CN113980052A - 一种单磷酸酯配体及其制备方法和在氢甲酰化反应中的应用 - Google Patents
一种单磷酸酯配体及其制备方法和在氢甲酰化反应中的应用 Download PDFInfo
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- 239000003446 ligand Substances 0.000 title claims abstract description 45
- 238000007037 hydroformylation reaction Methods 0.000 title claims abstract description 33
- 150000004712 monophosphates Chemical class 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- -1 Methyl Chemical group 0.000 claims description 39
- 239000010948 rhodium Substances 0.000 claims description 33
- 239000003054 catalyst Substances 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 229910052703 rhodium Inorganic materials 0.000 claims description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 10
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 10
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 10
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 10
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 229940125782 compound 2 Drugs 0.000 claims description 6
- 229940126214 compound 3 Drugs 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000001624 naphthyl group Chemical group 0.000 claims description 6
- 239000005977 Ethylene Substances 0.000 claims description 5
- 229940125904 compound 1 Drugs 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-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
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 claims description 3
- 150000004696 coordination complex Chemical class 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 claims description 3
- MBVAQOHBPXKYMF-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;rhodium Chemical class [Rh].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MBVAQOHBPXKYMF-LNTINUHCSA-N 0.000 claims description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- DVWQNBIUTWDZMW-UHFFFAOYSA-N 1-naphthalen-1-ylnaphthalen-2-ol Chemical class C1=CC=C2C(C3=C4C=CC=CC4=CC=C3O)=CC=CC2=C1 DVWQNBIUTWDZMW-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 230000000536 complexating effect Effects 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl chloride Substances ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical group [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims 1
- 238000010668 complexation reaction Methods 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 6
- 239000001301 oxygen Substances 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 230000009257 reactivity Effects 0.000 abstract description 3
- 239000002815 homogeneous catalyst Substances 0.000 abstract 1
- 150000001299 aldehydes Chemical class 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006757 chemical reactions by type Methods 0.000 description 3
- 238000011010 flushing procedure Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 description 1
- CRVWRJPBOGHSNN-UHFFFAOYSA-N [Rh+].C1(=CC=CC=C1)PC1=CC=CC=C1.C1=CCCC=CCC1 Chemical class [Rh+].C1(=CC=CC=C1)PC1=CC=CC=C1.C1=CCCC=CCC1 CRVWRJPBOGHSNN-UHFFFAOYSA-N 0.000 description 1
- XSRWPJFTHDOKTA-UHFFFAOYSA-M [Rh]Cl.C1CC=CCCC=C1 Chemical class [Rh]Cl.C1CC=CCCC=C1 XSRWPJFTHDOKTA-UHFFFAOYSA-M 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- NBBJYMSMWIIQGU-UHFFFAOYSA-N propionic aldehyde Natural products CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
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- 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
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65744—Esters of oxyacids of phosphorus condensed with carbocyclic or heterocyclic rings or ring systems
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
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- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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Abstract
本发明属于均相催化剂配体技术领域,具体为一种单磷酸酯配体及其制备方法和在氢甲酰化反应中的应用。本发明公开的单磷酸酯配体,其结构式如下式所示。此配体在氢甲酰化反应中表现出高的反应活性,在水氧条件下性质稳定,且对于异构产物有较高的选择性。
Description
技术领域
本发明属于催化反应配体技术领域,具体涉及单磷酸酯配体及其制备方法和应用。
背景技术
烯烃氢甲酰化制备醛类化合物是目前工业化应用规模最大的均相催化反应,其醛类产品的年产量以达到1200万吨。氢甲酰化反应所用到的催化剂主要为Rh基和Co基络合物催化剂。其中Rh基催化剂活性高,所用反应条件温和,且对产物醛的化学选择性高而得到了广泛的应用,因此,Rh基催化剂已经成为氢甲酰化工业化装置的主流催化剂。芳基乙烯在Rh基络合物催化剂的催化下与合成气经氢甲酰化反应选择性的制备芳基丙醛,具有特殊结构的芳基丙烯的异构醛产物可作为药物中间体有着重要的应用。通过配体结构的改变控制氢甲酰化反应过程中的区域选择性,诱导反应向异构化路径进行,进而提高异构醛与构醛的比例,是高选择性获取异构醛的技术关键,也是该反应亟待解决的技术难题。配体的结构对于催化剂的活性和选择性有着关键的影响,双齿及多齿膦配体是目前研究的热点,大量具有新型双齿或多齿结构的亚磷酸酯配体被报导,BASF,Dow,Shell等外国化工企业也申请了众多关于亚磷酸酯配体在氢甲酰化反应中应用的专利,而目前关于单磷酸酯配体及其催化剂的报导却很少。亚磷酸酯配体在芳基乙烯氢甲酰化反应中有着较高的区域选择性,但是对水,微量氧或者加热条件敏感,容易分解,造成催化剂的活性以及对异构醛的选择性快速下降。
发明内容
本发明的目的在于提供一种单磷酸酯配体及其制备方法以及在氢甲酰化反应中的应用。本发明提供的催化剂在水氧条件下性质稳定,在氢甲酰化反应中表现出良好的反应活性,且对于异构醛产物有着高的选择性。
本发明提供用于氢甲酰化反应的单磷酸酯配体,其结构式如式(I)所示:
其中,所述R0为H,C1-C6烷基,甲氧基,或苯基。
所述X为下述结构式(i)、(ii)和(iii)中之一种:
式中,R1=R2,R3=R4,R5=R6,且/或R1,R2,R3,R4,R5和R6分别独立地为H,F,Cl,Br,NO2,甲基,乙基,正丙基,异丙基,正丁基,异丁基,叔丁基,甲氧基,乙氧基,异丙氧基,苯基,萘基。
上述式结构式(I)所示单磷酸酯配体,优选以下结构式中一种:
其中,R1=R2,R3=R4,R5=R6,且/或R1,R2,R3,R4,R5和R6分别独立地为H,F,Cl,Br,NO2,甲基,乙基,正丙基,异丙基,正丁基,异丁基,叔丁基,甲氧基,乙氧基,异丙氧基,苯基,萘基。R0为H,C1-C6烷基,甲氧基,或苯基。
本发明提供的上述单磷酸酯配体的制备方法,具体为:由化合物1、化合物2或化合物3,化合物4在碱的催化作用下于有机溶剂中制备得到所述化合物(I);这里,化合物1为邻位取代的联萘二酚,化合物2为邻位取代的螺环二酚,化合物3为邻位取代的环己烷稠合螺二氢茚二酚,化合物4为O,O-1,1'-联萘基磷酰氯,其结构式依次为:
其中,R1=R2,R3=R4,R5=R6,且/或R1,R2,R3,R4,R5和R6分别独立地为H,F,Cl,Br,NO2,甲基,乙基,正丙基,异丙基,正丁基,异丁基,叔丁基,甲氧基,乙氧基,异丙氧基,苯基,萘基。R0为H,C1-C6烷基,甲氧基,或苯基。
反应式分为三中:
反应式(一)
反应式(二)
反应式(三)
其中,所述碱为正丁基锂、二异丙基乙基胺、乙二胺、二乙胺、三乙胺、三丁胺中的一种或几种的组合;所述有机溶剂为四氢呋喃、N,N-二甲基甲酰胺、甲苯、***、甲基叔丁基醚、二氧六环、二氯甲烷、二氯乙烷中一种或多种。
其中,由化合物1、化合物2或化合物3,与化合物4的摩尔比例为1:1到1:6之间。
本发明还提供前述单磷酸酯配体在氢甲酰化反应中的应用。实验表明,单磷酸酯配体在氢甲酰化反应中表现出高的反应活性,在水氧条件下性质稳定,且对于异构产物有较高的选择性。
所述单磷酸酯配体在氢甲酰化反应中的应用,具体步骤为:
(1)首先,制备催化剂:将铑金属化合物与单磷酸酯配体在有机溶剂中原位络合形成Rh金属络合物催化剂;
其中,所述铑金属化合物选自铑的卤化物、羰基铑络合物、乙酰丙酮基铑络合物,环辛二烯基铑络合物的一种或多种;优选的铑金属化合物为RhCl3、Rh(CO)2acac、Rh4(CO)12或Rh6(CO)16,二苯基膦(1,5-环辛二烯)铑(I)二聚体,(1,5-环辛二烯)氯铑(I)二聚体中的一种或多种。
以铑金属化合物中铑原子物质的量计,铑金属化合物和单磷酸酯配体的摩尔比为1:1-1:50(1:(1-50)),优选为1:3-1:8(1:(3-8))。
(2)用所述催化剂催化氢甲酰化反应的底物。
所述底物具有以下结构的芳基乙烯类化合物:
其中,R1为甲基,乙基,正丙基,异丙基,叔丁基,异丁基,甲氧基,氰基,羟基,卤素原子中的一种或几种;R1取代基在苯环上1-6任意位置。R2为氢,甲基,乙基,正丙基,异丙基,叔丁基,异丁基,甲氧基,氰基,羟基,卤素原子中的一种或几种;R2取代基在苯环上1-6除R1之外的任意位置。
芳基乙烯氢甲酰化反应中,优选芳基烯烃具有以下结构之一种(分别记为化合物6、化合物7、化合物8、化合物9):
其中,所述氢甲酰化反应的反应温度为20-100℃,优选为30-90℃。氢甲酰化反应的反应时间为0.5-48h。
其中,所述氢甲酰化反应的所需的气体为一氧化碳与氢气的混合气,两种气体的比例在1:5到5:1之间,优选为1:1;反应压力为0.1-5MPa,优选为2-4MPa;
其中,所选有机溶剂为甲苯,二甲苯,均三甲苯,二氯甲烷,正己烷,环己烷,二氧六环,四氢呋喃或其组合。
其中,所述催化剂在反应体系中的用量以铑金属化合物的质量计为0.001-1%,优选为0.05-0.5%;
其中,一氧化碳和氢气的摩尔比为3:1-1:3,优选为2:1-1:2。
本发明所述的芳基乙烯氢甲酰化反应,具体过程如下:
(1)向反应釜持续性通入惰性气体,在气流保护下,分别加入单磷酸酯配体,Rh金属化合物和有机溶剂,并在惰性气体保护下搅拌1-2h;
(2)在惰性气体保护下向反应釜内加入反应物的有机溶液,随后冲入合成气,于指定温度下搅拌,待反应结束后放出气体,获得产物。
本发明有益效果
本发明提供了一种单磷酸酯配体,制备方法简单,水氧稳定性高于双齿及多齿亚磷酸酯配体,其与Rh金属化合物形成的催化剂对水,氧有着高的稳定性。特别地,本发明所述的单磷酸酯配体在芳基乙烯氢甲酰化反应中具有高的反应活性以及对异构醛的选择性,特别适合大规模工业化生产。
具体实施方式
为了更好的理解本发明的技术方案,下面通过实施例对上述路线及方法进行具体描述,但本发明的内容不局限于以下实施例。
实施例1,(S,R)-5aa的制备
在史莱克管中依次加入1aa(5mmol),4aa(5mmol),5倍当量的三乙胺,20ml四氢呋喃。加料完毕后氮气置换三次,于40℃反应16小时,待反应结束后蒸干溶剂,采用柱层析方法将产物得到产物(S,R)-5aa,分离收率为90%。
按照实施例1中所述的方法,采用不用的手性二酚试剂与4a反应,可相应的制备得到不同的配体,具体为33种,分别记为配体L2-L34;如表1所示。
表1,单磷酸酯配体L2-L34
实施例2,单磷酸酯配体在氢甲酰化反应中的应用
本实施例中在惰性气体保护下,将0.01mmolRh(CO)acac与0.03mmold单磷酸酯配体在20ml甲苯中混合搅拌2h,得到Rh络合物催化剂。
将上述溶液加入到高压反应釜中,同时加入20mmol苯乙烯,通入合成气置换6次后,将压力冲至3.0MPa,加热温度升至35℃搅拌24h,待反应结束后泄压。产品经过气相色谱分析。
表2不同单磷酸酯配体在苯乙烯氢甲酰反应中的活性表现
实施例3具有特殊结构的芳基乙烯氢甲酰化反应
本实施例在无水无氧氛围下,将0.01mmolRh(CO)acac与0.03mmold单磷酸酯配体在20ml甲苯中混合搅拌2h,得到Rh络合物催化剂。将上述溶液加入到高压反应釜中,同时加入20mmol苯乙烯,通入合成气置换6次后,将压力冲至4.0MPa,加热温度升至40℃搅拌24h,待反应结束后泄压。产品经过气相色谱分析。
表3具有特殊结构的芳基乙烯氢甲酰化反应结果
Claims (10)
3.一种如权利要求1或2所述的单磷酸酯配体的制备方法,其特征在于,由化合物1、化合物2或化合物3,与化合物4在碱的催化作用下于有机溶剂中制备得到所述化合物(I);这里,化合物1为邻位取代的联萘二酚,化合物2为邻位取代的螺环二酚,化合物3为邻位取代的环己烷稠合螺二氢茚二酚,化合物4为O,O-1,1'-联萘基磷酰氯,其结构式依次为:
其中,R1=R2,R3=R4,R5=R6,且/或R1,R2,R3,R4,R5和R6分别独立地为H,F,Cl,Br,NO2,甲基,乙基,正丙基,异丙基,正丁基,异丁基,叔丁基,甲氧基,乙氧基,异丙氧基,苯基,萘基。R0为H,C1-C6烷基,甲氧基,或苯基;
其反应式分为三种:
反应式(一):
反应式(二):
反应式(三):
4.根据权利要求3所述的单磷酸酯配体的制备方法,其特征在于,所述碱为正丁基锂、二异丙基乙基胺、乙二胺、二乙胺、三乙胺、三丁胺中的一种或几种的组合;所述有机溶剂为四氢呋喃、N,N-二甲基甲酰胺、甲苯、***、甲基叔丁基醚、二氧六环、二氯甲烷、二氯乙烷中一种或多种;由化合物、化合物2或化合物3,与化合物4的摩尔比例为1:1到1:6之间。
6.根据权利要求5所述的应用,其特征在于,所述铑金属化合物选自铑的卤化物、羰基铑络合物、乙酰丙酮基铑络合物,环辛二烯基铑络合物的一种或多种;
以铑金属化合物中铑原子物质的量计,铑金属化合物和单磷酸酯配体的摩尔比为1:1-1:50(1:(1-50))。
8.根据权利要求6所述的应用,其特征在于,氢甲酰化反应中所用有机溶剂为甲苯、二甲苯、均三甲苯、二氯甲烷、正己烷、环己烷、二氧六环、四氢呋喃中的一种或几种。
9.根据权利要求6所述的应用,其特征在于,氢甲酰化反应中,所述催化剂在反应体系中的用量以铑金属化合物的质量计为0.001-1%;氢甲酰化反应的所需的气体为一氧化碳与氢气的混合气,一氧化碳和氢气的摩尔比为3:1-1:3。
10.一种基于权利要求1或2所述单磷酸酯配体的催化剂,是由铑金属化合物与单磷酸酯配体在有机溶剂中原位络合形成的Rh金属络合物催化剂。
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