CN104185506A - 钌络合物或锇络合物及其制备方法和用途 - Google Patents
钌络合物或锇络合物及其制备方法和用途 Download PDFInfo
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- CN104185506A CN104185506A CN201280046966.8A CN201280046966A CN104185506A CN 104185506 A CN104185506 A CN 104185506A CN 201280046966 A CN201280046966 A CN 201280046966A CN 104185506 A CN104185506 A CN 104185506A
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- Prior art keywords
- alkyl
- represent
- aryl
- formula
- ruthenium
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- 238000000034 method Methods 0.000 title claims abstract description 17
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims description 14
- 229910052707 ruthenium Inorganic materials 0.000 title claims description 14
- 229910052762 osmium Inorganic materials 0.000 title claims description 6
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 title claims description 6
- 238000002360 preparation method Methods 0.000 title description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 45
- 239000003054 catalyst Substances 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 38
- -1 halide derivative of silane Chemical class 0.000 claims description 37
- 239000003446 ligand Substances 0.000 claims description 33
- 150000001450 anions Chemical group 0.000 claims description 26
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 19
- 229910052731 fluorine Inorganic materials 0.000 claims description 15
- 150000001336 alkenes Chemical class 0.000 claims description 14
- 238000000354 decomposition reaction Methods 0.000 claims description 14
- 125000001153 fluoro group Chemical group F* 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 230000007935 neutral effect Effects 0.000 claims description 13
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 12
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 10
- 238000005649 metathesis reaction Methods 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- 125000001424 substituent group Chemical group 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 125000000623 heterocyclic group Chemical group 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 239000012327 Ruthenium complex Substances 0.000 claims description 6
- 238000006317 isomerization reaction Methods 0.000 claims description 6
- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 claims description 4
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical group C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 4
- 125000003368 amide group Chemical group 0.000 claims description 4
- 125000001188 haloalkyl group Chemical group 0.000 claims description 4
- 125000001072 heteroaryl group Chemical group 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- 238000007363 ring formation reaction Methods 0.000 claims description 4
- 125000005420 sulfonamido group Chemical group S(=O)(=O)(N*)* 0.000 claims description 4
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 238000006276 transfer reaction Methods 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 125000006711 (C2-C12) alkynyl group Chemical group 0.000 claims description 2
- ADLVDYMTBOSDFE-UHFFFAOYSA-N 5-chloro-6-nitroisoindole-1,3-dione Chemical compound C1=C(Cl)C([N+](=O)[O-])=CC2=C1C(=O)NC2=O ADLVDYMTBOSDFE-UHFFFAOYSA-N 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 150000001361 allenes Chemical class 0.000 claims description 2
- 239000000010 aprotic solvent Substances 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 150000004696 coordination complex Chemical class 0.000 claims description 2
- 125000000468 ketone group Chemical group 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 claims 2
- 150000001408 amides Chemical class 0.000 claims 1
- 150000004820 halides Chemical class 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 11
- 239000002184 metal Substances 0.000 abstract description 8
- 239000007789 gas Substances 0.000 description 19
- 238000004587 chromatography analysis Methods 0.000 description 15
- 229910052799 carbon Inorganic materials 0.000 description 14
- 150000001721 carbon Chemical group 0.000 description 13
- 150000001993 dienes Chemical class 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 8
- 125000001183 hydrocarbyl group Chemical group 0.000 description 8
- 238000007366 cycloisomerization reaction Methods 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 6
- ZBZJXHCVGLJWFG-UHFFFAOYSA-N trichloromethyl(.) Chemical compound Cl[C](Cl)Cl ZBZJXHCVGLJWFG-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 235000011007 phosphoric acid Nutrition 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 206010011416 Croup infectious Diseases 0.000 description 4
- 240000007817 Olea europaea Species 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 201000010549 croup Diseases 0.000 description 4
- WACQKHWOTAEEFS-UHFFFAOYSA-N cyclohexane;ethyl acetate Chemical compound CCOC(C)=O.C1CCCCC1 WACQKHWOTAEEFS-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 239000001307 helium Substances 0.000 description 4
- 229910052734 helium Inorganic materials 0.000 description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 4
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 238000000935 solvent evaporation Methods 0.000 description 4
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 4
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 3
- 238000005865 alkene metathesis reaction Methods 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- LSPHULWDVZXLIL-UHFFFAOYSA-N (+/-)-Camphoric acid Chemical compound CC1(C)C(C(O)=O)CCC1(C)C(O)=O LSPHULWDVZXLIL-UHFFFAOYSA-N 0.000 description 2
- HBENZIXOGRCSQN-VQWWACLZSA-N (1S,2S,6R,14R,15R,16R)-5-(cyclopropylmethyl)-16-[(2S)-2-hydroxy-3,3-dimethylpentan-2-yl]-15-methoxy-13-oxa-5-azahexacyclo[13.2.2.12,8.01,6.02,14.012,20]icosa-8(20),9,11-trien-11-ol Chemical compound N1([C@@H]2CC=3C4=C(C(=CC=3)O)O[C@H]3[C@@]5(OC)CC[C@@]2([C@@]43CC1)C[C@@H]5[C@](C)(O)C(C)(C)CC)CC1CC1 HBENZIXOGRCSQN-VQWWACLZSA-N 0.000 description 2
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 125000005605 benzo group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000000392 cycloalkenyl group Chemical group 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 238000001035 drying Methods 0.000 description 2
- 125000002541 furyl group Chemical group 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Substances C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N o-dihydroxy-benzene Natural products OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- RMVRSNDYEFQCLF-UHFFFAOYSA-N phenyl mercaptan Natural products SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 2
- 229930015698 phenylpropene Natural products 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- 150000003303 ruthenium Chemical class 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000001544 thienyl group Chemical group 0.000 description 2
- PHDIJLFSKNMCMI-ITGJKDDRSA-N (3R,4S,5R,6R)-6-(hydroxymethyl)-4-(8-quinolin-6-yloxyoctoxy)oxane-2,3,5-triol Chemical compound OC[C@@H]1[C@H]([C@@H]([C@H](C(O1)O)O)OCCCCCCCCOC=1C=C2C=CC=NC2=CC=1)O PHDIJLFSKNMCMI-ITGJKDDRSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- IICQZTQZQSBHBY-HWKANZROSA-N (e)-non-2-ene Chemical compound CCCCCC\C=C\C IICQZTQZQSBHBY-HWKANZROSA-N 0.000 description 1
- 125000006039 1-hexenyl group Chemical group 0.000 description 1
- IICQZTQZQSBHBY-UHFFFAOYSA-N 2t-nonene Natural products CCCCCCC=CC IICQZTQZQSBHBY-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- HIHOEGPXVVKJPP-JTQLQIEISA-N 5-fluoro-2-[[(1s)-1-(5-fluoropyridin-2-yl)ethyl]amino]-6-[(5-methyl-1h-pyrazol-3-yl)amino]pyridine-3-carbonitrile Chemical compound N([C@@H](C)C=1N=CC(F)=CC=1)C(C(=CC=1F)C#N)=NC=1NC=1C=C(C)NN=1 HIHOEGPXVVKJPP-JTQLQIEISA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- 241000931705 Cicada Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920001153 Polydicyclopentadiene Polymers 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 125000005600 alkyl phosphonate group Chemical group 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 239000004410 anthocyanin Substances 0.000 description 1
- 229930002877 anthocyanin Natural products 0.000 description 1
- 235000010208 anthocyanin Nutrition 0.000 description 1
- 150000004636 anthocyanins Chemical class 0.000 description 1
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 description 1
- 150000001502 aryl halides Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 125000004617 chromonyl group Chemical group O1C(=CC(C2=CC=CC=C12)=O)* 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 239000004913 cyclooctene Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- GVOISEJVFFIGQE-YCZSINBZSA-N n-[(1r,2s,5r)-5-[methyl(propan-2-yl)amino]-2-[(3s)-2-oxo-3-[[6-(trifluoromethyl)quinazolin-4-yl]amino]pyrrolidin-1-yl]cyclohexyl]acetamide Chemical compound CC(=O)N[C@@H]1C[C@H](N(C)C(C)C)CC[C@@H]1N1C(=O)[C@@H](NC=2C3=CC(=CC=C3N=CN=2)C(F)(F)F)CC1 GVOISEJVFFIGQE-YCZSINBZSA-N 0.000 description 1
- JHJNPOSPVGRIAN-SFHVURJKSA-N n-[3-[(1s)-1-[[6-(3,4-dimethoxyphenyl)pyrazin-2-yl]amino]ethyl]phenyl]-5-methylpyridine-3-carboxamide Chemical compound C1=C(OC)C(OC)=CC=C1C1=CN=CC(N[C@@H](C)C=2C=C(NC(=O)C=3C=C(C)C=NC=3)C=CC=2)=N1 JHJNPOSPVGRIAN-SFHVURJKSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- YCBSHDKATAPNIA-UHFFFAOYSA-N non-3-ene Chemical compound CCCCCC=CCC YCBSHDKATAPNIA-UHFFFAOYSA-N 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
- 238000006053 organic reaction Methods 0.000 description 1
- 125000001715 oxadiazolyl group Chemical group 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 125000003566 oxetanyl group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- VBQCHPIMZGQLAZ-UHFFFAOYSA-N phosphorane Chemical class [PH5] VBQCHPIMZGQLAZ-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003304 ruthenium compounds Chemical class 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 125000002769 thiazolinyl group Chemical group 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000012982 x-ray structure analysis Methods 0.000 description 1
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Abstract
本发明的主题为式(1)所定义的新型金属络合物。本发明还涉及式(1)所定义的所述新型金属络合物的制备方法及其用途。
Description
本发明涉及用作预(催化剂)的新型金属络合物,其制造方法以及其在烯烃的复分解过程、异构化反应和环异构化反应中的用途,其制造方法以及其在烯烃复分解、异构化反应和环异构化反应以及在烯烃以及氢转移反应中的用途。本发明在广泛理解的有机反应中是有用的。
目前发现在有机合成中烯烃复分解的用途的研究有很大进展。现有技术披露了几种用作(预)催化剂的钌的卡宾络合物,它们具有对各种复分解反应的高活性以及对官能团的广泛耐受性。以上性质的组合保证了该类型的(预)催化剂在有机合成中的应用。
就实际应用而言,尤其是在工业规模上,非常理想的是,对于在提高温度下的很长的时间里这种钌络合物是稳定的,并且可以在没有保护气氛下储存和/或纯化和/或使用。还很重要的是,根据反应条件该催化剂表现出不同的反应活性,并且在反应后可以容易地将其去除。
已经公开了许多在烯烃复分解反应中有活性的钌的络合物(参见:Org.Lett.1999,1,953–956;J.Chem.Soc.Chem.Commun.1999,601-602)。已知稳定性的增加与催化活性的降低相关(对比:J.Amer.Chem.Soc.2000,122,8168-8179;Tetrahedron Lett.2000,41,9973-9976)。在通过亚苄基配体的立体或电子因素活化的(预)催化剂的情况下,也已知了这些优点和局限性(催化活性对比参见:Angew.Chem.Int.Ed.2002,114,4210-4212;Angew.Chem.Int.Ed.2002,114,2403-2405)。
也给出了阴离子的效果(参见:Angew.Chem.Int.Ed.2007,46,7206-7209;Organometallics,2010,29,6045–6050;Organometallics,2011,30,3971–3980)以及NHC配体对(预)催化剂的活性和选择性的效果(参见:Chem.Rev.2010,110,1746–1787;Chem.Rev.2009,109,3708–3742)。从这些报道中,得知将氯离子配体换为含氧酸残基增加了(预)催化剂的稳定性。
出人意料的是结果表明本发明的式1所定义的含有由氧原子形成的螯合环的新型钌络合物是热稳定的并且表现了好的催化活性。
另外,该化合物显著改变了反应选择性,这取决于所使用的:溶剂和/或烷烃的酸或卤素衍生物或硅烷的卤素衍生物或N-卤代酰亚胺或N-卤代酰胺的加入,这使得能够通过改变这些因素来控制整个催化过程。
本发明的式1所定义的络合物在广泛的反应中是有用的。通过进行大量复分解环合反应,以及均复分解(homometatheses),交叉复分解(cross metatheses)以及“烯烃-炔烃”复分解(烯-炔)(metatheses of the“alkene-alkyne”(ene-yne))、开环聚合反应(ring-opening polymerisation reactions(ROMP))、烯烃异构化反应(olefin isomerisation reactions)、烯烃环异构化反应(olefin cycloisomerisation reactions)以及氢迁移反应(hydrogen transfer reactions)。
作为本发明主题的化合物的高极性并且更易于从反应产物中分离钌化合物出去,这在制药工业的化合物合成中非常显著。
本发明的主题为式1所定义的含有硝基负离子(nirtoanion)的新型金属络合物:
其中:
M表示钌或锇;
L1和L2表示中性配体;
X表示阴离子配体;
Z表示氮原子;
Y表示氧原子;
R1、R2彼此独立地表示氢原子、氟原子、C1-C25烷基、C1-C25全氟烷基、C2-C25烯(alkene)、C3-C7环烷基、C2-C25烯基(alkenyl)、C3-C25环烯基、C2-C25炔基、C3-C25环炔基、C1-C25烷氧基、C5-C24芳基、C5-C20杂芳基或3元-12元杂环,其中所述烷基可以连接成环,其中优选表示氢、硝基(-NO2)、氰基基团(-CN)、羧基(-COOH)、羧基(-COOR’)、酰胺基(-CONR’2)、磺酰基(-SO2R’)、甲酰基(-CHO)、磺酰氨基(-SO2NR’2)或酮基(-COR’)、其中R’含义如下:C1-C5烷基、C1-C5全氟烷基、C5-C24芳基。
在优选的实施流程中,式1的R1表示氢原子或甲基;R2表示氢原子以及阴离子配体X表示氟原子,-CN、-SCN、-OR4、-SR4、-O(C=O)R4、-O(SO2)R4、-OSiR3 4,其中R4表示C1-C12烷基、C3-C12环烷基、C2-C12烯基或C5-C20芳基并且可以被C1-C12烷基、C1-C12全卤代烷基、C1-C12烷氧基或氟原子中的至少一个所取代;并且
中性配体L1和L2彼此独立地选自-P(R5)3、-P(OR5)3或由式2a、2b、2c、2d、2e、2f、2g、2h、2i、2j、2k、2l、2m、2n、2o或2p表示的N-杂环卡宾配体:
其中:
各个R5彼此独立地表示C1-C12烷基、C3-C12环烷基、C5-C20芳基、5元-12元杂芳环;
各个R6、R7、R8、R9和R10彼此独立地表示氢原子、C1-C12烷基、C3-C12环烷基、C2-C12烯基或C5-C20芳基并且可以被至少一个C1-C12烷基、C1-C12全卤代烷基、C1-C12烷氧基或氟原子取代,并且基团R6、R7、R8、R9和R10可以相互连接。
卡宾配体典型地可以为配位的(coordinated),如结构2a至结构2h中所示,或为非典型的如结构2i至结构2p中所示(异常卡宾”参见:Chem.Rev.2009、109、3445)。
在另一个优选地实施方案中,式1的阴离子配体X表示氯原子;并且
中性配体L1表示-P(R5)3,其中取代基R5与如上定义的含义;并且
中性配体L2表示式2a或式2b所定义的配体:
其中取代基R6、R7、R8和R9表示如上所定义的。
本发明的主题还为生产式1所定义的金属络合物的方法,其包括式3所定义的化合物与具有式4a、4b、4c或4d所定义的钌的卡宾络合物的反应:
其中R1、R2、Z、Y具有如上所定义的含义,而R3、R13、R14彼此独立地表示氢原子、氟原子、C1-C25烷基、C1-C25全氟烷基、C2-C25烯(alkene)、C3-C7环烷基、C2-C25烯基(alkenyl)、C3-C25环烯基、C2-C25炔基、C3-C25环炔基、C1-C25烷氧基、C5-C24芳基、C5-C20杂芳基或3元-12元杂环,其中烷基可以连接成环,其中优选表示氢、硝基(-NO2)、氰基基团(-CN)、羧基(-COOH)、羧基(-COOR’)、酰胺基(-CONR’2)、磺酰基(-SO2R’)、甲酰基(-CHO)、磺酰氨基(-SO2NR’2)、酮(-COR’),其中R’含义如下:C1-C5烷基、C1-C5全氟烷基、C5-C24芳基;
R1表示氢、氟原子、C1-C12烷基、C3-C12环烷基、C2-C12烯基、C3-C12环烯基、C2-C12炔基、C3-C12环炔基、C1-C12烷氧基、C5-C20芳基、C5-C20杂芳基或3元-12元杂环;
其中:
M表示钌或锇;
L1、L2和L3彼此独立地表示中性配体;
X1和X2彼此独立地表示阴离子配体;
R11与式1的R1具有相同含义;
R12表示氢原子、C5-C20芳基、C5-C20杂芳基、乙烯基或丙二烯基。
优选地,反应在1分钟至250小时的时间段内在0℃至150℃温度下进行。
优选地,反应在氯化溶剂或芳香烃溶剂或质子溶剂或非质子溶剂,诸如醇或铜或其混合物中进行。
优选地,反应在选自二氯甲烷和/或甲苯的溶剂中进行。
本发明还涉及式1所定义的钌络合物在复分解反应中作为(预)催化剂的用途。
优选地,式1所定义的钌络合物在环合复分解反应、均复分解、交叉复分解、“烯烃-炔烃”复分解(烯-炔)、ROMP聚合中以及在烯烃的环异构化反应中用作(预)催化剂。
术语“氟原子”表示选自F、Cl、Br或I的元素。
术语“卡宾”表示包含具有两个价数和两个未成对电子的中性碳原子。术语“卡宾”还包括卡宾类似物,其中碳原子为另一个诸如硼、硅、锗、锡、铅、氮、磷、硫、硒和碲的化学元素取代。
术语“烷基”指具有指定数目碳原子的饱和的直链或支链烃取代基。烃基取代基的实例为-甲基、-乙基、-正丙基、-正丁基、-正戊基、-正己基、-正庚基、-正辛基、-正壬基和-正癸基。代表性的-(C1-C10)支链烷基包含-异丙基、-仲丁基、-异丁基、-叔丁基、-异戊基、-新戊基、-1-甲基丁基、-2-甲基丁基、-3-甲基丁基、-1,1-二甲丙基、-1,2- 二甲基丙基、-1-甲基戊基、2-甲基戊基、-3-甲基戊基、-4-甲基戊基、-1-乙基丁基、-2-乙基丁基、-3-乙基丁基、-1,1-二甲基丁基、-1,2-二甲基丁基、-1,3-二甲基丁基、-2,2-二甲基丁基、-2,3-二甲基丁基、-3,3-二甲基丁基、-1-甲基己基、-2-甲基己基、-3-甲基己基、-4-甲基己基、-5-甲基己基、-1,2-二甲基戊基、-1,3-二甲基戊基、-1,2-二甲基己基、-1,3-二甲基己基、-3,3-二甲基己基、-1,2-二甲基庚基、-1,3-二甲基庚基和-3,3-二甲基庚基等。
术语“烷氧基”指通过氧原子连接的如上所定义的烷基取代基。
术语“全氟代烷基”指如上所定义的烷基、其中所有氢原子已为相同的或不同的原子的氟原子替代。
术语“环烷基”指具有指定数目碳原子的饱和的单环或多环的烃取代基。环烷基取代基的实例为-环丙基、-环丁基、-环戊基、-环己基、-环庚基、-环辛基、-环壬基和-环癸基等。
术语“烯基”指具有指定数目碳原子并且含有至少一个碳碳双键的不饱和的直链或支链非环烃取代基。烯基取代基的实例为-乙烯基、-烯丙基、1-丁烯基、2-丁烯基、-异丁烯基、-1-戊烯基、2-亚戊烯、3-甲基-1-丁烯基、2-甲基-2-丁烯基、-2,3-二甲基-2-丁烯、1-己烯基、-2-己烯基、3-己烯基-、1-庚烯基、2-庚烯基、3-庚烯基、-1-辛烯基、-2-辛烯基、-3-辛烯基、-1-壬烯基、2-壬烯基、3-壬烯基、-1-癸烯基、-2-癸烯基和-3-癸烯基等。
术语“环烯基”指具有指定数目碳原子并且含有至少一个碳碳双键的不饱和的单环或多环的烃取代基。环烯基取代基的实例为-环戊烯基、-环戊二烯基、-环己烯、-环己二烯基、-环庚烯基、-环庚二烯基、-环庚三烯基、-环辛烯基、-环辛二烯基、-环辛三烯基、-环辛四烯、环壬烯基、-环壬二烯基、-环癸烯基和-环癸二烯基等。
术语“炔基”指具有指定数目碳原子并且含有至少一个碳碳叁键的不饱和的直链或支链烃取代基。炔基取代基的实例为-乙炔基、-丙炔基、-1-丁炔基、-2-丁炔基、-1-戊炔基、-2-戊炔基、-3-甲基-1-丁炔基、-4-戊炔基、-1-己炔、-2-己炔基和-5-己炔基等。
术语“环炔基”指具有指定数目碳原子并且含有至少一个碳碳叁键 的饱和的单环或多环的烃取代基。环炔基取代基的实例为-环己炔基、-环庚炔基或-环辛炔基等。
术语“芳基”指具有指定数目碳原子的芳香性的单环或多环的烃取代基。芳基取代基的实例为-苯基、-甲苯基、-二甲苯基和-萘基等。
术语“杂芳基”指具有指定数目碳原子并且其中至少一个碳原子被选自O、N和S的杂原子替代的单环或多环的烃取代基。杂芳基取代基的实例为-呋喃基、-噻吩基、-咪唑基、噁唑基、噻唑基、-异噁唑基、-三唑基、噁二唑基、-噻二唑基、-四唑基、吡啶基(-pirydyl)、-嘧啶基(-pirymidyl)、-三嗪基(-triazynyl)、-吲哚基、-苯并[b]呋喃基、-苯并[b]噻吩基、-吲唑基、-苯并咪唑基、-氮杂吲哚基、-喹啉、-异喹啉基和-咔唑等。
术语“杂环”指具有指定数目碳原子并且其中至少一个碳原子为选自O、N和S杂原子所替代的饱和或部分不饱和的单环或多环的烃取代基。杂环取代基的实例为-呋喃基、-噻吩基、-吡咯基、-噁唑基、-咪唑基、-噻唑基、-异噁唑基、-吡唑基、-异噻唑基、-三嗪基、-吡咯烷酮基(-pyrolidynonyl,)、-吡咯烷基(-pyrolidynyl)、-乙内酰脲、-环氧乙烷基、氧杂环丁烷基(-oxethanyl)、-四氢呋喃基、-四氢噻吩基、-喹啉基、-异喹啉基、-色酮基(chromonyl)、cumarinyl、-吲哚基、-吲嗪基、苯并[b]呋喃基、-苯并[b]噻吩基、-吲唑基、-嘌呤基(-purynyl)、-4H-喹嗪基(-4H-quinolizynyl)、-异喹啉基、-喹啉基、-酞嗪基、-萘啶基(-naphthyrydynyl)、咔唑基和β-咔啉基等。
术语“中性配体”指能够与金属中心(钌原子)配位的不带电的取代基。这类配体的实例为胺、膦及其氧化物,烷基膦(alkyl phosphorines)和烷基膦(alkane phosphorines)和膦烷(phosphoranes),胂及其氧化物,醚,烷基硫化物和芳基硫化物,配位的烃(coordinated hydrocarbons),烷基卤化物和芳基卤化物。
术语“茚基”指通过具有茚骨架(苯并环戊二烯)的不饱和烃取代基。
术语“杂茚基”指如上所定义的茚基取代基,其中至少一个碳原子为选自氮、氧和硫的杂原子替代。
术语“阴离子配体”指能够与金属中心配位的具有能够部分或全部 补偿(compensation)给金属中心电子(metallic centre charge)的电子的取代基。这类配体的实例可以为氟化物、氯化物、溴化物、碘化物、氰化物(cianide)、花色素苷及硫氰酸根阴离子(thiocyanin anions)、羧酸根阴离子、醇阴离子、酚类阴离子、硫醇阴离子和硫酚阴离子、带变位电荷(displaced charge)的烃阴离子(即环戊二烯)、(有机)硫酸根离子和(有机)磷酸及其酯(如即烷基磺酸的阴离子及芳基磺酸的阴离子、烷基磷酸基的阴离子和芳基磷酸的阴离子、硫酸烷基酯的阴离子及硫酸芳基酯的阴离子、磷酸烷基酯的阴离子及磷酸芳基酯的阴离子、烷基磷酸烷基酯的阴离子及芳基磷酸芳基酯的阴离子)。可能的话,阴离子配体可能拥有链接的L1、L2、L3基团,诸如邻苯二酚阴离子(katechol anion)、乙酰丙酮根阴离子、水杨醛阴离子。阴离子配体(X1、X2)以及中性配体(L1、L2、L3)可能链接形成多齿配体,例如:双齿配体(X1、X2)、三齿配体(X1、X2、L1)、四齿配体(X1、X2、L1、L2)、双齿配体(X1、L1)、三齿配体(X1、L1、L2)、四齿配体(X1、L1、L2、L3)、双齿配体(L1、L2)、三齿配体(L1、L2、L3)。这类配体的实例为邻苯二酚阴离子、乙酰丙酮根阴离子以及水杨醛阴离子。
以下实施例解释了新型络合物的生产和用途。
实施例I:
式所定义的催化剂的合成(根据流程I)
将式4a所定义的固体卡宾金属络合物放置于使用保护氩气气氛在舒伦克(Schlenk)容器中,其中M表示钌,X1和X2表示氯,L1表示三环己基膦(PCy3),L2表示式2a所定义的NHC配体,其中R6和R9表示2,4,6-三甲基苯基,R7、R8以及R11为氢并且R12为苯基(所谓格鲁布斯(Grubbs)II代催化剂,102mg,0.12mmol),加入去氧的二氯甲烷(2ml)。随后,加入式3a所定义的化合物(13.1mg、0.15mmol)。
将所得溶液在室温下混合20小时。从该时间起,所有后续操作都是在露天,不需要保护氦气保护。将反应混合物在蒸发器中浓缩并且将其置于硅胶装填色谱柱上。色谱柱用乙酸乙酯-环己烷溶液(10%v/v)展开,收集绿色馏分。将溶剂蒸发后,获得了络合物1a的橄榄色微晶固体(52.6mg,产率55%)。
1H NMR(500MHz,CDCl3):d=14.27(d,J=3Hz,1H),7.02-6.90(m,4H),6.42(d,J=3Hz,1H),3.88-3.86(m,2H),3.82–3.79(m,2H),2.59(s,3H),2.52(s,3H),2.46(s,3H),2.33(s,3H),2.31(s,3H),1.98(s,3H),1.75-1.56(m,21H),1.11-1.00(m,9H),0.92-0.85(m,3H);
13C NMR(125MHz,CDCl3):d=249.2,219.3,218.7,138.8,138.6,138.4,138.0,137.6,137.5,136.3,133.8,130.4,130.0,129.9,129.1,128.9,51.6,51.2,35.6,35.1,33.1,33.0,29.3, 28.9,27.8,27.7,27.6,27.5,27.0,26.5,26.3,26.1,21.2,21.1,19.3,18.7,18.6,16.9;
31P NMRNMR(202MHz,CDCl3):d=34.2(s,1P);
IR(KBr):2925,2850,1813,1512,1483,1430,1379,1266,1169,1041,849,743cm -1
MS(FD/FI):实测为C41H61 35ClN3O2P102Ru式的m/z:795.3(M+)。
实施例II:
式1b所定义的催化剂的合成(根据流程I)
将式4a所定义的固体卡宾金属络合物放置于使用保护氩气气氛在舒伦克(Schlenk)容器中,其中M表示钌,X1和X2表示氯,L1表示三环己基膦(PCy3),L2表示式2a所定义的NHC配体,其中R6和R9表示2,4,6-三甲基苯基,R7、R8以及R11为氢并且R12为苯基(所谓格鲁布斯(Grubbs)II代催化剂,149mg,0.16mmol),加入干燥去氧的二氯甲烷(2ml)。随后,加入式3a所定义的化合物(17.4mg、0.20mmol):将所得溶液在室温下混合15小时。从该时间起,所有后续的操作都是在露天,不需要保护氦气保护。将反应混合物在蒸发器中浓缩并且将其置于硅胶装填色谱柱上。色谱柱用乙酸乙酯-环己烷溶液(10%v/v)展开,收集绿色馏分。将溶剂蒸发后,获得了络合物1b的橄榄色微晶固体(93.3mg,产率66%)。
1H NMR(600MHz,CDCl3):d=13.81(d,J=3Hz,1H),7.36-7.10(m,6H),6.29(d,J=3Hz,1H),4.20-4.10(m,1H),4.10-4.00(m,1H),4.00-3.80(m,3H),3.75-3.65(m,1H),3.65-3.55(m,1H),2.70-2.64(m,1H),1.70-1.64(m,3H), 1.60-1.50(m,18H),1.39-1.35(m,3H),1.26-1.19(m,10H),1.15-1.08(m,9H),1,07-0.92(m,14H);
13C NMR(150MHz,CDCl3):d=246.4,222.2,221.7,148.64,148.60,148.5,147.4,137.5,135.1,130.0,129.7,129.0,125.2,124.2,124.1,123.9,77.2,77.0,76.8,54.0,53.7,33.2,33.0,29.6,28.7,28.5,28.3,27.9,27.8,27.2,27.2,26.9,26.6,26.3,26.1,23.4,22.8,22.0;
31P NMRNMR(202MHz,CDCl3):d=35.3(s,1P);
IR(KBr):2962,2927,2851,1431,1414,1383,1326,1269,1238,1170,1047,803,758,734cm-1;
MS(FD/FI):实测为C47H73 35ClN3O2P102Ru式的m/z:879.3(M+)。
化合物1b的X-射线结构分析
实施例III:
式1c所定义的催化剂的合成(根据流程I)
将式4a所定义的固体卡宾金属络合物放置于使用保护氩气气氛在舒伦克容器中,其中M表示钌,X1和X2表示氯,L1表示三环己基膦(PCy3),L2表示式2a所定义的NHC配体,其中R6和R9表示2,4,6-三甲基苯基,R7、R8以及R11为氢并且R12为苯基(所谓格鲁布斯(Grubbs)II代催化剂,20.7mg,0.024mmol),加入去氧的二氯甲烷(0.3ml)。随后,我们加入式3b所定义的化合物(5mg、0.049mmol)。
将所得溶液在室温下混合20小时。从该时间起,所有后续的操作都是在露天,不需要保护氦气保护。将反应混合物在蒸发器中浓缩并且将其置于硅胶装填色谱柱上。色谱柱用乙酸乙酯-环己烷溶液(10%v/v)展开,收集绿色馏分。将溶剂蒸发后,我们获得了络合物1c的橄榄色微晶固体(9.5mg,产率50%)。
1H NMR(500MHz,CDCl3):7.03(s,1H),6.93(s,1H),6.92(s,1H),6.88(s,1H),6.65(s,1H),4.06-3.97(m,1H),3.88-3.72(m,3H),2.59(s,3H),2.54(s,3H),2.46(s,3H),2.31(s,6H),2.00(s,3H),1.91(s,3H),1.75-1.54(m,16H),1.30-1.00(m,15H),0.92-0.81(m,3H);
13C NMR(125MHz,CDCl3):d=271.1,271.0,217.9,217.2,139.0,138.7,138.6,138.3,138.2,138.0,136.6,133.6,129.91,129.85,129.4,128.6,51.9,51.5,35.2,33.6,33.4,28.9,28.8,27.9,27.8,27.6,27.5,26.9,26.5,21.1,21.0,19.2,18.7,18.5,16.6;
31P NMRNMR(202MHz,CDCl3):d=27.0(s,1P);
IR(用CHCl3成膜):2927,2851,1481,1444,1268,1185,850, 752,624cm-1;
MS(FD/FI):实测为C42H63 35ClN3O2P102Ru式的m/z:809.2(M+)。
实施例IV:
式1d所定义的催化剂的合成(根据流程I)
将式4a所定义的固体卡宾金属络合物放置于使用保护氩气气氛在舒伦克(Schlenk)容器中,其中M表示钌,X1和X2表示氯,L1表示三环己基膦(PCy3),L2表示式2a所定义的NHC配体,其中R6和R9表示2,4,6-三甲基苯基,R7,R8以及R11为氢并且R12为苯基(所谓格鲁布斯(Grubbs)II代催化剂,168mg,0.18mmol),加入干燥去氧的二氯甲烷(2ml)。随后加入式3b的所定义的化合物(22.7mg,0.23mmol):将所得溶液在室温下混合15小时。从该时间起,所有后续的操作都是在露天,不需要保护氦气保护。将反应混合物在蒸发器中浓缩并且将其置于硅胶装填色谱柱上。色谱柱用乙酸乙酯-环己烷溶液(10%v/v)展开,收集绿色馏分。将溶剂蒸发后,我们获得了络合物1d的橄榄色微晶固体(83.1mg,产率52%)。
1H NMR(600MHz,CDCl3):d=7.40-7.10(m,6H),6.67(s,1H),4.10-4.00(m,1H),3.98-3.87(m,2H),3.68-3.54(m,3H),3.75-3.65(m,1H),3.65-3.55(m,1H),2.41-2.32(m,1H),2.16(s,3H),1.77(s,3H),1.69-1.59(m),1.57-1.48(m),1.39-1.29(m),1.25-1.20(m),1.20-1.12(m),1.11-1.02(m),1.01-0.91(m)。
13C NMR(150MHz,CDCl3):d=268.3,219.5,219.0,149.3,148.8,148.5,147.3,138.1,130.4,129.9,128.9,124.8,124.2,123.2,77.2,77.0,76.8,55.0,53.9,55.4,35.3,33.4,30.9,29.2,28.8,28.6, 28.2,27.95,27.88,27.8,27.1,26.95,26.87,26.6,26.4,26.1,25.9,23.9,23.2,22.3,21.7;
31P NMRNMR(202MHz,CDCl3):d=26.4(s,1P);
IR(用CHCl3成膜):2962,2928,2851,1436,1414,1268,1234,1185,803,756,616cm-1
MS(FD/FI):实测为C49H75 35ClN3O2P102Ru式的m/z:893.4(M+)。
化合物1在环合复分解反应,交叉复分解(cross-metatheses),“烯烃-炔烃”复分解(烯-炔)以及烯烃的环异构化反应中作为催化剂的用途的实施例。
实施例V:
程序A:在舒伦克容器中,置入二烯(48.4mg,0.20mmol)的甲苯(2ml)溶液,加入六氯乙烷(1.9mg,4%mol),并且随后加入催化剂1a(1.6mg,1%mol)。将容器内含物在80℃的温度下混合2小时。将未处理的反应后混合物用气相色谱分析。复分解产物的产率为100%。
程序B:在舒伦克容器中,置入二烯(48.0mg,0.20mmol)的甲苯(2ml)溶液,加入三甲基氯硅烷(0.9mg,4%mol),并且随后加入催化剂1a(1.6mg,1%mol)。将容器内含物在80℃的温度下混合2小时。将未处理的反应后(raw post-reaction)混合物用气相色谱分析。复分解产物的产率为85%。
程序C:在舒伦克容器中,置入二烯(31.2mg,0.13mmol)的四氯化碳(0.6ml)溶液,并且随后加入催化剂1b(5.1mg,5%mol)。将容器内含物在60℃的温度下混合4小时。将未处理的反应后混合物用气相色谱分析。复分解产物的产率为98%。
程序D:在舒伦克容器中,置入二烯(30.7mg,0.13mmol)的四氯化碳(0.6ml)溶液,并且随后加入催化剂1a(5.0mg,5%mol)。将容 器内含物在60℃的温度下混合2小时。将未处理的反应后混合物用气相色谱分析。复分解产物的产率为100%。
实施例VI:
在舒伦克容器中,置入二烯(74.1mg,0.29mmol)的甲苯(1.5ml)溶液,加入六氯乙烷(3.7mg,4%mol),并且随后加入催化剂1a(12mg,5%mol)。将容器内含物在80℃的温度下混合29小时。将未处理的反应后混合物用气相色谱分析。转化率为99%。
实施例VII:
在舒伦克容器中,置入二烯(77.9mg,0.31mmol)的甲苯(1.5ml)溶液,加入六氯乙烷(5.1mg,7%mol),并且随后加入催化剂1a(11.9mg,5%mol)。将容器内含物在80℃的温度下混合14小时。将未处理的反应后混合物用气相色谱分析。转化率为100%。
在舒伦克容器中,置入二烯(92.7mg,0.31mmol)的甲苯(1.5ml)溶液,加入六氯乙烷(4.4mg,6%mol),并且随后加入催化剂1a(12.0mg,5%mol)。将容器内含物在80℃的温度下混合2小时。将未处理的反应后混合物用气相色谱分析。转化率为100%。
实施例IX:
在舒伦克容器中,置入二烯(76.0mg,0.31mmol)的甲苯(1.5ml)溶液,加入六氯乙烷(4.6mg,7%mol),并且随后加入催化剂1a(11.9mg,5%mol)。将容器内含物在80℃的温度下混合3小时。将未处理的反应后混合物用气相色谱分析。转化率为100%。
实施例X:
在舒伦克容器中,置入二烯(83.4mg,0.30mmol)的甲苯(1.5ml)溶液,加入六氯乙烷(3.8mg,4%mol),并且随后加入催化剂1a(11.9mg,5%mol)。将容器内含物在80℃的温度下混合53小时。将未处理的反应后混合物用气相色谱分析。转化率为84%。
实施例XI:
在舒伦克容器中,置入二烯(50.3mg,0.30mmol)的四氯化碳(1.5ml)溶液,并且随后加入催化剂1a(12.2mg,5%mol)。将容器内含物在65℃的温度下混合3小时。将未处理的反应后混合物用气相色谱分析。转化率为100%。
实施例XII:
在舒伦克容器中,置入二乙酰氧基丁烯(diacetoxybutenu)(110.0mg,0.64mmol)和烯丙基苯(allylbenzene)(35.8mg,0.30mmol)的甲苯 (1.5ml)溶液,加入樟脑磺酸(camphorosulphonic acid)(4.7mg,7%mol),并且随后加入催化剂1a(12.1mg,5%mol)。将容器内含物在温度80℃下混合29小时。将未处理的反应后混合物用气相色谱分析。复分解产物的产率为41%。
实施例XIII:
在舒伦克容器中,置入烯炔(76.1mg,0.31mmol)的甲苯(1.5ml)溶液,加入樟脑磺酸(4.5mg,6%mol),并且随后加入催化剂1a(12.4mg,5%mol)。将容器内含物在80℃的温度下混合24小时。将未处理的反应后混合物用气相色谱分析。转化率为100%。
实施例XIV:
在舒伦克容器中,置入二烯(73.5mg,0.31mmol)的甲醇(1.5ml)溶液,并且随后加入催化剂1a(11.7mg,5%mol)。将容器内含物在65℃的温度下混合42小时。将未处理的反应后混合物用气相色谱分析。环异构化反应的产率为82%。
实施例XV:
在舒伦克容器中,置入二烯(77.4mg,0.31mmol)的甲醇(1.5ml)溶液,并且随后加入催化剂1a(11.9mg,5%mol)。将容器内含物在温度65℃下混合50小时。将未处理的反应后混合物用气相色谱分析。环异构化产物的产率(efficiency)为88%。
实施例XVI:
在舒伦克容器中,置入烯烃(54.1mg,0.25mmol)的三氟乙醇(2ml)溶液,并且随后加入催化剂1a(10.8mg,5%mol)。将容器内含物在温度65℃下混合71小时。将未处理的反应后混合物用气相色谱分析。异构化产物的产率(efficiency)为77%。
实施例XVII:
在舒伦克容器中,置入降冰片烯(187mg,1.4mmol)的二氯甲烷(5ml)溶液,并且随后将其在40oC的温度下混合。随后加入三甲基氯硅烷(6.1mg,4%mol)和催化剂1a(11.1mg,1%mol)。将将容器内含物在相同温度下混合10分钟,此后将其倒入另一个含有15ml的甲醇的容器中并且生成白色固体沉淀,将该白色固体滤出并且通过真空泵减压干燥。获得白色固体形式的产物(119mg,90%产率(efficiency))。
实施例XVIII:
聚双环戊二烯的制备:在烧瓶中装入双环戊二烯(132mg,1.0mmol)的甲苯(5mL)溶液并且在室温下将其混合。随后,加入三甲基氯硅烷(1.1mg,1%mol)和催化剂1a(0.2mg,0.025%mol)的甲苯溶液并且将烧瓶内含物在室温下混合10分钟。随后,在烧杯中补充甲苯并且将其加热至沸点以洗去未反应的双环戊二烯。将不溶性的聚合物用甲苯冲洗并且在100℃的温度下减压干燥12小时。双环戊二烯的转化率为99%。
实施例XIX:
在舒伦克容器中,置入催化剂1a(15.7mg,2%mol)的四氢呋喃(2.5ml)溶液,并且加入氢化钠(2.8mg,7%mol)。在该混合物中加入苯乙酮(120.3mg,1.0mmol)和异丙醇(2.5ml)。将容器内含物在70℃的温度下混合5小时。将未处理的混合物用硅胶柱色谱(用环己烷:乙酸乙酯20:1洗脱)纯化。获得95mg的液态产物(产率(efficiency)78%)。
Claims (11)
1.式1所定义的金属络合物:
其中:
M表示钌或锇;
L1和L2表示中性配体;
X表示阴离子配体;
Z表示氮原子;
Y表示氧原子;
R1、R2彼此独立地表示氢原子、氟原子、C1-C25烷基、C1-C25全氟烷基、C2-C25烯、C3-C7环烷基、C2-C25烯基、C3-C25环烯基、C2-C25炔基、C3-C25环炔基、C1-C25烷氧基、C5-C24芳基、C5-C20杂芳基或3元-12元杂环,其中所述烷基可以连接成环,优选表示氢、硝基(-NO2)、氰基基团(-CN)、羧基(-COOH)、羧基(-COOR’)、酰胺基(-CONR’2)、磺酰基(-SO2R’)、甲酰基(-CHO)、磺酰氨基(-SO2NR’2)、酮(-COR’)、其中R’含义如下:C1-C5烷基、C1-C5全氟烷基、C5-C24芳基。
2.如权利要求1所述的络合物,其特征如下
所述阴离子配体X表示氟原子,-CN、-SCN、-OR4、-SR4、-O(C=O)R4、-O(SO2)R4、-OSiR3 4,其中R4表示C1-C12烷基、C3-C12环烷基、C2-C12烯基或C5-C20芳基并且可以被C1-C12烷基、C1-C12全卤代烷基、C1-C12烷氧基或氟原子中的至少一个所取代;
R1表示氢原子或甲基;
R2表示氢原子;
中性配体L1和L2彼此独立地选自-P(R5)3、-P(OR5)3或由式2a、2b、2c、2d、2e、2f、2g、2h、2i、2j、2k、2l、2m、2n、2o或2p表示的N-杂环卡宾配体:
其中:
各个R5彼此独立地表示C1-C12烷基、C3-C12环烷基、C5-C20芳基、5元-12元杂芳环;
各个R6、R7、R8、R9和R10彼此独立地表示氢原子、C1-C12烷基、C3-C12环烷基、C2-C12烯基或C5-C20芳基并且可以被至少一个C1-C12烷基、C1-C12全卤代烷基、C1-C12烷氧基或氟原子取代,并且基团R6、R7、R8、R9和R10可以相互连接。
3.如权利要求1或权利要求2所述的络合物,其特征如下
X表示氯原子;
R1表示氢原子或甲基;
R2表示氢原子
中性配体L1表示-P(R5)3,其中取代基R5与如上定义的含义相同;并且
中性配体L2表示式2a或式2b所定义的配体:
其中取代基R6、R7、R8和R9表示如上所定义的。
4.生产如权利要求1所定义的钌络合物的方法,其特征在于式3所定义的所述化合物与式4a、4b、4c或4d所定义的钌的卡宾络合物反应:
其中R1、R2、Z、Y1、Y2具有如上所定义的含义,而R3、R13、R14彼此独立地表示氢原子、氟原子、C1-C25烷基、C1-C25全氟烷基、C2-C25烯、C3-C7环烷基、C2-C25烯基、C3-C25环烯基、C2-C25炔基、C3-C25环炔基、C1-C25烷氧基、C5-C24芳基、C5-C20杂芳基或3元-12元杂环,其中所述烷基可以连接成环,优选表示氢、硝基(-NO2)、氰基基团(-CN)、羧基(-COOH)、羧基(-COOR’)、酰胺基(-CONR’2)、磺酰基(-SO2R’)、甲酰基(-CHO)、磺酰氨基(-SO2NR’2)或酮基(-COR’)、其中R’含义如下:C1-C5烷基、C1-C5全氟烷基或C5-C24芳基;
R1表示氢、氟原子、C1-C12烷基、C3-C12环烷基、C2-C12烯基、C3-C12环烯基、C2-C12炔基、C3-C12环炔基、C1-C12烷氧基、C5-C20芳基、C5-C20杂芳基或3元-12元杂环;
其中
M表示钌或锇;
L1、L2和L3彼此独立地表示中性配体;
X1和X2彼此独立地表示阴离子配体;
R11与式1的R1具有相同含义;
R12表示氢原子、C5-C20芳基、C5-C20杂芳基、乙烯基或丙二烯基。
5.如权利要求4所述的方法,其特征在于所述反应在1分钟至250小时的时间段内、在0℃至150℃温度下进行。
6.如权利要求4或权利要求5所述的方法,其特征在于所述反应在质子溶剂或非质子溶剂、氯化溶剂或芳香烃溶剂或其混合物中进行。
7.如权利要求4至权利要求6中任一项权利要求所述的方法,其特征在于所述反应在选自二氯甲烷和/或甲苯的溶剂中进行。
8.如权利要求1中的式1所定义的钌络合物在烯烃的复分解过程、烯烃的异构化和烯烃的环异构化中以及在氢转移反应中作为(预)催化剂的用途。
9.如权利要求8所述的用途,其特征在于钌的络合物在环合复分解反应、均复分解、交叉复分解、“烯烃-炔烃”复分解(烯-炔)中或在ROMP聚合反应中用作(预)催化剂。
10.如权利要求9所述的用途,其特征在于钌的络合物在双环戊二烯开环复分解聚合中用作(预)催化剂。
11.如权利要求8或权利要求9所述的用途,其特征在于所述反应在酸或者烷烃的卤化物衍生物和硅烷的卤化物衍生物或者N-卤代酰亚胺和酰胺的存在下进行。
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