CN108774263A - 一种烯丙基氧化膦类化合物的合成方法 - Google Patents
一种烯丙基氧化膦类化合物的合成方法 Download PDFInfo
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- -1 phosphine compound Chemical class 0.000 title claims abstract description 43
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 title claims abstract description 37
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- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 23
- 238000010189 synthetic method Methods 0.000 title claims abstract description 15
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- 125000005907 alkyl ester group Chemical group 0.000 claims abstract description 8
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- 239000011737 fluorine Chemical group 0.000 claims description 4
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- LYGJENNIWJXYER-BJUDXGSMSA-N nitromethane Chemical group [11CH3][N+]([O-])=O LYGJENNIWJXYER-BJUDXGSMSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
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- 238000004679 31P NMR spectroscopy Methods 0.000 description 18
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- 239000003960 organic solvent Substances 0.000 description 17
- 235000010265 sodium sulphite Nutrition 0.000 description 17
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 14
- 239000007787 solid Substances 0.000 description 13
- AIMDYNJRXHEXEL-KPKJPENVSA-N [(e)-3-phenylprop-1-enyl]benzene Chemical group C=1C=CC=CC=1C\C=C\C1=CC=CC=C1 AIMDYNJRXHEXEL-KPKJPENVSA-N 0.000 description 9
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 description 8
- 239000000284 extract Substances 0.000 description 7
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 7
- ASUOLLHGALPRFK-UHFFFAOYSA-N phenylphosphonoylbenzene Chemical class C=1C=CC=CC=1P(=O)C1=CC=CC=C1 ASUOLLHGALPRFK-UHFFFAOYSA-N 0.000 description 7
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- 238000003810 ethyl acetate extraction Methods 0.000 description 5
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 5
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- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 4
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- MDDUHVRJJAFRAU-YZNNVMRBSA-N tert-butyl-[(1r,3s,5z)-3-[tert-butyl(dimethyl)silyl]oxy-5-(2-diphenylphosphorylethylidene)-4-methylidenecyclohexyl]oxy-dimethylsilane Chemical compound C1[C@@H](O[Si](C)(C)C(C)(C)C)C[C@H](O[Si](C)(C)C(C)(C)C)C(=C)\C1=C/CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MDDUHVRJJAFRAU-YZNNVMRBSA-N 0.000 description 4
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 description 3
- KKUKTXOBAWVSHC-UHFFFAOYSA-N Dimethylphosphate Chemical compound COP(O)(=O)OC KKUKTXOBAWVSHC-UHFFFAOYSA-N 0.000 description 3
- ZHIPXAFNKGZMSC-UHFFFAOYSA-N bis(4-methylphenyl)-oxophosphanium Chemical compound C1=CC(C)=CC=C1[P+](=O)C1=CC=C(C)C=C1 ZHIPXAFNKGZMSC-UHFFFAOYSA-N 0.000 description 3
- 239000012230 colorless oil Substances 0.000 description 3
- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 description 3
- WZPMZMCZAGFKOC-UHFFFAOYSA-N diisopropyl hydrogen phosphate Chemical compound CC(C)OP(O)(=O)OC(C)C WZPMZMCZAGFKOC-UHFFFAOYSA-N 0.000 description 3
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 description 3
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 3
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- 230000007704 transition Effects 0.000 description 2
- QVLHEZWJUVSJBV-UHFFFAOYSA-N 1,2-bis(prop-1-enyl)benzene Chemical class CC=CC1=CC=CC=C1C=CC QVLHEZWJUVSJBV-UHFFFAOYSA-N 0.000 description 1
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 1
- 238000004293 19F NMR spectroscopy Methods 0.000 description 1
- AIMDYNJRXHEXEL-UHFFFAOYSA-N 3-phenylprop-1-enylbenzene Chemical group C=1C=CC=CC=1CC=CC1=CC=CC=C1 AIMDYNJRXHEXEL-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 238000006579 Tsuji-Trost allylation reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
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- 238000011930 enantioselective total synthesis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
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- 229910052755 nonmetal Inorganic materials 0.000 description 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N para-benzoquinone Natural products O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical class CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical class COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical class C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
- C07F9/5333—Arylalkane phosphine oxides or thioxides
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种烯丙基氧化膦类化合物的合成方法，具体涉及在温和无过渡金属存在下合成烯丙基磷酰化合物的方法，所述合成方法包括如下步骤：将芳基氧化膦或者亚磷酸三烷酯和2,3‑二氯‑5,6‑二氰基‑1,4‑苯醌加入到溶剂中，在室温下搅拌，经萃取、干燥、过滤、硅胶柱层析分析提纯和减压蒸馏处理制得所需烯丙基氧化膦类化合物。该方法在温和条件下快速高效一步构建碳‑磷键，反应涉及二芳基氧化膦或者亚磷酸三烷酯对于二芳基丙烯的亲核加成，本发明所述方法简单高效，而且可适应底物范围广泛，为烯丙基芳基膦化合物的制备提供了新的方法。
Description
技术领域
本发明属于有机合成技术领域，更具体地，涉及一种烯丙基氧化膦类化合物的合成方法。
背景技术
烯丙基膦化合物作为一种重要的有机合成中间体，被广泛应用于全合成化学、生物化学、药物化学、农业化学、材料科学等领域(Chemistry and Application of H-Phosphonates,Elsevier Science,2006.；Synthesis of Carbon-Phosphorus Bonds,Second Edition,CRC press,2003.；P-Heterocycles as Ligands in HomogeneousCatalytic Reactions.Chem.Rev.,2010,110,4257.；Phosphorous:An Outline of ItsChemistry,Biochemistry and uses,1995,1038.；Enantioselective total synthesisof didesepoxyrhizoxion.Tetrahedron Lett.1995,36,4741.)。这使得对烯丙基的官能化反应成为有机合成化学中十分重要的一部分，该领域研究主要集中在烯丙基位引入高活性的辅助基团，这类反应称为Tsuji-Trost反应(Tetrahedron Letters.1965,6,4387，Angew.Chem.Int.Ed.2008,47,4878–4881)。虽然该方法可以高效的得到烯丙基官能化产物，但是较低的原子经济性和需要对于底物预活化在有机合成中存在着局限性。利用过渡金属催化的C-H键活化直接构建烯丙基氧化膦类化合物简洁、高效且符合原子经济性，但是因为过渡金属的存在，对于其应用于药物及材料领域又面临着一定的局限(Org.Biomol.Chem.2015,13,3561.)。基于以上相关文献的报道，所用的方法都需要过渡金属，底物需要预官能化，试剂对于环境比较敏感，所以开发高效，简便，绿色，经济的合成烯丙基膦化合物的方法具有重要意义。
发明内容
本发明的目的是为了克服现有技术的不足，提供一种合成烯丙基膦化合物的方法。该方法只需在非金属氧化剂的作用下，在室温下搅拌反应，使芳基氧化膦或者亚磷酸三烷酯化合物对于二芳基丙烯亲核加成，即可得烯丙基膦化合物。不需添加金属催化剂，不需要高温，具有高转化率，原子经济性，简便且环境友好型的特点。
10、本发明所采用的技术方案：一种烯丙基氧化膦类化合物的合成方法，所述合成方法包括如下步骤：将芳基氧化膦或者亚磷酸三烷酯和2,3-二氯-5,6-二氰基-1,4-苯醌加入到溶剂中，在室温下搅拌，经萃取、干燥、过滤、硅胶柱层析分析提纯和减压蒸馏处理制得所需烯丙基氧化膦类化合物；反应方程式如下：
优选地，所述烯丙基氧化膦类化合物是二芳基丙烯化合物。
优选地，所述二芳基丙烯化合物的结构通式(1)为
其中，Ar1为含有甲基、甲氧基、叔丁基、氟、氯、溴取代的苯环或苯基。
优选地，所述二芳基氧化膦化合物的结构通式为(2)
其中，Ar2为含有氢、甲基、甲氧基、氟、氯、溴取代基的苯环或苯基。
优选地，所述亚磷酸三烷酯的结构通式为(3)
R为甲基，乙基，异丙基，苯基。
优选地，所述溶剂为硝基甲烷。
优选地，所述二芳基丙烯、二芳基氧化膦或者亚磷酸三烷酯、2,3-二氯-5,6-二氰基-1,4-苯醌的反应摩尔比为1:2:1.5。
优选地，所述搅拌的时间为5～7h，所述萃取的溶剂为乙酸乙酯，所述干燥的试剂为无水硫酸钠，所述干燥的温度为20～25℃，所述干燥的时间为10～15min。
优选地，所述减压蒸馏的温度为35～45℃，所述减压蒸馏的压力为-0.085～-0.095MPa。
与现有技术相比，本发明的有益效果是：
1.本发明采用2,3-二氯-5,6-二氰基-1,4-苯醌为氧化剂，该氧化剂易于获取与保存，且效果明显。
2.本发明采用氧化剂使芳基氧化膦脱去质子或者亚磷酸三烷酯脱去烷氧基进而和二芳基丙烯形成的碳正离子亲核加成的方法合成烯丙基膦化合物，原料简单，反应可适底物范围广，合成简单，反应条件温和，产率高，副产物少，解决了现有技术中底物需要预官能团化，原子利用率低，使用过渡金属，反应底物对于水敏感，成本高，产物难以分离等问题，为烯丙基膦化合物的制备提供了简便、高效、经济的新方法。
附图说明
图1为施例1中最终产物的1H NMR图谱。
图2为实施例1中最终产物的13C NMR图谱。
图3为施例1中最终产物的31PNMR图谱。
具体实施方式
下面通过实施例对本发明进行具体描述，有必要在此指出的是本实施例只用于对本发明进行进一步说明，但不能理解为对本发明保护范围的限制，该领域的技术熟练人员可以根据上述本发明的内容做出一些非本质的改进和调整。
除非特别说明，本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。
实施例1合成(E)-(1,3-二苯基烯丙基)二苯基膦氧化物
称取0.2mmol 1,3-二苯丙烯，0.3mmol2,3-二氯-5,6-二氰基-1,4-苯醌加入15mL耐压反应管中，加入磁力搅拌子和2mL硝基甲烷，室温下搅拌反应5min，TLC监测，然后加入0.4mmol二苯基氧化膦反应6h如式(1)所示。反应结束后用20ml亚硫酸钠溶液，10mL乙酸乙酯萃取，用无水硫酸钠在25℃下干燥10分钟并过滤，最后用旋转蒸发仪在-0.09MPa，40℃下进行减压蒸馏除去有机溶剂，即可得到产物(E)-(1,3-二苯基烯丙基)二苯基氧化膦，产率为90％。(E)-(1,3-二苯基烯丙基)二苯基膦氧化物的核磁表征图谱如图1和图2所示。其中，图1为(E)-(1,3-二苯基烯丙基)二苯基膦氧化物的1H NMR图谱，图2为(E)-(1,3-二苯基烯丙基)二苯基膦氧化物的13C NMR图谱。(E)-(1,3-二苯基烯丙基)二苯基膦氧化物通过核磁表征与现有谱图特征结构得到确认。该化合物的表征数据如下：White solid:mp213.2-214.3℃；1H NMR(400MHz,CDCl3)δ7.88–7.83(m,2H),7.60–7.56(m,2H),7.53–7.45(m,3H),7.41–7.29(m,5H),7.24–7.16(m,8H),6.62–6.55(m,1H),6.33(dd,J＝15.7,2.9Hz,1H),4.37(t,J＝9.2Hz,1H).13C NMR(100MHz,CDCl3)δ136.9(d,J＝2.3Hz),136.0(d,J＝6.0Hz),134.5(d,J＝11.2Hz),131.9(d,J＝98.2Hz),131.8,131.7(d,J＝11.3Hz),131.6(d,J＝96.8Hz),131.6(d,J＝2.6Hz),131.5(d,J＝8.6Hz),129.6(d,J＝5.8Hz),128.7(d,J＝1.3Hz),128.6(d,J＝11.4Hz),128.5,128.3(d,J＝11.6Hz),127.7,127.3(d,J＝2.1Hz),126.5(d,J＝0.9Hz),124.7(d,J＝7.2Hz),52.5(d,J＝65.1Hz).31P NMR(162MHz,CDCl3)δ31.5.HRMS(ESI-TOF)m/z:calcd for C27H23NaOP[M+Na]+:417.1379；Found:417.1384.
实施例2合成((E)-(1,3-双(4-溴苯基)烯丙基)二苯基膦氧化物
称取0.2mmol(E)-(1,3-双(4-溴苯基)丙烯，0.3mmol2,3-二氯-5,6-二氰基-1,4-苯醌加入15mL耐压反应管中，加入磁力搅拌子和2mL硝基甲烷，室温下搅拌反应5min，TLC监测，然后加入0.4mmol二苯基氧化膦反应5h。反应结束后用20ml亚硫酸钠溶液，10mL乙酸乙酯萃取，用无水硫酸钠在25℃下干燥15分钟并过滤，最后用旋转蒸发仪在-0.09MPa，40℃下进行减压蒸馏除去有机溶剂，即可得到产物(E)-(1,3-邻二甲基苯基烯丙基)二苯基氧化膦，产率为100％。((E)-(1,3-双(4-溴苯基)烯丙基)二苯基膦氧化物通过核磁表征数据如下：White solid:mp209.7-210.5℃；1H NMR(400MHz,CDCl3)δ7.85–7.81(m,2H),7.61–7.56(m,2H),7.54–7.41(m,4H),7.35(d,J＝8.0Hz,6H),7.24(d,J＝7.5Hz,2H),7.05(d,J＝8.3Hz,2H),6.53–6.45(m,1H),6.21(dd,J＝15.8,3.3Hz,1H),4.31(t,J＝9.2Hz,1H).13CNMR(100MHz,CDCl3)δ135.5(d,J＝2.3Hz),134.9(d,J＝5.8Hz),133.6(d,J＝11.0Hz),132.1(d,J＝2.6Hz),131.9(d,J＝2.1Hz),131.8(d,J＝1.3Hz),131.7(d,J＝2.1Hz),131.6,131.5(d,J＝6.3Hz),131.4(d,J＝98.4Hz),131.3(d,J＝8.7Hz),131.3(d,J＝97.7Hz),131.2(d,J＝5.7Hz),128.7(d,J＝11.6Hz),128.5(d,J＝11.7Hz),125.0(d,J＝7.2Hz),121.7(d,J＝0.6Hz),121.5(d,J＝2.8Hz),51.8(d,J＝64.7Hz).31P NMR(162MHz,CDCl3)δ30.8.HRMS(ESI-TOF)m/z:calcd for C27H21Br2NaOP[M+Na]+:572.9589；Found:572.9585.
实施例3合成(E)-(1,3-二-对甲苯基丙-1-烯-1-基)二苯基膦氧化物
称取0.2mmol(E)-(1,3-二-对甲苯基丙烯，0.3mmol2,3-二氯-5,6-二氰基-1,4-苯醌加入15mL耐压反应管中，加入磁力搅拌子和2mL硝基甲烷，室温下搅拌反应5min，TLC监测，然后加入0.4mmol二苯基氧化膦反应7h。反应结束后用20ml亚硫酸钠溶液，10mL乙酸乙酯萃取，用无水硫酸钠在20℃下干燥15分钟并过滤，最后用旋转蒸发仪在-0.09MPa，45℃下进行减压蒸馏除去有机溶剂，即可得到产物(E)-(1,3-二-对甲苯基丙-1-烯-1-基)二苯基膦氧化物，产率为100％。(E)-(1,3-二-对甲苯基丙-1-烯-1-基)二苯基膦氧化物通过核磁表征数据如下：White solid:mp186.3-188.7℃；1H NMR(400MHz,CDCl3)δ7.85–7.81(m,2H),7.63–7.58(m,2H),7.50–7.38(m,4H),7.34–7.32(m,2H),7.22(d,J＝7.1Hz,2H),7.10(d,J＝8.0Hz,2H),7.03(d,J＝8.0Hz,4H),6.54–6.46(m,1H),6.26(dd,J＝15.8,3.5Hz,1H),4.34(t,J＝9.6Hz,1H),2.27(d,J＝7.8Hz,6H).13C NMR(100MHz,CDCl3)δ137.5,136.8(d,J＝2.4Hz),134.2(d,J＝11.5Hz),134.1(d,J＝2.4Hz),132.9(d,J＝5.9Hz),132.0(d,J＝96.6Hz),131.9(d,J＝8.5Hz),131.7(d,J＝97.4Hz),131.7(d,J＝20.1Hz),131.5(d,J＝8.8Hz),129.4(d,J＝5.6Hz),129.4,129.2,128.5(d,J＝11.4Hz),128.3(d,J＝11.5Hz),126.4(d,J＝0.8Hz),123.7(d,J＝7.0Hz),51.9(d,J＝65.3Hz),21.2(d,J＝9.9Hz).31P NMR(162MHz,CDCl3)δ31.6.HRMS(ESI-TOF)m/z:calcd for C29H27NaOP[M+Na]+:445.1692；Found:445.1694.
实施例4合成(E)-(1,3-二(萘-2-基)烯丙基)二苯基膦氧化物
称取0.2mmol(E)-1,3-二-萘丙烯0.3mmol，2,3-二氯-5,6-二氰基-1,4-苯醌加入15mL耐压反应管中，加入磁力搅拌子和2mL硝基甲烷，室温下搅拌反应5min，TLC监测，然后加入0.4mmol二苯基氧化膦反应6h。反应结束后用20ml亚硫酸钠溶液，10mL乙酸乙酯萃取，用无水硫酸钠在25℃下干燥10分钟并过滤，最后用旋转蒸发仪在-0.09MPa，40℃下进行减压蒸馏除去有机溶剂，即可得到产物(E)-(1,3-二(萘-2-基)烯丙基)二苯基膦氧化物，产率为79％。(E)-(1,3-二(萘-2-基)烯丙基)二苯基膦氧化物通过核磁表征数据如下：Whitesolid:mp235.1-236.1℃；1H NMR(400MHz,CDCl3)δ7.92–7.87(m,3H),7.78–7.72(m,6H),7.66–7.61(m,2H),7.55–7.35(m,10H),7.30–7.26(m,3H),6.83–6.75(m,1H),6.49(dd,J＝15.7,3.4Hz,1H),4.60(t,J＝9.4Hz,1H).13C NMR(150MHz,CDCl3)δ134.9(d,J＝11.3Hz),134.2(d,J＝2.5Hz),133.6,133.5(d,J＝4.6Hz),133.1,132.6(d,J＝1.1Hz),132.1(d,J＝2.5Hz),131.9(d,J＝8.5Hz),131.8(d,J＝2.2Hz),131.6(d,J＝97.4Hz),131.5(d,J＝8.8Hz),131.5(d,J＝97.5Hz),128.7(d,J＝11.6Hz),128.6(d,J＝6.7Hz),128.4,128.4(d,J＝11.6Hz),128.2,128.1(d,J＝4.9Hz),127.7(d,J＝5.8Hz),127.6(d,J＝5.2Hz),126.4(d,J＝1.5Hz),126.4,126.2,126.0(d,J＝3.9Hz),124.9(d,J＝7.2Hz),123.8,52.7(d,J＝65.0Hz).31PNMR(162MHz,CDCl3)δ31.9.HRMS(ESI-TOF)m/z:calcd for C35H27NaOP[M+Na]+:517.1692；Found:517.1683.
实施例5合成(E)-(1,3-双(3-甲氧基苯基)烯丙基)二苯基氧化膦
称取0.2mmol(E)-(1,3-双(3-甲氧基苯基)丙烯，0.3mmol2,3-二氯-5,6-二氰基-1,4-苯醌加入15mL耐压反应管中，加入磁力搅拌子和2mL硝基甲烷，室温下搅拌反应5min，TLC监测，然后加入0.4mmol二苯基氧化膦反应6h。反应结束后用20ml亚硫酸钠溶液，10mL乙酸乙酯萃取，用无水硫酸钠在25℃下干燥10分钟并过滤，最后用旋转蒸发仪在-0.08MPa，45℃下进行减压蒸馏除去有机溶剂，即可得到产物(E)-(1,3-双(3-甲氧基苯基)烯丙基)二苯基氧化膦，产率为81％。(E)-(1,3-双(3-甲氧基苯基)烯丙基)二苯基氧化膦通过核磁表征数据如下：White solid:mp133.5-134.8℃；1H NMR(400MHz,CDCl3)δ7.87–7.82(m,2H),7.63–7.58(m,2H),7.51–7.32(m,7H),7.16–7.11(m,2H),6.93(d,J＝10.1Hz,2H),6.81–6.72(m,2H),6.60–6.52(m,1H),6.29(dd,J＝15.7,3.2Hz,1H),4.34(t,J＝9.5Hz,1H),3.76(s,3H),3.76(s,3H).13C NMR(100MHz,CDCl3)δ159.8(d,J＝9.1Hz),138.3(d,J＝2.3Hz),137.4(d,J＝6.0Hz),131.9(d,J＝2.5Hz),131.9(d,J＝95.9Hz),131.8(d,J＝8.5Hz),131.7(d,J＝2.6Hz),131.6(d,J＝97.3Hz),131.5(d,J＝8.8Hz),129.6(d,J＝1.1Hz),129.5,128.6(d,J＝11.5Hz),128.3(d,J＝11.7Hz),124.8(d,J＝7.2Hz),122.0(d,J＝6.0Hz),119.3,114.8(d,J＝5.7Hz),113.6,113.3(d,J＝1.8Hz),111.6(d,J＝0.8Hz),55.3(d,J＝3.1Hz),52.5(d,J＝64.9Hz).31P NMR(162MHz,CDCl3)δ31.4.HRMS(ESI-TOF)m/z:calcd forC29H27O3PH[M+H]+:455.17706；Found:455.17639.
实施例6合成(E)-(1,3-双(4-氟苯基)烯丙基)二苯基氧化膦
称取0.2mmol(E)-(1,3-双(4-氟苯基)丙烯，0.3mmol2,3-二氯-5,6-二氰基-1,4-苯醌加入15mL耐压反应管中，加入磁力搅拌子和2mL硝基甲烷，室温下搅拌反应5min，TLC监测，然后加入0.4mmol二苯基氧化膦反应6h。反应结束后用20ml亚硫酸钠溶液，10mL乙酸乙酯萃取，用无水硫酸钠在25℃下干燥15分钟并过滤，最后用旋转蒸发仪在-0.09MPa，45℃下进行减压蒸馏除去有机溶剂，即可得到产物(E)-(1,3-双(4-氟苯基)烯丙基)二苯基氧化膦，产率为100％。(E)-(1,3-双(4-氟苯基)烯丙基)二苯基氧化膦通过核磁表征数据如下：White solid:mp165.5-166.7℃；1H NMR(600MHz,CDCl3)δ7.87–7.84(m,2H),7.59–7.56(m,2H),7.53–7.46(m,5H),7.41–7.39(m,1H),7.34–7.30(m,4H),7.16(dd,J＝8.6,5.4Hz,2H),6.93–6.89(m,4H),6.47–6.42(m,1H),6.26(dd,J＝15.8,3.4Hz,1H),4.35(t,J＝9.2Hz,1H).13C NMR(150MHz,CDCl3)δ162.5(d,JC-F＝247.2Hz),162.1(dd,JC-F＝246.2,JC-P＝2.0Hz),133.4(d,JC-P＝11.1Hz),132.8(d,JC-P＝5.0Hz),132.0(d,JC-P＝2.3Hz),131.8(d,JC-P＝2.4Hz),131.7(d,JC-P＝8.5Hz),131.4(d,JC-P＝99.2Hz),131.4(d,JC-P＝97.0Hz),131.3(d,JC-P＝8.6Hz),131.1(d,JC-P＝7.9Hz),131.0(d,JC-P＝7.9Hz),128.6(d,JC-P＝11.5Hz),128.4(d,JC-P＝11.5Hz),128.0(d,JC-P＝8.0Hz),124.2(d,JC-P＝5.5Hz),115.6(d,JC-P＝21.3Hz),115.5(d,JC-P＝21.6Hz),51.4(d,JC-P＝65.4Hz).31P NMR(243MHz,CDCl3)δ31.3.19F NMR(376MHz,CDCl3)δ-106.6(d,J＝93.4Hz).HRMS(ESI-TOF)m/z:calcd forC27H21F2NaOP[M+Na]+:453.1190；Found:453.1188.
实施例7合成(E)-(1,3-双(4-氯苯基)烯丙基)二苯基膦氧化物
称取0.2mmol(E)-(1,3-双(4-氯苯基)丙烯，0.3mmol2,3-二氯-5,6-二氰基-1,4-苯醌加入15mL耐压反应管中，加入磁力搅拌子和2mL硝基甲烷，室温下搅拌反应5min，TLC监测，然后加入0.4mmol二苯基氧化膦反应6h。反应结束后用20ml亚硫酸钠溶液，10mL乙酸乙酯萃取，用无水硫酸钠在25℃下干燥10分钟并过滤，最后用旋转蒸发仪在-0.09MPa，35℃下进行减压蒸馏除去有机溶剂，即可得到产物(E)-(1,3-双(4-氯苯基)烯丙基)二苯基膦氧化物，产率为100％。(E)-(1,3-双(4-氯苯基)烯丙基)二苯基膦氧化物通过核磁表征数据如下：White solid:mp191.9-192.8℃；1H NMR(600MHz,CDCl3)δ7.85–7.82(m,2H),7.60–7.57(m,2H),7.53–7.51(m,1H),7.49–7.46(m,2H),7.43–7.40(m,1H),7.33(td,J＝7.6,2.8Hz,2H),7.30(dd,J＝8.3,1.3Hz,2H),7.20(dd,J＝8.5,1.7Hz,4H),7.11(d,J＝8.5Hz,2H),6.51–6.46(m,1H),6.23(dd,J＝15.8,3.6Hz,1H),4.33(t,J＝9.2Hz,1H).13C NMR(150MHz,CDCl3)δ135.1(d,J＝2.2Hz),134.4(d,J＝5.9Hz),133.6(d,J＝2.4Hz),133.5,133.3(d,J＝2.5Hz),132.1(d,J＝2.5Hz),131.9(d,J＝2.4Hz),131.8(d,J＝11.5Hz),131.7(d,J＝8.5Hz),131.3(d,J＝8.7Hz),131.1(d,J＝22.8Hz),130.8(d,J＝5.8Hz),128.9(d,J＝0.9Hz),128.8,128.7(d,J＝11.5Hz),128.5(d,J＝11.6Hz),127.7,124.9(d,J＝7.1Hz),51.7(d,J＝64.7Hz).31P NMR(243MHz,CDCl3)δ31.1.HRMS(EI)calcd forC27H21Cl2NaOP[M+Na]+:485.0599；Found:485.0597.
实施例8合成(E)-双(3,5-二甲基苯基)(1,3-二苯基烯丙基)氧化膦
称取0.2mmol(E)-双(3,5-二甲基苯基)(1,3-二苯基)丙烯，0.3mmol2,3-二氯-5,6-二氰基-1,4-苯醌加入15mL耐压反应管中，加入磁力搅拌子和2mL硝基甲烷，室温下搅拌反应5min，TLC监测，然后加入0.4mmol双(3,5-二甲基苯基)氧化膦反应7h。反应结束后用20ml亚硫酸钠溶液，10mL乙酸乙酯萃取，用无水硫酸钠在25℃下干燥10分钟并过滤，最后用旋转蒸发仪在-0.09MPa，45℃下进行减压蒸馏除去有机溶剂，即可得到产物(E)-双(3,5-二甲基苯基)(1,3-二苯基烯丙基)氧化膦，产率为78％。(E)-双(3,5-二甲基苯基)(1,3-二苯基烯丙基)氧化膦通过核磁表征数据如下：White solid:mp211.2-212.6℃；1H NMR(400MHz,CDCl3)δ7.43(d,J＝11.1Hz,2H),7.36(d,J＝8.0Hz,2H),7.26–7.15(m,10H),7.12(s,1H),7.00(s,1H),6.61–6.53(m,1H),6.31(dd,J＝15.8,3.7Hz,1H),4.33(t,J＝9.5Hz,1H),2.32(s,6H),2.22(s,6H).13C NMR(100MHz,CDCl3)δ138.1(d,J＝12.1Hz),137.8(d,J＝12.2Hz),137.0(d,J＝2.4Hz),136.4(d,J＝5.9Hz),134.3(d,J＝11.2Hz),133.5(d,J＝2.8Hz),133.3(d,J＝2.9Hz),131.6(d,J＝96.1Hz),131.4(d,J＝96.2Hz),129.7(d,J＝5.7Hz),129.5(d,J＝8.4Hz),129.2(d,J＝8.7Hz),128.5(d,J＝1.6Hz),128.5(s),127.6(s),127.1(d,J＝2.2Hz),126.5(d,J＝1.1Hz),125.2(d,J＝7.2Hz),52.5(d,J＝64.4Hz),21.4(d,J＝11.7Hz).31P NMR(162MHz,CDCl3)δ31.9.HRMS(ESI-TOF)m/z:calcd forC31H31OPH[M+H]+:451.21853；Found:453.21805.
实施例9合成(E)-(1,3-二苯基烯丙基)二对甲苯基氧化膦
称取0.2mmol(E)-1,3-二苯基丙烯0.3mmol，2,3-二氯-5,6-二氰基-1,4-苯醌加入15mL耐压反应管中，加入磁力搅拌子和2mL硝基甲烷，室温下搅拌反应5min，TLC监测，然后加入0.4mmol对二甲苯基氧化膦反应6h。反应结束后用20ml亚硫酸钠溶液，10mL乙酸乙酯萃取，用无水硫酸钠在25℃下干燥10分钟并过滤，最后用旋转蒸发仪在-0.09MPa，45℃下进行减压蒸馏除去有机溶剂，即可得到产物(E)-(1,3-二苯基烯丙基)二对甲苯基氧化膦，产率为86％。(E)-(1,3-二苯基烯丙基)二对甲苯基氧化膦通过核磁表征数据如下：Whitesolid:mp216.6-217.2℃；1H NMR(400MHz,CDCl3)δ7.70(dd,J＝10.6,8.1Hz,2H),7.44(dd,J＝10.9,8.1Hz,2H),7.34(dd,J＝6.7,1.4Hz,2H),7.26–7.14(m,5H),7.09(dd,J＝8.0,2.5Hz,2H),6.62–6.54(m,1H),6.32(dd,J＝15.9,3.5Hz,1H),4.33(t,J＝9.6Hz,1H),2.37(s,3H),2.29(s,3H).13C NMR(100MHz,CDCl3)δ142.2(d,J＝2.6Hz),141.9(d,J＝2.8Hz),136.9(d,J＝2.3Hz),136.4(d,J＝5.8Hz),134.3(d,J＝11.3Hz),131.8(d,J＝8.8Hz),131.5(d,J＝9.0Hz),129.6(d,J＝5.7Hz),129.3(d,J＝11.9Hz),129.0(d,J＝12.0Hz),128.9(d,J＝99.0Hz),128.6(d,J＝1.6Hz),128.6(d,J＝99.6Hz),128.5(s),127.6(s),127.1(d,J＝2.2Hz),126.5(d,J＝1.2Hz),125.2(d,J＝7.2Hz),52.6(d,J＝65.2Hz),21.7(d,J＝0.9Hz),21.6(d,J＝1.0Hz).31P NMR(162MHz,CDCl3)δ31.5.HRMS(ESI-TOF)m/z:calcdforC29H27OPH[M+H]+:423.18723；Found:423.18689.
实施例10合成(E)-(1,3-二苯基烯丙基)双(4-氟苯基)氧化膦
称取0.2mmol(E)-1,3-二苯基丙烯，0.3mmol2,3-二氯-5,6-二氰基-1,4-苯醌加入15mL耐压反应管中，加入磁力搅拌子和2mL硝基甲烷，室温下搅拌反应5min，TLC监测，然后加入0.4mmol双(4-氟苯基)氧化膦反应6h。反应结束后用20ml亚硫酸钠溶液，10mL乙酸乙酯萃取，用无水硫酸钠在20℃下干燥10分钟并过滤，最后用旋转蒸发仪在-0.08MPa，45℃下进行减压蒸馏除去有机溶剂，即可得到产物(E)-(1,3-二苯基烯丙基)双(4-氟苯基)氧化膦，产率为100％。(E)-(1,3-二苯基烯丙基)双(4-氟苯基)氧化膦通过核磁表征数据如下：White solid:mp199.8-201.6℃；1H NMR(400MHz,CDCl3)δ7.83(dd,J＝14.3,9.0Hz,2H),7.54(dd,J＝14.4,9.3Hz,2H),7.33–7.15(m,12H),7.03–6.99(m,2H),6.61–6.53(m,1H),6.35(dd,J＝15.7,2.4Hz,1H),4.31(t,J＝8.9Hz,1H).31P NMR(162MHz,CDCl3)δ30.4.19FNMR(376MHz,CDCl3)δ-106.5,-106.8.13C NMR(100MHz,CDCl3)δ165.2(dd,JC-F＝253.9,JC-P＝2.7Hz),164.9(dd,JC-F＝254.1,JC-P＝2.3Hz),136.6(d,JC-P＝1.8Hz),135.6(d,JC-P＝5.8Hz),134.9(d,JC-P＝11.4Hz),134.10(d,J＝37.8Hz),134.10(dd,JC-F＝38.0,JC-P＝18.4Hz),131.6(d,JC-P＝95.7Hz),131.2(d,JC-P＝96.5Hz),129.5(d,J＝5.6Hz),128.8,128.6,127.9,127.5,126.5,124.1(d,JC-P＝7.2Hz),116.1(dd,JC-F＝19.2,JC-P＝10.4Hz),115.8(dd,JC-F＝19.3,JC-P＝10.5Hz),52.8(d,JC-P＝65.4Hz).HRMS(ESI-TOF)m/z:calcdforC27H21F2OPH[M+H]+:431.13708；Found:431.13696.
实施例11合成(E)-双(4-氯苯基)(1,3-二苯基烯丙基)氧化膦
称取0.2mmol(E)-1,3-二苯基丙烯，0.3mmol2,3-二氯-5,6-二氰基-1,4-苯醌加入15mL耐压反应管中，加入磁力搅拌子和2mL硝基甲烷，室温下搅拌反应5min，TLC监测，然后加入0.4mmol双(4-氯苯基)氧化膦反应6h。反应结束后用20ml亚硫酸钠溶液，10mL乙酸乙酯萃取，用无水硫酸钠在20℃下干燥10分钟并过滤，最后用旋转蒸发仪在-0.09MPa，40℃下进行减压蒸馏除去有机溶剂，即可得到产物(E)-双(4-氯苯基)(1,3-二苯基烯丙基)氧化膦，产率为96％。(E)-双(4-氯苯基)(1,3-二苯基烯丙基)氧化膦通过核磁表征数据如下：Whitesolid:mp218.7-219.4℃；1H NMR(400MHz,CDCl3)δ7.78–7.73(m,2H),7.50–7.45(m,4H),7.34–7.20(m,12H),6.59–6.51(m,1H),6.36(dd,J＝15.8,3.3Hz,1H),4.31(t,J＝9.3Hz,1H).13CNMR(100MHz,CDCl3)δ138.8(d,J＝2.2Hz),138.5,136.5,135.4(d,J＝5.6Hz),135.1(d,J＝10.9Hz),133.2(d,J＝9.0Hz),132.8(d,J＝9.2Hz),130.1(d,J＝98.5Hz),129.8(d,J＝95.3Hz),129.5(d,J＝5.0Hz),129.1(d,J＝11.9Hz),128.9,128.8(d,J＝13.1Hz),128.7,128.0,127.6,126.6,123.9(d,J＝6.7Hz),52.5(d,J＝65.7Hz).31P NMR(162MHz,CDCl3)δ30.1.HRMS(ESI-TOF)m/z:calcd forC27H21Cl2OPH[M+H]+:463.07798；Found:463.07739.
实施例12合成(E)-(1,3-二苯基烯丙基)二(萘-1-基)氧化膦
称取0.2mmol(E)-1,3-二苯基丙烯，0.3mmol2,3-二氯-5,6-二氰基-1,4-苯醌加入15mL耐压反应管中，加入磁力搅拌子和2mL硝基甲烷，室温下搅拌反应5min，TLC监测，然后加入0.4mmol二(萘-1-基)氧化膦反应6h。反应结束后用20ml亚硫酸钠溶液，10mL乙酸乙酯萃取，用无水硫酸钠在25℃下干燥10分钟并过滤，最后用旋转蒸发仪在-0.09MPa，45℃下进行减压蒸馏除去有机溶剂，即可得到产物(E)-(1,3-二苯基烯丙基)二(萘-1-基)氧化膦，产率为96％。(E)-(1,3-二苯基烯丙基)二(萘-1-基)氧化膦通过核磁表征数据如下：Whitesolid:mp 238.1-239.5℃；1H NMR(400MHz,CDCl3)δ8.78(d,J＝8.4Hz,1H),8.60(d,J＝8.5Hz,1H),8.15(dd,J＝14.2,7.0Hz,1H),7.97(d,J＝8.1Hz,1H),7.87–7.74(m,4H),7.49(t,J＝6.5Hz,1H),7.42–7.28(m,7H),7.22–7.06(m,8H),6.84–6.75(m,1H),6.40(dd,J＝15.8,2.4Hz,1H),4.80(t,J＝9.0Hz,1H).13C NMR(100MHz,CDCl3)δ136.9(d,J＝5.7Hz),136.8(d,J＝1.8Hz),134.4(d,J＝9.6Hz),134.3(d,J＝5.1Hz),134.1(d,J＝2.0Hz),133.9,133.7(d,J＝9.0Hz),133.1(d,J＝2.9Hz),132.9(d,J＝2.9Hz),132.2(d,J＝9.9Hz),129.7(d,J＝5.9Hz),129.7(d,J＝93.2Hz),129.5(d,J＝93.5Hz),128.8(d,J＝17.5Hz),128.5(d,J＝1.4Hz),128.4,127.6,127.2(d,J＝20.3Hz),127.2(d,J＝4.6Hz),127.1,126.7(d,J＝4.4Hz),126.5(d,J＝0.4Hz),126.3(d,J＝18.0Hz),125.9(d,J＝6.4Hz),124.4(d,J＝13.5Hz),124.2(d,J＝13.7Hz),52.1(d,J＝66.8Hz).31P NMR(162MHz,CDCl3)δ36.1.HRMS(ESI-TOF)m/z:calcdfor C35H27OPH[M+H]+:495.18723；Found:495.18689.
实施例13合成(E)-(1,3-二苯基烯丙基)双(4-甲氧基苯基)氧化膦
称取0.2mmol(E)-1,3-二苯基丙烯，0.3mmol2,3-二氯-5,6-二氰基-1,4-苯醌加入15mL耐压反应管中，加入磁力搅拌子和2mL硝基甲烷，室温下搅拌反应5min，TLC监测，然后加入0.4mmol双(4-甲氧基苯基)氧化膦反应6h。反应结束后用20ml亚硫酸钠溶液，10mL乙酸乙酯萃取，用无水硫酸钠在25℃下干燥10分钟并过滤，最后用旋转蒸发仪在-0.09MPa，45℃下进行减压蒸馏除去有机溶剂，即可得到产物(E)-(1,3-二苯基烯丙基)双(4-甲氧基苯基)氧化膦，产率为96％。(E)-(1,3-二苯基烯丙基)双(4-甲氧基苯基)氧化膦通过核磁表征数据如下：White solid:mp 221.7-222.8℃；1H NMR(400MHz,CDCl3)δ7.72(t,J＝9.3Hz,2H),7.46(t,J＝9.2Hz,2H),7.32(d,J＝7.5Hz,2H),7.28–7.15(m,8H),6.96(d,J＝6.9Hz,2H),6.81(d,J＝7.0Hz,2H),6.59(dt,J＝15.8,8.1Hz,1H),6.34(dd,J＝15.7,3.4Hz,1H),4.31(t,J＝9.8Hz,1H),3.80(d,J＝22.3Hz,6H).13C NMR(100MHz,CDCl3)δ162.5(d,J＝2.5Hz),162.3(d,J＝2.3Hz),136.9(d,J＝2.2Hz),136.2(d,J＝5.6Hz),134.5(d,J＝12.0Hz),133.8(d,J＝9.8Hz),133.5(d,J＝10.1Hz),129.7(d,J＝5.7Hz),128.7(d,J＝99.7Hz),128.7(d,J＝1.4Hz),128.6,127.9(d,J＝97.8Hz),127.7,127.2(d,J＝1.5Hz),126.6(d,J＝0.8Hz),124.9(d,J＝7.3Hz),114.2(d,J＝12.6Hz),113.9(d,J＝12.7Hz),55.4(d,J＝8.0Hz),52.9(d,J＝65.8Hz).31P NMR(162MHz,CDCl3)δ32.2.HRMS(ESI-TOF)m/z:calcd forC29H27O3PH[M+H]+:455.17706；Found:455.17651.
实施例14合成(E)-(1,3-二苯基烯丙基)磷酸二甲酯
称取0.2mmol(E)-1,3-二苯基丙烯，0.3mmol 2,3-二氯-5,6-二氰基-1,4-苯醌加入15mL耐压反应管中，加入磁力搅拌子和2mL硝基甲烷，室温下搅拌反应5min，TLC监测，然后加入0.4mmol亚磷酸三甲酯反应6h。反应结束后用20ml亚硫酸钠溶液，10mL乙酸乙酯萃取，用无水硫酸钠在25℃下干燥10分钟并过滤，最后用旋转蒸发仪在-0.09MPa，45℃下进行减压蒸馏除去有机溶剂，即可得到产物(E)-(1,3-二苯基烯丙基)磷酸二甲酯，产率为84％。(E)-(1,3-二苯基烯丙基)磷酸二甲酯通过核磁表征数据如下：Colorless oil 1H NMR(400MHz,CDCl3)δ7.47–7.45(m,2H),7.39–7.34(m,4H),7.31–7.20(m,4H),6.61–6.48(m,2H),4.02(dd,J＝24.8,7.8Hz,1H),3.73(d,J＝10.7Hz,3H),3.55(d,J＝10.6Hz,3H).13CNMR(100MHz,CDCl3)δ136.7(d,J＝2.7Hz),135.8(d,J＝7.4Hz),133.9(d,J＝13.9Hz),129.1(d,J＝7.0Hz),128.9(d,J＝2.2Hz),128.7,127.9(d,J＝0.5Hz),127.5(d,J＝2.9Hz),126.6(d,J＝1.7Hz),124.4(d,J＝9.7Hz),53.6(d,J＝7.2Hz),49.1(d,J＝137.4Hz).31P NMR(162MHz,CDCl3)δ27.1.HRMS(ESI-TOF)m/z:calcd forC17H19O3PH[M+H]+:303.11446；Found:303.11432.
实施例15合成(E)-(1,3-二苯基烯丙基)磷酸二乙酯
称取0.2mmol(E)-1,3-二苯基丙烯，0.3mmol 2,3-二氯-5,6-二氰基-1,4-苯醌加入15mL耐压反应管中，加入磁力搅拌子和2mL硝基甲烷，室温下搅拌反应5min，TLC监测，然后加入0.4mmol亚磷酸三乙酯反应6h。反应结束后用20ml亚硫酸钠溶液，10mL乙酸乙酯萃取，用无水硫酸钠在25℃下干燥10分钟并过滤，最后用旋转蒸发仪在-0.09MPa，45℃下进行减压蒸馏除去有机溶剂，即可得到产物(E)-(1,3-二苯基烯丙基)磷酸二乙酯，产率为95％。(E)-(1,3-二苯基烯丙基)磷酸二乙酯通过核磁表征数据如下：Colorless oil 1H NMR(400MHz,CDCl3)δ7.46–7.44(m,2H),7.38–7.19(m,8H),6.60–6.48(m,1H),4.12–3.92(m,4H),3.86–3.76(m,1H),1.26(t,J＝7.0Hz,3H),1.12(t,J＝7.1Hz,3H).13C NMR(100MHz,CDCl3)δ136.9(d,J＝2.8Hz),136.0(d,J＝7.4Hz),133.8(d,J＝13.9Hz),129.4(d,J＝5.0Hz),129.2(d,J＝7.0Hz),128.8(d,J＝2.2Hz),128.7(d,J＝3.3Hz),128.6,127.8(d,J＝0.5Hz),124.7(d,J＝9.6Hz),62.9(d,J＝7.2Hz),62.8(d,J＝7.3Hz),49.5(d,J＝137.3Hz),16.5(d,J＝5.9Hz),16.3(d,J＝5.8Hz).31P NMR(162MHz,CDCl3)δ24.8.HRMS(ESI-TOF)m/z:calcd forC19H23O3PH[M+H]+:331.14576；Found:331.14523.
实施例16合成(E)-(1,3-二苯基烯丙基)磷酸二异丙酯
称取0.2mmol(E)-1,3-二苯基丙烯，0.3mmol 2,3-二氯-5,6-二氰基-1,4-苯醌加入15mL耐压反应管中，加入磁力搅拌子和2mL硝基甲烷，室温下搅拌反应5min，TLC监测，然后加入0.4mmol亚磷酸三异丙酯反应6h。反应结束后用20ml亚硫酸钠溶液，10mL乙酸乙酯萃取，用无水硫酸钠在25℃下干燥10分钟并过滤，最后用旋转蒸发仪在-0.09MPa，45℃下进行减压蒸馏除去有机溶剂，即可得到产物(E)-(1,3-二苯基烯丙基)磷酸二异丙酯，产率为80％。(E)-(1,3-二苯基烯丙基)磷酸二异丙酯通过核磁表征数据如下：Colorless oil1HNMR(400MHz,CDCl3)δ7.47–7.45(m,2H),7.38–7.19(m,8H),6.58–6.47(m,1H),4.73–4.45(m,2H),3.96–3.88(m,1H),1.30(d,J＝6.2Hz,3H),1.23(dd,J＝9.1,6.2Hz,6H),0.93(d,J＝6.2Hz,3H).13C NMR(100MHz,CDCl3)δ137.1(d,J＝2.8Hz),136.5(d,J＝7.1Hz),133.6(d,J＝13.9Hz),129.3(d,J＝7.1Hz),128.7(d,J＝2.1Hz),128.6,127.7,127.2(d,J＝2.8Hz),126.5(d,J＝1.7Hz),125.3(d,J＝9.5Hz),71.4(d,J＝7.4Hz),71.0(d,J＝7.5Hz),50.2(d,J＝138.9Hz),24.4(d,J＝3.1Hz),24.3(d,J＝3.3Hz),23.9(d,J＝5.7Hz),23.4(d,J＝5.8Hz).31P NMR(162MHz,CDCl3)δ23.1.HRMS(ESI-TOF)m/z:calcd forC21H27O3PH[M+H]+:359.17706；Found:359.17648.
实施例17合成(E)-(1,3-二苯基烯丙基)磷酸二苯酯
称取0.2mmol(E)-1,3-二苯基丙烯，0.3mmol 2,3-二氯-5,6-二氰基-1,4-苯醌加入15mL耐压反应管中，加入磁力搅拌子和2mL硝基甲烷，室温下搅拌反应5min，TLC监测，然后加入0.4mmol亚磷酸三苯酯反应6h。反应结束后用20ml亚硫酸钠溶液，10mL乙酸乙酯萃取，用无水硫酸钠在25℃下干燥10分钟并过滤，最后用旋转蒸发仪在-0.09MPa，45℃下进行减压蒸馏除去有机溶剂，即可得到产物(E)-(1,3-二苯基烯丙基)磷酸二苯酯，产率为72％。(E)-(1,3-二苯基烯丙基)磷酸二苯酯通过核磁表征数据如下：White solid:mp121.1-121.6℃；1H NMR(400MHz,CDCl3)δ7.52(d,J＝7.5Hz,2H),7.38–7.35(m,4H),7.31–7.16(m,8H),7.12–7.06(m,4H),6.87(d,J＝8.1Hz,2H),6.69–6.57(m,2H),4.37(dd,J＝25.0,7.5Hz,1H).13CNMR(100MHz,CDCl3)δ150.8(d,J＝5.2Hz),150.6(d,J＝5.0Hz),136.6(d,J＝2.9Hz),135.1(d,J＝14.7Hz),135.0(d,J＝7.4Hz),129.7(d,J＝10.5Hz),129.5(d,J＝7.5Hz),129.1(d,J＝2.3Hz),128.7(d,J＝19.6Hz),128.7,128.2(d,J＝18.9Hz),128.1,127.9(d,J＝3.0Hz),126.7(d,J＝1.8Hz),125.2(d,J＝10.1Hz),123.5(d,J＝9.9Hz),120.8(d,J＝4.4Hz),120.6(d,J＝4.3Hz),49.6(d,J＝138.3Hz).31P NMR(162MHz,CDCl3)δ17.4.HRMS(ESI-TOF)m/z:calcd forC27H23O3PH[M+H]+:427.14576；Found:427.14526.
对于本领域的技术人员来说，可根据以上描述的技术方案以及构思，做出其它各种相应的改变以及变形，而所有的这些改变以及变形都应该属于本发明权利要求的保护范围之内。
Claims (9)
1.一种烯丙基氧化膦类化合物的合成方法，其特征在于：所述合成方法包括如下步骤：将芳基氧化膦或者亚磷酸三烷酯和2,3-二氯-5,6-二氰基-1,4-苯醌加入到溶剂中，在室温下搅拌，经萃取、干燥、过滤、硅胶柱层析分析提纯和减压蒸馏处理制得所需烯丙基氧化膦类化合物；反应方程式如下：
。
2.根据权利要求1所述的一种烯丙基氧化膦类化合物的合成方法，其特征在于：所述烯丙基氧化膦类化合物是二芳基丙烯化合物。
3.根据权利要求2所述的一种烯丙基氧化膦类化合物的合成方法，其特征在于：所述二芳基丙烯化合物的结构通式(1)为
其中，Ar1为含有甲基、甲氧基、叔丁基、氟、氯、溴取代基的苯环或苯基。
4.根据权利要求1所述的一种烯丙基氧化膦类化合物的合成方法，其特征在于：所述二芳基氧化膦化合物的结构通式为(2)
其中，Ar2为含有甲基、甲氧基、氟、氯、溴取代基的苯环或苯基。
5.根据权利要求1所述的一种烯丙基氧化膦类化合物的合成方法，其特征在于：所述亚磷酸三烷酯的结构通式为(3)
R为甲基，乙基，异丙基，苯基。
6.根据权利要求1所述的一种烯丙基氧化膦类化合物的合成方法，其特征在于：所述溶剂为硝基甲烷。
7.根据权利要求1所述的一种烯丙基氧化膦类化合物的合成方法，其特征在于：所述二芳基丙烯、二芳基氧化膦或者亚磷酸三烷酯、2,3-二氯-5,6-二氰基-1,4-苯醌的反应摩尔比为1:2:1.5。
8.根据权利要求1所述的一种烯丙基氧化膦类化合物的合成方法，其特征在于：所述搅拌的时间为5～7h，所述萃取的溶剂为乙酸乙酯，所述干燥的试剂为无水硫酸钠，所述干燥的温度为20～25℃，所述干燥的时间为10～15min。
9.根据权利要求1所述的一种烯丙基氧化膦类化合物的合成方法，其特征在于：所述减压蒸馏的温度为35～45℃，所述减压蒸馏的压力为-0.085～-0.095MPa。
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