4
J. Chen et al. / Tetrahedron xxx (2012) 1e5
were added to a sealed tube. The reaction mixture was stirred
under argon atmosphere at 120 ꢀC for the desired time until
complete consumption of starting material as monitored by TLC.
Then cooled to room temperature and extracted with diethyl ether
(three times). Without dry, the solvent was removed under reduced
pressure. The crude product was added to p-toluenesulfonyl chlo-
ride in water solution and stirred at room temperature until the
reaction was completed at room temperature (monitored by TLC).
Then, extracted with diethyl ether (three times). The combined
organic phase was then dried with anhydrous Na2SO4 and the
solvent was removed under reduced pressure. The remaining res-
idue was purified by column chromatography (petroleum ether/
ethyl acetate) on silica gel to provide the desired aryl hydrazines
derivatives.
110.3, 21.6, 21.1. HRMS (ESI): calcd for C14H17N2O3S [MþH]þ:
293.3637; found: 293.3631.
Compound 2h: Yellow solid, mp 101e102 ꢀC; IR (KBr)
n
(cmꢁ1):
3251, 3126, 3215, 2995, 2212, 1644, 1258, 1142, 1042, 854, 558. 1H
NMR (CDCl3, 400 MHz, ppm)
: 7.75 (d, J¼8.2 Hz, 2H), 7.24e7.20 (m,
4H), 7.11e7.05 (m, 4H), 2.36 (s, 3H). 13C NMR (CDCl3, 100 MHz, ppm)
d
d
: 143.9, 136.6, 136.1, 129.6, 129.3, 127.3, 125.3, 121.5. HRMS (ESI):
calcd for C13H14N3O4S [MþH]þ: 308.3369; found: 308.3372.
Compound 2i: Yellow solid, mp 102e103 ꢀC; IR (KBr)
n
(cmꢁ1):
3361, 3167, 3134, 3015, 2308, 1852, 1275, 1062, 895, 586. 1H NMR
(CDCl3, 400 MHz, ppm)
: 7.66 (d, J¼8.2 Hz, 2H), 7.26e7.21 (m, 4H),
7.12e7.06 (m, 4H), 2.37 (s, 3H). 13C NMR (CDCl3, 100 MHz, ppm)
d
d
:
143.9, 136.6, 136.2, 129.6, 129.6, 127.3, 125.3, 121.6. HRMS (ESI):
calcd for C13H14N3O4S [MþH]þ: 308.3369; found: 308.3374.
Compound 2j: Yellow solid, mp 146e147 ꢀC; IR (KBr)
n
(cmꢁ1):
4.2.1. Physical and spectra data of products 2aem. Compound 2a:
3418, 3335, 3230, 2920, 2430,1604,1328,1157,1077, 861, 547.1H NMR
(CDCl3, 400 MHz, ppm)
: 7.76 (d, J¼8.0 Hz, 2H), 7.25 (d, J¼8.0 Hz,1H),
6.45e6.30 (m, 4H), 5.57 (br, 1H), 2.41 (s, 3H), 2.17 (s, 6H). 13C NMR
(CDCl3,100 MHz, ppm) : 146.3,144.3,138.8,135.0,129.6,128.3,130.0,
Pale yellow solid, mp 154e155 ꢀC; IR (KBr)
n
(cmꢁ1): 3437, 3243,
d
2924, 2429, 1641, 1607, 1321, 1159, 1076, 860. 1H NMR (CDCl3,
400 MHz, ppm)
: 7.76 (d, J¼8.0 Hz, 2H), 7.26e6.30 (m, 8H), 5.65 (br,
1H), 2.40 (s, 3H). 13C NMR (CDCl3, 100 MHz, ppm)
: 146.2, 144.5,
d
d
d
111.0, 21.5, 21.1. MS (EI, m/z): 290 [Mþ]. HRMS (ESI): calcd for
134.8, 129.7, 129.0, 128.2, 121.1, 113.4, 21.6. HRMS (ESI): calcd for
C
15H19N2O2S [MþH]þ: 291.3924; found: 291.3926.
C
13H15N2O2S [MþH]þ: 163.3374; found: 163.3377.
Compound 2k: Yellow solid, mp 155e156 ꢀC; IR (KBr) (cmꢁ1):
n
Compound 2b: Pale yellow solid, mp 149e150 ꢀC; IR (KBr)
(cmꢁ1): 3443, 3341, 3242, 2958, 2360, 1641, 1616, 1564, 1325,
3415, 3311, 3231, 2446, 1637, 1566, 1327, 1160, 1076, 861, 554. 1H
n
NMR (CDCl3, 400 MHz, ppm)
d
: 7.79 (d, J¼8.0 Hz, 2H), 7.68e6.39 (m,
1158, 816, 555. 1H NMR (CDCl3, 400 MHz, ppm)
d: 7.76 (d, J¼8.0 Hz,
9H), 6.40 (br, 1H), 2.34 (s, 3H). 13C NMR (CDCl3, 100 MHz, ppm)
d:
2H), 7.27e7.17 (m, 2H), 6.92 (d, J¼8.0 Hz, 2H), 6.63 (d, J¼8.0 Hz, 2H),
144.6,143.7,134.9,134.1,129.7,129.1,128.2,127.6,127.9,126.5,126.4,
123.6, 115.5, 108.0, 21.5. MS (EI, m/z): 312 [Mþ]. HRMS (ESI): calcd
for C17H17N2O2S [MþH]þ: 313.3980; found: 313.3986.
6.15 (s, 1H), 2.49 (s, 3H), 2.41 (s, 3H). 13C NMR (CDCl3, 100 MHz,
ppm) d: 144.4, 143.9, 134.9, 129.8, 129.7, 128.2, 124.7, 113.6, 21.6,
20.5. HRMS (ESI): calcd for C14H17N2O2S [MþH]þ: 277.3639; found:
Compound 2l: Yellow solid, mp 147e148 ꢀC; IR (KBr) (cmꢁ1):
n
277.3641.
3265, 3142, 3201, 2953, 2095, 1156, 1008, 849. 1H NMR (DMSO,
Compound 2c: Yellow solid, mp 145e146 ꢀC; IR (KBr)
n
(cmꢁ1):
400 MHz, ppm)
d
: 947 (s, 1H), 7.17 (d, J¼8.2 Hz, 2H), 7.54 (s,1H), 7.41
3345, 3249, 3042, 2957, 2921, 1926, 1845, 1734, 1655, 1623, 1494,
(d, J¼8.2 Hz, 2H), 6.95e6.79 (m, 4H), 2.39 (s, 3H). 13C NMR (DMSO,
1324, 1156, 818, 800, 708, 556. 1H NMR (CDCl3, 400 MHz, ppm)
d:
100 MHz, ppm) d: 162.4,160.1,150.4,148.4,141.4,136.3,134.8,132.8.
7.75 (d, J¼8.4 Hz, 2H), 7.24 (d, J¼8.0 Hz, 2H), 6.98 (t, J¼8.0 Hz, 1H),
HRMS (ESI): calcd for C13H14FN2O2S [MþH]þ: 281.3281; found:
6.63e6.39 (m, 3H), 5.61 (br, 1H), 2.39 (s, 3H), 2.04 (s, 3H). 13C NMR
281.3285.
(CDCl3, 100 MHz, ppm)
d: 146.2, 144.3, 138.9, 134.9, 129.6, 128.8,
Compound 2m: Yellow solid, mp 155e156 ꢀC; IR (KBr) (cmꢁ1):
n
128.2, 122.0, 114.1, 110.6, 21.6, 21.4. HRMS (ESI): calcd for
3444, 3341, 3246, 3149, 3133, 2451, 2074, 1924, 1620, 1600, 1497,
C
14H17N2O2S [MþH]þ: 277.3639; found: 277.3633.
1324, 1158, 1087, 955, 864, 709, 558. 1H NMR (CDCl3, 400 MHz,
Compound 2d: Yellow solid, mp 142e143 ꢀC; IR (KBr)
n
(cmꢁ1):
ppm)
d
: 7.76 (d, J¼8.0 Hz, 2H), 7.28e6.28 (m, 6H), 5.75 (s, 1H), 2.41
3327, 3239, 2958, 2428, 1642, 1567, 1443, 1326, 1159, 1076, 950, 861,
548. 1H NMR (CDCl3, 400 MHz, ppm)
: 7.73 (d, J¼8.4 Hz, 2H),
7.25e6.70 (m, 6H), 5.16 (s, 1H), 2.38 (s, 3H), 2.11 (s, 3H). 13C NMR
(CDCl3, 100 MHz, ppm) : 144.5, 143.9, 134.8, 130.3, 129.7, 128.2,
(s, 3H). 13C NMR (CDCl3, 100 MHz, ppm)
d
: 148.1, 148.0, 144.9, 134.4,
d
130.3, 130.2, 129.8, 128.2, 108.8, 108.7, 107.8, 107.6, 21.6. HRMS (ESI):
calcd for C13H14FN2O2S [MþH]þ: 281.3281; found: 281.3282.
d
Compound 2n: Pale yellow solid, mp 165e156 ꢀC; IR (KBr)
n
126.9, 121.9, 120.8, 112.8, 21.6, 17.0. HRMS (ESI): calcd for
(cmꢁ1): 3411, 3241, 2958, 2444, 1799, 1641, 1567, 1478, 1333, 1158,
950, 861, 529. 1H NMR (CDCl3, 400 MHz, ppm)
: 7.56 (d, J¼8.0 Hz,
2H), 7.23e6.69 (m, 6H), 6.33 (s, 1H), 4.99 (s, 1H), 2.39 (s, 3H). 13
C
14H17N2O2S [MþH]þ: 277.3639; found: 277.3635.
d
Compound 2e: Yellow solid, mp 150e151 ꢀC; IR (KBr)
n
(cmꢁ1):
C
3445, 3249, 2957, 2921, 2471, 1927, 1812, 1614, 1595, 1323, 1159,
NMR (CDCl3, 100 MHz, ppm) d: 154.2, 143.8, 135.9, 129.6, 128.8,
1091, 859, 696, 554. 1H NMR (CDCl3, 400 MHz, ppm)
d: 7.58 (d,
127.3, 125.9, 115.9, 21.6. MS (EI, m/z): 278 [Mþ]. HRMS (ESI): calcd
for C13H15N2O3S [MþH]þ: 279.3374; found: 279.3371.
J¼8.0 Hz, 2H), 7.21 (d, J¼8.0 Hz, 2H), 6.97 (d, J¼8.4 Hz, 2H), 6.75 (d,
J¼8.8 Hz, 2H), 6.49 (s, 1H), 3.76 (s, 3H), 2.39 (s, 3H). 13C NMR (CDCl3,
Compound 2o: Yellow solid, mp 138e140 ꢀC; IR (KBr)
n
(cmꢁ1):
100 MHz, ppm)
d
: 157.9, 143.3, 140.0, 129.6, 128.9, 127.3, 125.4, 114.4,
3412, 3241, 3132, 2919, 2448, 1915, 1639, 1617, 1509, 1491, 1469,
55.4, 21.6. HRMS (ESI): calcd for C14H17N2O3S [MþH]þ: 293.3637;
1333, 1239, 1070, 954, 827, 715, 696. 1H NMR (CDCl3, 400 MHz,
found: 293.3632.
ppm)
d
: 7.66 (d, J¼8.4 Hz, 2H), 7.63e6.56 (m, 6H), 6.51 (s, 1H), 2.36
: 163.0, 155.3, 148.3, 141.5,
Compound 2f: Yellow solid, mp 151e152 ꢀC; IR (KBr)
n
(cmꢁ1):
(s, 3H). 13C NMR (CDCl3, 100 MHz, ppm)
d
3565, 3385, 3156, 2952, 2410, 1614, 1420, 1154, 1041, 858, 535. 1H
NMR (CDCl3, 400 MHz, ppm) : 9.56 (s, 1H), 7.76 (s, 1H), 7.71 (d,
134.7, 134.3, 132.7, 111.5, 109.3, 105.3, 26.3. HRMS (ESI): calcd for
d
C
13H15N2O3S [MþH]þ: 279.3374; found: 279.372.
J¼8.2 Hz, 1H), 7.41 (d, J¼8.2 Hz, 1H), 7.12 (d, J¼8.2 Hz, 1H), 6.80 (d,
Compound 2p: Yellow solid, mp 135e136 ꢀC; IR (KBr) (cmꢁ1):
n
J¼8.2 Hz, 1H), 2.39 (s, 6H). 13C NMR (CDCl3, 100 MHz, ppm)
d
: 152.9,
3501, 3283, 2451, 1795, 1597, 1496, 1160, 1090, 940, 812, 535. 1H NMR
148.5, 141.3, 134.8, 133.5, 132.8, 127.5, 119.4, 26.2. HRMS (ESI): calcd
(CDCl3, 400 MHz, ppm)
d
: 7.61 (d, J¼7.2 Hz, 2H), 7.27e6.73 (m, 6H), 6.57
for C13H14ClN2O2S [MþH]þ: 297.2986; found: 297.2981.
(s, 1H), 6.48 (s, 1H), 2.39 (s, 3H). 13C NMR (CDCl3, 100 MHz, ppm)
d:
Compound 2g: Yellow solid, mp 141e142 ꢀC; IR (KBr)
n
(cmꢁ1):
150.5, 144.3, 134.8, 129.6, 128.1, 127.5, 125.5, 122.8, 120.9, 117.0,
21.6. HRMS (ESI): calcd for C13H14N2O3S [MþH]þ: 277.06471; found:
277.06464.
3344, 3247, 3032, 2926, 1916, 1846, 1728, 1655, 1625, 1318, 1159,
812, 713, 553. 1H NMR (CDCl3, 400 MHz, ppm)
d: 7.73 (d, J¼8.4 Hz,
2H), 7.22 (d, J¼8.0 Hz, 2H), 6.87 (t, J¼8.0 Hz, 1H), 6.63e6.38 (m, 3H),
Compound 2q: Yellow solid, mp 173e174 ꢀC; IR (KBr) (cmꢁ1):
n
5.57 (br, 1H), 2.34 (s, 3H), 2.01 (s, 3H). 13C NMR (CDCl3, 100 MHz,
3445, 2934, 2409, 1634, 1631, 1321, 1164, 1056, 956, 850. 1H NMR
(CDCl3, 400 MHz, ppm)
: 7.86 (d, J¼8.0 Hz, 2H), 7.26e6.30 (m, 7H),
ppm)
d: 144.3, 142.4, 137.8, 133.9, 129.5, 128.4, 127.8, 121.5, 114.0,
d