Copper-Catalyzed Synthesis of Sulfenamides Utilizing Diaryl Disulfides with Alkyl Amines

Abstract

The copper-catalyzed coupling of diaryl disulfides with alkyl amines can afford various sulfenamides in good yields. Furthermore, the present reaction is efficient and can be used for both of the aryl sulfide groups on disulfide.

sulfenamide - copper catalyst - diaryl disulfide - alkyl­amine

References and Notes

1a Davis FA. J. Org. Chem.  2006,  71:  8993 

1b Craine L. Raban M. Chem. Rev.  1989,  89:  689 

2a Matsuo J.-i. Iida D. Tatani K. Mukaiyama T. Bull. Chem. Soc. Jpn.  2002,  75:  223 

2b Matsuo J.-i. Iida D. Yamanaka H. Mukaiyama T. Tetrahedron  2003,  59:  6739 

3a Kuniyasu H. Kato T. Asano S. Ye J.-H. Ohmori T. Morita M. Hiraike H. Fujiwara S.-i. Terao J. Kurosawa H. Kambe N. Tetrahedron Lett.  2006,  47:  1141 

3b Kondo T. Baba A. Nishi Y. Mitsudo T.-a. Tetrahedron Lett.  2004,  45:  1469 

3c Zyk NV. Beloglzkina EK. Gazzaeva R. Tyurin VS. Titanyuk ID. Phosphorus, Sulfur Silicon Relat. Elem.  1999,  155:  33 

4a Miura Y. Asada H. Kinoshita M. Bull. Chem. Soc. Jpn.  1977,  50:  1855 

4b Heimer NE. Field L. J. Org. Chem.  1970,  35:  3012 

5a Davis FA. Friedman AJ. Kluger EW. Skibo EB. Fretz ER. Milicia AP. LeMasters WC. Bentley MD. Lacadie JA. Douglass IB. J. Org. Chem.  1977,  42:  967 

5b Davis FA. Slgeir WAR. Evans S. Schwartz A. Goff DL. Palmer R. J. Org. Chem.  1973,  38:  2809 

Intramolecular S-N bond formation is also reported:

6a Correa A. Tellitu I. Domínguez E. SanMartin R. Org. Lett.  2006,  8:  4811 

6b Jin CK. Moon J.-K. Lee WS. Nam KS. Synlett  2003,  1967 

7 Taniguchi N. J. Org. Chem.  2004,  69:  915 

8a Taniguchi N. Synlett  2006,  1351 

8b Taniguchi N. J. Org. Chem.  2007,  72:  1241 

8c Taniguchi N. J. Org. Chem.  2006,  71:  7874 

9

Typical Procedure
To a mixture of CuI (9.5 mg, 0.05 mmol), TMEDA (5.8 mg, 0.05 mmol), and DMSO (0.3 mL) were added (PhS)₂ (109.2 mg, 0.5 mmol) and Et₂NH (76.8 mg, 1.05 mmol), and the mixture was stirred at 65 °C for 18 h in air. After the residue was dissolved in Et₂O, the solution was washed with H₂O and sat. NaCl and dried over anhyd MgSO₄. The crude product was distilled (140 °C/30 Pa) to give N-(phenylthio)-N,N-diethylamine (134.8 mg, 74%).^5a N -(Phenylthio)- N , N -diethylamine
IR (neat): 2970, 2847, 1582, 1475, 1438, 1374 cm^-1. ¹H NMR (270 MHz, CDCl₃): δ = 7.34-7.25 (m, 4 H), 7.15-7.08 (m, 1 H), 3.00 (q, J = 7.1 Hz, 4 H), 1.18 (t, J = 7.1 Hz, 6 H). ¹³C NMR (67.5 MHz, CDCl₃): δ = 141.2, 128.4, 125.3, 125.0, 52.1, 13.7. Anal. Calcd for C₁₀H₁₅NS: C, 66.25; H, 8.34; N, 7.73. Found: C, 65.92; H, 8.02; N, 7.80.
N -(Phenylthio)pyrrolidine
IR (neat): 2967, 2845, 1582, 1475, 1438 cm^-1. ¹H NMR (270 MHz, CDCl₃): δ = 7.31-7.27 (m, 4 H), 7.18-7.14 (m, 1 H), 3.13-3.09 (m, 4 H), 1.87-1.82 (m, 4 H). ¹³C NMR (67.5 MHz, CDCl₃): δ = 139.4, 128.6, 126.3, 125.9, 55.2, 25.6. Anal. Calcd for C₁₀H₁₃NS: C, 66.99; H, 7.31; N, 7.81. Found: C, 66.70; H, 7.24; N, 7.84.
N -(Phenylthio)- N -(methyl)aminoethanol
IR (neat) 3391, 2940, 2880, 1582, 1476, 1438 cm^-1. ¹H NMR (270 MHz, CDCl₃): δ = 7.40-7.23 (m, 5 H), 3.77 (t, J = 5.1 Hz, 2 H), 3.02 (t, J = 5.1 Hz, 2 H), 2.87 (s, 3 H), 2.00 (br, 1 H). ¹³C NMR (67.5 MHz, CDCl₃): δ = 136.3, 129.4, 128.8, 127.5, 60.8, 59.9, 47.3. Anal. Calcd for C₉H₁₃NS: C, 58.98; H, 7.15; N, 7.64. Found: C, 59.17; H, 7.11; N, 7.24.
N -(Phenylthio)- N -butylamine
IR (neat): 3338, 2957, 2929, 1582, 1476, 1438 cm^-1. ¹H NMR (270 MHz, CDCl₃): δ = 7.34-7.24 (m, 4 H), 7.15-7.10 (m, 1 H), 2.93 (q, J = 6.9 Hz, 2 H), 2.80 (br, 1 H), 1.56-1.50 (m, 2 H), 1.48-1.31 (m, 2 H), 0.90 (t, J = 7.2 Hz, 3 H). ¹³C NMR (67.5 MHz, CDCl₃): δ = 141.9, 128.7, 125.2, 123.8, 51.9, 32.5, 20.0, 13.9. Anal. Calcd for C₁₀H₁₅NS: C, 66.25; H, 8.34; N, 7.73. Found: C, 66.46; H, 8.05; N, 7.70.
N -(Phenylthio)- N -(tert -butyl)amine ^4a,5a
IR (neat): 3327, 2969, 1582, 1476, 1361 cm^-1. ¹H NMR (270 MHz, CDCl₃): δ = 7.34 (d, J = 7.6 Hz, 2 H), 7.26 (t, J = 7.6 Hz, 2 H), 7.05 (t, J = 7.6 Hz, 1 H), 2.78 (br, 1 H), 1.17 (s, 9 H). ¹³C NMR (67.5 MHz, CDCl₃): δ = 144.4, 128.4, 124.4, 122.4, 54.7, 29.2. Anal. Calcd for C₁₀H₁₅NS: C, 66.25; H, 8.34; N, 7.73. Found: C, 65.98; H, 8.20; N, 7.54.

10

N -(2-Methylphenylthio)- N , N -diethylamine IR (neat): 2970, 2849, 1589, 1463, 1378 cm^-1. ¹H NMR (270 MHz, CDCl₃): δ = 7.50 (d, J = 7.9 Hz, 1 H), 7.15 (t, J = 7.9 Hz, 1 H), 7.07-6.97 (m, 2 H), 3.05 (q, J = 7.0 Hz, 4 H), 2.20 (s, 3 H), 1.17 (t, J = 7.0 Hz, 6 H). ¹³C NMR (67.5 MHz, CDCl₃): δ = 141.2, 131.6, 129.7, 125.8, 124.0, 122.8, 52.1, 18.5, 13.5. Anal. Calcd for C₁₁H₁₇NS: C, 67.64; H, 8.77; N, 7.17. Found: C, 67.34; H, 8.71; N, 7.02.
N -(4-Methylphenylthio)- N , N -diethylamine
IR (neat): 2970, 2830, 1597, 1489, 1374 cm^-1. ¹H NMR (270 MHz, CDCl₃): δ = 7.25 (d, J = 7.9 Hz, 2 H), 7.10 (d, J = 7.9 Hz, 2 H), 2.93, (q, J = 7.0 Hz, 4 H), 2.32 (s, 3 H), 1.19 (t, J = 7.0 Hz, 6 H). ¹³C NMR (67.5 MHz, CDCl₃): δ = 136.0, 135.8, 129.3, 127.3, 51.9, 21.0, 13.7. Anal. Calcd for C₁₁H₁₇NS: C, 67.64; H, 8.77; N, 7.17. Found: C, 67.51; H, 8.79; N, 7.22.
N -(4-Methoxylphenylthio)- N , N -diethylamine
IR (neat): 2971, 2835, 1590, 1492 cm^-1. ¹H NMR (270 MHz, CDCl₃): δ = 7.36 (d, J = 8.7 Hz, 2 H), 6.87 (d, J = 8.7 Hz, 2 H), 3.80 (s, 3 H), 2.81 (q, J = 7.0 Hz, 4 H), 1.21 (t, J = 7.0 Hz, 6 H). ¹³C NMR (67.5 MHz, CDCl₃): δ = 159.5, 132.8, 126.9, 114.1, 55.3, 51.4, 13.7. Anal. Calcd for C₁₁H₁₇NOS: C, 62.52; H, 8.11; N, 6.63. Found: C, 62.47; H, 8.03; N, 6.42.
N -(2-Methylphenylthio)- N -(tert -butyl)amine
IR (neat): 3322, 2969, 1589, 1463, 1361 cm^-1. ¹H NMR (270 MHz, CDCl₃): δ = 7.65 (d, J = 7.9 Hz, 1 H), 7.18, (t, J = 7.9 Hz, 1 H), 7.05-6.95 (m, 2 H), 2.60 (br, 1 H), 2.23 (s, 3 H), 1.19 (s, 9 H). ¹³C NMR (67.5 MHz, CDCl₃): δ = 142.5, 131.5, 129.5, 125.9, 123.9, 122.4, 54.6, 29.2, 18.5. Anal. Calcd for C₁₁H₁₇NS: C, 67.64; H, 8.77; N, 7.17. Found: C, 67.54; H, 8.79; N, 6.97.
N -(4-Methylphenylthio)- N -(tert -butyl)amine
IR (neat): 3325, 2969, 1598, 1490, 1361 cm^-1. ¹H NMR (270 MHz, CDCl₃): δ = 7.25 (d, J = 8.2 Hz, 2 H), 7.08 (d, J = 8.2 Hz, 2 H), 2.80 (br, 1 H), 2.30 (s, 3 H), 1.17 (s, 9 H). ¹³C NMR (67.5 MHz, CDCl₃): δ = 140.8, 134.3, 129.2, 122.9, 54.8, 29.2, 20.9. Anal. Calcd for C₁₁H₁₇NS: C, 67.64; H, 8.77; N, 7.17. Found: C, 67.35; H, 8.71; N, 6.92.

11 Adams R. Reifschneider W. Ferretti A. Org. Synth., Coll. Vol. V   John Wiley & Sons; New York: 1973.  p.107-110