M.E. Bouillon, H.H. Meyer / Tetrahedron 72 (2016) 3151e3161
3157
4.1.1.1. 4-(4-Aminophenyl)-4-methylcyclohexa-2,5-dienimine (10/
19a). 46%; colourless, vitreous solid; 1H NMR (90 MHz, CDCl3)
4.1.1.7. 4-(4-Amino-2-chlorophenyl)-4-methylcyclohexa-2,5-
dienimine (19j). 59%; colourless, vitreous solid; 1H NMR (90 MHz,
d
[ppm] 1.54 (s, CH3), 3.7 (s, NH2), 6.19 (d, J¼11 Hz, 2ꢁCH), 6.34 (d,
CDCl3)
d
[ppm] 1.61 (s, CH3), 3.4 (s, NH2), 6.24 (d, J¼11 Hz, 2ꢁCH),
J¼11 Hz, 2ꢁCH), 6.62 (d, J¼8 Hz, 2ꢁAreH), 6.8 (br s, NH) 7.07 (d,
6.40 (d, J¼11 Hz, 2ꢁCH), 6.53 (dd, J1¼8 Hz, J2¼2 Hz, AreH), 6.65 (d,
J¼8 Hz, 2ꢁAreH); IR (CHCl3) v [cmꢂ1] 3450 (br), 3380 (br), 3250
J¼2 Hz, AreH), 7.1 (br s, NH) 7.16 (d, J¼8 Hz, AreH); IR (CHCl3) v
~
~
(br), 3000, 2970, 2930, 2870, 1665, 1620, 1575, 1510, 1455, 1430,
1340, 1280, 1185, 1165, 1085, 890, 825; MS (EI, 70 eV) m/z (%) 198
(98, Mþ), 197 (80), 183 (100), 182 (23), 171 (23), 156 (34); calcd for
[cmꢂ1] 3500 (br), 3400 (br), 3260 (br), 3040, 2980, 2930, 2870,
1655, 1620, 1605, 1570, 1490, 1460, 1430, 1280, 1250, 1160, 1085,
1050, 890, 850, 825; MS (EI, 70 eV) m/z (%) 234 (17, Mþ), 233 (16),
232 (47), 231 (17), 219 (13), 217 (38), 207 (11), 205 (31), 197 (100),
196 (52), 195 (20), 192 (13), 190 (29), 182 (48), 170 (17), 154 (21), 140
(12), 127 (26); calcd for C13H13ClN2: C 67.09, H 5.63, N 12.04; found:
C 67.00, H 5.65, N 12.03.
C
13H14N2: C 78.75, H 7.12, N 14.13; found: C 78.70, H 7.01, N 14.03.
4.1.1.2. 4-(4-Aminophenyl)-4-ethylcyclohexa-2,5-dienimine
(19b). 38%; colourless, vitreous solid; 1H NMR (90 MHz, CDCl3)
d
[ppm] 0.85 (t, J¼7.5 Hz, CH3), 2.00 (q, J¼7.5 Hz, CH2), 3.6 (br s,
NH2), 6.27 (d, J¼10 Hz, 2ꢁCH), 6.40 (d, J¼10 Hz, 2ꢁCH), 6.67 (d,
J¼8.5 Hz, 2ꢁArH), 7.12 (d, J¼8.5 Hz, 2ꢁArH), NH (not observed); IR
4.1.1.8. 4-(4-Amino-3-chlorophenyl)-4-methylcyclohexa-2,5-
dienimine (19k). 53%; colourless, vitreous solid; 1H NMR (90 MHz,
(CHCl3) v [cmꢂ1] 3460 (br), 3400 (br), 3250 (br), 3020, 3000, 2960,
CDCl3)
d
[ppm] 1.52 (s, CH3), 4.1 (br s, NH2), 6.26 (s, 4ꢁCH), 6.68 (d,
~
2940, 2880,1660,1620,1570,1510,1430,1280,1190,1160,1090, 905,
895, 825; MS (EI, 70 eV) m/z (%) 212 (50, Mþ), 211 (12), 197 (29), 184
(27), 183 (100), 156 (24), 140 (12), 77 (24); calcd for C14H16N2: C
79.21, H 7.60, N 13.20; found: C 79.16, H 7.58, N 13.11.
J¼8 Hz, AreH), 6.96 (dd, J1¼8 Hz, J2¼2 Hz, AreH), 7.15 (d, J¼2 Hz,
ArH), NH (not observed); IR (CHCl3) v [cmꢂ1] 3500 (br), 3400 (br),
~
3200 (br), 3030, 3000, 2970, 2880, 1660, 1620, 1600, 1570, 1500,
1460, 1430, 1400,1300, 1160, 1090, 890, 840, 820; MS (EI, 70 eV) m/z
(%) 234 (23, Mþ), 233 (35), 232 (68), 231 (70), 219 (37), 218 (29), 217
(100), 207 (18), 205 (43), 197 (39), 196 (37), 192 (23), 190 (56), 182
(61), 181 (35), 154 (41), 127 (45); calcd for C13H13ClN2: C 67.09, H
5.63, N 12.04; found: C 66.81, H 5.71, N 11.99.
4.1.1.3. 4-(4-Aminophenyl)-4-isopropylcyclohexa-2,5-dienimine
(19c). 27%; colourless, vitreous solid; 1H NMR (90 MHz, CDCl3)
d
[ppm] 0.87 (d, J¼7 Hz, 2ꢁCH3), 2.40 (sept, J¼7 Hz, CH), 4.0 (br s,
NH2), 6.40 (br s, 4ꢁCH), 6.62 (d, J¼9 Hz, 2ꢁAreH), 7.05 (d, J¼9 Hz,
2ꢁAreH), NH (not observed); IR (CHCl3) v [cmꢂ1] 3450 (br), 3400
4.1.1.9. 4-(4-Aminophenyl)-2,4-dimethylcyclohexa-2,5-dienimine
~
(br), 3250 (br), 3020, 3000, 2960, 2880, 1660, 1620, 1600 (w), 1570,
1510, 1430, 1380, 1280, 1190, 1160, 890, 820; MS (EI, 70 eV) m/z (%)
226 (16, Mþ), 211 (11), 184 (36), 183 (100), 168 (22), 167 (19), 156
(20), 149 (15); calcd for C15H18N2: C, 79.61, H, 8.02, N, 12.38; found:
C, 79.69, H, 8.07, N, 12.34.
(19l). 61%; colourless, vitreous solid; 1H NMR (90 MHz, CDCl3)
d
[ppm] 1.52 (s, CH3), 1.95 (d, J¼1 Hz, CH3), 3.8 (br s, NH2), 6.17 (dt,
J1¼2 Hz, J2¼1 Hz, CH), 6.18 (d, J¼10 Hz, CH), 6.33 (dd, J1¼10 Hz,
J2¼2 Hz, CH), 6.59 (d, J¼9 Hz, 2ꢁAreH), 7.05 (d, J¼9 Hz, 2 AreH), 7.2
(br s, NH); IR (CHCl3) v [cmꢂ1] 3450 (br), 3400 (br), 3250 (br), 3020,
~
3000, 2970, 2930, 2870, 1660, 1620, 1570, 1510, 1455, 1430, 1375,
1305, 1280, 1185, 900, 880, 830; MS (EI, 70 eV) m/z (%) 212 (44, Mþ),
211 (47), 198 (20), 197 (100), 196 (30), 195 (18), 185 (11), 182 (72),
181 (19), 180 (27), 170 (24), 168 (14), 152 (15), 143 (21); calcd for
4.1.1.4. 4-(4-Aminophenyl)-4-cyclopropylcyclohexa-2,5-
dienimine (19d). 22%; colourless, vitreous solid; 1H NMR (90 MHz,
CDCl3)
d
[ppm] 0.2e0.7 (m, 2ꢁCH2), 1.1e1.5 (m, CH), 3.2e5.0 (br s,
NH, NH2), 6.14 (d, J¼11 Hz, 2ꢁCH), 6.30 (d, J¼11 Hz, 2ꢁCH), 6.68 (d,
C14H16N2: C 79.20, H 7.60, N 13.20; found: C 79.10, H 7.60, N 13.14.
~
v
J¼9 Hz, 2ꢁAreH), 7.24 (d, J¼9 Hz, 2ꢁAreH); IR (CHCl3)
[cmꢂ1]:3400 (br), 3250 (br), 3000, 2960, 1670, 1625, 1570, 1520,
1515, 1430, 1340, 1280, 1185, 1165, 1025, 900, 830, 660; MS (EI,
70 eV) m/z (%) 224 (100, Mþ), 222 (17), 191 (20), 190 (26), 181 (91),
168 (18), 159 (31), 133 (54), 93 (24), 77 (30), 63 (20); calcd for
4.1.1.10. 4-(4-Aminophenyl)-3,4-dimethylcyclohexa-2,5-
dienimine (19m). 55%; colourless, crystalline solid; mp 116e120 ꢀC
(ether); 1H NMR (90 MHz, CDCl3)
d [ppm] 1.52 (s, CH3), 1.62 (d,
J¼1 Hz, CH3), 3.7 (br s, NH2), 6.11 (m, CH), 6.18 (s, 2ꢁCH), 6.59 (d,
~
C
15H16N2: C 80.32, H 7.19, N 12.49; found: C 80.24, H 7.17, N 12.38.
J¼8 Hz, 2ꢁArH), 6.77 (d, J¼8 Hz, 2ꢁArH), 8.2 (br s, NH); IR (CHCl3) v
[cmꢂ1] 3450 (br), 3400 (br), 3250 (br), 3040, 3000, 2970, 2940,
2880, 1660, 1620, 1570, 1510, 1430, 1375, 1280, 1180, 1170, 1140,
1010, 900, 870, 825; MS (EI, 70 eV) m/z (%) 212 (70, Mþ), 211 (78),
197 (100), 196 (34), 195 (19), 185 (34), 182 (30), 181 (15), 180 (18),
170 (56), 169 (15), 168 (17), 167 (13); calcd for C14H16N2: C 79.20, H
7.60, N 13.20; found: C 79.01, H 7.55, N 13.12.
4.1.1.5. 4-(4-Aminophenyl)-4-butylcyclohexa-2,5-dienimine
(19e). 17%; colourless, vitreous solid; 1H NMR (90 MHz, CDCl3)
d
[ppm] 0.88 (t, J¼7 Hz, CH3), 1.28 (m, 2ꢁCH2), 1.94 (m, CH2), 3.7 (br
s, NH2), 6.31 (s, 4ꢁCH), 6.61 (d, J¼9 Hz, 2ꢁAreH), 7.08 (d, J¼9 Hz,
2ꢁAreH), NH (not observed); IR (CHCl3) v [cmꢂ1] 3450 (br), 3400
~
(br), 3200 (br), 3020, 3000, 2960, 2930, 2860, 1660, 1620, 1570,
1510, 1475, 1440, 1340, 1280, 1185, 1160, 1100, 890, 825; MS (EI,
70 eV) m/z (%) 240 (22, Mþ), 197 (16), 184 (31), 183 (100), 156 (18),
85 (46), 83 (61); calcd for C16H20N2: C 79.96, H 8.39, N 11.66; found:
C 79.79, H 8.25, N 11.51.
4.1.1.11. 4-(4-Amino-2-methylphenyl)-4-methylcyclohexa-2,5-
dienimine (19n). 53%; colourless, vitreous solid; 1H NMR (90 MHz,
CDCl3)
d [ppm] 1.54 (s, CH3), 2.10 (s, CH3), 3.4 (br s, NH2), 6.27 (s,
4ꢁCH), 6.40 (d, J¼2.5 Hz, AreH), 6.52 (dd, J1¼8 Hz, J2¼2.5 Hz, AreH)
7.0 (br s, NH), 7.15 (d, J¼8 Hz, AreH); IR (CHCl3) v [cmꢂ1] 3450 (br),
~
4.1.1.6. 4-(4-Aminophenyl)-2-chloro-4-methylcyclohexa-2,5-
3400 (br), 3250 (br), 3040, 3000, 2970, 2930, 2880,1650,1620,1600
(w), 1570, 1500, 1460, 1430, 1265, 1080, 1020, 890, 860, 830; MS (EI,
70 eV) m/z (%) 212 (100, Mþ), 211 (26), 197 (75), 196 (24), 195 (20),
182 (23), 181 (19), 180 (24), 170 (22), 143 (31); calcd for C14H16N2: C
79.20, H 7.60, N 13.20; found: C 79.02, H 7.53, N 13.08.
dienimine (19i). 53%; colourless, vitreous solid; 1H NMR (90 MHz,
CDCl3)
d
[ppm] 1.60 (s, CH3), 3.72 (br s, NH2), 6.35 (dd, J1¼9.5 Hz,
J2¼2 Hz, CH), 6.49 (d, J¼9.5 Hz, CH), 6.56 (d, J¼2 Hz, CH), 6.65 (d,
J¼8 Hz, 2ꢁAreH), 7.06 (d, J¼8 Hz, 2ꢁAreH), 9.7 (br s, NH); IR
(CHCl3) v [cmꢂ1] 3450 (br), 3400 (br), 3260 (br), 3030, 3000, 2970,
~
2940, 2870, 2840, 1650, 1620, 1610, 1580, 1510, 1410, 1375, 1280,
1185, 1010, 980, 900, 820; MS (EI, 70 eV) m/z (%) 234 (8, Mþ), 233
(10), 232 (25), 231 (19), 219 (15), 217 (47), 197 (100), 196 (38), 195
(23), 192 (6), 190 (19), 182 (71), 181 (30), 180 (27), 170 (17), 154 (26);
calcd for C13H13ClN2: C 67.09, H 5.63, N 12.04; found: C 66.96, H
5.57, N 12.04.
4.1.1.12. 4-(4-Aminophenyl)-2,4,6-trimethylcyclohexa-2,5-
dienimine (12/19o). 83%; colourless, crystalline solid; mp
132e133 ꢀC (ethyl acetate/petrol ether); 1H NMR (90 MHz, CDCl3)
d
[ppm] 1.50 (s, CH3), 1.98 (s, 2ꢁCH3), 3.6 (br s, NH2), 6.19 (s, 2ꢁCH),
6.60 (d, J¼8 Hz, 2ꢁAreH), 7.05 (d, J¼8 Hz, 2ꢁAreH), 8.3 (br s, NH);
13C NMR (50 MHz, CDCl3)
[ppm] 167.90 (s), 145.31 (s), 144.51 (d),
d