JP3831012B2 - Method for oxidizing conjugated compounds - Google Patents
Method for oxidizing conjugated compounds Download PDFInfo
- Publication number
- JP3831012B2 JP3831012B2 JP18486696A JP18486696A JP3831012B2 JP 3831012 B2 JP3831012 B2 JP 3831012B2 JP 18486696 A JP18486696 A JP 18486696A JP 18486696 A JP18486696 A JP 18486696A JP 3831012 B2 JP3831012 B2 JP 3831012B2
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- Japan
- Prior art keywords
- group
- general formula
- compound represented
- elements
- conjugated
- Prior art date
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- 150000001875 compounds Chemical class 0.000 title claims description 67
- 238000000034 method Methods 0.000 title claims description 27
- 230000001590 oxidative effect Effects 0.000 title claims description 5
- -1 imide compound Chemical class 0.000 claims description 70
- 125000000217 alkyl group Chemical group 0.000 claims description 42
- 238000007254 oxidation reaction Methods 0.000 claims description 38
- 230000003647 oxidation Effects 0.000 claims description 32
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 28
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 27
- 229910052760 oxygen Inorganic materials 0.000 claims description 27
- 239000001301 oxygen Substances 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 24
- 150000001993 dienes Chemical class 0.000 claims description 21
- 125000003118 aryl group Chemical group 0.000 claims description 19
- 150000003839 salts Chemical class 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 17
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 17
- 125000001424 substituent group Chemical group 0.000 claims description 17
- 125000002252 acyl group Chemical group 0.000 claims description 16
- 125000003545 alkoxy group Chemical group 0.000 claims description 14
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 11
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 10
- 125000005843 halogen group Chemical group 0.000 claims description 10
- 150000002825 nitriles Chemical class 0.000 claims description 10
- 230000000737 periodic effect Effects 0.000 claims description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 9
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 9
- 229910001882 dioxygen Inorganic materials 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- CFMZSMGAMPBRBE-UHFFFAOYSA-N 2-hydroxyisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(O)C(=O)C2=C1 CFMZSMGAMPBRBE-UHFFFAOYSA-N 0.000 claims description 7
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 6
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 6
- 150000008065 acid anhydrides Chemical class 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 6
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 6
- 150000002602 lanthanoids Chemical class 0.000 claims description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 5
- 229910052768 actinide Inorganic materials 0.000 claims description 5
- 150000001255 actinides Chemical class 0.000 claims description 5
- 150000001639 boron compounds Chemical class 0.000 claims description 5
- 229910021474 group 7 element Inorganic materials 0.000 claims description 5
- 229910021472 group 8 element Inorganic materials 0.000 claims description 5
- 150000004820 halides Chemical class 0.000 claims description 5
- 150000003623 transition metal compounds Chemical group 0.000 claims description 5
- 125000002723 alicyclic group Chemical group 0.000 claims description 4
- 239000004327 boric acid Substances 0.000 claims description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 4
- 229910021478 group 5 element Inorganic materials 0.000 claims description 4
- 229910021476 group 6 element Inorganic materials 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- 125000006574 non-aromatic ring group Chemical group 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- JFNLZVQOOSMTJK-UHFFFAOYSA-N norbornene Chemical group C1C2CCC1C=C2 JFNLZVQOOSMTJK-UHFFFAOYSA-N 0.000 claims description 2
- 125000005619 boric acid group Chemical group 0.000 claims 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 150000002009 diols Chemical class 0.000 description 16
- 239000011572 manganese Substances 0.000 description 11
- 239000010949 copper Substances 0.000 description 10
- ORTVZLZNOYNASJ-UPHRSURJSA-N (z)-but-2-ene-1,4-diol Chemical compound OC\C=C/CO ORTVZLZNOYNASJ-UPHRSURJSA-N 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 150000008064 anhydrides Chemical class 0.000 description 7
- 239000010948 rhodium Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 6
- 239000011651 chromium Substances 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 239000011964 heteropoly acid Substances 0.000 description 6
- 150000003949 imides Chemical class 0.000 description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 6
- 229910052750 molybdenum Inorganic materials 0.000 description 6
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- 235000010338 boric acid Nutrition 0.000 description 5
- 229960002645 boric acid Drugs 0.000 description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 5
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 5
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- 239000007800 oxidant agent Substances 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 229910052703 rhodium Inorganic materials 0.000 description 5
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- 229910052721 tungsten Inorganic materials 0.000 description 5
- 229910052720 vanadium Inorganic materials 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 150000001241 acetals Chemical class 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 239000010955 niobium Substances 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 229910052707 ruthenium Inorganic materials 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 0 CCC(C)(C1N=O)C(*)(CC)C1[N+](*(C)=*)[O-] Chemical compound CCC(C)(C1N=O)C(*)(CC)C1[N+](*(C)=*)[O-] 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- JCXJVPUVTGWSNB-UHFFFAOYSA-N Nitrogen dioxide Chemical compound O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical class [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- 125000005595 acetylacetonate group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910052795 boron group element Inorganic materials 0.000 description 2
- ITMIAZBRRZANGB-UHFFFAOYSA-N but-3-ene-1,2-diol Chemical compound OCC(O)C=C ITMIAZBRRZANGB-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 208000012839 conversion disease Diseases 0.000 description 2
- 150000001925 cycloalkenes Chemical group 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical group C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052762 osmium Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- 239000003586 protic polar solvent Substances 0.000 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 description 2
- 229910052702 rhenium Inorganic materials 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
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- 235000007079 manganese sulphate Nutrition 0.000 description 1
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- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- FRYUOUHISNWFTE-UHFFFAOYSA-L manganese(2+);dithiocyanate Chemical compound [Mn+2].[S-]C#N.[S-]C#N FRYUOUHISNWFTE-UHFFFAOYSA-L 0.000 description 1
- SGGOJYZMTYGPCH-UHFFFAOYSA-L manganese(2+);naphthalene-2-carboxylate Chemical compound [Mn+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 SGGOJYZMTYGPCH-UHFFFAOYSA-L 0.000 description 1
- SZINCDDYCOIOJQ-UHFFFAOYSA-L manganese(2+);octadecanoate Chemical compound [Mn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O SZINCDDYCOIOJQ-UHFFFAOYSA-L 0.000 description 1
- ZGIHUCQOMWIMKH-UHFFFAOYSA-L manganese(2+);propanoate Chemical compound [Mn+2].CCC([O-])=O.CCC([O-])=O ZGIHUCQOMWIMKH-UHFFFAOYSA-L 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- MLSKXPOBNQFGHW-UHFFFAOYSA-N methoxy(dioxido)borane Chemical compound COB([O-])[O-] MLSKXPOBNQFGHW-UHFFFAOYSA-N 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- WUJISAYEUPRJOG-UHFFFAOYSA-N molybdenum vanadium Chemical compound [V].[Mo] WUJISAYEUPRJOG-UHFFFAOYSA-N 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- HKFZDVPCCOOGEV-UHFFFAOYSA-N nickel(3+);borate Chemical compound [Ni+3].[O-]B([O-])[O-] HKFZDVPCCOOGEV-UHFFFAOYSA-N 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- MCSAJNNLRCFZED-UHFFFAOYSA-N nitroethane Chemical compound CC[N+]([O-])=O MCSAJNNLRCFZED-UHFFFAOYSA-N 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- MOWNZPNSYMGTMD-UHFFFAOYSA-N oxidoboron Chemical compound O=[B] MOWNZPNSYMGTMD-UHFFFAOYSA-N 0.000 description 1
- VGTPKLINSHNZRD-UHFFFAOYSA-N oxoborinic acid Chemical compound OB=O VGTPKLINSHNZRD-UHFFFAOYSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 125000001148 pentyloxycarbonyl group Chemical group 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 125000004742 propyloxycarbonyl group Chemical group 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- GKLVYJBZJHMRIY-UHFFFAOYSA-N technetium atom Chemical compound [Tc] GKLVYJBZJHMRIY-UHFFFAOYSA-N 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- AUHHYELHRWCWEZ-UHFFFAOYSA-N tetrachlorophthalic anhydride Chemical compound ClC1=C(Cl)C(Cl)=C2C(=O)OC(=O)C2=C1Cl AUHHYELHRWCWEZ-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- NFMWFGXCDDYTEG-UHFFFAOYSA-N trimagnesium;diborate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]B([O-])[O-].[O-]B([O-])[O-] NFMWFGXCDDYTEG-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- MDCWDBMBZLORER-UHFFFAOYSA-N triphenyl borate Chemical compound C=1C=CC=CC=1OB(OC=1C=CC=CC=1)OC1=CC=CC=C1 MDCWDBMBZLORER-UHFFFAOYSA-N 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 125000003774 valeryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、共役化合物（例えば、共役ジエン類、α，β−不飽和ニトリル、α，β−不飽和カルボン酸又はその誘導体など）から対応する酸化物、特にジオール類などの酸化物を製造する上で有用な酸化方法に関する。
【０００２】
【従来の技術】
ポリアミドなどの合成樹脂、無水マレイン酸、可塑剤などの合成原料としてブテンジオールが利用されている。また、ブテンジオールから誘導されるブタンジオールは、例えば、テトラヒドロフラン、ブチロラクトン、ポリエステルやポリウレタンの合成原料として有用である。前記ブテンジオールやブタンジオールは、レッペ反応を利用してブチンジオールを生成させ、生成したブチンジオールを還元触媒を用いて水素添加することにより得ることができる。
一方、石油精製工程においてブタジエンなどの共役ジエンは多量に生成する。そのため、ブタジエンなどの共役ジエンから対応するブテンジオールなどのアルケンジオールを直接生成できるならば工業的に有用である。共役ジエンからジオールを製造する方法として、硝酸を用いて共役ジエンを酸化し、ジオール生成させることも考えられる。しかし、硝酸酸化により生成するＮ2ＯおよびＮＯxを処理するために、高価な排ガス処理施設が必要となる。そのため、資源及び環境上の観点から、分子状酸素又は空気を酸化剤として直接利用する触媒的な酸化法によりアルケンジオールを効率よく製造可能ならばさらに有用である。
【０００３】
また、酸素又は空気を酸化剤として利用する酸化方法が、共役ジエン類以外の共役化合物、例えば、アクリル酸又はその誘導体などのα，β−不飽和部位の酸化においても有効であり、効率よく対応する酸化物を製造することできれば、この酸素による酸化方法は極めて有用となる。
しかし、酸素酸化、特に温和な条件下での酸素酸化により、共役ジエン類、アクリル酸又はその誘導体などの共役化合物から、対応するジオール類又はその誘導体（例えば、アルケンジオール、アセタールなど）を高い選択率および収率で生成させることは困難である。
【０００４】
【発明が解決しようとする課題】
従って、本発明の目的は、排ガス処理を特に必要とせず、酸素により共役化合物を効率よく酸化できる方法を提供することにある。
本発明の他の目的は、分子状酸素により、高い反応転化率および選択率で、共役化合物から対応するジオール類又はその誘導体を生成できる酸化方法を提供することにある。
本発明のさらに他の目的は、温和な条件下、酸素により共役化合物を効率よく酸化できる酸化方法を提供することにある。
本発明の別の目的は、温和な条件下、排ガス処理を特に必要とせず、共役化合物から対応するジオール類又はその誘導体を高い転化率及び選択率で製造できる方法を提供することにある。
【０００５】
【課題を解決するための手段】
本発明者らは、前記目的を達成するため鋭意検討した結果、Ｎ−ヒドロキシフタルイミドなどのイミド化合物を触媒として用いると、常圧の酸素雰囲気下であっても、共役ジエン類、アクリル酸又はその誘導体などの共役化合物から、ジオール類又はその誘導体が高い転化率および選択率で直接かつ効率よく生成することを見いだし、本発明を完成した。
すなわち、本発明の酸化方法は、一般式（１）
【０００６】
【化６】
（式中、Ｒ1及びＲ2は、同一又は異なって、水素原子、ハロゲン原子、アルキル基、アリール基、シクロアルキル基、ヒドロキシル基、アルコキシ基、カルボキシル基、アルコキシカルボニル基、アシル基を示し、Ｒ1及びＲ2は互いに結合して二重結合、または芳香族性又は非芳香族性の環を形成してもよい。Ｘは酸素原子又はヒドロキシル基を示し、ｎは１〜３の整数を示す）
で表されるイミド化合物で構成された酸化触媒の存在下、共役化合物と酸素とを接触させることにより共役化合物を酸化する。前記酸化触媒は、一般式（１）で表されるイミド化合物と助触媒とで構成してもよい。助触媒は、遷移金属化合物（例えば、酸化物、有機酸塩、無機酸塩、ハロゲン化物、錯体、およびヘテロポリ酸又はその塩など）やホウ素化合物などで構成できる。
【０００８】
共役化合物には、共役ジエン類、α，β−不飽和ニトリル又は一般式（２）
【０００９】
【化７】
（式中、Ｒ1は、水素原子又はメチル基を示し、Ｘは、−ＯＲ2（Ｒ2は、水素原子、アルキル基、アリール基、シクロアルキル基、ヒドロキシアルキル基、グリシジル基を示す），−ＮＲ3Ｒ4（Ｒ3およびＲ4は、同一又は異なって、水素原子、アルキル基、ヒドロキシアルキル基を示す）を示す）
で表される化合物が含まれる。一般式（２）で表される化合物には、例えば、α，β−不飽和カルボン酸又はその誘導体などが含まれる。
また、本発明の方法では、前記イミド化合物で構成された触媒、又は前記イミド化合物と助触媒とで構成された触媒系の存在下、共役ジエン類、α，β−不飽和ニトリル又は一般式（２）で表される共役化合物と酸素とを接触させることにより、アルケンジオール又は一般式（３ａ）又は（３ｂ）
【００１１】
【化８】
（式中、Ｙは、酸素原子又は−ＯＲ5b（Ｒ5aおよびＲ5bは、同一又は異なって、水素原子、アルキル基、アシル基を示す）を示し、ｎは０又は１を示す。式中「…」は、単結合又は二重結合を示す。Ｒ1、Ｘは前記に同じ。但し、Ｙが酸素原子であるとき、ｎは０、「…」は二重結合であり、Ｙが−ＯＲ5bであるとき、ｎは１、「…」は単結合である）
で表される化合物を製造する。
なお、本明細書において「共役化合物」、「共役ジエン類」、「α，β−不飽和ニトリル」、「α，β−不飽和カルボン酸又はその誘導体」を単に「基質」という場合がある。また、「アクリル酸、メタクリル酸又はそれらの誘導体」を「（メタ）アクリル酸又はその誘導体」と総称する場合がある。また、「共役化合物」とは、二重結合と単結合とが交互に並んだ化合物（例えば、ブタジエンなど）に限らず、不飽和結合（二重結合および三重結合）が単結合を介して又は介することなく交互に並んだ化合物（例えば、共役ポリエンなど）も含む意味に用いる。そのため、不飽和ジオールが、「共役ジエン類」に対応する酸化物である限り、単一の二重結合のみならず、複数の二重結合や三重結合を有する不飽和ジオールも「アルケンジオール」と総称する。
【００１３】
【発明の実施の形態】
［イミド化合物］
前記一般式（１）で表されるイミド化合物において、置換基Ｒ1及びＲ2のうちハロゲン原子には、ヨウ素、臭素、塩素およびフッ素が含まれる。アルキル基には、例えば、メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、ｓｅｃ−ブチル、ｔ−ブチル、ペンチル、ヘキシル、ペプチル、オクチル、デシル基などの炭素数１〜１０程度の直鎖状又は分岐鎖状アルキル基が含まれる。好ましいアルキル基としては、例えば、炭素数１〜６程度、特に炭素数１〜４程度の低級アルキル基が挙げられる。
アリール基には、フェニル基、ナフチル基などが含まれ、シクロアルキル基には、シクロペンチル、シクロヘキシル、シクロオクチル基などが含まれる。アルコキシ基には、例えば、メトキシ、エトキシ、プロポキシ、イソプロポキシ、ブトキシ、イソブトキシ、ｔ−ブトキシ、ペンチルオキシ、ヘキシルオキシ基などの炭素数１〜１０程度、好ましくは炭素数１〜６程度、特に炭素数１〜４程度の低級アルコキシ基が含まれる。
【００１４】
アルコキシカルボニル基には、例えば、メトキシカルボニル、エトキシカルボニル、プロポキシカルボニル、イソプロポキシカルボニル、ブトキシカルボニル、イソブトキシカルボニル、ｔ−ブトキシカルボニル、ペンチルオキシカルボニル、ヘキシルオキシカルボニル基などのアルコキシ部分の炭素数が１〜１０程度のアルコキシカルボニル基が含まれる。好ましいアルコキシカルボニル基にはアルコキシ部分の炭素数が１〜６程度、特に１〜４程度の低級アルコキシカルボニル基が含まれる。
アシル基としては、例えば、ホルミル、アセチル、プロピオニル、ブチリル、イソブチリル、バレリル、イソバレリル、ピバロイル基などの炭素数１〜６程度のアシル基が例示できる。
【００１５】
前記置換基Ｒ1及びＲ2は、同一又は異なっていてもよい。また、前記一般式（１）において、Ｒ1およびＲ2は互いに結合して、二重結合、または芳香族性又は非芳香族性の環を形成してもよい。好ましい芳香族性又は非芳香族性環は５〜１２員環、特に６〜１０員環程度であり、複素環又は縮合複素環であってもよいが、炭化水素環である場合が多い。このような環には、例えば、非芳香族性脂環族環（シクロヘキサン環などの置換基を有していてもよいシクロアルカン環、シクロヘキセン環などの置換基を有していてもよいシクロアルケン環など）、非芳香族性橋かけ環（５−ノルボルネン環などの置換基を有していてもよい橋かけ式炭化水素環など）、ベンゼン環、ナフタレン環などの置換基を有していてもよい芳香族環が含まれる。前記環は、芳香族環で構成される場合が多い。
【００１６】
好ましいイミド化合物には、下記式（１ａ）〜（１ｆ）で表される化合物が含まれる。
【００１７】
【化９】
（式中、Ｒ3〜Ｒ6は、同一又は異なって、水素原子、アルキル基、ヒドロキシル基、アルコキシ基、カルボキシル基、アルコキシカルボニル基、アシル基、ニトロ基、シアノ基、アミノ基、ハロゲン原子を示す。Ｒ1、Ｒ2およびｎは一般式（１）に同じ）
置換基Ｒ3〜Ｒ6において、アルキル基には、前記例示のアルキル基と同様のアルキル基、特に炭素数１〜６程度のアルキル基が含まれ、アルコキシ基には、前記と同様のアルコキシ基、特に炭素数１〜４程度の低級アルコキシ基、アルコキシカルボニル基には、前記と同様のアルコキシカルボニル基、特にアルコキシ部分の炭素数が１〜４程度の低級アルコキシカルボニル基が含まれる。また、アシル基としては、前記と同様のアシル基、特に炭素数１〜６程度のアシル基が例示され、ハロゲン原子としては、フッ素、塩素、臭素原子が例示できる。置換基Ｒ3〜Ｒ6は、通常、水素原子、炭素数１〜４程度の低級アルキル基、カルボキシル基、ニトロ基、ハロゲン原子である場合が多い。
【００１９】
前記一般式（１）において、Ｘは酸素原子又はヒドロキシル基を示し、ｎは、通常、１〜３程度、好ましくは１又は２である。一般式（１）で表される化合物は酸化反応において一種又は二種以上使用できる。
前記一般式（１）で表されるイミド化合物に対応する酸無水物には、例えば、無水コハク酸、無水マレイン酸などの飽和又は不飽和脂肪族ジカルボン酸無水物、テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸（１，２−シクロヘキサンジカルボン酸無水物）、１，２，３，４−シクロヘキサンテトラカルボン酸−１，２−無水物などの飽和又は不飽和非芳香族性環状多価カルボン酸無水物（脂環族多価カルボン酸無水物）、無水ヘット酸、無水ハイミック酸などの橋かけ環式多価カルボン酸無水物（脂環族多価カルボン酸無水物）、無水フタル酸、テトラブロモ無水フタル酸、テトラクロロ無水フタル酸、無水ニトロフタル酸、無水トリメリット酸、メチルシクロヘキセントリカルボン酸無水物、無水ピロメリット酸、無水メリト酸、１，８；４，５−ナフタレンテトラカルボン酸二無水物などの芳香族多価カルボン酸無水物が含まれる。
【００２０】
好ましいイミド化合物としては、例えば、Ｎ−ヒドロキシコハク酸イミド、Ｎ−ヒドロキシマレイン酸イミド、Ｎ−ヒドロキシヘキサヒドロフタル酸イミド、Ｎ，Ｎ′−ジヒドロキシシクロヘキサンテトラカルボン酸イミド、Ｎ−ヒドロキシフタル酸イミド、Ｎ−ヒドロキシテトラブロモフタル酸イミド、Ｎ−ヒドロキシテトラクロロフタル酸イミド、Ｎ−ヒドロキシヘット酸イミド、Ｎ−ヒドロキシハイミック酸イミド、Ｎ−ヒドロキシトリメリット酸イミド、Ｎ，Ｎ′−ジヒドロキシピロメリット酸イミド、Ｎ，Ｎ′−ジヒドロキシナフタレンテトラカルボン酸イミドなどが挙げられる。特に好ましい化合物には、脂環族多価カルボン酸無水物、なかでも芳香族多価カルボン酸無水物から誘導されるＮ−ヒドロキシイミド化合物、例えば、Ｎ−ヒドロキシフタル酸イミドなどが含まれる。
【００２１】
前記イミド化合物は、慣用のイミド化反応、例えば、対応する酸無水物とヒドロキシルアミンＮＨ2ＯＨとを反応させて酸無水物基を開環した後、閉環してイミド化することにより調整できる。
このようなイミド化合物は、酸化活性が高く、穏和な条件であっても、共役化合物の酸化反応を触媒的に促進できる。そのため、共役化合物を効率よく高い選択率で酸化でき、対応する共役化合物の酸化物（例えば、アルコール類、アルデヒド類やカルボン酸類など）、特にジオール類又はその誘導体（例えば、アルケンジオールやアセタールなど）などを生成させることができる。さらに、前記一般式（１）で表されるイミド化合物と助触媒との共存下で共役化合物を酸化すると、転化率及び／又は選択率をさらに向上できる。
【００２２】
［助触媒］
助触媒としての共酸化剤には、金属化合物、例えば、遷移金属化合物や、ホウ素化合物などの周期表１３族元素（ホウ素Ｂ、アルミニウムＡｌなど）を含む化合物が含まれる。共酸化剤は、一種又は二種以上組合わせて使用できる。
前記遷移金属の元素としては、例えば、周期表３族元素（例えば、スカンジウムＳｃ、イットリウムＹの外、ランタンＬａ，セリウムＣｅ、サマリウムＳｍなどのランタノイド元素、アクチノイドＡｃなどのアクチノイド元素）、４族元素（チタンＴｉ、ジルコニウムＺｒ、ハフニウムＨｆなど）、５族元素（バナジウムＶ、ニオブＮｂ、タンタルＴａなど）、６族元素（クロムＣｒ、モリブデンＭｏ、タングステンＷなど）、７族元素（マンガンＭｎ、テクネチウムＴｃ、レニウムＲｅなど）、８族元素（鉄Ｆｅ、ルテニウムＲｕ、オスミウムＯｓなど）、９族元素（コバルトＣｏ、ロジウムＲｈ、イリジウムＩｒなど）、１０族元素（ニッケルＮｉ、パラジウムＰｄ、白金Ｐｔなど）、１１族元素（銅Ｃｕ、銀Ａｇ，金Ａｕなど）などが挙げられる。
【００２３】
好ましい助触媒を構成する元素には、遷移金属の元素（例えば、ランタノイド元素、アクチノイド元素などの周期表３族元素、Ｖ、Ｎｂなどの５族元素、Ｃｒ，Ｍｏ，Ｗなどの６族元素，Ｍｎ，Ｔｃ，Ｒｅなどの７族元素、Ｆｅ，Ｒｕなどの８族元素，Ｃｏ、Ｒｈなどの９族元素、Ｎｉなどの１０族元素，Ｃｕなどの１１族元素）、Ｂなどの１３族元素が含まれる。特に、前記一般式（１）で表されるイミド化合物と組合わせたとき、Ｃｅなどのランタノイド元素、Ｖなどの５族元素、Ｍｏ、Ｗなどの６族元素、Ｍｎなどの７族元素、Ｆｅ、Ｒｕなどの８族元素、Ｃｏ、Ｒｈなどの９族元素、Ｎｉなどの１０族元素、Ｃｕなどの１１族元素を含む化合物は、高い活性を示す。
助触媒は、前記元素を含み、かつ酸化能を有する限り特に制限されず、金属単体、水酸化物などであってもよいが、通常、前記元素を含む金属酸化物、複酸化物または酸素酸塩、有機酸塩、無機酸塩、ハロゲン化物、前記金属元素を含む配位化合物（錯体）やヘテロポリ酸又はその塩などである場合が多い。また、ホウ素化合物としては、例えば、水酸化ホウ素（例えば、ボラン、ジボラン、テトラボラン、ペンタボラン、デカボランなど）、ホウ酸（例えば、オルトホウ酸、メタホウ酸、四ホウ酸など）、ホウ酸塩（例えば、ホウ酸ニッケル、ホウ酸マグネシウム、ホウ酸マンガンなど）、Ｂ2Ｏ3などのホウ素酸化物、ボザラン、ボラゼン、ボラジン、ホウ素アミド、ホウ素イミドなどの窒素化合物、ＢＦ3、ＢＣｌ3、テトラフルオロホウ酸塩などのハロゲン化物、ホウ酸エステル（例えば、ホウ酸メチル、ホウ酸フェニルなど）などが挙げられる。好ましいホウ素化合物には、水素化ホウ素、オルトホウ酸などのホウ酸又はその塩など、特にホウ酸が含まれる。これらの助触媒は一種又は二種以上使用できる。
【００２４】
水酸化物には、例えば、Ｍｎ（ＯＨ）2、ＭｎＯ（ＯＨ）などが含まれる。金属酸化物には、例えば、Ｓｍ2Ｏ3、ＴｉＯ2、ＣｒＯ、Ｃｒ2Ｏ3、ＭｏＯ3、ＭｎＯ、Ｍｎ3Ｏ4、Ｍｎ2Ｏ3、ＭｎＯ2、Ｍｎ2Ｏ7、ＦｅＯ、Ｆｅ2Ｏ3、ＲｕＯ2、ＲｕＯ4、ＣｏＯ、ＣｏＯ2、Ｃｏ2Ｏ3、ＲｈＯ2、Ｒｈ2Ｏ3、Ｃｕ2Ｏ3などが含まれ、複酸化物または酸素酸塩としては、例えば、ＭｎＡｌ2Ｏ4、ＭｎＴｉＯ3、ＬａＭｎＯ3、Ｋ2Ｍｎ2Ｏ5、ＣａＯ・ｘＭｎＯ2（ｘ＝０．５，１，２，３，５）、マンガン酸塩［例えば、Ｎａ3ＭｎＯ4、Ｂａ3（ＭｎＯ4）2などのマンガン(V)酸塩、Ｋ2ＭｎＯ4、Ｎａ2ＭｎＯ4、ＢａＭｎＯ4などのマンガン(VI)酸塩、ＫＭｎＯ4、ＮａＭｎＯ4、ＬｉＭｎＯ4、ＮＨ4ＭｎＯ4、ＣｓＭｎＯ4、ＡｇＭｎＯ4、Ｃａ（ＭｎＯ4）2、Ｚｎ（ＭｎＯ4）2、Ｂａ（ＭｎＯ4）2、Ｍｇ（ＭｎＯ4）2、Ｃｄ（ＭｎＯ4）2などの過マンガン酸塩］が含まれる。
【００２５】
有機酸塩としては、例えば、酢酸コバルト、酢酸マンガン、プロピオン酸コバルト、プロピオン酸マンガン、ナフテン酸コバルト、ナフテン酸マンガン、ステアリン酸コバルト、ステアリン酸マンガン、チオシアン酸マンガンや対応するＣｅ塩、Ｃｒ塩、Ｆｅ塩、Ｎｉ塩、Ｐｄ塩、Ｃｕ塩などが例示され、無機酸塩としては、例えば、硝酸コバルト、硝酸マンガン、硝酸ニッケル、硝酸銅などの硝酸塩やこれらに対応する硫酸塩、リン酸塩および炭酸塩（例えば、硫酸コバルト、硫酸マンガン、リン酸コバルト、リン酸マンガン、炭酸マンガンなど）が挙げられる。また、ハロゲン化物としては、例えば、ＳｍＣｌ3、ＭｎＣｌ2、ＭｎＣｌ3、ＦｅＣｌ2、ＦｅＣｌ3、ＲｕＣｌ3、ＣｏＣｌ2、ＲｈＣｌ2、ＲｈＣｌ3、ＮｉＣｌ2、ＰｄＣｌ2、ＰｔＣｌ2、ＣｕＣｌ、ＣｕＣｌ2などの塩化物やこれらに対応するフッ化物や臭化物（例えば、ＭｎＦ2、ＭｎＢｒ2、ＭｎＦ3など）などのハロゲン化物、Ｍ1ＭｎＣｌ3、Ｍ1 2ＭｎＣｌ4、Ｍ1 2ＭｎＣｌ5、Ｍ1 2ＭｎＣｌ6（Ｍ1は一価金属を示す）などの複ハロゲン化物などが挙げられる。
【００２６】
錯体を形成する配位子としては、ＯＨ（ヒドロキシ）、メトキシ、エトキシ、プロポキシ、ブトキシ基などのアルコキシ基、アセチル、プロピオニルなどのアシル基、メトキシカルボニル（アセタト）、エトキシカルボニルなどのアルコキシカルボニル基、アセチルアセトナト、シクロペンタジエニル基、塩素、臭素などのハロゲン原子、ＣＯ、ＣＮ、酸素原子、Ｈ2Ｏ（アコ）、ホスフィン（例えば、トリフェニルホスフィンなどのトリアリールホスフィン）などのリン化合物、ＮＨ3（アンミン）、ＮＯ、ＮＯ2（ニトロ）、ＮＯ3（ニトラト）、エチレンジアミン、ジエチレントリアミン、ピリジン、フェナントロリンなどの窒素含有化合物などが挙げられる。錯体又は錯塩において、同種又は異種の配位子は一種又は二種以上配位していてもよい。
【００２７】
好ましい錯体には、遷移金属元素（例えば、Ｃｅなどのランタノイド元素やアクチノイド元素が属する周期表３族元素、Ｍｎなどの周期表７族元素、Ｆｅ、Ｒｕなどの周期表８族元素、Ｃｏ、Ｒｈなどの周期表９族元素、Ｎｉ、Ｐｄ、Ｐｔなどの周期表１０族元素、Ｃｕなどの周期表１１族元素など）を含む錯体が含まれる。また、配位子は、例えば、ＯＨ、アルコキシ基、アシル基、アルコキシカルボニル基、アセチルアセトナト、ハロゲン原子、ＣＯ、ＣＮ、Ｈ2Ｏ（アコ）、トリフェニルホスフィンなどのリン化合物や、ＮＨ3、ＮＯ2、ＮＯ3を含めて窒素含有化合物である場合が多い。前記遷移金属元素と配位子は適当に組合わせて錯体を構成することができ、例えば、セリウムアセチルアセトナト、マンガンアセチルアセトナト、コバルトアセチルアセトナト、ルテニウムアセチルアセトナト、銅アセチルアセトナトなどであってもよい。
【００２８】
ヘテロポリ酸を形成するポリ酸は、例えば、周期表５族又は６族元素、例えば、Ｖ（バナジン酸）、Ｍｏ（モリブデン酸）およびＷ（タングステン酸）の少なくとも一種である場合が多く、中心原子は特に制限されず、例えば、Ｃｕ、Ｂｅ、Ｂ、Ａｌ、Ｓｉ、Ｇｅ、Ｓｎ、Ｔｉ、Ｔｈ、Ｎ、Ｐ、Ａｓ、Ｓｂ、Ｖ、Ｎｂ、Ｔａ、Ｃｒ、Ｍｏ、Ｗ、Ｓ、Ｓｅ、Ｔｅ、Ｍｎ、Ｉ、Ｆｅ、Ｃｏ、Ｎｉ、Ｒｈ、Ｏｓ、Ｉｒ、Ｐｔ、Ｃｕなどであってもよい。ヘテロポリ酸の具体例としては、例えば、コバルトモリブデン酸塩、コバルトタングステン酸塩、モリブデンタングステン酸塩、バナジウムモリブデン酸塩、バナドモリブドリン酸塩などが挙げられる。
助触媒としては、Ｖ、ＭｏおよびＷの少なくとも一種の元素を含むヘテロポリ酸塩（例えば、バナジウム−モリブデン系のヘテロポリ酸又はその塩など）、遷移金属化合物（例えば、ランタノイド元素、Ｍｎ、Ｒｕ、ＣｏおよびＣｕの少なくとも一種の元素を含む遷移金属化合物）を用いる場合が多い。
【００２９】
一般式（１）で表されるイミド化合物、又はこのイミド化合物および前記助触媒で構成される触媒系は、均一系であってもよく、不均一系であってもよい。また、触媒系は、担体に触媒成分が担持された固体触媒であってもよい。担体としては、活性炭、ゼオライト、シリカ、シリカ−アルミナ、ベントナイトなどの多孔質担体を用いる場合が多い。固体触媒における触媒成分の担持量は、担体１００重量部に対して、一般式（１）で表されるイミド化合物０．１〜５０重量部、好ましくは０．５〜３０重量部、さらに好ましくは１〜２０重量部程度である。また、助触媒の担持量は、担体１００重量部に対して、０．１〜３０重量部、好ましくは０．５〜２５重量部、さらに好ましくは１〜２０重量部程度である。
前記一般式（１）で表されるイミド化合物の使用量は、広い範囲で選択でき、例えば、共役化合物１モルに対して０．００１モル（０．１モル％）〜１モル（１００モル％）、好ましくは０．００１モル（０．１モル％）〜０．５モル（５０モル％）、さらに好ましくは０．０１〜０．３０モル程度であり、０．０１〜０．２５モル程度である場合が多い。
【００３０】
また、助触媒（共酸化剤）の使用量も、反応性および選択率を低下させない範囲で適当に選択でき、例えば、共役化合物１モルに対して０．０００１モル（０．１モル％）〜０．７モル（７０モル％）、好ましくは０．０００１〜０．５モル、さらに好ましくは０．００１〜０．３モル程度であり、０．０００５〜０．１モル（例えば、０．００５〜０．１モル）程度である場合が多い。
なお、一般式（１）で表されるイミド化合物に対する助触媒の割合は、反応速度、選択率を損なわない範囲で選択でき、例えば、イミド化合物１モルに対して、助触媒０．００１〜１０モル、好ましくは０．００５〜５モル、さらに好ましくは０．０１〜３モル程度であり、０．０１〜５モル程度である場合が多い。
ヘテロポリ酸又はその塩を助触媒として使用する場合、基質１００重量部に対して０．１〜２５重量部、好ましくは０．５〜１０重量部、さらに好ましくは１〜５重量部程度である。
【００３１】
［共役化合物］
このような酸化触媒を利用すると、共役化合物を効率よく酸素酸化でき、共役化合物の酸化物（アルコール類、アルデヒド類など）、特にジオール類又はその誘導体を高い選択率で生成させることができる。さらに、酸化反応が進行すると、対応するカルボン酸類が生成する場合もある。そのため、本発明の方法では、前記酸化触媒の存在下、共役化合物と酸素とを接触させて酸化する。
共役化合物には、共役ジエン類、α，β−不飽和ニトリル、α，β−不飽和カルボン酸又はその誘導体などが含まれる。
共役ジエン類には、例えば、ブタジエン（１，３−ブタジエン）、イソプレン（２−メチル−１，３−ブタジエン）などの共役二重結合を有する化合物、二重結合と三重結合とを有する化合物（ビニルアセチレン、ジビニルアセチレンなど）およびこれらの誘導体などが含まれる。共役ジエン類の誘導体には、例えば、２−クロロブタジエン、２，３−ジクロロブタジエンなどのハロゲン原子（ヨウ素、臭素、塩素およびフッ素原子）を有する化合物、２−エチルブタジエン、２，３−ジメチルブタジエンなどのアルキル基（例えば、メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、ｓｅｃ−ブチル、ｔ−ブチルなどの炭素数１〜４程度の低級アルキル基）を有する化合物、ブタジエン−１−カルボン酸などのカルボキシル基を有する化合物などが例示できる。好ましい共役ジエン類は、ブタジエンおよびイソプレンである。
【００３２】
共役ジエン類の酸素酸化によりアルケンジオールが生成する。生成するアルケンジオールは、共役ジエン類に対応するジオールである限り、ヒドロキシル基の置換位置は特に制限されない。例えば、ブタジエンの酸化により生成するブテンジオールは、２−ブテン−１，４−ジオール、１−ブテン−３，４−ジオールなどであってもよく、ブテンジオールはシス体又はトランス体のいずれであってもよい。
α，β−不飽和ニトリルには、例えば、（メタ）アクリロニトリルなどが含まれる。
一般式（２）で表される共役化合物は、α，β−不飽和カルボン酸又はその誘導体に相当する。
【００３３】
【化１０】
（式中、Ｒ1は、水素原子又はメチル基を示し、Ｘは、−ＯＲ2（Ｒ2は、水素原子、アルキル基、アリール基、シクロアルキル基、ヒドロキシアルキル基、グリシジル基を示す），−ＮＲ3Ｒ4（Ｒ3およびＲ4は、同一又は異なって、水素原子、アルキル基、ヒドロキシアルキル基を示す）を示す）
一般式（２）において置換基Ｒ2のうち、アルキル基には、メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、ｓｅｃ−ブチル、ｔ−ブチル、ペンチル、ヘキシル、ヘプチル、２−エチルヘキシル、オクチル、デシル、テトラデシル基などの炭素数１〜２０程度の直鎖又は分岐鎖状アルキル基が含まれる。好ましいアルキル基には、炭素数１〜１５程度のアルキル基、特に炭素数１〜１２程度（例えば、１〜１０程度）のアルキル基が含まれる。アリール基には、フェニル基、ナフチル基などが含まれる。シクロアルキル基には、シクロペンチル、シクロヘキシル、シクロオクチル基などの５〜１０員環のシクロアルキル基が含まれる。
【００３５】
ヒドロキシアルキル基には、２−ヒドロキシエチル、２−ヒドロキシプロピル、４−ヒドロキシブチル、ヒドロキシペンチル基などの炭素数２〜１０程度のヒドロキシアルキル基が含まれる。好ましいヒドロキシアルキル基には、炭素数２〜４程度のヒドロキシアルキル基、特に炭素数２又は３程度のヒドロキシアルキル基が含まれる。
置換基Ｒ2は、通常、水素原子、炭素数１〜１０のアルキル基、炭素数２又は３のヒドロキシルアルキル基、グリシジル基などである場合が多い。
このような置換基を有する化合物として、例えば、（メタ）アクリル酸；（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ｎ−ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸２−エチルヘキシル、（メタ）アクリル酸ラウリルなどの（メタ）アクリル酸アルキルエステル；（メタ）アクリル酸−２−ヒドロキシエチル、（メタ）アクリル酸−２−ヒドロキシプロピルなどのヒドロキシルアルキル（メタ）アクリレート；（メタ）アクリル酸グリシジルなどが挙げられる。
【００３６】
Ｘで表される−ＮＲ3Ｒ4において、置換基Ｒ3及びＲ4のうち、アルキル基には、メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、ｓｅｃ−ブチル、ｔ−ブチル、ペンチル基などの炭素数１〜１０程度のアルキル基が挙げられる。好ましいアルキル基には、炭素数１〜６程度のアルキル基、特に炭素数１〜４程度のアルキル基が挙げられる。ヒドロキシアルキル基には、ヒドロキシ−Ｃ1-10アルキル、好ましくはヒドロキシメチル、ヒドロキシエチル基が含まれる。
置換基Ｒ3及びＲ4は、同一又は異なっていてもよく、通常、水素原子、炭素数１〜４程度のアルキル基、炭素数１又は２のヒドロキシアルキル基である場合が多い。
【００３７】
このような置換基を有する化合物として、例えば、（メタ）アクリルアミド、Ｎ−メチル（メタ）アクリルアミド、Ｎ−メチロール（メタ）アクリルアミドなどの（メタ）アクリルアミド誘導体などが挙げられる。
これらのα，β−不飽和ニトリル、α，β−不飽和カルボン酸又はその誘導体を酸素との接触により酸化させると、α，β−不飽和結合部位が選択的に酸化され、高い転化率及び選択率で一般式（３ａ）又は（３ｂ）
【００３８】
【化１１】
（式中、Ｙは、酸素原子又は−ＯＲ5b（Ｒ5aおよびＲ5bは、同一又は異なって、水素原子、アルキル基、アシル基を示す）を示し、ｎは０又は１を示す。式中「…」は、単結合又は二重結合を示す。Ｒ1、Ｘは一般式（２）に同じ。但し、Ｙが酸素原子であるとき、ｎは０、「…」結合は二重結合であり、Ｙが−ＯＲ5bであるとき、ｎは１、「…」結合は単結合である）
で表される化合物が生成する。
前記一般式（３ａ）又は（３ｂ）で表される化合物において、置換基Ｒ5aおよびＲ5bのうち、アルキル基には、例えば、メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、ｓｅｃ−ブチル、ｔ−ブチル基などのＣ1-6アルキル基、アシル基には、アセチル、プロピオニル基などのＣ2-6アシル基が含まれる。これらのアルキル基、アシル基は、溶媒との反応により生成する場合がある。
【００４０】
この酸化反応では、ジオール類（Ｙが−ＯＲ5bで、Ｒ5aおよびＲ5bがともに水素原子である化合物）が、基本的に生成すると思われ、脱水反応により、アルデヒド又はその誘導体（Ｙが酸素原子である化合物）が生成する場合がある。また、反応溶媒として、プロトン性溶媒（酢酸、プロピオン酸などの有機酸、メタノール、エタノール、ｎ−プロパノール、イソプロパノール、ｎ−ブタノール、ｔ−ブタノールなどのアルコール類など）を用いると、アセタール又はアシルオキシ化合物などのジオール誘導体（Ｙが−ＯＲ5bであり、Ｒ5aおよびＲ5bの少なくとも一方がアルキル基又はアシル基である化合物）が生成する場合がある。これらのアルデヒド又はその誘導体、またはアセタールなどのジオール誘導体は、ジオール類と等価な化合物である。
【００４１】
例えば、反応溶媒として、メタノールを用い、アクリロニトリルを酸化させると、１，１−ジメトキシプロピオニトリルが生成する場合がある。また、メタノール溶媒中、アクリル酸メチルを酸化させると、１，１−ジメトキシプロピオン酸メチルが生成する場合がある。
共役化合物の酸化に利用される酸素は、活性酸素であってもよいが、分子状酸素を利用するのが経済的に有利である。分子状酸素は特に制限されず、純粋な酸素を用いてもよく、窒素、ヘリウム、アルゴン、二酸化炭素などの不活性ガスで希釈した酸素を使用してもよい。操作性及び安全性のみならず経済性などの点から、空気を使用するのが好ましい。
酸素の使用量は、基質の種類に応じて選択でき、通常、基質１モルに対して、０．５モル以上（例えば、１モル以上）、好ましくは１〜１００モル、さらに好ましくは２〜５０モル程度である。基質に対して過剰モルの酸素を使用する場合が多く、特に空気や酸素などの分子状酸素を含有する雰囲気下で反応させるのが有利である。
本発明の酸化方法は、反応に不活性な有機溶媒中で行うことができる。反応に不活性な有機溶媒としては、例えば、プロトン性溶媒（例えば、酢酸、プロピオン酸などの有機酸；メタノール、エタノール、ｎ−プロパノール、イソプロパノール、ｎ−ブタノール、ｔ−ブタノールなどのアルコール類など）、ニトリル類（例えば、アセトニトリル、プロピオニトリル、ベンゾニトリルなど）、アミド類（例えば、ホルムアミド、アセトアミド、ジメチルホルムアミド（ＤＭＦ）など）、脂肪族炭化水素（例えば、ヘキサン、オクタンなど）、芳香族炭化水素（例えば、ベンゼン、トルエンなど）、ハロゲン化炭化水素（例えば、クロロホルム、ジクロロメタン、ジクロロエタン、四塩化炭素、クロロベンゼンなど）、ニトロ化合物（例えば、ニトロベンゼン、ニトロメタン、ニトロエタンなど）、エステル類（例えば、酢酸エチル、酢酸ブチル、プロピオン酸エチル、プロピオン酸ブチル、安息香酸メチル、安息香酸エチルなど）、エーテル類（例えば、ジメチルエーテル、ジエチルエーテル、ジイソプロピルエーテル、ジオキサン、テトラヒドロフランなど）、これらの混合溶媒などが挙げられる。なお、過剰の基質を用いることにより、基質を反応溶媒として利用してもよい。
【００４２】
本発明の方法は、比較的温和な条件であっても円滑に酸化反応が進行するという特色がある。反応温度は、基質の種類などに応じて適当に選択でき、例えば、０〜３００℃、好ましくは３０〜２５０℃、さらに好ましくは４０〜２００℃程度であり、通常、４０〜１５０℃程度で反応する場合が多い。また、反応は、常圧又は加圧下で行うことができ、加圧下で反応させる場合には、通常、１〜１００ａｔｍ（例えば、１．５〜８０ａｔｍ）、好ましくは２〜７０ａｔｍ、さらに好ましくは５〜５０ａｔｍ程度である場合が多い。反応時間は、反応温度及び圧力に応じて、例えば、３０分〜４８時間、好ましくは１〜３６時間、さらに好ましくは２〜２４時間程度の範囲から適当に選択できる。
反応は、分子状酸素の存在下又は分子状酸素の流通下、回分式、半回分式、連続式などの慣用の方法により行うことができる。反応終了後、反応生成物は、慣用の方法、例えば、瀘過、濃縮、蒸留、抽出、晶析、再結晶、カラムクロマトグラフィーなどの分離手段や、これらを組合わせた分離手段により、容易に分離精製できる。
【００４３】
本発明は、共役化合物から対応する酸化物、例えば、共役ジエン類から対応する酸化物であるアルケンジオール（例えば、ブタジエンから、ポリアミドなどの合成樹脂、無水マレイン酸、可塑剤、ブタンジオールなどの合成原料として使用されるブテンジオール）を製造する上で有用である。
【００４４】
【発明の効果】
本発明の酸化方法では、▲１▼前記イミド化合物又は▲２▼このイミド化合物と助触媒とで構成された酸化触媒を用いるため、排ガス処理を特に必要とせず、酸素酸化により共役化合物を効率よく酸化でき、経済性及び安全性の点でも有利である。また、分子状酸素により、高い反応転化率および選択率で、共役化合物から対応する酸化物を生成できる。さらに、温和な条件であっても、酸素により共役化合物を効率よく酸化できる。そのため、共役化合物から対応する酸化物、特に、ジオール類又はその誘導体を高い転化率及び選択率で製造する上で有用である。
【００４５】
【実施例】
以下に、実施例に基づいて本発明を詳細に説明するが、本発明はこれらの実施例により何ら限定されるものではない。
実施例１
ブタジエン１．０８ｇ（２０ミリモル）、Ｎ−ヒドロキシフタルイミド０．２６ｇ（１．６ミリモル）、コバルトアセチルアセトナートＣｏ（ＡＡ）2 ０．０３ｇ（０．１２ミリモル）、アセトニトリル２５ｍｌの混合物を、酸素雰囲気下、６０℃で６時間撹拌した。反応液中の生成物をガスクロマトグラフィー分析により調べたところ、ブタジエンの転化率３５％で、２−ブテン−１，４−ジオール（ブタジエン基準の選択率６３％、収率２２％）と、１−ブテン−３，４−ジオール（ブタジエン基準の選択率２３％、収率８％）とが得られた。アルコール体の選択率は８６％である。
【００４６】
実施例２
アクリロニトリル１．０６ｇ（２０ミリモル）、Ｎ−ヒドロキシフタルイミド０．２６ｇ（１．６ミリモル）、コバルトアセチルアセトナートＣｏ（ＡＡ）2０．０３ｇ（０．１２ミリモル）、メタノール２５ｍｌの混合物を、酸素雰囲気下、５０℃で３時間撹拌した。反応液中の生成物をガスクロマトグラフィー分析により調べたところ、アクリロニトリルの転化率９９％で、１，１−ジメトキシプロピオニトリルが収率９９％で得られた。
実施例３
アクリル酸メチル１．７２ｇ（２０ミリモル）、Ｎ−ヒドロキシフタルイミド０．２６ｇ（１．６ミリモル）、コバルトアセチルアセトナートＣｏ（ＡＡ）2０．０３ｇ（０．１２ミリモル）、メタノール２５ｍｌの混合物を、酸素雰囲気下、５０℃で３時間撹拌した。反応液中の生成物をガスクロマトグラフィー分析により調べたところ、アクリル酸メチルの転化率９９％で、１，１−ジメチルプロピオン酸メチルが収率９９％で得られた。[0001]
BACKGROUND OF THE INVENTION
The present invention produces corresponding oxides, particularly oxides such as diols, from conjugated compounds (eg, conjugated dienes, α, β-unsaturated nitriles, α, β-unsaturated carboxylic acids or derivatives thereof). It relates to an oxidation method useful above.
[0002]
[Prior art]
Butenediol is used as a synthetic raw material for synthetic resins such as polyamide, maleic anhydride, and plasticizers. In addition, butanediol derived from butenediol is useful as a raw material for synthesizing, for example, tetrahydrofuran, butyrolactone, polyester, and polyurethane. The butenediol and butanediol can be obtained by producing butynediol using the Reppe reaction and hydrogenating the produced butynediol using a reduction catalyst.
On the other hand, conjugated dienes such as butadiene are produced in large quantities in the petroleum refining process. Therefore, it is industrially useful if the corresponding alkenediol such as butenediol can be produced directly from the conjugated diene such as butadiene. As a method for producing a diol from a conjugated diene, it is conceivable to oxidize the conjugated diene using nitric acid to generate a diol. However, N produced by nitric acid oxidation2In order to treat O and NOx, an expensive exhaust gas treatment facility is required. Therefore, from the viewpoint of resources and environment, it is further useful if alkenediol can be efficiently produced by a catalytic oxidation method that directly uses molecular oxygen or air as an oxidizing agent.
[0003]
In addition, the oxidation method using oxygen or air as an oxidant is also effective in the oxidation of conjugated compounds other than conjugated dienes, for example, α, β-unsaturated sites such as acrylic acid or its derivatives, and can be handled efficiently. If an oxide to be produced can be produced, this oxidation method using oxygen is extremely useful.
However, by oxygen oxidation, especially oxygen oxidation under mild conditions, the corresponding diols or derivatives thereof (eg, alkenediols, acetals, etc.) are highly selected from conjugated compounds such as conjugated dienes, acrylic acid or derivatives thereof. It is difficult to produce at a rate and yield.
[0004]
[Problems to be solved by the invention]
Accordingly, an object of the present invention is to provide a method that can efficiently oxidize a conjugated compound with oxygen without particularly requiring exhaust gas treatment.
Another object of the present invention is to provide an oxidation method capable of producing a corresponding diol or derivative thereof from a conjugated compound with molecular oxygen with high reaction conversion and selectivity.
Still another object of the present invention is to provide an oxidation method capable of efficiently oxidizing a conjugated compound with oxygen under mild conditions.
Another object of the present invention is to provide a method capable of producing a corresponding diol or derivative thereof from a conjugated compound with high conversion and selectivity without requiring an exhaust gas treatment under mild conditions.
[0005]
[Means for Solving the Problems]
As a result of intensive studies to achieve the above object, the present inventors have found that when an imide compound such as N-hydroxyphthalimide is used as a catalyst, conjugated dienes, acrylic acid or the like can be used even under an atmospheric pressure of oxygen. The inventors have found that diols or derivatives thereof are directly and efficiently produced from conjugated compounds such as derivatives with high conversion and selectivity, thereby completing the present invention.
That is, the oxidation method of the present invention has the general formula (1)
[0006]
[Chemical 6]
(Wherein R1And R2Are the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cycloalkyl group, a hydroxyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or an acyl group, and R1And R2May bond to each other to form a double bond, or an aromatic or non-aromatic ring. X represents an oxygen atom or a hydroxyl group, and n represents an integer of 1 to 3)
The conjugated compound is oxidized by bringing the conjugated compound into contact with oxygen in the presence of an oxidation catalyst composed of an imide compound represented by the formula: The oxidation catalyst may be composed of an imide compound represented by the general formula (1) and a promoter. The cocatalyst can be composed of a transition metal compound (for example, an oxide, an organic acid salt, an inorganic acid salt, a halide, a complex, and a heteropolyacid or a salt thereof), a boron compound, or the like.
[0008]
Conjugated compounds include conjugated dienes, α, β-unsaturated nitriles or general formula (2)
[0009]
[Chemical 7]
(Wherein R1Represents a hydrogen atom or a methyl group, and X represents —OR2(R2Represents a hydrogen atom, an alkyl group, an aryl group, a cycloalkyl group, a hydroxyalkyl group or a glycidyl group), -NRThreeRFour(RThreeAnd RFourAre the same or different and represent a hydrogen atom, an alkyl group, or a hydroxyalkyl group))
The compound represented by these is included. The compound represented by the general formula (2) includes, for example, α, β-unsaturated carboxylic acid or a derivative thereof.
In the method of the present invention, a conjugated diene, an α, β-unsaturated nitrile or a general formula (in the presence of a catalyst composed of the imide compound or a catalyst system composed of the imide compound and a cocatalyst 2) By contacting the conjugated compound represented by oxygen and oxygen, the alkenediol or the general formula (3a) or (3b)
[0011]
[Chemical 8]
Wherein Y is an oxygen atom or -OR5b(R5aAnd R5bAre the same or different and each represents a hydrogen atom, an alkyl group or an acyl group, and n represents 0 or 1. In the formula, “...” represents a single bond or a double bond. R1, X is the same as above. However, when Y is an oxygen atom, n is 0, “...” Is a double bond, and Y is —OR.5bWhere n is 1 and “...” Is a single bond)
The compound represented by these is manufactured.
In the present specification, “conjugated compound”, “conjugated dienes”, “α, β-unsaturated nitrile”, “α, β-unsaturated carboxylic acid or derivative thereof” may be simply referred to as “substrate”. Further, “acrylic acid, methacrylic acid or derivatives thereof” may be collectively referred to as “(meth) acrylic acid or derivatives thereof”. In addition, the “conjugated compound” is not limited to a compound in which double bonds and single bonds are alternately arranged (for example, butadiene and the like), and an unsaturated bond (double bond and triple bond) is formed via a single bond or It is used to mean including compounds (for example, conjugated polyenes) arranged alternately without intervening. Therefore, as long as the unsaturated diol is an oxide corresponding to “conjugated dienes”, an unsaturated diol having not only a single double bond but also a plurality of double bonds or triple bonds is also referred to as “alkene diol”. Collectively.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
[Imide compound]
In the imide compound represented by the general formula (1), the substituent R1And R2Among them, the halogen atom includes iodine, bromine, chlorine and fluorine. Examples of the alkyl group include straight chain having about 1 to 10 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, t-butyl, pentyl, hexyl, peptyl, octyl and decyl groups. Branched alkyl groups are included. Preferable alkyl groups include, for example, lower alkyl groups having about 1 to 6 carbon atoms, particularly about 1 to 4 carbon atoms.
Aryl groups include phenyl groups, naphthyl groups, and the like, and cycloalkyl groups include cyclopentyl, cyclohexyl, cyclooctyl groups, and the like. The alkoxy group includes, for example, about 1 to 10 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, t-butoxy, pentyloxy and hexyloxy groups, preferably about 1 to 6 carbon atoms, particularly carbon. A lower alkoxy group of about 1 to 4 is included.
[0014]
In the alkoxycarbonyl group, for example, the carbon number of the alkoxy moiety such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, t-butoxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl group and the like is 1 About 10 to 10 alkoxycarbonyl groups are included. Preferred alkoxycarbonyl groups include lower alkoxycarbonyl groups having about 1 to 6, particularly about 1 to 4 carbon atoms in the alkoxy moiety.
Examples of the acyl group include acyl groups having about 1 to 6 carbon atoms such as formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl, and pivaloyl groups.
[0015]
The substituent R1And R2May be the same or different. In the general formula (1), R1And R2May be bonded to each other to form a double bond or an aromatic or non-aromatic ring. A preferable aromatic or non-aromatic ring is a 5- to 12-membered ring, particularly a 6- to 10-membered ring, and may be a heterocyclic ring or a condensed heterocyclic ring, but is often a hydrocarbon ring. Such a ring includes, for example, a non-aromatic alicyclic ring (a cycloalkene ring which may have a substituent such as a cyclohexane ring and a cycloalkene ring which may have a substituent such as a cyclohexene ring). Ring), non-aromatic bridged ring (such as bridged hydrocarbon ring optionally having substituent such as 5-norbornene ring), benzene ring, naphthalene ring and the like Also good aromatic rings are included. The ring is often composed of an aromatic ring.
[0016]
Preferred imide compounds include compounds represented by the following formulas (1a) to (1f).
[0017]
[Chemical 9]
(Wherein RThree~ R6Are the same or different and each represents a hydrogen atom, an alkyl group, a hydroxyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, an acyl group, a nitro group, a cyano group, an amino group, or a halogen atom. R1, R2And n are the same as those in the general formula (1))
Substituent RThree~ R6The alkyl group includes the same alkyl group as the above exemplified alkyl group, particularly an alkyl group having about 1 to 6 carbon atoms, and the alkoxy group includes the same alkoxy group as described above, particularly 1 to 4 carbon atoms. The lower alkoxy group and alkoxycarbonyl group of the same level include the same alkoxycarbonyl group as described above, particularly a lower alkoxycarbonyl group having about 1 to 4 carbon atoms in the alkoxy moiety. Examples of the acyl group include the same acyl groups as described above, particularly those having about 1 to 6 carbon atoms, and examples of the halogen atom include fluorine, chlorine, and bromine atoms. Substituent RThree~ R6Is usually a hydrogen atom, a lower alkyl group having about 1 to 4 carbon atoms, a carboxyl group, a nitro group, or a halogen atom.
[0019]
In the general formula (1), X represents an oxygen atom or a hydroxyl group, and n is usually about 1 to 3, preferably 1 or 2. The compound represented by General formula (1) can be used 1 type, or 2 or more types in an oxidation reaction.
Examples of the acid anhydride corresponding to the imide compound represented by the general formula (1) include saturated or unsaturated aliphatic dicarboxylic anhydrides such as succinic anhydride and maleic anhydride, tetrahydrophthalic anhydride, and hexahydro anhydride. Saturated or unsaturated non-aromatic cyclic polyvalent carboxylic acid anhydrides such as phthalic acid (1,2-cyclohexanedicarboxylic acid anhydride) and 1,2,3,4-cyclohexanetetracarboxylic acid-1,2-anhydride (Alicyclic polyvalent carboxylic acid anhydride), crosslinked cyclic polyvalent carboxylic acid anhydride (alicyclic polyvalent carboxylic acid anhydride) such as het acid anhydride and hymic anhydride, phthalic anhydride, tetrabromophthalic anhydride Acid, tetrachlorophthalic anhydride, nitrophthalic anhydride, trimellitic anhydride, methylcyclohexeric carboxylic anhydride, pyromellitic anhydride, melittic anhydride 1,8; aromatic polycarboxylic anhydrides such as 4,5-naphthalene tetracarboxylic dianhydride are included.
[0020]
Preferred imide compounds include, for example, N-hydroxysuccinimide, N-hydroxymaleimide, N-hydroxyhexahydrophthalimide, N, N'-dihydroxycyclohexanetetracarboxylic imide, N-hydroxyphthalimide, N-hydroxytetrabromophthalimide, N-hydroxytetrachlorophthalimide, N-hydroxyhetamic imide, N-hydroxyhymic imide, N-hydroxytrimellitic imide, N, N'-dihydroxypyromellitic acid Examples thereof include imide and N, N′-dihydroxynaphthalenetetracarboxylic imide. Particularly preferred compounds include alicyclic polycarboxylic anhydrides, especially N-hydroxyimide compounds derived from aromatic polycarboxylic anhydrides, such as N-hydroxyphthalimide.
[0021]
The imide compound is prepared by a conventional imidization reaction such as a corresponding acid anhydride and hydroxylamine NH.2It can be adjusted by reacting with OH to open the acid anhydride group and then closing and imidizing.
Such an imide compound has a high oxidation activity and can promote the oxidation reaction of the conjugated compound catalytically even under mild conditions. Therefore, conjugated compounds can be oxidized efficiently and with high selectivity, and oxides of corresponding conjugated compounds (for example, alcohols, aldehydes and carboxylic acids), particularly diols or derivatives thereof (for example, alkene diols and acetals) Etc. can be generated. Furthermore, when the conjugated compound is oxidized in the coexistence of the imide compound represented by the general formula (1) and the cocatalyst, the conversion and / or selectivity can be further improved.
[0022]
[Cocatalyst]
The co-oxidant as a co-catalyst includes a metal compound, for example, a compound containing a group 13 element of the periodic table (boron B, aluminum Al, etc.) such as a transition metal compound or a boron compound. A co-oxidant can be used 1 type or in combination of 2 or more types.
Examples of the transition metal element include Group 3 elements in the periodic table (for example, scandium Sc and yttrium Y, lanthanoid elements such as lanthanum La, cerium Ce, and samarium Sm, and actinoid elements such as actinoid Ac), group 4 elements (Titanium Ti, Zirconium Zr, Hafnium Hf, etc.) Group 5 elements (Vanadium V, Niobium Nb, Tantalum Ta, etc.), Group 6 elements (Chromium Cr, Molybdenum Mo, Tungsten W, etc.), Group 7 elements (Manganese Mn, Technetium) Tc, rhenium Re, etc.), group 8 elements (iron Fe, ruthenium Ru, osmium Os, etc.), group 9 elements (cobalt Co, rhodium Rh, iridium Ir, etc.), group 10 elements (nickel Ni, palladium Pd, platinum Pt, etc.) ), Group 11 elements (copper Cu, silver Ag, gold Au, etc.) It is below.
[0023]
The elements constituting the preferred promoter include transition metal elements (for example, Group 3 elements of the periodic table such as lanthanoid elements and actinoid elements, Group 5 elements such as V and Nb, Group 6 elements such as Cr, Mo and W, Group 7 elements such as Mn, Tc and Re, Group 8 elements such as Fe and Ru, Group 9 elements such as Co and Rh, Group 10 elements such as Ni, Group 11 elements such as Cu), and Group 13 elements such as B Is included. In particular, when combined with the imide compound represented by the general formula (1), lanthanoid elements such as Ce, group 5 elements such as V, group 6 elements such as Mo and W, group 7 elements such as Mn, Fe A compound containing a Group 8 element such as Ru, a Group 9 element such as Co or Rh, a Group 10 element such as Ni, or a Group 11 element such as Cu exhibits high activity.
The co-catalyst is not particularly limited as long as it contains the element and has an oxidizing ability, and may be a simple metal, a hydroxide or the like, but usually a metal oxide, double oxide or oxygen acid containing the element It is often a salt, an organic acid salt, an inorganic acid salt, a halide, a coordination compound (complex) containing the metal element, a heteropolyacid or a salt thereof. Examples of the boron compound include boron hydroxide (for example, borane, diborane, tetraborane, pentaborane, decaborane), boric acid (for example, orthoboric acid, metaboric acid, tetraboric acid, etc.), borate (for example, Nickel borate, magnesium borate, manganese borate, etc.), B2OThreeBoron oxide such as bozarane, borazene, borazine, boron amide, boron imide, etc., BFThree, BClThree, Halides such as tetrafluoroborate, and borate esters (for example, methyl borate, phenyl borate, etc.). Preferred boron compounds include boric acid such as borohydride, orthoboric acid or salts thereof, in particular boric acid. These promoters can be used alone or in combination of two or more.
[0024]
Examples of hydroxides include Mn (OH)2, MnO (OH) and the like. Examples of the metal oxide include Sm.2OThreeTiO2, CrO, Cr2OThree, MoOThree, MnO, MnThreeOFour, Mn2OThree, MnO2, Mn2O7, FeO, Fe2OThree, RuO2, RuOFour, CoO, CoO2, Co2OThree, RhO2, Rh2OThree, Cu2OThreeAs the double oxide or oxyacid salt, for example, MnAl2OFour, MnTiOThreeLaMnOThree, K2Mn2OFive, CaO · xMnO2(X = 0.5, 1, 2, 3, 5), manganate [for example, NaThreeMnOFour, BaThree(MnOFour)2Manganese (V) acid salts such as K2MnOFour, Na2MnOFour, BaMnOFourManganese (VI) acid salts such as KMnOFourNaMnOFourLiMnOFour, NHFourMnOFour, CsMnOFour, AgMnOFour, Ca (MnOFour)2Zn (MnOFour)2, Ba (MnOFour)2Mg (MnOFour)2, Cd (MnOFour)2Permanganate] and the like.
[0025]
Examples of the organic acid salt include cobalt acetate, manganese acetate, cobalt propionate, manganese propionate, cobalt naphthenate, manganese naphthenate, cobalt stearate, manganese stearate, manganese thiocyanate and corresponding Ce salt, Cr salt, Fe salts, Ni salts, Pd salts, Cu salts, etc. are exemplified, and as inorganic acid salts, for example, nitrates such as cobalt nitrate, manganese nitrate, nickel nitrate, copper nitrate, and sulfates, phosphates corresponding to these, and the like Examples of the carbonate include cobalt sulfate, manganese sulfate, cobalt phosphate, manganese phosphate, and manganese carbonate. Examples of the halide include SmCl.Three, MnCl2, MnClThree, FeCl2, FeClThree, RuClThreeCoCl2, RhCl2, RhClThreeNiCl2, PdCl2, PtCl2, CuCl, CuCl2And their corresponding fluorides and bromides (for example, MnF2, MnBr2, MnFThreeHalide) such as M)1MnClThree, M1 2MnClFour, M1 2MnClFive, M1 2MnCl6(M1Represents a monovalent metal) and the like.
[0026]
As a ligand forming a complex, an alkoxy group such as OH (hydroxy), methoxy, ethoxy, propoxy, butoxy group, an acyl group such as acetyl, propionyl, an alkoxycarbonyl group such as methoxycarbonyl (acetato), ethoxycarbonyl, Halogen atoms such as acetylacetonato, cyclopentadienyl group, chlorine, bromine, CO, CN, oxygen atom, H2Phosphorus compounds such as O (aquo) and phosphine (for example, triarylphosphine such as triphenylphosphine), NHThree(Ammin), NO, NO2(Nitro), NOThreeAnd nitrogen-containing compounds such as (nitrato), ethylenediamine, diethylenetriamine, pyridine, and phenanthroline. In the complex or complex salt, the same or different ligands may be coordinated with one or more.
[0027]
Preferred complexes include transition metal elements (for example, lanthanoid elements such as Ce and periodic table group 3 elements to which actinoid elements belong, periodic table group 7 elements such as Mn, periodic table group 8 elements such as Fe and Ru, Co, Rh, etc. A periodic table group 9 element such as Ni, Pd, Pt and the like, and a periodic table group 11 element such as Cu. The ligand may be, for example, OH, alkoxy group, acyl group, alkoxycarbonyl group, acetylacetonato, halogen atom, CO, CN, H2Phosphorus compounds such as O (aquo) and triphenylphosphine, NHThree, NO2, NOThreeAre often nitrogen-containing compounds. The transition metal element and the ligand can be combined appropriately to form a complex, such as cerium acetylacetonate, manganese acetylacetonate, cobalt acetylacetonate, ruthenium acetylacetonate, copper acetylacetonate, etc. There may be.
[0028]
The polyacid forming the heteropolyacid is, for example, often a group 5 or 6 element of the periodic table, for example, at least one of V (vanadic acid), Mo (molybdic acid) and W (tungstic acid). Is not particularly limited, for example, Cu, Be, B, Al, Si, Ge, Sn, Ti, Th, N, P, As, Sb, V, Nb, Ta, Cr, Mo, W, S, Se, Te, Mn, I, Fe, Co, Ni, Rh, Os, Ir, Pt, Cu and the like may be used. Specific examples of the heteropoly acid include cobalt molybdate, cobalt tungstate, molybdenum tungstate, vanadium molybdate, vanadomolybdophosphate, and the like.
Examples of the cocatalyst include heteropoly acid salts containing at least one element of V, Mo, and W (for example, vanadium-molybdenum-based heteropoly acids or salts thereof), transition metal compounds (for example, lanthanoid elements, Mn, Ru, Co, and the like). And a transition metal compound containing at least one element of Cu).
[0029]
The catalyst system composed of the imide compound represented by the general formula (1) or the imide compound and the cocatalyst may be a homogeneous system or a heterogeneous system. The catalyst system may be a solid catalyst having a catalyst component supported on a carrier. As the carrier, porous carriers such as activated carbon, zeolite, silica, silica-alumina and bentonite are often used. The supported amount of the catalyst component in the solid catalyst is 0.1 to 50 parts by weight, preferably 0.5 to 30 parts by weight, more preferably 100 parts by weight of the imide compound represented by the general formula (1). About 1 to 20 parts by weight. The amount of the cocatalyst supported is 0.1 to 30 parts by weight, preferably 0.5 to 25 parts by weight, and more preferably about 1 to 20 parts by weight with respect to 100 parts by weight of the carrier.
The amount of the imide compound represented by the general formula (1) can be selected within a wide range. For example, 0.001 mol (0.1 mol%) to 1 mol (100 mol%) with respect to 1 mol of the conjugated compound. ), Preferably 0.001 mol (0.1 mol%) to 0.5 mol (50 mol%), more preferably about 0.01 to 0.30 mol, and about 0.01 to 0.25 mol In many cases.
[0030]
The amount of the cocatalyst (co-oxidant) used can be appropriately selected within a range that does not decrease the reactivity and selectivity. For example, 0.0001 mol (0.1 mol%) to 1 mol of the conjugated compound 0.7 mol (70 mol%), preferably 0.0001 to 0.5 mol, more preferably about 0.001 to 0.3 mol, and 0.0005 to 0.1 mol (for example, 0.005 It is often about 0.1 mol).
In addition, the ratio of the cocatalyst with respect to the imide compound represented by the general formula (1) can be selected within a range that does not impair the reaction rate and selectivity. Mol, preferably 0.005 to 5 mol, more preferably about 0.01 to 3 mol, and often about 0.01 to 5 mol.
When heteropoly acid or a salt thereof is used as a cocatalyst, it is 0.1 to 25 parts by weight, preferably 0.5 to 10 parts by weight, and more preferably about 1 to 5 parts by weight with respect to 100 parts by weight of the substrate.
[0031]
[Conjugated compound]
By using such an oxidation catalyst, the conjugated compound can be efficiently oxidized with oxygen, and oxides (alcohols, aldehydes, etc.) of the conjugated compound, particularly diols or derivatives thereof can be generated with high selectivity. Furthermore, when the oxidation reaction proceeds, a corresponding carboxylic acid may be generated. Therefore, in the method of the present invention, the conjugated compound and oxygen are brought into contact with each other and oxidized in the presence of the oxidation catalyst.
Conjugated compounds include conjugated dienes, α, β-unsaturated nitriles, α, β-unsaturated carboxylic acids or derivatives thereof.
Examples of the conjugated dienes include compounds having a conjugated double bond such as butadiene (1,3-butadiene) and isoprene (2-methyl-1,3-butadiene), and compounds having a double bond and a triple bond ( Vinyl acetylene, divinyl acetylene and the like) and derivatives thereof. The derivatives of conjugated dienes include, for example, compounds having halogen atoms (iodine, bromine, chlorine and fluorine atoms) such as 2-chlorobutadiene and 2,3-dichlorobutadiene, 2-ethylbutadiene, and 2,3-dimethylbutadiene. A compound having an alkyl group (for example, a lower alkyl group having about 1 to 4 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, t-butyl), butadiene-1-carboxylic acid, etc. A compound having a carboxyl group can be exemplified. Preferred conjugated dienes are butadiene and isoprene.
[0032]
Alkenediol is formed by oxygen oxidation of conjugated dienes. As long as the alkenediol produced is a diol corresponding to the conjugated diene, the substitution position of the hydroxyl group is not particularly limited. For example, butene diol produced by oxidation of butadiene may be 2-butene-1,4-diol, 1-butene-3,4-diol, etc., butene diol is either a cis isomer or a trans isomer. May be.
Examples of the α, β-unsaturated nitrile include (meth) acrylonitrile.
The conjugated compound represented by the general formula (2) corresponds to an α, β-unsaturated carboxylic acid or a derivative thereof.
[0033]
[Chemical Formula 10]
(Wherein R1Represents a hydrogen atom or a methyl group, and X represents —OR2(R2Represents a hydrogen atom, an alkyl group, an aryl group, a cycloalkyl group, a hydroxyalkyl group or a glycidyl group), -NRThreeRFour(RThreeAnd RFourAre the same or different and represent a hydrogen atom, an alkyl group, or a hydroxyalkyl group))
Substituent R in general formula (2)2Among them, the alkyl group includes methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, t-butyl, pentyl, hexyl, heptyl, 2-ethylhexyl, octyl, decyl, tetradecyl groups and the like. About 20 linear or branched alkyl groups are included. The preferred alkyl group includes an alkyl group having about 1 to 15 carbon atoms, particularly an alkyl group having about 1 to 12 carbon atoms (for example, about 1 to 10). The aryl group includes a phenyl group, a naphthyl group, and the like. Cycloalkyl groups include 5- to 10-membered cycloalkyl groups such as cyclopentyl, cyclohexyl, and cyclooctyl groups.
[0035]
The hydroxyalkyl group includes a hydroxyalkyl group having about 2 to 10 carbon atoms such as 2-hydroxyethyl, 2-hydroxypropyl, 4-hydroxybutyl, and hydroxypentyl group. Preferred hydroxyalkyl groups include hydroxyalkyl groups having about 2 to 4 carbon atoms, especially hydroxyalkyl groups having about 2 or 3 carbon atoms.
Substituent R2Is usually a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxyl alkyl group having 2 or 3 carbon atoms, or a glycidyl group.
Examples of the compound having such a substituent include (meth) acrylic acid; (meth) methyl acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, (meth ) Isobutyl acrylate, (meth) acrylic acid hexyl, (meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid alkyl esters such as lauryl acrylate; (meth) acrylic acid-2-hydroxyethyl, (meta ) Hydroxylalkyl (meth) acrylates such as 2-hydroxypropyl acrylate; glycidyl (meth) acrylate and the like.
[0036]
-NR represented by XThreeRFourA substituent RThreeAnd RFourAmong them, examples of the alkyl group include alkyl groups having about 1 to 10 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, t-butyl, and pentyl groups. Preferred alkyl groups include an alkyl group having about 1 to 6 carbon atoms, particularly an alkyl group having about 1 to 4 carbon atoms. Hydroxyalkyl groups include hydroxy-C1-10Alkyl, preferably hydroxymethyl, hydroxyethyl groups are included.
Substituent RThreeAnd RFourMay be the same or different and are usually a hydrogen atom, an alkyl group having about 1 to 4 carbon atoms, or a hydroxyalkyl group having 1 or 2 carbon atoms in many cases.
[0037]
Examples of the compound having such a substituent include (meth) acrylamide derivatives such as (meth) acrylamide, N-methyl (meth) acrylamide, and N-methylol (meth) acrylamide.
When these α, β-unsaturated nitriles, α, β-unsaturated carboxylic acids or derivatives thereof are oxidized by contact with oxygen, α, β-unsaturated bond sites are selectively oxidized, and a high conversion rate and General formula (3a) or (3b)
[0038]
Embedded image
Wherein Y is an oxygen atom or -OR5b(R5aAnd R5bAre the same or different and each represents a hydrogen atom, an alkyl group or an acyl group, and n represents 0 or 1. In the formula, “...” represents a single bond or a double bond. R1, X is the same as in general formula (2). However, when Y is an oxygen atom, n is 0, the “...” bond is a double bond, and Y is —OR5bWhere n is 1 and the "..." bond is a single bond)
Is produced.
In the compound represented by the general formula (3a) or (3b), the substituent R5aAnd R5bAmong them, the alkyl group includes, for example, C such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, t-butyl group and the like.1-6Alkyl and acyl groups include C and C such as acetyl and propionyl groups.2-6Acyl groups are included. These alkyl groups and acyl groups may be generated by reaction with a solvent.
[0040]
In this oxidation reaction, diols (Y is —OR5bAnd R5aAnd R5bIs a hydrogen atom), and an aldehyde or a derivative thereof (a compound in which Y is an oxygen atom) may be generated by a dehydration reaction. Further, when a protic solvent (an organic acid such as acetic acid or propionic acid, an alcohol such as methanol, ethanol, n-propanol, isopropanol, n-butanol, or t-butanol) is used as a reaction solvent, an acetal or an acyloxy compound Diol derivatives (Y is -OR5bAnd R5aAnd R5bA compound in which at least one of them is an alkyl group or an acyl group) may be produced. These aldehydes or derivatives thereof, or diol derivatives such as acetal are compounds equivalent to diols.
[0041]
For example, when methanol is used as a reaction solvent and acrylonitrile is oxidized, 1,1-dimethoxypropionitrile may be generated. Further, when methyl acrylate is oxidized in a methanol solvent, methyl 1,1-dimethoxypropionate may be generated.
The oxygen used for the oxidation of the conjugated compound may be active oxygen, but it is economically advantageous to use molecular oxygen. The molecular oxygen is not particularly limited, and pure oxygen may be used, or oxygen diluted with an inert gas such as nitrogen, helium, argon, or carbon dioxide may be used. From the viewpoint of not only operability and safety but also economy, it is preferable to use air.
The amount of oxygen used can be selected according to the type of the substrate, and is usually 0.5 mol or more (for example, 1 mol or more), preferably 1 to 100 mol, more preferably 2 to 50, relative to 1 mol of the substrate. It is about a mole. In many cases, an excess molar amount of oxygen relative to the substrate is used, and it is particularly advantageous to carry out the reaction in an atmosphere containing molecular oxygen such as air or oxygen.
The oxidation method of the present invention can be carried out in an organic solvent inert to the reaction. Examples of the organic solvent inert to the reaction include protic solvents (for example, organic acids such as acetic acid and propionic acid; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, and t-butanol). Nitriles (eg acetonitrile, propionitrile, benzonitrile, etc.), amides (eg formamide, acetamide, dimethylformamide (DMF) etc.), aliphatic hydrocarbons (eg hexane, octane etc.), aromatic carbonization Hydrogen (eg, benzene, toluene, etc.), halogenated hydrocarbons (eg, chloroform, dichloromethane, dichloroethane, carbon tetrachloride, chlorobenzene, etc.), nitro compounds (eg, nitrobenzene, nitromethane, nitroethane, etc.), esters (eg, Ethyl acetate, butyl acetate, ethyl propionate, butyl propionate, methyl benzoate, ethyl benzoate, etc.), ethers (eg, dimethyl ether, diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, etc.), mixed solvents thereof, etc. Is mentioned. In addition, you may utilize a substrate as a reaction solvent by using an excess substrate.
[0042]
The method of the present invention is characterized in that the oxidation reaction proceeds smoothly even under relatively mild conditions. The reaction temperature can be appropriately selected depending on the type of the substrate, and is, for example, 0 to 300 ° C., preferably 30 to 250 ° C., more preferably about 40 to 200 ° C., and the reaction is usually performed at about 40 to 150 ° C. There are many cases to do. The reaction can be carried out under normal pressure or under pressure. When the reaction is carried out under pressure, it is usually 1 to 100 atm (for example, 1.5 to 80 atm), preferably 2 to 70 atm, and more preferably 5 It is often about 50 atm. The reaction time can be appropriately selected from the range of, for example, 30 minutes to 48 hours, preferably 1 to 36 hours, more preferably 2 to 24 hours, depending on the reaction temperature and pressure.
The reaction can be performed by a conventional method such as batch, semi-batch, or continuous in the presence of molecular oxygen or in the flow of molecular oxygen. After completion of the reaction, the reaction product can be easily separated by a conventional method, for example, separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or a combination of these. Separation and purification are possible.
[0043]
The present invention relates to the synthesis of alkenediol (eg, butadiene, synthetic resin such as polyamide, maleic anhydride, plasticizer, butanediol, etc., which is a corresponding oxide from a conjugated compound, for example, a corresponding oxide from conjugated dienes. This is useful in producing butenediol used as a raw material.
[0044]
【The invention's effect】
In the oxidation method of the present invention, (1) the imide compound or (2) an oxidation catalyst composed of the imide compound and a cocatalyst is used, so that exhaust gas treatment is not particularly required, and the conjugated compound is efficiently formed by oxygen oxidation. It can be oxidized and is advantageous in terms of economy and safety. In addition, molecular oxygen can produce the corresponding oxide from the conjugated compound with high reaction conversion and selectivity. Furthermore, even under mild conditions, the conjugated compound can be efficiently oxidized with oxygen. Therefore, it is useful for producing a corresponding oxide from a conjugated compound, in particular, a diol or a derivative thereof with high conversion and selectivity.
[0045]
【Example】
EXAMPLES The present invention will be described in detail below based on examples, but the present invention is not limited to these examples.
Example 1
Butadiene 1.08 g (20 mmol), N-hydroxyphthalimide 0.26 g (1.6 mmol), cobalt acetylacetonate Co (AA)2 A mixture of 0.03 g (0.12 mmol) and 25 ml of acetonitrile was stirred at 60 ° C. for 6 hours under an oxygen atmosphere. When the product in the reaction solution was examined by gas chromatography analysis, the conversion of butadiene was 35%, 2-butene-1,4-diol (63% selectivity based on butadiene, yield 22%), 1 -Butene-3,4-diol (23% selectivity based on butadiene, 8% yield). The selectivity for the alcohol is 86%.
[0046]
Example 2
Acrylonitrile 1.06 g (20 mmol), N-hydroxyphthalimide 0.26 g (1.6 mmol), cobalt acetylacetonate Co (AA)2A mixture of 0.03 g (0.12 mmol) and 25 ml of methanol was stirred at 50 ° C. for 3 hours under an oxygen atmosphere. When the product in the reaction solution was examined by gas chromatography analysis, the conversion of acrylonitrile was 99% and 1,1-dimethoxypropionitrile was obtained in a yield of 99%.
Example 3
1.72 g (20 mmol) of methyl acrylate, 0.26 g (1.6 mmol) of N-hydroxyphthalimide, cobalt acetylacetonate Co (AA)2A mixture of 0.03 g (0.12 mmol) and 25 ml of methanol was stirred at 50 ° C. for 3 hours under an oxygen atmosphere. When the product in the reaction solution was examined by gas chromatography analysis, methyl acrylate conversion was 99%, and methyl 1,1-dimethylpropionate was obtained in 99% yield.
Claims (10)
で表されるイミド化合物で構成された酸化触媒の存在下、共役化合物と酸素とを接触させる共役化合物の酸化方法であって、
（ i ）前記一般式（１）で表されるイミド化合物が、下記式（１ａ）〜（１ｆ）で表される化合物であり、
（ ii ）前記共役化合物が、共役ジエン類、α，β−不飽和ニトリル又は一般式（２）
で表される化合物である酸化方法。 General formula (1)
A method for oxidizing a conjugated compound in which a conjugated compound and oxygen are brought into contact with each other in the presence of an oxidation catalyst composed of an imide compound represented by :
( I ) The imide compound represented by the general formula (1) is a compound represented by the following formulas (1a) to (1f),
( Ii ) The conjugated compound is a conjugated diene, an α, β-unsaturated nitrile or the general formula (2)
The oxidation method which is a compound represented by these.
で表される共役化合物と酸素とを接触させ、アルケンジオール、一般式（３ａ）又は（３ｂ）
で表される化合物を製造する方法であって、
前記一般式（１）で表されるイミド化合物が、前記式（１ａ）〜（１ｆ）で表される化合物である製造方法。 In the presence of a catalyst composed of an imide compound represented by the general formula (1) or a catalyst system composed of an imide compound represented by the general formula (1) and a promoter, conjugated dienes, α, β -Unsaturated nitrile or general formula (2)
And a conjugated compound represented by the formula (3a) or (3b):
A method of manufacturing a compound represented by,
The manufacturing method whose imide compound represented by the said General formula (1) is a compound represented by the said Formula (1a)-(1f).
Priority Applications (10)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18486696A JP3831012B2 (en) | 1996-02-09 | 1996-07-15 | Method for oxidizing conjugated compounds |
| DE69721662T DE69721662T2 (en) | 1996-02-07 | 1997-02-06 | USE OF AN OXIDATION CATALYST SYSTEM AND OXIDATION METHOD IN WHICH THE SYSTEM IS USED |
| EP02009780A EP1258292B1 (en) | 1996-02-07 | 1997-02-06 | Oxidation catalytic system and oxidation process using same |
| CN97190284A CN1098124C (en) | 1996-02-07 | 1997-02-06 | Oxidation catalyst system and process for oxidation with the same |
| ES97902584T ES2199340T3 (en) | 1996-02-07 | 1997-02-06 | USE OF AN OXIDATION CATALYSTING SYSTEM AND OXIDATION PROCESS THAT RECURNS THIS SYSTEM. |
| PCT/JP1997/000279 WO1997028897A1 (en) | 1996-02-07 | 1997-02-06 | Oxidation catalyst system and process for oxidation with the same |
| US08/913,881 US5958821A (en) | 1996-02-07 | 1997-02-06 | Oxidation catalytic system and oxidation process using the same |
| KR1019970707044A KR100472895B1 (en) | 1996-02-07 | 1997-02-06 | Oxidation Catalytic System and Oxidation Process Using the Same |
| EP97902584A EP0824962B1 (en) | 1996-02-07 | 1997-02-06 | Use of an oxidation catalyst system and process for oxidation with the same |
| DE69729229T DE69729229T2 (en) | 1996-02-07 | 1997-02-06 | Oxidation catalyst system and its use in an oxidation process |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8-47920 | 1996-02-09 | ||
| JP4792096 | 1996-02-09 | ||
| JP18486696A JP3831012B2 (en) | 1996-02-09 | 1996-07-15 | Method for oxidizing conjugated compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09278675A JPH09278675A (en) | 1997-10-28 |
| JP3831012B2 true JP3831012B2 (en) | 2006-10-11 |
Family
ID=26388128
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18486696A Expired - Fee Related JP3831012B2 (en) | 1996-02-07 | 1996-07-15 | Method for oxidizing conjugated compounds |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3831012B2 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE69834077T2 (en) * | 1997-01-14 | 2006-08-24 | Daicel Chemical Industries, Ltd., Sakai | NITRATION OR CARBOXYLATION CATALYSTS |
| JP4464476B2 (en) | 1999-02-19 | 2010-05-19 | ダイセル化学工業株式会社 | Oxidation method |
| JP4197207B2 (en) * | 1999-03-09 | 2008-12-17 | ダイセル化学工業株式会社 | Method for producing organic sulfur acid or salt thereof |
| US6548713B2 (en) * | 2000-03-10 | 2003-04-15 | Daicel Chemical Industries, Ltd. | Process for the preparation of organic compounds with manganese catalysts or the like |
| KR100817338B1 (en) | 2000-04-04 | 2008-03-26 | 다이셀 가가꾸 고교 가부시끼가이샤 | Separation Method of Imide Compound |
| JP4640877B2 (en) * | 2000-06-14 | 2011-03-02 | ダイセル化学工業株式会社 | Method for producing organic compound using imide compound as catalyst |
| JP4651181B2 (en) | 2000-11-01 | 2011-03-16 | ダイセル化学工業株式会社 | Separation method of reaction product and catalyst |
-
1996
- 1996-07-15 JP JP18486696A patent/JP3831012B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH09278675A (en) | 1997-10-28 |
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