CN1622926A - 甲苯衍生物的制备方法 - Google Patents
甲苯衍生物的制备方法 Download PDFInfo
- Publication number
- CN1622926A CN1622926A CNA038027135A CN03802713A CN1622926A CN 1622926 A CN1622926 A CN 1622926A CN A038027135 A CNA038027135 A CN A038027135A CN 03802713 A CN03802713 A CN 03802713A CN 1622926 A CN1622926 A CN 1622926A
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- Prior art keywords
- component
- weight
- hydrogenation
- desired method
- metal
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Links
- 150000003613 toluenes Chemical class 0.000 title claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 title abstract description 3
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 31
- 239000001257 hydrogen Substances 0.000 claims abstract description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 26
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 9
- 235000019445 benzyl alcohol Nutrition 0.000 claims abstract description 6
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 5
- 150000002367 halogens Chemical class 0.000 claims abstract description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- -1 phenyl aldehyde Chemical class 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 16
- WVDDGKGOMKODPV-UHFFFAOYSA-N hydroxymethyl benzene Natural products OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 229910052703 rhodium Inorganic materials 0.000 claims description 6
- 239000010948 rhodium Substances 0.000 claims description 6
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 5
- 239000004411 aluminium Substances 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052785 arsenic Inorganic materials 0.000 claims description 4
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- 229910052793 cadmium Inorganic materials 0.000 claims description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 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 4
- 150000002739 metals Chemical class 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
- 150000002910 rare earth metals Chemical class 0.000 claims description 4
- 229910052702 rhenium Inorganic materials 0.000 claims description 4
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 239000011135 tin Substances 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 3
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 3
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 3
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 3
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 125000001033 ether group Chemical group 0.000 claims 1
- 239000000155 melt Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 18
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 abstract 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 abstract 1
- 150000003935 benzaldehydes Chemical class 0.000 abstract 1
- 150000003938 benzyl alcohols Chemical class 0.000 abstract 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 150000001299 aldehydes Chemical group 0.000 description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 5
- 229910002651 NO3 Inorganic materials 0.000 description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 5
- 230000009466 transformation Effects 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 239000002638 heterogeneous catalyst Substances 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- UALKQROXOHJHFG-UHFFFAOYSA-N 1-ethoxy-3-methylbenzene Chemical compound CCOC1=CC=CC(C)=C1 UALKQROXOHJHFG-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052728 basic metal Inorganic materials 0.000 description 2
- 150000003818 basic metals Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- QDOAVFZGLCBVQL-UHFFFAOYSA-N bismuth Chemical compound [Bi].[Bi].[Bi] QDOAVFZGLCBVQL-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical group 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229920001515 polyalkylene glycol Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
- 150000003527 tetrahydropyrans Chemical class 0.000 description 2
- 239000006200 vaporizer Substances 0.000 description 2
- MSHFRERJPWKJFX-UHFFFAOYSA-N 4-Methoxybenzyl alcohol Chemical compound COC1=CC=C(CO)C=C1 MSHFRERJPWKJFX-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000014493 Crataegus Nutrition 0.000 description 1
- 241001092040 Crataegus Species 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000005684 Liebig rearrangement reaction Methods 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- BULOCEWDRJUMEL-UHFFFAOYSA-N benzene formaldehyde Chemical compound C=O.C1=CC=CC=C1.C=O BULOCEWDRJUMEL-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- JGDFBJMWFLXCLJ-UHFFFAOYSA-N copper chromite Chemical compound [Cu]=O.[Cu]=O.O=[Cr]O[Cr]=O JGDFBJMWFLXCLJ-UHFFFAOYSA-N 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000006324 decarbonylation Effects 0.000 description 1
- 238000006606 decarbonylation reaction Methods 0.000 description 1
- 230000017858 demethylation Effects 0.000 description 1
- 238000010520 demethylation reaction Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 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
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- KCDXJAYRVLXPFO-UHFFFAOYSA-N syringaldehyde Chemical compound COC1=CC(C=O)=CC(OC)=C1O KCDXJAYRVLXPFO-UHFFFAOYSA-N 0.000 description 1
- YIBXWXOYFGZLRU-UHFFFAOYSA-N syringic aldehyde Natural products CC12CCC(C3(CCC(=O)C(C)(C)C3CC=3)C)C=3C1(C)CCC2C1COC(C)(C)C(O)C(O)C1 YIBXWXOYFGZLRU-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/22—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by reduction
-
- 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
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Abstract
本发明涉及一种制备式(I)的甲苯衍生物的方法，其中R1、R2和R3相互独立地为氢、卤素、C1－C6烷基、羟基或C1－C6烷氧基。所述衍生物通过在催化剂存在下用氢气氢化式(II)的苯甲醛[IIa：X＝CHO，X＝CH[OC1－C6烷基] 2]和/或苄基醇[IIb：X＝CH2－OH，X＝CH2OC1－C6烷基]而制备，所述催化剂更详细地描述于说明书中。
Description
本发明涉及一种通过在催化剂存在下用氢气氢化式II的苯甲醛和/或苄基醇而制备甲苯衍生物I的方法：
其中R1、R2和R3相互独立地为氢、卤素、C1-C6烷基、羟基或C1-C6烷氧基：
将苯甲醛或苄基醇II催化氢化得到相应的甲苯衍生物I原则上由文献已知。
合成(Synthesis)，第8卷(1993)，第799页公开了在10％活性炭载钯存在下将溶于乙酸中的3，4，5-三甲氧基苯甲醛氢化得到3，4，5-三甲氧基甲苯。
根据莱比锡化学年鉴(Liebigs Annalen der Chemie)1976，第7/8辑，第1445页，以类似方式在10％活性炭载钯存在下也是在冰乙酸中氢化丁香醛(4-羟基-3，5-二甲氧基苯甲醛)，得到4-羟基-3，5-二甲氧基甲苯。
美国化学会志(The Journal of American Chemical Society)第79卷(1957)，第179-184页描述了在冰乙酸中在活性炭载钯(10％)存在下氢化3，4，5-三甲氧基苄基醇。
所有上述方法的缺点在于在反应中形成的水与乙酸一起形成腐蚀性溶剂混合物并将昂贵的贵金属用作氢化催化剂。
EP 606072报道了在含有铂族金属的二氧化钛成型体存在下氢化苯甲醛。原料以浓度仅为1％的水溶液或乙醇溶液使用，因此在高度稀释下使用。氢化的产率低，而且选择性极低。产生的副产物是环被氢化且脱甲基的苯。
为了将对甲氧基苄基醇氢化成对甲氧基甲苯，根据有机化学杂志(J.Org.Chem.)，1949，14，第1089页，使用亚铬酸铜催化剂以及作为溶剂的甲醇。仅一般性地提到了对甲氧基苯甲醛向对甲氧基甲苯的直接转化，但没有由实施例证实。该方法的缺点是使用含铬的催化剂。
苄基醇的氢化进一步描述于欧洲化学杂志(Chem.Eur.J.)(2000)，6(2)，第313-320页中。使用昂贵的贵金属催化剂，如碳载铑或Al2O3载体上的铑，这些催化剂此外还产生高比例的环氢化产物。
本发明的目的是开发一种制备取代的甲苯化合物的方法，该方法可以高产率和选择性进行并避免所述缺点。在该方法中尤其应避免昂贵的贵金属催化剂、含铬催化剂以及腐蚀性溶剂。应尽可能完全地防止副反应如得到环己烷衍生物的环氢化、醛官能团的脱羰基或取代基如烷氧基或卤素在苯基环上的消去。
我们发现该目的由一种通过在催化剂存在下用氢气氢化式II的苯甲醛和/或苄基醇而制备甲苯衍生物I的方法实现：
其中R1、R2和R3相互独立地为氢、卤素、C1-C6烷基、羟基或C1-C6烷氧基：
所述催化剂包括具有下列组成的催化剂：
(a)至少一种选自钴、镍和铜的金属和/或至少一种该金属的氧化物、氢氧化物或盐；
(b)0-50重量％的一种或多种选自铂、铑、铁、银、钼、钨、锰、铼、锌、镉、铅、铝、锆、锡、磷、硅、砷、锑、铋、钛和稀土金属的金属和/或一种或多种该金属的氧化物、氢氧化物或盐，和
(c)0-5重量％的碱金属氧化物或碱土金属氧化物、碱金属氢氧化物或碱土金属氢氧化物或碱金属盐或碱土金属盐，
其中组分(a)-(c)的总和为100重量％，条件是不额外使用载体。
催化剂的可能实施方案包括：
(a)基于组分(a)-(c)的总和为40-99重量％的一种或多种选自钴、镍和铜的金属和/或一种或多种该金属的氧化物、氢氧化物或盐；
(b)基于组分(a)-(c)的总和为0.1-40重量％的一种或多种选自铂、铑、铁、银、钼、钨、锰、铼、锌、镉、铅、铝、锆、锡、磷、硅、砷、锑、铋和稀土金属的金属和/或一种或多种该金属的氧化物、氢氧化物或盐，和
(c)基于组分(a)-(c)的总和为0.05-5重量％的一种或多种碱金属氧化物或碱土金属氧化物、碱金属氢氧化物或碱土金属氢氧化物或碱金属盐或碱土金属盐。
下面描述某些优选的实施方案，在每种情况下优选含义适用于单一组分以及不同组分的结合。下面给出的量基于组分(a)-(c)的总和。在这些值中不考虑任何可能存在的载体。
优选的催化剂是其中组分(a)占5-100重量％的那些。特别优选的是含有40-99重量％组分(a)的催化剂。
此外，优选其中组分(b)的存在量为0-50重量％，尤其是1-40重量％的催化剂。
优选的催化剂含有作为组分(b)的至少一种选自铂、铑、铁、银、钼、钨、锰、铼、锌、镉、铅、铝、锆、锡、磷、硅、砷、锑、铋和稀土金属的金属的氧化物、氢氧化物或盐。
特别优选的催化剂含有作为组分(b)的至少一种选自铝、硅、锆、钼、锰和磷的金属的氧化物、氢氧化物或盐。
用于本发明催化剂中的组分(c)优选为选自锂、钾、铯、镁和钙以及尤其优选钠的碱金属和碱土金属的氧化物或盐。
可以使用的原料尤其是式IIa和IIb的化合物，它们单独使用或混合使用，其中R1-R3具有上述含义并且R4为氢或C1-C6烷基。在某些情况下，已经证明有利的是以其缩醛形式使用醛IIa。缩醛可以通过使用文献中常用的方法由醛IIa与C1-C6醇反应而制备。
催化剂可以溶解形式的均相催化剂或多相催化剂使用。多相催化剂可以是载体化催化剂、固体催化剂或阮内催化剂，它们以固定床、悬浮或湍动形式使用。合适的载体材料例如是氧化物如氧化铝、二氧化硅、铝硅酸盐、氧化镧、二氧化钛、二氧化锆、氧化镁、氧化锌和沸石以及活性炭及其混合物。
多相催化剂通常按如下方式制备：在载体材料存在或不存在(取决于想要的催化剂类型)下将组分(a)的前体任选与组分(b)(促进剂)的前体一起和/或任选与痕量组分(c)的前体一起沉淀，以及任选将所得催化剂前体加工成棒或片，干燥并随后煅烧。载体化催化剂通常也可以通过用组分(a)以及任选的(b)和/或(c)的溶液浸渍载体而得到[各组分可同时或依次加入]，或通过本身已知的方式将组分(a)以及任选的(b)和/或(c)喷雾于载体上而得到。若需要，粘合剂可以用于催化剂的生产中。
组分(a)的合适前体通常是上述金属的易水溶性盐，如硝酸盐、氯化物、乙酸盐、甲酸盐和硫酸盐，优选硝酸盐。
组分(b)的合适前体通常是上述金属的易水溶性盐或复合盐，如硝酸盐、氯化物、乙酸盐、甲酸盐和硫酸盐，优选硝酸盐。
组分(c)的合适前体通常为上述碱金属和碱土金属的易水溶性盐，如氢氧化物、碳酸盐、硝酸盐、氯化物、乙酸盐、甲酸盐和硫酸盐，优选氢氧化物和碳酸盐。
沉淀通常在水溶液中进行，任选通过添加沉淀试剂、改变pH或改变温度。
所得催化剂前体组合物通常在80-150℃，优选80-120℃的温度下预干燥。
煅烧通常在150-500℃，优选200-450℃的温度下在空气或氮气气流中进行。
合适的话钝化催化剂表面，这通常在20-80℃，优选25-35℃的温度下使用氧气/氮气混合物如空气进行。
所得煅烧的和可能钝化的催化剂组合物通常暴露于还原性气氛下(“活化”)，例如通过在100-500℃，优选150-400℃的温度下暴露于包含游离氢气的气流中2-60小时。气流优选由20-100体积％氢气和0-50体积％惰性气体如氮气组成。
由于优选直接在合成反应器中活化催化剂，因而存在加工经济性的优点。
本发明催化剂的特征在于高活性且在基本彻底的转化率下可以获得高通过量。
氢化可以分批进行，但尤其连续进行。在连续操作情况下，氢化可以以塔底相或喷淋程序在气相或液相中进行。
式IIa和IIb的原料可以通过开头引用的文献中所述的方法得到。
化合物IIa和IIb可以无溶剂氢化，例如在气相中或作为熔体。在某些情况下已经证明有利的是添加溶剂。
合适的溶剂是对原料II和目标产物I具有足够溶解能力且在氢化条件下稳定的那些。这类溶剂的实例是醚类，如四氢呋喃、二噁烷、四氢吡喃、聚乙二醇二烷基醚或聚乙二醇单烷基醚，水，醇类，如甲醇、乙醇、叔丁醇、环己醇，烷基苯，如甲苯和二甲苯类，酚类，如邻苯二酚、间苯二酚、氢醌、1，2，3-苯三酚或这些酚类的烷基醚。也可使用其混合物。
优选的溶剂是四氢呋喃、二噁烷、四氢吡喃、聚乙二醇二烷基醚、聚乙二醇单烷基醚、烷基苯、水和醇或这些化合物的混合物。尤其合适的那些是醚类或醚/水混合物。还优选醇和醇/水混合物，尤其是甲醇和甲醇/水混合物。
将原料II在所述溶剂中的浓度例如为1-60重量％的溶液氢化。
在优选的实施方案中，氢化在气相中不使用溶剂进行。
氢化在任选20-280℃的温度和任选1-300巴的压力，优选100-260℃的温度和20-250巴的压力下进行。
用于氢化的氢气通常相对于起始化合物II以较大的化学计算量过量使用。
氢气可以作为再循环气体再循环到反应中。所用氢气通常具有工业级纯度。然而，混入惰性气体如氮气不会干扰反应进程。
可以通过本发明氢化制备的化合物I是可以用于制备药物、精细化学品和植物保护化合物的有用中间体。
下面参考实施例更详细描述本发明。百分数为重量百分数。
本发明催化剂的实例：
催化剂A：60重量％CuO；40重量％Al2O3；
催化剂B：65.4重量％CoO；20.2重量％CuO；8.3重量％Mn3O4；3.5重量％MoO3；2.4重量％P2O5；0.2重量％Na2O；
催化剂C：74.0重量％NiO；2.2重量％MoO3；23.8重量％CuO；载于作为ZrO2的载体上；
催化剂D：77.7重量％NiO，13.6重量％SiO2，5.8重量％Al2O3，4.7重量％ZrO2。
催化剂A的活化
在可电加热的反应器中将50g催化剂A[其中通入100l(S.T.P.)/h的氮气流]由室温加热到250℃。在接下来的12小时内将5l(S.T.P.)/h的氢气加入氮气流中。然后在随后的5小时将氮气用纯氢气代替。
催化剂B、C和D在大气压力下的活化
在将催化剂加入容量为1升的可电加热的反应器中之后，在300l/h的氮气流下将温度由室温开始每小时增加约20℃，直至达到290℃。然后在6小时内用氢气代替氮气。为此，每小时将氢气含量增加50l/h并同时使氮气含量降低50l/h。当达到300l/h的氢气进料时，将反应器温度升至300-310℃并在300l/h氢气下保持48小时。在氩气下冷却之后除去催化剂并在四甘醇二甲醚下储存。
制备式I的甲苯衍生物
实施例1
在铜催化剂存在下在气相中氢化3，4，5-三甲氧基苯甲醛
在由蒸发器、反应器和冷凝器组成的气相设备中进行试验。起始化合物在蒸发器中在Raschig环上在氢气的逆流料流中汽化。使被起始化合物饱和的氢气流在预活化的催化剂上反应。然后将气流通入冷凝器中，由该冷凝器可以排出转化成液态的产物。在反应过程中氢化设备中的氢气压力为1巴。
每小时将4.5g 3，4，5-三甲氧基苯甲醛在Raschig环上在氢气的逆流料流中汽化并在260℃的温度下通过50g预活化的催化剂A。氢气/原料比(mol/mol)大约为4∶1。在94％的转化率下，获得85％的选择性。
实施例2
在镍催化剂存在下3，4，5-三甲氧基苯甲醛在液相中氢化
将1g位于催化剂篮式插件中的催化剂D放于300ml加压反应器中并加入10g在100g甲醇中的3，4，5-三甲氧基苯甲醛。使用纯净氢气在200巴的恒定压力和180℃的温度下进行氢化。继续氢化直到不再吸收氢气。然后解压反应器。醛转化率为100％。所需甲苯衍生物的产率基于醛的总用量为91％。
实施例3
在钴催化剂存在下在液相中氢化3，4，5-三甲氧基苯甲醛
以类似于实施例2的方式在1g催化剂B存在下将10g溶于100g四氢呋喃中的3，4，5-三甲氧基苯甲醛氢化。醛转化率为100％。所需甲苯衍生物的产率基于醛的总用量为96％。
实施例4
3，4，5-三甲氧基苯甲醛熔体在液相中氢化
以类似于实施例2的方式在1g催化剂C存在下将10g 3，4，5-三甲氧基苯甲醛在无溶剂下氢化。醛转化率为100％。所需甲苯衍生物的产率基于醛的总用量为94％。
Claims (10)
1.一种通过在催化剂存在下用氢气氢化式II的苯甲醛和/或苄基醇而制备式I的甲苯衍生物的方法：
其中R1、R2和R3相互独立地为氢、卤素、C1-C6烷基、羟基或C1-C6烷氧基：
IIa：X＝CHOX＝CH[OC1-C6烷基]2IIb：X＝CH2-OHX＝CH2OC1-C6烷基
所述催化剂包括具有下列组成的催化剂：
(a)至少一种选自钴、镍和铜的金属和/或至少一种该金属的氧化物、氢氧化物或盐；
(b)0-50重量％的一种或多种选自铂、铑、铁、银、钼、钨、锰、铼、锌、镉、铅、铝、锆、锡、磷、硅、砷、锑、铋、钛和稀土金属的金属和/或一种或多种该金属的氧化物、氢氧化物或盐，和
(c)0-5重量％的碱金属氧化物或碱土金属氧化物、碱金属氢氧化物或碱土金属氢氧化物或碱金属盐或碱土金属盐，
其中组分(a)-(c)的总和为100重量％，条件是不额外使用载体。
2.如权利要求1所要求的方法，其中组分(a)占组分(a)-(c)的总和的40-99重量％。
3.如权利要求1或2所要求的方法，其中组分(b)占组分(a)-(c)的总和的1-40重量％。
4.如权利要求1-3中任一项所要求的方法，其中组分(c)占组分(a)-(c)的总和的0.05-5重量％。
5.如权利要求1-4中任一项所要求的方法，其中氢化在溶剂中进行。
6.如权利要求5所要求的方法，其中溶剂为醚、烷基苯、水或醇或其混合物。
7.如权利要求1-4中任一项所要求的方法，其中氢化在气相中进行。
8.如权利要求1-4中任一项所要求的方法，其中氢化在化合物II的熔体中进行。
9.如权利要求1-4中任一项所要求的方法，其中氢化在20-250巴的压力和100-260℃的温度下进行。
10.如权利要求1-9中任一项所要求的方法，用于制备3，4，5-三甲氧基甲苯。
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| DE10202837.0 | 2002-01-24 | ||
| DE10202837 | 2002-01-24 |
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| EP (1) | EP1470094A1 (zh) |
| JP (1) | JP2005515248A (zh) |
| KR (1) | KR20040077781A (zh) |
| CN (1) | CN1257870C (zh) |
| AR (1) | AR038314A1 (zh) |
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| EA (1) | EA007065B1 (zh) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101531574B (zh) * | 2009-04-14 | 2012-07-25 | 大连理工大学 | 一种制备3,4,5-三甲氧基甲苯的方法 |
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| JP5784742B2 (ja) * | 2010-11-02 | 2015-09-24 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | フェニルシクロヘキサンの製造方法 |
| CN102746100A (zh) * | 2011-04-20 | 2012-10-24 | 中国石油化工股份有限公司 | 制备异丙苯的方法 |
| KR101930087B1 (ko) | 2011-07-26 | 2018-12-18 | 에스케이이노베이션 주식회사 | 방향족 카르복시산 및/또는 방향족 카르복시산 알킬 에스테르 제조 공정에서 발생하는 부산물로부터 방향족 탄화수소 제조방법 |
| US9259715B2 (en) | 2012-10-17 | 2016-02-16 | Archer Daniels Midland Company | Hydrogenolysis catalysts and uses thereof |
| US9205412B2 (en) | 2013-03-01 | 2015-12-08 | Clariant Corporation | Catalyst for polyol hydrogenolysis |
| RU2625656C1 (ru) * | 2016-02-17 | 2017-07-18 | Общество с ограниченной ответственностью "Научно-производственное объединение "НИИПАВ" (ООО НПО "НИИПАВ") | Способ получения алкилдиметиламинов |
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| FR678954A (fr) * | 1928-11-19 | 1930-04-07 | Expl Des Matieres Organiques S | Procédé pour la transformation des crésols en benzène et méthylbenzène en présence d'un catalyseur de réduction ou d'hydrogénation, avec ou sans addition de gazhydrogène |
| DE904529C (de) * | 1942-08-07 | 1954-02-18 | Bayer Ag | Verwendung eines Nickel, Chromoxyd und Aluminiumoxyd enthaltenden Hydrierungskatalysators |
| US2682562A (en) * | 1951-05-10 | 1954-06-29 | Us Interior | Reduction of aromatic carbinols |
| EP0053884A1 (en) | 1980-11-27 | 1982-06-16 | Johnson Matthey Public Limited Company | Three dimensional interstitial catalyst supports, its manufacture and use |
| DE4300297C2 (de) | 1993-01-08 | 1998-01-29 | Degussa | Verfahren zur selektiven katalytischen Hydrierung der Carbonylgruppe von 4-Carboxylbenzaldehyd |
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| CN101531574B (zh) * | 2009-04-14 | 2012-07-25 | 大连理工大学 | 一种制备3,4,5-三甲氧基甲苯的方法 |
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| MXPA04006744A (es) | 2005-06-08 |
| JP2005515248A (ja) | 2005-05-26 |
| US20050032627A1 (en) | 2005-02-10 |
| CA2473936A1 (en) | 2003-07-31 |
| ZA200406665B (en) | 2006-06-28 |
| EA200400876A1 (ru) | 2004-12-30 |
| CN1257870C (zh) | 2006-05-31 |
| BR0306939A (pt) | 2004-12-14 |
| PL372164A1 (en) | 2005-07-11 |
| KR20040077781A (ko) | 2004-09-06 |
| UA78982C2 (en) | 2007-05-10 |
| US7230141B2 (en) | 2007-06-12 |
| WO2003062174A1 (de) | 2003-07-31 |
| EP1470094A1 (de) | 2004-10-27 |
| AR038314A1 (es) | 2005-01-12 |
| EA007065B1 (ru) | 2006-06-30 |
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