CN104211735B - A kind of metal complex part, metal complex and its preparation method and application, high molecular polymer and its preparation method and application - Google Patents
A kind of metal complex part, metal complex and its preparation method and application, high molecular polymer and its preparation method and application Download PDFInfo
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- CN104211735B CN104211735B CN201410412074.6A CN201410412074A CN104211735B CN 104211735 B CN104211735 B CN 104211735B CN 201410412074 A CN201410412074 A CN 201410412074A CN 104211735 B CN104211735 B CN 104211735B
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- 150000004696 coordination complex Chemical group 0.000 title claims abstract description 37
- 229920000642 polymer Polymers 0.000 title claims description 18
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 290
- -1 small molecule cycloolefins Chemical class 0.000 claims abstract description 288
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 229920002521 macromolecule Polymers 0.000 claims abstract description 9
- 125000003118 aryl group Chemical group 0.000 claims description 367
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 252
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 160
- 239000001257 hydrogen Substances 0.000 claims description 148
- 229910052739 hydrogen Inorganic materials 0.000 claims description 148
- 238000006467 substitution reaction Methods 0.000 claims description 125
- 150000002431 hydrogen Chemical class 0.000 claims description 119
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 69
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 55
- 229910052736 halogen Inorganic materials 0.000 claims description 53
- 150000002367 halogens Chemical group 0.000 claims description 53
- 125000000217 alkyl group Chemical group 0.000 claims description 49
- 229910052760 oxygen Inorganic materials 0.000 claims description 49
- 125000003545 alkoxy group Chemical group 0.000 claims description 46
- 239000001301 oxygen Substances 0.000 claims description 42
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 39
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 claims description 39
- 229910052757 nitrogen Inorganic materials 0.000 claims description 35
- 229910052710 silicon Inorganic materials 0.000 claims description 30
- 238000005865 alkene metathesis reaction Methods 0.000 claims description 28
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 28
- 239000010703 silicon Substances 0.000 claims description 28
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 26
- 125000000266 alpha-aminoacyl group Chemical group 0.000 claims description 26
- 239000000758 substrate Substances 0.000 claims description 26
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 claims description 24
- 239000003054 catalyst Substances 0.000 claims description 23
- 239000000178 monomer Substances 0.000 claims description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 21
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical group O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 21
- 150000001925 cycloalkenes Chemical group 0.000 claims description 20
- 125000003282 alkyl amino group Chemical group 0.000 claims description 19
- 125000000623 heterocyclic group Chemical group 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- 239000005864 Sulphur Substances 0.000 claims description 14
- 125000004104 aryloxy group Chemical group 0.000 claims description 14
- 238000005649 metathesis reaction Methods 0.000 claims description 13
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 13
- 125000003368 amide group Chemical group 0.000 claims description 11
- 239000000460 chlorine Substances 0.000 claims description 10
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
- 229910052801 chlorine Inorganic materials 0.000 claims description 9
- 239000003814 drug Substances 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- 239000002608 ionic liquid Substances 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- 125000005842 heteroatom Chemical group 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 125000004417 unsaturated alkyl group Chemical group 0.000 claims description 7
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 claims description 6
- 239000004973 liquid crystal related substance Substances 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 5
- 150000003857 carboxamides Chemical class 0.000 claims description 5
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 5
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 5
- 229940079593 drug Drugs 0.000 claims description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 239000002861 polymer material Substances 0.000 claims description 3
- 125000004414 alkyl thio group Chemical group 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 238000003402 intramolecular cyclocondensation reaction Methods 0.000 claims description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims 2
- JXASPPWQHFOWPL-UHFFFAOYSA-N Tamarixin Natural products C1=C(O)C(OC)=CC=C1C1=C(OC2C(C(O)C(O)C(CO)O2)O)C(=O)C2=C(O)C=C(O)C=C2O1 JXASPPWQHFOWPL-UHFFFAOYSA-N 0.000 claims 1
- 125000001769 aryl amino group Chemical group 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 125000005708 carbonyloxy group Chemical group [*:2]OC([*:1])=O 0.000 claims 1
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 26
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 238000007151 ring opening polymerisation reaction Methods 0.000 abstract description 7
- 230000000704 physical effect Effects 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 1012
- 229910052786 argon Inorganic materials 0.000 description 506
- 239000007789 gas Substances 0.000 description 505
- 239000012327 Ruthenium complex Substances 0.000 description 407
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 369
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 250
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 226
- 230000015572 biosynthetic process Effects 0.000 description 136
- 238000003786 synthesis reaction Methods 0.000 description 136
- 238000006073 displacement reaction Methods 0.000 description 127
- 238000001914 filtration Methods 0.000 description 127
- 239000012265 solid product Substances 0.000 description 125
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 123
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 123
- 239000012043 crude product Substances 0.000 description 123
- USPLDBATMHXKKD-UHFFFAOYSA-N dichloromethane;pentane Chemical compound ClCCl.CCCCC USPLDBATMHXKKD-UHFFFAOYSA-N 0.000 description 123
- 239000000706 filtrate Substances 0.000 description 123
- 239000004576 sand Substances 0.000 description 123
- 239000000741 silica gel Substances 0.000 description 123
- 229910002027 silica gel Inorganic materials 0.000 description 123
- 238000010898 silica gel chromatography Methods 0.000 description 123
- 238000005160 1H NMR spectroscopy Methods 0.000 description 118
- 150000003254 radicals Chemical class 0.000 description 112
- 238000012360 testing method Methods 0.000 description 112
- 239000002585 base Substances 0.000 description 106
- 125000004433 nitrogen atom Chemical group N* 0.000 description 59
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 50
- CFHIDWOYWUOIHU-UHFFFAOYSA-N oxomethyl Chemical compound O=[CH] CFHIDWOYWUOIHU-UHFFFAOYSA-N 0.000 description 50
- 238000007363 ring formation reaction Methods 0.000 description 50
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 40
- 125000001424 substituent group Chemical group 0.000 description 36
- 125000001841 imino group Chemical group [H]N=* 0.000 description 32
- 239000003446 ligand Substances 0.000 description 30
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 30
- 238000000034 method Methods 0.000 description 27
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 22
- 229910052707 ruthenium Inorganic materials 0.000 description 20
- 239000000047 product Substances 0.000 description 19
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 17
- 238000006555 catalytic reaction Methods 0.000 description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 14
- 125000002252 acyl group Chemical group 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 13
- 125000003375 sulfoxide group Chemical group 0.000 description 13
- 238000003556 assay Methods 0.000 description 12
- 239000011261 inert gas Substances 0.000 description 12
- 238000000746 purification Methods 0.000 description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 12
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 7
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 7
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 7
- 229910052727 yttrium Inorganic materials 0.000 description 7
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 6
- 150000002118 epoxides Chemical class 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Substances C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 125000005422 alkyl sulfonamido group Chemical group 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 239000007809 chemical reaction catalyst Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000002971 oxazolyl group Chemical group 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 125000002098 pyridazinyl group Chemical group 0.000 description 3
- 150000003222 pyridines Chemical class 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LBUJPTNKIBCYBY-UHFFFAOYSA-N 1,2,3,4-tetrahydroquinoline Chemical compound C1=CC=C2CCCNC2=C1 LBUJPTNKIBCYBY-UHFFFAOYSA-N 0.000 description 2
- MCMWRWKXPXXZAS-UHFFFAOYSA-N 6-chloro-3-[3-(4-chloro-3,5-dimethylphenoxy)propyl]-1h-indole-2-carboxylic acid Chemical compound CC1=C(Cl)C(C)=CC(OCCCC=2C3=CC=C(Cl)C=C3NC=2C(O)=O)=C1 MCMWRWKXPXXZAS-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 125000005257 alkyl acyl group Chemical group 0.000 description 2
- 125000005277 alkyl imino group Chemical group 0.000 description 2
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 125000002393 azetidinyl group Chemical group 0.000 description 2
- 230000037429 base substitution Effects 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 2
- 235000013877 carbamide Nutrition 0.000 description 2
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 125000006575 electron-withdrawing group Chemical group 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N formamide Substances NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 150000003948 formamides Chemical class 0.000 description 2
- 125000002541 furyl group Chemical group 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 125000003453 indazolyl group Chemical class N1N=C(C2=C1C=CC=C2)* 0.000 description 2
- 125000003387 indolinyl group Chemical group N1(CCC2=CC=CC=C12)* 0.000 description 2
- 125000005956 isoquinolyl group Chemical group 0.000 description 2
- 125000001786 isothiazolyl group Chemical group 0.000 description 2
- 125000000842 isoxazolyl group Chemical group 0.000 description 2
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 2
- 125000002950 monocyclic group Chemical group 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 125000006574 non-aromatic ring group Chemical group 0.000 description 2
- 125000003386 piperidinyl group Chemical group 0.000 description 2
- 229940002612 prodrug Drugs 0.000 description 2
- 239000000651 prodrug Substances 0.000 description 2
- 125000003226 pyrazolyl group Chemical group 0.000 description 2
- 125000005493 quinolyl group Chemical group 0.000 description 2
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 125000000547 substituted alkyl group Chemical group 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 125000001544 thienyl group Chemical group 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- QYMGRIFMUQCAJW-UHFFFAOYSA-N 1,2-dihydropyrazine Chemical compound C1NC=CN=C1 QYMGRIFMUQCAJW-UHFFFAOYSA-N 0.000 description 1
- YNGDWRXWKFWCJY-UHFFFAOYSA-N 1,4-Dihydropyridine Chemical compound C1C=CNC=C1 YNGDWRXWKFWCJY-UHFFFAOYSA-N 0.000 description 1
- VMLKTERJLVWEJJ-UHFFFAOYSA-N 1,5-naphthyridine Chemical compound C1=CC=NC2=CC=CN=C21 VMLKTERJLVWEJJ-UHFFFAOYSA-N 0.000 description 1
- GMAWQTHVIIUMFA-UHFFFAOYSA-N 1-[2-(2,4-dichlorophenoxy)acetyl]-n-(2-sulfanylethyl)piperidine-4-carboxamide Chemical compound C1CC(C(=O)NCCS)CCN1C(=O)COC1=CC=C(Cl)C=C1Cl GMAWQTHVIIUMFA-UHFFFAOYSA-N 0.000 description 1
- OXBLVCZKDOZZOJ-UHFFFAOYSA-N 2,3-Dihydrothiophene Chemical compound C1CC=CS1 OXBLVCZKDOZZOJ-UHFFFAOYSA-N 0.000 description 1
- ZABMHLDQFJHDSC-UHFFFAOYSA-N 2,3-dihydro-1,3-oxazole Chemical compound C1NC=CO1 ZABMHLDQFJHDSC-UHFFFAOYSA-N 0.000 description 1
- JKTCBAGSMQIFNL-UHFFFAOYSA-N 2,3-dihydrofuran Chemical compound C1CC=CO1 JKTCBAGSMQIFNL-UHFFFAOYSA-N 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- LMOJCFKMCAPGGY-UHFFFAOYSA-N 2-[8-(1,3-benzothiazol-2-ylcarbamoyl)-3,4-dihydro-1h-isoquinolin-2-yl]-5-[3-(4-pyrazolo[3,4-d]pyrimidin-1-ylphenoxy)propyl]-1,3-thiazole-4-carboxylic acid Chemical compound C1=CC=C2SC(NC(=O)C=3C=CC=C4CCN(CC4=3)C3=NC(=C(S3)CCCOC=3C=CC(=CC=3)N3C4=NC=NC=C4C=N3)C(=O)O)=NC2=C1 LMOJCFKMCAPGGY-UHFFFAOYSA-N 0.000 description 1
- HHOGMIYMABYION-UHFFFAOYSA-N 2-amino-1h-pyrimido[4,5-d]pyrimidin-4-one Chemical compound C1=NC=C2C(=O)NC(N)=NC2=N1 HHOGMIYMABYION-UHFFFAOYSA-N 0.000 description 1
- RSEBUVRVKCANEP-UHFFFAOYSA-N 2-pyrroline Chemical compound C1CC=CN1 RSEBUVRVKCANEP-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- 241000254173 Coleoptera Species 0.000 description 1
- FKLJPTJMIBLJAV-UHFFFAOYSA-N Compound IV Chemical compound O1N=C(C)C=C1CCCCCCCOC1=CC=C(C=2OCCN=2)C=C1 FKLJPTJMIBLJAV-UHFFFAOYSA-N 0.000 description 1
- GKQLYSROISKDLL-UHFFFAOYSA-N EEDQ Chemical compound C1=CC=C2N(C(=O)OCC)C(OCC)C=CC2=C1 GKQLYSROISKDLL-UHFFFAOYSA-N 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- VXDNQJCXIVLMQW-YFKPBYRVSA-N [(2s)-1-(2-amino-6-oxo-3h-purin-9-yl)-3-hydroxypropan-2-yl]oxymethylphosphonic acid Chemical compound N1C(N)=NC(=O)C2=C1N(C[C@@H](CO)OCP(O)(O)=O)C=N2 VXDNQJCXIVLMQW-YFKPBYRVSA-N 0.000 description 1
- 125000004062 acenaphthenyl group Chemical group C1(CC2=CC=CC3=CC=CC1=C23)* 0.000 description 1
- 125000000641 acridinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3C=C12)* 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 125000004448 alkyl carbonyl group Chemical group 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 125000002527 bicyclic carbocyclic group Chemical group 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000000259 cinnolinyl group Chemical class N1=NC(=CC2=CC=CC=C12)* 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000004598 dihydrobenzofuryl group Chemical group O1C(CC2=C1C=CC=C2)* 0.000 description 1
- 125000004582 dihydrobenzothienyl group Chemical group S1C(CC2=C1C=CC=C2)* 0.000 description 1
- 125000005056 dihydrothiazolyl group Chemical group S1C(NC=C1)* 0.000 description 1
- 125000005058 dihydrotriazolyl group Chemical group N1(NNC=C1)* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000003392 indanyl group Chemical group C1(CCC2=CC=CC=C12)* 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 150000002547 isoxazolines Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical compound [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 0.000 description 1
- 125000002757 morpholinyl group Chemical group 0.000 description 1
- RMFJTEMHOPPQER-UHFFFAOYSA-N n-(carbamoylamino)formamide Chemical group NC(=O)NNC=O RMFJTEMHOPPQER-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 125000001715 oxadiazolyl group Chemical group 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- QPUMEZIFDXYGPG-UHFFFAOYSA-N piperazine 1H-pyrrole Chemical compound N1CCNCC1.N1C=CC=C1 QPUMEZIFDXYGPG-UHFFFAOYSA-N 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 125000005936 piperidyl group Chemical group 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003214 pyranose derivatives Chemical class 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- DNXIASIHZYFFRO-UHFFFAOYSA-N pyrazoline Chemical compound C1CN=NC1 DNXIASIHZYFFRO-UHFFFAOYSA-N 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010107 reaction injection moulding Methods 0.000 description 1
- VIHDTGHDWPVSMM-UHFFFAOYSA-N ruthenium;triphenylphosphane Chemical compound [Ru].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 VIHDTGHDWPVSMM-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000009329 sexual behaviour Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 125000000565 sulfonamide group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000005958 tetrahydrothienyl group Chemical group 0.000 description 1
- 125000001113 thiadiazolyl group Chemical group 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000004568 thiomorpholinyl group Chemical group 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
- C07F15/0046—Ruthenium compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/46—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with hetero atoms directly attached to the ring nitrogen atom
- C07D207/48—Sulfur atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/58—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
- C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
- C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
- C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/96—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from other synthetic polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
- B01J2231/54—Metathesis reactions, e.g. olefin metathesis
- B01J2231/543—Metathesis reactions, e.g. olefin metathesis alkene metathesis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/821—Ruthenium
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The invention discloses a kind of metal complex part, metal complex and its preparation method and application.The b of metal complex II of present invention structural formula is as follows.The metal complex of the present invention has the advantages that catalytic activity is higher, the diversity of structure and physical property, and diversified optimum choice is provided for the catalytic applications of various raw materials.The invention also discloses the various functions macromolecule new material of the catalyzed ring opening polymerization of various types of small molecule cycloolefins reaction (ROMP) generation and its application, structure are as follows.
Description
The application is Application No. 2009101757906, and the applying date is September in 2009 27, a kind of entitled " gold
Belong to complex ligands, metal complex and its preparation method and application, high molecular polymer and its preparation method and application " it is special
The divisional application of profit application.
Technical field
The present invention relates to a kind of part, complex compound and its preparation method and application, a kind of polymer and preparation method thereof and
Using being specifically related to a kind of metal complex part, metal complex and its preparation method and application, a kind of high molecular polymerization
Thing and its preparation method and application.
Background technology
The research and development of olefin metathesis double decomposition ruthenium catalyst and pass through alkene using new and effective ruthenium complex catalyst
Catalysed metathesis ring-opening polymerisation (ROMP:Ring Opening Metathesis Polymerization) method prepare it is all kinds of
The multifunctional macromolecule such as high strength and high hardness new material oneself cause extensive attention.The wound of ruthenium complex catalyst in the field
The seminars such as beginning people Grubbs have reported different types of ruthenium complex catalyst and by associated olefinic catalysed metathesis open loops
Polymerisation and reaction and injection molding process (RIM:Reaction Injection Molding) technology prepare it is all kinds of multi-functional
Macromolecule new material, wherein the key for preparing all kinds of multifunctional macromolecule new materials is effective ROMP catalyst.
Olefin catalytic polymerization product (ROMP-RIM) has higher impact strength and bending modulus, is not easy by temperature shadow
Ring, there are the very good mechanical properties such as fabulous corrosion resistance, low-density, built in traffic, electrical equipment, sports and amusement facility, building
The fields such as material, casting, communication are built all to have broad application prospects.Current main ROMP new material industrializations manufacturer is promise
Bel encourages the U.S. Materia Inc. of winner professor Grubbs offer ROMP patented technologies and the Hercules public affairs in the U.S.
The ZEON companies of department, Goodrich companies and Japan.
Oneself has obtained industrial applications to some current olefin catalytic polymerization products, but its shortcoming passes through ruthenium catalyst open loop
The method of polymerization prepares intensity and modulus of all kinds of multi-functional macromolecule new materials etc. and is in above the average, needs further to be ground
Send out alkene ring-opening polymerization catalyst and its polymerization reaction monomer and processing technology more effective, reach the mesh for improving mechanical performance
's.
The content of the invention
The present invention is anti-in order to solve existing olefin metathesis reaction catalyst and associated olefinic catalysed metathesis ring-opening polymerisation
The shortcomings that answering, the intensity and modulus of olefinic polymerization product is improved by researching and developing the performance of raising olefin metathesis reaction catalyst
Etc. mechanical performance.The novel metal complexes part of the present invention is characterized in the part formed with oxygen atom and/or nitrogen-atoms
It can be formed with metal especially ruthenium ion relatively stable and have the metal complex catalyst of greater activity, the present invention is in metal complex
Different type, different physical characteristics, the part of different catalytically active are introduced in thing catalyst, so as to be chemical industry, medicine and height
The synthetically prepared of molecule new material provides more effective various, different activities metal complex catalysts, is olefin metathesis
The optimization of reaction and products thereof provides the selection of more catalysis techniques.
Therefore, an object of the present invention is to provide the olefin metathesis metal complex that a kind of structural formula is Formulas I a, Ib, Ic
Thing part：
Wherein, Z CH2Or
M=0 or 1, n=0 or 1；
During n=1, X1And Y1It independently is nitrogen, oxygen, sulphur, CH2, substituted or unsubstituted C1-C20Alkyl, substitution or unsubstituted
C6-C20Aryl, substituted or unsubstituted C6-C20Aryloxy group, substituted or unsubstituted C2-C20Heterocyclic aryl, carbonyl, connection take
Generation or unsubstituted C1-C20Carbonyl, the substituted or unsubstituted C of connection of alkyl1-C20The carbonyl of alkoxy, imino group, substitution or
Unsubstituted C1-C20Alkyl imino base or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently is hydrogen, substitution or not taken
The C in generation6-C20Aryl, substituted or unsubstituted C2-C20Heterocyclic radical, substituted or unsubstituted C1-C20Alkyl, formoxyl, substitution or
Unsubstituted C1-C20Alkyl formyl radical, substituted or unsubstituted C6-C20Aryl formoxyl or substituted or unsubstituted C2-C20It is miscellaneous
Ring group formoxyl；Or Rc, Rd connect cyclization with N atoms；X1The parent of each group connection represented is Y1, wherein connection Y portion
Point can be each group in itself or group various substituents, Y1The parent of each group connection represented is X1, wherein
Connect R2Part can be group in itself or group various substituents；
During m=0, Y is nitrogen, oxygen, substituted or unsubstituted C1-C20Alkoxy, substituted or unsubstituted C6-C20Aryloxy group,
Substituted or unsubstituted C2-C20Heterocyclic aryl, carbonyl, the substituted or unsubstituted C of connection1-C20The carbonyl of alkyl, connection substitution or
Unsubstituted C1-C20Carbonyl, imino group, the substituted or unsubstituted C of alkoxy1-C20Alkyl imino base or such as formula RcRdShown in N-
Group；Wherein, Rc and Rd independently is hydrogen, substituted or unsubstituted C6-C20Aryl, substituted or unsubstituted C2-C20Heterocycle
Base, substituted or unsubstituted C1-C20Alkyl, formoxyl, substituted or unsubstituted C1-C20Alkyl formyl radical, substitution or unsubstituted
C6-C20Aryl formoxyl or substituted or unsubstituted C2-C20Heterocyclic radical formoxyl；Or Rc, Rd connect cyclization with N atoms；
In Formulas I a, Y represent group connection parent be X, wherein connect the other end part can be each group in itself or
The various substituents of group；In Formulas I b, the parent for the group connection that Y is represented be aromatic ring, the parent that the group that Y is represented in Ic connects
To connect R3Carbon；
During m=1, X is nitrogen, oxygen, sulphur, CH, CH2, carbonyl；Y is nitrogen, oxygen, CH, methylene, substituted or unsubstituted C1-C20
Alkoxy, substituted or unsubstituted C6-C20Aryl, substituted or unsubstituted C6-C20Aryloxy group, substituted or unsubstituted C2-C20
Heterocyclic aryl, the substituted or unsubstituted C of connection1-C20Carbonyl, the substituted or unsubstituted C of connection of alkyl1-C20The carbonyl of alkoxy
Base, imino group, substituted or unsubstituted C1-C20Alkyl imino base, unsubstituted C1-C20Alkyl imino base or such as formula RcRdN- institutes
The group shown；Wherein, Rc and Rd independently is hydrogen, substituted or unsubstituted C6-C20Aryl, substituted or unsubstituted C2-C20It is miscellaneous
Ring group, substituted or unsubstituted C1-C20Alkyl, formoxyl, substituted or unsubstituted C1-C20Alkyl formyl radical, substitution do not take
The C in generation6-C20Aryl formoxyl or substituted or unsubstituted C2-C20Heterocyclic radical formoxyl；Or Rc, Rd and N atom connect into
Ring；The parent for the group connection that X is represented be Y, wherein the part for connecting the other end can be each group in itself or group
Various substituents；Y represent group connection parent be X, wherein connect the other end part can be each group in itself,
Can be the various substituents of group；Between can be singly-bound or double bond；
R1For hydrogen, substituted or unsubstituted C1-C20Alkyl, substituted or unsubstituted C1-C20Alkoxy, substitution or unsubstituted
C1-C20Alkylthio group, the substituted or unsubstituted C of connection1-C20Carbonyl, the substituted or unsubstituted C of connection of alkoxy6-C20Fragrant oxygen
Carbonyl, the substituted or unsubstituted C of connection of base6-C20The carbonyl of heterocyclic radical epoxide, substituted or unsubstituted C6-C20Aryl, substitution
Or unsubstituted C6-C20Aryloxy group or substituted or unsubstituted C2-C20Heterocyclic radical；
R2For hydrogen, substituted or unsubstituted C1-C20Alkyl, substituted or unsubstituted C1-C20Alkoxy, substitution or unsubstituted
C1-C20Alkylthio group, substituted or unsubstituted C1-C20Alkyl siloxy, substituted or unsubstituted C2-C20Heterocyclic radical, substitution or
Unsubstituted C6-C20Aryl, C6-C20Aryloxy group, aldehyde radical, the substituted or unsubstituted C of connection1-C20The carbonyl of alkyl, connection substitution
Or unsubstituted C6-C20Carbonyl, the substituted or unsubstituted C of connection of aryl2-C20The carbonyl of heterocyclic radical or such as formula RcRdShown in N-
Group；Wherein, Rc and Rd independently is hydrogen, formoxyl, substituted or unsubstituted C1-C20Alkyl formyl radical, substitution do not take
The C in generation6-C20Aryl formoxyl or substituted or unsubstituted C2-C20Heterocyclic radical formoxyl；Or Rc, Rd and N atom connect into
Ring；
R3For hydrogen, substituted or unsubstituted C1-C20Alkyl, substituted or unsubstituted C1-C20Alkoxy, substitution or unsubstituted
C1-C20Alkylthio group, C2-C20Heterocyclic radical, substituted or unsubstituted C6-C20Aryl, substituted or unsubstituted C6-C20Aryloxy group,
Connect substituted or unsubstituted C1-C20Carbonyl, the substituted or unsubstituted C of connection of alkoxy6-C20The carbonyl of aryloxy group, connection
Substituted or unsubstituted C6-C20The carbonyl of heterocyclic radical epoxide or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently are
Hydrogen, formoxyl, substituted or unsubstituted C1-C20Alkyl formyl radical, substituted or unsubstituted C6-C20Aryl formoxyl or substitution or
Unsubstituted C2-C20Heterocyclic radical formoxyl；Or Rc, Rd connect cyclization with N atoms；
E is hydrogen, halogen, nitro, itrile group, sulfoxide group, sulfuryl, aldehyde radical, C1-C20Alkyl, C1-C20Alkoxy, C1-C20Alkane sulphur
Base, C1-C20Alkane silicon substrate, C1-C20Alkyl siloxy, C2-C20Heterocyclic radical, C6-C20Aryl, C6-C20Aryloxy group, connection C1-C20Alkane
Carbonyl, the connection C of base6-C20Carbonyl, the connection C of aryl2-C20Carbonyl, the connection C of heterocyclic radical1-C20The carbonyl of alkoxy, connection
C6-C20Carbonyl, the connection C of aryloxy group6-C20Carbonyl, aminoacyl, the connection C of heterocyclic radical epoxide1-C20The carbonyl of alkyl amino,
Connect C6-C20Carbonyl, the connection C of arylamino2-C20Carbonyl, urea groups, the substituted or unsubstituted C of heterocyclylamino group1-C20Alkane
Base urea groups, substituted or unsubstituted C6-C20Aryl-ureido, substituted or unsubstituted C2-C20Heterocyclic radical urea groups, connection C1-C20Alkane
Sulfonyl, the connection C of base amino6-C20Sulfonyl, the connection C of arylamino2-C20The sulfonyl of heterocyclylamino group or such as formula
RcRdGroup shown in N-；Wherein, Rc and Rd independently is hydrogen, substituted or unsubstituted C6-C20It is aryl, substituted or unsubstituted
C2-C20Heterocyclic radical, substituted or unsubstituted C1-C20Alkyl, formoxyl, substituted or unsubstituted C1-C20Alkyl formyl radical, substitution
Or unsubstituted C6-C20Aryl formoxyl, substituted or unsubstituted C2-C20Heterocyclic radical formoxyl, substituted or unsubstituted C1-C20
Alkyl sulphonyl, substituted or unsubstituted C6-C20Aryl sulfonyl or substituted or unsubstituted C2-C20Heterocyclyl sulfonyl；Or
Person Rc, Rd connect cyclization with N atoms；
E1For hydrogen, halogen, nitro, itrile group, C1-C20Alkyl, C1-C20Alkoxy, C1-C20Alkylthio group, C1-C20Alkane silicon substrate,
C1-C20Alkyl siloxy, C2-C20Heterocyclic radical, substituted or unsubstituted amino, aminoacyl, connection C1-C20The carbonyl of alkyl amino
Base, C6-C20Aryl, C6-C20Aryloxy group, sulfoxide group, sulfuryl, aldehyde radical, connection C1-C20The carbonyl of alkyl, connection substitute or not taken
The C in generation6-C20Carbonyl, the substituted or unsubstituted C of connection of aryl2-C20Carbonyl, the connection C of heterocyclic radical1-C20The carbonyl of alkoxy
Base, connection C6-C20Carbonyl, the connection C of arylamino2-C20Carbonyl, urea groups, the substituted or unsubstituted C of heterocyclylamino group1-C20
Alkyl urea groups, substituted or unsubstituted C1-C20Alkyl urea groups, substituted or unsubstituted C6-C20Aryl-ureido or substitution do not take
The C in generation2-C20Heterocyclic radical urea groups；
E2For hydrogen, halogen, C1-C20Alkyl, C1-C20Alkoxy, C1-C20Alkylthio group, C1-C20Alkane silicon substrate, C1-C20Alkyl silicon
Epoxide, aminoacyl, connection C1-C20Carbonyl, the connection C of alkyl amino6-C20Carbonyl, the connection C of arylamino2-C20Heterocyclic radical
Carbonyl, the C of amino6-C20Aryl, C6-C20Aryloxy group, C2-C20Heterocyclic aryl, aldehyde radical, connection C1-C20The carbonyl of alkyl, connection
C6-C20Carbonyl, the connection C of aryl2-C20Carbonyl, the connection C of heterocyclic radical1-C20Carbonyl, the connection C of alkoxy6-C20Aryloxy
Carbonyl, connection C2-C20The carbonyl of heterocyclylamino group or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently be hydrogen,
Substituted or unsubstituted C6-C20Aryl, substituted or unsubstituted C2-C20Heterocyclic radical, substituted or unsubstituted C1-C20Alkyl, first
Acyl group, substituted or unsubstituted C1-C20Alkyl formyl radical, substituted or unsubstituted C6-C20Aryl formoxyl, substitution or unsubstituted
C2-C20Heterocyclic radical formoxyl, substituted or unsubstituted C1-C20Alkyl sulphonyl, substituted or unsubstituted C6-C20Arylsulfonyl
Base or substituted or unsubstituted C2-C20Heterocyclyl sulfonyl；Or Rc, Rd connect cyclization with N atoms；
E3For hydrogen, halogen, C1-C20Alkyl, C1-C20Alkoxy, C1-C20Alkylthio group, C1-C20Alkyl siloxy, C6-C20Virtue
Epoxide, C6-C20Aryl, C2-C20Heterocyclic aryl, connection C1-C20Carbonyl, the substituted or unsubstituted C of connection of alkoxy6-C20Virtue
Carbonyl, the substituted or unsubstituted C of connection of epoxide6-C20The carbonyl of heterocyclic radical epoxide or such as formula RcRdGroup shown in N-；Wherein,
Rc and Rd independently is hydrogen, substituted or unsubstituted C6-C20Aryl, substituted or unsubstituted C2-C20Heterocyclic radical, substitution do not take
The C in generation1-C20Alkyl, formoxyl, substituted or unsubstituted C1-C20Alkyl formyl radical, substituted or unsubstituted C6-C20Aryl first
Acyl group, substituted or unsubstituted C2-C20Heterocyclic radical formoxyl, substituted or unsubstituted C1-C20Alkyl sulphonyl, substitution do not take
The C in generation6-C20Aryl sulfonyl or substituted or unsubstituted C2-C20Heterocyclyl sulfonyl；Or Rc, Rd and N atom connect into
Ring；
E4、E5、E6And E7It independently is hydrogen, halogen, nitro, itrile group, sulfoxide group, sulfuryl, aldehyde radical, substituted or unsubstituted
C1-C20Alkyl, substituted or unsubstituted C1-C20Alkoxy, C1-C20Alkylthio group, C1-C20Alkane silicon substrate, C1-C20Alkane siloxy, take
Generation or unsubstituted C2-C20Heterocyclic radical, substituted or unsubstituted amino, aminoacyl, the substituted or unsubstituted C of connection1-C20Alkane
Carbonyl, the substituted or unsubstituted C of connection of base amino6-C20Carbonyl, the substituted or unsubstituted C of connection of arylamino2-C20It is miscellaneous
Carbonyl, the substituted or unsubstituted C of connection of ring group amino1-C20Carbonyl, the substituted or unsubstituted C of connection of alkyl6-C20Aryl
Carbonyl, the substituted or unsubstituted C of connection2-C20Carbonyl, the substituted or unsubstituted C of connection of heterocyclic radical1-C20The carbonyl of alkoxy
Base, the substituted or unsubstituted C of connection6-C20Carbonyl, the substituted or unsubstituted C of connection of aryloxy group6-C20The carbonyl of heterocyclic radical epoxide
Base, urea groups, substituted or unsubstituted C1-C20Alkyl urea groups, substituted or unsubstituted C1-C20Alkyl urea groups, substitution or unsubstituted
C6-C20Aryl-ureido or substituted or unsubstituted C2-C20Heterocyclic radical urea groups, substituted or unsubstituted C6-C20Aryl, substitution or
Unsubstituted C6-C20Aryloxy group or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently is hydrogen, substituted or unsubstituted
C6-C20Aryl, substituted or unsubstituted C2-C20Heterocyclic radical, substituted or unsubstituted C1-C20Alkyl, formoxyl, substitution do not take
The C in generation1-C20Alkyl formyl radical, substituted or unsubstituted C6-C20Aryl formoxyl, substituted or unsubstituted C2-C20Heterocyclic radical first
Acyl group, substituted or unsubstituted C1-C20Alkyl sulphonyl, substituted or unsubstituted C6-C20Aryl sulfonyl or substitution do not take
The C in generation2-C20Heterocyclyl sulfonyl；Or Rc, Rd connect cyclization with N atoms.
In the present invention, preferably, in Formulas I a, Ib, Ic,
Z is CH2Or TsNHN=；
M=0 or 1, n=0 or 1；
During n=1, X1And Y1It independently is nitrogen, oxygen, sulphur, CH2, substituted or unsubstituted C1-C15Alkyl, substitution or unsubstituted
C6-C15Aryl, substituted or unsubstituted C6-C15Aryloxy group, substituted or unsubstituted C2-C15Heterocyclic aryl, carbonyl, connection take
Generation or unsubstituted C1-C15Carbonyl, the substituted or unsubstituted C of connection of alkyl1-C15The carbonyl of alkoxy, imino group, substitution or
Unsubstituted C1-C15Alkyl imino base or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently is hydrogen, substitution or not taken
The C in generation6-C15Aryl, substituted or unsubstituted C2-C15Heterocyclic radical, substituted or unsubstituted C1-C15Alkyl, formoxyl, substitution or
Unsubstituted C1-C15Alkyl formyl radical, substituted or unsubstituted C6-C15Aryl formoxyl or substituted or unsubstituted C2-C15It is miscellaneous
Ring group formoxyl；Or Rc, Rd connect cyclization with N atoms；X1The parent of each group connection represented is Y1, wherein connecting another
The part at end can be each group in itself or group various substituents；Y1Represent each group connection parent be
X1, wherein connection the other end part can be each group in itself or group various substituents；
During m=0, Y is nitrogen, oxygen, substituted or unsubstituted C1-C15Alkoxy, substituted or unsubstituted C6-C15Aryloxy group,
Substituted or unsubstituted C2-C15Heterocyclic aryl, the substituted or unsubstituted C of connection1-C15The carbonyl of alkyl, connection substitute or not taken
The C in generation1-C15Carbonyl, the substituted or unsubstituted C of connection of alkyl1-C15It is the carbonyl of alkoxy, imino group, substituted or unsubstituted
C1-C15Alkyl imino base or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently is hydrogen, substituted or unsubstituted C6-
C15Aryl, substituted or unsubstituted C2-C15Heterocyclic radical, substituted or unsubstituted C1-C15Alkyl, formoxyl, substitution or unsubstituted
C1-C15Alkyl formyl radical, substituted or unsubstituted C6-C15Aryl formoxyl or substituted or unsubstituted C2-C15Heterocyclic radical first
Acyl group；Or Rc, Rd connect cyclization with N atoms；In Formulas I a, the parent for the group connection that Y is represented is X, wherein connecting the other end
Part can be each group in itself or group various substituents；In Formulas I b, the parent for the group connection that Y is represented
For aromatic ring, the parent for the group connection that Y is represented in Ic is connection R3Carbon；
During m=1, X is nitrogen, oxygen, sulphur, CH, CH2, carbonyl；Y is nitrogen, oxygen, CH, methylene, substituted or unsubstituted C1-C15
Alkoxy, substituted or unsubstituted C6-C15Aryl, substituted or unsubstituted C6-C15Aryloxy group, substituted or unsubstituted C2-C15
Heterocyclic aryl, the substituted or unsubstituted C of connection1-C15Carbonyl, the substituted or unsubstituted C of connection of alkyl1-C15The carbonyl of alkoxy
Base, substituted or unsubstituted C1-C15Imido grpup；Such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently be hydrogen, substitution or
Unsubstituted C6-C15Aryl, substituted or unsubstituted C2-C15Heterocyclic radical, substituted or unsubstituted C1-C15Alkyl, formoxyl, take
Generation or unsubstituted C1-C15Alkyl formyl radical, substituted or unsubstituted C6-C15Aryl formoxyl or substituted or unsubstituted C2-
C15Heterocyclic radical formoxyl；Or Rc, Rd connect cyclization with N atoms；The parent for the group connection that X is represented is Y, wherein connecting another
The part at end can be each group in itself or group various substituents；The parent for the group connection that Y is represented is X, its
It is middle connection the other end part can be each group in itself or group various substituents；Between can be single
Key or double bond；
R1For hydrogen, substituted or unsubstituted C1-C15Alkyl, substituted or unsubstituted C1-C15Alkoxy, substitution or unsubstituted
C1-C15Alkylthio group, the substituted or unsubstituted C of connection1-C15The carbonyl of alkoxy, substituted or unsubstituted C6-C15Aryl, take
Generation or unsubstituted C6-C15Aryloxy group or substituted or unsubstituted C2-C15Heterocyclic radical；
R2For hydrogen, substituted or unsubstituted C1-C15Alkyl, substituted or unsubstituted C1-C15Alkoxy, substitution or unsubstituted
C1-C15Alkylthio group, substituted or unsubstituted C1-C15Alkane siloxy, substituted or unsubstituted C2-C15Heterocyclic radical, C6-C15Virtue
Base, C6-C15Aryloxy group, aldehyde radical, the substituted or unsubstituted C of connection1-C15Carbonyl, the substituted or unsubstituted C of connection of alkyl1-C15
The carbonyl of alkoxy or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently is hydrogen, formoxyl, substituted or unsubstituted
C1-C15Alkyl formyl radical, substituted or unsubstituted C6-C15Aryl formoxyl or substituted or unsubstituted C2-C15Heterocyclic radical formyl
Base；Or Rc, Rd connect cyclization with N atoms；
R3For hydrogen, substituted or unsubstituted C1-C15Alkyl, substituted or unsubstituted C1-C15Alkoxy, substitution or unsubstituted
C1-C15Alkylthio group, substituted or unsubstituted C2-C15Heterocyclic radical, substituted or unsubstituted C6-C15Aryl, substitution or unsubstituted
C6-C15Aryloxy group, the substituted or unsubstituted C of connection1-C15The carbonyl of alkoxy or such as formula RcRdGroup shown in N-；Wherein,
Rc and Rd independently is hydrogen, formoxyl, substituted or unsubstituted C1-C15Alkyl formyl radical, substituted or unsubstituted C6-C15Aryl
Formoxyl or substituted or unsubstituted C2-C15Heterocyclic radical formoxyl；Or Rc, Rd connect cyclization with N atoms；
E is hydrogen, halogen, nitro, itrile group, sulfoxide group, sulfuryl, aldehyde radical, C1-C15Alkyl, C1-C15Alkoxy, C1-C15Alkane sulphur
Base, C1-C15Alkane silicon substrate, C1-C15Alkane siloxy, C2-C15Heterocyclic radical, C6-C15Aryl, C6-C15Aryloxy group, connection C1-C15Alkyl
Carbonyl, connection C6-C15Carbonyl, the connection C of aryl2-C15Carbonyl, the connection C of heterocyclic radical1-C15Carbonyl, the aminoacyl of alkoxy
Base, connection C1-C15Carbonyl, the connection C of alkyl amino6-C15Carbonyl, the connection C of arylamino2-C15The carbonyl of heterocyclylamino group,
Urea groups, substituted or unsubstituted C1-C15Alkyl urea groups or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently be hydrogen,
Aryl, C2-C20Heterocyclic radical, C1-C20Alkyl, formoxyl, C1-C15Alkyl formyl radical, C6-C15Aryl formoxyl, C2-C15Heterocyclic radical
Formoxyl, C1-C15Alkyl sulphonyl, C6-C20Aryl sulfonyl or C2-C20Heterocyclyl sulfonyl；Or Rc, Rd and N atom
Connection cyclization；
E1For hydrogen, halogen, nitro, sulfuryl, C1-C15Alkyl, C1-C15Alkoxy, C1-C15Alkylthio group, C1-C15Alkane silicon substrate,
C1-C15Alkane siloxy, C2-C15Heterocyclic radical, C6-C15Aryl, C6-C15Aryloxy group, aldehyde radical, connection C1-C15The carbonyl of alkyl, connection
C1-C15Carbonyl, aminoacyl, the connection C of alkoxy1-C15Carbonyl, urea groups, the substituted or unsubstituted C of alkyl amino1-C15Alkane
Base urea groups, substituted or unsubstituted C1-C15Alkyl, connection C1-C15The sulfonyl of amino or such as formula RcRdGroup shown in N-；Its
In, Rc and Rd independently are hydrogen, aryl, C2-C20Heterocyclic radical, C1-C20Alkyl, formoxyl, C1-C15Alkyl formyl radical, C6-C15Virtue
Base formoxyl, C2-C15Heterocyclic radical formoxyl, C1-C15Alkyl sulphonyl, C6-C20Aryl sulfonyl or C2-C20Heterocyclic radical sulphonyl
Base；Or Rc, Rd connect cyclization with N atoms；
E2For hydrogen, halogen, C1-C15Alkyl, C1-C15Alkoxy, C1-C15Alkylthio group, C1-C15Alkane silicon substrate, C1-C15Alkane silica
Base, C6-C15Aryl, C6-C15Aryloxy group, C2-C15Heterocyclic aryl, aldehyde radical, connection C1-C15Carbonyl, the connection C of alkyl1-C15Alcoxyl
Carbonyl, aminoacyl, the substituted or unsubstituted C of connection of base1-C15The carbonyl of alkyl amino or such as formula RcRdGroup shown in N-；
Wherein, Rc and Rd independently is hydrogen, C6-C15Aryl, C2-C15Heterocyclic radical, C1-C15Alkyl, formoxyl, C1-C15Alkyl formyl radical,
C6-C15Aryl formoxyl, C2-C15Heterocyclic radical formoxyl；Or Rc, Rd connect cyclization with N atoms；
E3For hydrogen, halogen, C1-C15Alkyl, C1-C15Alkoxy, C1-C15Alkylthio group, C1-C15Alkane siloxy, C6-C15Virtue
Base, C6-C15Aryloxy group, C2-C15Heterocyclic aryl, connection C1-C15Carbonyl, aminoacyl, the connection C of alkoxy1-C15Alkyl amino
Carbonyl or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently is hydrogen, C6-C15Aryl, C2-C15Heterocyclic radical, substitution
Or unsubstituted C1-C15Alkyl, formoxyl, substituted or unsubstituted C1-C15Alkyl formyl radical, substituted or unsubstituted C6-C15
Aryl formoxyl；Or Rc, Rd connect cyclization with N atoms；
E4、E5、E6And E7It independently is hydrogen, halogen, nitro, itrile group, sulfoxide group, sulfuryl, aldehyde radical, substituted or unsubstituted
C1-C15Alkyl, substituted or unsubstituted C1-C15Alkoxy, C1-C15Alkylthio group, C1-C15Alkane silicon substrate, C1-C15Alkane siloxy, take
Generation or unsubstituted C2-C15Heterocyclic radical, aminoacyl, connection C1-C15Carbonyl, the connection C of alkyl amino6-C15Arylamino
Carbonyl, connection C2-C15Carbonyl, the substituted or unsubstituted C of connection of heterocyclylamino group1-C15The carbonyl of alkyl, connection substitution or not
Substituted C1-C15Carbonyl, urea groups, the substituted or unsubstituted C of alkoxy1-C15Alkyl urea groups, substituted or unsubstituted C1-C15
Alkylsulfonamido, connection C1-C15The sulphonyl of alkyl amino, substituted or unsubstituted C6-C15It is aryl, substituted or unsubstituted
C6-C15Aryloxy group or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently is hydrogen, substituted or unsubstituted C6-C20Virtue
Base, substituted or unsubstituted C2-C15Heterocyclic radical, substituted or unsubstituted C1-C15Alkyl, formoxyl, C1-C15Alkyl formyl radical,
C6-C15Aryl formoxyl, C2-C15Heterocyclic radical formoxyl, substituted or unsubstituted C1-C15Alkyl sulphonyl, substitution or unsubstituted
C6-C15Aryl sulfonyl or substituted or unsubstituted C2-C15Heterocyclyl sulfonyl；Or Rc, Rd connect cyclization with N atoms.
In the present invention, more preferably, in Formulas I a, Ib, Ic,
Z is CH2Or
M=0 or 1, n=0 or 1；
During n=1, X1For oxygen, CH2, substituted or unsubstituted C6-C12Aryl；Y1For oxygen, nitrogen, carbonyl, connection substitution or not
Substituted C1-C8Carbonyl, the substituted or unsubstituted C of connection of alkyl1-C8The carbonyl of alkoxy, imino group, substitution or unsubstituted
C1-C8Imino group；Wherein, X1The parent of each group connection represented is Y1, Y1The parent of each group connection represented is X1；
During m=0, Y is nitrogen, oxygen, carbonyl, the substituted or unsubstituted C of connection1-C8The carbonyl of alkyl, connection substitute or not taken
The C in generation1-C8Carbonyl, imino group, the substituted or unsubstituted C of alkoxy1-C8Imido grpup or such as formula RcRdGroup shown in N-；Its
In, Rc and Rd independently are hydrogen, substituted or unsubstituted C1-C8Aryl, substituted or unsubstituted C2-C12Heterocyclic radical or substitution or
Unsubstituted C1-C8Alkyl；Or Rc, Rd connect cyclization with N atoms；In Formulas I a, the parent for the group connection that Y is represented is X, formula
In Ib, the parent for the group connection that Y is represented be aromatic ring, and the parent of the group connection that Y is represented in Ic is connects R3Carbon；
During m=1, X is nitrogen, oxygen, methine, methylene, carbonyl；Y is nitrogen, oxygen, substituted or unsubstituted C6-C12Aryl,
Connect substituted or unsubstituted C1-C8Carbonyl, the substituted or unsubstituted C of connection of alkyl1-C8The carbonyl of alkoxy, imino group,
Substituted or unsubstituted C1-C8Alkyl imino base or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently is hydrogen, substitution
Or unsubstituted C6-C12Aryl, substituted or unsubstituted C2-C12Heterocyclic radical or substituted or unsubstituted C1-C8Alkyl；Or Rc,
Rd with N atoms connect cyclization；The parent for the group connection that X is represented is Y, wherein the part of the connection other end can be each group sheet
The various substituents of body or group；The parent for the group connection that Y is represented be X, wherein the part for connecting the other end can be with
Be each group in itself or group various substituents；Between can be singly-bound or double bond；
R1For hydrogen or substituted or unsubstituted C6-C12Aryl；
R2For methyl, isopropyl, substituted or unsubstituted C1-C8Alkyl or substituted or unsubstituted C6-C12Aryl；
R3For hydrogen, substituted or unsubstituted C1-C8Alkyl, substituted or unsubstituted C1-C8Alkoxy, C6-C12Aryl, C6-
C12Aryloxy group, C2-C12Heterocyclic aryl, connection C1-C8The carbonyl of alkoxy or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd
It independently is hydrogen, formoxyl, substituted or unsubstituted C1-C8Alkyl formyl radical, substituted or unsubstituted C6-C12Aryl formoxyl
Or substituted or unsubstituted C2-C12Heterocyclic radical formoxyl；Or Rc, Rd connect cyclization with N atoms；
E is hydrogen, halogen, nitro, C1-C8Alkyl, C1-C8Alkoxy, C6-C12Aryl, connection C1-C8The carbonyl of alkyl, connect
Meet C1-C8Carbonyl, the connection C of alkoxy1-C8Carbonyl, the connection C of alkyl amino1-C8Carbonyl, the connection C of alkyl amino6-C12Virtue
Carbonyl, the connection C of base amino2-C12Carbonyl, the substituted or unsubstituted C of connection of heterocyclylamino group1-C8The sulphonyl of alkyl amine group
Base；Or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently is hydrogen, aryl, C2-C12Heterocyclic radical, C1-C8Alkyl, first
Acyl group, C1-C8Alkyl formyl radical, C6-C12Aryl formoxyl, C2-C12Heterocyclic radical formoxyl, substituted or unsubstituted C1-C8Alkyl
Sulfonyl, substituted or unsubstituted C6-C12Aryl sulfonyl or substituted or unsubstituted C2-C12Heterocyclyl sulfonyl；Or Rc,
Rd with N atoms connect cyclization；
E1For hydrogen, halogen, nitro, C1-C8Alkyl, C1-C8Alkoxy, connection C1-C8Carbonyl, the C of alkyl amino6-C12Virtue
Base, C6-C12Aryloxy group, connection C1-C8The carbonyl of alkoxy or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently are
Hydrogen, C6-C12Aryl, C2-C12Heterocyclic radical, C1-C8Alkyl, formoxyl, C1-C8Alkyl formyl radical, C6-C12Aryl formoxyl, C2-
C12Heterocyclic radical formoxyl, substituted or unsubstituted C1-C8Alkyl sulphonyl, substituted or unsubstituted C6-C8Aryl sulfonyl takes
Generation or unsubstituted C2-C12Heterocyclyl sulfonyl；Or Rc, Rd connect cyclization with N atoms；
E2For hydrogen, halogen, C1-C8Alkyl, C1-C8Alkoxy, C6-C12Aryl, C6-C12Aryloxy group, C2-C12Heterocyclic aryl,
Connect substituted or unsubstituted C1-C8The carbonyl of alkoxy or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently are
Hydrogen, C6-C12Aryl, C2-C12Heterocyclic radical, C1-C8Alkyl, formoxyl, C1-C8Alkyl formyl radical, C6-C12Aryl formoxyl, C2-
C12Heterocyclic radical formoxyl；Or Rc, Rd connect cyclization with N atoms；
E3For hydrogen, halogen, C1-C8Alkyl, C1-C8Alkoxy, C6-C12Aryl, C6-C12Aryloxy group, connection C1-C8Alkoxy
Carbonyl or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently is hydrogen, C6-C12Aryl, C2-C12Heterocyclic radical, substitution
Or unsubstituted C1-C8Alkyl, formoxyl, substituted or unsubstituted C1-C8Alkyl formyl radical, substituted or unsubstituted C6-C12Virtue
Base formoxyl；Or Rc, Rd connect cyclization with N atoms；
E4、E5、E6And E7It independently is hydrogen, halogen, nitro, substituted or unsubstituted C1-C8It is alkyl, substituted or unsubstituted
C1-C8Alkoxy, substituted or unsubstituted C1-C8Alkyl amino, formamido, substituted or unsubstituted C1-C8Alkyl formamides
Base, connection C1-C8Carbonyl, the connection C of alkyl amino6-C12Carbonyl, the connection C of arylamino2-C12The carbonyl of heterocyclylamino group,
Connect C1-C8Carbonyl, sulfoamido, the substituted or unsubstituted C of alkoxy6-C12Aryl, substituted or unsubstituted C6-C12Fragrant oxygen
Base or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently is hydrogen, substituted or unsubstituted C6-C20Aryl, C2-C12It is miscellaneous
Ring group, C1-C8Alkyl, formoxyl, C1-C8Alkyl formyl radical, C6-C12Aryl formoxyl, C2-C12Heterocyclic radical formoxyl, substitution or
Unsubstituted C1-C8Alkyl sulphonyl, substituted or unsubstituted C6-C12Aryl sulfonyl, substituted or unsubstituted C2-C12Heterocycle
Base sulfonyl；Or Rc, Rd connect cyclization with N atoms.
In the optimal implementation of the present invention, in Formulas I a, Ib and Ic,
Z is CH2Or
N=0 or 1；
During n=1, X1For CH2Or phenyl；Y1For oxygen or carbonyl；
During m=0, Y C1-C4Alkyl amino or C1-C3Alkoxy；
During m=1, X is carbonyl, CH2, CH or benzyl；Y be nitrogen, NH,C1-C4Alkoxy, C5It is miscellaneous
Epoxy radicals or C1-C3Alkane siloxy；Can be singly-bound or double bond between X and Y；
R1For the phenyl of hydrogen, phenyl or nitro substitution；
R2For C1-C3Alkyl or C1-C3Alkoxy；
R3For hydrogen or C6Aryl；
E is halogen, nitro, C1-C4Alkyl, C1-C4Alkoxy, C1-C4Alkoxy carbonyl, C1-C8Alkyl amino sulfonyl,
C6-C12N-aryl sulfonyl；
E1And E2For independently hydrogen, halogen, C1-C4Alkyl or C1-C4Alkoxy；E3For hydrogen；
E4、E5And E7Independently to be hydrogen, C1-C4Alkyl or C1-C4Alkoxy；
E6For hydrogen, halogen, C1-C4Alkyl or C1-C6Alkoxy；
In Ia, as n=0, R2For hydrogen, halogen, C1-C4Alkyl or C1-C4Alkoxy.
The second object of the present invention is to provide the metal complex that a kind of structural formula is Formula II a, IIb, IIc：
Wherein, M is metal Ru (Ru), tungsten (W) or nickel (Ni)；
L1And L2It independently is halogen (Cl, Br- or I), RCOO-Or ArO-Anion；
L3For a kind of complex ligands of electron；
L is a kind of complex ligands of electron；
Wherein, Z CH2Or
M=0 or 1, n=0 or 1；During n=0, p=0 or 1；During n=1, p=0；
During n=1, X1And Y1It independently is nitrogen, oxygen, sulphur, CH2, substituted or unsubstituted C1-C20Alkyl, substitution or unsubstituted
C6-C20Aryl, substituted or unsubstituted C6-C20Aryloxy group, substituted or unsubstituted C2-C20Heterocyclic aryl, carbonyl, connection take
Generation or unsubstituted C1-C20Carbonyl, the substituted or unsubstituted C of connection of alkyl1-C20The carbonyl of alkoxy, imino group, substitution or
Unsubstituted C1-C20Alkyl imino base or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently is hydrogen, substitution or not taken
The C in generation6-C20Aryl, substituted or unsubstituted C2-C20Heterocyclic radical, substituted or unsubstituted C1-C20Alkyl, formoxyl, substitution or
Unsubstituted C1-C20Alkyl formyl radical, substituted or unsubstituted C6-C20Aryl formoxyl or substituted or unsubstituted C2-C20It is miscellaneous
Ring group formoxyl；Or Rc, Rd connect cyclization with N atoms；X1The parent of each group connection represented is Y1, wherein connection Y portion
Point can be each group in itself or group various substituents, Y1The parent of each group connection represented is X1, wherein
Connect R2Part can be group in itself or group various substituents；
During m=0, Y is nitrogen, oxygen, substituted or unsubstituted C1-C20Alkoxy, substituted or unsubstituted C6-C20Aryloxy group,
Substituted or unsubstituted C2-C20Heterocyclic aryl, carbonyl, the substituted or unsubstituted C of connection1-C20The carbonyl of alkyl, connection substitution or
Unsubstituted C1-C20Carbonyl, imino group, the substituted or unsubstituted C of alkoxy1-C20Alkyl imino base or such as formula RcRdShown in N-
Group；Wherein, Rc and Rd independently is hydrogen, substituted or unsubstituted C6-C20Aryl, substituted or unsubstituted C2-C20Heterocycle
Base, substituted or unsubstituted C1-C20Alkyl, formoxyl, substituted or unsubstituted C1-C20Alkyl formyl radical, substitution or unsubstituted
C6-C20Aryl formoxyl or substituted or unsubstituted C2-C20Heterocyclic radical formoxyl；Or Rc, Rd connect cyclization with N atoms；
In Formulas I a, Y represent group connection parent be X, wherein connect the other end part can be each group in itself or
The various substituents of group；In Formulas I b, the parent for the group connection that Y is represented be aromatic ring, the parent that the group that Y is represented in Ic connects
To connect R3Carbon；
During m=1, X is nitrogen, oxygen, sulphur, CH, CH2, carbonyl；Y is nitrogen, oxygen, CH, methylene, substituted or unsubstituted C1-C20
Alkoxy, substituted or unsubstituted C6-C20Aryl, substituted or unsubstituted C6-C20Aryloxy group, substituted or unsubstituted C2-C20
Heterocyclic aryl, the substituted or unsubstituted C of connection1-C20Carbonyl, the substituted or unsubstituted C of connection of alkyl1-C20The carbonyl of alkoxy
Base, imino group, substituted or unsubstituted C1-C20Alkyl imino base, unsubstituted C1-C20Alkyl imino base or such as formula RcRdN- institutes
The group shown；Wherein, Rc and Rd independently is hydrogen, substituted or unsubstituted C6-C20Aryl, substituted or unsubstituted C2-C20It is miscellaneous
Ring group, substituted or unsubstituted C1-C20Alkyl, formoxyl, substituted or unsubstituted C1-C20Alkyl formyl radical, substitution do not take
The C in generation6-C20Aryl formoxyl or substituted or unsubstituted C2-C20Heterocyclic radical formoxyl；Or Rc, Rd and N atom connect into
Ring；The parent for the group connection that X is represented be Y, wherein the part for connecting the other end can be each group in itself or group
Various substituents；Y represent group connection parent be X, wherein connect the other end part can be each group in itself,
Can be the various substituents of group；Between can be singly-bound or double bond；
R1For hydrogen, substituted or unsubstituted C1-C20Alkyl, substituted or unsubstituted C1-C20Alkoxy, substitution or unsubstituted
C1-C20Alkylthio group, the substituted or unsubstituted C of connection1-C20Carbonyl, the substituted or unsubstituted C of connection of alkoxy6-C20Fragrant oxygen
Carbonyl, the substituted or unsubstituted C of connection of base6-C20The carbonyl of heterocyclic radical epoxide, substituted or unsubstituted C6-C20Aryl, substitution
Or unsubstituted C6-C20Aryloxy group or substituted or unsubstituted C2-C20Heterocyclic radical；
R2For hydrogen, substituted or unsubstituted C1-C20Alkyl, substituted or unsubstituted C1-C20Alkoxy, substitution or unsubstituted
C1-C20Alkylthio group, substituted or unsubstituted C1-C20Alkyl siloxy, substituted or unsubstituted C2-C20Heterocyclic radical, substitution or
Unsubstituted C6-C20Aryl, C6-C20Aryloxy group, aldehyde radical, the substituted or unsubstituted C of connection1-C20The carbonyl of alkyl, connection substitution
Or unsubstituted C6-C20Carbonyl, the substituted or unsubstituted C of connection of aryl2-C20The carbonyl of heterocyclic radical or such as formula RcRdShown in N-
Group；Wherein, Rc and Rd independently is hydrogen, formoxyl, substituted or unsubstituted C1-C20Alkyl formyl radical, substitution do not take
The C in generation6-C20Aryl formoxyl or substituted or unsubstituted C2-C20Heterocyclic radical formoxyl；Or Rc, Rd and N atom connect into
Ring；
R3For hydrogen, substituted or unsubstituted C1-C20Alkyl, substituted or unsubstituted C1-C20Alkoxy, substitution or unsubstituted
C1-C20Alkylthio group, C2-C20Heterocyclic radical, substituted or unsubstituted C6-C20Aryl, substituted or unsubstituted C6-C20Aryloxy group,
Connect substituted or unsubstituted C1-C20Carbonyl, the substituted or unsubstituted C of connection of alkoxy6-C20The carbonyl of aryloxy group, connection
Substituted or unsubstituted C6-C20The carbonyl of heterocyclic radical epoxide or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently are
Hydrogen, formoxyl, substituted or unsubstituted C1-C20Alkyl formyl radical, substituted or unsubstituted C6-C20Aryl formoxyl or substitution or
Unsubstituted C2-C20Heterocyclic radical formoxyl；Or Rc, Rd connect cyclization with N atoms；
E is hydrogen, halogen, nitro, itrile group, sulfoxide group, sulfuryl, aldehyde radical, C1-C20Alkyl, C1-C20Alkoxy, C1-C20Alkane sulphur
Base, C1-C20Alkane silicon substrate, C1-C20Alkyl siloxy, C2-C20Heterocyclic radical, C6-C20Aryl, C6-C20Aryloxy group, connection C1-C20Alkane
Carbonyl, the connection C of base6-C20Carbonyl, the connection C of aryl2-C20Carbonyl, the connection C of heterocyclic radical1-C20The carbonyl of alkoxy, connection
C6-C20Carbonyl, the connection C of aryloxy group6-C20Carbonyl, aminoacyl, the connection C of heterocyclic radical epoxide1-C20The carbonyl of alkyl amino,
Connect C6-C20Carbonyl, the connection C of arylamino2-C20Carbonyl, urea groups, the substituted or unsubstituted C of heterocyclylamino group1-C20Alkane
Base urea groups, substituted or unsubstituted C6-C20Aryl-ureido, substituted or unsubstituted C2-C20Heterocyclic radical urea groups, connection C1-C20Alkane
Sulfonyl, the connection C of base amino6-C20Sulfonyl, the connection C of arylamino2-C20The sulfonyl of heterocyclylamino group or such as formula
RcRdGroup shown in N-；Wherein, Rc and Rd independently is hydrogen, substituted or unsubstituted C6-C20It is aryl, substituted or unsubstituted
C2-C20Heterocyclic radical, substituted or unsubstituted C1-C20Alkyl, formoxyl, substituted or unsubstituted C1-C20Alkyl formyl radical, substitution
Or unsubstituted C6-C20Aryl formoxyl, substituted or unsubstituted C2-C20Heterocyclic radical formoxyl, substituted or unsubstituted C1-C20
Alkyl sulphonyl, substituted or unsubstituted C6-C20Aryl sulfonyl or substituted or unsubstituted C2-C20Heterocyclyl sulfonyl；Or
Person Rc, Rd connect cyclization with N atoms；
E1For hydrogen, halogen, nitro, itrile group, C1-C20Alkyl, C1-C20Alkoxy, C1-C20Alkylthio group, C1-C20Alkane silicon substrate,
C1-C20Alkyl siloxy, C2-C20Heterocyclic radical, substituted or unsubstituted amino, aminoacyl, connection C1-C20The carbonyl of alkyl amino
Base, C6-C20Aryl, C6-C20Aryloxy group, sulfoxide group, sulfuryl, aldehyde radical, connection C1-C20The carbonyl of alkyl, connection substitute or not taken
The C in generation6-C20Carbonyl, the substituted or unsubstituted C of connection of aryl2-C20Carbonyl, the connection C of heterocyclic radical1-C20The carbonyl of alkoxy
Base, connection C6-C20Carbonyl, the connection C of arylamino2-C20Carbonyl, urea groups, the substituted or unsubstituted C of heterocyclylamino group1-C20
Alkyl urea groups, substituted or unsubstituted C1-C20Alkyl urea groups, substituted or unsubstituted C6-C20Aryl-ureido or substitution do not take
The C in generation2-C20Heterocyclic radical urea groups；
E2For hydrogen, halogen, C1-C20Alkyl, C1-C20Alkoxy, C1-C20Alkylthio group, C1-C20Alkane silicon substrate, C1-C20Alkyl silicon
Epoxide, aminoacyl, connection C1-C20Carbonyl, the connection C of alkyl amino6-C20Carbonyl, the connection C of arylamino2-C20Heterocyclic radical
Carbonyl, the C of amino6-C20Aryl, C6-C20Aryloxy group, C2-C20Heterocyclic aryl, aldehyde radical, connection C1-C20The carbonyl of alkyl, connection
C6-C20Carbonyl, the connection C of aryl2-C20Carbonyl, the connection C of heterocyclic radical1-C20Carbonyl, the connection C of alkoxy6-C20Arylamino
Carbonyl, connection C2-C20The carbonyl of heterocyclylamino group or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently be hydrogen,
Substituted or unsubstituted C6-C20Aryl, substituted or unsubstituted C2-C20Heterocyclic radical, substituted or unsubstituted C1-C20Alkyl, first
Acyl group, substituted or unsubstituted C1-C20Alkyl formyl radical, substituted or unsubstituted C6-C20Aryl formoxyl, substitution or unsubstituted
C2-C20Heterocyclic radical formoxyl, substituted or unsubstituted C1-C20Alkyl sulphonyl, substituted or unsubstituted C6-C20Arylsulfonyl
Base or substituted or unsubstituted C2-C20Heterocyclyl sulfonyl；Or Rc, Rd connect cyclization with N atoms；
E3For hydrogen, halogen, C1-C20Alkyl, C1-C20Alkoxy, C1-C20Alkylthio group, C1-C20Alkyl siloxy, C6-C20Virtue
Epoxide, C6-C20Aryl, C2-C20Heterocyclic aryl, connection C1-C20Carbonyl, the substituted or unsubstituted C of connection of alkoxy6-C20Virtue
Carbonyl, the substituted or unsubstituted C of connection of epoxide6-C20The carbonyl of heterocyclic radical epoxide or such as formula RcRdGroup shown in N-；Wherein,
Rc and Rd independently is hydrogen, substituted or unsubstituted C6-C20Aryl, substituted or unsubstituted C2-C20Heterocyclic radical, substitution do not take
The C in generation1-C20Alkyl, formoxyl, substituted or unsubstituted C1-C20Alkyl formyl radical, substituted or unsubstituted C6-C20Aryl first
Acyl group, substituted or unsubstituted C2-C20Heterocyclic radical formoxyl, substituted or unsubstituted C1-C20Alkyl sulphonyl, substitution do not take
The C in generation6-C20Aryl sulfonyl or substituted or unsubstituted C2-C20Heterocyclyl sulfonyl；Or Rc, Rd and N atom connect into
Ring；
E4、E5、E6And E7It independently is hydrogen, halogen, nitro, itrile group, sulfoxide group, sulfuryl, aldehyde radical, substituted or unsubstituted
C1-C20Alkyl, substituted or unsubstituted C1-C20Alkoxy, C1-C20Alkylthio group, C1-C20Alkane silicon substrate, C1-C20Alkane siloxy, take
Generation or unsubstituted C2-C20Heterocyclic radical, substituted or unsubstituted amino, aminoacyl, the substituted or unsubstituted C of connection1-C20Alkane
Carbonyl, the substituted or unsubstituted C of connection of base amino6-C20Carbonyl, the substituted or unsubstituted C of connection of arylamino2-C20It is miscellaneous
Carbonyl, the substituted or unsubstituted C of connection of ring group amino1-C20Carbonyl, the substituted or unsubstituted C of connection of alkyl6-C20Aryl
Carbonyl, the substituted or unsubstituted C of connection2-C20Carbonyl, the substituted or unsubstituted C of connection of heterocyclic radical1-C20The carbonyl of alkoxy
Base, the substituted or unsubstituted C of connection6-C20Carbonyl, the substituted or unsubstituted C of connection of aryloxy group6-C20The carbonyl of heterocyclic radical epoxide
Base, urea groups, substituted or unsubstituted C1-C20Alkyl urea groups, substituted or unsubstituted C1-C20Alkyl urea groups, substitution or unsubstituted
C6-C20Aryl-ureido or substituted or unsubstituted C2-C20Heterocyclic radical urea groups, substituted or unsubstituted C6-C20Aryl, substitution or
Unsubstituted C6-C20Aryloxy group or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently is hydrogen, substituted or unsubstituted
C6-C20Aryl, substituted or unsubstituted C2-C20Heterocyclic radical, substituted or unsubstituted C1-C20Alkyl, formoxyl, substitution do not take
The C in generation1-C20Alkyl formyl radical, substituted or unsubstituted C6-C20Aryl formoxyl, substituted or unsubstituted C2-C20Heterocyclic radical first
Acyl group, substituted or unsubstituted C1-C20Alkyl sulphonyl, substituted or unsubstituted C6-C20Aryl sulfonyl or substitution do not take
The C in generation2-C20Heterocyclyl sulfonyl；Or Rc, Rd connect cyclization with N atoms.
In the present invention, L is preferably a of following structural III, III b, III c or III d in described IIa, IIb and IIc：
Wherein, R4And R5It independently is C1-C20Alkyl, C6-C20Aryl, C1-C20Heterocyclic radical, aldehyde radical, connection C1-C20Alkyl
Carbonyl, formamido, C1-C20Alkyl amido, urea groups, substituted or unsubstituted C1-C20Alkyl urea groups, sulfoamido or
C1-C20Alkylsulfonamido；
R6And R7It independently is hydrogen, C1-C20Alkyl, C1-C20Alkoxy, C1-C20Alkylthio group, C1-C20Alkane silicon substrate, C1-C20Alkane
Base siloxy, C6-C20Aryl, C6-C20Aryloxy group, C2-C20Heterocyclic radical, sulfoxide group, sulfuryl, aldehyde radical, connection C1-C20The carbonyl of alkyl
Base, connection C1-C20Carbonyl, formamido, the C of alkoxy1-C20Alkyl amido, urea groups, substituted or unsubstituted C1-C20
Alkyl urea groups, sulfoamido, C1-C20Alkylsulfonamido, halogen, nitro or itrile group；
R8And R9It independently is substituted or unsubstituted C1-C20Alkyl, C1-C20Alkoxy, C6-C20Aryl, C6-C20Fragrant oxygen
Base or C2-C20Heterocyclic radical；
In a of formula III, preferably, R4And R5It is aryl；R6And R7It is hydrogen.
More preferably, L structural formula is a of formula III or III d；R4And R5It is 2,4,6- trimethylphenyls；R6And R7It independently is hydrogen
Or III d；R8And R9It is cyclohexyl.
In the another embodiment of the present invention, in the c of II a- of formula II,
Metal (M) is ruthenium；
L1And L2It is chlorion；
L is III a or III d；Wherein R4、R5、R6、R7、R8And R9It is identical with aforementioned definitions；
M=0 or 1, n=0 or 1；During n=0, p=0 or 1；During n=1, p=0；
During p=1, L3The pyridine radicals being substituted for one or more of ortho position, meta and contraposition, the nitrogen-atoms of pyridine radicals
Parent is connected, pyridine radicals meta and the substituent aligned are independently halogen, nitro, itrile group, sulfoxide group, sulfuryl, C1-C15Alkane
Base, C1-C15Alkoxy, C1-C15Alkylthio group, C1-C15Alkane silicon substrate, C1-C15Alkyl siloxy, C6-C15Aryloxy group, C1-C15Alkane
Base amido, substituted or unsubstituted C6-C15Aryl, substituted or unsubstituted C2-C15Heterocyclic aryl, carbonyl, connection substitution or not
Substituted C1-C15Carbonyl, the substituted or unsubstituted C of connection of alkyl1-C15Carbonyl, formamido, the C of alkoxy1-C15Alkyl
Formamido, urea groups, substituted or unsubstituted C1-C15Alkyl urea groups, sulfoamido or C1-C15Alkylsulfonamido；
During n=1, p=0, X1And Y1It independently is nitrogen, oxygen, sulphur, CH2, substituted or unsubstituted C1-C15Alkyl, substitution or
Unsubstituted C6-C15Aryl, substituted or unsubstituted C6-C15Aryloxy group, substituted or unsubstituted C2-C15Heterocyclic aryl, carbonyl,
Connect substituted or unsubstituted C1-C15Carbonyl, the substituted or unsubstituted C of connection of alkyl1-C15The carbonyl of alkoxy, imino group,
Substituted or unsubstituted C1-C15Alkyl imino base or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently is hydrogen, substitution
Or unsubstituted C6-C15Aryl, substituted or unsubstituted C2-C15Heterocyclic radical, substituted or unsubstituted C1-C15Alkyl, formoxyl,
Substituted or unsubstituted C1-C15Alkyl formyl radical, substituted or unsubstituted C6-C15Aryl formoxyl is substituted or unsubstituted
C2-C15Heterocyclic radical formoxyl；Or Rc, Rd connect cyclization with N atoms；X1The parent of each group connection represented is Y1, wherein connecting
The part for connecing the other end can be each group in itself or group various substituents；Y1Each group connection represented
Parent is X1, wherein connection the other end part can be each group in itself or group various substituents；
During m=0, Y is nitrogen, oxygen, substituted or unsubstituted C1-C15Alkoxy, substituted or unsubstituted C6-C15Aryloxy group,
Substituted or unsubstituted C2-C15Heterocyclic aryl, the substituted or unsubstituted C of connection1-C15The carbonyl of alkyl, connection substitute or not taken
The C in generation1-C15Carbonyl, the substituted or unsubstituted C of connection of alkyl1-C15It is the carbonyl of alkoxy, imino group, substituted or unsubstituted
C1-C15Alkyl imino base or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently is hydrogen, substituted or unsubstituted C6-
C15Aryl, substituted or unsubstituted C2-C15Heterocyclic radical, substituted or unsubstituted C1-C15Alkyl, formoxyl, substitution or unsubstituted
C1-C15Alkyl formyl radical, substituted or unsubstituted C6-C15Aryl formoxyl or substituted or unsubstituted C2-C15Heterocyclic radical first
Acyl group；Or Rc, Rd connect cyclization with N atoms；In Formulas I a, the parent for the group connection that Y is represented is X, wherein connecting the other end
Part can be each group in itself or group various substituents；In Formulas I b, the parent for the group connection that Y is represented
For aromatic ring, the parent for the group connection that Y is represented in Ic is connection R3Carbon；
During m=1, X is nitrogen, oxygen, sulphur, CH, CH2, carbonyl；Y is nitrogen, oxygen, CH, methylene, substituted or unsubstituted C1-C15
Alkoxy, substituted or unsubstituted C6-C15Aryl, substituted or unsubstituted C6-C15Aryloxy group, substituted or unsubstituted C2-C15
Heterocyclic aryl, the substituted or unsubstituted C of connection1-C15Carbonyl, the substituted or unsubstituted C of connection of alkyl1-C15The carbonyl of alkoxy
Base, substituted or unsubstituted C1-C15Imido grpup；Such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently be hydrogen, substitution or
Unsubstituted C6-C15Aryl, substituted or unsubstituted C2-C15Heterocyclic radical, substituted or unsubstituted C1-C15Alkyl, formoxyl, take
Generation or unsubstituted C1-C15Alkyl formyl radical, substituted or unsubstituted C6-C15Aryl formoxyl or substituted or unsubstituted C2-
C15Heterocyclic radical formoxyl；Or Rc, Rd connect cyclization with N atoms；The parent for the group connection that X is represented is Y, wherein connecting another
The part at end can be each group in itself or group various substituents；The parent for the group connection that Y is represented is X, its
It is middle connection the other end part can be each group in itself or group various substituents；Between can be single
Key or double bond；
R1For hydrogen, substituted or unsubstituted C1-C15Alkyl, substituted or unsubstituted C1-C15Alkoxy, substitution or unsubstituted
C1-C15Alkylthio group, the substituted or unsubstituted C of connection1-C15The carbonyl of alkoxy, substituted or unsubstituted C6-C15Aryl, take
Generation or unsubstituted C6-C15Aryloxy group or substituted or unsubstituted C2-C15Heterocyclic radical；
R2For hydrogen, substituted or unsubstituted C1-C15Alkyl, substituted or unsubstituted C1-C15Alkoxy, substitution or unsubstituted
C1-C15Alkylthio group, substituted or unsubstituted C1-C15Alkane siloxy, substituted or unsubstituted C2-C15Heterocyclic radical, C6-C15Virtue
Base, C6-C15Aryloxy group, aldehyde radical, the substituted or unsubstituted C of connection1-C15Carbonyl, the substituted or unsubstituted C of connection of alkyl1-C15
The carbonyl of alkoxy or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently is hydrogen, formoxyl, substituted or unsubstituted
C1-C15Alkyl formyl radical, substituted or unsubstituted C6-C15Aryl formoxyl or substituted or unsubstituted C2-C15Heterocyclic radical formyl
Base；Or Rc, Rd connect cyclization with N atoms；
R3For hydrogen, substituted or unsubstituted C1-C15Alkyl, substituted or unsubstituted C1-C15Alkoxy, substitution or unsubstituted
C1-C15Alkylthio group, substituted or unsubstituted C2-C15Heterocyclic radical, substituted or unsubstituted C6-C15Aryl, substitution or unsubstituted
C6-C15Aryloxy group, the substituted or unsubstituted C of connection1-C15The carbonyl of alkoxy or such as formula RcRdGroup shown in N-；Wherein,
Rc and Rd independently is hydrogen, formoxyl, substituted or unsubstituted C1-C15Alkyl formyl radical, substituted or unsubstituted C6-C15Aryl
Formoxyl or substituted or unsubstituted C2-C15Heterocyclic radical formoxyl；Or Rc, Rd connect cyclization with N atoms；
E is hydrogen, halogen, nitro, itrile group, sulfoxide group, sulfuryl, aldehyde radical, C1-C15Alkyl, C1-C15Alkoxy, C1-C15Alkane sulphur
Base, C1-C15Alkane silicon substrate, C1-C15Alkane siloxy, C2-C15Heterocyclic radical, C6-C15Aryl, C6-C15Aryloxy group, connection C1-C15Alkyl
Carbonyl, connection C6-C15Carbonyl, the connection C of aryl2-C15Carbonyl, the connection C of heterocyclic radical1-C15Carbonyl, the aminoacyl of alkoxy
Base, connection C1-C15Carbonyl, the connection C of alkyl amino6-C15Carbonyl, the connection C of arylamino2-C15The carbonyl of heterocyclylamino group,
Urea groups, substituted or unsubstituted C1-C15Alkyl urea groups or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently be hydrogen,
Aryl, C2-C20Heterocyclic radical, C1-C20Alkyl, formoxyl, C1-C15Alkyl formyl radical, C6-C15Aryl formoxyl, C2-C15Heterocyclic radical
Formoxyl, C1-C15Alkyl sulphonyl, C6-C20Aryl sulfonyl or C2-C20Heterocyclyl sulfonyl；Or Rc, Rd and N atom
Connection cyclization；
E1For hydrogen, halogen, nitro, sulfuryl, C1-C15Alkyl, C1-C15Alkoxy, C1-C15Alkylthio group, C1-C15Alkane silicon substrate,
C1-C15Alkane siloxy, C2-C15Heterocyclic radical, C6-C15Aryl, C6-C15Aryloxy group, aldehyde radical, connection C1-C15The carbonyl of alkyl, connection
C1-C15Carbonyl, aminoacyl, the connection C of alkoxy1-C15Carbonyl, urea groups, the substituted or unsubstituted C of alkyl amino1-C15Alkane
Base urea groups, substituted or unsubstituted C1-C15Alkyl, connection C1-C15The sulfonyl of amino or such as formula RcRdGroup shown in N-；Its
In, Rc and Rd independently are hydrogen, aryl, C2-C20Heterocyclic radical, C1-C20Alkyl, formoxyl, C1-C15Alkyl formyl radical, C6-C15Virtue
Base formoxyl, C2-C15Heterocyclic radical formoxyl, C1-C15Alkyl sulphonyl, C6-C20Aryl sulfonyl or C2-C20Heterocyclic radical sulphonyl
Base；Or Rc, Rd connect cyclization with N atoms；
E2For hydrogen, halogen, C1-C15Alkyl, C1-C15Alkoxy, C1-C15Alkylthio group, C1-C15Alkane silicon substrate, C1-C15Alkane silica
Base, C6-C15Aryl, C6-C15Aryloxy group, C2-C15Heterocyclic aryl, aldehyde radical, connection C1-C15Carbonyl, the connection C of alkyl1-C15Alcoxyl
Carbonyl, aminoacyl, the substituted or unsubstituted C of connection of base1-C15The carbonyl of alkyl amino or such as formula RcRdGroup shown in N-；
Wherein, Rc and Rd independently is hydrogen, C6-C15Aryl, C2-C15Heterocyclic radical, C1-C15Alkyl, formoxyl, C1-C15Alkyl formyl radical,
C6-C15Aryl formoxyl, C2-C15Heterocyclic radical formoxyl；Or Rc, Rd connect cyclization with N atoms；
E3For hydrogen, halogen, C1-C15Alkyl, C1-C15Alkoxy, C1-C15Alkylthio group, C1-C15Alkane siloxy, C6-C15Virtue
Base, C6-C15Aryloxy group, C2-C15Heterocyclic aryl, connection C1-C15Carbonyl, aminoacyl, the connection C of alkoxy1-C15Alkyl amino
Carbonyl or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently is hydrogen, C6-C15Aryl, C2-C15Heterocyclic radical, substitution
Or unsubstituted C1-C15Alkyl, formoxyl, substituted or unsubstituted C1-C15Alkyl formyl radical, substituted or unsubstituted C6-C15
Aryl formoxyl；Or Rc, Rd connect cyclization with N atoms；
E4、E5、E6And E7It independently is hydrogen, halogen, nitro, itrile group, sulfoxide group, sulfuryl, aldehyde radical, substituted or unsubstituted
C1-C15Alkyl, substituted or unsubstituted C1-C15Alkoxy, C1-C15Alkylthio group, C1-C15Alkane silicon substrate, C1-C15Alkane siloxy, take
Generation or unsubstituted C2-C15Heterocyclic radical, aminoacyl, connection C1-C15Carbonyl, the connection C of alkyl amino6-C15Arylamino
Carbonyl, connection C2-C15Carbonyl, the substituted or unsubstituted C of connection of heterocyclylamino group1-C15The carbonyl of alkyl, connection substitution or not
Substituted C1-C15Carbonyl, urea groups, the substituted or unsubstituted C of alkoxy1-C15Alkyl urea groups, substituted or unsubstituted C1-C15
Alkylsulfonamido, connection C1-C15The sulphonyl of alkyl amino, substituted or unsubstituted C6-C15It is aryl, substituted or unsubstituted
C6-C15Aryloxy group or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently is hydrogen, substituted or unsubstituted C6-C20Virtue
Base, substituted or unsubstituted C2-C15Heterocyclic radical, substituted or unsubstituted C1-C15Alkyl, formoxyl, C1-C15Alkyl formyl radical,
C6-C15Aryl formoxyl, C2-C15Heterocyclic radical formoxyl, substituted or unsubstituted C1-C15Alkyl sulphonyl, substitution or unsubstituted
C6-C15Aryl sulfonyl or substituted or unsubstituted C2-C15Heterocyclyl sulfonyl；Or Rc, Rd connect cyclization with N atoms.
More preferably, in the c of II a- of formula II,
M=0 or 1, n=0 or 1；During n=0, p=0 or 1；During n=1, p=0；
During p=1, L3The pyridine radicals being substituted for one or more of ortho position, meta and contraposition, the nitrogen-atoms of pyridine radicals
Parent is connected, pyridine radicals meta and the substituent aligned are independently halogen, nitro, itrile group, sulfoxide group, sulfuryl, C1-C8Alkyl,
C1-C8Alkoxy, C1-C8Alkylthio group, C1-C8Alkane silicon substrate, C1-C8Alkyl siloxy, C6-C12Aryloxy group, C1-C8Alkyl amine group, take
Generation or unsubstituted C6-C12Aryl, substituted or unsubstituted C2-C12Heterocyclic aryl, carbonyl, the substituted or unsubstituted C of connection1-C8
Carbonyl, the substituted or unsubstituted C of connection of alkyl1-C8Carbonyl, formamido, the C of alkoxy1-C8Alkyl amido, urea
Base, substituted or unsubstituted C1-C8Alkyl urea groups, sulfoamido or C1-C8Alkylsulfonamido；
During n=1, p=0, X1For oxygen, CH2, substituted or unsubstituted C6-C12Aryl；Y1For oxygen, nitrogen, carbonyl, connection substitution
Or unsubstituted C1-C8Carbonyl, the substituted or unsubstituted C of connection of alkyl1-C8The carbonyl of alkoxy, imino group, substitution or not
Substituted C1-C8Imino group；Wherein, X1The parent of each group connection represented is Y1, Y1Represent each group connection parent be
X1；
During m=0, Y is nitrogen, oxygen, carbonyl, the substituted or unsubstituted C of connection1-C8The carbonyl of alkyl, connection substitute or not taken
The C in generation1-C8Carbonyl, imino group, the substituted or unsubstituted C of alkoxy1-C8Imido grpup or such as formula RcRdGroup shown in N-；Its
In, Rc and Rd independently are hydrogen, substituted or unsubstituted C6-C12Aryl, substituted or unsubstituted C2-C12Heterocyclic radical or substitution or
Unsubstituted C1-C8Alkyl；Or Rc, Rd connect cyclization with N atoms；In Formulas I a, the parent for the group connection that Y is represented is X, formula
In Ib, the parent for the group connection that Y is represented be aromatic ring, and the parent of the group connection that Y is represented in Ic is connects R3Carbon；
During m=1, X is nitrogen, oxygen, methine, methylene, carbonyl；Y is nitrogen, oxygen, substituted or unsubstituted C6-C12Aryl,
Connect substituted or unsubstituted C1-C8Carbonyl, the substituted or unsubstituted C of connection of alkyl1-C8The carbonyl of alkoxy, imino group,
Substituted or unsubstituted C1-C8Alkyl imino base or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently is hydrogen, substitution
Or unsubstituted C6-C12Aryl, substituted or unsubstituted C2-C12Heterocyclic radical or substituted or unsubstituted C1-C8Alkyl；Or Rc,
Rd with N atoms connect cyclization；The parent for the group connection that X is represented is Y, wherein the part of the connection other end can be each group sheet
The various substituents of body or group；The parent for the group connection that Y is represented be X, wherein the part for connecting the other end can be with
Be each group in itself or group various substituents；Between can be singly-bound or double bond；
R1For hydrogen or substituted or unsubstituted C6-C12Aryl；
R2For methyl, isopropyl, substituted or unsubstituted C1-C8Alkyl or substituted or unsubstituted C6-C12Aryl；
R3For hydrogen, substituted or unsubstituted C1-C8Alkyl, substituted or unsubstituted C1-C8Alkoxy, C6-C12Aryl, C6-
C12Aryloxy group, C2-C12Heterocyclic aryl, connection C1-C8The carbonyl of alkoxy or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd
It independently is hydrogen, formoxyl, substituted or unsubstituted C1-C8Alkyl formyl radical, substituted or unsubstituted C6-C12Aryl formoxyl
Or substituted or unsubstituted C2-C12Heterocyclic radical formoxyl；Or Rc, Rd connect cyclization with N atoms；
E is hydrogen, halogen, nitro, C1-C8Alkyl, C1-C8Alkoxy, C6-C12Aryl, connection C1-C8The carbonyl of alkyl, connect
Meet C1-C8Carbonyl, the connection C of alkoxy1-C8Carbonyl, the connection C of alkyl amino1-C8Carbonyl, the connection C of alkyl amino6-C12Virtue
Carbonyl, the connection C of base amino2-C12Carbonyl, the substituted or unsubstituted C of connection of heterocyclylamino group1-C8The sulphonyl of alkyl amine group
Base；Or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently is hydrogen, aryl, C2-C12Heterocyclic radical, C1-C8Alkyl, first
Acyl group, C1-C8Alkyl formyl radical, C6-C12Aryl formoxyl, C2-C12Heterocyclic radical formoxyl, substituted or unsubstituted C1-C8Alkyl
Sulfonyl, substituted or unsubstituted C6-C12Aryl sulfonyl or substituted or unsubstituted C2-C12Heterocyclyl sulfonyl；Or Rc,
Rd with N atoms connect cyclization；
E1For hydrogen, halogen, nitro, C1-C8Alkyl, C1-C8Alkoxy, connection C1-C8Carbonyl, the C of alkyl amino6-C12Virtue
Base, C6-C12Aryloxy group, connection C1-C8The carbonyl of alkoxy or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently are
Hydrogen, C6-C12Aryl, C2-C12Heterocyclic radical, C1-C8Alkyl, formoxyl, C1-C8Alkyl formyl radical, C6-C12Aryl formoxyl, C2-
C12Heterocyclic radical formoxyl, substituted or unsubstituted C1-C8Alkyl sulphonyl, substituted or unsubstituted C6-C8Aryl sulfonyl takes
Generation or unsubstituted C2-C12Heterocyclyl sulfonyl；Or Rc, Rd connect cyclization with N atoms；
E2For hydrogen, halogen, C1-C8Alkyl, C1-C8Alkoxy, C6-C12Aryl, C6-C12Aryloxy group, C2-C12Heterocyclic aryl,
Connect substituted or unsubstituted C1-C8The carbonyl of alkoxy or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently are
Hydrogen, C6-C12Aryl, C2-C12Heterocyclic radical, C1-C8Alkyl, formoxyl, C1-C8Alkyl formyl radical, C6-C12Aryl formoxyl, C2-
C12Heterocyclic radical formoxyl；Or Rc, Rd connect cyclization with N atoms；
E3For hydrogen, halogen, C1-C8Alkyl, C1-C8Alkoxy, C6-C12Aryl, C6-C12Aryloxy group, connection C1-C8Alkoxy
Carbonyl or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently is hydrogen, C6-C12Aryl, C2-C12Heterocyclic radical, substitution
Or unsubstituted C1-C8Alkyl, formoxyl, substituted or unsubstituted C1-C8Alkyl formyl radical, substituted or unsubstituted C6-C12Virtue
Base formoxyl；Or Rc, Rd connect cyclization with N atoms；
E4、E5、E6And E7It independently is hydrogen, halogen, nitro, substituted or unsubstituted C1-C8It is alkyl, substituted or unsubstituted
C1-C8Alkoxy, substituted or unsubstituted C1-C8Alkyl amino, formamido, substituted or unsubstituted C1-C8Alkyl formamides
Base, connection C1-C8Carbonyl, the connection C of alkyl amino6-C12Carbonyl, the connection C of arylamino2-C12The carbonyl of heterocyclylamino group,
Connect C1-C8Carbonyl, sulfoamido, the substituted or unsubstituted C of alkoxy6-C12Aryl, substituted or unsubstituted C6-C12Fragrant oxygen
Base or such as formula RcRdGroup shown in N-；Wherein, Rc and Rd independently is hydrogen, substituted or unsubstituted C6-C12Aryl, C2-C12It is miscellaneous
Ring group, C1-C8Alkyl, formoxyl, C1-C8Alkyl formyl radical, C6-C12Aryl formoxyl, C2-C12Heterocyclic radical formoxyl, substitution or
Unsubstituted C1-C8Alkyl sulphonyl, substituted or unsubstituted C6-C12Aryl sulfonyl, substituted or unsubstituted C2-C12Heterocycle
Base sulfonyl；Or Rc, Rd connect cyclization with N atoms.
In the optimal implementation of the one of the present invention, in the c of II a- of formula II,
M is ruthenium；L isThricyclohexyl phosphorus；L1And L2It is chlorine；
N=0 or 1；
During n=0, p=0 or 1；During n=1, p=0；
During p=1, L3The pyridyl ligands being substituted for meta and/or contraposition, the nitrogen-atoms connection parent of pyridine radicals, pyrrole
The meta of piperidinyl and the substituent of contraposition are respectively halogen, C1-C3Alkoxy, C1-C6Alkyl amine group, substituted or unsubstituted C6-
C12Aryl；
During n=1, p=0, X1For CH2Or phenyl；Y1For oxygen or carbonyl；
During m=0, Y C1-C4Alkyl amino or C1-C3Alkoxy；
During m=1, X is carbonyl, CH2, CH or benzyl；Y be nitrogen, NH,C1-C4Alkoxy, C5It is miscellaneous
Epoxy radicals or C1-C3Alkane siloxy；Can be singly-bound or double bond between X and Y；
R1For hydrogen, C6Aryl or the benzyl of nitro substitution；
R2For C1-C3Alkyl or C1-C3Alkoxy；
R3For hydrogen or C6Aryl；
E is halogen, nitro, C1-C4Alkyl, C1-C4Alkoxy, C1-C4Alkoxy carbonyl, C1-C8Alkyl amino sulfonyl,
C6-C12N-aryl sulfonyl；
E1And E2For independently hydrogen, halogen, C1-C4Alkyl or C1-C4Alkoxy；E3For hydrogen；
E4、E5And E7Independently to be hydrogen, C1-C4Alkyl or C1-C4Alkoxy；
E6For hydrogen, halogen, C1-C4Alkyl or C1-C6Alkoxy；
In Ia, as n=0, R2For hydrogen, halogen, C1-C4Alkyl or C1-C4Alkoxy.
The third object of the present invention is to provide a kind of preparation method of metal complex, and it can appointing by following three kinds of methods
One kind is made：
Method one includes following three steps：
The structural formula of above-mentioned metal complex intermediate (Va, Vb, Vc) is as follows：
1) under inert gas shielding, by the substituted or unsubstituted Tosylhydrazone as shown in SM-2 in inorganic strong alkali
Anhydrous organic solvent in generate Cabbeen transition state；Wherein, Ra、Rb、Rc、RdAnd ReAlone for hydrogen, C1-C8Alkyl or C1-C8Alkane
Epoxide；
2) under inert gas shielding, Cabbeen transition state and ML that step 1) obtains1L2(PPh)3Reaction, generate metal complex
Thing intermediate compound IV；Wherein, M, L1And L2Definition with described in claim any one of 5-11, but L1And L2It is not RCOO-；
3) under inert gas shielding, the metal complex intermediate and complex ligands Ia, Ib or Ic that step 2) obtains are anti-
Metal complex intermediate Va, Vb or Vc should be generated；Wherein, Va, Vb or Vc be in IIa, IIb or IIc L be PPh3When change
Compound, wherein M, L1、L2、Y、Y1、R1、R2、E、E1、E2And E3It is the same as those described above；
Preferably, L1And L2It is chlorine.
Wherein, in step 1), described Ra、Rb、Rc、RdAnd ReIt is preferably hydrogen；Described inorganic strong alkali is preferably
One or more in sodium methoxide, caustic alcohol, sodium tert-butoxide and sodium hydrogen, more preferably caustic alcohol；The use of described inorganic strong alkali
Amount is preferably 1-3 times, more preferably 1.5-2 times of SM-2 moles；Described anhydrous organic solvent is preferably without water beetle
One or more in alcohol, ethanol, the tert-butyl alcohol and tetrahydrofuran, more preferably absolute ethyl alcohol；Described anhydrous organic solvent
Dosage is preferably 5-30 times of SM-2 moles, more preferably 15 times；The temperature of described reaction is preferably 45-75 DEG C,
More preferably 55-65 DEG C；
In step 2), the temperature of described reaction is preferably -50 DEG C to -85 DEG C, more preferably -65 DEG C to -75 DEG C；Institute
The ML stated1L2L3Dosage be preferably 0.3-1.0 times, more preferably 0.6-0.7 times of SM-2 moles；Described ML1L2
(PPh)3Preferably RuCl2P(Ph3)3；
In step 3), the temperature of described reaction is preferably -50 DEG C to -85 DEG C, more preferably -65 DEG C to -75 DEG C；Institute
Complex ligands Ia, Ib or Ic for stating dosage are preferably 1-3 times of complex intermediate mole, more preferably 1.5-2
Times；
Above-mentioned steps 1) in-step 3), the time of reaction is untill detection reaction completely.
Work as ML1L2L is RuCl2P(Ph3)3When, Va, Vb and Vc of generation are as follows：
Method two：By Va, Vb or Vc described in method one under inert gas shielding respectively with except PPh3Outer
The complex ligands L reactions of other electrons generate following metal complex IIa, IIb or IIc, wherein, p=0, M, L, L1、L2、
Y、Y1、R1、R2、E、E1、E2And E3It is as defined above described, but L is not PPh3；
Wherein, preferably, generation metal complex IIa, IIb or IIc in, L be thricyclohexyl phosphorus orMes=2,4,6- trimethylphenyls；The temperature of described reaction is preferably 20 DEG C to 75 DEG C, with network
Compound ligand i IIa is more preferably 60 DEG C to 75 DEG C when reacting, and is more preferably 20 DEG C to 35 when being reacted with complex ligands IIId
℃；Described IIIa or IIId dosage are preferably 1-3 times of complex intermediate Va, Vb or Vc mole, more preferably
For 1.5-2 times；
Method three：By IIa, IIb or IIc under inert gas shielding respectively with addition to thricyclohexyl phosphorus other to electricity
The complex ligands L reactions of son generate following metal complex IIa, IIb or IIc, wherein, as reactant IIa, IIb or
In IIc：P=0, M, L1、L2、Y、Y1、R1、R2、E、E1、E2And E3As defined above described, L is thricyclohexyl phosphorus；As product
IIa, IIb or IIc in：P=0, M, L1、L2、Y、Y1、R1、R2、E、E1、E2And E3It is as defined above described, but L is not three hexamethylenes
Base phosphorus；
Method four：Under inert gas shielding, by product IIa, IIb described in any one of method one to method three
Or the complex ligands L of IIc and electron3Reaction generation IIa, IIb or IIc, wherein, IIa, IIb of the product of this method
Or in IIc：P=1, M, L, L1、L2、L3、Y、Y1、R1、R2、E、E1、E2And E3It is the same as those described above；In method four, the temperature of described reaction
Degree is preferably 20 DEG C to 35 DEG C.
Method one is into method four, preferably, L1And L2It is chlorine.
Here each reaction condition in method three and method four is the normal condition of this two class reaction.
In the present invention, when Z is CH2When, metal complex ligand i a of the invention can be prepared by following reaction：
Wherein, the conditions of the reaction can be the normal condition of such Suzuki reactions.Similarly, when Z is CH2When, Ib and Ic
Also it can be reacted and prepared by this class.
Wherein Y, Y1、R1、R2、E、E1、E2And E3It is as defined above.
The metal complex of the present invention can also be prepared by other two methods, be prior art, their route is such as
Shown in lower：
Preparation method one：
Each reaction condition in this route is the normal condition of this few class reaction.
In this route, the Z in Ia, Ib or Ic is tolysulfonyl -2- hydrazono-s (TsNHN).First from amino-sulfonyl and
The benzaldehyde of the electron-withdrawing groups such as sulfonamide substitution and tolysulfonyl hydrazine reaction generation Ia, Ib or Ic, then in inert gas shielding
Under, Cabbeen is generated in the ethanol solution of caustic alcohol or sodium methoxide, afterwards and RuCl2P(Ph3)3Reaction generation is containing triphenyl phosphorus
Ruthenium complex (Va-Vc), ruthenium complex (Va-Vc) generate part (L) with thricyclohexyl phosphorus reaction again under inert gas shielding
For III d ruthenium complex (IIa-IIc), according to chemism by complex compound (Va-Vc) or complex compound that obtained part is III d
(IIa-IIc) it is more preferable that the catalytic activity that generation part is III a is reacted with five-membered ring part (IIIa) under inert gas shielding
The c of II a- of complex compound catalyst II.
Preparation method two：
Thus IIa and IIb route can equally be prepared.Each reaction condition in this route is the routine of this few class reaction
Condition；Wherein, EWG is electron withdraw group, L be thricyclohexyl phosphorus or
Mes is 2,4,6- trimethylphenyls.
In above two syntheti c route, M is ruthenium (Ru), L1=L2=Cl；Y、Y1、R1、R2、E、E1、E2And E3Definition it is same
Before.
In the present invention, described heterocyclic radical is preferably heterocyclic aryl.
The fourth object of the present invention is to provide the above-mentioned c of II a- of formula II metal complex in olefin metathesis metathesis reaction
Make the application of catalyst.
Wherein, described olefin metathesis metathesis reaction be preferably intramolecular cyclization olefin metathesis metathesis reaction,
Intermolecular olefin metathesis metathesis reaction (CM) or intermolecular cycloolefin ring opening metathesis polymerzation (ROMP).
The described cycloolefin for olefinic polyreaction (ROMP) is preferably tensioned cycloolefin structure or more
Cycloolefin structure, described cycloolefin structure or polycyclic olefin structure are substituted or non-substituted structure, and they are at one
Or contain F, Cl, Br, N, O, Si, S, P, B, C in multiple rings6-C15Aromatic series and C4-C15One kind in aromatic heterocycle substituent or
It is a variety of.
In the preferred embodiments of the present invention, described cycloolefin structure contains 4 or 5 or 7-16 carbon atom, or
Multiple hetero atoms or heteroatom group；Described polycyclic olefin structure is the polycyclic olefin structure containing 2 to 6 rings；Described
Polycyclic olefin is one or more of cyclopentadiene or its molecule hydrogen by C1-C15Saturation or undersaturated alkyl, substitution or not
Substituted C1-C15Amido, substituted or unsubstituted C1-C15Alkoxy, substituted or unsubstituted C6-C15Aryloxy group, substitution or not
Substituted C1-C15Heterocyclic oxy group, substituted or unsubstituted C1-C15Alkylthio group, substituted or unsubstituted C6-C15Arylthio, connection
Substituted or unsubstituted C1-C15Carbonyl, formyloxy, formamido, the substituted or unsubstituted C of alkoxy1-C15Alkyl
Epoxide, substituted or unsubstituted C1-C15Alkyl amido, substituted or unsubstituted C6-C15Arylcarbonyloxy or substitution
Or unsubstituted C6-C15The derivative of aryl carboxamides base substitution.
In another preferred embodiments of the present invention, described polycyclic olefin is following polycyclic olefin structure VIa and VIb：
Wherein：
A is O, S, C1-C15Saturation or undersaturated alkyl, substituted or unsubstituted C1-C15Alkoxy, substitution or unsubstituted
C1-C15Aryloxy group, substituted or unsubstituted C1-C15Heterocyclic oxy group, substituted or unsubstituted C1-C15Alkylthio group, connection substitution
Or unsubstituted C1-C15The carbonyl of alkoxy, substituted or unsubstituted C1-C15Alkyl amine group, substituted or unsubstituted C1-C15Virtue
Base amido, substituted or unsubstituted C1-C15Alkyl amido, substituted or unsubstituted C1-C15Aryl carboxamides base or substitution
Or unsubstituted C1-C15Heterocyclic radical formamido；
R10And R11It independently is hydrogen, halogen, substituted or unsubstituted C1-C15Alkyl, substituted or unsubstituted C1-C15Alkane
Epoxide, substituted or unsubstituted C1-C15Alkylthio group, substituted or unsubstituted C1-C15Alkane siloxy, C6-C15Aryloxy group, C6-C15
Aryl, C2-C15Heterocyclic radical, C2-C15Heterocyclic aryl, the substituted or unsubstituted C of connection1-C15The carbonyl of alkoxy, formamido,
Substituted or unsubstituted C1-C15Alkyl amido, C1-C15Alkylsulfonamido, urea groups, substituted or unsubstituted C1-C15Alkane
Base urea groups, ionic liquid monomer, liquid crystal monomer, active drug molecule；In Formula IV a, R10And R11It is not linked to be cyclic structure or company
Circlewise structure.
In another preferred embodiments of the present invention, described polycyclic olefin is following polycyclic olefin structure VIIa-VIIb：
Wherein：
A is O, S, C1-C15Saturation or undersaturated alkyl, substituted or unsubstituted C1-C15Alkoxy, substitution or unsubstituted
C1-C15Aryloxy group, substituted or unsubstituted C1-C15Heterocyclic oxy group, substituted or unsubstituted C1-C15Alkylthio group, connection substitution
Or unsubstituted C1-C15Carbonyl, formamido, the substituted or unsubstituted C of alkoxy1-C15Alkyl amido, substitution or not
Substituted C1-C15Aryl carboxamides base or substituted or unsubstituted C1-C15Heterocyclic radical formamido；
R12For substituted or unsubstituted C1-C15Alkyl, substituted or unsubstituted C1-C15It is alkoxy, substituted or unsubstituted
C1-C15Alkylthio group, substituted or unsubstituted C1-C15Alkane siloxy, C6-C15Aryloxy group, C6-C15Aryl, C2-C15Heterocyclic radical, company
Meet substituted or unsubstituted C1-C15Carbonyl, formamido, the substituted or unsubstituted C of alkoxy1-C15Formamido, C1-C15
Alkylsulfonamido, urea groups, substituted or unsubstituted C1-C15Alkyl urea groups, ionic liquid monomer, liquid crystal monomer or active medicine
Molecule；
R13And R14It independently is substituted or unsubstituted C1-C15Alkyl, substituted or unsubstituted C1-C15Alkoxy, substitution
Or unsubstituted C1-C15Alkylthio group, substituted or unsubstituted C1-C15Alkane siloxy, C6-C15Aryloxy group, C6-C15Aryl, C2-C15
Heterocyclic radical, the substituted or unsubstituted C of connection1-C15Carbonyl, formamido, the substituted or unsubstituted C of alkoxy1-C15Formamide
Base, C1-C15Alkylsulfonamido, urea groups, substituted or unsubstituted C1-C15Alkyl urea groups, ionic liquid monomer, liquid crystal monomer or
Active drug molecule.
In the present invention, described intermolecular cycloolefin ring opening metathesis polymerzation is preferably to prepare high molecular polymerization
The polymerisation of thing material, the organic solvent of reaction is preferably dichloromethane, dichloroethanes, chloroform, toluene, dimethylbenzene, chlorine
One or more in benzene and ionic liquid., can not be added with when the raw material cycloolefin or polycyclic olefin of reaction are liquid
Solvent.
It is described as made from intermolecular cycloolefin ring opening metathesis polymerzation in the another preferred embodiments of the present invention
High molecular polymer, it is as shown in Formula IV c, VId, VIe, VIIc, VIId, Poly-DCPD；
Wherein, R10、R11、R12、R13And R14It independently is hydrogen, halogen, nitro, itrile group, aldehyde radical, substituted or unsubstituted C1-
C20Alkyl, C1-C20Alkoxy, substituted or unsubstituted C1-C20Aryloxy group, C1-C20Heterocyclic radical epoxide, C1-C20Alkylthio group, C1-
C20Alkane silicon substrate, C1-C20Alkyl siloxy, C2-C20Heterocyclic radical, substituted or unsubstituted C6-C20Aryl, C6-C20Aryloxy group, connection
C1-C20Carbonyl, the connection C of alkyl6-C20Carbonyl, the connection C of aryl2-C20Carbonyl, the connection C of heterocyclic radical6-C20The carbonyl of aryloxy group
Base, connection C6-C20Carbonyl, the substituted or unsubstituted C of connection of heterocyclic radical epoxide1-C20The epoxide carbonyl of saturation or unsaturated alkyl
Base, aminoacyl, the substituted or unsubstituted C of connection1-C20The carbonyl of saturation or unsaturated alkyl amino, connection C6-C20Aryl ammonia
Carbonyl, the connection C of base2-C20Carbonyl, urea groups, the substituted or unsubstituted C of heterocyclylamino group1-C20Alkyl urea groups, substitution or not
Substituted C6-C20Aryl-ureido, substituted or unsubstituted C2-C20Heterocyclic radical urea groups, connection C1-C20The sulfonyl of alkyl amino,
Connect C6-C20The sulfonyl or connection C of arylamino2-C20The sulfonyl of heterocyclylamino group；n1For 102-104；m1For 102-104。
Preferably, above-mentioned high molecular polymer is in Formula IV c, VId, VIe, VIIc, VIId, Poly-DCPD：
R10、R11、R12、R13And R14It independently is hydrogen, halogen, nitro, itrile group, aldehyde radical, substituted or unsubstituted C1-C15Alkane
Base, C1-C15Alkoxy, C1-C15Heterocyclic oxy group, C1-C15Alkylthio group, C1-C15Alkane silicon substrate, C1-C15Alkyl siloxy, C2-C15It is miscellaneous
Ring group, substituted or unsubstituted C6-C15Aryl, substituted or unsubstituted C6-C15Aryloxy group, connection C1-C15The carbonyl of alkyl, connect
Meet C6-C15Carbonyl, the connection C of aryl2-C15Carbonyl, the substituted or unsubstituted C of connection of heterocyclic radical1-C15Saturation or unsaturated hydrocarbons
The Epoxide carbonyl of base, connection C6-C15Carbonyl, the connection C of aryloxy group6-C15The carbonyl of heterocyclic radical epoxide, aminoacyl, connection take
Generation or unsubstituted C1-C15The carbonyl of saturation or unsaturated alkyl amino, connection C6-C15Carbonyl, the connection C of arylamino2-C15
Carbonyl, urea groups, the substituted or unsubstituted C of heterocyclylamino group1-C15Alkyl urea groups, substituted or unsubstituted C6-C15Aryl ureas
Base, substituted or unsubstituted C2-C15Heterocyclic radical urea groups, connection C1-C15Sulfonyl, the connection C of alkyl amino6-C15Arylamino
Sulfonyl, connection C2-C15The sulfonyl of heterocyclylamino group；n1For 102-104；m1For 102-104。
More preferably, described high molecular polymer is in Formula IV c, VId, VIe, VIIc, VIId, Poly-DCPD：
R10、R11、R12、R13And R14It independently is hydrogen, halogen, substituted or unsubstituted C1-C8Alkyl, C1-C8Alkoxy,
C1-C8Alkylthio group, C1-C8Alkane silicon substrate, C1-C8Alkyl siloxy, C2-C8Heterocyclic radical, substituted or unsubstituted C6-C12Aryl, substitution
Or unsubstituted C6-C12Aryloxy group, connection C1-C8Carbonyl, the connection C of alkyl6-C12Carbonyl, the connection C of aryl2-C8Heterocyclic radical
Carbonyl, the substituted or unsubstituted C of connection1-C8Saturation or the Epoxide carbonyl of unsaturated alkyl, connection C6-C12The carbonyl of aryloxy group
Base, connection C6-C8Carbonyl, aminoacyl, the substituted or unsubstituted C of connection of heterocyclic radical epoxide1-C8Saturation or unsaturated alkyl
Carbonyl, the connection C of amino6-C12Carbonyl, the connection C of arylamino2-C8Carbonyl, the connection C of heterocyclylamino group1-C8Alkyl amino
Sulfonyl, connection C6-C12Sulfonyl, the connection C of arylamino2-C8The sulfonyl of heterocyclylamino group；n1For 102-104；m1For
102-104。
Optimal, described high molecular polymer is in Formula IV c, VId, VIe, VIIc, VIId, Poly-DCPD：
In VIc：
A is CH2Or oxygen；
R11And R10Alone for connect C1-C3Saturation or the Epoxide carbonyl of unsaturated alkyl, connection is non-substituted or is taken by CN
The C in generation6-C12The carbonyl of aryloxy group, connect by C6—C12The C of aryl substitution1-C3The carbonyl of alkoxy, connect by C6—C12Fragrant oxygen
The carbonyl of the alkoxy of base substitution, the C for connecting unsubstituted or CN substitutions6-C12Aryloxy group, connection C1-C3Saturation or unsaturated alkyl
The carbonyl of amino, connect by C6The C of aryl substitution1-C3The carbonyl or connection C of alkyl amino2-C5The carbonyl of heterocyclic radical；
In VIIc：
A is CH2, oxygen；
R12For C1-C5Saturation or undersaturated alkyl, by C1-C3The C of alkoxy substitution1-C3Alkyl, it is optionally substituted by a hydroxyl group
C1-C3Alkyl, by C1-C3The C of alkyl acyloxy substitution1-C3Alkyl, by C6-C12The C of aryl substitution1-C3Alkyl, it is connected C1-
C3The C of the carbonyl substitution of alkoxy1-C3Alkyl, by C1-C3The C of alkoxy carbonyl group substitution6-C12Aryl, quiltSubstitution
Aryl or C1-C3Alkoxy；
In VIId：
A is CH2Or oxygen；
R14And R13It is C1-C3Alkyl.
The invention further relates to a kind of high molecular polymerization as shown in Formula IV c, VId, VIe, VIIc, VIId and Poly-DCPD
Thing, wherein, R10、R11、R12、R13、R14、n1And m1As described above.
Described high molecular polymer can be made by any of following two methods：
Method one：When raw material monomer is liquid, it comprises the following steps：
Under inert gas shielding, the metal complex catalyst of raw material monomer and the present invention carry out heating response, you can system
Obtain VIc, VId, VIe, VIIc, VIId or Poly-DCPD.
Method two：When raw material monomer is solid or liquid, it comprises the following steps：
Under inert gas shielding, in anhydrous organic solvent, the metal complex catalyst of raw material monomer and the present invention are from 20
DEG C progressively it is warming up to 75 DEG C of reactions, you can VIc, VId, VIe, VIIc, VIId or Poly-DCPD is made.
In described method one：The dosage of catalyst is preferably the 0.5%-10% of raw material monomer mole, heating
The temperature of reaction is preferably 30-120 DEG C；In described method two：The dosage of catalyst is preferably raw material monomer mole
The 0.01%-5% of amount, anhydrous organic solvent are preferably dichloroethanes (DCE).
When high molecular polymer is Poly-DCPD, it can be made by method one, and step is as follows：
Wherein, n1For 102-104；m1For 102-104。
Argon gas is passed through in liquid bicyclopentadiene monomer (DCPD) to rush oxygen, then is rapidly joined this project etc. and filtered out
Ruthenium catalyst (0.1-5 ‰), reaction solution gradually becomes viscous and exothermic after heating response a few minutes between 30-120 degree, finally gathers
Conjunction obtains poly bis ring cyclopentadienyl diene polymeric solid product (Poly-DCPD).Polymer P oly-DCPD solids have good hardness
(>80Gpa), bending modulus (>20Gpa) and heat distortion temperature (>200℃).
When high molecular polymer is VIc, it can be made by method two, and step is as follows：
1) under inert gas shielding, olefinic monomer raw material VIa is dissolved in anhydrous solvent (such as dichloroethanes DCE), filled
Argon catches up with oxygen, then rapidly joins the ruthenium catalyst (0.1 ‰ -5%) that this project etc. filters out, and reaction, which progressively heats up (20-75 DEG C), to be added
Thermal response, reaction solution gradually become viscous；
2) reaction solution is slowly toppled over after reaction overnight and be precipitated out in ethanol, produced filtering and drying to obtain polymer solids
Thing (VIc), yield 80-98%；Wherein, R10、R11、n1It is as defined above.
The invention further relates to high molecular polymer prepare the explosion-proof lamp of high intensity and high rigidity, tire material,
Effective carrier, tooth patching material, Liquid Crystalline Polymeric Materials, conductive polymer new material, film or the spinning of macromolecule medicament prodrug
Application in wire material.
In the present invention, described alkyl is to include the saturated aliphatic hydrocarbon with specified carbon number purpose side chain or straight chain
Base；Such as in " C1-C10Either have 1,2,3,4,5,6,7,8,9 or 10 in branched structure defined in alkyl " to be included in straight chain
The group of individual carbon atom.For example, " C1-C10Alkyl " specifically include methyl, ethyl, n-propyl, isopropyl, normal-butyl, the tert-butyl group,
Isobutyl group, amyl group, hexyl, heptyl, octyl group, nonyl and decyl etc..
Described " alkoxy " represent alkyl be connected with oxygen atom after generation group, i.e., " RO- ", R is alkyl.
Described " aryl " refers to the monocyclic or bicyclic carbocyclic that 7 atoms are may be up in each ring of any stabilization, its
In at least one ring be aromatic rings；The example of above-mentioned aryl unit include phenyl, naphthyl, tetralyl, indanyl,
Xenyl, phenanthryl, anthryl or acenaphthenyl (acenaphthyl).It is appreciated that be two ring substituents in aryl substituent, and its
In in the case of a ring is non-aromatic ring, connection is carried out by aromatic ring.
What " heterocyclic aryl " represented in each ring up to 7 atoms stablizes monocyclic or two rings, and wherein at least one ring is
Aromatic rings and contain the hetero atoms that 1-4 is selected from O, N and S；Heterocyclic aryl within the range defined herein includes but is not limited to：
Acridinyl, carbazyl, cinnolines base, quinoxalinyl, pyrazolyl, indyl, BTA base, furyl, thienyl, benzothiophene
It is base, benzofuranyl, quinolyl, isoquinolyl, oxazolyl, isoxazolyls, indyl, pyrazinyl, pyridazinyl, pyridine radicals, phonetic
Piperidinyl, pyrrole radicals, tetrahydroquinoline.As the definition of following heterocycle, " heterocyclic aryl " is it should also be understood that be to include any contain
The N- oxide derivatives of azepine aryl.Heterocyclic aryl substituent is two ring substituents wherein and a ring is non-aromatic ring
Or not comprising in the case of heteroatomic, it will be understood that connection by aromatic ring or passes through the hetero atom comprising ring and carried out respectively.
" alkylthio group " represent alkyl be connected with sulphur atom after generation group, i.e., " RS- ", R is alkyl.
" aryloxy group " represent aryl be connected with oxygen atom after generation group, i.e., " RO- ", R is aryl.
" fragrant amino " refers to " NH3" in a hydrogen be substituted with aryl after amino.
" alkyl imino " refers to the imino group for being connected with alkyl, and alkyl can be connected on the carbon of imino group or on nitrogen；" substitution
Alkyl imino " refer to one or more of alkyl imino hydrogen it is substituted after group.
" substituted amino " is " NH3" in any one or more hydrogen it is substituted after group.Substituent can be C6-
C20Aryl, formoxyl, C1-C20Alkyl acyl, the C of substitution1-C20Alkyl acyl, alkyl sulphonyl, the C of substitution1-C20Alkyl sulphur
Acyl group etc..
Wherein, " alkyl sulphonyl " is connected with the group of alkyl, " substituted alkyl sulphonyl " for the sulphur atom on sulfonyl
Group after being substituted with a substituent for one or more of alkyl sulphonyl hydrogen；" alkyl acyl " be acyl group in carbon atom or
Nitrogen-atoms is connected to the acyl group of alkyl, and " substituted alkyl acyl " is that any one or more hydrogen in alkyl acyl are substituted base
Group after substitution.
" heterocyclic radical " is fragrance or nonaromatic heterocycles containing one or more of the hetero atom selected from O, N and S, and
And including bicyclic groups.Therefore, " heterocyclic radical " includes above-mentioned heterocyclic aryl and its dihydro or tetrahydrochysene analog." heterocyclic radical "
Other examples include but is not limited to it is following：Benzimidazolyl, benzofuranyl, benzopyrazoles base, BTA base, benzo thiophene
It is fen base, benzoxazolyl, carboline base, furyl, imidazole radicals, indolinyl, indyl, indazolyl, isobenzofuran-base, different
Indyl, isoquinolyl, isothiazolyl, isoxazolyl, oxazolyl, oxazoline, isoxazolines, oxygen cyclobutyl, pyranose, pyrrole
Piperazine base, pyrazolyl, pyridazinyl, pyridopyridine base, pyridazinyl, pyridine radicals, pyrimidine radicals, pyrrole radicals, quinazolyl, quinolyl,
Quinoxalinyl, THP trtrahydropyranyl, thiadiazolyl group, thiazolyl, thienyl, triazolyl, azetidinyl, 1,4- alkyl dioxins,
Hexahydro azatropylidene base, piperazinyl, piperidyl, pyrrolidinyl, morpholinyl, thio-morpholinyl, dihydrobenzo imidazole radicals, dihydrobenzo
Furyl, dihydrobenzo thienyl, Er hydrogen benzoxazolyl, dihydrofuran base, glyoxalidine base, indolinyl, dihydro are different
Oxazolyl, dihydro isothiazolyl, Er Qing oxadiazolyls, dihydro-oxazole base, dihydro pyrazine base, pyrazoline base, dihydropyridine base,
Dihydro-pyrimidin base, pyrrolin base, EEDQ base, dihydro tetrazole radical, thiodiazoline base, dihydro-thiazolyl, dihydro-thiophene
Base, dihydro triazolyl, dihydro azetidinyl, methylenedioxyphenyl formoxyl, tetrahydrofuran base and tetrahydro-thienyl and
Its N- oxide.Heterocyclic radical can be attached through carbon atom or hetero atom with central element.
" substituted heterocyclic radical " be heterocyclic radical in any one or more hydrogen be substituted with a substituent after group.
" alkyl amido " is carbon in formamido or nitrogen is ined succession the group of alkyl, " substituted alkyl amido "
Group after being substituted with a substituent for any one or more hydrogen in alkyl amido.
" siloxy " is that structural formula is R1R2R3SiO- group；" alkyl siloxy " is R1R2R3R in SiO-1、R2And R3In
At least one is alkyl, and remaining is the group of hydrogen；" substituted alkyl siloxy " is one or more of alkyl siloxy
Group after hydrogen is substituted.
" alkyl amido " is the generation group after the hydrogen on hydrogen or nitrogen in formamido on carbon is substituted by alkyl；
" substituted alkyl amido " is the group after one or more of alkyl amido hydrogen is substituted with a substituent.
" alkane silicon substrate " is structure R1R2R3In Si-, R1、R2And R3In at least one be alkyl, remaining be hydrogen group.
" aminoacyl " is for structural formulaGroup.
" carbonyl of connection alkyl amino " is that the nitrogen in aminoacyl connects the group formed after alkyl；" substituted connection
Group of the carbonyl of alkyl amino " for one or more of the carbonyl of connection alkyl amino hydrogen after substituted.
" alkyl urea groups " is the group after one or more hydrogen in urea groups on nitrogen are substituted by alkyl；" substituted ureine
Base " is the group after one or more of alkyl urea groups hydrogen is substituted.
Raw material involved in the present invention and reagent are commercially available unless otherwise specified.
The positive effect of the present invention is：
1st, the present invention is fully ground by designing and synthesizing metal complex part and corresponding metal especially ruthenium complex
Study carefully the influence of the substituent and its position of substitution of different ligands to the catalytic activity and stability of catalyst, the results showed that the present invention
Metal complex catalyst have higher olefin metathesis metathesis reaction catalytic activity, and with amino-sulfonyl,
The adjacent alkoxystyrene complex ligands of the electron-withdrawing groups such as sulfoamido, carbonyl, chlorine substitution significantly improve respective metal complexing
The catalytic activity and stability of thing.The present invention metal complex catalyst can be effectively used for intramolecular alkene ring closure reaction,
Intermolecular cycloolefin ring-opening polymerization etc., there is extensive industry application value, be new chemical materialses and pharmaceutical synthesis etc.
Field provides a kind of new synthetic method by olefin metathesis metathesis reaction.
2nd, the novel metal complexes structural formula of present invention design synthesis is the c of II a- of formula II, its chemical catalysis performance and thing
Rationality energy and its various Sexual behavior mode of application increase significantly and improved compared with Grubbs-Hoveyda catalyst, and optimize gold
Belong to the preparation method of complex compound, largely reduce preparation cost, be the industry metaplasia of the catalytic reaction of metal complex
Production provides an effectively practical new method.
3rd, the present invention have developed by being prepared under the conditions of different monomer process by the catalyzed ring opening polymerization reaction of cycloolefin
The high molecular polymer new material of different performance and preparation method thereof.
4th, the main application of high molecular polymer new material prepared by the present invention is the explosion-proof green wood of high intensity and high rigidity
Material, tire new material, effective new support of macromolecule medicament prodrug, tooth patching material, Liquid Crystalline Polymeric Materials, conductive polymer
Deng new material, it can also be used to which film and spinning prepare new material.It can be provided more for the development of human society in field of new materials
More preferable new product.
Embodiment:
The present invention according to researched and developed about olefin metathesis reaction catalyst data (patent US20070043180A1,
WO2007003135A1, WO96004289A1, WO97003096A1, US 20020107138A1, US 6921735B2 and chemistry
Meeting magazine J.Am.Chem.Soc.1999,121,791-799, J.Am.Chem.Soc.2000,122,8168-8179), by not
The complexing of the complex ligands (3a-3cz, 5a-5z, 7a-7t, 9a-9j, 11a-11j) and ruthenium complex intermediate of same type is anti-
Different types of metal ruthenium complex (4a-4u, 6a-6v, 8a-8e, 10a-10e, 12a-12f) should be prepared for, and is passed through respectively
The catalytic cyclization and ring-opening polymerization of alkene have studied different type complex ligands structure and substituent effect to its phase
The influence of metal complex catalytic activity is answered, and have extensively studied different type metal complex catalyst and gathered by alkene open loop
The high polymer material that reaction prepares different performance is closed, and further research and development optimize different types of new complex compound for preparing
High molecular polymer new material of different performance and preparation method thereof and multiple use.
It is using complex ligands (3a-3cz) synthesis ruthenium complex 4a-4cz below according to relevant documents and materials：
It is complex compound 4a-4cz structural formula (1a below:Cy=cyclohexyl, 1b:Mes=2,4,6- trimethylbenzenes)：
It is ruthenium complex 4a-4cz synthesis below:
The ruthenium complex 4a of embodiment 1 synthesis
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 3a (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain green solid product 4a, yield with methanol or pentane-DCM：32%.
After testing, ruthenium complex (4a)1HNMR(400MHz,CDCl3):δ 18.68 (s, Ru=CH), 7.23-6.65 (m,
10H, aromatic H), 6.36 (dd, J=2.8,9.6Hz, 1H, aromatic H), 6.03 (d, J=12.8Hz, 1H,
NCH2),4.14-3.90(m,4H,NCH2CH2N),3.85(s,3H,OCH3), 3.47 (d, J=12.8Hz, 1H, NCH2),2.89-
1.62(m,18H,aromatic CH3).
The ruthenium complex 4b of embodiment 2 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 3b (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1a
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain green solid product 4b, yield with methanol or pentane-DCM：35%.
After testing, ruthenium complex (4b)1HNMR(400MHz,CDCl3):δ 19.28 (d, J=8.4Hz, Ru=CH),
7.45 (d, J=8.8Hz, 2H, aromatic H), 7.31-7.16 (m, 3H, aromatic H), 6.83 (d, J=8.8Hz, 2H,
Aromatic H), 5.13 (t, J=12.4Hz, 1H, NH), 7.96 (d, J=12.4Hz, 1H, NCH2), 3.85 (d, J=
12.4Hz,1H,NCH2),3.80(s,3H,OCH3),2.28-1.24(m,33H,PCy3).
The ruthenium complex 4c of embodiment 3 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 3c (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain green solid product 4c, yield with methanol or pentane-DCM：14%.
After testing, ruthenium complex (4c)1HNMR(400MHz,CDCl3):δ 18.99 (s, Ru=CH), 7.483-7.444
(m,1H,aromatic H),7.192-6.862(m,7H,aromatic H),6.715-6.662(m,1H,aromatic H),
5.293 (t, J=13.2Hz, 1H, NHCH2),4.19-3.58(m,8H,NHCH2,NCH2CH2N, NCH3),2.52-2.37(m,
18H,aromatic CH3).
The ruthenium complex 4d of embodiment 4 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 3d (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1a
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain green solid product 4d, yield with methanol or pentane-DCM：13%.
After testing, ruthenium complex (4d)1HNMR(400MHz,CDCl3):δ 19.42 (d, J=8.8Hz, Ru=CH),
7.65 (d, J=9.2Hz, 2H, aromatic H), 7.35-7.17 (m, 3H, aromatic H), 6.93 (d, J=9.2Hz, 2H,
Aromatic H), 5.76 (d, J=12.4Hz, 1H, NH), 3.80 (s, 3H, OCH3), 3.70 (d, J=12.4Hz, 1H, NH),
2.57(s,3H,OCH3),2.29-1.21(m,33H,PCy3).
The ruthenium complex 4e of embodiment 5 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 3e (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain green solid product 4e, yield with methanol or pentane-DCM：13%.
After testing, ruthenium complex (4e)1HNMR(400MHz,CDCl3):δ 18.90 (s, Ru=CH), 7.21-7.15 (m,
1H,aromatic H),7.05-6.94(m,5H,aromatic H),6.87(m,2H,aromatic H),6.66-6.60(m,
3H, aromatic H), 6.38 (dd, J=2.4,9.6Hz, 1H, aromatic H), 5.293 (t, J=13.2Hz, 1H,
NHCH2),4.19-3.55(m,8H,NHCH2,NCH2CH2N, NCH3),2.86-2.10(m,18H,aromatic CH3).
The ruthenium complex 4f of embodiment 6 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 3f (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1a
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain green solid product 4f, yield with methanol or pentane-DCM：28%.
After testing, ruthenium complex (4f)1HNMR(400MHz,CDCl3):δ7.69-7.60(m,2H,aromatic H),
7.58-7.50(m,2H,aromatic H),7.47-7.41(m,1H,aromatic H),7.26-7.22(m,1H,aromatic
), H 6.6.91-6.83 (m, 2H, aromatic H), 5.32 (t, J=12.4Hz, 1H, NH), 4.97 (d, J=12.4Hz, 1H,
NCH2), 3.87 (d, J=12.4Hz, 1H, NCH2),3.78(s,3H,OCH3),2.38-1.13(m,33H,PCy3).
The ruthenium complex 4g of embodiment 7 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 3g (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain green solid product 4g, yield with methanol or pentane-DCM：7%.
After testing, ruthenium complex (4a)1HNMR(400MHz,CDCl3):δ 18.83 (s, Ru=CH), 7.51-7.49 (m,
1H,aromatic H),7.17-7.06(m,5H,aromatic H),6.95(m,1H,aromatic H),6.88(m,1H,
Aromatic H), 6.77 (m, 1H, aromatic H), 6.68-6.65 (m, 3H, aromatic H), 6.11 (d, J=
12.8Hz,1H,NCH2),4.4-3.89(m,4H,NCH2CH2N),3.83(s,3H,OCH3), 3.45 (d, J=12Hz, 1H,
NCH2),2.86-1.56(m,21H,NCH3,aromatic CH3).
The ruthenium complex 4h of embodiment 8 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 3h (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1a
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain green solid product 4h, yield with methanol or pentane-DCM：29%.
After testing, ruthenium complex (4h)1HNMR(400MHz,CDCl3):δ 19.31 (d, J=8.4Hz, Ru=CH),
7.57-7.50 (m, 4H, aromatic H), 7.31-7.29 (m, 1H, aromatic H), 7.148 (d, J=5.6Hz, 1H,
Aromatic H), 6.84-6.81 (m, 2H, aromatic H), 5.78 (d, J=12Hz, 1H, NCH2),3.71(s,3H,
OCH3), 3.62 (d, J=12Hz, 1H, NCH2),2.51(s,3H,NCH3),2.22-1.13(m,33H,PCy3).
The ruthenium complex 4j of embodiment 9 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 3j (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain green solid product 4j, yield with methanol or pentane-DCM：37%.
After testing, ruthenium complex (4j)1HNMR(400MHz,CDCl3):δ 18.83 (s, Ru=CH), 7.50-6.39 (m,
11H, aromatic H), 5.21 (t, J=12.4Hz, 1H, NH), 4.69-3.46 (m, 9H, NHCH2,NCH2CH2N, OCH3),
2.62-2.08(m,18H,aromatic CH3).
The ruthenium complex 4k of embodiment 10 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 3k (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1a
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain green solid product 4k, yield with methanol or pentane-DCM：52%.
After testing, ruthenium complex (4k)1HNMR(400MHz,CDCl3):δ 19.35 (d, J=9.9Hz, Ru=CH),
8.11 (d, J=8.1Hz, 1H, aromatic H), 7.34-6.85 (m, 6H, aromatic H), 5.48 (d, J=12Hz, 1H,
NCH2), 5.27 (t, J=6Hz, 1H, NH), 3.93 (d, J=12Hz, 1H, NCH2),3.88(s,3H,OCH3),2.33-1.24
(m,33H,PCy3).
The ruthenium complex 4m of embodiment 11 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 3m (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain green solid product 4m, yield with methanol or pentane-DCM：84%.
After testing, ruthenium complex (4m)1HNMR(400MHz,CDCl3):δ 18.89 (s, Ru=CH), 7.60-6.45 (m,
11H,aromatic H),5.13-3.52(m,8H,NHCH2,NCH2CH2N, OCH), 2.95-2.10 (m, 18H, aromatic
CH3), 0.95 (d, J=6.4Hz, 6H, OCH (CH3)2).
The ruthenium complex 4n of embodiment 12 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 3n (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1a
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain green solid product 4n, yield with methanol or pentane-DCM：58%.
After testing, ruthenium complex (4n)1HNMR(400MHz,CDCl3):δ 19.55 (d, J=9.9Hz, Ru=CH),
8.14 (d, J=8.1Hz, 1H, aromatic H), 7.36-6.83 (m, 6H, aromatic H), 5.46 (d, J=12Hz, 1H,
NCH2), 5.13 (t, J=6Hz, 1H, NH), 4.56 (m, 1H, OCH), 3.90 (d, J=12Hz, 1H, NCH2),2.30-1.25(m,
39H,PCy3).
The ruthenium complex 4p of embodiment 13 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 3p (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain green solid product 4p, yield with methanol or pentane-DCM：10%.
After testing, ruthenium complex (4p)1HNMR(400MHz,CDCl3):δ 18.97 (s, Ru=CH), 7.50-6.58 (m,
11H,aromatic H),5.26-3.52(m,8H,NHCH2,NCH2CH2N, OCH), 3.48-2.07 (m, 18H, aromatic
CH3), 1.23 (d, J=6.4Hz, 6H, OCH (CH3)2).
The ruthenium complex 4n of embodiment 14 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 3q (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1a
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain green solid product 4q, yield with methanol or pentane-DCM：31%.
After testing, ruthenium complex (4q)1HNMR(400MHz,CDCl3):δ 19.56 (d, J=9.9Hz, Ru=CH),
8.20 (d, J=8.1Hz, 1H, aromatic H), 7.66-6.84 (m, 6H, aromatic H), 5.46 (d, J=12Hz, 1H,
NCH2), 5.22 (t, J=6Hz, 1H, NH), 4.56 (m, 1H, OCH), 3.95 (d, J=12Hz, 1H, NCH2),2.34-0.87(m,
39H,PCy3).
The ruthenium complex 4r of embodiment 15 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 3r (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain green solid product 4r, yield with methanol or pentane-DCM：14%.
After testing, ruthenium complex (4n)1HNMR(400MHz,CDCl3):δ 18.91 (s, Ru=CH), 7.53-6.62 (m,
12H, aromatic H), 5.31 (t, J=12.4Hz, 1H, NH), 4.73-3.53 (m, 9H, NHCH2,NCH2CH2N,OCH3),
2.56-1.78(m,18H,aromatic CH3).
The ruthenium complex 4s of embodiment 16 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 3s (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1a
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain green solid product 4s, yield with methanol or pentane-DCM：37%.
After testing, ruthenium complex (4s)1HNMR(400MHz,CDCl3):δ 19.55 (d, J=9.9Hz, Ru=CH),
8.20 (d, J=8.1Hz, 1H, aromatic H), 7.64-6.86 (m, 7H, aromatic H), 5.52 (d, J=12Hz, 1H,
NCH2), 5.35 (t, J=6Hz, 1H, NH), 3.96 (d, J=12Hz, 1H, NCH2),3.91(s,3H,OCH3),2.34-1.22
(m,33H,PCy3).
The ruthenium complex 4t of embodiment 17 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 3t (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain green solid 4t, impure, thick yield with methanol or pentane-DCM：21%, nothing1HNMR analysis knots
Fruit.
The ruthenium complex 4u of embodiment 18 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 3u (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain green solid 4u, impure, thick yield with methanol or pentane-DCM：7%, nothing1HNMR analysis knots
Fruit.
The ruthenium complex 4v of embodiment 19 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 3v (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain green solid product 4v, yield with methanol or pentane-DCM：45%.
After testing, ruthenium complex (4v)1HNMR(400MHz,CDCl3):δ 18.914 (s, Ru=CH), 7.535 (dd, J
=1.2,8.0Hz, 1H, aromatic H), 7.225 (m, 1H, aromatic H), 7.056-6.947 (m, 5H, aromatic
), H 6.810 (m, 1H, aromatic H), 6.712 (d, J=8.0Hz, 1H, aromatic H), 6.651 (t, J=7.6Hz,
1H, aromatic H), 6.462 (dd, J=2.4,9.6Hz, 1H, aromatic H), 5.198 (t, J=11.2Hz, 1H, NH),
4.658 (d, J=11.2Hz, 1H, NCH2),4.180-3.857(m,6H,NCH2CH2N,OCH2), 3.549 (d, J=11.2Hz,
1H,NCH2),2.790-2.000(m,18H,aromatic CH3),1.19(m,OCH2CH3).
The ruthenium complex 4w of embodiment 20 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 3w (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain green solid product 4w, yield with methanol or pentane-DCM：7%.
After testing, ruthenium complex (4w)1HNMR(400MHz,CDCl3):δ 16.500 (s, Ru=CH), 7.680 (m, 1H,
aromatic H),7.099(s,4H,aromatic H),6.984-6.800(m,6H,aromatic H),4.650(m,1H,
OCH),4.229-4.178(m,6H,NCH2,NCH2CH2N),3.884(s,3H,OCH3),2.645(s,3H,NCH3),2.495(s,
12H,aromatic CH3),2.347(s,6H,18H,aromatic CH3),0.912(m,6H,OCH(CH3)2).
The ruthenium complex 4x of embodiment 21 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 3x (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain green solid product 4x, yield with methanol or pentane-DCM：40%.
After testing, ruthenium complex (4x)1HNMR(400MHz,CDCl3):δ 16.517 (s, Ru=CH), 7.580 (m, 1H,
aromatic H),7.094(s,4H,aromatic H),6.925-6.597(m,6H,aromatic H),4.521(m,1H,
NH),4.352(s,2H,NCH2),4.180(s,4H,NCH2CH2N),3.887(s,6H,OCH3),2.494(s,12H,
aromatic CH3),2.402(s,6H,aromatic CH3).
The ruthenium complex 4y of embodiment 22 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 3y (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain green solid product 4y, yield with methanol or pentane-DCM：50%.
After testing, ruthenium complex (4y)1HNMR(400MHz,CDCl3):δ 19.034 (s, Ru=CH), 8.376 (d, J=
2.0Hz, 1H, aromatic H), 7.690 (d, J=1.6.0Hz, 1H, aromatic H), 7.437 (d, J=7.6Hz, 1H,
aromatic H),7.206-7.029(m,5H,aromatic H),6.834-6.590(m,3H,aromatic H),5.240
(t, J=12Hz, 1H, NH), 4.660 (d, J=12Hz, 1H, NCH2),4.451(m,1H,OCH3),4.202-4.051(m,4H,
NCH2CH2), N 3.615 (d, J=12Hz, 1H, NCH2),2.692-2.026(m,18H,aromatic CH3), 1.177 (d, J=
5.6Hz,6H,OCH(CH3)2).
The ruthenium complex 4z of embodiment 23 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 3z (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain green solid product 4z, yield with methanol or pentane-DCM：49%.
After testing, ruthenium complex (4z)1HNMR(400MHz,CDCl3):δ 16.524 (s, Ru=CH), 7.590 (m, 1H,
aromatic H),7.092(s,4H,aromatic H),6.916-6.838(m,4H,aromatic H),6.752-6.657
(m,2H,aromatic H),4.590(m,1H,NH,OCH),4.347(s,2H,NCH2),4.179(s,4H,NCH2CH2N),
3.886(s,3H,OCH3),2.493(s,12H,aromatic CH3),2.399(s,6H,18H,aromatic CH3),0.931
(m,6H,OCH(CH3)2).
The ruthenium complex 4aa of embodiment 24 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3aa (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
The DCM dried with 30mL, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex
1a (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed to obtain green solid product 4aa, yield with methanol or pentane-DCM：55%.
After testing, ruthenium complex (4aa)1H-NMR(400MHz,CDCl3):δ 19.454 (d, J=9.6Hz, Ru=CH),
8.175 (d, J=7.6Hz, 1H, aromatic H), 7.397-7.325 (m, 2H, aromatic H), 7.205-7.113 (m,
2H,aromatic H),6.949-6.880(m,2H,aromatic H),5.523(m,1H,NCH2),5.225(m,1H,NH),
4.159-3.942(m,3H,NCH2,OCH2),2.358-0.812(m,36H,PCy3,OCH2CH3).
The ruthenium complex 4ab of embodiment 25 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3ab (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
The DCM dried with 30mL, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed to obtain green solid product 4ab, yield with methanol or pentane-DCM：8%.
After testing, ruthenium complex (4ab)1H-NMR(400MHz,CDCl3):δ 19.110 (s, 1H, Ru=CH), 8.364
(dd, J=2.0,8.0Hz, 1H, aromatic H), 7.289-6.646 (m, 10H, aromatic H), 5.303 (t, J=
13.6Hz,1H,NCH2), 4.226 (d, J=13.2Hz, 1H, NCH2),4.104(s,3H,OCH3),3.800(s,4H,
NCH2CH2), N 3.686 (d, J=13.2Hz, 1H, NCH2),2.646-2.075(m,18H,aromatic CH3).
The ruthenium complex 4ac of embodiment 26 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3ac (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
The DCM dried with 30mL, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex
1a (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed to obtain green solid product 4ac, yield with methanol or pentane-DCM：63%.
After testing, ruthenium complex (4ac)1H-NMR(400MHz,CDCl3):δ 17.370 (d, J=4.4Hz, Ru=CH),
7.740-7.674 (m, 2H, aromatic H), 7.111 (d, J=8.4Hz, aromatic H), 6.893-6.826 (m, 2H,
aromatic H),6.758-6.663(m,2H,aromatic H),4.656(s,1H,NH),4.479(s,2H,NCH2),
4.334(s,3H,OCH3),3.896(s,3H,OCH3),2.345-1.272(m,33H,18H,PCy3).
The ruthenium complex 4ad of embodiment 27 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3ad (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
The DCM dried with 30mL, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed to obtain green solid product 4ad, yield with methanol or pentane-DCM：3%.
After testing, ruthenium complex (4ad)1H-NMR(400MHz,CDCl3):δ 18.639 (s, 1H, Ru=CH), 7.542-
7.470 (m, 2H, aromatic H), 7.287-7.692 (m, 10H, aromatic H), 5.513 (d, J=13.2Hz, 1H,
NCH2), 4.152 (d, J=13.2Hz, 1H, NCH2),4.083-3.769(m,7H,NCH2CH2N,OCH3),3.195(s,3H,
NCH3),2.409(m,18H,aromatic CH3).
The ruthenium complex 4ae of embodiment 28 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3ae (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
The DCM dried with 30mL, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed to obtain green solid product 4ae, yield with methanol or pentane-DCM：50%.
After testing, ruthenium complex (4ae)1H-NMR(400MHz,CDCl3):δ 19.034 (s, 1H, Ru=CH), 8.376
(d, J=2.0Hz, 1H, aromatic H), 7.690 (d, J=1.6.0Hz, 1H, aromatic H), 7.437 (d, J=
7.6Hz,1H,aromatic H),7.206-7.029(m,5H,aromatic H),6.834-6.590(m,3H,aromatic
), H 5.240 (t, J=12Hz, 1H, NH), 4.660 (d, J=12Hz, 1H, NCH2),4.451(m,1H,OCH3),4.202-
4.051(m,4H,NCH2CH2), N 3.615 (d, J=12Hz, 1H, NCH2),2.692-2.026(m,18H,aromatic CH3),
1.177 (d, J=5.6Hz, 6H, OCH (CH3)2).
The ruthenium complex 4af of embodiment 29 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3af (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
The DCM dried with 30mL, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed to obtain green solid product 4af, yield with methanol or pentane-DCM：15%.
After testing, ruthenium complex (4af)1H-NMR(400MHz,CDCl3):δ 18.541 (s, 1H, Ru=CH), 7.446
(d, J=8.0Hz, 1H, aromatic H), 7.239-7.191 (m, 4H, aromatic H), 7.058-6.958 (m, 6H,
Aromatic H), 6.143 (d, J=13.2Hz, 1H, NCH2), 5.393 (d, J=13.2Hz, 1H, NCH2),4.074-3.770
(m,7H,NCH2CH2N,OCH3),3.518(s,3H,NCH3),2.648-2.303(m,18H,aromatic CH3).
The ruthenium complex 4ag of embodiment 30 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3ag (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
The DCM dried with 30mL, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed to obtain green solid product 4ag, yield with methanol or pentane-DCM：4%.
After testing, ruthenium complex (4ag)1H-NMR(400MHz,CDCl3):δ 19.093 (s, 1H, Ru=CH), 7.514-
6.701 (m, 13H, aromatic H), 5.310 (m, 1H, NH), 4.300 (d, J=12.9Hz, 1H, NCH2),4.044(s,4H,
NCH2CH2), N 3.612 (d, J=12.9Hz, 1H, NCH2),2.452(s,12H,aromatic CH3),2.332(s,6H,
aromatic CH3).
The ruthenium complex 4ah of embodiment 31 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3ah (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
The DCM dried with 30mL, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed to obtain green solid product 4ah, yield with methanol or pentane-DCM：5%.
After testing, ruthenium complex (4ah)1H-NMR(400MHz,CDCl3):δ 19.093 (s, 1H, Ru=CH), 7.503-
6.691 (m, 12H, aromatic H), 5.274 (m, 1H, NH), 4.330 (d, J=12.9Hz, 1H, NCH2),4.043(s,4H,
NCH2CH2), N 3.586 (d, J=12.9Hz, 1H, NCH2),2.445(s,12H,aromatic CH3),2.371(s,6H,
aromatic CH3).
The ruthenium complex 4am of embodiment 32 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3am (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
The DCM dried with 30mL, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed to obtain green solid product 4am, yield with methanol or pentane-DCM：40%.
After testing, ruthenium complex (4am)1H-NMR(400MHz,CDCl3):δ 18.83 (s, 1H, Ru=CH), 7.36-
6.14 (m, 10H, aromatic H), 5.12 (t, J=12.4Hz, 1H, NH), 4.50-3.42 (m, 12H, NHCH2,NCH2CH2N,
OCH3),2.62-2.05(m,18H,aromatic CH3).
The ruthenium complex 4an of embodiment 33 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3an (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
The DCM dried with 30mL, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed to obtain green solid product 4an, yield with methanol or pentane-DCM：51%.
After testing, ruthenium complex (4an)1H-NMR(400MHz,CDCl3):δ 18.90 (s, 1H, Ru=CH), 7.60-
6.36 (m, 10H, aromatic H), 5.25 (t, J=12Hz, 1H, NH), 4.78 (d, J=12Hz, 1H, NCH2),4.05(s,
4H,NCH2CH2N),3.53(s,3H,OCH3), 3.43 (d, J=12Hz, 1H, NCH2),2.56-2.13(m,21H,aromatic
CH3).
The ruthenium complex 4ap of embodiment 34 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3ap (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
The DCM dried with 30mL, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed to obtain green solid product 4ap, yield with methanol or pentane-DCM：50%.
After testing, ruthenium complex (4ap)1H-NMR(400MHz,CDCl3):δ 18.90 (s, 1H, Ru=CH), 7.38-
6.37(m,9H,aromatic H),4.85(m,2H,NH,NCH2),3.99(s,4H,NCH2CH2N), 3.80 (d, J=12Hz,
1H,NCH2),3.31(s,3H,OCH3),2.69-0.85(m,38H,C(CH3)3,aromatic CH3).
The ruthenium complex 4aq of embodiment 35 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3aq (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
The DCM dried with 30mL, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed to obtain green solid product 4aq, yield with methanol or pentane-DCM：37%.
After testing, ruthenium complex (4aq)1H-NMR(400MHz,CDCl3):δ 19.08 (s, 1H, Ru=CH), 7.97-
6.33(m,10H,aromatic H),5.08(m,2H,NH,OCH),4.34(m,1H,NCH2),4.02(s,4H,NCH2CH2N),
3.41(m,1H,NCH2),2.53-2.31(m,18H,aromatic CH3),1.29(s,9H,C(CH3)3),0.89-0.87(m,
6H,OCH(CH3)2).
The ruthenium complex 4ar of embodiment 36 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3ar (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
The DCM dried with 30mL, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed to obtain green solid product 4ar, yield with methanol or pentane-DCM：54%.
After testing, ruthenium complex (4ar)1H-NMR(400MHz,CDCl3):δ 18.85 (s, 1H, Ru=CH), 7.26-
6.07 (m, 10H, aromatic H), 5.04 (t, J=13.2Hz, 1H, NH), 4.48 (m, 1H, NCH2),4.39-4.33(m,
2H,OCH),4.15-4.02(m,4H,NCH2CH2N),3.65(m,1H,NCH2),2.66-2.05(m,18H,aromatic
CH3),1.55(m,6H,OCH(CH3)2),1.38(m,6H,OCH(CH3)2).
The ruthenium complex 4as of embodiment 37 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3as (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
The DCM dried with 30mL, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed to obtain green solid product 4as, yield with methanol or pentane-DCM：46%.
After testing, ruthenium complex (4as)1H-NMR(400MHz,CDCl3):δ 18.98 (s, 1H, Ru=CH), 7.66-
6.39 (m, 10H, aromatic H), 5.17 (t, J=13.2Hz, 1H, NH), 4.71 (d, J=13.2Hz, 1H, NCH2),
4.36(m,1H,OCH),4.06(brs,4H,NCH2CH2), N 3.42 (d, J=13.2Hz, 1H, NCH2),2.63-2.09(m,
21H,aromatic CH3),1.09(m,6H,OCH(CH3)2).
The ruthenium complex 4at of embodiment 38 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3at (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
The DCM dried with 30mL, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex
1a (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed to obtain green solid product 4at, yield with methanol or pentane-DCM：37%.
After testing, ruthenium complex (4at)1H-NMR(400MHz,CDCl3):δ 19.46 (d, J=9.9Hz, Ru=CH),
8.15 (d, J=8.1Hz, 1H, aromatic H), 7.33-7.13 (m, 3H, aromatic H), 6.46 (m, 2H, aromatic
H),5.26(m,2H,NCH2),3.79(s,3H,OCH3),3.76(s,3H,OCH3),2.26-1.25(m,33H,PCy3).
The ruthenium complex 4aw of embodiment 39 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3aw (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
The DCM dried with 30mL, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex
1a (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed to obtain green solid product 4aw, yield with methanol or pentane-DCM：8%.
After testing, ruthenium complex (4aw)1H-NMR(400MHz,CDCl3):δ 19.43 (d, J=9.9Hz, Ru=CH),
8.57 (d, J=8.1Hz, 1H, aromatic H), 7.26-6.78 (m, 5H, aromatic H), 5.29 (m, 2H, OCH, NH),
4.53(m,1H,NCH2),3.72(m,1H,NCH2),2.26-1.24(m,48H,PCy3,C(CH3)3,OCH(CH3)2).
The ruthenium complex 4az of embodiment 40 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3az (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
The DCM dried with 30mL, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed to obtain green solid product 4az, yield with methanol or pentane-DCM：31%.
After testing, ruthenium complex (4az)1H-NMR(400MHz,CDCl3):δ 18.53 (s, 1H, Ru=CH), 7.26-
5.75 (m, 10H, aromatic H), 4.88 (d, J=11.2Hz, 1H, NCH2),4.52-4.43(m,2H,OCH),4.14-
3.88(m,5H,NCH2,NCH2CH2N),2.98-1.39(m,27H,NCH3,aromatic CH3,OCH(CH3)2).
The ruthenium complex 4ba of embodiment 41 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3ba (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
The DCM dried with 30mL, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed to obtain green solid product 4ba, yield with methanol or pentane-DCM：44%.
After testing, ruthenium complex (4ba)1H-NMR(400MHz,CDCl3):δ 18.99 (s, 1H, Ru=CH), 7.45-
6.36(m,9H,aromatic H),5.05(m,2H,OCH,NH),3.98-3.91(m,5H,NCH2,NCH2CH2N),3.72(d,J
=13.2Hz, 1H, NCH2),2.48-2.34(m,19H,C(CH3)3,aromatic CH3),1.45-0.95(m,21H,OCH
(CH3)2,C(CH3)3).
The ruthenium complex 4bb of embodiment 42 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3bb (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
The DCM dried with 30mL, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed to obtain green solid product 4bb, yield with methanol or pentane-DCM：42%.
After testing, ruthenium complex (4bb)1H-NMR(400MHz,CDCl3):19.02 (s, 1H, Ru=CH), 7.21-
6.82 (m, 8H, aromatic H), 6.40 (dd, J=9.6Hz, 1.6Hz, aromatic H), 5.206 (m, 1H, NH), 4.06-
4.00(m,5H,NCH2,NCH2CH2NH),3.7(s,3H,OCH3), 3.54 (d, J=13.2Hz, 1H, NCH2),2.48-2.18(m,
24H,aromatic CH3).
The ruthenium complex 4be of embodiment 43 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3be (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
The DCM dried with 30mL, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed to obtain green solid product 4be, yield with methanol or pentane-DCM：48%.
After testing, ruthenium complex (4be)1H-NMR(400MHz,CDCl3):δ 18.88 (s, 1H, Ru=CH), 7.57-
6.44 (m, 11H, aromatic H), 5.36 (t, J=13.2Hz, 1H, NH), 4.16-4.02 (m, 5H, NCH2,NCH2CH2N),
4.01 (d, J=13.2Hz, 1H, NCH2),2.75-2.00(m,19H,CH(CH3)2,aromatic CH3),1.01-0.90(m,
6H,CH(CH3)2).
The ruthenium complex 4bg of embodiment 44 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3bg (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
The DCM dried with 30mL, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed to obtain green solid product 4bg, yield with methanol or pentane-DCM：52%.
After testing, ruthenium complex (4bg)1H-NMR(400MHz,CDCl3):δ 18.95 (s, 1H, Ru=CH), 7.43-
6.36(m,10H,aromatic H),4.00(m,6H,NCH2,NCH2CH2N),2.67-2.06(m,20H,CH(CH3)2,
aromatic CH3),0.90-0.83(m,12H,CH(CH3)2).
The ruthenium complex 4bj of embodiment 45 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3bj (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
The DCM dried with 30mL, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed to obtain green solid product 4bj, yield with methanol or pentane-DCM：64%.
After testing, ruthenium complex (4bj)1H-NMR(400MHz,CDCl3):δ 18.88 (s, 1H, Ru=CH), 7.25-
6.36 (m, 9H, aromatic H), 5.40 (t, J=13.2Hz, 1H, NH), 4.14-4.00 (m, 6H, NCH2,NCH2CH2N),
2.77-1.90(m,27H,aromatic CH3).
The ruthenium complex 4bk of embodiment 46 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3bk (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
The DCM dried with 30mL, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed to obtain green solid product 4bk, yield with methanol or pentane-DCM：26%.
After testing, ruthenium complex (4bk)1H-NMR(400MHz,CDCl3):δ 18.91 (s, 1H, Ru=CH), 7.63-
6.42 (m, 10H, aromatic H), 5.27 (t, J=13.2Hz, 1H, NH), 4.13-4.01 (m, 5H, NCH2,NCH2CH2N),
3.44 (d, J=13.2Hz, 1H, NCH2),2.46-2.00(m,21H,aromatic CH3).
The ruthenium complex 4bn of embodiment 47 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3bn (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
The DCM dried with 30mL, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed to obtain green solid product 4bn, yield with methanol or pentane-DCM：38%.
After testing, ruthenium complex (4bn)1H-NMR(400MHz,CDCl3):δ 18.75 (s, 1H, Ru=CH), 7.26-
6.21(m,9H,aromatic H),4.05-3.85(m,5H,NCH2,NCH2CH2N),3.72(s,3H,OCH3), 3.34 (d, J=
13.2Hz,1H,NCH2),2.82-0.95(m,30H,NCH3,aromatic CH3).
The ruthenium complex 4br of embodiment 48 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3br (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
The DCM dried with 30mL, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed to obtain green solid product 4br, yield with methanol or pentane-DCM：14%.
After testing, ruthenium complex (4br)1H-NMR(400MHz,CDCl3):δ 18.89 (s, 1H, Ru=CH), 7.69-
6.43 (m, 10H, aromatic H), 5.23 (dd, J=13.2,11.3Hz, 1H, NH), 4.16-3.94 (m, 5H, NCH2,
NCH2CH2), N 3.46 (d, J=11.3Hz, 1H, NCH2),2.62-1.00(m,21H,aromatic CH3).
The ruthenium complex 4bs of embodiment 49 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3bs (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
The DCM dried with 30mL, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex
1a (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed to obtain green solid product 4bs, yield with methanol or pentane-DCM：17%.
After testing, ruthenium complex (4bs)1H-NMR(400MHz,CDCl3):δ 19.53 (d, J=9.9Hz, Ru=CH),
8.43 (d, J=8.1Hz, 1H, aromatic H), 7.57-6.79 (m, 5H, aromatic H), 5.43 (dd, J=13.2,
11.3Hz, 1H, NH), 4.60 (d, J=13.2Hz, 1H, NCH2), 3.72 (d, J=11.3Hz, 1H, NCH2),2.29-0.95(m,
36H,PCy3,aromatic CH3,).
The ruthenium complex 4bv of embodiment 50 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3bv (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
The DCM dried with 30mL, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed to obtain green solid product 4bv, yield with methanol or pentane-DCM：90%.
After testing, ruthenium complex (4bv)1H-NMR(400MHz,CDCl3):δ 18.75 (s, 1H, Ru=CH), 7.50-
7.44(m,2H,aromatic H),7.04-6.36(m,9H,aromatic H),5.32-5.21(m,1H,NH),4.65(d,J
=13.2Hz, 1H, NCH2),4.16-4.04(m,4H,NCH2CH2N),3.59(s,3H,OCH3), 3.48 (d, J=13.2Hz,
1H,NCH2),2.62-2.32(m,18H,aromatic CH3).
The ruthenium complex 4bw of embodiment 51 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3bw (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
The DCM dried with 30mL, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex
1a (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed to obtain green solid product 4bw, yield with methanol or pentane-DCM：49%.
After testing, ruthenium complex (4bw)1H-NMR(400MHz,CDCl3):δ 19.39 (d, J=10Hz, Ru=CH),
8.11 (d, J=8Hz, 1H, aromatic H), 7.64-7.06 (m, 2H, aromatic H), 7.16-6.87 (m, 4H,
aromatic H),5.47(m,1H,NH),5.24(m,1H,NCH2), 3.92 (d, J=13.6Hz, 1H, NCH2),3.80(s,3H,
OCH3),2.30-0.87(m,33H,PCy3).
The ruthenium complex 4bx of embodiment 52 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3bx (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
The DCM dried with 30mL, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed to obtain green solid product 4bx, yield with methanol or pentane-DCM：65%.
After testing, ruthenium complex (4bx)1H-NMR(300MHz,CDCl3):δ 18.82 (s, 1H, Ru=CH), 7.47-
7.43(m,2H,aromatic H),7.01-6.56(m,9H,aromatic H),5.12-5.09(m,1H,NH),4.56-4.45
(m,2H,OCH,NHCH2),4.40-4.15(m,4H,NCH2CH2N),3.48-3.45(m,1H,NHCH2),2.64-2.04(m,
18H,aromatic CH3), 1.10 (d, J=6.4Hz, 6H, OCH (CH3)2).
The ruthenium complex 4cc of embodiment 53 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3cc (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
The DCM dried with 30mL, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed to obtain green solid product 4cc, yield with methanol or pentane-DCM：23%.
After testing, ruthenium complex (4cc)1H-NMR(300MHz,CDCl3):δ 18.97 (s, 1H, Ru=CH), 8.54-
8.45(m,2H,aromatic H),6.66-6.96(m,8H,aromatic H),4.16-4.10(m,1H,NH),4.03(s,
4H,NCH2CH2N),2.63-1.75(m,22H,NHCH2,aromatic CH3), 0.92 (d, J=7.6Hz, OCH (CH3)2),
0.83 (d, J=7.6Hz, OCH (CH3)2).
The ruthenium complex 4cd of embodiment 54 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3cd (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
The DCM dried with 30mL, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed to obtain green solid product 4cd, yield with methanol or pentane-DCM：42%.
After testing, ruthenium complex (4cd)1H-NMR(400MHz,CDCl3):δ 19.02 (s, 1H, Ru=CH), 7.87
(dd, J=8,1.2Hz, 1H, aromatic H), 7.44 (dd, J=7.2,1.2Hz, 1H, aromatic H), 7.25-7.03
(m,9H,aromatic H),5.37-5.30(m,1H,NH),4.76-4.74(m,1H,NCH2),4.16-4.01(m,4H,
NCH2CH2N),3.58-3.54(m,4H,NCH2,OCH3),2.75(s,6H,NCH3),2.73-1.98(m,18H,aromatic
CH3).
The ruthenium complex 4cf of embodiment 55 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3cf (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
The DCM dried with 30mL, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed to obtain green solid product 4cf, yield with methanol or pentane-DCM：32%.
After testing, ruthenium complex (4cf)1H-NMR(300MHz,CDCl3):δ 19.03 (s, 1H, Ru=CH), 7.48-
6.63(m,10H,aromatic H),5.53(m,1H,NH),4.81-4.78(m,1H,NHCH2),4.00(s,4H,
NCH2CH2N),2.51-2.49(m,1H,NHCH2),2.51-2.32(m,18H,aromatic CH3), 1.12 (d, J=7.6Hz,
OCH(CH3)2), 1.04 (d, J=7.6Hz, OCH (CH3)2).
The ruthenium complex 4cg of embodiment 56 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3cg (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
The DCM dried with 30mL, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed to obtain green solid product 4cg, yield with methanol or pentane-DCM：51%.
After testing,1H-NMR(300MHz,CDCl3):δ 19.06 (s, 1H, Ru=CH), 7.87 (d, J=7.6Hz, 1H,
Aromatic H), 7.42 (d, J=7.6Hz, 1H, aromatic H), 7.29 (d, J=12Hz, 1H, aromatic H),
7.11-6.56(m,8H,aromatic H),5.22-5.19(m,1H,NH),4.63-4.64(m,1H,NHCH2),4.45-4.42
(m,1H,OCH),4.14-4.01(m,4H,NCH2CH2N),3.56-3.53(m,1H,NHCH2),3.12-3.07(m,4H,
NCH2),2.67-2.36(m,18H,aromatic CH3),1.99-1.00(m,24H,CH2CH2CH2CH3,OCH(CH3)2).
The ruthenium complex 4ch of embodiment 57 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3ch (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
The DCM dried with 30mL, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed to obtain green solid product 4ch, yield with methanol or pentane-DCM：74%.
After testing, ruthenium complex (4ch)1H-NMR(300MHz,CDCl3):δ 19.06 (s, 1H, Ru=CH), 7.87
(d, J=7.6Hz, 1H, aromatic H), 7.42 (d, J=7.6Hz, 1H, aromatic H), 7.11-6.56 (m, 9H,
aromatic H),5.27-5.20(m,1H,NH),4.64-4.61(m,1H,NHCH2),4.46-4.44(m,1H,OCH),
4.14-4.01(m,4H,NCH2CH2N),3.59-3.56(m,1H,NHCH2),3.12-3.07(m,4H,NCH2),2.75(s,6H,
NCH3),2.67-2.36(m,18H,aromatic CH3), 1.13 (d, J=6.0Hz, 6H, OCH (CH3)2).
The ruthenium complex 4cj of embodiment 58 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3cj (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
The DCM dried with 30mL, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex
1a (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed to obtain green solid product 4cj, yield with methanol or pentane-DCM：77%.
After testing, ruthenium complex (4cj)1H-NMR(400MHz,CDCl3):δ 19.56 (d, J=9.6Hz, Ru=CH),
8.21 (d, J=8.0Hz, 1H, aromatic H), 8.09 (d, J=2Hz, 1H, aromatic H), 8.10 (dd, J=7.6,
2Hz,1H,aromatic H),7.34-6.87(m,4H,aromatic H),5.47-5.44(m,1H,NH),5.33-5.27(m,
1H,NCH2),4.62-4.56(m,1H,OCH),3.99-3.96(m,1H,NCH2),2.80(s,6H,NCH3),2.30-1.24(m,
39H,PCy3,OCH(CH3)2).
The ruthenium complex 4ck of embodiment 59 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3ck (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
The DCM dried with 30mL, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed to obtain green solid product 4ck, yield with methanol or pentane-DCM：47%.
After testing, ruthenium complex (4ck)1H-NMR(400MHz,CDCl3):δ 18.99 (s, 1H, Ru=CH), 7.88
(dd, J=8,2Hz, 1H, aromatic H), 7.44 (dd, J=7.2,1.2Hz, 1H, aromatic H), 7.28-6.63 (m,
9H,aromatic H),5.35-5.28(m,1H,NH),4.75-4.72(m,1H,NCH2),4.16-4.12(m,4H,
NCH2CH2N),3.61(s,3H,OCH3),3.56-3.52(m,4H,NCH2),3.10-3.06(m,4H,NCH2),2.63-2.05
(m,18H,aromatic CH3),1.37-0.98(m,14H,CH2CH2CH3).
The ruthenium complex 4cm of embodiment 60 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3cm (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
The DCM dried with 30mL, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed to obtain green solid product 4cm, yield with methanol or pentane-DCM：27%.
After testing, ruthenium complex (4cm)1H-NMR(400MHz,CDCl3):δ 19.03 (s, 1H, Ru=CH), 7.60 (d,
J=7.6Hz, 1H, aromatic H), 7.43 (d, J=3.6Hz, 1H, aromatic H), 7.14 (s, 1H, aromatic H),
7.09-7.00(m,5H,aromatic H),6.81-6.57(m,3H,aromatic H),5.22(m,1H,NH),4.64-4.61
(m,1H,NCH2),4.64-4.42(m,2H,OCH,NH),4.15-4.02(m,4H,NCH2CH2N),3.16(m,1H,NCH2),
3.17(m,1H,NCH),2.67-2.00(m,18H,aromatic CH3),1.85-1.00(m,16H,CH2CH2,OCH(CH3)2).
The ruthenium complex 4cn of embodiment 61 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3cn (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
The DCM dried with 30mL, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed to obtain green solid product 4cn, yield with methanol or pentane-DCM：26%.
After testing, ruthenium complex (4cn)1H-NMR(400MHz,CDCl3):δ 18.96 (s, 1H, Ru=CH), 7.95 (d,
J=7.6Hz, 1H, aromatic H), 7.45 (d, J=8Hz, 1H, aromatic H), 7.35 (s, 1H, aromatic H),
7.07-7.03(m,5H,aromatic H),6.78-6.65(m,3H,aromatic H),5.31(m,1H,NH),4.76-4.73
(m,1H,NCH2),4.38-4.37(m,1H,NH),4.14-4.03(m,4H,NCH2CH2N),3.60(s,3H,OCH3),3.56-
3.53(m,1H,NCH2),3.14-3.13(m,1H,NCH),2.66-1.27(m,34H,aromatic CH3,CH2CH2,OCH
(CH3)2).
The ruthenium complex 4cp of embodiment 62 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3cp (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
The DCM dried with 30mL, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed to obtain green solid product 4cp, yield with methanol or pentane-DCM：68%.
After testing, ruthenium complex (4cp)1H-NMR(400MHz,CDCl3):δ 18.90 (s, 1H, Ru=CH), 7.27-
6.77 (m, 9H, aromatic H), 6.41 (d, J=8.0Hz, 1H, aromatic H), 5.43 (t, J=13.2Hz, 1H, NH),
4.18-4.00(m,5H,NCH2,NCH2CH2), N 3.25 (d, J=13.6Hz, NCH2),2.76-1.27(m,24H,aromatic
CH3).
The ruthenium complex 4cr of embodiment 63 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3cr (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
The DCM dried with 30mL, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed to obtain green solid product 4cr, yield with methanol or pentane-DCM：59%.
After testing, ruthenium complex (4cr)1H-NMR(400MHz,CDCl3):δ 18.82 (s, 1H, Ru=CH), 8.15
(dd, J=6.4,1.2Hz, 2H, aromatic H), 7.51 (d, J=1.2Hz, 1H, aromatic H), 7.44 (d, J=
1.2Hz, 1H, aromatic H), 7.05-6.99 (m, 5H, aromatic H), 8.15 (d, J=6.4Hz, 2H, aromatic
H),6.59-6.56(m,1H,aromatic H),5.22(m,1H,NH),4.63(m,1H,NHCH2),4.41(m,1H,OCH),
3.96(m,4H,NCH2CH2N),3.55-3.52(m,1H,NHCH2),2.66-2.33(m,18H,aromatic CH3),1.14
(d, J=6.4Hz, 6H, OCH (CH3)2).
The ruthenium complex 4cs of embodiment 64 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3cs (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
The DCM dried with 30mL, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed to obtain green solid product 4cs, yield with methanol or pentane-DCM：82%.
After testing, ruthenium complex (4cs)1H-NMR(400MHz,CDCl3):δ 18.73 (s, 1H, Ru=CH), 7.45-
6.60 (m, 7H, aromatic H), 6.44 (dd, J=8.0,1.2Hz, 1H, aromatic H), 6.38 (dd, J=7.6,
2.4Hz,1H,aromatic H),5.06(m,1H,NH),4.17-3.92(m,7H,NCH2,NCH2CH2N,OCH2),3.55(m,
1H,NCH2),2.44-1.00(m,7H,aromatic CH3).
The ruthenium complex 4ct of embodiment 65 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3ct (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
The DCM dried with 30mL, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex
1a (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed to obtain green solid product 4ct, yield with methanol or pentane-DCM：57%.
After testing, ruthenium complex (4ct)1H-NMR(400MHz,CDCl3):δ 19.40 (d, J=10Hz, Ru=CH),
7.40 (d, J=7.6Hz, 1H, aromatic H), 7.31-7.29 (m, 2H, aromatic H), 7.26 (dd, J=7.6,2Hz,
1H,aromatic H),6.84-6.82(m,2H,aromatic H),5.15(m,1H,NH),4.93(m,1H,NCH2),3.96-
3.83(m,3H,OCH2,NCH2),2.28-1.00(m,40H,PCy3,CH2CH2CH3).
The ruthenium complex 4cu of embodiment 66 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3cu (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
The DCM dried with 30mL, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed to obtain green solid product 4cu, yield with methanol or pentane-DCM：65%.
After testing, ruthenium complex (4cu)1H-NMR(400MHz,CDCl3):δ 18.68 (s, 1H, Ru=CH), 7.28-
6.96 (m, 10H, aromatic H), 6.37 (d, J=8.5Hz, 1H, aromatic H), 5.31 (m, 3H, NCH2,OCH2),
4.71-4.01(m,5H,NH,NCH2CH2), N 3.58 (d, J=12.8Hz, 1H, NCH2),2.89-1.29(m,21H,OCH2CH3,
aromatic CH3).
The ruthenium complex 4cw of embodiment 67 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3cw (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
The DCM dried with 30mL, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed to obtain green solid product 4cw, yield with methanol or pentane-DCM：85%.
After testing, ruthenium complex (4cw)1H-NMR(400MHz,CDCl3):δ 18.68 (s, 1H, Ru=CH), 7.28-
6.42 (m, 10H, aromatic H), 6.37 (d, J=8.5Hz, 1H, aromatic H), 5.05 (m, 1H, NCH2),4.06-
3.93(m,7H,NH,NCH2CH2N,OCH2), 3.57 (d, J=12.8Hz, 1H, NCH2),2.89-1.29(m,29H,CH2CH3,
aromatic CH3).
The ruthenium complex 4cy of embodiment 68 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3cy (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
The DCM dried with 30mL, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed to obtain green solid product 4cy, yield with methanol or pentane-DCM：70%.
After testing, ruthenium complex (4cy)1H-NMR(400MHz,CDCl3):δ 18.68 (s, 1H, Ru=CH), 7.28-
6.61 (m, 10H, aromatic H), 6.41 (d, J=8.5Hz, 1H, aromatic H), 5.05 (m, 1H, NCH2),4.52-
4.06(m,6H,NH,NCH2CH2N, OCH), 3.57 (d, J=12.8Hz, 1H, NCH2),2.89-1.29(m,24H,CH2CH3,
aromatic CH3).
The ruthenium complex 4cz of embodiment 69 synthesis
One 50mL, two mouthfuls of flasks sequentially add part 3cz (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
The DCM dried with 30mL, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex
1a (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed to obtain green solid product 4cz, yield with methanol or pentane-DCM：64%.
After testing, ruthenium complex (4cz)1H-NMR(400MHz,CDCl3):δ 19.28 (d, J=8.4Hz, Ru=CH),
7.46 (d, J=8.8Hz, 2H, aromatic H), 7.40-7.18 (m, 3H, aromatic H), 6.84 (d, J=8.8Hz, 2H,
Aromatic H), 5.21 (t, J=12.4Hz, 1H, NH), 4.93 (d, J=12.4Hz, 1H, NCH2),4.50(m,1H,OCH),
3.90-3.86(m,1H,NCH2),2.30-1.21(m,39H,CH2CH3,PCy3).
It is using complex ligands (5a-5z) synthesis ruthenium complex 6a-6z below according to relevant documents and materials：
It is complex compound 6a-6z structural formula (1a below:Cy=cyclohexyl, 1b:Mes=2,4,6- trimethylbenzenes)：
The ruthenium complex 6a of embodiment 70 synthesis
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 5a (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain greenish yellow solid product 6a, yield with methanol or pentane-DCM：79%.
After testing, ruthenium complex (6a)1HNMR(400MHz,CDCl3):δ 18.529 (s, 1H, Ru=CH), 8.587 (s,
1H, N=CH), 7.283-6.490 (m, 11H, aromatic H), 4.160 (s, 4H, NCH2CH2N),2.50(s,12H,
aromatic CH3),2.42(s,6H,aromatic CH3).
The ruthenium complex 6b of embodiment 71 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 5b (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1a
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain greenish yellow solid product 6b, yield with methanol or pentane-DCM：77%.
After testing, ruthenium complex (6a)1HNMR(400MHz,CDCl3):δ 19.197 (d, J=10.8Hz, Ru=CH),
8.819 (d, J=9.2Hz, 1H, N=CH), 7.835 (m, 1H, aromatic H), 7.795 (d, J=8.4Hz, 1H,
aromatic H),7.453(m,4H,aromatic H),2.459-1.291(m,33H,PCy3).
The ruthenium complex 6c of embodiment 72 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 5c (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain greenish yellow solid product 6c, yield with methanol or pentane-DCM：96%.
After testing, ruthenium complex (6c)1HNMR(400MHz,CDCl3):δ 18.516 (s, 1H, Ru=CH), 8.599 (s,
1H, N=CH), 7.283-7.133 (m, 7H, aromatic H), 7.017 (d, J=8.8Hz, 1H, aromatic H), 6.800
(m, 1H, aromatic H), 6.091 (d, J=8.8Hz, 1H, aromatic H), 4.160 (s, 4H, NCH2CH2N),3.837
(s,3H,OCH3),2.514(m,18H,aromatic CH3).
The ruthenium complex 6d of embodiment 73 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 5d (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1a
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain greenish yellow solid product 6d, yield with methanol or pentane-DCM：65%.
After testing, ruthenium complex (6d)1HNMR(400MHz,CDCl3):δ 19.639 (d, J=11.6Hz, Ru=CH),
8.868 (d, J=13.6Hz, 1H, N=CH), 7.865-7.842 (m, 3H, aromatic H), 7.430-7.97 (m, 2H,
aromatic H),6.999-6.976(m,2H,aromatic H),3.768(s,3H,OCH3),2.310-1.074(m,33H,
PCy3).
The ruthenium complex 6e of embodiment 74 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 5e (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain greenish yellow solid product 6e, yield with methanol or pentane-DCM：31%.
After testing, ruthenium complex (6e)1HNMR(400MHz,CDCl3):δ 18.731 (s, 1H, Ru=CH), 8.619 (s,
1H, N=CH), 7.670-7.456 (m, 3H, aromatic H), 7.113 (s, 4H, aromatic H), 6.779-6.651 (m,
5H,aromatic H),4.131(s,4H,NCH2CH2N),3.810(s,3H,OCH3),2.493(m,18H,aromatic
CH3).
The ruthenium complex 6f of embodiment 75 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 5f (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1a
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain greenish yellow solid product 6f, yield with methanol or pentane-DCM：7%.
After testing, ruthenium complex (6f)1HNMR(400MHz,CDCl3):δ 19.373 (d, J=11.7Hz, Ru=CH),
8.836 (d, J=9.3Hz, 1H, N=CH), 7.877-7.682 (m, 6H, aromatic H), 6.974 (d, J=8.7Hz, 2H,
aromatic H),3.885(s,3H,OCH3),2.496-1.275(m,33H,PCy3).
The ruthenium complex 6g of embodiment 76 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 5g (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain greenish yellow solid product 6g, yield with methanol or pentane-DCM：24%.
After testing, ruthenium complex (6g)1HNMR(400MHz,CDCl3):δ 18.741 (s, 1H, Ru=CH), 8.602 (s,
1H, N=CH), 7.692-7.485 (m, 3H, aromatic H), 7.120-7.042 (m, 8H, aromatic H), 6.798 (d, J
=8.7Hz, 1H, aromatic H), 4.131 (s, 4H, NCH2CH2N),2.495(m,18H,aromatic CH3).
The ruthenium complex 6h of embodiment 77 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 5h (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1a
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain greenish yellow solid product 6h, yield with methanol or pentane-DCM：27%.
After testing, ruthenium complex (6h)1HNMR(400MHz,CDCl3):δ 18.95 (d, J=6.4Hz, Ru=CH),
10.26 (d, J=9.2Hz, 1H, N=CH), 7.985-7.256 (m, 8H, aromatic H), 2.430-0.854 (m, 33H,
PCy3).
The ruthenium complex 6j of embodiment 78 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 5j (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain greenish yellow solid product 6j, yield with methanol or pentane-DCM：38%.
After testing, ruthenium complex (6j)1HNMR(400MHz,CDCl3):δ 18.751 (s, 1H, Ru=CH), 8.647 (s,
1H, N=CH), 7.710-6.789 (m, 13H, aromatic H), 4.197 (s, 4H, NCH2CH2N),2.490(m,18H,
aromatic CH3).
The ruthenium complex 6k of embodiment 79 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 5k (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1a
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain greenish yellow solid product 6k, yield with methanol or pentane-DCM：15%.
After testing, ruthenium complex (6k)1HNMR(400MHz,CDCl3):δ 19.45 (d, J=6.4Hz, Ru=CH),
8.868 (d, J=9.3Hz, 1H, N=CH), 7.896-7.259 (m, 9H, aromatic H), 2.491-1.268 (m, 33H,
PCy3).
The ruthenium complex 6m of embodiment 80 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 5m (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain greenish yellow solid product 6m, yield with methanol or pentane-DCM：17%.
After testing, ruthenium complex (6m)1HNMR(400MHz,CDCl3):δ 18.595 (s, 1H, Ru=CH), 8.579 (s,
1H, N=CH), 7.480-7.292 (m, 2H, aromatic H), 7.016 (d, J=8.8Hz, 2H, aromatic H), 6.743-
6.687(m,3H,aromatic H),4.165(s,4H,NCH2CH2N),3.845(s,3H,OCH3),2.519(m,18H,
aromatic CH3).
The ruthenium complex 6n of embodiment 81 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 5n (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain greenish yellow solid product 6n, yield with methanol or pentane-DCM：40%.
After testing, ruthenium complex (6n)1HNMR(400MHz,CDCl3):δ 18.522 (s, 1H, Ru=CH), 8.592 (s,
1H, N=CH), 7.292-6.838 (m, 10H, aromatic H), 6.838-6.818 (m, 1H, aromatic H), 4.167 (s,
4H,NCH2CH2N),2.517(m,18H,aromatic CH3).
The ruthenium complex 6p of embodiment 82 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 5p (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1a
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain greenish yellow solid product 6p, yield with methanol or pentane-DCM：47%.
After testing, ruthenium complex (6p)1HNMR(400MHz,CDCl3):δ 19.214 (d, J=11.2Hz, Ru=CH),
8.819 (d, J=9.2Hz, 1H, N=CH), 7.893-7.858 (m, 3H, aromatic H), 7.507-7.416 (m, 4H,
aromatic H),2.501-1.573(m,33H,PCy3).
The ruthenium complex 6q of embodiment 83 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 5q (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain greenish yellow solid product 6q, yield with methanol or pentane-DCM：33%.
After testing, ruthenium complex (6q)1HNMR(400MHz,CDCl3):δ 18.541 (s, 1H, Ru=CH), 8.634 (s,
1H, N=CH), 7.292-6.849 (m, 11H, aromatic H), 6.849-6.835 (m, 1H, aromatic H), 4.169 (s,
4H,NCH2CH2N),2.510(m,18H,aromatic CH3).
The ruthenium complex 6r of embodiment 84 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 5r (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1a
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain greenish yellow solid product 6r, yield with methanol or pentane-DCM：8%.
After testing, ruthenium complex (6r)1HNMR(400MHz,CDCl3):δ 19.25 (d, J=10.8Hz, Ru=CH),
8.856 (d, J=9.2Hz, 1H, N=CH), 7.894 (m, 3H, aromatic H), 7.521-7.428 (m, 5H, aromatic
H),2.508-1.742(m,33H,PCy3).
The ruthenium complex 6s of embodiment 85 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 5s (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain greenish yellow solid product 6s, yield with methanol or pentane-DCM：37%.
After testing, ruthenium complex (6s)1HNMR(400MHz,CDCl3):δ 16.52 (s, 1H, Ru=CH), 8.43 (s,
1H, N=CH), 8.10 (s, 1H, aromatic H), 7.46-7.22 (m, 2H, aromatic H), 7.73-6.96 (m, 8H,
aromatic H),4.19(s,4H,NCH2CH2N),3.947(s,3H,OCH3),3.87(s,3H,OCH3),2.49(s,12H,
aromatic CH3),2.48(s,6H,aromatic CH3).
The ruthenium complex 6t of embodiment 86 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 5t (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1a
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain greenish yellow solid product 6t, yield with methanol or pentane-DCM：-- %.
After testing, ruthenium complex (6t)1HNMR(400MHz,CDCl3):δ 17.43 (d, J=4.8Hz, Ru=CH),
8.56 (s, 1H, N=CH), 8.32-8.10 (m, 2H, aromatic H), 7.28-6.96 (m, 5H, aromatic H), 4.40
(s,3H,OCH3),3.86(s,3H,OCH3),2.33-1.30(m,33H,PCy3).
The ruthenium complex 6u of embodiment 87 synthesis:
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 5u (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1a
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain gray solid product 6u, yield with methanol or pentane-DCM：17%.
After testing, ruthenium complex (6u)1HNMR(400MHz,CDCl3):δ 17.40 (d, J=11.1Hz, Ru=CH),
8.519 (m, 1H, N=CH), 8.333-8.190 (m, 4H, aromatic H), 7.405-7.175 (m, 3H, aromatic H),
4.39(s,3H,OCH3),2.31-0.82(m,33H,PCy3).
The ruthenium complex 6v of embodiment 88 synthesis
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 5v (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1a
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain red solid product 6v, yield with methanol or pentane-DCM：28%.Product be not it is very stable, very
Difficult purification assays ruthenium complex 6v's1H-NMR structures, but its impure ruthenium complex 6v can be directly used for olefin metathesis double decomposition
Catalytic reaction.
The ruthenium complex 6w of embodiment 89 synthesis
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 5w (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain green solid product 6w, yield with methanol or pentane-DCM：22%.
After testing, ruthenium complex (6w)1H-NMR(400MHz,CDCl3):δ 18.659 (s, 1H, Ru=CH), 8.556
(s, 1H, N=CH), 7.499-7.337 (m, 2H, aromatic H), 7.256 (s, 4H, aromatic H), 7.004-6.397
(m,5H,aromatic H),4.138(s,4H,NCH2CH2N),3.805(s,3H,OCH3),2.493(m,18H,aromatic
CH3).
The ruthenium complex 6y of embodiment 90 synthesis
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 5y (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain green solid product 6y, yield with methanol or pentane-DCM：9%.
After testing, ruthenium complex (6y)1H-NMR(400MHz,CDCl3):δ 18.96 (s, 1H, Ru=CH), 8.43 (s,
1H, N=CH), 7.42-6.94 (m, 9H, aromatic H), 6.39 (d, J=9.2Hz, 1H, aromatic H), 4.01 (s,
4H,NCH2CH2N),2.67-2.28(m,20H,aromatic CH,aromatic CH3), 0.92 (d, J=7.6Hz, OCH
(CH3)2), 0.83 (d, J=7.6Hz, OCH (CH3)2).
The ruthenium complex 6z of embodiment 91 synthesis
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 5z (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain green solid product 6z, yield with methanol or pentane-DCM：9%.
After testing, ruthenium complex (6z)1H-NMR(400MHz,CDCl3):δ 18.60 (s, 1H, Ru=CH), 9.88 (s,
1H, N=CH), 7.79-6.96 (m, 8H, aromatic H), 6.54 (d, J=9.2Hz, 1H, aromatic H), 4.18 (s,
4H,NCH2CH2N),2.48-2.31(m,27H,aromatic CH3).
It is using complex ligands (7a-7t) synthesis ruthenium complex 8a-8t below according to relevant information：
It is complex compound 8a-8t structural formula (1a below:Cy=cyclohexyl, 1b:Mes=2,4,6- trimethylbenzenes)：
The ruthenium complex 8a of embodiment 92 synthesis
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 7a (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain green solid product 8a, yield with methanol or pentane-DCM：32%.
After testing, ruthenium complex (8a)1HNMR(400MHz,CDCl3):δ 16.80 (s, 1H, Ru=CH), 7.07 (s,
4H, aromatic H), 6.94 (m, 1H, aromatic H), 6.30 (d, J=6.4Hz, 1H, aromatic H), 4.11 (s,
4H,NCH2CH2N),2.69(s,6H,NCH3),2.49(s,(s,12H,aromatic CH3),2.42(s,6H,aromatic
CH3).
The ruthenium complex 8b of embodiment 93 synthesis
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 7b (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain green solid product 8b, yield with methanol or pentane-DCM：79%.
After testing, ruthenium complex (8b)1HNMR(400MHz,CDCl3):δ 16.695 (s, 1H, Ru=CH), 7.368 (m,
1H, aromatic H), 7.037-6.91 (m, 6H, aromatic H), 6.717 (d, J=7.6Hz, 1H, aromatic H),
5.050 (d, J=11.6Hz, 1H, NCH2),3.876-3.846(m,4H,NCH2CH2N),3.519(s,3H,OCH3),3.438
(d, J=11.6Hz, 1H, NCH2),2.85-1.50(m,21H,NCH3,aromatic CH3).
The ruthenium complex 8c of embodiment 94 synthesis
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 7c (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain green solid product 8c, yield with methanol or pentane-DCM：9%.
After testing, ruthenium complex (8c)1HNMR(400MHz,CDCl3):δ 16.967 (s, 1H, Ru=CH), 8.400
(dd, J=8.8,2.4Hz, 1H, aromatic H), 7.65 (d, J=2.4Hz, 1H, aromatic H), 7.29 (d, J=
8.8Hz,1H,aromatic H),7.07(s,4H,aromatic H),4.199(s,4H,NCH2CH2N),2.567(s,6H,N
(CH3)2,2.473(s,12H,aromatic CH3),2.390(s,6H,aromatic CH3).
The ruthenium complex 8d of embodiment 95 synthesis
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 7d (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain green solid product 8d, yield with methanol or pentane-DCM：24%.
After testing, ruthenium complex (8d)1HNMR(400MHz,CDCl3):δ 16.691 (s, 1H, Ru=CH), 8.356
(dd, J=8.8,2.4Hz, 1H, aromatic H), 7.618 (d, J=2.4Hz, 1H, aromatic H), 7.180 (d, J=
8.8Hz,1H,aromatic H),7.167-6.999(m,4H,aromatic H),4.164-3.795(m,6H,aromatic
H),2.838-2.076(m,21H,NCH3,aromatic CH3), 0.574 (t, J=6.8Hz, 3H, CH2CH3).
The ruthenium complex 8e of embodiment 96 synthesis
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 7e (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain green solid product 8e, yield with methanol or pentane-DCM：74%.
After testing, ruthenium complex (8e)1HNMR(400MHz,CDCl3):δ 16.559 (s, 1H, Ru=CH), 8.331
(dd, J=8.4,2.4Hz, 1H, aromatic H), 7.563 (d, J=2.4Hz, 1H, aromatic H), 7.197-6.939
(m, 5H, aromatic H), 5.215 (d, J=11.2Hz, 1H, NCH2),4.210-3.959(m,4H,NCH2CH2N),3.559
(s,3H,OCH3), 3.535 (d, J=11.2Hz, 1H, NCH2),2.938-0.923(m,21H,NCH3,aromatic CH3)。
The ruthenium complex 8f of embodiment 97 synthesis
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 7f (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain green solid product 8f, yield with methanol or pentane-DCM：8%.
After testing, ruthenium complex (8f)1HNMR(400MHz,CDCl3):δ 16.820 (s, 1H, Ru=CH), 7.171-
7.007 (m, 7H, aromatic H), 6.773 (d, J=2Hz, 1H, aromatic H), 6.602 (d, J=2.8Hz, 1H,
Aromatic H), 6.550 (d, J=8.4Hz, 1H, aromatic H), 4.116 (s, 4H, NCH2CH2N),3.262(s,3H,
OCH3),2.734(s,3H,NCH3),2.572-2.260(m,18H,aromatic CH3).
The ruthenium complex 8g of embodiment 98 synthesis
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 7g (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1a
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain green solid product 8g, yield with methanol or pentane-DCM：9%.
After testing, ruthenium complex (8g)1H-NMR(400MHz,CDCl3):δ 17.661 (m, 1H, Ru=CH), 7.573
(d, J=2Hz, 1H, aromatic H), 7.477 (d, J=3Hz, 1H, aromatic H), 7.433 (dd, J=2,8.4Hz,
1H, aromatic H), 7.270 (d, J=3Hz, 1H, aromatic H), 6.983 (d, J=8.4Hz, 1H, aromatic H),
4.626 (d, J=13.2Hz, 1H, NCH2), 3.978 (d, J=13.2Hz, 1H, NCH2),3.646(s,3H,OCH3),2.836
(s,3H,NCH3),2.412-0.837(m,33H,PCy3).
The ruthenium complex 8h of embodiment 99 synthesis
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 7h (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain green solid product 8h, yield with methanol or pentane-DCM：37%.
After testing, ruthenium complex (8h)1H-NMR(400MHz,CDCl3):δ 16.843 (s, 1H, Ru=CH), 7.184
(d, J=8.4Hz, 1H, aromatic H), 7.807 (m, 5H, aromatic H), 6.748 (m, 1H, aromatic H),
6.619 (d, J=8.8Hz, 1H, aromatic H), 6.320 (d, J=8.4Hz, 1H, aromatic H), 4.294-4.238
(m,1H,OCH),4.109(s,4H,NCH2CH2), N 3.846 (d, J=14.0Hz, 1H, NCH2), 3.094 (d, J=14.0Hz,
1H,NCH2),2.737(s,3H,NCH3),2.429-2.278(m,18H,aromatic CH3), 1.095 (d, J=6Hz, 6H,
OCH(CH3)2).
The ruthenium complex 8j of embodiment 100 synthesis
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 7h (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1a
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain green solid product 8j, yield with methanol or pentane-DCM：48%.
After testing, ruthenium complex (8j)1H-NMR(400MHz,CDCl3):δ 17.584 (d, J=6.0Hz, 1H, Ru=
), CH 7.585-7.549 (m, 2H, aromatic H), 7.478 (d, J=8.4Hz, 1H, aromatic H), 7.223 (dd, J=
2.4,8.8Hz, 1H, aromatic H), 7.137 (d, J=8.4Hz, 1H, aromatic H), 6.784 (d, J=8.8Hz, 1H,
Aromatic H), 4.802 (d, J=12.8Hz, 1H, NCH2), 4.500-4.470 (m, 1H, OCH), 4.049 (d, J=
12.8Hz,1H,NCH2),2.704(s,3H,NCH3),2.384-0.780(m,39H,PCy3,OCH(CH3)2).
The ruthenium complex 8k of embodiment 101 synthesis
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 7k (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain green solid product 8k, yield with methanol or pentane-DCM：77%.
After testing, ruthenium complex (8k)1H-NMR(400MHz,CDCl3):δ 16.872 (s, 1H, Ru=CH), 7.409
(dd, J=2,8.4Hz, 1H, aromatic H), 7.187-7.132 (m, 5H, aromatic H), 7.031 (d, J=8.4Hz,
1H, aromatic H), 6.925 (d, J=7.2Hz, 1H, aromatic H), 6.772-6.757 (m, 2H, aromatic H),
6.652 (t, J=7.2Hz, 1H, aromatic H), 4.655 (d, J=12.4Hz, 1H, NCH2),4.477-4.432(m,1H,
OCH),4.015-3.983(m,5H,NCH2CH2N,NCH2),2.535-2.304(m,18H,aromatic CH3),2.246(s,
3H,NCH3), 1.285 (d, J=6Hz, 6H, OCH (CH3)2).
The ruthenium complex 8m of embodiment 102 synthesis
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 7m (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1a
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain green solid product 8m, yield with methanol or pentane-DCM：23%.
After testing, ruthenium complex (8m)1H-NMR(400MHz,CDCl3):δ 17.718 (m, 1H, Ru=CH), 7.846
(d, J=6.4Hz, 1H, aromatic H), 7.572 (d, J=2Hz, 1H, aromatic H), 7.528 (dd, J=2.4,
8.4Hz,1H,aromatic H),7.333-7.233(m,2H,aromatic H),6.980-6.890(m,2H,aromatic
), H 4.939 (d, J=12.4Hz, 1H, NCH2),4.588-4.543(m,1H,OCH),4.245-4.207(m,1H,NCH2),
2.639(s,3H,NCH3),2.418-0.810(m,39H,PCy3,OCH(CH3)2).
The ruthenium complex 8q of embodiment 103 synthesis
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 7q (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain green solid product 8q, yield with methanol or pentane-DCM：59%.
After testing, ruthenium complex (8g)1H-NMR(400MHz,CDCl3):δ 16.80 (s, 1H, Ru=CH), 8.18 (dd,
J=8.8,2.4Hz, 1H, aromatic H), 7.46 (d, J=2.4Hz, 1H, aromatic H), 7.23 (d, J=8.8Hz,
1H,aromatic H),7.07(s,4H,aromatic H),4.11(s,4H,NCH2CH2N),3.91(s,3H,COOCH3),
2.58(s,6H,N(CH3)2,2.47(s,12H,aromatic CH3),2.43(s,6H,aromatic CH3).
The ruthenium complex 8s of embodiment 104 synthesis
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 7s (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain green solid product 8s, yield with methanol or pentane-DCM：43%.
After testing, ruthenium complex (8s)1H-NMR(400MHz,CDCl3):δ 16.64 (s, 1H, Ru=CH), 8.34 (dd,
J=8.4,2.4Hz, 1H, aromatic H), 7.54 (d, J=2.4Hz, 1H, aromatic H), 7.25-6.93 (m, 5H,
Aromatic H), 5.17 (d, J=11.2Hz, 1H, NCH2),4.84-4.83(m,1H,OCH),4.14-3.93(m,4H,
NCH2CH2), N 3.45 (d, J=11.2Hz, 1H, NCH2),2.89-1.19(m,27H,NCH3,aromatic CH3,OCH
(CH3)2).
The ruthenium complex 8t of embodiment 105 synthesis
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 7t (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain green solid product 8t, yield with methanol or pentane-DCM：87%.
After testing, ruthenium complex (8t)1H-NMR(400MHz,CDCl3):δ 16.82 (s, 1H, Ru=CH), 7.12-
7.02(m,5H,aromatic H),6.64(m,1H,aromatic H),6.51-6.48(m,1H,aromatic H),4.15
(s,4H,NCH2CH2N),3.95-3.92(m,1H,NH,NCH2),3.74(s,3H,OCH3),2.50-2.37(m,18H,
aromatic CH3), 0.96 (d, J=6.4Hz, 1H, CH3).
It is using complex ligands (9a-9j) synthesis ruthenium complex 10a-10j below according to relevant information：
It is complex compound 10a-10j structural formula (1a below:Cy=cyclohexyl, 1b:Mes=2,4,6- trimethylbenzenes)：
The ruthenium complex 10a of embodiment 106 synthesis
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 9a (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain green solid product 10a, yield with methanol or pentane-DCM：19%.Product be not it is very stable,
It is difficult to purification assays ruthenium complex 10a1HNMR structures, but its impure ruthenium complex 10a can be directly used for olefin metathesis and answer
Decompose catalytic reaction.
The ruthenium complex 10b of embodiment 107 synthesis
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 9b (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1a
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain green solid product 10b, yield with methanol or pentane-DCM：15%.Product be not it is very stable,
It is difficult to purification assays ruthenium complex 10b1HNMR structures, but its impure ruthenium complex 10b can be directly used for olefin metathesis and answer
Decompose catalytic reaction.
The ruthenium complex 10c of embodiment 108 synthesis
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 9c (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain red brown solid product 10c, yield with methanol or pentane-DCM：4%.
After testing, ruthenium complex (10c)1HNMR(400MHz,CDCl3):δ 18.675 (s, 1H, Ru=CH), 8.436
(dd, J=8.4,2.4Hz, 1H, aromatic H), 8.200 (d, J=8.4Hz, 1H, aromatic H), 7.604 (d, J=
2.4Hz,1H,aromatic H),7.132(s,4H,aromatic H),4.140(s,4H,NCH2CH2N),3.973(s,3H,
OCH3),2.481(s,12H,aromatic CH3),2.459(s,6H,aromatic CH3).
The ruthenium complex 10d of embodiment 109 synthesis
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 9d (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain yellow solid product 10d, yield with methanol or pentane-DCM：34%.
After testing, ruthenium complex (10d)1HNMR(400MHz,CDCl3):δ 18.71 (s, 1H, Ru=CH), 8.42 (dd,
J=9,2.4Hz, 1H, aromatic H), 8.18 (d, J=9Hz, 1H, aromatic H), 7.60 (d, J=2.4Hz, 1H,
aromatic H),7.13(s,4H,aromatic H),5.25(m,1H,OCH(CH3)2),4.13(s,4H,NCH2CH2N),
2.46(m,18H,aromatic CH3), 1.24 (d, 6H, J=6Hz, CH (CH3)2).
The ruthenium complex 10e of embodiment 110 synthesis
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 9e (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain green solid product 10e, yield with methanol or pentane-DCM：34%.
After testing, ruthenium complex (10e)1HNMR(400MHz,CDCl3):δ 18.56 (s, 1H, Ru=CH), 7.977 (d,
J=8.8Hz, 1H, aromatic H), 8.18 (dd, J=8.8,2.4Hz, 1H, aromatic H), 7.105 (s, 4H,
Aromatic H), 7.064 (d, J=2.4Hz, 1H, aromatic H), 5.226 (m, 1H, OCH (CH3)2),4.114(s,4H,
NCH2CH2N),2.451(m,18H,aromatic CH3), 1.281 (d, 6H, J=6Hz, CH (CH3)2).
The ruthenium complex 10f of embodiment 111 synthesis
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 9f (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain yellow solid product 10f, yield with methanol or pentane-DCM：41%.
After testing, ruthenium complex (10f)1HNMR(400MHz,CDCl3):δ 18.75 (s, 1H, Ru=CH), 8.446
(dd, J=8.8,1.6Hz, 1H, aromatic H), 8.208 (d, J=8.8Hz, 1H, aromatic H), 7.637 (d, J=
1.6Hz, 1H, aromatic H), 7.388-7.250 (m, 2H), 7.168 (s, 4H, aromatic H), 6.828 (d, J=
8.8Hz,1H,aromatic H),5.370(s,2H,OCH2),4.529(m,1H,OCH(CH3)2),4.151(s,4H,
NCH2CH2N),2.511(m,18H,aromatic CH3), 1.395 (d, 6H, J=6Hz, CH (CH3)2).
The ruthenium complex 10g of embodiment 112 synthesis
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 9g (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain green solid product 10g, yield with methanol or pentane-DCM：53%.
After testing, ruthenium complex (10g)1HNMR(400MHz,CDCl3):δ 18.601 (s, 1H, Ru=CH), 8.011
(d, J=8.4Hz, 1H, aromatic H), 7.590 (dd, J=1.6,8.4Hz, 1H, aromatic H), 7.306-7.228
(m, 1H, aromatic H), 7.237 (dd, J=2.8,8.8Hz, 1H, aromatic H), 6.811 (d, J=8.8Hz, 1H,
Aromatic H), 6.713 (d, J=2.0Hz, 1H, aromatic H), 5.334 (s, 2H, OCH2),4.515(m,1H,OCH
(CH3)2),4.159(s,4H,NCH2CH2N),2.514(s,12H,aromatic CH3),2.482(s,6H,aromatic
CH3), 1.277 (d, 6H, J=6Hz, CH (CH3)2).
The ruthenium complex 10h of embodiment 113 synthesis
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 9h (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain green solid product 10h, yield with methanol or pentane-DCM：23%.
After testing, ruthenium complex (10h)1HNMR(400MHz,CDCl3):δ 18.603 (s, 1H, Ru=CH), 8.003
(d, J=8.8Hz, 1H, aromatic H), 7.553 (d, J=8.4Hz, 1H, aromatic H), 7.320-7.288 (m, 1H,
aromatic H),7.140(s,4H,aromatic H),7.008-6.703(m,4H,aromatic H),5.378(s,2H,
OCH2),4.560(m,1H,OCH(CH3)2),4.158(s,4H,NCH2CH2N),2.712(s,12H,aromatic CH3),
2.515(s,6H,aromatic CH3), 1.315 (d, 6H, J=6Hz, CH (CH3)2).
The ruthenium complex 10j of embodiment 114 synthesis
One 50mL, two mouthfuls of flasks sequentially added after being replaced with argon gas part 9j (10mmol), CuCl (30mmol, 3eq) and
The DCM that 30mL is dried, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex 1b
(12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
Crude product, then washed to obtain green solid product 10j, yield with methanol or pentane-DCM：37%.
After testing, ruthenium complex (10j)1H-NMR(400MHz,CDCl3):1H-NMR(400MHz,CDCl3):δ18.74
(s, 1H, Ru=CH), 8.21 (dd, J=8,2.4Hz, 1H, aromatic H), 8.08 (d, J=8Hz, 1H, aromatic H),
7.54 (d, J=2.4Hz, 1H, aromatic H), 7.12 (s, 4H, aromatic H), 5.32 (m, 1H, OCH (CH3)2),5.25
(m,1H,OCH(CH3)2),4.13(s,4H,NCH2CH2N),2.47(m,18H,aromatic CH3), 1.43 (d, J=6Hz, CH
(CH3)2), 1.24 (d, 6H, J=6Hz, CH (CH3)2).
It is using complex ligands (11a-11j) synthesis ruthenium complex 12a-12j below according to relevant information：
It is complex compound 12a-12j structural formula (1a below:Cy=cyclohexyl, 1b:Mes=2,4,6- trimethylbenzenes)：
The ruthenium complex 12a of embodiment 115 synthesis
One 50mL, two mouthfuls of flasks sequentially add ligand 1 1a (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
The DCM dried with 30mL, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed to obtain green solid product 12a, yield with methanol or pentane-DCM：75%.Product is not very steady
It is fixed, it is difficult to purification assays ruthenium complex 12a structure, but its impure ruthenium complex 12a can be directly used for olefin metathesis subdivision
Solve catalytic reaction.
The ruthenium complex 12b of embodiment 116 synthesis
One 50mL, two mouthfuls of flasks sequentially add ligand 1 1b (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
The DCM dried with 30mL, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed to obtain green solid product 12b, yield with methanol or pentane-DCM：57%.Product is not very steady
It is fixed, it is difficult to purification assays ruthenium complex 12b structure, but its impure ruthenium complex 12b can be directly used for olefin metathesis subdivision
Solve catalytic reaction.
The ruthenium complex 12c of embodiment 117 synthesis
One 50mL, two mouthfuls of flasks sequentially add ligand 1 1c (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
The DCM dried with 30mL, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed to obtain green solid product 12c, yield with methanol or pentane-DCM：40%.Product is not very steady
It is fixed, it is difficult to purification assays ruthenium complex 12c structure, but its impure ruthenium complex 12c can be directly used for olefin metathesis subdivision
Solve catalytic reaction.
The ruthenium complex 12d of embodiment 118 synthesis
One 50mL, two mouthfuls of flasks sequentially add ligand 1 1d (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
The DCM dried with 30mL, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed to obtain green solid product 12d, yield with methanol or pentane-DCM：42%.Product is not very steady
It is fixed, it is difficult to purification assays ruthenium complex 12d structure, but its impure ruthenium complex 12d can be directly used for olefin metathesis subdivision
Solve catalytic reaction.
The ruthenium complex 12e of embodiment 119 synthesis
One 50mL, two mouthfuls of flasks sequentially add ligand 1 1e (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
The DCM dried with 30mL, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed to obtain green solid product 12e, yield with methanol or pentane-DCM：69%.Product is not very steady
It is fixed, it is difficult to purification assays ruthenium complex 12e structure, but its impure ruthenium complex 12e can be directly used for olefin metathesis subdivision
Solve catalytic reaction.
The ruthenium complex 12f of embodiment 120 synthesis
One 50mL, two mouthfuls of flasks sequentially add ligand 1 1f (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
The DCM dried with 30mL, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed to obtain green solid product 12f, yield with methanol or pentane-DCM：63%.Product is not very steady
It is fixed, it is difficult to purification assays ruthenium complex 12f structure, but its impure ruthenium complex 12f can be directly used for olefin metathesis subdivision
Solve catalytic reaction.
The ruthenium complex 12g of embodiment 121 synthesis
One 50mL, two mouthfuls of flasks sequentially add ligand 1 1g (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
The DCM dried with 30mL, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed to obtain green solid product 12g, yield with methanol or pentane-DCM：69%.Product is not very steady
It is fixed, it is difficult to purification assays ruthenium complex 12g structure, but its impure ruthenium complex 12g can be directly used for olefin metathesis subdivision
Solve catalytic reaction.
The ruthenium complex 12h of embodiment 122 synthesis
One 50mL, two mouthfuls of flasks sequentially add ligand 1 1h (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
The DCM dried with 30mL, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed to obtain green solid product 12h, yield with methanol or pentane-DCM：61%.Product is not very steady
It is fixed, it is difficult to purification assays ruthenium complex 12h structure, but its impure ruthenium complex 12h can be directly used for olefin metathesis subdivision
Solve catalytic reaction.
The ruthenium complex 12j of embodiment 123 synthesis
One 50mL, two mouthfuls of flasks sequentially add ligand 1 1j (10mmol), CuCl (30mmol, 3eq) after being replaced with argon gas
The DCM dried with 30mL, then with argon gas displacement three times afterwards with argon gas ball protection enclosed system.Argon gas protection is lower to add ruthenium complex
1b (12mmol), in room temperature reaction 0.5 hour.Reaction terminates, and adds silica gel sand after filtering in filtrate, is obtained through silica gel column chromatography
To crude product, then washed to obtain green solid product 12j, yield with methanol or pentane-DCM：46%.Product is not very steady
It is fixed, it is difficult to purification assays ruthenium complex 12j structure, but its impure ruthenium complex 12j can be directly used for olefin metathesis subdivision
Solve catalytic reaction.
It is using ruthenium complex (13-SM) synthesis ruthenium complex 13a-13ag below according to relevant information：
It is ruthenium complex 13a-13ag structural formula (1a below:Cy=cyclohexyl, 1b:Mes=2,4,6- trimethylbenzenes)：
The ruthenium complex 13a of embodiment 124 synthesis
One 25mL, two mouthfuls of flasks add ruthenium complex (0.1g) after being replaced with argon gas, and argon gas is used afterwards three times with argon gas displacement
Ball protects enclosed system, adds substituted pyridine (1mL) in room temperature reaction 0.5 hour.Reaction terminates, and adds pentane (- 10
DEG C, 20mL), greenish yellow solid product 13a, yield are obtained after filtering：47%.
After testing, ruthenium complex (13a)1H-NMR(400MHz,CDCl3):δ17.33(s,1H),8.71(s,1H),
8.56 (d, J=3.2Hz, 1H), 7.84 (d, J=6.0Hz, 1H), 7.41-7.34 (m, 1H), 7.23-7.21 (m, 1H), 7.01
(dd, J=3.2,9.6Hz), 5.23-5.21 (m, 1H), 2.37-0.90 (m, 33H)
The ruthenium complex 13b of embodiment 125 synthesis
One 25mL, two mouthfuls of flasks add ruthenium complex (0.1g) after being replaced with argon gas, and argon gas is used afterwards three times with argon gas displacement
Ball protects enclosed system, adds substituted pyridine (1mL) in room temperature reaction 0.5 hour.Reaction terminates, and adds pentane (- 10
DEG C, 20mL), greenish yellow solid product 13b, yield are obtained after filtering：48%.
After testing, ruthenium complex (13b)1H-NMR(400MHz,CDCl3):δ16.49(s,1H),8.90-8.50(m,
2H), 7.86 (d, J=7.2Hz, 1H), 7.47 (dd, J=2.0,7.2Hz, 1H), 7.33 (m, 1H), 7.27 (m, 1H), 7.08
(s, 3H), 6.90 (d, J=1.6Hz, 1H), 6.74-6.72 (m, 1H), 4.87-4.84 (m, 1H), 4.19 (s, 4H), 2.48-
2.42 (m, 18H), 1.27 (d, J=4.0Hz, 6H)
The ruthenium complex 13d of embodiment 126 synthesis
One 25mL, two mouthfuls of flasks add ruthenium complex (0.1g) after being replaced with argon gas, and argon gas is used afterwards three times with argon gas displacement
Ball protects enclosed system, adds substituted pyridine (1mL) in room temperature reaction 0.5 hour.Reaction terminates, and adds pentane (- 10
DEG C, 20mL), greenish yellow solid product 13d, yield are obtained after filtering：42%.
After testing, ruthenium complex (13d)1H-NMR(400MHz,CDCl3):δ17.33(s,1H),8.55(m,4H),
7.71(m,1H),7.50(m,1H),7.33-7.28(m,4H),7.02(m,1H),5.23(m,1H),2.34-1.30(m,33H).
The ruthenium complex 13e of embodiment 127 synthesis
One 25mL, two mouthfuls of flasks add ruthenium complex (0.1g) after being replaced with argon gas, and argon gas is used afterwards three times with argon gas displacement
Ball protects enclosed system, adds substituted pyridine (1mL) in room temperature reaction 0.5 hour.Reaction terminates, and adds pentane (- 10
DEG C, 20mL), greenish yellow solid product 13e, yield are obtained after filtering：95%.
After testing, ruthenium complex (13e)1H-NMR(400MHz,CDCl3):δ 16.56 (s, 1H), 7.47 (dd, J=
2.0,7.2Hz, 1H), 7.31-7.27 (m, 5H), 7.20-7.19 (m, 3H), 7.08-6.94 (m, 1H), 6.72 (d, J=
6.4Hz, 1H), 4.85-4.81 (m, 1H), 4.18 (s, 3H), 3.85 (s, 4H), 2.48-2.31 (m, 18H), 1.26 (d, J=
6.0Hz,6H).
The ruthenium complex 13g of embodiment 128 synthesis
One 25mL, two mouthfuls of flasks add ruthenium complex (0.1g) after being replaced with argon gas, and argon gas is used afterwards three times with argon gas displacement
Ball protects enclosed system, adds substituted pyridine (1mL) in room temperature reaction 0.5 hour.Reaction terminates, and adds pentane (- 10
DEG C, 20mL), greenish yellow solid product 13g, yield are obtained after filtering：52%.
After testing, ruthenium complex (13g)1H-NMR(400MHz,CDCl3):δ16.49(s,1H),8.67(m,2H),
7.47 (d, J=5.6Hz, 1H), 7.37 (m, 3H), 7.08 (s, 3H), 6.73 (d, J=6.8Hz, 1H), 4.85-4.83 (m,
1H), 4.19 (s, 4H), 2.48-2.41 (m, 18H), 1.26 (d, J=4.4Hz, 6H)
The ruthenium complex 13h of embodiment 129 synthesis
One 25mL, two mouthfuls of flasks add ruthenium complex (0.1g) after being replaced with argon gas, and argon gas is used afterwards three times with argon gas displacement
Ball protects enclosed system, adds substituted pyridine (1mL) in room temperature reaction 0.5 hour.Reaction terminates, and adds pentane (- 10
DEG C, 20mL), greenish yellow solid product 13h, yield are obtained after filtering：59%.
After testing, ruthenium complex (13h)1H-NMR(400MHz,CDCl3):δ16.52(s,1H),8.60-8.51(m,
2H), 7.67 (d, J=8.0Hz, 2H), 7.46 (d, J=2.4Hz, 1H), 7.06 (s, 4H), 6.88 (d, J=2.4Hz, 1H),
6.71 (d, J=8.0Hz, 2H), 4.84-4.81 (m, 1H), 4.16 (s, 4H), 2.45-2.39 (m, 18H), 1.24 (d, J=
4.0Hz,6H).
The ruthenium complex 13j of embodiment 130 synthesis
One 25mL, two mouthfuls of flasks add ruthenium complex (0.1g) after being replaced with argon gas, and argon gas is used afterwards three times with argon gas displacement
Ball protects enclosed system, adds substituted pyridine (1mL) in room temperature reaction 0.5 hour.Reaction terminates, and adds pentane (- 10
DEG C, 20mL), greenish yellow solid product 13j, yield are obtained after filtering：81%.
After testing, ruthenium complex (13j)1H-NMR(400MHz,CDCl3):δ 16.56 (s, 1H), 7.90 (d, J=
3.2Hz, 2H), 7.83-7.30 (m, 9H), 7.21 (s, 4H), 6.72 (d, J=7.6Hz, 1H), 4.84-4.82 (m, 1H), 4.19
(s, 4H), 2.48-2.31 (m, 18H), 1.26 (d, J=4.8Hz, 6H)
The ruthenium complex 13k of embodiment 131 synthesis
One 25mL, two mouthfuls of flasks add ruthenium complex (0.1g) after being replaced with argon gas, and argon gas is used afterwards three times with argon gas displacement
Ball protects enclosed system, adds substituted pyridine (1mL) in room temperature reaction 0.5 hour.Reaction terminates, and adds pentane (- 10
DEG C, 20mL), greenish yellow solid product 13k, yield are obtained after filtering：36%.
After testing, ruthenium complex (13k)1H-NMR(400MHz,CDCl3):δ17.39(s,1H),8.89(s,2H),
8.63 (d, J=3.2Hz, 2H), 7.86-6.98 (m, 6H), 6.99 (d, J=4.0Hz, 2H), 5.19 (m, 1H), 2.37-0.89
(m,39H).
The ruthenium complex 13m of embodiment 132 synthesis
One 25mL, two mouthfuls of flasks add ruthenium complex (0.1g) after being replaced with argon gas, and argon gas is used afterwards three times with argon gas displacement
Ball protects enclosed system, adds substituted pyridine (1mL) in room temperature reaction 0.5 hour.Reaction terminates, and adds pentane (- 10
DEG C, 20mL), greenish yellow solid product 13m, yield are obtained after filtering：35%.
After testing, ruthenium complex (13m)1H-NMR(400MHz,CDCl3):δ 17.39 (s, 1H), 8.83 (d, J=
15.6Hz,2H),8.61(s,2H),7.86-7.38(m,6H),7.00(m,1H),5.20(m,1H),2.37-0.89(m,39H).
The ruthenium complex 13n of embodiment 133 synthesis
One 25mL, two mouthfuls of flasks add ruthenium complex (0.1g) after being replaced with argon gas, and argon gas is used afterwards three times with argon gas displacement
Ball protects enclosed system, adds substituted pyridine (1mL) in room temperature reaction 0.5 hour.Reaction terminates, and adds pentane (- 10
DEG C, 20mL), greenish yellow solid product 13n, yield are obtained after filtering：49%.
After testing, ruthenium complex (13n)1H-NMR(400MHz,CDCl3):δ 16.56 (s, 1H), 8.75 (d, J=
3.2Hz, 2H), 8.07-7.47 (m, 8H), 7.21 (s, 4H), 6.72 (d, J=7.6Hz, 1H), 4.84-4.82 (m, 1H), 4.19
(s, 4H), 2.69-2.31 (m, 18H), 1.24 (d, J=4.8Hz, 6H)
The ruthenium complex 13p of embodiment 134 synthesis
One 25mL, two mouthfuls of flasks add ruthenium complex (0.1g) after being replaced with argon gas, and argon gas is used afterwards three times with argon gas displacement
Ball protects enclosed system, adds substituted pyridine (1mL) in room temperature reaction 0.5 hour.Reaction terminates, and adds pentane (- 10
DEG C, 20mL), greenish yellow solid product 13p, yield are obtained after filtering：52%.
After testing, ruthenium complex (13p)1H-NMR(400MHz,CDCl3):δ17.39(s,1H),8.85(s,2H),
8.57 (d, J=3.2Hz, 2H), 7.85-7.02 (m, 7H), 5.20 (m, 1H), 3.88 (s, 3H), 2.37-0.89 (m, 39H)
The ruthenium complex 13q of embodiment 135 synthesis
One 25mL, two mouthfuls of flasks add ruthenium complex (0.1g) after being replaced with argon gas, and argon gas is used afterwards three times with argon gas displacement
Ball protects enclosed system, adds substituted pyridine (1mL) in room temperature reaction 0.5 hour.Reaction terminates, and adds pentane (- 10
DEG C, 20mL), greenish yellow solid product 13q, yield are obtained after filtering：81%.
After testing, ruthenium complex (13q)1H-NMR(400MHz,CDCl3):δ 16.56 (s, 1H), 7.53 (d, J=
3.2Hz,2H),7.54-7.38(m,5H),7.04-6.72(m,8H),4.84-4.82(m,1H),4.19(s,3H),3.80(s,
4H), 2.69-2.31 (m, 18H), 1.26 (d, J=4.8Hz, 6H)
The ruthenium complex 13r of embodiment 136 synthesis
One 25mL, two mouthfuls of flasks add ruthenium complex (0.1g) after being replaced with argon gas, and argon gas is used afterwards three times with argon gas displacement
Ball protects enclosed system, adds substituted pyridine (1mL) in room temperature reaction 0.5 hour.Reaction terminates, and adds pentane (- 10
DEG C, 20mL), greenish yellow solid product 13r, yield are obtained after filtering：37%.
After testing, ruthenium complex (13r)1H-NMR(400MHz,CDCl3):δ18.67(s,1H),8.40(m,1H),
7.47-6.91 (m, 13H), 6.58 (m, 1H), 4.12 (m, 6H), 2.63-2.27 (m, 19H), 1.00 (d, J=4.0Hz, 6H)
The ruthenium complex 13s of embodiment 137 synthesis
One 25mL, two mouthfuls of flasks add ruthenium complex (0.1g) after being replaced with argon gas, and argon gas is used afterwards three times with argon gas displacement
Ball protects enclosed system, adds substituted pyridine (1mL) in room temperature reaction 0.5 hour.Reaction terminates, and adds pentane (- 10
DEG C, 20mL), greenish yellow solid product 13s, yield are obtained after filtering：73%.
After testing,1H-NMR(400MHz,CDCl3):δ18.67(s,1H),8.43(s,1H),7.45-7.35(m,3H),
7.19-6.93 (m, 10H), 6.60 (d, J=7.6Hz, 1H), 4.15 (m, 6H), 2.52-2.28 (m, 19H), 1.08-0.89 (m,
6H).
The ruthenium complex 13t of embodiment 138 synthesis
One 25mL, two mouthfuls of flasks add ruthenium complex (0.1g) after being replaced with argon gas, and argon gas is used afterwards three times with argon gas displacement
Ball protects enclosed system, adds substituted pyridine (1mL) in room temperature reaction 0.5 hour.Reaction terminates, and adds pentane (- 10
DEG C, 20mL), greenish yellow solid product 13t, yield are obtained after filtering：55%.
After testing, ruthenium complex (13t)1H-NMR(400MHz,CDCl3):δ18.69(s,1H),8.42(s,2H),
7.44-6.93 (m, 15H), 6.60 (dd, J=2.0,7.6Hz, 2H), 4.14 (s, 6H), 2.52-2.27 (m, 18H), 0.98 (d,
J=4.4Hz, 6H)
The ruthenium complex 13u of embodiment 139 synthesis
One 25mL, two mouthfuls of flasks add ruthenium complex (0.1g) after being replaced with argon gas, and argon gas is used afterwards three times with argon gas displacement
Ball protects enclosed system, adds substituted pyridine (1mL) in room temperature reaction 0.5 hour.Reaction terminates, and adds pentane (- 10
DEG C, 20mL), greenish yellow solid product 13u, yield are obtained after filtering：63%.
After testing, ruthenium complex (13u)1H-NMR(400MHz,CDCl3):δ18.69(s,1H),8.42(s,2H),
7.62-6.93 (m, 16H), 6.60 (dd, J=2.0,7.6Hz, 2H), 4.14 (s, 6H), 2.52-2.27 (m, 18H), 0.98 (d,
J=4.4Hz, 6H)
The ruthenium complex 13v of embodiment 140 synthesis
One 25mL, two mouthfuls of flasks add ruthenium complex (0.1g) after being replaced with argon gas, and argon gas is used afterwards three times with argon gas displacement
Ball protects enclosed system, adds substituted pyridine (1mL) in room temperature reaction 0.5 hour.Reaction terminates, and adds pentane (- 10
DEG C, 20mL), greenish yellow solid product 13v, yield are obtained after filtering：90%.
After testing,1H-NMR(400MHz,CDCl3):δ18.69(s,1H),8.42(s,2H),7.86-6.93(m,15H),
6.60 (dd, J=2.0,7.6Hz, 2H), 4.14 (s, 6H), 3.87 (s, 3H), 2.52-2.27 (m, 18H), 0.98 (d, J=
4.4Hz,6H).
The ruthenium complex 13w of embodiment 141 synthesis
One 25mL, two mouthfuls of flasks add ruthenium complex (0.1g) after being replaced with argon gas, and argon gas is used afterwards three times with argon gas displacement
Ball protects enclosed system, adds substituted pyridine (1mL) in room temperature reaction 0.5 hour.Reaction terminates, and adds pentane (- 10
DEG C, 20mL), greenish yellow solid product 13w, yield are obtained after filtering：49%.
After testing, ruthenium complex (13w)1H-NMR(400MHz,CDCl3):δ18.67(s,1H),8.40(m,1H),
7.69-6.90 (m, 13H), 6.60 (m, 1H), 4.12 (m, 6H), 2.62-2.17 (m, 19H), 1.00 (d, J=4.0Hz, 6H)
The ruthenium complex 13x of embodiment 142 synthesis
One 25mL, two mouthfuls of flasks add ruthenium complex (0.1g) after being replaced with argon gas, and argon gas is used afterwards three times with argon gas displacement
Ball protects enclosed system, adds substituted pyridine (1mL) in room temperature reaction 0.5 hour.Reaction terminates, and adds pentane (- 10
DEG C, 20mL), greenish yellow solid product 13x, yield are obtained after filtering：97%.
After testing, ruthenium complex (13x)1H-NMR(400MHz,CDCl3):δ16.57(s,1H),7.63-6.69(m,
11H), 4.83-4.81 (m, 1H), 4.16 (s, 4H), 2.45-2.39 (m, 21H), 1.24 (d, J=4.0Hz, 6H)
The ruthenium complex 13y of embodiment 143 synthesis
One 25mL, two mouthfuls of flasks add ruthenium complex (0.1g) after being replaced with argon gas, and argon gas is used afterwards three times with argon gas displacement
Ball protects enclosed system, adds substituted pyridine (1mL) in room temperature reaction 0.5 hour.Reaction terminates, and adds pentane (- 10
DEG C, 20mL), greenish yellow solid product 13y, yield are obtained after filtering：81%.
After testing, ruthenium complex (13y)1H-NMR(400MHz,CDCl3):δ16.85(s,1H),8.40-6.83(m,
15H), 4.95 (m, 1H), 4.16 (s, 3H), 3.80 (s, 4H), 2.46-2.23 (m, 18H), 1.29 (d, J=4.4Hz, 6H)
The ruthenium complex 13z of embodiment 144 synthesis
One 25mL, two mouthfuls of flasks add ruthenium complex (0.1g) after being replaced with argon gas, and argon gas is used afterwards three times with argon gas displacement
Ball protects enclosed system, adds substituted pyridine (1mL) in room temperature reaction 0.5 hour.Reaction terminates, and adds pentane (- 10
DEG C, 20mL), greenish yellow solid product 13z, yield are obtained after filtering：78%.
After testing, ruthenium complex (13z)1H-NMR(400MHz,CDCl3):δ16.85(s,1H),8.42-7.07(m,
15H), 4.95 (m, 1H), 4.19 (s, 4H), 2.45-2.29 (m, 18H), 1.29 (d, J=4.4Hz, 6H)
The ruthenium complex 13aa of embodiment 145 synthesis
One 25mL, two mouthfuls of flasks add ruthenium complex (0.1g) after being replaced with argon gas, and argon gas is used afterwards three times with argon gas displacement
Ball protects enclosed system, adds substituted pyridine (1mL) in room temperature reaction 0.5 hour.Reaction terminates, and adds pentane (- 10
DEG C, 20mL), greenish yellow solid product 13aa, yield are obtained after filtering：85%.
After testing, ruthenium complex (13aa)1H-NMR(400MHz,CDCl3):δ16.85(s,1H),8.47-6.85(m,
16H), 4.94 (m, 1H), 4.19 (s, 4H), 2.40-2.29 (m, 18H), 1.29 (d, J=4.4Hz, 6H)
The ruthenium complex 13ab of embodiment 146 synthesis
One 25mL, two mouthfuls of flasks add ruthenium complex (0.1g) after being replaced with argon gas, and argon gas is used afterwards three times with argon gas displacement
Ball protects enclosed system, adds substituted pyridine (1mL) in room temperature reaction 0.5 hour.Reaction terminates, and adds pentane (- 10
DEG C, 20mL), greenish yellow solid product 13ab, yield are obtained after filtering：96%.
After testing, ruthenium complex (13ab)1H-NMR(400MHz,CDCl3):δ17.00(s,1H),8.47-6.82(m,
11H), 4.90 (m, 1H), 4.17 (s, 4H), 2.48-2.41 (m, 18H), 1.26 (d, J=4.4Hz, 6H)
The ruthenium complex 13ac of embodiment 147 synthesis
One 25mL, two mouthfuls of flasks add ruthenium complex (0.1g) after being replaced with argon gas, and argon gas is used afterwards three times with argon gas displacement
Ball protects enclosed system, adds substituted pyridine (1mL) in room temperature reaction 0.5 hour.Reaction terminates, and adds pentane (- 10
DEG C, 20mL), greenish yellow solid product 13ac, yield are obtained after filtering：95%.
After testing, ruthenium complex (13ac)1H-NMR(400MHz,CDCl3):δ17.00(s,1H),8.47-6.83(m,
11H), 4.91 (m, 1H), 4.17 (s, 4H), 2.48-2.41 (m, 18H), 1.26 (d, J=4.4Hz, 6H)
The ruthenium complex 13ad of embodiment 148 synthesis
One 25mL, two mouthfuls of flasks add ruthenium complex (0.1g) after being replaced with argon gas, and argon gas is used afterwards three times with argon gas displacement
Ball protects enclosed system, adds substituted pyridine (1mL) in room temperature reaction 0.5 hour.Reaction terminates, and adds pentane (- 10
DEG C, 20mL), greenish yellow solid product 13ad, yield are obtained after filtering：33%.
After testing, ruthenium complex (13ad)1H-NMR(400MHz,CDCl3):δ18.65(s,1H),8.56(s,1H),
7.84-6.40(m,15H),4.22(s,4H),3.80(s,3H),2.49-2.29(m,18H).
The ruthenium complex 13ae of embodiment 149 synthesis
One 25mL, two mouthfuls of flasks add ruthenium complex (0.1g) after being replaced with argon gas, and argon gas is used afterwards three times with argon gas displacement
Ball protects enclosed system, adds substituted pyridine (1mL) in room temperature reaction 0.5 hour.Reaction terminates, and adds pentane (- 10
DEG C, 20mL), greenish yellow solid product 13ae, yield are obtained after filtering：68%.
After testing, ruthenium complex (13ae)1H-NMR(400MHz,CDCl3):δ18.65(s,1H),8.53(s,1H),
7.84-6.00(m,19H),4.14(s,4H),3.86(s,3H),3.80(s,3H),2.49-2.29(m,18H).
The ruthenium complex 13af of embodiment 150 synthesis
One 25mL, two mouthfuls of flasks add ruthenium complex (0.1g) after being replaced with argon gas, and argon gas is used afterwards three times with argon gas displacement
Ball protects enclosed system, adds substituted pyridine (1mL) in room temperature reaction 0.5 hour.Reaction terminates, and adds pentane (- 10
DEG C, 20mL), greenish yellow solid product 13af, yield are obtained after filtering：59%.
After testing, ruthenium complex (13af)1H-NMR(400MHz,CDCl3):δ18.65(s,1H),8.56(s,1H),
7.51-6.39(m,19H),4.14(s,4H),3.80(s,3H),2.42-2.29(m,18H).
The ruthenium complex 13ag of embodiment 151 synthesis
One 25mL, two mouthfuls of flasks add ruthenium complex (0.1g) after being replaced with argon gas, and argon gas is used afterwards three times with argon gas displacement
Ball protects enclosed system, adds substituted pyridine (1mL) in room temperature reaction 0.5 hour.Reaction terminates, and adds pentane (- 10
DEG C, 20mL), greenish yellow solid product 13ag, yield are obtained after filtering：69%.
After testing, ruthenium complex (13ag)1H-NMR(400MHz,CDCl3):δ18.65(s,1H),8.56(s,1H),
7.50-6.39(m,20H),4.14(s,4H),3.80(s,3H),2.42-2.29(m,18H).
Substantially effectively to optimize the synthetic method of all kinds of ruthenium catalysts, cost and resource consumption are reduced, the present invention is to several
Class ruthenium catalyst employs different synthetic routes.When raw material 4-SM generates Cabbeen intermediate in the presence of caustic alcohol, then directly
Connect and RuCl2(PPh3)3Reaction generates unstable ruthenium complex intermediate 4-1；Intermediate 4-1 triphenyl phosphorus part can quilt
Another part PCy3The stable ruthenium complex 4bf of (4-2) generation.Ruthenium complex intermediate 4-1 or 4bf and part H2IMes(4-3)
Directly substitution generates more stable and higher catalytic activity ruthenium catalyst 4be.Ruthenium complex 4be and part 4- chloropyridines (4-4)
Reaction directly complexing generation 13s:
It is below ruthenium complex intermediate 4-1, ruthenium catalyst 4be, 4bf and 13s an easy synthetic route：
The ruthenium complex 4bf of embodiment 152 synthesis
One 500mL three-necked flask sequentially adds ligand stock 4-SM (33g, 100mmol, 1.0eq.) after being replaced with argon gas
It is dissolved in 300mL ethanol, NaOEt (400mmol, 4.0eq.) is rapidly added under stirring, is heated to 60 DEG C of reaction half an hour.30 points
120mL water is added after clock, with extraction into heptane (200mL × 3).Combining extraction liquid, (150mL is washed with saturated sodium carbonate solution
× 2), saturated common salt water washing (150mL × 2), about 50mL is concentrated at 0 DEG C after anhydrous sodium sulfate drying.Yield presses 50%
Reaction in next step is calculated to feed intake.
By RuCl2(PPh3)3(29g, 20mmol) is dissolved in 250mL dichloromethane, is cooled to -78 DEG C, adds -70 DEG C
Above-mentioned diazonium pentane solution (~60mL).After 5 minutes, reaction temperature is slowly increased to room temperature, add CuCl (14.7g,
100mmol).After 15 minutes, filtering.After filtrate concentration, column chromatography purifying, with gradient elution agent (2: 1 n-hexanes/dichloromethane
To absolute dichloromethane).Product section is concentrated, n-hexane washing, vacuum drying is obtained among the unstable ruthenium complexs of 12.3g
Body 4-1.
Intermediate 4-1 (15.0mmol) is dissolved in dichloromethane (30mL), adds three rings phosphorus (PCy3,30mmol,
2.0eq.), after 20 DEG C are reacted half an hour, with dark green solid is obtained after chromatography column separating purification product, with methanol and just oneself
Alkane washing obtains green solid product 4bf, thick yield after drying：53%.Product 4bf is not very stable, it is difficult to purification assays ruthenium
Complex compound 4bf's1H-NMR structures, but its impure ruthenium complex 4bf can be directly used for preparing 4be or olefin metathesis double decomposition
Catalytic reaction.
The ruthenium complex 4be of embodiment 153 synthesis
One 50mL, two mouthfuls of flasks sequentially add ruthenium complex 4bf (5.0mmol) and H after being replaced with argon gas2IMes(H)
(CCl3) (4-3,10.0mmol, 2.0eq.) be dissolved in 30mL drying be dissolved in toluene, then with argon gas displacement use argon gas afterwards three times
Ball protects enclosed system, is heated to 80 DEG C, reaction in 1.5 hours terminates rear crystallisation by cooling filtering, and silica gel is added in filtrate after filtering
Dark green solid crude product is obtained after column chromatography, the green solid product stablized then is washed with methanol or pentane-DCM
4be, yield：59%.
After testing, ruthenium complex (4be)1H-NMR(400MHz,CDCl3):δ 18.88 (s, 1H, Ru=CH), 7.57-
6.44 (m, 11H, aromatic H), 5.36 (t, J=13.2Hz, 1H, NH), 4.16-4.02 (m, 5H, NCH2,NCH2CH2N),
4.01 (d, J=13.2Hz, 1H, NCH2),2.75-2.00(m,19H,CH(CH3)2,aromatic CH3),1.01-0.90(m,
6H,CH(CH3)2).
Ruthenium complex 13s preparation reacted by above-mentioned ruthenium complex 4be and part 4- chloropyridines (4-4) be directly complexed and
Into about preparing experiment and the synthesis of the ruthenium complex 13s described in analysis result detailed in Example 137.
Application Example of the ruthenium complex catalyst in olefin metathesis double decomposition cyclization：
There is generation in another patent (US20070043180A1) delivered before making the present invention below for the present inventor
Complex compound 14a, 14b of table and other four representational catalyst 14c, 14d, 14e, 14f structural formula：
Some ruthenium complex catalysts in these ruthenium catalysts (14a-14f) and the present invention are selectively used for following
The catalytic cyclization reaction and ring-opening polymerization of cycloolefin prepare the experiment of the high molecular polymer new material of difference in functionality, and with
The catalytic effect contrast for the similar catalyst that the present invention lists discusses.
Ruthenium complex catalysed olefin metathesis reaction experimental procedure：50mg substrate is placed in bis- mouthfuls of round-bottomed flasks of 25mL
In, addition 1mL newly steams after being replaced 5 times with argon gas dichloromethane and 5mg catalyst.Under argon gas protection, reactant mixture
It is stirred at room temperature complete to reaction.The conversion ratio of reaction is monitored to obtain by HPLC.It is ruthenium complex below in different alkene
Catalytic activity research in transposition metathesis reaction：
Effect example 1:
In order to contrast the catalytic activity of the ruthenium complex containing different substituents, now the different rutheniums of embodiment synthesis are complexed
The catalytic activity and relative catalytic activity of thing metathesis reaction are compared.
Metathesis cyclization reaction experiment in olefin hydrocarbon molecules：50mg reaction substrates 15 are separately added into the neck bottles of 25ml bis-, with three
Logical displacement makes inside be full of argon gas, adds 1.0ml dichloromethane with syringe, is stirred at room temperature after making to be completely dissolved, is separately added into
2mol% above-mentioned ruthenium complex catalyst (4a-4cz, 6a-6z, 8a-8t, 10a-10j).Respectively at 10min, 30min,
1.0hr, 3.0hr, 5.0hr, 8.0hr, 15.0hr are sampled, with HPLC and LC-MS tracking reactions.Calculated and produced with normalized method
The conversion ratio of thing, reaction result are shown in Table 2.
Olefin metathesis double decomposition cyclisation product (16)1HNMR(400MHz,CDCl3):δ=7.78 (d, 2H, J=
8.21Hz), 7.31 (m, 7H), 6.01 (m, 1H), 4.47 (m, 2H), 4.30 (m, 2H), 2.41 (s, 3H) molecular weight (M+H+)：
M/z calculated values are 300.1, test value 300.2.
The Intra-molecular condensation catalyst 4a-4cz of table 1-1. alkene 15 Activity Assessment
Except more than ten individual new catalysts listed in above-mentioned table 1-1 have preferable activity in ruthenium catalyst 4a-4cz, its
Remaining listed ruthenium catalyst it is active poor, it can be seen that the ruthenium complex that the substituent electronic effect of Novel Ligands is formed to it
Catalytic activity have significant influence.
The Intra-molecular condensation catalyst 6a-6z of table 1-2. alkene 15 Activity Assessment
Except tri- new catalysts of 6s, 6t and 6v listed in above-mentioned table 1-2 have preferable work in ruthenium catalyst 6a-6z
Property, catalytic activity is substantially better than the similar catalyst 14f that oneself knows.Remaining ruthenium catalyst it is active very poor, it can be seen that it is new
The catalytic activity for the ruthenium complex that the substituent electronic effect of part is formed on it has significant influence.
The Intra-molecular condensation catalyst 8a-8t of table 1-3. alkene 15 Activity Assessment
Except tri- new catalysts of 8c, 8e and 8h listed in above-mentioned table 1-3 have preferable work in ruthenium catalyst 8a-8t
Property, catalytic activity is substantially better than the similar catalyst 14d that oneself knows.Ruthenium catalyst listed by remaining it is active poor, it can be seen that
The catalytic activity for the ruthenium complex that the substituent electronic effect of Novel Ligands is formed on it has significant influence.
The Intra-molecular condensation catalyst 10a-10j of table 1-4. alkene 15 Activity Assessment
Urged in ruthenium catalyst 10a-10j except 10c, 10d, 10e, 10f and 10g five listed in above-mentioned table 1-4 is new
Agent has preferable activity, and catalytic activity is substantially better than the similar catalyst 14e that oneself knows.Remaining ruthenium catalyst activity compared with
Difference, it can be seen that the catalytic activity for the ruthenium complex that the substituent electronic effect of Novel Ligands is formed to it has significant shadow
Ring.
The Intra-molecular condensation catalyst 13a-13ag of table 1-5. alkene 15 Activity Assessment
Except four new catalysts listed in above-mentioned table 1-5 have poor activity in ruthenium catalyst 13a-13ag, its
The cyclisation activity of remaining ruthenium catalyst is very poor, it can be seen that the ruthenium complex that the substituent electronic effect of Novel Ligands is formed to it
Catalytic activity have significant influence.But it is anti-that some of which catalyst 13a-13ag can be effectively used for cycloolefin ring-opening polymerisation
Should.
Except the several catalyst for having preferable activity listed in above-mentioned each table in above-mentioned all kinds of new ruthenium catalysts, remaining
Cyclization (RCM) activity of the ruthenium catalyst of preparation is very poor, the results showed that does not have substituent on new complex ligands phenyl ring
Ruthenium complex (14f) and substituted base ruthenium complex (such as 6g and 6m) catalytic activity it is very low, urging for alkene can not be triggered
Change cyclization (RCM).As can be seen here the present invention in new oxygen-containing or nitrogen coordination atom part substituent electronic effect to it
The catalytic activity of the ruthenium complex of formation has significant influence.Table 1-1,1-2,1-3,1-4,1-5 result shows, of the invention
All kinds of new catalyst 4c, 4g, 4t, 4u, 4w, 4x, 4aa, 4ab, 4cf, 6s, 6u, 8c, 8e, 8h, 8k, 10c, 10d, 10e,
10f, 10g are good to the expression activitiy of alkene 15, and ring closure reaction largely terminates in 1.5-3hr, are catalyzed in the current field
The good new olefin double decomposition cyclization catalyst of expression activitiy.
Effect example 2:
In order to contrast the catalytic activity of all kinds of ruthenium complexs containing different substituents, now to having in above-described embodiment preferably
The catalytic activity and relative catalytic activity of the ruthenium complex catalyst of activity are compared.
Olefin hydrocarbon molecules intramolecular cyclization reaction is tested：50mg reaction substrates 17 are separately added into the neck bottles of 25ml bis-, are put with threeway
Changing makes inside be full of argon gas, adds 1.0ml dichloromethane with syringe, is stirred at room temperature after making to be completely dissolved, is separately added into 2mol%
The good ruthenium complex catalyst of above-mentioned expression activitiy.Respectively at 10min, 30min, 1.0hr, 3.0hr, 5.0hr, 8.0hr,
15.0hr is sampled, with HPLC and LC-MS tracking reactions.The conversion ratio of product is calculated with normalized method, reaction result is shown in Table
2。
Olefin metathesis double decomposition cyclisation product (12)1HNMR(400MHz,CDCl3):δ=7.78 (d, 2H, J=8.21Hz),
7.31 (m, 7H), 6.01 (m, 1H), 4.47 (m, 2H), 4.30 (m, 2H), 2.41 (s, 3H) molecular weight (M+H+)：The theoretical meters of m/z
Calculation value is 300.1, test value 300.2.
The Activity Assessment of all kinds of catalyst of Intra-molecular condensation of the alkene 17 of table 2.
The result of table 2 shows, the work of all kinds of new catalyst 4c, 4t, 4x, 4af, 6s, 8e, 10d of the invention to alkene 17
Property it is relatively good, ring closure reaction largely terminates in 1.5-3hr, is the new olefin that catalytic activity is relatively good in the current field
Double decomposition cyclization catalyst.
Effect example 3:
In order to preferably determine the difference between different high activated catalysts, this patent devises one existing two and inhales electricity
There are two methyl substituted substrates 19 on sub- fluoro, alkene again, substrate 19, which imitates the difficult characteristic that transposition double decomposition cyclisation occurs, makes catalysis
Activity difference between agent (11a-j) determines obviously to be come.
Metathesis cyclization reaction experiment in olefin hydrocarbon molecules：50mg reaction substrate Multi substituted benzenes are separately added into the neck bottles of 25ml bis-
Vinethene alkene 19, inside is full of argon gas with threeway displacement, add 1.0ml dichloromethane with syringe, being stirred at room temperature makes completely
After dissolving, 3mol% above-mentioned ruthenium complex catalyst (12a-12h) is separately added into.Respectively at 10min, 30min, 1.0hr,
3.0hr, 5.0hr, 8.0hr, 15.0hr are sampled, with HPLC and LC-MS tracking reactions.Turning for product is calculated with normalized method
Rate, dependent dynamics result are listed in table 3.
Olefin metathesis double decomposition cyclisation product (20)1HNMR(CDCl3：δ=7.26ppm):7.15 (d, 1H, J=
2.74Hz), 6.84 (d, 1H, J=2.34Hz), 6.34 (dt, 1H, J=1.95,9.78Hz), 5.86 (d, 1H, J=9.78Hz),
4.95(m,2H).Molecular weight (M+H+)：M/z calculated values are 200.99, test value 201.1.
The Intra-molecular condensation catalytic activity of the alkene 19 of table 3. is assessed
The result of table 3 shows, new catalyst 12a, 12b, 12d, 12e, 12g, 12h of the invention to the activity of alkene 19 very
Good, ring closure reaction largely terminated in 30 minutes, was best a kind of new of catalytic activity in the current catalytic cyclization field
Olefin metathesis cyclization catalyst.
Application Example of the ruthenium complex catalyst in alkene ring-opening polymerization：
In order to further research and develop the machinery of more effective alkene ring-opening polymerization catalyst and its high molecular polymer new material
Performance, the difference between different high activated catalysts is preferably determined, implemented by the effect of following alkene ring-opening polymerization
Example 4-7 contrasts the mechanicalnesses such as the intensity and modulus for improving olefin metathesis reaction catalyst and high molecular polymer product to research and develop
Energy.
Effect example 4:
Method one；Alkene ring-opening polymerization tests (catalytic polymerization in solvent)：Cyclo-octene (21) raw material monomer is dissolved in
In the anhydrous solvent (such as dichloroethanes DCE) of 20 times of amounts (20x), argon filling catches up with oxygen, then rapidly joins the ruthenium that this project etc. filters out
Catalyst (0.1 ‰ -5%), preferably progressively heating (20-75 DEG C) heating response, reaction solution gradually become viscous for reaction.Reaction is overnight
Reaction solution is slowly toppled over afterwards and is precipitated out in ethanol, ethanol immersion, filtering and drying to obtain polymer solids product (22), production
Rate is 70%-98%.
Method two；Alkene ring-opening polymerization tests (solvent-free catalytic polymerization)：Lead in Breakup of Liquid Ring octene monomers (21)
Enter argon gas to rush oxygen, then rapidly join the ruthenium catalyst (0.1-5 ‰) that this project etc. filters out, heated between 20-120 degree
Reaction solution gradually becomes viscous and exothermic after reaction a few minutes, and finally polymerization obtains open loop high molecular polymer solid product (22).
As a result show, new catalyst 8c, 8d, 4j, 4m, 4p, 4r, 4c, 8c, 8e of the invention polymerize to cyclo-octene (21)
The expression activitiy of reaction is good, catalytic polymerate (22) have preferable tensile strength and modulus (>1.5Gpa), it is the current neck
The relatively good new olefin metathesis polymerization catalysts of catalytic activity in domain.Open loop high molecular polymer (22) heating can melt
Change and be dissolved in weak polar solvent (such as petroleum ether, paraffin oil), be processed further can be used for the explosion-proof lamp for preparing high intensity
Or spinning processing high-strength products.
Effect example 5:
Method one；Alkene ring-opening polymerization tests (catalytic polymerization in solvent)：ENB (23) raw material monomer is molten
In the anhydrous solvent (such as dichloroethanes DCE) of 20 times of amounts (20x), argon filling catches up with oxygen, then rapidly joins what this project etc. filtered out
Ruthenium catalyst (0.1 ‰ -5%), preferably progressively heating (20-75 DEG C) heating response, reaction solution gradually become viscous for reaction.Reacted
Reaction solution is slowly toppled over after night and is precipitated out in ethanol, ethanol immersion, filtering and drying to obtain polynorbornene solid product
(24), yield 75%-98%.
Method two；Alkene ring-opening polymerization tests (solvent-free catalytic polymerization)：In liquid norbornene monomer (23)
Be passed through argon gas to rush oxygen, then rapidly join the ruthenium catalyst (0.1-5 ‰) that this project etc. filters out, between 25-100 DEG C plus
Reaction solution gradually becomes viscous and exothermic after thermal response a few minutes, finally obtains polynorbornene solid product (24).
As a result show, new catalyst 4c, 4h, 4j, 4m, 4p, 4r, 8c, 8d, 8e of the invention are to ENB (23)
Expression activitiy is good, and catalytic polymerization terminates in 10-60min, and polynorbornene product (24) has preferable intensity, hardness
And stretch modulus, it is the new olefin metathesis polymerization catalysts that catalytic activity is relatively good in the current field.Open loop is high
Molecularly Imprinted Polymer (24) is processed further can be used for the explosion-proof lamp or spinning material for preparing high intensity.
Effect example 6:
Method one；Alkene ring-opening polymerization tests (catalytic polymerization in solvent)：By bicyclic luxuriant diene (DCPD, 25) monomer
Raw material is dissolved in the anhydrous solvent (such as dichloroethanes DCE) of 20 times of amounts (20x), and argon filling catches up with oxygen, then rapidly joins the sieve such as this project
The ruthenium catalyst (0.1 ‰ -5%) selected, preferably progressively heating (20-75 DEG C) heating response, reaction solution gradually become viscous for reaction.
Reaction solution is slowly toppled over after reaction overnight and is precipitated out in ethanol, ethanol immersion, filtering and drying to obtain poly bis ring cyclopentadienyl diene
(Poly-DCPD) solid product (26), yield 75%-98%.
Method two；Alkene ring-opening polymerization tests (solvent-free catalytic polymerization)：In liquid bicyclopentadiene monomer
Argon gas is passed through in (DCPD, 25) to rush oxygen, then rapidly joins the ruthenium catalyst (0.1-5 ‰) that this project etc. filters out, in 30-
Reaction solution gradually becomes viscous and exothermic after heating response a few minutes between 120 degree, and finally polymerization obtains poly bis ring cyclopentadienyl diene (Poly-
DCPD) polymeric solid product (26).
Catalytic result shows, new catalyst 4c, 4h of the invention, 4j, 4m, 4p, 4am, 4be, 4bg, 4bx, 4cg, 8a,
8b, 8c, 8d, 8e, 8h, 8q are preferable to the polymerization catalytic activity of alkene DCPD (25), are homogeneous catalysis activity in the current field
Relatively good new olefin metathesis polymerization catalysts.Polymerisation is carried out preferably, under the conditions of differential responses at 40-60 DEG C
Catalytic polymerization terminates in 10-60min.It polymerize especially with 4c, 4am, 4be, 4cg or with new catalysts such as 8h anti-
The poly bis ring cyclopentadienyl diene product (26) that should be obtained has good intensity, hardness and bending modulus.
Polymer (26) the performance test results show that Poly-DCPD solid polymers prepared by solvent-free catalytic polymerization have
Have good hardness (>80Gpa), bending modulus (>20Gpa) and heat distortion temperature (>200 DEG C), main performance index is better than mesh
Similar poly bis ring cyclopentadienyl diene (Poly-DCPD) product of preceding U.S. Materia companies and Nippon Zeon.Add during catalytic polymerization
Add the copolymers such as antioxidant or the crosslinking agent of a small amount of (0.1-5%) that poly bis ring cyclopentadienyl diene product (26) hardness and modulus can be improved
Etc. physical property, different high intensity, high rigidity, resistance to low can be made up of injection molding processing technology (ROMP-RIM) from now on
Temperature, poly bis ring cyclopentadienyl diene (26) product of acid and alkali-resistance, have in industry and life and have been widely used.
Effect example 7:
Alkene ring-opening polymerization is tested：Olefinic monomer (27) raw material is dissolved in the anhydrous solvent (such as two of 15 times of amounts (15x)
Chloroethanes DCE) in, argon filling catches up with oxygen, then rapidly joins the ruthenium catalyst (0.1 ‰ -5%) that this project etc. filters out, and reaction is best
Progressively heat up (20-75 DEG C) heating response, and reaction solution gradually becomes viscous.Reaction solution is slowly toppled in ethanol after reaction overnight
It is precipitated out, ethanol immersion, filtering and drying to obtain white polymer solid product (28), yield 80-98%.Open loop macromolecule
Polymer (28) is processed further can be used for the spinning material for preparing high intensity.
Effect example 8:
" Linker " is the group for connecting cycloolefin monomers and functional group " G ", including but not limited to O, S, C1-C15Saturation or
Undersaturated alkyl, substituted or unsubstituted C1-C15Amido, substituted or unsubstituted C1-C15It is alkoxy, substituted or unsubstituted
C6-C15Aryloxy group, substituted or unsubstituted C1-C15Heterocyclic oxy group, substituted or unsubstituted C1-C15Alkylthio group, substitution do not take
The C in generation6-C15Arylthio, the substituted or unsubstituted C of connection1-C15The carbonyl of alkoxy, formyloxy, formamido, substitution or
Unsubstituted C1-C15Alkyl carbonyloxy, substituted or unsubstituted C1-C15Alkyl amido, substituted or unsubstituted C6-C15
Arylcarbonyloxy, substituted or unsubstituted C6-C15Aryl carboxamides base；
" G " is the compound for having property or purposes, the small molecule liquid crystal that can be such as connected with " Linker " (29d,
29e, 29f) and the material such as small-molecule drug (29g, " G " are medicine " Lipitor "), being generated after the monomer ring-opening polymerisation of connection has
The prodrug (30g) of property or purposes high molecule liquid crystal (30d, 30e, 30f) and macromolecule surface appendix.
Following is the structure of high molecular polymer (30) prepared by the catalyzed ring opening polymerization reaction of cycloolefin：
Alkene ring-opening polymerization is tested：Olefinic monomer raw material (29) is dissolved in the anhydrous solvent (such as two of 20 times of amounts (20x)
Chloroethanes DCE) in, argon filling catches up with oxygen, then rapidly joins the ruthenium catalyst (0.1 ‰ -5%) that this project etc. filters out, and reaction is best
Progressively heat up (20-75 DEG C) heating response, and reaction solution gradually becomes viscous.Reaction solution is slowly toppled in ethanol after reaction overnight
It is precipitated out, ethanol immersion, filtering and drying to obtain polymer solids product (30), yield 80%-98%.
Relevant preferable polymerization results are summarized and are listed as follows (table 4)：
The result of table 4 shows, small molecule liquid crystal or medicine the monomer energy under the New Ruthenium catalyst action that this item mesh sieve is selected
Polymerization generation have specific characteristics can or the prodrug (30g) of purposes high molecule liquid crystal (30d, 30e, 30f) and macromolecule surface appendix.It is living
Property test result shows, the work of new catalyst 4a, 4c, 4e, 4g, 6e, 6e and 13a of the invention to olefinic monomer (29a-g)
Property it is relatively good, polymerisation terminates in 5-15hr, under the conditions of the catalytic polymerization of optimization, yield be higher than 90%.Polymerization test
As a result show, different types of ruthenium catalyst is solvent-free and have the catalysis under solvent condition to different monomers polymerization in the present invention
Activity has obvious difference, and especially some new ruthenium catalyst (such as 4a, 6e) catalytic activity in cyclization are very low, but
Then there is good catalytic activity, thus in cyclisation (RCM) and the reaction of the class of ring-opening polymerisation (ROMP) two in solvent in polymerisation
In show good selectivity and catalytic activity.
Effect example 9:
Alkene ring-opening polymerization is tested：Olefinic monomer raw material is dissolved in anhydrous solvent (such as two chloroethenes of 20 times of amounts (20x)
Alkane DCE) in, argon filling catches up with oxygen, then rapidly joins the ruthenium catalyst (4a or 6e, 0.1 ‰ -5%) that this project etc. filters out, and reaction is most
Good (20-75 DEG C) heating response that progressively heats up, reaction solution gradually become viscous.Reaction solution is slowly poured over ethanol after reaction overnight
In be precipitated out, ethanol immersion, filtering and drying to obtain polymer solids, yield 60%-98%.
Following is the structure of high molecular polymer 32 (VIc) prepared by the catalyzed ring opening polymerization reaction of cycloolefin：
Relevant preferable polymerization results are summarized and are listed as follows (table 5)：
The result of table 5 shows that the small molecule monomer (31a-31s) of the group containing difference in functionality is urged in the New Ruthenium that this item mesh sieve is selected
Can polymerize generation under agent effect has higher-strength and the high molecular polymer of modulus, wherein polymer 32a, 32b, 32n, 32q
The modulus and tensile strength tested after processing film forming are respectively 0.5-3.0Gpa and 20-40MPa, are processed available for spinning.
Effect example 10:
Alkene ring-opening polymerization is tested：Olefinic monomer raw material 33 (VIIa) is dissolved in the anhydrous solvent of 20 times of amounts (20x)
In (such as dichloroethanes DCE), argon filling catches up with oxygen, then rapidly joins the ruthenium catalyst (0.1 ‰ -5%) that this project etc. filters out, reaction
Preferably progressively heat up (20-75 DEG C) heating response, and reaction solution gradually becomes viscous.Reaction solution is slowly poured over second after reaction overnight
It is precipitated out in alcohol, ethanol immersion, filtering and drying to obtain polymer solids, yield is about 60%-98%.
Following is high molecular polymer 34 (VIIc) structure prepared by the catalyzed ring opening polymerization reaction of cycloolefin：
Relevant preferable polymerization results are summarized and are listed as follows (table 6)：
The result of table 6 shows that the small molecule monomer (33a-33s) of the group containing difference in functionality is urged in the New Ruthenium that this item mesh sieve is selected
Agent effect is lower, which to be polymerize to generate, higher-strength and the high molecular polymer of modulus (34), wherein polymer 34a, 34b, 34c,
The modulus and tensile strength tested after 34v, 34w, 34x processing film forming are respectively 1.0-16Gpa and 30-50MPa, wherein polymer
34c and 34x (modulus of film forming test is up to 16Gpa) process high-strength products more suitable for spinning, are to be opened at present by alkene
The best a kind of high molecular polymer structure of modulus in the product that cyclopolymerization (ROMP) obtains.
Effect example 11:
Alkene ring-opening polymerization is tested：Olefinic monomer raw material 35 (VIIb) is dissolved in the anhydrous solvent of 20 times of amounts (20x)
In (such as dichloroethanes DCE), argon filling catches up with oxygen, then rapidly joins the ruthenium catalyst (0.1 ‰ -5%) that this project etc. filters out, reaction
Preferably progressively heat up (20-75 DEG C) heating response, and reaction solution gradually becomes viscous.Reaction solution is slowly poured over second after reaction overnight
It is precipitated out in alcohol, ethanol immersion, filtering and drying to obtain polymer solids 36 (VIId), yield is about 85-98%.
Following is high molecular polymer (VIId) structure prepared by the catalyzed ring opening polymerization reaction of cycloolefin：
Test result shows that polymer 36a-36d modulus and tensile strength is relatively low, respectively less than 0.5GPa and 10MPa,
Processing characteristics is not so good as 34c and 34x.
Effect example 12:
By two or more cycloolefin monomers raw materials (such as 21,23,25,27,29,31,33 in the effect above embodiment 5-11
Or 35) mixing is dissolved in anhydrous solvent (such as dichloroethanes DCE), it is anti-to add the new ruthenium catalyst heating that this item mesh sieve is selected
Answer, the high-molecular copolymer of different performance can be prepared, specific copolyreaction is as follows：
Alkene ring-opening polymerization is tested：Two or more cycloolefin monomers raw materials are dissolved in the anhydrous of 20 times of amounts (20x)
In solvent (such as dichloroethanes DCE), argon filling catches up with oxygen, then rapidly joins the ruthenium catalyst (0.1 ‰ -5%) that this project etc. filters out,
Preferably progressively heating (20-75 DEG C) heating response, reaction solution gradually become viscous for reaction.Reaction solution is slowly toppled over after reaction overnight
It is precipitated out in ethanol, ethanol immersion, filtering and drying to obtain polymer solids, yield is about 65%-98%.
Two or more above-mentioned cycloolefin monomers can by copolyreaction under some catalyst actions of this Project-developing
Different high-molecular copolymer new materials is prepared, the structure about each analog copolymer is as follows：
Test result shows that the modulus and tensile strength tested after polymer 37j and 37u processing film forming are respectively 2.0-
10Gpa and 40-70MPa, available for film forming or spinning processing high-strength products.
The effect above embodiment 7-11 results show that (film forming modulus is up to the high molecular polymer that structure is 34c and 34x
16Gpa) it is modulus is best in the product that obtains at present by alkene ring-opening polymerisation (ROMP) a kind of ROMP polymer architectures.Urge
Agent 4a and 6e have preferable activity and selectivity.
The instrument and raw material that are related in embodiment are described as follows below：
Ir data is the Fourier Transform AVATAR using Thermo Nicolet companiesTM
360E.S.PTMRadar stealthy materials are analyzed to obtain, with cm-1Represented for unit.
Proton nmr spectra is that Varian Mercury Plus 400 (400MHz) nuclear magnetic resonance spectrometer is analyzed to obtain.Chemical shift
Recorded using tetramethylsilane as internal standard, (CHCl is represented in units of ppm3：δ=7.26ppm).The data message of record is such as
Under：Chemical shift and its split point and coupling constant (s:Singlet；d:Doublet；t:Triplet；q:Quartet；br:Broad peak；m:
Multiplet).
Mass spectrometric data needs except other, is all divided using Finnigan Finnigan LCQ Advantage LC-MS instrument
Analysis, all reactions are all operated under the conditions of the anhydrous and oxygen-free of dry argon gas protection.Solid metal-organic compound is in argon gas
Stored in protection drying box.
All column chromatography silica gels (200-300 mesh) are bought from Haiyang Chemical Plant, Qingdao.
Tetrahydrofuran and ether are obtained by distillation, add metallic sodium and benzophenone wherein during distillation.Dichloromethane
Alkane, pentane and hexane are handled with calcium hydride.Cl2Ru=CHPh (PCy3)(H2IMes it is) that (Jason is prepared according to document
S.Kingsbury,Joseph P.A.Harrity,Peter J.Bonitatebus,Jr.,Amir H.Hoveyda*,
J.Am.Chem.Soc.1999,121,791；American Chemical Society's magazine 1999 year 121 volume page 791).Other all chemical reagent from
Shanghai Reagent Company buys.
Claims (17)
1. structural formula is Formula II b metal complex：
Wherein, M is metal Ru；
L isOr thricyclohexyl phosphorus；Mes=2,4,6- trimethylphenyls；
L1And L2It is chlorine；
N=1；
P=0, X1For CH2Or phenyl；Y1For oxygen or carbonyl；
M=0, Y are carbonyl, C1-C4Alkyl amino or C1-C8Alkoxy carbonyl；
R1For hydrogen；
R2For C1-C3Alkyl or C1-C3Alkoxy；
E is halogen, nitro, C1-C4Alkoxy carbonyl, C1-C8Alkyl amino sulfonyl, C6-C12N-aryl sulfonyl；
E1And E2For independently hydrogen, halogen, C1-C4Alkyl or C1-C4Alkoxy；E3For hydrogen.
2. following any metal complex,
3. the metal complex described in claim 2 makees the application of catalyst in olefin metathesis metathesis reaction.
4. application according to claim 3, it is characterised in that：Described olefin metathesis metathesis reaction is intramolecular cyclization
Olefin metathesis metathesis reaction, intermolecular olefin metathesis metathesis reaction or intermolecular cycloolefin ring opening metathesis polymerization
Reaction.
5. application according to claim 4, it is characterised in that：The described cycloolefin for polymerisation is tensioned
Cycloolefin structure or polycyclic olefin structure；They are substituted or non-substituted structures, and they contain in one or more rings
F、Cl、Br、N、O、Si、S、P、B、C6-C15Aromatic series and C4-C15One or more in aromatic heterocycle substituent.
6. application according to claim 5, it is characterised in that：Described cycloolefin structure contains 4 or 5 or 7-16
Individual carbon atom, or multiple hetero atoms.
7. application according to claim 5, it is characterised in that：Described polycyclic olefin structure is more containing 2 to 6 rings
Cycloolefin structure.
8. according to the application described in claim 5, it is characterised in that：Described cycloolefin is in cyclopentadiene or its molecule
One or more hydrogen by C1-C15Saturation or undersaturated alkyl, substituted or unsubstituted C1-C15Amido, substitution or unsubstituted
C1-C15Alkoxy, substituted or unsubstituted C6-C15Aryloxy group, substituted or unsubstituted C1-C15Heterocyclic oxy group, substitution or not
Substituted C1-C15Alkylthio group, substituted or unsubstituted C6-C15Arylthio, the substituted or unsubstituted C of connection1-C15The carbonyl of alkoxy
Base, formyloxy, formamido, substituted or unsubstituted C1-C15Alkyl carbonyloxy, substituted or unsubstituted C1-C15Alkyl
Formamido, substituted or unsubstituted C6-C15Arylcarbonyloxy or substituted or unsubstituted C6-C15Aryl carboxamides base
Substituted derivative.
9. according to the application described in claim 7, it is characterised in that：Described polycyclic olefin is following polycyclic olefin structure
VIa and VIb：
Wherein：
A is O, S, C1-C15Saturation or undersaturated alkyl, substituted or unsubstituted C1-C15Alkoxy, substituted or unsubstituted C1-
C15Aryloxy group, substituted or unsubstituted C1-C15Heterocyclic oxy group, substituted or unsubstituted C1-C15Alkylthio group, connection substitution do not take
The C in generation1-C15The carbonyl of alkoxy, substituted or unsubstituted C1-C15Alkyl amine group, substituted or unsubstituted C1-C15Arylamine
Base, substituted or unsubstituted C1-C15Alkyl amido, substituted or unsubstituted C1-C15Aryl carboxamides base or substitution or not
Substituted C1-C15Heterocyclic radical formamido；
R10And R11It independently is hydrogen, halogen, substituted or unsubstituted C1-C15Alkyl, substituted or unsubstituted C1-C15Alkoxy,
Substituted or unsubstituted C1-C15Alkylthio group, substituted or unsubstituted C1-C15Alkane siloxy, C6-C15Aryloxy group, C6-C15Aryl,
C2-C15Heterocyclic radical, C2-C15Heterocyclic aryl, the substituted or unsubstituted C of connection1-C15The carbonyl of alkoxy, formamido, substitution or
Unsubstituted C1-C15Alkyl amido, C1-C15Alkylsulfonamido, urea groups, substituted or unsubstituted C1-C15Alkyl urea groups,
Ionic liquid monomer, liquid crystal monomer, active drug molecule；In Formula IV a, R10And R11It is not linked to be cyclic structure or is linked to be ring-type
Structure.
10. according to the application described in claim 7, it is characterised in that：Described polycyclic olefin is following polycyclic olefin knot
Structure VIIa-VIIb：
Wherein：
A is O, S, C1-C15Saturation or undersaturated alkyl, substituted or unsubstituted C1-C15Alkoxy, substituted or unsubstituted C1-
C15Aryloxy group, substituted or unsubstituted C1-C15Heterocyclic oxy group, substituted or unsubstituted C1-C15Alkylthio group, connection substitution do not take
The C in generation1-C15Carbonyl, formamido, the substituted or unsubstituted C of alkoxy1-C15It is alkyl amido, substituted or unsubstituted
C1-C15Aryl carboxamides base or substituted or unsubstituted C1-C15Heterocyclic radical formamido；
R12For substituted or unsubstituted C1-C15Alkyl, substituted or unsubstituted C1-C15Alkoxy, substituted or unsubstituted C1-C15
Alkylthio group, substituted or unsubstituted C1-C15Alkane siloxy, C6-C15Aryloxy group, C6-C15Aryl, C2-C15Heterocyclic radical, connection substitution
Or unsubstituted C1-C15Carbonyl, formamido, the substituted or unsubstituted C of alkoxy1-C15Formamido, C1-C15Alkyl sulphur
Amide groups, urea groups, substituted or unsubstituted C1-C15Alkyl urea groups, ionic liquid monomer, liquid crystal monomer or active drug molecule；
R13And R14It independently is substituted or unsubstituted C1-C15Alkyl, substituted or unsubstituted C1-C15Alkoxy, substitution or not
Substituted C1-C15Alkylthio group, substituted or unsubstituted C1-C15Alkane siloxy, C6-C15Aryloxy group, C6-C15Aryl, C2-C15Heterocycle
Base, the substituted or unsubstituted C of connection1-C15Carbonyl, formamido, the substituted or unsubstituted C of alkoxy1-C15Formamido,
C1-C15Alkylsulfonamido, urea groups, substituted or unsubstituted C1-C15Alkyl urea groups, ionic liquid monomer, liquid crystal monomer or work
Property drug molecule.
11. application according to claim 4, it is characterised in that：Described intermolecular cycloolefin ring opening metathesis polymerization
React to prepare the polymerisation of macromolecule polymer material.
12. application according to claim 11, it is characterised in that：The described polymerization for preparing macromolecule polymer material is anti-
The organic solvent answered is one kind or more in dichloromethane, dichloroethanes, chloroform, toluene, dimethylbenzene, chlorobenzene and ionic liquid
Kind.
13. application according to claim 11, it is characterised in that：Described intermolecular cycloolefin ring opening metathesis polymerization
In reaction, when raw material cycloolefin or polycyclic olefin are liquid, organic solvent is not added with.
14. application according to claim 11, it is characterised in that：Described high molecular polymer be as Formula IV c, VId,
Shown in VIe, VIIc, VIId, Poly-DCPD；
Wherein, R10、R11、R12、R13And R14It independently is hydrogen, halogen, nitro, itrile group, aldehyde radical, substituted or unsubstituted C1-C20Alkane
Base, C1-C20Alkoxy, substituted or unsubstituted C1-C20Aryloxy group, C1-C20Heterocyclic radical epoxide, C1-C20Alkylthio group, C1-C20Alkane
Silicon substrate, C1-C20Alkyl siloxy, C2-C20Heterocyclic radical, substituted or unsubstituted C6-C20Aryl, C6-C20Aryloxy group, connection C1-
C20Carbonyl, the connection C of alkyl6-C20Carbonyl, the connection C of aryl2-C20Carbonyl, the connection C of heterocyclic radical6-C20The carbonyl of aryloxy group,
Connect C6-C20Carbonyl, the substituted or unsubstituted C of connection of heterocyclic radical epoxide1-C20Saturation or the Epoxide carbonyl of unsaturated alkyl,
Aminoacyl, the substituted or unsubstituted C of connection1-C20The carbonyl of saturation or unsaturated alkyl amino, connection C6-C20Arylamino
Carbonyl, connection C2-C20Carbonyl, urea groups, the substituted or unsubstituted C of heterocyclylamino group1-C20Alkyl urea groups, substitution do not take
The C in generation6-C20Aryl-ureido, substituted or unsubstituted C2-C20Heterocyclic radical urea groups, connection C1-C20The sulfonyl of alkyl amino, connect
Meet C6-C20The sulfonyl or connection C of arylamino2-C20The sulfonyl of heterocyclylamino group；n1For 102-104；m1For 102-104。
15. application according to claim 14, it is characterised in that：In Formula IV c, VId, VIe, VIIc, VIId, Poly-
In DCPD,
R10、R11、R12、R13And R14It independently is hydrogen, halogen, nitro, itrile group, aldehyde radical, substituted or unsubstituted C1-C15Alkyl,
C1-C15Alkoxy, C1-C15Heterocyclic oxy group, C1-C15Alkylthio group, C1-C15Alkane silicon substrate, C1-C15Alkyl siloxy, C2-C15Heterocycle
Base, substituted or unsubstituted C6-C15Aryl, substituted or unsubstituted C6-C15Aryloxy group, connection C1-C15The carbonyl of alkyl, connection
C6-C15Carbonyl, the connection C of aryl2-C15Carbonyl, the substituted or unsubstituted C of connection of heterocyclic radical1-C15Saturation or unsaturated alkyl
Epoxide carbonyl, connection C6-C15Carbonyl, aminoacyl, the substituted or unsubstituted C of connection of heterocyclic radical epoxide1-C15Saturation or not
Carbonyl, the connection C of saturated hydrocarbyl amino2-C15Carbonyl, urea groups, the substituted or unsubstituted C of heterocyclylamino group1-C15Ureine
Base, substituted or unsubstituted C6-C15Aryl-ureido, substituted or unsubstituted C2-C15Heterocyclic radical urea groups, connection C1-C15Alkyl ammonia
Sulfonyl, the connection C of base6-C15Sulfonyl, the connection C of arylamino2-C15The sulfonyl of heterocyclylamino group；n1For 102-104；
m1For 102-104。
16. application according to claim 15, it is characterised in that：In Formula IV c, VId, VIe, VIIc, VIId, Poly-
In DCPD, R10、R11、R12、R13And R14In, the substituted or unsubstituted C of described connection1-C15The oxygen of saturation or unsaturated alkyl
Base carbonyl is connection C6-C15The carbonyl of aryloxy group；The substituted or unsubstituted C of described connection1-C15Saturation or unsaturated alkyl ammonia
The carbonyl of base is connection C6-C15The carbonyl of arylamino.
17. application according to claim 15, it is characterised in that：In Formula IV c, VId, VIe, VIIc, VIId, Poly-
In DCPD,
R10、R11、R12、R13And R14It independently is hydrogen, halogen, substituted or unsubstituted C1-C8Alkyl, C1-C8Alkoxy, C1-C8Alkane
Sulfenyl, C1-C8Alkane silicon substrate, C1-C8Alkyl siloxy, C2-C8Heterocyclic radical, substituted or unsubstituted C6-C12Aryl, substitution do not take
The C in generation6-C12Aryloxy group, connection C1-C8Carbonyl, the connection C of alkyl6-C12Carbonyl, the connection C of aryl2-C8The carbonyl of heterocyclic radical,
Connect substituted or unsubstituted C1-C8Saturation or the Epoxide carbonyl of unsaturated alkyl, connection C6-C12The carbonyl of aryloxy group, connection
C6-C8Carbonyl, aminoacyl, the substituted or unsubstituted C of connection of heterocyclic radical epoxide1-C8The carbonyl of saturation or unsaturated alkyl amino
Base, connection C6-C12Carbonyl, the connection C of arylamino2-C8Carbonyl, the connection C of heterocyclylamino group1-C8The sulphonyl of alkyl amino
Base, connection C6-C12Sulfonyl, the connection C of arylamino2-C8The sulfonyl of heterocyclylamino group；n1For 102-104；m1For 102-
104。
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| WO2017185324A1 (en) * | 2016-04-29 | 2017-11-02 | Xia, Ling | Group 8 transition metal catalysts and method for making same and process for use of same in olefin disproportionation reactions |
| WO2018236191A1 (en) * | 2017-06-23 | 2018-12-27 | 광주과학기술원 | Ligand for forming ruthenium complex, ruthenium complex catalyst, production method therefor and use thereof |
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