JP4953070B2 - カルボニル化合物の製造方法及びカルボニル化合物製造用触媒 - Google Patents
カルボニル化合物の製造方法及びカルボニル化合物製造用触媒 Download PDFInfo
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- JP4953070B2 JP4953070B2 JP2007058925A JP2007058925A JP4953070B2 JP 4953070 B2 JP4953070 B2 JP 4953070B2 JP 2007058925 A JP2007058925 A JP 2007058925A JP 2007058925 A JP2007058925 A JP 2007058925A JP 4953070 B2 JP4953070 B2 JP 4953070B2
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- carbonyl compound
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- hydrogen
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- 239000003054 catalyst Substances 0.000 title claims description 26
- 150000001728 carbonyl compounds Chemical class 0.000 title claims description 20
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 28
- -1 alcohol compound Chemical class 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 125000003118 aryl group Chemical group 0.000 claims description 13
- 150000003624 transition metals Chemical class 0.000 claims description 13
- 229910052723 transition metal Inorganic materials 0.000 claims description 11
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- 125000002947 alkylene group Chemical group 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 claims description 5
- 125000003827 glycol group Chemical group 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 239000003446 ligand Substances 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 description 8
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 2-octanone Chemical compound CCCCCCC(C)=O ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 229910052763 palladium Inorganic materials 0.000 description 6
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 5
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical class CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- AXHVNJGQOJFMHT-UHFFFAOYSA-N 1-tert-butyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C(C)(C)C AXHVNJGQOJFMHT-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000001632 sodium acetate Substances 0.000 description 3
- 235000017281 sodium acetate Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 150000003613 toluenes Chemical class 0.000 description 3
- DHDHJYNTEFLIHY-UHFFFAOYSA-N 4,7-diphenyl-1,10-phenanthroline Chemical compound C1=CC=CC=C1C1=CC=NC2=C1C=CC1=C(C=3C=CC=CC=3)C=CN=C21 DHDHJYNTEFLIHY-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical group C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 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
- IRZVKYGINSGOOD-UHFFFAOYSA-N carbanide;palladium(2+) Chemical compound [CH3-].[CH3-].[Pd+2] IRZVKYGINSGOOD-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000009518 sodium iodide Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- HZYABSBSRWFZEG-BSWSSELBSA-N (1E,3E)-octa-1,3-dien-1-ol Chemical compound CCCC\C=C\C=C\O HZYABSBSRWFZEG-BSWSSELBSA-N 0.000 description 1
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 description 1
- UKSZBOKPHAQOMP-SVLSSHOZSA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 UKSZBOKPHAQOMP-SVLSSHOZSA-N 0.000 description 1
- SLIBCJURSADKPV-UHFFFAOYSA-N 1,10-dihydro-1,10-phenanthroline-4,7-dione Chemical compound N1C=CC(=O)C2=CC=C3C(=O)C=CNC3=C21 SLIBCJURSADKPV-UHFFFAOYSA-N 0.000 description 1
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 1
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- JHDFNETXVFHWEE-UHFFFAOYSA-N 2-(4-oxo-1h-pyridin-2-yl)-1h-pyridin-4-one Chemical compound OC1=CC=NC(C=2N=CC=C(O)C=2)=C1 JHDFNETXVFHWEE-UHFFFAOYSA-N 0.000 description 1
- MWZBAQUWFFYXLJ-UHFFFAOYSA-N 2-[2-[2-[2-(4-butylpyridin-2-yl)pyridin-4-yl]oxyethoxy]ethoxy]ethanol Chemical compound CCCCC1=CC=NC(C=2N=CC=C(OCCOCCOCCO)C=2)=C1 MWZBAQUWFFYXLJ-UHFFFAOYSA-N 0.000 description 1
- YVPXQMYCTGCWBE-UHFFFAOYSA-N 2-isocyano-2,4,4-trimethylpentane Chemical compound CC(C)(C)CC(C)(C)[N+]#[C-] YVPXQMYCTGCWBE-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical group C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Chemical group C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
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- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000012327 Ruthenium complex Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical group C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000005577 anthracene group Chemical group 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
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- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
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- YNHIGQDRGKUECZ-UHFFFAOYSA-L bis(triphenylphosphine)palladium(ii) dichloride Chemical compound [Cl-].[Cl-].[Pd+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-L 0.000 description 1
- 125000002837 carbocyclic group Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- WDTAKLSLSSTQOJ-UHFFFAOYSA-N chembl2063509 Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 WDTAKLSLSSTQOJ-UHFFFAOYSA-N 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- XSWSEQPWKOWORN-UHFFFAOYSA-N dodecan-2-ol Chemical compound CCCCCCCCCCC(C)O XSWSEQPWKOWORN-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
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- 150000002170 ethers Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
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- 150000004715 keto acids Chemical class 0.000 description 1
- SGNSAMGUMVFALJ-UHFFFAOYSA-N n,n'-dichloroethane-1,2-diamine Chemical compound ClNCCNCl SGNSAMGUMVFALJ-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
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- 239000012074 organic phase Substances 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
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- PENAXHPKEVTBLF-UHFFFAOYSA-L palladium(2+);prop-1-ene;dichloride Chemical compound [Pd+]Cl.[Pd+]Cl.[CH2-]C=C.[CH2-]C=C PENAXHPKEVTBLF-UHFFFAOYSA-L 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
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- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical group C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229960005235 piperonyl butoxide Drugs 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical group C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Chemical group 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 150000008054 sulfonate salts Chemical class 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- FAGLEPBREOXSAC-UHFFFAOYSA-N tert-butyl isocyanide Chemical compound CC(C)(C)[N+]#[C-] FAGLEPBREOXSAC-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229930192474 thiophene Chemical group 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Polyethers (AREA)
- Pyridine Compounds (AREA)
Description
(1)下記一般式(1)
下記一般式(2)
で表されるアルコール化合物を、水を溶媒に用いて、酸素存在下に反応させる、
下記一般式(3)
で表されるカルボニル化合物の製造方法。
(2)前記アルコールが、水に不要な高級アルコールであることを特徴とする(1)に記載のカルボニル化合物の製造方法。
(3)下記一般式(2)
で表されるアルコール化合物を、水を溶媒に用いて、酸素存在下に反応させて、
下記一般式(3)
で表されるカルボニル化合物を製造するための触媒であって、
下記一般式(1)
(4)前記アルコールが、水に不要な高級アルコールであることを特徴とする(3)に記載のカルボニル化合物製造用触媒。
前記一般式(1)中のR1は、水素または低級アルキル基を示す。低級アルキル基としては炭素数1〜4個のアルキル基であり、具体的にはメチル基、エチル基、プロピル基、イソプロピル基、ブチル基、t−ブチル基等があげられる。
Rは、水素または、二つのRが互いに結合してビニレン基になっているものがあげられる。
Aは、酸素または酸素ではさまれたフェニレン基またはアルキレン基を示す。アルキレン基としては、炭素数2〜20の2価アルキレン基で、具体的にはエチレン、プロピレン、ブチレン、へキシレン、デシレン、ドデシレン、オクタデシレン等である。
nは、3〜300を示し、望ましくは3〜150である。
等が挙げられる。
本発明で用いられる遷移金属錯体として具体的には、アリルクロロパラジウムダイマー、酢酸パラジウム、ビス(1,5−シクロオクタジエン)パラジウム、トリス(ジベンジリデンアセトン)ジパラジウム、ビス(ジベンジリデンアセトン)パラジウム、アリル(シクロペンタジエニル)パラジウム、ビス(アセチルアセトナト)パラジウム、ビス(トリフェニルホスフィン)ジクロロパラジウム、エチレンビス(トリフェニルホスフィン)パラジウム、ビス(t−ブチルイソシアニド)ジメチルパラジウム、ビス(1,1,3,3−テトラメチルブチルイソシアニド)ジメチルパラジウム、ジネオペンチル(2,2’−ビピリジル)パラジウム、ジクロロエチレンジアミンパラジウム、塩化パラジウム等のパラジウム錯体である。
この反応触媒系における遷移金属錯体とビピリジン系化合物の混合比は、第10族遷移金属原子とビピリジン系化合物の窒素原子の当量比にして第10族遷移金属原子1に対し窒素原子1〜20望ましくは2〜10がよい。
R2およびR3が結合して環を形成している例としては、テトラメチレン基・ペンタメチレン基、フェニレンプロピレン基等があげられる。
(実施例1)
水素化ナトリウム318mg、4,7−ジヒドロキシ−1,10−フェナントロリン0.9g、脱水ジメチルホルムアミド40mlを加え、室温で30分間撹拌した。さらに化合物Br(CH2)10O(CH2CH2O)nMe(n=11.7)10.9gを加え、60℃で一昼夜撹拌した。溶媒を除去したのちクロロホルムで希釈し、セライトろ過で固体を除去した。再度溶媒を留去して得られた残渣をアルミナクロマトグラフィーで分離精製した。その結果、下記の配位子Aを収量1.0gで得た。得られた配位子AのNMRの測定結果を示す。
1H NMR (CDCl3) : δ 9.30 (d, 2H), 8.26 (s, 2H), 7.20 (d, 2H), 4.36 (t, 4H), 3.65 (br, 109 H), 3.60-3.54 (m, 4H), 3.45 (t, 4H), 3.38 (s, 6 H), 2.02 (q, 4H), 1.59 (q, 8H), 1.45-1.27 (br, 24H). 13C NMR (CDCl3) : δ 150.81, 121.06, 119.07, 103.55, 71.86, 71,45, 70.49, 70.43, 69.98, 58.95, 29.56, 29.43, 29.40, 29.27, 28.82, 26.02, 25.98.
4,4´−ジヒドロキシ−2,2´−ビピリジン1.0g(5.3mmol)、炭酸ナトリウム2.5g(23.6mmol)、ヨウ化ナトリウム0.91g(1.1eq、6.1mmol)、脱水ジメチルホルムアミド40mlを加え、70℃で30分撹拌した。さらに化合物Cl(CH2CH2O)nMe(n=11.7)3.51gを加え、24時間加熱攪拌した。ヨウ化ナトリウムおよび炭酸ナトリウムを追加してさらに24時間加熱攪拌をした後、溶媒を留去した。残渣をクロロホルムで希釈しセライトろ過で固体を除去した後、再度溶媒を留去し、得られた残渣をシリカゲルクロマトグラフィーで分離精製した。その結果、配位子Bを収量965mgで得た。得られた配位子BのNMRの測定結果を示す。
1H NMR (CDCl3) : δ 8.47 (br, 2H), 7.92 (br, 2H), 6.91 (br, 2H), 3.75-3.39 (t, 100H), 3.32 (s, 6H). 13C NMR (CDCl3) : δ 72.51, 71.78, 70.74, 70.41, 70.10, 69.13, 63.58, 61.49, 58.87.
窒素気流下、酢酸パラジウム51.4mg、配位子A480mg、純水22mlを加え、室温で一昼夜撹拌を行い、触媒溶液A(Pd換算で0.01mol/l)を調整した。
窒素気流下、酢酸ナトリウム33mg、2−オクタノール179mg、内部標準としてt−ブチルトルエン38mg、脱水トルエン0.2ml、触媒溶液A2.0mlを加え、空気3MPa加圧下、100℃に加熱し6時間反応を行った。2−オクタノンが収率91%で得られた。
窒素気流下、酢酸パラジウム51.4mg、配位子B292mg、純水22mlを加え、室温で一昼夜撹拌を行い、触媒溶液B(Pd換算で0.01mol/l)を調整した。
窒素気流下、酢酸ナトリウム33mg、2−オクタノール179mg、内部標準としてt−ブチルトルエン38mg、脱水トルエン0.2ml、触媒溶液B2.0mlを加え、空気3MPa加圧下、100℃に加熱し6時間反応を行った。2−オクタノンが収率8%で得られた。
窒素気流下、酢酸パラジウム51.4mg、バソフェナントロリンジスルホンサンジナトリウム塩118mg、純水22mlを加え、室温で一昼夜撹拌を行い、触媒溶液(Pd換算で0.01mol/l)を調整した。
窒素気流下、酢酸ナトリウム33mg、2−オクタノール179mg、内部標準としてt−ブチルトルエン38mg、脱水トルエン0.2ml、上記触媒溶液2.0mlを加え、空気3MPa加圧下、100℃に加熱し6時間反応を行った。2−オクタノンが収率0.4 %で得られた。
Claims (4)
- 下記一般式(1)
下記一般式(2)
で表されるアルコール化合物を、水を溶媒に用いて、酸素存在下に反応させる、
下記一般式(3)
で表されるカルボニル化合物の製造方法。 - 前記アルコールが、水に不要な高級アルコールであることを特徴とする請求項1に記載のカルボニル化合物の製造方法。
- 下記一般式(2)
で表されるアルコール化合物を、水を溶媒に用いて、酸素存在下に反応させて、
下記一般式(3)
で表されるカルボニル化合物を製造するための触媒であって、
下記一般式(1)
- 前記アルコールが、水に不要な高級アルコールであることを特徴とする請求項3に記載のカルボニル化合物製造用触媒。
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