Reactions of primary amines with tetracyanoethylene

Abstract

Primary amines, 3-triethoxysilylpropylamine, 3-silatranylpropylamine, and cyclohexylamine, react with tetracyanoethylene in acetonitrile at room temperature via addition at the cyano group to afford the corresponding amidines. N-Cyclohexyltricyanoacrylamidine exists as a mixture of two of the three possible isomers, while N-(3-triethoxysilylpropyl)tricyanoacrylamidine and N-(3-silatranylpropyl)tricyanoacrylamidine exist mainly as a single isomer containing NH 2 group. N-(3-Triethoxysilylpropyl)tricyanoacrylamidine was used to prepare gels and films.

Reactions of Tetracyanoethylene withN′-Arylbenzamidines: A Route to 2-Phenyl-3H-imidazo[4,5-b]quinoline-9-carbonitriles

“…DEPT135 or APT NMR studies identified quaternary and tertiary carbons, which are indicated by (s) and (d) notations, respectively. 1670w, 1651w, 1603m, 1593m, 1562s, 1557s, 1493m, 1454w, 1445m, 1375m, 1323m, 1315m, 1310m, 1285m, 1263m, 1184w, 1159w, 1126s, 1071m, 1039w, 1030m, 1007m, 1001w, 941w, 935w, 918m, 910m, 881m, 847w, 814w, 783s, 729m; 1695w, 1684w, 1653w, 1636w, 1607w, 1593w, 1568w, 1539w, 1512s, 1466w, 1447w, 1420w, 1387w, 1321m, 1312m, 1302m, 1254s, 1180w, 1171w, 1125m, 1065w, 1028w, 910w, 841m, 812w, 799w, 775w, 1591m, 1560s, 1510m, 1497w, 1470w, 1447m, 1385m, 1379m, 1323s, 1315m, 1296s, 1265m, 1213w, 1179w, 1128s, 1072m, 1065m, 1040w, 1030m, 1022w, 1007m, 980w, 966w, 945w, 933w, 912m, 880m, 845w, 830m, 810m, 806w, 798w, 781m, 746m; 1605m, 1593m, 1562m, 1508s, 1447m, 1418w, 1379m, 1323m, 1314m, 1292m, 1287m, 1265w, 1238m, 1223m, 1184w, 1155m, 1126s, 1096w, 1071m, 1042w, 1030m, 1008m, 982w, 943w, 933w, 916m, 883m, 849m, 841m, 822w, 802w, 783m, 750m; 1562m, 1493s, 1447m, 1408w, 1383w, 1323m, 1304m, 1294m, 1277w, 1265w, 1188w, 1128m, 1094m, 1071w, 1030w, 1016m, 945w, 939w, 930w, 912m, 880w, 837m, 822w, 806w, 781m, 760w, 739w ), 1703w, 1688s, 1605m, 1593m, 1564m, 1497w, 1474s, 1447w, 1406w, 1393w, 1370w, 1327m, 1304s, 1277m, 1242w, 1128s, 1086w, 1076w, 1065m, 1036m, 1011w, 982w, 957w, 932w, 912m, 887w, 874m, 847w, 829m, 818w, 797m, 781s, 745m; δ H (500 MHz; CDCl 3 ) 8.12 (1H, br s, NH), 7.58 (1H,d,J 8.5 Ar H),7.55 (1H,dd,J 7.5,7.5,Ar H),7.47 (2H,d,J 7.5,Ar H),7.38 (2H,dd,J 7.8,7.8,Ar H) (MH + ,2), 350 (8), 329 (4), 303 (2), 250 (65), 248 (100), 207 (8), 199 (9), 181 (7), 127 (8), 111 (22), 109 (4), 105 (15), 97…”

“…11,12 The chemistry of TCNE has been extensively reviewed. 7,13−19 With primary or secondary aliphatic amines and with most primary and secondary aromatic amines, the reaction with TCNE gives N-tricyanovinylamines 1, although with an excess of amine, 1,1-diamino-2,2-dicyanoethylenes 2 13,20,21 or 1,2diamino-1,2-dicyanoethylenes 3 22 are formed. TCNE does not react with tertiary aliphatic amines, but it readily reacts with both tertiary and secondary aromatic amines, attacking the arene to give 4-tricyanovinyl-arylamines 4 via the initial formation of a 1:1 π complex.…”