Download PDF
Synlett 2007(18): 2797-2800  
DOI: 10.1055/s-2007-991085
LETTER
© Georg Thieme Verlag Stuttgart · New York

Waste-Free and Environment-Friendly Uncatalyzed Synthesis of Dithiocarbamates under Solvent-Free Conditions

Najmedin Azizi*b, Forogh Ebrahimia, Elham Aakbaria, Fezzeh Aryanasaba, Mohammad R. Saidi*a
a Department of Chemistry, Sharif University of Technology, 11365 Tehran, Iran
Fax: +98(21)66012983; e-Mail: saidi@sharif.edu;
b Chemistry and Chemical Engineering Research Center of Iran, 14335 Tehran, Iran
Further Information

Publication History

Received 24 January 2007
Publication Date:
12 October 2007 (online)

    Permissions and Reprints All articles of this category

Abstract

A mild, convenient, and practical one-pot procedure for the direct synthesis of dithiocarbamates has been developed by condensation of amines, CS2, and a Michael acceptor, under solvent-free conditions at room temperature in good to excellent yields.

Key words

amines - dithiocarbamates - solvent-free - carbon disulfide - waste-free

12

The reaction was very exothermic and should be controlled by slow addition of amine and maintaining the temperature by using an ice bath.

13

Selected Spectroscopic DataTable 1, Entry 1: 1H NMR (500 MHz, CDCl3): δ = 0.92-0.96 (6 H, m), 2.53 (2 H, t, J = 6.7 Hz), 3.12 (2 H, t, J = 6.2 Hz), 3.42 (2 H, q, J = 6.7 Hz), 3.67 (2 H, t, J = 6.7 Hz). 13C NMR (125 MHz, CDCl3): δ = 9.4, 11.7, 18.2, 32.0, 47.2, 49.9, 118.6, 192.7.
Table 1, Entry 2: 1H NMR (500 MHz, CDCl3): δ = 1.30-1.51 (6 H, m), 2.74 (2 H, t, J = 6.2 Hz), 3.39 (2 H, t, J = 6.3 Hz), 3.75 (2 H, m), 4.12 (2 H, m). 13C NMR (125 MHz, CDCl3): δ = 18.5, 25.9, 32.2, 51.9, 53.4, 54.2, 118.7, 193.0. Anal. Calcd (%) for C9H14N2S2: C, 50.43; H, 6.58; N, 13.07. Found: C, 50.80; N, 12.92; H, 6.62.
Table 1, Entry 3: 1H NMR (500 MHz, CDCl3): δ = 1.72-1.92 (4 H, m), 2.66 (2 H, t, J = 6.5 Hz), 3.29 (2 H, t, J = 6.5 Hz), 3.43 (2 H, t, J = 6.7 Hz), 3.64 (2 H, t, J = 6.7 Hz). 13C NMR (125 MHz, CDCl3): δ = 18.6, 24.5, 26.2, 31.6, 51.1, 53.9, 55.5, 118.7, 190.0. Anal. Calcd for C8H12N2S2: C, 47.97; H, 6.04; N, 13.98. Found: C, 48.30; H, 5.82, N, 13.69.
Table 1, Entry 7: 1H NMR (500 MHz, CDCl3): δ = 2.82 (2 H, t, J = 6.2 Hz), 3.46 (2 H, t, J = 6.3 Hz), 4.88 (2 H, s), 7.26-7.39 (5 H, m), 8.02 (1 H, br s, NH). 13C NMR (125 MHz, CDCl3): δ = 18.9, 31.4, 51.5, 119.0, 128.3, 128.8, 129.7, 136.5, 196.0.
Table 1, Entry 10: 1H NMR (500 MHz, CDCl3): δ = 0.77 (3 H, t, J = 7.3 Hz), 1.07 (3 H, d, J = 6.4 Hz), 1.41-1.51 (4 H, m), 2.65 (2 H, t, J = 6.6 Hz), 3.35 (2 H, J = 6.7 Hz), 4.37-4.38 (1 H, m), 7.73 (1 H, br s, NH). 13C NMR (125 MHz, CDCl3): δ = 10.8, 18.5, 19.4, 29.7, 31.1, 55.1, 55.2, 119.1, 194.3.
Table 1, Entry 11: 1H NMR (500 MHz, CDCl3): δ = 0.93-0.99 (6 H, m), 2.47 (2 H, t, J = 6.4 Hz), 3.20 (2 H, t, J = 6.5 Hz), 3.44 (3 H, s), 3.45 (2 H, q, J = 6.9 Hz), 3.70 (2 H, q, J = 6.9 Hz). 13C NMR (125 MHz; CDCl3): δ = 11.7, 12.9, 31.7, 33.9, 46.9, 49.6, 51.6, 171.9, 194.4.
Table 1, Entry 12: 1H NMR (500 MHz, CDCl3): δ = 1.41-1.47 (6 H, m), 2.53 (2 H, t, J = 6.4 Hz), 3.42-4.01 (9 H, m). 13C NMR (125 MHz, CDCl3): δ = 24.5, 25.8, 31.8, 34.0, 44.3, 51.5, 51.8, 52.9, 172.1, 194.5. Anal. Calcd (%) for C10H17NO2S2: C, 48.55; N, 5.66; H, 6.93. Found: C, 48.70; N, 5.79; H, 6.95.
Table 1, Entry 13: 1H NMR (500 MHz, CDCl3): δ = 1.76-1.86 (4 H, m), 2.57 (2 H, t, J = 6.7 Hz), 3.28-3.46 (7 H, m), 3.64-3.66 (2 H, m). 13C NMR (125 MHz, CDCl3): δ = 24.5, 26.3, 31.2, 34.1, 50.8, 51.8, 55.2, 172.3, 191.7.
Table 1, Entry 15: 1H NMR (500 MHz, CDCl3): δ = 2.82 (2 H, t, J = 6.7 Hz), 3.52 (2 H, t, J = 6.7 Hz), 3.67 (3 H, s), 4.90 (2 H, s), 7.33-7.35 (5 H, m), 7.90 (1 H, br s, NH). 13C NMR (125 MHz, CDCl3): δ = 30.3, 34.6, 51.4, 52.3, 128.3, 128.6, 129.3, 135.7, 172.8, 197.7.
Table 1, Entry 17: 1H NMR (500 MHz, CDCl3): δ = 0.89 (3 H, t, J = 7.2 Hz), 1.19 (3 H, d, J = 5.3 Hz), 1.51-1.61 (2 H, m), 2.74 (2 H, t, J = 6.8 Hz), 3.44 (2 H, t, J = 6.8 Hz), 3.66 (3 H, s), 4.52 (1 H, m), 7.38 (1 H, br s, NH). 13C NMR (125 MHz, CDCl3): δ = 10.6, 20.9, 29.1, 30.9, 34.2, 52.1, 54.7, 54.8, 172.8, 196.0.
Table 1, Entry 19: 1H NMR (500 MHz, CDCl3): δ = 1.01-1.06 (6 H, m), 1.94 (3 H, s), 2.72 (2 H, t, J = 6.6 Hz), 3.23 (2 H, t, J = 6.6 Hz), 3.52 (2 H, q, J = 7.1 Hz), 3.79 (2 H, q, J = 7.1 Hz). 13C NMR (125 MHz, CDCl3): δ = 11.8, 12.7, 30.1, 30.6, 43.3, 46.9, 49.6, 195.2, 206.9.
Table 1, Entry 21: 1H NMR (500 MHz, CDCl3): δ = 1.38-1.76 (7 H, m), 2.53 (2 H, t, J = 6.1 Hz), 3.01-3.44 (6 H, m). 13C NMR (125 MHz, CDCl3): δ = 23.8, 25.9, 29.9, 43.1, 50.7, 55.1, 191.7, 206.3. Anal. Calcd (%) for C9H15NOS2: C, 49.73; H, 6.96; N, 6.44. Found: C, 49.53; H, 6.82; N, 6.61.
Table 1, Entry 25: 1H NMR (500 MHz, CDCl3-CCl4): δ = 1.58 (3 H, d, J = 6.8 Hz), 2.14 (3 H, s), 2.89 (2 H, t, J = 6.1 Hz), 3.40 (2 H, t, J = 6.1 Hz), 5.81 (1 H, q, J = 6.8 Hz), 7.26-7.35 (5 H, m), 8.18 (1 H, br s, NH). 13C NMR (125 MHz, CDCl3): δ = 21.3, 29.0, 30.4, 43.3, 56.4, 127.0, 128.2, 129.3, 141.7, 196.8, 207.6.
Table 1, Entry 28: 1H NMR (500 MHz, CDCl3): δ = 1.26-1.31 (6 H, m), 3.68-4.21 (6 H, m), 5.76 (1 H, dd, J = 4.1, 10.2 Hz), 7.24-7.69 (8 H, m), 8.00-8.01 (2 H, m). 13C NMR (125 MHz, CDCl3): δ = 127.9, 128.5, 128.7, 129.1, 129.6, 134.1, 137.6, 140.8, 190.8, 197.4.
Table 1, Entry 30: 1H NMR (500 MHz, CDCl3): δ = 1.93-2.05 (4 H, m), 3.58-4.02 (6 H, m), 5.83 (1 H, dd, J = 4.1, 9.8 Hz), 7.27-7.56 (8 H, m), 8.00 (2 H, d, J = 7.3 Hz). 13C NMR (125 MHz, CDCl3): δ = 24.6, 26.5, 51.0, 54.6, 55.3, 128.0, 128.6, 128.8, 129.0, 129.4, 133.6, 137.0, 140.0, 191.5, 197.4.