1258
Čmelík, Čajan, Marek, Pazdera:
ate (0.60 g, 5.66 m m ol) gave 0.23 g (74%) of 6h , m .p. 104–105 °C (Et2O). IR: 3062 (w), 2981
(w), 2905 (w), 2854 (w), 1676 (s), 1591 (w), 1549 (w), 1451 (s), 1424 (m ), 1370 (m ), 1335 (s),
1270 (s), 1214 (m ), 1170 (w), 1112 (w), 1027 (m ). 1H NMR (500 MHz, CDCl3): 1.53 t, 3 H, J =
7.1 (CH3CH2); 2.75 s, 3 H (CH3CO); 4.54 q, 2 H, J = 7.1 (CH2); 7.47–8.37 m , 5 H (Ph ). 13C NMR
(500 MHz, CDCl3): 14.6 (CH3CH2), 18.1 (CH3CO), 62.2 (CH2), 124.3 (C-4), 128.6, 130.1,
133.1, 134.2 (Ph ), 163.5 (COO), 177.3 (CH3CO), 180.9, 181.7 (C-3, C-5). For C14H13NO3S3
(339.4) calculated: 49.54% C, 3.86% H, 4.13% N; foun d: 49.17% C, 3.68% H, 4.12% N.
N-[4-Carbamoyl-3-(methylsulfanyl)-1,2-dithiol-1-ium-5-yl]benzimidate (6i). Com poun d 3f
(0.30 g, 1.01 m m ol), m ethyl iodide (0.13 m l, 2.09 m m ol) and triethylam ine (0.29 m l, 2.08 m m ol)
gave 0.28 g (89%) of 6i, m .p. 206 °C (decom p.; CHCl3). IR: 3258 (m ), 3128 (w), 3058 (w),
2971 (w), 2903 (w), 1660 (s), 1593 (w), 1548 (s), 1490 (w), 1425 (s), 1378 (w), 1318 (m ),
1285 (s), 1172 (m ), 1113 (w), 1067 (w), 1025 (w), 1003 (w). 1H NMR (500 MHz, CDCl3): 2.72 s,
3 H (CH3); 5.94 s, br, 1 H (NH2); 7.50–8.21 m , 5 H (Ph ); 10.41 s, br, 1 H (NH2). 13C NMR
(500 MHz, CDCl3): 19.0 (CH3), 123.4 (C-4), 128.9, 129.6, 133.2, 134.0 (Ph ), 164.6 (COO),
176.3 (Ph CO), 182.0 (C-5), 187.1 (C-3). For C12H10N2O2S3 (310.4) calculated: 46.43% C,
3.25% H, 9.02% N; foun d: 46.12% C, 3.11% H, 9.09% N.
N-[3-(Benzylsulfanyl)-4-cyano-1,2-dithiol-1-ium-5-yl]benzimidate (6j). Com poun d 3d (0.10 g,
0.36 m m ol), ben zyl brom ide (0.064 m l, 0.54 m m ol) an d trieth ylam in e (0.076 m l, 0.54 m m ol)
gave 0.08 g (60%) of 6j, m .p. 186–187 °C (CHCl3). IR: 3065 (w), 3028 (w), 2918 (w), 2223
(w), 1590 (m ), 1548 (s), 1458 (m ), 1429 (m ), 1328 (s), 1277 (s), 1168 (m ), 1112 (w), 1017
(w). 1H NMR (500 MHz, DMSO-d6): 4.78 s, 2 H (CH2); 7.39–7.67 m , 8 H (Ph ), 8.23–8.25 m ,
2 H (Ph ). 13C NMR (500 MHz, DMSO-d6): 104.6 (C-4), 112.3 (CN), 128.3, 128.8, 129.2,
129.4, 132.8, 133.4, 134.2 (Ph ), 176.3 (Ph CO), 181.9, 182.6 (C-3, C-5). For C18H12N2OS3
(368.5) calculated: 58.67% C, 3.28% H, 7.60% N; foun d: 58.44% C, 3.19% H, 7.40% N.
N-[3-(Benzylsulfanyl)-4-(ethoxycarbonyl)-1,2-dithiol-1-ium-5-yl]benzimidate (6k ). Com poun d
3e (0.50 g, 1.54 m m ol), ben zyl iodide (0.39 m l, 3.10 m m ol) an d an h ydrous sodium carbon -
ate (1.00 g, 9.43 m m ol) gave 0.42 g (66%) of 6k, m .p. 112–113 °C (CHCl3). IR: 3061 (w),
3032 (w), 2983 (w), 2921 (w), 1681 (m ), 1594 (w), 1547 (s), 1493 (w), 1451 (s), 1369 (m ),
1337 (s), 1272 (s), 1216 (w), 1172 (w), 1112 (w), 1023 (m ). 1H NMR (500 MHz, CDCl3):
1.51 t, 3 H, J = 7.2 (CH3CH2); 4.42 s, 2 H (CH2S); 4.52 q, 2 H, J = 7.2 (CH3CH2); 7.34–
8.37 m , 10
H
(Ph ). 13C NMR (500 MHz, CDCl3): 14.6 (CH3CH2), 40.0 (CH2S), 62.2
(CH3CH2), 125.1 (C-4), 128.6, 129.2, 129.5, 130.2, 133.1, 134.0, 134.2 (Ph ), 163.5 (COO),
177.3 (Ph CO), 178.0 (C-5), 181.4 (C-3). For C20H17NO3S3 (415.5) calculated: 57.81% C,
4.12% H, 3.37% N; foun d: 57.72% C, 4.16% H, 3.45% N.
N-[3-(Benzylsulfanyl)-4-carbamoyl-1,2-dithiol-1-ium-5-yl]benzimidate (6l). Com poun d 3e
(0.30 g, 1.01 m m ol), ben zyl brom ide (0.15 m l, 1.26 m m ol) an d trieth ylam in e (0.18 m l,
1.29 m m ol) gave 0.33 g (85%) of 6l, m .p. 205 °C (subl.; CHCl3). IR: 3450 (w), 3262 (m ),
3137 (w), 3062 (w), 3027 (w), 2971 (m ), 2926 (w), 2903 (w), 2867 (w), 1660 (s), 1569 (m ),
1546 (m ), 1495 (w), 1422 (s), 1390 (m ), 1309 (s), 1181 (s), 1028 (w). 1H NMR (CF3COOD):
4.82 s, 2 H (CH2); 7.46–8.09 m , 10 H (Ph ). 13C NMR (CF3COOD): 44.5 (CH2), 123.8 (C-4),
128.9, 130.7, 131.3, 131.9, 132.1, 132.2, 132.4, 138.8 (Ph ), 167.7 (Ph CO), 170.5 (CONH2),
177.2 (C-5), 190.5 (C-3). For C18H14N2O2S3 (386.5) calculated: 55.94% C, 3.65% H, 7.25% N;
foun d: 55.87% C, 3.69% H, 7.14% N.
N-[4-Cyano-3-(methylsulfanyl)-1,2-dithiol-1-ium-5-yl]-2,2-dimethylpropanimidate (6m ). Com -
poun d 3d (0.10 g, 0.39 m m ol), m eth yl iodide (0.048 m l, 0.77 m m ol) an d trieth ylam in e
(0.108 m l, 0.77 m m ol) gave 0.04 g (36%) of 6m , m .p. 160 °C (subl.; CHCl3). IR: 2973 (m ),
2927 (w), 2869 (w), 2220 (m ), 1568 (m ), 1545 (s), 1427 (s), 1385 (m ), 1326 (s), 1286 (s),
Collect. Czech. Chem. Commun. (Vol. 68) (2003)