6.85–6.77 (m, 4H, ArH), 6.50 (d, J(P,H) = 7 Hz, 2H, ArH),
5.29 (d, J(P,H) = 18 Hz, 1H, NH) ppm. 13C NMR (CDCl3, d),
133.2, 132.7, 132.0 (d, 3J(P,C) = 14 Hz), 129.7, 128.7, 128.3 (d,
J(P,C) = 14 Hz), 127.8, 120.8 (d, 3J(P,C) = 11 Hz), 111.2 (d,
2e. 460 mg as slightly pink white solid in 98% yield. Mp
198–199 1C. Selected IR (KBr, cmꢀ1): 3168 (vs, NH), 1617(m),
1599(m), 1505(s), 1433(s), 1362(s), 1220(m), 1102(m), 956(m),
815(s), 748(vs), 694(m), 574(m, PQSe). 1H NMR (acetone-d6, d),
8.09–690 (m, 12H, ArH), 2.05 (s, 2H, NH) ppm. 13C NMR
(acetone-d6, d), 144.1, 134.2, 136.1, 129.1, 128.4, 127.8, 127.6,
127.2, 126.6, 126.2, 125.3, 124.7, 123.7, 118.5 ppm. 31P NMR
(acetone-d6, d), 82.5 (s, J(P,Seexo) = 810 Hz) ppm. 77Se NMR
(acetone-d6, d), ꢀ193.5 (d, J(P,Seexo) = 810 Hz). MS (CI+,
4
4J(P,C) = 8 Hz), 110.5 (d, J(P,C) = 8 Hz) ppm. 31P NMR
(CDCl3, d), 75.5 (s, J(P,Seexo) = 842 Hz) ppm. 77Se NMR
(CDCl3, d), ꢀ115.7 (d, J(P,Seexo) = 842 Hz) ppm. MS
(CI+, m/z): 371 [M + H]+. Accurate mass measurement
(EIMS): 370.0133, calculated mass for C18H15N2PSe:
370.0133.
m/z): 470 [M
+
H]+. Anal. calcd for C26H19N2PSe
(469.38): C, 66.5; H, 4.1; N, 6.0%. Found: C, 66.1; H, 4.4;
N, 6.3%.
2b. 306 mg as white solid in 65% yield. Mp 211–212 1C.
Selected IR (KBr, cmꢀ1): 3056(w), 3017(w), 2892(w), 2843(w),
1595(m), 1492(vs), 1435(m), 1383(m), 1283(s), 1134(s),
1098(m), 1044(m), 911(m), 864(m), 735(s), 718(m), 688(m),
562(s, PQSe). 1H NMR (CDCl3, d), 7.83 (dd, J(H,H) =
7.2 Hz, 3J(P,H) = 15.3 Hz, 2H, ArH), 7.46 (m, J(H,H) =
7.2 Hz, 3H, ArH), 7.39–7.7.15 (m, 10H, ArH), 6.69 (dd,
J(H,H) = 7.2 Hz, 2H, ArH), 6.54 (d, J(H,H) = 7.2 Hz, 2H,
ArH), 4.68 (d, 3J(P,H) = 15.8 Hz, 4H, NCH2) ppm. 13C NMR
(CDCl3, d), 136.4 (J(P,C) = 3.1 Hz), 136.3 (d, J(P,C) =
106 Hz), 135.9, 135.7, 132.7, 132.0 (d, 3J(P,C) = 14.5 Hz),
128.5, 128.4, 128.2, 127.4, 127.4, 120.1, 109.4 (d, J(P,C) = 6.2 Hz),
4a. A toluene (10 cmꢀ3) refluxing mixture of 2-amino-
benzenethiol (0.12 g, 1.0 mmol) and WR (0.54 g, 1.0 mmol)
was carried out for 7 h. The red suspension disappeared and a
black red suspension was formed. The mixture was dried
in vacuo to remove toluene and the residue was dissolved in
dichloromethane. The unique compound 7a (160 mg, white
solid) was obtained after fresh chromatographic purification
(silica gel, dichloromethane as eluent) and crystallization from
dichloromethane–hexane in 52% yield. Mp: 160–162 1C.
Selected IR (KBr, cmꢀ1): 3211(s), 1579(m), 1470(s), 1454(m),
1438(m), 1368(s), 1293(m), 1260(m), 1096(s), 892(s), 743(vs),
687(m), 555(s), 489(m). 1H NMR (CD2Cl2, d), 8.08–7.98
(m, 2H, ArH), 7.57–7.43 (m, 3H, ArH), 7.23–7.20
(m, J(H,H) = 8.2 Hz, 1H, ArH), 7.13–7.06 (m, J(H,H) =
8.2 Hz, 1H, ArH), 6.93–6.87 (m, J(H,H) = 8.2 Hz, 2H, ArH),
5.68 (d, 2J(P,H) = 13.5 Hz, 1H, NH) ppm. 13C NMR
3
46.4 (d, J(P,C) = 7.3 Hz) ppm. 31P NMR (CDCl3, d), 84.7
(s, J(P,Seexo) = 842 Hz) ppm. 77Se NMR (CDCl3, d), ꢀ188.7
(d, J(P,Seexo
)
= 842 Hz) ppm. MS (ES+, m/z): 497
[M + Na]+. Accurate mass measurement (EIMS): 470.0785,
calculated mass for C26H23N2P76Se: 470.0786.
2c. 250 mg as milky white solid in 67% yield. Mp
195–197 1C. Selected IR (KBr, cmꢀ1): 3248(vs, NH),
1589(vs), 1359(s), 1107(m), 1057(s), 908(s), 809(s), 748(s),
683(s), 607(m, PQSe). 1H NMR (CDCl3, d), 8.12 (m,
J(H,H) = 7 Hz, 2H, ArH), 7.65–7.53 (m, 11H, ArH), 7.01
(d, J(H,H) = 7 Hz, 2H, ArH), 6.28 (d, J(P,H) = 13 Hz, 2H,
NH) ppm. 13C NMR (CDCl3, d), 139.1 (d, 1J(P,C) = 107 Hz),
1
4
(CD2Cl2, d), 138.7 (d, J(P,C) = 93.4 Hz), 132.7 (d, J(P,C) =
3.1 Hz), 131.2 (d, 2J(P,C) = 14.5 Hz), 128.4 (d, 2J(P,C) =
15.6 Hz), 126.7, 124.2 (d, 3J(P,C) = 6.2 Hz), 121.8, 113.0,
112.9 ppm. 31P NMR (CD2Cl2, d), 74.4 (s, J(P,Seexo) =
840 Hz) ppm. 77Se NMR (CD2Cl2, d), ꢀ32.5 (d, J(P,Seexo) =
842 Hz) ppm. Mass spectrum (EI+): m/z 311 [M]+, 231
2
3
Se]+, 154 [M
ꢀ
C6H5Se]+. Anal. calcd for
136.2, 135.9 (d, J(P,C) = 52 Hz), 132.1, 130.6 (d, J(P,C) =
13 Hz), 128.8 (d, 3J(P,C) = 15 Hz), 127.4, 121.5, 111.9
(d, 4J(P,C) = 7 Hz) ppm, 31P NMR (CDCl3, d), 40.5 (s,
J(P,Seexo) = 817 Hz) ppm. 77Se NMR (CDCl3, d), ꢀ182.1
(d, J(P,Seexo) = 820 Hz) ppm. MS (CI+, m/z): 373 [M + H]+.
Anal. calcd for C18H17N2PSe (372.03): C, 58.1; H, 4.6; N,
7.5%. Found: C, 58.4; H, 4.7; N, 7.3%.
[M
ꢀ
C12H10NPSSe: C, 46.5; H, 3.3; N, 4.5%. Found: C, 46.7; H,
3.1; N, 4.7%.
4b. A mixture of 4-methyl-1,2-benzenedithiol (66.0 mg,
0.5 mmol) and WR (270 mg, 0.5 mmol) in toluene (20 cmꢀ3
)
was refluxed for 7 h. The red suspension disappeared and a
reddish yellow solution was formed. Upon cooling to RT, the
mixture was dried in vacuo. The residue was dissolved in
dichloromethane and was purified by column chromatography
(silica gel, dichloromethane as eluent) to afford compound 7b
(100 mg) as greenish yellow paste in 59% yield. Mp:
150–151 1C. Selected IR (KBr, cmꢀ1): 3215(m), 2935(m),
1576(m), 1472(s), 1439(m), 1366(s), 1294(m), 1096(s), 895(s),
742(vs), 685(m), 554(s), 490(m). 1H NMR (CD2Cl2, d),
8.20–8.10 (m, 2H, ArH), 7.54–7.43 (m, 3H, ArH), 7.27–7.20
2d. 402 mg as white solid in 96% yield. Mp 201–203 1C. The
NMR spectra of 31P and 77Se showed that the product is a
mixture of two diastereoisomers. Selected IR (KBr, cmꢀ1):
3168(s, NH), 1493(m), 1434(s), 1365(s), 1285(m), 1229(m),
1
1102(s), 753(s), 690(m), 584(m, PQSe). H NMR (CD2Cl2, d),
8.00–7.73 (2ꢃ m, 10H, ArH), 7.56–7.17 (2ꢃ m, 20H, ArH),
6.89 (2ꢃ d, J(P,H) = 8.6 Hz, 4H, NH) ppm. 13C NMR
(CD2Cl2, 25 1C, d), 136.2, 133.0, 132.5, 132.1, 131.9, 131.7,
129.5, 129.3, 129.0, 128.7, 128.3, 128.1, 127.9, 127.0, 126.7,
126.5, 126.1, 125.8, 125.5, 125.2, 124.9, 124.5, 124.4 ppm. 31P
NMR (CD2Cl2, d), 83.5 (s, J(P,Se) = 805 Hz) ppm; 84.5
(s, J(P,Se) = 805 Hz) ppm. 77Se NMR (CD2Cl2, d), ꢀ207.0 (d,
J(P,Seexo) = 805 Hz) ppm; ꢀ209.8 (d, J(P,Seexo) = 805 Hz)
ppm. Mass spectrum (EI+): m/z 420 [M + H]+, 217
[M ꢀ C6H6NPSe]+. Anal. calcd for C22H17N2PSe: C, 63.0;
H, 4.1; N, 6.7%. Found: C, 63.3; H, 3.8; N, 6.6%.
(m, 2H, AeH), 7.02–6.99 (m, 1H, ArH), 2.29 (s, 3H, CH3). 13
C
NMR (CD2Cl2, d), 138.2, 136.7, 135.8, 135.6, 133.0, 132.9,
131.0 (d, 2J(P,C) = 13.5 Hz), 128.7, 128.6, 128.5, 126.2
3
3
(d, J(P,C) = 8.3 Hz), 125.4 (d, J(P,C) = 8.3 Hz), 20.9 ppm.
31P NMR (CD2Cl2, d), 71.3 (s, J(P,Seexo) = 836 Hz) ppm.
77Se NMR (CD2Cl2, d), ꢀ34.6 (d, J(P,Seexo) = 835 Hz)
ppm. Mass spectrum (EI+): m/z 342 [M]+, 294 [M ꢀ Se]+.
ꢁc
This journal is The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2010 New J. Chem., 2010, 34, 1565–1571 | 1569