H-3Ј/H-5Ј, H-4), 7.47 (2 H, d, J 8.8, H-2Ј/H-6Ј), 7.90 (1 H, d,
J 7.5, H-6), 11.20 (1 H, s, NH) and 13.28 (1 H, br s, CO2H );
δC(75 MHz; DMSO-d6; Me4Si) 26.2 (COMe), 117.4 (C-2Ј/C-6Ј),
125.7 (C-5), 127.2 (C-4Ј), 127.4 (C-3), 128.8 (C-1), 129.6 (C-3Ј/
(C-4Ј), 126.9 (C-5), 129.7 (C-3Ј/C-5Ј), 130.4 (C-3a), 132.7
(C᎐N), 136.3 (C-6), 141.5 (C-4Ј), 141.6 (C-7a), 142.9 (C-1Ј) and
᎐
183.7 (C᎐O); m/z (EI) 288.013677 (C H9 Cl N2 O S requires
᎐
14
288.012413), 288 (Mϩ, 100%), 271 (7), 259 (6), 225 (5), 197 (6),
177 (3), 162 (66), 149 (6), 134 (26) and 121 (13).
C-5Ј), 131.8 (C-6), 132.4 (C᎐N), 133.0 (C-4), 137.0 (C-2), 142.2
᎐
(C-1Ј), 168.3 (CO2 H) and 193.4 (COMe); m/z (EI) 348.031462
(C16 H13 Cl N2 O3 S requires 348.033516), 348 ( Mϩ, 36%), 271
(8), 305 (2), 287 (2), 247 (8), 229 (5), 194 (11), 152 (100), 126 (61)
and 99 (31).
Collection of X-ray diffraction data and the structure analysis of
3b
Orange plate crystals of 3b were grown by allowing a saturated
solution of 3b in chloroform–methanol (10 : 1, v/v) to evaporate
slowly at room temperature over 6–7 days. Crystal dimensions
of the thin plate were about 0.27 × 0.24 × 0.05 mm, producing
problems with the absorption correction which is apparent in
the ADPs (anisotropic displacement parameters) displayed in
Fig. 1. The crystal data were collected with a Siemens SMART
CCD diffractometer [graphite monochromator] operating in
the omega scan mode (0.3Њ). The data were reduced with the
Siemens–Bruker program suite XSCANS,14 and the structure
was solved by the direct method using SHELXTL PLUS pro-
grams.15 All non-hydrogen atoms were refined anisotropically
by a full-matrix, least-squares procedure based on F 2 using all
unique data. GOF = 0.935, residual electron density between
0.482 and Ϫ0.379 e ÅϪ3. The hydrogen atoms were located from
the difference Fourier electron density synthesis and were then
refined isotropically using a ‘riding model’.
1-Benzothiophene-2,3-dione 2-(N-phenylhydrazone) 3a
To a mixture of 1,1Ј-carbonyldiimidazole (2.0 g, 12.5 mmol)
and compound 2a (3.1 g, 10 mmol) was added dry tetra-
hydrofuran (50 cm3), and the resulting solution was stirred at rt
for 1–2 h. The solvent was then removed in vacuo and the resi-
due was immediately treated with water (40 cm3) and extracted
with chloroform (2 × 40 cm3). The combined organic extracts
were dried (Na2SO4), the solvent chloroform was evaporated
and the residual solid product was recrystallized from CHCl3–
petroleum ether (bp 40–60 ЊC). Yield 1.9 g (74%); mp 194–195
ЊC (Lit.10 194 ЊC) (Found: C, 65.9; H,3.9; N, 11.1; S, 12.5.
C14H10N2OS requires C, 66.1; H, 4.0; N, 11.0; S, 12.6%);
νmax(KBr)/cmϪ1 3217, 3180, 1656, 1586, 1488, 1445, 1264, 1223,
1107 and 1062; δH(300 MHz; DMSO-d6; Me4Si) 6.99 (1 H, m,
H-4Ј), 7.34 (5 H, m, H-2Ј/H-6Ј, H-3Ј/H-5Ј, H-5), 7.67 (1 H, dd,
J 6.9 and 7.2, H-6), 7.75 (1 H, d, J 6.9, H-7), 7.78 (1 H, d, J 6.8,
H-4) and 10.89 (1 H, s, NH); δC(75 MHz; DMSO-d6; Me4Si)
115.3 (C-2Ј/C-6Ј), 123.2 (C-4Ј), 125.7 (C-4), 126.4 (C-7), 126.8
Acknowledgements
(C-5), 129.8 (C-3Ј/C5Ј), 130.5 (C-3a), 131.9 (C᎐N), 136.2 (C-6),
᎐
We wish to thank the Advanced Pharmaceutical Industries
Co. Ltd., Amman – Jordan for financial support.
141.7 (C-7a), 143.8 (C-1Ј) and 183.8 (C᎐O); m/z (EI)
᎐
254.052626 (C14 H10 N2 O S requires 254.051385), 254 (Mϩ,
100%), 237 (7), 225 (14), 197 (8), 167 (23), 162 (36), 149 (94),
134 (18) and 121 (16).
References
1-Benzothiophene-2,3-dione 2-[N-(4-methylphenyl)hydrazone]
3b
1 B. A. Abu Thaher, J. A. Zahra and M. M. El-Abadelah,
J. Heterocycl. Chem., 2002, 39, 901.
2 P. Trimarco and C. Lastrucci, J. Heterocycl. Chem., 1976, 13, 913.
3 (a) R. N. Butler and F. L. Scott, Chem. Ind. (London), 1970,
1216; (b) H. Ulrich, in The Chemistry of Imidoyl Halides,
Plenum Press, New York, 1968, Chapter 7, pp. 174–192; (c) A. F.
Hegarty, J. B. Aylward and F. L. Scott, J. Chem. Soc. C, 1967, 2587;
(d ) P. Dalla Corce, P. Del Buttero, E. Licandro and S. Maiorana,
Synthesis, 1979, 299; (e) G. Heubach, Liebigs Ann. Chem., 1980,
1376; ( f ) H. M. Hassaneen, H. A. H. Mousa and N. M. Abed,
Heterocycles, 1988, 27, 695; (g) T. Benincori and F. Sannicoló,
J. Org. Chem., 1988, 53, 1309.
4 (a) V. A. Galishev, V. N. Chistokletov and A. A. Petrov, Zh. Obshch.
Khim., 1975, 45, 1695; (b) A. S. Shawali and C. Párkányi,
J. Heterocycl. Chem., 1980, 17, 833.
5 M. M. El-Abadelah, A. Q. Hussein and B. A. Abu Thaher,
Heterocycles, 1991, 32, 1879.
6 N. F. Eweiss and A. Osman, J. Heterocycl. Chem., 1980, 17, 1713.
7 R. Fusco and R. Romani, Gazz. Chim. Ital., 1946, 76, 419.
8 (a) R. R. Phillips, Org. React., 1959, 10, 143; (b) H. C. Yao and
P. Resnick, J. Am. Chem. Soc., 1962, 84, 3514.
9 G. C. Barrett, M. M. El-Abadelah and M. K. Hargreaves, J. Chem.
Soc. C, 1970, 1986.
This compound was prepared from 2b (3.3 g, 10 mmol) and
1,1Ј-carbonyldiimidazole (2.0 g, 12.5 mmol) by following the
same procedure and experimental conditions described above
for 3a. Yield 2.0 g (75%); mp 198–200 ЊC (Lit.12 198 ЊC) (Found:
C, 67.2; H, 4.4; N, 10.3; S, 11.8. C15H12N2OS requires C, 67.1;
H, 4.5; N, 10.4; S, 11.95%); νmax(KBr)/cmϪ1 3226, 3183, 1659,
1600, 1498, 1262 and 1098; δH(300 MHz; DMSO-d6; Me4Si)
2.23 (3 H, s, Me), 7.13 (2 H, d, J 8.3, H-3Ј/H-5Ј), 7.26 (2 H, d,
J 8.3, H-2Ј/H-6Ј), 7.36 (1 H, dd, J 7.8 and 7.1, H-5), 7.67 (1 H,
dd, J 7.1 and 8.0, H-6), 7.74 (1 H, d, J 8.0, H-7), 7.77 (1 H, d,
J 7.8, H-4) and 10.82 (1 H, s, NH); δC(75 MHz; DMSO-d6;
Me4Si) 20.9 (Me), 115.3 (C-2Ј/C-6Ј), 125.6 (C-7), 126.3 (C-4),
126.7 (C-5), 130.3 (C-3Ј/C-5Ј), 130.7 (C-3a), 131.3 (C᎐N), 132.3
᎐
(C-1Ј), 136.0 (C-6), 141.5 (C-4Ј), 141.6 (C-7a) and 183.6 (C᎐O);
᎐
m/z (EI) 268.068604 (C15 H12 N2 O S requires 268.067035), 268
(Mϩ, 100%), 251 (10), 239 (9), 197 (5), 167 (19), 162 (39), 149
(63), 134 (18), and 121 (10).
10 K. Auwers and K. Müller, Justus Liebigs Ann. Chem., 1911, 381,
1-Benzothiophene-2,3-dione 2-[N-(4-chlorophenyl)hydrazone] 3c
276.
11 C. H. Yoder, R. C. Barth, W. M. Richter and F. A. Snavely,
J. Org. Chem., 1972, 25, 4121.
12 V. A. Bren’, M. I. Knyazhanskii, A. É. Lyubarskaya, V. S.
Orekhovskii, G. D. Palui, V. P. Rybalkin and Kh. A. Kurdanov,
Izv. Sev. Kavk. Nauchn. Tsentra Vyssh. Shk. Estestv. Nauki, 1984, 63
(Chem. Abstr., 1985, 103, 53899b).
13 V. P. Rybalkin, N. I. Makarova, A. É. Lyubarskaya, V. A. Bren’ and
V. I. Minkin, Zh. Org. Khim., 1990, 26, 335 (Chem. Abstr., 1990, 113,
77450f).
14 Bruker AXS SADABS program multiscan V2.03.
15 G. M. Sheldrick, SHELXTL PLUS System of computer programs
for the determination of crystal structure from the X-Ray diffraction
data, Vers.5.10.DOS/WIN 95/NT.
This compound was prepared from 2c (3.5 g, 10 mmol) and
1,1Ј-carbonyldiimidazole (2.0 g, 12.5 mmol) by following the
same procedure and experimental conditions described above
for 3a. Yield 2.4 g (82%); mp 241–243 ЊC (Found: C, 58.1; H,
3.1; Cl, 12.1; N, 9.6; S, 10.9. C14H9ClN2OS requires C, 58.2; H,
3.1; Cl, 12.3; N, 9.7; S, 11.1%); νmax(KBr)/cmϪ1 3218, 3183,
1659, 1537, 1483, 1262, 1220, 1084 and 1062; δH(300 MHz;
DMSO-d6; Me4Si) 7.37 (5 H, m, H-2Ј/H-6Ј, H-3Ј/H-5Ј, H-5),
7.68 (1 H, dd, J 7.3 and 7.7, H-6), 7.75 (1 H, d, J 7.7, H-7), 7.78
(1 H, d, J 7.5, H-4) and 10.94 (1 H, s, NH); δC(75 MHz; DMSO-
d6; Me4Si) 116.8 (C-2Ј/C-6Ј), 125.7 (C-7), 126.5 (C-4), 126.7
O r g . B i o m o l . C h e m . , 2 0 0 3 , 1, 8 2 2 – 8 2 5
825