WO2007116112A1 - Method for preparing oxymes using gold catalysts - Google Patents
Method for preparing oxymes using gold catalysts Download PDFInfo
- Publication number
- WO2007116112A1 WO2007116112A1 PCT/ES2007/070065 ES2007070065W WO2007116112A1 WO 2007116112 A1 WO2007116112 A1 WO 2007116112A1 ES 2007070065 W ES2007070065 W ES 2007070065W WO 2007116112 A1 WO2007116112 A1 WO 2007116112A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- gold
- combinations
- process according
- solvent
- carried out
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 69
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 39
- 239000010931 gold Substances 0.000 title claims abstract description 39
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000003054 catalyst Substances 0.000 title claims abstract description 29
- 150000002828 nitro derivatives Chemical class 0.000 claims abstract description 5
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims abstract description 4
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical group ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 claims description 32
- 239000002904 solvent Substances 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 17
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 238000005984 hydrogenation reaction Methods 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 7
- 150000002923 oximes Chemical class 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- DJBRXNRKYAWTBL-UHFFFAOYSA-N 1-nitrocyclohexene Chemical compound [O-][N+](=O)C1=CCCCC1 DJBRXNRKYAWTBL-UHFFFAOYSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical class ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000003607 modifier Substances 0.000 claims description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 4
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 claims description 3
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 239000000852 hydrogen donor Substances 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- MFEVGQHCNVXMER-UHFFFAOYSA-L 1,3,2$l^{2}-dioxaplumbetan-4-one Chemical compound [Pb+2].[O-]C([O-])=O MFEVGQHCNVXMER-UHFFFAOYSA-L 0.000 claims description 2
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 2
- 229910000003 Lead carbonate Inorganic materials 0.000 claims description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 239000001273 butane Substances 0.000 claims description 2
- 229930188620 butyrolactone Natural products 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 239000001506 calcium phosphate Substances 0.000 claims description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 2
- 235000011010 calcium phosphates Nutrition 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 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
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 239000006184 cosolvent Substances 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910000464 lead oxide Inorganic materials 0.000 claims description 2
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 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
- 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 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052753 mercury Inorganic materials 0.000 claims description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000012454 non-polar solvent Substances 0.000 claims description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 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
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- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 239000007790 solid phase Substances 0.000 claims description 2
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- 125000003158 alcohol group Chemical group 0.000 claims 1
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- 229910052746 lanthanum Inorganic materials 0.000 claims 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims 1
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Classifications
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- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
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- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
- C07C249/10—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes from nitro compounds or salts thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/32—Oximes
- C07C251/34—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
- C07C251/44—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with the carbon atom of at least one of the oxyimino groups being part of a ring other than a six-membered aromatic ring
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- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
Definitions
- the present invention deals with a new process for the production of oximes by selective hydrogenation of the corresponding nitro ⁇ , ⁇ -unsaturated compound using gold catalysts.
- the oximes specifically, the cyclohexanone oxime is a key product as an intermediate in the production of epsilon-caprolactam, a precursor to nylon-6.
- commercial processes for the production of cyclohexanone oxime include the reaction of cyclohexanone with hydroxylamine sulfate and ammonia. This process is far from ideal, considering the large number of steps required and the generation of sulfates as a byproduct.
- Various processes have been proposed in order to improve the production process of cyclohexanone oxime. In most cases, the direct use of hydroxylamine or its generation in situ in the reaction medium is considered, assuming a relatively high degree of danger due to the high explosive index of the product.
- cyclohexanone oxime Some variants of the above processes for producing cyclohexanone oxime disclose different forms for the production of hydrogen peroxide in situ, prior to its reaction with ammonia.
- the CN- 1,472, 197 patent relates to a process of producing cyclohexanone oxime by ammoximation of cyclohexanone with ammonia and H 2 O 2 produced by the method of the anthraquinone.
- US Patent 5,599,987 the production of cyclohexanone oxime is disclosed by a process similar, but in which hydrogen peroxide is obtained by oxidation of isopropanol with O 2 .
- JP-2001-213,854 an alternative route for the production of cyclohexanone oxime is proposed in which benzene is used as the starting product to form cyclohexene by partial dehydrogenation with a catalyst.
- 1-nitro-1-cyclohexene is obtained by a nitration reaction and as a last step a catalyst B is used to produce the cyclohexanone oxime through the partial hydrogenation of the nitro ⁇ - ⁇ -unsaturated compound.
- the present invention relates to a process for the preparation of oximes characterized in that it comprises a catalytic hydrogenation of the corresponding nitro ⁇ , ⁇ -unsaturated compound using a gold catalyst.
- the oxime is cyclohexanone oxime and the nitro compound is 1-nitro-1-cyclohexene.
- it is a process for the preparation of the cyclohexanone oxime characterized in that it comprises a catalytic hydrogenation of 1-nitro-1-cyclohexene using gold catalysts.
- the gold catalysts of the present invention catalyze the selective hydrogenation of nitro ⁇ , ⁇ -unsaturated groups to the corresponding oxime, avoiding the direct hydrogenation of the double bond to form the saturated nitro compound.
- gold can be supported on an inorganic support.
- Gold, or modified gold, as explained later in this report, can be supported in order to increase its dispersion and decrease the particle size on supports of inorganic or carbonaceous nature, as is known in the field. of metal catalysts.
- the percentage by weight of gold with respect to the solid support on which it is supported is preferably between 0.1 and 15% gold and more preferably between 0.5 and 5% gold.
- gold can be applied in metallic or ionic form on the support.
- said support is selected from active carbon, iron oxide, titanium oxide, cerium oxide, magnesium oxide, zirconium oxide, silica gel, silicic acid, lanthanum oxide, alumina, zinc oxide, calcium carbonate, calcium phosphate, calcium sulfate, barium sulfate, lead oxide, lead sulfate, lead carbonate and combinations thereof.
- said support is selected from iron oxide, titanium oxide, cerium oxide, silica and combinations thereof.
- the molar ratio between gold and the nitro compound is preferably between 0.01 and 10%, more preferably between 0.05 and 3%.
- the gold may be doped with a second metal.
- a metal other than gold as a modifier or dopant is introduced into the catalyst of the process.
- This metal modifier can improve the catalytic properties of the material.
- this doped or modified gold may also be supported, as explained above.
- the modifying metal is selected from palladium, platinum, rhodium, nickel, copper, ruthenium, lead, mercury, bismuth, germanium, cadmium, arsenic, antimony, silver, iron, manganese, cobalt, ruthenium and combinations thereof .
- the weight ratio of gold to said modifying metal is preferably 1: 0.001 and more preferably 1: 0.5.
- the process of the present invention further comprises a source of hydrogen that can be any hydrogen donor molecule.
- the hydrogen source is selected from ammonium formate, formic acid, decaborane, cyclohexene, cyclohexadiene, phosphoric acid and combinations thereof.
- the process is preferably carried out at atmospheric pressure and at a temperature between 25 0 C and
- the source of hydrogen is molecular hydrogen. This process is preferably carried out at a pressure between 1 and 100 bar and at a temperature between 2O 0 C and 25O 0 C, and more preferably at a pressure between 5 and 50 bar and at a temperature between 100 0 C and 15O 0 C.
- the hydrogenation reaction can be carried out with or without solvent.
- a particularly interesting advantage of the use of gold, according to the present invention is that the choice of the reaction solvent is not critical. It is possible to use solvents that are not normally inert in the presence of palladium and platinum catalysts.
- solvent it is preferably selected from water, alcohols preferably selected from methanol, ethanol, n-propanol, isopropanol, n-butanol, isomeric butane, cyclohexanol and combinations thereof; ethers preferably selected from diethyl ether, methyl tert-butyl ether, tetrahydrofuran, dioxane, dimethoxyethane and combinations thereof; esters preferably selected from ethyl acetate, butyl acetate and combinations thereof; ketones preferably selected from butyrolactone, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and combinations thereof; carboxylic acids preferably selected from acetic acid, propionic acid and combinations thereof; aprotic dipole solvents preferably selected from dimethylformamide, N-methylpyrrolidine, dimethylacetamide, sulfo
- Said solvent serves as a means of dissolution or to facilitate separation processes.
- said solvent is selected from toluene, xylene, tetrahydrofuran, dioxane, methyl ethyl ketone, methanol, ethanol and combinations thereof.
- the process of the present invention can also be carried out in the presence of one or more co-solvents.
- Said co-solvent is preferably selected from ethanol, acetone, acetonitrile and combinations thereof.
- the process is carried out in the absence of solvent.
- the reagents that are hydrogenated during the process are preferably in the liquid, gas or coexistence phase of both.
- the process of the present invention can be carried out in the gas-solid phase (catalyst) or in a gas-liquid-solid system (catalyst).
- said process can be carried out in a reactor in discontinuous or continuous mode, and catalyst recovery can be enhanced by recirculation or regeneration.
- the use of gold as a catalyst can be complemented with any promoter additive.
- Example-1 Preparation of catalyst 1.5% A11 / TIO2
- the gold catalyst supported on titanium oxide was prepared by deposition-precipitation technique. Deposition-precipitation of gold was carried out by adding the support to an aqueous solution of HAuCU (0.01M), previously adjusted to pH 7 with NaOH. To prepare 1 g of catalyst, 75 mg of HAuCU should be used. The mixture was kept stirring at 343 K under vigorous stirring for 2 hours, controlling the pH to a value of 7. The sample was then filtered, washed with deionized water until the chlorides were removed, dried under vacuum at 353 K and calcined at 673 K in air.
- Example-2 Preparation of cyclohexanone oxime with H 2 using 1.5% Au / TiO 2 catalyst
- Example-3 Preparation of cyclohexanone oxime with ammonium formate using catalyst 1.5% Au / Ti ⁇ 2
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Abstract
The present invention relates to a method for preparing oxymes that comprises catalytic hydrogenation of the corresponding a, ß-unsaturated nitrocompound using a gold catalyst.
Description
TÍTULOTITLE
PROCEDIMIENTO PARA LA PREPARACIÓN DE OXIMAS UTILIZANDO CATALIZADORES DE ORO.PROCEDURE FOR THE PREPARATION OF OXYMS USING GOLD CATALYSTS.
Campo de la técnicaTechnical field
La presente invención trata de un nuevo procedimiento para la producción de oximas mediante una hidrogenación selectiva del correspondiente compuesto nitro α,β- insaturado utilizando catalizadores de oro.The present invention deals with a new process for the production of oximes by selective hydrogenation of the corresponding nitro α, β-unsaturated compound using gold catalysts.
AntecedentesBackground
Las oximas, en concreto, la oxima de ciclohexanona es un producto clave como intermedio en la producción de epsilon-caprolactama, precursor de nylon-6. Actualmente los procesos comerciales para la producción de oxima de ciclohexanona incluyen la reacción de ciclohexanona con sulfato de hidroxilamina y amoníaco. Dicho proceso está lejos de ser ideal, considerando el gran número de pasos que requiere y la generación de sulfatos como subproducto. Diversos procesos han sido planteados con tal de mejorar el proceso de producción de oxima de ciclohexanona. En la mayoría de los casos se plantea el uso directo de hidroxilamina o su generación in situ en el medio de reacción, asumiendo un grado de peligrosidad relativamente elevado por el alto índice de explosividad del producto.The oximes, specifically, the cyclohexanone oxime is a key product as an intermediate in the production of epsilon-caprolactam, a precursor to nylon-6. Currently, commercial processes for the production of cyclohexanone oxime include the reaction of cyclohexanone with hydroxylamine sulfate and ammonia. This process is far from ideal, considering the large number of steps required and the generation of sulfates as a byproduct. Various processes have been proposed in order to improve the production process of cyclohexanone oxime. In most cases, the direct use of hydroxylamine or its generation in situ in the reaction medium is considered, assuming a relatively high degree of danger due to the high explosive index of the product.
En las patentes US-4,745,221; US-5,312,987; US-5,227,525; US-5,683,952; US- 5,691,266, US-5,874,596 y CN-1,468,841 se divulgan diferentes usos de materiales titano-silicatos como catalizadores para la producción de oxima de ciclohexanona a partir de peróxido de hidrógeno y amoníaco. Dichos procesos se basan, a su vez, en el proceso de obtención de hidroxilamina a partir de H2O2 y NH3 divulgado por SUMITOMO y ENICHEM en JP-7,070,781 y US-5,320,819, respectivamente.In US Pat. Nos. 4,745,221; US 5,312,987; US 5,227,525; US 5,683,952; US 5,691,266, US 5,874,596 and CN 1,468,841 disclose different uses of titanium silicate materials as catalysts for the production of cyclohexanone oxime from hydrogen peroxide and ammonia. These processes are based, in turn, on the process of obtaining hydroxylamine from H 2 O 2 and NH 3 disclosed by SUMITOMO and ENICHEM in JP-7,070,781 and US-5,320,819, respectively.
Algunas variantes de los procesos anteriores para producir oxima de ciclohexanona divulgan distintas formas para la producción de peróxido de hidrógeno in situ, previamente a su reacción con amoníaco. La patente CN- 1,472, 197 se refiere a un proceso de producción de oxima de ciclohexanona por amoximación de ciclohexanona con amoníaco y H2O2 producido por el método de la antraquinona. En la patente US- 5,599,987 se divulga la producción de oxima de ciclohexanona por un procedimiento
similar, pero en el que el peróxido de hidrógeno se obtiene por oxidación de isopropanol con O2.Some variants of the above processes for producing cyclohexanone oxime disclose different forms for the production of hydrogen peroxide in situ, prior to its reaction with ammonia. The CN- 1,472, 197 patent relates to a process of producing cyclohexanone oxime by ammoximation of cyclohexanone with ammonia and H 2 O 2 produced by the method of the anthraquinone. In US Patent 5,599,987 the production of cyclohexanone oxime is disclosed by a process similar, but in which hydrogen peroxide is obtained by oxidation of isopropanol with O 2 .
En todos los ejemplos mostrados anteriormente existen varios problemas comunes que limitan o dificultan su aplicación industrial. En primer lugar, el proceso de obtención de ciclohexanona, por deshidrogenación de ciclohexanol u oxidación directa de ciclohexano, presenta todavía numerosos inconvenientes, considerando los rendimientos de reacción y las enormes dificultades asociadas a posteriores procesos de separación. Por otra parte, la manipulación de hidroxilamina o la generación de peróxido de hidrógeno como paso previo a una amoxidación, presenta numerosas dificultades prácticas debido a la alta explosividad de las mezclas reactivas y a la gran complejidad de las operaciones implicadas.In all the examples shown above there are several common problems that limit or hinder their industrial application. In the first place, the process of obtaining cyclohexanone, by dehydrogenation of cyclohexanol or direct oxidation of cyclohexane, still has numerous drawbacks, considering the reaction yields and the enormous difficulties associated with subsequent separation processes. On the other hand, the manipulation of hydroxylamine or the generation of hydrogen peroxide as a previous step to amoxidation, presents numerous practical difficulties due to the high explosiveness of the reactive mixtures and the great complexity of the operations involved.
En la patente JP-2001-213,854 se propone una ruta alternativa para la producción de oxima de ciclohexanona en la que se utiliza benceno como producto de partida para formar ciclohexeno por deshidrogenación parcial con un catalizador. A continuación 1 -nitro -1 -ciclohexeno es obtenido mediante una reacción de nitración y como última etapa se utiliza un catalizador B para producir la oxima de ciclohexanona a través de la hidrogenación parcial del compuesto nitro α-β-insaturado. A pesar de que el proceso resulta potencialmente interesante, la falta de selectividad de los catalizadores propuestos hasta la fecha, basados principalmente en la química del paladio y platino, para la transformación de 1 -nitro- 1 -ciclohexeno a oxima de ciclohexanona disminuye en gran medida la viabilidad del proceso.In JP-2001-213,854, an alternative route for the production of cyclohexanone oxime is proposed in which benzene is used as the starting product to form cyclohexene by partial dehydrogenation with a catalyst. Next, 1-nitro-1-cyclohexene is obtained by a nitration reaction and as a last step a catalyst B is used to produce the cyclohexanone oxime through the partial hydrogenation of the nitro α-β-unsaturated compound. Although the process is potentially interesting, the lack of selectivity of the catalysts proposed to date, based mainly on the chemistry of palladium and platinum, for the transformation of 1-nitro-1-cyclohexene to cyclohexanone oxime greatly decreases measure the viability of the process.
La utilización de catalizadores oro soportado para la hidrogenación selectiva de 1 -nitro -1 -ciclohexeno a ciclohexanona oxima no ha sido contemplada hasta el momento en ninguno de los ejemplos anteriores. En la presente invención se ha encontrado sorprendentemente que el oro, por sí mismo, es un catalizador activo y selectivo para llevar a cabo este proceso, empleando H2 u otra molécula donante de hidrógeno como agente reductor.The use of supported gold catalysts for the selective hydrogenation of 1-nitro-1-cyclohexene to cyclohexanone oxime has not been contemplated so far in any of the previous examples. In the present invention it has been surprisingly found that gold, by itself, is an active and selective catalyst to carry out this process, using H 2 or another hydrogen donor molecule as the reducing agent.
Objeto de la invención La presente invención se refiere a un procedimiento para la preparación de oximas caracterizado porque comprende una hidrogenación catalítica del correspondiente compuesto nitro α,β-insaturado utilizando un catalizador de oro.
En una realización preferente, la oxima es la oxima de ciclohexanona y el compuesto nitro es el 1 -nitro- 1-ciclohexeno. Según esta realización preferente, se trata de un procedimiento para la preparación de la oxima de ciclohexanona caracterizado porque comprende una hidrogenación catalítica de 1 -nitro -1-ciclohexeno utilizando catalizadores de oro.Object of the invention The present invention relates to a process for the preparation of oximes characterized in that it comprises a catalytic hydrogenation of the corresponding nitro α, β-unsaturated compound using a gold catalyst. In a preferred embodiment, the oxime is cyclohexanone oxime and the nitro compound is 1-nitro-1-cyclohexene. According to this preferred embodiment, it is a process for the preparation of the cyclohexanone oxime characterized in that it comprises a catalytic hydrogenation of 1-nitro-1-cyclohexene using gold catalysts.
Los catalizadores de oro de la presente invención catalizan la hidrogenación selectiva de grupos nitro α, β-insaturados a la correspondiente oxima, evitando la hidrogenación directa del doble enlace para formar el compuesto nitro saturado.The gold catalysts of the present invention catalyze the selective hydrogenation of nitro α, β-unsaturated groups to the corresponding oxime, avoiding the direct hydrogenation of the double bond to form the saturated nitro compound.
En dicho procedimiento, el oro puede estar soportado en un soporte inorgánico. El oro, o el oro modificado, tal cómo se explica más adelante en esta memoria, se puede soportar con el fin de aumentar su dispersión y disminuir el tamaño de partícula sobre soportes de naturaleza inorgánica o carbonácea, tal y como es conocido en el campo de los catalizadores metálicos.In such a procedure, gold can be supported on an inorganic support. Gold, or modified gold, as explained later in this report, can be supported in order to increase its dispersion and decrease the particle size on supports of inorganic or carbonaceous nature, as is known in the field. of metal catalysts.
El porcentaje en peso de oro respecto al soporte sólido en el que está soportado está preferentemente comprendido entre un 0.1 y un 15 % de oro y más preferentemente entre un 0.5 y un 5 % de oro.The percentage by weight of gold with respect to the solid support on which it is supported is preferably between 0.1 and 15% gold and more preferably between 0.5 and 5% gold.
Según lo expuesto anteriormente, el oro se puede aplicar en forma metálica o iónica en el soporte.As stated above, gold can be applied in metallic or ionic form on the support.
Según una realización particular, dicho soporte está seleccionado entre carbón activo, óxido de hierro, óxido de titanio, óxido de cerio, óxido de magnesio, óxido de zirconio, gel de sílice, ácido silícico, óxido de lantano, alúmina, óxido de zinc, carbonato calcico, fosfato calcico, sulfato calcico, sulfato de bario, óxido de plomo, sulfato de plomo, carbonato de plomo y combinaciones de los mismos.According to a particular embodiment, said support is selected from active carbon, iron oxide, titanium oxide, cerium oxide, magnesium oxide, zirconium oxide, silica gel, silicic acid, lanthanum oxide, alumina, zinc oxide, calcium carbonate, calcium phosphate, calcium sulfate, barium sulfate, lead oxide, lead sulfate, lead carbonate and combinations thereof.
De manera preferente, dicho soporte está seleccionado entre óxido de hierro, óxido de titanio, óxido de cerio, sílice y combinaciones de los mismos.Preferably, said support is selected from iron oxide, titanium oxide, cerium oxide, silica and combinations thereof.
En el procedimiento de la presente invención, la relación molar entre el oro y el compuesto nitro (relación oro/nitro) se encuentra preferentemente entre 0.01 y 10 % más preferentemente entre 0.05 y 3 %.In the process of the present invention, the molar ratio between gold and the nitro compound (gold / nitro ratio) is preferably between 0.01 and 10%, more preferably between 0.05 and 3%.
Según una realización particular, el oro puede estar dopado con un segundo metal. Según esta realización particular, se introduce un metal distinto de oro como modificador o dopante, en el catalizador del procedimiento. Este metal modificador puede mejorar las propiedades catalíticas del material. Además, este oro dopado o modificado también puede estar soportado, tal y como se ha explicado anteriormente.
De manera preferente, el metal modificador está seleccionado entre paladio, platino, rodio, níquel, cobre, rutenio, plomo, mercurio, bismuto, germanio, cadmio, arsénico, antimonio, plata, hierro, manganeso, cobalto, rutenio y combinaciones de los mismos. Además, la relación en peso de oro a dicho metal modificador es preferentemente de 1:0.001 y más preferentemente de 1:0.5.According to a particular embodiment, the gold may be doped with a second metal. According to this particular embodiment, a metal other than gold as a modifier or dopant is introduced into the catalyst of the process. This metal modifier can improve the catalytic properties of the material. In addition, this doped or modified gold may also be supported, as explained above. Preferably, the modifying metal is selected from palladium, platinum, rhodium, nickel, copper, ruthenium, lead, mercury, bismuth, germanium, cadmium, arsenic, antimony, silver, iron, manganese, cobalt, ruthenium and combinations thereof . In addition, the weight ratio of gold to said modifying metal is preferably 1: 0.001 and more preferably 1: 0.5.
El procedimiento de la presente invención comprende, además, una fuente de hidrógeno que puede ser cualquier molécula donante de hidrógeno.The process of the present invention further comprises a source of hydrogen that can be any hydrogen donor molecule.
Según una realización preferente, la fuente de hidrógeno está seleccionada entre formiato amónico, ácido fórmico, decaborano, ciclohexeno, ciclohexadieno, ácido fosfórico y combinaciones de los mismos. Según esta realización, el procedimiento se lleva a cabo preferentemente a presión atmosférica y a una temperatura entre 250C yAccording to a preferred embodiment, the hydrogen source is selected from ammonium formate, formic acid, decaborane, cyclohexene, cyclohexadiene, phosphoric acid and combinations thereof. According to this embodiment, the process is preferably carried out at atmospheric pressure and at a temperature between 25 0 C and
12O0C.12O 0 C.
Según otra realización preferente, la fuente de hidrógeno es hidrógeno molecular. Este procedimiento se lleva a cabo preferentemente a una presión entre 1 y 100 bares y a una temperatura entre 2O0C y 25O0C, y de manera más preferente a una presión entre 5 y 50 bares y a una temperatura entre 1000C y 15O0C.According to another preferred embodiment, the source of hydrogen is molecular hydrogen. This process is preferably carried out at a pressure between 1 and 100 bar and at a temperature between 2O 0 C and 25O 0 C, and more preferably at a pressure between 5 and 50 bar and at a temperature between 100 0 C and 15O 0 C.
En este procedimiento, la reacción de hidrogenación se puede llevar a cabo con o sin disolvente. Una ventaja particularmente interesante del uso de oro, de acuerdo con la presente invención, consiste en que la elección del disolvente de reacción no es crítica. Es posible utilizar disolventes que normalmente no son inertes en presencia de catalizadores de paladio y platino.In this procedure, the hydrogenation reaction can be carried out with or without solvent. A particularly interesting advantage of the use of gold, according to the present invention, is that the choice of the reaction solvent is not critical. It is possible to use solvents that are not normally inert in the presence of palladium and platinum catalysts.
En caso de que el procedimiento se realice con disolvente, éste está preferentemente seleccionado entre agua, alcoholes preferentemente seleccionados entre metanol, etanol, n-propanol, isopropanol, n-butanol, butanoles isoméricos, ciclohexanol y combinaciones de los mismos; éteres preferentemente seleccionados entre dietil éter, metil tert-butil éter, tetrahidrofurano, dioxano, dimetoxietano y combinaciones de los mismos; esteres preferentemente seleccionados entre etil acetato, butil acetato y combinaciones de los mismos; cetonas preferentemente seleccionadas entre butirolactona, acetona, metil etil cetona, metil isobutil cetona, ciclohexanona y combinaciones de las mismas; ácidos carboxílicos preferentemente seleccionados entre ácido acético, ácido propiónico y combinaciones de los mismos; disolventes dipolares apróticos preferentemente seleccionados entre dimetilformamida, N-metilpirrolidina, dimetilacetamida, sulfolano, dimetil sulfóxido, acetonitrilo y combinaciones de los
mismos; disolventes apolares preferentemente seleccionados entre tolueno, xileno y combinaciones de los mismos; hidrocarburos aromáticos clorados, cloruro de metileno, aléanos C3-C7, ciclohexano y combinaciones de los mismos. Dicho disolvente sirve como medio de disolución o para facilitar los procesos de separación. De manera preferente, dicho disolvente está seleccionado entre tolueno, xileno, tetrahidrofurano, dioxano, metil etil cetona, metanol, etanol y combinaciones de los mismos.In case the process is carried out with solvent, it is preferably selected from water, alcohols preferably selected from methanol, ethanol, n-propanol, isopropanol, n-butanol, isomeric butane, cyclohexanol and combinations thereof; ethers preferably selected from diethyl ether, methyl tert-butyl ether, tetrahydrofuran, dioxane, dimethoxyethane and combinations thereof; esters preferably selected from ethyl acetate, butyl acetate and combinations thereof; ketones preferably selected from butyrolactone, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and combinations thereof; carboxylic acids preferably selected from acetic acid, propionic acid and combinations thereof; aprotic dipole solvents preferably selected from dimethylformamide, N-methylpyrrolidine, dimethylacetamide, sulfolane, dimethyl sulfoxide, acetonitrile and combinations of the themselves; apolar solvents preferably selected from toluene, xylene and combinations thereof; chlorinated aromatic hydrocarbons, methylene chloride, C3-C7 alloys, cyclohexane and combinations thereof. Said solvent serves as a means of dissolution or to facilitate separation processes. Preferably, said solvent is selected from toluene, xylene, tetrahydrofuran, dioxane, methyl ethyl ketone, methanol, ethanol and combinations thereof.
El procedimiento de la presente invención puede además realizarse en presencia de uno o más co-disolventes. Dicho co-disolvente está preferentemente seleccionado entre etanol, acetona, acetonitrilo y combinaciones de los mismos.The process of the present invention can also be carried out in the presence of one or more co-solvents. Said co-solvent is preferably selected from ethanol, acetone, acetonitrile and combinations thereof.
Según una realización particular, el procedimiento se lleva a cabo en ausencia de disolvente. Según esta realización, los reactivos que se hidrogenan durante el procedimiento se encuentran preferentemente en fase líquida, gaseosa o en coexistencia de ambas. El procedimiento de la presente invención, se puede llevar a cabo en fase gas- sólido (catalizador) o en un sistema gas-líquido-sólido (catalizador).According to a particular embodiment, the process is carried out in the absence of solvent. According to this embodiment, the reagents that are hydrogenated during the process are preferably in the liquid, gas or coexistence phase of both. The process of the present invention can be carried out in the gas-solid phase (catalyst) or in a gas-liquid-solid system (catalyst).
Además, dicho procedimiento se puede llevar a cabo en un reactor en modo discontinuo o continuo, y la recuperación del catalizador puede realzarse mediante recirculación o regeneración. De acuerdo con la presente invención, el uso de oro como catalizador puede ser complementado con cualquier aditivo promotor.Furthermore, said process can be carried out in a reactor in discontinuous or continuous mode, and catalyst recovery can be enhanced by recirculation or regeneration. In accordance with the present invention, the use of gold as a catalyst can be complemented with any promoter additive.
El proceso de la presente invención se describe a continuación utilizando ejemplos, los cuales son únicamente ilustrativos y no deben limitar el ámbito de aplicación de la presente invención.The process of the present invention is described below using examples, which are illustrative only and should not limit the scope of the present invention.
Ejemplo-1: Preparación del catalizador 1,5% A11/TÍO2Example-1: Preparation of catalyst 1.5% A11 / TIO2
El catalizador de oro soportado sobre óxido de titanio fue preparado por la técnica de deposición-precipitación. La deposición-precipitación del oro fue llevada a cabo adicionando el soporte a una disolución acuosa de HAuCU (0,01M), previamente ajustada a un pH 7 con NaOH. Para preparar 1 g de catalizador, 75 mg de HAuCU deben ser utilizados. La mezcla se mantuvo agitando a 343 K bajo agitación vigorosa durante 2 horas, controlando el pH a un valor de 7. A continuación la muestra fue
filtrada, lavada con agua desionizada hasta que los cloruros fueron eliminados, secada a vacío a 353 K y calcinada a 673 K en aire.The gold catalyst supported on titanium oxide was prepared by deposition-precipitation technique. Deposition-precipitation of gold was carried out by adding the support to an aqueous solution of HAuCU (0.01M), previously adjusted to pH 7 with NaOH. To prepare 1 g of catalyst, 75 mg of HAuCU should be used. The mixture was kept stirring at 343 K under vigorous stirring for 2 hours, controlling the pH to a value of 7. The sample was then filtered, washed with deionized water until the chlorides were removed, dried under vacuum at 353 K and calcined at 673 K in air.
Ejemplo-2: Preparación de ciclohexanona oxima con H2 utilizando el catalizador 1,5% Au/TiO2 Example-2: Preparation of cyclohexanone oxime with H 2 using 1.5% Au / TiO 2 catalyst
En un autoclave, 2.6 g de catalizador, preparado de acuerdo al Ejemplo 1, son añadidos a una disolución de 13 g de 3-nitroestireno en 100 mL de tolueno, y 1.1 g de o-xileno es usado como patrón interno de la reacción. El contenido del autoclave se calienta hasta 120 ° C y se presuriza con 9 bares de hidrógeno, fijándose un nivel de agitación de 1000 r.p.m. La evolución de la reacción fue seguida en relación al consumo de gas (presión en el interior del reactor) y mediante análisis de la fase líquida por cromatografía de gases y espectrometría de masas. Después de 6 horas de reacción, 3- aminoestireno fue producido con un rendimiento del 94 %.In an autoclave, 2.6 g of catalyst, prepared according to Example 1, are added to a solution of 13 g of 3-nitrostyrene in 100 mL of toluene, and 1.1 g of o-xylene is used as the internal standard of the reaction. The contents of the autoclave are heated to 120 ° C and pressurized with 9 bars of hydrogen, setting a stirring level of 1000 rpm. The evolution of the reaction was followed in relation to gas consumption (pressure inside the reactor) and by analysis of the liquid phase by gas chromatography and mass spectrometry. After 6 hours of reaction, 3- amino styrene was produced in 94% yield.
Ejemplo-3: Preparación de ciclohexanona oxima con formiato amónico utilizando el catalizador l,5%Au/Tiθ2Example-3: Preparation of cyclohexanone oxime with ammonium formate using catalyst 1.5% Au / Tiθ2
En un autoclave, 2.6 g de catalizador, preparado de acuerdo al Ejemplo 1, son añadidos a una disolución de 13 g de 3-nitroestireno en 100 mL de tolueno, y 1.1 g de o-xileno es usado como patrón interno de la reacción. El contenido del autoclave se calienta hasta 120 ° C y se presuriza con 9 bares de hidrógeno, fijándose un nivel de agitación de 1000 r.p.m. La evolución de la reacción fue seguida en relación al consumo de gas (presión en el interior del reactor) y mediante análisis de la fase líquida por cromatografía de gases y espectrometría de masas. Después de 6 horas de reacción, 3- aminoestireno fue producido con un rendimiento del 94 %.
In an autoclave, 2.6 g of catalyst, prepared according to Example 1, are added to a solution of 13 g of 3-nitrostyrene in 100 mL of toluene, and 1.1 g of o-xylene is used as the internal standard of the reaction. The contents of the autoclave are heated to 120 ° C and pressurized with 9 bars of hydrogen, setting a stirring level of 1000 rpm. The evolution of the reaction was followed in relation to gas consumption (pressure inside the reactor) and by analysis of the liquid phase by gas chromatography and mass spectrometry. After 6 hours of reaction, 3- amino styrene was produced in 94% yield.
Claims
1.-. Un procedimiento para la preparación de oximas caracterizado porque comprende una hidrogenación catalítica del correspondiente compuesto nitro α,β-insaturado utilizando un catalizador de oro. one.-. A process for the preparation of oximes characterized in that it comprises a catalytic hydrogenation of the corresponding nitro α, β-unsaturated compound using a gold catalyst.
2.- Un procedimiento según la reivindicación 1 caracterizado porque la oxima es la oxima de ciclohexanona y el compuesto nitro es el 1 -nitro -1-ciclohexeno.2. A process according to claim 1 characterized in that the oxime is cyclohexanone oxime and the nitro compound is 1-nitro-1-cyclohexene.
3.- Un procedimiento según la reivindicación 1, caracterizado porque el oro se encuentra soportado en un soporte inorgánico.3. A method according to claim 1, characterized in that the gold is supported on an inorganic support.
4.- Un procedimiento según la reivindicación 3, caracterizado porque el oro está presente en un porcentaje en peso comprendido entre un 0.1 y un 15 % de oro respecto al soporte inorgánico en el que está soportado.4. A method according to claim 3, characterized in that the gold is present in a weight percentage comprised between 0.1 and 15% gold with respect to the inorganic support on which it is supported.
5.- Un procedimiento según la reivindicación 4, caracterizado porque el oro está presente en un porcentaje en peso comprendido entre un 0.5 y un 5 % de oro respecto al soporte inorgánico en el que está soportado. 5. A method according to claim 4, characterized in that the gold is present in a weight percentage comprised between 0.5 and 5% gold with respect to the inorganic support on which it is supported.
6.- Un procedimiento según la reivindicación 3, caracterizado porque el oro se aplica en forma metálica o iónica en el soporte inorgánico.6. A method according to claim 3, characterized in that the gold is applied in metallic or ionic form in the inorganic support.
7.- Un procedimiento según la reivindicación 3, caracterizado porque el soporte inorgánico está seleccionado entre carbón activo, óxido de hierro, óxido de titanio, óxido de cerio, óxido de magnesio, óxido de zirconio, gel de sílice, ácido silícico, óxido de lantano, alúmina, óxido de zinc, carbonato calcico, fosfato calcico, sulfato calcico, sulfato de bario, óxido de plomo, sulfato de plomo, carbonato de plomo y combinaciones de los mismos.7. A method according to claim 3, characterized in that the inorganic support is selected from active carbon, iron oxide, titanium oxide, cerium oxide, magnesium oxide, zirconium oxide, silica gel, silicic acid, oxide of lanthanum, alumina, zinc oxide, calcium carbonate, calcium phosphate, calcium sulfate, barium sulfate, lead oxide, lead sulfate, lead carbonate and combinations thereof.
8.- Un procedimiento según la reivindicación 7, caracterizado porque el soporte inorgánico está seleccionado entre óxido de hierro, óxido de titanio, óxido de cerio, sílice y combinaciones de los mismos.8. A method according to claim 7, characterized in that the inorganic support is selected from iron oxide, titanium oxide, cerium oxide, silica and combinations thereof.
9.- Un procedimiento según la reivindicación 1, caracterizado porque la relación molar oro/nitro se encuentra entre 0.01 y 10 %.9. A method according to claim 1, characterized in that the gold / nitro molar ratio is between 0.01 and 10%.
10.- Un procedimiento según la reivindicación 9, caracterizado porque la relación molar oro/nitro se encuentra entre 0.05 y 3 %. 10. A method according to claim 9, characterized in that the gold / nitro molar ratio is between 0.05 and 3%.
11.- Un procedimiento según la reivindicación 1, caracterizado porque se introduce además del oro un metal distinto de oro como modificador en el catalizador.11. A method according to claim 1, characterized in that, in addition to gold, a metal other than gold is introduced as a modifier in the catalyst.
12.- Un procedimiento según la reivindicación 11, caracterizado porque la relación en peso de oro a metal modificador es de 1:0.001. 12. A method according to claim 11, characterized in that the weight ratio of gold to metal modifier is 1: 0.001.
13.- Un procedimiento según la reivindicación 12, caracterizado porque la relación en peso de oro a metal modificador es de 1:0.5.13. A method according to claim 12, characterized in that the weight ratio of gold to metal modifier is 1: 0.5.
14.- Un procedimiento según la reivindicación 11, caracterizado porque el metal modificador está seleccionado entre paladio, platino, rodio, níquel, cobre, rutenio, plomo, mercurio, bismuto, germanio, cadmio, arsénico, antimonio, plata, hierro, manganeso, cobalto, rutenio y combinaciones de los mismos.14. A method according to claim 11, characterized in that the modifying metal is selected from palladium, platinum, rhodium, nickel, copper, ruthenium, lead, mercury, bismuth, germanium, cadmium, arsenic, antimony, silver, iron, manganese, cobalt, ruthenium and combinations thereof.
15.- Un procedimiento según la reivindicación 1, caracterizado porque la hidrogenación se realiza con una fuente de hidrógeno que es una molécula donante de hidrógeno. 15. A process according to claim 1, characterized in that the hydrogenation is carried out with a hydrogen source that is a hydrogen donor molecule.
16.- Un procedimiento según la reivindicación 15, caracterizado porque la fuente de hidrógeno está seleccionada entre formiato amónico, ácido fórmico, decaborano, ciclohexeno, ciclohexadieno, ácido fosfórico y combinaciones de los mismos. 16. A method according to claim 15, characterized in that the source of hydrogen is selected from ammonium formate, formic acid, decaborane, cyclohexene, cyclohexadiene, phosphoric acid and combinations thereof.
17.- Un procedimiento según la reivindicación 16, caracterizado porque se lleva a cabo a presión atmosférica y a una temperatura entre 250C y 12O0C. 17.- A process according to claim 16, characterized in that is carried out at atmospheric pressure and a temperature between 25 0 C and 12O 0 C.
18.- Un procedimiento según la reivindicación 15, caracterizado porque la fuente de hidrógeno es hidrógeno molecular.18. A method according to claim 15, characterized in that the source of hydrogen is molecular hydrogen.
19.- Un procedimiento según la reivindicación 18, caracterizado porque se lleva a cabo a una presión entre 1 y 100 bares y a una temperatura entre 2O0C y 25O0C. 19. A method according to claim 18, characterized in that it is carried out at a pressure between 1 and 100 bar and at a temperature between 2O 0 C and 25O 0 C.
20.- Un procedimiento según la reivindicación 19, caracterizado porque se lleva a cabo a una presión entre 5 y 50 bares y a una temperatura entre 1000C y 15O0C. 20. A method according to claim 19, characterized in that it is carried out at a pressure between 5 and 50 bar and at a temperature between 100 0 C and 15 0 0 C.
21.- Un procedimiento según la reivindicación 1, caracterizado porque se lleva a cabo en presencia de un disolvente seleccionado entre agua, alcoholes, éteres, esteres, cetonas, ácidos carboxílicos, disolventes dipolares apróticos, disolventes apolares, hidrocarburos aromáticos clorados, cloruro de metileno, aléanos C3-C7, ciclohexano y combinaciones de los mismos. 21. A process according to claim 1, characterized in that it is carried out in the presence of a solvent selected from water, alcohols, ethers, esters, ketones, carboxylic acids, aprotic dipole solvents, apolar solvents, chlorinated aromatic hydrocarbons, methylene chloride , C3-C7 alloys, cyclohexane and combinations thereof.
22.- Un procedimiento según la reivindicación 21, caracterizado porque el disolvente es un alcohol seleccionado entre metanol, etanol, n-propanol, isopropanol, n-butanol, butanoles isoméricos, ciclohexanol y combinaciones de los mismos. 22. A process according to claim 21, characterized in that the solvent is an alcohol selected from methanol, ethanol, n-propanol, isopropanol, n-butanol, isomeric butane, cyclohexanol and combinations thereof.
23.- Un procedimiento según la reivindicación 21, caracterizado porque el disolvente es un éter seleccionado entre dietil éter, metil tert-butil éter, tetrahidrofurano, dioxano, dimetoxietano y combinaciones de los mismos.23. A process according to claim 21, characterized in that the solvent is an ether selected from diethyl ether, methyl tert-butyl ether, tetrahydrofuran, dioxane, dimethoxyethane and combinations thereof.
24.- Un procedimiento según la reivindicación 21, caracterizado porque el disolvente es un éster seleccionado entre etil acetato, butil acetato y combinaciones de los mismos. 24. A process according to claim 21, characterized in that the solvent is an ester selected from ethyl acetate, butyl acetate and combinations thereof.
25.- Un procedimiento según la reivindicación 21, caracterizado porque el disolvente es una cetona seleccionada entre, butirolactona, acetona, metil etil cetona, metil isobutil cetona, ciclohexanona y combinaciones de las mismas.25. A process according to claim 21, characterized in that the solvent is a ketone selected from, butyrolactone, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and combinations thereof.
26.- Un procedimiento según la reivindicación 21, caracterizado porque el disolvente es un ácido carboxílico seleccionado entre ácido acético, ácido propiónico y combinaciones de los mismos.26.- A process according to claim 21, characterized in that the solvent is a carboxylic acid selected from acetic acid, propionic acid and combinations thereof.
27.- Un procedimiento según la reivindicación 21, caracterizado porque el disolvente es un disolvente dipolar aprótico seleccionado entre dimetilformamida, N-metilpirrolidina, dimetilacetamida, sulfolano, dimetil sulfóxido, acetonitrilo y combinaciones de los mismos.27. A process according to claim 21, characterized in that the solvent is an aprotic dipolar solvent selected from dimethylformamide, N-methylpyrrolidine, dimethylacetamide, sulfolane, dimethyl sulfoxide, acetonitrile and combinations thereof.
28.- Un procedimiento según la reivindicación 21, caracterizado porque el disolvente es un disolvente apolar seleccionado entre tolueno, xileno y combinaciones de los mismos.28. A process according to claim 21, characterized in that the solvent is an apolar solvent selected from toluene, xylene and combinations thereof.
29.- Un procedimiento según la reivindicación 21, caracterizado porque el disolvente empleado está seleccionado entre tolueno, xileno, tetrahidrofurano, dioxano, metil etil cetona, metanol, etanol y combinaciones de los mismos.29. A process according to claim 21, characterized in that the solvent used is selected from toluene, xylene, tetrahydrofuran, dioxane, methyl ethyl ketone, methanol, ethanol and combinations thereof.
30.- Un procedimiento según la reivindicación 1, caracterizado porque se lleva a cabo en presencia de un disolvente y de uno o más co-disolventes.30. A process according to claim 1, characterized in that it is carried out in the presence of a solvent and one or more co-solvents.
31.- Un procedimiento según la reivindicación 30, caracterizado porque el co-disolvente está seleccionado entre etanol, acetona, acetonitrilo y combinaciones de los mismos. 31. A process according to claim 30, characterized in that the co-solvent is selected from ethanol, acetone, acetonitrile and combinations thereof.
32.- Un procedimiento según la reivindicación 1, caracterizado porque la reacción se lleva a cabo en ausencia de disolvente.32. A process according to claim 1, characterized in that the reaction is carried out in the absence of solvent.
33.- Un procedimiento según una de las reivindicaciones anteriores, caracterizado porque la reacción de hidrogenación se lleva a cabo en fase gas-sólido.33. A process according to one of the preceding claims, characterized in that the hydrogenation reaction is carried out in the gas-solid phase.
34.- Un procedimiento según una de las reivindicaciones anteriores, caracterizado porque la reacción de hidrogenación se lleva a cabo en un sistema gas-líquido-sólido.34. A process according to one of the preceding claims, characterized in that the hydrogenation reaction is carried out in a gas-liquid-solid system.
35.- Un procedimiento según una de las reivindicaciones anteriores, caracterizado porque se lleva a cabo en un reactor en modo discontinuo.35. A method according to one of the preceding claims, characterized in that it is carried out in a reactor in discontinuous mode.
36.- Un procedimiento según una de las reivindicaciones anteriores caracterizado porque se lleva a cabo en un reactor en modo continuo. 36. A method according to one of the preceding claims characterized in that it is carried out in a reactor in continuous mode.
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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ES2337004A1 (en) * | 2008-10-16 | 2010-04-19 | Universidad Politecnica De Valencia | Procedure for the selective hydrogenation of nitrocycloalkanes to obtain cyclic oximes |
WO2014191589A1 (en) * | 2013-05-27 | 2014-12-04 | Consejo Superior De Investigaciones Científicas (Csic) | Method for obtaining directly cyclohexanone oxime from nitro derivatives |
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EP0346674A1 (en) * | 1988-06-13 | 1989-12-20 | Mitsubishi Kasei Corporation | Process for preparing oximes |
JP2001213854A (en) * | 2000-02-02 | 2001-08-07 | Asahi Kasei Corp | Method for producing cyclohexanone oxime |
-
2006
- 2006-04-12 ES ES200601117A patent/ES2289925B2/en not_active Expired - Fee Related
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2007
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Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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EP0346674A1 (en) * | 1988-06-13 | 1989-12-20 | Mitsubishi Kasei Corporation | Process for preparing oximes |
JP2001213854A (en) * | 2000-02-02 | 2001-08-07 | Asahi Kasei Corp | Method for producing cyclohexanone oxime |
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DATABASE WPI Week 200175, Derwent World Patents Index; AN 2001-650716 * |
KABALKA ET AL.: "The palladium assisted transfer reduction of a,b-unsaturated nitroalkenes to oximes using ammonium formate", SYNTHETIC COMMUNICATIONS, vol. 20, no. 16, 1990, pages 2453 - 2458 * |
SEUNG HWANG LEE ET AL.: "Catalytic transfer hydrogenation of conjugated nitroalkenes using decarborane: synthesis of oximes", ORGANIC AND BIOMOLECULAR CHEMISTRY, vol. 1, no. 7, 2003, pages 1099 - 1100 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ES2337004A1 (en) * | 2008-10-16 | 2010-04-19 | Universidad Politecnica De Valencia | Procedure for the selective hydrogenation of nitrocycloalkanes to obtain cyclic oximes |
WO2010043738A1 (en) * | 2008-10-16 | 2010-04-22 | Universidad Politécnica De Valencia (Upv) | Procedure for the selective hydrogenation of nitrocycloalkanes to obtain cyclic oximes |
WO2014191589A1 (en) * | 2013-05-27 | 2014-12-04 | Consejo Superior De Investigaciones Científicas (Csic) | Method for obtaining directly cyclohexanone oxime from nitro derivatives |
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