Trifluoroethylanilines

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parts of acetic anhydride are added and the mixture is heated for 2 hours at 110° C. The product which crys tallizes massively by cooling is filtered, washed and

The present invention concerns trifluoroethylani dried. 34 parts of 2-(2,2,2-trifluoroethyl)acetanilide are lines, which are new compounds and are capable of 5 obtained, melting point 187 C.

being used as intermediate products for preparing dye Analysis: Calculated for C% 55.29: H% 4.60: N% stuffs, pharmaceutical products or phytopharmaceuti 6.45: F% 26.27: CHFNO. Found: C% 55.4: H% cal products. 4.64: N9% 6.30: F%. 25.6.

According to the present invention trifluoroethylani Gradually, so as not to exceed the temperature of 0 lines are provided having the following general for- 10 C., 32.6 parts of the acetyl derivative is introduced into mula: 90 parts by volume of H2SO4 at 66 Be. 6.5 parts of nitric acid (density = 1.52) are added with stirring without

CHCF, (I) exceeding O C., the mixture is stirred for 1 hour at this temperature, then for 2 hours whilst allowing the tem perature to rise to approximately 20 C. The mixture is

NH poured onto 500 parts of crushed ice. The precipitate is filtered, washed until neutral and dried. 37 parts of in which the nucleus A is unsubstituted or substituted 4-nitro-2-(2,2,2-trifluoroethyl) acetanilide are obtained by one or two nitro, amino, alkyl or alkoxy group or which is recrystallized in acetic acid for analysis - melt chlorine or bromine atom and the alkyl and alkoxy ing point: 238 C.

groups each contain up to two carbon atoms. Calculated for CHFNO: C% 45.80: H% 3.43: It is known that N-(2,2,2-trifluoroethyl) aniline may N2, 10.69: Found: C% 45.3: H% 3.07: N9%. 109: be prepared by reacting aniline with 1,1,1-trifluoro-2- The NMR spectrum confirms that it is the 4-nitro chloroethane. This reaction is described in U.S. Pat. derivative free from any isomer. No. 2,618,630 (column 17, Example Q). It is carried out 2. 53 parts of this nitrated derivative are heated under in a glass apparatus, i.e. in the absence of metallic salts. reflux in a mixture comprising 300 parts by volume of However, it has been found that the same reaction, 2N hydrochloric acid and 150 parts by volume of etha carried out in the presence of a metallic salt, such as an nol until completely dissolved. The mixture is cooled iron, nickel, cobalt or copper salt, produced not only and the solution is rendered alkaline by the addition of N-(2,2,2-trifluoroethyl) aniline, but also 2-(2,2,2-tri- 30 aqueous caustic soda, then extracted in ether. After fluoroethyl) aniline.

With substituted anilines, such as alkyl- or alkoxyani evaporation, ethyl) aniline 43.8 parts of 4-nitro-2-(2,2,2-trifluoro are obtained which, when recrystallized lines, having at least one free position ortho to the from toluene, melts at 101 C. amino group, the corresponding 2-(2,2,2-trifluoroethyl) anilines are also formed. 35 EXAMPLE 3 Anilines of formula I containing nitro, chlorine or A mixture comprising 21.7 parts of 2-trifluoroethyl bromine substituents in nucleus. A may, however, be acetanilide, 9 parts of anhydrous sodium acetate, 200 obtained by nitrating, chlorinating or brominating 2 parts of glacial acetic acid and 16 parts of bromine is (2,2,2-trifluoroethyl) N-acyl anilines and subsequently hydrolysing the acyl group. 40 stirred for 2 hours at ambient temperature, then at 40 C. for 15 minutes, and finally for one hour at 60 C.

The invention is illustrated by the following Exam After ples where the parts indicated are parts by weight un water.cooling, the solution is poured into 500 parts of The precipitate is filtered, washed and dried. 23 less otherwise stated.

parts of 2-(2,2,2-trifluoroethyl)-4-bromoacetanilide are

EXAMPLE 1. 45 obtained, melting point 216 C.

465 parts of aniline and 237 parts of 1-chloro-2,2,2-tri This product is brought back to boiling point for 6 fluoroethane are heated for 6 hours at 250-255 C. in a hours in 200 parts of 2N hydrochloric acid and 100 parts stainless steel autoclave. After being cooled, the con of ethanol. After cooling, the mixture is made alkaline tents of the autoclave are poured into 1000 parts by by the addition of 70 parts by volume of 30% caustic volume of 2N sulphuric acid. The mixture, which is 50 soda lye. The precipitate is extracted with ether. After strongly acidic, is subjected to distillation with steam. the solvent has been evaporated, 19 parts of 2-(2,2,2-tri The distillate causes an organic layer to be deposited fluoroethyl)-4-bromoaniline are obtained which is re which is dissolved in 500 parts by volume of benzene. crystallized from hexane for analysis, melting point This benzene solution is extracted with 4 times 100 parts 100-101° C.

of N hydrochloric acid. The aqueous phase, rendered 55 Analysis: Calculated for 0%. 37.79: H% 2.75: N% alkaline with a solution of caustic soda, is again ex 5.51: CHBrFN. Found: C%. 38.5: H%. 2.94: N% 5.61. tracted with benzene. After the benzene has been dried The compounds of formula I may be used for prepar and evaporated, 62 parts of a white solid are obtained ing azo dyestuffs, according to the known process of which, after recrystallization from hexane, melts at 49' diazotization-coupling. When, for example, orthotri C. The IR and NMR spectra confirm that it is 2-(2,2,2- 60 fluoroethylaniline is diazotised and coupled with 1-phe trifluoroethyl) aniline. nyl-3-methyl-5-pyrazolone one obtains a dyestuff This compound is not formed when the reaction is which, in its disperse state, dyes polyester fibres in a effected without any metals for example, in a vitrified yellow shade. When coupled with 1-dimethylamino-3- steel autoclave. W acetylaminobenzene, it (i.e. the orthotrifluoroethylani 65 line) produces a dyestuff which dyes these same fibres

EXAMPLE 2 in an orange-yellow shade.

35 parts of 2-(2,2,2-trifluoroethyl) aniline are dis We claim:

solved in 100 parts by volume of glacial acetic acid. 40 1. Compound of the formula:

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