How dehydrochlorinating 1,1-bis(halogenfree)-2,2,2 - trichloroethanol

 

(57) Abstract:

Use: as intermediate DDT. The inventive dehydrochlorination of 1,1-bis(halogenfree) -2,2,2-trichloroethanol. The synthesis conditions is the use of an aqueous solution of alkali metal hydroxide in the presence of a phase transfer agent, preferably chloride of dimethylbenzylamine at 90 - 105oC. for 2 h. p. F.-ly.

The invention relates to a method of dehydrocorydaline 1,1-bis(R-phenyl)-2,2,2-trichloroethanol. The family of 1,1-bis(R-phenyl)-2,2,2-trichloroethanol is known. For example, 1,1-bis-(chlorophenyl)-2,2,2-trichloroethane (DDT) is an intermediate product for the synthesis of 1,1-bis(chlorophenyl)-2,2,2-trichloroethane, commonly called dicofol, which is acaricidal (remedy against mites), primenyaemym for cotton and fruit trees. DDT dehydrochlorinated to 1,1-bis(chlorophenyl)-2,2-dichloroethylene (DDE), which hairout to obtain 1,1-bis-(chlorophenyl)-1,2,2,2-tetrachlorethane (chlorine-DDT), which is hydrolized to dicofol.

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The known method [1] including the dehydrochlorination of diphenyltrichloroethane (C6H5)2CH-CCL3to diphenyldichlorosilane (C6H5)2With CCL2that x2">

The known method [2] including the dehydrochlorination of 1,1-bis-(n-chlorophenyl)-2,2,2-trichloroethane (n-ClC6H4)2CH-CCl3under the action of the hydroxide of an alkali metal, which is carried out in ethanol or isopropanol.

The known method [3] including the dehydrochlorination bis-(parahydroxybenzoic)-trichloroethane (4-HOC6H4)2CH-CCl3in methanol in the presence of ion exchange resin of the Quaternary ammonium main character.

The presence of a solvent, such as benzene, ethanol, isopropanol or methanol, can be disturbing, when after surgery dehydrochlorinating need to begin to chlorination, as this solvent can gloriouse.

If you want to select the product obtained by dehydrochlorination, the presence of a solvent makes the separation more difficult.

How dehydrochlorinating 1,1-bis(R-phenyl)-2,2,2-trichloroethanol using an aqueous solution of alkali metal hydroxide is that the process is carried out in the absence of solvent and in the presence of a phase transfer agent.

The radical R may represent one or more substituents: halogen, Akilov, hydroxyl groups (OH), NO2gr is to say methoxy - or ethoxypropan. You can also have a combination of various substituents on the same phenyl, the substituents on each of fanilow, only one substituted phenyl, or any combination of these substituents. Although the process can be performed in a wide range of pressures, typically operate with a pressure sufficient to maintain the 1,1-bis(R-phenyl(-2,2,2-trichloroethane and an aqueous solution of alkali metal hydroxide in a liquid state. The phase transfer agent is a compound that allows contact between the subject dehydrochlorination compound and a hydroxide of an alkali metal. There are numerous compounds that have this feature. You can, for example, the use of Quaternary ammonium compounds. Successfully applied chloride of dimethylbenzylamine.

According to the invention can be added to the solution of alkali metal hydroxide for a few tricks during the reaction or to increase the content of the alkali metal hydroxide in the reaction medium by adding anhydrous or highly concentrated alkali metal hydroxide such as potassium hydroxide or sodium hydroxide in the form of flakes, so you can restore your consumption of alkaline hydroxide, metahit the organic phase, containing to be dehydrochlorination product and dehydrochlorinating product, and the alkaline aqueous phase; this can be done by simple decantation.

P R I m e R 1 (comparative). Melt 420 g of 1,1-bis-(chlorophenyl)-2,2,2-trichloroethane and poured with stirring at 100-105aboutWith 270 g of a 50% aqueous sodium hydroxide solution. After reaction for 20 h, diluted by 300 g of water. Desantirovaniya organic phase is washed twice using 100 g of water, get 371,9 g of a mixture consisting of 1,1-bis-(chlorophenyl)-2,2-dichloroethylene and 1,1-bis-(chlorophenyl)-2,2,2-trichloroethane (15,5%).

P R I m m e R 2 (comparative). To a solution containing 250 g of 1,1-bis-(chlorophenyl)-2,2,2-trichloroethane in 250 g of Isobutanol is added to 60.6 g of a 50% aqueous sodium hydroxide solution and two drops of antifoam. Heated under stirring until the azeotropic distillation of a mixture of isobutyl alcohol-water soaking at a temperature of education phlegmy for 1 h to Separate the water by azeotropic distillation of a mixture of water-Isobutanol, constantly adding Isobutanol.

After separation of the water is filtered at ambient temperature selected solid phase and the Isobutanol is distilled from the liquid phase. Get 217,9 g of 1,1-bis-(chlorophenyl)-2,2-performance). To a solution containing 250 g of 1,1-bis-(chlorophenyl)-2,2,2-trichloroethane 100 g monochlorbenzene, 50aboutTo add 201,5 g of 28% sodium hydroxide solution and 2.0 g of chloride of dimethylbenzylamine. Heated at a temperature of education phlegmy (90aboutC) for 20 hours Separated by decanting the organic phase, which was washed with water three times 100, After the distillation of monochlorbenzene get 219,3 g of 1,1-bis-(chlorophenyl)-2,2-dichloroethylene (yield 97.8 per cent ) of 0.10% content of 1,1-bis-(chlorophenyl)-2,2,2-trichloroethane.

P R I m e R 4 (comparative). To 248,8 g 27,2% aqueous sodium hydroxide solution, maintained at 93aboutC, add 150 g of 1,1-bis-(chlorophenyl)-2,2,2-trichloroethane in solid form. Add 1.4 g of the chloride of dimethylbenzylamine. The temperature rises from 93 to 103aboutC. Continue adding solid 1,1-bis-(chlorophenyl)-2,2,2-trichloroethane to the total mass of 300, Again add 1.1 g of the chloride of dimethylbenzylamine and keep the temperature between 100 and 105aboutWith over 14 hours 30 minutes By decanting separated and the organic phase is washed three times by 100 g of 1H. solution of sulfuric acid and water (100 g). Get 263,7 g of 1,1-bis-(chlorophenyl)-2,2-dichloroethylene (output 98,0% ) 0,09% content 1,1-barroway load at 100aboutWith 990 kg of 1,1-bis-(chlorophenyl)-2,2,2-trichloroethane in solid form. Download duration 2 h to avoid formation of solid arrays inside the reactor. Add 5 kg of chloride of dimethylbenzylamine maintaining continuous intensive stirring for 4 h at 100aboutC. After 1 h of rest separating the aqueous phase and add 268 kg of a 50% aqueous sodium hydroxide solution, then continue the dehydrochlorination with stirring at 100aboutC for 10 h After dilution through 560 kg of water and 1 h of rest is drained organic phase and retain the aqueous phase for the next operation. The organic phase is then washed 3 times by 250 kg 1 n sulfuric acid solution, get 879 kg of 1,1-bis-(chlorophenyl)-2,2,2-trichloroethane.

P R I m e R 6. Conduct a process as in example 5, except that in the beginning have the technical 1,1-bis-(chlorophenyl)-2,2,2-trichloroethane in the molten state at 92aboutC.

Add 1,1-bis-(chlorophenyl)-2,2,2-trichloroethane in the liquid state to the alkaline aqueous phase from the previous operation dehydrochlorinating and initiate the dehydrochlorination the addition of 5 kg of chloride of dimethylbenzylamine maintaining continuous intensive mixing in t is="ptx2">

1. HOW DEHYDROCHLORINATING 1,1-BIS(HALOGENFREE)-2,2,2-TRICHLOROETHANOL using an aqueous solution of alkali metal hydroxide at elevated temperature, wherein the process is conducted in the absence of solvent and in the presence of a phase transfer agent selected from Quaternary ammonium compounds.

2. The method according to p. 1, characterized in that the Quaternary ammonium compounds used chloride of dimethylbenzylamine.

3. The method according to p. 1, wherein the process is conducted at 90 - 105oC.

 

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