G.-W. Wang, Y.-B. Shen, X.-L. Wu
FULL PAPER
7.1 Hz, 1 H), 5.04 (d, J = 7.1 Hz, 1 H), 2.70 (s, 3 H) ppm. 13C
NMR (75 MHz, CDCl3): δ = 140.36 (C), 139.41 (C), 134.04 (C),
129.22 (2ϫCH), 129.17 (2ϫCH), 128.93 (2ϫCH), 128.40 (CH),
amine derivatives in yields of up to 98%. The very low cata-
lyst loadings (ca. 0.6 mol-%) and recyclability of the 12-
phosphotungstic acid made this protocol attractive.
127.47 (2ϫCH), 60.79 (CH), 42.11 (CH) ppm. IR (KBr): ν = 3279,
˜
3058, 2928, 1598, 1491, 1449, 1320, 1153, 1092, 1054, 977, 906,
846, 808, 763, 744, 699, 560, 520 cm–1. HRMS (EI-TOF): m/z [M –
2 H]+ calcd. for C14H1235ClNO2S 293.0277; found 293.0273.
Experimental Section
General: Reagents and solvents were obtained from commercial
sources and were not further purified before use. All melting points
are uncorrected. IR spectra were recorded in KBr pellets and are
reported in cm–1. 1H NMR spectra were recorded at 300 MHz and
are reported in parts per million (ppm) relative to tetramethylsilane
(δ = 0.00 ppm). 13C NMR spectra were recorded at 75 MHz and
are reported in parts per million (ppm) relative to CDCl3 (δ =
77.0 ppm). High-resolution mass spectra (HRMS) were recorded
with the EI mode.
N-[(4-Chlorophenyl)(phenyl)methyl]benzamide (3bd): 1H NMR
(300 MHz, CDCl3): δ = 7.82 (d, J = 7.2 Hz, 2 H), 7.52 (t, J =
7.2 Hz, 1 H), 7.44 (t, J = 7.5 Hz, 2 H), 7.39–7.23 (m, 9 H), 6.61 (d,
J = 7.4 Hz, 2 H), 6.43 (d, J = 7.4 Hz, 1 H) ppm. 13C NMR
(75 MHz, CDCl3): δ = 166.66 (C=O), 141.12 (C), 140.14 (C),
134.18 (C), 133.52 (C), 131.94 (CH), 129.05 (2ϫCH), 128.99
(2ϫCH), 128.93 (2ϫCH), 128.80 (2ϫCH), 128.00 (CH), 127.69
(2ϫCH), 127.19 (2ϫCH), 57.09 (CH) ppm. IR (KBr): ν = 3254,
˜
3058, 3028, 1635, 1579, 1535, 1490, 1449, 1411, 1323, 1252, 1178,
1087, 1014, 931, 853, 839, 791, 751, 719, 695, 613, 582, 480 cm–1.
HRMS (EI-TOF): m/z [M]+ calcd. for C20H1635ClNO 321.0920;
found 321.0914.
N-[Phenyl(p-tolyl)methyl]-p-toluenesulfonamide (3ca): 1H NMR
(300 MHz, CDCl3): δ = 7.56 (d, J = 8.1 Hz, 2 H), 7.21–7.19 (m, 3
H), 7.15–7.08 (m, 4 H), 7.02 (d, J = 8.1 Hz, 2 H), 6.97 (d, J =
8.1 Hz, 2 H), 5.52 (d, J = 6.9 Hz, 1 H), 4.94 (d, J = 6.9 Hz, 1 H),
2.38 (s, 3 H), 2.28 (s, 3 H) ppm. 13C NMR (75 MHz, CDCl3): δ =
143.26 (C), 140.86 (C), 137.83 (C), 137.62 (C), 137.50 (CH), 129.46
(2ϫCH), 129.37 (2ϫCH), 128.64 (2ϫCH), 127.62 (CH), 127.45
(4ϫCH), 127.38 (2ϫCH), 61.29 (CH), 21.60 (CH3), 21.14 (CH3)
Typical Procedure for the Nucleophilic Substitution of Benzylic
Alcohols with Nitrogen Nucleophiles: 12-Phosphotungstic acid
(5 mg) was added to a solution of alcohol 1 (0.25 mmol) and nitro-
gen nucleophile 2 (0.25 mmol) in 1,4-dioxane (2 mL) in a test tube.
The tube was sealed, and the mixture was stirred at 80 °C for 12 h.
Upon completion, the reaction mixture was filtered to remove
PWA, and the organic solution was concentrated to dryness in
vacuo. The residue was separated on a silica gel column with petro-
leum ether/ethyl acetate (4:1) as the eluent to provide the desired
product 3: 3aa (82.6 mg, 98%), 3ab (73.5 mg, 91%), 3ac (60.7 mg,
93%), 3ad (63.9 mg, 89%), 3ae (73.7 mg, 97%), 3ba (87.2 mg,
94%), 3bb (83.2 mg, 93%), 3bc (71.6 mg, 97%), 3bd (72.4 mg,
90%), 3be (77.9 mg, 92%), 3ca (76.3 mg, 87%), 3cb (75.8 mg,
90%), 3cd (66.2 mg, 88%), 3da (59.1 mg, 86%), 3dd (39.4 mg,
70%), 3ea (88.9 mg, 98%), 3eb (82.0 mg, 94%), 3ed (75.1 mg,
96%), 3ee (75.1 mg, 91%), and 3fa (34.5 mg, 53%).
ppm. IR (KBr): ν = 3261, 3058, 3028, 2922, 1599, 1513, 1493, 1433,
˜
1321, 1163, 1093, 1045, 932, 905, 842, 810, 701, 677, 573 cm–1.
HRMS (EI-TOF): m/z [M]+ calcd. for C21H21NO2S 351.1293;
found 351.1299.
N-[Phenyl(p-tolyl)methyl]benzensulfonamide (3cb): 1H NMR
(300 MHz, CDCl3): δ = 7.67 (d, J = 7.2 Hz, 2 H), 7.46 (t, J =
7.5 Hz, 1 H), 7.32 (t, J = 7.7 Hz, 2 H), 7.20–7.14 (m, 3 H), 7.11–
7.07 (m, 2 H), 7.00 (d, J = 8.1 Hz, 2 H), 6.96 (d, J = 8.1 Hz, 2 H),
5.56 (d, J = 6.9 Hz, 1 H), 5.25 (d, J = 6.9 Hz, 1 H), 2.27 (s, 3 H)
ppm. 13C NMR (75 MHz, CDCl3): δ = 140.69 (C), 140.60 (C),
137.69 (C), 137.54 (C), 132.44 (CH), 129.39 (2ϫCH), 128.86
(2ϫCH), 128.66 (2ϫCH), 127.68 (CH), 127.44 (2ϫCH), 127.42
(2ϫCH), 127.30 (2ϫCH), 61.32 (CH), 21.13 (CH3) ppm. IR
Typical Procedure for the Nucleophilic Substitution of Simple Ali-
phatic Alcohols with p-Toluenesulfonamide (2a): 12-Phosphotungstic
acid (5 mg) was added to a solution of alcohol 1 (2.5 mmol) and
p-toluenesulfonamide (2a, 0.25 mmol) in a test tube. The tube was
sealed, and the mixture was stirred at a given temperature for a
designated time (monitored by TLC). Upon completion, the reac-
tion mixture was filtered to remove PWA, and the organic solution
was concentrated to dryness in vacuo. The residue was separated
on a silica gel column with petroleum ether/ethyl acetate (4:1) as
the eluent to afford the desired product 3: 3ga (43.0 mg, 68%), 3ha
(26.4 mg, 58%), and 3ia (32.6 mg, 66%).
(KBr): ν = 3251, 3053, 2926, 1510, 1449, 1435, 1317, 1160, 1090,
˜
1049, 928, 844, 755, 723, 702, 687, 592, 555, 480 cm–1. HRMS (EI-
TOF): m/z [M]+ calcd. for C20H19NO2S 337.1137; found 337.1144.
Compounds 3aa,[8f] 3ab,[8f] 3ac,[12] 3ad,[13] 3ae,[8f] 3ba,[14] 3be,[8f,9d]
3da,[8a,15] 3dd,[8a,16] 3ea,[17] 3eb,[18] 3ed,[18] 3ee,[9b] 3fa,[19] 3ga,[15]
3ha,[20] and 3ia[21] had been reported previously, and their identities
were confirmed by comparison of their melting points and spectro-
scopic data with the reported data. Characterization data for the
new compounds 3bb, 3bc, 3bd, 3ca, 3cb, and 3cd are shown below.
N-[(4-Chlorophenyl)(phenyl)methyl]benzenesulfonamide (3bb): 1H
NMR (300 MHz, CDCl3): δ = 7.67 (d, J = 7.8 Hz, 2 H), 7.50 (t, J
= 7.4 Hz, 1 H), 7.36 (t, J = 7.7 Hz, 2 H), 7.22–7.17 (m, 5 H), 7.07–
7.02 (m, 4 H), 5.58 (d, J = 6.8 Hz, 1 H), 5.05 (d, J = 6.8 Hz, 1 H)
ppm. 13C NMR (75 MHz, CDCl3): δ = 140.41 (C), 140.08 (C),
139.04 (C), 133.77 (C), 132.73 (CH), 129.02 (2ϫCH), 128.95
(4ϫCH), 128.85 (2ϫCH), 128.15, 127.43 (2ϫCH), 127.30
N-[Phenyl(p-tolyl)methyl]benzamide (3cd): 1H NMR (300 MHz,
CDCl3): δ = 7.81 (d, J = 6.9 Hz, 2 H), 7.51 (t, J = 7.2 Hz, 1 H),
7.43 (t, J = 7.4 Hz, 2 H), 7.37–7.27 (m, 5 H), 7.19 (d, J = 8.1 Hz,
2 H), 7.15 (d, J = 8.1 Hz, 2 H), 6.64 (d, J = 7.8 Hz, 1 H), 6.41 (d,
J = 7.8 Hz, 1 H), 2.34 (s, 3 H) ppm. 13C NMR (75 MHz, CDCl3):
δ = 166.59 (C=O), 141.79 (C), 138.72 (C), 137.39 (C), 134.49 (C),
132.73 (CH), 129.55 (2ϫCH), 128.81 (2ϫCH), 128.72 (2ϫCH),
127.58 (3ϫCH), 127.55 (2ϫCH), 127.18 (2ϫCH), 57.34 (CH),
21.18 (CH ) ppm. IR (KBr): ν = 3311, 3056, 3031, 2920, 1639,
˜
3
1579, 1522, 1489, 1357, 1317, 1247, 1181, 1082, 1054, 1026, 927,
856, 796, 776, 741, 703, 691, 577, 479 cm–1. HRMS (EI-TOF): m/z
[M]+ calcd. for C21H19NO 301.1467; found 301.1461.
(2ϫCH), 60.97 ppm. IR (KBr): ν = 3251, 3056, 1599, 1490, 1449,
˜
1436, 1319, 1162, 1091, 1048, 927, 845, 804, 753, 725, 686, 591,
559, 479 cm–1. HRMS (EI-TOF): m/z [M – 2 H]+ calcd. for
C19H1435ClNO2S 355.0434; found 355.0435.
N-[(4-Chlorophenyl)(phenyl)methyl]methanesulfonamide (3bc): 1H
NMR (300 MHz, CDCl3): δ = 7.38–7.25 (m, 9 H), 5.74 (d, J =
Acknowledgments
The authors are grateful for the financial support from the
National Natural Science Foundation of China (Nos. 20621061 and
20772117).
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Eur. J. Org. Chem. 2008, 4367–4371