1. No category

化学学报
Supporting Information
钯催化炔溴和烯烃偶联合成共轭烯炔的研究
温燕梅 a
江焕峰 b,*
(a 广东海洋大学理学院
(b 华南理工大学化学与化工学院
湛江
广州
524088)
510640)
A. 仪器与试剂----------------------------------------------------------------- S2
B. 表征数据-------------------------------------------------------------------- S2
C. 参考文献-------------------------------------------------------------------- S9
D. 新化合物核磁谱图------------------------------------------------------- S11
S1
A. 仪器与试剂
德 国 Bruker 公 司 Tensor 27 型 FI-IR 光 谱 仪 ， 美 国 Finnigan 公 司 Trace DSQ
GC-MS 气 质 联 用 仪 ， 德 国 Bruker 公 司 400MHz DRX-400 核 磁 共 振 仪 ， 德 国
Elementar公司Vario EL元素分析仪，河南省予华仪器有限公司X-5型显微熔点仪，
未校正。
所用的化学原料试剂全部从Alfa, Aldrich等公司购买，没有进一步的纯化；
常用溶剂购自广州试剂公司；薄层层析硅胶由硅胶GF254 (青岛海洋化工厂)和
CMC自制；柱层析用硅胶为化学纯试剂(青岛海洋化工厂)；炔基溴按参考文献[1]
合成。
B. 表征数据
3aa: 浅黄色固体，产率 90%；m. p. 97-98 ℃; 1H NMR (400 MHz, CDCl3) δ
7.49 (d, J = 6.4 Hz, 2H), 7.44 (d, J = 7.2 Hz, 2H), 7.37–7.30 (m, 6H), 7.06 (d, J =
16.4 Hz, 1H), 6.40 (d, J = 16.4 Hz, 1H);
13
C NMR (100 MHz, CDCl3) δ 141.29,
136.36, 131.54, 128.76, 128.65, 128.36, 128.21, 126.33, 123.43, 108.15, 91.76, 88.90
ppm; IR (KBr): 2924, 1442, 951, 750, 687 cm-1; MS (EI, 70 eV) m/z (%): 204 (M+,
100), 101 (23), 89 (9)。1H NMR 和 13C NMR 与 Venkataraman 等的数据[2]一致。
3ab: 黄色固体，产率88%；m. p. 107-109 ℃; 1H NMR (400 MHz, CDCl3) δ
7.78–7.68 (m, 7H), 7.54–7.42 (m, 5H), 7.13 (d, J = 16.0 Hz, 1H), 6.44 (d, J = 16.0 Hz,
1H); 13C NMR (100 MHz, CDCl3) δ 141.43, 133.89, 133.55, 131.64, 131.53, 128.54,
128.47, 128.31, 127.81, 127.07, 126.59, 126.47, 126.34, 123.54, 122.83, 108.48,
92.27, 89.23 ppm; IR (KBr): 1438, 957, 814, 743, 690, 482; HRMS EI (m/z): calcd
for C20H14, 254.1096; found, 254.1091.
3ac: 黄色粘稠, 产率91%; 1H NMR (400 MHz, CDCl3) δ 7.49 (d, J = 4.0 Hz,
3H), 7.33–7.31 (m, 3H), 7.22 (d, J = 15.2 Hz, 1H), 7.20–7.17 (m, 3H), 6.30 (d, J =
16.0 Hz, 1H), 2.40 (s, 3H);
13
C NMR (100 MHz, CDCl3) δ 139.07, 135.89, 135.30,
131.56, 130.60, 128.55, 128.39, 128.23, 126.28, 124.96, 123.43, 109.11, 91.40, 89.24,
19.87 ppm; IR (KBr): 2924, 1595, 1485, 1032, 951, 751, 699; MS (EI, 70 eV) m/z
(%): 218 (M+, 100), 202 (92), 189 (9), 141 (12), 115 (15), 95 (9); 1H NMR和13C
NMR 与Morrison等的数据[3]一致。
S2
3ad: 黄色固体，产率82%；m. p. 99-100 ℃; 1H NMR (400 MHz, CDCl3) δ
7.49–7.32 (m, 9H), 7.05 (d, J = 16.0 Hz, 0.85H), 6.37 (d, J = 16.0 Hz, 0.85H), 1.34 (s,
9H); 13C NMR (100 MHz, CDCl3) δ 151.97, 141.18, 138.49, 133.64, 131.51, 131.46,
128.61, 128.42, 128.35, 128.11, 126.12, 125.72, 125.28, 123.55, 107.25, 106.46,
91.44, 89.19, 34.74, 31.25 ppm; IR (KBr): 2968, 1463, 1363, 955, 853, 813, 753, 688;
HRMS EI (m/z): calcd for C20H20, 260.1565; found, 260.1561.
3ae: 浅黄色固体，产率 87%; m. p. 96-97 ℃; 1H NMR (400 MHz, CDCl3) δ
7.51–7.46 (m, 2H), 7.39–7.32 (m, 5H), 7.01 (d, J = 16.4 Hz, 0.92H), 6.93–6.87 (m,
2H), 6.25 (d, J = 16.0 Hz, 0.92H), 3.83 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 160.11,
140.89, 131.46, 129.22, 128.35, 128.02, 127.69, 123.62, 114.21, 105.70, 91.01, 89.28,
55.35 ppm; IR (KBr): 2931, 1602, 1510, 1442, 1256, 1177, 957, 812, 754, 691; MS
(EI, 70 eV) m/z (%): 234 (M+, 100), 201 (28), 191 (54), 165 (18), 94 (11); 1H NMR和
13
C NMR 与Alami等的数据[4]一致。
3af: 浅黄色固体，产率 75%; m. p. 90-92 ℃; 1H NMR (400 MHz, CDCl3) δ
7.49–7.33 (m, 7H), 7.05 (d, J = 8.0 Hz, 2H), 7.01 (d, J = 16.0 Hz, 1H ), 6.31 (d, J =
16.0 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 164.19, 161.72, 139.99, 132.61, 132.57,
131.54, 128.39, 128.27, 127.99, 127.91, 123.36, 115.91, 115.70, 107.93, 107.90,
91.76, 88.69 ppm; IR (KBr): 2925, 1597, 1507, 1441, 1230, 956, 816, 756, 691; MS
(EI, 70 eV) m/z (%): 222 (M+, 100), 110(17); HRMS EI (m/z): calcd for C16H11F,
222.0845; found, 222.0841。
3ag: 白色固体，产率 80%; m. p. 98-99 ℃; 1H NMR (400 MHz, CDCl3) δ
7.51–7.47 (m, 2H), 7.37–7.34 (m, 3H), 6.93 (d, J = 16.8 Hz, 1H), 6.73 (d, J = 16.4 Hz,
1H); 13C NMR (100 MHz, CDCl3) δ 142.97, 132.47, 131.73, 128.87, 128.46, 124.98,
124.96, 122.67, 117.34, 117.27, 107.55, 95.08, 88.19 ppm; IR (KBr):1608, 1520,
1495, 996, 951,757, 690; HRMS EI (m/z): calcd for C16H7F5, 294.0468; found,
294.0463.
3ah: 白色固体，产率 78%; m. p. 93-94 ℃; 1H NMR (400 MHz, CDCl3) δ
7.47–7.28 (m, 9H), 6.96 (d, J = 16.4 Hz, 0.89H), 6.37 (d, J = 16.0 Hz, 0.89H);
13
C
NMR (100 MHz, CDCl3) δ 139.91, 131.93, 131.56, 128.41, 127.75, 126.76, 123.25,
122.54, 113.98, 108.96, 92.43, 88.59 ppm; IR (KBr): 2925, 1597, 1507, 1441, 1230,
S3
956, 816, 756, 691; HRMS EI (m/z): calcd for C16H11Br, 282.0044; found, 282.0040.
3ai : 黄色固体，产率 72%; m. p. 86-87 ℃; 1H NMR (400 MHz, CDCl3) δ 8.28
(s, 1H), 8.14 (d, J = 8.0 Hz, 1H), 7.72 (d, J = 8.0 Hz, 1H), 7.54–7.47 (m, 3H), 7.35 (t,
J = 3.2 Hz, 3H), 7.06 (d, J = 16.4 Hz, 1H), 6.53 (d, J = 16.0 Hz, 1H); 13C NMR (100
MHz, CDCl3) δ 148.73, 138.36, 138.09, 131.88, 131.66, 129.72, 128.66, 128.44,
122.93, 122.90, 120.78, 111.63, 93.71, 87.86 ppm; IR (KBr): 2923, 1525, 1347, 947,
753, 685; MS (EI, 70 eV) m/z (%): 249(M+, 25), 202 (39), 105 (100), 91 (50), 77 (28);
HRMS EI (m/z): calcd for C16H11NO2, 249.0790; found, 247.0783。
3aj : 白色固体，产率 62%; m. p. 100-102 ℃; 1H NMR (400 MHz, CDCl3) δ
7.52–7.33 (m, 10H), 6.14 (s, 1H), 2.43 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 148.36,
140.89, 131.37, 128.46, 128.35, 128.14, 128.03, 125.48, 123.77, 106.59, 95.27, 88.23,
18.72 ppm; IR (KBr): 2924, 1442, 951, 750, 687 cm-1; MS (EI, 70 eV) m/z (%): 218
(M+, 100), 202 (88), 115 (17); 1H NMR和13C NMR 与 Dabdoub等的数据[5]一致。
3ak: 蓝色粘稠, 产率95%; 1H NMR (400 MHz, CDCl3) δ 8.59 (d, J = 4.4 Hz,
1H), 7.65 (t, J = 8.0 Hz, 1H), 7.51–7.48 (m, 2H), 7.35–7.33 (m, 3H), 7.27 (d, J = 7.2
Hz, 1H), 7.19–7.16 (m, 1H), 7.07 (d, J = 16.0 Hz, 1H), 6.98 (d, J = 16.0 Hz, 1H); 13C
NMR (100 MHz, CDCl3) δ 154.21, 149.74, 139.89, 136.66, 131.70, 128.45, 128.37,
123.23, 122.93, 122.31, 112.81, 93.73, 88.68 ppm; IR (KBr): 3053, 2925, 1615, 1581,
1467, 1432, 1254, 1150, 954, 757, 690; MS (EI, 70 eV) m/z (%): 204 (M+, 100), 176
(5), 151 (3); HRMS EI (m/z): calcd for C15H11N, 205.0891; found, 205.0887。
3ba : 白色固体，产率 84%; m. p. 86-88 ℃; 1H NMR (400 MHz, CDCl3) δ
7.43–7.24 (m, 7H), 7.14 (d, J = 8.0 Hz, 2H), 7.02 (d, J = 16.4 Hz, 0.90H), 6.38 (d, J =
16.4 Hz, 0.90H), 2.36 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 140.89, 138.38, 136.46,
131.44, 129.15, 128.75, 128.54, 126.29, 120.36, 108.35, 92.02, 88.29, 21.53 ppm; IR
(KBr): 3028, 2924, 1913, 1505, 1446, 1074, 956, 818, 751, 690, 533; HRMS EI (m/z):
calcd for C17H14, 218.1096; found, 218.1091.
3ca : 黄色固体，产率 88%; m. p. 105-107 ℃; 1H NMR (400 MHz, CDCl3) δ
7.43–7.24 (m, 9H), 7.03 (d, J = 16.0 Hz, 0.82H), 6.40 (d, J = 16.4 Hz, 0.82H), 1.32 (s,
9H); 13C NMR (100 MHz, CDCl3) δ 151.51, 140.88, 136.46, 131.28, 128.75, 128.54,
128.30, 126.29, 125.47, 125.39, 120.40, 108.39, 92.02, 88.29, 34.82, 31.20 ppm; IR
S4
(KBr): 2963, 1598, 1501, 1448, 1267, 950, 834, 747, 690, 561; HRMS EI (m/z): calcd
for C20H20, 260.1565; found, 260.1561.
3da : 浅黄色固体，产率 92%; m. p. 91-92 ℃; 1H NMR (400 MHz, CDCl3) δ
7.35–7.29 (m, 4H), 7.24–7.15 (m, 3H), 6.91 (d, J = 16.0 Hz, 0.92H), 6.78 (t, J = 8.8
Hz, 2H), 6.29 (d, J = 16.4 Hz, 0.92H), 3.72 (s, 3H); 13C NMR (100 MHz, CDCl3) δ
159.62, 140.47, 136.52, 133.00, 128.74, 128.28, 126.24, 115.56, 113.88, 108.43,
91.88, 87.67, 55.31 ppm; IR (KBr): 2929, 2190, 1598, 1506, 1246, 1031, 950, 829,
746, 689; HRMS EI (m/z): calcd for C17H14O, 234.1045; found, 234.1048.
3ea : 黄色固体，产率 41%; m. p. 84-86℃; 1H NMR (400 MHz, CDCl3) δ
7.44–7.27 (m, 7H), 7.24–7.12 (m, 2H), 7.04 (d, J = 16.0 Hz, 0.93H), 6.39 (d, J = 16.0
Hz, 0.93H), 2.34 (s, 3H);
13
C NMR (100 MHz, CDCl3) δ 141.13, 138.02, 136.39,
132.10, 129.12, 128.74, 128.60, 128.59, 128.25, 126.30, 123.21, 108.23, 91.95, 88.55,
29.71, 21.24 ppm; IR (KBr): 2924, 1485, 950, 782, 699; HRMS EI (m/z): calcd for
C17H14, 218.1096; found, 218.1091.
3fa: 黄色粘稠, 产率 74%; 1H NMR (400 MHz, CDCl3) δ 7.47–7.27 (m, 6H),
7.23–7.12 (m, 3H), 7.03 (d, J = 16.4 Hz, 0.82H), 6.43 (d, J = 16.4 Hz, 0.82H), 2.49 (s,
3H); 13C NMR (100 MHz, CDCl3) δ 140.94, 140.12, 138.18, 136.44, 131.89, 129.49,
128.78, 128.60, 128.28, 126.33, 125.62, 123.19, 108.41, 92.82, 90.77, 20.79 ppm; IR
(KBr): 2923, 1486, 949, 751, 690; HRMS EI (m/z): calcd for C17H14, 218.1096; found,
218.1091。
3ga : 白色固体，产率 63%; m. p. 110-112℃; 1H NMR (400 MHz, CDCl3) δ
7.48–7.44 (m, 4H), 7.35–7.28 (m, 5H), 7.05 (d, J = 16.4 Hz, 1H), 6.36 (d, J = 16.0 Hz,
1H); 13C NMR (100 MHz, CDCl3) δ 141.75, 136.19, 132.91, 131.63, 130.92, 128.78,
126.36, 122.40, 107.79, 90.61, 90.04, 65.64 ppm; IR (KBr): 2925, 1727, 1620, 1483,
1391, 1252, 1070, 824, 751, 690; HRMS EI (m/z): calcd for C16H11Br, 282.0044;
found, 282.0040.
3ha: 黄色粘稠, 产率 69%; 1H NMR (400 MHz, DMSO) δ 7.52 (d, J = 7.2 Hz,
2H), 7.39–7.27 (m, 3H), 6.89 (d, J = 16.4 Hz, 0.87H), 6.41 (d, J = 16.4 Hz, 0.87H),
5.24 (s, 0.9H), 1.99–1.87 (m, 1H), 1.57–1.41 (m, 5H), 0.99–0.94 (m, 6H); 13C NMR
(100 MHz, CDCl3) δ 141.22, 136.21, 128.71, 128.60, 126.23, 107.74, 95.59, 82.73,
S5
68.63, 51.95, 30.94, 25.23, 24.14 ppm; IR (KBr): 3422, 2955, 2253, 2126, 1655, 1027,
824, 761; MS (EI, 70 eV) m/z (%): 228 (M+, 3), 213 (12), 171 (100), 157 (27), 128
(52); HRMS EI (m/z): calcd for C16H20O, 228.1514; found, 228.1519。
3ia: 黄色粘稠, 产率 56%; 1H NMR (400 MHz, CDCl3) δ 7.39–7.20 (m, 5H),
6.86 (d, J = 16.0 Hz, 1H), 6.15 (d, J = 16.4 Hz, 1H), 2.49–2.17 (m, 2H), 1.60–1.25 (m,
8H), 0.92–0.84 (m, 3H);
13
C NMR (100 MHz, CDCl3) δ 139.95, 136.62, 128.64,
128.19, 126.04, 108.93, 93.09, 79.72, 31.39, 29.71, 28.78, 22.57, 19.67, 14.07 ppm;
IR (KBr): 2928, 2857, 1714, 1458, 952, 747, 694; MS (EI, 70 eV) m/z (%): 212 (M+,
28), 183 (9), 169 (13), 155 (25), 141 (100), 128 (46), 115 (60); HRMS EI (m/z): calcd
for C16H20, 212.1565; found, 212.1568。
3al：黄色粘稠, 产率 95%; 1H NMR (400 MHz, CDCl3) δ 7.48 (d, J = 8.0 Hz,
2H), 7.39–7.32 (m, 3H), 6.99 (d, J = 16.0 Hz, 1H), 6.32 (d, J = 16.0 Hz, 1H), 3.78 (s,
3H); 13C NMR (101 MHz, CDCl3) δ 166.39, 131.98, 129.55, 129.36, 128.49, 125.40,
122.15, 98.40, 86.32, 51.90 ppm; IR (KBr): 2951, 2197, 1723, 1620, 1437, 1316,
1268, 1036, 959, 756, 690; MS (EI, 70 eV) m/z (%): 186 (M+, 100), 171 (17), 155
(58), 143 (24), 127 (59), 115 (46), 77 (22); 1H NMR 和 13C NMR 与 Uemura 等的数
据[6]一致。
3bl：黄色固体，产率 94%; m. p. 74-76 ℃; 1H NMR (400 MHz, CDCl3) δ 7.37
(d, J = 8.0 Hz, 2H), 7.14 (d, J = 8.0 Hz, 2H), 6.98 (d, J = 16.0 Hz, 1H), 6.28 (d, J =
15.6 Hz, 1H), 3.77 (s, 3H), 2.35 (s, 3H);
13
C NMR (101 MHz, CDCl3) δ 166.41,
139.73, 131.92, 129.26, 129.07, 125.57, 119.11, 98.94, 85.93, 51.80, 21.57 ppm; IR
(KBr): 2954, 2193, 1717, 1621, 1599, 1508, 1316, 1259, 1172, 1030, 959, 916, 740;
MS (EI, 70 eV) m/z (%): 200 (M+, 100), 169 (48), 129 (87), 115 (68), 89 (11), 63(13);
1
H NMR 和 13C NMR 与 Ranu 等的数据[7]一致。
3dl：白色固体，产率 97%; m. p. 103-104 ℃; 1H NMR (400 MHz, CDCl3) δ
7.41 (d, J = 8.8 Hz, 2H), 6.98 (d, J = 16.0 Hz, 1H), 6.86 (d, J = 8.8 Hz, 2H), 6.25 (d, J
= 16.0 Hz, 1H), 3.81 (s, 3H), 3.76 (s, 3H);
13
C NMR (101 MHz, CDCl3) δ 166.55,
160.51, 133.66, 128.49, 125.73, 114.17, 99.08, 85.57, 55.32, 51.80 ppm; IR (KBr):
2954, 2190, 1708, 1597, 1508, 1329, 1250, 1197, 1028, 960, 825, 718; MS (EI, 70 eV)
m/z (%): 216 (M+, 74), 201 (100), 185 (30), 173 (16), 157 (18), 145 (40); HRMS EI
S6
(m/z): calcd for C13H12O3, 216.0786; found, 216.0789。
3gl：浅黄色固体，产率 75%; m. p. 90-92 ℃; 1H NMR (400 MHz, CDCl3) δ
7.47 (d, J = 8.8 Hz, 2H), 7.32 (d, J = 8.4 Hz, 2H), 6.95 (d, J = 15.6 Hz, 1H), 6.31 (d, J
= 15.6 Hz, 1H), 3.77 (s, 3H); 13C NMR (101 MHz, CDCl3) δ 166.22, 133.33, 131.81,
129.97, 124.98, 123.82, 121.08, 97.13, 87.32, 51.95 ppm; IR (KBr): 2950, 1718, 1620,
1315, 1256, 1174, 959, 826; MS (EI, 70 eV) m/z (%): 264 (M+, 31), 248 (15), 170
(76), 126 (100), 99 (18), 74 (30), 63 (38); HRMS EI (m/z): calcd for C12H9BrO2,
263.9786; found, 263.9782。
3jl：浅黄色固体，产率 78%; m. p. 77-78 ℃; 1H NMR (400 MHz, CDCl3) δ
7.47–7.43 (m, 2H), 7.02 (t, J = 8.4 Hz, 2H), 6.95 (d, J = 15.6 Hz, 1H), 6.28 (d, J =
16.0 Hz, 1H), 3.76 (s, 3H);
13
C NMR (101 MHz, CDCl3) δ 166.27, 164.35, 161.85,
134.04, 129.59, 125.13, 118.30, 115.75, 97.29, 86.10, 51.86 ppm; IR (KBr): 2953,
2200, 1725, 1620, 1595, 1505, 1436, 1317, 1231, 1171, 1028, 960, 837, 741; MS (EI,
70 eV) m/z (%): 204 (M+, 100), 189 (89), 173 (61), 125 (68), 99 (17), 75 (23); HRMS
EI (m/z): calcd for C12H9FO2, 204.0587; found, 204.0584。
3kl：黄色粘稠，产率 98%; 1H NMR (400 MHz, CDCl3) δ 6.74 (d, J = 16.0 Hz,
1H), 6.12 (d, J = 15.6 Hz, 1H), 3.72 (s, 3H), 2.37–2.33 (m, 2H), 1.57–1.49 (m, 2H),
1.41–1.34 (m, 2H), 1.31–1.26 (m, 2H), 0.87 (t, J = 6.4 Hz, 3H); 13C NMR (101 MHz,
CDCl3) δ 166.56, 128.74, 126.39, 101.01, 51.64, 31.25, 28.51, 28.25, 22.48, 19.73,
13.97 ppm; IR (KBr): 2932, 2859, 2214, 1727, 1620, 1434, 1304, 1158, 962, 860;
MS (EI, 70 eV) m/z (%): 180(M+,2), 163(18), 133 (48), 119 (44), 105 (100), 91 (75);
NMR 和 13C NMR 与 Unelius 等的数据[8]一致。
3ll：黄色粘稠，产率 82%; 1H NMR (400 MHz, CDCl3) δ 6.73 (d, J = 16.0 Hz,
1H), 6.11 (d, J = 16.0 Hz, 1H), 3.74 (s, 3H), 1.60 (s, 1H), 0.93–0.88 (m, 1H),
0.83–0.79 (m, 1H);
13
C NMR (101 MHz, CDCl3) δ 166.10, 127.83, 125.79, 103.90,
72.90, 51.15, 8.61, ppm; IR (KBr): 2926, 2855, 2208, 1725, 1620,, 1434, 1303, 1163,
961; MS (EI, 70 eV) m/z (%): 150 (M+, 59), 107 (71), 91 (82), 79 (92), 65 (100);
HRMS EI (m/z): calcd for C9H10O2, 150.0681; found, 150.0684。
3ml：黄色粘稠，产率 90%; 1H NMR (400 MHz, CDCl3) δ 6.72 (dt, J = 16.0, 2.4
Hz, 1H), 6.17 (d, J = 15.6 Hz, 1H), 3.74 (s, 3H), 2.58–2.54 (m, 2H), 2.49 (t, J = 7.2
S7
Hz, 2H), 1.94–1.87 (m, 2H); 13C NMR (101 MHz, CDCl3) δ 166.29, 129.87, 125.38,
118.85, 96.92, 79.41, 51.84, 24.21, 18.81, 16.22 ppm; IR (KBr): 2952, 2216, 1717,
1619, 1433, 1266, 1156, 961, 860; MS (EI, 70 eV) m/z (%):177(M+, 8), 162 (12), 149
(100), 134 (61), 117 (91), 105 (49), 91 (100); HRMS EI (m/z): calcd for C10H11NO2,
177.0790; found, 177.0788。
3nl：黄色粘稠，产率 87%; 1H NMR (400 MHz, CDCl3) δ 6.75 (dt, J = 16.0, 2.4
Hz, 2H), 6.14 (d, J = 16.0 Hz, 2H), 3.74 (s, 6H), 2.42–2.37 (m, 4H), 1.67–1.49 (m,
6H);
13
C NMR (101 MHz, CDCl3) δ 166.56, 128.97, 126.25, 100.44, 78.15, 51.74,
28.02, 27.74, 19.64 ppm; IR (KBr): 1433, 1303, 12662935, 2860, 2212, 1723, 1618,,
1175, 960, 858, 715; MS (EI, 70 eV) m/z (%): 228 (M+, 21), 197 (44), 169 (68), 141
(100), 128 (42), 91 (62), 77 (62); HRMS EI (m/z): calcd for C17H20O4, 288.1362;
found, 288.1357。
3am：黄色粘稠, 产率 90%; 1H NMR (400 MHz, CDCl3) δ 7.50–7.48 (m, 2H),
7.37–7.35 (m, 3H), 6.98 (d, J = 15.6 Hz, 1H), 6.32 (d, J = 16.0 Hz, 1H), 4.19 (t, J =
6.4 Hz, 2H), 1.70–1.65 (m, 2H), 1.47–1.37 (m, 2H), 0.96 (t, J = 7.2 Hz, 3H);
13
C
NMR (100 MHz, CDCl3) δ 166.02, 131.97, 130.09, 129.31, 128.48, 125.06, 122.22,
98.27, 86.38, 64.70, 30.67, 19.16, 13.73; IR (KBr): 3685, 3106, 1717,1407, 1361,
1313, 1257,1172; MS (EI, 70 eV) m/z (%): 228 (M+, 23), 172 (100), 155 (45), 127
(45), 116 (33), 77 (22); 1H NMR 和 13C NMR 与 Ranu 等的数据[9]一致。
3an：黄色粘稠, 产率82%; 1H NMR (400 MHz, CDCl3) δ 7.51–7.49 (m, 2H),
7.39–7.31 (m, 3H), 6.50 (dd, J1 = 1.2 Hz, J2 = 17.2 Hz , 1H), 6.20–6.13 (m, 1H), 5.92
(dd, J1 = 1.2 Hz, J2 = 10.4 Hz, 1H), 4.92 (s, 2H);
13
C NMR (100 MHz, CDCl3) δ
165.20, 132.67, 132.10, 129.51, 128.46, 127.50, 121.18, 78.85, 76.00, 73.04, 71.30,
52.69; IR (KBr): 3682, 3299, 2248,1732, 1257, 1173; MS (EI, 70 eV) m/z (%): 210
(M+, 19), 181 (25), 153 (23), 138 (100), 127 (20), 55 (29); HRMS EI (m/z): calcd for
C14H10O2, 210.0681; found, 210.0677。
3ao：黄色粘稠, 产率80%; 1H NMR (400 MHz, CDCl3) δ 7.51–7.48 (m, 2H),
7.41–7.34 (m, 3H), 7.04 (d, J = 16.0 Hz, 1H), 6.34 (d, J = 16.0 Hz, 1H), 4.52–4.48 (m,
2H), 3.58–3.55 (m, 2H);
13
C NMR (100 MHz, CDCl3) δ 165.35, 132.02, 131.69,
129.46, 129.03, 128.51, 127.83, 126.28, 122.06, 99.15, 86.24, 64.05, 28.53; IR (KBr):
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3684, 3074, 2197,1719, 1615, 1253,1164; MS (EI, 70 eV) m/z (%): 278(M+, 36), 172
(40), 155 (94), 127 (100), 115 (67), 107 (38) ; HRMS EI (m/z): calcd for C13H11BrO2,
277.9942; found, 277.9939。
3ap：黄色粘稠, 产率87%; 1H NMR (400 MHz, CDCl3) δ 7.53–7.50 (m, 2H),
7.41–7.35 (m, 3H), 7.11 (d, J = 16.0 Hz, 1H), 6.37 (d, J = 16.0 Hz, 1H), 4.58 (q, J =
8.4 Hz, 2H); 13C NMR (100 MHz, CDCl3) δ 164.20, 132.13, 129.69, 128.58, 127.76,
127.60, 124.37, 121.91, 100.24, 86.07, 61.35 (q, 37 Hz); IR (KBr): 3683, 3080,
1736,1409, 1287, 1164; MS (EI, 70 eV) m/z (%): 254(M+, 94), 171 (100), 155 (52),
143 (23), 127 (77), 115 (64), 77(42); HRMS EI (m/z): calcd for C13H9F3O, 238.0605;
found, 238.0600。
3aq：黄色粘稠, 产率 86%; 1H NMR (400 MHz, CDCl3) δ 7.50–7.48 (m, 2H),
7.44–7.36 (m, 3H), 6.70 (d, J = 16.0 Hz, 1H), 5.80 (d, J = 16.0 Hz, 1H);
13
C NMR
(100 MHz, CDCl3) δ 132.07, 131.05, 129.97, 128.62, 121.33, 117.14, 108.02, 100.74,
85.35; IR (KBr): 3675, 3099, 1734,1515, 1459, 1370; MS (EI, 70 eV) m/z (%): 153
(M+, 100), 126 (44); 1H NMR 和 13C NMR 与 Ranu 等的数据[9]一致。
3ar：白色固体, 产率76%; m. p. 87-89 ℃; 1H NMR (400 MHz, CDCl3) δ
7.47–7.43 (m, 2H), 7.36–7.31 (m, 3H), 6.89 (d, J = 15.2 Hz, 1H), 6.26 (d, J = 15.6 Hz,
1H), 1.41 (s, 9H);
13
C NMR (100 MHz, CDCl3) δ 163.94, 133.69, 131.83, 128.94,
128.41, 122.58, 120.76, 96.02, 86.84, 51.66, 28.79; IR (KBr): 3680, 3261, 3075, 2965,
1643, 1607, 1347; MS (EI, 70 eV) m/z (%): 227 (M+, 18), 171 (43), 155 (100), 143
(34), 127 (44), 77 (17); HRMS EI (m/z): calcd for C15H17NO, 227.1310; found,
227.1307。
C. 参考文献
1
Hofmeister, H.; Annen, K.; Laurent, H.; Wiechert, R. Angew. Chem. Int. Ed. 1984,
23, 727.
2
Bates, C. G.; Saejueng, P.; Venkataraman, D. Org. Lett. 2004, 6, 1441.
3
Aitken, R. A.; Boeters, C.; Morrison, J. J. J. Chem. Soc., Perkin Trans. 1, 1997,
17, 2625.
4
Tikad, A.; Hamze, A.; Provot, O.; Brion,J.-D.; Alami, M. Eur. J. Org. Chem. 2010,
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4, 725.
5
Dabdoub, M. J.; Dabdoub, V. B. Tetrahedron Lett. 1992, 33, 2261.
6
Nishimura, T.; Araki, H.; Maeda, Y.; Uemura, S. Org. Lett. 2003, 5, 2997.
7
8
Ranu, B. C.; Adak, L.; Chattopadhyay, K. J. Org. Chem. 2008, 73, 5609
Baeckstroem, P.; Jacobsson, U.; Norin, T.; Unelius, C. R. Tetrahedron 1988, 44,
2541.
9
Ranu, B. C.; Chattopadhyay, K. Org. Lett. 2007, 9, 2409.
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B. 核新化合物磁谱图
3ab
3ab
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3ad
3ad
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3af
3af
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3ag
3ag
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3ah
3ah
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NO2
3ai
NO2
3ai
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3ak
3ak
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3ba
3ba
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3ca
3ca
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3da
3da
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3ea
3ea
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3f a
3f a
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3ga
3ga
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3ha
3ha
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3ia
3ia
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3dl
3dl
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3gl
3gl
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3ll
3ll
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3ml
3ml
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3nl
3nl
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3an
3an
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3ao
3ao
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3ap
3ap
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3ar
3ar
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