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

Nobukazu Taniguchi

doi:10.1055/s-2007-984539

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Synlett 2007(12): 1917-1920
DOI: 10.1055/s-2007-984539

LETTER

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

Nobukazu Taniguchi*
Department of Chemistry, Fukushima Medical University, Fukushima 960-1295, Japan
Fax: +81(24)5471369; e-Mail: taniguti@fmu.ac.jp;

Further Information

Publication History

Received 18 April 2007
Publication Date:
27 June 2007 (online)

Abstract
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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.

Key words

sulfenamide - copper catalyst - diaryl disulfide - alkylamine

References and Notes

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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.