Oxidation of Anilines with tert-Butyl Hydroperoxide
J . Org. Chem., Vol. 61, No. 10, 1996 3325
2a : mp 197-199 °C (lit.28 mp 205-206 °C); IR (KBr) 1531,
1379 cm-1; 1H NMR (CDCl3) δ 1.31 (s, 18H), 1.22 (s, 9H), 7.37
(s, 2H); 13C NMR (CDCl3) δ 147.34 (C1), 140.37 (C2/6), 123.76
(C3/5), 151.57 (C4), 36.54 (C7), 31.48 (C8), 35.36 (C9), 31.48
(C10). Anal. Calcd for C18H29NO2: C, 74.18; H, 10.03; N, 4.81.
Found: C, 74.29; H, 9.84; N, 4.65.
30.89 (C8). Anal. Calcd for C14H20N2O4: C, 59.99; H, 7.19;
N, 9.99. Found: C, 60.33; H, 7.71; N, 9.32.
2e-2: mp 104-105 °C; IR (KBr) 1533, 1377 cm-1; 1H NMR
(CDCl3) δ 1.35 (s, 18H), 3.78 (s, 3H), 6.92 (d, J ) 8.6 Hz, 2H),
7.39 (d, J ) 8.8 Hz, 2H), 7.49 (s, 2H); 13C NMR (CDCl3) δ
148.33 (C1), 141.50 (C2/6), 125.37 (C3/5), 141.73 (C4), 36.50
(C7), 31.45 (C8), 133.39 (C9), 128.67 (C10/14), 114.62 (C11/
13), 159.90 (C12), 55.63 (C15). Anal. Calcd for C21H27NO3:
C, 73.87; H, 7.97; N, 4.10. Found: C, 74.20; H, 7.87; N, 3.79.
2e-3: mp 101-102 °C; IR (KBr) 1535, 1377 cm-1; 1H NMR
(CDCl3) δ 1.38 (s, 18H), 2.02 (s, 6H), 2.33 (s, 3H), 6.98 (s, 2H),
7.22 (s, 2H); 13C NMR (CDCl3) δ 147.94 (C1), 141.17 (C2/6),
127.98 (C3/5), 141.79 (C4), 36.51 (C7), 31.50 (C8), 138.47 (C9),
136.07 (C10/14), 128.61 (C11/13), 137.48 (C12), 21.10 (C15/
17), 21.28 (C16). Anal. Calcd for C23H31NO2: C, 78.15; H,
8.84; N, 3.96. Found: C, 77.98; H, 8.74; N, 3.90.
2e-4: mp 119-120 °C; IR (KBr) 1531, 1379 cm-1; 1H NMR
(CDCl3) δ 1.42 (s, 18H), 2.41 (s, 3H), 7.27 (d, J ) 8.0 Hz, 2H),
7.42 (d, J ) 8.2 Hz, 2H), 7.58 (s, 2H); 13C NMR (CDCl3) δ
148.73 (C1), 141.70 (C2/6), 125.85 (C3/5), 142.28 (C4), 36.72
(C7), 31.65 (C8), 141.70 (C9), 127.67 (C10/14), 130.06 (C11/
13), 138.28 (C12), 21.57 (C15). Anal. Calcd for C21H27NO2:
C, 77.50; H, 8.36; N, 4.30. Found: C, 77.32; H, 8.42; N, 4.22.
3a : mp 45-47 °C; IR (KBr) 1574, 1363 cm-1 1H NMR
;
(CDCl3) δ 0.91 (s, 9H), 1.20 (s, 9H), 1.31 (s, 18H), 6.29 (s, 2H),
9.68 (s, 1H, NH); 13C NMR (CDCl3) δ 168.29 (C1), 146.01 (C2/
6), 134.80 (C3/5), 83.38 (C4),* 35.17 (C7), 30.82 (C8), 78.85
(C9),* 26.64 (C10),* 41.36 (C11), 25.87 (C12).* Anal. Calcd
for C22H39NO2: C, 75.59; H, 11.25; N, 4.01. Found: C, 75.78;
H, 11.40; N, 4.01. The asterisks denote signals not to be
assigned.
2e-5: mp 80-82 °C; IR (KBr) 1531, 1377 cm-1 1H NMR
;
(CDCl3) δ 1.43 (s, 18H), 7.39-7.55 (m, 5H), 7.61 (s, 2H); 13C
NMR (CDCl3) δ 148.40 (C1), 141.34 (C2/6), 125.63 (C3/5),
141.94 (C4), 36.31 (C7), 31.21 (C8), 140.71 (C9), 127.41(C10/
3b: mp 72-73 °C; IR (KBr) 1574, 1363 cm-1 1H NMR
;
14), 128.93 (C11/13), 127.92 (C12). Anal. Calcd for C20H25
-
(CDCl3) δ 1.20 (s, 9H), 1.27 (s, 3H), 1.30 (s, 18H), 6.20 (s, 2H);
13C NMR (CDCl3) δ 167.58 (C1), 145.23 (C2/6), 134.80 (C3/5),
77.18 (C4),* 34.87 (C7), 30.64 (C8), 78.97 (C9),* 26.58 (C10),
24.68 (C11). Anal. Calcd for C19H33NO2: C, 74.22; H, 10.82;
N, 4.56. Found: C, 74.48; H, 11.22; N, 4.46.
NO2: C, 77.14; H, 8.09; N, 4.50. Found: C, 76.92; H, 8.15; N,
4.11.
2e-6: mp 154-155 °C; IR (KBr) 1531, 1377 cm-1; 1H NMR
(CDCl3) δ 1.35 (s, 18H), 7.35 (d, J ) 8.7 Hz, 2H), 7.38 d, J )
8.6 Hz, 2H), 7.49 (s, 2H); 13C NMR (CDCl3) δ 148.57 (C1),
141.50 (C2/6), 125.36 (C3/5), 140.64 (C4), 36.23 (C7), 31.10
(C8), 139.00 (C9), 128.55 (C10/14), 129.01 (C11/13), 134.08
(C12). Anal. Calcd for C20H24ClNO2: C, 69.45; H, 7.00; N,
4.05. Found: C, 69.04; H, 7.25; N, 4.21.
3e-2: mp 56-58 °C; IR (KBr) 1578, 1363 cm-1 1H NMR
;
(CDCl3) δ 1.23 (s, 9H), 1.32 (s, 18H), 3.73 (s, 3H), 6.31 (s, 2H),
6.7-7.3 (m, 4H); 13C NMR (CDCl3) δ 167.64 (C1), 144.93 (C2/
6), 134.33 (C3/5), 80.28 (C4),* 35.05 (C7), 30.64 (C8), 79.32
(C9),* 26.64 (C10), 133.31 (C11), 127.12 (C12/16), 113.71 (C13/
15), 159.00 (C14), 55.13 (C17). Anal. Calcd for C25H37NO3:
C, 75.15; H, 9.33; N, 3.51. Found: C, 74.74; H, 9.33; N, 3.47.
2f: mp 41-42 °C (lit.30 mp 43-44 °C); IR (KBr) 1520, 1369
cm-1 1H NMR (CDCl3) δ 2.26 (s, 6H), 2.29 (s, 3H), 6.89 (s,
;
2H); 13C NMR (CDCl3) δ 149.78 (C1), 129.59 (C2/6), 129.43 (C3/
3e-4: mp 55-57 °C; IR (KBr) 1574, 1365 cm-1 1H NMR
;
5), 140.30 (C4), 21.03 (C7), 17.54 (C8).
(CDCl3) δ 1.24 (s, 9H), 1.32 (s, 18H), 2.30 (s, 3H), 6.35 (s, 2H),
7.02-7.28 (m, 4H); 13C NMR (CDCl3) δ 167.76 (C1), 145.05
(C2/6), 134.33 (C3/5), 80.51 (C4),* 35.11 (C7), 30.70 (C8), 79.38
(C9),* 26.70 (C10), 138.32 (C11), 125.80 (C12/16), 129.02 (C13/
15), 137.19 (C14), 21.10 (C17). Anal. Calcd for C25H37NO2:
C, 78.28; H, 9.72; N, 3.65. Found: C, 77.66; H, 9.61; N, 3.37.
2g: mp 146-147 °C (lit.31 mp 144-145 °C); IR (KBr) 1531,
1367 cm-1; 1H NMR (CDCl3) δ 7.69 (s, 2H), 7.66-7.71 (m, 2H),
7.45-7.55 (m, 13H); 13C NMR (CDCl3) δ 148.70 (C1), 135.14
(C2/6), 143.06 (C4), 136.62 (C7), 138.91 (C9), 129.20, 128.93,
128.85, 128.76, 128.63, 128.25, 127.44 (7Carom-H).
1
2k : mp 105-106 °C; IR (KBr) 1525, 1341 cm-1; H NMR
3e-5: mp 58-59 °C; IR (KBr) 1574, 1365 cm-1 1H NMR
;
(CDCl3) δ 1.25 (s, 18H), 7.67 (t, J ) 1.7 Hz, 1H), 7.99 (d, J )
1.7 Hz, 2H); 13C NMR (CDCl3) δ 148.32 (C1), 117.77 (C2/6),
152.69 (C3/5), 128.77 (C4), 35.24 (C7), 31.23 (C8). Anal. Calcd
for C14H21NO2: C, 71.46; H, 8.99; N, 5.95. Found: C, 70.75;
H, 9.03; N, 6.04.
(CDCl3) δ 1.36 (s, 18H), 1.23 (s, 9H), 6.38 (s, 2H), 7.18-7.45
(m, 5H); 13C NMR (CDCl3) δ 167.76 (C1), 145.17 (C2/6), 134.45
(C3/5), 80.63 (C4),* 35.11 (C7), 30.64 (C8), 79.50 (C9),* 26.64
(C10), 141.52 (C11), 125.86 (C12/16), 128.31 (C13/15), 127.47
(C14). Anal. Calcd for C24H35NO2: C, 78.01; H, 9.55; N, 3.79.
Found: C, 77.68; H, 9.51; N, 3.66.
2l: mp 84-85 °C; IR (KBr) 1541, 1346 cm-1 1H NMR
;
(CDCl3) δ 1.35 (s, 18H), 8.28 (s, 2H); 13C NMR (CDCl3) δ 147.31
3e-6: mp 83-84 °C; IR (KBr) 1580, 1365 cm-1 1H NMR
;
(C1), 122.14 (C2/6), 143.65 (C3/5), 152.32 (C4), 36.81 (C7),
(CDCl3) δ 1.24 (s, 9H), 1.32 (s, 18H), 6.31 (s, 2H), 7.26 (s, 4H),
9.96 (s, 1H, NH); 13C NMR (CDCl3) δ 167.64 (C1), 145.64 (C2/
6), 133.32 (C3/5), 80.32 (C4),* 35.12 (C7), 30.64 (C8), 79.71
(C9),* 26.66 (C10), 139.99 (C11), 127.34 (C12/16), 128.49 (C13/
15), 133.32 (C14). Anal. Calcd for C24H34ClNO2: C, 71.35;
H, 8.48; N, 3.37. Found: C, 70.95; H, 8.50; N, 3.40.
(28) Burgers, J .; Hoefnagel, M. A.; Verkade, P. E.; Visser, E. H.;
Wepster, M. Recl. Trav. Chim. Pay-Bas 1958, 77, 491. Burgers, J .; van
Hartingsveldt, W.; van Keulen, F.; Verkade, P. E.; Visser, H.; Wepster,
B. M. Recl. Trav. Chim. Pays-Bas 1956, 75, 1327.
(29) Cauquis, G.; Fauvelot, G.; Rigaudy, F. Bull. Soc. Chim. Fr.
1968, 4928.
(30) Powell, G.; J ohnson, F. R. Organic Syntheses; Wiley: New York,
1950; Collect. Vol. II, p 449.
(31) Dimroth, K.; Berndt, A.; Reichardt, C. Organic Syntheses;
Wiley: New York, 1973; Collect. Vol. V, p 1128.
5: liquid; IR (neat) 1649, 1365 cm-1; 1H NMR (CDCl3) δ 1.20
(s, 9H), 1.90 (s, 6H), 6.62 (s, 2H); 13C NMR (CDCl3) δ 187.01
(C1), 134.86 (C2/6), 145.71 (C3/5), 76.05 (C4),* 23.43 (C7), 15.80
(C8), 79.62 (C9),* 26.41 (C10); MS 224 (M+).