The Journal of Organic Chemistry
Article
4
9
4.6. IR (thin film) ν : 3083, 2940, 2781, 1625, 1595, 1487, 1316,
48, 906, 756 cm . EIMS m/z: M 147 (41.8), 132 (100), 117 (62.3).
56%) by flash chromatography in 30:1 petroleum ether/diethyl ether.
max
−1
+
1
H NMR (400 MHz, CDCl ): δ 7.74 (d, J = 2.4 Hz, 1H), 7.49 (dd, J =
3
HRMS-EI: calcd for C H N, 147.1048; found, 147.1046.
8.4, 2.0 Hz, 1H), 6.91 (dd, J = 17.6, 10.8 Hz, 1H), 6.74 (d, J = 8.4 Hz,
1H), 5.65 (dd, J = 17.6, 1.2 Hz, 1H), 5.28 (dd, J = 10.8, 0.8 Hz, 1H),
10
13
N,N,5-Trimethyl-2-vinylaniline (1c). Following the general proce-
dure, this product was isolated as a colorless oil (687.8 mg, 85%) by
flash chromatography in petroleum ether. 1H NMR (400 MHz,
2.70 (s, 6H). 13C NMR (100 MHz, CDCl ): δ 151.5, 136.9, 135.6,
3
134.2, 133.8, 120.2, 114.2, 85.5, 44.3. IR (thin film) ν : 3082, 2941,
max
−
1
CDCl ): δ 7.40 (d, J = 8.0 Hz, 1H), 7.06 (dd, J = 17.6, 10.8 Hz, 1H),
2830, 2783, 1621, 1578, 1482, 1106, 945, 815 cm . EIMS m/z:
3
+
6
1
.85−6.84 (m, 2H), 5.65 (dd, J = 17.6, 1.2 Hz, 1H), 5.22 (dd, J = 10.8,
M 273 (64.3), 258 (32.5), 144 (23.8), 131 (100). HRMS-EI: calcd for
.2 Hz, 1H), 2.75 (s, 6H), 2.36 (s, 3H). 13C NMR (100 MHz,
C H NI, 273.0015; found, 273.0017.
10
12
CDCl ): δ 151.7, 138.2, 134.8, 129.0, 126.7, 123.2, 118.8, 112.3, 44.6,
N,N-Dimethyl-5-(trifluoromethyl)-2-vinylaniline (1j). Following
3
2
1
1.5. IR (thin film) ν : 3082, 2925, 2854, 2779, 1623, 1605, 1498,
315, 901, 816 cm . EIMS m/z: M 161 (35.8), 146 (100), 131
the general procedure, this product was isolated as a colorless oil
max
−1
+
1
(569.7 mg, 55%) by flash chromatography in petroleum ether. H
(
77.3). HRMS-EI: calcd for C H N, 161.1204; found, 161.1203.
5
NMR (400 MHz, CDCl ): δ 7.53 (d, J = 7.6 Hz, 1H), 7.26−7.22 (m,
11
15
3
-Methoxy-N,N-dimethyl-2-vinylaniline (1d). Following the gen-
eral procedure, this product was isolated as a colorless oil (747.6 mg,
4%) by flash chromatography in 5:1 petroleum ether/dichloro-
2H), 7.02 (dd, J = 17.6, 11.2 Hz, 1H), 5.75 (d, J = 18.0 Hz, 1H), 5.36
(d, J = 10.8 Hz, 1H), 2.77 (s, 6H). 13C NMR (100 MHz, CDCl ): δ
3
8
152.0, 135.0, 134.2, 130.1 (q, J = 31.3 Hz), 127.4, 124.3 (q, J = 270.5
1
19
methane. H NMR (400 MHz, CDCl ): δ 7.44 (d, J = 8.0 Hz, 1H),
Hz), 118.7 (q, J = 3.7 Hz), 115.1, 114.7 (q, J = 3.6 Hz), 44.2. F NMR
3
7
.00 (dd, J = 18.0, 11.2 Hz, 1H), 6.61−6.57 (m, 2H), 5.60 (d, J = 17.6
(376 MHz, CDCl ): δ −62.5 (s, 3F). IR (thin film) νmax: 3087, 2947,
3
13
−1
+
Hz, 1H), 5.18 (d, J = 10.8 Hz, 1H), 3.83 (s, 3H), 2.76 (s, 6H).
C
2791, 1337, 1169, 1123, 694 cm . EIMS m/z: M 215 (52.7), 200
NMR (100 MHz, CDCl ): δ 160.0, 153.2, 134.5, 127.9, 124.8, 111.2,
(100). HRMS-EI: calcd for C H NF , 215.0922; found, 215.0926.
3
11 12
3
1
1
06.8, 104.7, 55.2, 44.5. IR (thin film) ν : 3080, 2941, 2831, 2782,
602, 1500, 1320, 1236, 1097 cm . EIMS m/z: M 177 (35.5), 162
Ethyl 3-(Dimethylamino)-4-vinylbenzoate (1k). Following the
general procedure, this product was isolated as a yellow oil (383.5
max
−1
+
(
1
100), 147 (41.5). HRMS-EI: calcd for C H NO, 177.1154; found,
mg, 35%) by flash chromatography in 5:1 petroleum ether/ethyl
11
15
1
77.1153.
,5-Dimethoxy-N,N-dimethyl-2-vinylaniline (1e). Following the
acetate. H NMR (400 MHz, CDCl ): δ 8.10 (d, J = 2.0 Hz, 1H), 7.87
3
4
(dd, J = 8.8, 2.0 Hz, 1H), 6.94−6.87 (m, 2H), 5.74 (dd, J = 17.6, 1.2
general procedure, this product was isolated as a pale yellow oil (1.00
Hz, 1H), 5.29 (dd, J = 11.2, 1.2 Hz, 1H), 4.35 (q, J = 7.2 Hz, 2H), 2.79
(s, 6H), 1.37 (t, J = 7.2 Hz, 3H). 13C NMR (100 MHz, CDCl ): δ
g, 97%) by flash chromatography in 10:1 petroleum ether/ethyl
3
1
acetate. H NMR (400 MHz, CDCl ): δ 7.06 (dd, J = 17.6, 11.2 Hz,
166.7, 155.5, 135.0, 130.4, 129.8, 129.1, 123.2, 116.9, 113.8, 60.6, 43.9,
3
1
1
H), 7.00 (s, 1H), 6.62 (s, 1H), 5.54 (d, J = 17.6 Hz, 1H), 5.14 (d, J =
14.4. IR (thin film) ν : 3085, 2980, 2836, 2789, 1711, 1601, 1296,
max
1.2 Hz, 1H), 3.86 (s, 3H), 3.85 (s, 3H), 2.66 (s, 6H). 13C NMR (100
−1
+
1248, 1113, 757.3 cm . EIMS m/z: M 219 (90.9), 204 (48.9), 174
MHz, CDCl ): δ 149.2, 145.8, 144.9, 133.8, 124.4, 111.3, 109.4, 102.9,
(50.6), 131 (100). HRMS-EI: calcd for C H NO , 219.1259; found,
3
13 17
2
5
1
6.2, 55.9, 45.1. IR (thin film) νmax: 3078, 2937, 2827, 2780, 1603,
510, 1454, 1253, 1216, 997, 820 cm . EIMS m/z: M 207 (53.7),
219.1254.
−
1
+
1-Methoxy-2-vinylbenzene (1l). Following the general procedure,
1
92 (100), 161 (29.3). HRMS-EI: calcd for C H NO , 207.1259;
this product was isolated as a colorless oil (496.6 mg, 74%) by flash
12
17
2
1
found, 207.1263.
chromatography in petroleum ether. H NMR (400 MHz, CDCl ): δ
3
2
-Fluoro-N,N-dimethyl-6-vinylaniline (1f). Following the general
7.51 (dd, J = 7.8, 1.2 Hz, 1H), 7.29−7.25 (m, 1H), 7.10 (dd, J = 17.6,
10.8 Hz, 1H), 6.97 (t, J = 7.2 Hz, 1H), 6.90 (d, J = 8.4 Hz, 1H), 5.78
(dd, J = 18.0, 1.2 Hz, 1H), 5.30 (dd, J = 10.8, 1.2 Hz, 1H), 3.87 (s,
procedure, this product was isolated as a colorless oil (595.1 mg, 72%)
by flash chromatography in petroleum ether. H NMR (400 MHz,
CDCl ): δ 7.29 (d, J = 7.6 Hz, 1H), 7.20 (dd, J = 17.6, 10.8 Hz, 1H),
1
3H). 13C NMR (100 MHz, CDCl ): δ 156.8, 131.7, 128.9, 126.8,
3
3
7
.06−7.00 (m, 1H), 6.97−6.92 (m, 1H), 5.69 (dd, J = 18.0, 1.2 Hz,
126.6, 120.7, 114.5, 110.9, 55.5. IR (thin film) νmax: 3073, 3002, 2956,
H), 5.29 (d, J = 11.2 Hz, 1H), 2.82 (s, 6H). 13C NMR (100 MHz,
−1
1
2836, 1624, 1598, 1488, 1463, 1244, 1055, 909, 750 cm . EIMS m/z:
+
CDCl ): δ 161.4 (d, J = 247.2 Hz), 138.2 (d, J = 10.2 Hz), 137.7 (d, J
M 134 (40.8), 119 (45.0), 91 (100). HRMS-EI: calcd for C H O,
3
9
10
=
3
5.1 Hz), 133.6 (d, J = 2.9 Hz), 124.9 (d, J = 9.5 Hz), 121.3 (d, J =
.0 Hz), 115.7 (d, J = 21.1 Hz), 114.7, 44.13, 44.09. 19F NMR (376
MHz, CDCl ): δ −117.3 (s, 1F). IR (thin film) ν : 3081, 2927, 2794,
134.0732; found, 134.0728.
1-(Benzyloxy)-2-vinylbenzene (1m). Following the general proce-
dure, this product was isolated as a colorless oil (657.6 mg, 63%) by
flash chromatography in petroleum ether. 1H NMR (400 MHz,
3
max
−1
+
1
571, 1457, 1242, 944, 802, 750 cm . EIMS m/z: M 165 (58.4), 150
(
1
100), 135 (84.9). HRMS-EI: calcd for C H NF, 165.0954; found,
CDCl ): δ 7.55 (d, J = 7.6 Hz, 1H), 7.49−7.33 (m, 5H), 7.27−7.15
10
12
3
65.0950.
-Chloro-N,N-dimethyl-2-vinylaniline (1g). Following the general
(m, 2H), 7.03−6.95 (m, 2H), 5.82 (dd, J = 17.6, 1.6 Hz, 1H), 5.30 (d,
J = 11.2, 1.6 Hz, 1H), 5.13 (s, 2H). 13C NMR (100 MHz, CDCl ): δ
5
3
procedure, this product was isolated as a colorless oil (741.8 mg, 82%)
by flash chromatography in 10:1 petroleum ether/ethyl acetate. H
156.0, 137.2, 131.7, 129.5, 128.9, 128.6, 127.9, 127.5, 127.4, 127.2,
1
126.6, 121.0, 114.5, 112.5, 70.3. IR (thin film) ν : 3065, 3032, 2927,
max
−1
+
NMR (400 MHz, CDCl ): δ 7.38 (d, J = 8.4 Hz, 1H), 7.00−6.93 (m,
1597, 1487, 1451, 1239, 1014, 910, 749, 696 cm . EIMS m/z: M 210
3
3
2
1
2
H), 5.66 (dd, J = 17.6, 1.2 Hz, 1H), 5.27 (dd, J = 11.2, 1.2 Hz, 1H),
(22.6), 91 (100), 65 (15.5). HRMS-EI: calcd for C H O, 210.1045;
15
14
.73 (s, 6H). 13C NMR (100 MHz, CDCl ): δ 152.8, 134.2, 133.7,
found, 210.1042.
N,N-Dibenzyl-2-vinylaniline (1n). Following the general procedure,
3
30.2, 128.0, 122.2, 118.4, 113.5, 44.3. IR (thin film) νmax: 3084, 2983,
−1
944, 2832, 2788, 1624, 1587, 1489, 960, 838, 817 cm . EIMS m/z:
this product was isolated as a yellow oil (523.8 mg, 35%) by flash
+
1
M 181 (34.0), 166 (74.3), 131 (100). HRMS-EI: calcd for
chromatography in petroleum ether. H NMR (400 MHz, CDCl ): δ
3
C H ClN, 181.0658; found, 181.0659.
7.60 (d, J = 6.4 Hz, 1H), 7.46 (dd, J = 17.6, 10.8 Hz, 1H), 7.33−7.28
(m, 10H), 7.17 (t, J = 6.8 Hz, 1H), 7.08 (t, J = 6.8 Hz, 1H), 6.92 (d, J
1
0
12
5-Bromo-N,N-dimethyl-2-vinylaniline (1h). Following the general
procedure, this product was isolated as a colorless oil (519.6 mg, 91%)
by flash chromatography in 10:1 petroleum ether/ethyl acetate. H
= 7.2 Hz, 1H), 5.80 (dd, J = 18.0, 1.2 Hz, 1H), 5.37 (dd, J = 15.2, 1.2
1
13
Hz, 1H), 4.19 (s, 4H). C NMR (100 MHz, CDCl ): δ 149.0, 138.2,
3
NMR (400 MHz, CDCl ): δ 7.31 (d, J = 8.8 Hz, 1H), 7.13−7.11 (m,
134.7, 133.1, 128.8, 128.3, 128.0, 127.0, 126.8, 123.2, 122.1, 113.8,
3
2
H), 6.95 (dd, J = 18.0, 10.8 Hz, 1H), 5.62 (d, J = 17.6 Hz, 1H), 5.28
56.7. IR (thin film) νmax: 3084, 3061, 3027, 2841, 1627, 1595, 1494,
d, J = 11.2 Hz, 1H), 2.73 (s, 6H). 13C NMR (100 MHz, CDCl ): δ
1451, 909, 759, 697 cm . EIMS m/z: M 299 (5.2), 208 (85.9), 91
−1
+
(
3
1
53.0, 134.2, 130.6, 128.3, 125.1, 121.9, 121.4, 113.6, 44.3. IR (thin
(100). HRMS-EI: calcd for C H N, 299.1674; found, 299.1670.
22
21
−1
film) νmax: 3080, 2943, 2832, 2787, 1582, 1485, 954, 822, 696 cm .
EIMS m/z: M 225 (14.2), 212 (16.3), 210 (17.1), 183 (21.3), 131
1-(2-Vinylphenyl)pyrrolidine (1o). Following the general proce-
dure, this product was isolated as a colorless oil (596.1 mg, 69%) by
flash chromatography in petroleum ether. 1H NMR (400 MHz,
+
(
100). HRMS-EI: calcd for C H BrN, 225.0153; found, 225.0148.
10 12
4
-Iodo-N,N-dimethyl-2-vinylaniline (1i). Following the general
CDCl ): δ 7.43 (dd, J = 8.0, 1.6 Hz, 1H), 7.24−7.19 (m, 1H), 7.03
3
procedure, this product was isolated as a pale yellow oil (764.2 mg,
(dd, J = 17.6, 10.8 Hz, 1H), 6.94−6.91 (m, 2H), 5.61 (dd, J = 17.6, 1.6
F
dx.doi.org/10.1021/jo502040t | J. Org. Chem. XXXX, XXX, XXX−XXX