CN102753560A - 双金属配合物及其在生产碳酸二芳基酯中的用途 - Google Patents
双金属配合物及其在生产碳酸二芳基酯中的用途 Download PDFInfo
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- CN102753560A CN102753560A CN2010800567568A CN201080056756A CN102753560A CN 102753560 A CN102753560 A CN 102753560A CN 2010800567568 A CN2010800567568 A CN 2010800567568A CN 201080056756 A CN201080056756 A CN 201080056756A CN 102753560 A CN102753560 A CN 102753560A
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- Prior art keywords
- formula
- compound
- residue
- diaryl carbonate
- catalyzer
- Prior art date
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- Granted
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- -1 diaryl carbonate Chemical compound 0.000 title claims abstract description 41
- 239000010949 copper Substances 0.000 claims abstract description 11
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 10
- 239000010941 cobalt Substances 0.000 claims abstract description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- 230000000536 complexating effect Effects 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 9
- 238000005832 oxidative carbonylation reaction Methods 0.000 claims description 9
- 239000000460 chlorine Substances 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- VDXUUGGONYMWFW-UHFFFAOYSA-N 1,10-phenanthroline-2,3-dione Chemical compound C1=CN=C2C3=NC(=O)C(=O)C=C3C=CC2=C1 VDXUUGGONYMWFW-UHFFFAOYSA-N 0.000 claims description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- XLJMAIOERFSOGZ-UHFFFAOYSA-N cyanic acid Chemical compound OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 238000005984 hydrogenation reaction Methods 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 101100242031 Mus musculus Pdha2 gene Proteins 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000001350 alkyl halides Chemical class 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 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 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 125000002837 carbocyclic group Chemical group 0.000 claims description 2
- 230000006315 carbonylation Effects 0.000 claims description 2
- 238000005810 carbonylation reaction Methods 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 125000003392 indanyl group Chemical group C1(CCC2=CC=CC=C12)* 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 claims description 2
- 229940006461 iodide ion Drugs 0.000 claims description 2
- 150000002611 lead compounds Chemical class 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 125000005245 nitryl group Chemical group [N+](=O)([O-])* 0.000 claims description 2
- 125000005561 phenanthryl group Chemical group 0.000 claims description 2
- 239000011149 active material Substances 0.000 claims 1
- 150000004703 alkoxides Chemical class 0.000 claims 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 47
- 229910052763 palladium Inorganic materials 0.000 abstract description 21
- 239000003054 catalyst Substances 0.000 abstract description 12
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical group C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 abstract description 9
- 239000003446 ligand Substances 0.000 abstract description 5
- 230000001590 oxidative effect Effects 0.000 abstract 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000000203 mixture Substances 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 5
- 150000004054 benzoquinones Chemical group 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- 230000031709 bromination Effects 0.000 description 4
- 238000005893 bromination reaction Methods 0.000 description 4
- 238000004587 chromatography analysis Methods 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- 238000000434 field desorption mass spectrometry Methods 0.000 description 4
- 238000011010 flushing procedure Methods 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 150000001868 cobalt Chemical class 0.000 description 3
- 239000008246 gaseous mixture Substances 0.000 description 3
- 239000013067 intermediate product Substances 0.000 description 3
- 150000002696 manganese Chemical class 0.000 description 3
- 150000002941 palladium compounds Chemical class 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- CRBJBYGJVIBWIY-UHFFFAOYSA-N 2-isopropylphenol Chemical compound CC(C)C1=CC=CC=C1O CRBJBYGJVIBWIY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- TWIIVLKQFJBFPW-UHFFFAOYSA-N acetaminosalol Chemical group C1=CC(NC(=O)C)=CC=C1OC(=O)C1=CC=CC=C1O TWIIVLKQFJBFPW-UHFFFAOYSA-N 0.000 description 2
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 150000004714 phosphonium salts Chemical class 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 230000003245 working effect Effects 0.000 description 2
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- VLJSLTNSFSOYQR-UHFFFAOYSA-N 3-propan-2-ylphenol Chemical compound CC(C)C1=CC=CC(O)=C1 VLJSLTNSFSOYQR-UHFFFAOYSA-N 0.000 description 1
- PCSIZKSNIWJKSK-UHFFFAOYSA-N 4,5-dinitrobenzene-1,2-diamine Chemical compound NC1=CC([N+]([O-])=O)=C([N+]([O-])=O)C=C1N PCSIZKSNIWJKSK-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- GCNTZFIIOFTKIY-UHFFFAOYSA-N 4-hydroxypyridine Chemical compound OC1=CC=NC=C1 GCNTZFIIOFTKIY-UHFFFAOYSA-N 0.000 description 1
- YQUQWHNMBPIWGK-UHFFFAOYSA-N 4-isopropylphenol Chemical compound CC(C)C1=CC=C(O)C=C1 YQUQWHNMBPIWGK-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- GYCKQBWUSACYIF-UHFFFAOYSA-N Ethyl salicylate Chemical compound CCOC(=O)C1=CC=CC=C1O GYCKQBWUSACYIF-UHFFFAOYSA-N 0.000 description 1
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- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 229930192627 Naphthoquinone Natural products 0.000 description 1
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- 230000001133 acceleration Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
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- 229910001619 alkaline earth metal iodide Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- LBKPGNUOUPTQKA-UHFFFAOYSA-N ethyl n-phenylcarbamate Chemical compound CCOC(=O)NC1=CC=CC=C1 LBKPGNUOUPTQKA-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
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- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
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- 229910001511 metal iodide Inorganic materials 0.000 description 1
- NBTOZLQBSIZIKS-UHFFFAOYSA-N methoxide Chemical compound [O-]C NBTOZLQBSIZIKS-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- OSWPMRLSEDHDFF-UHFFFAOYSA-N methyl salicylate Chemical compound COC(=O)C1=CC=CC=C1O OSWPMRLSEDHDFF-UHFFFAOYSA-N 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
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- 229910052762 osmium Inorganic materials 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 229940090668 parachlorophenol Drugs 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010405 reoxidation reaction Methods 0.000 description 1
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Abstract
本发明涉及双金属配合物，其中所述配体包含络合铜、锰或钴的萨罗汾单元和络合钯的菲咯啉单元，且两个体系通过共轭系统相连。此外，本发明涉及所述双金属配合物作为催化剂，用于将芳族羟基化合物氧化羰基化成碳酸二芳基酯的应用，借助于所述双金属配合物作为催化剂生产碳酸二芳基酯的方法，以及使用根据本发明的双金属配合物作为催化剂通过芳族羟基化合物的氧化羰基化生产的碳酸二芳基酯。
Description
技术领域
本发明涉及双金属配合物，其中配体包含络合铜、锰或钴的萨罗汾单元和络合钯的菲咯啉单元，且两个体系通过共轭体系连接。此外，本发明涉及所述双金属配合物作为催化剂，用于将芳族羟基化合物氧化羰基化成碳酸二芳基酯的应用，借助于双金属配合物作为催化剂生产碳酸二芳基酯的方法，以及使用本发明的双金属配合物作为催化剂通过芳族羟基化合物的氧化羰基化生产的碳酸二芳基酯。
碳酸二芳基酯适用于按照熔融酯交换法制备聚碳酸酯(参见例如在Chemistry and Physics of Polycarbonates，Polymer Reviews中，H.Schnell，第9卷，John Wiley and Sons，Inc.，1964)，适用于苯氨基甲酸乙酯的生产或者是药物领域和植物保护领域的活性物质的中间产物。
众所周知，通过芳族羟基化合物的相界面光气化作用(肖特-鲍曼反应)可得到碳酸二芳基酯。然而，这种方法具有很大的缺点，如光气和溶剂如二氯甲烷的使用。
碳酸二芳基酯也可在CO、O2和贵金属催化剂存在下，通过芳族羟基化合物的氧化直接羰基化来制备(参见例如DE-OS 27 38 437，US-A 4,349,485，US-A5,231,210，EP-A 667 336，EP A 858 991，US-A 5,760,272)。作为贵金属，优选使用钯。另外，使用了助催化剂(如锰盐或钴盐)、碱、溴化物源、季盐、不同的醌类或对苯二酚类和干燥剂。在这种情况中可在溶剂如氯苯中进行。
在已知的现有技术例如J.Mol.Cat.A：Chem.2000，151，37-45中，相对于贵金属盐，过量使用了铜盐、锰盐或钴盐，所以由此仅能低效利用催化剂和助催化剂。
另外，已知方法不具有足够的催化剂使用寿命。尤其发生金属钯的沉积。
因此根据已知的现有技术，存在对催化剂的需求，所述催化剂能实现不使用额外量的铜盐、锰盐或钴盐作为助催化剂进行反应并提高催化剂(例如转化数，TON)的效率。另外，存在对提供具有更高稳定性的催化剂的需求。
所述待解决的问题通过双金属配合物令人惊奇地得以解，在所述双金属配合物中将第二种金属相对于钯化学计量地嵌入配合物中。该化合物导致能以增效的方式利用助催化剂，并且相对于比较体系双金属催化剂的使用寿命得以增加。
已发现这样的双金属催化剂，在其中催化活性的钯和氧化还原活性的助催化剂被组合在一个分子中，并以此实现导致增效作用的加速的钯的再次氧化。
式(1)的双金属络合物公开于WO2008/054024中作为光敏剂用于光伏电池：
其中M＝Ru、Os、Fe、Re、Rh，且M′＝Ni、Co、Zn、Mn、Pt、Pd。键接到菲咯啉单元的金属还必须通过其它联吡啶配体络合。这些配合物不适合作为氧化羰基化如由苯酚、一氧化碳和氧气制备碳酸二苯基酯的催化剂，因为由于在金属中心M上配位位置被联吡啶单元阻塞，不再提供配位位置用于积聚反应物。作为用于氧化羰基反应的催化活性的金属(金属中心M)优选钯，其位于由两个顺位的和两个弱配合的配体组成的配位层中(J.Mol.Cat.A：Chem.2000，151，37-45)。
此外，这些配体和络合物的合成公开于European Journal of InorganicChemistry 2003，10，1900-1910中。此处，采用了两种策略，从菲咯啉单元开始构建并且在配体完全合成后才络合，和从萨罗汾单元开始构建，其中选择模板法，在该方法中合成在中心离子Ni(II)存在下进行。为此作为中间产物需要3，4-二硝基萨罗汾-Ni(II)-配合物，式(2)，其合成公开于Dalton Transactions 2009，10，1792-1800及其该处引用的文献。
对于某些应用，特别是在催化中，期望的是这样的配合物，其在菲咯啉单元中的金属离子没有被另外的联吡啶配体络合。此外，模板路径可更简单地施行，而仍然没有公开铜作为中心原子。
现在已经发现，可由3，4-二硝基萨罗汾-Cu(II)-配合物制备另外包含可与卤化钯配合物反应形成双金属配合物的菲咯啉单元的配体，在其中钯未通过另外的联吡啶配体来稳定。这里预期的是使钯通过两个菲咯啉单元进行配位，因为两个单齿配体Hal比联吡啶螯合剂更容易被取代。然而，没有出现形成钯双菲咯啉-配合物。
因此，本发明的主题是通式(3)的配合物，
其中
R表示氢、氟、氯、硝基基团或C1-C22烷基残基，优选表示甲基、异丙基或叔丁基，最特别优选叔丁基，或C6-C22芳基残基，优选表示苯基、甲苯基、2-(1，4-二羟基)苯基。
Hal 表示氯离子、溴离子或碘离子，优选表示氯离子或溴离子，最特别优选溴离子，或烃氧化物，如苯氧化物或甲氧化物，或弱配位阴离子如三氟甲磺酸根、甲苯磺酸根、甲磺酸根、四氟硼酸根、高氯酸根和六氟磷酸根和
M1表示铜、锰或钴。
本发明另一个主题是通式4a和4b的配合物，其作为制备根据本发明的双金属配合物的中间产物出现，
其中R和M1具有如上所述的含义。
本发明的主题也是式3的双金属配合物作为催化剂用于芳族羟基化合物的氧化羰基化以形成碳酸二芳基酯的应用，以及利用式3的配合物作为催化剂通过芳族羟基化合物的氧化羰基化制备的碳酸二芳基酯。
式3化合物的合成，是通过式4a化合物的硝基的氢化以形成式4b的化合物，然后4b的化合物与式5的菲咯啉二酮反应
生成式6的配体
并与式7的化合物配位，
PdHal2L2(7)
其中Hal具有如上所述的定义，且L表示任选存在的配体，例如乙腈、三芳基膦、环辛二烯或降冰片二烯。
用于制备式4a配合物需要的4，5-二硝基-邻苯二胺可例如根据参考文献Cheeseman G.W.H.J.Chem.Soc.，1962，1170来制备。生成式4b化合物的氢化反应在金属Ni、Co、Pd、Pt、Ru或Rh的催化剂存在下通过式4a的化合物与给氢试剂的氢化反应进行，所述给氢试剂如H2、肼、环己烯或甲酸，所述催化剂，可固定在如碳或无机物质的载体上。
与菲咯啉二酮的反应例如通过在溶剂中与等摩尔量的式4b的化合物在回流下共同加热进行，所述溶剂如甲醇、乙醇或异丙醇、氯仿、苯、甲苯或其混合物，其中任选可将生成的水通过共沸蒸馏除去。
式3的配合物的形成在常压下在从10℃到溶剂沸点的温度在溶剂中通过式6的配体与式7的化合物反应进行，所述溶剂如二氯甲烷、氯仿、1，2-二氯乙烷、苯、氯苯、DMF、乙醚、甲基叔丁基醚或THF。
式3的根据本发明的双金属配合物适合用于催化芳族羟基化合物氧化羰基化成碳酸二芳基酯。
用于根据本发明的方法的芳族羟基化合物是式8的那些
Ar-OH (8)，
其中
Ar表示苯基、萘基、蒽基、菲基、茚满残基、四氢萘基或具有1或2个选自N、O和S的杂原子的5-或6-元芳香杂环的残基，其中这些碳环和杂环残基可被具有苯基、氰基和卤素(如F、Cl、Br)的1或2个取代基如直链或支链的C1-C4烷基、直链或支链的C1-C4烷氧基、直链或支链的C1-C4烷氧羰基取代，并且其中所述杂环基也可与稠合的苯环相连。
式8的芳族羟基化合物的例子是：苯酚、邻甲酚、间甲酚和对甲酚、邻异丙基苯酚、间异丙基苯酚和对异丙基苯酚、相应的卤代苯酚和烷氧苯酚，如对氯苯酚和对甲氧基苯酚，水杨酸甲酯、水杨酸乙酯，此外萘、蒽和菲的单羟基化合物，以及4-羟基吡啶和羟基喹啉。优选使用苯酚和任选取代的苯酚，最特别优选苯酚。
由氧化羰基化制备碳酸二芳基酯是在根据本发明的式3催化剂的存在下通过芳香羟基化合物与一氧化碳和氧气的反应进行的。
借助于根据本发明的式3催化剂的芳族羟基化合物的氧化羰基化在液相中，在或不在溶剂中，所述溶剂如氯苯、二氯苯、甲苯、二甲苯、DMF、二甲基乙酰胺、四氢呋喃、NMP、碳酸亚乙酯或碳酸丙烯酯，在25-150℃，优选60-110℃的温度下，在一氧化碳/氧气混合物以分压比1∶1-99∶1，优选98∶2-60∶40存在下，任选在其它惰性气体如氮气、氩气或二氧化碳存在下，其中惰性气体与活性气体的分压比可为98∶2-2∶98，优选95∶5-50∶50，并且其中总压力为1巴-100巴，优选5巴-20巴。
另外的氧化还原物质，如醌、碱金属碘化物或碱土金属碘化物、锰化合物、钴化合物或铜化合物，也能够以1∶1-1∶100，优选1∶2-1∶20的钯化合物与氧化还原物质重量比存在。醌的例子是苯醌、萘醌和蒽醌及其取代产物。锰化合物、钴化合物或酮化合物的例子是其氧化物、卤化物、乙酰丙酮化物或羧化物。
鎓盐如铵盐、鏻盐或锍盐，铅化合物如烷基铅或铅的氧化物，聚合物如聚乙烯吡咯烷酮，卤代烷如二溴乙烷能够以1∶1-1∶200，优选1∶10-1∶50的钯化合物对助催化剂或助剂的重量比作为其它助催化剂或助剂使用。特别优选以1∶1-1∶200，优选1∶10-1∶50的钯化合物与助剂重量比使用铵或鏻化合物的溴化物。
使用式3的根据本发明的配合物作为催化剂制备的碳酸二芳基酯可用于制备聚碳酸酯或异氰酸酯。
下述实施例意在说明本发明而没有限制其范围。
实施例
4，5-二硝基邻苯二胺根据参考文献Cheeseman G.W.H.，J.Chem.Soc.，1962，1170的按照图1来制备。
实施例1
按照图2制备[DNtBuSalCu](根据本发明相当于式4a)
将0.69g(3.48mmol)Cu(OAc)2·H2O在20mL的乙醇中的溶液加入到0.68g(3.48mmol)的4，5-二硝基邻苯二胺和1.63g(6.96mmol)的3，5-二叔丁基水杨醛在80mL乙醇中的混合物中。将所述混合物回流加热80分钟。然后滤出沉淀，用正己烷洗涤，且在真空中干燥。
产率：1.27g(50％)
场解吸质谱(FD-MS，D+甲苯)m/z(％)：691(100)(C36H44CuN4O6)
实施例2
按照图3制备[DAtBuSalCu](根据本发明相当于式4b)
将1.27g(1.83mmol)[DNtBuSalCu]和0.2g的Pd/C(10％)在100mL的THF中的悬浮液在250ml的高压釜中用40巴的氢气压力加载，在室温下搅拌12小时，然后过滤。将滤液在真空中浓缩，残留物用己烷洗涤，然后在真空中干燥。
产率：1.16g(100％)
FD-MS(D+甲苯)m/z(％)：631(100)(C36H48CuN4O2)
实施例3
按照图4制备[PhenpzSalCu](根据本发明相当于式6)
将0.5g(0.79mmol)[DAtBuSalCu]在30mL的甲醇中的悬浮液滴加到0.16g(0.79mmol)的菲咯啉二酮在20ml甲醇中的溶液中。然后回流加热2小时，其中形成红色沉淀，将其过滤，利用石油醚洗涤且在真空中干燥。
产率：0.5g(78％)
FD-MS(D+甲苯)m/z(％)：805(100)(C48H50CuN6O2)
实施例4
按照图5制备[PdPhenpzSalCu](根据本发明相当于式1)
将0.01g(0.06mmol)[Pd(CH3CN)2Cl2]溶液加到0.05g(0.06mmol)[PhenpzSalCu]在5ml二氯甲烷的溶液中，并在室温下搅拌16小时。在真空中抽去挥发性组分，并且残余物被掺以己烷。然后将沉淀的产物滤出且在真空中干燥。
产率：0.025g(42％)
FD-MS(D+甲苯)m/z(％)：981(10)(C48H50Cl2CuN6O2Pd)，805(100)(C48H50CuN6O2)
实施例5
[PdPhenpzSalCu]作为催化剂用于制备碳酸二苯基酯的用途
将894mg(9.5mmol)的苯酚、8.5mg(0.0086mmol)的[PdPhenpzSalCu]、32mg(0.29mmol)的苯醌、222mg(0.69mmol)的溴化四丁铵和110mg的分子筛(3埃)的混合物用10巴的97％CO和3％O2的混合物冲洗三次，然后用18巴该体混合物加载。然后在以900转/分钟的搅拌下加热到90℃。反应3小时后用气相色谱分析反应混合物，得到产率为5.1mg(0.024mmol)碳酸二苯基酯，相当于催化剂的TON，基于钯为2.8和基于铜为2.8。
实施例6
将954mg(10.1mmol)的苯酚、9.1mg(0.0093mmol)的[PdPhenpzSalCu]、43.8mg(0.39mmol)的苯醌、212mg(0.66mmol)的溴化四丁铵和110mg的分子筛(3埃)的混合物用10巴的97％CO和3％O2的混合物冲洗三次，然后用18巴该气体混合物加载。然后在以900转/分钟的搅拌下加热到90℃。反应14小时后用气相色谱分析反应混合物，得到产率为5.8mg(0.027mmol)碳酸二苯基酯，相当于催化剂的TON，基于钯为3.0和基于铜为3.0。
在使用根据本发明的化合物时，基于钯和铜的TON随反应时间而增加。
比较实施例7
仿照参考文献J.Mol.Cat.A：Chem 2000，151，37-45的重复。
将920mg(9.78mmol)的苯酚、4.6mg(0.012mmol)的[Pd(Phen)Cl2]、20mg(0.056mmol)的[Co(acac)3]、31.8mg(0.29mmol)的苯醌、219mg(0.66mmol)的溴化四丁铵和110mg的分子筛(3埃)的混合物用10巴的97％CO和3％O2的混合物冲洗三次，然后用18巴该气体混合物加载。然后在以900转/分钟的搅拌下加热到90℃。反应3小时后用气相色谱分析反应混合物，得到产率为5.8mg(0.027mmol)碳酸二苯基酯，相当于催化剂的TON，基于钯为3.4和基于钴为0.5。
比较实施例8
将994mg(10.6mmol)的苯酚、4.3mg(0.011mmol)的[Pd(Phen)Cl2]、18.2mg(0.050mmol)的[Co(acac)3]、36.2mg(0.33mmol)的苯醌、203mg(0.60mmol)的溴化四丁铵和110mg的分子筛(3埃)的混合物用10巴的97％CO和3％O2的混合物冲洗三次，然后用18巴该气体混合物加载。然后在以900转/分钟的搅拌下加热到90℃。反应14小时后，利用气相色谱分析反应混合物，得到产率为4.7mg(0.022mmol)的碳酸二苯基酯，相当于催化剂的TON，基于钯为2.7和基于钴为0.4。
在比较实施例中，除了钯催化剂外，添加钴盐作为助催化剂是必需的。钯与助催化剂的摩尔比是1∶6.5，而在按照实施例5和6利用双金属配合物时，比例为1∶1。
表1
| 实施例5 | 实施例6 | 比较实施例7 | 比较实施例8 | |
| TON(Pd) | 2.8(3h) | 3.0(14h) | 3.4(3h) | 2.7(14h) |
| TON(Cu) | 2.8(3h) | 3.0(14h) | - | - |
| TON(Co) | - | - | 0.5(3h) | 0.4(14h) |
在比较实施例中，基于钯和钴的TONs在延长反应时间时降低。根据实施例5和相应的比较实施例7和8的双金属催化剂的对比证明，相对于现有技术的催化剂，根据本发明的双金属催化剂的稳定性更高。
在比较实施例7和8中，基于助催化剂的TON比按照实施例5和6使用根据本发明的双金属催化剂时低。
Claims (11)
1.式(3)的化合物
其中
R表示氢、氟、氯、硝基基团、C1-C22烷基残基或C6-C22芳基残基，
Hal表示氯离子、溴离子或碘离子、烷氧化物，或弱配位阴离子和
M1表示铜、锰或钴。
2.用于制备式3化合物的方法，所述方法通过式4a化合物的硝基的氢化生成式4b的化合物，然后与式5的菲咯啉二酮反应
生成式6的配体
并且与式7的化合物络合，
PdHal2L2(7)
其中Hal具有如上所述的含义且L表示任选存在的配体。
3.通式4a和4b的化合物，
其中R和M1具有如上所述的含义。
4.根据权利要求1的式3的一种或多种双金属化合物作为催化剂的用途。
5.根据权利要求1的式3的一种或多种双金属化合物用于芳族羟基化合物氧化羰基化成碳酸二芳基酯的用途。
6.碳酸二芳基酯，其可在使用根据权利要求1的式3配合物的条件下通过芳族羟基化合物的氧化羰基化反应得到。
7.制备碳酸二芳基酯的方法，其特征在于，使芳族羟基化合物在根据权利要求1的式3催化剂存在下与一氧化碳和氧气反应。
8.根据权利要求7的方法，其特征在于，使用式8的羟基化合物
Ar-OH(8)
其中
Ar表示苯基、萘基、蒽基、菲基、茚满基、四氢萘基或具有1或2个选自N、O和S中杂原子的5-或6-元芳香杂环的残基，其中这些碳环和杂环残基可被具有苯基、氰基和卤素(例如F、Cl、Br)的1或2个取代基如直链或支链的C1-C4烷基、直链或支链的C1-C4烷氧基、直链或支链的C1-C4烷氧羰基取代，并且其中所述杂环残基也可与稠合的苯环相连。
9.根据权利要求7或8的方法，其特征在于，使用了另外的氧化还原活性物质。
10.根据权利要求7到9任一项的方法，其特征在于，另外使用了助催化剂或助剂。
11.根据权利要求10的方法，其特征在于，使用了鎓盐、铅化合物、聚合物、卤代烷。
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| DE102009058053A DE102009058053A1 (de) | 2009-12-14 | 2009-12-14 | Bimetalliche Komplexe und ihre Verwendung in der Diarylcarbonatherstellung |
| DE102009058053.0 | 2009-12-14 | ||
| PCT/EP2010/069323 WO2011073087A1 (de) | 2009-12-14 | 2010-12-09 | Bimetallische komplexe und ihre verwendung in der diarylcarbonatherstellung |
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| CN113903934A (zh) * | 2021-10-11 | 2022-01-07 | 先进能源产业研究院(广州)有限公司 | 一种多孔Pd-PdO纳米棒的制备方法及其应用 |
| CN113903934B (zh) * | 2021-10-11 | 2023-12-08 | 先进能源产业研究院(广州)有限公司 | 一种多孔Pd-PdO纳米棒的制备方法及其应用 |
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| US8987446B2 (en) | 2015-03-24 |
| JP2013513633A (ja) | 2013-04-22 |
| WO2011073087A1 (de) | 2011-06-23 |
| CN102753560B (zh) | 2016-01-06 |
| ES2547311T3 (es) | 2015-10-05 |
| DE102009058053A1 (de) | 2011-06-16 |
| EP2513126A1 (de) | 2012-10-24 |
| SG180834A1 (en) | 2012-07-30 |
| US20130018186A1 (en) | 2013-01-17 |
| EP2513126B1 (de) | 2015-07-29 |
| RU2012129672A (ru) | 2014-01-27 |
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