CN106040305A - 一种烯烃异构催化剂体系及其应用 - Google Patents
一种烯烃异构催化剂体系及其应用 Download PDFInfo
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- CN106040305A CN106040305A CN201610425077.2A CN201610425077A CN106040305A CN 106040305 A CN106040305 A CN 106040305A CN 201610425077 A CN201610425077 A CN 201610425077A CN 106040305 A CN106040305 A CN 106040305A
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- alkene
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- 239000003054 catalyst Substances 0.000 title claims abstract description 79
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 63
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 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 abstract description 58
- 239000012327 Ruthenium complex Substances 0.000 claims abstract description 16
- 230000003197 catalytic effect Effects 0.000 claims abstract description 16
- 238000003419 tautomerization reaction Methods 0.000 claims abstract description 11
- JGLMVXWAHNTPRF-CMDGGOBGSA-N CCN1N=C(C)C=C1C(=O)NC1=NC2=CC(=CC(OC)=C2N1C\C=C\CN1C(NC(=O)C2=CC(C)=NN2CC)=NC2=CC(=CC(OCCCN3CCOCC3)=C12)C(N)=O)C(N)=O Chemical compound CCN1N=C(C)C=C1C(=O)NC1=NC2=CC(=CC(OC)=C2N1C\C=C\CN1C(NC(=O)C2=CC(C)=NN2CC)=NC2=CC(=CC(OCCCN3CCOCC3)=C12)C(N)=O)C(N)=O JGLMVXWAHNTPRF-CMDGGOBGSA-N 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract 2
- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 claims description 74
- 238000006317 isomerization reaction Methods 0.000 claims description 44
- NPBVQXIMTZKSBA-UHFFFAOYSA-N Chavibetol Natural products COC1=CC=C(CC=C)C=C1O NPBVQXIMTZKSBA-UHFFFAOYSA-N 0.000 claims description 37
- 239000005770 Eugenol Substances 0.000 claims description 37
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 claims description 37
- 229960002217 eugenol Drugs 0.000 claims description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- -1 hydroxy functional groups alkene Chemical class 0.000 claims description 15
- 238000006555 catalytic reaction Methods 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 7
- 229930195733 hydrocarbon Natural products 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 6
- 125000004356 hydroxy functional group Chemical group O* 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 150000001225 Ytterbium Chemical class 0.000 claims description 3
- 159000000013 aluminium salts Chemical class 0.000 claims description 3
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 3
- 159000000009 barium salts Chemical class 0.000 claims description 3
- 159000000007 calcium salts Chemical class 0.000 claims description 3
- 150000002471 indium Chemical class 0.000 claims description 3
- 159000000003 magnesium salts Chemical class 0.000 claims description 3
- 150000003325 scandium Chemical class 0.000 claims description 3
- 159000000000 sodium salts Chemical class 0.000 claims description 3
- 150000003746 yttrium Chemical class 0.000 claims description 3
- 150000003751 zinc Chemical class 0.000 claims description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical group OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 29
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 101100030361 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) pph-3 gene Proteins 0.000 abstract 3
- 230000033116 oxidation-reduction process Effects 0.000 abstract 1
- RXUUYDXKHLUSHV-UHFFFAOYSA-N magnesium;trifluoromethanesulfonic acid Chemical compound [Mg].OS(=O)(=O)C(F)(F)F RXUUYDXKHLUSHV-UHFFFAOYSA-N 0.000 description 11
- BVOSSZSHBZQJOI-UHFFFAOYSA-N 1-Hexen-3-ol Chemical compound CCCC(O)C=C BVOSSZSHBZQJOI-UHFFFAOYSA-N 0.000 description 10
- 238000004587 chromatography analysis Methods 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 238000010813 internal standard method Methods 0.000 description 8
- 238000003760 magnetic stirring Methods 0.000 description 8
- 238000005070 sampling Methods 0.000 description 8
- 238000005481 NMR spectroscopy Methods 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
- 238000001514 detection method Methods 0.000 description 7
- 238000004821 distillation Methods 0.000 description 7
- 238000004817 gas chromatography Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 230000006837 decompression Effects 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical group FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 4
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 235000013599 spices Nutrition 0.000 description 2
- PJANXHGTPQOBST-VAWYXSNFSA-N trans-stilbene Chemical group C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 2
- 241000628997 Flos Species 0.000 description 1
- BJIOGJUNALELMI-ONEGZZNKSA-N Isoeugenol Natural products COC1=CC(\C=C\C)=CC=C1O BJIOGJUNALELMI-ONEGZZNKSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- UCJNCJZFRKZIHY-UHFFFAOYSA-N barium;trifluoromethanesulfonic acid Chemical compound [Ba].OS(=O)(=O)C(F)(F)F UCJNCJZFRKZIHY-UHFFFAOYSA-N 0.000 description 1
- CFSYYJNGCPTQRE-UHFFFAOYSA-N calcium;trifluoromethanesulfonic acid Chemical compound [Ca].OS(=O)(=O)C(F)(F)F CFSYYJNGCPTQRE-UHFFFAOYSA-N 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- BJIOGJUNALELMI-ARJAWSKDSA-N cis-isoeugenol Chemical compound COC1=CC(\C=C/C)=CC=C1O BJIOGJUNALELMI-ARJAWSKDSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003254 gasoline additive Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- KOCDJSLUDZGVJX-UHFFFAOYSA-N indium;trifluoromethanesulfonic acid Chemical compound [In].OS(=O)(=O)C(F)(F)F KOCDJSLUDZGVJX-UHFFFAOYSA-N 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- QUJLPICXDXFRSN-UHFFFAOYSA-N scandium;trifluoromethanesulfonic acid Chemical compound [Sc].OS(=O)(=O)C(F)(F)F QUJLPICXDXFRSN-UHFFFAOYSA-N 0.000 description 1
- HGJLYMGBCAKBLK-UHFFFAOYSA-N sodium;trifluoromethanesulfonic acid Chemical compound [Na].OS(=O)(=O)C(F)(F)F HGJLYMGBCAKBLK-UHFFFAOYSA-N 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N trans-Stilbene Natural products C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- BJIOGJUNALELMI-UHFFFAOYSA-N trans-isoeugenol Natural products COC1=CC(C=CC)=CC=C1O BJIOGJUNALELMI-UHFFFAOYSA-N 0.000 description 1
- AHZJKOKFZJYCLG-UHFFFAOYSA-K trifluoromethanesulfonate;ytterbium(3+) Chemical compound [Yb+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F AHZJKOKFZJYCLG-UHFFFAOYSA-K 0.000 description 1
- MRVDPBDPQPBGMS-UHFFFAOYSA-N trifluoromethanesulfonic acid;yttrium Chemical compound [Y].OS(=O)(=O)C(F)(F)F MRVDPBDPQPBGMS-UHFFFAOYSA-N 0.000 description 1
- NGOCMUBXJDDBLB-UHFFFAOYSA-N trifluoromethanesulfonic acid;zinc Chemical compound [Zn].OS(=O)(=O)C(F)(F)F NGOCMUBXJDDBLB-UHFFFAOYSA-N 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
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- B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
- B01J31/0227—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts being perfluorinated, i.e. comprising at least one perfluorinated moiety as substructure in case of polyfunctional compounds
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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C37/001—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by modification in a side chain
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- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/32—Preparation of ethers by isomerisation
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
- C07C45/512—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being a free hydroxyl group
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Abstract
本发明公开了一种烯烃异构催化剂体系及其应用。所述催化剂体系为钌配合物RuH2CO(PPh3)3和第二种金属盐溶于溶剂中形成的有机溶液，所述第二种金属盐为含有非氧化还原活性金属离子的金属盐类，所述钌配合物RuH2CO(PPh3)3和第二种金属盐的摩尔比在1:0.5至1:4之间，所述钌配合物RuH2CO(PPh3)3的浓度在0.5毫摩尔/升至5毫摩尔/升之间。本发明的催化剂体系可以应用于烯烃双键异构、烯烃顺反异构或含羟基官能团的烯烃的互变异构，解决了钌配合物在催化烯烃异构体系中对空气敏感和要求高温的难题，反应条件温和，催化剂利用率高，体系稳定，易于实现，成本低廉。
Description
技术领域
本发明属于有机催化领域，更具体地，涉及一种烯烃异构催化剂体系及其应用。
背景技术
烯烃的异构化反应是指将单一结构的烯烃异构成其同分异构体的反应。烯烃的异构化反应在烯烃的制备工业中有广泛的应用，异链烯烃如异丁烯和异戊烯是重要的基本有机原料，异丁烯主要用于汽油添加剂、甲基叔丁基醚、聚异丁烯的生产中，异戊烯则是生产农药、医药和香料的重要中间体之一。异丁香酚及以其为原料合成的系列产品在食用以及日化香精中均占重要地位，同时作为合成各种香料的中间体，其在工业生产中也有很大的需求。将烯烃异构化成内烯烃也是精炼工业中的一种重要的反应，至今仍在石油化工上占有极其重要的地位并扩展到有机合成领域，例如将长链烯烃异构化成为内烯烃，可以用作润滑中所用材料的前体。在一些天然产物的合成中，异构化的考虑为合成策略的实现和路线的简化提供了方法。
目前用于烯烃异构化的催化剂有很多。现有的多相催化剂，反应条件较为苛刻，不仅需要较高的反应温度(120～200℃)，而且还需要一定的反应压力，从而导致反应设备的设计和制造方面都需要较高的成本。均相的钌配合物催化剂也有一些报道，如一些钌-氢类的催化剂，但反应过程中都要求严格的无氧无水化操作(高压釜氮气保护)，且反应温度较高，适用的异构化反应类型单一，烯烃种类限制单一，不利于实际生产的操作和有机合成方法学的推广。
发明内容
针对现有技术的以上缺陷或改进需求，本发明提供了一种烯烃异构催化剂体系及其应用，其目的在于通过联合使用钌配合物和第二种金属盐形成的催化剂体系，在温和的反应条件下均相催化烯烃的双键异构、顺反异构以及互变异构，由此解决多相催化反应条件苛刻、成本过高、均相钌催化剂体系要求严格无氧无水的技术问题。
为实现上述目的，按照本发明的一个方面，提供了一种催化剂体系，所述催化剂体系为第一种金属盐和第二种金属盐溶于有机溶剂中形成的有机溶液，所述第一种金属盐为钌配合物RuH2CO(PPh3)3，所述第二种金属盐为含有非氧化还原活性金属离子的金属盐类，所述第一种金属盐和第二种金属盐的摩尔比在1:0.5至1:4之间，所述第一种金属盐的浓度在0.5毫摩尔/升至5毫摩尔/升之间。
优选地，所述第二种金属盐包括镁盐、锌盐、钡盐、铟盐、镱盐、钇盐、钪盐、铝盐、钙盐和/或钠盐。
优选地，所述第二种金属盐为三氟甲磺酸盐、氯盐、硝酸盐和/或硫酸盐。
优选地，所述有机溶剂为甲醇、乙醇、异丙醇、三氯甲烷和/或甲苯。
按照本发明的另一方面，提供了一种所述的催化剂体系的应用，其应用于催化烯烃异构，包括烯烃双键异构、烯烃顺反异构或含羟基官能团的烯烃的互变异构。
优选地，所述烯烃为烯丙基芳烃、链状烯烃、含羟基官能团烯烃或环状二烯烃，所述烯丙基芳烃优选丁香酚。
优选地，当应用于催化烯烃双键异构或烯烃顺反异构时，权利要求1～4任意一项所述的催化剂体系中钌配合物RuH2CO(PPh3)3与烯烃的摩尔比在1:100至1:1600之间，催化温度为50℃至90℃，反应时间在0.5小时至3小时之间。
优选地，当应用于催化含羟基官能团的烯烃的互变异构时，权利要求1至4任意一项所述的催化剂体系中钌配合物RuH2CO(PPh3)3与烯烃的摩尔比在1:100至1:600之间，钌配合物RuH2CO(PPh3)3的浓度在1毫摩尔/升至5毫摩尔/升之间，催化温度为50℃至90℃，反应时间在1小时至3小时之间。
总体而言，通过本发明所构思的以上技术方案与现有技术相比，能够取得下列有益效果。
(1)本发明提供的烯烃异构催化剂体系，催化条件温和，能在较低温度和常压下催化烯烃异构，从而削减反应设备的设计和制造成本。
(2)本发明提供的烯烃异构催化剂体系，尤其适用于催化烯丙基芳烃、链状端烯烃、链状内烯烃或环状二烯烃异构，催化效率高，反应产率高，催化剂用量少。
(3)本发明解决了钌催化剂均相催化烯烃异构反应中严格要求无氧环境的难题，避免了反应设备的设计和制造方面所需要的较高成本。
(4)本发明提供的催化剂体系适用于烯烃双键异构、互变异构、烯烃顺反异构，反应类型多样化，烯烃种类广泛，有利于有机合成方法学的建立。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。此外，下面所描述的本发明各个实施方式中所涉及到的技术特征只要彼此之间未构成冲突就可以相互组合。
本发明中，一种催化剂体系，其特征在于，所述催化剂体系为第一种金属盐和第二种金属盐溶于有机溶剂中形成的有机溶液，所述第一种金属盐为钌配合物RuH2CO(PPh3)3，所述第二种金属盐为含有非氧化还原活性金属离子的金属盐类，所述第一种金属盐和第二种金属盐的摩尔比在1:0.5至1:4之间，所述第一种金属盐的浓度在0.5毫摩尔/升至5毫摩尔/升之间。
所述有机溶剂为甲醇、乙醇、异丙醇、三氯甲烷和/或甲苯。
所述第二种金属盐为含有非氧化还原活性金属离子的金属盐类，包括镁盐、锌盐、钡盐、铟盐、镱盐、钇盐、钪盐、铝盐、钙盐和/或钠盐。
所述第二种金属盐为三氟甲磺酸盐、氯盐、硝酸盐和/或硫酸盐。
本发明提供的催化剂体系，应用于催化烯烃异构，包括烯烃双键异构、烯烃顺反异构或含羟基官能团的烯烃的互变异构。所述烯烃为烯丙基芳烃、链状烯烃、含羟基官能团烯烃或环状二烯烃，所述烯丙基芳烃优选丁香酚，所述含羟基官能团烯烃优选1-己烯-3-醇。
当应用于催化烯烃双键异构或烯烃顺反异构时，所述的催化剂体系中钌配合物RuH2CO(PPh3)3与烯烃的摩尔比在1:100至1:1600之间，催化温度为50℃至90℃，反应时间在0.5小时至3小时之间。
当应用于催化含羟基官能团的烯烃的互变异构时，所述的催化剂体系中钌配合物RuH2CO(PPh3)3与烯烃的摩尔比在1:100至1:600之间，钌配合物RuH2CO(PPh3)3的浓度在1毫摩尔/升至5毫摩尔/升之间，催化温度为50℃至90℃，反应时间在1小时至3小时之间。
所述催化剂体系在使用时，按照预先设定的比例和浓度配制好催化剂体系，加入搅拌磁子，立即放入加热到设定温度且底部装有磁力搅拌器的油浴中并开始计反应时间，反应一定时间后取样用气相色谱分析，色谱分析结果采用内标法计算烯烃转化率和异构化产率，反应液减压蒸馏得到反应产物，用核磁共振分析定性检测产物。
以下为实施例：
实施例1-6
(1)不同溶剂下催化丁香酚异构化反应
一种催化剂体系，为主催化剂RuH2CO(PPh3)3和第二种金属盐三氟甲磺酸镁的有机溶液，主催化剂和三氟甲磺酸镁的摩尔比为1:,2，主催化剂的浓度为设定值。应用上述催化剂体系催化丁香酚异构化反应，主催化剂RuH2CO(PPh3)3和丁香酚的摩尔比为1:200，加入搅拌磁子，立即放入加热到80℃且底部装有磁力搅拌器的油浴中并开始计反应时间。反应0.5小时后取样用气相色谱分析，色谱分析结果采用内标法计算丁香酚转化率和异构化产率。反应液减压蒸馏得到反应产物，用核磁共振分析定性检测产物。
不同反应溶剂下，丁香酚异构化反应结果见下表：
注：a的反应时间为2小时。
实施例7-17
(2)加入不同第二种金属盐催化丁香酚异构化反应
一种催化剂体系，为主催化剂RuH2CO(PPh3)3和第二种金属盐的乙醇溶液，主催化剂和第二种金属盐的摩尔比为1:2，主催化剂的浓度为1毫摩尔/升。应用上述催化剂体系催化丁香酚异构化反应，主催化剂RuH2CO(PPh3)3和丁香酚的摩尔比为1:200，加入搅拌磁子，立即放入加热到80℃且底部装有磁力搅拌器的油浴中并开始计反应时间。反应0.5小时后取样用气相色谱分析，色谱分析结果采用内标法计算丁香酚转化率和异构化产率。反应液减压蒸馏得到反应产物，用核磁共振分析定性检测产物。
通过加入不同第二种金属盐，丁香酚异构化反应结果见下表：
| 实施例 | 第二种金属盐 | 丁香酚转化率/％ | 异构化产率/％ |
| 7 | 三氟甲磺酸钪 | 84.7 | 81.2 |
| 8 | 三氟甲磺酸铟 | 82.5 | 78.9 |
| 9 | 三氟甲磺酸镱 | 86.3 | 80.2 |
| 10 | 三氟甲磺酸钇 | 85.9 | 79.8 |
| 11 | 三氟甲磺酸钙 | 77.4 | 73.8 |
| 12a | 三氟甲磺酸锌 | 64.1 | 60.2 |
| 13a | 三氟甲磺酸钡 | 99.4 | 95.1 |
| 14a | 三氟甲磺酸钠 | 93.0 | 89.7 |
| 15 | 六水合氯化镁 | 99.8 | 99.4 |
| 16 | 六水合硝酸镁 | 90.8 | 90.0 |
| 17 | 硫酸镁 | 86.7 | 84.3 |
注：a的反应时间为2小时。当其他实施例反应时间延长至1小时，上述丁香酚的转化率均可达到100％左右，异构化产率均在90％以上。
实施例18-24
(3)第二种金属盐不同添加量催化丁香酚异构化反应
一种催化剂体系，为主催化剂RuH2CO(PPh3)3和三氟甲磺酸镁的乙醇溶液，主催化剂和三氟甲磺酸镁的摩尔比为设定值，主催化剂的浓度为1毫摩尔/升。应用上述催化剂体系催化丁香酚异构化反应，主催化剂RuH2CO(PPh3)3和丁香酚的摩尔比分别为1:200和1:1000时，加入搅拌磁子，立即放入加热到80℃且底部装有磁力搅拌器的油浴中并开始计反应时间。反应0.5小时后取样用气相色谱分析，色谱分析结果采用内标法计算丁香酚转化率和异构化产率。反应液减压蒸馏得到反应产物，用核磁共振分析定性检测产物。
通过加入不同量的第二种金属盐，丁香酚异构化反应结果见下表：
当主催化剂和丁香酚的比例是1:1000时，可以通过延长反应时间进一步提高丁香酚转化率。
实施例25-32
(4)丁香酚的不同添加量下催化丁香酚异构化反应
一种催化剂体系，为主催化剂RuH2CO(PPh3)3和三氟甲磺酸镁的乙醇溶液，主催化剂和三氟甲磺酸镁的摩尔比为1:2，主催化剂的浓度为1毫摩尔/升。应用上述催化剂体系催化丁香酚异构化反应，主催化剂RuH2CO(PPh3)3和丁香酚的摩尔比为设定值，加入搅拌磁子，立即放入加热到80℃且底部装有磁力搅拌器的油浴中并开始计反应时间。反应0.5小时后取样用气相色谱分析，色谱分析结果采用内标法计算丁香酚转化率和异构化产率。反应液减压蒸馏得到反应产物，用核磁共振分析定性检测产物。
通过加入不同量的丁香酚，丁香酚异构化反应结果见下表：
当丁香酚的比例大于1000时，可以通过延长反应时间进一步提高丁香酚转化率。上述实施例24-26，反应时间延长至2小时，丁香酚的转化率均可达到100％左右，异构化产率均在90％以上。
实施例33-36
(5)不同的反应时间下催化丁香酚异构化反应
一种催化剂体系，为主催化剂RuH2CO(PPh3)3和三氟甲磺酸镁的乙醇溶液，主催化剂和三氟甲磺酸镁的摩尔比为1:2，主催化剂的浓度为1毫摩尔/升。应用上述催化剂体系催化丁香酚异构化反应，主催化剂RuH2CO(PPh3)3和丁香酚的摩尔比为1:1000，加入搅拌磁子，立即放入加热到80℃且底部装有磁力搅拌器的油浴中并开始计反应时间。反应一定时间后取样用气相色谱分析，色谱分析结果采用内标法计算丁香酚转化率和异构化产率。
通过不同反应时间，丁香酚异构化反应结果见下表：
| 实施例 | 反应时间/分钟 | 丁香酚转化率/％ | 异构化产率/％ |
| 33 | 5 | 41.0 | 37.7 |
| 34 | 20 | 84.2 | 79.4 |
| 35 | 40 | 96.0 | 92.3 |
| 36 | 60 | 98.7 | 95.1 |
实施例37-46
(6)催化剂体系催化不同烯烃异构化反应
一种催化剂体系，为主催化剂RuH2CO(PPh3)3和三氟甲磺酸镁的乙醇溶液，主催化剂和三氟甲磺酸镁的摩尔比为1:2，主催化剂的浓度为1毫摩尔/升。应用上述催化剂体系催化不同烯烃异构化反应，主催化剂RuH2CO(PPh3)3和烯烃的摩尔比为设定值，加入搅拌磁子，立即放入加热到设定温度且底部装有磁力搅拌器的油浴中并开始计反应时间。反应结束后取样用气相色谱分析，色谱分析结果采用内标法计算不同烯烃转化率和异构化产率。反应液减压蒸馏得到反应产物，用核磁共振分析定性检测产物。
该催化剂体系催化不同烯烃异构化反应结果见下表：
注：a选用甲苯做溶剂，第二种金属盐为三氟甲磺酸铝。实施例46为烯烃顺反异构，产物为反式-二苯乙烯。
实施例47-51
(7)催化剂体系催化1-己烯-3-醇互变异构
一种催化剂体系，为主催化剂RuH2CO(PPh3)3和三氟甲磺酸铝的甲苯溶液，主催化剂和三氟甲磺酸铝的摩尔比为1:2，主催化剂的浓度为设定值。应用上述催化剂体系催化1-己烯-3-醇反应，主催化剂RuH2CO(PPh3)3和烯烃的摩尔比为设定值，加入搅拌磁子，立即放入加热到设定温度且底部装有磁力搅拌器的油浴中并开始计反应时间。反应结束后取样用气相色谱分析，色谱分析结果采用内标法计算1-己烯-3-醇转化率和异构化产率。反应液减压蒸馏得到反应产物，用核磁共振分析定性检测产物。
该催化剂体系催化1-己烯-3-醇互变异构化反应结果见下表：
注：a选用三氯甲烷做溶剂，第二种金属盐为三氟甲磺酸镁。
本领域的技术人员容易理解，以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。
Claims (8)
1.一种催化剂体系，其特征在于，所述催化剂体系为第一种金属盐和第二种金属盐溶于有机溶剂中形成的有机溶液，所述第一种金属盐为钌配合物RuH2CO(PPh3)3，所述第二种金属盐为含有非氧化还原活性金属离子的金属盐类，所述第一种金属盐和第二种金属盐的摩尔比在1:0.5至1:4之间，所述第一种金属盐的浓度在0.5毫摩尔/升至5毫摩尔/升之间。
2.如权利要求1所述的一种催化剂体系，其特征在于，所述第二种金属盐包括镁盐、锌盐、钡盐、铟盐、镱盐、钇盐、钪盐、铝盐、钙盐和/或钠盐。
3.如权利要求1所述的一种催化剂体系，其特征在于，所述第二种金属盐为三氟甲磺酸盐、氯盐、硝酸盐和/或硫酸盐。
4.如权利要求1所述的一种催化剂体系，其特征在于，所述有机溶剂为甲醇、乙醇、异丙醇、三氯甲烷和/或甲苯。
5.一种如权利要求1～4任意一项所述的催化剂体系的应用，其特征在于，应用于催化烯烃异构，包括烯烃双键异构、烯烃顺反异构或含羟基官能团的烯烃的互变异构。
6.如权利要求5所述的催化剂体系的应用，其特征在于，所述烯烃为烯丙基芳烃、链状烯烃、含羟基官能团烯烃或环状二烯烃，所述烯丙基芳烃优选丁香酚。
7.如权利要求5或6所述的催化剂体系的应用，其特征在于，当应用于催化烯烃双键异构或烯烃顺反异构时，权利要求1～4任意一项所述的催化剂体系中钌配合物RuH2CO(PPh3)3与烯烃的摩尔比在1:100至1:1600之间，催化温度为50℃至90℃，反应时间在0.5小时至3小时之间。
8.如权利要求5或6所述的催化剂体系的应用，其特征在于，当应用于催化含羟基官能团的烯烃的互变异构时，权利要求1至4任意一项所述的催化剂体系中钌配合物RuH2CO(PPh3)3与烯烃的摩尔比在1:100至1:600之间，钌配合物RuH2CO(PPh3)3的浓度在1毫摩尔/升至5毫摩尔/升之间，催化温度为50℃至90℃，反应时间在1小时至3小时之间。
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