PAPER
Iodocyclization of N-[2-(Methylthio)phenyl]propiolamides
3037
3-Iodo-5-methyl-2-phenyl-7-(trifluoromethyl)benzo[b][1,4]thi-
azepin-4(5H)-one (2q)
White solid; mp 157.9–159.6 °C.
IR (KBr): 2916, 1643, 1339, 1128, 670 cm–1.
1H NMR (300 MHz, CDCl3): d = 7.79 (d, J = 8.0 Hz, 1 H), 7.65 (s,
1 H), 7.51–7.38 (m, 6 H), 3.60 (s, 3 H).
Acknowledgment
The authors thank the National Natural Science Foundation of Chi-
na (No 20872112), Zhejiang Provincial Natural Science Foundation
of China (Y407116), and Program for New Century Excellent Ta-
lents in University (No. NCET-06-0711) for financial support.
13C NMR (75 MHz, CDCl3): d = 166.5, 148.8, 144.7, 140.5, 139.9,
134.2, 132.0, 130.5, 129.9, 128.7, 127.4 (q, JC,F = 270.6 Hz), 122.6,
120.5, 92.0, 39.5.
19F NMR (282 MHz, CDCl3): d = –62.7 (s).
References
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LRMS (EI, 70 eV): m/z (%) = 461 (M+, 8), 334 (100), 294 (43), 129
(60).
HRMS (EI): m/z calcd for C17H11F3INOS (M+): 460.9558; found:
460.9555.
5-Methyl-2,3-diphenylbenzo[b][1,4]thiazepin-4(5H)-one (4a)
A mixture of 2a (78.6 mg, 0.2 mmol), potassium phenyltrifluoro-
borate (38.6 mg, 0.21 mmol), Pd(OAc)2 (2.5 mg, 0.01 mmol), Ph3P
(105 mg, 0.4 mmol), Cs2CO3 (195.5 mg, 0.6 mmol) in THF–H2O
(10:1; 5.5 mL) was stirred under N2 at 100 °C for 10 h. Then brine
(10 mL) was added and the aqueous phase was extracted with Et2O
(3 × 10 mL). The combined organic layers were dried (Na2SO4) and
evaporated under reduced pressure. The residue was purified by
flash column chromatography on silica gel (hexane–EtOAc) to af-
ford 4a; yield: 61.0 mg (89%); white solid; mp 156.2–158.2 °C.
IR (KBr): 3010, 2912, 1637, 1367, 743, 690 cm–1.
1H NMR (300 MHz, CDCl3): d = 7.77 (d, J = 7.8 Hz, 1 H), 7.34–
7.24 (m, 7 H), 7.15–7.06 (m, 6 H), 3.55 (s, 3 H).
13C NMR (75 MHz, CDCl3): d = 169.2, 145.0, 144.9, 138.5, 137.9,
137.4, 136.5, 132.7, 130.1, 130.0, 129.7, 128.3, 127.9, 127.8, 127.5,
125.6, 124.9, 37.4.
LRMS (EI, 70 eV): m/z (%) = 343 (M+, 20), 283 (33), 226 (100),
121 (81).
(2) For reviews, see: (a) Bariwal, J. B.; Upadhyay, K. D.;
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HRMS (EI): m/z calcd for C22H17NOS (M+): 343.1031; found:
(5) (a) Geyer, H. M.; Watzman, J. P.; Buchley, J. P. J. Pharm.
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343.1030.
5-Phenyl[1,4]thiazepino[2,3,4-de]phenanthridin-7(9H)-one (5e)
A mixture of 2e (59.5 mg, 0.1 mmol), PdCl2(PPh3)2 (4 mg, 0.005
mmol), KOAc (20 mg, 0.2 mmol) in DMF (2 mL) was stirred under
N2 at 140 °C for 14 h. Then brine (10 mL) was added and the aque-
ous phase extracted with Et2O (3 × 10 mL). The combined organic
layers were dried (Na2SO4) and evaporated under reduced pressure.
The residue was purified by flash column chromatography on silica
gel (hexane–EtOAc) to afford the desired product 5e; yield: 17.8 mg
(52%); light yellow solid; mp 210.0–212.2 °C.
IR (KBr): 2925, 1628, 1342, 1370, 761 cm–1.
1H NMR (300 MHz, CDCl3): d = 7.83–7.73 (m, 4 H), 7.61 (d,
J = 7.8 Hz, 1 H), 7.43–7.25 (m, 7 H), 6.40 (s, 1 H), 6.07 (d, J = 14.6
Hz, 1 H), 4.20 (d, J = 14.6 Hz, 1 H).
Balasubramaniyan, P.; Shaikh, A. S. Tetrahedron 1986, 42,
2731. (d) Sashida, H.; Satoh, H. Chem. Pharm. Bull. 2004,
52, 413.
13C NMR (75 MHz, CDCl3): d = 166.5, 150.7, 139.2, 137.8, 134.7,
132.3, 132.2, 131.5, 131.2, 129.9, 128.5, 128.4, 128.2, 127.8, 126.3,
126.1, 125.4, 123.7, 123.5, 45.2.
LRMS (EI, 70 eV): m/z (%) = 341 (M+, 64), 312 (71), 280 (100),
129 (49).
HRMS (EI): m/z calcd for C22H15NOS (M+): 341.0874; found:
341.0874.
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Synthesis 2009, No. 18, 3029–3038 © Thieme Stuttgart · New York