SU243614A1 - METHOD OF OBTAINING ORTHO-AMINO DERIVATIVES OF PHENILTRYTFORMOMETHMULSULFIDE OR SULPHOXIDE - Google Patents

Description

A method is proposed for the preparation of ortho-amino derivatives of phenyl trifluoromethyl sulfide or sulfoxide, or sulfone, which can be used in the synthesis of dyes and drugs.

The method consists in the fact that the phthalimide derivative of o-thioanisidine is chlorinated, the resulting derivative is subjected to fluorination with hydrogen fluoride or antimony trifluoride. The compound thus obtained is oxidized and hydrolyzed. Depending on the oxidant used, a sulfoxide or sulfone is obtained.

Synthesis Examples

o-F talimidophenylmethylsulfide. A solution of 57 g (0.41 g ‑ ly) of o-aminothioaiisol and 137 g (0.92 g-mol) of phthalic anhydride in 500 ml of glacial acetic acid is boiled for 1 hour, poured into 5 l of hot water, made up until boiling and leave for 12 hours. The precipitation is filtered, washed with 1% potassium hydroxide solution, water and dried. Yield 107.8 g (97.8%); T. Il. 159-160 ° C (from acetic acid).

Found,%: N 5.25, 5.26.

After the above process, it is dissolved in 90 ml of chloroform and distilled off with 20 ml of chloroform for final drying of the solution. The solution is cooled to give up to 5 ° C, cooled out with a 200 W lamp, and chlorine is passed in for 1.5 hours with stirring. The temperature is adjusted so that in the first 5-7 minutes it rises to 25-28 ° C and then it is kept within these limits until the end of chlorination. The solution is then left to stand at room temperature for 1 hour, chloroform is distilled off in the vacuum, and the residue is washed with a small amount of ether.

Yield 19.4 g (78.6%); m.p. 125-126 ° С (from heptane).

Paydeno,%: C1 28.52, 28.69.

CisngClgNOsS.

Calculated,%: C1 28.58.

o-F talimidophenyltr and fluorine methyl sulfide, a) A mixture of 21.4 g (0.058 g-mol) of trichloromethyl sulfide and 25 g (0.14 g-mol) of anhydrous finely divided SbPy is heated for 30 minutes at 140 ° C and vigorous stirring. After cooling, it is dissolved in ether, filtered off, the ethereal solution is washed with 20% hydrochloric acid, water and dried. The ether is distilled off, dissolved in hot hexane and filtered to remove impurities. Yield 12.4 g (66.7%); m.p. 109-110 ° С (from hexane). CisHsFsNOaS. Calculated,%: F 17.63. b) To 5 2 trichloromethyl sulfide, 15 ml of anhydrous distilled hydrogen fluoride are poured into the autoclave while cooling. The autoclave is heated for 3 hours in a boiling water bath, cooled to 0 ° C, and excess HF is distilled off. The residue is dissolved in ether, filtered from impurities, the ether is distilled off. Yield 2.42 g (56.0%); m.p. 108-109 ° С (from hexane). o-Trifluoromethylmercaptoaniline. To a boiling solution of 4 g of trifluoromethyl sulfide in 10 ml of alcohol was slowly added 2.8 ml of a 25% aqueous solution of hydrazine hydrate, boiled for 30 minutes, and then another 15 minutes with 3 ml of 20% hydrochloric acid acid. The alcohol is distilled off in vacuo, cooled, and hydrazidephthalic acid is filtered off. A solution of potassium hydroxide is added to the filtrate to an alkaline reaction, and the amine is extracted with ether. The ether solution is washed with water, dried, the ether is distilled off, the product is distilled in vacuo. Yield 2.1 g (87%); m.p. 90-91 ° С (15 mm 30-31 ° С. рт. Ст.); so nl F 29.12, 29.14. Found%: C HeFsNS. Calculated,%: F 29.5. o-Phthalimidophenyl trifluoromethyl sulfoxide. 8 g of trifluoromethyl sulfide, 80 ml of acetic acid and 28 ml of 26% hydrogen peroxide are heated for 1.5 hours - at 95 ° C, poured onto ice, the precipitate is filtered, washed with water, and dried. Yield 7.61 g (90.6%); m.p. 131-132 ° С (from a mixture of heptane with benzene). Found,%: F 16.46, 16.64; O sulfoxide 4.4z, 4.43. CisHsFsNOsS. Calculated,%: F 16.79; o sulfoxide 4.72. o-Trifluoromethylsulfoxidoanil and n. 2 g of trifluoromethylsulfoxide and 5 ml of 0% H2SO4 are stirred for 10 minutes at 115 ° C, cooled, poured onto ice, ieralized, extracted with ether. The ethereal solution is washed with water, dried. The ether is distilled off and the product is distilled under vacuum. Yield 1.1 g (87%); m.p. 77-78 ° C (0.05 mm Hg. Art.). Cobalt salt is obtained by passing anhydrous HC1 to a benzene amine solution. The product melts at 140-142 ° C (with decomposition). Found%: C1 14.24, 14.33. C7H7C1F3NOS. Calculated,%: C1 14.43. o-F talimidophenyltrifluoromethylsulfone. 7 g of trifluoromethyl sulfide, 8.65 g of chromic anhydride and 30 ml of glacial acetic acid are boiled for 1 hour, then poured onto ice. The precipitate is filtered, washed with water, dried. Yield 6.92 g (89.7%); m.p. 181-182 ° (from a mixture of benzene and heptane). Found%: F 16.30, 16.33. Ci3H8F3N04S .. Calculated,%: F 16.04. o-A minophenyl trifluoromethylsulf o n. 6.92 g of trifluoromethyl sulfone and 17 ml of 80% H2SO4 are stirred for one hour at 120 ° C, poured onto ice, and neutralized. The product is filtered. Yield 3.97 g (90.5%); m.p. 43-44 ° C. Subject of the Inventions A method for producing ortho-amino derivatives of phenyl trifluoromethyl sulfide or sulfoxide, or sulfone, characterized in that the phthalimide o-thioanisidine derivative is sequentially treated with chlorine, antimony trifluoride or hydrogen fluoride when heated, the resulting product, or directly, is subjected to it, or directly subjected to it, it is subjected to heat, or hydrogen fluoride trifluoride or hydrogen fluoride. either pre-oxidized with hydrogen peroxide or chromic anhydride followed by hydrolysis and isolation of the target product by conventional methods.