The preparation of N-cyanoammonium salts

N-Cyano-N,N,N-trialkylammonium salts. Synthesis and reactions

“…The cation of the intermediate is subsequently attacked by bromide ion to form a dialkylcyanamide and an alkyl bromide. Concurrent with our report of the preparation of Acyano-A, A, A-trialky lammonium fluoroborates, 6 Fodor and Abidi reported the characterization of the 1:1 adducts of cyanogen bromide and tertiary amines stabilized as tosy lates. 7 It was also reported that the A-cyano-A, A, A-trialkylammonium hexachloroantimonates were prepared using antimony pentachloride-cyanogen chloride complex as shown below.…”

“…Caled for C7Hi6N2BF4 (214.02): C, 39.28; , 7.06; N, 13.09. Found: C, 39.12; , 7.01; N, 13.27. IV-Cyano-MMAf-tri-n-butylammonium fluoroborate was prepared by the same procedure as that of (Vcyano -AA, AA (V-triethylammonium fluoroborate with the extension of the time for the adduct formation to about 5 hr (97% yield) and was recrystallized from ethyl acetate by adding petroleum ether: mp 79-80°; ir (Nujol mull) 2265 (weak, CN) and 1050-1100 cm-1; nmr (acetone-de) 1.01 (t, CHa, 9 ), 1.27-1.77 (m, CH2, 6 ), 1.83-2.40 (m, CH2, 6 H), and 4.15-4.27 (m, CH2N+, 6 H); uv tail (acetonitrile) 240 nm (E 40).…”

“…The ether-extracted portion was distilled to give 1.10 g (82%) of ZV-methyl-ZVethylaniline. Diethylcyanamide was analyzed as follows: ir (thin film) 2213 cm-1 (strong, CN); nmr (CCI3) 1.25 (t, CH$, 6 H) and 3.20 (q, CH2, 4 H); mass spectrum m/e (rel abundance) 98 (M+, 34), 87 (6), 85 (42), 84 (6), 83 (6), 70 (11), 69 (12), 58 (25), 56 (6) , 55 (100), 53 (6), 49 (9), 48 (10), 47 (22), 44 (9), 43 (98), 42 (20), 41 (6).…”

“…The first fractions contained most of the ZV-methylcyananilide and weighed about 0.05 g. The ether-insoluble portion gave, after base treatment, 1.40 g (83%) of ZV-methyl-ZV-n-butylaniline, which was purified by column chromatography on silica gel using 10:1 cyclohexane-ethyl acetate as solvent. The nmr spectrum (CC14) had signals at 0.91 (t, CH3, 3 ), 1.07-1.80 (br, CH2, 4 H), 2.85 (s, CH3, 3 ), 3.17 (t, CH2, 2 H), 6.43-6.63 (m, phenyl ring, 3 ), 6.91-7.23 (m, phenyl ring, 2 H). Di-n-butylcyanamide was characterized as follows: bp 70-71°( 0.5 mm); ir (thin film) 2205 cm-1 (strong, CN); nmr (CC14) 0.97 (t, CH3, 6 ), 1.20-1.90 (m, CH2, 8 H), 2.97 (t, CH2, 4 H); mass spectrum m/e (rel abundance) 154 (M+, 23), 139 (7) , 125 (9), 112 (10), 111 (44), 98 (9), 97 (7), 86 (8), 83 (7), 70 (11), 69 (100), 57 (44), 55 (19), 43 (13), 42 (10), 41 (41), 39 (8).…”

“…The nmr spectrum (CC14) had signals at 0.91 (t, CH3, 3 ), 1.07-1.80 (br, CH2, 4 H), 2.85 (s, CH3, 3 ), 3.17 (t, CH2, 2 H), 6.43-6.63 (m, phenyl ring, 3 ), 6.91-7.23 (m, phenyl ring, 2 H). Di-n-butylcyanamide was characterized as follows: bp 70-71°( 0.5 mm); ir (thin film) 2205 cm-1 (strong, CN); nmr (CC14) 0.97 (t, CH3, 6 ), 1.20-1.90 (m, CH2, 8 H), 2.97 (t, CH2, 4 H); mass spectrum m/e (rel abundance) 154 (M+, 23), 139 (7) , 125 (9), 112 (10), 111 (44), 98 (9), 97 (7), 86 (8), 83 (7), 70 (11), 69 (100), 57 (44), 55 (19), 43 (13), 42 (10), 41 (41), 39 (8).…”