COMMUNICATIONS
1
liquid; H NMR (400 MHz, CDCl3): d=7.10 (d, J=8.4 Hz,
2H), 6.84–6.81 (m, 2H), 6.35 (d, J=12.4 Hz, 1H), 5.56 (d,
J=12.4 Hz, 1H), 3,80 (s, 3H), 0.99 (s, 9H); 13C NMR
(100 MHz, CDCl3): d=157.9, 142.5, 131.6, 130.0, 126.7,
112.9, 55.1, 34.0, 31.2; LR-MS (EI, 70 eV): m/z (%)=190
(M+, 37), 175 (100); HR-MS (ESI): m/z=191.1439, calcd.
for C13H19O ([M+H]+): 191.1436.
3015, 2935, 1519, 1468 cmÀ1; LR-MS (EI, 70 eV) m/z (%):
240 (M+ +2, 17), 238 (M+, 18), 225 (20), 223 (21), 159 (32),
144 (100); HR-MS (ESI): m/z=239.0430, calcd. for
C12H16Br ([M+H]+): 239.0435.
(E)-1-(3,3-Dimethylbut-1-en-1-yl)-2-methoxybenzene
(17):[10j] yield: 15.8 mg (27%); Rf =0.7 (PE); colorless liquid;
1H NMR (400 MHz, CDCl3): d=7.45 (dd, J=1.6 Hz, 7.6 Hz,
1H), 7.20–7.16 (m, 1H), 6.92 (d, J=7.2 Hz, 1H), 6.85 (d, J=
8.0 Hz, 1H), 6.65 (d, J=16.0 Hz, 1H), 6.24 (d, J=16.4 Hz,
1H), 3.85 (s, 3H), 1.13 (s, 9H); 13C NMR (100 MHz,
CDCl3): d=156.3, 142.3, 127.7, 127.0, 126.0, 120.6, 118.8,
110.7, 55.4, 33.6, 29.6; LR-MS (EI, 70 eV): m/z (%)=190
(M+, 45),
1-(3,3-Dimethylbut-1-en-1-yl)-4-fluorobenzene (12): yield:
33.1 mg (62%); E/Z=1.1:1; Rf =0.8 (PE); colorless liquid;
1H NMR (400 MHz, CDCl3): d=7.34–7.30 (m, 2.09H), 7.14–
7.11 (m, 1.98H), 7.01–6.99 (m, 4.04H), 6.34 (d, J=12.4 Hz,
0.99H), 6.28–6.14 (m, 2.13H), 5.60 (d, J=12.4 Hz, 1H), 1.11
(s, 9.54H), 0.97 (s, 9H); 13C NMR (100 MHz, CDCl3): d=
163.1, 160.7, 143.3, 141.6, 135.1, 134.2, 130.4 (d, J=7.7 Hz,
1C), 127.4 (d, J=7.7 Hz, 1C), 126.0, 123.5, 115.3 (d, J=
21.3 Hz, 1C), 114.4 (d, J=21.0 Hz, 1C); IR: n=3030, 3021,
2945, 1539, 1471 cmÀ1; LR-MS (EI, 70 eV): m/z (%)=178
(M+, 31), 163 (100), 135 (31), 109 (33); HR-MS (ESI): m/z=
179.1231, calcd. for C12H16F ([M+H]+): 179.1236.
(Z)-1-(3,3-Dimethylbut-1-en-1-yl)-2-methoxybenzene
(17’):[10j] yield: 15.8 mg (27%); Rf =0.6 (PE); colorless
1
liquid; H NMR (400 MHz, CDCl3): d=7.25–7.21 (m, 1H),
7.14 (d, J=7.6 Hz, 1H), 6.91–6.83 (m, 2H), 6.25 (d, J=
12.4 Hz, 1H), 5.69 (d, J=12.4 Hz, 1H), 3.84 (s, 3H), 0.98 (s,
9H); 13C NMR (100 MHz, CDCl3): d=156.6, 143.0, 130.9,
128.1, 127.9, 122.7, 119.6, 110.0, 55.3, 34.2, 30.7; LR-MS (EI,
70 eV): m/z (%)=190 (M+, 42), 175 (100); HR-MS (ESI):
m/z=191.1436, calcd. for C13H19O ([M+H]+): 191.1430.
1-Chloro-4-(3,3-dimethylbut-1-en-1-yl)benzene
(13):[10f]
yield: 40.6 mg (68%); E/Z=1:2.7; Rf =0.8 (PE); colorless
liquid; 1H NMR (400 MHz, CDCl3): d=7.30–7.23 (m,
4.06H), 7.11 (d, J=8.0 Hz, 2.08H), 6.32 (d, J=12.4 Hz, 1H),
6.24 (s, 0.76H), 15.62 (d, J=12.4 Hz, 0.99H), 1.11 (s,
3.56H), 0.97 (s, 9.08H); 13C NMR (100 MHz, CDCl3): d=
143.4, 142.5, 137.7, 136.5, 132.8, 132.0, 130.3, 128.5, 127.7,
127.2, 125.7, 123.4, 34.2, 33.4, 31.2, 29.5; LR-MS (EI, 70 eV):
m/z (%)=196 (M+ +2, 12), 194 (M+, 35), 179 (100), 144
(43); HR-MS (ESI); m/z=195.0930, calcd. for C12H16Cl
([M+H]+): 195.0935.
1-Bromo-4-(3,3-dimethylbut-1-en-1-yl)benzene (14): yield:
50.6 mg (71%); E/Z=1:1; Rf =0.8 (PE); colorless liquid;
1H NMR (400 MHz, CDCl3): d=7.41–7.38 (m, 4H), 7.24–
7.21 (m, 2H), 7.05 (d, J=12.4 Hz, 2H), 6.29 (d, J=12.4 Hz,
1.01H), 6.24 (d, J=1.2 Hz, 1.90H), 5.62 (d, J=12.4 Hz,
0.98H), 1.11 (s, 9H), 0.97 (s, 9.05H); 13C NMR (100 MHz,
CDCl3): d=143.4, 142.6, 138.2, 136.9, 131.5, 130.6, 127.5,
125.7, 123.4, 120.3, 120.1, 34.2, 33.4, 31.2, 29.4; IR: n=3022,
3016, 2932, 1515, 1478 cmÀ1; LR-MS (EI, 70 eV): m/z (%)=
240 (M+ +2, 18), 238 (M+, 18), 223 (4), 159 (16), 144 (100);
240 (M+ +2, 25), 238 (M+, 26), 223 (4), 159 (17), 144 (100);
HR-MS (ESI): m/z=239.0441, calcd. for C12H16Br ([M+
H]+): 239.0435.
1-Chloro-2-(3,3-dimethylbut-1-en-1-yl)benzene
(18):[10k]
yield: 43.5 mg (74%); E/Z=1:5; Rf =0.8 (PE); colorless
liquid; 1H NMR (400 MHz, CDCl3): d=7.35–7.33 (m,
1.15H), 7.24–7.13 (m, 3.08H), 6.69 (d, J=12.4 Hz, 0.21H),
6.23 (d, J=12.8 Hz, 1.11H), 5.69 (d, J=12.4 Hz, 0.95H),
1.14 (s, 1.78H), 0.96 (s, 9H); 13C NMR (100 MHz, CDCl3):
d=144.7, 143.5, 138.1, 133.2, 131.3, 130.6, 129.6, 129.5, 128.8,
127.9, 127.7, 126.7, 126.6, 125.7, 123.9, 121.1, 34.4, 31.9, 30.6,
29.5; LR-MS (EI, 70 eV): m/z (%)=196 (M+ +2, 11), 194
(M+, 36), 179 (100), 144 (44); HR-MS (ESI): m/z=195.0942,
calcd. for C12H16Cl ([M+H]+): 195.0935.
1-(3,3-Dimethylbut-1-en-1-yl)-2,4-dimethoxybenzene (19):
yield: 42.4 mg (64%); E/Z=4.9:1; Rf =0.6 (PE); colorless
1
liquid; H NMR (400 MHz, CDCl3): d=7.36 (d, J=8.4 Hz,
0.23H), 7.03 (t, J=4.4 Hz, 1.04H), 6.56 (d, J=16.4 Hz,
0.25H), 6.44–6.41 (m, 2.62H), 6.19 (d, J=12.4 Hz, 1.01H),
6.13 (d, J=12.4 Hz, 0.20H), 5.65 (d, J=12.4 Hz, 1.03H),
3.82 (s, 1.40H), 3.80 (s, 6.02H), 1.12 (s, 1.84H), 0.98 (s, 9H);
13C NMR (100 MHz, CDCl3): d=159.7(2C), 157.6, 157.3,
143.0, 140.3, 131.1, 126.6, 122.5, 120.6, 120.0, 118.4, 104.5,
103.2, 98.3, 98.0, 55.4, 55.3 (2C), 34.0, 33.5, 30.8, 29.7; IR:
n=3050, 3035, 2955, 1529, 1428, 1155 cmÀ1; LR-MS (EI,
70 eV): m/z (%)=220 (M+, 37), 205 (100); HR-MS (ESI):
m/z=221.1540, calcd. for C14H21O2 ([M+H]+): 221.1542.
1,4-Bis[(Z)-3,3-dimethylbut-1-en-1-yl]benzene (20): yield:
49.6 mg (68%); Rf =0.8 (PE); colorless liquid; 1H NMR
(400 MHz, CDCl3): d=7.09 (s, 4H), 6.40 (t, J=12.4 Hz,
2H), 5.59 (d, J=12.4 Hz, 2H), 0.98 (s, 18H); 13C NMR
(100 MHz, CDCl3): d=142.7, 137.3, 128.1, 127.0, 34.2, 31.2;
IR: n=3101, 3075, 2932, 1510, 1461 cmÀ1; LR-MS (EI,
70 eV): m/z (%)=242 (M+, 83), 227 (46), 171 (65), 157 (93),
57 (100); HR-MS (ESI): m/z=243.2110, calcd. for C18H27
([M+H]+): 243.2113.
4-(3,3-Dimethylbut-1-en-1-yl)benzonitrile (15):[10h,10i] yield:
36.1 mg (65%); E/Z=1:5.5; Rf =0.6 (PE); colorless liquid;
1H NMR (400 MHz, CDCl3): d=7.57 (d, J=8.0 Hz, 2.54H),
7.43 (d, J=8.4 Hz, 0.61H), 7.30–7.27 (m, 2.16H), 6.42–6.28
(m, 1.56H), 5.70 (d, J=12.8 Hz, 1.05H), 1.13 (s, 1.65H),
0.96 (s, 9H); 13C NMR (100 MHz, CDCl3): d=145.9, 144.6,
144.4, 132.3, 131.4, 129.7, 126.5, 125.2, 123.4, 119.1, 110.0,
34.4, 33.7, 31.1, 29.3; LR-MS (EI, 70 eV): m/z (%)=185
(M+, 29), 170 (100), 142 (34); HR-MS (ESI): m/z=186.1280,
calcd. for C13H16N ([M+H]+): 186.1283.
1-Bromo-3-(3,3-dimethylbut-1-en-1-yl)benzene (16): yield:
47.9 mg (66%); E/Z=1.4:1; Rf =0.8 (PE); colorless liquid;
1H NMR (400 MHz, CDCl3): d=7.52 (t, J=1.6 Hz, 1.29H),
7.35–7.29 (m, 3.51H), 7.25 (t, J=1.6 Hz, 1.70H), 7.17–7.09
(m, 3.42H), 6.31 (d, J=12.8 Hz, 1.01H), 6.30–6.23 (m,
2.74H), 5.62 (d, J=12.8 Hz, 1H), 1.11 (s, 12.16H), 0.97 (s,
9H); 13C NMR (100 MHz, CDCl3): d=143.6, 143.3, 141.5,
140.2, 131.8, 129.9, 129.5, 129.2, 129.1, 128.8, 127.6, 125.4,
124.7, 123.3, 122.7, 121.6, 34.3, 33.5, 31.1, 29.4; IR: n=3020,
(Z)-3-(3,3-Dimethylbut-1-en-1-yl)pyridine (21): yield:
23.7 mg (48%); Rf =0.5 (PE:EA=20:1); colorless liquid;
1H NMR (400 MHz, CDCl3): d=8.47 (s, 2H), 7.53 (d, J=
7.6 Hz, 1H), 7.27–7.24 (m, 1H), 6.31 (d, J=12.8 Hz, 1H),
5.75 (d, J=12.8 Hz, 1H), 0.97 (s, 9H); 13C NMR (100 MHz,
CDCl3): d=149.2, 147.0, 145.2, 136.6 (2C), 135.1, 122.8, 34.4,
31.2; IR (cmÀ1): 3220, 3115, 2945, 1589, 1498; LR-MS (EI,
Adv. Synth. Catal. 2016, 358, 1903 – 1909
1907
ꢁ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim