CN100400508C - 一种合成E-β-苯硒基-γ-羰基-α,β不饱和酸酯的方法 - Google Patents
一种合成E-β-苯硒基-γ-羰基-α,β不饱和酸酯的方法 Download PDFInfo
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- 239000002253 acid Substances 0.000 title claims abstract description 36
- 150000002148 esters Chemical class 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 24
- 230000002194 synthesizing effect Effects 0.000 title abstract 2
- ISSRNKWZFQZREN-UHFFFAOYSA-N C1(=CC=CC=C1)[Se](=O)(=O)Cl Chemical compound C1(=CC=CC=C1)[Se](=O)(=O)Cl ISSRNKWZFQZREN-UHFFFAOYSA-N 0.000 claims abstract description 19
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 24
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000004440 column chromatography Methods 0.000 claims description 3
- 125000004799 bromophenyl group Chemical group 0.000 claims description 2
- 239000012141 concentrate Substances 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract 1
- 239000003153 chemical reaction reagent Substances 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- 239000000758 substrate Substances 0.000 description 11
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 7
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 125000004494 ethyl ester group Chemical group 0.000 description 4
- YYZUSRORWSJGET-UHFFFAOYSA-N ethyl octanoate Chemical compound CCCCCCCC(=O)OCC YYZUSRORWSJGET-UHFFFAOYSA-N 0.000 description 4
- -1 ester compound Chemical class 0.000 description 3
- CLLUFLLBRNCOLB-UHFFFAOYSA-N ethyl 2-phenylbutanoate Chemical class CCOC(=O)C(CC)C1=CC=CC=C1 CLLUFLLBRNCOLB-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- RDQLMGNSDJJFOC-UHFFFAOYSA-N C(CCC)(=O)OCC.C1=CC=CC2=CC=CC=C12 Chemical class C(CCC)(=O)OCC.C1=CC=CC2=CC=CC=C12 RDQLMGNSDJJFOC-UHFFFAOYSA-N 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- WJCXADMLESSGRI-UHFFFAOYSA-N phenyl selenohypochlorite Chemical compound Cl[Se]C1=CC=CC=C1 WJCXADMLESSGRI-UHFFFAOYSA-N 0.000 description 1
- 230000037081 physical activity Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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Abstract
本发明涉及一种合成E-β-苯硒基-γ-羰基-α,β不饱和酸酯的方法,在碳酸锂的作用下,苯硒氯与α-联烯酸酯发生反应,生成E-β-苯硒基-γ-羰基-α,β不饱和酸酯化合物,本方法操作简单,原料和试剂易得,反应具有高度的区域和立体选择性,产物易分离纯化,适用于合成各种取代的E-β-苯硒基-γ-羰基-α,β不饱和酸酯。
Description
技术领域
本发明涉及一种合成E-β-苯硒基-γ-羰基-α,β不饱和酸酯的方法,即通过PhSeCl和α-联烯酸酯反应,合成E-β-苯硒基-γ-羰基-α,β不饱和酸酯的方法。
背景技术
E-γ-羰基-α,β不饱和酸酯是有机合成中重要的中间体之一,具有多种重要的生理活性,在生物技术领域,医药及农药等方面有巨大的开发利用价值,但β-苯硒基取代的E-γ-羰基-α,β不饱和酸酯,即E-β-苯硒基-γ-羰基-α,β不饱和酸酯,还没有文献报道过它的合成方法,本发明合成了这类化合物。
发明内容
本发明的目的就是提供一种合成E-β-苯硒基-γ-羰基-α,β不饱和酸酯的方法,反应可引入不同的取代基。
本发明提供了合成E-β-苯硒基-γ-羰基-α,β不饱和酸酯的方法,总的发明构思是:在碳酸锂的作用下,乙腈为溶剂,苯硒氯与α-联烯酸酯发生反应,生成E-β-苯硒基-γ-羰基-α,β不饱和酸酯化合物。反应式如下:
R1,R2,R3=烷基,芳基等基团,其中烷基为CnH2n+1(n=1-9),芳基为苯基,萘基,对溴苯基,其步骤是:
(1)在室温下将苯硒氯加入到乙腈的有机溶剂中,搅拌下溶解,再加入碳酸锂,搅拌,再加入α-联烯酸酯,反应1~50小时;
(2)短柱过滤,浓缩,快速柱层析,获得E-β-苯硒基-γ-羰基-α,β不饱和酸酯。
本发明所述的反应溶剂为乙腈。
本发明所述的碳酸锂与α-联烯酸酯的摩尔比为0.1~10∶1。
本发明所述的苯硒氯与α-联烯酸酯的摩尔比为1~5∶1。
本发明的所述的α-联烯酸酯的乙腈溶液的浓度为0.01~1M。
本发明具有以下优点:1)反应时间短;2)反应的区域和立体选择性非常好;3)能同时引入多个取代基;4)产物易分离纯化。
本发明创新点在于发展了一种合成E-β-苯硒基-γ-羰基-α,β不饱和酸酯的方法。
本方法所得的相应的E-β-苯硒基-γ-羰基-α,β不饱和酸酯的产率为63-95%。
具体实施方式
以下实例有助于理解本发明,但不限于本发明的内容。
实施例1
室温下,在25mL单口瓶中加入苯硒氯(79.3mg,0.41mmol),加入5mL乙腈溶液,搅拌溶解,再加入碳酸锂(45.0mg,0.61mmol),滴加含2-甲基-2,3-双烯辛酸乙酯(35.6mg,0.20mmol)的1mL乙腈溶液,短柱过滤掉碳酸锂,浓缩溶液,快速柱层析,得产物E-α-甲基-β-苯硒基-γ-羰基-α,β不饱和辛酸乙酯53.1mg,产率为77%,产物为无色液体。
1H NMR(400MHz,CDCl3)δ7.53(d,J=8.0Hz,2H),7.39-7.27(m,3H),4.13(q,J=7.0Hz,2H),2.32(t,J=7.4Hz,2H),2.06(s,3H),1.22(t,J=7.0Hz,3H),1.22-1.13(m,2H),1.10-0.99(m,2H),0.73(t,J=7.4Hz,3H);
13C NMR(CDCl3,100MHz):δ201.9,164.7,150.1,136.6,129.33,129.30,125.3,124.2,61.3,42.0,24.6,21.9,17.2,13.9,13.8;
MS(m/z):354(M+(80Se),28.85),352(M+(78Se)orM+(77Se)+1,16.29),356(M+(82Se),5.72),350(M+(76Se),7.31),351(M+(77Se)orM+(76Se)+1,9.26),355(M+(80Se)+1,7.13),41(100);
IR(neat,cm-1):2958,2932,1704,1591,1477,1465,1439,1366,1270,1156,1133,1022.
HRMS calcd for C17H22O3 80SeNa+(M++Na):377.0638.Found:377.0622.
实施例2
按实施例1所述的方法,不同的是所用底物和试剂为:苯硒氯(77.4mg,0.40mmol),碳酸锂(44.3mg,0.60mmol),2-丙基-2,3-双烯辛酸乙酯(41.2mg,0.20mmol),得产物E-α-丙基-β-苯硒基-γ-羰基-α,β不饱和辛酸乙酯51.2mg,产率为68%。产物为无色液体。
1H NMR(400 MHz,CDCl3)δ7.51(d,J=8.0Hz,2H),7.37-7.26(m,3H),4.13(q,J=7.1Hz,2H),2.53(t,J=7.6Hz,2H),2.36(t,J=7.6Hz,2H),1.61-1.50(m,2H),1.22(t,J=7.1Hz,3H),1.23-1.15(m,2H),1.12-1.01(m,2H),0.99(t,J=7.4Hz,3H),0.74(t,J=7.0Hz,3H);
13C NMR(CDCl3,100MHz):δ201.7,165.1,148.8,136.2,130.8,129.3,129.1,125.7,61.2,41.9,34.2,24.8,21.9,21.5,13.9,13.8,13.7;
MS(m/z):382(M+(80Se),28.09),380(M+(78Se)or M+(77Se)+1,14.60),384(M+(82Se),5.61),378(M+(76Se),5.32),379(M+(77Se)or M+(76Se)+1,7.12),381(M+(78Se)+1,4.31),383(M+(80Se)+1,7.41),41(100);
IR(neat,cm-1):2962,2931,2871,1756,1708,1578,1477,1464,1439,1281,1223,1155,1021.
HRMS calcd for C19H26O3 80SeNa+(M++Na):405.0952.Found:405.0932.
实施例3
按实施例1所述的方法,不同的是所用底物和试剂为:苯硒氯(77.8mg,0.41mmol),碳酸锂(43.5mg,0.59mmol),2-苄基-2,3-双烯辛酸乙酯(51.1mg,0.20mmol),得产物E-α-苄基-β-苯硒基-γ-羰基-α,β不饱和辛酸乙酯57.3mg,产率为67%。产物为无色液体。
1H NMR(400MHz,CDCl3)δ7.49(d,J=7.6Hz,2H),7.35-7.15(m,8H),4.04(q,J=7.2Hz,2H),3.89(s,2H),2.35(d,J=7.6Hz,2H),1.23-1.13(m,2H),1.10(t,J=7.2Hz,3H),1.08-0.97(m,2H),0.70(t,J=7.4Hz,3H);
13C NMR(CDCl3,100 MHz):δ201.5,164.6,151.5,137.9,136.5,129.38,129.32,128.49,128.42,128.3,126.4,125.3,61.3,42.0,37.6,24.7,21.9,13.7;
MS(m/z):430(M+(80Se),17.49),428(M+(78Se)or M+(77Se)+1,13.93),432(M+(82Se),9.84),426(M+(76Se),4.21),427(M+(77Se)or M+(76Se)+1,11.68),431(M+(80Se)+1,33.09),429(M+(78Se)+1,22.64),433(M+(82Se)+1,7.06),57(100);
IR(neat,cm-1):2958,2932,2871,1706,1577,1494,1477,1453,1439,1270,1201,1021.
HRMS calcd for C23H26O3 80SeNa+(M++Na):453.0954.Found:453.0932.
实施例4
按实施例1所述的方法,不同的是所用底物和试剂为:苯硒氯(78.9mg,0.41mmol),碳酸锂(44.3mg,0.60mmol),2-甲基-2,3-双烯十一酸乙酯(45.4mg,0.20mmol),得产物E-α-甲基-β-苯硒基-γ-羰基-α,β不饱和十一酸乙酯53.5mg,产率为67%。产物为无色液体。
1H NMR(400MHz,CDCl3)δ7.53(d,J=7.2Hz,2H),7.38-7.27(m,3H),4.13(q,J=7.2Hz,2H),2.32(t,J=7.8Hz,2H),2.07(s,3H),1.23(t,J=7.2Hz,3H),1.26-1.06(m,8H),1.04-0.95(m,2H),0.85(t,J=7.2Hz,3H);
13C NMR(CDCl3,100 MHz):δ201.8,164.8,149.9,136.5,129.3,125.5,124.5,61.2,42.3,31.6,28.9,28.7,22.52,22.49,17.2,14.0,13.9;
MS(m/z):396(M+(80Se),17.30),394(M+(78Se)or M+(77Se)+1,9.93),398(M+(82Se),4.29),392(M+(76Se),3.85),393(M+(77Se)or M+(76Se)+1,4.37),397(M+(80Se)+1,7.05),395(M+(78Se)+1,4.71),193(100);
IR(neat,cm-1):2955,2928,2855,1706,1591,1578,1477,1465,1439,1270,1153,1022.
HRMS calcd for C20H28O3 80SeNa+(M++Na):419.1109.Found:419.1091.
实施例5
按实施例1所述的方法,不同的是所用底物和试剂为:苯硒氯(78.5mg,0.41mmol),碳酸锂(44.0mg,0.59mmol),2-丙基-2,3-双烯十一酸乙酯(49.8mg,0.20mmol),得产物E-α-丙基-β-苯硒基-γ-羰基-α,β不饱和十一酸乙酯52.3 mg,产率为63%。产物为无色液体。
1H NMR(400MHz,CDCl3)δ7.51(d,J=8.0Hz,2H),7.37-7.26(m,3H),4.13(q,J=7.1Hz,2H),2.53(t,J=7.8Hz,2H),2.36(t,J=7.6Hz,2H),1.61-1.51(m,2H),1.22(t,J=7.1 Hz,3H),1.27-1.07(m,8H),0.99(t,J=7.4Hz,3H),1.05-0.95(m,2H),0.85(t,J=7.0Hz,3H);
13C NMR(CDCl3,100MHz):δ201.8,165.1,148.7,136.2,131.0,129.3,129.1,125.8,61.2,42.2,34.3,31.6,28.9,28.8,22.7,22.5,21.5,14.04,13.98,13.9;
MS(m/z):427(M+(82Se)+1,3.80),426(M+(82Se),5.88),425(M+(80Se)+1,20.35),424(M+(80Se),11.43),423(M+(78Se)+1,14.02),422(M+(78Se)or M+(77Se)+1,8.87),421(M+(77Se)orM+(76Se)+1,6.89),420(M+(76Se),2.93),43(100);
IR(neat,cm-1):2958,2928,1757,1707,1578,1477,1463,1439,1277,1222,1153,1021.
HRMS calcd for C22H32O3 80SeNa+(M++Na):447.1423.Found:447.1406.
实施例6
按实施例1所述的方法,不同的是所用底物和试剂为:苯硒氯(77.1mg,0.40mmol),碳酸锂(42.7mg,0.58mmol),2-甲基-4-苯基-2,3-双烯丁酸乙酯(40.0mg,0.20mmol),得产物E-α-甲基-β-苯硒基-γ-羰基-α,β不饱和苯丁酸乙酯56.6 mg,产率为77%。产物为无色液体。
1H NMR(400MHz,CDCl3)δ7.60(d,J=7.6Hz,2H),7.42(t,J=7.2Hz,1H),7.33-7.24(m,4H),7.18(t,J=7.2Hz,1H),7.04(t,J=7.6Hz,2H),3.93(q,J=7.2Hz,2H),2.20(s,3H),0.90(t,J=7.2Hz,3H);
13C NMR(CDCl3,100MHz):δ192.0,164.2,148.8,137.5,135.9,132.8,129.2,128.7,128.6,128.1,124.6,124.3,61.2,16.9,13.4;
MS(m/z):374(M+(80Se),17.43),372(M+(78Se)or M+(77Se)+1,8.24),376(M+(82Se),3.55),370(M+(76Se),3.56),371(M+(77Se)or M+(76Se)+1,3.37),375(M+(80Se)+1,4.13),373(M+(78Se)+1,2.74),377(M+(82Se)+1,0.86),105(100);
IR(neat,cm-1):3059,2982,2935,1708,1668,1596,1580,1476,1449,1439,1366,1270,1176,1144,1021,999.
HRMS calcd for C19H18O3 80SeNa+(M++Na):397.0326.Found:397.0311.
实施例7
按实施例1所述的方法,不同的是所用底物和试剂为:苯硒氯(114.0mg,0.60mmol),碳酸锂(43.7mg,0.59mmol),2-丙基-4-苯基-2,3-双烯丁酸乙酯(46.8mg,0.20mmol),得产物E-α-丙基-β-苯硒基-γ-羰基-α,β不饱和苯丁酸乙酯67.0mg,产率为82%。产物为无色液体。
1H NMR(400MHz,CDCl3)δ7.61(d,J=9.6Hz,2H),7.43(t,J=9.6Hz,1H),7.28(t,J=10.8Hz,4H),7.19(t,J=10.0Hz,1H),7.05(t,J=10.0Hz,2H),3.93(t,J=9.8Hz,2H),2.66(t,J=10.2Hz,2H),1.79-1.64(m,2H),1.09(t,J=9.8Hz,3H),0.90(t,J=9.4Hz,3H);
13C NMR(100MHz,CDCl3)δ191.8,164.3,148.1,137.4,135.9,132.7,130.4,129.2,128.7,128.6,128.1,124.4,61.1,33.9,21.4,14.2,13.3;
MS(70eV,EI)m/z(%):404(M+(82Se),1.35),403(M+(80Se)+1,1.38),402(M+(80Se),5.88),401(M+(78Se)+1,1.03),400(M+(78Se)or M+(77Se)+1,3.15),399(M+(77Se)or M+(76Se)+1,1.26),398(M+(76Se),1.24),105(100);
IRv(cm-1):2961,2871,1707,1671,1596,1581,1449,1439,1280,1243,1220,1146,1021;
HRMS calcd for C21H22O3 80SeNa+(M++Na):425.0640.Found:425.0624.
实施例8
按实施例1所述的方法,不同的是所用底物和试剂为:苯硒氯(78.0mg,0.41mmol),碳酸锂(45.7mg,0.62mmol),2-苄基-4-苯基-2,3-双烯丁酸乙酯(54.2mg,0.19mmol),得产物E-α-苄基-β-苯硒基-γ-羰基-α,β不饱和苯丁酸乙酯67.3mg,产率为77%。产物为无色液体。
1H NMR(400MHz,CDCl3)δ7.62(d,J=6.8Hz,2H),7.44(t,J=6.6Hz,3H),7.38(t,J=7.6Hz,2H),7.33-7.25(m,5H),7.22(t,J=7.4Hz,1H),7.07(t,J=7.6Hz,2H),4.08(s,2H),3.93(q,J=7.2Hz,2H),0.88(t,J=7.2Hz,3H);
13C NMR(100MHz,CDCl3)δ191.5,164.1,150.3,138.1,137.4,136.0,132.7,129.3,128.9,128.8,128.7,128.62,128.56,128.1,126.5,124.4,61.3,37.5,13.3;
MS(70eV,EI)m/z(%):453(M+(82Se)+1,3.78),452(M+(82Se),7.36),451(M+(80Se)+1,16.83),450(M+(80Se),26.36),449(M+(78Se)+1,11.69),448(M+(78Se)or M+(77Se)+1,15.50),447(M+(77Se)or M+(76Se)+1,8.02),446(M+(76Se),5.74),105(100);
IRv(cm-1):3060,2981,1707,1670,1596,1450,1270,1022;
HRMS calcd for C25H22O3 80SeNa+(M++Na):473.0642.Found:473.0618.
实施例9
按实施例1所述的方法,不同的是所用底物和试剂为:苯硒氯(78.0mg,0.41mmol),碳酸锂(44.7mg,0.60mmol),2-甲基-4-对溴苯基-2,3-双烯丁酸乙酯(56.1mg,0.20mmol),得产物E-α-甲基-β-苯硒基-γ-羰基-α,β不饱和对溴苯丁酸乙酯56.5mg,产率为63%。产物为固体,熔点:70-71℃(hexane).
1H NMR(400MHz,CDCl3)δ7.38(d,J=8.4Hz,2H),7.35(d,J=8.4Hz,2H),7.20(d,J=8.0Hz,2H),7.15(t,J=7.6Hz,1H)7.00(t,J=7.6Hz,2H),3.89(q,J=7.1Hz,2H),2.12(s,3H),0.89(t,J=7.1Hz,,3H);
13C NMR(100 MHz,CDCl3)δ191.0,164.2,148.2,137.5,134.9,131.4,130.1,129.4,128.9,127.8,125.1,124.1,61.3,16.9,13.5;
MS(70eV,EI)m/z(%):456(M+(82Se,81Br),5.53),455(M+(80Se,81Br)+1 or M+(82Se,79Br)+1,6.65),454(M+(80Se,81Br)or M+(82Se,79Br),32.61),453(M+(80Se,79Br)+1 or M+(78Se,81Br)+1,8.45),452(M+(80Se,79Br)or M+(78Se,81Br)or M+(77Se,81Br)+1,41.11),451(M+(77Se,81Br)orM+(78Se,79Br)+1 or M+(76Se,81Br)+1,8.04),450(M+(78Se,79Br)or M+(76Se,81Br)or M+(77Se,79Br)+1,18.45),449(M+(77Se,79Br)or M+(76Se,79Br)+1 or M+(74Se,81Br)+1,5.37),448(M+(76Se,79Br)or M+(74Se,81Br),5.59),446(M+(74Se,79Br),0.52),183(100);
IRv(cm-1):2980,1704,1668,1586,1478,1439,1272,1247,1173,1145,1021,1010;
Anal.calcd for C19H17BrO3Se:C50.47,H3.79.Found:C50.48,H3.79.
实施例10
按实施例1所述的方法,不同的是所用底物和试剂为:苯硒氯(115.9mg,0.61mmol),碳酸锂(44.7mg,0.60mmol),2-丙基-4-对溴苯基-2,3-双烯丁酸乙酯(60.6mg,0.20mmol),得产物E-α-丙基-β-苯硒基-γ-羰基-α,β不饱和对溴苯丁酸乙酯80.3 mg,产率为85%。产物为液体。
1H NMR(400MHz,CDCl3)δ7.46(d,J=9.0Hz,2H),7.42(d,J=9.0Hz,2H),7.26(d,J=7.6Hz,2H),7.21(t,J=7.4Hz,1H),7.07(t,J=7.8Hz,2H),3.96(q,J=7.3Hz,2H),2.64(t,J=8.0Hz,2H),1.76-1.64(m,2H),1.08(t,J=7.3Hz,3H),0.95(t,J=7.2Hz,3H);
13C NMR(100MHz,CDCl3)δ190.9,164.3,147.5,137.4,134.9,131.5,130.8,130.1,129.4,128.9,127.7,124.3,61.2,33.9,21.4,14.2,13.5;
MS(70eV,EI)m/z(%):484(M+(82Se,81Br),4.93),483(M+(80Se,81Br)+1 or M+(82Se,79Br)+1,5.75),482(M+(80Se,81Br)or M+(82Se,79Br),26.48),481(M+(80Se,79Br)+1 or M+(78Se,81Br)+1,7.85),480(M+(80Se,79Br)or M+(78Se,81Br)or M+(77Se,81Br)+1,34.11),479(M+(77Se,81Br)orM+(78Se,79Br)+1 or M+(76Se,81Br)+1,7.14),478(M+(78Se,79Br)or M+(76Se,81Br)or M+(77Se,79Br)+1,16.18),477(M+(77Se,79Br)or M+(76Se,79Br)+1 or M+(74Se,81Br)+1,4.64),476(M+(76Se,79Br)or M+(74Se,81Br),4.54),474(M+(74Se,79Br),0.35),183(100);
IRv(cm-1):2960,2931,2871,1705,1673,1586,1281,1247,1219,1010;
HRMS calcd for C21H21 79BrO3 80SeNa+(M++Na):502.9738.Found:502.9724。
实施例11
按实施例1所述的方法,不同的是所用底物和试剂为:苯硒氯(114.3mg,0.60mmol),碳酸锂(41.3mg,0.56mmol),2-甲基-4-萘基-2,3-双烯丁酸乙酯(51.3mg,0.20mmol),得产物E-α-甲基-β-苯硒基-γ-羰基-α,β不饱和萘丁酸乙酯80.4mg,产率为93%。产物为液体。
1H NMR(400MHz,CDCl3)δ8.63(d,J=8.4Hz,1H),8.02(d,J=7.2Hz,1H),7.92(d,J=8.4Hz,1H),7.76(d,J=8.0Hz,1H),7.44-7.36(m,3H),7.26(d,J=7.6Hz,2H),6.97(t,J=7.4Hz,1H),6.87(t,J=7.8Hz,2H),3.91(q,J=7.1Hz,2H),2.27(s,3H),0.83(t,J=7.1Hz,3H);
13C NMR(75MHz,CDCl3)δ193.6,164.8,149.5,137.2,134.0,133.6,132.6,131.5,130.6,128.9,128.6,128.0,127.9,126.02,125.99,125.5,124.6,123.9,61.1,17.4,13.4;
MS(70eV,EI)m/z(%):427(M+(82Se)+1,5.15),426(M+(82Se),21.16),425(M+(80Se)+1,2.94),424(M+(80Se),10.79),423(M+(78Se)+1,4.33),421(M+(77Se)or M+(76Se)+1,3.62),155(100);
IR v(cm-1):3056,2982,1705,1662,1592,1508,1439,1271,1233,1146,1021;
HRMS calcd for C23H20O3 80SeNa+(M++Na):447.0484.Found:447.0462.
实施例12
按实施例1所述的方法,不同的是所用底物和试剂为:苯硒氯(115.2mg,0.60mmol),碳酸锂(44.6mg,0.60mmol),2-丙基-4-萘基-2,3-双烯丁酸乙酯(57.3mg,0.20mmol),得产物E-α-丙基-β-苯硒基-γ-羰基-α,β不饱和萘丁酸乙酯82.4mg,产率为89%。产物为液体。
1H NMR(400MHz,CDCl3)δ8.50(d,J=8.4Hz,1H),8.01(d,J=7.2Hz,1H),7.92(d,J=8.4Hz,1H),7.76(d,J=8.4Hz,1H),7.46-7.34(m,3H),7.24(d,J=7.6Hz,2H),7.00(t,J=7.2Hz,1H),6.89(t,J=7.6Hz,2H),3.91(q,J=7.2Hz,2H),2.73(t,J=7.8Hz,2H),1.81-1.69(m,2H),1.12(t,J=7.2Hz,3H),0.84(t,J=7.2Hz,3H);
13C NMR(100MHz,CDCl3)δ193.6.165.1,148.2,137.0,133.7,133.6,132.3,131.8,130.7,128.8,128.7,127.9,127.8,126.02,125.96,124.9,123.9,61.0,34.6,21.4,14.1,13.4;
MS(EI)m/z(%):455(M+(82Se)+1,1.81),454(M+(82Se),7.82),453(M+(80Se)+1,0.94),452(M+(80Se),3.72),451(M+(78Se)+1,1.50),450(M+(78Se)or M+(77Se)+1,1.74),155(100);
IR v(cm-1):2960,2871,1706,1664,1590,1575,1275,1234,1219,1146,1021;
HRMS calcd for C25H24O3 80SeNa+(M++Na):475.0798.Found:475.0776.
最后,还需要注意的是,以上列举的仅是本发明的具体实施例。显然,本发明不限于以上实施例,还可以有许多变形。
本发明可用其他的不违背本发明的精神和主要特征的具体形式来概述。因此,无论从哪一点来看,本发明的上述实施方案都只能认为是对本发明的说明而不能限制本发明,权利要求书指出了本发明的范围,而上述的说明并未指出本发明的范围,因此,在与本发明的权利要求书相当的含义和范围内的任何改变,都应认为是包括在权利要求书的范围内。
Claims (4)
1.一种合成E-β-苯硒基-γ-羰基-α,β不饱和酸酯的方法,在碳酸锂的作用下,苯硒氯与α-联烯酸酯发生反应,生成E-β-苯硒基-γ-羰基-α,β不饱和酸酯,反应式如下:
R1,R2,R3=烷基、芳基,其中烷基为CnH2n+1,式中n=1-9,芳基为苯基、萘基、对溴苯基,其步骤是:
(1)在室温下将苯硒氯加入到乙腈的有机溶剂中,搅拌下溶解,再加入碳酸锂,搅拌,再加入α-联烯酸酯,反应1~50小时;
(2)短柱过滤,浓缩,快速柱层析,获得E-β-苯硒基-γ-羰基-α,β不饱和酸酯。
2.根据权利要求1所述的合成E-β-苯硒基-γ-羰基-α,β不饱和酸酯的方法,其特征是所述的碳酸锂与α-联烯酸酯的摩尔比为0.1~10∶1。
3.根据权利要求1所述的合成E-β-苯硒基-γ-羰基-α,β不饱和酸酯的方法,其特征是所述的苯硒氯与α-联烯酸酯的摩尔比为1~5∶1。
4.根据权利要求1所述的合成E-β-苯硒基-γ-羰基-α,β不饱和酸酯的方法,其特征是α-联烯酸酯的乙腈溶液的浓度为0.01~1M。
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Effect of EtOH on the E-Iodohydroxylation of 1,2-AllenylicSulfoxides with I_2. 傅春玲,陈国飞,邓友前.Chinese Journal of Chemistry,No.9. 2004 |
Effect of EtOH on the E-Iodohydroxylation of 1,2-AllenylicSulfoxides with I_2. 傅春玲,陈国飞,邓友前.Chinese Journal of Chemistry,No.9. 2004 * |
有机硒化合物的反应选择性及其在有机合成中的应用. 孟双明,李晓陆,陶学郁.河北大学学报(自然科学版),第4期. 1994 |
有机硒化合物的反应选择性及其在有机合成中的应用. 孟双明,李晓陆,陶学郁.河北大学学报(自然科学版),第4期. 1994 * |
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联烯的自由基反应. 潘峰,傅春玲,麻生明.有机化学,第24卷第10期. 2004 * |
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