Synlett 2012; 23(19): 2789-2794
DOI: 10.1055/s-0032-1317521
letter
© Georg Thieme Verlag Stuttgart · New York

Significantly Fast Synthesis of S-Glycosyl N-Substituted Dithiocarbamate and S-Glycosyl S′-Substituted Trithiocarbonate Derivatives under Solvent-Free Conditions

Manas Jana
Division of Molecular Medicine, Bose Institute, P-1/12, C. I. T. Scheme VII M, Kolkata 700054, India   Fax: +91(33)23553886   Email: akmisra69@gmail.com
,
Anup Kumar Misra*
Division of Molecular Medicine, Bose Institute, P-1/12, C. I. T. Scheme VII M, Kolkata 700054, India   Fax: +91(33)23553886   Email: akmisra69@gmail.com
› Author Affiliations
Further Information

Publication History

Received: 17 August 2012

Accepted after revision: 08 October 2012

Publication Date:
13 November 2012 (online)


Abstract

A series of S-glycosyl N-substituted dithiocarbamate and S-glycosyl S′-substituted trithiocarbonate derivatives have been synthesized under solvent-free conditions. Three-component reaction of glycosyl bromides with carbon disulfide and thiols or amines in the presence or absence of triethylamine furnished excellent yields of the target compounds in a short reaction time.

 
  • References and Notes

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    • 14a Degani I, Fochi R, Gatti A, Regondi V. Synthesis 1986; 894
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  • 18 General Experimental Conditions for the Synthesis of S-Glycosyl N-Substituted Dithiocarbamate Derivatives A mixture of amine (1.2 mmol), CS2 (1.5 mmol) was allowed to stir for 5 min at r.t. To the reaction mixture was added glycosyl bromide (1.0 mmol), and the reaction mixture was allowed to stir at r.t. for the appropriate time as mentioned in Table 1. Excess reagents were removed under reduced pressure. H2O was added to the crude product, and the mixture was stirred at r.t. The solid product, which precipitated out immediately, was filtered, washed with H2O dried, and recrystallized from EtOH. Representative spectroscopic data of selected products are as follows. 2,3,4,6-Tetra-O-acetyl-β-d-glucopyranosyl 4-Morpholine Carbodithioate (5) White solid; mp 132–133 °C; [α]D +26.3 (c 0.5, CHCl3). IR (KBr): 2966, 1747, 1469, 1426, 1377, 1219, 1112, 1057, 1030, 996, 922, 825, 610 cm–1. 1H NMR (500 MHz, CDCl3): δ = 5.86 (d, J = 10.5 Hz, 1 H, H-1), 5.34 (t, J = 9.5 Hz, 1 H, H-2), 5.29 (t, J = 9.5 Hz, 1 H, H-3), 5.11 (t, J = 10.0 Hz, 1 H, H-4), 4.28 (dd, J = 13.0, 5.0 Hz, 1 H, H-6a), 4.12 (dd, 12,5, 2.0 Hz, 1 H, H-6b), 3.89–3,85 (m, 1 H, H-5), 3.80–3.70 (m, 4 H, CH2), 2.07, 2.04, 2.03, 2.01 (4 s, 12 H, 4 COCH3). 13C NMR (125 MHz, CDCl3): δ = 192.4 (C=S), 170.4, 169.8, 169.4, 169.3 (4 COCH3), 86.7 (C-1), 76.3 (C-5), 74.3 (C-3), 68.5 (C-4), 68.0 (C-2), 66.2 (CH2), 65.9 (CH2), 61.6 (C-6), 51.6 (CH2), 50.7 (CH2), 20.8, 20.7, 20.6 (2 C, 4 COCH3). ESI-MS: m/z = 516.1 [M + Na]+. Anal. Calcd for C19H27NO10S2 (493.10): C, 46.24; H, 5.51. Found: C, 46.10; H, 5.70. (2,3,4,6-Tetra-O-acetyl-β-d-glucopyranosyl)-N-cyclopropylmethyl-N-propyl Dithiocarbamate (6) White solid; mp 78–80 °C. [α]D +12.5 (c 0.5, CHCl3). IR (KBr): 2940, 1747, 1478, 1382, 1243, 1222, 1079, 1036, 913, 830, 606 cm–1. 1H NMR (500 MHz, CDCl3): δ = 5.87 (d, J = 10.0 Hz, 1 H, H-1), 5.35 (t, J = 9.0 Hz, 1 H, H-3), 5.27 (t, J = 9.5 Hz, 1 H, H-2), 5.11 (t, J = 9.0 Hz, 1 H, H-4), 4.29 (dd, J = 12.5, 4.5 Hz, 1 H, H-6a), 4.12 (d, J = 12.0 Hz, 1 H, H-6b), 4.03–3.96 (m, 1 H), 3.92–3.87 (m, 2 H, H-5, CH2), 3.86–3.72 (m, 1 H), 3.65–3.51 (m, 2 H), 2.07, 2.03, 2.01, (3 s, 12 H, 4 COCH3), 1.80–1.65 (m, 2 H), 1.35–1.25 (m, 1 H), 0.98–0.90 (m, 3 H), 0.63–0.57 (m, 2 H), 0.35–0.32 (m, 2 H). 13C NMR (125 MHz, CDCl3): δ = 192.0 (C=S), 170.5, 169.8, 169.3, (2 C, 4 COCH3), 87.2 (C-1), 76.2 (C-5), 74.5 (C-3), 68.6 (C-4), 68.1 (C-2), 61.6 (C-6), 59.4 (CH2), 57.0 (CH2), 19.3 (CH2), 20.8, 20.7, 20.6, 20.5 (4 COCH3), 11.3 (CH3), 8.9 (CH), 4.3, 4.0 (CH2). ESI-MS: m/z = 542.1 [M + Na]+. Anal. Calcd for C22H33NO9S2 (519.16): C, 50.85; H, 6.40. Found: C, 50.70; H, 6.60.
  • 19 General Experimental Conditions for the Synthesis of S-Glycosyl S′-Substituted Trithiocarbonate Derivative To a mixture of thiol (1.2 mmol), CS2 (1.5 mmol) and glycosyl bromide (1.0 mmol) was added Et3N (0.1 mmol), and the reaction mixture was allowed to stir at r.t. for the appropriate time as mentioned in Table 2. Excess reagents were removed under reduced pressure. H2O was added to the crude product, and the mixture was stirred at r.t. The solid product which precipitated out immediately was filtered, washed with H2O, dried, and recrystallized from EtOH. Representative spectroscopic data of selected products are as follows. S-(2,3,4,6-Tetra-O-acetyl-β-d-glucopyranosyl)-S′-(p-methylphenyl) Trithiocarbonate (16) White solid; mp 107–108 °C. [α]D –17.2 (c 0.5, CHCl3). IR (KBr): 2939, 1747, 1382, 1224, 1039, 918, 809, 604 cm–1. 1H NMR (500 MHz, CDCl3): δ = 7.37 (d, J = 9.0 Hz, 2 H, ArH), 7.08 (d, J = 9.0 Hz, 2 H, ArH), 5.16 (t, J = 9.5 Hz, 1 H, H-3), 4.98 (t, J = 9.5 Hz, 1 H, H-2), 4.89 (t, J = 9.5 Hz, 1 H, H-4), 4.60 (d, J = 10.0 Hz, 1 H, H-1), 4.21–4.13 (m, 2 H, H-6ab), 3.68–3.64 (m, 1 H, H-5), 2.34 (s, 3 H, CH3), 2.09, 2.07, 2.02, 1.99 (4 s, 12 H, 4 COCH3). 13C NMR (125 MHz, CDCl3): δ = 194.7 (C=S), 170.3, 170.0, 169.2, 169.0 (4 COCH3), 138.7–127.4 (ArC), 85.7 (C-1), 75.8 (C-5), 74.0 (C-3), 69.9 (C-2), 68.1 (C-4), 62.0 (C-6), 21.2 (CH3), 20.7, 20.6 (2 C), 20.5 (4 COCH3). ESI-MS: m/z = 553.0 [M + Na]+. Anal. Calcd for C22H26O9S3 (530.07): C, 49.80; H, 4.94. Found: C, 49.64; H, 5.14. S-(2,3,4,6-Tetra-O-acetyl-β-d-glucopyranosyl)-S′-(p-methoxylphenyl) Trithiocarbonate (17) White solid; mp 88–90 °C. [α]D –20.4 (c 0.5, CHCl3). IR (KBr): 2940, 1747, 1494, 1383, 1226, 1038, 831 cm–1. 1H NMR (500 MHz, CDCl3): δ = 7.45 (d, J = 9.0 Hz, 2 H, ArH), 6.84 (d, J = 9.0 Hz, 2 H, ArH), 5.19 (t, J = 9.5 Hz, 1 H, H-3), 4.99 (t, J = 9.5 Hz, 1 H, H-2), 4.88 (t, J = 9.5 Hz, 1 H, H-3), 4.56 (d, J = 10.0 Hz, 1 H, H-1), 4.22–4.16 (m, 2 H, H-6ab), 3.81 (s, 3 H, OCH3), 3.69–3.66 (m, 1 H, H-5), 2.10, 2.07, 2.01, 1.98 (4 s, 12 H, 4 COCH3). 13C NMR (125 MHz, CDCl3): δ = 195.3 (C=S), 170.6, 170.2, 169.4, 169.2 (4 COCH3), 160.4–114.4 (ArC), 85.6 (C-1), 75.7 (C-5), 74.0 (C-3), 69.9 (C-2), 68.1 (C-4), 62.0 (C-6), 55.3 (OCH3), 20.8, 20.7, 20.6, 20.5 (4 COCH3). ESI-MS: m/z = 569.0 [M + Na]+. Anal. Calcd for C22H26O10S3 (546.06): C, 48.34; H, 4.79. Found: C, 48.17; H, 4.95.