5
N-(Methyl(oxo)(phenyl)-λ6-sulfanylidene)benzenesulfonamide
(2d): White solid in 67% yield; m.p.: 91-92 °C; 1H NMR (400
MHz, CDCl3) δ: 8.05-7.92 (m, 4H), 7.74-7.68 (m, 1H), 7.63-7.56
CDCl3) δ: 7.82-7.77 (m, 2H), 7.66-7.62 (m, 2H), 7.51-7.41 (m,
ACCEPTED MANUSCRIPT
3H), 7.39-7.30 (m, 3H), 2.81 (s, 3H); 13C NMR (100 MHz,
CDCl3) δ: 144.0, 135.7, 132.5, 131.3, 130.0, 128.7, 126.1, 125.8,
39.0; IR (KBr, cm-1): 3012.6, 2919.2, 1445.5, 1283.1, 754.8;
HRMS (EI-TOF) m/z: M+ Calcd for C13H13NO2S2 279.0388;
Found 279.0389.
N-(Tert-butyl(methyl)-λ4-sulfanylidene)benzenesulfonamide
(4d): White solid in 63% yield; m.p.: 55.6-55.9 °C; 1H NMR (400
MHz, CDCl3) δ: 7.92-7.87 (m, 2H), 7.56-7.45 (m, 3H), 1.22 (s,
9H), 0.07 (s, 3H); 13C NMR (100 MHz, CDCl3) δ: 143.5, 132.3,
129.0, 127.1, 54.8, 30.3, 1.2. IR (KBr, cm-1): 3290.4, 2980.1,
1315.1, 1148.4, 603.4; HRMS (EI-TOF) m/z: M+ Calcd for
C11H17NO2S2 259.0701; Found 259.0702.
(m, 2H), 7.54-7.50 (m, 1H), 7.48-7.43 (m, 2H), 3.43 (s, 3H); 13
C
NMR (100 MHz, CDCl3) δ: 143.5, 138.4, 134.6, 132.4, 129.9,
128.8, 127.6, 126.7, 46.8. IR (KBr, cm-1): 3025.8, 2929.2, 1449.4,
1239.1, 745.0, 509.2; HRMS (EI-TOF) m/z: M+ Calcd for
C13H13NO3S2 295.0337; Found 295.0338.
N-((4-acetylphenyl)(methyl)(oxo)- λ6 -sulfanylidene)
benzenesulfonamide (2e): White solid in 32% yield; m.p.: 138.5-
139.2 °C; 1H NMR (400 MHz, CDCl3) δ: 8.13 (d, J = 2.0 Hz, 4H),
7.95 (dt, J = 7.3, 1.4 Hz, 2H), 7.57-7.50 (m, 1H), 7.46 (dd, J =
8.3, 6.6 Hz, 2H), 3.42 (s, 3H), 2.66 (s, 3H); 13C NMR (101 MHz,
CDCl3) δ: 196.5, 143.2, 142.3, 141.5, 132.5, 129.5, 128.9, 128.1,
126.7, 46.5, 27.1; IR (KBr, cm-1): 2996.0, 2915.9, 1685.8, 1397.7,
1232.4, 731.4, 609.7; HRMS (EI-TOF) m/z: M+ Calcd for
C15H15NO4S2 337.0442; Found 337.0446.
N-((4-acetylphenyl)(methyl)-λ4-sulfanylidene)
benzenesulfonamide (4e): White solid in 59% yield; m.p.:
107.4-107.6 °C; H NMR (400 MHz, CDCl3) δ : 8.01-7.97 (m,
1
2H), 7.83-7.79 (m, 2H), 7.79 -7.75 (m, 2H), 7.43-7.38 (m, 1H),
7.38-7.33 (m, 2H), 2.86 (s, 3H), 2.58 (s, 3H); 13C NMR (101
MHz, CDCl3) δ: 196.7, 143.8, 140.6, 140.0, 131.6, 129.6, 128.8,
126.1 (d, J = 5.9 Hz), 38.9, 26.9; IR (KBr, cm-1): 3002.8, 2919.9,
1689.5, 1362.8, 1285.0, 962.7, 830.2, 760.0; HRMS (EI-TOF)
m/z: M+ Calcd for C15H15NO3S2 321.0493; Found 321.0496.
4-Methyl-N-(methyl(oxo)(phenyl)-λ6-
sulfanylidene)benzenesulfonamide (2g): White solid in 45%
yield; m.p.: 102°C; 1H NMR (400 MHz, CDCl3) δ: 8.03-7.98 (m,
2H), 7.88-7.81 (m, 2H), 7.73-7.66 (m, 1H), 7.62-7.57 (m, 2H),
7.27-7.23 (m, 2H), 3.42 (s, 3H), 2.39 (s, 3H); 13C NMR (100
MHz, CDCl3) δ: 143.0, 140.7, 138.5, 134.5, 129.8, 129.4, 127.6,
126.8, 46.8, 21.6.
Methyl-2-(S-methyl-N-
(phenylsulfonyl)sulfinimidoyl)benzoate (4f): White solid in
Fluoro-N-(methyl(oxo)(phenyl)-λ6-
44% yield; m.p.: 148.8-150.3 °C; 1H NMR (400 MHz, CDCl3) δ:
sulfanylidene)benzenesulfonamide (2h): White solid in 70%
yield; m.p.: 123.4-125.6 °C; 1H NMR (400 MHz, CDCl3) δ: 8.03-
7.95 (m, 4H), 7.75-7.67 (m, 1H), 7.65-7.58 (m, 2H), 7.16-7.08
(m, 2H), 3.44 (s, 3H); 13C NMR (100 MHz, CDCl3) δ: 164.9 (d, J
= 253.6 Hz), 139.7 (d, J = 3.2 Hz), 138.3, 134.7, 129.9, 129.5 (d,
J = 9.3 Hz), 127.6, 115.9 (d, J = 22.6 Hz), 46.8; 19F NMR (376
MHz, CDCl3) δ: -106.32 (s, 1F). IR (KBr, cm-1): 3070.3, 3958.1,
1704.3, 1156.6, 1022.9, 688.2; HRMS (EI-TOF) m/z: M+ Calcd
for C13H12FNO3S2 313.0243; Found 313.0246.
8.50 (dd, J = 8.1, 1.2 Hz, 1H), 8.09 (dd, J = 7.7, 1.5 Hz, 1H),
7.90-7.85 (m, 2H), 7.76 (td, J = 7.8, 1.4 Hz, 1H), 7.60 (td, J = 7.6,
1.3 Hz, 1H), 7.44-7.36 (m, 3H), 3.96 (s, 3H), 2.91 (s, 3H); 13C
NMR (101 MHz, CDCl3) δ: 165.9, 144.4, 140.1, 134.7, 131.8,
131.3 (d, J = 3.6 Hz), 128.8, 127.4, 126.6, 126.3, 53.3, 40.1; IR
(KBr, cm-1): 3037.5, 2955.0, 2360.4, 1711.4, 1284.3, 1140.0,
950.0, 755.7; HRMS (EI-TOF) m/z: M+ Calcd for C15H15NO4S2
337.0442; Found 337.0445.
N-(3-(S-methyl-N-
4-Chloro-N-(methyl(oxo)(phenyl)-λ6-
(phenylsulfonyl)sulfinimidoyl)phenyl)acetamide(4g):
Colorless oil in 38% yield; 1H NMR (400 MHz, CDCl3) δ: 8.79 (s,
1H), 8.02 (t, J = 1.6 Hz, 1H), 7.88 (dd, J = 7.9, 1.5 Hz, 2H), 7.74
(d, J = 2.7 Hz, 1H), 7.47-7.39 (m, 3H), 7.33-7.30 (m, 2H), 2.81 (s,
3H), 2.16 (s, 3H); 13C NMR (101 MHz, CDCl3) δ: 169.9, 143.6,
140.4, 136.0, 131.8, 130.5, 129.0, 126.3, 123.8, 120.5, 116.6,
77.2, 38.3, 29.8; IR (KBr, cm-1): 3318.7, 3065.8, 2924.9 , 1689.8,
1592.2, 1278.5, 1141.5, 950.0, 751.9; HRMS (EI-TOF) m/z: M+
Calcd for C15H16N2O3S2 336.0602; Found 336.0601.
sulfanylidene)benzenesulfonamide (2i): White solid in 72%
yield; m.p.: 113.8-115.9 °C; 1H NMR (400 MHz, CDCl3) δ: 8.03-
7.98 (m, 2H), 7.93-7.87 (m, 2H), 7.75-7.68 (m, 1H), 7.65-7.57
(m, 2H), 7.46-7.40 (m, 2H), 3.44 (s, 3H); 13C NMR (100 MHz,
CDCl3) δ: 142.1, 138.7, 138.2, 134.7, 130.0, 129.1, 128.3, 127.6,
46.9. IR (KBr, cm-1): 3021.0, 2918.8, 1582.4, 1320.3, 1054.0,
766.4, 531.6; HRMS (EI-TOF) m/z: M+ Calcd for
C13H12ClNO3S2 328.9947; Found 328.9946.
N-(Methyl(oxo)(phenyl)-λ6-sulfanylidene)-4-
N-((4-chlorophenyl)(cyanomethyl)-λ4-
nitrobenzenesulfonamide (2j): White solid in 69% yield; m.p.:
sulfanylidene)benzenesulfonamide (4h): White solid in 33%
1
1
148-151 °C; H NMR (400 MHz, CDCl3) δ: 8.34-8.29 (m, 2H),
yield; m.p.: 113.9-115.3 °C; H NMR (400 MHz, CDCl3) δ: 7.89
8.19-8.13 (m, 2H), 8.03-8.01 (m, 2H), 7.78-7.73 (m, 1H), 7.68-
7.63 (m, 2H), 3.47 (s, 3H); 13C NMR (100 MHz, CDCl3) δ: 149.9,
149.1, 138.0, 135.0, 130.1, 128.2, 127.5, 124.2, 47.1.
4-Methyl-N-(oxodiphenyl-λ6-
-7.84 (m, 2H), 7.83-7.78 (m, 2H), 7.58-7.53 (m, 2H), 7.52-7.47
(m, 1H), 7.44 (dd, J = 8.3, 6.5 Hz, 2H), 4.08 (d, J = 2.8 Hz, 2H);
13C NMR (101 MHz, CDCl3) δ: 143.0, 141.1, 132.3, 130.9, 129.8,
129.1, 128.3, 126.3, 110.0, 77.2, 43.0; IR (KBr, cm-1): 3058.0,
2922.1, 2253.0, 1471.8, 1302.1, 1152.9, 820.2, 747.8; HRMS
(EI-TOF) m/z: M+ Calcd for C14H11ClN2O2S2 337.995; Found
337.997.
sulfanylidene)benzenesulfonamide (2k): White solid in 57%
1
yield; m.p.: 142.5-143.0 °C ; H NMR (400 MHz, CDCl3) δ:
8.05-7.98 (m, 4H), 7.86-7.82 (m, 2H), 7.61-7.55 (m, 2H), 7.53-
7.45 (m, 4H), 7.24-7.20 (m, 2H), 2.38 (s, 3H); 13C NMR (100
MHz, CDCl3) δ: 142.9, 141.0, 139.9, 133.9, 129.7, 129.3, 127.9,
126.8, 21.6.
N-((4-hydroxyphenyl)(methyl)-λ4-sulfanylidene)
benzenesulfonamide (4i): White solid in 22% yield; m.p.: 146.6-
1
148.1 °C; H NMR (400 MHz, CDCl3) δ: 7.91-7.86 (m, 2H),
7.52-7.41 (m, 5H), 6.91 (d, J = 8.4 Hz, 2H), 2.77 (s, 3H); 13C
NMR (101 MHz, CDCl3) δ: 161.5, 143.6, 131.8, 129.0, 128.4,
126.3, 124.8, 117.6, 38.2; IR (KBr, cm-1): 3288.7, 2925.1, 1580.2,
1287.6, 1146.9, 841.5, 590.0; HRMS (EI-TOF) m/z: M+ Calcd
for C13H13NO3S2 295.0337; Found 295.0340.
N-(Dimethyl-λ4-sulfanylidene)benzenesulfonamide
(4a):
White solid in 37% yield; m.p.: 129-131 °C; 1H NMR (400 MHz,
CDCl3) δ: 7.88-7.80 (m, 2H), 7.49-7.38 (m, 3H), 2.65 (s, 6H); 13
NMR (100 MHz, CDCl3) δ: 144.1, 131.5, 128.8, 126.2, 35.9.
C
N-(Diphenyl-λ4-sulfanylidene)benzenesulfonamide
(4b):
4-Methyl-N-(methyl(phenyl)-λ4-
White solid in 65% yield; m.p.: 126-127 °C; 1H NMR (400 MHz,
CDCl3) δ: 7.90-7.80 (m, 2H), 7.65-7.55 (m, 4H), 7.53-7.29 (m,
9H); 13C NMR (100 MHz, CDCl3) δ: 144.2, 136.4, 132.5, 131.3,
130.0, 128.7, 127.3, 126.3.
sulfanylidene)benzenesulfonamide (4j): White solid in 92%
yield; m.p.: 130 °C; 1H NMR (400 MHz, CDCl3) δ: 7.76-7.62 (m,
4H), 7.54-7.41 (m, 3H), 7.16-7.10 (m, 2H), 2.82 (s, 3H), 2.32 (s,
3H); 13C NMR (100 MHz, CDCl3) δ: 141.8, 141.2, 136.0, 132.5,
130.0, 129.3, 126.3, 125.9, 39.1, 21.5.
N-(Methyl(phenyl)-λ4-sulfanylidene)benzenesulfonamide (4c):
White solid in 79% yield; m.p.: 107-110 °C; 1H NMR (400 MHz,