高等学校化学学报 ›› 2016, Vol. 37 ›› Issue (5): 902.doi: 10.7503/cjcu20150883
收稿日期:
2015-11-19
出版日期:
2016-05-10
发布日期:
2016-04-20
作者简介:
联系人简介: 陈战国, 男, 博士, 副教授, 主要从事有机合成及天然产物结构改造方面的研究. E-mail:基金资助:
DU Manfei, HOU Dan, HUI Wenping, CHEN Zhanguo*()
Received:
2015-11-19
Online:
2016-05-10
Published:
2016-04-20
Contact:
CHEN Zhanguo
E-mail:chzhg@snnu.edu.cn
Supported by:
摘要:
以β-硝基苯乙烯衍生物为底物, 丙烯酰胺和N-溴代丁二酰亚胺(NBS)为氮源和卤素源, 建立了碳-碳双键上的选择性氨溴加成反应新体系. 以二氯甲烷为溶剂, 在没有惰性气体保护及乙醇钠促进下, β-硝基苯乙烯衍生物与丙烯酰胺和NBS于室温反应即可高收率地获得α-氨基-β,β-二溴加成产物, 最高收率达83%; 以甲醇为溶剂, 在无水碳酸钠作用下, β-甲基-β-硝基苯乙烯衍生物也可高收率地获得相应的邻位氨溴加成产物, 最高收率达97%. 共考察了25种不同结构β-硝基苯乙烯衍生物的氨溴加成反应, 结果表明, 该反应具有广泛的适应性. 采用核磁共振波谱及质谱表征了产物的结构, 并提出了可能的反应机理.
中图分类号:
TrendMD:
杜曼飞, 侯丹, 惠文萍, 陈战国. β-硝基苯乙烯衍生物与丙烯酰胺及N-溴代丁二酰亚胺的区域专一性氨溴加成反应. 高等学校化学学报, 2016, 37(5): 902.
DU Manfei, HOU Dan, HUI Wenping, CHEN Zhanguo. Regiospecific Aminobromination of β-Nitrostyrene Derivatives with Acrylamide and N-Bromobutanimide†. Chem. J. Chinese Universities, 2016, 37(5): 902.
Compd. | m.p.(Ref.)/℃ | Compd. | m.p.(Ref.)/℃ |
---|---|---|---|
1a | 57.1—58.5(58[ | 14a | 65.7—66.8(65—66[ |
2a | 100.1—102.1(102—102.5[ | 15a | 54.0—54.4(55[ |
3a | 84.4—86.0(85.5—87.5[ | 16a | 47.6—49(48[ |
4a | 143.6—144.2 | 17a | 71.5—72.0 |
5a | 133.6—135.1(133.5—134.5[ | 18a | 87.0—87.4(87—88[ |
6a | 98—99(98—99[ | 19a | 94.0—94.8(95[ |
7a | 101—103(101—102.5[ | 20a | 96.4—97.3(96—97[ |
8a | 114.3—115.4(113—114[ | 21a | 64.0—65.1(66[ |
9a | 149.3—150.6(151—153[ | 22a | 86—89(86—87[ |
10a | 56.2—57.8 | 23a | 92.6—93.8(93—95[ |
11a | 123.1—124.3(124.5—126[ | 24a | 113.8—114.1(114—115[ |
12a | 105.4—105.8(106—107[ | 25a | 73.5—74.8(74[ |
13a | 120—122(121—122[ |
Table 1 Melting points of β-nitrostyrene derivatives 1a—25a
Compd. | m.p.(Ref.)/℃ | Compd. | m.p.(Ref.)/℃ |
---|---|---|---|
1a | 57.1—58.5(58[ | 14a | 65.7—66.8(65—66[ |
2a | 100.1—102.1(102—102.5[ | 15a | 54.0—54.4(55[ |
3a | 84.4—86.0(85.5—87.5[ | 16a | 47.6—49(48[ |
4a | 143.6—144.2 | 17a | 71.5—72.0 |
5a | 133.6—135.1(133.5—134.5[ | 18a | 87.0—87.4(87—88[ |
6a | 98—99(98—99[ | 19a | 94.0—94.8(95[ |
7a | 101—103(101—102.5[ | 20a | 96.4—97.3(96—97[ |
8a | 114.3—115.4(113—114[ | 21a | 64.0—65.1(66[ |
9a | 149.3—150.6(151—153[ | 22a | 86—89(86—87[ |
10a | 56.2—57.8 | 23a | 92.6—93.8(93—95[ |
11a | 123.1—124.3(124.5—126[ | 24a | 113.8—114.1(114—115[ |
12a | 105.4—105.8(106—107[ | 25a | 73.5—74.8(74[ |
13a | 120—122(121—122[ |
Compd. | Appearance | Yield*(%) | m.p./℃ | HRMS(calcd.), m/z[M+Na]+ |
---|---|---|---|---|
1b | White solid | 83 | 109.1—112.0 | 398.8948(398.8956) |
2b | White solid | 50 | 151.5—154.5 | 412.9104(412.9112) |
3b | White solid | 53 | 152.0—153.4 | 428.9033(428.9062) |
4b | Faint yellow solid | 43 | 142.4—144.8 | 458.9156(458.9167) |
5b | Yellow solid | 52 | 145.1—147.3 | 458.9140(458.9167) |
6b | Faint yellow solid | 50 | 167.0—168.7 | 536.8280(536.8272) |
7b | White solid | 48 | 153.7—156.3 | 416.8851(416.8862) |
8b | White solid | 56 | 162.3—164.5 | 432.8554(432.8586) |
9b | White solid | 56 | 142.2—148.7 | 476.8056(476.8061) |
10b | White solid | 57 | 141.2—143.0 | 466.8175(466.8176) |
11b | White solid | 81 | 138.9—140.8 | 443.8801(443.8807) |
12b | Faint yellow solid | 73 | 118.4—120.6 | 443.8802(443.8807) |
13b | Faint yellow solid | 58 | 169.4—171.5 | 448.9109(448.9112) |
14b | White solid | 93 | 144.8—148.5 | 335.0001(335.0007) |
15b | White solid | 44 | 153.0—154.2 | 349.0156(349.0164) |
16b | White solid | 51 | 128.9—129.6 | 365.0081(365.0113) |
17b | White solid | 44 | 109.8—112.0 | 395.0209(395.0219) |
18b | White solid | 19 | 173.5—175.1 | 395.0209(395.0219) |
19b | White solid | 16 | 149.7—152.0 | 425.0287(425.0324) |
20b | White solid | 45 | 177.4—179.5 | 472.9286(472.9324) |
21b | White solid | 52 | 139.9—141.9 | 352.9884(352.9913) |
22b | White solid | 54 | 156.1—160.5 | 368.9588(368.9618) |
23b | White solid | 55 | 146.2—149.6 | 412.9086(412.9112) |
24b | Faint yellow solid | 97 | 176.1—178.1 | 379.9825(379.9858) |
25b | Orange red solid | 60 | 150.9—152.7 | 379.9827(379.9858) |
Table 2 Appearance, yields, melting points and HRMS data for compounds 1b—25b
Compd. | Appearance | Yield*(%) | m.p./℃ | HRMS(calcd.), m/z[M+Na]+ |
---|---|---|---|---|
1b | White solid | 83 | 109.1—112.0 | 398.8948(398.8956) |
2b | White solid | 50 | 151.5—154.5 | 412.9104(412.9112) |
3b | White solid | 53 | 152.0—153.4 | 428.9033(428.9062) |
4b | Faint yellow solid | 43 | 142.4—144.8 | 458.9156(458.9167) |
5b | Yellow solid | 52 | 145.1—147.3 | 458.9140(458.9167) |
6b | Faint yellow solid | 50 | 167.0—168.7 | 536.8280(536.8272) |
7b | White solid | 48 | 153.7—156.3 | 416.8851(416.8862) |
8b | White solid | 56 | 162.3—164.5 | 432.8554(432.8586) |
9b | White solid | 56 | 142.2—148.7 | 476.8056(476.8061) |
10b | White solid | 57 | 141.2—143.0 | 466.8175(466.8176) |
11b | White solid | 81 | 138.9—140.8 | 443.8801(443.8807) |
12b | Faint yellow solid | 73 | 118.4—120.6 | 443.8802(443.8807) |
13b | Faint yellow solid | 58 | 169.4—171.5 | 448.9109(448.9112) |
14b | White solid | 93 | 144.8—148.5 | 335.0001(335.0007) |
15b | White solid | 44 | 153.0—154.2 | 349.0156(349.0164) |
16b | White solid | 51 | 128.9—129.6 | 365.0081(365.0113) |
17b | White solid | 44 | 109.8—112.0 | 395.0209(395.0219) |
18b | White solid | 19 | 173.5—175.1 | 395.0209(395.0219) |
19b | White solid | 16 | 149.7—152.0 | 425.0287(425.0324) |
20b | White solid | 45 | 177.4—179.5 | 472.9286(472.9324) |
21b | White solid | 52 | 139.9—141.9 | 352.9884(352.9913) |
22b | White solid | 54 | 156.1—160.5 | 368.9588(368.9618) |
23b | White solid | 55 | 146.2—149.6 | 412.9086(412.9112) |
24b | Faint yellow solid | 97 | 176.1—178.1 | 379.9825(379.9858) |
25b | Orange red solid | 60 | 150.9—152.7 | 379.9827(379.9858) |
Compd. | 1H NMR(CDCl3), δ | 13C NMR(CDCl3), δ |
---|---|---|
1b | 7.46(dd, J=7.4, 2.1 Hz, 2H, ArH), 7.42—7.3(m, 3H, ArH), 6.71(d, J=9.9 Hz, 1H, NH), 6.45—6.40(m, 1H, CH), 6.40—6.33(m, 1H, CH), 6.20(dd, J=16.9, 10.2 Hz, 1H, CH), 5.77(dd, J=10.2, 1.2 Hz, 1H, CH) | 164.2, 133.2, 129.8, 129.6, 129.1, 129.0, 128.7, 93.06, 62.78 |
2b | 7.38(d, J=8.2 Hz, 2H, ArH), 7.18(d, J =8.0 Hz, 2H, ArH), 7.01(d, J=10.1 Hz, 1H, NH), 6.42(d, J=10.1 Hz, 1H, CH), 6.39(dd, J=17.0, 1.1 Hz, 1H, CH), 6.26(dd, J=17.0, 10.3 Hz, 1H, CH), 5.77(dd, J=10.3, 1.0 Hz, 1H, CH), 2.36(s, 3H, CH3) | 164.5, 139.9, 130.3, 129.7, 129.4, 129.0, 128.9, 93.56, 62.69, 21.20 |
3b | 7.32(d, J=8.8 Hz, 2H, ArH), 7.15(d, J=10.1 Hz, 1H, NH), 6.78(d, J=8.8 Hz, 2H, ArH), 6.33(d, J=10.1 Hz, 1H, CH), 6.28(d, J=17.0 Hz, 1H, CH), 6.18(dd, J=17.0, 10.2 Hz, 1H, CH), 5.65(d, J=11.4 Hz, 1H, CH), 3.70(s, 3H, OCH3) | 164.6, 160.5, 130.5, 129.7, 128.9, 125.2, 114.0, 93.97, 62.51, 55.31 |
4b | 7.02(dd, J=8.4, 2.1 Hz, 1H, ArH), 6.93(d, J=2.1 Hz, 1H, ArH), 6.83(d, J=8.4 Hz, 1H, ArH), 6.70(d, J=9.6 Hz, 1H, NH), 6.38(d, J=17.0 Hz, 1H, CH), 6.34(d, J=10.0 Hz, 1H, CH), 6.21(dd, J=16.9, 10.3 Hz, 1H, CH), 5.78(d, J=10.4 Hz, 1H, CH), 3.87(s, 6H, 2OCH3) | 164.3, 150.2, 148.9, 129.6, 129.0, 125.4, 121.5, 112.5, 111.0, 93.46, 62.74, 56.11, 55.90 |
5b | 7.01(dd, J=8.4, 2.1 Hz, 1H, ArH), 6.93(d, J=2.1 Hz, 1H, ArH), 6.84(d, J=8.4 Hz, 1H, CH), 6.63(d, J=9.9 Hz, 1H, NH), 6.39(d, J=17.0 Hz, 1H, ArH), 6.33(d, J=10.0 Hz, 1H, CH), 6.21(dd, J=16.9, 10.3 Hz, 1H, CH), 5.78(d, J=10.3 Hz, 1H, CH), 3.88(s, 3H, OCH3), 3.87(s, 3H, OCH3) | 164.2, 150.2, 148.9, 129.6, 129.0, 125.4, 121.4, 112.5, 111.0, 93.41, 62.73, 56.12, 55.91 |
6b | 7.08(s, 1H, ArH), 7.01(s, 1H, ArH), 6.98(d, J=9.6 Hz, 1H, CH), 6.75(d, J=9.5 Hz, 1H, NH), 6.36(d, J=16.9 Hz, 1H, CH), 6.14(dd, J=16.9, 10.3 Hz, 1H, CH), 5.74(d, J=10.4 Hz, 1H, CH), 3.88(s, 3H, OCH3), 3.85(s, 3H, OCH3) | 164.0, 150.5, 148.7, 129.2, 125.6, 117.7, 116.0, 110.5, 92.43, 61.13, 56.31, 56.20 |
7b | 7.48(dd, J=8.7, 5.1 Hz, 2H, ArH), 7.06(t, J=8.6 Hz, 2H, ArH), 6.99(d, J=9.9 Hz, 1H, NH), 6.42(d, J=9.6 Hz, 1H, CH), 6.35(d, J=1.2 Hz, 1H, CH), 6.22(dd, J=16.9, 10.1 Hz, 1H, CH), 5.77(dd, J=10.1, 1.2 Hz, 1H, CH) | 165.0, 164.5, 161.7, 131.2, 131.0, 129.4, 129.3, 129.2, 129.1, 115.9, 115.7, 93.04, 62.23 |
8b | 7.42(d, J=8.6 Hz, 2H, ArH), 7.34(d, J=8.6 Hz, 2H, ArH), 6.94(d, J=9.9 Hz, 1H, NH), 6.42(s, 1H, CH), 6.40—6.33(m, 1H, CH), 6.21(dd, J=16.9, 10.1 Hz, 1H, CH), 5.78(dd, J=10.1, 1.2 Hz, 1H, CH) | 164.4, 136.0, 131.8, 130.5, 129.4, 129.3, 129.0, 92.64, 62.28 |
9b | 7.50(d, J=8.6 Hz, 2H, ArH), 7.35(d, J=8.5 Hz, 2H, ArH), 6.93(d, J=9.9 Hz, 1H, NH), 6.40(s, 1H, CH), 6.38—6.32(m, 1H, CH), 6.20(dd, J=16.9, 10.1 Hz, 1H, CH), 5.77(dd, J=10.1, 1.2 Hz, 1H, CH) | 164.4, 132.3, 131.9, 130.8, 129.4, 129.3, 124.3, 92.49, 62.36 |
10b | 7.62(d, J=2.1 Hz, 1H, ArH), 7.47(d, J=8.4 Hz, 1H, ArH), 7.35(dd, J=8.4, 2.2 Hz, 1H, ArH), 6.95(d, J=9.8 Hz, 1H, NH), 6.41(d, J=8.8 Hz, 1H, CH), 6.39(s, 1H, CH), 6.24(dd, J=16.9, 10.3 Hz, 1H, CH), 5.82(d, J=10.4 Hz, 1H, CH) | 164.4, 134.4, 133.5, 133.0, 131.0, 130.6, 129.7, 129.2, 128.6, 91.92, 61.92 |
11b | 8.24(d, J=8.8 Hz, 2H, ArH), 7.72(d, J=8.8 Hz, 2H, ArH), 6.88(d, J=9.7 Hz, 1H, NH), 6.52(d, J=9.8 Hz, 1H, CH), 6.40(dd, J=16.9, 1.2 Hz, 1H, CH), 6.22(dd, J=16.9, 10.2 Hz, 1H, CH), 5.82(dd, J=10.2, 1.1 Hz, 1H, CH) | 164.4, 148.5, 140.3, 130.4, 129.9, 129.0, 123.7, 91.25, 62.25 |
12b | 7.43—7.35(m, 2H, ArH), 7.32—7.29(m, 2H, ArH), 6.73(d, J=10.0 Hz, 1H, NH), 6.34(d, J=10.1 Hz, 1H, CH), 6.30(dd, J=16.9, 0.9 Hz, 1H, CH), 6.14(dd, J=17.0, 10.3 Hz, 1H, CH), 5.69(d, J=10.4 Hz, 1H, CH) | 164.3, 133.3, 129.8, 129.6, 129.1, 129.0, 128.7, 93.12, 62.82 |
13b | 7.97(s, 1H, ArH), 7.86(t, J=7.9 Hz, 3H, ArH), 7.62—7.52(m, 3H, ArH), 6.89(d, J=9.8 Hz, 1H, NH), 6.61(d, J=10.0 Hz, 1H, CH), 6.41(d, J=16.9 Hz, 1H, CH), 6.26(dd, J=16.9, 10.3 Hz, 1H, CH), 5.80(d, J=10.3 Hz, 1H, CH) | 164.3, 133.6, 132.7, 130.5, 129.6, 129.5, 129.1, 128.6, 128.4, 127.7, 127.3, 126.8, 125.4, 93.04, 63.01 |
14b | 7.34(dd, J=5.0, 1.8 Hz, 3H, ArH), 7.29—7.25(m, 2H, ArH), 6.37(dd, J=17.0, 0.9 Hz, 1H, CH), 6.24(dd, J=17.0, 10.3 Hz, 1H, CH), 5.83(d, J=9.7 Hz, 1H, CH), 5.76(dd, J=10.3, 0.9 Hz, 1H), 2.25(s, 3H, CH3) | 164.6, 134.1, 130.2, 129.4, 129.0, 128.2, 96.19, 60.63, 29.55 |
15b | 7.14(s, 4H, ArH), 6.36(dd, J=17.0, 1.5 Hz, 1H, CH), 6.23(dd, J=17.0, 10.0 Hz, 1H, CH), 5.80(d, J=9.7 Hz, 1H, CH), 5.74(dd, J=10.0, 1.5 Hz, 1H, CH), 2.33(d, J=8.9 Hz, 3H, CH3), 2.22(d, J=14.5 Hz, 3H, CH3) | 164.7, 139.3, 131.1, 130.2, 129.6, 129.3, 128.5, 128.1, 96.61, 60.37, 29.34, 21.09 |
16b | 7.19(d, J=8.7 Hz, 2H, ArH), 6.84(d, J=8.8 Hz, 2H, ArH), 6.36(dd, J=17.0, 1.2 Hz, 1H, CH), 6.23(dd, J=17.0, 10.3 Hz, 1H, CH), 5.80(d, J=9.7 Hz, 1H, CH), 5.74(dd, J=10.3, 1.2 Hz, 1H, CH), 3.78(s, 3H, CH3), 2.24(s, 3H, CH3) | 164.6, 160.2, 130.2, 129.8, 129.4, 128.1, 126.0, 114.4, 114.1, 96.7, 60.11, 55.29, 29.4 |
17b | 7.74(d, J=9.4 Hz, 1H, NH), 6.88(d, J=8.0 Hz, 1H, ArH), 6.83(s, 1H, ArH), 6.76(d, J=8.2 Hz, 1H, ArH), 6.31(d, J=17.1 Hz, 1H, CH), 6.25(t, J=13.4 Hz, 1H, CH), 5.89(d, J=9.5 Hz, 1H, CH), 5.66(d, J=8.7 Hz, 1H, CH), 3.80(s, 3H, OCH3), 3.77(s, 3H, OCH3), 2.25(s, 3H, CH3) | 165.0, 149.7, 149.0, 130.1, 128.2, 126.5, 121.0, 111.8, 111.2, 96.9, 60.40, 55.98, 55.81, 28.87 |
18b | 7.51(d, J=8.7 Hz, 1H, ArH), 6.72(dd, J=7.5, 5.8 Hz, 1H, ArH), 6.51(dd, J=5.8, 3.0 Hz, 1H, ArH), 6.45(d, J=2.6 Hz, 1H, CH), 6.38(dt, J=17.1, 3.7 Hz, 1H, CH), 6.26(t, J=6.5 Hz, 1H, CH), 5.75(dd, J=10.1, 1.4 Hz, 1H, CH), 3.86(s, 3H, OCH3), 3.74(s, 3H, OCH3), 2.27(s, 3H, CH3) | 164.5, 160.4, 157.2, 136.1, 129.9, 128.3, 105.8, 103.8, 100.2, 93.82, 59.33, 56.43, 55.58, 28.24 |
19b | 6.46(s, 2H, ArH), 6.39(dd, J=17.0, 1.1 Hz, 1H, CH), 6.26(dd, J=17.0, 10.3 Hz, 1H, CH), 5.78(dd, J=10.3, 1.1 Hz, 1H, CH), 5.72(d, J=9.6 Hz, 1H, CH), 3.82(s, 9H, 3OCH3), 2.25(s, 3H, CH3) | 164.6, 153.5, 138.9, 130.1, 129.4, 128.3, 105.4, 95.68, 60.93, 60.82, 56.28, 29.71 |
20b | 7.04(t, J=17.9 Hz, 2H, ArH), 6.56(s, 1H, CH), 6.43—6.38(m, 1H, CH), 6.29—6.26(m, 1H, CH), 5.77(d, J=10.3 Hz, 1H, CH), 3.86(s, 3H, OCH3), 3.78(s, 3H, OCH3), 2.27(s, 3H, CH3) | 164.5, 150.1, 149.3, 129.9, 128.4, 125.8, 116.2, 116.0, 115.7, 109.6, 94.06, 60.40, 59.44, 21.04 |
21b | 7.27(dd, J=6.0, 2.7 Hz, 2H, ArH), 7.02(t, J=8.6 Hz, 2H, ArH), 6.37(dd, J=17.0, 1.1 Hz, 1H, CH), 6.23(dd, J=17.0, 10.3 Hz, 1H, CH), 5.85(d, J=9.6 Hz, 1H, CH), 5.76(dd, J=10.3, 1.1 Hz, 1H, CH), 2.25(s, 3H, CH3) | 164.7, 163.9, 130.5, 130.1, 130.1, 129.9, 128.5, 116.1, 116.0, 96.41, 59.98, 29.41 |
22b | 7.31(d, J=8.5 Hz, 2H, ArH), 7.22(d, J=8.5 Hz, 2H, ArH), 6.37(dd, J=17.0, 1.1 Hz, 1H, CH), 6.23(dd, J=17.0, 10.3 Hz, 1H, CH), 5.83(d, J=9.6 Hz, 1H, CH), 5.76(dd, J=10.3, 1.1 Hz, 1H, CH), 2.25(s, 3H, CH3) | 164.7, 135.5, 132.7, 130.0, 129.9, 129.6, 129.2, 128.9, 128.5, 96.17, 60.06, 29.39 |
23b | 7.47(d, J=8.5 Hz, 2H, ArH), 7.16(d, J=8.5 Hz, 2H, ArH), 6.37(dd, J=17.0, 1.0 Hz, 1H, CH), 6.23(dd, J=17.0, 10.3 Hz, 1H, CH), 5.81(d, J=9.6 Hz, 1H, CH), 5.77(dd, J=10.3, 1.0 Hz, 1H, CH), 2.25(s, 3H, CH3) | 164.7, 133.2, 132.2, 131.9, 130.2, 129.9, 129.9, 128.5, 123.7, 96.03, 60.13, 29.44 |
24b | 8.21(d, J=7.0 Hz, 3H, ArH, NH), 7.49(d, J=8.7 Hz, 2H, ArH), 6.39(d, J=16.3 Hz, 1H, CH), 6.2(dd, J=17.0, 10.3 Hz, 1H, CH), 5.92(d, J=9.3 Hz, 1H, CH), 5.82(d, J=10.4 Hz, 1H, CH), 2.30(s, 3H, CH3) | 171.6, 165.3, 148.2, 141.7, 130.0, 129.9, 129.5, 129.0, 123.7, 96.59, 59.95, 21.04 |
25b | 7.99(dd, J=20.3, 8.1 Hz, 1H, ArH), 7.72(d, J=53.7 Hz, 1H, ArH), 7.63—7.50(m, 2H, ArH), 7.01(dd, J=31.6, 8.0 Hz, 1H, CH), 6.79—6.66(m, 1H, CH), 6.34(dd, J=27.1, 16.6 Hz, 1H, CH), 5.75(dd, J=17.5, 9.7 Hz, 1H, CH), 2.27(d, J=6.2 Hz, 3H, CH3) | 164.7, 149.9, 133.9, 133.4, 130.2, 129.6, 128.0, 125.6, 125.4, 102.3, 54.90, 29.98 |
Table 3 1H NMR and 13C NMR data for compounds 1b—25b*
Compd. | 1H NMR(CDCl3), δ | 13C NMR(CDCl3), δ |
---|---|---|
1b | 7.46(dd, J=7.4, 2.1 Hz, 2H, ArH), 7.42—7.3(m, 3H, ArH), 6.71(d, J=9.9 Hz, 1H, NH), 6.45—6.40(m, 1H, CH), 6.40—6.33(m, 1H, CH), 6.20(dd, J=16.9, 10.2 Hz, 1H, CH), 5.77(dd, J=10.2, 1.2 Hz, 1H, CH) | 164.2, 133.2, 129.8, 129.6, 129.1, 129.0, 128.7, 93.06, 62.78 |
2b | 7.38(d, J=8.2 Hz, 2H, ArH), 7.18(d, J =8.0 Hz, 2H, ArH), 7.01(d, J=10.1 Hz, 1H, NH), 6.42(d, J=10.1 Hz, 1H, CH), 6.39(dd, J=17.0, 1.1 Hz, 1H, CH), 6.26(dd, J=17.0, 10.3 Hz, 1H, CH), 5.77(dd, J=10.3, 1.0 Hz, 1H, CH), 2.36(s, 3H, CH3) | 164.5, 139.9, 130.3, 129.7, 129.4, 129.0, 128.9, 93.56, 62.69, 21.20 |
3b | 7.32(d, J=8.8 Hz, 2H, ArH), 7.15(d, J=10.1 Hz, 1H, NH), 6.78(d, J=8.8 Hz, 2H, ArH), 6.33(d, J=10.1 Hz, 1H, CH), 6.28(d, J=17.0 Hz, 1H, CH), 6.18(dd, J=17.0, 10.2 Hz, 1H, CH), 5.65(d, J=11.4 Hz, 1H, CH), 3.70(s, 3H, OCH3) | 164.6, 160.5, 130.5, 129.7, 128.9, 125.2, 114.0, 93.97, 62.51, 55.31 |
4b | 7.02(dd, J=8.4, 2.1 Hz, 1H, ArH), 6.93(d, J=2.1 Hz, 1H, ArH), 6.83(d, J=8.4 Hz, 1H, ArH), 6.70(d, J=9.6 Hz, 1H, NH), 6.38(d, J=17.0 Hz, 1H, CH), 6.34(d, J=10.0 Hz, 1H, CH), 6.21(dd, J=16.9, 10.3 Hz, 1H, CH), 5.78(d, J=10.4 Hz, 1H, CH), 3.87(s, 6H, 2OCH3) | 164.3, 150.2, 148.9, 129.6, 129.0, 125.4, 121.5, 112.5, 111.0, 93.46, 62.74, 56.11, 55.90 |
5b | 7.01(dd, J=8.4, 2.1 Hz, 1H, ArH), 6.93(d, J=2.1 Hz, 1H, ArH), 6.84(d, J=8.4 Hz, 1H, CH), 6.63(d, J=9.9 Hz, 1H, NH), 6.39(d, J=17.0 Hz, 1H, ArH), 6.33(d, J=10.0 Hz, 1H, CH), 6.21(dd, J=16.9, 10.3 Hz, 1H, CH), 5.78(d, J=10.3 Hz, 1H, CH), 3.88(s, 3H, OCH3), 3.87(s, 3H, OCH3) | 164.2, 150.2, 148.9, 129.6, 129.0, 125.4, 121.4, 112.5, 111.0, 93.41, 62.73, 56.12, 55.91 |
6b | 7.08(s, 1H, ArH), 7.01(s, 1H, ArH), 6.98(d, J=9.6 Hz, 1H, CH), 6.75(d, J=9.5 Hz, 1H, NH), 6.36(d, J=16.9 Hz, 1H, CH), 6.14(dd, J=16.9, 10.3 Hz, 1H, CH), 5.74(d, J=10.4 Hz, 1H, CH), 3.88(s, 3H, OCH3), 3.85(s, 3H, OCH3) | 164.0, 150.5, 148.7, 129.2, 125.6, 117.7, 116.0, 110.5, 92.43, 61.13, 56.31, 56.20 |
7b | 7.48(dd, J=8.7, 5.1 Hz, 2H, ArH), 7.06(t, J=8.6 Hz, 2H, ArH), 6.99(d, J=9.9 Hz, 1H, NH), 6.42(d, J=9.6 Hz, 1H, CH), 6.35(d, J=1.2 Hz, 1H, CH), 6.22(dd, J=16.9, 10.1 Hz, 1H, CH), 5.77(dd, J=10.1, 1.2 Hz, 1H, CH) | 165.0, 164.5, 161.7, 131.2, 131.0, 129.4, 129.3, 129.2, 129.1, 115.9, 115.7, 93.04, 62.23 |
8b | 7.42(d, J=8.6 Hz, 2H, ArH), 7.34(d, J=8.6 Hz, 2H, ArH), 6.94(d, J=9.9 Hz, 1H, NH), 6.42(s, 1H, CH), 6.40—6.33(m, 1H, CH), 6.21(dd, J=16.9, 10.1 Hz, 1H, CH), 5.78(dd, J=10.1, 1.2 Hz, 1H, CH) | 164.4, 136.0, 131.8, 130.5, 129.4, 129.3, 129.0, 92.64, 62.28 |
9b | 7.50(d, J=8.6 Hz, 2H, ArH), 7.35(d, J=8.5 Hz, 2H, ArH), 6.93(d, J=9.9 Hz, 1H, NH), 6.40(s, 1H, CH), 6.38—6.32(m, 1H, CH), 6.20(dd, J=16.9, 10.1 Hz, 1H, CH), 5.77(dd, J=10.1, 1.2 Hz, 1H, CH) | 164.4, 132.3, 131.9, 130.8, 129.4, 129.3, 124.3, 92.49, 62.36 |
10b | 7.62(d, J=2.1 Hz, 1H, ArH), 7.47(d, J=8.4 Hz, 1H, ArH), 7.35(dd, J=8.4, 2.2 Hz, 1H, ArH), 6.95(d, J=9.8 Hz, 1H, NH), 6.41(d, J=8.8 Hz, 1H, CH), 6.39(s, 1H, CH), 6.24(dd, J=16.9, 10.3 Hz, 1H, CH), 5.82(d, J=10.4 Hz, 1H, CH) | 164.4, 134.4, 133.5, 133.0, 131.0, 130.6, 129.7, 129.2, 128.6, 91.92, 61.92 |
11b | 8.24(d, J=8.8 Hz, 2H, ArH), 7.72(d, J=8.8 Hz, 2H, ArH), 6.88(d, J=9.7 Hz, 1H, NH), 6.52(d, J=9.8 Hz, 1H, CH), 6.40(dd, J=16.9, 1.2 Hz, 1H, CH), 6.22(dd, J=16.9, 10.2 Hz, 1H, CH), 5.82(dd, J=10.2, 1.1 Hz, 1H, CH) | 164.4, 148.5, 140.3, 130.4, 129.9, 129.0, 123.7, 91.25, 62.25 |
12b | 7.43—7.35(m, 2H, ArH), 7.32—7.29(m, 2H, ArH), 6.73(d, J=10.0 Hz, 1H, NH), 6.34(d, J=10.1 Hz, 1H, CH), 6.30(dd, J=16.9, 0.9 Hz, 1H, CH), 6.14(dd, J=17.0, 10.3 Hz, 1H, CH), 5.69(d, J=10.4 Hz, 1H, CH) | 164.3, 133.3, 129.8, 129.6, 129.1, 129.0, 128.7, 93.12, 62.82 |
13b | 7.97(s, 1H, ArH), 7.86(t, J=7.9 Hz, 3H, ArH), 7.62—7.52(m, 3H, ArH), 6.89(d, J=9.8 Hz, 1H, NH), 6.61(d, J=10.0 Hz, 1H, CH), 6.41(d, J=16.9 Hz, 1H, CH), 6.26(dd, J=16.9, 10.3 Hz, 1H, CH), 5.80(d, J=10.3 Hz, 1H, CH) | 164.3, 133.6, 132.7, 130.5, 129.6, 129.5, 129.1, 128.6, 128.4, 127.7, 127.3, 126.8, 125.4, 93.04, 63.01 |
14b | 7.34(dd, J=5.0, 1.8 Hz, 3H, ArH), 7.29—7.25(m, 2H, ArH), 6.37(dd, J=17.0, 0.9 Hz, 1H, CH), 6.24(dd, J=17.0, 10.3 Hz, 1H, CH), 5.83(d, J=9.7 Hz, 1H, CH), 5.76(dd, J=10.3, 0.9 Hz, 1H), 2.25(s, 3H, CH3) | 164.6, 134.1, 130.2, 129.4, 129.0, 128.2, 96.19, 60.63, 29.55 |
15b | 7.14(s, 4H, ArH), 6.36(dd, J=17.0, 1.5 Hz, 1H, CH), 6.23(dd, J=17.0, 10.0 Hz, 1H, CH), 5.80(d, J=9.7 Hz, 1H, CH), 5.74(dd, J=10.0, 1.5 Hz, 1H, CH), 2.33(d, J=8.9 Hz, 3H, CH3), 2.22(d, J=14.5 Hz, 3H, CH3) | 164.7, 139.3, 131.1, 130.2, 129.6, 129.3, 128.5, 128.1, 96.61, 60.37, 29.34, 21.09 |
16b | 7.19(d, J=8.7 Hz, 2H, ArH), 6.84(d, J=8.8 Hz, 2H, ArH), 6.36(dd, J=17.0, 1.2 Hz, 1H, CH), 6.23(dd, J=17.0, 10.3 Hz, 1H, CH), 5.80(d, J=9.7 Hz, 1H, CH), 5.74(dd, J=10.3, 1.2 Hz, 1H, CH), 3.78(s, 3H, CH3), 2.24(s, 3H, CH3) | 164.6, 160.2, 130.2, 129.8, 129.4, 128.1, 126.0, 114.4, 114.1, 96.7, 60.11, 55.29, 29.4 |
17b | 7.74(d, J=9.4 Hz, 1H, NH), 6.88(d, J=8.0 Hz, 1H, ArH), 6.83(s, 1H, ArH), 6.76(d, J=8.2 Hz, 1H, ArH), 6.31(d, J=17.1 Hz, 1H, CH), 6.25(t, J=13.4 Hz, 1H, CH), 5.89(d, J=9.5 Hz, 1H, CH), 5.66(d, J=8.7 Hz, 1H, CH), 3.80(s, 3H, OCH3), 3.77(s, 3H, OCH3), 2.25(s, 3H, CH3) | 165.0, 149.7, 149.0, 130.1, 128.2, 126.5, 121.0, 111.8, 111.2, 96.9, 60.40, 55.98, 55.81, 28.87 |
18b | 7.51(d, J=8.7 Hz, 1H, ArH), 6.72(dd, J=7.5, 5.8 Hz, 1H, ArH), 6.51(dd, J=5.8, 3.0 Hz, 1H, ArH), 6.45(d, J=2.6 Hz, 1H, CH), 6.38(dt, J=17.1, 3.7 Hz, 1H, CH), 6.26(t, J=6.5 Hz, 1H, CH), 5.75(dd, J=10.1, 1.4 Hz, 1H, CH), 3.86(s, 3H, OCH3), 3.74(s, 3H, OCH3), 2.27(s, 3H, CH3) | 164.5, 160.4, 157.2, 136.1, 129.9, 128.3, 105.8, 103.8, 100.2, 93.82, 59.33, 56.43, 55.58, 28.24 |
19b | 6.46(s, 2H, ArH), 6.39(dd, J=17.0, 1.1 Hz, 1H, CH), 6.26(dd, J=17.0, 10.3 Hz, 1H, CH), 5.78(dd, J=10.3, 1.1 Hz, 1H, CH), 5.72(d, J=9.6 Hz, 1H, CH), 3.82(s, 9H, 3OCH3), 2.25(s, 3H, CH3) | 164.6, 153.5, 138.9, 130.1, 129.4, 128.3, 105.4, 95.68, 60.93, 60.82, 56.28, 29.71 |
20b | 7.04(t, J=17.9 Hz, 2H, ArH), 6.56(s, 1H, CH), 6.43—6.38(m, 1H, CH), 6.29—6.26(m, 1H, CH), 5.77(d, J=10.3 Hz, 1H, CH), 3.86(s, 3H, OCH3), 3.78(s, 3H, OCH3), 2.27(s, 3H, CH3) | 164.5, 150.1, 149.3, 129.9, 128.4, 125.8, 116.2, 116.0, 115.7, 109.6, 94.06, 60.40, 59.44, 21.04 |
21b | 7.27(dd, J=6.0, 2.7 Hz, 2H, ArH), 7.02(t, J=8.6 Hz, 2H, ArH), 6.37(dd, J=17.0, 1.1 Hz, 1H, CH), 6.23(dd, J=17.0, 10.3 Hz, 1H, CH), 5.85(d, J=9.6 Hz, 1H, CH), 5.76(dd, J=10.3, 1.1 Hz, 1H, CH), 2.25(s, 3H, CH3) | 164.7, 163.9, 130.5, 130.1, 130.1, 129.9, 128.5, 116.1, 116.0, 96.41, 59.98, 29.41 |
22b | 7.31(d, J=8.5 Hz, 2H, ArH), 7.22(d, J=8.5 Hz, 2H, ArH), 6.37(dd, J=17.0, 1.1 Hz, 1H, CH), 6.23(dd, J=17.0, 10.3 Hz, 1H, CH), 5.83(d, J=9.6 Hz, 1H, CH), 5.76(dd, J=10.3, 1.1 Hz, 1H, CH), 2.25(s, 3H, CH3) | 164.7, 135.5, 132.7, 130.0, 129.9, 129.6, 129.2, 128.9, 128.5, 96.17, 60.06, 29.39 |
23b | 7.47(d, J=8.5 Hz, 2H, ArH), 7.16(d, J=8.5 Hz, 2H, ArH), 6.37(dd, J=17.0, 1.0 Hz, 1H, CH), 6.23(dd, J=17.0, 10.3 Hz, 1H, CH), 5.81(d, J=9.6 Hz, 1H, CH), 5.77(dd, J=10.3, 1.0 Hz, 1H, CH), 2.25(s, 3H, CH3) | 164.7, 133.2, 132.2, 131.9, 130.2, 129.9, 129.9, 128.5, 123.7, 96.03, 60.13, 29.44 |
24b | 8.21(d, J=7.0 Hz, 3H, ArH, NH), 7.49(d, J=8.7 Hz, 2H, ArH), 6.39(d, J=16.3 Hz, 1H, CH), 6.2(dd, J=17.0, 10.3 Hz, 1H, CH), 5.92(d, J=9.3 Hz, 1H, CH), 5.82(d, J=10.4 Hz, 1H, CH), 2.30(s, 3H, CH3) | 171.6, 165.3, 148.2, 141.7, 130.0, 129.9, 129.5, 129.0, 123.7, 96.59, 59.95, 21.04 |
25b | 7.99(dd, J=20.3, 8.1 Hz, 1H, ArH), 7.72(d, J=53.7 Hz, 1H, ArH), 7.63—7.50(m, 2H, ArH), 7.01(dd, J=31.6, 8.0 Hz, 1H, CH), 6.79—6.66(m, 1H, CH), 6.34(dd, J=27.1, 16.6 Hz, 1H, CH), 5.75(dd, J=17.5, 9.7 Hz, 1H, CH), 2.27(d, J=6.2 Hz, 3H, CH3) | 164.7, 149.9, 133.9, 133.4, 130.2, 129.6, 128.0, 125.6, 125.4, 102.3, 54.90, 29.98 |
Entry | Substrate | T/℃ | Promoter | Molar fraction of promoter(%) | Solvent | t/h | Product | Yieldb(%) |
---|---|---|---|---|---|---|---|---|
1 | 1a | 25 | K3PO4 | 110 | CH2Cl2 | 24 | 1b | 47 |
2 | 1a | 25 | K2CO3 | 110 | CH2Cl2 | 24 | 1b | 58 |
3 | 1a | 25 | Na2CO3 | 110 | CH2Cl2 | 24 | 1b | 58 |
4 | 1a | 25 | NaOH | 110 | CH2Cl2 | 24 | 1b | 34 |
5 | 1a | 25 | KOH | 110 | CH2Cl2 | 24 | 1b | 51 |
6 | 1a | 25 | CH3COONa | 110 | CH2Cl2 | 24 | 1b | 25 |
7 | 1a | 25 | CH3ONa | 110 | CH2Cl2 | 24 | 1b | 60 |
8 | 1a | 25 | Ethylenediamine | 110 | CH2Cl2 | 24 | 1b | Trace |
9 | 1a | 25 | Triethylamine | 110 | CH2Cl2 | 24 | 1b | Trace |
10 | 1a | 25 | CH3CH2ONa | 110 | CH2Cl2 | 24 | 1b | 83 |
11 | 1a | 25 | CH3CH2ONa | 200 | CH2Cl2 | 24 | 1b | 46 |
12 | 1a | 25 | CH3CH2ONa | 150 | CH2Cl2 | 24 | 1b | 53 |
13 | 1a | 25 | CH3CH2ONa | 100 | CH2Cl2 | 24 | 1b | 52 |
14 | 1a | 25 | CH3CH2ONa | 50 | CH2Cl2 | 24 | 1b | 47 |
15 | 1a | 25 | CH3CH2ONa | 0 | CH2Cl2 | 24 | 1b | Trace |
16 | 1a | 25 | CH3CH2ONa | 110 | CH3CN | 24 | 1b | 35 |
17 | 1a | 25 | CH3CH2ONa | 110 | CH3OH | 24 | 1b | 26 |
18 | 1a | 25 | CH3CH2ONa | 110 | DMF | 24 | 1b | 10 |
19 | 1a | 25 | CH3CH2ONa | 110 | CHCl3 | 24 | 1b | 37 |
20 | 1a | 25 | CH3CH2ONa | 110 | C6H5CH3 | 24 | 1b | 30 |
21 | 1a | 25 | CH3CH2ONa | 110 | CH3COCH3 | 24 | 1b | 20 |
22 | 1a | 25 | CH3CH2ONa | 110 | THF | 24 | 1b | NRc |
23 | 1a | Reflux | CH3CH2ONa | 110 | CH2Cl2 | 24 | 1b | 80 |
24 | 14a | 25 | K3PO4 | 110 | CH2Cl2 | 24 | 14b | 12 |
25 | 14a | 25 | K2CO3 | 110 | CH2Cl2 | 24 | 14b | 7 |
26 | 14a | 25 | Na2CO3 | 110 | CH2Cl2 | 24 | 14b | 24 |
27 | 14a | 25 | NaOH | 110 | CH2Cl2 | 24 | 14b | 10 |
28 | 14a | 25 | KOH | 110 | CH2Cl2 | 24 | 14b | Trace |
29 | 14a | 25 | CH3COONa | 110 | CH2Cl2 | 24 | 14b | NRc |
30 | 14a | 25 | CH3ONa | 110 | CH2Cl2 | 24 | 14b | Trace |
31 | 14a | 25 | CH3CH2ONa | 110 | CH2Cl2 | 24 | 14b | Trace |
32 | 14a | 25 | Ethylenediamine | 110 | CH2Cl2 | 24 | 14b | NRc |
33 | 14a | 25 | Triethylamine | 110 | CH2Cl2 | 24 | 14b | NRc |
34 | 14a | 25 | Na2CO3 | 110 | CH3CN | 24 | 14b | 14 |
35 | 14a | 25 | Na2CO3 | 110 | DMF | 24 | 14b | Trace |
36 | 14a | 25 | Na2CO3 | 110 | CHCl3 | 24 | 14b | 23 |
37 | 14a | 25 | Na2CO3 | 110 | C6H5CH3 | 24 | 14b | Trace |
38 | 14a | 25 | Na2CO3 | 110 | CH3COCH3 | 24 | 14b | 15 |
39 | 14a | 25 | Na2CO3 | 110 | THF | 24 | 14b | NRc |
40 | 14a | 25 | Na2CO3 | 110 | CH3OH | 24 | 14b | 93 |
41 | 14a | 25 | Na2CO3 | 150 | CH3OH | 24 | 14b | 45 |
42 | 14a | 25 | Na2CO3 | 100 | CH3OH | 24 | 14b | 38 |
43 | 14a | 25 | Na2CO3 | 50 | CH3OH | 24 | 14b | 58 |
44 | 14a | 25 | Na2CO3 | 0 | CH3OH | 24 | 14b | Trace |
45 | 14a | Reflux | Na2CO3 | 110 | CH3OH | 2 | 14b | 27 |
Table 4 Effects of catalyst and temperature as well as solvent to the aninobronation of β-nitrostyrenea
Entry | Substrate | T/℃ | Promoter | Molar fraction of promoter(%) | Solvent | t/h | Product | Yieldb(%) |
---|---|---|---|---|---|---|---|---|
1 | 1a | 25 | K3PO4 | 110 | CH2Cl2 | 24 | 1b | 47 |
2 | 1a | 25 | K2CO3 | 110 | CH2Cl2 | 24 | 1b | 58 |
3 | 1a | 25 | Na2CO3 | 110 | CH2Cl2 | 24 | 1b | 58 |
4 | 1a | 25 | NaOH | 110 | CH2Cl2 | 24 | 1b | 34 |
5 | 1a | 25 | KOH | 110 | CH2Cl2 | 24 | 1b | 51 |
6 | 1a | 25 | CH3COONa | 110 | CH2Cl2 | 24 | 1b | 25 |
7 | 1a | 25 | CH3ONa | 110 | CH2Cl2 | 24 | 1b | 60 |
8 | 1a | 25 | Ethylenediamine | 110 | CH2Cl2 | 24 | 1b | Trace |
9 | 1a | 25 | Triethylamine | 110 | CH2Cl2 | 24 | 1b | Trace |
10 | 1a | 25 | CH3CH2ONa | 110 | CH2Cl2 | 24 | 1b | 83 |
11 | 1a | 25 | CH3CH2ONa | 200 | CH2Cl2 | 24 | 1b | 46 |
12 | 1a | 25 | CH3CH2ONa | 150 | CH2Cl2 | 24 | 1b | 53 |
13 | 1a | 25 | CH3CH2ONa | 100 | CH2Cl2 | 24 | 1b | 52 |
14 | 1a | 25 | CH3CH2ONa | 50 | CH2Cl2 | 24 | 1b | 47 |
15 | 1a | 25 | CH3CH2ONa | 0 | CH2Cl2 | 24 | 1b | Trace |
16 | 1a | 25 | CH3CH2ONa | 110 | CH3CN | 24 | 1b | 35 |
17 | 1a | 25 | CH3CH2ONa | 110 | CH3OH | 24 | 1b | 26 |
18 | 1a | 25 | CH3CH2ONa | 110 | DMF | 24 | 1b | 10 |
19 | 1a | 25 | CH3CH2ONa | 110 | CHCl3 | 24 | 1b | 37 |
20 | 1a | 25 | CH3CH2ONa | 110 | C6H5CH3 | 24 | 1b | 30 |
21 | 1a | 25 | CH3CH2ONa | 110 | CH3COCH3 | 24 | 1b | 20 |
22 | 1a | 25 | CH3CH2ONa | 110 | THF | 24 | 1b | NRc |
23 | 1a | Reflux | CH3CH2ONa | 110 | CH2Cl2 | 24 | 1b | 80 |
24 | 14a | 25 | K3PO4 | 110 | CH2Cl2 | 24 | 14b | 12 |
25 | 14a | 25 | K2CO3 | 110 | CH2Cl2 | 24 | 14b | 7 |
26 | 14a | 25 | Na2CO3 | 110 | CH2Cl2 | 24 | 14b | 24 |
27 | 14a | 25 | NaOH | 110 | CH2Cl2 | 24 | 14b | 10 |
28 | 14a | 25 | KOH | 110 | CH2Cl2 | 24 | 14b | Trace |
29 | 14a | 25 | CH3COONa | 110 | CH2Cl2 | 24 | 14b | NRc |
30 | 14a | 25 | CH3ONa | 110 | CH2Cl2 | 24 | 14b | Trace |
31 | 14a | 25 | CH3CH2ONa | 110 | CH2Cl2 | 24 | 14b | Trace |
32 | 14a | 25 | Ethylenediamine | 110 | CH2Cl2 | 24 | 14b | NRc |
33 | 14a | 25 | Triethylamine | 110 | CH2Cl2 | 24 | 14b | NRc |
34 | 14a | 25 | Na2CO3 | 110 | CH3CN | 24 | 14b | 14 |
35 | 14a | 25 | Na2CO3 | 110 | DMF | 24 | 14b | Trace |
36 | 14a | 25 | Na2CO3 | 110 | CHCl3 | 24 | 14b | 23 |
37 | 14a | 25 | Na2CO3 | 110 | C6H5CH3 | 24 | 14b | Trace |
38 | 14a | 25 | Na2CO3 | 110 | CH3COCH3 | 24 | 14b | 15 |
39 | 14a | 25 | Na2CO3 | 110 | THF | 24 | 14b | NRc |
40 | 14a | 25 | Na2CO3 | 110 | CH3OH | 24 | 14b | 93 |
41 | 14a | 25 | Na2CO3 | 150 | CH3OH | 24 | 14b | 45 |
42 | 14a | 25 | Na2CO3 | 100 | CH3OH | 24 | 14b | 38 |
43 | 14a | 25 | Na2CO3 | 50 | CH3OH | 24 | 14b | 58 |
44 | 14a | 25 | Na2CO3 | 0 | CH3OH | 24 | 14b | Trace |
45 | 14a | Reflux | Na2CO3 | 110 | CH3OH | 2 | 14b | 27 |
Entry | Substrate | Product | Yield b(%) | Entry | Substrate | Product | Yield b(%) |
---|---|---|---|---|---|---|---|
1 | 1a | 1b | 83 | 14 | 14a | 14b | 93 |
2 | 2a | 2b | 43 | 15 | 15a | 15b | 44 |
3 | 3a | 3b | 40 | 16 | 16a | 16b | 51 |
4 | 4a | 4b | 43 | 17 | 17a | 17b | 44 |
5 | 5a | 5b | 52 | 18 | 18a | 18b | 19 |
6 | 6a | 6b | 50 | 19 | 19a | 19b | 16 |
7 | 7a | 7b | 57 | 20 | 20a | 20b | 45 |
8 | 8a | 8b | 56 | 21 | 21a | 21b | 52 |
9 | 9a | 9b | 56 | 22 | 22a | 22b | 54 |
10 | 10a | 10b | 57 | 23 | 23a | 23b | 55 |
11 | 11a | 11b | 81 | 24 | 24a | 24b | 97 |
12 | 12a | 12b | 73 | 25 | 25a | 25b | 60 |
13 | 13a | 13b | 58 |
Table 5 Aminobromination of β-nitrostyren derivatives with acrylamide and NBS promoted by basea
Entry | Substrate | Product | Yield b(%) | Entry | Substrate | Product | Yield b(%) |
---|---|---|---|---|---|---|---|
1 | 1a | 1b | 83 | 14 | 14a | 14b | 93 |
2 | 2a | 2b | 43 | 15 | 15a | 15b | 44 |
3 | 3a | 3b | 40 | 16 | 16a | 16b | 51 |
4 | 4a | 4b | 43 | 17 | 17a | 17b | 44 |
5 | 5a | 5b | 52 | 18 | 18a | 18b | 19 |
6 | 6a | 6b | 50 | 19 | 19a | 19b | 16 |
7 | 7a | 7b | 57 | 20 | 20a | 20b | 45 |
8 | 8a | 8b | 56 | 21 | 21a | 21b | 52 |
9 | 9a | 9b | 56 | 22 | 22a | 22b | 54 |
10 | 10a | 10b | 57 | 23 | 23a | 23b | 55 |
11 | 11a | 11b | 81 | 24 | 24a | 24b | 97 |
12 | 12a | 12b | 73 | 25 | 25a | 25b | 60 |
13 | 13a | 13b | 58 |
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