CN1152037C - 包含阳离子杂环卡宾的有机金属配合物 - Google Patents
包含阳离子杂环卡宾的有机金属配合物 Download PDFInfo
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- CN1152037C CN1152037C CNB998076651A CN99807665A CN1152037C CN 1152037 C CN1152037 C CN 1152037C CN B998076651 A CNB998076651 A CN B998076651A CN 99807665 A CN99807665 A CN 99807665A CN 1152037 C CN1152037 C CN 1152037C
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- 125000002524 organometallic group Chemical group 0.000 title claims abstract description 27
- 150000001875 compounds Chemical class 0.000 claims abstract description 76
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 5
- 150000002500 ions Chemical class 0.000 claims description 30
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- 238000002360 preparation method Methods 0.000 claims description 19
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 13
- -1 halogen ion Chemical class 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 229910052733 gallium Inorganic materials 0.000 claims description 12
- 239000010948 rhodium Substances 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 11
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 9
- 239000004411 aluminium Substances 0.000 claims description 9
- 239000003446 ligand Substances 0.000 claims description 9
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 229910052707 ruthenium Inorganic materials 0.000 claims description 8
- 150000001336 alkenes Chemical class 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229910052703 rhodium Inorganic materials 0.000 claims description 7
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 7
- 150000001450 anions Chemical class 0.000 claims description 6
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical group [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 4
- 238000007037 hydroformylation reaction Methods 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 150000007530 organic bases Chemical class 0.000 claims description 4
- 230000000737 periodic effect Effects 0.000 claims description 4
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 4
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 4
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 claims description 3
- 150000007529 inorganic bases Chemical class 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 229910001423 beryllium ion Inorganic materials 0.000 claims description 2
- 238000005669 hydrocyanation reaction Methods 0.000 claims description 2
- 150000002527 isonitriles Chemical class 0.000 claims description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052753 mercury Inorganic materials 0.000 claims description 2
- 150000008301 phosphite esters Chemical class 0.000 claims description 2
- 150000003008 phosphonic acid esters Chemical class 0.000 claims description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 230000007704 transition Effects 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 229910052723 transition metal Inorganic materials 0.000 claims 1
- 150000003624 transition metals Chemical class 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 10
- 239000002243 precursor Substances 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 50
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 25
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 20
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
- 239000000203 mixture Substances 0.000 description 18
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 18
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 18
- 239000000243 solution Substances 0.000 description 16
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 14
- 238000001953 recrystallisation Methods 0.000 description 14
- 238000010992 reflux Methods 0.000 description 13
- 239000007787 solid Substances 0.000 description 10
- 238000005406 washing Methods 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 8
- 238000013019 agitation Methods 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- OIRDBPQYVWXNSJ-UHFFFAOYSA-N methyl trifluoromethansulfonate Chemical class COS(=O)(=O)C(F)(F)F OIRDBPQYVWXNSJ-UHFFFAOYSA-N 0.000 description 6
- 235000009518 sodium iodide Nutrition 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical class CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000007872 degassing Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 150000003852 triazoles Chemical class 0.000 description 4
- 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 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-WFGJKAKNSA-N acetone d6 Chemical compound [2H]C([2H])([2H])C(=O)C([2H])([2H])[2H] CSCPPACGZOOCGX-WFGJKAKNSA-N 0.000 description 3
- 125000005907 alkyl ester group Chemical group 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- XVENFWPVABIFLP-UHFFFAOYSA-N nickel;oxalic acid Chemical compound [Ni].OC(=O)C(O)=O XVENFWPVABIFLP-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- ZISBERBYDAQBBB-UHFFFAOYSA-N [Rh].C(C)C(=O)C(=O)C=C=O Chemical compound [Rh].C(C)C(=O)C(=O)C=C=O ZISBERBYDAQBBB-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001449 anionic compounds Chemical class 0.000 description 2
- 229910052728 basic metal Inorganic materials 0.000 description 2
- 150000003818 basic metals Chemical class 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000006459 hydrosilylation reaction Methods 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 150000002891 organic anions Chemical class 0.000 description 2
- 150000002892 organic cations Chemical group 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- LXNAVEXFUKBNMK-UHFFFAOYSA-N palladium(II) acetate Substances [Pd].CC(O)=O.CC(O)=O LXNAVEXFUKBNMK-UHFFFAOYSA-N 0.000 description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 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
- 238000007341 Heck reaction Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 150000004646 arylidenes Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 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
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- WFQOOXRITNHSFG-UHFFFAOYSA-N mercury;oxalic acid Chemical compound [Hg].OC(=O)C(O)=O WFQOOXRITNHSFG-UHFFFAOYSA-N 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 230000001035 methylating effect Effects 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- DXCSBPNCZRYVDN-UHFFFAOYSA-N phenoxyphosphinous acid Chemical compound OPOC1=CC=CC=C1 DXCSBPNCZRYVDN-UHFFFAOYSA-N 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- NDJBHBQUEAGIOB-UHFFFAOYSA-N propan-2-yl trifluoromethanesulfonate Chemical compound CC(C)OS(=O)(=O)C(F)(F)F NDJBHBQUEAGIOB-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- DNXIASIHZYFFRO-UHFFFAOYSA-N pyrazoline Chemical compound C1CN=NC1 DNXIASIHZYFFRO-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F19/00—Metal compounds according to more than one of main groups C07F1/00 - C07F17/00
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/04—Nickel compounds
- C07F15/045—Nickel compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic Table without C-Metal linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/006—Palladium compounds
- C07F15/0066—Palladium compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0073—Rhodium compounds
- C07F15/008—Rhodium compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Polymerization Catalysts (AREA)
Abstract
本发明涉及包含阳离子杂环卡宾的新型有机金属配合物。本发明还涉及由双阳离子杂环前体化合物制备上述有机金属配合物的方法。最后,本发明也涉及所述有机金属配合物在许多化学反应中作为催化剂的用途。
Description
本发明涉及包含阳离子杂环卡宾的新型有机金属配合物。
本发明也涉及作为制备此类有机金属配合物的途径的双阳离子杂环前体化合物。
本发明还涉及上述有机金属配合物的制备方法。
最后,本发明也涉及所述有机金属配合物在一些化学反应中作为催化剂的用途。
现有技术中已经公开过包含杂环卡宾的有机金属配合物。专利EP-A-0,721,953公开了包含衍生于咪唑啉或吡唑啉的非阳离子杂环卡宾和元素周期表第8、9和10族金属的配合物。专利EP-A-0,798,041公开了包含衍生于具有5-、6-或7-元环并包含一个或多个氮和/或硫原子的各种化合物的非阳离子杂环卡宾和一种选自钯、铑、镍、钌和钴的金属的配合物。
此类配合物是非常稳定的化合物,同时在分解过程中还具有不形成有毒副产物的优点。然而,它们的缺点是不能用于高酸性介质中,且氧化态为0的金属配合物不溶于水,这限制了它们的应用领域。
因而本发明首先涉及包含杂环卡宾的有机金属配合物,其特征在于它们对应于通式(I):
[(Z+X-)mMLn]Y (I)
其中:
-Z+表示1,2,4-三唑鎓-5-亚基离子,其中至少一部分环原子被含烃基团取代,
-L表示配位体,其可以是离子或中性的,
-M表示选自The Chemical Rubber公司的“化学和物理手册,第51版”(1970-1971)中公开的元素周期表中1b、2b、3b、4b、5b、6b、7b和8族过渡元素的金属,
-X-表示有机或无机阴离子,
-m表示1~6的整数,
-n表示0~5的整数,
-m和n之和等于或小于6,
-Y表示使得金属配合物呈电中性的阴离子或阳离子。
为方便起见,也包括反电离子Y的式(I)的化合物在本申请中被称为有机金属配合物或金属配合物。
1,2,4-三唑鎓-5-亚基离子Z+对应于通式(II):
其中R1、R2、R3和R4可相同或不同地表示:
-直链或支链烷基或环烷基,
-芳基,
-包含一个或多个取代基的烷基,所述取代基例如是芳基、烷氧基、卤原子或亲水性基团如:
-COOM1、-SO3M1或-PO3M1,M1表示选自质子的无机或有机阳离子残基、衍生于碱金属或碱土金属的阳离子或其中符号R可相同或不同地表示氢原子或具有1~4个碳原子的烷基的铵阳离子-N(R)4,
-N(R)3Ya,式中符号R可相同或不同地表示氢原子或具有1~12个碳原子的烷基,Ya表示无机或有机阴离子,
-OH,
-芳基或芳烷基或在环上包含一个或多个取代基的环烷基,所述取代基例如是烷基、烷氧基、卤原子或亲水性基团如:
-COOM1、-SO3M1或-PO3M1,M1表示选自质子的无机或有机阳离子残基、衍生于碱金属或碱土金属的阳离子或其中符号R可相同或不同地表示氢原子或具有1~12个碳原子的烷基的铵阳离子-N(R)4,
-N(R)3Ya,式中符号R可相同或不同地表示氢原子或具有1~12个碳原子的烷基,Ya表示无机或有机阴离子,
-OH,
R3也表示氢原子,
R1和/或R4各自也可表示通过亚烷基或亚芳基与1,2,4-三唑鎓-5-亚基离子的氮原子键合的有机配位体残基,该配位体残基有可能是亚磷酸酯残基、亚膦酸酯残基、次膦酸酯残基、膦残基或脂族、脂环族、芳族或杂环叔胺残基并用作与金属M的配位体L。
上述有机配位体残基可例如衍生于被上面定义的取代基所取代的或未取代的亚磷酸苯酯或烷基酯,或被上面定义的取代基所取代的或未取代的次膦酸苯酯或烷基酯,或被上面定义的取代基所取代的或未取代的亚膦酸苯酯或烷基酯,或被上面定义的取代基所取代的或未取代的苯膦或烷基膦。
在这种情况下,被如上所定义的R1和/或R4基团取代的1,2,4-三唑鎓-5-亚基离子是二齿或三齿配位体。
L表示离子配位体例如卤化物或氰化物,或中性配位体例如一氧化碳、异腈、膦、有机亚磷酸酯、膦酸酯或亚膦酸酯。
M优选表示选自镍、钴、铁、钌、铑、钯、锇、铱、铂、铜、银、金、锌、镉或汞的金属。
这些金属可以呈它们的各种氧化态,包括O氧化态。
X-阴离子是有机或无机阴离子,例如卤化物,但是优选选自根据所考虑的金属M所定义的弱配位阴离子。它们主要地构成1,2,4-三唑鎓-5-亚基离子的反电离子。
作为此类弱配位阴离子的非限制性例子,可以提及三氟甲烷磺酸根、四氟硼酸根、六氟磷酸根、四氯化铝、四溴化铝、四氟化铝、四碘化铝、四氯化镓、四溴化镓、四氟化镓或四碘化镓。
本发明还涉及双阳离子杂环化合物在通式(I)的有机金属配合物的制备中作为前体的用途。这些双阳离子杂环化合物对应于通式(III):
其中
-符号R1、R2、R3和R4具有上面对于式(II)的1,2,4-三唑鎓-5-亚基离子所示的含义,
-X-表示一种阴离子,例如对于通式(I)所示的那些。
通式(III)的双阳离子杂环化合物能够通过使其中X和R2具有上面所示含义的式XR2化合物与带有R1、R3和R4取代基的三唑衍生物反应而制备。所述制备方法也可分几个步进行,每一步在于使三唑衍生物依据需要引入到所用三唑式中的取代基与式XR1或XR3或XR4的化合物反应,以便得到式(III)的双阳离子杂环化合物。反应条件能够按照T.J.Curphey和K.S.Prasad的文章,Journal of Org.Chem.,1972,37,2259所述的操作方法进行修改。
式(I)的有机金属配合物能够通过在无机或有机碱存在下使通式(III)的双阳离子杂环化合物与金属M的化合物反应而制备。这种碱可以是金属M的化合物的缔合阴离子或可被独立地加入到反应混合物中。该反应一般可通过向化合物(III)的溶液或悬浮液中加入金属M的化合物和如果需要加入无机或有机碱在液态介质中进行。很显然,各种反应物的加入次序可以改变。反应在室温下或优选例如在25~150℃的温度下进行。该温度惯常是于其中进行合成的液体的回流温度。式(I)的配合物的分离可按照化学常用方法进行,例如通过过滤、离心或萃取。式(I)的配合物和式(III)的双阳离子杂环化合物一般由核磁共振(NMR)或红外或X-射线衍射来表征。
式(I)的有机金属配合物能够被用作许多化学反应的催化剂。
大多数式(I)的有机金属配合物以及式(III)的双阳离子杂环化合物在大多数非极性或弱极性有机溶剂如链烷烃、环烷烃、卤代链烷烃、芳烃、烷基芳烃或醚中呈现弱溶解性或呈现不溶性。与此相反,它们可溶于极性溶剂中。因此,双阳离子化合物特别可溶于四氢呋喃、二甲基亚砜(DMSO)、腈类(例如乙腈)或水中。因此本发明的有机金属配合物特别可溶于腈类(例如乙腈)、DMSO或水中。这些性能使得这些各种化合物更容易地分离,特别是通过液/液萃取。另外,这使得有可能在两相介质中进行催化。
作为此类反应的非限制性例子,可以提及特别是在钌配合物存在下链烯烃或炔烃的氢化硅烷化作用,在钌或铑配合物存在下酮的氢化硅烷化作用,在钯配合物存在下的Heck反应,在钌、铑、铂或钯配合物存在下烯烃、醛、酸、烯酰胺和硝基芳香化合物的氢化作用,在铑配合物存在下烯烃的加氢甲酰化和醛化作用,在镍配合物存在下烯烃的氢氰化作用,在钌配合物存在下呋喃的合成,在钌配合物存在下烯烃的易位作用,或在镍配合物存在下丙烯酸酯的聚合反应。
式(III)的前体的合成实施例
实施例1化合物(IIIa)的合成:
按照J.Org.Chem.,1972,37,p.2259所述的操作方法,在搅拌和在1,2-二氯乙烷中回流下用三氟甲磺酸甲酯对1H-1,2,4-甲基三唑进行两次甲基化(在环的2和4位)。
将形成的棕色沉淀物过滤,并用1,2-二氯乙烷洗涤直到获得白色粉末为止。该固体(IIIa)的熔点是160-162℃。
其特征在于:
-RMN1H(DMSO-d6):δ4,22(s,3H,CH3N),4,50(s,6H,CH3N),10,79(s,2H,Hcycl)
-RMN13C(H)(CD3CN):δ38,67(s,CH3N),38,87(s,2 CH3N),120,35(q,1JCF=320,1Hz,CF3),147,72(s,2 Ccycl).
实施例2化合物(IIIb)的合成:
该合成分两步进行。首先,通过向三氟甲磺酸异丙酯在1,2-二氯乙烷中的溶液中化学计量加入1H-1,2,4-甲基三唑(在搅拌下回流3小时),将异丙基结合在4位上(R4基团)。得到黄色油形式的产率为91%的下式化合物:
将2.5ml三氟甲磺酸甲酯(22mmol)加入5g(18mmol)该化合物在20ml 1,2-二氯乙烷的溶液中,将混合物在搅拌下回流24小时。形成棕色沉淀物,将该沉淀物过滤,然后用1,2-二氯乙烷洗涤直到获得白色粉末为止。
该固体(IIIb)的熔点是163-165℃,相对于所加入的中间体化合物的产率是73%。
其特征在于:
-RMN 1H(CD3CN):δ1,65(d,3JHH=6,58Hz,6H,CH3CH),4,34(s,3H,CH3N),5,03(sept,3JHH=6,58Hz,1H,[CH3]2CHN),10,22(s,2H,Hcycl)-RMN13C(CD3CN):δ21,51(s,CH3CH),38,71(s,CH3N),58,88(s,[CH3]2CHN),120,35(q,1JCF=320,1Hz,CF3);145,22(s,2 Ccycl)
实施例3化合物(IIIc)的合成:
该合成分两步进行。首先,按照J.Prakt.Chem.,1988,330,3,325所述的操作方法制备下式的化合物:
在搅拌下在三氟甲磺酸甲酯中回流加热该化合物4天。形成棕色沉淀物,将该沉淀物过滤,然后用1,2-二氯乙烷洗涤直到获得白色粉末为止。相对于第二步中加入的化合物,以产率50%获得该固体(IIIc)。
其特征在于:
-RMN 1H(CD3CN):δ4,22(s,3H,CH3N),7,4-8,4(未分辨峰,H苯基),10,34(s,1H,H环)
实施例4化合物(IIId)的合成:
该合成分两步进行。首先,按照J.Prakt.Chem.,1988,330,3,325所述操作方法制备下式的化合物:
在搅拌下在1,2-二氯乙烷中与3当量三氟甲磺酸甲酯一起回流加热该化合物2天。形成棕色沉淀物,将该沉淀物过滤,然后用1,2-二氯乙烷洗涤直到获得白色粉末为止。相对于第二步中加入的化合物,以产率69%获得该固体(IIId),其熔点是190.5-191.3℃。
其特征在于:
-RMN 1H(CD3CN):δ3,04(s,3H,CH3),4,19(s,3H,CH3N),7,8-8,1(未分辨峰,10H,1苯基H),10,51(s,1H,H环)
-RMN 13C(CD3CN):δ12,31(s,CH3C),38,04(s,CH3N),126,70(s,2CH苯基),128,02(s,C苯基)128,49(s,2CH 苯基),130,07(s,C苯基),131,56(s,2CH苯基),131,83(s,2CH苯基),134,04(s,1CH 苯基).135,88(s,1CH苯基),120,35(q,1JCF=320,1Hz,CF3).145,58(s,CH环),157,66(s,
C 环 CH3)
质子偶合谱显示三唑环中CH的偶合常数1JCH=240Hz。
实施例5化合物(IIIe)的合成:
该合成分两步进行。首先,按照J.Prakt.Chem.,1988,330,3,325所述操作方法制备下式化合物:
在搅拌下在1,2-二氯乙烷中与3当量三氟甲磺酸甲酯一起回流加热该化合物2天。形成棕色沉淀物,将该沉淀物过滤,然后用1,2-二氯乙烷洗涤直到获得白色粉末为止。相对于第二步中加入的化合物,以产率71%获得该固体(IIIe),其熔点是180.0℃。
其特征在于:
-RMN 1H(CD3CN):δ4,08(s,3H,CH3N),4,20(s,3H CH3N),4,46(s,3H,CH3N),7,8-8,1(未分辨峰,10H,5H苯基),10,16(s,1H,H环)
-RMN 13C(CD3CN):δ37,88(s,CH3N),38,36(s.CH3N),39,42(s,CH3N),130,78(s,C苯基),131,97(s,2CH苯基),132,15(s,2CH苯基),137,35(s,CH苯基),131,83(s,2CH苯基),120,35(q,1JCF=320,1Hz,CF3),147,35(s,CH环),156,48(s,
C 环).
实施例6化合物(IIIf)的合成:
该合成分两步进行。首先,按照J.Prakt.Chem.,1988,330,3,325所述操作方法制备下式化合物:
在搅拌下在1,2-二氯乙烷中与3当量三氟甲磺酸甲酯一起回流加热该化合物2天。形成棕色沉淀物,将该沉淀物过滤,然后用1,2-二氯乙烷洗涤直到获得白色粉末为止。相对于第二步中加入的化合物,以产率95%获得该固体(IIIf),其熔点是194.4℃。
-RMN 1H(丙酮d6):δ3,35(s,3H,CH3C),4,46(s,3H,CH3N),4,69(s,3H,CH3N),4,77(s,3H,CH3N),10,77(s,1H,H环)
-RMN 13C(丙酮d6):δ10,53(s,CH3C),35,91(s,CH3N),36,26(s,CH3N),37,99(s,CH3N),120,35(q,1JCF=320.1Hz,CF3),145,35(s,CH环),157,31(s,C 环CH3).
式(I)的有机金属配合物的合成实施例
实施例7Ag(I)化合物(Ia)的合成:
将0.4g(2.4mmol)乙酸银加入到实施例1中制备的1g双阳离子化合物(IIIa)在20ml四氢呋喃(THF)中的悬浮液中。在回流下搅拌该混合物2小时。形成与THF不混溶的棕色油,用10ml THF洗涤几次。蒸发溶剂后,获得光敏性棕色固体(相对于双阳离子化合物(IIIa)的产率是82%)。
该配合物具有下面特征值:
-RMN 1H(CD3CN):δ4,01(s,3H,NCH3),4,19(s,3H,CH3N-NCH3),4,22(s,3H,CH3N-NCH3),9,72(s,1H,CH).
-RMN 13C(CD3CN):δ37,2(NCH3),38,5(NCH3),38,6(NCH3),121,1(q,1JCF=320,1Hz,CF3),144,8(CH);189,2(CAg).
实施例8Hg(II)化合物(Ib)的合成:
将0.16g二乙酸汞(事先在50℃真空下被干燥12小时)和1ml二甲基亚砜(DMSO)加入到实施例5中制备的0.43g双阳离子化合物(IIIe)在20ml四氢呋喃(THF)中的悬浮液中。在室温下搅拌该混合物24小时。形成仅可溶于高极性溶剂中的棕色沉淀物。该固体用THF洗涤几次以便除去痕量乙酸。通过乙醚在该配合物的甲醇溶液中缓慢扩散,将由此获得的配合物重结晶。重结晶的配合物(Ib)的熔点是85.4-87℃。相对于双阳离子化合物(IIIe)得到产率86%。
该配合物具有下面特征值:
-RMN 1H(CD3OD):δ4,70(s,12H,NCH3,4JH-Hq=12.8),4,29(s,6H,CH3N,4JH-Hg=8,5Hz),7,9-8,2(未分辨峰,10H,H苯基).
-RMN 13C(CD3OD):δ38,79(CH3N-NCH3),41,75(NCH3),121,1(q,1JCF=320,1Hz,CF3),156,88(C-Ph,(3J+2J)C-Hg=86Hz),183,78(CHg,J1 CHq=3275Hz)
其结构也由X-射线衍射确定。
实施例9 Ni(II)化合物(Ic)的合成:
将实施例5中制备的2.4g双阳离子化合物(IIIe)加入0.442g二乙酸镍和0.75g碘化钠在50ml THF中的悬浮液中。在回流下搅拌该混合物2小时。形成着色沉淀物,将该沉淀物过滤并用THF洗涤几次。在-30℃在丙酮/乙醚混合物中将由此获得的配合物重结晶。重结晶的配合物(Ic)是红色的,其熔点是310.7℃(分解:晶体变黑)。相对于双阳离子化合物(IIIe)得到产率85%。
该配合物具有下面特征值:
-RMN 1H(丙酮-d6):δ7,8-8,0(宽,10H,H苯基),4,88-4,84(2s,6H,NCH3),4,54-4,49(2s,6H,CH3N),4,42-4,41(2s,6H,CH3N).
-RMN 13C(CD3OD):δ37,0(CH3N),37,9(CH3N),38,4(CH3N),121,1(q,1JCF=320,1Hz,CF3),130.5-130,8-134,8(C苯基),153,4(C-Ph),188,2(C-Ni)
其结构也由X-射线衍射确定。
实施例10Ni(II)化合物(Id)的合成:
将实施例6中制备的0.425g双阳离子化合物(IIIf)加入0.090g二乙酸镍和0.15g碘化钠在25ml THF中的悬浮液中。在回流下搅拌该混合物2小时。形成着色沉淀物,将该沉淀物过滤并用THF洗涤几次。在-30℃在丙酮/乙醚混合物中将由此获得的配合物重结晶。重结晶的配合物(Id)是红色的,其熔点是300-305℃(分解:晶体变黑)。相对于双阳离子化合物(IIIf)得到产率79%。
该配合物具有下面特征值:
-RMN 1H(丙酮-d6):δ4,88-4,84(2s,6H,NCH3),4,54-4,49(2s,6H,CH3N),4,42-4,41(2s,6H,CH3N),2,63(s,6H,C-CH3).
-RMN 13C(CD3OD):δ13,86(C-CH3),36,1(CH3N),37,6(CH3N),38,5(CH3N),121,1(q,1JCF=320,1Hz,CF3),154,8(
C-Me),187,6(C-Ni).
其结构也由X-射线衍射确定。
实施例11Ni(II)化合物(Ie)的合成:
将实施例1中制备的0.935g双阳离子化合物(IIIa)加入0.200g二乙酸镍和0.34g碘化钠在30ml THF中的悬浮液中。在回流下搅拌该混合物2小时。形成着色沉淀物,将该沉淀物过滤并用THF洗涤几次。通过乙醚在该配合物的乙腈溶液中缓慢扩散,将由此获得的配合物重结晶。在-30℃在丙酮/乙醚混合物中进行重结晶。重结晶的配合物(Ie)是红色的。相对于双阳离子化合物(IIIa)得到产率70%。
该配合物具有下面特征值:
-RMN 1H(丙酮-d6):δ4,38-4,35(2s,6H,CH3N),4,68-4,65(2s,6H,CH3N),4,99-4,96(2s,6H,NCH3),9,32(s,2H,CH)
实施例12Pd(II)化合物(If)的合成:
将实施例5中制备的0.472g双阳离子化合物(IIIe)加入0.112g二乙酸钯和0.30g碘化钠在60ml THF中的悬浮液中。在回流下搅拌该混合物2小时。形成着色沉淀物,将该沉淀物过滤并用乙醚洗涤几次。在-30℃在丙酮/乙醚混合物中将由此得到的配合物重结晶。其呈黄色晶体形式。重结晶的配合物(If)的熔点是211-213℃(分解:晶体变成棕色)。在反应过程中,所有三氟甲磺酸根阴离子都被碘阴离子取代。相对于双阳离子化合物(IIIe)得到产率51%。
该配合物具有下面特征值:
-RMN 1H(DMSO-d6):δ7,8-8,1(宽,10H,H苯基),4,49-4,53(2s,6H,NCH3),4,21(s,6H,CH3N),4,10-4,13(2s,6H,CH3N).
-RMN 13C(DMSO-d6):δ37,2(CH3N),38,3(CH3N),39,9(CH3N),130,1-130,9-134,5(C苯基),152,4(C-Ph),174,5(C-Pd)
其结构也由X-射线衍射确定。
实施例13Pd(II)化合物(Ig)的合成:
将实施例6中制备的0.425g双阳离子化合物(IIIf)加入0.112g二乙酸钯和0.30g碘化钠在60ml THF中的悬浮液中。在回流下搅拌该混合物2小时。形成着色沉淀物,将该沉淀物过滤并用乙醚洗涤几次。在-30℃在丙酮/乙醚混合物中将由此得到的配合物重结晶。其呈红色晶体形式。重结晶的配合物(Ig)的熔点是206-212℃(分解:晶体变成棕色)。在反应过程中,所有三氟甲磺酸根阴离子都被碘阴离子取代。相对于双阳离子化合物(IIIf)得到产率60%。
该配合物具有下面特征值:
-RMN 1H(DMSO-d6):δ4,41-4,40(2s,6H,NCH3),4,29(s,6H,CH3N),4,16-4,15(2s,6H,CH3N),2,95(6H,C-CH3).
实施例14Ni(O)化合物(Ih)的合成:
合成方法A
在40ml无水和脱气的乙腈中稀释1ml四羰基镍。将380μl吡啶和660μl三乙胺加入所得到溶液中。使用滴液漏斗滴加实施例6中制备的2.0g双阳离子化合物(IIIf)在60ml无水和脱气的乙腈中的溶液。观察到气体排出,溶液变成黄色。当加入所有溶液时,持续搅拌另外1小时。通过在真空下蒸发溶剂使反应溶液的体积减少三分之二,然后加入200ml脱气的乙醚。形成配合物(Ih)的沉淀物,将该沉淀物过滤并用乙醚洗涤几次。在-30℃在丙酮/乙醚混合物中将由此得到的配合物重结晶。其呈黄色晶体形式。无法准确测定其熔点(分解:晶体变成棕色)。相对于双阳离子化合物(IIIf)得到产率26%。
该配合物具有下面特征值:
-RMN 1H(DMSO-d6):δ4,00(s,6H,NCH3),3,99(s,6H,CH3N),3,78(s,6H,CH3N),2,72(6H,C-CH3)
由红外光谱观测到在1982cm-1和1906cm-1处的谱带(CO)。
其结构也由X-射线衍射确定。
由元素分析发现:
-28.99%C(理论值28.89%)
-3.36%H(理论值3.63%)
-12.39%N(理论值12.62%)。
合成方法B
将150mg活化金属Zn粉(10当量)加入实施例10中制备的0.2g有机金属配合物(Id)在10ml无水和脱气的乙腈中的溶液中。将溶液放置于一氧化碳气氛下。在搅拌开始的同时进行反应。溶液变黄。使用真空管过滤溶液,然后用方法A中所述的方式对其进行处理(加入乙醚以便沉淀有机金属配合物)。相对于加入的有机金属配合物(Id),得到的产率是48%。进行与方法A中相同的分析和表征,且结果相同。
实施例15Rh(I)化合物(Ij)的合成:
将0.277g二(羰基)乙酰丙酮铑在10ml THF中的溶液加入实施例6中制备的0.456g双阳离子化合物(IIIf)和0.16g NaI在40ml THF中的悬浮液中。在50℃搅拌混合物2天。在蒸发溶剂后回收棕色固体,并用乙醚洗涤几次。相对于双阳离子化合物(IIIf)的产率是70%。
该配合物具有下面特征值:
-RMN 1H(DMSO-d6):δ4,47(s,3H,NCH3),4,28(s,3H,CH3N),4,20(s,3H,CH3N),2,96(s,3H,C-CH3)
-RMN 13C(DMSO-d6):δ10,5(s,C-CH3),35,2(s,NCH3),36,8(s,CH3N),37,9(s,CH3N),154,2(s,C-CH3),183,0(d,1J(Rh-C)=82,9Hz,CO),188,1(d,1J(Rh-C)=42,2Hz,C卡宾).
由红外光谱观测到在1975cm-1处的谱带(CO)。
实施例16Rh(I)化合物(Ik)的合成:
将0.200g二(羰基)乙酰丙酮铑在10ml THF中的溶液加入实施例1中制备的0.16g双阳离子化合物(IIIa)在10ml THF中的悬浮液中。在50℃搅拌混合物15小时。形成棕色固体沉淀物,该沉淀物用乙醚洗涤几次。相对于双阳离子化合物(IIIa),配合物(Ik)的产率是67%。
该配合物具有下面特征值:
-RMN 1H(DMSO-d6):δ4,20(s,3H,NCH3),4,22(s,3H,CH3N),4,25(s,3H,CH3N),9,66(s,1H,CH).
-RMN 13C(DMSO-d6):δ38,6(s,NCH3),38,7(s,NCH3),39,1(s,CH3N),37,9(s,CH3N),121.1(q,1JCF=320,1Hz,CF3),145,5(s,CH),186,1(d,1J(Rh-C)=76Hz,CO),187,9(d,1J(Rh-C)=43,3Hz,C卡宾)
由红外光谱观测到在2029(i)cm-1和1985(m)cm-1处的谱带(CO)。
实施例17由Rh(I)化合物(Ij)催化苯乙烯的加氢甲酰化作用
在包含双层夹套的100ml不锈钢反应器中进行苯乙烯的加氢甲酰化作用,该夹套的作用是在使用恒温器控制的温度下通过油循环进行加热。反应器的盖装有在压力下送气或排气阀、精确测压计、安全阀和能够借助注射器转移溶液的球阀。将Teflon_坩埚安装在高压釜内,该坩埚包含一个用于搅拌反应物的磁力棒。
将实施例15中制备的Rh(I)配合物(Ij)(40mg)以及100mg三苯膦(相对于催化剂为5当量)加入Teflon_坩埚中。密闭高压釜,并用氩气吹扫3次。随后加入15ml四氢呋喃、5ml苯乙烯和60mg三乙胺(相对于催化剂为4当量)。然后形成一氧化碳压力(15巴)和氢气压力(15巴)。在磁力搅拌下将高压釜加热到60℃。在此温度下反应4小时后,将高压釜在丙酮/液氮混合物中快速冷却,并在1小时内进行减压。通过气相色谱(VPC)分析反应混合物的试样。
得到下面结果:
-苯乙烯的转化率:95%
-醛类的选择性:97%
-支链醛/直链醛之比:95/5
-催化剂的回旋频率:75h-1(由相对于反应时间的平均值计算,对于所有产物取相同的VPC响应因子)。
实施例18由Rh(I)化合物(Ik)催化苯乙烯的加氢甲酰化作用
重复实施例17,使用实施例16中制备的40mg配合物(Ik),不使用三苯膦。
在80℃反应3小时后,将高压釜在丙酮/液氮混合物中快速冷却,并在1小时内进行减压。通过气相色谱(VPC)分析反应混合物的试样。
得到下面结果:
-苯乙烯的转化率:96%
-醛类的选择性:100%
-支链醛/直链醛之比:25/75
-催化剂的回旋频率:79h-1(由相对于反应时间的平均值计算,对于所有产物取相同的VPC响应因子)。
Claims (11)
2、权利要求1的有机金属配合物,其特征在于L表示选自卤离子或氰离子的离子配位体或选自一氧化碳、异腈、膦、有机亚磷酸酯、膦酸酯或亚膦酸酯的中性配位体。
3、权利要求1或2的有机金属配合物,其特征在于M表示选自镍、钌、铑、钯、银或汞的金属。
4、权利要求1或2的有机金属配合物,其特征在于X-阴离子是弱配位阴离子,并主要地构成1,2,4-三唑鎓-5-亚基离子的反电离子。
5、权利要求4的有机金属配合物,其特征在于弱配位阴离子X-选自三氟甲磺酸根、四氟硼酸根、六氟磷酸根、四氯化铝、四溴化铝、四氟化铝、四碘化铝、四氯化镓、四溴化镓、四氟化镓或四碘化镓。
7、权利要求6的制备方法,其特征在于反应在25-150℃的温度下,在液体介质中进行,其中向化合物(III)的溶液或悬浮液中加入金属M的化合物和无机或有机碱,或变换反应物的加入次序进行制备。
8、权利要求1~5中任一项的式(I)所示有机金属配合物的用途,用于在铑配合物存在下烯烃的加氢甲酰化和醛化作用,在镍配合物存在下烯烃的氢氰化作用。
10、权利要求9的化合物,其特征在于X-为弱配位阴离子,并且主要地构成1,2,4-三唑鎓-5-亚基离子的反电离子。
11、权利要求10的化合物,其特征在于弱配位阴离子X-选自三氟甲磺酸根、四氟硼酸根、六氟磷酸根、四氯化铝、四溴化铝、四氟化铝、四碘化铝、四氯化镓、四溴化镓、四氟化镓或四碘化镓。
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FR2813081B1 (fr) * | 2000-08-17 | 2005-12-23 | Rhodia Chimie Sa | Procede de preparation d'huiles silicones par hydrosilylation de synthons contenant au moins un cycle hydrocarbone dans lequel est inclus un atome d'oxygene en presence d'un complexe metallique catalytique |
US6843923B2 (en) * | 2001-08-03 | 2005-01-18 | Canadus Technologies Llc | Compositions for removing metal ions from aqueous process solutions and methods of use thereof |
EP1568702A4 (en) * | 2002-11-12 | 2008-08-06 | Zakrytoe Aktsionernoe Obschest | Palladium Complexes with Heterocyclic Ligands |
US6911546B2 (en) * | 2002-12-26 | 2005-06-28 | International Business Machines Corporation | Catalytic depolymerization of polymers containing electrophilic linkages using nucleophilic reagents |
US20080267867A1 (en) * | 2003-09-05 | 2008-10-30 | Youngs Wiley J | Metal Complexes of N-Heterocyclic Carbenes as Radiopharmaceuticals and Antibiotics |
US8519146B2 (en) * | 2004-09-07 | 2013-08-27 | The University Of Akron | Metal complexes of N-heterocyclic carbenes as antibiotics |
US8648205B2 (en) * | 2003-09-05 | 2014-02-11 | The University Of Akron | Metal complexes of N-heterocyclic carbenes |
DE102004060247A1 (de) * | 2004-12-15 | 2006-06-29 | Studiengesellschaft Kohle Mbh | Neue N-heterocyclische Carbene und ihre Anwendung in der Katalyse |
WO2007148334A1 (en) | 2006-06-20 | 2007-12-27 | Ben-Gurion University Of The Negev Research And Development Authority | Amphiphilic peptides and hydrogel matrices thereof for bone repair |
EA010431B1 (ru) * | 2006-08-17 | 2008-08-29 | Общество С Ограниченной Ответственностью "Радифенс" | Координационное соединение палладия и способ его получения |
US20100016621A1 (en) * | 2006-09-28 | 2010-01-21 | Yugen Zhang | Hydrosilylation |
CN102027001A (zh) * | 2007-06-20 | 2011-04-20 | 新加坡科技研究局 | N-杂环卡宾金属环催化剂和方法 |
US9457056B2 (en) * | 2007-12-04 | 2016-10-04 | Ben-Gurion University Of The Negev Research And Development Authority | Peptides comprising alternating hydrophobic and anionic amino acids for treatment of osteoporosis |
WO2011146155A2 (en) * | 2010-02-12 | 2011-11-24 | The Regents Of The University Of California | Organo-metallic frameworks derived from carbenophilic metals and method of making same |
GB201009656D0 (en) * | 2010-06-09 | 2010-07-21 | Univ St Andrews | Carboxylation catalysts |
CN102503963B (zh) * | 2011-09-13 | 2014-04-23 | 江西师范大学 | 一种锌金属-有机配位聚合物及其制备方法 |
CN103833652A (zh) * | 2012-11-26 | 2014-06-04 | 海洋王照明科技股份有限公司 | 三氮唑类离子液体及其制备方法和应用 |
CN104098607B (zh) * | 2014-07-07 | 2016-04-20 | 苏州大学 | 含三环己基膦的单膦单氮杂环卡宾镍(ii)配合物及其应用 |
JP6515930B2 (ja) | 2014-08-12 | 2019-05-22 | 国立大学法人九州大学 | ヒドロシリル化反応触媒 |
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DE102016206303A1 (de) * | 2016-04-14 | 2017-10-19 | Technische Universität Berlin | Katalysator zur Hydroformylierung von Olefinen und dessen Verwendung |
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CN109939737B (zh) * | 2019-03-07 | 2021-02-23 | 清华大学 | 卡宾钴催化剂、其制备方法及其在催化氢化醛和酮化合物中的应用 |
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DE4447066A1 (de) * | 1994-12-29 | 1996-07-04 | Hoechst Ag | Heterocyclische Carbene enthaltende Metallkomplexverbindungen |
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