CN106279274B - 一种通过烯烃合成β‑羰基膦酸酯衍生物的制备方法 - Google Patents
一种通过烯烃合成β‑羰基膦酸酯衍生物的制备方法 Download PDFInfo
- Publication number
- CN106279274B CN106279274B CN201610627616.0A CN201610627616A CN106279274B CN 106279274 B CN106279274 B CN 106279274B CN 201610627616 A CN201610627616 A CN 201610627616A CN 106279274 B CN106279274 B CN 106279274B
- Authority
- CN
- China
- Prior art keywords
- och
- acid ester
- phosphonic acid
- phenyl
- alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 150000003008 phosphonic acid esters Chemical class 0.000 title claims abstract description 22
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- -1 Phosphite ester Chemical class 0.000 claims abstract description 22
- 229910052927 chalcanthite Inorganic materials 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 38
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 36
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 33
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 30
- 239000002904 solvent Substances 0.000 claims description 19
- 238000004440 column chromatography Methods 0.000 claims description 15
- 238000000926 separation method Methods 0.000 claims description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 13
- 241001597008 Nomeidae Species 0.000 claims description 11
- 239000003208 petroleum Substances 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 9
- 238000003786 synthesis reaction Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 150000001344 alkene derivatives Chemical class 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 125000002541 furyl group Chemical group 0.000 claims description 4
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 claims description 3
- LQJBNNIYVWPHFW-QXMHVHEDSA-N gadoleic acid Chemical class CCCCCCCCCC\C=C/CCCCCCCC(O)=O LQJBNNIYVWPHFW-QXMHVHEDSA-N 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims 2
- 239000003480 eluent Substances 0.000 claims 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- 150000002825 nitriles Chemical class 0.000 claims 1
- 239000003960 organic solvent Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 6
- 239000002905 metal composite material Substances 0.000 abstract description 4
- 150000001728 carbonyl compounds Chemical class 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 15
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 13
- 238000005160 1H NMR spectroscopy Methods 0.000 description 13
- 238000004679 31P NMR spectroscopy Methods 0.000 description 13
- 239000007832 Na2SO4 Substances 0.000 description 13
- 239000012074 organic phase Substances 0.000 description 13
- 229910052938 sodium sulfate Inorganic materials 0.000 description 13
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 9
- 239000002585 base Substances 0.000 description 8
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 6
- WBYWAXJHAXSJNI-VOTSOKGWSA-N trans-cinnamic acid Chemical compound OC(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-N 0.000 description 5
- 239000000284 extract Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 235000013985 cinnamic acid Nutrition 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 2
- 239000002027 dichloromethane extract Substances 0.000 description 2
- 125000004494 ethyl ester group Chemical group 0.000 description 2
- BPMFZUMJYQTVII-UHFFFAOYSA-N guanidinoacetic acid Chemical compound NC(=N)NCC(O)=O BPMFZUMJYQTVII-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- NIONDZDPPYHYKY-SNAWJCMRSA-N (2E)-hexenoic acid Chemical compound CCC\C=C\C(O)=O NIONDZDPPYHYKY-SNAWJCMRSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical group C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 description 1
- WGGLDBIZIQMEGH-UHFFFAOYSA-N 1-bromo-4-ethenylbenzene Chemical class BrC1=CC=C(C=C)C=C1 WGGLDBIZIQMEGH-UHFFFAOYSA-N 0.000 description 1
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical class COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 1
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 1
- LXZFMKLKTRIZDJ-UHFFFAOYSA-N 2-(furan-2-yl)prop-2-enoic acid Chemical class OC(=O)C(=C)C1=CC=CO1 LXZFMKLKTRIZDJ-UHFFFAOYSA-N 0.000 description 1
- CPDDDTNAMBSPRN-UHFFFAOYSA-N 3-(4-bromophenyl)prop-2-enoic acid Chemical class OC(=O)C=CC1=CC=C(Br)C=C1 CPDDDTNAMBSPRN-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical class CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 1
- 238000006546 Horner-Wadsworth-Emmons reaction Methods 0.000 description 1
- 229910021576 Iron(III) bromide Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910002567 K2S2O8 Inorganic materials 0.000 description 1
- SCHRRICRQNJJKN-UHFFFAOYSA-N P.[O] Chemical compound P.[O] SCHRRICRQNJJKN-UHFFFAOYSA-N 0.000 description 1
- QROGIFZRVHSFLM-QHHAFSJGSA-N [(e)-prop-1-enyl]benzene Chemical compound C\C=C\C1=CC=CC=C1 QROGIFZRVHSFLM-QHHAFSJGSA-N 0.000 description 1
- DBWGAXVWWNKFNI-UHFFFAOYSA-N [O].C1(=CC=CC=C1)[P]C1=CC=CC=C1 Chemical compound [O].C1(=CC=CC=C1)[P]C1=CC=CC=C1 DBWGAXVWWNKFNI-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- XNCRUNXWPDJHGV-UHFFFAOYSA-N alpha-Methyl-cinnamic acid Chemical compound OC(=O)C(C)=CC1=CC=CC=C1 XNCRUNXWPDJHGV-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- URCAYJXJXYLGTI-UHFFFAOYSA-N ethene fluorobenzene Chemical class C=C.FC1=CC=CC=C1 URCAYJXJXYLGTI-UHFFFAOYSA-N 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001338 liquidmetal Inorganic materials 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- UORVCLMRJXCDCP-UHFFFAOYSA-N propynoic acid Chemical compound OC(=O)C#C UORVCLMRJXCDCP-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- FEONEKOZSGPOFN-UHFFFAOYSA-K tribromoiron Chemical compound Br[Fe](Br)Br FEONEKOZSGPOFN-UHFFFAOYSA-K 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
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4056—Esters of arylalkanephosphonic acids
- C07F9/4059—Compounds containing the structure (RY)2P(=X)-(CH2)n-C(=O)-(CH2)m-Ar, (X, Y = O, S, Se; n>=1, m>=0)
-
- 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
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
-
- 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
-
- 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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
- C07F9/65515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a five-membered ring
Landscapes
- 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)
- Crystallography & Structural Chemistry (AREA)
Abstract
本发明公开了一种通过烯烃合成β‑羰基膦酸酯衍生物的方法，属于有机化学领域。该方法以烯烃（或烯酸）和H‑亚磷酸酯为原料，以CuSO4·5H2O为催化剂，加热反应，合成β‑羰基膦酸酯衍生物。该方法原料廉价易得，操作简单，反应条件温和，合成产率较高，适用于工业化生产。该类衍生物常作为中间体合成α,β‑不饱和羰基化合物，此外，该类衍生物也具有很广泛的生物活性和显著的金属复合能力，在药物化学、生物化学、无机化学中有着不可取代的作用。
Description
技术领域
本发明涉及一种在CuSO4·5H2O催化下，通过烯烃合成β-羰基膦酸酯衍生物的方法，属有机化学领域。
背景技术
β-羰基膦酸酯在有机磷化学中占据着非常重要的地位，具有很广泛的生物活性和显著的金属复合能力，在有机合成、药物化学、生物化学、无机化学中有着不可取代的作用。在有机合成领域常作为反应的中间体，用于合成α,β-不饱和羰基化合物。例如著名的Horner-Wadsworth-Emmons反应就是利用β-羰基膦酸酯和醛(或酮)在碱的作用下合成α,β-不饱和羰基化合物；在药物化学上，它作为手性前体物质被广泛应用于合成具有药理活性的手性β-羟基、β-卤代和α-氨基膦酸类化合物等；在生物化学领域，由于具有广泛的生物活性，可参与生物体内的物质代谢活动，此外也可以合成具有生物活性的β-氨基磷酸和β-羟基磷酸类衍生物；在无机化学方面，由于具有显著的金属复合能力，可用做液液金属离子的萃取剂等。因此，发展高效、简单的方法来合成β-羰基膦酸酯，一直是化学工作者研究的热点内容。
目前，关于β-羰基膦酸酯的制备方法有很多，大致可分为以下几类:第一类Arbuzov反应:利用卤代物和亚磷酸三乙脂在高温条件下加热制备β-羰基膦酸酯(Pure.Appl.Chem,1964,9(2):307～336)；第二类：羧酸脂和烷基磷酸酯在强碱的作用下合成β-羰基膦酸酯(J.Org.Chem,2009,74(19):7574～7576)；第三类；用β-羟基膦酸酯为原料，通过氧化制备β-羰基膦酸酯(Tetrahedron,2009,65(20):4017～4024)；第四类：通过芳香烃C-H键的活化与磷酰基乙酸的反应来制备β-羰基磷酸酯(J.Org.Chem,2008,73(16):6397～9400)；第五类：利用炔基磷酸酯的水解合成β-羰基磷酸酯(Adv.Synth.Catal,2012,354(13):2427～2432)；第六类：以炔烃衍生物和H-亚磷酸酯溶为原料，以CuSO4·5H2O和AgNO3作为催化剂，K2S2O8做氧化剂合成β-羰基磷酸酯：第七类：利用烯烃或炔酸和H-亚磷酸酯，在 CuBr2/FeBr3，或者是CuOTf/FeCl3的共催化下来制备β-羰基磷酸酯(Angew.Chem.Int.Ed.2011,50,9097-9199，Chem Comm,2015,51,7839-7842)。然而，这些合成方法存在步骤繁杂，使用贵金属催化剂、反应条件苛刻、底物适用性差，反应体系复杂，副产物较多，收率低，对环境不友好，以及所用试剂难以保存且价格昂贵等缺点。因此，急需寻找一种原料便宜易得，收率较高且操作简单、在温和条件下合成β-羰基膦酸酯衍生物的方法，对促进此类化合物的开发利用，保护我国自主知识产权的研发具有非常重要的意义。
发明内容
基于上述研究背景，本发明的目的在于：以便宜易得的CuSO4·5H2O做催化剂，烯烃衍生物和H-亚磷酸酯为原料，提供一种操作简便、条件温和、产率较高且通过一步反应得到β-羰基膦酸酯衍生物的制备方法。
为实现本发明目的，本发明化合物的制备如下列反应式进行：
其中，X代表如下基团：-H,-COOH；R代表苯基或取代苯基或呋喃基或烷基，其中苯基上的取代基团如：-CH3，-OCH3，-F，-Cl，-Br，-I，-NO2，-COCH3，-NHCOCH3，烷基为C4-C12的烷基；R’代表如下基团：H,-CH3，-Ph，-OCH3，-F，-Cl，-Br，-I，-NO2，-COCH3；R1和R2代表如下基团：-OCH3，-OCH2CH3，-OCH2CH2CH3，-OCH2CH2CH2CH3，-OCH(CH3)2，-OCH2Ph，-CH3，-CH2CH3，-CH2CH2CH3，-CH2Ph，-Ph，-O-Ph等基团。
优选如下：X代表如下基团：-H,-COOH；R代表苯基或取代苯基或呋喃基或烷基，其中苯基上的取代基为：-CH3，-OCH3，-F，-Cl，-Br，-I，-NO2，烷基为C4-C12的烷基；R’代表H,-CH3；R1和R2代表如下基团：-OCH3，-OCH2CH3，-OCH2CH2CH3，-OCH2CH2CH2CH3，-OCH(CH3)2，-OCH2Ph，-CH2Ph，-Ph，-O-Ph等基团。
具体技术方案通过以下步骤实施：首先将烯烃衍生物或烯酸衍生物和H-亚 磷酸酯溶解在溶剂中，然后加入CuSO4·5H2O做催化剂，在40℃-70℃条件下反应，待反应结束后，冷却至室温，经萃取，干燥，减压蒸馏除去溶剂，用石油醚和乙酸乙酯(V/V＝1:1)做为洗脱剂，经柱层析分离得到β-羰基膦酸酯衍生物。
烯烃衍生物或烯酸衍生物与H-亚磷酸酯和CuSO4·5H2O摩尔比为1:2:0.1。
所述溶剂为乙腈、甲苯、二氧六环、甲醇、乙醇、二氯甲烷、氯仿、THF、和DMSO等中一种或多种作为溶剂，优选乙腈作为溶剂。
反应温度优选60℃；反应时间2-4h，优选2h。
本发明所用试剂均市售可得。
本发明有益效果在于：通过烯烃合成β-羰基膦酸酯衍生物，所用催化剂便宜易得，原料简单易得且易保存，反应条件温和，实验操作简单，产物易于提纯，合成产率较高，达41％-92％，有利于工业化生产，为制备具有广泛的生物活性和显著的金属复合能力的β-羰基膦酸酯衍生物提供了一种新的途径。
具体实施方式
下面通过实施例对本发明进行进一步的阐述，但并不意味着本发明的内容局限于实施例。
实施例1二乙基-(2-氧代-2-苯基)膦酸酯
苯乙烯(0.104g,1mmol)或者苯基丙烯酸(0.148g,1mmol)，H-亚磷酸二乙基酯(0.276g,2mmol),CuSO4·5H2O(0.026g,0.1mmol),乙腈10mL于25mL的三口烧瓶中，在油浴中加热到60℃，在此温度下继续反应2h，用TLC板检测反应进程，待反应完毕后，用二氯甲烷萃取(15x 3mL)，合并有机相，用Na2SO4干燥，减压蒸馏除去溶剂，经柱层析分离(石油醚/乙酸乙酯,V/V＝1:1)，即得黄色油状目标化合物，产率91％。
1H NMR(CDCl3,400MHz,)δ:7.90(d,2H,J＝7.6Hz),7.46(t,1H,J＝7.2Hz),7.35(t,2H,J＝7.6Hz),4.05-3.98(m,4H),3.56(d,2H,J＝22.8Hz),1.15(t,6H,J＝7.2Hz)；13C NMR(CDCl3,100MHz)；δ:191.8(d,JP-C＝6.5Hz),136.4(JP-C＝1.9Hz),133.6,128.9,128.5,62.6(d,JP-C＝6.4Hz),38.9(d,JP-C 129.3Hz),16.1(d,JP-C＝6.4Hz)；31P NMR(CDCl3,400MHz)δ:17.9；HRMS:calcd for C12H17O4P[M+H]+ 257.0937,found 257.0941.
实施例2二异丙基-(2-氧代-2-苯基)膦酸酯
苯乙烯(0.104g,1mmol)或者苯基丙烯酸(0.148g,1mmol)，H-亚磷酸二异丙基酯(0.332g,2mmol),CuSO4·5H2O(0.026g,0.1mmol),乙腈10mL于25mL的三口烧瓶中，在油浴中加热到50℃，在此温度下继续反应4h，用TLC板检测反应进程，待反应完毕后，用二氯甲烷萃取(15x 3mL)，合并有机相，用Na2SO4干燥，减压蒸馏除去溶剂，经柱层析分离(石油醚/乙酸乙酯,V/V＝1:1)，即得到黄色油状目标化合物，产率87％。
1H NMR(CDCl3,400MHz,)δ:8.04(d,2H,J＝7.2Hz),7.59(t,1H,J＝7.6Hz),7.49(t,2H,J＝8.0Hz),4.80-4.69(m,2H),3.61(d,2H,J＝22.8),1.29(dd,12H,J＝3.2Hz,6.8Hz)；13C NMR(CDCl3,100MHz)；δ:192.1(d,JP-C＝6.6Hz),136.7,133.5,129.1,128.5,71.5(d,JP-C＝6.6Hz),39.7(d,JP-C＝129.5Hz),23.8(dd,JP-C＝5.1Hz,21.1Hz)；31P NMR(CDCl3,400MHz)δ:17.9；HRMS:calcd for C14H21O4P[M+Na]+307.1070,found 307.1069
实施例3二苄基-(2-氧代-2-苯基)膦酸酯
苯乙烯(0.104g,1mmol)或者苯基丙烯酸(0.148g,1mmol)，H-亚磷酸二苄基酯(0.524g,2mmol),CuSO4·5H2O(0.026g,0.1mmol),乙醇10mL于25mL的三口烧瓶中，在油浴中加热到60℃，在此温度下继续反应2h，用TLC板检测反应进程，待反应完毕后，用二氯甲烷萃取(15x 3mL)，合并有机相，用Na2SO4干燥，减压蒸馏除去溶剂，经柱层析分离(石油醚/乙酸乙酯,V/V＝1:1)，即得黄色油状目标化合物，产率91％。
1H NMR(CDCl3,400MHz,)δ:7.95(d,2H,J＝7.6Hz),7.54(t,1H,J＝7.2Hz),7.40(t,2H,J＝7.6Hz),7.34-7.28(10H),5.09-4.98(m,4H),3.68(d,2H,J＝22.4)；13C NMR(CDCl3,100MHz)；δ:191.7(d,JP-C＝6.5Hz),136.44(d,JP-C＝2.4Hz),135.9(d,JP-C＝5.2Hz),133.7,129.0,128.7,128.6,128.5,128.1,68.1(d,JP-C＝6.5Hz),38.6(d,JP-C＝130.8)；31P NMR(CDCl3,400MHz)δ:21.3；HRMS:calcd for C22H21O4P[M+H]+381.1250,found 381.1256
实施例4二苯基-(2-氧代-2-苯基)膦酸酯
苯乙烯(0.104g,1mmol)或者苯基丙烯酸(0.148g,1mmol)，H-亚磷酸二苯基酯(0.468g,2mmol),CuSO4·5H2O(0.026g,0.1mmol),二氯甲烷10mL于25mL的三口烧瓶中，在油浴中加热到60℃，在此温度下继续反应2h，用TLC板检测反应进程，待反应完毕后，用二氯甲烷萃取(15x 3mL)，合并有机相，用Na2SO4干燥，减压蒸馏除去溶剂，经柱层析分离(石油醚/乙酸乙酯,V/V＝1:1)，即得黄色油状目标化合物，产率79％。
1H NMR(CDCl3,400MHz,)δ:8.04(d,2H,J＝7.2Hz),7.61(t,1H,J＝7.2Hz),7.50(t,2H,7.6Hz),7.32-7.18(m,4H),7.17-7.15(m,6H),3.94(d,2H,22.8Hz)；13C NMR(CDCl3,100MHz)；δ:190.7(d,JP-C＝6.9Hz),150.3(d,JP-C＝8.9Hz),136.4,134.0,129.8,129.1,128.8,125.5,120.6(d,JP-C＝4.4Hz),37.8(d,132.7Hz)；31P NMR(CDCl3,400MHz)δ:13.1；HRMS:calcd for C20H17O4P[M+H]+353.0937,found 307.0941
实施例5二苯基-(2-氧代-2-苯基)膦氧
苯乙烯(0.104g,1mmol)或者苯基丙烯酸(0.148g,1mmol)，二苯基磷氧(0.404g,2mmol),CuSO4·5H2O(0.026g,0.1mmol),乙腈10mL于25mL的三口烧瓶中，在油浴中加热到60℃，在此温度下继续反应2h，用TLC板检测反应进程，待反应完毕后，用二氯甲烷萃取(15x3mL)，合并有机相，用Na2SO4干燥，减压蒸馏除去溶剂，经柱层析分离(石油醚/乙酸乙酯,V/V＝1:1)，即得黄色油状目标化合物，产率92％。
1H NMR(CDCl3,400MHz,)δ:7.95(d,2H,J＝7.6Hz),7.81-7.76(m,4H),7.49-7.35(m,9H),4.13(d,2H,J＝15.2Hz)；13C NMR(CDCl3,100MHz)；δ:192.8(d,JP-C＝5.6Hz),136.9,133.6,132.3(d,JP-C＝5.2Hz),132.2,131.2(d,JP-C＝4.8Hz),129.2,128.6,43.1(d,JP-C＝58.0Hz)；31P NMR(CDCl3,400MHz)δ:26.9；HRMS:calcd for C20H17O2P[M+H]+321.1039,found321.1040.
实施例6二乙基-(2-氧代-2-(4-甲基苯基)膦酸酯
4-甲基苯乙烯(0.118g,1mmol)或者4-甲基肉桂酸(0.162g,1mmol)，H-亚磷酸二乙基酯(0.276g,2mmol),CuSO4·5H2O(0.026g,0.1mmol),氯仿10mL于25mL的三口烧瓶中，在油浴中加热到40℃，在此温度下继续反应4h，用TLC板检测反应进程，待反应完毕后，用二氯甲烷萃取(15x 3mL)，合并有机相，用Na2SO4干燥，减压蒸馏除去溶剂，经柱层析分离(石油醚/乙酸乙酯,V/V＝1:1)，即得黄色油状目标化合物，产率85％。
1H NMR(CDCl3,400MHz,)δ:7.90(d,2H,J＝8.0Hz),6.25(d,2H,J＝8.0Hz),4.16-4.09(m,4H),3.60(d,2H,22.8Hz),2.40(3H),1.27(t,6H,J＝7.2Hz)；13C NMR(CDCl3,100MHz)；δ:191.5(d,JP-C＝6.5Hz),144.7,134.1,129.3,129.2,62.7(d,JP-C＝6.5Hz),38.3(d,JP-C＝129.4Hz),21.7,16.2(d,JP-C＝6.2Hz)；31P NMR(CDCl3,400MHz)δ:21.3；HRMS:calcd for C13H19O4P[M+H]+271.1094,found271.1095.
实施例7二乙基-(2-(4-甲氧基苯基)-2-氧代)膦酸酯
4-甲氧基苯乙烯(0.134g,1mmol)或者4-甲氧肉桂酸(0.178g,1mmol)，H-亚磷酸二乙基酯(0.276g,2mmol),CuSO4·5H2O(0.026g,0.1mmol),DMSO 10mL于25mL的三口烧瓶中，在油浴中加热到70℃，在此温度下继续反应2h，用TLC板检测反应进程，待反应完毕后，用二氯甲烷萃取(15x 3mL)，合并有机 相，用Na2SO4干燥，减压蒸馏除去溶剂，经柱层析分离(石油醚/乙酸乙酯,V/V＝1:1)，即得黄色油状目标化合物，产率74％。
1H NMR(CDCl3,400MHz,)δ:7.98(d,2H,J＝8.8Hz),6.92(d,2H,J＝8.8Hz),4.16-4.08(m,4H),3.85(s,3H),3.57(d,2H,J＝22.8Hz),1.27(t,6H,J＝7.2Hz)； 13C NMR(CDCl3,100MHz)；δ:190.2(d,JP-C＝6.1Hz),164.0,131.5,129.6(d,JP-C＝2.0Hz),113.8,62.7(d,JP-C＝7.5Hz),55.5,38.7(d,JP-C＝129.3Hz),16.2(d,JP-C＝6.3Hz)；31P NMR(CDCl3,400MHz)δ:20.7；HRMS:calcd for C13H19O5P[M+Na]+309.0862,found 309.0862.
实施例8二乙基-(2-(4-氟苯基)-2-氧代)膦酸酯
4-氟苯乙烯(0.122g,1mmol)或者4-氟肉桂酸(0.166g,1mmol)，H-亚磷酸二乙基酯(0.276g,2mmol),CuSO4·5H2O(0.026g,0.1mmol),乙腈10mL于25mL的三口烧瓶中，在油浴中加热到60℃，在此温度下继续反应2h，用TLC板检测反应进程，待反应完毕后，用二氯甲烷萃取(15x 3mL)，合并有机相，用Na2SO4干燥，减压蒸馏除去溶剂，经柱层析分离(石油醚/乙酸乙酯,V/V＝1:1)，即得黄色油状目标化合物，产率80％。
1H NMR(CDCl3,400MHz,)δ:8.03-8.00(q,2H,J＝5.6Hz,8.8Hz),7.10(t,2H,J＝8.4Hz),4.12-4.05(m,4H),3.56(d,2H,J＝22.8Hz),1.24(t,6H,J＝7.2Hz)；13C NMR(CDCl3,100MHz)；δ:190.3(d,JP-C＝6.5Hz),166.1(d,JF-C＝254.5Hz),132.9,131.8(d,JF-C＝9.4Hz),115.7(d,JF-C＝21.8Hz),62.7(d,JP-C＝6.5Hz),38.6(d,JP-C＝128.8Hz),16.2(d,JP-C＝6.3Hz)；31P NMR(CDCl3,400MHz)δ:19.7；HRMS:calcd for C12H16FO4P[M+H]+275.0843,found 275.0847.
实施例9二乙基-(2-(4-溴苯基)-2-氧代)膦酸酯
4-溴苯乙烯(0.184g,1mmol)或者4-溴肉桂酸(0.227g,1mmol)，H-亚磷酸二乙基酯(0.276g,2mmol),CuSO4·5H2O(0.026g,0.1mmol),乙腈10mL于25 mL的三口烧瓶中，在油浴中加热到40℃，在此温度下继续反应4h，用TLC板检测反应进程，待反应完毕后，用二氯甲烷萃取(15x 3mL)，合并有机相，用Na2SO4干燥，减压蒸馏除去溶剂，经柱层析分离(石油醚/乙酸乙酯,V/V＝1:1)，即得黄色油状目标化合物，产率75％。
1H NMR(CDCl3,400MHz,)δ:7.86(d,2H,J＝8.4Hz),7.59(d,2H,J＝7.6Hz),4.15-4.08(m,4H),3.58(d,2H,J＝22.8Hz),1.27(t,6H,J＝8.8Hz)；13C NMR(CDCl3,100MHz)；δ:190.9(d,JP-C＝6.7Hz),135.2,131.9,130.6,129.1,62.8(d,JP-C＝6.5Hz),38.6(d,JP-C＝128.4Hz),16.3(d,JP-C＝6.2Hz)；31P NMR(CDCl3,400MHz)δ:19.3；HRMS:calcd forC12H16BrO4P[M+H]+335.0042,found335.0041.
实施例10二乙基-(2-(4-硝基苯基)-2-氧代)膦酸酯
4-硝基苯乙烯(0.149g,1mmol)或者4-硝基肉桂酸(0.193g,1mmol)，H-亚磷酸二乙基酯(0.276g,2mmol),CuSO4·5H2O(0.026g,0.1mmol),甲苯10mL于25mL的三口烧瓶中，在油浴中加热到50℃，在此温度下继续反应3h，用TLC板检测反应进程，待反应完毕后，用二氯甲烷萃取(15x 3mL)，合并有机相，用Na2SO4干燥，减压蒸馏除去溶剂，经柱层析分离(石油醚/乙酸乙酯,V/V＝1:1)，即得黄色油状目标化合物，产率70％。
1H NMR(CDCl3,400MHz,)δ:8.31(d,2H,J＝8.8Hz),8.18(d,2H,J＝8.8Hz),4.18-4.11(m,4H),3.67(d,2H,J＝23.2Hz),1.28(t,6H,J＝7.2Hz)；13C NMR(CDCl3,100MHz)；δ:190.6(d,JP-C＝6.7Hz),150.6,140.8,130.2,1233.8,63.0(d,JP-C＝6.5Hz),39.2(d,JP-C＝128.0Hz),16.3(d,JP-C＝6.3Hz)；31P NMR(CDCl3,400MHz)δ:18.7；HRMS:calcd forC12H16NO6P[M+H]+302.0788,found 302.0791.实施例11二乙基-(1-甲基-2-苯基)-2-氧代)膦酸酯
β-甲基苯乙烯(0.118g,1mmol)或者α-甲基肉桂酸(0.162g,1mmol)，H- 亚磷酸二乙基酯(0.276g,2mmol),CuSO4·5H2O(0.026g,0.1mmol),乙腈10mL于25mL的三口烧瓶中，在油浴中加热到60℃，在此温度下继续反应2h，用TLC板检测反应进程，待反应完毕后，用二氯甲烷萃取(15x 3mL)，合并有机相，用Na2SO4干燥，减压蒸馏除去溶剂，经柱层析分离(石油醚/乙酸乙酯,V/V＝1:1)，即得黄色油状目标化合物，产率70％。
1H NMR(CDCl3,400MHz,)δ:8.02(d,2H,J＝7.2Hz),7.59(t,1H,J＝7.6Hz),7.49(t,2H,J＝7.6Hz),4.26-4.06(m,5H),1.56(dd,3H,J＝5.6Hz,18.0Hz),1.30(t,6H,J＝7.2Hz)；13C NMR(CDCl3,100MHz)；δ:196.5(d,JP-C＝5.0Hz),136.9,133.3,128.8,128.5,62.7(dd,J＝6.8Hz,JP-C＝10.3Hz),41.3(d,JP-C＝129.5Hz),16.3(dd,JP-C＝6.0Hz,14.5Hz),12.2(d,JP-C＝6.6Hz)；31P NMR(CDCl3,400MHz)δ:23.4；HRMS:calcd for C13H19O4P[M+H]+271.1094,found 271.1094.
实施例12二乙基-(2-呋喃)-2-氧代)膦酸酯
2-呋喃丙烯酸(0.138g,1mmol)，H-亚磷酸二乙基酯(0.276g,2mmol),CuSO4·5H2O(0.026g,0.1mmol),乙腈10mL于25mL的三口烧瓶中，在油浴中加热到60℃，在此温度下继续反应2h，用TLC板检测反应进程，待反应完毕后，用二氯甲烷萃取(15x 3mL)，合并有机相，用Na2SO4干燥，减压蒸馏除去溶剂，经柱层析分离(石油醚/乙酸乙酯,V/V＝1:1)，即得黄色油状目标化合物，产率71％。
1H NMR(CDCl3,400MHz,)δ:7.56(s,1H),7.23(d,1H,J＝3.2Hz),6.50(q,1H,J＝1.2Hz,3.6Hz),4.10-4.03(m,4H),3.42(d,2H,J＝22.4Hz),1.21(t,6H,J＝6.8Hz)；13C NMR(CDCl3,100MHz)；δ:179.9(d,JP-C＝6.9Hz),152.2,147.2,119.0,112.7,62.6(d,JP-C＝6.4Hz),38.1(d,JP-C＝129.1Hz),16.2(d,JP-C＝6.3Hz)；31P NMR(CDCl3,400MHz)δ:19.5；HRMS:calcd for C10H15O5P[M+H]+247.0730,found 247.0736.
实施例13二乙基-(2-正丁基-2-氧代)膦酸酯
正己烯(0.84g,1mmol)或己烯酸(0.128g,1mmol)，H-亚磷酸二乙基酯(0.276g,2mmol),CuSO4·5H2O(0.026g,0.1mmol),乙腈10mL于25mL的三口烧瓶中，在油浴中加热到60℃，在此温度下继续反应2h，用TLC板检测反应进程，待反应完毕后，用二氯甲烷萃取(15x3mL)，合并有机相，用Na2SO4干燥，减压蒸馏除去溶剂，经柱层析分离(石油醚/乙酸乙酯,V/V＝1:1)，即得黄色油状目标化合物，产率41％。
1H NMR(CDCl3,400MHz,)δ:4.10-4.03(m,4H),3.42(d,2H,J＝22.4Hz),2.41(t,2H,J＝8.8Hz),1.53(m,2H),1.29-1.36(m,8H)，0.92(t 3H,J＝14.8Hz)；13C NMR(CDCl3,100MHz)；δ:194.5(d,JP-C＝6.9Hz),62.6(d,JP-C＝6.4Hz),38.1(d,JP-C＝129.1Hz),43.9,31.3,22.9,22.4,16.2(d,JP-C＝6.3Hz),14.1；31P NMR(CDCl3,400MHz)δ:21.6；HRMS:calcdfor C10H22O4P[M+H]+237.1250,found 237.1255.。
Claims (5)
1.合成通式 ( I )所示一类β-羰基膦酸酯衍生物的方法，其特征在于，通过如下步骤实现：首先将烯烃衍生物或烯酸衍生物和H-亚磷酸酯溶解在有机溶剂中，然后加入CuSO4·5H2O做催化剂，在 40℃-70℃下反应；待反应结束后，使反应体系冷却至室温，经萃取，干燥，减压蒸馏除去溶剂，用石油醚和乙酸乙酯做为洗脱剂，经柱层析分离得到β-羰基膦酸酯衍生物；
( I )
其中，X代表如下基团：-H, -COOH; R代表苯基或取代苯基或呋喃基或烷基，其中苯基上的取代基为：-CH3，-OCH3，-F，-Cl，-Br，-I， -NO2，-COCH3，-NHCOCH3，烷基为C4-C12的烷基；R’代表如下基团：H, -CH3；R1和R2分别代表如下基团：-OCH3，-OCH2CH3，-OCH2CH2CH3，-OCH2CH2CH2CH3，-OCH(CH3)2，-OCH2Ph，-CH3，-CH2CH3，-CH2CH2CH3，-CH2Ph，-Ph，-O-Ph。
2.如权利要求1所述的合成β-羰基膦酸酯衍生物的方法，其特征在于，
X代表如下基团：-H, -COOH; R代表苯基或取代苯基或呋喃基或烷基，其中苯基上的取代基为：-CH3，-OCH3，-F，-Cl，-Br，-I， -NO2，烷基为C4-C12的烷基；R’代表H, -CH3；R1和R2代表如下基团：-OCH3，-OCH2CH3，-OCH2CH2CH3，-OCH2CH2CH2CH3，-OCH(CH3)2，-OCH2Ph， -CH2Ph，-Ph，-O-Ph。
3.如权利要求1所述的合成β-羰基膦酸酯衍生物的方法，其特征在于，
所述的反应溶剂为乙腈、甲苯、二氧六环、甲醇、乙醇、二氯甲烷、氯仿、THF或DMSO。
4.如权利要求1所述的合成β-羰基膦酸酯衍生物的方法，其特征在于，反应溶剂选乙腈，反应温度选60℃。
5.如权利要求1所述的合成β-羰基膦酸酯衍生物的方法，其特征在于，烯烃或烯酸衍生物与H-亚磷酸酯和CuSO4·5H2O摩尔比为1 : 2 : 0.1。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610627616.0A CN106279274B (zh) | 2016-08-01 | 2016-08-01 | 一种通过烯烃合成β‑羰基膦酸酯衍生物的制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610627616.0A CN106279274B (zh) | 2016-08-01 | 2016-08-01 | 一种通过烯烃合成β‑羰基膦酸酯衍生物的制备方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106279274A CN106279274A (zh) | 2017-01-04 |
| CN106279274B true CN106279274B (zh) | 2017-11-14 |
Family
ID=57664536
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610627616.0A Expired - Fee Related CN106279274B (zh) | 2016-08-01 | 2016-08-01 | 一种通过烯烃合成β‑羰基膦酸酯衍生物的制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106279274B (zh) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113773345B (zh) * | 2021-10-07 | 2024-05-03 | 湖南科技学院 | 一种制备β-羰基膦酸酯类化合物的方法 |
| CN114213457B (zh) * | 2022-01-21 | 2022-09-09 | 杭州师范大学 | 一种化工中间体有机膦及其衍生物的制备方法 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102924511B (zh) * | 2011-08-11 | 2016-03-23 | 成都地奥制药集团有限公司 | β-羰基膦酸酯化合物的制备方法 |
| CN104341449A (zh) * | 2014-09-30 | 2015-02-11 | 苏州大学 | 一种β-羰基膦酸酯衍生物的制备方法 |
| CN104370960B (zh) * | 2014-09-30 | 2017-08-01 | 苏州大学 | 一种β‑羟基膦酸酯衍生物的制备方法 |
| CN104497044B (zh) * | 2014-12-11 | 2017-04-05 | 华侨大学 | 一种制备β‑羰基膦酸酯的方法 |
-
2016
- 2016-08-01 CN CN201610627616.0A patent/CN106279274B/zh not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN106279274A (zh) | 2017-01-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101910159B (zh) | 杂环取代吡啶衍生物的制备方法 | |
| CN106279274B (zh) | 一种通过烯烃合成β‑羰基膦酸酯衍生物的制备方法 | |
| KR20100096207A (ko) | 헤테로사이클릭 고리 및 포스폰옥시메틸기 치환성 피리딘 유도체, 및 이를 포함하는 항진균제 | |
| CA2112283A1 (en) | Thiazolidinedione derivatives, their production and use | |
| Olszewski | Asymmetric synthesis of α-hydroxymethylphosphonates and phosphonic acids via hydrophosphonylation of aldehydes with chiral H-phosphonate | |
| CN102924511A (zh) | β-羰基膦酸酯化合物的制备方法 | |
| Liu et al. | I2O5/DBU mediated direct α-phosphoryloxylation of ketones with H-phosphonates leading to α-hydroxyketone phosphates | |
| CN101146812B (zh) | 光学活性铵盐化合物、其制造中间体和制造方法 | |
| CN106892942A (zh) | 一种β‑胺基乙基膦酸衍生物的制备方法 | |
| CN104277072B (zh) | 一种(e)-2-芳基乙烯基膦酸酯衍生物的制备方法 | |
| CN105732619A (zh) | 一种5,6,7,8-四氢吡啶并[2,3-d]嘧啶类化合物的合成方法 | |
| Shoberu et al. | Phosphinoyl radical-initiated vicinal hydroxy-phosphorylation of alkenes | |
| Yuan et al. | Silver-catalyzed synthesis of 2-arylvinylphosphonates by cross-coupling of β-nitrostyrenes with H-phosphites | |
| CN105566384A (zh) | 一种(E)-2-芳基-α,β-不饱和羰基膦酸酯衍生物的制备方法 | |
| CN100408587C (zh) | 手性膦硫脲化合物、合成方法及其应用 | |
| CN101085769A (zh) | 一种α－吡喃酮类衍生物的合成方法 | |
| CN112500433A (zh) | 一种磷酸特地唑胺的制备方法 | |
| CN108586531A (zh) | 一种2-膦酰基喹喔啉类化合物及其制备方法 | |
| Bhadury et al. | An effective route to fluorine containing asymmetric α‐aminophosphonates using chiral Bronsted acid catalyst | |
| CN105037428B (zh) | 一种香豆素‑3‑膦酸酯衍生物的制备方法 | |
| Rahm et al. | Preparation of chiral enantiopure 2-(hydroxyalkyl) pyridine derivatives. Use of the chiral pool | |
| CN105272997A (zh) | 含二氟炔丙基的化合物、制备方法及应用 | |
| CN104945434B (zh) | (2﹣二取代膦苯基)-1-烷基-吲哚膦配体及其合成方法和应用 | |
| CN105037422A (zh) | 一种吲哚膦酸酯衍生物的制备方法 | |
| Shevchuk et al. | Multigram Synthesis of Difluoromethylene Phosphonic and Phosphinic Amides and Phosphine Oxides via Formal [2, 3]-Sigmatropic Allyl Phosphite–Allylphosphonate Rearrangement |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information |
Inventor after: Li Xu Inventor after: Li Yuning Inventor after: Zhang Xin Inventor after: Liu Haitao Inventor after: Hao Xudong Inventor after: Chen Qian Inventor after: Wang Jianli Inventor after: Guo Libing Inventor after: Wang Jinliang Inventor after: Zhou Xiaonan Inventor before: Li Xu Inventor before: Chen Qian Inventor before: Liu Haitao Inventor before: Wang Jianli Inventor before: Hao Xudong Inventor before: Guo Libing Inventor before: Wang Jinliang Inventor before: Zhou Xiaonan Inventor before: Li Yuning |
|
| CB03 | Change of inventor or designer information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20171114 Termination date: 20210801 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |