CN1158118A - 芳香醛的制备 - Google Patents
芳香醛的制备 Download PDFInfo
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- CN1158118A CN1158118A CN95195139A CN95195139A CN1158118A CN 1158118 A CN1158118 A CN 1158118A CN 95195139 A CN95195139 A CN 95195139A CN 95195139 A CN95195139 A CN 95195139A CN 1158118 A CN1158118 A CN 1158118A
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- aromatic aldehyde
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- 150000003934 aromatic aldehydes Chemical class 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title 1
- -1 amino, methylamino, dimethylamino Chemical group 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 23
- 150000002148 esters Chemical class 0.000 claims abstract description 18
- 239000001257 hydrogen Substances 0.000 claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000003118 aryl group Chemical group 0.000 claims abstract description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims abstract description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000005984 hydrogenation reaction Methods 0.000 claims description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 6
- 239000013543 active substance Substances 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims description 6
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 5
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 claims description 5
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- NIBFJPXGNVPNHK-UHFFFAOYSA-N 2,2-difluoro-1,3-benzodioxole-4-carbaldehyde Chemical group C1=CC(C=O)=C2OC(F)(F)OC2=C1 NIBFJPXGNVPNHK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- RHDGNLCLDBVESU-UHFFFAOYSA-N but-3-en-4-olide Chemical compound O=C1CC=CO1 RHDGNLCLDBVESU-UHFFFAOYSA-N 0.000 claims description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000010574 gas phase reaction Methods 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 3
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 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 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 2
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 2
- ZEYHEAKUIGZSGI-UHFFFAOYSA-N 4-methoxybenzoic acid Chemical compound COC1=CC=C(C(O)=O)C=C1 ZEYHEAKUIGZSGI-UHFFFAOYSA-N 0.000 claims 2
- 229910052693 Europium Inorganic materials 0.000 claims 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 14
- 230000008569 process Effects 0.000 abstract description 7
- 150000002431 hydrogen Chemical class 0.000 abstract description 6
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 abstract 2
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 abstract 2
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 abstract 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 abstract 1
- 239000007792 gaseous phase Substances 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 229910052747 lanthanoid Inorganic materials 0.000 abstract 1
- 150000002602 lanthanoids Chemical class 0.000 abstract 1
- 229910001928 zirconium oxide Inorganic materials 0.000 abstract 1
- 230000009466 transformation Effects 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000003822 preparative gas chromatography Methods 0.000 description 5
- 150000001299 aldehydes Chemical class 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 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 4
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 4
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 2
- 125000004343 1-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 2
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- NZNMSOFKMUBTKW-UHFFFAOYSA-N cyclohexanecarboxylic acid Chemical compound OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 239000006200 vaporizer Substances 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- MNCMBBIFTVWHIP-UHFFFAOYSA-N 1-anthracen-9-yl-2,2,2-trifluoroethanone Chemical group C1=CC=C2C(C(=O)C(F)(F)F)=C(C=CC=C3)C3=CC2=C1 MNCMBBIFTVWHIP-UHFFFAOYSA-N 0.000 description 1
- 125000003890 2-phenylbutyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006201 3-phenylpropyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])C([H])([H])* 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
- 125000004860 4-ethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229930194542 Keto Natural products 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000002078 anthracen-1-yl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C([*])=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 125000000748 anthracen-2-yl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C([H])=C([*])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000008901 benefit Effects 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
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000003599 food sweetener Nutrition 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 229910000311 lanthanide oxide Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- OVWYEQOVUDKZNU-UHFFFAOYSA-N m-tolualdehyde Chemical compound CC1=CC=CC(C=O)=C1 OVWYEQOVUDKZNU-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- YQUVCSBJEUQKSH-UHFFFAOYSA-N protochatechuic acid Natural products OC(=O)C1=CC=C(O)C(O)=C1 YQUVCSBJEUQKSH-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000003765 sweetening agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- WKOLLVMJNQIZCI-UHFFFAOYSA-N vanillic acid Chemical compound COC1=CC(C(O)=O)=CC=C1O WKOLLVMJNQIZCI-UHFFFAOYSA-N 0.000 description 1
- TUUBOHWZSQXCSW-UHFFFAOYSA-N vanillic acid Natural products COC1=CC(O)=CC(C(O)=O)=C1 TUUBOHWZSQXCSW-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C07C45/41—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by hydrogenolysis or reduction of carboxylic groups or functional derivatives thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/313—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of doubly bound oxygen containing functional groups, e.g. carboxyl groups
Abstract
本发明公开一种制备通式(I)芳香醛的方法，其中R1，R2，R3，R4和R5代表氢原子，C1-C6烷基，C3-C8环烷基，芳基，羟基，C1-C4烷氧基，苯氧基，C7-C12烷基苯基，C7-C12苯基烷基，氨基，甲基氨基，二甲基氨基或卤原子，R1也可代表甲酰或COOR6，且R6代表氢原子，C1-C6烷基，C3-C8环烷基，芳基，C7-C12烷基苯基或C7-C12苯基烷基，制备上述醛的方法是将通式(Ⅱ)的芳香羧酸或它们的酯，其中R1，R2，R3，R4，R5和R6的定义同上，或者是R2，R3，R4和R5的定义同上R6和R1一起形成一个-CH2-桥)与氢气于从200至450℃的温度和从0.1到20巴的压力下在一种催化剂存在下进行气相反应，催化剂的催化活性物质包含80至99.9％(重量)氧化锆和0.1到20％(重量)一种或多种镧系元素。
Description
本发明涉及一种通过将适当的羧酸或它们的酯与氢气在氧化锆和含镧系元素催化剂存在下进行气相反应制备芳香醛的方法。
通过气相加氢反应可使羧酸如苯甲酸或环己烷羧酸或它们的酯转化成相应的醛是已知的。
US-A-3,935,265公开了芳香羧酸烷基酯可于400到600℃下在Al2O3上用氢气进行加氢反应。例如苯甲酸甲酯可经选择性37％(转化率：39％)的反应得到苯甲醛。例如还可进一步将Ru/Sn(EP-A-539,274)、氧化锰(EP-A 290,096，US-A-4,585,899)、氧化铁(EP-A-304 853)、氧化钒和/或二氧化钛(US-A-4,950,799，EP-A-414 065)、Cu/Y2O3(US-A-4,585,900)、Cr2O3/ZrO2(EP-A-150 961)或镧系元素氧化物/Al2O3催化剂(US-A-4,328,373，EP-A-101111)用于芳香羧酸的加氢反应中。
在已知的加氢方法中，部分由于加氢反应的温度很高，大多数情况下仅能达到较低的收率和选择性。
本发明的目的是消除上述缺点。
现在我们已经发现通过采用一种制备通式I芳香醛的新颖改进方法可达到该目的
其中R1，R2，R3，R4和R5是氢原子，C1到C6烷基，C3到C8环烷基，芳基，羟基，C1到C4烷氧基，苯氧基，C7到C12烷基苯基，C7到C12苯基烷基，氨基，甲基氨基，二甲基氨基或卤原子；且R2，R3或R4另外又可是甲酰或COOR6R6是氢原子，C1到C6烷基，C3到C8环烷基，芳基，C7到C12烷基苯基或C7到C12苯基烷基，该方法包括将通式II的芳香羧酸或它们的酯
其中R1，R2，R3，R4，R5和R6定义同上或其中的R2，R3，R4和R5定义同上面R6和R1一起形成一个-CH2-桥与氢气于从200到450℃和从0.1到20巴下在一种催化剂存在下进行气相反应，催化剂的催化活性物质包含从80到99.9％(重量)氧化锆和0.1到20％(重量)一种或多种镧系元素。
按照本发明的方法可按下文实施：
按照本发明，芳香羧酸或它们的酯II与氢气一般是在一种催化剂存在下于从200到450℃，优选从250到400℃，特别优选从300到380℃和从0.1到20巴，优选从0.7到5巴，特别优选大气压(常压)下进行反应，催化剂的催化活性物质含从60到99.9％，特别是从80到99.9％(重量)氧化锆和一种或多种镧系元素。所需温度和所需压力取决于催化剂活性以及原料和产物的热稳定性。
适用的催化剂是载体催化剂，但优选立方、四方、单斜晶型的氧化锆无载体催化剂，优选单斜晶型，优选用一种或多种镧系元素掺杂的催化剂。一般来说，催化活性物质含80到99.9％(重量)，优选90到99.9％(重量)，特别优选从92到99.9％(重量)氧化锆和0.1到20％(重量)一种或多种镧系元素，优选0.1到10％(重量)镧、铈、镨、钕、钐、销或它们的混合物，特别优选从1到8％(重量)氧化镧(III)。一般来说通过用镧系元素的盐溶液(水溶液和醇溶液)浸渍氧化锆进行掺杂。
该催化剂还可进一步包含掺杂量0.001到10％(重量)的补充掺杂剂(例如铬、铁、镱、锰)。优选无上述补充掺杂剂的催化剂。
氧化锆的BET表面积可在较大的范围内变动，一般来说为5到150m2/g，优选20到150m2/g，特别优选40到120m2/g。
这类催化剂可按已知方法制备，例如通过将预先制成的片状、粒状和挤出物状的载体浸渍、干燥并煅烧的方法来制备。
优选使用的载体催化剂可在相对较长的时期内呈现高活性，已失活的催化剂可通过用含分子氧的气体如空气于350到500℃下处理使其再生。
通常催化剂的装填量保持每公斤催化剂每小时催化0.01到10，优选0.01到3kg羧酸(酯)。
入口气体中的氢气浓度取决于羧酸(酯)浓度。一般来说，氢气与羧酸(酯)的摩尔比为2∶1到100∶1，优选10∶1到70∶1。也可用甲酸作为氢气源。
加入一种惰性稀释剂也有一定的好处。一般来说可使用氮气、水或反应条件下惰性的气态化合物如烃、芳烃或醚。
该反应在气相中进行，用一种固定床催化剂连续进行固体床反应，例如用液相或滴液床工艺，或是用一种流化催化剂进行流化床反应。优选在一个固体床内进行操作。
为提高反应选择性，加氢反应中形成的副产物，例如醇，可送回到合成阶段。
或I和II中取代基R1，R2，R3，R4，R5和R6各自独立地有如下定义：R1，R2，R3，R4，R5和R6——氢原子；-C1到C6烷基，优选C1到C4烷基如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基和叔丁基，特别优选甲基和乙基；——C3到C8环烷基如环丙基、环丁基、环戊基、环己基和环辛基，优选环戊基、环己基和环辛基，特别优选环戊基和环己基；——芳基如苯基、1-萘基、2-萘基、1-蒽基、2-蒽基、和9-蒽基，优选苯基、1-萘基和2-萘基，特别优选苯基；——C7到C12烷基苯基如2-甲基苯基、3-甲基苯基、4-甲基苯基、2，4-二甲基苯基、2，5-二甲基苯基、2，6-二甲基苯基、3，4-二甲基苯基、3，5-二甲基苯基、2，3，4-三甲基苯基、2，3，5-三甲基苯基、2，3，6-三甲基苯基、2，4，6-三甲基苯基、2-乙基苯基、3-乙基苯基、4-乙基苯基、2-正丙基苯基、3-正丙基苯基和4-正丙基苯基，优选2-甲基苯基、3-甲基苯基、4-甲基苯基、2，4-二甲基苯基、2，5-二甲基苯基、2，6-二甲基苯基、3，4-二甲基苯基和3，5-二甲基苯基，特别优选2-甲基苯基、3-甲基苯基、4-甲基苯基；——C7到C10苯基烷基如苯甲基、1-苯基乙基、2-苯基乙基、1-苯基丙基、2-苯基丙基、3-苯基丙基、1-苯基丁基、2-苯基丁基、3-苯基丁基和4-苯基丁基，优选苯甲基、1-苯基乙基和2-苯基乙基，特别优选苯甲基，R2，R3，和R4-羟基；-C1到C4烷氧基如甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、异丁氧基、仲丁氧基和叔丁氧基，优选甲氧基、乙氧基、正丙氧基和异丙氧基，特别优选甲氧基和乙氧基；——苯氧基；——氨基；——甲氨基；——二甲基氨基；——卤原子如氟、氯、溴和碘，优选氟、氯和溴，特别优选氯和溴，且R2，R3或R4——甲酰(-CHO-)或COOR6。式II中，R6和R1可进一步一起形成一个-CH2-桥。
可以是任何所需的取代方式，即取代基的位置可以在例如2，3，4-、2，3，5-、2，3，6-、3，4，5-、3，4，6-或4，5，6-位。
所用的原料是芳香单或二羧酸或羧酸酯II，例如苯甲酸(酯)，对苯二甲酸(酯)，邻苯二甲酸(酯)，间苯二甲酸(酯)，烷基取代的、烷氧基取代的、二烷基取代的或烷氧基烷基取代的羧酸(酯)，优选的酯是甲基、乙基、丙基、异丙基、丁基、异丁基、叔丁基、环戊基、环己基、苯基和苯甲基酯，特别优选的化合物是苯甲酸、对苯二甲酸、邻苯二甲酸、2-，3-和4-甲基苯甲酸、4-异丙基苯甲酸、4-叔丁基苯甲酸、2-苯并[C]呋喃酮、香草酸和相应酸的甲基酯。
在二羧酸的加氢反应中，首先形成醛羧酸酯，若需要的话，该化合物可用作中间体，在不完全转化的情况中，醛羧酸的收率达到最大值。
当转化率继续增加时，由于进一步的加氢反应，可以注意到优先形成二醛。
通过采用按照本发明的方法可以选择一种简单的方式制备以前很难得到的醛。
醛I适合用作香料和增香剂，或者用作例如药物或作物保护活性化合物的中间体(乌尔曼工业化学百科全书(Ullmann’s Encyclo-pedia of Industrial Chemistry)A3卷，469-74页)
实施例催化剂制备实施例1
片状(催化剂A、E或F)或挤出状(催化剂B，C或D)单晶型二氧化锆(BET表面积：40到85m2/g)用一种已充分混合的镧系元素硝酸盐水溶液浸渍，并在室温下保持2小时，然后将该催化剂于120℃下干燥15小时，随后控制从400到500℃的温度2到4小时。
这样得到的催化剂中镧系元素的含量如下：催化剂A(表面积67m2/g)：3％(重量)镧催化剂B(表面积46m2/g)：3％(重量)镨催化剂C(表面积46m2/g)：3％(重量)铈催化剂D(表面积46m2/g)：3％(重量)镧系元素(分布：48％CeO2，
26.3％La2O3，5.7％Pr2O3和19.7％Nd2O3)催化剂E(表面积85m2/g)：3％(重量)镧催化剂F(表面积53m2/g)：3％(重量)镧实施例2
将芳香羧酸(酯)II以每小时从4到8g的量用溶剂(THF)或不用溶剂送入到一个蒸发器(＜300℃)里，从蒸发器中与100L/h氢气用滴液床工艺在100g催化剂上通过。经反应后流出的气态物料在冷阱中浓缩并用气相色谱法进行分析，所得结果列于表1实施例3
将每小时6g对苯二甲酸二甲酯(熔融体)用100L/h氢气蒸发，并于350℃下用滴液床工艺在100g催化剂E上通过，从反应中流出的气态物料在冷阱中浓缩并用气相色谱法进行分析。得到的主产物为32％对苯二醛和27％4-甲酰苯甲酸甲酯(转化率：78％)。实施例4
将每小时8g 2-甲基苯甲酸(熔融体)用200L/h氢气蒸发，并于350℃下用滴液床工艺在100g催化剂F上通过，经反应后流出的气态物料在冷阱中浓缩并用气相色谱法进行分析。2-甲基苯甲醛的收率为93％(转化率：99％)实施例5
将每小时5g 3-甲基苯甲酸(熔融体)用100L/h氢气蒸发，并于360℃下用滴液床工艺在100g催化剂F上通过，经反应后流出的气态物料在冷阱中浓缩并用气相色谱法进行分析。3-甲基苯甲醛的收率为92％(转化率：99％)实施例6
将每小时8g 2-苯并[C]呋喃酮(熔融体)用100L/h氢气蒸发，并于400℃下用滴液床工艺在100g催化剂F上通过，从反应中流出的气态物料在冷阱中浓缩并用气相色谱法进行分析。2-甲基苯甲醛的收率为16％(转化率：26％)
表1原料化合物：
1)溶剂：THF
| 催化剂 | R | 羧酸浓度(％重量)1) | 温度[℃] | 醛[％] | 转化率[％] | 选择性[％] |
| A | H | 100 | 340 | 98 | 100 | 98 |
| A | H | 20 | 350 | 98 | 100 | 98 |
| A | Me | 100 | 340 | 96 | 99 | 97 |
| A | t-Bu | 100 | 340 | 90 | 94 | 96 |
| A | t-Bu | 20 | 340 | 93 | 97 | 96 |
| A | OMe | 10 | 350 | 77 | 99 | 78 |
| B | H | 100 | 360 | 95 | 100 | 95 |
| C | H | 100 | 360 | 96 | 100 | 96 |
| D | H | 100 | 360 | 97 | 99 | 98 |
| F | i-Pr | 100 | 350 | 90 | 98 | 92 |
| F | LN | 10 | 350 | 47 | 99 | 47 |
Claims (7)
1、一种制备通式I芳香醛的方法：
其中R1，R2，R3，R4和R5是氢原子，C1到C6烷基，C3到C8环烷基，芳基，羟基，C1到C4烷氧基，苯氧基，C7到C12烷基苯基，C7到C12苯基烷基，氨基，甲基氨基，二甲基氨基或卤原子；且R2，R3或R4另外又可是甲酰或COOR6R6是氢原子，C1到C6烷基，C3到C8环烷基，芳基，C7到C12烷基苯基或C7到C12苯基烷基，该方法包括将通式II的芳香羧酸或它们的酯
其中R1，R2，R3，R4，R5和R6定义同上或其中的R2，R3，R4和R5定义同上面R6和R1一起形成一个-CH2-桥与氢气于从200到450℃和从0.1到20巴下在一种催化剂存在下进行气相反应，催化剂的催化活性物质包含从80到99.9％(重量)氧化锆和0.1到20％(重量)一种或多种镧系元素。
2、一种如权利要求1的制备芳香醛的方法，其中的催化剂包含从90到99.9％(重量)催化活性物质氧化锆和从0.1到10％(重量)镧系元素镧、铈、镨、钕、钐、铕或它们的混合物。
3、一种如权利要求1的制备芳香醛的方法，其中的催化剂包含从92到99％(重量)催化活性物质氧化锆和从1到8％(重量)氧化镧(III)。
4、一种如权利要求1的制备芳香醛的方法，其中的二氧化锆是单斜晶型的。
5、一种如权利要求1的制备芳香醛的方法，其中将苯甲酸、2-甲基苯甲酸、3-甲基苯甲酸、4-甲基苯甲酸、4-异丙基苯甲酸、4-甲氧基苯甲酸、2-苯并[C]呋喃酮或对苯二甲酸或者它们的酯进行加氢反应得到相应的单或二醛。
6、一种如权利要求1的制备芳香醛的方法，氢气与羧酸(酯)的摩尔比是从2∶1到100∶1。
7、一种如权利要求1的制备芳香醛的方法，其中的反应是在一个固体床中进行。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4428994A DE4428994A1 (de) | 1994-08-16 | 1994-08-16 | Verfahren zur Herstellung von aromatischen Aldehyden |
| DEP4428994.4 | 1994-08-16 | ||
| DE19944446009 DE4446009A1 (de) | 1994-12-22 | 1994-12-22 | Verfahren zur Herstellung von aromatischen Aldehyden |
| DEP4446009.0 | 1994-12-22 |
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| CN1158118A true CN1158118A (zh) | 1997-08-27 |
| CN1086375C CN1086375C (zh) | 2002-06-19 |
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| US (1) | US5763676A (zh) |
| EP (1) | EP0777639B1 (zh) |
| JP (1) | JPH10504296A (zh) |
| CN (1) | CN1086375C (zh) |
| AU (1) | AU3343895A (zh) |
| DE (1) | DE59504504D1 (zh) |
| WO (1) | WO1996005161A1 (zh) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102989499A (zh) * | 2012-12-18 | 2013-03-27 | 陕西省石油化工研究设计院 | 一种用于制备对叔丁基苯甲醛的催化剂及制备方法 |
| CN106964343A (zh) * | 2017-04-11 | 2017-07-21 | 北京恩泽福莱科技有限公司 | 一种苯甲酸甲酯加氢制备苯甲醛的催化剂及其制备方法 |
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| FR2720296B1 (fr) * | 1994-05-27 | 1996-07-12 | Rhone Poulenc Chimie | Composés à base d'alumine, d'oxyde de cérium et d'oxyde de zirconium à réductibilité élevée, leur procédé de préparation et leur utilisation dans la préparation de catalyseurs. |
| DE19505858A1 (de) * | 1995-02-21 | 1996-10-31 | Basf Ag | Verfahren zur Herstellung von Epoxiden mittels aromatischer Peroxycarbonsäuren |
| JP5236194B2 (ja) * | 2007-03-15 | 2013-07-17 | 健二 山本 | アルデヒド類の製造方法、シリンガ酸の製造方法及び３，４，５−トリヒドロキシベンズアルデヒドの製造方法 |
| GB201817785D0 (en) * | 2018-10-31 | 2018-12-19 | Givaudan Sa | Organic compounds |
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| US4328373A (en) * | 1980-03-17 | 1982-05-04 | The Dow Chemical Company | Method of preparing aldehydes |
| DE3562619D1 (en) * | 1984-01-18 | 1988-06-16 | Mitsubishi Chem Ind | Catalytic process of producing aromatic aldehydes |
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1995
- 1995-08-10 AU AU33438/95A patent/AU3343895A/en not_active Abandoned
- 1995-08-10 US US08/793,055 patent/US5763676A/en not_active Expired - Fee Related
- 1995-08-10 WO PCT/EP1995/003167 patent/WO1996005161A1/de active IP Right Grant
- 1995-08-10 DE DE59504504T patent/DE59504504D1/de not_active Expired - Fee Related
- 1995-08-10 EP EP95929832A patent/EP0777639B1/de not_active Expired - Lifetime
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102989499A (zh) * | 2012-12-18 | 2013-03-27 | 陕西省石油化工研究设计院 | 一种用于制备对叔丁基苯甲醛的催化剂及制备方法 |
| CN102989499B (zh) * | 2012-12-18 | 2014-12-31 | 陕西省石油化工研究设计院 | 一种用于制备对叔丁基苯甲醛的催化剂及制备方法 |
| CN106964343A (zh) * | 2017-04-11 | 2017-07-21 | 北京恩泽福莱科技有限公司 | 一种苯甲酸甲酯加氢制备苯甲醛的催化剂及其制备方法 |
| CN106964343B (zh) * | 2017-04-11 | 2020-06-02 | 北京恩泽福莱科技有限公司 | 一种苯甲酸甲酯加氢制备苯甲醛的催化剂及其制备方法 |
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| Publication number | Publication date |
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| CN1086375C (zh) | 2002-06-19 |
| EP0777639A1 (de) | 1997-06-11 |
| DE59504504D1 (de) | 1999-01-21 |
| EP0777639B1 (de) | 1998-12-09 |
| WO1996005161A1 (de) | 1996-02-22 |
| AU3343895A (en) | 1996-03-07 |
| US5763676A (en) | 1998-06-09 |
| JPH10504296A (ja) | 1998-04-28 |
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