CN104428306B - 新的钌络合物、其在复分解反应中的应用以及用于进行复分解反应的方法 - Google Patents
新的钌络合物、其在复分解反应中的应用以及用于进行复分解反应的方法 Download PDFInfo
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- CN104428306B CN104428306B CN201380036034.XA CN201380036034A CN104428306B CN 104428306 B CN104428306 B CN 104428306B CN 201380036034 A CN201380036034 A CN 201380036034A CN 104428306 B CN104428306 B CN 104428306B
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- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000005649 metathesis reaction Methods 0.000 title claims description 36
- 230000008569 process Effects 0.000 title abstract description 4
- 150000003303 ruthenium Chemical class 0.000 title 1
- 239000003054 catalyst Substances 0.000 claims abstract description 45
- 150000001875 compounds Chemical class 0.000 claims description 55
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 45
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 claims description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 239000001257 hydrogen Substances 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 17
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 claims description 16
- -1 Phenyl Chemical group 0.000 claims description 13
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 239000012190 activator Substances 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical group C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000005843 halogen group Chemical group 0.000 claims description 8
- 150000001336 alkenes Chemical class 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 7
- 238000000354 decomposition reaction Methods 0.000 claims description 7
- 230000000977 initiatory effect Effects 0.000 claims description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 7
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 6
- 238000005686 cross metathesis reaction Methods 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 238000006798 ring closing metathesis reaction Methods 0.000 claims description 5
- LSMWOQFDLBIYPM-UHFFFAOYSA-N 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydro-2h-imidazol-1-ium-2-ide Chemical group CC1=CC(C)=CC(C)=C1N1[C-]=[N+](C=2C(=CC(C)=CC=2C)C)CC1 LSMWOQFDLBIYPM-UHFFFAOYSA-N 0.000 claims description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 4
- XZDYFCGKKKSOEY-UHFFFAOYSA-N 1,3-bis[2,6-di(propan-2-yl)phenyl]-4,5-dihydro-2h-imidazol-1-ium-2-ide Chemical group CC(C)C1=CC=CC(C(C)C)=C1N1CCN(C=2C(=CC=CC=2C(C)C)C(C)C)[C]1 XZDYFCGKKKSOEY-UHFFFAOYSA-N 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical class [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 150000001993 dienes Chemical class 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 229910000077 silane Chemical class 0.000 claims description 3
- 125000006652 (C3-C12) cycloalkyl group Chemical group 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 230000001737 promoting effect Effects 0.000 claims description 2
- 239000012041 precatalyst Substances 0.000 claims 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims 1
- 239000007848 Bronsted acid Substances 0.000 claims 1
- 239000002841 Lewis acid Substances 0.000 claims 1
- WRLRISOTNFYPMU-UHFFFAOYSA-N [S].CC1=CC=CC=C1 Chemical compound [S].CC1=CC=CC=C1 WRLRISOTNFYPMU-UHFFFAOYSA-N 0.000 claims 1
- 150000002431 hydrogen Chemical group 0.000 claims 1
- 150000007517 lewis acids Chemical class 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 238000005865 alkene metathesis reaction Methods 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- YMWUJEATGCHHMB-DICFDUPASA-N dichloromethane-d2 Chemical compound [2H]C([2H])(Cl)Cl YMWUJEATGCHHMB-DICFDUPASA-N 0.000 description 26
- 239000003446 ligand Substances 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 238000006467 substitution reaction Methods 0.000 description 10
- 239000012298 atmosphere Substances 0.000 description 9
- 150000001450 anions Chemical group 0.000 description 8
- 150000001721 carbon Chemical group 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 230000007935 neutral effect Effects 0.000 description 7
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 150000002367 halogens Chemical class 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- 125000003545 alkoxy group Chemical group 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 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 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 4
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 125000001188 haloalkyl group Chemical group 0.000 description 4
- 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 4
- 239000000758 substrate Substances 0.000 description 4
- 150000005763 3-bromopyridine Chemical class 0.000 description 3
- 239000005864 Sulphur Chemical group 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000000536 complexating effect Effects 0.000 description 3
- 229940126214 compound 3 Drugs 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 150000003233 pyrroles Chemical class 0.000 description 3
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 3
- 125000006710 (C2-C12) alkenyl group Chemical group 0.000 description 2
- 150000003919 1,2,3-triazines Chemical class 0.000 description 2
- 125000001399 1,2,3-triazolyl group Chemical class N1N=NC(=C1)* 0.000 description 2
- 150000003920 1,2,4-triazines Chemical class 0.000 description 2
- 238000004679 31P NMR spectroscopy Methods 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical class C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 2
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 239000012327 Ruthenium complex Substances 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- WACQKHWOTAEEFS-UHFFFAOYSA-N cyclohexane;ethyl acetate Chemical compound CCOC(C)=O.C1CCCCC1 WACQKHWOTAEEFS-UHFFFAOYSA-N 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- 230000005059 dormancy Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000002757 morpholinyl group Chemical group 0.000 description 2
- 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 2
- 239000003921 oil Substances 0.000 description 2
- RMVRSNDYEFQCLF-UHFFFAOYSA-N phenyl mercaptan Natural products SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 150000003053 piperidines Chemical class 0.000 description 2
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 229960000834 vinyl ether Drugs 0.000 description 2
- 125000006649 (C2-C20) alkynyl group Chemical group 0.000 description 1
- ZRPFJAPZDXQHSM-UHFFFAOYSA-L 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazole;dichloro-[(2-propan-2-yloxyphenyl)methylidene]ruthenium Chemical compound CC(C)OC1=CC=CC=C1C=[Ru](Cl)(Cl)=C1N(C=2C(=CC(C)=CC=2C)C)CCN1C1=C(C)C=C(C)C=C1C ZRPFJAPZDXQHSM-UHFFFAOYSA-L 0.000 description 1
- JKTCBAGSMQIFNL-UHFFFAOYSA-N 2,3-dihydrofuran Chemical compound C1CC=CO1 JKTCBAGSMQIFNL-UHFFFAOYSA-N 0.000 description 1
- ZWVHTXAYIKBMEE-UHFFFAOYSA-N 2-hydroxyacetophenone Chemical class OCC(=O)C1=CC=CC=C1 ZWVHTXAYIKBMEE-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 125000003358 C2-C20 alkenyl group Chemical group 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- YPWFISCTZQNZAU-UHFFFAOYSA-N Thiane Chemical compound C1CCSCC1 YPWFISCTZQNZAU-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000001412 amines Chemical class 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
- 229910052789 astatine Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 230000010002 chemokinesis Effects 0.000 description 1
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 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 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000005043 dihydropyranyl group Chemical group O1C(CCC=C1)* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- 125000002541 furyl group Chemical group 0.000 description 1
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- 230000005802 health problem Effects 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 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
- 230000007246 mechanism Effects 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 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
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 125000005936 piperidyl group Chemical group 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005958 tetrahydrothienyl group Chemical group 0.000 description 1
- 150000003475 thallium Chemical class 0.000 description 1
- 150000003476 thallium compounds Chemical class 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 239000011988 third-generation catalyst Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- FZGRPBJBMUNMQH-UHFFFAOYSA-N trimethyl-$l^{3}-chlorane Chemical compound CCl(C)C FZGRPBJBMUNMQH-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及通式1的金属络合物。本发明还涉及式1的金属络合物作为用于烯烃复分解反应的(预)催化剂的用途,以及用于进行烯烃复分解反应的方法。
Description
技术领域
本发明涉及新的金属络合物、其作为(预)催化剂在复分解反应中的应用以及用于进行复分解反应的方法。
背景技术
烯烃的复分解在有机合成中是重要的工具(Handbook of Metathesis,Vol.I-III,Grubbs,R.H.,ed.;Wiley-VCH,2003)。
活性催化烯烃的复分解的许多钌络合物是本领域中公知的(参见,综述Vougioukalakis,G.C.;Grubbs,R.H.Chem.Rev.2010,110,1746)。第三代络合物(如Gru-III、Ind-III)据证实是开环复分解聚合(ROMP)反应中非常有用的(预)催化剂。
第三代催化剂非常迅速地引发复分解反应,但是在某些复分解应用如铸模ROMP聚合中,优选使用(预)催化剂,其在添加至底物后并不立即引发反应,而是在通过化学物质、温度或光的合适引发后引发反应。特征在于延迟引发的络合物通常称为“休眠催化剂”(Monsaert,S.;Vila,A.L.;Drozdzak,R.;Van Der Voort,P.;Verpoort,F.,Chem.Soc.Rev.,2009,38,3360;R.Drozdzak,N.Nishioka,G.Recher,F.Verpoort,Macromol.Symp.2010,293,1-4)。示例性的“休眠催化剂”有络合物A-F以及最近获得的P-1和P-2(Pietraszuk,C.;Rogalski,S.;B.;M.;Kubicki,M.;Spólnik,G.;Danikiewicz,W.;K.;Pazio,A.;Szadkowska,A.;A.;Grela,K.,Chem.Eur.J,2012,18,6465-6469)。
铸模ROMP聚合使得能获得完成的产品。二环戊二烯是铸模聚合常用的单体之一。聚二环戊二烯通过二环戊二烯的聚合获得,其特征在于低水分吸收以及对压力和高温的抗性。这也是为什么交通工具和化学工业的特殊容器越来越多地通过二环戊二烯的(铸模)ROMP聚合制造的原因。
从实际工业应用的角度出发,在它们的合成和纯化期间以及在它们于复分解反应中使用时,(预)催化剂在氧以及水分的存在下稳定是极其重要的。用于烯烃复分解的稳定和活性的(预)催化剂(如G、H和I)的开发使得能明显拓宽这种转化的可能应用范围。然而,这些络合物仍然在惰性气体气氛和无水溶剂中制备并用于复分解反应,因为它们对氧和水分的稳定性是有限的。
据发现,在结构中具有共价金属-氧或金属-硫键的式1所示的钌络合物非常稳定,并且无需任何保护性惰性气体气氛并且在分析级溶剂(proanalysi)中就可以制备:
在合适地激活后,通式1的络合物活跃地催化在空气存在下进行的复分解反应。而且,通式1的络合物仅在由化学物质激活后活跃地催化复分解反应,并且它们非常难以被热激活。这些性质使得能完美地控制引发反应的时间;这样的性质是非常有用的,特别是用于ROMP类型的反应。出人意料地观察到通式1的络合物使得能通过在空气中进行的ROMP类型反应获得聚二环戊二烯,所用的(预)催化剂的量明显低于使用传统络合物的情况。即使是100ppm(百万分之,基于重量)的包含NHC配体(N-杂环碳烯配体)的本发明的络合物,也有效地催化二环戊二烯(DCPD)的聚合。这个量对应于单体比(预)催化剂约65,000:1的摩尔比。因此,(预)催化剂的这个量小于催化剂G的情况的一半(M.Perring,N.B.Bowden Langmuir,2008,24,10480-10487)。而且,包含两个膦配体的本发明的(预)催化剂在聚二环戊二烯的ROMP反应中比结构上类似的络合物G’更具活性。此外,还出人意料地发现,与Hoveyda-Grubbs类型的传统络合物的情况相比,电子受体取代基在(预)催化剂的起始速率的效果上是相反的(K.Grela,S.Harutyunyan,A.Michrowska,Angew.Chem.Int.Ed.2002,41,No.21)。
通过改变其配体影响(预)催化剂的性质的可能性,以及由此导致的对特定反应优化调节其活性的可能性是非常有价值的。通常,与包含SIMes配体的(预)催化剂相比,对于在其结构中包含N-杂环SIPr配体的催化剂观察到更高的稳定性,但是它们在复分解反应中的差异通常不是非常明显。出人意料地发现,N-杂环碳烯配体(NHC)的改变对本发明的通式1的络合物的效率具有很高的效果。据发现,包含NHC配体,SIPr的催化剂1有效地催化闭环复分解的反应以及烯炔(ene-yne)反应,而其证实了在ROMP类型反应和CM(交叉复分解)反应中较低的活性。反过来,包含NHC配体,SIMes的通式1的催化剂非常有效地催化CM反应以及ROMP类型反应,而其证实了在闭环复分解反应中较低的效率。
发明内容
本发明涉及通式1的络合物:
其中
X为阴离子配体;
Y为氧或硫;
L1和L2独立地表示中性配体;
R1为氢、C1-20烷基、C2-20烯基、C2-20炔基或C5-10芳基;
R2、R3、R4和R5独立地为氢、卤素、C1-C16烷基、C1-C16烷氧基、C1-C16全氟烷基、C3-C7环烷基、C2-C16烯基、C5-C14芳基、C5-C14全氟芳基、C3-C12杂环基、-OR6、-NO2、-COOH、-COOR6、-CONR6R7、-SO2NR6R7、-SO2R6、-CHO、-COR6,其中R6和R7独立地为C1-C6烷基、C1-C6全氟烷基、C5-C14芳基、C5-C14全氟芳基;
R2、R3、R4和R5可以任选地连接在一起以形成取代或未被取代的稠和C4-8碳环,或者取代或未被取代的稠和芳环;
条件是如果X为氯,Y为氧,L1为三环己基膦,R1、R2、R3和R4的每一个为氢,并且R5为甲基,则L2与L1不同。
由上述条件从本发明的范围排除的配合物的晶体结构已经由J.N.Coalter etal.,Chem.Commun.2001,1158-1159描述。
优选地,在式1中,取代基R1、R2、R3、R4和R5以及Y如上所定义,并且
X为卤素、-OR8、-O(C=O)R8、-O(SO2)R8,其中R8为C1-C12烷基、C3-C12环烷基、C5-C14芳基,其任选地被C1-C6烷基、C1-C6全卤代烷基、C1-C6烷氧基或卤素中的至少一个取代;
L1具有式PR9(R10)(R11),其中R9、R10和R11独立地为C1-12烷基、C1-12烷氧基、C3-12环烷基、C5-14芳基、C5-14芳氧基、C5-12杂环基;
并且R9、R10和R11中的两个取代基可以额外地连接在一起以形成环系统;或者L1为N-杂环化合物;
L2为N-杂环碳烯配体。
优选地,在式1中,取代基R1、R2、R3、R4和R5以及Y如上所定义,并且
X为卤素、-OR8、-O(C=O)R8、-O(SO2)R8,其中R8为C1-C12烷基、C3-C12环烷基、C5-C14芳基,其任选地被C1-C6烷基、C1-C6全卤代烷基、C1-C6烷氧基或卤素中的至少一个取代;
L1和L2独立地具有式PR9(R10)(R11),其中R9、R10和R11独立地为C1-12烷基、C1-12烷氧基、C3-12环烷基、C5-14芳基、C5-14芳氧基、C5-12杂环基;
并且R9、R10和R11中的两个取代基可以额外地连接在一起以形成环系统;或者
L1或L2为选自包括以下的组中的N-杂环化合物:吡啶、4-(N,N-二甲基氨基)吡啶、3-溴吡啶、哌啶、吗啉、哒嗪、嘧啶、吡嗪、哌嗪、1,2,3-三唑、1,3,4-三唑、1,2,3-三嗪以及1,2,4-三嗪。
更优选地,在式1中,
X为氯;
R1为氢;
R2、R3、R4和R5独立地为氢或硝基;
Y为氧;
L1为三环己基膦、三苯基膦、吡啶或3-溴吡啶;
L2为式2a或2b的配体:
其中:
R12、R13独立地为C1-C12烷基、C3-C12环烷基、C2-C12烯基、C5-C14芳基,其任选地被C1-C6烷基、C1-C6全卤代烷基、C1-C6烷氧基或卤素中的至少一个取代;
R14、R15、R16、R17独立地为氢、C1-C12烷基、C3-C12环烷基、C2-C12烯基、C5-C14芳基,其任选地被C1-C6烷基、C1-C6全卤代烷基、C1-C6烷氧基或卤素中的至少一个取代;并且
R14、R15、R16、R17可以任选地连接在一起以形成取代或未被取代的稠和C4-8碳环,或者取代或未被取代的稠和芳环。
更优选地,在式1中,
X为氯;
R1为氢;
R2、R3、R4和R5独立地为氢或硝基;
Y为氧;
L1为三环己基膦;
L2为SIMes或SIPr配体:
本发明还涉及通式1的络合物作为复分解反应中的(预)催化剂的用途,其中所有的取代基如权利要求1中所定义。
优选地,通式1的络合物用作闭环复分解、交叉复分解、同复分解(homometathesis)、烯炔类型复分解反应中的(预)催化剂;更优选地,通式1的络合物用作开环复分解聚合反应中的(预)催化剂。
本发明还涉及一种用于进行烯烃的复分解反应的方法,其中使至少一种烯烃与作为(预)催化剂的通式1的络合物接触。
优选地,复分解反应在有机溶剂中进行;更优选地,有机溶剂为二氯甲烷、二氯乙烷、甲苯、乙酸乙酯。
优选地,复分解反应在没有任何溶剂的情况下进行。
优选地,复分解反应在化学激活剂的存在下进行;更优选地,化学激活剂为布朗斯台德或路易斯(Lewis)酸或者烷烃或硅烷的卤代衍生物;最优选地,激活剂为氯化氢、三甲基氯硅烷或对甲苯磺酸。
优选地,复分解反应为二环戊二烯的开环复分解聚合。
优选地,通式1的(预)催化剂以固体形式添加至二环戊二烯。
在一优选实施方案中,将二环戊二烯与通式1的(预)催化剂的混合物加热至30℃或更高的温度,由此引发聚合反应。
优选地,起始原料包含至少94wt.%的二环戊二烯。
在优选的方法中,复分解反应在20-120℃的温度下进行。
在优选的方法中,复分解反应进行1分钟-24小时的时间段。
优选地,复分解反应在促进形成交联键的添加剂的存在下进行。
在一优选实施方案中,复分解反应利用等于或小于1000ppm的量的(预)催化剂进行。
在整个本发明的说明书和权利要求书中,如果关于物质的量使用ppm(百万分之)单位,这些单位为基于重量使用的。
由于发明人并不意图为任何特定的催化机理所束缚,因此术语“(预)催化剂”用于表示本发明的络合物可以自身是催化剂,或者可以是为实际催化剂的活性物质的前体。
未如下定义的基团的定义应当具有本领域中已知的最广泛的含义。
术语“任选地取代”表示所关注的基团中的一个或多个氢原子被指定的基团代替,条件是这样的取代使得形成稳定的化合物。
术语“卤代”或“卤素”表示选自F、Cl、Br、I的元素。
术语“烷基”表示饱和的、直链或支链的烃取代基,其具有指定数目的碳原子。烷基的非限制性实例有甲基、乙基、丙基、异丙基、丁基、仲丁基、叔丁基、戊基。
术语“烷氧基”指通过氧原子连接的上文定义的烷基取代基。
术语“全氟烷基”指上文定义的烷基,其中所有的氢都被卤素原子代替,其中卤素原子可以相同或不同。
术语“环烷基”指饱和的单或多环烃取代基,其具有指定数目的碳原子。环烷基取代基的非限制实例有环丙基、环丁基、环戊基、环己基。
术语“烯基”指非环状的、直链或支链的烃链,其具有指定数目的碳原子并且包含至少一个碳碳双键。烯基的非限制性实例有乙烯基、烯丙基、1-丁烯基、2-丁烯基。
术语“芳基”指芳香的、单或多环烃取代基,其具有指定数目的碳原子。芳基的非限制性实例有苯基、均三甲苯基、蒽基。
术语“杂环基”指具有指定数目的碳原子的芳香以及非芳香的环状取代基,其中一个或多个碳原子被诸如氮、磷、硫、氧的杂原子代替,条件是在环中没有两个直接连接的氧或硫原子。非芳香杂环基在环中可以包含4-10个原子,而芳香杂环基在环中必需具有至少5个原子。苯并稠和的系统也属于杂环基。非芳香杂环基的非限制性实例有吡咯烷基、四氢呋喃基、二氢呋喃基、四氢噻吩基、四氢吡喃基、二氢吡喃基、四氢噻喃基、哌啶基、吗啉基、硫代吗啉基、2-吡咯啉基、吲哚啉基。芳香杂环基的非限制性实例有吡啶基、咪唑基、嘧啶基、吡唑基、三唑基、吡嗪基、呋喃基、噻吩基。上述基团可以通过碳原子或氮原子连接。例如,通过结合吡咯获得的取代基可以是吡咯-1-基(N-连接)或吡咯-3-基(C-连接)。
术语“中性配体”指不具有电荷的取代基,其能够与钌原子配位。此类配体的非限制性实例有N-杂环碳烯配体、胺、亚胺、膦及其氧化物、烷基和芳基亚磷酸酯及磷酸酯、醚、烷基和芳基硫化物、配位的烃、卤代烷烃和卤代芳烃。术语“中性配体”还涵盖N-杂环化合物,它们的非限制性实例有吡啶、4-(N,N-二甲基氨基)吡啶(DMAP)、3-溴吡啶、哌啶、吗啉、哒嗪、嘧啶、吡嗪、哌嗪、1,2,3-三唑、1,3,4-三唑、1,2,3-三嗪和1,2,4-三嗪。
中性配体L1和L2可以与亚苄基配体结合,并且它们可以结合在一起以形成二齿配体(L1-L2);而且中性配体可以与阴离子配体X结合以形成多齿配体。
术语“阴离子配体”指能够与金属中心配位的取代基,其带有的电荷能够补偿金属中心的电荷,其中这样的补偿可以是完全或部分的。阴离子配体的非限制性实例有氟化物、氯化物、溴化物或碘化物阴离子、羧酸阴离子、醇和酚阴离子、巯基和硫酚阴离子、(有机)硫酸和(有机)磷酸阴离子以及其酯的阴离子。阴离子配体(X)和中性配体(L1、L2)可以结合在一起,从而形成多齿配体。多齿配体的非限制性实例有二齿配体(X1-L1)、三齿配体(X1-L1-L2)。此类配体的非限制性实例有2-羟基苯乙酮的阴离子、乙酰丙酮的阴离子。
术语“碳烯”指包含具有2的价数和两个未配对价电子的中性碳原子的分子。术语“碳烯”还涵盖碳烯类似物,其中碳原子被其他化学元素代替,例如硼、硅、氮、磷、硫。术语“碳烯”特别地指N-杂环碳烯(NHC)配体。NHC配体的非限制性实例有:
促进形成交联键的优选物质的非限制性实例有叔丁基过氧化物、二叔丁基过氧化物及其混合物。
具体实施方式
催化剂制备的实施例
实施例1合成本发明的络合物1a
将可商购的络合物G’(200mg,0.24mmol)置于烧瓶中,添加二氯甲烷(15ml)。然后添加下式的化合物(58mg,0.48mmol)和三环己基膦(0.136mg,0.49mmol):
将所得的溶液在40℃的温度下搅拌30分钟。将反应混合物冷却并引入填充了硅胶的色谱柱的顶端。将柱用乙酸乙酯-环己烷(0-10体积%)的溶液洗脱,并收集绿色部分。将溶剂蒸发后获得绿色固体状的络合物1a(126mg,65%收率)。
1H NMR(300MHz,CD2Cl2)δppm:16.60(s,1H),7.20(dd,J=1.8Hz,J=7.8Hz,1H),7.14-7.09(m,1H),6.90(d,J=8.4Hz,1H),6.47-6.42(m,1H),2.02-0.85(m,66H).13C NMR:(125MHz,CD2Cl2)δppm:279.34,181.48,149.47,131.29,122.44,117.26,113.05,32.30,29.93,29.65,29.43,28.27,27.89,26.87,23.11,14.28.31P NMR(124.5MHz,CD2Cl2)δppm:36.5.
实施例2合成本发明的络合物2
将可商购的络合物G’(200mg,0.24mmol)置于烧瓶中,并添加无水的脱氧二氯甲烷(6ml)。然后添加下式的化合物(80mg,0.48mmol)和三环己基膦(136mg,0.49mmol):
将所得的溶液在室温下搅拌24小时。将反应混合物引入填充了硅胶的色谱柱的顶端(洗脱液:乙酸乙酯/环己烷,0-10体积%)。将溶剂蒸发后获得棕色固体状的络合物2(144mg,70%收率)。
1H NMR(500MHz,CD2Cl2)δppm:17.05(s,1H),8.21(d,J=2.7Hz,1H),8.00(dd,J=9.3,2.7Hz,1H),6.83(d,J=9.3Hz,1H),1.97-0.77(m,66H).
13C NMR:(125MHz,CD2Cl2)δppm:280.71,185.31,147.04,135.13,126.50,118.18,116.07,35.79,35.31,32.53,32.45,32.38,29.82,29.52,28.16,28.12,28.08,27.77,27.73,27.69,27.32,27.28,27.22,26.68,26.55.
实施例3合成本发明的络合物3
将可商购的络合物G(200mg,0.24mmol)置于烧瓶中,向其中添加二氯甲烷(6ml)。然后添加下式的化合物(63mg,0.47mmol)和三环己基膦(132mg,0.47mmol):
将所得的溶液在40℃的温度下搅拌5小时。将反应混合物引入填充了硅胶的色谱柱的顶端(洗脱液:乙酸乙酯/环己烷,0-10体积%)。将溶剂蒸发后获得绿色固体状的络合物3(140mg,72%收率)。
1H NMR(500MHz,CD2Cl2)δppm:15.85(s,1H),7.07(s,1H),7.00-6.96(m,3H),6.66(d,J=8.4Hz,1H),6.44(dd,J=7.7,1.4Hz,1H),6.24(s,1H),6.20(t,J=7.2Hz,1H),4.01-3.96(m,1H),3.83-3.70(m,2H),3.64-3.59(m,1H),2.63(s,3H),2.54(s,3H),2.50(s,3H),2.35(s,3H),2.27(s,3H),1.66-1.50(m,13H),1.29(s,3H),1.11-0.70(m,20H).13C NMR:(125MHz,CD2Cl2)δppm:281.36,222.21,221.66,180.31,148.30,139.54,139.17,138.78,137.63,137.32,136.98,134.69,130.23,130.05,129.70,129.00,122.38,116.17,111.26,32.52,32.39,29.45,28.92,28.23,28.15,28.12,28.04,27.34,27.03,21.33,21.14,19.40,18.92,18.66,16.76.31P NMR(124.5MHz,CDCl3)δppm:29.11.
实施例4合成本发明的络合物3
将可商购的络合物G(1.0g,1.18mmol)置于烧瓶中,向其中添加二氯甲烷(24ml)。然后添加下式的化合物(141mg,1.17mmol)和三环己基膦(330mg,1.18mmol):
将所得的溶液在40℃的温度下搅拌5小时。将反应混合物引入填充了硅胶的色谱柱的顶端(洗脱液:乙酸乙酯/环己烷,0-10体积%)。将溶剂蒸发后,获得绿色固体状的络合物3(797mg,82%收率)。NMR数据与实施例3一致。
实施例5合成本发明的络合物4
将可商购的络合物G(200mg,0.24mmol)置于烧瓶中,向其中添加二氯甲烷(6ml)。然后添加下式的化合物(78mg,0.47mmol)和三环己基膦(132mg,0.47mmol):
将所得的溶液在40℃的温度下搅拌1小时。将反应混合物引入填充了硅胶的色谱柱的顶端(洗脱液:乙酸乙酯/环己烷,0-10体积%)。将溶剂蒸发后,获得棕色固体状的络合物4(104mg,50%收率)。
1H NMR(500MHz,CD2Cl2)δppm:16.42(s,1H),8.00(dd,J=9.3,2.7Hz,1H),7.53(d,J=2.7Hz,1H),7.12(s,1H),7.06(s,2H),6.69(d,J=9.3Hz,1H),6.22(s,1H),4.07-4.03(m,1H),3.88-3.77(m,2H),3.73-3.67(m,1H),2.64(s,3H),2.56(s,3H),2.51(s,3H),2.39(s,3H),2.27(s,3H),1.64-1.50(m,13H),1.46(m,3H),1.12-0.75(m,20H).13C NMR:(125MHz,CD2Cl2)δppm:282.23(d),220.27,219.73,184.63(d),145.82,139.23(d),139.08,138.89,137.46,136.76,136.69,134.24,134.00,130.55,130.36,129.41(d),125.78,117.59,115.27,52.14(d),51.63(d),34.52,32.77,32.64,29.40,28.91,28.00(m),26.90(d),22.73,21.34,21.01,19.41,18.63,18.53,17.10,14.21.
实施例6合成本发明的络合物5
利用保护性氩气气氛,将固体碳烯络合物4(100mg,0.115mmol)置于Schlenk烧瓶中,然后添加无水的脱氧二氯甲烷(7ml)和无水吡啶(93μl,1.15mmol)。将所得的溶液在40℃的温度下搅拌24小时。将反应混合物引入填充了硅胶的色谱柱的顶端。自那之后,所有的后续操作都在空气中进行,无需使用保护性氩气气氛。将柱用乙酸乙酯-环己烷的溶液(0-10体积%)洗脱。将溶剂蒸发后,获得棕色固体状的络合物5(42mg,54%收率)。
1H NMR(500MHz,CD2Cl2)δppm:16.82(s,1H),8.04(dd,J=9.3,2.7Hz,2H),7.58(s,2H),7.51(m,1H),7.13(d,J=4.5Hz,4H),6.96(s,1H),6.71(d,J=9.3Hz,2H),3.95-3.90(m,4H),2.49(s,9H),2.25(s,9H).13C NMR:(125MHz,CD2Cl2)δppm:284.48,219.30,184.74,150.09,134.63,126.06,123.98,117.54,115.74,35.90,27.16,25.79,24.42,20.93,18.36.
实施例7合成本发明的络合物6
根据络合物3(实施例4中)所述的方法制备络合物6,获得绿色固体状的产物,收率为70%。
1H NMR(500MHz,CD2Cl2)δppm:15.67(s,1H),7.41(d,J=4.7Hz,2H),7.38-7.34(m,2H),7.28(t,J=7.7Hz,1H),6.90-6.87(m,1H),6.67-6.63(m,2H),6.31(dd,J=1.5Hz,J=7.5Hz,1H),6.07(t,J=7.5Hz,1H),4.15-4.04(m,2H),3.94-3.88(m,2H),3.80-3.77(m,1H),3.75-3.68(m,2H),2.33(heptet,J=7.0Hz,1H),1.66-1.45(m,21H),1.41-1.38(m,3H),1.29(d,J=7.0Hz,3H),1.21(d,J=7.0Hz,3H),1.08(d,J=7.0Hz,3H),1.04-0.98(m,9H),0.91(d,J=7.0Hz,3H),0.89-0.85(m,6H),0.79-0.70(m,3H),0.32(d,J=7.0Hz,3H).13CNMR:(125MHz,CD2Cl2)δppm:281.27,224.79,224.23,180.87,152.55,149.53,149.20,148.87,147.47,138.38,136.02,130.06,129.05,125.44,124.45,124.29,124.05,122.74,117.33,111.44,31.87,31.74,29.70,29.03,28.23,27.34,26.89,24.26,23.84,23.03,21.35.
在以下实施例中,所用的特定反应条件如对应的表中所示,并且将合适的络合物用作(预)催化剂。
实施例8闭环复分解
将二烯S1(100mg,0.416mmol)置于Schlenk烧瓶中,然后添加二氯甲烷(DCM)(4ml)和三甲基氯硅烷(10mol%)[在实验编号3和13的情况下,
没有添加化学激活剂],然后添加(预)催化剂(1mol%)。将烧瓶的内容物在40℃的温度下搅拌。将添加了乙烯基-乙醚的原始反应混合物(为了终止反应)利用气相色谱分析。结果如下表所示。
a-收率基于GC分析GC的结果计算
实施例9闭环复分解
将二烯S2(100mg,0.393mmol)置于Schlenk烧瓶中,然后添加DCM(4ml)和三甲基氯硅烷(10mol%)[在实验编号3和4的情况下,没有添加化学激活剂],然后添加(预)催化剂(1mol%)。将烧瓶的内容物在40℃的温度下搅拌。将添加了乙烯基-乙醚的原始反应混合物(为了终止反应)利用气相色谱分析。结果如下表所示。
a-收率基于GC分析GC的结果计算
实施例10交叉复分解
将底物S3a(178mg,1.48mmol)和S3b(510mg,2.96mmol)在DCM(14ml)中的溶液置于Schlenk中,然后添加三甲基氯硅烷(10mol%),然后添加(预)催化剂(1mol%)。将烧瓶的内容物在40℃的温度下搅拌24小时。反应过程通过气相色谱监测。利用柱色谱分离产物P3。结果如下表所示。
实施例11烯炔类型复分解
将底物S4(300mg,1.21mmol)在DCM(12ml)中的溶液置于Schlenk烧瓶中,然后添加三甲基氯硅烷(10mol%)[在实验编号4的情况下,没有添加化学激活剂],然后添加(预)催化剂(1mol%)。将烧瓶的内容物在40℃的温度下搅拌。利用柱色谱分离产物P4。结果如下表所示。
a-收率基于GC分析GC的结果计算
实施例12开环复分解聚合
制备聚二环戊二烯:在空气中,将二环戊二烯(1g,7.56mmol)装入聚合瓶中,融化后,将其置于28℃的油浴中。然后添加适量的(预)催化剂(实验2、3、6-11中作为固体,或者作为最少量二氯甲烷中的溶液)以及化学激活剂(相对于(预)催化剂的4当量,在实验1-3的情况下没有添加激活剂),然后将该瓶转移至适当温度(如下表所示)的浴,并保持适当的时间(如下表所示)。然后向瓶中添加甲苯并回流,以洗去未反应的二环戊二烯。将不溶的聚二环戊二烯,P5用甲苯洗涤并减压干燥12h。实验结果如下表所示。
a–以以下形式适量添加:纯TMSCl,1,4-二噁烷中的4M HCl,1,4-二噁烷中的1M p-TsOH
实施例13开环复分解聚合
制备聚二环戊二烯:在空气中,将二环戊二烯(10g,76mmol)装入聚合瓶中,融化后,将其置于28℃的油浴中。然后添加(预)催化剂4(作为最少量二氯甲烷中的溶液),并将该瓶在28℃的浴中保持24h。未观察到底物转化(瓶仅包含液态单体)。然后向瓶添加HCl(相对于(预)催化剂的4单量,1,4-二噁烷中的溶液),并将瓶转移至60℃的浴。10分钟后,向瓶添加甲苯并回流以洗去未反应的二环戊二烯。将不溶的聚二环戊二烯(P5)用甲苯洗涤并减压干燥12h。收率>99%。
如实施例8-13所示,在化学激活后,本发明的通式1的络合物有效地促进烯烃复分解反应。特别地,络合物3和4在二环戊二烯的开环聚合(ROMP)中表现出非常高的效率。由于通式1的络合物的延迟引发特征,可以以非常高的程度控制聚合反应的引发。根据文献数据的结果,式D和D’的现有技术络合物表现出类似的性质和效率。然而,这些络合物通过使用合适的铊衍生物合成,其存在健康问题(合成中使用的铊化合物毒性很高),并且使得这样的络合物的合成更耗时和复杂化。通式1的络合物的性质可以通过选择合适的配体加以明显的改变。此外,通式1的络合物的高稳定性使得可以在氧的存在下进行聚合过程;由于这一点,无需将可商购的二环戊二烯脱氧,并且在方法自身过程中无需使用惰性气体气氛。出人预料地发现,聚合反应的过程(聚合物的形式)可以通过选择激活剂来控制。例如,如果使用氯化氢用于激活,使用200ppm的络合物4使得可以在10分钟内获得坚硬固体状的聚合物;而使用对甲苯磺酸(p-TsOH)则使得可以获得凝胶形式的聚合物。一些通式1的络合物额外优势在于其在纯的液态DCPD中的优异溶解性。这使得无需事先将(预)催化剂溶于有机溶剂中。如实施例8、12和13所示,包含电子受体基团的通式1的络合物引发复分解反应比未取代的络合物要慢。因此,与Hoveyda-Grubbs类型的传统络合物(H和I)相比,这个效果是相反的。如实施例12和13所示,这在DCPD聚合的情况下具有重要意义。络合物4与单体的混合物可以甚至在计划开始铸模聚合前24h制备,而络合物3在这时使得单体发生部分聚合。
Claims (21)
1.通式1的络合物
其中
X为卤素;
Y为氧;
L1具有式PR9(R10)(R11),其中R9、R10和R11独立地为C3-12环烷基,或者L1为吡啶;
L2为式2a的配体:
其中R12、R13独立地为苯基,其任选地被C1-C6烷基中的至少一个取代;
R14、R15、R16、R17为氢;
R1为氢或-C1-20烷基;
R2、R3、R4和R5独立地为氢、C1-C16烷基或-NO2。
2.权利要求1的络合物,其特征在于,在式1中,
X为氯;
R1为氢;
R2、R3、R4和R5独立地为氢或-NO2;
Y为氧;
L1为三环己基膦或吡啶;
L2为式2a的配体:
其中
R12、R13独立地为苯基,其任选地被C1-C6烷基中的至少一个取代;
R14、R15、R16、R17为氢。
3.权利要求1或2的络合物,其特征在于,在式1中,
X为氯;
R1为氢;
R2、R3、R4和R5独立地为氢或-NO2;
Y为氧;
L1为三环己基膦;
L2为SIMes或SIPr配体:
4.权利要求1的通式1的络合物在复分解反应中作为预催化剂或催化剂的用途。
5.权利要求4的用途,其特征在于,所述通式1的络合物用作闭环复分解、交叉复分解、同复分解或烯炔类型复分解反应中的预催化剂或催化剂。
6.权利要求4的用途,其特征在于,所述通式1的络合物用作开环复分解聚合反应中的预催化剂或催化剂。
7.一种用于进行烯烃的复分解反应的方法,其特征在于,使至少一种烯烃与作为预催化剂或催化剂的根据权利要求1的通式1的络合物接触。
8.权利要求7的方法,其特征在于,所述复分解反应在有机溶剂中进行。
9.权利要求8的方法,其特征在于,所述有机溶剂为二氯甲烷、二氯乙烷、甲苯、乙酸乙酯。
10.权利要求7的方法,其特征在于,所述复分解反应在没有任何溶剂的情况下进行。
11.权利要求7-10中任一项的方法,其特征在于,所述复分解反应在化学激活剂的存在下进行。
12.权利要求11的方法,其特征在于,所述化学激活剂为布朗斯台德或路易斯酸或者烷烃或硅烷的卤代衍生物。
13.权利要求12的方法,其特征在于,所述激活剂为氯化氢、三甲基氯硅烷或对甲苯磺酸。
14.权利要求7-13中任一项的方法,其特征在于,所述复分解反应为二环戊二烯的开环复分解聚合。
15.权利要求14的方法,其特征在于,通式1的预催化剂或催化剂以固体形式添加至二环戊二烯。
16.权利要求14-15中任一项的方法,其特征在于,将二环戊二烯与通式1的预催化剂或催化剂的混合物加热至30℃或更高的温度,由此引发所述聚合反应。
17.权利要求14-16中任一项的方法,其特征在于,起始原料包含至少94wt.%的二环戊二烯。
18.权利要求7-17中任一项的方法,其特征在于,所述复分解反应在20-120℃的温度下进行。
19.权利要求7-18中任一项的方法,其特征在于,所述复分解反应进行1分钟-24小时的时间段。
20.权利要求7-19中任一项的方法,其特征在于,所述复分解反应在促进形成交联键的添加剂的存在下进行。
21.权利要求7-20中任一项的方法,其特征在于,所述复分解反应利用等于或小于1000ppm的量的所述预催化剂或催化剂进行。
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PCT/EP2013/065839 WO2014016422A1 (en) | 2012-07-27 | 2013-07-26 | Novel ruthenium complexes, their use in the metathesis reactions, and a process for carrying out the metathesis reaction |
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PL238806B1 (pl) | 2015-09-30 | 2021-10-04 | Apeiron Synthesis Spolka Akcyjna | Kompleks rutenu i sposób jego wytwarzania, związek pośredni stosowany w tym sposobie oraz zastosowanie kompleksu rutenu i związku pośredniego w metatezie olefin |
US10857530B2 (en) * | 2015-12-10 | 2020-12-08 | Umicore Ag & Co. Kg | Olefin metathesis catalysts |
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TWI794520B (zh) | 2018-06-29 | 2023-03-01 | 日商住友電木股份有限公司 | 作為 3d 列印材料之聚環烯烴單體及由能夠產生光酸之化合物活化之催化劑 |
JP7466908B2 (ja) * | 2018-06-29 | 2024-04-15 | アペイロン シンセシス エス アー | オレフィンメタセシス用の触媒前駆体としての有機ルテニウム錯体 |
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KR20220042380A (ko) | 2019-07-25 | 2022-04-05 | 프로메러스, 엘엘씨 | 광학재료로서의 안정적인 폴리시클로올레핀 중합체 및 무기 나노입자 조성물 |
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IL236128A (en) | 2017-07-31 |
JP6121533B2 (ja) | 2017-04-26 |
EP2877478A1 (en) | 2015-06-03 |
SG11201408224SA (en) | 2015-01-29 |
EP2877478B1 (en) | 2016-11-16 |
AU2013294909B2 (en) | 2015-11-19 |
WO2014016422A1 (en) | 2014-01-30 |
PL400162A1 (pl) | 2014-02-03 |
JP2015525776A (ja) | 2015-09-07 |
RU2586213C1 (ru) | 2016-06-10 |
CN104428306A (zh) | 2015-03-18 |
IL236128A0 (en) | 2015-02-01 |
CA2875956C (en) | 2016-01-19 |
PL2877478T3 (pl) | 2017-05-31 |
US20150158896A1 (en) | 2015-06-11 |
US9328132B2 (en) | 2016-05-03 |
KR101749238B1 (ko) | 2017-06-20 |
AU2013294909A1 (en) | 2015-01-22 |
KR20150023672A (ko) | 2015-03-05 |
CA2875956A1 (en) | 2014-01-30 |
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