CN1688531A - 制备醛化合物的方法 - Google Patents
制备醛化合物的方法 Download PDFInfo
- Publication number
- CN1688531A CN1688531A CNA038245809A CN03824580A CN1688531A CN 1688531 A CN1688531 A CN 1688531A CN A038245809 A CNA038245809 A CN A038245809A CN 03824580 A CN03824580 A CN 03824580A CN 1688531 A CN1688531 A CN 1688531A
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- CN
- China
- Prior art keywords
- alkyl
- ligand
- amylene
- compound
- independently
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- -1 aldehyde compounds Chemical class 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- 239000003446 ligand Substances 0.000 claims abstract description 82
- 238000000034 method Methods 0.000 claims abstract description 33
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- 238000007037 hydroformylation reaction Methods 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 230000008569 process Effects 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims description 84
- 239000010948 rhodium Substances 0.000 claims description 49
- 239000002253 acid Substances 0.000 claims description 40
- 150000004702 methyl esters Chemical class 0.000 claims description 39
- 229910052703 rhodium Inorganic materials 0.000 claims description 35
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 35
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 16
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 15
- 150000002894 organic compounds Chemical class 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 125000003545 alkoxy group Chemical group 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 125000004104 aryloxy group Chemical group 0.000 claims description 8
- 125000004429 atom Chemical group 0.000 claims description 8
- UIUWNILCHFBLEQ-NSCUHMNNSA-N trans-pent-3-enoic acid Chemical compound C\C=C\CC(O)=O UIUWNILCHFBLEQ-NSCUHMNNSA-N 0.000 claims description 7
- XWJBRBSPAODJER-UHFFFAOYSA-N 1,7-octadiene Chemical compound C=CCCCCC=C XWJBRBSPAODJER-UHFFFAOYSA-N 0.000 claims description 6
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 6
- SHCSFZHSNSGTOP-UHFFFAOYSA-N Methyl 4-pentenoate Chemical compound COC(=O)CCC=C SHCSFZHSNSGTOP-UHFFFAOYSA-N 0.000 claims description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 5
- 150000002825 nitriles Chemical class 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 4
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 claims description 4
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 claims description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- 125000004448 alkyl carbonyl group Chemical group 0.000 claims description 4
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 4
- 125000005129 aryl carbonyl group Chemical group 0.000 claims description 4
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 claims description 4
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000013110 organic ligand Substances 0.000 claims description 4
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 4
- 125000003107 substituted aryl group Chemical group 0.000 claims description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 3
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 claims description 3
- HVAMZGADVCBITI-UHFFFAOYSA-N pent-4-enoic acid Chemical compound OC(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-N 0.000 claims description 3
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 claims description 2
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 claims description 2
- YCTDZYMMFQCTEO-FNORWQNLSA-N (E)-3-octene Chemical compound CCCC\C=C\CC YCTDZYMMFQCTEO-FNORWQNLSA-N 0.000 claims description 2
- IYWJIYWFPADQAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;ruthenium Chemical compound [Ru].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O IYWJIYWFPADQAN-LNTINUHCSA-N 0.000 claims description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 2
- GGRQQHADVSXBQN-FGSKAQBVSA-N carbon monoxide;(z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].[O+]#[C-].[O+]#[C-].C\C(O)=C\C(C)=O GGRQQHADVSXBQN-FGSKAQBVSA-N 0.000 claims description 2
- WCASXYBKJHWFMY-UHFFFAOYSA-N crotyl alcohol Chemical compound CC=CCO WCASXYBKJHWFMY-UHFFFAOYSA-N 0.000 claims description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 claims description 2
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 claims description 2
- 239000004913 cyclooctene Substances 0.000 claims description 2
- 150000001941 cyclopentenes Chemical class 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 229940087305 limonene Drugs 0.000 claims description 2
- 235000001510 limonene Nutrition 0.000 claims description 2
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 claims description 2
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 claims description 2
- LIINGNMKNRSOGW-UHFFFAOYSA-N oct-7-enal Chemical compound C=CCCCCCC=O LIINGNMKNRSOGW-UHFFFAOYSA-N 0.000 claims description 2
- 229940055577 oleyl alcohol Drugs 0.000 claims description 2
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 claims description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical group CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 2
- 229930015698 phenylpropene Natural products 0.000 claims description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229940095068 tetradecene Drugs 0.000 claims description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 4
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims 1
- QTYUSOHYEPOHLV-FNORWQNLSA-N 1,3-Octadiene Chemical compound CCCC\C=C\C=C QTYUSOHYEPOHLV-FNORWQNLSA-N 0.000 claims 1
- ILPBINAXDRFYPL-UHFFFAOYSA-N 2-octene Chemical compound CCCCCC=CC ILPBINAXDRFYPL-UHFFFAOYSA-N 0.000 claims 1
- ZQDPJFUHLCOCRG-UHFFFAOYSA-N 3-hexene Chemical compound CCC=CCC ZQDPJFUHLCOCRG-UHFFFAOYSA-N 0.000 claims 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims 1
- AHAREKHAZNPPMI-UHFFFAOYSA-N hexa-1,3-diene Chemical compound CCC=CC=C AHAREKHAZNPPMI-UHFFFAOYSA-N 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 15
- 125000004437 phosphorous atom Chemical group 0.000 abstract description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 7
- 239000011574 phosphorus Substances 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 abstract description 5
- WKEDVNSFRWHDNR-UHFFFAOYSA-N salicylanilide Chemical group OC1=CC=CC=C1C(=O)NC1=CC=CC=C1 WKEDVNSFRWHDNR-UHFFFAOYSA-N 0.000 abstract 1
- 229950000975 salicylanilide Drugs 0.000 description 37
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 24
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 21
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N phenyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 description 20
- 238000005984 hydrogenation reaction Methods 0.000 description 18
- 238000002360 preparation method Methods 0.000 description 17
- 238000004679 31P NMR spectroscopy Methods 0.000 description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- 150000001299 aldehydes Chemical class 0.000 description 15
- 150000001336 alkenes Chemical class 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000002474 experimental method Methods 0.000 description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 229960000969 phenyl salicylate Drugs 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229950011260 betanaphthol Drugs 0.000 description 8
- 238000009833 condensation Methods 0.000 description 8
- 230000005494 condensation Effects 0.000 description 8
- 229910000765 intermetallic Inorganic materials 0.000 description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- MCWXGJITAZMZEV-UHFFFAOYSA-N dimethoate Chemical compound CNC(=O)CSP(=S)(OC)OC MCWXGJITAZMZEV-UHFFFAOYSA-N 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 238000005304 joining Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 230000022244 formylation Effects 0.000 description 3
- 238000006170 formylation reaction Methods 0.000 description 3
- 125000000962 organic group Chemical group 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- DTCCTIQRPGSLPT-UHFFFAOYSA-N 2-pentenal Chemical class CCC=CC=O DTCCTIQRPGSLPT-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000004494 ethyl ester group Chemical group 0.000 description 2
- 238000010265 fast atom bombardment Methods 0.000 description 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 2
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 2
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 2
- WUCQRXWCJPCWTQ-UHFFFAOYSA-N pent-3-enal Chemical class CC=CCC=O WUCQRXWCJPCWTQ-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 2
- YIYBQIKDCADOSF-ONEGZZNKSA-N trans-pent-2-enoic acid Chemical compound CC\C=C\C(O)=O YIYBQIKDCADOSF-ONEGZZNKSA-N 0.000 description 2
- JMFDVDRXRIZZGX-UHFFFAOYSA-N (2-methyl-4-oxobutyl) acetate Chemical group O=CCC(C)COC(C)=O JMFDVDRXRIZZGX-UHFFFAOYSA-N 0.000 description 1
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 1
- ILPBINAXDRFYPL-HWKANZROSA-N (E)-2-octene Chemical compound CCCCC\C=C\C ILPBINAXDRFYPL-HWKANZROSA-N 0.000 description 1
- ILPBINAXDRFYPL-HYXAFXHYSA-N (Z)-2-octene Chemical compound CCCCC\C=C/C ILPBINAXDRFYPL-HYXAFXHYSA-N 0.000 description 1
- YCTDZYMMFQCTEO-ALCCZGGFSA-N (Z)-3-octene Chemical compound CCCC\C=C/CC YCTDZYMMFQCTEO-ALCCZGGFSA-N 0.000 description 1
- WUCQRXWCJPCWTQ-NSCUHMNNSA-N (e)-pent-3-enal Chemical class C\C=C\CC=O WUCQRXWCJPCWTQ-NSCUHMNNSA-N 0.000 description 1
- RYPKRALMXUUNKS-HYXAFXHYSA-N (z)-hex-2-ene Chemical compound CCC\C=C/C RYPKRALMXUUNKS-HYXAFXHYSA-N 0.000 description 1
- PRBHEGAFLDMLAL-UHFFFAOYSA-N 1,5-Hexadiene Natural products CC=CCC=C PRBHEGAFLDMLAL-UHFFFAOYSA-N 0.000 description 1
- SJJCQDRGABAVBB-UHFFFAOYSA-N 1-hydroxy-2-naphthoic acid Chemical compound C1=CC=CC2=C(O)C(C(=O)O)=CC=C21 SJJCQDRGABAVBB-UHFFFAOYSA-N 0.000 description 1
- ZSDQQJHSRVEGTJ-UHFFFAOYSA-N 2-(6-amino-1h-indol-3-yl)acetonitrile Chemical compound NC1=CC=C2C(CC#N)=CNC2=C1 ZSDQQJHSRVEGTJ-UHFFFAOYSA-N 0.000 description 1
- YKOLZVXSPGIIBJ-UHFFFAOYSA-N 2-Isopropylaniline Chemical compound CC(C)C1=CC=CC=C1N YKOLZVXSPGIIBJ-UHFFFAOYSA-N 0.000 description 1
- MLPVBIWIRCKMJV-UHFFFAOYSA-N 2-ethylaniline Chemical compound CCC1=CC=CC=C1N MLPVBIWIRCKMJV-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- RYPKRALMXUUNKS-HWKANZROSA-N 2E-hexene Chemical compound CCC\C=C\C RYPKRALMXUUNKS-HWKANZROSA-N 0.000 description 1
- ALKYHXVLJMQRLQ-UHFFFAOYSA-N 3-Hydroxy-2-naphthoate Chemical class C1=CC=C2C=C(O)C(C(=O)O)=CC2=C1 ALKYHXVLJMQRLQ-UHFFFAOYSA-N 0.000 description 1
- BWRRWBIBNBVHQF-UHFFFAOYSA-N 4-(3-pyridin-2-yl-1,2,4-oxadiazol-5-yl)butanoic acid Chemical compound O1C(CCCC(=O)O)=NC(C=2N=CC=CC=2)=N1 BWRRWBIBNBVHQF-UHFFFAOYSA-N 0.000 description 1
- YBAZINRZQSAIAY-UHFFFAOYSA-N 4-aminobenzonitrile Chemical compound NC1=CC=C(C#N)C=C1 YBAZINRZQSAIAY-UHFFFAOYSA-N 0.000 description 1
- QSNSCYSYFYORTR-UHFFFAOYSA-N 4-chloroaniline Chemical compound NC1=CC=C(Cl)C=C1 QSNSCYSYFYORTR-UHFFFAOYSA-N 0.000 description 1
- KRZCOLNOCZKSDF-UHFFFAOYSA-N 4-fluoroaniline Chemical compound NC1=CC=C(F)C=C1 KRZCOLNOCZKSDF-UHFFFAOYSA-N 0.000 description 1
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
- C07F9/6584—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms having one phosphorus atom as ring hetero atom
- C07F9/65842—Cyclic amide derivatives of acids of phosphorus, in which one nitrogen atom belongs to the ring
- C07F9/65846—Cyclic amide derivatives of acids of phosphorus, in which one nitrogen atom belongs to the ring the phosphorus atom being part of a six-membered ring which may be condensed with another ring system
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- C07F9/02—Phosphorus compounds
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Abstract
本发明涉及一种在含有VIII族金属和具有两个结合至N-水杨酰替苯胺基团的三价磷原子的二齿磷配位体存在下,由不饱和化合物通过加氢甲酰基化制备有机醛化合物的方法。
Description
发明领域
本发明涉及一种在含有VIII族金属和具有两个结合至N-水杨酰替苯胺基团的三价磷原子的二齿磷配位体存在下,由不饱和化合物通过加氢甲酰基化制备有机醛化合物的方法。
发明背景
具有三价磷原子的配位体的特征为每个三价磷原子和三个有机基团结合。磷酰胺化合物的特征为所述磷原子通过至少一个P-N键和一个或两个P-O键连接至所述有机基团(即分别为磷酰二胺(phosphorodiamidites)和磷酰胺(phosphoramidites))。二齿磷配位体的特征还在于在所述分子中存在有两个磷原子,并且一个有机桥连基(Q)将两个磷原子相连。其他与单个磷原子键合的有机基团通常称为末端基团(R)。
众多的专利(US4,769,498等)和其它文献描述了烯烃的加氢甲酰基化方法,其中,通过结合铑和含有通过有机二羟基桥连基链接的两个磷原子的有机二齿亚磷酸酯配位体形成一种有效的均相加氢甲酰基化催化体系。在这些亚磷酸酯配位体中的末端基团几乎均为取代的苯酚或类似于所述桥连基的有机二羟基。
二齿亚磷酸酯配位体
仅有几篇文献公开了用于烯烃加氢甲酰基化的有机二齿磷酰胺配位体和铑的实例(WO 9616923,US5,710,344等),磷酰胺配位体的实例包括如下的几种。
二齿磷酰胺-亚磷酸酯 二齿磷酰二胺
然而,没有发现现有技术描述使用有机二齿亚磷酸酯或磷酰胺配位体用于烯烃加氢甲酰基化的均相铑催化体系,其中所述有机二齿亚磷酸酯或磷酰胺配位体由两个通过有机二羟基桥连基连接并带有N-水杨酰替苯胺末端基团的磷原子组成。N-水杨酰替苯胺是以下两种结构的共振杂化分子。
发明概述
本发明公开的是从不饱和有机化合物制备有机醛化合物的加氢甲酰基化方法,所述方法包括:使不饱和有机化合物与一氧化碳、氢气和催化系统接触,所述催化系统包含VIII族金属和至少一种具有两个三价磷原子的二齿有机配位体或至少两种这样的二齿有机配位体的组合,所述配位体选自结构I、II、III、IV、V和VI:
结构I 结构II
结构III 结构IV
结构V 结构VI
其中X1-X4是C1-C6烷基、烷氧基、芳氧基、NR6R7、Cl、F或CF3;R1独立选自取代芳基、苯基或稠合芳环体系;R2和R3独立选自氢、烷基、芳基、三芳基甲硅烷基、三烷基甲硅烷基、烷氧基羰基(carboalkoxy)、芳氧基羰基(carboaryloxy)、芳氧基、烷氧基、烷基羰基、芳基羰基或腈;R4和R5独立选自氢、烷基、烷氧基;R6和R7独立选自烷基和芳基。
本发明还公开了由以上结构I至VI代表的具有两个三价磷原子的新的二齿配位体组合物。
发明详述
本发明提供了一种使用高性能(即高选择性和/或高活性)催化剂体系和新的二齿配位体制备有机醛的加氢甲酰基化方法。在含有VIII族金属或含有VIII族金属化合物、具有两个三价磷原子的二齿配位体的催化系统存在下,使用加氢甲酰基化方法,由烯键式不饱和化合物制备醛。使用本发明的方法获得了对醛的高选择性及相对高的催化活性。
当以内不饱和有机化合物为原料时,该方法的优点更为显著。与末端烯烃相对比,以内不饱和化合物为原料,使用现有技术的加氢甲酰基化方法通常导致对醛的选择性较低,更多的烯烃双键被氢化,和/或更低的催化活性。本发明方法的另一优点是具有较高的线性度[线性醛/(线性醛+支化醛)]。
本发明的目的通过在VIII族金属催化的加氢甲酰基化方法中,使用至少一种下式的配位体来实现:
结构I 结构II
结构III 结构IV
结构V 结构VI
其中X1-X4是C1-C6烷基、烷氧基、芳氧基、NR6R7、Cl、F或CF3;
R1选自取代芳基、苯基或稠合芳环体系;
R2和R3各自独立选自氢、烷基、芳基、三芳基甲硅烷基、三烷基甲硅烷基、烷氧基羰基、芳氧基羰基、芳氧基、烷氧基、烷基羰基、芳基羰基或腈;
R4和R5独立选自氢、烷基、烷氧基;
R6和R7是独立选自烷基和芳基。
本发明的配位体的实例有:
配位体1 配位体2
配位体3 配位体4
配位体5 配位体6
配位体7 配位体8
配位体9 配位体10
配位体11
配位体12 配位体13
N-水杨酰替苯胺可通过用苯胺将水杨酸苯酯酰胺化制备或通过用苯胺处理水杨酰氯(通常用SOCl2、PCl3或POCl3原位制得)制备。两种化学反应均会产生1-羟基-2-萘甲酸或2-羟基-3-萘甲酸衍生物而得到萘基类似物。
N-水杨酰替苯胺可与三氯化磷(PCl3)得到化合物,其中所述N-水杨酰替苯胺的作用是作为所述磷原子的双阴离子螯合物。下面显示了两种可能的产物结构(A和B),它们的不同之处在于与磷连接的N-水杨酰替苯胺原子(键合异构体)。对于以下提供的例子,在140ppm区域观察到31P NMR单峰。
我们已经发现,当存在碱(如三乙胺)时,则所述产物A、B或A和B的组合将与有机桥基(未取代或取代的2,2′-联苯酚或1,1′-联-2-萘酚)反应形成可用于本发明方法的单一配位体或混合配位体。取决于所述桥基和N-水杨酰替苯胺基,A或B在140ppm的31P NMR峰转变为在109-121ppm区域的单峰或多重峰。至于所述配位体产物混合物,NMR分析表明磷原子处于不同的化学环境中。
本发明的催化剂体系可按照已知形成络合物的方法,任选在适合的溶剂中,通过混合适合的VIII族金属或VIII族金属化合物和含磷配位体而制得。
适合的VIII族金属的实例有钌、铑和铱。适合的VIII族金属化合物的实例有如Ru3(CO)12、Ru(NO3)3、RuCl3(Ph3P)3、Ru(acac)3、Ir4(CO)12、IrSO4、RhCl3、Rh(NO3)3、Rh(OAC)3、Rh2O3、Rh(acac)(CO)2、[Rh(OAc)(COD)]2、Rh4(CO)12、Rh6(CO)16、RhH(CO)(Ph3P)3、[Rh(OAc)(CO)2]2和[RhCl(COD)]2(其中“acac”是乙酰丙酮根;“Ac”是乙酰基;“COD”是1,5-环辛二烯;而“Ph”是苯基)。然而,应注意到所述VIII族金属化合物不限于上面列出的化合物。所述VIII金属源优选为铑。适合的VIII族金属化合物源包括但不限于VIII族金属的氢化物、卤化物、有机酸盐、乙酰丙酮酸盐、无机酸盐、氧化物、碳基化合物和胺化合物。
用于本发明中的不饱和有机化合物在分子中必须具有至少一个“C=C”键,并优选具有2至20个碳原子。用于本发明的适合的烯键式不饱和有机化合物包括但不限于线性末端烯烃。这类化合物的一些实例为乙烯、丙烯、1-丁烯、1-戊烯、1-己烯、1-辛烯、1-壬烯、1-癸烯、1-十四碳烯、1-十六碳烯、1-十八碳烯、1-二十碳烯和1-十二碳烯;支化末端烯烃,例如异丁烯和2-甲基-1-丁烯;线性内烯烃,如顺式和反式-2-丁烯、顺式和反式-2-己烯、顺式和反式-3-己烯、顺式和反式-2-辛烯以及顺式和反式-3-辛烯;支化内烯烃,如2,3-二甲基-2-丁烯、2-甲基-2-丁烯和2-甲基-2-戊烯;末端烯烃-内烯烃的混合物,如通过丁烯二聚作用制备的辛烯、低级烯烃(包括丙烯、正丁烯、异丁烯等)的从二聚物至四聚物的烯烃低聚物异构体混合物;和脂环族烯烃,如环戊烯、环己烯、1-甲基环己烯、环辛烯和柠檬烯。丁二烯、乙酸甲代烯丙酯、3-戊烯酸和具有6至20个碳原子的不饱和有机化合物(如3-戊烯酸烷基酯)均可用于本发明中。
适合的烯烃化合物包括被不饱和烃基取代的化合物,这类化合物包括含有芳族取代基如苯乙烯、α-甲基苯乙烯和烯丙基苯的化合物;和二烯烃化合物,如丁二烯、1,5-己二烯、1,7-辛二烯和降冰片二烯。发现采用本发明的方法,可以高收率从丁二烯制备3-戊烯醛。
所述不饱和有机化合物可被一个或更多含氧、硫、氮或磷等杂原子的基团取代。这些被杂原子取代的不饱和有机化合物包括但不限于乙烯基甲基醚、油酸甲酯、油醇、烯丙醇、甲代烯丙醇、乙酸甲代烯丙酯、2-戊烯酸甲酯、3-戊烯酸甲酯、4-戊烯酸甲酯、3-戊烯酸、4-戊烯酸、1,7-辛二烯、7-辛烯-1-醛、丙烯腈、丙烯酸酯、丙烯酸甲酯、甲基丙烯酸酯和甲基丙烯酸甲酯。
一种特殊的内不饱和有机化合物为3-戊烯酸和3-戊烯酸C1-C6烷基酯化合物。可通过公开的方法由这些化合物制备的末端醛化合物可有利地用于制备γ-己内酰胺或己二酸,它们分别是Nylon-6和Nylon-6,6的前体。3-戊烯酸C1-C6烷基酯的实例有3-戊烯酸甲酯、乙酯、丙酯、异丙酯、叔丁酯、戊酯和环己酯。优选3-戊烯酸甲酯和乙酯,因为它们更容易得到。
3-戊烯酸和3-戊烯酸C1-C6烷基酯化合物可存在于分别含有2-和4-戊烯酸和2-和4-戊烯酸C1-C6烷基酯化合物的混合物中。因为这些化合物作为3-异构体,以相似方式反应,得到所需的末端醛,在本发明的方法中,可直接使用各种异构体的混合物。
实施所述加氢甲酰基化方法的条件取决于具体的不饱和有机化合物原料。反应温度可为约室温至约200℃、优选约50℃至约150℃。压力可从常压至20MPa,优选从0.15至10MPa,更优选从0.2至5MPa。通常,所述压力等于氢气的分压加上一氧化碳的分压。然而,还存在有惰性气体。氢气和一氧化碳的摩尔比通常在10∶1至1∶10之间,并优选在6∶1至1∶2之间。
通常在反应介质中的VIII族金属或VIII族金属化合物的浓度在10至10,000ppm之间,更优选在100-1000ppm之间,按游离金属计算。
多齿磷配位体与VIII族金属或VIII族金属化合物的摩尔比为约0.5至100,并优选从1至10(配位体的摩尔数/金属的摩尔数)。
溶剂可以是从本身参与加氢甲酰基化的反应物的混合物,如原料不饱和化合物,所述醛产物和/或副产物。任选可使用非反应物混合物的溶剂。适用于本发明的溶剂包括饱和烃(如煤油、矿物油或环己烷)、醚(如二苯醚或四氢呋喃)、酮(如丙酮、环己酮)、腈(如乙腈、己二腈或苄腈)、芳烃(如甲苯、苯或二甲苯)、酯(如戊酸甲酯、己内酯)、Texanol(购自Union Carbide)或二甲基甲酰胺。
下述非限定性的实施例举例说明了本发明的各种实施方案。
实施例
实施例1:用铑和得自N-水杨酰替苯胺、PCl3 和联萘酚的配位体混 合物1实施3-戊烯酸甲酯的加氢甲酰基化
(a)配位体混合物1的制备
在一个充满氮气的干燥箱子中,在装有无水四氢呋喃(50ml)的烧瓶中混合N-水杨酰替苯胺(4.26g,20mmol)、PCl3(2.74g,20mmol)和无水三乙胺(4.04g,40mmol)。整夜搅拌后,31P NMR分析显示在140ppm有一个单峰。向所述四氢呋喃溶液中加入无水三乙胺(2.02g,20mmol)和1,1′-联-2-萘酚(2.86g,10mmol),然后搅拌混合物过夜。再次的31P NMR分析表明全部转化为新的化合物,在117-118.5ppm之间有几个峰。蒸发四氢呋喃,然后加入乙醚(30mL)溶解所需产物。过滤分离铵盐后,蒸发醚滤液获得剩余物。从CH2Cl2/己烷中结晶得到黄色固体。FAB(快速原子轰击)MS:m/e=769(M+,C46H30O6N2P2计算值768.7)。
(b)用铑和实施例1a的配位体混合物实施3-戊烯酸甲酯的加氢甲酰基
化;
在一个25mL的搪玻璃压力容器中加入5mL 11.4g(100mmol)3-戊烯酸甲酯、0.068g(0.2mmol)二羰基·(2,2,6,6-四甲基-3,5-庚二酮根)合铑、0.78g(1.0mmol)实施例1a的混合物和1.00g十四烷(GC内标)在100mL甲苯中的溶液。所述压力容器通过首先用氮气(两次)然后用1∶1 CO/H2(两次)换气除去空气。然后使容器增压至75psi CO并搅拌加热至100℃下2小时。关闭加热并使所述压力容器冷却至室温。放出多余的气体然后用GC分析产物。3-戊烯酸甲酯的转化率(%3-戊烯酸甲酯加上已反应的4-戊烯酸甲酯):80.3%;线性度[100×5-甲酰基戊酸甲酯/(5-甲酰基戊酸甲酯+支化的甲酰基戊酸酯)]:84.8%;选择性(100×5-甲酰基戊酸甲酯/所有产物):73.3%。
实施例2:用铑和得自2′-甲基-N-水杨酰替苯胺、PCl3 和2,2′-二羟基- 1,1′-联萘-3,3′-二甲酸二甲酯的配位体混合物2实施3-戊烯酸甲酯的加 氢甲酰基化
(a)配位体化合物2的制备
按现有文献(Organic Syntheses,Coll,3卷,765)的描述,从水杨酸苯酯(42.8g,0.20mol)、2-甲苯胺(26.7g,0.25mol)和1,2,4-三氯苯(41mL)沸腾混合物中蒸馏出苯酚。把冷却的产物混合物转移至一个250mL的锥形瓶中并与正己烷(75mL)一起沸腾30分钟。通过真空过滤从所述热混合物中分离出固体产物。用更多的己烷洗涤所述固体直至滤液无色。干燥得到纯2′-甲基-N-水杨酰替苯胺(41g,90%),为白色固体。
在一个充满氮气的干燥箱子中,在含有无水四氢呋喃(50ml)的烧瓶中混合2′-甲基-N-水杨酰替苯胺(2.27g,10mmol)、PCl3(1.37g,10mmol)和无水三乙胺(2.02g,20mmol)。整夜搅拌后,31P NMR分析显示在141ppm有一个单峰。向所述四氢呋喃溶液中加入无水三乙胺(1.01g,10mmol)和2,2′-二羟基-1,1′-联萘-3,3′-二甲酸二甲酯(2.01g,5mmol),然后整夜搅拌混合物。再次的31P NMR分析表明全部转化为新的化合物,在116-119ppm之间有几个峰。蒸发所述四氢呋喃然后加入无水乙醚(30mL)以溶解所需的产物。过滤分离铵盐后,蒸发所述醚滤液而获得用作为催化剂的剩余物。
(b)用铑和实施例2a的配位体混合物实施3-戊烯酸甲酯的加氢甲酰基
化;
用得自实施例2a的混合物(45.6mg/5mL)代替得自实施例1a的混合物,重复实施例1b的实验。GC分析显示了80.6%的3-戊烯酸甲酯转化率,71.2%的对5-甲酰基戊酸甲酯选择率和88.7%的线性度。
实施例3:用铑和得自2′-甲基-N-水杨酰替苯胺、PCl3 和联萘酚的配 位体混合物3实施3-戊烯酸甲酯的加氢甲酰基化
(a)配位体混合物3的制备
按实施例2a的描述,将水杨酸苯酯和2-甲苯胺缩合制备2-甲基-N-水杨酰替苯胺并纯化。然后使用实施例2a中描述的方法,由2-甲基-N-水杨酰替苯胺和1,1′-联-2-萘酚制备配位体混合物。31PNMR(121.77MHz):在109-120ppm之间有几个峰。
(b)用铑和实施例3a制备的配位体混合物实施3-戊烯酸甲酯与的加氢
甲酰基化;
用得自实施例3a的混合物(45.6mg/5mL)代替实施例1a制备的混合物,重复实施例1b的实验。GC结果在表1中给出。
实施例4:用铑和得自N-水杨酰替苯胺、PCl3 和联萘酚的配位体混 合物4实施3-戊烯酸甲酯的加氢甲酰基化
(a)配位体混合物4的制备
按实施例1a所述,由N-水杨酰替苯胺和2,2′-联苯酚制备在实施例1a中制备的联苯酚类似物的配位体混合物。31PNMR(121.77MHz):112ppm有单峰并在138ppm和113ppm有小峰。
(b)用铑和实施例4a制备的配位体混合物实施3-戊烯酸甲酯的加氢甲
酰基化;
用得自实施例4a的混合物(33.4mg/5mL)代替得自实施例1a的混合物,重复实施例1b的实验。GC结果在表1中给出。
实施例5:用铑和得自4′-氯-N-水杨酰替苯胺、PCl3 和联萘酚的配位 体混合物5实施3-戊烯酸甲酯的加氢甲酰基化
(a)配位体混合物5的制备
按实施例2a所述,通过水杨酸苯酯和4-氯苯胺的缩合制备4′-氯-N-水杨酰替苯胺并纯化。
在干燥氮气气氛下,在含有无水甲苯(40ml)的烧瓶中混合4′-氯-N-水杨酰替苯胺(2.79g,11mmol)、PCl3(4.6g,34mmol)和无水三乙胺(4.55g,45mmol),并回流4小时。在所述干燥箱中,过滤分离出铵盐,然后用无水甲苯洗涤(2×10mL)。蒸发合并的滤液。31P NMR分析显示在139.4ppm有一个单峰。
将1,1′-联-2-萘酚(1.43g,5mmol)和4′-氯-N-水杨酰替苯胺/PCl3的反应产物(2.95g,10mmol)溶解在无水乙醚(50mL)中,然后逐加无水三乙胺(1.01g,10mmol)。在整夜搅拌后,再次的31P NMR分析显示完全转化为新化合物,具有117.1ppm的化学位移。过滤分离出铵盐后,蒸发醚滤液而获得橙色粉末。
(b)用铑和得自实施例5a的配位体混合物5实施3-戊烯酸甲酯的加氢
加酰化;
用得自实施例5a的混合物(41.9mg/5mL)代替得自实施例1a的混合物,重复实施例1b的实验。GC结果在表1中给出。
实施例6:用铑和得自4′-甲基-N-水杨酰替苯胺、PCl3 和联萘酚的配 位体混合物6实施3-戊烯酸甲酯的加氢加酰化
(a)配位体混合物6的制备
按实施例2a所述,通过水杨酸苯酯和4-甲苯胺的缩合制备4′-甲基-N-水杨酰替苯胺并纯化。然后使用实施例5a描述的方法,由4′-甲基-N-水杨酰替苯胺和联萘酚制备配位体混合物。 31PNMR(121.77MHz):在117.1-117.8ppm之间有几个峰。
(b)用铑和来自实施例6a的配位体混合物实施3-戊烯酸甲酯的加氢加
酰化;
用得自实施例6a的混合物(39.8mg/5mL)代替得自实施例1a的混合物,重复实施例1b的实验。GC结果在表1中给出。
实施例7:用铑和来自4′-甲氧基-N-水杨酰替苯胺、PCl3 和联萘酚的 配位体混合物7实施3-戊烯酸甲酯的加氢加酰化
(a)配位体混合物7的制备
按实施例2a所述,通过水杨酸苯酯和4-氨基苯甲醚的缩合制备4′-甲氧基-N-水杨酰替苯胺并纯化。然后使用实施例5a描述的方法,由4′-甲氧基-N-水杨酰替苯胺和1,1′-联-2-萘酚制备配位体的混合物。31P NMR(121.77MHz):在116-118ppm之间有几个峰。
(b)用铑和得自实施例7a的配位体混合物实施3-戊烯酸甲酯的加氢加
酰化;
用得自实施例7a的混合物(41.4mg/5mL)代替得自实施例1a的混合物,重复实施例1b的实验。GC结果在表1中给出。
实施例8:用铑和得自4′-氟-N-水杨酰替苯胺、PCl3 和联萘酚的配位 体混合物8实施3-戊烯酸甲酯的加氢加酰化
(a)配位体混合物8的制备
按实施例2a所述,通过水杨酸苯酯和4-氟苯胺的缩合制备4′-氟-N-水杨酰替苯胺并纯化。然后使用实施例5a描述的方法,由4′-氟-N-水杨酰替苯胺和1,1′-联-2-萘酚制备配位体混合物。31PNMR(121.77MHz):在117.1-117.7ppm之间有几个峰。
(b)用铑和来自实施例8a的配位体混合物实施3-戊烯酸甲酯的加氢加
酰化
用得自实施例8a的混合物(40.2mg/5mL)代替得自实施例1a的混合物,重复实施例1b的实验。GC结果在表1中给出。
实施例9:用铑和来自2′-乙基-N-水杨酰替苯胺、PCl3 和联萘酚的配 位体混合物9实施3-戊烯酸甲酯的加氢加酰化
(a)配位体混合物9的制备
按实施例2a所述,通过水杨酸苯酯和2-乙苯胺的缩合制备2′-乙基-N-水杨酰替苯胺并纯化。然后使用实施例2a描述的方法,由2′-乙基-N-水杨酰替苯胺和1,1′-联-2-萘酚制备配位体混合物。31PNMR(121.77MHz):在117.1-118.8ppm之间有数个峰。
(b)用铑和来自实施例9a的配位体混合物实施3-戊烯酸甲酯的加氢加
酰化
用得自实施例9a的混合物(41.2mg/5mL)代替得自实施例1b的混合物,重复实施例1b的实验。GC结果在表1中给出。
实施例10:用铑和得自4′-氰基-N-水杨酰替苯胺、PCl3 和联萘酚的配 位体混合物10实施3-戊烯酸甲酯的加氢加酰化
(a)配位体混合物10的制备
按实施例2a所述,通过水杨酸苯酯和4-氨基-苄腈的缩合制备4′-氰基-N-水杨酰替苯胺并纯化。然后使用实施例5a描述的方法,由4′-氰基-N-水杨酰替苯胺和1,1′-联-2-萘酚制备配位体混合物。31PNMR(121.77MHz):在116.4-117.7ppm之间有数个峰。
(b)用铑和来自实施例10a的配位体混合物实施3-戊烯酸甲酯的加氢
加酰化
用得自实施例10a的混合物(40.9mg/5mL)代替得自实施例1a的混合物,重复实施例1b的实验。GC结果在表1中给出。
实施例11:用铑和得自2′-异丙基-N-水杨酰替苯胺、PCl3 和联萘酚的 配位体混合物11实施3-戊烯酸甲酯的加氢加酰化
(a)配位体混合物11的制备
按实施例2a所述,通过水杨酸苯酯和2-异丙苯胺的缩合制备2′-异丙基-N-水杨酰替苯胺并纯化。然后使用实施例2a描述的方法,由2′-异丙基-N-水杨酰替苯胺和联萘酚制备配位体混合物。31PNMR(121.77MHz):在117.1-120.9ppm之间有数个峰。
(b)用铑和来自实施例11a的配位体混合物实施3-戊烯酸甲酯的加氢
加酰化;
用得自实施例11a的混合物(42.6mg/5mL)代替得自实施例1a的混合物,重复实施例1b的实验。GC结果在表1中给出。
表1:用得自铑和实施例3a-11a制备的配位体混合物的催化剂的3-
戊烯酸甲酯加氢加酰化结果
实施例 | 配位体 | 3-戊烯酸甲酯转化率(%) | C6醛线性度(%) | C6线性醛选择性(%) |
3 | 3 | 33.0 | 91.0 | 68.5 |
4 | 4 | 75.9 | 77.5 | 67.2 |
5 | 5 | 29.8 | 83.4 | 65.5 |
6 | 6 | 58.8 | 85.4 | 64.4 |
7 | 7 | 18.8 | 79.0 | 59.2 |
8 | 8 | 62.3 | 80.2 | 58.0 |
9 | 9 | 70.4 | 80.8 | 57.3 |
10 | 10 | 16.5 | 85.4 | 56.2 |
11 | 11 | 85.4 | 67.9 | 50.7 |
实施例12-13:用铑和实施例5a和6a中制备的配位体混合物实施1,3-
丁二烯的加氢甲酰基化
重复实施例1b的实验,不同之处在于用等量的1,3-丁二烯代替3-戊烯酸甲酯、溶剂为四氢呋喃、CO/H2总压为1000psi(6.8MPa)、温度为90℃、分别使用实施例5a和6a中制备的配位体。在反应2小时后,对产物的分析显示为未反应的1,3-丁二烯、戊醛(还原产物)、戊烯醛(主要是反式-3-戊烯醛)和C6二醛(主要是1,4-丁二醛)的混合物。结果总结在表2中(每100摩尔丁二烯形成的摩尔数)。
表2:用铑和在实施例5a或6a中制备的配位体混合物实施1,3-丁二
烯的加氢甲酰基化。
实施例 | 配位体 | 未反应的1,3-丁二烯(mol) | 戊烯醛(mol) | 3-戊烯醛(mol) | C6二醛(mol) |
12 | 5 | 14.4 | 1.1 | 57.7 | 1.7 |
13 | 6 | 46.4 | 0.0 | 16.6 | 0.0 |
实施例14-15:用铑和在实施例11a中制备的配位体混合物实施乙酸
甲代烯丙酯(1-乙酸2-甲基-2-丙烯基酯)的加氢甲酰基化
重复实施例11b的实验,不同之处在于:用等量的乙酸甲代烯丙酯代替3-戊烯酸甲酯、温度为90℃、在该温度(90℃)下CO/H2的压力可变化,让反应进行4个小时,GC对产物分析显示只有末端醛、4-乙酸基-3-甲基丁醛(4Ac3MB)和还原产物、乙酸异丁酯(i-BuOAc)。结果总结在表3中。
表3:用铑和在实施例11a中制备的配位体混合物实施乙酸甲代烯丙
酯的加氢甲酰基化。
实施例 | CO/H2压力(psi) | 乙酸甲代烯丙酯转化率(%) | 4Ac3MB选择性(%) | i-BuAc选择性(%) | 醛的线性度(%) |
14 | 75 | 72.1 | 69.7 | 7.4 | 100 |
15 | 150 | 74.2 | 72.2 | 8.0 | 100 |
Claims (11)
1.一种从不饱和有机化合物制备有机醛化合物的加氢甲酰基化方法,所述方法包括:使不饱和有机化合物与一氧化碳、氢气和催化系统接触,所述催化系统包含VIII族金属和至少一种具有两个三价磷原子的二齿有机配位体或至少两种这样的二齿有机配位体的组合,所述配位体选自结构I、II、III、IV、V和VI:
结构I 结构II
结构III 结构IV
结构V 结构VI
其中X1-X4是C1-C6烷基、烷氧基、芳氧基、NR6R7、Cl、F或CF3;
R1独立选自取代芳基、苯基或稠合芳环体系;
R2和R3独立选自氢、烷基、芳基、三芳基甲硅烷基、三烷基甲硅烷基、烷氧基羰基、芳氧基羰基、芳氧基、烷氧基、烷基羰基、芳基羰基或腈;
R4和R5独立选自氢、烷基、烷氧基;
R6和R7独立选自烷基和芳基。
2.权利要求1的方法,其中所述VIII族金属为钌、铑或铱。
3.权利要求2的方法,其中VIII族金属以Ru3(CO)12、Ru(NO3)3、RuCl3(Ph3P)3、Ru(acac)3、Ir4(CO)12、IrSO4、RhCl3、Rh(NO3)3、Rh(OAC)3、Rh2O3、Rh(acac)(CO)2、[Rh(OAc)(COD)]2、Rh4(CO)12、Rh6(CO)16、RhH(CO)(Ph3P)3、[Rh(OAc)(CO)2]2或[RhCl(COD)]2的形式提供。
4.权利要求2的方法,其中所述催化系统含有铑。
5.权利要求1的方法,其中所述不饱和化合物选自乙烯、丙烯、1-丁烯、1-戊烯、1-己烯、1-辛烯、1-壬烯、1-癸烯、1-十四碳烯、1-十六碳烯、1-十八碳烯、1-二十碳烯和1-十二碳烯、异丁烯、2-甲基-1-丁烯、2-丁烯、2-己烯、3-己烯、2-辛烯、3-辛烯、2,3-二甲基-2-丁烯、2-甲基-2-丁烯、2-甲基-2-戊烯、辛烯、丙烯、正丁烯、异丁烯、环戊烯、环己烯、1-甲基环己烯、环辛烯、柠檬烯、丁二烯、乙酸甲代烯丙酯、3-戊烯酸和3-戊烯酸烷基酯。
6.权利要求1的方法,其中所述不饱和有机化合物选自苯乙烯、α-甲基苯乙烯、烯丙基苯、己二烯、辛二烯和降冰片二烯。
7.权利要求1的方法,其中所述不饱和有机化合物选自乙烯基甲基醚、油酸甲酯、油醇、烯丙醇、甲代烯丙醇、乙酸甲代烯丙酯、2-戊烯酸甲酯、3-戊烯酸甲酯、4-戊烯酸甲酯、3-戊烯酸、4-戊烯酸、1,7-辛二烯、7-辛烯-1-醛、丙烯腈、丙烯酸酯、丙烯酸甲酯、甲基丙烯酸酯和甲基丙烯酸甲酯。
8.权利要求1的方法,其中所述不饱和化合物为3-戊烯酸或3-戊烯酸C1-C6烷基酯化合物。
10.权利要求9的组成,其中R2和R3各自为烷氧基羰基,在其中R为C1-C8烷基。
11.一种含有至少两种权利要求9的配位体的组合的组合物。
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