CN116063348A - 一种基于新型磷-碳键偶联反应合成芳基磷化合物的方法 - Google Patents
一种基于新型磷-碳键偶联反应合成芳基磷化合物的方法 Download PDFInfo
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- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 42
- 239000011574 phosphorus Substances 0.000 title claims abstract description 40
- -1 aryl phosphorus compound Chemical class 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 14
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 13
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 31
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 12
- 150000003624 transition metals Chemical class 0.000 claims abstract description 12
- 238000006880 cross-coupling reaction Methods 0.000 claims abstract description 8
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 5
- 125000003282 alkyl amino group Chemical group 0.000 claims abstract description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims abstract description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- 238000003786 synthesis reaction Methods 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 229940117389 dichlorobenzene Drugs 0.000 claims description 2
- IZWRXCGNSVOSAT-UHFFFAOYSA-L dichloronickel;diphenyl(propyl)phosphane Chemical compound Cl[Ni]Cl.C=1C=CC=CC=1P(CCC)C1=CC=CC=C1 IZWRXCGNSVOSAT-UHFFFAOYSA-L 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- WMKGGPCROCCUDY-UHFFFAOYSA-N 1,5-diphenylpenta-1,4-dien-3-one Chemical compound C=1C=CC=CC=1C=CC(=O)C=CC1=CC=CC=C1 WMKGGPCROCCUDY-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 239000000758 substrate Substances 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract 1
- 229910052794 bromium Chemical group 0.000 abstract 1
- 239000000460 chlorine Substances 0.000 abstract 1
- 125000001072 heteroaryl group Chemical group 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 13
- 238000005481 NMR spectroscopy Methods 0.000 description 12
- 238000004009 13C{1H}-NMR spectroscopy Methods 0.000 description 9
- 238000000607 proton-decoupled 31P nuclear magnetic resonance spectroscopy Methods 0.000 description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000010898 silica gel chromatography Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- JXBAVRIYDKLCOE-UHFFFAOYSA-N [C].[P] Chemical compound [C].[P] JXBAVRIYDKLCOE-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 150000002903 organophosphorus compounds Chemical class 0.000 description 2
- 150000003003 phosphines Chemical class 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UKSZBOKPHAQOMP-SVLSSHOZSA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 UKSZBOKPHAQOMP-SVLSSHOZSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- YNHIGQDRGKUECZ-UHFFFAOYSA-N dichloropalladium;triphenylphosphanium Chemical compound Cl[Pd]Cl.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-N 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000171 higher toxicity Toxicity 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- CCRMAATUKBYMPA-UHFFFAOYSA-N trimethyltin Chemical compound C[Sn](C)C.C[Sn](C)C CCRMAATUKBYMPA-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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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
- C07F9/5022—Aromatic phosphines (P-C aromatic linkage)
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Abstract
本发明公开了一种基于新型磷‑碳键偶联反应合成芳基磷化合物的方法。本发明的芳基磷化合物的化学式为：R1 3‑nPArn，所述的芳基磷化合物是由卤化磷试剂R1 3‑nPXn和芳基三烷基锡试剂ArSnR2 3在过渡金属催化剂的催化下发生交叉偶联反应进行合成；其中，R1为苯基、烷基或烷胺基，X为氯原子或溴原子，R2为甲基或正丁基，Ar为苯基、取代苯基、芳杂基或取代杂芳基。本发明的方法能以较好的收率合成芳基磷化合物，且本发明的合成方法具有底物兼容性好、反应条件温和、副产物少、易分离纯化的优点。
Description
技术领域
本发明涉及一种基于新型磷-碳键偶联反应合成芳基磷化合物的方法，属于有机合成技术领域。
背景技术
芳基磷是一类重要的有机磷化合物，在医药合成、有机合成、材料等领域均扮演着重要角色[1-4]。目前，三芳基磷化合物合成的常用方法是使用卤化磷与有机锂、有机锌、有机镁或有机汞等活泼金属有机试剂直接反应。这些金属有机试剂普遍具有较高的活性，对水、氧气极其敏感，不利于长期储藏，并且在实验中需要使用非常繁琐和严格的操作。同时，这些金属有机试剂普遍具有较强的亲核性，因而对反应底物的取代基具有较高要求。例如，这些金属有机试剂对氟(F)、腈基(CN)、醛/羰基等取代基团并不兼容。此外，有机汞试剂还具有较高的毒性，如实验操作不当，会对实验者的身体健康造成极大损害。
针对上述三芳基磷化合物合成的局限性，科研人员近年来开始利用过渡金属催化的方法来构筑磷-碳键[6,7]。该方法为医药合成、有机合成、材料等领域的发展提供了更大的支持。相较于过渡金属催化碳-碳偶联反应，过渡金属催化磷-碳偶联的方法比较单一。磷试剂(如亚磷酸二烷基酯、次膦酸酯、伯膦、仲膦、三芳基膦)通常作为亲核试剂参与磷-碳偶联反应(图1)。虽然磷中心形成单个磷-碳键已经具有较高的选择性和产率，但是单个磷中心形成多个磷-碳键仍然具有很大难度。到目前为止，只有少数文献报道了单个磷中心形成三个磷-碳键的反应[8,9]，但是，该反应仅限于炔碳类底物。
参考文献：
[1]Xie C,Smaligo A J,Song X R,et al.Phosphorus-Based Catalysis[J].ACSCentral Science,2021,7(4):536-558.
[2]Guo H C,Fan Y C,Sun Z H,et al.Phosphine Organocatalysis[J].Chemical Reviews,2018,118(20):10049-10293.
[3]Hirai M,Tanaka N,Sakai M,et al.Structurally Constrained Boron-,Nitrogen-,Silicon-,and Phosphorus-Centered Polycyclic pi-Conjugated Systems[J].Chemical Reviews,2019,119(14):8291-8331.
[4]Orton G R F,Pilgrim B S,Champness N R.The chemistry of phosphinesin constrained,well-defined microenvironments[J].Chemical Society Reviews,2021.
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发明内容
本发明所要解决的技术问题是：如何利用含磷-卤键的商业化的磷试剂与有机锡试剂发生交叉偶联形成一个或多个磷-碳键，以合成芳基磷化合物。
为了解决上述技术问题，本发明提供了一种基于新型磷-碳键偶联反应合成芳基磷化合物的方法，所述的芳基磷化合物的化学式为：R1 3-nPArn，所述的芳基磷化合物是由卤化磷试剂R1 3-nPXn和芳基三烷基锡试剂ArSnR2 3溶于溶剂中，然后在过渡金属催化剂的催化下加热发生交叉偶联反应进行合成；
其中，n为1、2或3，R1为苯基、烷基或烷胺基，卤原子X为氯原子或溴原子，R2为甲基或正丁基，Ar为下列结构式中的任意一种：
上述结构式中的FG为H、烷基、烷氧基、F原子、F原子取代的烷基、苯基或三甲基硅基。
优选地，所述的烷胺基为二乙基胺基，所述的烷基为甲基或叔丁基，所述的F原子取代的烷基为三氟甲基。
优选地，所述过渡金属催化剂选自钯催化剂和/或镍催化剂，所述过渡金属催化剂的用量为卤化磷试剂摩尔量的5～20％。
更优选地，所述钯催化剂选自醋酸钯、二氯双三苯基磷钯、三二亚苄基丙酮二钯和四(三苯基磷)钯中的至少一种；所述镍催化剂选自二乙酰丙酮镍和1,3-双(二苯基膦丙烷)二氯化镍中的一种或两种。
最优选地，所述过渡金属催化剂选自钯催化剂，所述钯催化剂选自醋酸钯和/或四(三苯基磷)钯。
优选地，所述的溶剂选自苯、甲苯、二甲苯、氯苯、二氯苯、四氢呋喃和二氧六环中的至少一种。
优选地，所述卤化磷试剂和芳基三烷基锡试剂的投料量按照卤化磷试剂中卤原子X和芳基三烷基锡的摩尔比为1:2～3的比例进行计算。
优选地，所述交叉偶联反应的温度为20～150℃，时间为8～72h。
更优选地，所述反应的时间为20～30h。
优选地，所述芳基三烷基锡试剂ArSnR2 3是通过下式反应制备而成：
上述芳基三烷基锡试剂可以通过常见的方法合成，如文献报道的芳基卤化合物在钯催化下用六甲基二锡进行取代。
与现有技术相比，本发明的有益效果在于：
(1)本发明提供了一种在过渡金属催化剂的催化下，利用含磷-卤键的商业化的磷试剂与有机锡试剂发生交叉偶联形成磷-碳键，合成芳基磷化合物的新方法，该方法能以较好的收率合成芳基磷化合物；
(2)本发明的合成方法具有底物兼容性好、反应条件温和、副产物少、易分离纯化的优点。
附图说明
图1为传统的磷-碳键偶联机理示意图；
图2为本发明提供的芳基磷化合物的合成路线。
具体实施方式
为使本发明更明显易懂，兹以优选实施例，作详细说明如下。
在下述实施例中，所使用到的试剂、材料以及仪器如没有特殊的说明，均可商购获得。
本发明提供了一种芳基磷化合物的合成方法，合成路线如下：
本发明通过卤化磷试剂与芳基三烷基锡试剂发生交叉偶联形成磷-碳键合成芳基磷化合物，下表列出了采用该方法合成的一部分有机磷化合物：
其中，芳基三烷基锡试剂通过以下方法合成：
在无水无氧条件下将化合物1(1eq.)溶解于干燥的THF中(0.1M)，在-78℃下逐滴加入n-BuLi的正己烷溶液(1.05～1.1eq.,1～2.5M)。之后缓慢回至室温搅拌3h。反应结束之后将反应液倒入水中，用二氯甲烷萃取，取有机相，用无水Na2SO4干燥后过滤，旋蒸除去低沸点溶剂，最后经过减压蒸馏得到目标有机锡化合物。
实施例1
化合物a～h的合成：取干燥的史莱克管，在无水无氧条件下将醋酸钯(5mmol％)、PCl3(0.5mmol)和ArSnR2 3(3.75mmol)溶解于1mL甲苯溶剂中，在100℃下加热24h后，通过硅胶柱层析分离得到产物。
化合物a，分离产率97％。1H NMR(400MHz，CDCl3)：δ7.58(dd，J＝1.1，5.0Hz，1H)，7.36(ddd，J＝1.1，3.5，6.3Hz，1H)，7.09(ddd，J＝1.4，3.5，4.9Hz，1H)；13C{1H}NMR(101MHz，CDCl3)：δ135.51(d，J＝27.6Hz)，132.02，128.05(d，J＝8.3Hz)；31P{1H}NMR(162MHz，CDCl3)：δ-46.25。
化合物b，分离收率73％。1H NMR(400MHz，CDCl3)：δ7.87-7.74(m，6H)，7.70(dd，J＝7.3，0.8Hz，3H)，7.42-7.30(m，6H)；13C{1H}NMR(101MHz，CDCl3)：δ144.02，140.08(d，J＝9.4Hz)，138.80(d，J＝23.7Hz)，133.31(d，J＝28.2Hz)，125.38，124.66，124.27，122.48；31P{1H}NMR(162MHz，CDCl3)：δ-38.66。
化合物c，分离产率61％。1H NMR(400MHz，CDCl3)：δ7.66(d，J＝1.7Hz，3H)，6.80(ddd，J＝0.7，1.9，3.1Hz，3H)，6.41(dt，J＝1.8，3.4Hz，3H)；13C{1H}NMR(101MHz，CDCl3)：δ98.04，97.65，89.99(d，J＝7.5Hz)，86.97(d，J＝1.9Hz)；31P{1H}NMR(162MHz，CDCl3)：δ-77.75.
化合物d，分离产率52％。1H NMR(500MHz，CDCl3)：δ7.58(dd，J＝1.2，7.7Hz，3H)，7.54(d，J＝8.3Hz，3H)，7.33(ddd，J＝1.3，7.1，8.4Hz，3H)，7.28-7.26(m，3H)，7.24(t，J＝7.4Hz，3H)；13C{1H}NMR(126MHz，CDCl3)：δ158.27(d，J＝3.2Hz)，150.99(d，J＝4.8Hz)，127.97(d，J＝6.5Hz)，125.73，123.17，121.60，118.53(d，J＝22.6Hz)，111.90；31P{1H}NMR(202MHz，CDCl3)：δ-67.72。
化合物e，分离产率56％。1H NMR(400MHz，CDCl3)：δ8.72(dt，J＝1.4，4.8Hz，3H)，7.62(tt，J＝2.0，7.7Hz，3H)，7.41(ddt，J＝1.1，2.1，7.8Hz，3H)，7.22(ddt，J＝1.2，4.8，7.5Hz，3H)；13C{1H}NMR(101MHz，CDCl3)：δ161.97，150.60(d，J＝11.9Hz)，136.07，129.43(d，J＝20.0Hz)，122.98；31P{1H}NMR(162MHz，CDCl3)：δ-0.72。
化合物f，分离产率31％。1H NMR(400MHz，CDCl3)：δ6.82(q，J＝2.4Hz，3H)，6.14(ddd，J＝1.0，2.6，3.6Hz，3H)，5.98(ddd，J＝0.9，1.8，3.6Hz，3H)，3.62(s，9H)；13C{1H}NMR(101MHz，CDCl3)：δ126.60(d，J＝3.0Hz)，125.58(d，J＝10.2Hz)，118.27(d，J＝5.0Hz)，108.49(d，J＝3.7Hz)，35.24(d，J＝12.3Hz)；31P{1H}NMR(162MHz，CDCl3):δ-73.07.
化合物g，分离产率10％。1H NMR(400MHz，CDCl3)：δ7.23(dd，J＝8.7，1.4Hz，6H)，6.88(dd，J＝8.7，1.0Hz，6H)，3.80(s，9H)；13C{1H}NMR(101MHz，CDCl3)：δ160.24，135.08(d，J＝20.8Hz)，128.94，114.27(d，J＝7.7Hz)，55.32；31P{1H}NMR(162MHz，CDCl3)：δ-10.16。
化合物h，分离产率62％。1H NMR(400MHz，CDCl3)：δ7.59-7.53(m，6H)，7.40-7.30(m，9H)；13C{1H}NMR(101MHz，CDCl3)：δ132.26(d，J＝2.0Hz)，129.55，128.45，122.18，105.80(d，J＝11.4Hz)，79.53(d，J＝6.7Hz)；31P{1H}NMR(162MHz，CDCl3)：δ-88.30。
实施例2
化合物i的合成：取干燥的史莱克管，在无水无氧条件下将四(三苯基磷)钯(5mmol％)、PhPCl2(0.5mmol)和ArSnR2 3(2.5mmol)溶解于1mL甲苯溶剂中，在100℃下加热24h后，通过硅胶柱层析分离得到产物。
化合物i，分离收率88％。1H NMR(400MHz，CDCl3)：δ7.60(dd，J＝4.9，1.1Hz，2H)，7.42-7.29(m，7H)，7.12(ddd，J＝4.8，3.5，1.3Hz，2H)；13C{1H}NMR(101MHz，CDCl3)：δ138.90，138.48(d，J＝24.3Hz)，136.30(d，J＝27.4Hz)，132.24，132.06，128.93，128.48(d，J＝6.8Hz)，128.09(d，J＝8.3Hz)；31P{1H}NMR(162MHz，CDCl3)：δ-34.11。
实施例3
化合物j的合成：取干燥的史莱克管，在无水无氧条件下将醋酸钯(5mmol％)、Ph2PCl(0.5mmol)和ArSnR2 3(1.25mmol)溶解于1mL甲苯溶剂中，在100℃下加热24h后，通过硅胶柱层析(石油醚作洗脱剂)分离得到产物。
化合物j，分离收率76％。1H NMR(400MHz，CDCl3)：δ7.59(dd，J＝4.9，1.0Hz，1H)，7.44-7.27(m，11H)，7.13(td，J＝4.1，1.2Hz，1H)；13C NMR(101MHz，CDCl3):δ138.12，138.03，136.48(d，J＝26.4Hz)，133.23(d，J＝19.7Hz)，132.16，128.99，128.58(d，J＝7.0Hz)，128.18(d，J＝7.9Hz)；31P NMR(162MHz，CDCl3)：δ-19.94。
上述实施例仅为本发明的优选实施例，并非对本发明任何形式上和实质上的限制，应当指出，对于本技术领域的普通技术人员，在不脱离本发明的前提下，还将可以做出若干改进和补充，这些改进和补充也应视为本发明的保护范围。
Claims (6)
1.一种基于新型磷-碳键偶联反应合成芳基磷化合物的方法，其特征在于，所述的芳基磷化合物的化学式为：R1 3-nPArn，所述的芳基磷化合物是由卤化磷试剂R1 3-nPXn和芳基三烷基锡试剂ArSnR2 3溶于溶剂中，然后在过渡金属催化剂的催化下加热发生交叉偶联反应进行合成；
其中，n为1、2或3，R1为苯基、烷基或烷胺基，卤原子X为氯原子或溴原子，R2为甲基或正丁基，Ar为下列结构式中的任意一种：
上述结构式中的FG为H、烷基、烷氧基、F原子、F原子取代的烷基、苯基或三甲基硅基。
2.如权利要求1所述的基于新型磷-碳键偶联反应合成芳基磷化合物的方法，其特征在于，所述的过渡金属催化剂选自钯催化剂和/或镍催化剂，所述过渡金属催化剂的用量为卤化磷试剂摩尔量的5～20％。
3.如权利要求2所述的基于新型磷-碳键偶联反应合成芳基磷化合物的方法，其特征在于，所述钯催化剂选自醋酸钯、二氯双三苯基磷钯、三二亚苄基丙酮二钯和四(三苯基磷)钯中的至少一种；所述镍催化剂选自二乙酰丙酮镍和1,3-双(二苯基膦丙烷)二氯化镍中的一种或两种。
4.如权利要求1所述的基于新型磷-碳键偶联反应合成芳基磷化合物的方法，其特征在于，所述的溶剂选自苯、甲苯、二甲苯、氯苯、二氯苯、四氢呋喃和二氧六环中的至少一种。
5.如权利要求1所述的基于新型磷-碳键偶联反应合成芳基磷化合物的方法，其特征在于，所述卤化磷试剂和芳基三烷基锡试剂的投料量按照卤化磷试剂中卤原子X和芳基三烷基锡的摩尔比为1:2～3的比例进行计算。
6.如权利要求1所述的基于新型磷-碳键偶联反应合成芳基磷化合物的方法，其特征在于，所述交叉偶联反应的温度为20～150℃，时间为8～72h。
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