1268
N-(Cyclohex-2-enyl)phenothiazine (7b) 1H-NMR (CDCl3) d 1.78—
1.86 (1H, m), 1.95—2.04 (2H, m), 2.14—2.24 (2H, m), 2.29—2.37 (1H, m),
4.71—4.77 (1H, m), 5.94—5.98 (1H, m), 6.18—6.22 (1H, m), 6.89 (2H, dt,
Jꢀ0.8, 6.0 Hz), 7.07—7.11 (4H, m), 7.15 (2H, dd, Jꢀ0.8, 6.4 Hz); 13C-NMR
(CDCl3) d 22.7 (t), 24.9 (t), 26.9 (t), 58.3 (d), 117.1 (d), 122.4 (d), 125.8 (s),
126.9 (d), 127.3 (d), 129.8 (d), 131.4 (d), 145.6 (s); EI-MS m/z: 279 (Mꢁ),
207, 167, 149, 121, 104; HR-MS m/z: 279.1081 (Calcd for C18H17NS:
279.1082).
Vol. 53, No. 10
149.5 (s); EI-MS m/z: 218 (Mꢁ), 201, 190, 173, 157, 143, 117, 115, 79, 77;
HR-MS m/z: 217.0974 (Calcd for C12H13N2O2: 217.0977).
N,N-Diallyl-4-nitroaniline (4e) 1H-NMR (CDCl3) d 4.02 (4H, ddd,
Jꢀ1.6, 1.6, 4.8 Hz), 5.16 (2H, ddt, Jꢀ1.6, 2.0, 17.2 Hz), 5.23 (2H, ddt,
Jꢀ1.6, 2.0, 10.4 Hz), 5.84 (2H, ddt, Jꢀ4.8, 10.4, 17.2 Hz), 6.62 (2H, d,
Jꢀ9.2 Hz), 8.07 (2H, d, Jꢀ9.2 Hz); 13C-NMR (CDCl3) d 52.9 (t), 110.7 (d),
116.8 (t), 126.0 (d), 131.7 (d), 137.1 (s), 153.2 (s); EI-MS m/z: 218 (Mꢁ),
202, 191, 171, 157, 145, 130, 117, 91, 77; HR-MS m/z: 218.1054 (Calcd for
C13H17N2O2: 218.1055).
N-Allyl-2-nitroaniline (3c)83,84) mp 51—53 °C; IR (KBr) cmꢂ1: 3387;
1H-NMR (CDCl3) d 3.93 (2H, ddd, Jꢀ0.8, 1.2, 4.4 Hz), 5.21 (1H, ddt,
Jꢀ0.8, 0.8, 8.4 Hz), 5.28 (1H, ddt, Jꢀ0.8, 1.2, 14.0 Hz), 5.92 (1H, ddt,
Jꢀ4.4, 8.4, 14.0 Hz), 6.60 (1H, ddd, Jꢀ0.8, 5.6, 6.4 Hz), 6.78 (1H, d,
Jꢀ6.8 Hz), 7.38 (1H, ddd, Jꢀ0.8, 5.6, 6.8 Hz), 8.10 (1H, ddd, Jꢀ0.8, 0.8,
6.4 Hz), 8.15 (1H, bs); 13C-NMR (CDCl3) d 45.2 (t), 114.1 (d), 115.4 (d),
116.8 (t), 126.6 (d), 131.9 (s), 133.3 (d), 136.1 (d), 145.3 (s); EI-MS m/z:
178 (Mꢁ), 151, 131, 130, 119, 105, 91, 78, 77; HR-MS m/z: 178.0742
(Calcd for C9H10N2O2: 178.0742).
N-Cinnamyl-4-nitroaniline (5e)82) mp 142—143 °C; IR (KBr) cmꢂ1
:
3349; 1H-NMR (CDCl3) d 4.03 (2H, dd, Jꢀ1.2, 5.6 Hz), 4.83 (1H, bs), 6.26
(1H, dt, Jꢀ1.6, 16.0 Hz), 6.57—6.63 (3H, m), 7.24—7.37 (5H, m), 8.09
(2H, d, Jꢀ8.8 Hz); 13C-NMR (CDCl3) d 45.4 (t), 111.3 (d), 124.6 (d), 126.4
(d), 127.9 (d), 128.6 (d), 132.6 (d), 136.2 (s), 138.1 (s), 153.1 (s); EI-MS
m/z: 254 (Mꢁ), 237, 221, 207, 177, 130, 117, 115, 91, 77; HR-MS m/z:
254.1054 (Calcd for C15H14N2O2: 254.1055).
N,N-Dicinnamyl-4-nitroaniline (6e)82) mp 157—158 °C; 1H-NMR
(CDCl3) d 4.25 (4H, dd, Jꢀ1.2, 5.2 Hz), 6.23 (2H, dt, Jꢀ5.2, 16.0 Hz), 6.52
(2H, dt, Jꢀ1.2, 16.0 Hz), 6.76 (2H, d, Jꢀ9.6 Hz), 7.24—7.37 (10H, m), 8.13
(2H, d, Jꢀ9.6 Hz); 13C-NMR (CDCl3) d 52.5 (t), 110.9 (d), 123.3 (d), 126.3
(d), 126.4 (d), 128.0 (d), 128.7 (d), 132.3 (d), 136.2 (s), 137.8 (s), 153.3 (s);
EI-MS m/z: 370 (Mꢁ), 279, 265, 189, 167, 149, 117, 115, 91, 77; HR-MS
m/z: 370.1683 (Calcd for C24H22N2O2: 370.1681).
N-Cinnamyl-2-nitroaniline (5c)82) mp 70—71 °C; IR (KBr) cmꢂ1
:
3386; 1H-NMR (CDCl3) d 4.14 (2H, dd, Jꢀ1.6, 5.6 Hz), 6.29 (1H, dt,
Jꢀ5.6, 16.0 Hz), 6.62 (1H, dt, Jꢀ1.6, 16.0 Hz), 6.67 (1H, dd, Jꢀ1.6,
7.2 Hz), 6.89 (1H, dd, Jꢀ1.2, 8.8 Hz), 7.22—7.27 (1H, m), 7.30—7.38 (4H,
m), 7.42 (1H, ddd, Jꢀ1.6, 6.8, 8.8 Hz), 8.19 (1H, dd, Jꢀ1.6, 8.8 Hz), 8.25
(1H, bs); 13C-NMR (CDCl3) d 44.9 (t), 114.1 (d), 115.6 (d), 124.7 (d), 126.4
(d), 126.8 (d), 127.8 (d), 128.6 (d), 132.1 (s), 132.2 (d), 136.2 (d), 136.3 (s),
145.2 (s); EI-MS m/z: 254 (Mꢁ), 219, 207, 130, 117, 115, 91, 77; HR-MS
m/z: 254.1053 (Calcd for C15H14N2O2: 254.1055).
3-(4-Nitrophenylamino)cyclohexene (7e)82) mp 99—101 °C; IR (KBr)
cmꢂ1: 3422; H-NMR (CDCl3) d 1.63—1.77 (3H, m), 1.91—2.06 (1H, m),
1
2.06—2.09 (2H, m), 4.08 (1H, bs), 4.66—4.71 (1H, m), 5.70 (1H, ddt,
Jꢀ1.6, 3.2, 10.0 Hz), 5.93 (1H, ddt, Jꢀ1.6, 3.6, 10.0 Hz), 6.54 (2H, d,
Jꢀ9.2 Hz), 8.06 (2H, d, Jꢀ9.2 Hz); 13C-NMR (CDCl3) d 19.4 (t), 24.9 (t),
28.5 (t), 47.7 (d), 111.3 (d), 126.6 (d), 126.6 (d), 131.7 (d), 137.6 (s), 152.5
(s); EI-MS m/z: 218 (Mꢁ), 202, 190, 171, 143, 130, 123, 117, 108, 81, 79,
77; HR-MS m/z: 218.1055 (Calcd for C12H14N2 O2: 218.1055).
3-(2-Nitrophenylamino)cyclohexene (7c) IR (KBr) cmꢂ1: 3375; 1H-
NMR (CDCl3) d 1.63—1.82 (3H, m), 1.96—2.18 (3H, m), 4.17—4.23 (1H,
m), 5.75 (1H, ddt, Jꢀ2.0, 3.2, 10.0 Hz), 5.96 (1H, ddt, Jꢀ1.6, 3.6, 10.0 Hz),
6.63 (1H, ddd, Jꢀ1.6, 6.8, 8.4 Hz), 6.91 (1H, d, Jꢀ8.4 Hz), 7.42 (1H, ddd,
Jꢀ1.6, 6.8, 8.4 Hz), 8.09 (1H, bs), 8.18 (1H, dd, Jꢀ1.6, 8.4 Hz); 13C-NMR
(CDCl3) d 19.5 (t), 24.9 (t), 28.7 (t), 47.4 (d), 114.1 (d), 115.1 (d), 126.6 (d),
127.1 (d), 131.6 (d), 136.1 (d), 136.1 (s), 144.6 (s); EI-MS m/z: 218 (Mꢁ),
200, 190, 183, 171, 157, 144, 131, 106, 79, 77; HR-MS m/z: 217.0974
(Calcd for C12H13N2O2: 217.0977).
N-Cinnamyl-4-cyanoaniline (5f) IR (KBr) cmꢂ1: 3428, 2215; 1H-
NMR (CDCl3) d 3.93 (2H, dd, Jꢀ1.6, 5.6 Hz), 4.60 (1H, bs), 6.22 (1H, dt,
Jꢀ5.6, 12.0 Hz), 6.57 (1H, dt, Jꢀ1.6, 16.0 Hz), 6.58 (2H, d, Jꢀ8.8 Hz),
7.21—7.25 (1H, m), 7.30 (2H, dd, Jꢀ6.8, 8.0 Hz), 7.34 (2H, d, Jꢀ6.8 Hz),
7.38 (2H, d, Jꢀ8.8 Hz); 13C-NMR (CDCl3) d 45.1 (t), 98.3 (s), 112.4 (d),
120.6 (s), 125.3 (d), 126.3 (d), 127.7 (d), 128.6 (d), 132.0 (d), 133.6 (d),
136.4 (s), 151.2 (s); EI-MS m/z: 234 (Mꢁ), 217, 117, 115, 91, 77; HR-MS
m/z: 234.1157 (Calcd for C16H14N2: 234.1157).
1
N-Allyl-3-nitroaniline (3d) mp 64—65 °C; IR (KBr) cmꢂ1: 3406; H-
NMR (CDCl3) d 3.82 (2H, ddd, Jꢀ1.2, 1.6, 4.0 Hz), 4.32 (1H, bs), 5.20 (1H,
ddt, Jꢀ1.2, 1.2, 8.0 Hz), 5.29 (1H, ddt, Jꢀ1.2, 1.6, 14.0 Hz), 5.91 (1H, ddt,
Jꢀ4.0, 8.0, 14.0 Hz), 6.88 (1H, dd, Jꢀ1.6, 6.4 Hz), 7.25 (1H, dd, Jꢀ6.4,
6.4 Hz), 7.38 (1H, dd, Jꢀ1.6, 2.0 Hz), 7.49 (1H, d, Jꢀ2.0, 6.4 Hz); 13C-NMR
(CDCl3) d 46.1 (t), 106.4 (d), 111.8 (d), 116.8 (t), 118.9 (d), 129.7 (d), 134.1
(d), 148.9 (s), 149.3 (s); EI-MS m/z: 178 (Mꢁ), 151, 131, 130, 117, 105,
104, 77; HR-MS m/z: 178.0743 (Calcd for C9H10N2O2: 178.0742).
N,N-Diallyl-3-nitroaniline (4d) 1H-NMR (CDCl3) d 3.99 (4H, ddd,
Jꢀ1.2, 1.6, 3.6 Hz), 5.18 (2H, ddt, Jꢀ1.2, 1.6, 13.6 Hz), 5.21 (2H, ddt,
Jꢀ1.2, 1.2, 8.4 Hz), 5.85 (2H, ddt, Jꢀ3.6, 8.4, 13.6 Hz), 6.93 (1H, ddd,
Jꢀ0.8, 2.0, 6.8 Hz), 7.28 (1H, ddd, Jꢀ1.2, 6.8, 8.0 Hz), 7.47—7.49 (2H, m);
13C-NMR (CDCl3) d 52.9 (t), 106.4 (d), 110.8 (d), 116.6 (t), 117.8 (d), 129.6
(d), 132.6 (d), 149.2 (s), 149.4 (s); EI-MS m/z: 218 (Mꢁ), 191, 171, 157,
145, 130, 117, 91, 77; HR-MS m/z: 218.1052 (Calcd for C13H17N2O2:
218.1055).
N,N-Dicinnamyl-4-cyanoaniline (6f) mp 93—95 °C; IR (KBr) cmꢂ1
:
2212; 1H-NMR (CDCl3) d 4.19 (4H, dd, Jꢀ1.2, 5.2 Hz), 6.22 (2H, dt,
Jꢀ5.2, 16.0 Hz), 6.50 (2H, dt, Jꢀ1.2, 16.0 Hz), 6.77 (2H, d, Jꢀ8.8 Hz),
7.22—7.26 (2H, m), 7.31 (4H, dd, Jꢀ6.8, 8.0 Hz), 7.35 (4H, d, Jꢀ6.8 Hz),
7.47 (2H, d, Jꢀ8.8 Hz); 13C-NMR (CDCl3) d 52.1 (t), 98.1 (s), 112.0 (d),
120.5 (s), 123.8 (d), 126.4 (d), 127.8 (d), 128.6 (d), 131.9 (d), 133.6 (d),
136.3 (s), 151.3 (s); EI-MS m/z: 350 (Mꢁ), 259, 245, 231, 198, 169, 144,
129, 117, 115, 102, 91, 77; HR-MS m/z: 350.1785 (Calcd for C25H22N2:
350.1782).
3-(4-Cyanophenylamino)cyclohexene (7f) IR (KBr) cmꢂ1: 3423, 2213;
1H-NMR (CDCl3) d 1.59—1.76 (3H, m), 1.87—1.93 (1H, m), 1.98—2.09
(2H, m), 4.01 (1H, bs), 4.28—4.38 (1H, m), 5.69 (1H, ddt, Jꢀ2.0, 3.2,
10.0 Hz), 5.90 (1H, ddt, Jꢀ1.6, 3.6, 10.0 Hz), 6.56 (2H, d, Jꢀ8.8 Hz), 7.39
(2H, d, Jꢀ8.8 Hz); 13C-NMR (CDCl3) d 19.4 (t), 25.0 (t), 28.5 (t), 47.4 (d),
98.2 (s), 112.4 (d), 120.6 (s), 127.0 (d), 131.3 (d), 133.7 (d), 150.4 (s); EI-
MS m/z: 198 (Mꢁ), 197, 170, 169, 153, 129, 119, 118, 91, 79, 77; HR-MS
m/z: 198.1155 (Calcd for C13H14N2: 198.1157).
N-Cinnamyl-3-nitroaniline (5d) mp 115—116 °C; IR (KBr) cmꢂ1
:
3393; 1H-NMR (CDCl3) d 3.92 (2H, dd, Jꢀ1.2, 5.6 Hz), 4.26 (1H, bs), 6.24
(1H, dt, Jꢀ5.6, 16.0 Hz), 6.60 (1H, dt, Jꢀ1.2, 16.0 Hz), 6.87 (1H, dd,
Jꢀ2.0, 8.4 Hz), 7.20—7.40 (7H, m), 7.49 (1H, dd, Jꢀ2.0, 8.0 Hz); 13C-NMR
(CDCl3) d 45.8 (t), 106.6 (d), 112.0 (d), 118.8 (d), 125.5 (d), 126.4 (d),
127.8 (d), 128.6 (d), 129.7 (d), 132.2 (d), 136.5 (d), 148.7 (s), 149.4 (s); EI-
MS m/z: 254 (Mꢁ), 237, 207, 159, 117, 115, 91; HR-MS m/z: 254.1053
(Calcd for C15H14N2O2: 254.1055).
Acknowledgments We gratefully acknowledge the National Science
Council of the Republic of China for financial support.
N,N-Dicinnamyl-3-nitroaniline (6d) 1H-NMR (CDCl3) d 4.18 (4H, dd,
Jꢀ1.6, 5.2 Hz), 6.23 (2H, dt, Jꢀ5.2, 16.0 Hz), 6.53 (2H, dt, Jꢀ1.6, 16.0 Hz),
7.03 (1H, dd, Jꢀ2.4, 8.4 Hz), 7.21—7.24 (2H, m), 7.51 (1H, dd, Jꢀ2.0,
8.0 Hz), 7.61 (1H, t, Jꢀ2.4 Hz), 7.27—7.36 (9H, m); 13C-NMR (CDCl3) d
52.4 (t), 106.5 (d), 111.0 (d), 118.0 (d), 124.2 (d), 126.4 (d), 127.7 (d), 128.6
(d), 129.8 (d), 132.0 (d), 136.4 (s), 149.2 (s), 149.2 (s); EI-MS m/z: 370
(Mꢁ), 355, 335, 327, 281, 253, 225, 207, 191, 165, 135, 115, 91, 77; HR-
MS m/z: 370.1679 (Calcd for C24H22N2O2: 370.1681).
References and Notes
1) Gagné M. R., Nolan S. P., Marks T. J., Organometallics, 9, 1716—
1718 (1990).
2) Walsh P. J., Baranger A. M., Bergman R. G., J. Am. Chem. Soc., 114,
1708—1719 (1992).
3) McGrane P. L., Jensen M., Livinghouse T., J. Am. Chem. Soc., 114,
5459—5460 (1992).
3-(3-Nitrophenylamino)cyclohexene (7d) mp 64—65 °C; IR (KBr)
4) Baranger A. M., Walsh P. J., Bergman R. G., J. Am. Chem. Soc., 115,
2753—2763 (1993).
1
cmꢂ1: 3406; H-NMR (CDCl3) d 1.59—1.76 (3H, m), 1.89—1.96 (1H, m),
2.02—2.10 (2H, m) 3.98—4.08 (1H, m), 4.10 (1H, bs), 5.71 (1H, ddt,
Jꢀ2.0, 3.2, 10.0 Hz), 5.89 (1H, ddt, Jꢀ2.0, 3.6, 10.0 Hz), 6.86 (1H, dd,
Jꢀ2.4, 8.0 Hz), 7.24 (1H, t, Jꢀ8.0 Hz), 7.38 (1H, t, Jꢀ2.4 Hz), 7.47 (1H, dd,
Jꢀ2.4, 8.0 Hz); 13C-NMR (CDCl3) d 19.5 (t), 25.1 (t), 28.6 (t), 47.9 (d),
106.6 (d), 111.5 (d), 119.1 (d), 127.4 (d), 129.8 (d), 131.1 (d), 148.0 (s),
5) Brunet J., Commenges G., Neibecker D., Philippot K., J. Organomet.
Chem., 469, 221—228 (1994).
6) Collman J. P., Hegedus L. S., Norton J. R., Finke R. G., “Principles
and Applications of Organotransition Metal Chemistry,” University
Science Books, Mill Valley, CA, 1987.