RU2536687C1 - Method of obtaining 3-(chloromethyl)-3-(alkoxymethyl)oxetanes - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to organic chemistry, namely to a method of obtaining 3-(chloromethyl)-3-(alkoxymethyl)oxetanes, consisting in the following: alkylation of 3,3-bis(chloromethyl)oxetane is carried out with aliphatic alcohols in the presence of catamine AB as a catalyst for 4 hours with the following component ratio, wt %: 3,3-bis(chloromethyl)oxetane 9.5; sodium hydroxide 2.4; catamine AB 0.15; dimethylsulphoxide 84; alcohol 3.95. Obtained compounds possess a number of valuable properties and can be widely applied as corrosion inhibitors, plasticisers, SAS, medicinal and biologically active preparations.

EFFECT: increased output of the target product with the improvement of its quality.

2 cl, 1 tbl, 1 ex

Description

The invention relates to organic chemistry, specifically to the production of 3- (chloromethyl) -3- (alkoxymethyl) oxetanes, which have a number of valuable properties and are widely used as corrosion inhibitors, plasticizers, surfactants, drugs and biologically active preparations.

A known method for producing 3- (chloromethyl) -3- (alkoxymethyl) oxetanes by alkylation of 3,3-bis (chloromethyl) oxetane with sodium alcoholates at a temperature of 120-180 ° C for 5 hours in the presence of a tetrabutylammonium iodide catalyst (I. Kireev, Kantor E.A., Valitov R.B., Rakhmankulov D.L. // ZhORKh. 1981.V.17. Issue 7. S.1536-1539).

The disadvantages of this method are the low yield of the target product, the use of an expensive catalyst and high temperature conditions of the process, as well as the low selectivity of the monoalkoxy derivative.

The technical problem, the solution of which is proposed in the present invention, is to develop a method for producing 3- (chloromethyl) -3- (alkoxymethyl) oxetanes, characterized by an increase in the yield of the target product.

This problem is solved in that the method for producing 3- (chloromethyl) -3- (alkoxymethyl) oxetanes by alkylation of 3,3-bis (chloromethyl) oxetane with aliphatic alcohols is carried out in the presence of sodium hydroxide, dimethyl sulfoxide and catamine AB as a catalyst for 4 hours.

The reaction of 3,3-bis (chloromethyl) oxetane with alcohol is carried out in the following ratio of components, wt.%: 3,3-bis (chloromethyl) oxetane 9.5; sodium hydroxide 2.4; Catamine AB 0.15; dimethyl sulfoxide 84; alcohol 3.95.

The method is as follows.

The 3,3-bis (chloromethyl) oxetane and catalyst (catamine AB) used in the reaction use directly prepared products.

The starting reagents must meet the following requirements:

-NaOH-GOST 4328-77;

MgSO ₄ GOST 4523-77;

- Ethanol - GOST 18300-87;

- Isopropanol - 9805-84;

- Butanol-5208-81;

- Catamine AB - TU 9392-003-48482528-99;

- Dimethyl sulfoxide - TU 6-09-3818-77.

Alcohol, solid sodium hydroxide, catamine AB and dimethyl sulfoxide are vigorously stirred under heating (65-70 ° C) until the alkali dissolves within 1 hour. To the resulting flask was added 3,3-bis (chloromethyl) oxetane. The molar ratio of 3,3-bis (chloromethyl) oxetane: NaOH: alcohol = 1: 1: 1. At the end of the reaction, the reaction mass is washed with distilled water and extracted with chloroform, the organic layer is dried over freshly calcined magnesium sulfate, filtered off, chloroform is distilled off at atmospheric pressure.

Example 1

In a four-necked round-bottom flask equipped with a mechanical stirrer, reflux condenser, thermometer and dropping funnel, 0.012 mol of ethanol, 0.012 mol of solid NaOH, 0.03 g of catamine AB, 15 ml of DMSO were charged. Intensively stirred with heating (65-70 ° C) until the alkali dissolves within 1 hour. Then, 0.012 mol of 3,3-bis (chloromethyl) oxetane was added. The reaction was carried out 3 hours before precipitation of NaCl. The mixture was washed with water and extracted with chloroform. The extract was dried over calcined magnesium sulfate. After distilling off the solvent, the reaction mixture was subjected to vacuum distillation.

The yield of 3- (chloromethyl) -3- (ethoxymethyl) oxetane is 92%.

The results of the syntheses are shown in table 1, the syntheses were carried out analogously to example 1. These examples do not exhaust the possibilities of the method in relation to aliphatic alcohols containing other alkyl radicals.

The proposed method allows to achieve an increase in the yield of 3- (chloromethyl) -3- (alkoxymethyl) oxetanes (90-95%), which will ensure widespread use of these compounds as corrosion inhibitors, plasticizers, surfactants, drugs and biologically active drugs.

Claims (2)

1. The method of producing 3- (chloromethyl) -3- (alkoxymethyl) oxetanes by alkylation of 3,3-bis (chloromethyl) oxetane with aliphatic alcohols is carried out in the presence of sodium hydroxide, dimethyl sulfoxide and catamine AB as a catalyst for 4 hours. 2. The method according to claim 1, characterized in that the reaction with 3,3-bis (chloromethyl) oxetane is carried out in the following ratio of components, wt.%: 3,3-bis (chloromethyl) oxetane 9.5; sodium hydroxide 2.4; Catamine AB 0.15; dimethyl sulfoxide 84; alcohol 3.95.