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Synlett 2007(12): 1917-1920  
DOI: 10.1055/s-2007-984539
LETTER
© Georg Thieme Verlag Stuttgart · New York

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;
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Publikationsverlauf

Received 18 April 2007
Publikationsdatum:
27. Juni 2007 (online)

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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

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.