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Synlett 2009(13): 2146-2148  
DOI: 10.1055/s-0029-1217548
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

A Novel Multicomponent Method for the Synthesis of 2-Thioxo-1,3-thiazolidin-4-ones

Abdolali Alizadeh*, Nasrin Zohreh
Department of Chemistry, Tarbiat Modares University, P.O. Box 14115-175, Tehran 18716, Iran
Fax: +98(21)88006544; e-Mail: abdol_alizad@yahoo.com; e-Mail: aalizadeh@modares.ac.ir;
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Publication History

Received 9 April 2009
Publication Date:
10 July 2009 (online)

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Abstract

An easy, highly efficient and simple one-pot approach to the synthesis of 2-thioxo-1,3-thiazolidin-4-ones is reported. The ­reaction of a primary amine and carbon disulfide in the presence of fumaryl chloride in water afforded the title compounds in good yield.

Key words

thiazolidine - rhodanine - carbon disulfide - fumaryl chloride - multicomponent reaction

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To a magnetically stirred mixture of benzylamine (0.11 g, 1 mmol) and H2O (3 mL as solvent), was added CS2 (0.15 g, 2 mmol). Then, fumaryl chloride (0.15 g, 1 mmol) was added and the reaction mixture was allowed to stir for 12 h. The reaction was extracted with CH2Cl2 (2 × 8 mL), and the solvent was dried and evaporated. The residue was purified by column chromatography (n-hexane-EtOAc, 4:1) to obtain product 8a as a yellow wax (0.24 g, 85%). IR (KBr): 3451-2625 (OH), 1718 (CO2H), 1671 (CO), 1343 and 1186 (C=S) cm-¹. ¹H NMR (500.1 MHz, CDCl3): δ = 3.04 (1 H, dd, ² J H,H = 18.0 Hz, ³ J H,H = 9.0 Hz, CHCH 2), 3.60 (1 H, dd, ² J H,H = 18.0 Hz, ³ J H,H = 3.5 Hz, CHCH 2), 4.45 (1 H, dd, ³ J H,H = 8.9 Hz, ³ J H,H = 3.5 Hz, CHCH2), 5.15 (1 H, d, ³ J H,H = 14.2 Hz, CH 2Ph), 5.24 (1 H, d, ³ J H,H = 14.2 Hz, CH 2Ph), 7.30 (2 H, t, ³ J H,H = 7.2 Hz, 2 × CH of Ph), 6.51-7.37 (1 H, br, OH), 7.40 (1 H, t, ³ J H,H = 7.7 Hz, CH of Ph), 7.45 (2 H, d, ³ J H,H = 7.1 Hz, 2 × CH of Ph). ¹³C NMR (125.7 MHz, CDCl3): δ = 36.33 (CHCH2), 45.46 (CHCH2), 47.83 (CH2Ph), 128.16 (CH of Ph), 128.59 (2 × CH of Ph), 128.86 (2 × CH of Ph), 134.60 (C ipso -CH2), 174.06 (NCO), 175.39 (CO2H), 200.05 (C=S). MS: m/z (%) = 281 (58) [M+], 265 (11), 237 (17), 148 (68), 91 (100), 77 (9), 65 (27), 55 (10). Anal. Calcd for C12H11NO3S2 (281.34): C, 51.23; H, 3.94; N, 4.98. Found: C, 51.29; H, 3.97; N, 4.95. Compound 8f: Yield: 0.19 g (80%). Yellow wax. IR (KBr): 3350-2610 (OH), 1719 (CO2H), 1679 (CO), 1348 and 1125 (C=S) cm-¹. ¹H NMR (500.1 MHz, CDCl3): δ = 0.94 (3 H, t, ³ J H,H = 7.4 Hz, NCH2CH2CH 3 ), 1.63-1.70 (2 H, m, NCH2CH 2CH3), 3.02 (1 H, dd, ² J H,H = 18.2 Hz, ³ J H,H = 9.2 Hz, CHCH 2), 3.28 (1 H, dd, ² J H,H = 18.0 Hz, ³ J H,H = 3.4 Hz, CHCH 2), 3.95 (2 H, t, ³ J H,H = 7.5 Hz, NCH 2CH2CH3), 4.42 (1 H, dd, ³ J H,H = 8.8 Hz, ³ J H,H = 3.6 Hz, CHCH2), 6.01-7.21 (1 H, br, OH). ¹³C NMR (125.7 MHz, CDCl3): δ = 11.14 (NCH2CH2 CH3), 20.08 (NCH2 CH2CH3), 36.63 (CHCH2), 45.54 (CHCH2), 46.33 (NCH2CH2CH3), 173.91 (NCO), 175.59 (CO2H), 200.57 (C=S). MS: m/z (%) = 233 (100) [M+], 215 (18), 200(10), 187 (31), 174 (22), 146 (15), 100 (61), 86 (32), 43 (30). Anal. Calcd for C8H11NO3S2 (233.30): C, 41.19; H, 4.75; N, 6.00. Found: C, 41.23; H, 4.77; N, 6.05. Compound 8i: Yield: 0.17 g (75%). Yellow wax. IR (KBr): 3445-3060 (OH), 1717 (CO2H), 1677 (CO), 1333 and 1200 (C=S)
cm-¹. ¹H NMR (500.1 MHz, CDCl3): δ = 3.04 (1 H, dd, ² J H,H = 17.6 Hz, ³ J H,H = 8.7 Hz, CHCH 2), 3.29 (1 H, dd, ² J H,H = 17.6 Hz, ³ J H,H = 3.5 Hz, CHCH 2), 4.45 (1 H, dd, ³ J H,H = 8.6 Hz, ³ J H,H = 3.4 Hz, CHCH2), 4.60-4.63 (2 H, m, CH 2N), 5.23-5.30 (2 H, m, CH=CH 2), 5.77-5.80 (1 H, m, CH=CH2), 6.35-7.28 (1 H, br, OH). ¹³C NMR (125.7 MHz, CDCl3): δ = 36.50 (CHCH2), 45.59 (CHCH2), 46.65 (NCH2), 119.58 (CH=CH2), 129.33 (CH=CH2), 173.93 (NCO), 175.10 (CO2H), 199.88 (C=S). MS: m/z (%) = 231 (39) [M+], 216 (44), 197 (27), 187 (51), 149 (45), 98 (57), 86 (39), 71 (61), 58 (78), 55 (100), 42 (73). Anal. Calcd for C8H9NO3S2 (231.28): C, 41.55; H, 3.92; N, 6.06. Found: C, 41.56; H, 3.95; N, 6.07.