Studies on Nitrile Salts. I. Dimerization of Nitriles Having α-Hydrogen in the Presence of Hydrogen Chloride

Abstract

The compositions and structures of several stable nitrile-HCl salts previously reported were reinvestigated. Most of them have been found to have the composition of 2RC≡N·2HCl and have been identified as N-(α-chloroalkenyl)alkylamidine hydrochlorides (3) by mass and NMR spectra analyses. However, the 2:3 adduct from chloroacetonitrile was confirmed to be N-(α,α,β-trichloroethyl)chloroacetamidine hydrochloride. The scope and limitations of the dimerization reaction of nitriles having α-hydrogen with HCl were studied. Most nitriles having α-hydrogen react with HCl to give N-(α-chloroalkenyl)alkylamidine hydrochlorides (3). Their hydrolysis to diacylamines (4) was also investigated.

Reaction of nitriles with thionyl chloride in the presence of hydrogen chloride. Formation of sulfinyl and sulfenyl chlorides and phenyl cyanosulfine

“…:i ci Reactions of Nitriles with Two a Hydrogens. When phenylacetonitrile (6a) was allowed to react with thionyl chloride in the presence of hydrogen chloride under the same conditions as described in the previous section, achloro-a-cyanophenylmethanesulfenyl chloride (7a) was obtained in 44% yield together with low yields of succinonitrile derivative 4f, , -dichlorophenylacetonitrile (8), trans-,/3-dicyanostilbene (9), and benzoyl cyanide (10) (recovery of 6a 3%) (eq 3).…”

“…The precipitates formed were filtered, washed with a small portion of ether, and dried in vacuo to give 1.53 g (27%) of 5, which was identified by comparison with an authentic sample. 8 The filtrate was concentrated and distilled under reduced pressure to give 1.94 g (43%) of If. The distillation residue was chromatographed on silica gel.…”

Synthesis oftrans-N-2-aryl(heteryl)ethenamidines

“…Subsequently a number of syntheses of such azabutadienes have appeared in the literature: Ring opening of 5-substituted-4-chloro-2-phenylpyrimidines by potassium amide in liquid ammonia (Va Meeteren and Van der Plas 1971); Grignard reactions or action of organolithium compounds on benzonitriles (Marxer 1972;Cook and Wakefield 1980;Compagnon et al 1982;Cook et al 1983); Dimerisation of nitdles having alpha hydrogen in the presence of hydrogen chloride + Contribution No. 752 from Research Centre * For correspondence 383 (Yanagida et al 1973;Yanagida 1975); Base treatment of N-(trans-styrylsulphonyl) amidines (Matier and Comer 1974, 1975, 1977; from N-vinyl-substituted chloroformamidines (Ried and Erie 1979); Acid decomposition of 5-amino-l-vinyl-4,5-dihydro-1 H-1,2, 3-triazole (lto et al 1983); Reaction of 2-aryl-4-arylidene-2-oxazolin-5-ones with nucleophiles (Islam et a11983) and reaction of electron-rich aromatics like indoles with 3-dimethylamino-2-(dimethylaminomethyleneamino) acrylic esters (Biere 1983). The last class of ethenamidines has been fruitfully cyclized to beta-carbolines.…”

Synthesis and structure of a product of interaction of acetonitrile with hydrogen bromide, [H2N=C(Me)−NH−C(Me)Br2]Br

“…Hydrochloride derivatives have received the most study by IH NMR and [R spectroscopy. Products of hydrolysis and alcoholysis of these derivatives were isolated and characterized, t, 7,8 Two schemes of interactions of nitriles with hydrogen halides were reported in the literature, t The first scheme, which was suggested based on the UV spectra and on the analysis of the data on the conductivity, assumes that the nitrilium cation [RC=NH] + and the polymeric anion X(HX)-n are formed in solutions. 9 According to the second scheme ([R spectral studies), the solutions contain the imonium halide cation and the halide anion solvated by molecules of hydrogen halide.…”