1376
K. Smith et al.
PAPER
Hz, exch., 1 H, NH), 5.83 (s, exch., 1 H, OH), 3.99 (d, J = 6 Hz, 2
H, CH2NH), 3.68 (s, 2 H, CH2COH), 2.79 [s, 6 H, N(CH3)2].
IR (FT): 3314, 2971, 1627, 1542, 1367, 1216, 1055 cm–1.
1H NMR (400 MHz, CDCl3): d = 7.42–7.21 (m, 9 H, C6H5, H-3, H-
4, H-5, H-6), 6.69 (br app. t, exch., 1 H, NH), 4.94 (dd, J = 9, 4 Hz,
1 H, CH), 4.53 (dd, J = 6, 14 Hz, 1 H, CHaHbNH), 4.33 (dd, J = 2,
14 Hz, 1 H, CHaHbNH), 3.10 (dd, J = 9, 14 Hz, 1 H, CHaHbCH),
3.01 (dd, J = 4, 14 Hz, 1 H, CHaHbCH), 2.78 (br, exch., 1 H, OH),
1.19 [s, 9 H, C(CH3)3].
13C NMR (100 MHz, DMSO-d6): d = 158.5 (C=O), 148.5 (C-1 of 2
C6H5), 140.9 (C-1), 135.4 (C-2), 131.8 (C-3), 128.0 (C-6), 127.9 (C-
3/C-5 of 2 C6H5), 126.8 (C-2/C-6 of 2 C6H5), 126.6 (C-4 of 2 C6H5),
126.0 (C-4), 125.4 (C-5), 77.8 (COH), 42.9 (CH2), 41.3 (CH2), 36.3
[N(CH3)2].
MS (EI): m/z (%) = 374 (2, [M]+), 357 (11), 268 (100), 252 (16),
239 (12), 206 (25).
MS (CI): m/z (%) = 375 (12, [MH]+), 374 (6, [M]+), 373 (5), 359
(33), 357 (89), 286 (10), 257 (12), 200 (81), 193 (100), 183 (71),
179 (17), 118 (24), 106 (55), 89 (87), 63 (15).
MS (ES+): m/z (%) = 397 (100, [M + Na]+), 375 (4, [MH]+), 358
(13), 357 (69), 270 (14), 269 (52), 191(34), 89 (78).
MS (ES–): m/z (%) = 374 (2, [M]–), 373 (8), 191 (100), 146 (9), 118
(21), 87 (25).
13C NMR (100 MHz, CDCl3): d = 178.7 (C=O), 144.6 (C-1), 137.7
(C-1 of C6H5), 137.6 (C-2), 130.8 (C-3), 130.3 (C-6), 128.9 (C-3/C-
5 of C6H5), 128.3 (C-4 of C6H5), 128.1 (C-4), 127.4 (C-5), 126.2 (C-
2/C-6 of C6H5), 76.2 (CH), 42.5 (CH2), 41.8 (CH2), 39.1 [C(CH3)3],
28.0 [C(CH3)3].
MS (EI): m/z (%) = 311 (6, [M]+), 295 (31), 294 (100), 278 (8).
MS (CI): m/z (%) = 329 (9, [M + NH4]+), 313 (13, [MH + 1]+), 312
(78, [MH]+), 294 (100), 234 (8), 206 (12), 205 (17), 192 (7), 119
(10), 102 (9).
HRMS-CI: m/z [MH]+ calcd for C20H26NO2: 312.1958; found:
312.1955.
HRMS-CI: m/z [M + NH4]+ calcd for C24H30N3O2: 392.2333; found:
392.2330.
Anal. Calcd for C20H25NO2: C, 77.14; H, 8.09; N, 4.50. Found: C,
77.21; H, 8.14; N, 4.54.
N¢-(2-Propylbenzyl)-N,N-dimethylurea (13)
Yield: 0.36 g (82%, 1.64 mmol); mp 59–61 °C.
N-{2-[2-Hydroxy-2-(4-methoxyphenyl)ethyl]benzyl}pival-
amide (16)
Yield: 0.61 g (89%, 1.79 mmol); mp 124–126 °C.
IR (FT): 3321, 2954, 1629, 1555, 1463, 1370, 1220, 1035 cm–1.
IR (FT): 3325, 2957, 1631, 1529, 1375, 1227 cm–1.
1H NMR (400 MHz, CDCl3): d = 7.20–7.05 (m, 4 H, H-3, H-4, H-
5, H-6), 4.58 (br, exch., 1 H, NH), 4.33 (br, 2 H, CH2NH), 2.80 [s,
6 H, N(CH3)2], 2.54 (t, J = 7 Hz, 2 H, CH2CH2CH3), 1.53 (app. sext,
J = 7 Hz, 2 H, CH2CH3), 0.89 (t, J = 7 Hz, 3 H, CH2CH3).
13C NMR (100 MHz, CDCl3): d = 158.6 (C=O), 141.3 (C-1), 137.1
(C-2), 129.9 (C-3), 129.1 (C-6), 127.8 (C-4), 126.5 (C-5), 42.9
(CH2NH), 36.6 [N(CH3)2], 34.9 (CH2CH2CH3), 24.8 (CH2CH3),
14.5 (CH2CH3).
1H NMR (400 MHz, CDCl3): d = 7.29 (d, J = 9 Hz, 2 H, H-2/H-6 of
4-methoxyphenyl), 7.28–7.20 (m, 4 H, H-3, H-4, H-5, H-6), 6.88 (d,
J = 9 Hz, 2 H, H-3/H-5 of 4-methoxyphenyl), 6.83 (br, exch., 1 H,
NH), 4.87 (dd, J = 4, 9 Hz, 1 H, CH), 4.49 (dd, J = 6, 14 Hz, 1 H,
CHaHbNH), 4.30 (dd, J = 4, 14 Hz, 1 H, CHaHbNH), 3.80 (s, 3 H,
OCH3), 3.22 (br, exch., 1 H, OH), 3.07 (dd, J = 9, 14 Hz, 1 H,
CHaHbCH), 2.94 (dd, J = 4, 14 Hz, 1 H, CHaHbCH), 1.17 [s, 9 H,
C(CH3)3].
13C NMR (100 MHz, CDCl3): d = 178.8 (C=O), 159.4 (C-4 of 4-
methoxyphenyl), 137.9 (C-1), 137.5 (C-2), 137.0 (C-1 of 4-meth-
oxyphenyl), 130.8 (C-3), 130.2 (C-6), 128.2 (C-4), 127.6 (C-2/C-6
of 4-methoxyphenyl), 127.3 (C-5), 114.2 (C-3/C-5 of 4-methoxy-
phenyl), 75.7 (CH), 55.7 (OCH3), 42.5 (CH2), 41.9 (CH2), 39.01
[C(CH3)3], 28.0 [C(CH3)3].
MS (EI): m/z (%) = 220 (31, [M]+), 177 (13), 148 (10), 132 (47),
117 (82), 105 (53), 91 (22), 89 (34), 77 (24), 72 (100), 65 (15), 46
(23), 44 (69), 42 (33).
MS (CI): m/z (%) = 441 (12, [2 M + 1]+), 238 (13, [M + NH4]+), 221
(100, [MH]+).
HRMS-CI: m/z [MH]+ calcd for C13H21N2O: 221.1648; found:
221.1648.
MS (EI): m/z (%) = 341 (5, [M]+), 324 (63), 323 (79), 308 (5), 266
(21), 254 (13), 238 (100).
MS (CI): m/z (%) = 357 (4, [M + NH4]+), 342 (8, [MH]+), 341 (20,
[M]+), 325 (24), 324 (100), 251 (4), 234 (6), 205 (7), 154 (8), 119
(15), 102 (7), 52 (10).
MS (ES+): m/z (%) = 364 (19, [M + Na]+), 324 (33), 223 (100).
MS (ES–): m/z (%) = 340 (12, [M – 1]–), 205 (12) 204 (100), 100
N¢-(2-Deuteriomethylbenzyl)-N,N-dimethylurea (14)
Yield: 0.32 g (83%, 1.66 mmol); mp 73–75 °C (Lit.29 undeuterated
analogue: mp 73–75 °C).
IR (FT): 3315, 2926, 1622, 1537, 1512, 1376, 12.35, 1027 cm–1.
1H NMR (400 MHz, CDCl3): d = 7.26–7.12 (m, 4 H, H-3, H-4, H-
5, H-6), 4.61 (br, exch., 1 H, NH), 4.42 (br, 2 H, CH2NH), 2.91 [s,
6 H, N(CH3)2], 2.31 (seen as three lines, 1:1:1, because of coupling
to D, 2 H, CH2D).
13C NMR (100 MHz, CDCl3): d = 158.7 (C=O), 137.5 (C-1), 136.8
(C-2), 130.8 (C-6), 128.7 (C-3), 127.8 (C-5), 126.5 (C-4), 43.6
(CH2NH), 36.6 [N(CH3)2], 19.4 (seen as three lines, 1:1:1, because
of coupling to D, CH2D).
(28).
HRMS-CI: m/z [MH]+ calcd for C21H28NO3: 342.2064; found:
342.2065.
N-[2-(2-Hydroxy-2-phenylpropyl)benzyl]pivalamide (17)
Yield: 0.52 g (80%, 1.60 mmol); mp 135–137 °C.
IR (FT): 3324, 2964, 1623, 1493, 1242, 1025 cm–1.
MS (EI): m/z (%) = 194 (15, [M + 1]+), 193 (43), 149 (11), 121 (37),
106 (71), 105 (66), 92 (21), 78 (24), 77 (21), 72 (100), 46 (32), 44
(79), 42 (27).
1H NMR (400 MHz, CDCl3): d = 7.43 (d, J = 8 Hz, 2 H, H-2/H-6 of
C6H5), 7.35 (t, J = 8 Hz, 2 H, H-3/H-5 of C6H5), 7.30–7.26 (m, 2 H,
H-4 of C6H5 and H-6), 7.20 (app. dt, J = 2, 8 Hz, 1 H, H-4), 7.12
(app. dt, J = 2, 8 Hz, 1 H, H-5), 6.87 (dd, J = 2, 8 Hz, 1 H, H-3), 6.55
(br app. t, exch., 1 H, NH), 4.44 (dd, J = 5, 14 Hz, 1 H, CHaHbNH),
4.37 (dd, J = 5, 14 Hz, 1 H, CHaHbNH), 3.17 (d, J = 14 Hz, 1 H,
CHaHbCOH), 3.12 (d, J = 14 Hz, 1 H, CHaHbCOH), 2.42 (s, exch.,
1 H, OH), 1.68 (s, 3 H, CH3COH), 1.21 [s, 9 H, C(CH3)3].
MS (CI): m/z (%) = 211 (17, [M + NH4]+), 195 (23), 194 (100,
[MH]+), 52 (20).
HRMS-CI: m/z [MH]+ calcd for C11H16DN2O: 194.1398; found:
194.1398.
N-[2-(2-Hydroxy-2-phenyethyl)benzyl]pivalamide (15)
Yield: 0.52 g (84%, 1.67 mmol); mp 133–134 °C.
Synthesis 2010, No. 8, 1371–1380 © Thieme Stuttgart · New York