CN101298462A - 含硫的复分解催化剂 - Google Patents
含硫的复分解催化剂 Download PDFInfo
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- CN101298462A CN101298462A CNA2008100956077A CN200810095607A CN101298462A CN 101298462 A CN101298462 A CN 101298462A CN A2008100956077 A CNA2008100956077 A CN A2008100956077A CN 200810095607 A CN200810095607 A CN 200810095607A CN 101298462 A CN101298462 A CN 101298462A
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000005649 metathesis reaction Methods 0.000 title claims description 19
- 239000005864 Sulphur Substances 0.000 title claims description 8
- 239000003054 catalyst Substances 0.000 title description 14
- -1 Olefin metal complex Chemical class 0.000 claims abstract description 44
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 239000003446 ligand Substances 0.000 claims abstract description 8
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 8
- 239000011593 sulfur Substances 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- 229910052762 osmium Inorganic materials 0.000 claims abstract description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 49
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 150000002148 esters Chemical class 0.000 claims description 14
- 229910052736 halogen Inorganic materials 0.000 claims description 12
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical group SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 claims description 6
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 4
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical group [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 claims description 3
- 229940124530 sulfonamide Drugs 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 3
- 150000003457 sulfones Chemical class 0.000 claims description 3
- 150000003555 thioacetals Chemical class 0.000 claims description 3
- 150000003568 thioethers Chemical class 0.000 claims description 3
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- GNVMUORYQLCPJZ-UHFFFAOYSA-M Thiocarbamate Chemical compound NC([S-])=O GNVMUORYQLCPJZ-UHFFFAOYSA-M 0.000 claims description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- RMGVZKRVHHSUIM-UHFFFAOYSA-N dithionic acid Chemical compound OS(=O)(=O)S(O)(=O)=O RMGVZKRVHHSUIM-UHFFFAOYSA-N 0.000 claims description 2
- 125000002462 isocyano group Chemical group *[N+]#[C-] 0.000 claims description 2
- 150000002891 organic anions Chemical class 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- OKQKDCXVLPGWPO-UHFFFAOYSA-N sulfanylidenephosphane Chemical compound S=P OKQKDCXVLPGWPO-UHFFFAOYSA-N 0.000 claims description 2
- 150000007970 thio esters Chemical class 0.000 claims description 2
- 125000005323 thioketone group Chemical group 0.000 claims description 2
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 claims description 2
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical group NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 125000004122 cyclic group Chemical group 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract 2
- 230000007935 neutral effect Effects 0.000 abstract 1
- 125000003107 substituted aryl group Chemical group 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 26
- 239000000243 solution Substances 0.000 description 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 6
- 150000002367 halogens Chemical class 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 125000005842 heteroatom Chemical group 0.000 description 5
- 229950001891 iprotiazem Drugs 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 101100519284 Cercospora nicotianae PDX1 gene Proteins 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 101100277598 Sorghum bicolor DES3 gene Proteins 0.000 description 3
- 238000005865 alkene metathesis reaction Methods 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 125000002524 organometallic group Chemical group 0.000 description 3
- 150000004714 phosphonium salts Chemical class 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 3
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 description 3
- 238000010898 silica gel chromatography Methods 0.000 description 3
- 101150073238 sor1 gene Proteins 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 2
- 230000035495 ADMET Effects 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 238000010535 acyclic diene metathesis reaction Methods 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 125000004414 alkyl thio group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 125000005110 aryl thio group Chemical group 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical class CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 2
- 150000003016 phosphoric acids Chemical class 0.000 description 2
- 239000002516 radical scavenger Substances 0.000 description 2
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- 238000011160 research Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- ZVJHJDDKYZXRJI-UHFFFAOYSA-N 1-Pyrroline Chemical compound C1CC=NC1 ZVJHJDDKYZXRJI-UHFFFAOYSA-N 0.000 description 1
- XQFYGXFPKONEPY-UHFFFAOYSA-N 2,3-diphenylfuran Chemical class O1C=CC(C=2C=CC=CC=2)=C1C1=CC=CC=C1 XQFYGXFPKONEPY-UHFFFAOYSA-N 0.000 description 1
- NAMYKGVDVNBCFQ-UHFFFAOYSA-N 2-bromopropane Chemical compound CC(C)Br NAMYKGVDVNBCFQ-UHFFFAOYSA-N 0.000 description 1
- YCMLQMDWSXFTIF-UHFFFAOYSA-N 2-methylbenzenesulfonimidic acid Chemical compound CC1=CC=CC=C1S(N)(=O)=O YCMLQMDWSXFTIF-UHFFFAOYSA-N 0.000 description 1
- 125000003682 3-furyl group Chemical group O1C([H])=C([*])C([H])=C1[H] 0.000 description 1
- 125000001541 3-thienyl group Chemical group S1C([H])=C([*])C([H])=C1[H] 0.000 description 1
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 1
- 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 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
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- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
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- 241000219289 Silene Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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- 150000001345 alkine derivatives Chemical class 0.000 description 1
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- 208000026935 allergic disease Diseases 0.000 description 1
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- 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
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- 125000004429 atom Chemical group 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
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- 150000001925 cycloalkenes Chemical class 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
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
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- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
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- OFSLDYNRTCQKFU-UHFFFAOYSA-N ethyl 2-methylcyclopentene-1-carboxylate Chemical class CCOC(=O)C1=C(C)CCC1 OFSLDYNRTCQKFU-UHFFFAOYSA-N 0.000 description 1
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- 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
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- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 1
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- REPWBKQJAMXHFL-UHFFFAOYSA-N phenylphosphane;hydrobromide Chemical class [Br-].[PH3+]C1=CC=CC=C1 REPWBKQJAMXHFL-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
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- 239000011541 reaction mixture Substances 0.000 description 1
- 238000006798 ring closing metathesis 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
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- 239000011780 sodium chloride Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 150000003558 thiocarbamic acid derivatives Chemical class 0.000 description 1
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Abstract
本发明涉及含硫的复分解催化剂,具体而言,本发明涉及式(I)的新型过渡金属络合物,其中各基团如说明书和权利要求书中所定义,本发明还涉及制备这些过渡金属络合物的方法,和所述过渡金属络合物在复分解反应中作为催化剂的应用。
Description
技术领域
本发明涉及式(I)的新型过渡金属络合物、制备这些过渡金属络合物的方法、和该过渡金属络合物在复分解(metathesis)反应中作为催化剂的应用
背景技术
复分解反应是指其中在双键或三键上的正式(formal)取代基被交换的化学反应。复分解反应包括非环状二烯的寡聚反应和聚合反应(ADMET),或环烯烃的聚合反应(ROMP),以及通过闭环复分解反应(Ring-ClosingMetathesis,RCM)合成不同大小的环状化合物。此外,已知不同烯烃的交叉复分解反应(crossed metatheses,CM)及烯烃和炔烃的复分解反应(烯-炔复分解反应)。大量基础研究对理解这种过渡金属催化的反应做出了显著的贡献(综述参见:Handbook of Metathesis,Ed.R.H.Grubbs,WILEY-VCH,Weinheim,2003)。
许多催化剂系统可用于烯烃复分解反应。特别是Schrock的研究提出钼的和钨的亚烷基络合物作为第一种明确定义的催化剂(J.S.Murdzek,R.R.Schrock,Organometallics,1987,6,1373-1374)。然而,发现这些络合物的缺点为其高敏感性。近来,已经建立了具有膦配体的钌-亚烷基络合物(P.Schwab等Angew.Chem.Int.Ed.Engl.1995,34,2039-2041;P.A.van derSchaaf等J.Organometallic Chem.2000,606,65-74)。这些络合物对极性官能团具有高耐受性,并且对空气和水稳定。作为配体的N-杂环卡宾(NHC)的引入不仅使这些系统的活性进一步增大,而且由于配体球(ligand sphere)显著的可变性,为该反应提供了新的控制方法(DE 19815275和T.Weskamp,W.C.Schattenmann,M.Spiegler,W.A.Herrmann Angew.Chem.1998,110,263-2633)。通过添加配位上更不稳定的配体进一步显著提高了催化活性(DE 19902439和T.Weskamp,F.J.Kohl,W.Hieringer,D.Gleich,W.A.Herrmann Angew.Chem.,1999,111,2573-2576)。代表性的实例为络合物A和B。
Gessler等人(Tetrahedron Lett.2000,41,9973-9976)和Garber等人(J.Am.Chem.Soc.2000,122,8168-8179)描述了同时含有异丙氧基亚苄基配体和N-杂环卡宾配体的钌络合物。这些所谓的“绿色”催化剂具有更高的稳定性且可以任选地循环使用。
专利WO 9900397描述了特别适合ROMP的催化剂C和D。这种高活性复分解催化剂的其他实例(E和F)描述于申请WO 2005094345中。
文献中描述了侧链中具有含硫单元的复分解催化剂的一些实例(P.A.van der Schaaf等J.Organometallic Chem.2000,606,65-74中的络合物H、专利CN 2005100803792中的络合物J1和M.Bieniek等J.Organomet.Chem.2006,691,5289中的络合物J2)。
然而,仍然需要新的烯烃复分解反应催化剂系统,所述催化剂系统稳定且此外还具有可控的高活性,并且可以用作现有催化剂的替代催化剂。特别是从整体上来看,从经济的和/或生态学的角度上考虑,所述催化剂应该优于现有技术的催化剂。
发明内容
出人意料地,目前已发现了式(I)的化合物
其中
M为Ru或Os,优选为Ru,
L和L’相同或不同,且分别独立地为不带电荷的电子供体,
X1和X2相同或不同,且分别为阴离子配体,
R是氢,环状、直链或支链烷基基团或任选地被取代的芳基基团,
Z是与金属直接配位的含硫单元,并且
A是共价连接Z单元和卡宾碳的桥,且n是0或1,优选为0。
使用本发明络合物的烯烃复分解反应的特征是在室温下的低活性和活性随温度升高而特别快速地升高。因此,本发明的化合物可以用作可热切换的(thermally switchable)催化剂。此外,本发明的络合物为对空气稳定的化合物,并具有卓越的热稳定性,且其活性与现有催化剂相比没有显著降低。
不带电荷的电子供体配体L和L’的变化使络合物的活性和选择性可以被适当地控制。本发明的络合物优选具有饱和或不饱和的NHC(N-杂环卡宾)作为L的配体。如同它们的配体球造型(modeling of the ligand sphere)具有多样性,它们还特别适合提供高的催化剂活性。在以下文献中通过举例的方式描述了所述配体:DE 19815275和T.Weskamp,W.C.Schattenmann,M.Spiegler,W.A.Herrmann Angew.Chem.1998,110,263-2633;DE 19902439和T.Weskamp,F.J.Kohl,W.Hieringer,D.Gleich,W.A.Herrmann Angew.Chem.,1999,111,2573-2576;EP 1180108。L’可以是L,或采用在WO9951344中列出的结构作为不带电荷的电子供体配体。
在本发明的络合物中,上述含硫的Z单元优选为选自以下的基团:硫醇、硫醚、硫缩醛、二硫化物、二硫代羧酸、硫酯、硫酮、硫醛、硫代氨基甲酸酯(thiocarbamates)、硫代氨基甲酸乙酯(thiourethanes)、硫化膦、硫代磷酸盐(酯)、硫代膦酸盐(酯)、磺酸盐(酯)、砜、磺酰胺、或含硫杂环,同时必须保证化合物Z-M,优选Z-Ru,是通过硫原子或硫上的氧原子形成的。当硫或氧原子与金属原子间的配合闭环形成五元、六元或七元环时,这将是优选的。
对于桥接分子部分A,本领域的技术人员可以原则上使用看来可用于本发明目的的基团:优选为由2至4个碳原子组成的碳骨架,特别优选为C2桥,其中两个碳原子可以具有sp2杂化,且所述基团有益地形成三元、四元、五元、六元、七元或八元环系统的一部分。所述环系统可任选具有一个或多个杂原子。可用的这种杂原子特别是氧、硫或氮原子。除所述sp2杂化外它们可以进一步不饱和,且优选为芳香性的(aromatic nature)。它们可以被其他基团单取代或多取代,特别是选自(C1-C8)-烷基、(C1-C8)-烷氧基、(C6-C18)-芳氧基、HO-(C1-C8)-烷基、(C2-C8)-烷氧基烷基、(C6-C18)-芳基、(C7-C19)-芳烷基、(C3-C18)-杂芳基、(C4-C19)-杂芳烷基、(C1-C8)-烷基-(C6-C18)-芳基、(C1-C8)-烷基-(C3-C18)-杂芳基、(C3-C8)-环烷基、(C1-C8)-烷基-(C3-C8)-环烷基、(C3-C8)-环烷基-(C1-C8)-烷基的基团。
此外,环系统也可以具有一个或多个取代基,特别是选自卤素、羟基、羧酸、酯、硅醚(silyl ether)、硫醚、硫缩醛、亚胺、硅烯醇醚、铵盐、酰胺、腈、全氟烷基基团、酮、醛,氨基甲酸盐(酯)、碳酸盐(酯)、氨基甲酸乙酯、磺酸盐(酯)、砜、磺酰胺、硝基基团、有机硅烷单元、膦酸盐(酯)和磷酸盐(酯)基团、和鏻盐(phosphonium salt)。
在本发明的络合物中,阴离子配体X1和X2优选为选自卤离子(特别是F-、Cl-、Br-)、拟卤离子、氢氧根(hydroxides)、烷氧基(alkoxide)或氨基(amides)(RO-、R2N-)、酚、硫醇、苯硫酚、羧酸根、碳酸根、磺酸根、硫酸根、磷酸根和膦酸根、烯丙基和环戊二烯基的无机或有机阴离子,拟卤离子优选为表示氰根、硫氰根、氰酸根、异氰酸根和异硫氰酸根,其中R基团满足以下定义。
特别优选通式(II)和(III)的络合物。
在这些络合物中,Z为-S-、-S(O)-和S(O)2-,
X1和X2采用上述定义,
Y、R、R’和R1至R4分别是独立地选自氢、(C1-C8)-烷基、(C1-C8)-烷氧基、(C6-C18)-芳氧基、HO-(C1-C8)-烷基、(C2-C8)-烷氧基烷基、(C6-C18)-芳基、(C7-C19)-芳烷基、(C3-C18)-杂芳基、(C4-C19)-杂芳烷基、(C1-C8)-烷基-(C6-C18)-芳基、(C1-C8)-烷基-(C3-C18)-杂芳基、(C3-C8)-环烷基、(C1-C8)-烷基-(C3-C8)-环烷基、(C3-C8)-环烷基-(C1-C8)-烷基的基团。此外,R’和R1至R4基团可以分别独立地为:(环)烷硫基(alkylthio)、(杂)芳硫基(arylthio)、烷基/芳基磺酰基、烷基/芳基亚磺酰基(sulphynyl),每种情况下任选地被以下基团取代:(C1-C8)-烷基、(C1-C8)-烷氧基、(C6-C18)-芳氧基、HO-(C1-C8)-烷基、(C2-C8)-烷氧基烷基、(C6-C18)-芳基、全氟烷基、卤素、(C1-C8)-酰氧基、(C1-C8)-酰基(C1-C8)-烷氧基羰基、(C1-C8)-烷基磺酰基或(C1-C8)-烷基亚磺酰基、(C6-C18)-芳基磺酰基或(C6-C18)-芳基亚磺酰基。
R1至R4同样可以是硝基、硫酸盐(酯)、胺、铵盐、磷酸盐(酯)和鏻盐。
R’基团可以与一个或多个彼此相连的R1到R4基团一起出现在环状化合物中。R1基团也可以与Y基团结合以形成(杂)环化合物。
本发明的化合物,特别是式(I)和(II)的化合物,优选地通过式(IV)的化合物中的膦配体和式(V)的配体间的交换反应制备。
其中每个基团都采用上述定义,且PR3为膦配体,优选为三环己基膦。
本发明的化合物,特别是式(I)和(II)的化合物,是由式(VI)的化合物优选在溶剂中制备,更优选在甲苯、苯、四氢呋喃或二氯甲烷中制备,最优选在二氯甲烷中制备。优选地,所述反应在能清除膦的化合物的存在下进行,更优选在CuCl2和CuCl的存在下进行,最优选在CuCl的存在下进行。基于式(IV)的化合物,优选在等摩尔量或过量的膦清除剂的存在下进行。当使用的膦清除剂为CuCl时,特别优选使用1至1.5当量。基于式(IV)的化合物,优选使用0.9至3当量的式(V)的化合物,特别优选使用1至2当量。反应优选在20至80℃的温度下进行,更优选在30至50℃的温度下进行。反应优选在惰性气体中进行,例如氮气或氩气。
本发明的化合物(I),特别是式(II)和(III)的化合物,可以用作复分解反应催化剂。例如,它们可以用于闭环复分解反应。更优选将它们用于ROMP和ADMET聚合反应。
烷基基团特别是指(C1-C8)-烷基基团,例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、戊基、己基、庚基或辛基,包括它们所有的键合异构体(bonding isomer)。
(C1-C8)-烷氧基基团与(C1-C8)-烷基基团相对应,条件是其通过氧原子与分子相连接。
(C2-C8)-烷氧基烷基是指烷基链被至少一个氧官能团阻断、但是两个氧原子不能互相连接的基团。碳原子的数目是指基团中存在的碳原子的总数。
(C3-C5)-亚烷基桥是具有三至五个碳原子的碳链,该链通过两个不同碳原子与所述分子相连。
以上段落所述的基团可以被卤素和/或包含氮、氧、磷、硫、硅原子的基团单取代或多取代。这些基团特别是在它们的链中具有一个或多个这些杂原子,或通过这些杂原子之一与所述分子相连的上述种类的烷基基团。
(C3-C8)-环烷基是指环丙基、环丁基、环戊基、环己基或环庚基基团等。它们可以被一个或多个卤素和/或包含氮、氧、磷、硫、硅原子的基团取代和/或为在环中具有氮、氧、磷、硫原子的基团,例如1-、2-、3-、4-哌啶基,1-、2-、3-吡咯烷基,2-、3-四氢呋喃基,2-、3-、4-吗啉基。
(C3-C8)-环烷基-(C1-C8)-烷基基团指通过上述烷基基团与所述分子相连的上述环烷基基团。
在本发明中,(C1-C8)-酰氧基是指具有最多8个碳原子、通过COO官能团与所述分子相连的如上所定义的烷基基团。
在本发明中,(C1-C8)-酰基是指最多具有8个碳原子、通过CO官能团与所述分子相连的如上所定义的烷基基团。
芳基基团特别是指(C6-C18)-芳基基团,其为具有6到18个碳原子的芳香基团。特别地,其包括例如苯基、萘基、蒽基、菲基、联苯基基团的化合物,或与所述分子稠合的上述类型的系统,例如任选被卤素、(C1-C8)-烷基、(C1-C8)-烷氧基、NH2、NH(C1-C8)-烷基、N((C1-C8)-烷基)2、OH、CF3、NH(C1-C8)-酰基、N((C1-C8)-酰基)2、(C1-C8)-酰基、(C1-C8)-酰氧基所取代的茚基(indenyl)系统。
(C7-C19)-芳烷基基团是通过(C1-C8)-烷基基团与所述分子相连的(C6-C18)-芳基基团。
在本发明中,(C3-C18)-杂芳基基团指包含3至18个碳原子并在环中包含杂原子(例如氮、氧或硫)的五元,六元或七元的芳环系统。这些芳香杂环化合物特别是指例如1-、2-、3-呋喃基,1-、2-、3-吡咯基,1-、2-、3-噻吩基,2-、3-、4-吡啶基,2-、3-、4-、5-、6-、7-吲哚基,3-、4-、5-吡唑基,2-、4-、5-咪唑基,吖啶基、喹啉基、菲啶基、2-、4-、5-、6-嘧啶基的基团。该基团可以被与以上芳基基团所述相同的基团所取代。
(C4-C19)-杂芳烷基是指与(C7-C19)-芳烷基基团对应的芳香杂环系统。
可用的卤素(Hal)包括氟、氯、溴和碘。
实施例
1.合成2-(异丙硫基)苯甲酸
在剧烈搅拌下,将KOH颗粒(17.3g,433mmol)缓慢加入硫代水杨酸(16.7g;109mmol;Fluka)和异丙基溴(20.0g;163mmol)的乙醇(125ml)悬浮液中。搅拌6小时后,将反应混合物倾入冰水混合物(1200ml)中,并用浓盐酸(约50ml)酸化。将沉淀的产物过滤,经50%乙醇水溶液(2×100ml)洗涤,并减压干燥。产量6.4g(30%)。
IR(膜):v 3084,3058,2962,2924,2865,1828,1625,1588,1463,1365,1243,1197,1155,1049,991,912,769,746cm-1;1H NMR(200MHz,DMSO-d6)δ1.74-1.82(d,6H,J=2.2Hz),4.02-4.12(七重峰,1H,J=6.6Hz),7.70(m,1H),7.66-7.72(m,1H),7.95-8.00(m,2H),8.36-8.42(m,1H);13CNMR(50MHz,DMSO-d6)δ22.4,35.3,124.6,128.3,131.1,132.1,140.3,167.2,205.6;MS(EI)m/z(rel强度)196(21,[M]+.),154(13),137(11),136(100),108(21),69(8),43(13),41(13),39(12);HRMS(EI):[M]+计算(C7H12O2S):196.05580;实测196.05604。
2.合成2-(异丙硫基)苯甲醛
在剧烈搅拌和氩气条件下,将硼烷-二甲基硫醚络合物(0.8ml,8mmol)于3℃下滴加到2-(异丙硫基)苯甲酸(0.98g,5mmol)的THF(10ml)溶液中。在冰浴中连续搅拌30分钟后,将反应置于室温下额外24小时。小心地加入甲醇(1.5ml),并将反应溶液减压浓缩。将残渣溶于二乙醚(50ml),并用饱和K2CO3溶液和NaCl溶液洗涤。用醚进一步萃取水溶液,将合并的有机相用MgSO4干燥并过滤,减压除去溶剂。将残渣溶于二氯甲烷(30ml),小心地与PCC(1.20g,5.6mmol)混合,并在室温下搅拌36小时。除去溶剂后,用硅胶柱色谱(10∶1己烷∶乙酸乙酯)纯化残渣。产量0.69g(76%)。
IR(膜):v 3686,3601,3362,3063,2968,2929,2867,2744,1950,1692,1648,1587,1559,1460,1442,1383,1368,1287,1242,1195,1156,1128,1073,1062,1052,1039,931,879,845,825,777,679,660,635,509cm-1;1H NMR(200MHz,CDCl3)δ1.30-1.40(d,6H,J=6.6Hz),3.38-3.48(七重峰,1H,J=6.8Hz),7.25-7.60(m,3H),7.84-7.92(m,1H),10.54(d,1H,J=0.63Hz);13CNMR(50MHz,CDCl3)δ22.9,38.8,126.7,130.1,132.4,133.8,135.8,140.3,191.9;MS(EI)m/z(rel强度)180(66,[M]+.),165(18),138(49),137(100),110(35),109(41),104(57),69(11),66(11),65(26),43(25),41(19),39(17);HRMS(EI):[M]+计算(C10H12OS):180.07122;实测180.07148。
3.合成2-异丙基亚磺酰基苯甲醛
将2-(异丙硫基)苯甲醛(0.33g,1.83mmol)的二氯甲烷(10ml)溶液与KHCO3水溶液(1.18g溶于10ml H2O)混合。在剧烈搅拌下,滴加溴(0.310g,1.93mmol)的二氯甲烷(1.5ml)溶液。连续搅拌20分钟后,加入一匙尖Na2SO3,除去有机相,用饱和NaCl溶液洗涤,用MgSO4干燥并过滤,并减压除去溶剂。用硅胶柱色谱(3∶1至1∶1己烷∶乙酸乙酯)纯化残渣。沉淀出淡黄色油状产物。产量0.304g(85%)。
IR(膜):v 3447,2963,2917,2864,2738,1702,1628,1607,1482,1439,1380,1264,1227,1183,1158,1121,1105,1037,992,950,932,852,803,751,697,635,593,578,535,506,446,418cm-1;1H NMR(200MHz,CDCl3)δ0.86-0.94(d,3H,J=6.8Hz),1.50-1.56(d,3H,J=7.1Hz),2.90-3.10(七重峰,1H,J=6.8Hz),7.60-8.00(m,1H),8.16-8.22(m,1H),10.01-10.06(d,1H J=0.63Hz);13C NMR(50MHz,CDCl3)δ21.7,38.2,124.4,130.5,133.9,135.2,144.9,198.5;MS(EI)m/z(rel强度)180(66,[M]+),165(18),138(49),137(100),110(35),109(41),104(57),69(11),66(11),65(26),43(25),41(19),39(17);HRMS(EI):[M]+计算(C7H10O2S):178.08162;实测178.08148。
4.Wittig烯化作用
在-78℃及氩气气氛下,将n-BuLi(1.5M,1.4ml,2.07mmol)滴加到甲基三苯基溴化鏻(0.690g,1.93mmol,Aldrich)的THF(8ml)悬浮液中。在一小时内将黄色反应液加热至室温。在重新冷冻至-78℃后,加入适合的醛(1.39mmol)的THF(5ml)溶液,然后缓慢加热混合物至室温并在此温度下搅拌1小时。在加入饱和NH4Cl溶液后,用乙酸乙酯(4×20ml)萃取水相。用MgSO4干燥合并的有机相,并减压除去溶剂。用硅胶柱色谱(2∶8环己烷∶乙酸乙酯)纯化残渣。
4a.2-异丙硫基-1-乙烯基苯
产量为74%。
IR(膜):v 3084,3058,2962,2924,2865,1828,1625,1588,1463,1365,1243,1197,1155,1049,991,912,769,746cm-1;1H NMR(500MHz,CDCl3)δ1.26(d,6H,J=6.7Hz),3.24-3.33(七重峰,1H,J=6.7Hz),5.30(dd,1H,J=1.2,11Hz),5.67(dd,1H,J=1.2,17.5Hz),7.18-7.27(m,2H),7.35(dd,1H,J=11,17.5Hz),7.42-7.47(m,1H),7.52-7.57(m,1H);13C NMR(125MHz,CD3CCD3)δ23.1,38.8,115.3,125.9,127.5,127.9,133.8,133.9,135.3,140.2;MS(EI)m/z(rel强度)178(9,[M]+.),136(10),135(100),134(14),91(18),77(2),65(1),43(2);HRMS(EI):[M]+计算(C11H14S):178.08162;实测178.08148。
4b.2-异丙基亚磺酰基-1-乙烯基苯
产量71%。
IR(膜):v 3686,3603,3411,2982,2933,2870,2543,2049,1969,1940,1856,1727,1628,1606,1562,1465,1440,1414,1384,1366,1193,1158,1125,1069,1024,990,956,926,891,875,638,582,549,506cm-1;1H NMR(400MHz,CDCl3)δ1.06(d,3H,J=7.0Hz),1.3(d,3H,J=7.0Hz),2.83-2.93(七重峰,1H,J=7.1Hz),5.41(dd,1H,J=0.83,11Hz),5.77(dd,1H,J=0.96,17.3Hz),6.93-7.02(q,1H,J=11Hz),7.44-7.58(m,2H),7.86-7.89(m,1H,J=11,17.5Hz);13C NMR(100MHz,CDCl3)δ13.1,17.1,53.2,117.8,124.8,125.7,128.3,130.7,131.6,135.9,139.8;MS(EI)m/z(rel强度)194(4,[M]+.),152(13),137(10),136(11),135(100),134(11),91(21),77(11),51(7),45(8),43(11),41(9),39(8);HRMS(EI):[M]+计算(C11H14OS):194.07654;实测194.07703。
5.合成Ru络合物
将合适的苯乙烯衍生物(0.132mmol)溶于3ml二氯甲烷中的溶液加入氯化铜(I)(13mg,0.12mmol)和三环己基膦[1,3-双(2,4,6-三甲基苯基)-4,5-二氢咪唑-2-亚基][苯亚甲基]钌(IV)二氯化物(102ml;0.12mmol)的二氯甲烷(2ml)悬浮液中。在40℃下搅拌20分钟后,减压浓缩反应液。将残渣溶于20ml乙酸乙酯,并用硅胶通过巴氏吸管(Pasteur pipette)过滤。再次减压浓缩滤液,并用极少量乙酸乙酯和冷戊烷洗涤残渣。
5a.络合物SR1
绿色微晶固体,产量86%。
IR(膜):v 2952,2908,2862,1606,1479,1420,1382,1262,1154,1055,1033,863,843,798,742cm-1;1H NMR(500MHz,CDCl3)δ0.99(d,6H,J=6.6Hz),2.37(s,6H),2.48(s,12H),3.18(七重峰,1H,J=6.6Hz),4.14(s,4H),6.73(d,1H,J=7.5Hz),7.03(s,4H),7.11-7.20(m,1H);7.40-7.52(m,2H),17.33(s,1H);13C NMR(125MHz,CD3COCD3)δ19.5,21.0,51.7,121.8,123.3,129.3,129.4,133.6,136.4,138.1,138.6,140.0,140.3,156.2,162.0,210.0,285.7;
MS(EI)m/z(rel强度)642(8,[M]+.),530(10),528(18),527(14),526(13),525(10),305(40),304(100),303(91),289(19),287(10),166(25),163(12),159(12),158(22),149(19),146(12),145(14),144(13),135(14),124(32),91(45),77(15),71(11),57(14),55(12),45(10),44(46),43(33),42(12),41(35),40(31),39(20),38(15),36(46);HRMS(EI):[M]+计算(C31H38N2 35Cl2S 102Ru):642.11762;实测642.11634。
图1:络合物SR1的晶体结构。
5b.络合物SOR1
浅绿色微晶固体,产量72%。
IR(膜):v 3447,2963,2917,2738,1702,1628,1607,1482,1439,1380,1264,1227,1183,1158,1121,1105,1037,992,950,932,852,803,751,697,635,593,578,535,506,446,418cm-1;1H NMR(500MHz,CDCl3)δ1.05(q,6H,J=6.7Hz),2.29(m,3H),2.35-2.45(m,12H),2.55(s,3H),3.61(七重峰,1H,J=6.7Hz),4.15(s,4H),6.74(d,1H,J=7.6Hz),6.95-7.05(m,4H),7.34(m,1H),7.65(m,1H)7.72-7.78(m,1H),16.81s,1H);13C NMR(125MHz,CDCl3)δ21.0,51.7,121.0,127.5,128.9,129.4,129.6,129.7,133.9,135.4,138.1,138.5,138.9,139.0,156.2,207.2,301.3;MS(ESI;m/z):658[M-Cl+CH3CN]+。
6.N,N-二烯丙基-对甲苯磺酰胺的闭环复分解反应
6a.在络合物SR1存在下
在氩气中,将N,N-二烯丙基-对甲苯磺酰胺(0.350mmol,84mg)的甲苯(17.5ml)溶液与5mol%(0.018mmol)由实施例5a得到的催化剂SR1混合,并在80℃下搅拌。将200μl反应液的等分试样加入500μl 2M乙基乙烯基醚的二氯甲烷溶液中,并通过GC分析。24小时后,发现转化至目标产物N-p-甲苯磺酰基-2,5-二氢吡咯的转化率为51%。
6b.在络合物SOR1存在下
在氩气中,将N,N-二烯丙基-对甲苯磺酰胺(0.350mmol,84mg)的二氯甲烷(17.5ml)溶液与5mol%(0.018mmol)由实施例5b得到的催化剂SOR1混合,并在室温下搅拌。将200μl反应液的等分试样加入500μl 2M乙基乙烯基醚的二氯甲烷溶液中,并通过GC分析。反应进程显示于图2中。
图2:在室温下及在5mol%络合物SOR1的存在下N,N-二烯丙基-对甲苯磺酰胺在二氯甲烷中的闭环复分解反应。
7.2-烯丙基-2-(2-甲基烯丙基)丙二酸二乙酯的闭环复分解反应
在氩气中,将2-烯丙基-2-(2-甲基烯丙基)丙二酸二乙酯(0.350mmol)的甲苯(17.5ml)溶液与1mol%(0.0035mmol)由实施例5b得到的催化剂SOR1混合,并在80℃下搅拌。将200μl反应液加入500μl 2M乙基乙烯基醚的二氯甲烷溶液中,并通过GC分析。1小时后,发现转化至目标产物4,4-双(乙氧基羰基)-1-甲基环戊烯的转化率为99%。
8.3-烯丙氧基-3,3-二苯基丙炔的烯-炔复分解反应
在氩气中,将3-烯丙氧基-3,3-二苯基丙炔(0.350mmol)的甲苯(17.5ml)溶液与5mol%(0.018mmol)由实施例5a得到的催化剂SR1混合,并在80℃下搅拌。将200μl反应液加入500μl 2M乙基乙烯基醚的二氯甲烷溶液中,并通过GC分析。1小时后,发现转化至目标产物3-乙烯基-2,5-二氢-2,2-二苯基呋喃的转化率为99%。
Claims (7)
2.如权利要求1所述的化合物,其特征在于:L为饱和或不饱和的NHC配体。
3.如权利要求1和/或2所述的化合物,其特征在于:Z是包含硫醇、硫醚、硫缩醛、二硫化物、二硫代羧酸、硫酯、硫酮、硫醛、硫代氨基甲酸酯、硫代氨基甲酸乙酯、硫化膦、硫代磷酸盐(酯)、硫代膦酸盐(酯)、磺酸盐(酯)、砜、磺酰胺、或含硫杂环的单元,同时必须保证化合物Z-Ru是通过硫原子或硫上的氧原子形成的。
4.如前述权利要求之一所述的化合物,其特征在于:分子部分A形成C2桥,所述桥中两个碳原子具有sp2杂化。
5.如前述一个或多个权利要求所述的化合物,其特征在于:X1和X2分别为选自卤离子,特别是F-、Cl-、Br-,拟卤离子、氢氧根、烷氧基或氨基、酚、硫醇、苯硫酚、羧酸根、碳酸根、磺酸根、硫酸根、磷酸根和膦酸根、烯丙基-和环戊二烯基-的无机或有机阴离子,所述拟卤离子优选为氰根、硫氰酸根、氰酸根、异氰酸根和异硫氰酸根。
7.如权利要求1的化合物在复分解反应中的应用。
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JP5787751B2 (ja) | 2008-04-08 | 2015-09-30 | エボニック デグサ ゲーエムベーハーEvonik Degussa GmbH | ルテニウムカルベン錯体を製造するための方法 |
WO2009142535A1 (ru) * | 2008-05-22 | 2009-11-26 | Общество С Ограниченной Ответственностью "Объединённый Центр Исследований И Разработок" | Катализатор метатезисной полимеризации дициклопентадиена |
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PL216649B1 (pl) * | 2011-06-06 | 2014-04-30 | Univ Warszawski | Nowe kompleksy rutenu, sposób ich wytwarzania oraz zastosowanie w reakcji metatezy olefin |
EP2826802B1 (en) | 2012-03-16 | 2021-03-10 | Zeon Corporation | Method for producing ring-opening metathesis polymer hydride, and resin composition |
US9776179B2 (en) | 2015-11-18 | 2017-10-03 | Provivi, Inc. | Production of fatty olefin derivatives via olefin metathesis |
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