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Vol.31 No. 11 RUSSIAN CHEMICAL REVIEWS November 1962

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Vol.31 No. 11 RUSSIAN CHEMICAL REVIEWS November 1962 Vol.31 No. 11 RUSSIAN CHEMICAL REVIEWS November 1962 evidently due to the ready polarisability of the cyano-group; also the presence of acids creates suitable conditions for REACTIONS OF NITRILES WITH HYDROGEN the appearance of electrophilic activity at the nitrile car- HALIDES AND NUCLEOPHILIC REAGENTS bon atom and the formation of new bonds between this atom and atoms of oxygen, sulphur, nitrogen, carbon, etc. Ε. Ν. Zil'berman Hydrogen halides are particularly important as acid catalysts for reactions of the cyano-group, and in many CONTENTS cases, especially with hydrogen chloride, they are specific 615 catalysts. The Pinner reaction (preparation of imidate I. Introduction salts), Hoesch reaction (preparation of ketimine salts), Gattermann reaction, Stephen reaction (preparation of Π. Reactions of nitriles with hydrogen halides 615 aldimine salts), and several other acid-catalysed reactions A. Nitrile hydrohalides of composition RCN.ηΗΧ 615 of nitriles are carried out in the presence of hydrogen halides, and do not occur with other protogenic or Lewis B. Some properties of solutions of hydrogen acids in the absence of hydrogen halides. In the literature halides in nitriles 617 these reactions are very often discussed without considera- tion of the nature of the products of the reaction of nitriles C. Nitrile hydrohalides of composition 2RCN.nHX 618 with hydrogen halides, which may be formed under the D. Preparation of 1, 3, 5-triazines 618 experimental conditions. These products are often for- mulated as imidoyl halides, although these have never been E. Hydrogen cyanide hydrohalides 619 isolated and there is no proof of their existence in the reac- ΠΙ. Reactions of nitriles with hydrogen halides and tion medium. There have been no attempts in the review literature to generalise the existing data on the reactions nucleophilic reagents 619 of nitriles with hydrogen halides in the absence of other A. Reactions with water 619 reagents. B. Reactions with alcohols 621 This review is intended to fill the existing gaps. We shall consider the structure of the hydrohalogenation pro- C. Reactions with organic acids 624 ducts of nitriles and hydrogen cyanide, and describe the D. Reactions with carbonyl compounds 625 reactions of nitriles with hydrogen halides and other re- E. Structure and chemical properties of amide agents: hydroxylic compounds (water, alcohols, and organic hydrohalides 625 acids), aldehydes and ketones, amines and aromatic com- pounds (the Gattermann and Hoesch reactions). The re- F. Selective reactivity of one cyano-group in duction of nitriles in the presence of hydrogen halides and adiponitrile 626 other matters related to these reactions of nitriles will also G. Reactions with amines 627 be considered. H. The Gattermann reaction 627 J. The Hoesch reaction 628 II. REACTIONS OF NITRILES WITH HYDROGEN HALIDES K. Reaction of dimeric nitrile salts (2RCN.MHX) with hydroxy-compounds 628 A. Nitrile Hydrohalides of Composition RCN.wHX IV. Reduction of nitriles in the presence of hydrogen Nitrile hydrochlorination products were first isolated chloride 629 in 1866 by Gautier2"4, and the hydrohalogenation of nitriles was much studied in the last century5"10. Several nitrile A. Preparation of aldehydes by the Stephen method 629 hydrohalides were apparently obtained in admixture with B. Preparation of bisamides in the reduction of other compounds in the bromination of aliphatic nitriles11»12. nitriles by the Stephen method 629 Until 1931 it was thought that one or two hydrogen halide molecules could add to nitriles in the cold, to form imidoyl C. Preparation of amines 630 halides and amino-halides respectively, but, after more careful study of the composition of the very unstable reac- I. INTRODUCTION tion products of nitriles and hydrogen halides, Hantzsch The ability of nitriles to form addition compounds with concluded13 that the monohydrochlorides were not obtained, nucleophilic and electrophilic reagents derives from the and that only the saltlike dihydrochlorides exist. Byhydro- electronic structure of the triple carbon—nitrogen bond1. bromination, however, Hantzsch obtained mono- and di- We have recently reviewed the reactions of nitriles with -hydrobromides. Hantzsch's experiments on hydrobromi- electrophilic reagents1, and these will be considered only nation were later repeated by Klages and Grill14, who to a limited extent. Because of the reduced electron den- showed that Hantzsch's results on nitrile monohydrobrom- sity at the carbon atom of the cyano-group, nitriles should ides were in error. In 1957 it was reported15 that treat- react very readily with nucleophilic reagents. Compounds ment of ΛΓ-acylaminoacetonitriles with hydrogen chloride in such as hydrogen sulphide and hydroxylamine do in fact the cold produces monohydrochlorides, and these were add to nitriles to form thioamides and amidoximes, but in stated to be the first isolated imidoyl chlorides or nitrilium general nitriles are very stable towards many other nucleo- salts; however, hydrogen chloride can add not only to the philic reagents (water, alcohols, amines, etc.). The reac- cyano-group, but also to the amide group, and this possi- tivity of nitriles is increased and the range of their reac- bility was not considered. Moreover, the hydrochlorides tions with nucleophilic reagents broadened in the presence obtained melted above 100°, and it is improbable that of acidic or alkaline compounds, the action of which is imidoyl halides would melt at such high temperatures. Up 615 Vol.31 No. Π RUSSIAN CHEMICAL REVIEWS November 1962 to the present, therefore, only nitrile dihydrohalides have but there was a band at 1180 cm"1 characteristic of been prepared (textbooks16 and monographs " still erron- the HC1J anion27. It was therefore concluded that for eously refer to the existence of solid monohydrohalogenated the dihydrochloride, unlike the dihydrobromide or di- nitriles). hydriodide, the most probable formula is (D). Janz did not consider this structure as proved, because (a) the The 1: 2 reaction products of nitriles and hydrogen structure of nitrile dihydrochlorides may be different in halides are also obtained by treating carboxylic acid amides 18 dilute solution than in the solid state, and (b) the measure- with PC1 ; these products have been shown to be iden- 25 5 ments were made at room temperature, while even at tical with those obtained by direct hydrochlorination of 13 + 6° acetonitrile dihydrochloride dissociates into the nitrile nitriles . Kirsanov has studied the reaction of carboxylic 32 19 21 and hydrogen chloride . acid amides with PC15, ~ and his data confirm the earlier suggestion22 that the primary reaction products are tri- The existing data are therefore insufficient to ascribe to chlorophosphazoacyl compounds: the dihydrochlorides a structure different from the struc- ο ture of the other dihydrohalides. In order to establish finally the structure of nitrile dihydrochlorides, their RCONH + PCU -» RC—N=PC1, + 2 HC1. 2 spectra must be investigated under conditions such that their These can be obtained in high yields if the hydrogen chlor- conversion into other nitrile - hydrogen chloride reaction ide is removed from the reaction zone. In the presence of products is excluded. the hydrogen chloride they decompose into nitriles and POC1 : It is of interest that no difference has been found in the 3 structures of solid cyanamide dihydrochloride and dihydro- ο bromide 33 and both salts have been given the same halo- RC—N=PC1 RCN + POC1,. S genoformamidinium halide structure: The resulting nitriles react further with the hydrogen chlor- ide in the normal fashion, i.e. to form the 1: 2 addition pro- ducts. The dihydrohalides described in the literature, which The 1: 2 addition products of nitriles with hydrogen are in all probability of structure (C), include the dihydro- halides have been given various structural formulae. In chlorides of acetonitrile32, bromo- andfluoro-acetonitrile34, the older literature they were considered to be amino- benzonitrile8, ^-tolunitrile13, and />-methoxybenzonitrile35, -halides (A).23 In 1931 Hantzsch13 suggested the for- the dihydrobromides of acetonitrile25, bromoacetonitrile34, mula (B), according to which they are hydrochlorides of phenylacetonitrile and benzonitrile14, and^-tolunitrile13, nitrilium salts, and this formula is met with today16. and the dihydriodides of acetonitrile25, phenylacetonitrile, Klages and Grill found14 that the properties of the nitrile o-, m-, and £-tolunitrile, o-, m-, and £-nitrobenzonitrile, dihydrohalides correspond best to those of imidoyl halide succinonitrile, terephthalonitrile, etc.10. salts24, i.e. halogenoiminium halides (C). Finally, Janz 25 Of the acetonitrile dihydrohalides, the hydriodide melts has suggested that the nitrile hydrochlorides may have at the highest temperature (above 100°); the hydrobromide formula (D): and hydrochloride melt at 75°-80° and about 20 respect- ively25'36. The thermal stability of the salts (ease of for- χ JiHt\+ mation) also increases in this order: RC-NHRC—H , [RCENH]+X-, HX RC^ X- [RCSNH] + [ΗΧ,Γ [ CH,CN.2HC1 < CH,CN.2HBr < CH,CN.2HI. X (A) (E) (C) (D) The stability of the halogenoimonium halides is related to the polarisability of the hydrogen halides36: the least The nitrile dihydrohalides show a high conductivity in polarisable hydrogen chloride forms the least stable salts, liquid sulphur dioxide14 and are therefore salts and cannot and the most polarisable hydrogen iodide the most stable be amino-halides (A). The nature
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