The scope of the reaction of halogen-s~ibstit~~ied nitriles and amines was extendecl by incl~~ding trilluoro-and dichloro-acetonitrile. Trifl~~oroacetonitrile reacts easily with primary and secondary aliphatic, primary aromatic, and heterocyclic amines to give the corresponding amidines. N-Mono-and N-di-substit~~ted dichloroacetamidii~es were prepared from dichloroacetonitrile and amii~es. Tricl~loroacetonitrile also affords N-substituted a~uidines with heterocyclic amines. ISTRODUCTIOK 7'he reaction of tric11loroacetonitrile with primary and secondary anlines has been investigated ancl discussed (1). The present worlr deals with the extension of the reaction, sing trifluoroacetonitrile ancl di-and mono-chloroaceto~~itrile, ancl a variety of amines. Trifl~~oroacctonitrile is expected to react even faster than tricl~loroacetouitrile owing to the stronger inductive effect (-Is) of the trifluorometl~yl group. Husted (2) synthesized a series of perfl~~oroalI~ylamidines by allowing the corresponcling nitriles to react with liquid ammonia in sealecl t~~b e s for 2 weeks. Reilly and Rrowil (3) isolated some N-methyl-, and N,N-dimethyl-perfluoi-oalkylan~idines by treating nitriles with methyland dimethyl-amine a t -60'. They assulnecl that aniline, being a iirealr base, could not produce any amidines. There are no literature data concerning the adclition of amines to the carbon-nitrogen triple bollcl of dicl~loroaceto~~itrile.

It has been shown by infrared spectroscopic study that the alleged N-aryl-~litroacetarnidines are in fact the salts of nitroacetonitrile with aromatic amines. RESULTS AND DISCUSSION

, was prepared by carrying \NHR \NH out the reaction in water, in water-methanol solutions, or in the absence of solvents.

A correlation between the infrared spectra and the structure of some N-mono-and N-disubstituted trifluoroacetamidines is presented. I t was found that there was a considerable similarity between the infrared spectra of trifluoroacetamidines and those of the corresponding trichloroacetamidines. Additional information of the existence of these amidines in the imino form, CF3-C(=NH)NHR, was provided by the infrared study of N,N-dideuterioamidines. INTRODUCTIONIn a previous communication (1) the evidence for the existence of N-alkyl-and N-aryltricl~loroacetamidines in the form I was presented.PrevorBek (2) in a study of the infrared spectra of N-substituted benzamidines (IIa and IIb) concluded that when R' was an alkyl group (ethyl) the benzamidines existed in the form IIa, but when R' was an aryl group (phenyl) the a~nidine had the structure IIb. CsH5-C-NHR'C~HS-C=NRrThe infrared spectrum of alkyl-substituted amidines IIa showed a very strong "amidine 11" band a t 1560 cm-I which was displaced in solution. In the spectra of deuterated amidines (IIa) this band was not present but a new band appeared a t 1400 c~n-'. There was no "amidine 11" band for the aryl-substituted benzamidines (IIb) between 1580-1500 cm-1 since such displacement of the band observed did not occur on deuteration and was not also sensitive to the brealiing of hydrogen bonds on dilution. Therefore the structure IIb of aryl-substituted benzamidines was accepted. Prevorsek (2) EXPERIMENTALThe trifluoroaceta~nidines used in this infrared study were prepared by known nlethods (4) or by procedures outlined in the previous paper (6). The deuterioarnidiiles were synthesized from nitriles and N,N-deuterioamirles according to the following reaction scheme : , 1954-1958, and 1958-1959. Can. J. Chem. Val. 39 (1961) 414Can. J. Chem. Downloaded from www.nrcresearchpress.com by 54.202.27.70 on 05/11/18For personal use only.

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