JP6080281B1 - Method for producing oxidation reaction product of hydrocarbon or derivative thereof - Google Patents
Method for producing oxidation reaction product of hydrocarbon or derivative thereof Download PDFInfo
- Publication number
- JP6080281B1 JP6080281B1 JP2016042137A JP2016042137A JP6080281B1 JP 6080281 B1 JP6080281 B1 JP 6080281B1 JP 2016042137 A JP2016042137 A JP 2016042137A JP 2016042137 A JP2016042137 A JP 2016042137A JP 6080281 B1 JP6080281 B1 JP 6080281B1
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- JP
- Japan
- Prior art keywords
- chlorine dioxide
- hydrocarbon
- raw material
- acid
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 94
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 92
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 80
- 239000007795 chemical reaction product Substances 0.000 title claims abstract description 72
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 68
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 65
- 238000006243 chemical reaction Methods 0.000 claims abstract description 119
- 239000002994 raw material Substances 0.000 claims abstract description 84
- 239000004155 Chlorine dioxide Substances 0.000 claims abstract description 75
- OSVXSBDYLRYLIG-UHFFFAOYSA-N chlorine dioxide Inorganic materials O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 claims abstract description 75
- 235000019398 chlorine dioxide Nutrition 0.000 claims abstract description 75
- 239000012074 organic phase Substances 0.000 claims abstract description 68
- 238000000034 method Methods 0.000 claims abstract description 25
- 230000001678 irradiating effect Effects 0.000 claims abstract description 6
- 239000008346 aqueous phase Substances 0.000 claims description 62
- 239000002904 solvent Substances 0.000 claims description 39
- 239000012071 phase Substances 0.000 claims description 25
- 239000002841 Lewis acid Substances 0.000 claims description 23
- 150000007517 lewis acids Chemical class 0.000 claims description 23
- 239000003960 organic solvent Substances 0.000 claims description 20
- 239000007848 Bronsted acid Substances 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- QBWCMBCROVPCKQ-UHFFFAOYSA-M chlorite Chemical group [O-]Cl=O QBWCMBCROVPCKQ-UHFFFAOYSA-M 0.000 claims description 9
- 229940005993 chlorite ion Drugs 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 4
- 238000011084 recovery Methods 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 239000000463 material Substances 0.000 abstract 2
- -1 shale gas Chemical compound 0.000 description 103
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 43
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 40
- 125000003118 aryl group Chemical group 0.000 description 32
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- 239000000758 substrate Substances 0.000 description 30
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 29
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 26
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 25
- 239000000126 substance Substances 0.000 description 25
- 239000000460 chlorine Substances 0.000 description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 21
- 125000001424 substituent group Chemical group 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 19
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 19
- 239000002253 acid Substances 0.000 description 17
- 125000000217 alkyl group Chemical group 0.000 description 16
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 16
- 239000010410 layer Substances 0.000 description 16
- 150000003839 salts Chemical class 0.000 description 16
- 239000012044 organic layer Substances 0.000 description 14
- 229910052801 chlorine Inorganic materials 0.000 description 13
- 229960003742 phenol Drugs 0.000 description 13
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 12
- 150000001336 alkenes Chemical class 0.000 description 11
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 150000003254 radicals Chemical class 0.000 description 10
- 229920006395 saturated elastomer Polymers 0.000 description 10
- 150000001491 aromatic compounds Chemical class 0.000 description 9
- 230000007246 mechanism Effects 0.000 description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 9
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 8
- 125000004122 cyclic group Chemical group 0.000 description 8
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 8
- 229960002218 sodium chlorite Drugs 0.000 description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 7
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 150000002576 ketones Chemical class 0.000 description 7
- 239000003345 natural gas Substances 0.000 description 7
- 230000001590 oxidative effect Effects 0.000 description 7
- 229930195734 saturated hydrocarbon Natural products 0.000 description 7
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 7
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000002252 acyl group Chemical group 0.000 description 6
- 150000001735 carboxylic acids Chemical class 0.000 description 6
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 6
- 229940077239 chlorous acid Drugs 0.000 description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- 235000019253 formic acid Nutrition 0.000 description 6
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 6
- 238000010574 gas phase reaction Methods 0.000 description 6
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 6
- 125000004430 oxygen atom Chemical group O* 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 125000001072 heteroaryl group Chemical group 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229910001919 chlorite Inorganic materials 0.000 description 4
- 229910052619 chlorite group Inorganic materials 0.000 description 4
- 229910001882 dioxygen Inorganic materials 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 229960002050 hydrofluoric acid Drugs 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005660 chlorination reaction Methods 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- QIMMUPPBPVKWKM-UHFFFAOYSA-N 2-methylnaphthalene Chemical compound C1=CC=CC2=CC(C)=CC=C21 QIMMUPPBPVKWKM-UHFFFAOYSA-N 0.000 description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- 238000004057 DFT-B3LYP calculation Methods 0.000 description 2
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 2
- 241000282326 Felis catus Species 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 125000003158 alcohol group Chemical group 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 2
- 125000004414 alkyl thio group Chemical group 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000002306 biochemical method Methods 0.000 description 2
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 150000001923 cyclic compounds Chemical class 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 229910052805 deuterium Inorganic materials 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- SQNZJJAZBFDUTD-UHFFFAOYSA-N durene Chemical compound CC1=CC(C)=C(C)C=C1C SQNZJJAZBFDUTD-UHFFFAOYSA-N 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002118 epoxides Chemical class 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
- 230000004151 fermentation Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- QFWPJPIVLCBXFJ-UHFFFAOYSA-N glymidine Chemical compound N1=CC(OCCOC)=CN=C1NS(=O)(=O)C1=CC=CC=C1 QFWPJPIVLCBXFJ-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- JGJLWPGRMCADHB-UHFFFAOYSA-N hypobromite Chemical compound Br[O-] JGJLWPGRMCADHB-UHFFFAOYSA-N 0.000 description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229940078552 o-xylene Drugs 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000011027 product recovery Methods 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- WOAHJDHKFWSLKE-UHFFFAOYSA-N 1,2-benzoquinone Chemical compound O=C1C=CC=CC1=O WOAHJDHKFWSLKE-UHFFFAOYSA-N 0.000 description 1
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 1
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- MAYPHUUCLRDEAZ-UHFFFAOYSA-N chlorine peroxide Chemical compound ClOOCl MAYPHUUCLRDEAZ-UHFFFAOYSA-N 0.000 description 1
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Abstract
【課題】本発明は、炭化水素またはその誘導体を原料として、効率よく前記炭化水素またはその誘導体の酸化反応生成物を製造できる方法を提供することを目的とする。【解決手段】 前記目的を達成するために、本発明による前記炭化水素またはその誘導体の酸化反応生成物の製造方法は、原料および二酸化塩素ラジカルの存在下、反応系に光照射する反応工程を含み、前記原料が、炭化水素またはその誘導体であり、前記反応系が、有機相を含む反応系であり、前記有機相が、前記原料および前記二酸化塩素ラジカルを含み、前記反応工程において、前記光照射により、前記原料が酸化され、前記原料の酸化反応生成物を生成することを特徴とする。【選択図】なしAn object of the present invention is to provide a method capable of efficiently producing an oxidation reaction product of a hydrocarbon or a derivative thereof using a hydrocarbon or a derivative thereof as a raw material. In order to achieve the above object, the method for producing an oxidation reaction product of the hydrocarbon or derivative thereof according to the present invention includes a reaction step of irradiating a reaction system with light in the presence of a raw material and a chlorine dioxide radical. The raw material is a hydrocarbon or a derivative thereof, the reaction system is a reaction system including an organic phase, the organic phase includes the raw material and the chlorine dioxide radical, and in the reaction step, the light irradiation The material is oxidized to produce an oxidation reaction product of the material. [Selection figure] None
Description
本発明は、炭化水素またはその誘導体の酸化反応生成物の製造方法に関する。 The present invention relates to a method for producing an oxidation reaction product of a hydrocarbon or a derivative thereof.
アルコール、カルボン酸等は、その産業上利用価値の高さから、種々の方法で工業的に製造されている。例えば、メタノールの製造方法としては、炭化水素の部分燃焼で得られる一酸化炭素と水素ガスとを高温・高圧で反応させる方法が一般的に用いられている。原料となる一酸化炭素および水素ガスは、例えば、メタン（天然ガス）の部分燃焼、水蒸気改質法等により製造することができる。また、発酵等の生化学的方法によりアルコール、カルボン酸等を製造することも一般に行われている。 Alcohols, carboxylic acids, and the like are industrially produced by various methods because of their high industrial utility value. For example, as a method for producing methanol, a method of reacting carbon monoxide obtained by partial combustion of hydrocarbons with hydrogen gas at a high temperature and a high pressure is generally used. Carbon monoxide and hydrogen gas as raw materials can be produced by, for example, partial combustion of methane (natural gas), a steam reforming method, or the like. In addition, it is also common to produce alcohols, carboxylic acids and the like by biochemical methods such as fermentation.
さらに、近年は、シェールガス等の天然ガスの有効利用のため、天然ガス中に含まれる炭化水素を酸化して、アルコール等の酸化反応生成物を製造する方法も提案されている。気相反応による製造方法としては、例えば、エタンを、鉄触媒の存在下、一酸化二窒素で酸化してエタノールを製造する方法（非特許文献１）等がある。また、液相反応による製造方法としては、メタンを、鉄触媒の存在下、アセトニトリル溶媒中で、過酸化水素により酸化してメタノールを製造する方法（非特許文献２）等がある。 Furthermore, in recent years, in order to effectively use natural gas such as shale gas, a method for producing an oxidation reaction product such as alcohol by oxidizing hydrocarbons contained in natural gas has been proposed. Examples of the production method by gas phase reaction include a method of producing ethanol by oxidizing ethane with dinitrogen monoxide in the presence of an iron catalyst (Non-patent Document 1). As a production method by liquid phase reaction, there is a method of producing methanol by oxidizing methane with hydrogen peroxide in an acetonitrile solvent in the presence of an iron catalyst (Non-patent Document 2).
しかしながら、炭化水素の部分燃焼による一酸化炭素の製造過程では、大量の二酸化炭素（温室効果ガス）を排出するという問題がある。また、発酵等の生化学的方法による製造においては、例えば、原料となる農作物（例えばトウモロコシ）を栽培する過程における施肥、農薬投下、収穫、運搬などにおいて多くのエネルギーを要するという問題がある。さらに、これらの方法は、炭化水素を原料としてアルコール、カルボン酸等を製造することができないので、天然ガス中等に含まれる炭化水素の有効利用には使えない。 However, in the process of producing carbon monoxide by partial combustion of hydrocarbons, there is a problem in that a large amount of carbon dioxide (greenhouse gas) is emitted. Further, in the production by biochemical methods such as fermentation, there is a problem that, for example, a lot of energy is required for fertilization, pesticide dropping, harvesting, transportation, etc. in the process of cultivating a crop (for example, corn) as a raw material. Furthermore, these methods cannot be used for effective utilization of hydrocarbons contained in natural gas and the like because alcohols, carboxylic acids and the like cannot be produced from hydrocarbons as raw materials.
一方、炭化水素を原料とする酸化反応生成物の製造方法には、以下のような課題がある。まず、気相反応による製造方法では、反応系中における分子の衝突頻度が低いため、反応効率が悪い。一方、酸化剤あるいは触媒を用いた固相・気相の反応が主に研究されているが、炭化水素の固体への吸着特性が低く、効率の良いものは報告されていない。このため、気相反応による製造方法では、高温・高圧等の激しい反応条件が必要であり、製造効率、コスト、安全管理等の問題がある。一方、液相反応による製造方法では、炭化水素（原料）から発生するラジカル（中間体）の反応制御が難しく、副反応が起こりやすい。これらの問題から、炭化水素を原料とする酸化反応生成物の製造方法は、いずれも、前記酸化反応生成物を効率よく製造することが出来ず、産業上の実用化に至っていないのが現状である。 On the other hand, the method for producing an oxidation reaction product using hydrocarbon as a raw material has the following problems. First, in the production method by gas phase reaction, the reaction efficiency is poor because the collision frequency of molecules in the reaction system is low. On the other hand, solid-phase and gas-phase reactions using an oxidant or a catalyst have been mainly studied, but there are no reports of efficient hydrocarbon adsorption properties due to low adsorption characteristics to hydrocarbon solids. For this reason, in the manufacturing method by a gas phase reaction, intense reaction conditions such as high temperature and high pressure are necessary, and there are problems such as manufacturing efficiency, cost, and safety management. On the other hand, in a production method using a liquid phase reaction, it is difficult to control the reaction of radicals (intermediates) generated from hydrocarbons (raw materials), and side reactions are likely to occur. Because of these problems, none of the methods for producing an oxidation reaction product using hydrocarbon as a raw material is capable of producing the oxidation reaction product efficiently and has not yet been put to practical use in industry. is there.
そこで、本発明は、炭化水素またはその誘導体を原料として、効率よく前記炭化水素またはその誘導体の酸化反応生成物を製造できる方法を提供することを目的とする。 Therefore, an object of the present invention is to provide a method capable of efficiently producing an oxidation reaction product of the hydrocarbon or its derivative using a hydrocarbon or its derivative as a raw material.
前記目的を達成するために、本発明による前記炭化水素またはその誘導体の酸化反応生成物の製造方法（以下、単に「本発明の製造方法」ということがある。）は、原料および二酸化塩素ラジカルの存在下、反応系に光照射する反応工程を含み、前記原料が、炭化水素またはその誘導体であり、前記反応系が、有機相を含む反応系であり、前記有機相が、前記原料および前記二酸化塩素ラジカルを含み、前記反応工程において、前記光照射により、前記原料が酸化され、前記原料の酸化反応生成物を生成することを特徴とする。 In order to achieve the above object, the method for producing an oxidation reaction product of the hydrocarbon or derivative thereof according to the present invention (hereinafter, sometimes simply referred to as “the production method of the present invention”) includes a raw material and a chlorine dioxide radical. A reaction step of irradiating the reaction system with light in the presence, the raw material is a hydrocarbon or a derivative thereof, the reaction system is a reaction system including an organic phase, and the organic phase is the raw material and the dioxide dioxide. It contains chlorine radicals, and in the reaction step, the raw material is oxidized by the light irradiation to generate an oxidation reaction product of the raw material.
本発明の製造方法によれば、炭化水素またはその誘導体を原料として、効率よく前記炭化水素またはその誘導体の酸化反応生成物を製造できる。 According to the production method of the present invention, an oxidation reaction product of the hydrocarbon or a derivative thereof can be efficiently produced using a hydrocarbon or a derivative thereof as a raw material.
以下、本発明について、例を挙げてさらに具体的に説明する。ただし、本発明は、以下の説明により限定されない。 Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following description.
本発明の製造方法は、前記反応工程において、少なくとも前記有機相に光照射しても良い。 In the production method of the present invention, at least the organic phase may be irradiated with light in the reaction step.
本発明の製造方法は、さらに、前記二酸化塩素ラジカルを生成させる二酸化塩素ラジカル生成工程を含んでいても良い。 The production method of the present invention may further include a chlorine dioxide radical generating step for generating the chlorine dioxide radical.
本発明の製造方法は、前記反応系が、さらに水相を含む二相反応系であっても良い。この場合において、本発明の製造方法は、さらに、前記二酸化塩素ラジカルを生成させる二酸化塩素ラジカル生成工程を含んでいても良く、前記二酸化塩素ラジカル生成工程において、前記水相が、前記二酸化塩素ラジカルの発生源を含み、前記二酸化塩素ラジカルの発生源から前記二酸化塩素ラジカルを生成させても良い。また、前記二酸化塩素ラジカル生成工程において、例えば、前記二酸化塩素ラジカルの発生源が亜塩素酸イオン（ＣｌＯ２ −）であり、前記亜塩素酸イオンにルイス酸およびブレーンステッド酸の少なくとも一方を作用させて前記二酸化塩素ラジカルを生成させても良い。 In the production method of the present invention, the reaction system may be a two-phase reaction system further including an aqueous phase. In this case, the production method of the present invention may further include a chlorine dioxide radical generation step for generating the chlorine dioxide radical, and in the chlorine dioxide radical generation step, the aqueous phase contains the chlorine dioxide radical. A generation source may be included, and the chlorine dioxide radical may be generated from the generation source of the chlorine dioxide radical. In the chlorine dioxide radical generating step, for example, the chlorine dioxide radical generation source is chlorite ion (ClO 2 − ), and at least one of Lewis acid and Bronsted acid is allowed to act on the chlorite ion. The chlorine dioxide radical may be generated.
本発明の製造方法は、前記反応工程後、さらに、前記酸化反応生成物の回収工程を含み、前記回収工程が、前記反応系から、前記酸化反応生成物を含む前記水相を回収する工程であっても良い。 The production method of the present invention further includes a step of recovering the oxidation reaction product after the reaction step, and the recovery step is a step of recovering the aqueous phase containing the oxidation reaction product from the reaction system. There may be.
本発明の製造方法は、例えば、温度がマイナス１００〜２００℃であり、圧力が０．１〜１０ＭＰａである雰囲気下で行なっても良い。または、本発明の製造方法は、例えば、温度が０〜４０℃であり、圧力が０．１〜０．５ＭＰａである雰囲気下で行なっても良い。 You may perform the manufacturing method of this invention in the atmosphere whose temperature is minus 100-200 degreeC and a pressure is 0.1-10 Mpa, for example. Or you may perform the manufacturing method of this invention in the atmosphere whose temperature is 0-40 degreeC and a pressure is 0.1-0.5 Mpa, for example.
本発明の製造方法は、例えば、前記反応工程において、前記水相に酸素（Ｏ２）が溶解した状態で光照射しても良い。 In the production method of the present invention, for example, in the reaction step, light irradiation may be performed in a state where oxygen (O 2 ) is dissolved in the aqueous phase.
本発明の製造方法において、前記有機相は、例えば、有機溶媒を含む。前記有機溶媒は、例えば、炭化水素溶媒、ハロゲン化溶媒、またはフルオラス溶媒であっても良い。 In the production method of the present invention, the organic phase includes, for example, an organic solvent. The organic solvent may be, for example, a hydrocarbon solvent, a halogenated solvent, or a fluorous solvent.
本発明の製造方法において、例えば、前記原料における前記炭化水素が、飽和炭化水素であっても良い。前記飽和炭化水素は、例えば、メタン、エタンまたはシクロヘキサンであっても良い。 In the production method of the present invention, for example, the hydrocarbon in the raw material may be a saturated hydrocarbon. The saturated hydrocarbon may be, for example, methane, ethane or cyclohexane.
本発明の製造方法において、例えば、前記原料における前記炭化水素が、非芳香族不飽和炭化水素であっても良い。 In the production method of the present invention, for example, the hydrocarbon in the raw material may be a non-aromatic unsaturated hydrocarbon.
本発明の製造方法において、例えば、前記原料における前記炭化水素が、芳香族炭化水素であっても良い。前記芳香族炭化水素は、例えば、ベンゼンであっても良い。 In the production method of the present invention, for example, the hydrocarbon in the raw material may be an aromatic hydrocarbon. The aromatic hydrocarbon may be, for example, benzene.
本発明の製造方法において、前記原料における前記炭化水素が、飽和炭化水素または非芳香族不飽和炭化水素である場合、例えば、前記酸化反応生成物が、アルコール、カルボン酸、アルデヒド、ケトン、過カルボン酸、およびヒドロペルオキシドからなる群から選択される少なくとも一つであっても良い。 In the production method of the present invention, when the hydrocarbon in the raw material is a saturated hydrocarbon or a non-aromatic unsaturated hydrocarbon, for example, the oxidation reaction product is an alcohol, a carboxylic acid, an aldehyde, a ketone, a percarboxylic acid. It may be at least one selected from the group consisting of an acid and a hydroperoxide.
本発明の製造方法において、前記原料における前記炭化水素がメタンである場合、例えば、前記酸化反応生成物が、メタノール、ギ酸、ホルムアルデヒド、およびメチルヒドロペルオキシドの少なくとも一つを含んでいても良い。 In the production method of the present invention, when the hydrocarbon in the raw material is methane, for example, the oxidation reaction product may contain at least one of methanol, formic acid, formaldehyde, and methyl hydroperoxide.
本発明の製造方法において、前記原料における前記炭化水素がエタンである場合、例えば、前記酸化反応生成物が、エタノール、酢酸、アセトアルデヒド、およびエチルヒドロペルオキシドの少なくとも一つを含んでいても良い。 In the production method of the present invention, when the hydrocarbon in the raw material is ethane, for example, the oxidation reaction product may contain at least one of ethanol, acetic acid, acetaldehyde, and ethyl hydroperoxide.
本発明の製造方法において、前記原料における前記炭化水素がシクロヘキサンである場合、例えば、前記酸化反応生成物が、シクロヘキサノール、シクロヘキサノン、シクロヘキサンヒドロペルオキシド、および開環酸化物（例えばアジピン酸など）の少なくとも一つを含んでいても良い。 In the production method of the present invention, when the hydrocarbon in the raw material is cyclohexane, for example, the oxidation reaction product is at least cyclohexanol, cyclohexanone, cyclohexane hydroperoxide, and a ring-opening oxide (such as adipic acid). One may be included.
本発明の製造方法において、前記原料における前記炭化水素が芳香族炭化水素である場合、例えば、前記酸化反応生成物が、フェノールおよびキノンの少なくとも一方を含んでいても良い。なお、「フェノール」は、ヒドロキシベンゼンを意味する場合と、芳香族（例えば芳香族炭化水素またはヘテロ芳香族）核の水素原子をヒドロキシ基（水酸基）で置換した芳香族ヒドロキシ化合物全般（ヒドロキシベンゼンを含む）を意味する場合とがあるが、本発明では、特に断らない限り、後者とする。また、「キノン」は、ｐ−ベンゾキノンを意味する場合と、芳香族（例えば芳香族炭化水素またはヘテロ芳香族）中の芳香環（例えばベンゼン環）の水素２原子を酸素２原子で置換した構造のジカルボニル化合物全般（ｐ−ベンゾキノンおよびｏ−ベンゾキノンを含む）を意味する場合とがあるが、本発明では、特に断らない限り、後者とする。 In the production method of the present invention, when the hydrocarbon in the raw material is an aromatic hydrocarbon, for example, the oxidation reaction product may contain at least one of phenol and quinone. “Phenol” means hydroxybenzene and general aromatic hydroxy compounds in which the hydrogen atom of an aromatic (for example, aromatic hydrocarbon or heteroaromatic) nucleus is substituted with a hydroxy group (hydroxyl group) (hydroxybenzene In the present invention, the latter is used unless otherwise specified. “Quinone” means p-benzoquinone and a structure in which two hydrogen atoms of an aromatic ring (eg, benzene ring) in an aromatic (eg, aromatic hydrocarbon or heteroaromatic) are substituted with two oxygen atoms. In general, the term “dicarbonyl compound” (including p-benzoquinone and o-benzoquinone) may mean the latter unless otherwise specified.
本発明の製造方法において、前記原料における前記炭化水素がベンゼンである場合、例えば、前記酸化反応生成物が、ヒドロキシベンゼン、ｐ−ベンゾキノン、о−ベンゾキノン、ヒドロキノン、およびカテコールの少なくとも一つを含んでいても良い。 In the production method of the present invention, when the hydrocarbon in the raw material is benzene, for example, the oxidation reaction product contains at least one of hydroxybenzene, p-benzoquinone, о-benzoquinone, hydroquinone, and catechol. May be.
本発明の製造方法は、より具体的には、例えば、以下のようにして行なうことができる。 More specifically, the production method of the present invention can be performed, for example, as follows.
［１．炭化水素またはその誘導体］
まず、原料（基質）である炭化水素またはその誘導体を準備する。前記原料は、炭化水素自体でも良いが、その誘導体であっても良い。
[1. Hydrocarbon or derivative thereof]
First, a hydrocarbon or derivative thereof as a raw material (substrate) is prepared. The raw material may be a hydrocarbon itself or a derivative thereof.
前記炭化水素は、特に限定されず、例えば、非芳香族でも芳香族でも良いし、飽和でも不飽和でも良い。より具体的には、前記炭化水素は、例えば、直鎖状または分枝状の飽和または不飽和炭化水素（例えば、直鎖状または分枝状のアルカン、直鎖状または分枝状のアルケン、直鎖状または分枝状のアルキン等）であっても良い。また、前記炭化水素は、例えば、非芳香族の環状構造を含む飽和または不飽和炭化水素（例えば、シクロアルカン、シクロアルケン等）であっても良い。また、前記炭化水素は、芳香族炭化水素であっても良い。また、前記炭化水素は、その構造中に、芳香族または非芳香族の環をそれぞれ１または複数有していても有していなくても良く、直鎖状または分枝状の飽和または不飽和炭化水素の炭化水素基を、それぞれ１または複数有していても有していなくても良い。前記炭化水素の具体例としては、例えば、メタン、エタン、プロパン、ｎ−ブタン、２−メチルプロパン、ｎ−ペンタン、ｎ−ヘキサン、エチレン、プロピレン、１，３−ブタジエン、アセチレン、シクロペンタン、シクロヘキサン、シクロヘプタン、シクロオクタン、メチルシクロヘキサン、シクロヘキセン、ベンゼン、トルエン、ｏ−キシレン、ｍ−キシレン、ｐ−キシレン、メシチレン、デュレン、ビフェニル、ナフタレン、１−メチルナフタレン、２−メチルナフタレン、アントラセン、フェナントレン、ピレン、スチレン等が挙げられる。 The hydrocarbon is not particularly limited. For example, the hydrocarbon may be non-aromatic or aromatic, and may be saturated or unsaturated. More specifically, the hydrocarbon is, for example, a linear or branched saturated or unsaturated hydrocarbon (for example, a linear or branched alkane, a linear or branched alkene, Linear or branched alkyne, etc.). The hydrocarbon may be, for example, a saturated or unsaturated hydrocarbon (for example, cycloalkane, cycloalkene, etc.) containing a non-aromatic cyclic structure. The hydrocarbon may be an aromatic hydrocarbon. Further, the hydrocarbon may or may not have one or more aromatic or non-aromatic rings in its structure, and may be linear or branched saturated or unsaturated. One or more hydrocarbon groups of hydrocarbons may be included or not included. Specific examples of the hydrocarbon include, for example, methane, ethane, propane, n-butane, 2-methylpropane, n-pentane, n-hexane, ethylene, propylene, 1,3-butadiene, acetylene, cyclopentane, and cyclohexane. , Cycloheptane, cyclooctane, methylcyclohexane, cyclohexene, benzene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, durene, biphenyl, naphthalene, 1-methylnaphthalene, 2-methylnaphthalene, anthracene, phenanthrene, Examples include pyrene and styrene.
また、本発明において、炭化水素の「誘導体」は、ヘテロ元素（炭素および水素以外の元素）を含む有機化合物とする。前記ヘテロ元素としては、特に限定されないが、例えば、酸素（Ｏ）、窒素（Ｎ）、硫黄（Ｓ）、ハロゲン等が挙げられる。前記ハロゲンとしては、例えば、フッ素（Ｆ）、塩素（Ｃｌ）、臭素（Ｂｒ）、ヨウ素（Ｉ）等が挙げられる。前記誘導体は、例えば、炭化水素基と、任意の置換基または原子団とが結合した構造の有機化合物であっても良い。また、例えば、複数の炭化水素基が任意の原子団により結合された構造の化合物であっても良く、さらに、前記炭化水素基が任意の1または複数の置換基により置換されていても良いし、置換されていなくても良い。そして、前記炭化水素基の部分を前記反応工程において酸化反応により酸化することで、前記炭化水素の誘導体の酸化反応生成物を製造しても良い。前記炭化水素基は、特に限定されないが、例えば、前記炭化水素から誘導される１価または２価以上の基が挙げられる。前記炭化水素基は、例えば、その炭素原子の１または２以上がヘテロ原子に置き換わっていても良い。具体的には、例えば、フェニル基の１つの炭素原子（およびそれに結合した水素原子）が窒素原子に置き換わっていることで、ピリジル基を形成していても良い。また、前記置換基または原子団としては、特に限定されないが、例えば、ヒドロキシ基、ハロゲン基（フルオロ基、クロロ基、ブロモ基、ヨード基等）、アルコキシ基、アリールオキシ基（例えばフェノキシ基等）、カルボキシ基、アルコキシカルボニル基、アリールオキシカルボニル基（例えばフェノキシカルボニル基等）、メルカプト基、アルキルチオ基、アリールチオ基（例えばフェニルチオ基等）、置換基を有するか有しないアミノ基（例えば、アミノ基、アルキルアミノ基、ジアルキルアミノ基等）、エーテル結合（−Ｏ−）、エステル結合（−ＣＯ−Ｏ−）、チオエーテル結合（−Ｓ−）等が挙げられる。 In the present invention, the “derivative” of hydrocarbon is an organic compound containing a hetero element (an element other than carbon and hydrogen). Although it does not specifically limit as said hetero element, For example, oxygen (O), nitrogen (N), sulfur (S), a halogen, etc. are mentioned. Examples of the halogen include fluorine (F), chlorine (Cl), bromine (Br), iodine (I), and the like. The derivative may be, for example, an organic compound having a structure in which a hydrocarbon group and an arbitrary substituent or atomic group are bonded. Further, for example, it may be a compound having a structure in which a plurality of hydrocarbon groups are bonded by an arbitrary atomic group, and the hydrocarbon group may be substituted by any one or more substituents. , It may not be substituted. Then, an oxidation reaction product of the hydrocarbon derivative may be produced by oxidizing the hydrocarbon group portion by an oxidation reaction in the reaction step. The hydrocarbon group is not particularly limited, and examples thereof include a monovalent or divalent or higher group derived from the hydrocarbon. In the hydrocarbon group, for example, one or more of the carbon atoms may be replaced with a hetero atom. Specifically, for example, a pyridyl group may be formed by replacing one carbon atom (and a hydrogen atom bonded thereto) of a phenyl group with a nitrogen atom. Further, the substituent or atomic group is not particularly limited, and for example, a hydroxy group, a halogen group (fluoro group, chloro group, bromo group, iodo group, etc.), an alkoxy group, an aryloxy group (eg, phenoxy group, etc.) , A carboxy group, an alkoxycarbonyl group, an aryloxycarbonyl group (for example, phenoxycarbonyl group), a mercapto group, an alkylthio group, an arylthio group (for example, phenylthio group), an amino group with or without a substituent (for example, an amino group, An alkylamino group, a dialkylamino group, etc.), an ether bond (—O—), an ester bond (—CO—O—), a thioether bond (—S—) and the like.
なお、本発明において、鎖状化合物（例えば、アルカン、不飽和脂肪族炭化水素等）または鎖状化合物から誘導される鎖状置換基（例えば、アルキル基、不飽和脂肪族炭化水素基等の炭化水素基）は、特に断らない限り、直鎖状でも分枝状でも良く、その炭素数は、特に限定されないが、例えば、１〜４０、１〜３２、１〜２４、１〜１８、１〜１２、１〜６、または１〜２（不飽和炭化水素基の場合は２以上）であっても良い。また、本発明において、環状の化合物（例えば、環状飽和炭化水素、非芳香族環状不飽和炭化水素、芳香族炭化水素、ヘテロ芳香族化合物等）または環状の化合物から誘導される環状の基（例えば、環状飽和炭化水素基、非芳香族環状不飽和炭化水素基、アリール基、ヘテロアリール基等）の環員数（環を構成する原子の数）は、特に限定されないが、例えば、５〜３２、５〜２４、６〜１８、６〜１２、または６〜１０であっても良い。また、置換基等に異性体が存在する場合は、特に断らない限り、どの異性体でも良く、例えば、単に「ナフチル基」という場合は、１−ナフチル基でも２−ナフチル基でも良い。 In the present invention, chain compounds (for example, alkanes, unsaturated aliphatic hydrocarbons, etc.) or chain substituents derived from chain compounds (for example, carbons such as alkyl groups, unsaturated aliphatic hydrocarbon groups, etc.) Unless otherwise specified, the hydrogen group) may be linear or branched, and the carbon number thereof is not particularly limited, but for example, 1 to 40, 1 to 32, 1 to 24, 1 to 18, 1 to 12, 1-6, or 1-2 (two or more in the case of an unsaturated hydrocarbon group) may be sufficient. In the present invention, a cyclic compound (for example, a cyclic saturated hydrocarbon, a non-aromatic cyclic unsaturated hydrocarbon, an aromatic hydrocarbon, a heteroaromatic compound, etc.) or a cyclic group derived from a cyclic compound (for example, The number of ring members (the number of atoms constituting the ring) of the cyclic saturated hydrocarbon group, non-aromatic cyclic unsaturated hydrocarbon group, aryl group, heteroaryl group, etc.) is not particularly limited. It may be 5-24, 6-18, 6-12, or 6-10. Further, when an isomer is present in a substituent or the like, unless otherwise specified, any isomer may be used. For example, when simply referred to as “naphthyl group”, it may be a 1-naphthyl group or a 2-naphthyl group.
また、本発明において、化合物（例えば、前記電子供与体・受容体連結分子等）に互変異性体または立体異性体（例：幾何異性体、配座異性体および光学異性体）等の異性体が存在する場合は、特に断らない限り、いずれの異性体も本発明に用いることができる。また、化合物（例えば、前記電子供与体・受容体連結分子等）が塩を形成し得る場合は、特に断らない限り、前記塩も本発明に用いることができる。前記塩は、酸付加塩でも良いが、塩基付加塩でも良い。さらに、前記酸付加塩を形成する酸は無機酸でも有機酸でも良く、前記塩基付加塩を形成する塩基は無機塩基でも有機塩基でも良い。前記無機酸としては、特に限定されないが、例えば、硫酸、リン酸、フッ化水素酸、塩酸、臭化水素酸、ヨウ化水素酸、次亜フッ素酸、次亜塩素酸、次亜臭素酸、次亜ヨウ素酸、亜フッ素酸、亜塩素酸、亜臭素酸、亜ヨウ素酸、フッ素酸、塩素酸、臭素酸、ヨウ素酸、過フッ素酸、過塩素酸、過臭素酸、および過ヨウ素酸等があげられる。前記有機酸も特に限定されないが、例えば、ｐ−トルエンスルホン酸、メタンスルホン酸、シュウ酸、ｐ−ブロモベンゼンスルホン酸、炭酸、コハク酸、クエン酸、安息香酸および酢酸等があげられる。前記無機塩基としては、特に限定されないが、例えば、水酸化アンモニウム、アルカリ金属水酸化物、アルカリ土類金属水酸化物、炭酸塩および炭酸水素塩等があげられ、より具体的には、例えば、水酸化ナトリウム、水酸化カリウム、炭酸カリウム、炭酸ナトリウム、炭酸水素ナトリウム、炭酸水素カリウム、水酸化カルシウムおよび炭酸カルシウム等があげられる。前記有機塩基も特に限定されないが、例えば、エタノールアミン、トリエチルアミンおよびトリス（ヒドロキシメチル）アミノメタン等があげられる。これらの塩の製造方法も特に限定されず、例えば、前記化合物に、前記のような酸や塩基を公知の方法により適宜付加させる等の方法で製造することができる。 In the present invention, the compound (for example, the electron donor / acceptor linking molecule) is an isomer such as a tautomer or a stereoisomer (eg, a geometric isomer, a conformer and an optical isomer). If present, any isomer can be used in the present invention unless otherwise specified. In addition, when a compound (for example, the electron donor / acceptor linking molecule or the like) can form a salt, the salt can also be used in the present invention unless otherwise specified. The salt may be an acid addition salt or a base addition salt. Furthermore, the acid forming the acid addition salt may be an inorganic acid or an organic acid, and the base forming the base addition salt may be an inorganic base or an organic base. The inorganic acid is not particularly limited. For example, sulfuric acid, phosphoric acid, hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, hypofluorite, hypochlorous acid, hypobromite, Hypoarousous acid, fluorinated acid, chlorous acid, bromic acid, iodic acid, fluoric acid, chloric acid, bromic acid, iodic acid, perfluoric acid, perchloric acid, perbromic acid, periodic acid, etc. Can be given. The organic acid is not particularly limited, and examples thereof include p-toluenesulfonic acid, methanesulfonic acid, oxalic acid, p-bromobenzenesulfonic acid, carbonic acid, succinic acid, citric acid, benzoic acid, and acetic acid. The inorganic base is not particularly limited, and examples thereof include ammonium hydroxide, alkali metal hydroxides, alkaline earth metal hydroxides, carbonates and hydrogen carbonates, and more specifically, for example, Examples thereof include sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, calcium hydroxide and calcium carbonate. The organic base is not particularly limited, and examples thereof include ethanolamine, triethylamine, and tris (hydroxymethyl) aminomethane. The method for producing these salts is not particularly limited, and for example, the salts can be produced by a method such as appropriately adding the above acid or base to the compound by a known method.
［２．反応系］
つぎに、前記反応系を準備する。前記反応系は、前述のとおり、有機相を含む。前記反応系は、例えば、有機相のみを含む一相反応系でもよいし、有機相と水相とを含む二相反応系でもよい。
[2. Reaction system]
Next, the reaction system is prepared. As described above, the reaction system includes an organic phase. The reaction system may be, for example, a one-phase reaction system including only an organic phase or a two-phase reaction system including an organic phase and an aqueous phase.
（１）有機相
まず、前記有機相について説明する。
(1) Organic Phase First, the organic phase will be described.
前記有機相は、前述のとおり、前記原料（炭化水素またはその誘導体）を含む。前記有機相は、例えば、前記原料が有機溶媒に溶解した有機相である。 As described above, the organic phase contains the raw material (hydrocarbon or derivative thereof). The organic phase is, for example, an organic phase in which the raw material is dissolved in an organic solvent.
前記有機溶媒は、特に限定されない。前記反応系が、水相と有機相を含む二相反応系の場合、前記有機溶媒は、前記二相系を形成し得る溶媒が好ましい。また、前記有機溶媒は、１種類のみ用いても複数種類併用しても良い。前記有機溶媒としては、例えば、前述のとおり、炭化水素溶媒、ハロゲン化溶媒、フルオラス溶媒等が挙げられる。なお、「フルオラス溶媒」は、ハロゲン化溶媒の１種であり、例えば、炭化水素の水素原子の全てまたは大部分がフッ素原子に置換された溶媒をいう。前記フルオラス溶媒は、例えば、炭化水素の水素原子数の５０％以上、６０％以上、７０％以上、８０％以上、または９０％以上がフッ素原子に置換された溶媒であっても良い。 The organic solvent is not particularly limited. When the reaction system is a two-phase reaction system including an aqueous phase and an organic phase, the organic solvent is preferably a solvent that can form the two-phase system. The organic solvent may be used alone or in combination. Examples of the organic solvent include a hydrocarbon solvent, a halogenated solvent, a fluorous solvent, and the like as described above. The “fluorous solvent” is one type of halogenated solvent, for example, a solvent in which all or most of the hydrogen atoms of the hydrocarbon are substituted with fluorine atoms. The fluorous solvent may be, for example, a solvent in which 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more of the number of hydrogen atoms of the hydrocarbon is substituted with fluorine atoms.
前記炭化水素溶媒としては、特に限定されないが、例えば、ｎ−ヘキサン、シクロヘキサン、ベンゼン、トルエン、ｏ−キシレン、ｍ−キシレン、ｐ−キシレン等が挙げられる。また、例えば、前記炭化水素溶媒が、原料である前記炭化水素を兼ねていても良い。 Although it does not specifically limit as said hydrocarbon solvent, For example, n-hexane, a cyclohexane, benzene, toluene, o-xylene, m-xylene, p-xylene etc. are mentioned. For example, the hydrocarbon solvent may also serve as the hydrocarbon as a raw material.
前記ハロゲン化溶媒としては、特に限定されないが、例えば、塩化メチレン、クロロホルム、四塩化炭素、四臭化炭素、および後述するフルオラス溶媒等が挙げられる。 The halogenated solvent is not particularly limited, and examples thereof include methylene chloride, chloroform, carbon tetrachloride, carbon tetrabromide, and a fluorous solvent described later.
前記フルオラス溶媒の例としては、例えば、下記化学式（Ｆ１）〜（Ｆ６）で表される溶媒等が挙げられ、その中でも、例えば、ＣＦ３（ＣＦ２）４ＣＦ３等が好ましい。フルオラス溶媒を用いることにより、例えば、溶媒自体の反応性が低いために、副反応を抑制または防止できるという利点がある。前記副反応としては、例えば、溶媒の酸化反応、塩素ラジカルによる溶媒の水素引き抜き反応や塩素化反応、および、前記原料（基質）由来のラジカルと溶媒との反応（例えば、前記原料がメタンの場合において、メチルラジカルと溶媒との反応）等が挙げられる。また、フルオラス溶媒は水と混和しにくいことにより、反応系（フルオラス相）と生成物回収系（水相）を分けることができるために、生成物のさらなる酸化反応を抑制する働きがある。 Examples of the fluorous solvent include, for example, solvents represented by the following chemical formulas (F1) to (F6), and among them, for example, CF 3 (CF 2 ) 4 CF 3 is preferable. The use of a fluorous solvent has an advantage that side reactions can be suppressed or prevented, for example, because the reactivity of the solvent itself is low. Examples of the side reaction include a solvent oxidation reaction, a solvent hydrogen abstraction reaction or chlorination reaction with chlorine radicals, and a reaction between a radical derived from the raw material (substrate) and a solvent (for example, when the raw material is methane). And the like). In addition, since the fluorous solvent is difficult to mix with water, the reaction system (fluorus phase) and the product recovery system (aqueous phase) can be separated, and thus has a function of suppressing further oxidation reaction of the product.
なお、前記有機溶媒の沸点については、特に限定されず、適宜選択可能である。前記反応工程において、温度を高温にする必要がある場合は、高沸点溶媒を選択することが好ましい。しかし、本発明の製造方法は、例えば、後述するように、加熱を行なわずに（例えば、常温常圧で）行なうことも可能である。そのような場合は、高沸点溶媒である必要はなく、むしろ、取扱い易さの観点から、沸点があまり高くない溶媒が好ましい。 The boiling point of the organic solvent is not particularly limited and can be appropriately selected. In the reaction step, when the temperature needs to be high, it is preferable to select a high boiling point solvent. However, the production method of the present invention can be performed without heating (for example, at normal temperature and pressure), as will be described later. In such a case, it is not necessary to be a high boiling point solvent, but rather, a solvent having a low boiling point is preferable from the viewpoint of ease of handling.
また、本発明において、「溶媒」（例えば、前記有機相における有機溶媒または前記水相における水）は、原料（前記炭化水素またはその誘導体）、ルイス酸、ブレーンステッド酸、ラジカル発生源等を溶解しても良いが、溶解しなくても良い。例えば、前記原料、ルイス酸、ブレーンステッド酸、ラジカル発生源等が、前記溶媒中に分散したり沈殿したりした状態で本発明の製造方法を行なっても良い。 In the present invention, the “solvent” (for example, the organic solvent in the organic phase or the water in the aqueous phase) dissolves the raw material (the hydrocarbon or a derivative thereof), Lewis acid, Bronsted acid, radical generation source, and the like. However, it does not have to be dissolved. For example, the production method of the present invention may be performed in a state where the raw material, Lewis acid, Bronsted acid, radical generation source, and the like are dispersed or precipitated in the solvent.
前記有機相中における、原料（基質）である前記炭化水素またはその誘導体の濃度は、特に限定されないが、例えば、０．０００１ｍｏｌ／Ｌ以上であっても良く、６０ｍｏｌ／Ｌ以下であっても良い。 The concentration of the hydrocarbon or derivative thereof as a raw material (substrate) in the organic phase is not particularly limited, and may be, for example, 0.0001 mol / L or more, or 60 mol / L or less. .
また、前記有機相は、前記原料（炭化水素またはその誘導体）および前記有機溶媒以外の他の成分を含んでいても良いし、含んでいなくても良い。前記他の成分としては、特に限定されないが、例えば、ブレーンステッド酸、ルイス酸、および酸素（Ｏ２）等が挙げられる。 The organic phase may or may not contain other components than the raw material (hydrocarbon or derivative thereof) and the organic solvent. Examples of the other component is not particularly limited, for example, Bronsted acids, Lewis acids, and oxygen (O 2), and the like.
前記有機相は、前述のように、前記二酸化塩素ラジカルを含む。前記反応系が、前記有機相のみの一相系である場合、例えば、前記二酸化塩素ラジカルを、前記反応系を構成する前記有機相以外で、別途、生成させ、生成した前記ラジカルを前記有機相により抽出してもよい。そして、この抽出した前記二酸化ラジカルを含む前記有機相を、前記反応系として、前記反応工程に供することができる。前記二酸化ラジカルの生成は、例えば、後述するように、別途準備した水相中で行うことができる（二酸化塩素ラジカル生成工程）。他方、前記反応系が、前記有機相と水相とを含む二相系である場合、例えば、前記反応系のうち、前記水相において、前記二酸化塩素ラジカルを生成させ、生成した二酸化塩素ラジカルを、前記有機相において、前記水相から抽出してもよい。そして、前記水相と前記二酸化塩素ラジカルを含む有機相とを含む二相反応系を、前記反応工程に供することができる。 The organic phase contains the chlorine dioxide radical as described above. When the reaction system is a one-phase system only of the organic phase, for example, the chlorine dioxide radical is separately generated other than the organic phase constituting the reaction system, and the generated radical is converted into the organic phase. You may extract by. The extracted organic phase containing the extracted radical dioxide can be used as the reaction system for the reaction step. The generation of the radical dioxide can be performed, for example, in a separately prepared aqueous phase as described later (chlorine dioxide radical generation step). On the other hand, when the reaction system is a two-phase system including the organic phase and the aqueous phase, for example, the chlorine dioxide radical is generated in the aqueous phase of the reaction system, and the generated chlorine dioxide radical is The organic phase may be extracted from the aqueous phase. And the two-phase reaction system containing the said aqueous phase and the organic phase containing the said chlorine dioxide radical can be used for the said reaction process.
（２）水相
つぎに、前記水相について説明する。前述のように、前記反応系は、前記有機相の他に、水相を含む二相反応系でもよい。また、前記反応系が、前記有機相のみの一相系である場合、前述のように、前記二酸化塩素ラジカルの生成のために、別途、前記水相を使用することもできる。
(2) Aqueous phase Next, the said aqueous phase is demonstrated. As described above, the reaction system may be a two-phase reaction system including an aqueous phase in addition to the organic phase. In addition, when the reaction system is a one-phase system including only the organic phase, as described above, the aqueous phase can be separately used for generating the chlorine dioxide radical.
前記水相は、例えば、二酸化塩素ラジカルの発生源を含んでいても良い。前記二酸化塩素ラジカルの発生源としては、例えば、後述するように、亜塩素酸ナトリウム（ＮａＣｌＯ２）等が挙げられる。また、前記水相は、例えば、さらに、ルイス酸およびブレーンステッド酸の少なくとも一方を含んでいても良い。前記水相は、例えば、亜塩素酸イオン（ＣｌＯ２ −）とブレーンステッド酸とを含む。前記水相は、例えば、前記亜塩素酸ナトリウム（ＮａＣｌＯ２）とブレーンステッド酸（例えば塩酸）が水に溶解した水相である。例えば、前記亜塩素酸ナトリウムとブレーンステッド酸が前記水相に溶解した状態で、後述する光照射（反応工程）を開始しても良い。または、前記二酸化塩素ラジカルの発生源が水相に含まれた状態で、前記有機相と前記水相とを接触させ、前記水相に光照射することで前記二酸化塩素ラジカルを発生させても良い。そして、そのまま光照射を続けることで、前記反応工程を行なっても良い。 The aqueous phase may contain a source of chlorine dioxide radicals, for example. Examples of the generation source of the chlorine dioxide radical include sodium chlorite (NaClO 2 ) and the like as described later. The aqueous phase may further contain at least one of a Lewis acid and a Bronsted acid, for example. The aqueous phase contains, for example, chlorite ions (ClO 2 − ) and a brainsted acid. The aqueous phase is, for example, an aqueous phase in which the sodium chlorite (NaClO 2 ) and brainsted acid (eg hydrochloric acid) are dissolved in water. For example, light irradiation (reaction process) described later may be started in a state where the sodium chlorite and the brainsted acid are dissolved in the aqueous phase. Alternatively, the chlorine dioxide radical may be generated by bringing the organic phase into contact with the aqueous phase and irradiating the aqueous phase with light in a state where the generation source of the chlorine dioxide radical is contained in the aqueous phase. . And you may perform the said reaction process by continuing light irradiation as it is.
前記水相は、例えば、前記二酸化塩素ラジカルの発生源を水と混合して製造することができる。また、さらに、前記二酸化塩素ラジカルの発生源および水以外の他の成分を適宜混合しても良いし、しなくても良い。前記他の成分としては、特に限定されないが、例えば、前記ルイス酸、前記ブレーンステッド酸、および前記酸素（Ｏ２）が挙げられる。 The aqueous phase can be produced, for example, by mixing the chlorine dioxide radical source with water. Furthermore, other components other than the chlorine dioxide radical source and water may or may not be mixed as appropriate. Examples of the other component is not particularly limited, for example, the Lewis acid, the Bronsted acids, and the oxygen (O 2) can be mentioned.
前記二酸化塩素ラジカルの発生源は、特に限定されないが、例えば、亜塩素酸（ＨＣｌＯ２）またはその塩である。亜塩素酸の塩としては、特に限定されないが、例えば、金属塩でも良い。前記金属塩は、例えば、アルカリ金属塩、アルカリ土類金属塩、希土類塩等でも良く、より具体的には、例えば、亜塩素酸ナトリウム（ＮａＣｌＯ２）、亜塩素酸リチウム（ＬｉＣｌＯ２）、亜塩素酸カリウム（ＫＣｌＯ２）、亜塩素酸マグネシウム（Ｍｇ（ＣｌＯ２）２）、亜塩素酸カルシウム（Ｃａ（ＣｌＯ２）２）等が挙げられる。これら亜塩素酸およびその塩は、１種類のみ用いても、複数種類併用しても良い。これらの中でも、コスト、取扱い易さ等の観点から、亜塩素酸ナトリウム（ＮａＣｌＯ２）が好ましい。 Although the generation source of the chlorine dioxide radical is not particularly limited, for example, chlorous acid (HClO 2 ) or a salt thereof. Although it does not specifically limit as a salt of chlorous acid, For example, a metal salt may be sufficient. The metal salt may be, for example, an alkali metal salt, an alkaline earth metal salt, a rare earth salt, and more specifically, for example, sodium chlorite (NaClO 2 ), lithium chlorite (LiClO 2 ), Examples include potassium chlorate (KClO 2 ), magnesium chlorite (Mg (ClO 2 ) 2 ), and calcium chlorite (Ca (ClO 2 ) 2 ). These chlorous acid and salts thereof may be used alone or in combination. Among these, sodium chlorite (NaClO 2 ) is preferable from the viewpoints of cost, ease of handling, and the like.
前記水相中において、前記亜塩素酸またはその塩の濃度は、特に限定されないが、亜塩素酸イオン（ＣｌＯ２ −）濃度に換算して、例えば、０．０００１ｍｏｌ／Ｌ以上であっても良く、１ｍｏｌ／Ｌ以下であっても良い。また、前記亜塩素酸イオン（ＣｌＯ２ −）のモル数は、例えば、前記原料（炭化水素またはその誘導体）のモル数の１／１０００００倍以上であっても良く、１０００倍以下であっても良い。 In the aqueous phase, the concentration of chlorous acid or a salt thereof is not particularly limited, but may be, for example, 0.0001 mol / L or more in terms of chlorite ion (ClO 2 − ) concentration. 1 mol / L or less may be sufficient. The number of moles of the chlorite ion (ClO 2 − ) may be, for example, 1 / 100,000 times or more, or 1000 times or less of the number of moles of the raw material (hydrocarbon or derivative thereof). good.
前記ルイス酸およびブレーンステッド酸は、１種類のみ用いても良いし、複数種類併用しても良い。また、ルイス酸およびブレーンステッド酸の一方のみを用いても両方を併用しても良いし、１つの物質がルイス酸およびブレーンステッド酸を兼ねていても良い。なお、本発明において、「ルイス酸」は、例えば、前記二酸化塩素ラジカル発生源に対してルイス酸として働く物質をいう。 Only one type of Lewis acid or Bronsted acid may be used, or a plurality of types may be used in combination. Further, only one of Lewis acid and Bronsted acid may be used or both may be used together, and one substance may also serve as Lewis acid and Bronsted acid. In the present invention, “Lewis acid” refers to, for example, a substance that acts as a Lewis acid for the chlorine dioxide radical generating source.
前記水相中における、前記ルイス酸およびブレーンステッド酸の少なくとも一方の濃度は、特に限定されず、例えば、原料（基質）および目的生成物（酸化反応生成物）の種類等に応じて適宜設定することができるが、例えば、０．０００１ｍｏｌ／Ｌ以上であっても良く、１ｍｏｌ／Ｌ以下であっても良い。 The concentration of at least one of the Lewis acid and the Bronsted acid in the aqueous phase is not particularly limited, and is appropriately set according to, for example, the type of raw material (substrate) and target product (oxidation reaction product). For example, it may be 0.0001 mol / L or more, or 1 mol / L or less.
前記ルイス酸は、例えば、有機物質でも良いし無機物質でも良い。前記有機物質としては、例えば、アンモニウムイオン、有機酸（例えばカルボン酸）等であっても良い。前記無機物質は、金属イオンおよび非金属イオンの一方または両方を含んでいても良い。前記金属イオンは、典型金属イオンおよび遷移金属イオンの一方または両方を含んでいても良い。前記無機物質は、例えば、アルカリ土類金属イオン（例えばＣａ２＋等）、希土類イオン、Ｍｇ２＋、Ｓｃ３＋、Ｌｉ＋、Ｆｅ２＋、Ｆｅ３＋、Ａｌ３＋、ケイ酸イオン、およびホウ酸イオンからなる群から選択される少なくとも一つであっても良い。前記アルカリ土類金属イオンとしては、例えば、カルシウム、ストロンチウム、バリウム、またはラジウムのイオンが挙げられ、より具体的には、例えば、Ｃａ２＋、Ｓｒ２＋、Ｂａ２＋、およびＲａ２＋が挙げられる。また、「希土類」は、スカンジウム２１Ｓｃ、イットリウム３９Ｙの２元素と、ランタン５７Ｌａからルテチウム７１Ｌｕまでの１５元素（ランタノイド）の計１７元素の総称である。希土類イオンとしては、例えば、前記１７元素のそれぞれに対する３価の陽イオンが挙げられる。また、前記ルイス酸のカウンターイオンとしては、例えば、トリフルオロメタンスルホン酸イオン（ＣＦ３ＳＯ３ −、またはＯＴｆ−とも表記する）、トリフルオロ酢酸イオン（ＣＦ３ＣＯＯ−）、酢酸イオン、フッ化物イオン、塩化物イオン、臭化物イオン、ヨウ化物イオン、硫酸イオン、硫酸水素イオン、亜硫酸イオン、硝酸イオン、亜硝酸イオン、リン酸イオン、亜リン酸イオン等が挙げられる。例えば、前記ルイス酸が、スカンジウムトリフレート（Ｓｃ（ＯＴｆ）３）等であっても良い。 The Lewis acid may be an organic substance or an inorganic substance, for example. Examples of the organic substance may include ammonium ions and organic acids (for example, carboxylic acids). The inorganic substance may contain one or both of metal ions and non-metal ions. The metal ion may contain one or both of a typical metal ion and a transition metal ion. The inorganic substance includes, for example, alkaline earth metal ions (for example, Ca 2+ ), rare earth ions, Mg 2+ , Sc 3+ , Li + , Fe 2+ , Fe 3+ , Al 3+ , silicate ions, and borate ions. It may be at least one selected from the group. Examples of the alkaline earth metal ions include calcium, strontium, barium, or radium ions. More specifically, examples include Ca 2+ , Sr 2+ , Ba 2+ , and Ra 2+ . “Rare earth” is a general term for 17 elements in total: 2 elements of scandium 21 Sc and yttrium 39 Y and 15 elements (lanthanoid) from lanthanum 57 La to lutetium 71 Lu. Examples of rare earth ions include trivalent cations for each of the 17 elements. Examples of the counter ion of the Lewis acid include trifluoromethanesulfonate ion (also expressed as CF 3 SO 3 − or OTf − ), trifluoroacetate ion (CF 3 COO − ), acetate ion, fluoride ion. Chloride ion, bromide ion, iodide ion, sulfate ion, hydrogen sulfate ion, sulfite ion, nitrate ion, nitrite ion, phosphate ion, phosphite ion and the like. For example, the Lewis acid may be scandium triflate (Sc (OTf) 3 ) or the like.
また、前記ルイス酸（カウンターイオンも含む）は、例えば、ＡｌＣｌ３、ＡｌＭｅＣｌ２、ＡｌＭｅ２Ｃｌ、ＢＦ３、ＢＰｈ３、ＢＭｅ３、ＴｉＣｌ４、ＳｉＦ４、およびＳｉＣｌ４からなる群から選択される少なくとも一つであっても良い。ただし、「Ｐｈ」はフェニル基を表し、「Ｍｅ」はメチル基を表す。 The Lewis acid (including counter ions) is selected from the group consisting of, for example, AlCl 3 , AlMeCl 2 , AlMe 2 Cl, BF 3 , BPh 3 , BMe 3 , TiCl 4 , SiF 4 , and SiCl 4. There may be at least one. However, “Ph” represents a phenyl group, and “Me” represents a methyl group.
前記ルイス酸のルイス酸性度は、例えば、０．４ｅＶ以上であるが、これには限定されない。前記ルイス酸性度の上限値は、特に限定されないが、例えば、２０ｅＶ以下である。なお、前記ルイス酸性度は、例えば、Ohkubo, K.; Fukuzumi, S. Chem. Eur. J., 2000, 6, 4532、J. AM. CHEM. SOC. 2002, 124, 10270-10271、またはJ. Org. Chem. 2003, 68, 4720-4726に記載の方法により測定することができ、具体的には、下記の方法により測定することができる。 The Lewis acidity of the Lewis acid is, for example, 0.4 eV or more, but is not limited thereto. The upper limit of the Lewis acidity is not particularly limited, but is, for example, 20 eV or less. The Lewis acidity is, for example, Ohkubo, K .; Fukuzumi, S. Chem. Eur. J., 2000, 6, 4532, J. AM. CHEM. SOC. 2002, 124, 10270-10271, or J Org. Chem. 2003, 68, 4720-4726, and specifically, can be measured by the following method.
（ルイス酸性度の測定方法）
下記化学反応式（１ａ）中のコバルトテトラフェニルポルフィリン、飽和Ｏ２およびルイス酸性度の測定対象物（例えば金属等のカチオンであり、下記化学反応式（１ａ）ではＭｎ＋で表される）を含むアセトニトリル（ＭｅＣＮ）を、室温において紫外可視吸収スペクトル変化の測定をする。得られた反応速度定数（kcat）からルイス酸性度の指標であるΔＥ値（ｅＶ）を算出することができる。kcatの値は大きいほど強いルイス酸性度を示す。また、有機化合物のルイス酸性度は、量子化学計算によって算出される最低空軌道（LUMO）のエネルギー準位からも、見積もることができる。正側に大きい値であるほど強いルイス酸性度を示す。
(Measurement method of Lewis acidity)
In the following chemical reaction formula (1a), cobalt tetraphenylporphyrin, saturated O 2 and Lewis acidity measurement objects (for example, cations such as metals, etc., represented by M n + in the following chemical reaction formula (1a)) Acetonitrile (MeCN) containing is measured for ultraviolet-visible absorption spectrum change at room temperature. From the obtained reaction rate constant (k cat ), a ΔE value (eV) that is an index of Lewis acidity can be calculated. The larger the k cat value, the stronger the Lewis acidity. The Lewis acidity of an organic compound can also be estimated from the lowest empty orbit (LUMO) energy level calculated by quantum chemical calculation. A larger value on the positive side indicates stronger Lewis acidity.
前記ブレーンステッド酸としては、特に限定されないが、例えば、無機酸でも有機酸でも良く、例えば、トリフルオロメタンスルホン酸、トリフルオロ酢酸、酢酸、フッ化水素酸、塩化水素酸、臭化水素酸、ヨウ化水素酸、硫酸、亜硫酸、硝酸、亜硝酸、リン酸、亜リン酸等が挙げられる。前記ブレーンステッド酸の酸解離定数ｐＫａは、例えば１０以下である。前記ｐＫａの下限値は、特に限定されないが、例えば、−１０以上である。 The brainsted acid is not particularly limited, and may be, for example, an inorganic acid or an organic acid. For example, trifluoromethanesulfonic acid, trifluoroacetic acid, acetic acid, hydrofluoric acid, hydrochloric acid, hydrobromic acid, iodine Examples include hydrofluoric acid, sulfuric acid, sulfurous acid, nitric acid, nitrous acid, phosphoric acid, phosphorous acid, and the like. Acid dissociation constant pK a of the Bronsted acid is, for example, 10 or less. The lower limit of the pK a is not particularly limited, for example, it is -10 or more.
前記酸素（Ｏ２）については、例えば、前記二酸化塩素ラジカル発生源、前記ルイス酸、前記ブレーンステッド酸、反応基質（原料）等を加える前または加えた後の水中および有機相の少なくとも一方に、空気または酸素ガスを吹き込むことにより、酸素を溶解させても良い。このとき、例えば、前記水中を、酸素（Ｏ２）で飽和させても良い。前記水相および有機相の少なくとも一方が前記酸素（Ｏ２）を含むことで、例えば、原料（基質）である前記炭化水素またはその誘導体の酸化反応をさらに促進させることができる。 About the oxygen (O 2 ), for example, at least one of water and an organic phase before or after adding the chlorine dioxide radical generating source, the Lewis acid, the Brainsted acid, the reaction substrate (raw material), etc. Oxygen may be dissolved by blowing air or oxygen gas. At this time, for example, the water may be saturated with oxygen (O 2 ). When at least one of the aqueous phase and the organic phase contains the oxygen (O 2 ), for example, the oxidation reaction of the hydrocarbon or its derivative as the raw material (substrate) can be further promoted.
なお、本発明において、前記水相における水は、前述のとおり、ルイス酸、ブレーンステッド酸、ラジカル発生源等を溶解しても良いが、溶解しなくても良い。例えば、ルイス酸、ブレーンステッド酸、ラジカル発生源等が、水中に分散したり沈殿したりした状態で本発明の製造方法を行なっても良い。 In the present invention, as described above, the water in the aqueous phase may dissolve the Lewis acid, the brainsted acid, the radical generation source, or the like, but may not dissolve it. For example, the production method of the present invention may be carried out in a state where a Lewis acid, a Bronsted acid, a radical source or the like is dispersed or precipitated in water.
［３．二酸化塩素ラジカル生成工程］
つぎに、本発明の製造方法において、前述のとおり、前記二酸化塩素ラジカルを生成させる二酸化塩素ラジカル生成工程を行なっても良い。
[3. Chlorine dioxide radical generation process]
Next, in the production method of the present invention, as described above, a chlorine dioxide radical generating step for generating the chlorine dioxide radical may be performed.
前記二酸化塩素ラジカル生成工程は、特に限定されないが、例えば、前記二酸化塩素ラジカル発生源（例えば、亜塩素酸またはその塩）を水に溶解させて静置し、亜塩素酸イオンから二酸化塩素ラジカルを自然発生させることで行なうことができる。このとき、例えば、前記水中に前記ルイス酸およびブレーンステッド酸の少なくとも一方が存在することで、二酸化塩素ラジカルの発生がさらに促進される。また、例えば、前述のとおり、前記水相に光照射することで前記二酸化塩素ラジカルを発生させても良い。しかしながら、前述のとおり、光照射せずに単に静置するのみでも、二酸化塩素ラジカルを発生させることができる。 The chlorine dioxide radical generation step is not particularly limited. For example, the chlorine dioxide radical generation source (for example, chlorous acid or a salt thereof) is dissolved in water and allowed to stand, and chlorine dioxide radicals are generated from chlorite ions. This can be done by generating naturally. At this time, for example, the presence of at least one of the Lewis acid and the Bronsted acid in the water further promotes the generation of chlorine dioxide radicals. Further, for example, as described above, the chlorine dioxide radical may be generated by irradiating the water phase with light. However, as described above, chlorine dioxide radicals can be generated by simply standing without irradiation.
水中において亜塩素酸イオンから二酸化塩素ラジカルが発生するメカニズム（機構）については、例えば、下記スキーム１のように推測される。ただし、下記スキーム１は、推測されるメカニズムの一例であり、本発明をなんら限定しない。下記スキーム１の第１の（上段の）反応式は、亜塩素酸イオン（ＣｌＯ２ −）の不均化反応であり、水中にルイス酸およびブレーンステッド酸の少なくとも一方が存在することで、平衡が右側に移動しやすくなると考えられる。下記スキーム１中の第２の（中段の）反応式は、二量化反応であり、第１の反応式で生成した次亜塩素酸イオン（ＣｌＯ−）と亜塩素酸イオンが反応して二酸化二塩素（Ｃｌ２Ｏ２）を生成する。この反応は、水中にプロトンＨ＋が多いほど、すなわち酸性であるほど進行しやすいと考えられる。下記スキーム１中の第３の（下段の）反応式は、ラジカル生成である。この反応では、第２の反応式で生成した二酸化二塩素が、亜塩素酸イオンと反応して二酸化塩素ラジカルを生成する。 About the mechanism (mechanism) which chlorine dioxide radical generate | occur | produces from chlorite ion in water, it presumes like the following scheme 1, for example. However, the following scheme 1 is an example of a presumed mechanism and does not limit the present invention. The first (top) reaction formula of the following scheme 1 is a disproportionation reaction of chlorite ion (ClO 2 − ), and at least one of Lewis acid and Bronsted acid is present in water. Is considered to be easier to move to the right. The second (middle stage) reaction formula in the following scheme 1 is a dimerization reaction, and a hypochlorite ion (ClO − ) and a chlorite ion generated in the first reaction formula react with each other. Chlorine (Cl 2 O 2 ) is produced. This reaction is considered to proceed more easily as the amount of proton H + in water increases, that is, the more acidic. The third (lower) reaction formula in the following scheme 1 is radical generation. In this reaction, dichlorine dioxide produced in the second reaction formula reacts with chlorite ions to produce chlorine dioxide radicals.
次工程の反応工程において、前記有機相と前記水相とを含む二相反応系を使用する場合は、例えば、前記二相反応系において前記二酸化塩素ラジカルを発生させた後、前記反応系をそのまま反応工程に供すればよい。また、次工程の反応工程において、前記有機相のみを含む一相反応系を使用する場合は、例えば、前記水相で前記二酸化塩素ラジカルを発生させ、発生した前記二酸化塩素ラジカルを前記有機相に抽出した後、前記水相を除去し、二酸化塩素ラジカルを含む前記有機相を前記一相反応系として、反応工程に供すればよい。 When using a two-phase reaction system including the organic phase and the aqueous phase in the reaction step of the next step, for example, after generating the chlorine dioxide radical in the two-phase reaction system, the reaction system is left as it is. What is necessary is just to use for a reaction process. Further, when using a one-phase reaction system including only the organic phase in the reaction step of the next step, for example, the chlorine dioxide radical is generated in the aqueous phase, and the generated chlorine dioxide radical is converted into the organic phase. After the extraction, the aqueous phase is removed, and the organic phase containing chlorine dioxide radicals may be used for the reaction step as the one-phase reaction system.
［４．反応工程］
つぎに、前記反応工程を行なう。以下、前記反応工程に使用する前記反応系として、前記有機相と前記水相とを含む二相反応系を例にあげて説明する。
[4. Reaction process]
Next, the reaction step is performed. Hereinafter, as the reaction system used in the reaction step, a two-phase reaction system including the organic phase and the aqueous phase will be described as an example.
まず、前記反応工程を行なうに先立ち、前記水相と前記有機相との二相を接触させる。このとき、前記水相と前記有機相とを混合してエマルジョン等の状態にしても良い。しかし、これに代えて、単に、水層（前記水相）と有機層（前記有機相）との二層が分離し、互いに界面のみで接触した状態で、前記反応工程を行なっても良い。 First, prior to performing the reaction step, the two phases of the aqueous phase and the organic phase are brought into contact. At this time, the aqueous phase and the organic phase may be mixed to form an emulsion or the like. However, instead of this, the reaction step may be performed in a state where two layers of the aqueous layer (the aqueous phase) and the organic layer (the organic phase) are separated and are in contact with each other only at the interface.
つぎに、前記反応工程では、例えば、前述のとおり、前記有機相に光照射する。前記有機相中の二酸化塩素ラジカル（ＣｌＯ２ ・）に光照射した場合、例えば、図１のようになると予測される。図１は、UCAM-B3LYP/6-311+G(d,p) def2TZVによる計算結果である。図１の左側は、光照射する前の二酸化塩素ラジカル（ＣｌＯ２ ・）分子の状態を表し、右側は、光照射後の状態を表す。図示のとおり、光照射前は塩素原子Ｃｌに２つの酸素原子Ｏがそれぞれ結合し、Ｃｌ−Ｏの結合長は１．５０２Å（０．１５０２ｎｍ）である。これに対し、光照射後は、一方の酸素原子Ｏのみが塩素原子Ｃｌに結合し、Ｃｌ−Ｏの結合長は２．５１６Å（０．２５１６ｎｍ）となり、他方の酸素原子は前記一方の酸素原子に結合した状態となる。これにより、Ｃｌ−Ｏ結合が切断されて塩素ラジカル（Ｃｌ・）および酸素分子（Ｏ２）が発生すると考えられる。ただし、図１は、計算結果による予測の一例であり、本発明をなんら限定しない。 Next, in the reaction step, for example, as described above, the organic phase is irradiated with light. The case of light irradiation to chlorine dioxide radicals in the organic phase (ClO 2 ·), for example, is expected to be as shown in Figure 1. FIG. 1 shows a calculation result by UCAM-B3LYP / 6-311 + G (d, p) def2TZV. Left side of FIG. 1 represents a state before the chlorine dioxide radical (ClO 2 ·) molecules that light irradiation, the right side represents the state after the light irradiation. As shown in the figure, two oxygen atoms O are bonded to chlorine atom Cl before light irradiation, and the bond length of Cl—O is 1.502１．５ (0.1502 nm). On the other hand, after light irradiation, only one oxygen atom O is bonded to the chlorine atom Cl, and the bond length of Cl—O is 2.516Å (0.2516 nm), and the other oxygen atom is the one oxygen atom. It will be in the state connected to. Thus, Cl-O bond is cleaved believed chlorine radical (Cl ·) and oxygen molecules (O 2) is generated. However, FIG. 1 is an example of prediction based on the calculation result, and does not limit the present invention.
図２に、前記反応工程の一例を模式的に示す。図示のとおり、この反応系は、反応容器中において、水層（前記水相）と有機層（前記有機相）との二層が分離し、互いに界面のみで接触している。上層が、水層（前記水相）２であり、下層が、有機層（前記有機相）１である。なお、図２は断面図であるが、見やすさのために、水層及び有機層のハッチは省略している。図示のとおり、水層（水相）中の亜塩素酸イオン（ＣｌＯ２ −）が酸と反応して、二酸化塩素ラジカル（ＣｌＯ２ ・）が発生する。二酸化塩素ラジカル（ＣｌＯ２ ・）は水に難溶であるため、有機層中に溶解する。つぎに、二酸化塩素ラジカル（ＣｌＯ２ ・）を含む有機層に光照射し、光エネルギーｈν（ｈはプランク定数、νは光の振動数）を与えることで、有機層中の二酸化塩素ラジカル（ＣｌＯ２ ・）が分解して塩素ラジカル（Ｃｌ・）および酸素分子（Ｏ２）が発生する。これにより、有機層（有機相）中の基質（原料、図中において符号ＲＨで表す）が酸化され、酸化反応生成物であるアルコール（図中において、符号Ｒ−ＯＨで表す）を生成する。アルコールは水溶性であるため、水層中に溶解する。ただし、図２は例示であって、本発明をなんら限定しない。例えば、図２は、酸化反応生成物が水溶性のアルコールである例を示しているが、前述のとおり、酸化反応生成物は水溶性のアルコールに限定されず、任意である。また、図２において、有機層（有機相）中の有機溶媒は、例えば、フルオラス溶媒であっても良いが、前記有機溶媒は、前述のとおり、フルオラス溶媒に限定されず、任意である。また、図２では、水層が上層で有機層が下層であるが、例えば、有機層の方が密度（比重）が低い場合は、有機層が上層になる。さらに、本発明の製造方法は、図２のように層分離した状態に限定されず、例えば、前述のとおり、エマルジョン等の状態で行っても良いし、撹拌等をしながら行なうこともできる。 FIG. 2 schematically shows an example of the reaction step. As shown in the figure, in this reaction system, two layers of an aqueous layer (the aqueous phase) and an organic layer (the organic phase) are separated in a reaction vessel and are in contact with each other only at the interface. The upper layer is an aqueous layer (the aqueous phase) 2 and the lower layer is an organic layer (the organic phase) 1. Although FIG. 2 is a cross-sectional view, the hatch of the water layer and the organic layer is omitted for easy viewing. As shown, the water layer chlorite ions (aqueous phase) in (ClO 2 -) reacts with the acid, chlorine dioxide radical (ClO 2 ·) is generated. Since chlorine dioxide radical (ClO 2 ·) is sparingly soluble in water, dissolved in an organic layer. Next, light irradiation to the organic layer containing the chlorine dioxide radical (ClO 2 ·), light energy hv (h is Planck's constant, [nu is the frequency of the light) to provide a chlorine dioxide radicals in the organic layer (ClO 2 · ) decomposes to generate chlorine radicals (Cl · ) and oxygen molecules (O 2 ). As a result, the substrate (raw material, represented by symbol RH in the figure) in the organic layer (organic phase) is oxidized to produce an alcohol (represented by symbol R-OH in the figure) which is an oxidation reaction product. Since alcohol is water-soluble, it dissolves in the aqueous layer. However, FIG. 2 is an illustration and does not limit the present invention. For example, FIG. 2 shows an example in which the oxidation reaction product is a water-soluble alcohol, but as described above, the oxidation reaction product is not limited to a water-soluble alcohol and is arbitrary. In FIG. 2, the organic solvent in the organic layer (organic phase) may be, for example, a fluorous solvent. However, as described above, the organic solvent is not limited to the fluorous solvent and is arbitrary. In FIG. 2, the aqueous layer is the upper layer and the organic layer is the lower layer. For example, when the organic layer has a lower density (specific gravity), the organic layer is the upper layer. Furthermore, the production method of the present invention is not limited to the layer-separated state as shown in FIG. 2. For example, as described above, the production method may be performed in an emulsion state or the like, or may be performed with stirring.
前記反応工程において、照射光の波長は特に限定されないが、例えば、２００ｎｍ以上、であっても良く、８００ｎｍ以下であっても良い。光照射時間も特に限定されないが、例えば、１ｍｉｎ以上であっても良く、１０００ｈ以下であっても良い。反応温度も特に限定されないが、例えば、０℃以上であっても良く、１００℃以下であっても良い。反応時の雰囲気圧も特に限定されないが、例えば、０．１ＭＰａ以上であっても良く、１００ＭＰａ以下であっても良い。本発明によれば、例えば、後述の実施例に示すように、加熱、加圧、減圧等を一切行わずに、常温（室温）および常圧（大気圧）下で、前記反応工程またはそれを含めた全ての工程を行なうことも可能である。なお、「室温」とは、特に限定されないが、例えば、５〜３５℃である。また、本発明によれば、例えば、後述の実施例に示すように、不活性ガス置換等を行なわずに、大気中で、前記反応工程またはそれを含めた全ての工程を行なうことも可能である。 In the reaction step, the wavelength of the irradiation light is not particularly limited, but may be, for example, 200 nm or more, or 800 nm or less. The light irradiation time is not particularly limited, but may be, for example, 1 min or more, or 1000 h or less. The reaction temperature is not particularly limited, but may be, for example, 0 ° C. or higher, or 100 ° C. or lower. The atmospheric pressure during the reaction is not particularly limited, but may be, for example, 0.1 MPa or more, or 100 MPa or less. According to the present invention, for example, as shown in the examples below, the reaction step or the reaction step is performed at room temperature (room temperature) and normal pressure (atmospheric pressure) without any heating, pressurization, decompression or the like. It is also possible to carry out all the steps including. The “room temperature” is not particularly limited, but is, for example, 5 to 35 ° C. Further, according to the present invention, for example, the reaction step or all the steps including it can be performed in the atmosphere without performing inert gas replacement or the like, as shown in the examples described later. is there.
前記光照射において、光源は特に限定されないが、例えば、太陽光等の自然光に含まれる可視光を利用すれば、簡便に励起可能である。また、例えば、前記自然光に代えて、またはこれに加え、キセノンランプ、ハロゲンランプ、蛍光灯、水銀ランプ等の光源を適宜用いても良いし、用いなくても良い。さらに、必要波長以外の波長をカットするフィルターを適宜用いても良いし、用いなくても良い。 In the light irradiation, the light source is not particularly limited, but can be easily excited by using visible light included in natural light such as sunlight. Further, for example, instead of or in addition to the natural light, a light source such as a xenon lamp, a halogen lamp, a fluorescent lamp, or a mercury lamp may or may not be used as appropriate. Furthermore, a filter that cuts wavelengths other than the necessary wavelength may or may not be used as appropriate.
エタンの酸化反応によりエタノールが生成されるメカニズム（機構）は、例えば、下記スキーム２のように推測される。ただし、下記スキーム２は、推測されるメカニズムの一例であり、本発明をなんら限定しない。下記スキーム２について具体的に説明すると、まず、図１でも示したように、二酸化塩素ラジカルが光照射により分解されて塩素ラジカル（Ｃｌ・）と酸素分子（Ｏ２）が発生する。前記塩素ラジカルは、エタンに対して水素引き抜き剤として働いてエチルラジカル（ＣＨ３ＣＨ２ ・）を発生させる。そして、前記酸素分子が、下記スキーム２に示すようにして前記エチルラジカルを酸化してエタノールを生成させる。 The mechanism (mechanism) by which ethanol is generated by the oxidation reaction of ethane is estimated as shown in the following scheme 2, for example. However, the following scheme 2 is an example of a presumed mechanism and does not limit the present invention. Specifically described below Scheme 2, first, as shown also in FIG. 1, the chlorine radical (Cl ·) and oxygen molecules (O 2) is generated chlorine radical dioxide is decomposed by light irradiation. The chlorine radicals generates an ethyl radical works as a hydrogen abstracting agent (CH 3 CH 2 ·) with respect to ethane. The oxygen molecules oxidize the ethyl radicals to produce ethanol as shown in Scheme 2 below.
また、亜塩素酸ナトリウムを用いて、メタンの酸化反応によりメタノールおよびギ酸が生成される場合の反応式は、例えば、下記スキーム３のようになる。ただし、下記スキーム３も一例であって、本発明を用いたメタンの酸化反応は、これに限定されない。 Moreover, the reaction formula in the case where methanol and formic acid are produced by the oxidation reaction of methane using sodium chlorite is, for example, as shown in Scheme 3 below. However, the following scheme 3 is also an example, and the oxidation reaction of methane using the present invention is not limited to this.
メタンの酸化反応によりメタノールが生成されるメカニズム（機構）は、例えば、下記スキーム４のように推測される。ただし、下記スキーム４は、推測されるメカニズムの一例であり、本発明をなんら限定しない。下記スキーム４について具体的に説明すると、エタンからエタノールが生成する場合（スキーム２）と同様に、まず、二酸化塩素ラジカルが光照射により分解されて塩素ラジカル（Ｃｌ・）と酸素分子（Ｏ２）が発生する。前記塩素ラジカルは、メタンに対して水素引き抜き剤として働いてメチルラジカル（ＣＨ３ ・）を発生させる。そして、前記酸素分子が、下記スキーム４に示すようにして前記メチルラジカルを酸化してメタノールを生成させる。 The mechanism (mechanism) by which methanol is generated by the oxidation reaction of methane is estimated as shown in Scheme 4 below, for example. However, the following scheme 4 is an example of a presumed mechanism and does not limit the present invention. Specifically described below Scheme 4, if the ethanol is produced from ethane in the same manner as (Scheme 2), first, the chlorine radicals are decomposed by chlorine radicals dioxide irradiation (Cl ·) and oxygen molecules (O 2) Will occur. The chlorine radicals may act as hydrogen-abstracting agent to generate methyl radicals (CH 3 ·) with respect to methane. Then, the oxygen molecules oxidize the methyl radicals to produce methanol as shown in Scheme 4 below.
また、本発明において、前記原料（基質）は、エタンまたはメタンのみに限定されず、前述のとおり、任意の炭化水素またはその誘導体であっても良い。原料（基質）である前記炭化水素またはその誘導体の例については、例えば、前述のとおりである。 In the present invention, the raw material (substrate) is not limited to ethane or methane, and may be any hydrocarbon or derivative thereof as described above. Examples of the hydrocarbon or a derivative thereof as a raw material (substrate) are as described above, for example.
本発明において、例えば、下記スキームＡのように、前記原料が下記化学式（Ａ１）で表され、その酸化反応生成物が、下記化学式（Ａ２）で表されるアルコールと、下記化学式（Ａ３）で表されるカルボン酸との少なくとも一方であっても良い。下記スキームＡにおいて、Ｒは、任意の原子または原子団であり、例えば、水素原子、炭化水素基またはその誘導体である。前記炭化水素基は任意であり、例えば、直鎖状でも分枝状でも、飽和でも不飽和でも、環状構造を含んでいても含んでいなくても良く、前記環状構造は、芳香環でも非芳香環でも良い。また、例えば、下記スキームＡにおいて、酸化反応生成物が、アルコールおよびカルボン酸の少なくとも一方に加え、またはそれに代えて、アルデヒドを含んでいても良い。 In the present invention, for example, as shown in the following scheme A, the raw material is represented by the following chemical formula (A1), and the oxidation reaction product is an alcohol represented by the following chemical formula (A2) and the following chemical formula (A3). It may be at least one of the represented carboxylic acids. In the following scheme A, R is an arbitrary atom or atomic group, for example, a hydrogen atom, a hydrocarbon group, or a derivative thereof. The hydrocarbon group is arbitrary, and may be, for example, linear, branched, saturated or unsaturated, and may or may not contain a cyclic structure. An aromatic ring may be used. Further, for example, in the following scheme A, the oxidation reaction product may contain an aldehyde in addition to or instead of at least one of the alcohol and the carboxylic acid.
前記スキームＡにおいて、原料（基質）（Ａ１）がメタンである場合、例えば、下記スキームＡ１のように、酸化反応生成物が、メタノールおよびギ酸の少なくとも一方を含んでいても良い。また、原料（基質）（Ａ１）がエタンである場合、例えば、下記スキームＡ２のように、酸化反応生成物が、エタノールおよび酢酸の少なくとも一方を含んでいても良い。ただし、下記スキームＡ１およびＡ２も例示であり、本発明の製造方法において、メタンまたはエタンの酸化反応は、これに限定されない。 In the scheme A, when the raw material (substrate) (A1) is methane, for example, as shown in the following scheme A1, the oxidation reaction product may contain at least one of methanol and formic acid. When the raw material (substrate) (A1) is ethane, for example, the oxidation reaction product may contain at least one of ethanol and acetic acid as shown in the following scheme A2. However, the following schemes A1 and A2 are also exemplary, and in the production method of the present invention, the oxidation reaction of methane or ethane is not limited thereto.
また、例えば、下記スキームＢのように、前記原料が下記化学式（Ｂ１）で表され、その酸化反応生成物が、下記化学式（Ｂ２）で表されるアルコールと、下記化学式（Ｂ３）で表されるカルボニル化合物（例えばケトン）との少なくとも一方であっても良い。下記スキームＢにおいて、Ｒは、任意の原子または原子団であり、例えば、炭化水素基またはその誘導体である。前記炭化水素基は任意であり、例えば、直鎖状でも分枝状でも、飽和でも不飽和でも、環状構造を含んでいても含んでいなくても良く、前記環状構造は、芳香環でも非芳香環でも良い。各Ｒは、互いに同一でも異なっていても良い。また、例えば、下記化学式（Ｂ１）、（Ｂ２）および（Ｂ３）のそれぞれにおいて、２つのＲが一体となって、それらが結合する炭素原子とともに環状構造を形成していても良い。 For example, as shown in the following scheme B, the raw material is represented by the following chemical formula (B1), and the oxidation reaction product is represented by the alcohol represented by the following chemical formula (B2) and the following chemical formula (B3). It may be at least one of a carbonyl compound (for example, ketone). In the following scheme B, R is any atom or atomic group, for example, a hydrocarbon group or a derivative thereof. The hydrocarbon group is arbitrary, and may be, for example, linear, branched, saturated or unsaturated, and may or may not contain a cyclic structure. An aromatic ring may be used. Each R may be the same as or different from each other. In addition, for example, in each of the following chemical formulas (B1), (B2), and (B3), two Rs may be integrated to form a cyclic structure together with the carbon atom to which they are bonded.
前記スキームＢにおいて、原料（基質）（Ｂ１）がシクロヘキサンである場合、例えば、下記スキームＢ１のように、酸化反応生成物が、シクロヘキサノールおよびシクロヘキサノンの少なくとも一方を含んでいても良い。ただし、下記スキームＢ１も例示であり、本発明の製造方法において、シクロヘキサンの酸化反応は、これに限定されない。 In the scheme B, when the raw material (substrate) (B1) is cyclohexane, the oxidation reaction product may contain at least one of cyclohexanol and cyclohexanone, for example, as in the following scheme B1. However, the following scheme B1 is also an example, and in the production method of the present invention, the oxidation reaction of cyclohexane is not limited thereto.
本発明において、例えば、下記スキームＣのように、前記原料が下記化学式（Ｃ１）で表される芳香族化合物であり、その酸化反応生成物が、下記化学式（Ｃ２）で表されるフェノールと、下記化学式（Ｃ３）で表されるキノンとの少なくとも一方であっても良い。下記スキームＣにおいて、各Ｒは、任意の原子または原子団であり、例えば、水素原子、炭化水素基またはその誘導体である。前記炭化水素基は任意であり、例えば、直鎖状でも分枝状でも、飽和でも不飽和でも、環状構造を含んでいても含んでいなくても良く、前記環状構造は、芳香環でも非芳香環でも良い。各Ｒは、互いに同一でも異なっていても良い。また、例えば、下記化学式（Ｃ１）、（Ｃ２）および（Ｃ３）のそれぞれにおいて、２つ以上のＲが一体となって、それらが結合するベンゼン環とともに環状構造を形成していても良い。ただし、下記スキームＣは例示であって、本発明を限定しない。すなわち、前述のとおり、本発明の製造方法において、原料（基質）である芳香族化合物は、下記化学式（Ｃ１）には限定されないし、前記芳香族化合物の酸化反応生成物も、下記（Ｃ２）および（Ｃ３）には限定されない。 In the present invention, for example, as in the following scheme C, the raw material is an aromatic compound represented by the following chemical formula (C1), and the oxidation reaction product thereof is phenol represented by the following chemical formula (C2): It may be at least one of quinones represented by the following chemical formula (C3). In the following scheme C, each R is an arbitrary atom or atomic group, for example, a hydrogen atom, a hydrocarbon group, or a derivative thereof. The hydrocarbon group is arbitrary, and may be, for example, linear, branched, saturated or unsaturated, and may or may not contain a cyclic structure. An aromatic ring may be used. Each R may be the same as or different from each other. In addition, for example, in each of the following chemical formulas (C1), (C2), and (C3), two or more Rs may be integrated to form a cyclic structure with a benzene ring to which they are bonded. However, the following scheme C is an example and does not limit the present invention. That is, as described above, in the production method of the present invention, the aromatic compound as the raw material (substrate) is not limited to the following chemical formula (C1), and the oxidation reaction product of the aromatic compound is also the following (C2). And (C3) is not limited.
前記スキームＣにおいて、原料（基質）（Ｃ１）がベンゼンである場合、例えば、下記スキームＡ１のように、酸化反応生成物が、ヒドロキシベンゼンおよびｐ−ベンゾキノンの少なくとも一方を含んでいても良い。ただし、下記スキームＣ１も例示であり、本発明の製造方法において、ベンゼンの酸化反応は、これに限定されない。 In the scheme C, when the raw material (substrate) (C1) is benzene, for example, as shown in the following scheme A1, the oxidation reaction product may contain at least one of hydroxybenzene and p-benzoquinone. However, the following scheme C1 is also an example, and in the production method of the present invention, the oxidation reaction of benzene is not limited thereto.
なお、前記原料（基質）が芳香族化合物である場合、前記芳香族化合物の芳香環に電子供与基が結合していると、例えば、前記原料芳香族化合物の酸化反応（酸化的置換反応を含む）が進行しやすいため好ましい。前記電子供与基は、１つでも複数でも良く、電子供与性の強いものが好ましい。より具体的には、前記原料芳香族化合物は、芳香環に、−ＯＲ１００、−ＮＲ２００ ２、およびＡｒ１００からなる群から選択される少なくとも一つの置換基が共有結合していることがより好ましい。前記Ｒ１００は、水素原子または任意の置換基であり、Ｒ１００が複数の場合は、各Ｒ１００は同一でも異なっていてもよい。前記Ｒ２００は、水素原子または任意の置換基であり、各Ｒ２００は同一でも異なっていてもよい。前記Ａｒ１００は、アリール基であり、Ａｒ１００が複数の場合は、各Ａｒ１００は同一でも異なっていてもよい。 When the raw material (substrate) is an aromatic compound, if an electron donating group is bonded to the aromatic ring of the aromatic compound, for example, an oxidation reaction (including an oxidative substitution reaction) of the raw material aromatic compound ) Is easy to proceed. One or a plurality of the electron donating groups may be used, and those having a strong electron donating property are preferred. More specifically, in the raw material aromatic compound, at least one substituent selected from the group consisting of —OR 100 , —NR 200 2 , and Ar 100 is covalently bonded to the aromatic ring. preferable. Wherein R 100 is a hydrogen atom or an arbitrary substituent, if R 100 is plural, each R 100 is may be the same or different. The R 200 is a hydrogen atom or an arbitrary substituent, and each R 200 may be the same or different. Wherein Ar 100 is an aryl group, if Ar 100 is a plurality, each Ar 100 may be the same or different.
前記Ａｒ１００は、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、ピリジン環、チオフェン環、ピレン環等の任意の芳香環から誘導される基であって良い。前記芳香環は環上にさらに１または複数の置換基を有していても良く、前記置換基は、複数の場合は同一でも異なっていても良い。前記Ａｒ１００は、例えば、フェニル基等が挙げられる。 The Ar 100 may be a group derived from any aromatic ring such as a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, pyridine ring, thiophene ring, pyrene ring. The aromatic ring may further have one or more substituents on the ring, and the plurality of substituents may be the same or different when there are a plurality. Examples of Ar 100 include a phenyl group.
また、前記Ｒ１００は、水素原子、アルキル基、アリール基、およびアシル基からなる群から選択される少なくとも一つであることが好ましい。前記アルキル基は、炭素数１〜６の直鎖もしくは分子アルキル基が好ましく、メチル基が特に好ましい。前記アシル基は、炭素数１〜６の直鎖もしくは分子アシル基が好ましい。前記アリール基は、例えば、前記Ａｒ１００と同様であり、例えばフェニル基である。 The R 100 is preferably at least one selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, and an acyl group. The alkyl group is preferably a linear or molecular alkyl group having 1 to 6 carbon atoms, and particularly preferably a methyl group. The acyl group is preferably a linear or molecular acyl group having 1 to 6 carbon atoms. The aryl group is the same as Ar 100 , for example, and is a phenyl group, for example.
また、前記Ｒ２００は、水素原子、アルキル基、アリール基、およびアシル基からなる群から選択される少なくとも一つであることが好ましい。前記アルキル基は、炭素数１〜６の直鎖もしくは分子アルキル基が好ましく、メチル基が特に好ましい。前記アシル基は、炭素数１〜６の直鎖もしくは分子アシル基が好ましい。前記アリール基は、例えば、前記Ａｒ１００と同様であり、例えばフェニル基である。前記−ＮＲ２００ ２としては、ジメチルアミノ基、ジフェニルアミノ基等、電子供与製置換基で置換されたアミノ基が、特に電子供与性が高いため好ましい。 In addition, R 200 is preferably at least one selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, and an acyl group. The alkyl group is preferably a linear or molecular alkyl group having 1 to 6 carbon atoms, and particularly preferably a methyl group. The acyl group is preferably a linear or molecular acyl group having 1 to 6 carbon atoms. The aryl group is the same as Ar 100 , for example, and is a phenyl group, for example. As the -NR 200 2, dimethylamino group, diphenylamino group, an amino group substituted with an electron donating made substituent is particularly preferable because of their high electron donating property.
また、原料（基質）である前記芳香族化合物は、例えば、芳香環にアルキル基等の置換基が共有結合しており、前記置換基を、前記反応工程により酸化しても良い。例えば、前記酸化剤が酸素原子を含み、前記芳香族化合物が、芳香環に共有結合したメチレン基（−ＣＨ２−）を含み、前記反応工程において、前記メチレン基（−ＣＨ２−）を酸化してカルボニル基（−ＣＯ−）に変換しても良い。この場合において、前記メチレン基およびカルボニル基に結合している原子または原子団は、特に制限されないが、水素原子、アルキル基、アリール基等が挙げられる。前記アルキル基は、炭素数１〜６の直鎖もしくは分枝アルキル基が好ましい。前記アルキル基、アリール基は、さらに１または複数の置換基で置換されていても良く、前記置換基は、複数の場合は同一でも異なっていても良い。例えば、前記メチレン基に水素が結合していれば、メチル基（−ＣＨ３）となり、酸化後はホルミル基（−ＣＨＯ）となる。前記メチレン基にメチル基が結合していれば、エチル基（−ＣＨ２ＣＨ３）となり、酸化後はアセチル基（−ＣＯＣＨ３）となる。前記メチレン基にフェニル基が結合していれば、ベンジル基（−ＣＨ２Ｐｈ）となり、酸化後はベンゾイル基（−ＣＯＰｈ）となる。また、例えば、芳香環に共有結合した前記置換基（酸化される前）がホルミル基（−ＣＨＯ）であり、酸化後にカルボキシ基（−ＣＯＯＨ）となっても良い。 Moreover, the aromatic compound which is a raw material (substrate), for example, has a substituent such as an alkyl group covalently bonded to an aromatic ring, and the substituent may be oxidized by the reaction step. For example, the oxidizing agent contains an oxygen atom, the aromatic compound contains a methylene group (—CH 2 —) covalently bonded to an aromatic ring, and the methylene group (—CH 2 —) is oxidized in the reaction step. Then, it may be converted to a carbonyl group (—CO—). In this case, the atom or atomic group bonded to the methylene group and carbonyl group is not particularly limited, and examples thereof include a hydrogen atom, an alkyl group, and an aryl group. The alkyl group is preferably a linear or branched alkyl group having 1 to 6 carbon atoms. The alkyl group and aryl group may be further substituted with one or more substituents, and the plurality of substituents may be the same or different. For example, if hydrogen is bonded to the methylene group, it becomes a methyl group (—CH 3 ), and after oxidation becomes a formyl group (—CHO). If a methyl group is bonded to the methylene group, it becomes an ethyl group (—CH 2 CH 3 ), and after oxidation, becomes an acetyl group (—COCH 3 ). If a phenyl group is bonded to the methylene group, it becomes a benzyl group (—CH 2 Ph), and becomes a benzoyl group (—COPh) after oxidation. In addition, for example, the substituent covalently bonded to the aromatic ring (before being oxidized) may be a formyl group (—CHO) and may be converted to a carboxy group (—COOH) after oxidation.
また、例えば、前記原料（基質）がオレフィンであっても良く、前記オレフィンは、例えば、芳香族オレフィンでも良いし、脂肪族オレフィンでも良い。前記オレフィンは、例えば、下記スキームＤ中の化学式（Ｄ１）で表されるオレフィンでも良い。また、前記オレフィンの酸化反応生成物は、特に限定されないが、例えば、下記スキームＤのように、エポキシドおよびジオールの少なくとも一方を含んでいても良い。下記化学式（Ｄ１）、（Ｄ２）および（Ｄ３）中、Ｒは、それぞれ、水素原子または任意の置換基であり、各Ｒは、互いに同一でも異なっていても良い。前記任意の置換基は、例えば、アルキル基、不飽和脂肪族炭化水素基、アリール基、ヘテロアリール基、ハロゲン、ヒドロキシ基（−ＯＨ）、メルカプト基（−ＳＨ）、またはアルキルチオ基（−ＳＲ、Ｒはアルキル基）であり、さらなる置換基で置換されていても良いし、置換されていなくても良い。前記アルキル基は、炭素数１〜６の直鎖もしくは分枝アルキル基であることがより好ましい。また、被酸化物である前記オレフィンは、オレフィン結合（炭素−炭素二重結合）を１つのみ含むオレフィンでも良いが、オレフィン結合を複数（２つ以上）含むオレフィンであっても良い。 For example, the raw material (substrate) may be an olefin, and the olefin may be an aromatic olefin or an aliphatic olefin, for example. The olefin may be, for example, an olefin represented by the chemical formula (D1) in the following scheme D. Moreover, the oxidation reaction product of the olefin is not particularly limited, but may contain, for example, at least one of an epoxide and a diol as shown in the following scheme D. In the following chemical formulas (D1), (D2) and (D3), R is a hydrogen atom or an arbitrary substituent, and each R may be the same as or different from each other. Examples of the optional substituent include an alkyl group, an unsaturated aliphatic hydrocarbon group, an aryl group, a heteroaryl group, a halogen, a hydroxy group (—OH), a mercapto group (—SH), or an alkylthio group (—SR, R is an alkyl group), which may be substituted with a further substituent or may be unsubstituted. The alkyl group is more preferably a linear or branched alkyl group having 1 to 6 carbon atoms. The olefin that is an oxide may be an olefin containing only one olefin bond (carbon-carbon double bond), but may be an olefin containing a plurality (two or more) of olefin bonds.
前記オレフィンは、例えば、芳香族オレフィンであっても良い。すなわち、例えば前記化学式（Ｄ１）によいて、Ｒの少なくとも一つが、芳香環（アリール基またはヘテロアリール基）であっても良い。本発明において、前記芳香族オレフィンは特に制限されないが、前記芳香族オレフィンの芳香環に電子供与基が結合していると、例えば、前記芳香族オレフィンの酸化反応（酸化的置換反応を含む）が進行しやすいため好ましい。前記電子供与基は、１つでも複数でも良く、電子供与性の強いものが好ましい。より具体的には、前記芳香族オレフィンは、芳香環に、前記−ＯＲ１００、−ＮＲ２００ ２、およびＡｒ１００からなる群から選択される少なくとも一つの置換基が共有結合していることがより好ましい。 The olefin may be, for example, an aromatic olefin. That is, for example, the chemical formula (D1) may be sufficient, and at least one of R may be an aromatic ring (aryl group or heteroaryl group). In the present invention, the aromatic olefin is not particularly limited, but when an electron donating group is bonded to the aromatic ring of the aromatic olefin, for example, an oxidation reaction (including an oxidative substitution reaction) of the aromatic olefin. This is preferable because it easily proceeds. One or a plurality of the electron donating groups may be used, and those having a strong electron donating property are preferred. More specifically, in the aromatic olefin, at least one substituent selected from the group consisting of the —OR 100 , —NR 200 2 , and Ar 100 is covalently bonded to the aromatic ring. preferable.
本発明の酸化反応生成物の製造方法において、前記オレフィンが、エチレン、プロピレン、スチレン、およびブタジエンからなる群から選択される少なくとも一つであっても良い。また、前記酸化反応生成物は、例えば、前述のように、エポキシドおよびジオールの少なくとも一方であっても良い。下記スキームＤ１〜Ｄ３に、その例を示す。ただし、下記スキームＤ１〜Ｄ３は例示であって、本発明において、エチレン、プロピレンおよびスチレンの酸化反応は、これに限定されない。 In the method for producing an oxidation reaction product of the present invention, the olefin may be at least one selected from the group consisting of ethylene, propylene, styrene, and butadiene. Further, the oxidation reaction product may be at least one of epoxide and diol as described above, for example. Examples thereof are shown in the following schemes D1 to D3. However, the following schemes D1 to D3 are examples, and in the present invention, the oxidation reaction of ethylene, propylene, and styrene is not limited thereto.
なお、本発明の製造方法において、得られる酸化反応生成物の比率（例えば、アルコールとカルボン酸との比率、フェノールとキノンとの比率等）は、反応条件を適宜設定することで調整できる。 In the production method of the present invention, the ratio of the obtained oxidation reaction product (for example, the ratio of alcohol to carboxylic acid, the ratio of phenol to quinone, etc.) can be adjusted by appropriately setting the reaction conditions.
また、本発明の製造方法において、前記原料（基質）の酸化反応生成物は、前記アルコール、カルボン酸、アルデヒド、ケトン、フェノール、キノン等に限定されず、例えば、それらに加え、またはそれらに代えて、前記原料（基質）の塩素化物（クロロ化物）等を含んでいても良い。なお、例えば、炭化水素の気相反応において塩素原子ラジカルＣｌ・が二分子関与する場合（例えば、塩素ガスＣｌ２を用いた気相反応）は、酸素分子Ｏ２の存在下であっても、塩素化が優先的に起こると推測される。本発明の製造方法では、二酸化塩素ラジカルの分解により塩素原子ラジカルＣｌ・および酸素分子Ｏ２が発生するが、液相で反応を行なうため、基質の塩素化が抑制されて前記アルコール、カルボン酸、アルデヒド、ケトン、フェノール、キノン等が優先的に生成すると推測される。ただし、これらの推測も例示であって、本発明をなんら限定しない。また、本発明によれば、水相と有機相の二相系で反応を行なうことにより、従来は液相反応が困難であった炭化水素ガス（例えば、メタン、エタン等）においても、液相で効率よく酸化反応を行なうことができる。このため、産業上利用価値がきわめて高い前記炭化水素ガスの酸化反応生成物（例えば、メタノール、ギ酸、エタノール、酢酸等）を、前記炭化水素ガスから効率よく製造することができる。 In the production method of the present invention, the oxidation reaction product of the raw material (substrate) is not limited to the alcohol, carboxylic acid, aldehyde, ketone, phenol, quinone, etc., for example, in addition to or in place of them. In addition, a chlorinated product (chlorinated product) of the raw material (substrate) may be included. Incidentally, for example, if the chlorine radical Cl · in the gas phase reaction of a hydrocarbon involving bimolecular (e.g., gas phase reaction using a chlorine gas Cl 2), even in the presence of molecular oxygen O 2, It is speculated that chlorination occurs preferentially. In the production method of the present invention, the chlorine atom radical Cl · and molecular oxygen O 2 is generated by decomposition of chlorine dioxide radicals, for carrying out the reaction in the liquid phase, the chlorination of the substrate is suppressed alcohols, carboxylic acids, It is presumed that aldehyde, ketone, phenol, quinone and the like are preferentially produced. However, these assumptions are also examples and do not limit the present invention. In addition, according to the present invention, the reaction is performed in a two-phase system of an aqueous phase and an organic phase. Thus, the oxidation reaction can be performed efficiently. For this reason, the oxidation reaction product (for example, methanol, formic acid, ethanol, acetic acid, etc.) of the hydrocarbon gas having a very high industrial utility value can be efficiently produced from the hydrocarbon gas.
さらに、前記反応工程後、必要に応じて、前記酸化反応生成物の回収工程を行なう。前記回収工程は、例えば、前述のとおり、前記反応系から、前記酸化反応生成物を含む前記水相を回収する工程であっても良い。低級アルコール、低級カルボン酸等である前記酸化反応生成物（例えば、メタノール、エタノール、ギ酸、カルボン酸等）は、前記水相に溶解しやすいためである。また、前記酸化反応生成物が、前記水相に難溶で前記有機相に易溶である場合（例えば、前記酸化反応生成物がベンゾキノンで、前記有機相の溶媒がベンゼンである場合等）は、前記反応系から、前記酸化反応生成物を含む前記有機相を回収しても良い。また、例えば、前記酸化反応生成物が前記水相にも前記有機相にも難溶である場合は、例えば、ろ過等により前記酸化反応生成物を回収しても良い。さらに、必要に応じて、回収した酸化反応生成物を単離精製する。単離精製方法は特に限定されず、一般的な有機合成反応に準じて、蒸留、ろ過等の方法を適宜用いて行なうことができる。 Further, after the reaction step, the oxidation reaction product recovery step is performed as necessary. For example, as described above, the recovery step may be a step of recovering the aqueous phase containing the oxidation reaction product from the reaction system. This is because the oxidation reaction product (for example, methanol, ethanol, formic acid, carboxylic acid, etc.) which is a lower alcohol, a lower carboxylic acid or the like is easily dissolved in the aqueous phase. In addition, when the oxidation reaction product is hardly soluble in the aqueous phase and easily soluble in the organic phase (for example, the oxidation reaction product is benzoquinone and the organic phase solvent is benzene). The organic phase containing the oxidation reaction product may be recovered from the reaction system. For example, when the oxidation reaction product is hardly soluble in both the aqueous phase and the organic phase, the oxidation reaction product may be recovered by, for example, filtration. Furthermore, the recovered oxidation reaction product is isolated and purified as necessary. The isolation and purification method is not particularly limited, and can be carried out appropriately using a method such as distillation or filtration according to a general organic synthesis reaction.
なお、前述のとおり、本発明の製造方法における前記反応工程は、有機相のみで行なうこともできる。例えば、前述したような二酸化塩素ラジカルの発生源を含む水相を別途準備し、前記水相で二酸化塩素ラジカルを生成させる（二酸化塩素ラジカル生成工程）。その後、前記二酸化塩素ラジカルを、前記水相から有機相中に分液法等で抽出する。前記原料（基質）は、前記二酸化塩素ラジカルの抽出に先立ち前記有機相中に添加しても良いし、前記二酸化塩素ラジカルの抽出と同時に、または、抽出後に前記有機相中に添加しても良い。その後、前記水相と前記有機相とが分離され（前記有機相単独の）、かつ、前記有機相が前記原料（基質）および前記二酸化塩素ラジカルを含む状態で、前述のように光照射して前記反応工程を行なう。しかしながら、本発明の製造方法における前記反応工程は、前記水相と前記有機相とを分離せずに接触させたまま（二相反応系で）行なうことが好ましい。このようにすれば、例えば、前述のとおり、水溶性の酸化反応生成物を前記水相中から簡便に回収できる等の利点がある。また、例えば、水相が二酸化塩素ラジカルの発生源を含む二相反応系で、前記二酸化塩素ラジカル生成工程と前記反応工程（原料の酸化反応生成物を生成する工程）とを同時に行えば、反応効率が良いという利点がある。 As described above, the reaction step in the production method of the present invention can be performed only in the organic phase. For example, an aqueous phase containing a chlorine dioxide radical generation source as described above is separately prepared, and chlorine dioxide radicals are generated in the aqueous phase (chlorine dioxide radical generation step). Thereafter, the chlorine dioxide radical is extracted from the aqueous phase into the organic phase by a liquid separation method or the like. The raw material (substrate) may be added to the organic phase prior to extraction of the chlorine dioxide radical, or may be added to the organic phase simultaneously with or after extraction of the chlorine dioxide radical. . Thereafter, the aqueous phase and the organic phase are separated (the organic phase alone), and the organic phase contains the raw material (substrate) and the chlorine dioxide radical, and is irradiated with light as described above. The reaction step is performed. However, it is preferable to carry out the reaction step in the production method of the present invention while keeping the aqueous phase and the organic phase in contact with each other without separation (in a two-phase reaction system). In this way, for example, as described above, there is an advantage that a water-soluble oxidation reaction product can be easily recovered from the aqueous phase. Further, for example, in a two-phase reaction system in which the aqueous phase includes a chlorine dioxide radical source, the chlorine dioxide radical generation step and the reaction step (step of generating a raw material oxidation reaction product) are performed simultaneously. There is an advantage that efficiency is good.
本発明によれば、例えば、二酸化塩素ラジカル水溶液に光照射するのみの極めて簡便な方法で、塩素原子ラジカルＣｌ・および酸素分子Ｏ２を発生させ、酸化反応を行なうことができる。そして、そのような簡便な方法で、例えば、常温および常圧等のきわめて温和な条件下でも、炭化水素またはその誘導体を効率よく酸化反応生成物に変換することが可能である。 According to the present invention, for example, the chlorine atom radical Cl · and the oxygen molecule O 2 can be generated and the oxidation reaction can be carried out by a very simple method of simply irradiating a chlorine dioxide radical aqueous solution with light. And by such a simple method, for example, it is possible to efficiently convert a hydrocarbon or a derivative thereof into an oxidation reaction product even under extremely mild conditions such as normal temperature and normal pressure.
さらに、本発明によれば、例えば、有毒な重金属触媒等を用いずに、前記原料（炭化水素またはその誘導体）の酸化反応生成物を得ることも出来る。これによれば、前述のとおり常温および常圧等のきわめて温和な条件下で反応が行えることと併せ、環境への負荷がきわめて小さい方法で前記酸化反応生成物を効率よく得ることも可能である。 Furthermore, according to the present invention, for example, an oxidation reaction product of the raw material (hydrocarbon or a derivative thereof) can be obtained without using a toxic heavy metal catalyst or the like. According to this, in addition to being able to perform the reaction under extremely mild conditions such as normal temperature and normal pressure as described above, it is also possible to efficiently obtain the oxidation reaction product by a method with a very low environmental load. .
以下、本発明の実施例について説明する。ただし、本発明は、以下の実施例には限定されない。 Examples of the present invention will be described below. However, the present invention is not limited to the following examples.
［実施例１〜７］
基質（原料）である炭化水素を有機溶媒に溶かし、有機相を作製した。一方、亜塩素酸ナトリウム（ＮａＣｌＯ２）および酸を水（Ｈ２ＯまたはＤ２Ｏ）に溶かし、その水溶液を酸素ガス（Ｏ２）で飽和させて水相を作製した。その後、前記水相と前記有機相とを同一の反応容器中に入れ、接触させて二相系とした。さらに、前記二相系に、大気中において、加圧および減圧を行なわず、室温（約２５℃）条件下、波長λ＞２９０ｎｍのキセノンランプで光照射した。なお、光照射中、前記二相系は、水層（水相）と有機層（有機相）とが二層に分離したままで、攪拌等は行わなかった。このようにして、前記基質（原料）である炭化水素の酸化反応生成物を製造した。
[Examples 1-7]
A hydrocarbon as a substrate (raw material) was dissolved in an organic solvent to prepare an organic phase. On the other hand, sodium chlorite (NaClO 2 ) and an acid were dissolved in water (H 2 O or D 2 O), and the aqueous solution was saturated with oxygen gas (O 2 ) to prepare an aqueous phase. Thereafter, the aqueous phase and the organic phase were placed in the same reaction vessel and brought into contact to form a two-phase system. Further, the two-phase system was irradiated with light with a xenon lamp having a wavelength λ> 290 nm at room temperature (about 25 ° C.) without applying pressure and reduced pressure in the atmosphere. During the light irradiation, the aqueous phase (aqueous phase) and the organic layer (organic phase) remained separated into two layers in the two-phase system, and stirring and the like were not performed. In this way, an oxidation reaction product of hydrocarbon as the substrate (raw material) was produced.
実施例１〜７のそれぞれにおける溶媒（有機溶媒および水）、基質（原料）、および酸の種類および使用量（濃度）と、亜塩素酸ナトリウム（ＮａＣｌＯ２）の使用量（濃度）とを、下記表１および２に示す。また、酸化反応生成物の収率、および光照射時間も、併せて下記表１および２に示す。なお、下記表１および２中において、「Ｄ」は、重水素を表す。実施例６において、ベンゼン（基質および溶媒を兼ねる）は、芳香環上の６つの水素が全て重水素に置換された、重水素化ベンゼン（ベンゼンｄ６）を用いた。また、基質の変換率および酸化反応生成物の収率は、反応前の基質および反応後の酸化反応生成物の１ＨＮＭＲをそれぞれ測定し、各成分のピーク強度比を対比して算出した。実施例４においては、さらに、酸化反応生成物をそれぞれ単離生成して重量を測定した。なお、実施例４においては、下記表１に記載した酢酸およびエタノール以外に、それらの反応により得られたと推測される酢酸エチルが微量検出された。 The solvent (organic solvent and water), substrate (raw material), and acid type and amount used (concentration) in each of Examples 1 to 7, and the amount (concentration) used of sodium chlorite (NaClO 2 ) Shown in Tables 1 and 2 below. The yield of the oxidation reaction product and the light irradiation time are also shown in Tables 1 and 2 below. In Tables 1 and 2 below, “D” represents deuterium. In Example 6, benzene (also serving as a substrate and a solvent) was deuterated benzene (benzene d6) in which all six hydrogens on the aromatic ring were replaced with deuterium. Further, the conversion rate of the substrate and the yield of the oxidation reaction product were calculated by measuring 1 HNMR of the substrate before the reaction and the oxidation reaction product after the reaction, and comparing the peak intensity ratio of each component. In Example 4, each oxidation reaction product was isolated and produced, and its weight was measured. In Example 4, in addition to acetic acid and ethanol described in Table 1 below, trace amounts of ethyl acetate presumed to have been obtained by the reaction were detected.
実施例１〜７に示すとおり、大気中、常温、常圧下において光照射するのみで、炭化水素から、アルコール、カルボン酸、ケトン、フェノール、キノン等の酸化反応生成物を効率よく製造することができた。また、本実施例では、光源としてキセノンランプを用いたが、太陽光またはＬＥＤ等を光源として用いれば、さらなる省エネルギーおよびコスト低減が可能である。 As shown in Examples 1 to 7, it is possible to efficiently produce oxidation reaction products such as alcohol, carboxylic acid, ketone, phenol, and quinone from hydrocarbons only by light irradiation in the atmosphere at room temperature and under normal pressure. did it. In this embodiment, a xenon lamp is used as the light source. However, if sunlight or LED is used as the light source, further energy saving and cost reduction can be achieved.
また、実施例１〜７に示すとおり、本発明によれば、炭化水素を原料（基質）として用いて、産業上利用価値がきわめて高い酸化反応生成物を効率よく得ることが可能である。例えば、実施例２で得られたメタノールおよびギ酸、実施例１および３〜５で得られたエタノールおよび酢酸は、いずれも、燃料、溶媒、化成品の原料等の各種用途に、多大な利用価値がある。また、実施例６で得られたヒドロキシベンゼンは、医薬品、化成品の原料等の各種用途に、ｐ−ベンゾキノンは、酸化剤、脱水素剤、重合禁止剤等の用途に、それぞれ、多大な利用価値がある。実施例７で得られたシクロヘキサノールとシクロヘキサノンとの混合物は、一般に、ＫＡオイル（ケトンアルコールオイル）と呼ばれる。ＫＡオイルは、さらに酸化してアジピン酸に変換し、ポリアミド樹脂（商品名ナイロン）の原料として使用できるので、産業上利用価値はきわめて高い。このように、炭化水素を原料（基質）として用いて、産業上利用価値がきわめて高い酸化反応生成物を効率よく得ることができる製造方法は、これまでにない。すなわち、本実施例によれば、本発明が、産業上利用価値の観点から、従来技術に対してきわめて大きな優位性を有することが確認された。 In addition, as shown in Examples 1 to 7, according to the present invention, it is possible to efficiently obtain an oxidation reaction product having an extremely high industrial utility value by using hydrocarbon as a raw material (substrate). For example, the methanol and formic acid obtained in Example 2 and the ethanol and acetic acid obtained in Examples 1 and 3 to 5 have great utility value for various uses such as fuels, solvents, and raw materials for chemical products. There is. Further, the hydroxybenzene obtained in Example 6 is used for various uses such as raw materials for pharmaceuticals and chemical products, and p-benzoquinone is used for various uses such as an oxidizing agent, a dehydrogenating agent, and a polymerization inhibitor. worth it. The mixture of cyclohexanol and cyclohexanone obtained in Example 7 is generally called KA oil (ketone alcohol oil). Since KA oil is further oxidized and converted to adipic acid and can be used as a raw material for polyamide resin (trade name nylon), its industrial utility value is extremely high. Thus, there has never been a production method that can efficiently obtain an oxidation reaction product having an extremely high industrial utility value using hydrocarbons as a raw material (substrate). That is, according to the present Example, it was confirmed that this invention has a very big advantage over a prior art from a viewpoint of industrial use value.
以上、説明したとおり、本発明の製造方法によれば、炭化水素またはその誘導体を原料として、効率よく前記炭化水素またはその誘導体の酸化反応生成物を製造できる。本発明によれば、例えば、光照射するのみの極めて簡便な方法で、常温および常圧等のきわめて温和な条件下でも、炭化水素またはその誘導体を効率よく酸化反応生成物に変換することが可能である。そして、本発明によれば、例えば、前記炭化水素またはその誘導体を原料として、アルコール、カルボン酸、ケトン、フェノール、キノン等の、産業上利用価値がきわめて高い酸化反応生成物を効率よく得ることも出来る。従来は、このような酸化反応生成物を、炭化水素を原料として効率よく得ることが出来なかったため、天然ガス等の炭化水素を原料として有効利用することがきわめて困難であった。これに対し、本発明によれば、天然ガス等の炭化水素を原料として有効利用できる。このため、本発明によれば、従来は石油等を原料として合成するしかなかった化合物も、天然ガス等を原料として極めて簡便に効率よく合成できるので、エネルギー問題等に対し、多大な貢献が可能である。さらに、本発明によれば、例えば、有毒な重金属触媒等を用いずに、前記原料（炭化水素またはその誘導体）の酸化反応生成物を得ることも出来る。これによれば、前述のとおり常温および常圧等のきわめて温和な条件下で反応が行えることと併せ、環境への負荷がきわめて小さい方法で前記酸化反応生成物を効率よく得ることも可能である。このように、本発明の産業上利用可能性は絶大である。 As described above, according to the production method of the present invention, an oxidation reaction product of the hydrocarbon or its derivative can be efficiently produced using the hydrocarbon or its derivative as a raw material. According to the present invention, for example, a hydrocarbon or a derivative thereof can be efficiently converted into an oxidation reaction product even under extremely mild conditions such as normal temperature and normal pressure by a very simple method of only light irradiation. It is. According to the present invention, for example, an oxidation reaction product having an extremely high industrial utility value such as alcohol, carboxylic acid, ketone, phenol, and quinone can be efficiently obtained using the hydrocarbon or its derivative as a raw material. I can do it. Conventionally, since such an oxidation reaction product could not be obtained efficiently using hydrocarbons as raw materials, it was extremely difficult to effectively use hydrocarbons such as natural gas as raw materials. On the other hand, according to the present invention, hydrocarbons such as natural gas can be effectively used as a raw material. For this reason, according to the present invention, a compound that has conventionally only been synthesized using petroleum or the like as a raw material can be synthesized very simply and efficiently using natural gas or the like as a raw material. It is. Furthermore, according to the present invention, for example, an oxidation reaction product of the raw material (hydrocarbon or a derivative thereof) can be obtained without using a toxic heavy metal catalyst or the like. According to this, in addition to being able to perform the reaction under extremely mild conditions such as normal temperature and normal pressure as described above, it is also possible to efficiently obtain the oxidation reaction product by a method with a very low environmental load. . Thus, the industrial applicability of the present invention is tremendous.
１ 有機層（有機相）
２ 水層（水相）
1 Organic layer (organic phase)
2 Water layer (aqueous phase)
Claims (12)
前記原料が、炭化水素またはその誘導体であり、
前記反応系が、有機相を含む反応系であり、
前記有機相が、前記原料および前記二酸化塩素ラジカルを含み、
前記反応工程において、前記光照射により、前記原料が酸化され、前記原料の酸化反応生成物を生成することを特徴とする酸化反応生成物の製造方法。 Including the reaction step of irradiating the reaction system with light in the presence of the raw material and chlorine dioxide radical,
The raw material is a hydrocarbon or a derivative thereof;
The reaction system is a reaction system including an organic phase,
The organic phase comprises the raw material and the chlorine dioxide radical;
In the reaction step, the raw material is oxidized by the light irradiation to generate an oxidation reaction product of the raw material.
前記二酸化塩素ラジカル生成工程において、前記水相が、前記二酸化塩素ラジカルの発生源を含み、前記二酸化塩素ラジカルの発生源から前記二酸化塩素ラジカルを生成させる請求項４記載の製造方法。 And a chlorine dioxide radical generating step for generating the chlorine dioxide radical,
The manufacturing method according to claim 4, wherein, in the chlorine dioxide radical generation step, the aqueous phase includes the generation source of the chlorine dioxide radical, and the chlorine dioxide radical is generated from the generation source of the chlorine dioxide radical.
前記回収工程が、前記反応系から、前記酸化反応生成物を含む前記水相を回収する工程である、請求項４から６のいずれか一項に記載の製造方法。 After the reaction step, further comprising a step of recovering the oxidation reaction product,
The manufacturing method according to any one of claims 4 to 6, wherein the recovery step is a step of recovering the aqueous phase containing the oxidation reaction product from the reaction system.
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| JP2016042137A JP6080281B1 (en) | 2016-03-04 | 2016-03-04 | Method for producing oxidation reaction product of hydrocarbon or derivative thereof |
| EP16875772.2A EP3398925B1 (en) | 2015-12-18 | 2016-12-16 | Method for producing oxidation reaction product of hydrocarbon or derivative thereof, and method for producing oxidation reaction product of olefin |
| CN201680074063.9A CN108602740B (en) | 2015-12-18 | 2016-12-16 | Method for producing oxidation reaction product of hydrocarbon or derivative thereof, and method for producing oxidation reaction product of olefin |
| US16/063,103 US10947190B2 (en) | 2015-12-18 | 2016-12-16 | Method for producing oxidation reaction product of hydrocarbon or derivative thereof, and method for producing oxidation reaction product of olefin |
| PCT/JP2016/087540 WO2017104798A1 (en) | 2015-12-18 | 2016-12-16 | Method for producing oxidation reaction product of hydrocarbon or derivative thereof, and method for producing oxidation reaction product of olefin |
| CN202210530076.XA CN114907188B (en) | 2015-12-18 | 2016-12-16 | Method for producing oxidation reaction product of hydrocarbon or derivative thereof, and method for producing oxidation reaction product of olefin |
| SA518391862A SA518391862B1 (en) | 2015-12-18 | 2018-06-23 | Method for producing oxidation reaction product of hydrocarbon or derivative thereof, and method for producing oxidation reaction product of olefin |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018076254A (en) * | 2016-11-09 | 2018-05-17 | 株式会社 エースネット | Method for producing diol body |
| JP2020002119A (en) * | 2017-12-16 | 2020-01-09 | 国立大学法人大阪大学 | Manufacturing method of oxidation reaction product of hydrocarbon or derivative thereof |
| US11827578B2 (en) | 2018-06-20 | 2023-11-28 | Osaka University | Method for producing oxidation reaction product of hydrocarbon or derivative thereof |
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| JP2014503457A (en) * | 2010-12-23 | 2014-02-13 | エイ．ピー．エフ． アクア システム アクチエンゲゼルシャフト | Method for producing a stable aqueous chlorine dioxide solution |
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| JPS5289625A (en) * | 1975-12-24 | 1977-07-27 | Rhone Poulenc Ind | Hydroxylation of aromatic compounds |
| JPS60139628A (en) * | 1983-12-16 | 1985-07-24 | モンテデイソン・エッセ・ピ・ア | Oxidation of aldehyde to carboxylic acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018076254A (en) * | 2016-11-09 | 2018-05-17 | 株式会社 エースネット | Method for producing diol body |
| JP2020002119A (en) * | 2017-12-16 | 2020-01-09 | 国立大学法人大阪大学 | Manufacturing method of oxidation reaction product of hydrocarbon or derivative thereof |
| JP7210007B2 (en) | 2017-12-16 | 2023-01-23 | 国立大学法人大阪大学 | Method for producing oxidation reaction product of hydrocarbon or derivative thereof |
| US11827578B2 (en) | 2018-06-20 | 2023-11-28 | Osaka University | Method for producing oxidation reaction product of hydrocarbon or derivative thereof |
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