DE1275043B - Process for the preparation of 2-trichloromethyl-alkylene oxides - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

German class:

Number:
File number:
Registration date:
Display day:

C07d

AOIn

12 ο -5/05
451-9 / 28

P 12 75 043.5-42 (D 47591)

June 25, 1965

August 14, 1968

The representation of 2-trichloromethylpropylene oxide is known by reacting 1,1,1-trichloroacetone with diazomethane. However, according to this production method, 2-trichloromethyl-propylene oxide is obtained and the corresponding homologous alkylene oxides are relatively expensive compounds, which so far have not been Provided an incentive for technical use.

There has now been a process for the preparation of 2-trichloromethyl-alkylene oxides of the general formula

¹ N

Process for the production of
2-trichloromethyl alkylene oxides

CUC - C

CH-R,

wherein Ri is hydrogen, a Ci- to Q-Alkyk Cycloalkyl- and aryl radical and R2 can be hydrogen and a C1 to C3 alkyl radical, found which characterized in that the monochlorination products of the corresponding 1-trichloromethyl-alkanols (l), which carry the chlorine atom in / 3-position to the trichloromethyl group, with alkaline ones Means treated in a manner known per se.

Such a smooth splitting off of the neighboring position chlorine atom to the hydroxyl group to form an epoxy group was not to foresee. It is well known that the corresponding non-chlorinated products, such as the l-Trichloromethyl-l-methyl-ethanol- (l), with aqueous alkali with elimination of the three chlorine atoms easily converts from the trichloromethyl group into α-oxyisobutyric acid or methacrylic acid. It it was therefore to be expected that upon the action of aqueous alkali on, for example, 1-trichloromethyl-1-methyl-2-chloro-ethanol- (l) not only the chlorine atom in the 2-position, but also the trichloromethyl group attacked quickly. There is also the possibility of cleavage in chloroacetone and chloroform had to be taken into account with an intricate composition Mixture of reaction products to be expected.

In contrast, but it has surprisingly been found that the elimination of hydrogen chloride with formation proceeds so quickly an epoxy group, that at temperatures of about -10 45 to about 5O ⁰ C 'occurs no significant attack of the alkali on the trichloromethyl and that, accordingly, the 2-trichloromethyl alkylene oxides can be produced in almost quantitative yield. ·

At least equivalent amounts of one are expedient for splitting off the hydrogen chloride Applicant:

Dynamit Nobel Aktiengesellschaft,

5210 Troisdorf

Named as inventor:

Dipl.-Chem. Dr. Hermann Richtzenhain,

5000 Cologne-Sülz;

Dipl.-Chem. Paul Riegger, 5300 Bonn

alkaline agent used. Under alkaline agents within the meaning of the invention, for. B. aqueous Solutions or suspensions of alkali and alkaline earth hydroxides, of alkali salts weaker Acids such as B. alkali carbonates, bicarbonates or borates, and also organic bases, for example Trialkylamines, such as. B. triethylamine, but preferably aqueous and / or alcoholic alkaline solutions are used.

The implementation of the monochlorination products of l-Trichloromethyl-alkanolen- (l) can both be carried out in heterogeneous phase as well as in homogeneous phase. In the first case, the starting material or its solution in an inert, water-immiscible solvent with an aqueous solution or suspension of an alkaline agent, preferably an alkali hydroxide, with intensive mixing, e.g. B. by means of a so-called "vibromixer" od. Like., Implemented and after the reaction has ended, the 2-trichloromethyl-alkylene oxide or its solution in separated from the solvent used from the aqueous phase. In the second case, the implementation in the presence of a suitable solubilizer, such as. B. alcohol od. Like. Made.

The reaction products can be used as contact insecticides, for example 2-Trichloromethyl-propylene oxide has been shown to be suitable for killing grain weevils in grain. To the Complete killing of grain weevils in grain within 24 hours is according to the German Patent specification 653 088 an amount of 7 g of dichloroacetone dimethyl ketal per 100 kg of grain required. When using 2-trichloromethyl-propylene oxide, an amount of 3.4 g per 100 kg is sufficient Cereals to get the same effect.

IM 590/481

example 1

In a beaker, 190 g of 1-trichloromethyl-1-methyl-2-chloro-ethanol (1) (with a purity of 97%) were emulsified in 100 ml of water with the aid of a "vibromixer". To this emulsion were added N sodium hydroxide solution within 10 minutes 425 ml 2, wherein the temperature was maintained by cooling to about 2O ⁰ C. The consumption of NaOH can be checked by adding an indicator (such as phenolphthalein). The result was a dispersion of the water-insoluble reaction product, which was separated from the water after adding methylene chloride as an extractant. Instead of methylene chloride, ethers, hydrocarbons, chlorinated hydrocarbons, such as. B. dichloroethane, tri- and perchlorethylene, use. By vacuum distillation of the reaction product, 152 g of 2-trichloromethyl-propylene oxide (boiling point 40 = 80 ° C., melting point = 52 ° C.) were obtained with 97% purity, corresponding to a yield of 96% of theory.

Example 2

To a solution of 51 g of 1-trichloromethyl-1-methyl-2-chloro-ethanoHl) (boiling point 11 = 95 ° C.) in 200 ml of 50 percent by volume alcohol, 116 ml of a 2N alcoholic sodium hydroxide solution were prepared within 10 minutes with stirring added by dissolving 40 g of sodium hydroxide in 50 ml of water and filling up with ethanol to 500 ml) while the temperature was maintained at about 2O ⁰ C. When the reaction had ended, the alcohol was distilled off under reduced pressure and the reaction product was taken up in ether. The 2-trichloromethyl-propylene oxide was obtained in almost quantitative yield by vacuum distillation.

oxide corresponding glycol in addition to small amounts of starting material.

Example 5,

In a beaker, 100 g of 1-trichloromethyl-l-methyl-2-chloro-ethanol-were (l) emulsified with a solution of 60 g of triethylamine in 500 ml of water hours by means of a "Vibromischers" at about 1 20 ⁰ C. The product "separated off from the aqueous solution" contained 63 g of 2-trichloromethylpropylene oxide.

Example 6

l-trichloromethyl-l-phenyl-2-chloroethanol was as described in Example 1, to i-trichloromethyl-1-phenyl-ethylene oxide implemented. The yield was 96% of theory.

Example 7

l-trichloromethyl-l-t-butyl ^ -chloro-ethanol was, as described in Example 1, to 1-trichloromethyl-1-t-butyl-ethylene oxide implemented. The yield was 94% of theory.

Example 8

1 - trichloromethyl -1 - methyl - 2 - chloro - propanol - (1) became, as described in Example 1, to I-trichloromethyl -1 - methyl - propylene oxide - (1,2) implemented. The yield was 79% of theory.

Claims (4)

Patent claims: 1. Process for the preparation of 2-trichloromethylalkylene oxides the general formula CH Example 3 40 34 g (0.2 mol) of l-trichloromethyl-l-methyl-2-chloroethanol- (l) were mixed with the equivalent amount of calcium hydroxide (7.4 g) in 80 ml of water by mechanical emulsification at a temperature of about 20 ^° C implemented. Towards the end of the reaction, 10 ml of ether were added in order to prevent the precipitating solid particles from entraining the starting substance. The reaction was over after 15 minutes. The reaction product was taken up in ether, the ether phase was dried and then distilled. The yield of 2-trichloromethyl-propylene oxide was 99% of theory. Example 4 55 In a beaker, 100 g of 1-trichloromethyl-l-methyl-2-chloro-ethanol-were (l) emulsified with 500 ml of water and 42 g of sodium bicarbonate by means of a "Vibromischers" at a temperature of about 20 ⁰ C. After 24 hours the reaction product was separated off. It contained 64.8 g of 2-trichloromethyl-propylene oxide and the Epworin Ri hydrogen, a Ci- to d-alkyl, cycloalkyl and aryl radical as well as R2 hydrogen and a Ci- to C3-alkyl radical, characterized in that one the monochlorination products of the corresponding l-trichloromethyl-alkanols (I), which carry the chlorine atom in the / S-position to the trichloromethyl group, are treated with alkaline agents in a manner known per se. 2. The method according to claim 1, characterized in that one is used as the alkaline agent aqueous and / or alcoholic alkali used. 3. The method according to claim 1, characterized in that there is used as an alkaline agent Triethylamine used. 4. The method according to claim 1 to 3, characterized in that 1-trichloromethyl-l-methyl-2-chloro-ethanol- (l) used as a starting product. References considered: U.S. Patent No. 2,700,686; Chemuches Zentrtlblatt, 1957, pp. 7025/7026.