CN1081622C - 羧酸衍生物的制备 - Google Patents
羧酸衍生物的制备 Download PDFInfo
- Publication number
- CN1081622C CN1081622C CN96194035A CN96194035A CN1081622C CN 1081622 C CN1081622 C CN 1081622C CN 96194035 A CN96194035 A CN 96194035A CN 96194035 A CN96194035 A CN 96194035A CN 1081622 C CN1081622 C CN 1081622C
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- China
- Prior art keywords
- oxide
- carboxylic acid
- acid derivative
- alkyl
- general formula
- 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.)
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- 150000001732 carboxylic acid derivatives Chemical class 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims description 4
- 238000000034 method Methods 0.000 claims abstract description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 9
- 239000002638 heterogeneous catalyst Substances 0.000 claims abstract description 8
- 239000007791 liquid phase Substances 0.000 claims abstract description 5
- 125000003118 aryl group Chemical group 0.000 claims abstract description 3
- 125000001072 heteroaryl group Chemical group 0.000 claims abstract description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 150000002825 nitriles Chemical class 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 239000004408 titanium dioxide Substances 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 229960001866 silicon dioxide Drugs 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 230000000737 periodic effect Effects 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 4
- 125000003349 3-pyridyl group Chemical group N1=C([H])C([*])=C([H])C([H])=C1[H] 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 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 claims description 3
- 125000004066 1-hydroxyethyl group Chemical group [H]OC([H])([*])C([H])([H])[H] 0.000 claims description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- 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 claims description 2
- 150000001257 actinium Chemical class 0.000 claims description 2
- 229910052810 boron oxide Inorganic materials 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 239000011964 heteropoly acid Substances 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 2
- 150000002602 lanthanoids Chemical class 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 2
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 2
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 2
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 150000003016 phosphoric acids Chemical class 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims 1
- 229910002027 silica gel Inorganic materials 0.000 claims 1
- 239000000741 silica gel Substances 0.000 claims 1
- -1 carboxylic acid nitriles Chemical class 0.000 abstract description 18
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 150000001298 alcohols Chemical class 0.000 abstract description 3
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 abstract 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 150000001733 carboxylic acid esters Chemical class 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 235000019504 cigarettes Nutrition 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-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
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 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 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 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 1
- 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 1
- FHKPTEOFUHYQFY-UHFFFAOYSA-N 2-aminohexanenitrile Chemical compound CCCCC(N)C#N FHKPTEOFUHYQFY-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 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 1
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 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
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 1
- 125000002853 C1-C4 hydroxyalkyl group Chemical group 0.000 description 1
- XBLVHTDFJBKJLG-UHFFFAOYSA-N Ethyl nicotinate Chemical compound CCOC(=O)C1=CC=CN=C1 XBLVHTDFJBKJLG-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
- DFPAKSUCGFBDDF-UHFFFAOYSA-N Nicotinamide Chemical compound NC(=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000001476 alcoholic effect 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- KBPGBEFNGHFRQN-UHFFFAOYSA-N bis(selanylidene)tin Chemical compound [Se]=[Sn]=[Se] KBPGBEFNGHFRQN-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 150000003950 cyclic amides Chemical class 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 125000004312 morpholin-2-yl group Chemical group [H]N1C([H])([H])C([H])([H])OC([H])(*)C1([H])[H] 0.000 description 1
- 125000002757 morpholinyl group Chemical group 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229960003966 nicotinamide Drugs 0.000 description 1
- 235000005152 nicotinamide Nutrition 0.000 description 1
- 239000011570 nicotinamide Substances 0.000 description 1
- 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 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 description 1
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/803—Processes of preparation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/06—Preparation of carboxylic acid amides from nitriles by transformation of cyano groups into carboxamide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/18—Preparation of carboxylic acid esters by conversion of a group containing nitrogen into an ester group
- C07C67/22—Preparation of carboxylic acid esters by conversion of a group containing nitrogen into an ester group from nitriles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
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Abstract
一种制备通式I的羧酸衍生物的方法，这里X是OR2或NH2，R1是C1-C20烷基、C1-C20羟基烷基、C3-C12环烷基、C4-C12烷基环烷基、C4-C12环烷基烷基、C5-C20烷基环烷基烷基、芳基、C7-C20芳烷基、C7-C20烷基芳基、具有5～8个碳原子的杂脂族或杂芳族环和R2是C1-C20烷基，通式I的羧酸衍生物是在50～300℃的温度下，在0.1～350巴的压力下，在多相催化剂的存在下由通式II的腈和通式III R1-C≡N (II)，R2-OH (III)，的醇制备的，其中该反应在液相中进行，在通式II和通式III中R1和R2分别具有上述含义。
Description
本发明涉及一种在二氧化钛催化剂上在升温的条件下由腈和醇制备羧酸衍生物的方法。
DE-A 27 14 767公开了一种通过腈与醇类和水在含金属的固体催化剂例如在载体如Al2O3、SiO2、ZrO2或TiO2上的铜、锌、铬、铋、锰、铁、镍、镉上的气相反应制备羧酸衍生物的方法。发现了作为副反应的脱水作用和醚化作用。
例如，EP-A412310公开了一种通过在含锰的催化剂上用水水合腈来制备羧酰胺的方法，例如正如在US-A4,613,684中公开的一样，在金属盐的存在下，或正如在EP-A561614中公开的一样，在气相中在固体催化剂上，或正如在EP-A392361中公开的一样在金属氧化物上，羧酰胺随后通过酸性催化可以与醇类反应得到羧酸衍生物。
工业应用中的缺陷是二步骤和副产物的形成，例如盐的产生或甲酰胺的生成。
DE-A 43 39 648公开了一种在二氧化钛催化剂上，在乙醇溶液中，通过氨基己腈与水反应制备己内酰胺(一种环状酰胺)的方法。
本发明的目的是消除上述缺陷。
我们已经发现可以这样实现本发明的目的，即通过一种制备通式I的羧酸衍生物的新的和改进的方法，
这里X是OR2或NH2，R1是C1-C20烷基、C1-C20羟基烷基、C3-C12环烷基、C4-C12烷基环烷基、C4-C12环烷基烷基、C5-C20烷基环烷基烷基、芳基、C7-C20芳烷基、C7-C20烷基芳基、具有5～8个碳原子的杂脂族或杂芳族环和R2是C1-C20烷基，通式I的羧酸衍生物是在50～300℃的温度下，在0.1～350巴的压力下，在多相催化剂的存在下由通式II
R1-C≡N (II)，的腈和通式III
R2-OH (III)，的醇制备的，其中该反应在液相中进行，在通式II和通式III中R1和R2分别具有上述含义。
本发明的方法可以以下面的方式行：
通常在压力稳定的设备例如高压釜和管式反应器、优选管式反应器中，在具有二氧化钛催化剂的液相中，在50～300℃、优选100～290℃、特别优选140～270℃的温度下，在0.1～350巴、优选1～200巴、特别优选30～140巴的压力下，将腈II与醇III接触，优选溶解在醇III中。通常结果是得到一种羧酸酯和羧酰胺I的醇溶液，通过常规的方法例如蒸馏、萃取或结晶方法可以从该溶液中得到羧酸酯和羧酰胺I。
羧酰胺可以与新的腈II一起返回反应器中。
固体腈II或固体醇III的反应可以在惰性溶剂中进行，例如在醚类中，优选在具有2～20个碳原子的醚中，特别优选在具有4～12个碳原子的醚中，例如在二乙醚、甲基叔丁基醚或四氢呋喃中，在烃中，优选在具有5～30个碳原子的烃中，特别优选在具有5～12个碳原子的烃例如甲苯和二甲苯中，或有利地在合适的羧酸酯I中进行。
合适的多相催化剂的例子是元素周期表第IIA、IIIA和IVA族元素的酸性、碱性或两性氧化物，例如氧化钙、氧化镁、氧化硼、氧化铝、氧化锡或二氧化硅，热解的二氧化硅，硅胶形式的二氧化硅，硅藻土，石英，以及元素周期表第IIB、IIIB、IVB、VB、VIB和VIIB族金属的氧化物例如氧化钛、特别是二氧化钛例如无定形的，金红石或锐钛矿形式的二氧化钛，氧化锆，氧化锌，氧化锰，氧化钒，氧化铌，氧化铁，氧化铬，氧化钼，氧化钨，镧系和锕系的氧化物例如氧化铈、氧化钍、氧化镨、氧化钐，混合稀土元素的氧化物或它们的混合物。也可以使用一些硫化物、硒化物和碲化物例如碲化锌、硒化锡、硫化钼、硫化钨、镍、锌或铬的硫化物。
上述化合物可以被元素周期表IA、IIA、IIIA、IVA、VA、VIA和VIIA族的化合物掺杂或包含它们。
其它适合的催化剂是沸石、磷酸盐和杂多酸、和酸性和碱性离子交换剂例如Naphion(原文如此)
如果合适的话，在各种情况下这些催化剂可以包含0.001-50重量％的铜、锡、锌、锰、铁、钴、镍、钌、钯、铂、银或铑或其混合物。
根据催化剂的组成，可以将催化剂作为非担载或担载催化剂使用。因此，例如，二氧化钛可以作为二氧化钛丸使用或以涂覆在载体上的二氧化钛薄层的形式使用。在载体例如二氧化硅、氧化铝和二氧化锆上涂覆二氧化钛的方法可以是文献中描述的所有方法。因此，可以通过水解有机钛化合物例如异丙氧化钛或丁氧化钛或通过水解TiCl4或其它无机含钛的化合物来涂覆的二氧化钛薄层。还可以使用含氧化钛的盐水。
例如可以在悬浮液中，优选在固定床中进行该反应。反应优选在固定床中进行，因为这可以使反应的连续进行变得容易，通常在固定床中产率和选择性是非常高的，因此导致短的停留时间和非常高的物料通过量。因为，根据迄今为止的观察，所使用的多相催化剂具有长的使用寿命，所以催化剂的消耗是非常低的。
在化合物I、II、III中取代基X、R1和R2具有下述含义：X-OR2-NH2R1，R2-C1-C20烷基、优选C1-C12烷基、特别优选C1-C8烷基例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、正己基、异己基、正庚基、异庚基、正辛基和异辛基，特别是C1-C4烷基例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基。-C1-C20羟基烷基、优选C1-C8羟基烷基、特别优选C1-C4羟基烷基例如羟基甲基、1-羟基乙基、2-羟基乙基和1-甲基-1-羟基乙基。-C3-C12环烷基、优选C5-C8环烷基例如环戊基、环己基、环庚基和环辛基，特别优选环戊基和环己基。-C4-C12烷基环烷基、优选C5-C10烷基环烷基和特别优选C5-C8烷基环烷基，-C4-C12环烷基烷基、优选C5-C10环烷基烷基和特别优选C5-C8环烷基烷基，-C5-C20烷基环烷基烷基、优选C6-C16烷基环烷基烷基和特别优选C7-C12烷基环烷基基，-芳基例如苯基、1-萘基和2-萘基，优选苯基，-C7-C20烷基芳基、优选C7-C16烷基芳基、优选C7-C12烷基苯基例如2-甲基苯基、3-甲基苯基、4-甲基苯基、2-乙基苯基、3-乙基苯基和4-乙基苯基，-C7-C20芳烷基、优选C7-C16芳烷基、优选C7-C12苯烷基例如苯基甲基、1-苯基乙基和2-苯基乙基、-具有5～8个碳原子的杂脂族环例如2-吗啉基、3-吗啉基、2-哌啶基、3-哌啶基和4-哌啶基，-具有5～8个碳原子的杂芳族环例如2-吡啶基、3-吡啶基、4-吡啶基、2-吡唑基、2-咪唑基、4(5)-咪唑基，优选3-吡啶基。
羧酸酯和羧酰胺I适合作为中间产物、塑料前体和适用于农作物保护和药物学。
实施例
实施例1
在220℃和80巴下，使20重量％的烟腈乙醇溶液流过填充有氧化钛(1.5mm的丸状)的管，同时加入1摩尔的水(以溶液的重量计为3.5％)。通过流速可变地调节停留时间。
来自反应的排出物的组成总结在表1中。
表1
实施例2
| 停留时间 | 烟腈 | 烟酸乙酯 | 烟酰胺 | 其它 |
| [分钟] | [％] | [％] | [％] | [％] |
| 15 | 5.1 | 5.4 | 9.4 | 0.1 |
| 30 | 1.9 | 8.6 | 9.1 | 0.4 |
| 60 | 0.6 | 11.3 | 7.4 | 0.7 |
如实施例1一样，在220℃和80巴下，在1摩尔水的存在下，泵送20重量％的烟腈乙醇溶液流过空管。没有反应发生。
Claims (10)
1、一种制备通式I的羧酸衍生物的方法，
这里X是OR2或NH2，R1是C1-C20烷基、C1-C20羟基烷基、C3-C12环烷基、C4-C12烷基环烷基、C4-C12环烷基烷基、C5-C20烷基环烷基烷基、芳基、C7-C20芳烷基、C7-C20烷基芳基、具有5～8个碳原子的杂脂族或杂芳族环和R2是C1-C20烷基，通式I的羧酸衍生物是在50～300℃的温度下，在0.1～350巴压力下，在多相催化剂的存在下由通式II
R1-C≡N (II)，的腈和通式III
R2-OH (III)，的醇制备的，其中该反应在液相中进行，在通式II和通式III中R1和R2分别具有上述含义。
2、根据权利要求1的制备羧酸衍生物的方法，其中多相催化剂是元素周期表第IIA、IIIA、IVA、IIB、IIIB、IVB、VB、VIB和VIIB族元素的酸性、碱性或两性氧化物、镧系和锕系的氧化物、混合稀土元素的氧化物或它们的混合物，或沸石、磷酸盐、杂多酸、酸性和碱性离子交换剂，它们可以被元素周期表IA、IIA、IIIA、IVA、VA、VIA和VIIA族的化合物掺杂或包含它们，也可以包含0.001-50重量％的铜、锡、锌、锰、铁、钴、镍、钌、钯、铂、银或铑或其混合物。
3、根据权利要求1和2之一的制备羧酸衍生物的方法，其中作为多相催化剂的是氧化钙、氧化镁、氧化硼、氧化铝、氧化锡、二氧化硅、硅胶、硅藻土、石英、二氧化钛、氧化锆、氧化锌、氧化锰、氧化钒、氧化铌、氧化铁、氧化铬、氧化钼、氧化钨、氧化铈、氧化钍、氧化镨、氧化钐和它们的混合物。
4、根据权利要求1和2之一的制备羧酸衍生物的方法，其中多相催化剂是氧化铝、氧化钛、氧化锆和它们的混合物。
5、根据权利要求1和2之一的制备羧酸衍生物的方法，其中将金红石、锐钛矿或它们的混合物作为二氧化钛使用。
6、根据权利要求1和2之一的制备羧酸衍生物的方法。其中反应在100～290℃的温度下进行。
7、根据权利要求1和2之一的制备羧酸衍生物的方法，其中反应在140～270℃的温度下进行。
8、根据权利要求1和2之一的制备羧酸衍生物的方法，其中反应在1～200巴的压力下在液相中进行。
9、根据权利要求1和2之一的制备羧酸衍生物的方法，其中反应在30～140巴的压力下进行。
10、根据权利要求1的制备羧酸衍生物的方法，其中R1是3-吡啶基、1-甲基-1-羟基乙基、1-羟基乙基或2-羟基乙基。
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| DE19518474.2 | 1995-05-19 | ||
| DE19518474A DE19518474A1 (de) | 1995-05-19 | 1995-05-19 | Verfahren zur Herstellung von Carbonsäurederivaten |
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| JP2780373B2 (ja) * | 1989-09-07 | 1998-07-30 | 三菱瓦斯化学株式会社 | α―ヒドロキシカルボン酸アミドの製造法 |
| US5268503A (en) * | 1992-03-16 | 1993-12-07 | Mitsui Toatsu Chemicals, Incorporated | Process for producing α,β-unsaturated carboxylic acid esters |
| DE4339648A1 (de) * | 1993-11-20 | 1995-05-24 | Basf Ag | Verfahren zur Herstellung von Caprolactam |
| DE4440927A1 (de) * | 1994-11-17 | 1996-05-23 | Basf Ag | Verfahren zur Herstellung von Nikotinsäureamid durch katalytische Hydratisierung von 3-Cyano-pyridin |
-
1995
- 1995-05-19 DE DE19518474A patent/DE19518474A1/de not_active Withdrawn
-
1996
- 1996-05-01 TW TW085105213A patent/TW347385B/zh active
- 1996-05-04 MY MYPI96001688A patent/MY117672A/en unknown
- 1996-05-07 HU HU9801403A patent/HU225063B1/hu not_active IP Right Cessation
- 1996-05-07 SK SK1550-97A patent/SK155097A3/sk unknown
- 1996-05-07 CA CA002218134A patent/CA2218134C/en not_active Expired - Fee Related
- 1996-05-07 KR KR1019970708257A patent/KR100384095B1/ko not_active IP Right Cessation
- 1996-05-07 AU AU58146/96A patent/AU713436B2/en not_active Ceased
- 1996-05-07 DE DE59604459T patent/DE59604459D1/de not_active Expired - Fee Related
- 1996-05-07 TR TR97/01393T patent/TR199701393T1/xx unknown
- 1996-05-07 US US08/952,239 patent/US6002010A/en not_active Expired - Fee Related
- 1996-05-07 CN CN96194035A patent/CN1081622C/zh not_active Expired - Fee Related
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- 1996-05-07 CZ CZ19973580A patent/CZ290156B6/cs not_active IP Right Cessation
- 1996-05-07 JP JP8534515A patent/JPH11505538A/ja active Pending
- 1996-05-07 EP EP96919686A patent/EP0825977B1/de not_active Expired - Lifetime
- 1996-05-07 PL PL96323388A patent/PL183753B1/pl not_active IP Right Cessation
- 1996-05-07 MX MX9708580A patent/MX9708580A/es active IP Right Grant
- 1996-05-07 WO PCT/EP1996/001890 patent/WO1996036592A2/de active IP Right Grant
- 1996-05-07 NZ NZ308484A patent/NZ308484A/en unknown
- 1996-05-07 ES ES96919686T patent/ES2143764T3/es not_active Expired - Lifetime
- 1996-05-07 UA UA97126156A patent/UA50739C2/uk unknown
- 1996-05-07 BR BR9608469A patent/BR9608469A/pt not_active Application Discontinuation
-
1997
- 1997-11-06 BG BG102026A patent/BG63869B1/bg unknown
- 1997-11-18 NO NO975296A patent/NO308465B1/no not_active Application Discontinuation
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5103055A (en) * | 1990-05-10 | 1992-04-07 | The Standard Oil Company | Water-promoted synthesis of amides from nitriles and alcohols |
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