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

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

References and Notes

• 1a Chakraborti AK. Shivani GR. J. Org. Chem.  2006,  71:  5785 
• 1b Tucker JL. Org. Process Res. Dev.  2006,  10:  315 
• 1c Sikchi SA. Hultin PG. J. Org. Chem.  2006,  71:  5888 
• 2a Tanaka K. Toda F. Chem. Rev.  2000,  100:  1025 
• 2b Shibahara F. Nozaki K. Hiyama T. J. Am. Chem. Soc.  2003,  125:  8555 
• 3a Caldas ED. Hosana Conceicüa M. Miranda MCC. Souza L. Lima JF. J. Agric. Food Chem.  2001,  49:  4521 
• 3b Erian AW. Sherif SM. Tetrahedron  1999,  55:  7957 
• 3c Wood TF. Gardner JH. J. Am. Chem. Soc.  1941,  63:  2741 
• 3d Beji M. Sbihi H. Baklouti A. Cambon A. J. Fluorine Chem.  1999,  99:  17 
• 4a Chen-Hsien W. Synthesis  1981,  622 
• 4b Mizunom T. Nishiguchi I. Okushi T. Hirashima T. Tetrahedron Lett.  1991,  32:  6867 
• 4c Chen YS. Schuphan I. Casida JE. J. Agric. Food Chem.  1979,  27:  709 
• 4d Rafin C. Veignie E. Sancholle M. Postal D. Len C. Villa P. Ronco G. J. Agric. Food Chem.  2000,  48:  5283 
• 5a Nieuwenhuizen PJ. Ehlers AW. Haasnoot JG. Janse SR. Reedijk J. Baerends EJ. J. Am. Chem. Soc.  1999,  121:  163 
• 5b Thorn GD. Ludwig RA. The Dithiocarbamates and Related Compounds   Elsevier; Amsterdam: 1962. 
• 5c Nice HR. Org. React.  1962,  12:  57 ; and references cited therein
• 6a Ronconi L. Marzano C. Zanello P. Corsini M. Miolo G. Macca C. Trevisan A. Fregona D. J. Med. Chem.  2006,  49:  1648 
• 6b Walter W. Bode K.-D. Angew. Chem., Int. Ed. Engl.  1967,  6:  281 
• 6c Elgemeie GH. Sayed SH. Synthesis  2001,  1747 
• 7a Hogarth PG. Inorg. Chem.  2005,  53:  7 
• 7b Zhao Y. Perez-Segarra W. Shi Q. Wei A. J. Am. Chem. Soc.  2005,  127:  7328 
• 7c Griffin TS. Woods TS. Klayman DL. In Advances in Heterocyclic Chemistry   Vol. 18:  Katritzky AR. Boulton AJ. Academic Press; New York: 1975.  p.99 
• 8a Tilles H. J. Am. Chem. Soc.  1959,  81:  714 
• 8b Chin-Hsien W. Synthesis  1981,  622 
• 8c Sugiyama HJ. Synth. Org. Chem. Jpn.  1980,  38:  555 
• 8d Walter W. Bode K.-D. Angew. Chem., Int. Ed. Engl.  1967,  6:  281 
• 9a Guo B. Ge Z. Chang T. Li R. Synth. Commun.  2001,  31:  3021 
• 9b Ziyaei-Halimjani A. Saidi MR. J. Sulfur Chem.  2005,  26:  149 
• 10a Azizi N. Saidi MR. Org. Lett.  2005,  7:  3649 
• 10b Azizi N. Aryanasab F. Torkiyan L. Ziyaei A. Saidi MR. J. Org. Chem.  2006,  71:  3634 
• 10c Azizi N. Torkiyan L. Saidi MR. Org. Lett.  2006,  8:  2079 
• 10d Azizi N. Aryanasab F. Saidi MR. Org. Biomol. Chem.  2006,  4:  4275 
• 11a Azizi N. Saidi MR. Eur. J. Org. Chem.  2003,  4630 
• 11b Azizi N. Saidi MR. Tetrahedron  2004,  60:  383 
• 11c Azizi N. Saidi MR. Organometallics  2004,  23:  1457 
• 11d Azizi N. Yousefi R. Saidi MR. J. Organomet. Chem.  2006,  691:  817 

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.