CN111440213A - 一种过渡金属催化芳香硝基c-no2转化为c-p键方法 - Google Patents
一种过渡金属催化芳香硝基c-no2转化为c-p键方法 Download PDFInfo
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- CN111440213A CN111440213A CN202010266280.6A CN202010266280A CN111440213A CN 111440213 A CN111440213 A CN 111440213A CN 202010266280 A CN202010266280 A CN 202010266280A CN 111440213 A CN111440213 A CN 111440213A
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- aromatic nitro
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- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 17
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 13
- -1 aromatic nitro compound Chemical class 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 18
- 150000002903 organophosphorus compounds Chemical class 0.000 claims abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000003446 ligand Substances 0.000 claims abstract description 9
- 230000009471 action Effects 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 239000000758 substrate Substances 0.000 claims abstract description 6
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 238000004440 column chromatography Methods 0.000 claims abstract description 5
- 238000001953 recrystallisation Methods 0.000 claims abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 12
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 125000001072 heteroaryl group Chemical group 0.000 claims description 6
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 claims description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 claims description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- 125000001624 naphthyl group Chemical group 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 3
- JRTIUDXYIUKIIE-KZUMESAESA-N (1z,5z)-cycloocta-1,5-diene;nickel Chemical compound [Ni].C\1C\C=C/CC\C=C/1.C\1C\C=C/CC\C=C/1 JRTIUDXYIUKIIE-KZUMESAESA-N 0.000 claims description 2
- LSMWOQFDLBIYPM-UHFFFAOYSA-N 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydro-2h-imidazol-1-ium-2-ide Chemical compound CC1=CC(C)=CC(C)=C1N1[C-]=[N+](C=2C(=CC(C)=CC=2C)C)CC1 LSMWOQFDLBIYPM-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 2
- 229910002666 PdCl2 Inorganic materials 0.000 claims description 2
- MUALRAIOVNYAIW-UHFFFAOYSA-N binap Chemical compound C1=CC=CC=C1P(C=1C(=C2C=CC=CC2=CC=1)C=1C2=CC=CC=C2C=CC=1P(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 MUALRAIOVNYAIW-UHFFFAOYSA-N 0.000 claims description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- MXFYYFVVIIWKFE-UHFFFAOYSA-N dicyclohexyl-[2-[2,6-di(propan-2-yloxy)phenyl]phenyl]phosphane Chemical compound CC(C)OC1=CC=CC(OC(C)C)=C1C1=CC=CC=C1P(C1CCCCC1)C1CCCCC1 MXFYYFVVIIWKFE-UHFFFAOYSA-N 0.000 claims description 2
- WDVGNXKCFBOKDF-UHFFFAOYSA-N dicyclohexyl-[3,6-dimethoxy-2-[2,4,6-tri(propan-2-yl)phenyl]phenyl]phosphane Chemical compound COC1=CC=C(OC)C(C=2C(=CC(=CC=2C(C)C)C(C)C)C(C)C)=C1P(C1CCCCC1)C1CCCCC1 WDVGNXKCFBOKDF-UHFFFAOYSA-N 0.000 claims description 2
- IOUCSUBTZWXKTA-UHFFFAOYSA-N dipotassium;dioxido(oxo)tin Chemical compound [K+].[K+].[O-][Sn]([O-])=O IOUCSUBTZWXKTA-UHFFFAOYSA-N 0.000 claims description 2
- JCYWCSGERIELPG-UHFFFAOYSA-N imes Chemical compound CC1=CC(C)=CC(C)=C1N1C=CN(C=2C(=CC(C)=CC=2C)C)[C]1 JCYWCSGERIELPG-UHFFFAOYSA-N 0.000 claims description 2
- LZWQNOHZMQIFBX-UHFFFAOYSA-N lithium;2-methylpropan-2-olate Chemical compound [Li+].CC(C)(C)[O-] LZWQNOHZMQIFBX-UHFFFAOYSA-N 0.000 claims description 2
- YOCBOYPGZVFUCQ-UHFFFAOYSA-L nickel(2+);tricyclohexylphosphane;dichloride Chemical compound Cl[Ni]Cl.C1CCCCC1P(C1CCCCC1)C1CCCCC1.C1CCCCC1P(C1CCCCC1)C1CCCCC1 YOCBOYPGZVFUCQ-UHFFFAOYSA-L 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical group [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 claims description 2
- 235000011056 potassium acetate Nutrition 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- VNFWTIYUKDMAOP-UHFFFAOYSA-N sphos Chemical compound COC1=CC=CC(OC)=C1C1=CC=CC=C1P(C1CCCCC1)C1CCCCC1 VNFWTIYUKDMAOP-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 claims description 2
- UGOMMVLRQDMAQQ-UHFFFAOYSA-N xphos Chemical compound CC(C)C1=CC(C(C)C)=CC(C(C)C)=C1C1=CC=CC=C1P(C1CCCCC1)C1CCCCC1 UGOMMVLRQDMAQQ-UHFFFAOYSA-N 0.000 claims description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims 1
- 239000003814 drug Substances 0.000 abstract description 3
- 229940079593 drug Drugs 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 239000000575 pesticide Substances 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 32
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- 238000004679 31P NMR spectroscopy Methods 0.000 description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 10
- 238000005859 coupling reaction Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- LXNAVEXFUKBNMK-UHFFFAOYSA-N acetic acid;palladium Chemical compound [Pd].CC(O)=O.CC(O)=O LXNAVEXFUKBNMK-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 239000012039 electrophile Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000007832 transition metal-catalyzed coupling reaction Methods 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-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
- C07F9/5022—Aromatic phosphines (P-C aromatic linkage)
-
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- 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
- C07F9/505—Preparation; Separation; Purification; Stabilisation
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- 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
- C07F9/505—Preparation; Separation; Purification; Stabilisation
- C07F9/5063—Preparation; Separation; Purification; Stabilisation from compounds having the structure P-H or P-Heteroatom, in which one or more of such bonds are converted into P-C bonds
- C07F9/5072—Preparation; Separation; Purification; Stabilisation from compounds having the structure P-H or P-Heteroatom, in which one or more of such bonds are converted into P-C bonds from starting materials having the structure P-H
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- 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
- C07F9/505—Preparation; Separation; Purification; Stabilisation
- C07F9/5063—Preparation; Separation; Purification; Stabilisation from compounds having the structure P-H or P-Heteroatom, in which one or more of such bonds are converted into P-C bonds
- C07F9/5077—Preparation; Separation; Purification; Stabilisation from compounds having the structure P-H or P-Heteroatom, in which one or more of such bonds are converted into P-C bonds from starting materials having the structure P-Metal, including R2P-M+
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- 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
- C07F9/505—Preparation; Separation; Purification; Stabilisation
- C07F9/5063—Preparation; Separation; Purification; Stabilisation from compounds having the structure P-H or P-Heteroatom, in which one or more of such bonds are converted into P-C bonds
- C07F9/5081—Preparation; Separation; Purification; Stabilisation from compounds having the structure P-H or P-Heteroatom, in which one or more of such bonds are converted into P-C bonds from starting materials having the structure >P-Het, Het being an heteroatom different from Hal or Metal
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- C07F9/50—Organo-phosphines
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Abstract
本发明提出一种过渡金属催化芳香硝基C‑NO2转化为C‑P键方法，包括在氮气保护氛围下，在有机溶剂中，以芳香硝基化合物和有机磷化合物为底物，通过过渡金属催化剂和配体的作用，在碱的作用下进行反应，经柱色谱或者重结晶方法得到芳香有机磷化合物。本发明方法操作简单、价格便宜、产物转化率高、底物适用性好；可用于合成有机磷化合物，在农药、医药、材料等领域均有广泛的应用价值。
Description
技术领域
本发明属于有机催化合成技术领域，具体涉及一种过渡金属催化芳香硝基C-NO2转化为C-P键方法。
背景技术
过渡金属催化的偶联反应是构建碳-碳(杂)键最有效和最常使用的合成方法之一。传统的偶联反应通常将(类)卤代芳烃作为亲电偶联组分，与金属试剂、亲核试剂、烯烃或炔烃发生多种偶联反应,构筑多种碳-碳或碳-杂键[J.Organomet.Chem.,2002,653]。此外，芳基重氮盐[Chem.Rev.,2006,106,4622.]、芳基肼[Chin.J.Org.Chem.,2016,36,1790]、芳香羧酸[J.Chem.Soc.Rev.,2011,40,5030]和芳香亚磺酸[Eur.J.Org.Chem.,2016,408；Chem.-Eur.J.,2016,22,8663]也被用作亲电偶联组分，参与多种偶联反应。尽管上述亲电偶联组分已被广泛用于偶联反应中，但拓展更多高效、价廉和来源易得的亲电组分还是非常有意义的。
芳香硝基化合物是制备芳香族化合物的重要原料，其来源广泛、价格便宜，同时它也是一种含能化合物的前体，可以作为新的亲电体来替代卤代芳烃。过渡金属催化芳基硝基化合物发生Suzuki交叉偶联反应[Angew.Chem.,Int.Ed.,2000,112,974；Angew.Chem.,Int.Ed.,2006,45,2720；J.Am.Chem.Soc.,1982,104,3727；Org.Lett.,2013,15,3966；Org.Lett.,2011,13,1726；Chin.J.Org.Chem.,2016,36,1021；RSC Adv.,2016,6,33380；Eur.J.Org.Chem.,2017,3244；Catal.Commun.,2017,94,33；J.Am.Chem.Soc.,2017,139,9423；Angew.Chem.,Int.Ed.,2017,56,13307]构建C-O、C-S、C-C和C-N键已有相关文献报道，但在构建C-P键未见相关文献和专利报道。因此，开发过渡金属催化芳基硝基化合物与有机磷化合物进行反应显得尤为重要。
发明内容
(一)要解决的技术问题
本发明提出一种过渡金属催化芳香硝基C-NO2转化为C-P键方法，以解决如何实现利用过渡金属催化芳香硝基化合物与有机磷化合物进行C-P键构建的技术问题。
(二)技术方案
为了解决上述技术问题，本发明提出一种过渡金属催化芳香硝基C-NO2转化为C-P键方法，该方法包括，在氮气保护氛围下，在有机溶剂中，以芳香硝基化合物和有机磷化合物为底物，通过过渡金属催化剂和配体的作用，在碱的作用下进行反应，经柱色谱或者重结晶方法得到芳香有机磷化合物；其中，芳香硝基化合物的结构式为Ar-NO2，其中Ar为苯基、取代苯基、萘基、芳杂基或取代芳杂基；
有机磷化合物的结构式为：
其中，R，R’独立地为苯基、取代苯基或烷基，Y独立地为TMS、K、Na、Li、H或者OH。
进一步地，过渡金属催化剂为Pd(acac)2、Pd(OAc)2、PdCl2、Pd(PPh3)2Cl2、Pd(dppf)Cl2、Pd2(dba)3、Pd(TFA)2、Pd2(allyl)2Cl2、Ni(COD)2、NiCl2(PCy3)2、NiCl2(PPh3)2中的任意一种。
进一步地，配体为BrettPhos、SPhos、IPr、IMes、SIMes、XPhos、RuPhos、PtBu3、DPPF、PPh3、PCy3、BINAP中的任意一种。
进一步地，有机溶剂为二氧六环、甲苯、四氢呋喃、N,N-二甲基甲酰胺、甲基叔丁基醚、正庚烷或乙二醇二甲醚中的任意一种。
进一步地，碱为叔丁醇钾、叔丁醇钠、叔丁醇锂、甲醇钠、乙醇钠、无水锡酸钾、碳酸钾、氟化铯、碳酸铯、乙酸钾或氢氧化钾中的任意一种。
进一步地，反应的温度为80～160℃，反应时间为12～48h，催化剂、配体和芳香硝基化合物的摩尔比为1:(1～10):(5～100)，芳香硝基化合物、有机磷化合物和碱的摩尔比为1:(1～5):(1～10)。
进一步地，反应的温度为120～140℃，反应时间为24～48h。
(三)有益效果
本发明提出一种过渡金属催化芳香硝基C-NO2转化为C-P键方法，包括在氮气保护氛围下，在有机溶剂中，以芳香硝基化合物和有机磷化合物为底物，通过过渡金属催化剂和配体的作用，在碱的作用下进行反应，经柱色谱或者重结晶方法得到芳香有机磷化合物。本发明方法操作简单、价格便宜、产物转化率高、底物适用性好；可用于合成有机磷化合物，在农药、医药、材料等领域均有广泛的应用价值。
本发明的有益效果具体包括：
1.本发明首次提出过渡金属催化芳基硝基化合物与有机磷化合物的偶联反应；
2.本发明中涉及的反应操作简单、原料来源广、收率高；
3.本发明可用于合成一系列有机磷化合物，在医药、农药、光电材料等领域均有广泛的应用前景。
具体实施方式
为使本发明的目的、内容和优点更加清楚，下面结合实施例，对本发明的具体实施方式作进一步详细描述。
本发明提出一种过渡金属催化芳香硝基C-NO2转化为C-P键方法，反应方程式如下：
芳香硝基化合物的结构式为Ar-NO2，其中Ar为苯基、取代苯基、萘基、芳杂基或取代芳杂基；
有机磷化合物的结构式为：
其中，R，R’独立地为苯基、取代苯基或烷基，Y独立地为TMS、K、Na、Li、H或者OH。
催化剂与配体的选择对产物的产率有所影响，本实施例主要介绍钯催化剂的具体操作方法，但本发明并不限于该类催化体系。
具体操作步骤如下：在氮气保护下，加入0.5mmol芳香硝基化合物，0.6mmol有机磷化合物，10％mmol Pd(dppf)Cl2和1.5mmol叔丁醇钾，抽真空充氮气三次。利用注射器加入10mL二氧六环，油浴加热到140℃，反应24h。冷却室温，TLC监测，加入水和少量醋酸，乙醚萃取，旋除溶剂，柱色谱分离获得相应的偶联产物。
实施例1
白色固体，收率90％。1H NMR(500MHz,Chloroform)δ7.61–7.41(m,6H),7.41–7.29(m,6H),7.05–6.81(m,2H),3.79(s,3H).31P NMR(202MHz,Chloroform)δ-6.40(s)。
实施例2
白色固体，收率93％。1H NMR(500MHz,Chloroform)δ8.16–7.82(m,2H),7.73–7.54(m,2H),7.54–7.22(m,9H),4.30(q,J＝11.8Hz,2H),1.30(t,J＝11.8Hz,3H).31P NMR(202MHz,Chloroform)δ-6.45(s)。采用NiCl2(PCy3)2，产品收率在86％，采用镍催化剂，效果要比钯效果差一点。
实施例3
白色固体，收率60％。1H NMR(500MHz,Chloroform)δ7.58–7.13(m,14H),2.34(s,3H).31P NMR(202MHz,Chloroform)δ-17.6(s)。
实施例4
白色固体，收率70％。1H NMR(500MHz,Chloroform)δ7.52–7.41(m,4H),7.40–7.27(m,6H),7.08-7.01(m,2H),6.82–6.68(m,2H).31P NMR(202MHz,Chloroform)δ-6.35(s)。
实施例5
白色固体，收率79％。1H NMR(500MHz,Chloroform)δ7.64–7.50(m,2H),7.50–7.42(m,4H),7.42–7.26(m,8H).31P NMR(202MHz,Chloroform)δ-6.40(s)。
实施例6
白色固体，收率91％。1H NMR(500MHz,Chloroform)δ7.96–7.79(m,3H),7.74-7.71(m,1H),7.57–7.42(m,7H),7.41–7.28(m,6H).31P NMR(202MHz,Chloroform)δ-13.3(s)。
实施例7
淡黄色液体，收率80％。1H NMR(500MHz,Chloroform)δ7.58–7.41(m,4H),7.39–7.25(m,6H),7.24–7.09(m,2H),6.94(dd,J＝15.9,7.6Hz,1H).31P NMR(202MHz,Chloroform)δ-19.3(s)。
实施例8
淡黄色液体，收率92％。1H NMR(500MHz,Chloroform)δ7.67–7.39(m,4H),7.41–7.22(m,3H),7.06–6.60(m,2H),3.79(s,3H),0.98(d,J＝4.2Hz,3H).31P NMR(202MHz,Chloroform)δ-27.2(s)。
实施例9
白色固体，收率85％。1HNMR(500MHz,Chloroform)δ7.79-7.72(m,6H),7.67–7.38(m,6H),7.13(d,J＝7.5Hz,2H),3.79(s,3H).31P NMR(202MHz,Chloroform)δ22.0(s)。
实施例10
淡黄色油状物，收率46％。1H NMR(500MHz,Chloroform)δ7.61–7.40(m,10H),7.41–7.20(m,13H),2.34(s,3H).31P NMR(202MHz,Chloroform)δ-17.6(s)。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明技术原理的前提下，还可以做出若干改进和变形，这些改进和变形也应视为本发明的保护范围。
Claims (7)
1.一种过渡金属催化芳香硝基C-NO2转化为C-P键方法，其特征在于，所述方法包括，在氮气保护氛围下，在有机溶剂中，以芳香硝基化合物和有机磷化合物为底物，通过过渡金属催化剂和配体的作用，在碱的作用下进行反应，经柱色谱或者重结晶方法得到芳香有机磷化合物；其中，所述芳香硝基化合物的结构式为Ar-NO2，其中Ar为苯基、取代苯基、萘基、芳杂基或取代芳杂基；
所述有机磷化合物的结构式为：
其中，R，R’独立地为苯基、取代苯基或烷基，Y独立地为TMS、K、Na、Li、H或者OH。
2.如权利要求1所述的方法，其特征在于，所述过渡金属催化剂为Pd(acac)2、Pd(OAc)2、PdCl2、Pd(PPh3)2Cl2、Pd(dppf)Cl2、Pd2(dba)3、Pd(TFA)2、Pd2(allyl)2Cl2、Ni(COD)2、NiCl2(PCy3)2、NiCl2(PPh3)2中的任意一种。
3.如权利要求1所述的方法，其特征在于，所述配体为BrettPhos、SPhos、IPr、IMes、SIMes、XPhos、RuPhos、PtBu3、DPPF、PPh3、PCy3、BINAP中的任意一种。
4.如权利要求1所述的方法，其特征在于，所述有机溶剂为二氧六环、甲苯、四氢呋喃、N,N-二甲基甲酰胺、甲基叔丁基醚、正庚烷或乙二醇二甲醚中的任意一种。
5.如权利要求1所述的方法，其特征在于，所述碱为叔丁醇钾、叔丁醇钠、叔丁醇锂、甲醇钠、乙醇钠、无水锡酸钾、碳酸钾、氟化铯、碳酸铯、乙酸钾或氢氧化钾中的任意一种。
6.如权利要求1所述的方法，其特征在于，所述反应的温度为80～160℃，反应时间为12～48h，催化剂、配体和芳香硝基化合物的摩尔比为1:(1～10):(5～100)，芳香硝基化合物、有机磷化合物和碱的摩尔比为1:(1～5):(1～10)。
7.如权利要求6所述的方法，其特征在于，所述反应的温度为120～140℃，反应时间为24～48h。
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