L. Yu. Ukhin et al. / Tetrahedron Letters 52 (2011) 5444–5447
5447
7.44 (s, 1H, NH2), 7.62 (t, 1H, H(6), J = 7.3 Hz), 7.66 (d, 1H, H(4),
J = 7.9 Hz), 7.79 (td, 1H, H(5), J = 7.5 Hz), 7.84 (d, 1H, H(7),
authors also thank Drs. V. Spiglasov and E. Shepelenko for the valu-
able advice.
J = 7.6 Hz) ppm; IR (neat):
mmax = 3400, 3340, 3304, 3250,
3201(NH), 1754, 1665 (CO), 1599 (aromatic C@C), 1060,
933 cmÀ1 (C–O–C). Anal. Calcd for C10H9NO3S: C, 53.80; H, 4.66;
N, 6.27; S, 14.36. Found: C, 53.86; H, 4.85; N, 6.64; S, 14.02; MS
(EI, 70 eV): m/z = 165 (M-CH2CONH2), 133 (MÀSCH2CONH2); the
product did not produce a stable molecular ion.
Supplementary data
Supplementary data (procedures and characterization data for
compounds) associated with this article can be found, in the online
General procedure for the synthesis of isoindolones 7. To a solution
of appropriate 3-acetoxyisoindolone 5 (1 mmol) in concentrated
H2SO4 (2 ml) or TFA (1 mL), thiosulfate 1 (1.0–1.1 mmol) was
added and the mixture triturated until dissolution of the starting
compounds. The reaction times and temperatures were as follows:
7a—1 h (20–25 °C); 7b—0.5 h (20–25 °C); 7c,d—1 min (at reflux),
7e–g—3 h (20–25 °C). The isoindolones were precipitated by addi-
tion of Et2O or a mixture of Et2O–iPrOH. The products were sepa-
rated, triturated with concentrated NH4OH (5 mL) and cooled
with ice until they solidified. The solid was filtered, washed with
H2O and dried.
References and notes
1. For a review, see: Distler, H. Angew. Chem., Int. Ed. Engl. 1967, 6, 544–553.
2. Bicherov, A. V.; Akopova, A. R.; Spiglazov, V. I.; Morkovnik, A. S. Russ. Chem. Bull.
Int. Ed. 2010, 59, 91–101.
3. Rambert, F.; Hermant, J.; Schweizer, D. In Comprehensive Medical Chemistry II;
Taylor, J. B., Trigge, D. J., Eds.; Elsevier, 2006; Vol. 8, p 149.
4. Al-Hamdany, R.; Al-Rawi, J. M.; Ibrahim, S. J. Prakt. Chem. 1987, 329, 126–130.
5. Wheeler, D. P.; Young, D. C.; Erley, D. S. J. Org. Chem 1957, 22, 547–556.
6. Sakulsombat, M.; Angelin, M.; Ramstrom, O. Tetrahedron Lett. 2010, 51, 75–78.
7. Mal, D.; Pahari, P. Chem. Rev. 2007, 107, 1892–1918.
8. Rathwell, K.; Brimble, M. A. Synthesis 2007, 643–662.
9. Bian, H.; Dudash, J.; Patel, M.; Rybczynski, P.; Zhang, Y. U.S. Patent 2007/
0099936 A1 2007; Chem. Abstr., 2007, 146, 484368.
10. Liebl, R.; Handtl, R. Liebigs Ann. Chem. 1985, 1092–1093.
11. Ukhin, L. Yu.; Suponitskii, K. Yu.; Belousova, L. V.; Orlova, Zh. I. Russ. Chem. Bull.
Int. Ed. 2009, 58, 2478–2487.
12. Crystallographic data (excluding structure factors) for the structure in this
paper have been deposited with the Cambridge Crystallographic Data Centre:
CCDC 816680. Copies of the data can be obtained free of charge on application
to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (fax: (+44) 1223-336-033; e-
mail: deposit@ccdc.cam.ac.uk).
13. The syntheses of the Bunte salts and acids 1a–c,e are described in Ref. 2 and
elsewhere: Haugland, R.; Kang, H., U.S. Patent, Publ. No: 20050250957; Chem.
Abstr., 2005, 143, 9187; Bretschneider, H. Monatsh. Chem. 1950, 81, 372–384;
Klayman, D. L.; Kenny, D.; Silverman, R. B.; Tomaszewski, J. E. J. Org. Chem.
1971, 36, 3681–3686; Foye, W. O.; Lanzillo, J. J.; Lowe, Y. H.; Kauffman, J. M. J.
Pharm. Sci. 1975, 64, 211–216. Compound 1d was prepared analogously to 1c,e
starting from b-piperidinoethyl chloride and sodium thiosulfate (see
Supplementary data for details).
Compound 7a: colorless crystals, mp 183–185 °C (MeCN). 1H
NMR (300 MHz, DMSO-d6): 2.53 (d, 1H, CH2, J = 14.2 Hz), 2.66 (d,
1H, CH2, J = 14.2 Hz), 6.74 (s, 1H, C(3)H), 6.88 (s, 1H, NH2), 7.22
(s, 1H, NH2), 7.27 (t, 1H, p-H of Ph, J = 7.4 Hz), 7.46 (t, 2H, m-H of
Ph, J = 7.8 Hz), 7.60–7.80 (m, 4H, C(4)H–C(7)H), 7.81 (d, 2H, o-H
of Ph, J = 7.5 Hz) ppm; IR (neat): mmax = 3408, 3288, 3238, 3187
(NH), 1686, 1630 (CO), 1620, 1600, 1494 cmÀ1 (arom.). Anal. Calcd
for C16H14N2O2S: C, 64.41; H, 4.73; N, 9.40; S, 10.74. Found: C,
64.23; H, 5.00; N, 9.63; S, 10.68; MS (EI, 70 eV): m/z = 298 (M+),
240 (MÀCH2CONH2), 208 (M-SCH2CONH2).
Acknowledgments
This work was supported by the Program of Scientific Develop-
ment of Southern Federal University (Grant No. 3-K-11-1). The