6166 J . Org. Chem., Vol. 63, No. 18, 1998
Moreno-Man˜as et al.
2.24 (s, 3H), 4.06 (dd, J ) 5.3 and 1.4 Hz, 4H), 6.24 (dt, J )
16.0 and 5.3 Hz, 2H), 6.51 (d, J ) 16.0 Hz, 2H), 6.73 (d, J )
1.61-1.87 (m, 3H), 1.94-2.24 (m, 3H), 4.26 (br s, 1H), 5.70
(m, 1H), 6.02 (m, 1H), 6.96 (d, J ) 9.5 Hz, 1H), 8.23 (dd, J )
9.5 and 2.9 Hz, 1H), 8.55 (d, J ) 7.3 Hz, 1H), 9.11 (d, J ) 2.9
Hz, 1H); 13C NMR (62.5 MHz, CDCl3) δ 19.3, 24.7, 28.5, 48.3,
114.1, 124.6, 125.0, 130.2, 130.5, 133.0, 135.8, 147.4; MS (m/
z) 263 (M+, 3), 81 (100), 79 (32), 41 (23). Anal. Calcd for
C12H13N3O4: C, 54.75; H, 4.98; N, 15.96. Found: C, 54.83 and
54.77; H, 4.95 and 4.83; N, 15.71 and 15.63.
8.0 Hz, 2H), 7.05 (d, J ) 8.0 Hz, 2H), 7.11-7.35 (m, 10H); 13
C
NMR (62.5 MHz, CDCl3) δ 20.2, 52.4, 113.0, 125.8, 126.2,
126.3, 127.3, 128.5, 129.7, 131.2, 136.9, 146.8. Anal. Calcd
for C25H25N: C, 88.45; H, 7.42; N, 4.13. Found: C, 88.11 and
88.27; H, 7.48 and 7.52; N, 4.15 and 4.15.
N-Cin n a m yld ip h en yla m in e, 19a . This compound is an
oil: IR (film) 1678, 1590, 1495, 1365, 1246, 1221, 966, 748,
694 cm-1; 1H NMR (250 MHz, CDCl3) δ 4.48 (dd, J ) 5.1 and
1.8 Hz, 2H), 6.30 (dt, J ) 16.1 and 5.1 Hz, 1H), 6.56 (d, J )
16.1 Hz, 1H), 6.88-7.40 (m, 15H); 13C NMR (62.5 MHz, CDCl3)
δ 54.3, 120.8, 121.3, 126.1, 126.3, 127.3, 128.4, 129.2, 131.3,
136.9, 147.8. Anal. Calcd for C21H19N: C, 88.38; H, 6.71; N,
4.91. Found: C, 88.15 and 87.87; H, 6.52 and 6.63; N, 4.73
and 4.73.
cis- An d tr a n s-5-Meth yl-3-(4-n itr op h en yla m in o)cyclo-
h exen e, cis-26 a n d tr a n s-26. Isomer cis-26 was eluted
second when obtained as a mixture of isomers and presented
the following data: mp 88-89 °C; IR (KBr) 3385, 1602, 1539,
1501, 1308, 824, 747, 690 cm-1; 1H NMR (250 MHz, CDCl3) δ
0.98 (d, J ) 6.5 Hz, 3H), 1.09 (ddd, J ) 12.3, 12.3, and 10.5
Hz, 1H), 1.58-1.71 (m, 1H), 1.72-1.90 (m, 1H), 2.05-2.19 (m,
2H), 4.10-4.21 (m, 1H), 4.51 (d, J ) 7.7 Hz, 1H), 5.55-5.62
(m, 1H), 5.78-5.86 (m, 1H), 6.51 (d, J ) 9.3 Hz, 2H), 8.03 (d,
J ) 9.3 Hz, 2H); 13C NMR (62.5 MHz, CDCl3) δ 21.9, 28.4,
33.7, 38.3, 50.1, 111.3, 126.5, 127.3, 130.3, 137.7, 152.5. Anal.
Calcd for C13H16N2O2: C, 67.22; H, 6.94; N, 12.06. Found: C,
67.19 and 67.14; H, 7.01 and 7.02; N, 11.95 and 12.02. Isomer
tr a n s-26 was eluted first and presented the following data:
mp 104-105 °C; IR (KBr) 3398, 1602, 1523, 1501, 1465, 1306,
827, 724, 691 cm-1; 1H NMR (250 MHz, CDCl3) δ 0.98 (d, J )
6.5 Hz, 3H), 1.42 (ddd, J ) 12.9, 11.7, and 4.7 Hz, 1H), 1.60-
1.90 (m, 2H), 2.14 (m, 1H), 4.01-4.10 (m, 1H), 4.61 (d, J ) 6.4
Hz, 1H), 5.68-5.77 (m, 1H), 5.90-5.98 (m, 1H), 6.50 (d, J )
9.4 Hz, 2H), 8.04 (d, J ) 9.4 Hz, 2H); 13C NMR (62.5 MHz,
CDCl3) δ 21.5, 24.1, 33.5, 35.7, 47.1, 111.1, 125.2, 126.5, 132.1,
137.7, 152.0.Anal. Calcd for C13H16N2O2: C, 67.22; H, 6.94;
N, 12.06. Found: 67.34 and 67.42; H, 7.00 and 7.09; N, 11.97
and 12.01.
N-Allyld ip h en yla m in e, 19b. This compound is an oil: IR
(film) 1591, 1495, 1365, 1250, 1224, 920, 749, 695 cm-1 1H
;
NMR (250 MHz, CDCl3) δ 4.36 (d, J ) 4.7 Hz, 2H), 5.16 (d, J
) 10.2 Hz, 1H), 5.26 (d, J ) 17.2 Hz, 1H), 5.93 (ddt, J ) 17.2,
10.2, and 4.7 Hz, 1H), 6.89-6.98 (m, 4H), 7.20-7.30 (m, 6H);
13C NMR (62.5 MHz, CDCl3) δ 54.7, 116.4, 120.7, 121.2, 129.2,
134.2, 147.8. Anal. Calcd for C15H15N: C, 86.08; H, 7.22; N,
6.69. Found: C, 85.88 and 85.77; H, 6.98 and 6.90; N, 6.62
and 6.86.
N-Cin n a m ylp h en oth ia zin e, 20. This compound is an
oil: IR (film) 1676, 1572, 1594, 1464, 1446, 1364, 1254, 1218,
968, 747, 694 cm-1; 1H NMR (250 MHz, CDCl3) δ 4.64 (d, J )
4.4, 2H), 6.36 (dt, J ) 16.1 and 4.4 Hz, 1H), 6.58 (d, J ) 16.1
Hz, 1H), 6.82-6.93 (m, 4H), 7.00-7.11 (m, 4H), 7.19-7.39 (m,
5H); 13C NMR (62.5 MHz, CDCl3) δ 50.9, 115.3, 122.4, 122.9,
124.8, 126.3, 126.8, 127.3, 127.7, 128.6, 132.0, 136.4, 144.4;
MS (m/z) 315 (M+, 8), 199 (16), 198 (100).
cis- An d tr a n s-5-Meth yl-3-(2,4-Din itr op h en yla m in o)-
cycloh exen e, cis-27 a n d tr a n s-27. Isomer cis-27 was eluted
first when obtained as a mixture of isomers and presented the
following data: mp 86-87 °C; IR (KBr) 3342, 1617, 1520, 1331,
N-Cin n a m yl-2-n itr oa n ilin e, 21. This compound presents
the following data: mp 70-71 °C (dichloromethane-hexanes);
IR (KBr) 3394, 1618, 1568, 1510, 1359, 1315, 1259, 971, 743,
1
689 cm-1; H NMR (250 MHz, CDCl3) δ 4.12 (d, J ) 5.5 Hz,
1
719 cm-1; H NMR (250 MHz, CDCl3) δ 1.03 (d, J ) 6.6 Hz,
2H), 6.27 (dt, J ) 15.7 and 5.5 Hz, 1H), 6.61 (d, J ) 15.7 Hz,
1H), 6.65 (t, J ) 7.8 Hz, 1H), 6.87 (d, J ) 8.4 Hz, 1H), 7.19-
7.46 (m, 6H), 8.18 (d, J ) 8.8 Hz, 1H), 8.24 (s, 1H); 13C NMR
(62.5 MHz, CDCl3) δ 44.8, 114.0, 115.5, 124.6, 126.3, 126.7,
127.8, 128.5, 132.2, 136.1, 145.1. Anal. Calcd for
3H), 1.31 (ddd, J ) 11.3, 11.3, and 10.6 Hz, 1H), 1.68-1.79
(m, 1H), 1.82-1.96 (m, 1H), 2.13-2.23 (m, 2H), 4.33-4.43 (m,
1H), 5.58-5.64 (m, 1H), 5.91-5.97 (m, 1H), 6.97 (d, J ) 9.7
Hz, 1H), 8.22 (dd, J ) 9.7 and 2.7 Hz, 1H), 8.53 (br d, J ) 7.0
Hz, 1H), 9.11 (d, J ) 2.7 Hz, 1H); 13C NMR (62.5 MHz, CDCl3)
δ 21.8, 28.2, 33.4, 37.9, 50.6, 114.2, 124.6, 125.6, 130.2, 130.3,
131.7, 135.8, 147.7; MS (m/z) 277 (M+, 6), 95 (100), 67 (44), 55
(15) 41 (24). Anal. Calcd for C13H15N3O4: C, 56.31; H, 5.45;
N, 15.15. Found: C, 56.52 and 56.50; H, 5.43 and 5.53; N,
14.85 and 14.93. Isomer tr a n s-27 was eluted second and
presented the following data: mp 168-171 °C; IR (KBr) 3367,
C
15H14N2O2: C, 70.85; H, 5.55; N, 11.02. Found: C, 70.84 and
70.75; H, 5.72 and 5.69; N, 10.98 and 11.00.
N-Cin n a m yl-4-n itr oa n ilin e, 22, a n d N,N-Dicin n a m yl-
4-n itr oa n ilin e, 23. Compound 22 presented the following
data: mp 142-144 °C (dichloromethane-hexanes); IR (KBr)
3357, 1601, 1538, 1325, 1278, 1181, 1108, 972, 829, 784 cm-1
;
1H NMR (250 MHz, CDCl3) δ 4.03 (dd, J ) 5.6 and 4.2 Hz,
2H), 4.75 (br s, 1H), 6.25 (dt, J ) 16.1 and 5.6 Hz, 1H), 6.55-
1584, 1521, 1422, 1328 cm-1 1H NMR (250 MHz, CDCl3) δ
;
6.66 (m, 3H), 7.20-7.43 (m, 5H), 8.09 (d, J ) 9.1 Hz, 2H); 13
C
0.99 (d, J ) 6.5 Hz, 3H), 1.52-1.62 (m, 1H), 1.65-1.75 (m,
1H), 1.77-1.90 (m, 2H), 2.24 (m, 1H), 4.24-4.31 (m, 1H), 5.74-
5.81 (m, 1H), 6.03-6.09 (m, 1H), 6.97 (d, J ) 9.7 Hz, 1H), 8.24
(dd, J ) 9.7 and 2.7 Hz, 1H), 8.54 (d, J ) 6.8 Hz, 1H), 9.12 (d,
J ) 2.7 Hz, 1H); 13C NMR (62.5 MHz, CDCl3) δ 21.4, 24.2,
33.4, 35.8, 47.6, 114.0, 123.7, 124.6, 130.3, 130.6, 133.5, 135.8,
147.2; MS (m/z) 277 (M+, 5), 95 (100), 67 (41), 55 (23), 41 (21).
Anal. Calcd for C13H15N3O4: C, 56.31; H, 5.45; N, 15.15.
Found: 56.51 and 56.55; H, 5.51 and 5.53; N, 14.88 and 14.86.
NMR (62.5 MHz, CDCl3) δ 45.4, 111.3, 124.6, 127.9, 128.6,
132.7, 136.2, 138.2, 153.1.
Compound 23 presented the following data: mp 157-158
°C (dichloromethane-hexanes); IR (KBr) 1591, 1512, 1488,
1360, 1297, 1109, 972, 826, 801 cm-1 1H NMR (250 MHz,
;
CDCl3) δ 4.25 (d, J ) 5.1 Hz, 4H), 6.23 (dt, J ) 16.0 and 5.1
Hz, 2H), 6.52 (d, J ) 16.1 Hz, 2H), 6.75 (d, J ) 9,5 Hz, 2H),
7.20-7.43 (m, 10H), 8.13 (d, J ) 9.5 Hz, 2H); 13C NMR (62.5
MHz, CDCl3) δ 52.4, 110.9, 123.3, 126.2, 126.4, 127.9, 128.6,
132.2, 136.2, 137.4, 153.2. Anal. Calcd for C24H22N2O2: C,
77.81; H, 5.99; N, 7.56. Found: C, 77.55 and 77.53; H, 5.82
and 5.71; N, 7.55 and 7.42.
3-(4-Nitr op h en yla m in o)cycloh exen e, 24. Aniline 24
presented the following data: mp 100-101 °C; IR (KBr) 3402,
3027, 1605, 1526, 1308, 828, 747, 731 cm-1; 1H NMR (250 MHz,
CDCl3) δ 1.52-2.12 (m, 6H), 3.98-4.14 (m, 1H), 4.50 (br d, J
) 6.7 Hz, 1H), 5.68 (m, 1H), 5.92 (m, 1H), 6.51 (d, J ) 9.3 Hz,
2H), 8.05 (d, J ) 9.3 Hz, 2H); 13C NMR (62.5 MHz, CDCl3) δ
19.3, 24.9, 28.5, 47.7, 111.3, 126.5, 126.6, 131.7, 137.8, 152.3.
Anal. Calcd for C12H14N2O2: C, 66.04; H, 6.46; N, 12.84.
Found: C, 66.08 and 66.08; H, 6.23 and 6.20; N, 12.66 and
12.70.
Ack n ow led gm en t. Financial support from DGICYT
(MEC of Spain, project PB93-0896 and a predoctoral
scholarship to L.M.), and from CIRIT (Generalitat de
Catalunya, project 96SGR-0030) is gratefully acknowl-
edged. We thank Dr. Teo Parella (Servei de Ressona`ncia
Magne`tica Nuclear. UAB) for his assistance.
Su p p or tin g In for m a tion Ava ila ble: IR, 1H NMR, and
13C NMR spectra of all allylated anilines (38 pages). Ordering
information is given on any current masthead page. This
material is contained in libraries on microfiche, immediately
follows this article in the microfilm version of the journal, and
can be ordered from the ACS; see any current masthead page
for ordering information.
3-(2,4-Din itr op h en yla m in o)cycloh exen e, 25. Aniline 25
presented the following data: mp 108 °C; IR (KBr) 3368, 1615,
1587, 1520, 1334, 1281 cm-1 1H NMR (250 MHz, CDCl3) δ
;
(25) Eisch, J . J .; Dluzniewski, T. J . Org. Chem. 1989, 54, 1269.
J O980209J