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

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.

Key words

dithiocarbamate - trithiocarbonate - carbohydrates - carbon disulfide - three-component reaction - solvent-free

• References and Notes

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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-6_a), 4.12 (dd, 12,5, 2.0 Hz, 1 H, H-6_b), 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-6_a), 4.12 (d, J = 12.0 Hz, 1 H, H-6_b), 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-6_ab), 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-6_ab), 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.