaine ester salt of F (yield 4=90%) 8- 9-

Claims (1)

[Claims] 1. General formula (1) % formula % () (wherein R is an alkyl group or alkenyl group having 8 to 22 carbon atoms, and R' is an alkylene group having 2 to 4 carbon atoms. First, Bi is an alkylene group having 1 to 3 carbon atoms, n is a number from 1 to about 1O, and when n is 2 or more, R' may be the same or different, and X is a halogen group. The general formula (Ro(*o)ncoy7(cn3)) characterized by reacting halocarginic acid nystertotrimethylamine represented by
, -Xe (Ill (wherein R, R', R', n and X are the same as in general formula I).