JP6784972B2 - Production method and equipment for 2,5-dialkoxy-2,5-dihydrofuran, etc. - Google Patents
Production method and equipment for 2,5-dialkoxy-2,5-dihydrofuran, etc. Download PDFInfo
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- JP6784972B2 JP6784972B2 JP2016198610A JP2016198610A JP6784972B2 JP 6784972 B2 JP6784972 B2 JP 6784972B2 JP 2016198610 A JP2016198610 A JP 2016198610A JP 2016198610 A JP2016198610 A JP 2016198610A JP 6784972 B2 JP6784972 B2 JP 6784972B2
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- 238000004519 manufacturing process Methods 0.000 title claims description 24
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 30
- 239000003115 supporting electrolyte Substances 0.000 claims description 19
- 239000004065 semiconductor Substances 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- -1 acetoxymethyl group Chemical group 0.000 claims description 10
- 229910052794 bromium Inorganic materials 0.000 claims description 10
- 239000008151 electrolyte solution Substances 0.000 claims description 10
- 230000001235 sensitizing effect Effects 0.000 claims description 10
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 10
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 9
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 9
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 8
- 230000003287 optical effect Effects 0.000 claims description 8
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 6
- 125000001539 acetonyl group Chemical group [H]C([H])([H])C(=O)C([H])([H])* 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004202 aminomethyl group Chemical group [H]N([H])C([H])([H])* 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 claims description 4
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- WGHUNMFFLAMBJD-UHFFFAOYSA-M tetraethylazanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.CC[N+](CC)(CC)CC WGHUNMFFLAMBJD-UHFFFAOYSA-M 0.000 claims description 4
- PUZYNDBTWXJXKN-UHFFFAOYSA-M tetraethylazanium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.CC[N+](CC)(CC)CC PUZYNDBTWXJXKN-UHFFFAOYSA-M 0.000 claims description 4
- 238000000034 method Methods 0.000 description 33
- 239000000975 dye Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- ARGCQEVBJHPOGB-UHFFFAOYSA-N 2,5-dihydrofuran Chemical compound C1OCC=C1 ARGCQEVBJHPOGB-UHFFFAOYSA-N 0.000 description 12
- 239000000758 substrate Substances 0.000 description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- WXFWXFIWDGJRSC-UHFFFAOYSA-N 2,5-dimethoxy-2,5-dihydrofuran Chemical compound COC1OC(OC)C=C1 WXFWXFIWDGJRSC-UHFFFAOYSA-N 0.000 description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 239000000049 pigment Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 238000005979 thermal decomposition reaction Methods 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- JJWJFWRFHDYQCN-UHFFFAOYSA-J 2-(4-carboxypyridin-2-yl)pyridine-4-carboxylate;ruthenium(2+);tetrabutylazanium;dithiocyanate Chemical compound [Ru+2].[S-]C#N.[S-]C#N.CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC.OC(=O)C1=CC=NC(C=2N=CC=C(C=2)C([O-])=O)=C1.OC(=O)C1=CC=NC(C=2N=CC=C(C=2)C([O-])=O)=C1 JJWJFWRFHDYQCN-UHFFFAOYSA-J 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- 239000001856 Ethyl cellulose Substances 0.000 description 3
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000003905 agrochemical Substances 0.000 description 3
- 229920001249 ethyl cellulose Polymers 0.000 description 3
- 235000019325 ethyl cellulose Nutrition 0.000 description 3
- 239000003205 fragrance Substances 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000434 metal complex dye Substances 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- JKTCBAGSMQIFNL-UHFFFAOYSA-N 2,3-dihydrofuran Chemical compound C1CC=CO1 JKTCBAGSMQIFNL-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229940006460 bromide ion Drugs 0.000 description 2
- 229910000435 bromine oxide Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- FMSOWMGJJIHFTQ-UHFFFAOYSA-N oxidobromine(.) Chemical class Br[O] FMSOWMGJJIHFTQ-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 229910052702 rhenium Inorganic materials 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 0 *C(*)(C=C1)OC1(*)O* Chemical compound *C(*)(C=C1)OC1(*)O* 0.000 description 1
- BUIVDANEHFRPEQ-UHFFFAOYSA-N 2,5-diethoxy-2,5-dihydrofuran Chemical compound CCOC1OC(OCC)C=C1 BUIVDANEHFRPEQ-UHFFFAOYSA-N 0.000 description 1
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 150000001648 bromium Chemical class 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 229960000956 coumarin Drugs 0.000 description 1
- 235000001671 coumarin Nutrition 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229940097275 indigo Drugs 0.000 description 1
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- LKKPNUDVOYAOBB-UHFFFAOYSA-N naphthalocyanine Chemical compound N1C(N=C2C3=CC4=CC=CC=C4C=C3C(N=C3C4=CC5=CC=CC=C5C=C4C(=N4)N3)=N2)=C(C=C2C(C=CC=C2)=C2)C2=C1N=C1C2=CC3=CC=CC=C3C=C2C4=N1 LKKPNUDVOYAOBB-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 230000002165 photosensitisation Effects 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000001007 phthalocyanine dye Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000003586 protic polar solvent Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 150000004060 quinone imines Chemical class 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052713 technetium Inorganic materials 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Description
本発明は、フランやその誘導体の光電解酸化により２，５−ジアルコキシ−２，５−ジヒドロフランやその誘導体を製造する方法や装置に関するものである。 The present invention relates to a method or apparatus for producing 2,5-dialkoxy-2,5-dihydrofuran or a derivative thereof by photoelectrolytic oxidation of furan or a derivative thereof.
２，５−ジアルコキシ−２，５−ジヒドロフランやその誘導体は、医農薬原料、ポリマー原料、香料などの合成の中間体として重要である。 2,5-Dialkoxy-2,5-dihydrofuran and its derivatives are important as intermediates in the synthesis of medical and agricultural chemical raw materials, polymer raw materials, fragrances and the like.
２，５−ジアルコキシ−２，５−ジヒドロフランやその誘導体の製造方法としては、アルコールに溶解したフランやその誘導体に臭素を滴下し、ついでアンモニアなどの塩基で処理して生成させる化学的方法（臭素法）が報告されている（例えば、非特許文献１）。しかし、収率が非常に低く同時に大量の臭化アンモニウムも生成するので分離工程を必要とする。また生成する２，５−ジアルコキシ−２，５−ジヒドロフランやその誘導体は酸に対して不安定であるので、２，５−ジアルコキシ−２，５−ジヒドロフランやその誘導体の単離段階で加熱操作すると、微量に残っている無機塩の作用によってしばしばタール化してしまうという欠点がある。 As a method for producing 2,5-dialkoxy-2,5-dihydrofuran and its derivatives, a chemical method in which bromine is added dropwise to furan dissolved in alcohol or its derivative, and then treated with a base such as ammonia to produce it. (Bromium method) has been reported (for example, Non-Patent Document 1). However, the yield is very low and a large amount of ammonium bromide is also produced at the same time, so a separation step is required. In addition, since the produced 2,5-dialkoxy-2,5-dihydrofuran and its derivatives are unstable to acids, the isolation stage of 2,5-dialkoxy-2,5-dihydrofuran and its derivatives When the heating operation is performed with, there is a drawback that it is often tarred by the action of a trace amount of the remaining inorganic salt.
これに対して、フランやその誘導体とアルコールを原料とし、支持電解質と電解溶媒からなる電解溶液を満たした電解槽を用いたアノード電極での酸化反応により２，５−ジアルコキシ−２，５−ジヒドロフランやその誘導体を電気化学的に製造する方法（電解酸化法）が報告されている（例えば、非特許文献２）。臭素法に比べて副生成物が少なく収率が高い上に、生成する２，５−ジアルコキシ−２，５−ジヒドロフランやその誘導体の単離も容易であり、大量合成に適している。 On the other hand, 2,5-dialkoxy-2,5-by an oxidation reaction at an anode electrode using an electrolytic tank filled with an electrolytic solution composed of a supporting electrolyte and an electrolytic solvent using furan or its derivative and alcohol as raw materials. A method for electrochemically producing dihydrofuran or a derivative thereof (electrolytic oxidation method) has been reported (for example, Non-Patent Document 2). Compared with the bromine method, there are few by-products and the yield is high, and the resulting 2,5-dihydrofuran and 2-5-dihydrofuran and their derivatives can be easily isolated, which is suitable for mass synthesis.
また、２，５−ジアルコキシ−２，５−ジヒドロフランやその誘導体の製造方法とは異なるが、水の電気化学反応による過酸化水素の製造方法において、半導体光電極に光を照射する過酸化水素の製造方法および製造装置が提案されている（例えば、特許文献１）。 Further, although different from the method for producing 2,5-dialkoxy-2,5-dihydrofuran and its derivatives, in the method for producing hydrogen peroxide by an electrochemical reaction of water, peroxidation in which a semiconductor photoelectrode is irradiated with light is performed. A method and an apparatus for producing hydrogen have been proposed (for example, Patent Document 1).
上述の電解酸化法による２，５−ジアルコキシ−２，５−ジヒドロフランやその誘導体の製造法は、臭素法に比べ多くの利点を有するが、本発明者らは同時に、高い電圧が必要で膨大な電力エネルギーを要するという問題点が存在することも認識した。
以上のような背景技術やそれらについて認識された問題点から、本発明は、フランやその誘導体とアルコールから効率よく２，５−ジアルコキシ−２，５−ジヒドロフランやその誘導体を製造することのできる新しい２，５−ジアルコキシ−２，５−ジヒドロフランやその誘導体の製造方法や製造装置を提供することを課題としている。
The method for producing 2,5-dialkoxy-2,5-dihydrofuran and its derivatives by the above-mentioned electrolytic oxidation method has many advantages over the bromine method, but the present inventors also require a high voltage at the same time. We also recognized that there is a problem that enormous power energy is required.
Based on the above background techniques and the problems recognized about them, the present invention can efficiently produce 2,5-dialkoxy-2,5-dihydrofuran and its derivatives from furan and its derivatives and alcohols. It is an object of the present invention to provide a method and an apparatus for producing new 2,5-dialkoxy-2,5-dihydrofuran and its derivatives.
本発明者らは、支持電解質の存在下、光を可視光応答性光アノード電極に照射し、光電解酸化反応によりフランやその誘導体とアルコールから２，５−ジアルコキシ−２，５−ジヒドロフランやその誘導体を製造できることを見出した。この方法は未だ報告されていない新規な２，５−ジアルコキシ−２，５−ジヒドロフランやその誘導体の製造方法である。 In the presence of the supporting electrolyte, the present inventors irradiate the visible light-responsive photoanode electrode with light, and by photoelectrolytic oxidation reaction, from furan or its derivative and alcohol, 2,5-dialkoxy-2,5-dihydrofuran And its derivatives have been found to be capable of being produced. This method is a novel method for producing 2,5-dialkoxy-2,5-dihydrofuran and its derivatives, which has not been reported yet.
本発明は、これらの知見に基づいて完成に至ったものであり、具体的には以下のことを特徴としている。
（１）次の一般式（１）
Ｒ3ＯＨ
（式中、Ｒ3は炭素数４以下のアルキル基を示す）で表されるアルコールから、支持電解質と、可視光応答性光アノード電極を用い、可視光応答性光アノード電極表面に光を照射して光電解酸化反応により次の一般式（２）
（２）前記可視光応答性光アノード電極が表面に増感色素を担持したｎ型半導体を有する（１）に記載の２，５−ジアルコキシ−２，５−ジヒドロフラン及び／又はその誘導体の製造方法。
（３）前記可視光応答性光アノード電極が表面にＢｉＶＯ4、ＷＯ3から選択される１種又は２種の可視光応答性ｎ型半導体を有するものである（１）に記載の２，５−ジアルコキシ−２，５−ジヒドロフラン及び／又はその誘導体の製造方法。
（４）前記支持電解質がテトラエチルアンモニウムブロミド、テトラブチルアンモニウムブロミドから選択される少なくとも１種である（１）〜（３）のいずれかに記載の２，５−ジアルコキシ−２，５−ジヒドロフラン及び／又はその誘導体の製造方法。
（５）前記支持電解質が、テトラエチルアンモニウムブロミド、テトラブチルアンモニウムブロミドから選択される少なくとも１種と、テトラフルオロほう酸テトラエチルアンモニウム、トリフルオロメタンスルホン酸テトラエチルアンモニウム、過塩素酸テトラエチルアンモニウムから選択される少なくとも１種との組み合わせである（１）〜（３）のいずれかに記載の２，５−ジアルコキシ−２，５−ジヒドロフラン及び／又はその誘導体の製造方法。
（６）可視光応答性光アノード電極とカソード電極を備え、電解液を収容する電解槽と、前記電解槽に、次の一般式（１）
Ｒ3ＯＨ
（式中、Ｒ3は炭素数４以下のアルキル基を示す）で表されるアルコールとを供給する供給装置とを具備する、次の一般式（２）
（７）前記可視光応答性光アノード電極が表面に増感色素を担持したｎ型半導体を有するものである（６）に記載の２，５−ジアルコキシ−２，５−ジヒドロフラン及び／又はその誘導体の製造装置。
（８）前記ｎ型半導体が、ＴｉＯ2、Ｎｂ2Ｏ5、及び、ＺｎＯから選択される１種である（７）に記載の２，５−ジアルコキシ−２，５−ジヒドロフラン及び／又はその誘導体の製造装置。
The present invention has been completed based on these findings, and is specifically characterized by the following.
(1) The following general formula (1)
(In the formula, R 3 represents an alkyl group having 4 or less carbon atoms), using a supporting electrolyte and a visible light responsive photoanode electrode, irradiate the surface of the visible light responsive photoanode electrode with light. Then, by the photoelectrolytic oxidation reaction, the following general formula (2)
(2) The 2,5-dialkoxy-2,5-dihydrofuran and / or a derivative thereof according to (1), wherein the visible light-responsive photoanode electrode has an n-type semiconductor having a sensitizing dye on its surface. Production method.
(3) 2.5 according to (1), wherein the visible light responsive photoanode electrode has one or two visible light responsive n-type semiconductors selected from BiVO 4 and WO 3 on the surface. -A method for producing dialkoxy-2,5-dihydrofuran and / or a derivative thereof.
(4) The 2,5-dihydrokoxy-2,5-dihydrofuran according to any one of (1) to (3), wherein the supporting electrolyte is at least one selected from tetraethylammonium bromide and tetrabutylammonium bromide. And / or a method for producing a derivative thereof.
(5) The supporting electrolyte is at least one selected from tetraethylammonium bromide and tetrabutylammonium bromide, and at least one selected from tetraethylammonium tetrafluoroborate, tetraethylammonium trifluoromethanesulfonate, and tetraethylammonium perchlorate. The method for producing 2,5-dialkoxy-2,5-dihydrofuran and / or a derivative thereof according to any one of (1) to (3), which is a combination with.
(6) The following general formula (1) is applied to an electrolytic cell provided with a visible light responsive optical anode electrode and a cathode electrode and accommodating an electrolytic solution, and the electrolytic cell.
(In the formula, R 3 represents an alkyl group having 4 or less carbon atoms), which comprises a supply device for supplying the alcohol represented by the following general formula (2).
(7) The 2,5-dialkoxy-2,5-dihydrofuran and / or according to (6), wherein the visible light responsive photoanode electrode has an n-type semiconductor having a sensitizing dye on its surface. Equipment for manufacturing the derivative.
(8) The 2,5-dialkoxy-2,5-dihydrofuran and / or according to (7), wherein the n-type semiconductor is one selected from TiO 2 , Nb 2 O 5 , and ZnO. Equipment for manufacturing the derivative.
本発明によれば、医農薬原料、ポリマー原料、香料などの合成の中間体として用いられる有用な一般式（２）で表される２，５−ジアルコキシ−２，５−ジヒドロフランやその誘導体を比較的安価に効率よく製造できる。 According to the present invention, 2,5-dialkoxy-2,5-dihydrofuran and its derivatives represented by the useful general formula (2) used as intermediates for the synthesis of medical and agricultural chemical raw materials, polymer raw materials, fragrances and the like. Can be manufactured relatively inexpensively and efficiently.
以下、本発明の一般式（２）で表される２，５−ジアルコキシ−２，５−ジヒドロフランやその誘導体の製造方法について、図面を参照しながら実施形態と実施例に基づいて詳細に説明する。なお、重複説明は適宜省略する。 Hereinafter, the method for producing 2,5-dihydrofuran and its derivatives represented by the general formula (2) of the present invention will be described in detail based on embodiments and examples with reference to the drawings. explain. The duplicate description will be omitted as appropriate.
図１に示す本発明の１実施形態の一般式（２）で表される２，５−ジアルコキシ−２，５−ジヒドロフラン及び／又はその誘導体の製造は、可視光応答性光アノード電極とカソード電極を備え、一般式（１）で表されるフラン及び／又はその誘導体、一般式Ｒ3ＯＨで表されるアルコール、および支持電解質を溶媒に溶解した電解液を満たした電解槽において行う。可視光応答性光アノード電極とカソード電極は直流電源を介して電気的に接続し、可視光応答性光アノード電極に光を照射することで光電解酸化反応を行う。定電位にて光電解酸化反応を行う場合、可視光応答性光アノード電極とカソード電極に加え参照電極を用いる。電解槽は図１のような一室型でも、隔膜を有する二室型のものでも良い。
照射に用いる光としては、波長が４００ｎｍから８００ｎｍの可視光を含む疑似太陽光などが挙げられる。
The production of 2,5-dihydrofuran and / or a derivative thereof represented by the general formula (2) of one embodiment of the present invention shown in FIG. 1 is carried out with a visible light responsive optical anode electrode. This is performed in an electrolytic cell provided with a cathode electrode and filled with an electrolytic solution in which furan and / or a derivative thereof represented by the general formula (1), alcohol represented by the general formula R 3 OH, and a supporting electrolyte are dissolved in a solvent. The visible light responsive optical anode electrode and the cathode electrode are electrically connected via a DC power source, and the visible light responsive optical anode electrode is irradiated with light to carry out a photoelectrolytic oxidation reaction. When the photoelectrolytic oxidation reaction is carried out at a constant potential, a reference electrode is used in addition to the visible light responsive photoanode electrode and cathode electrode. The electrolytic cell may be a one-chamber type as shown in FIG. 1 or a two-chamber type having a diaphragm.
Examples of the light used for irradiation include pseudo-sunlight including visible light having a wavelength of 400 nm to 800 nm.
図２において、可視光応答性光アノード電極では支持電解質に含まれる臭化物イオンが酸化され臭素の酸化体を生成する。この臭素酸化体が一般式（１）で表されるフラン及び／又はその誘導体を酸化して元の臭化物イオンへ回復する。この臭化物イオンは直ちに可視光応答性光アノード電極で再び酸化され臭素酸化体となるので、臭素の酸化還元系がメディエーターとして働く。一般式（１）で表されるフラン及び／又はその誘導体の酸化体は、一般式Ｒ3ＯＨで表されるアルコールと反応して一般式（２）で表される２，５−ジアルコキシ−２，５−ジヒドロフラン及び／又はその誘導体を生成する。 In FIG. 2, in the visible light responsive photoanode electrode, bromide ions contained in the supporting electrolyte are oxidized to generate an oxide of bromine. This bromine oxide oxidizes furan and / or its derivative represented by the general formula (1) and recovers to the original bromide ion. This bromide ion is immediately reoxidized at the visible light responsive photoanode electrode to become a bromine oxide, so that the redox system of bromine acts as a mediator. The oxide of furan and / or its derivative represented by the general formula (1) reacts with the alcohol represented by the general formula R 3 OH to form 2,5-dihydrokoxy represented by the general formula (2). Produces 2,5-dihydrofuran and / or its derivatives.
本発明の可視光応答性光アノード電極は、表面に増感色素を担持したｎ型半導体を導電性基材に備えたもの、又は可視光応答性ｎ型半導体を導電性基材に備えたものがよい。使用する導電性基材としては、フッ素ドープ酸化スズ（ＦＴＯ）、スズドープ酸化インジウム（ＩＴＯ）などの酸化物の導電性ガラス基材、カーボンや金属などの耐熱性の導電性基材などが挙げられる。電極の安定性や効率よく一般式（２）で表される２，５−ジアルコキシ−２，５−ジヒドロフラン及び／又はその誘導体を製造するための観点から、導電性酸化物を表面に有するガラス基材を使用することがより好ましい。導電性基材の形状は限定されないが、板状のものを好適に使用することができる。 The visible light responsive optical anode electrode of the present invention is provided with an n-type semiconductor having a sensitizing dye on its surface on a conductive substrate, or a visible light responsive n-type semiconductor provided on a conductive substrate. Is good. Examples of the conductive base material to be used include a conductive glass base material of an oxide such as fluorine-doped tin oxide (FTO) and tin-doped indium oxide (ITO), and a heat-resistant conductive base material such as carbon and metal. .. The surface has a conductive oxide from the viewpoint of stabilizing the electrode and efficiently producing 2,5-dihydrofuran and / or a derivative thereof represented by the general formula (2). It is more preferable to use a glass substrate. The shape of the conductive base material is not limited, but a plate-like material can be preferably used.
本発明の導電性基材に備えた表面に増感色素を担持したｎ型半導体は、可視光応答性のないＴｉＯ2、Ｎｂ2Ｏ5、ＺｎＯなどを挙げることができるが、ＴｉＯ2を用いることが好ましい。 Examples of the n-type semiconductor in which the sensitizing dye is supported on the surface of the conductive substrate of the present invention include TiO 2 , Nb 2 O 5 , and ZnO, which do not have visible light responsiveness, and TiO 2 is used. Is preferable.
本発明の導電性基材に備えた可視光応答性ｎ型半導体は、Ｂｉ、Ｖ、およびＷの中から選択され１以上の元素を含むことが好ましく、ＢｉＶＯ4、およびＷＯ3から選択される。ＷＯ3とＢｉＶＯ4を積層することがより好ましい。 The visible light responsive n-type semiconductor provided in the conductive substrate of the present invention is preferably selected from Bi, V, and W and contains one or more elements, and is selected from BiVO 4 and WO 3. .. It is more preferable to laminate WO 3 and BiVO 4 .
本発明の導電性基材に備えたｎ型半導体は、熱分解法や混合粉末の焼結法、電着法あるいはスパッタリングなどのような気相成膜法などの各種の方法により製造可能であるが、なかでも、製造方法が簡便な観点から、熱分解法で作製することが好ましい。例えば、薄膜形状で基材に担持する場合の塗布熱分解法については詳細を実施例において説明する。この熱分解法では元素を含む溶液（場合によってはコロイド溶液や懸濁液など）をよく混合して原料液を調製し、それを焼成することで作製する。熱分解法には、溶液で混合するので均一な組成物を作製できる利点があるが、特に、熱分解法の一種である塗布熱分解法では、薄膜を形成する場合に、塗布と焼成を繰り返して積層することで精密なものが作製できるなどの利点もある。本発明に用いる熱分解法は、元素を含む溶液を混合して焼成する方法ならばよく、ゾルゲル法、錯体重合法、有機金属分解法なども挙げることができる。溶液粘度や薄膜の多孔性を制御するためにポリエチレングリコールやエチルセルロースなどポリマーや有機物を溶液に添加しても良い。 The n-type semiconductor provided in the conductive substrate of the present invention can be produced by various methods such as a thermal decomposition method, a mixed powder sintering method, an electrodeposition method, and a vapor deposition method such as sputtering. However, among them, from the viewpoint of simple manufacturing method, it is preferable to manufacture by a thermal decomposition method. For example, the coating thermal decomposition method when the thin film is supported on the base material will be described in detail in Examples. In this pyrolysis method, a solution containing an element (in some cases, a colloidal solution, a suspension, etc.) is well mixed to prepare a raw material solution, which is then fired. The thermal decomposition method has an advantage that a uniform composition can be prepared because it is mixed with a solution. In particular, in the coating thermal decomposition method, which is a kind of thermal decomposition method, coating and firing are repeated when forming a thin film. There is also an advantage that a precise product can be manufactured by laminating. The thermal decomposition method used in the present invention may be any method as long as it is a method of mixing and firing a solution containing an element, and examples thereof include a sol-gel method, a complex polymerization method, and an organometallic decomposition method. Polymers and organic substances such as polyethylene glycol and ethyl cellulose may be added to the solution in order to control the viscosity of the solution and the porosity of the thin film.
本発明の可視光応答性光アノード電極として導電性基材に備えたｎ型半導体に担持する増感色素は、種々の可視光領域、又は可視光領域と赤外光領域に吸収を持つものを用いることができる。このような光増感色素には、構造上の制限は特になく、たとえば、クマリン系色素、アゾ系色素、キノン系色素、キノンイミン系色素、キナクリドン系色素、スクアリリウム系色素、シアニン系色素、メロシアニン系色素、トリフェニルメタン系色素、ポルフィリン系色素、フタロシアニン系色素、ペリレン系色素、インジゴ系色素、ナフタロシアニン系色素、および中心金属としてルテニウムなどを有するビピリジル錯体など、種々の色素が使用できる。その中でも、ビピリジル錯体、ターピリジル錯体のような金属錯体色素がより好ましい。なお、金属錯体色素の場合においては、Ｃｕ、Ｎｉ、Ｆｅ、Ｃｏ、Ｖ、Ｓｎ、Ｓｉ、Ｔｉ、Ｇｅ、Ｃｒ、Ｚｎ、Ｒｕ、Ｍｇ、Ａｌ、Ｐｂ、Ｍｎ、Ｉｎ、Ｍｏ、Ｙ、Ｚｒ、Ｎｂ、Ｓｂ、Ｌａ、Ｗ、Ｐｔ、Ｔａ、Ｉｒ、Ｐｄ、Ｏｓ、Ｇａ、Ｔｂ、Ｅｕ、Ｒｂ、Ｂｉ、Ｓｅ、Ａｓ、Ｓｃ、Ａｇ、Ｃｄ、Ｈｆ、Ｒｅ、Ａｕ、Ａｃ、Ｔｃ、Ｔｅ、Ｒｈなどの金属が用いられる。この中でも、Ｆｅ、Ｃｕ、Ｒｕ、Ｒｈ、Ｒｅ、Ｏｓ、Ｐｔなどの金属錯体色素がより好ましく、Ｒｕであることがさらに好ましい。 The sensitizing dye carried on the n-type semiconductor provided on the conductive substrate as the visible light responsive optical anode electrode of the present invention includes those having absorption in various visible light regions or visible light regions and infrared light regions. Can be used. There are no particular structural restrictions on such photosensitizing pigments, for example, coumarin pigments, azo pigments, quinone pigments, quinone imine pigments, quinacridone pigments, squarylium pigments, cyanine pigments, merocyanine pigments. Various dyes can be used, such as dyes, triphenylmethane dyes, porphyrin dyes, phthalocyanine dyes, perylene dyes, indigo dyes, naphthalocyanine dyes, and bipyridyl complexes having ruthenium as a central metal. Among them, metal complex dyes such as bipyridyl complex and turpyridyl complex are more preferable. In the case of metal complex dyes, Cu, Ni, Fe, Co, V, Sn, Si, Ti, Ge, Cr, Zn, Ru, Mg, Al, Pb, Mn, In, Mo, Y, Zr, Nb, Sb, La, W, Pt, Ta, Ir, Pd, Os, Ga, Tb, Eu, Rb, Bi, Se, As, Sc, Ag, Cd, Hf, Re, Au, Ac, Tc, Te, A metal such as Rh is used. Among these, metal complex dyes such as Fe, Cu, Ru, Rh, Re, Os, and Pt are more preferable, and Ru is even more preferable.
導電性基材に備えたｎ型半導体に増感色素を担持する方法としては、特に限定されず、公知の方法を採用することができる。例えば、上記の方法により得られた導電性基材に備えたｎ型半導体を、増感色素を含有する溶液に浸漬して化学吸着させて行うことができる。ここで使用する溶媒は、増感色素を溶解させるものであればよい。 The method of supporting the sensitizing dye on the n-type semiconductor provided on the conductive substrate is not particularly limited, and a known method can be adopted. For example, the n-type semiconductor provided on the conductive substrate obtained by the above method can be immersed in a solution containing a sensitizing dye and chemically adsorbed. The solvent used here may be any one that dissolves the sensitizing dye.
本発明に使用する支持電解質としては、メディエーターである臭素の酸化還元系を含む四級アンモニウム塩が好ましい。臭素の酸化還元系を含む四級アンモニウム塩としては、テトラエチルアンモニウムブロミド、テトラブチルアンモニウムブロミドなどが挙げられる。臭素の酸化還元系を含む四級アンモニウム塩は、他の四級アンモニウム塩と組み合わせて使用することがさらに好ましい。そのような他の四級アンモニウム塩としては、テトラフルオロほう酸テトラエチルアンモニウム、トリフルオロメタンスルホン酸テトラエチルアンモニウム、過塩素酸テトラエチルアンモニウムなどが挙げられる。 As the supporting electrolyte used in the present invention, a quaternary ammonium salt containing a redox system of bromine, which is a mediator, is preferable. Examples of the quaternary ammonium salt containing a redox system of bromine include tetraethylammonium bromide and tetrabutylammonium bromide. The quaternary ammonium salt containing the redox system of bromine is more preferably used in combination with other quaternary ammonium salts. Examples of such other quaternary ammonium salts include tetraethylammonium tetrafluoroborate, tetraethylammonium trifluoromethanesulfonate, tetraethylammonium perchlorate and the like.
本発明に使用する電解液の溶媒としては、一般式（１）で表されるフランやその誘導体、一般式Ｒ3ＯＨで表されるアルコール、および支持電解質を溶解し、カチオンラジカルと作用しない非プロトン性極性溶媒が好ましく、アセトニトリルがさらに好ましい。 As the solvent of the electrolytic solution used in the present invention, furan represented by the general formula (1) or a derivative thereof, an alcohol represented by the general formula R 3 OH, and a supporting electrolyte are dissolved and do not act on the cationic radical. Protic polar solvents are preferred, and acetonitrile is even more preferred.
本発明のカソード電極材料としては、限定されず、例えば、白金、金、銀、パラジウム、カーボンなどが挙げられるが、効率よく一般式（２）で表される２，５−ジアルコキシ−２，５−ジヒドロフランやその誘導体を製造するための観点から、白金を用いることが好ましい。 The cathode electrode material of the present invention is not limited, and examples thereof include platinum, gold, silver, palladium, carbon, etc., but 2,5-dihydrofuran-2, which is efficiently represented by the general formula (2), From the viewpoint of producing 5-dihydrofuran and its derivatives, it is preferable to use platinum.
以下、実施例によって本発明をさらに具体的に説明するが、本発明はこれらの実施例によって何ら限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
（実施例１）
増粘剤としてエチルセルロースを含むＴｉＯ2ペースト（住友大阪セメント）を導電性基板のＦＴＯ膜の表面にスクリーン印刷し５２５℃にて空気中で焼成した。これを下記式（３）
A TiO 2 paste (Sumitomo Osaka Cement) containing ethyl cellulose as a thickener was screen-printed on the surface of the FTO film of the conductive substrate and fired in air at 525 ° C. This is expressed by the following formula (3)
支持電解質としてテトラエチルアンモニウムブロミド（濃度０.０１Ｍ）とテトラフルオロほう酸テトラエチルアンモニウム（濃度０.０９Ｍ）を３０ｍＬのアセトニトリルに溶解させ、電解液を調製した。ナフィオン（登録商標）膜を隔膜とした二室型電解槽のアノード室にＮ７１９担持ＴｉＯ2可視光応答性光アノード電極と銀からなる参照電極を、カソード室に白金からなるカソード電極をそれぞれ設置し、直流電源のポテンシオ／ガルバノスタットを介してこれらの電極を電気的に接続した。アノード室とカソード室に調製した電解液を１５ｍＬずつ注入し、ソーラーシュミレーターと短波長カットフィルターを用いて可視光より短波長の光をカットした疑似太陽光（ＡＭ１.５）を照射して１.０Ｖ（標準水素電極（ＳＨＥ）に対する電位、以下、「Ｖ（ＳＨＥ）」と表示する）の一定電位で５Ｃの電気量を流した。 Tetraethylammonium bromide (concentration 0.01M) and tetraethylammonium tetrafluoroborate (concentration 0.09M) were dissolved in 30 mL of acetonitrile as supporting electrolytes to prepare an electrolytic solution. An N719-supported TiO 2 visible light-responsive optical anode electrode and a reference electrode made of silver were installed in the anode chamber of a two-chamber electrolytic cell having a Nafion (registered trademark) membrane as a diaphragm, and a cathode electrode made of platinum was installed in the cathode chamber. These electrodes were electrically connected via a cathode / galvanostat with a DC power supply. 1. Inject 15 mL of the prepared electrolyte into the anode chamber and the cathode chamber, and irradiate with pseudo-sunlight (AM1.5) that cuts light with a shorter wavelength than visible light using a solar simulator and a short wavelength cut filter. An electric quantity of 5C was passed at a constant potential of 0V (potential with respect to the standard hydrogen electrode (SHE), hereinafter referred to as “V (SHE)”).
次に、フラン０.８ｍＬ、アルコールとしてメタノール（ＣＨ3ＯＨ）２.２ｍＬをアノード室に注入し、１０分間攪拌した。その後、電解液２００μＬを採取し、ジエチルエーテルとイオン交換水にて分液処理を行い、有機層をガスクロマトグラフ（島津製作所社製、ＧＣ−２０１４）により分析したところ、下記式（４）
（比較例１）
Ｎ７１９色素を担持していない可視光応答性でないＴｉＯ2光アノード電極を用いたことを除いて実施例１と同様の操作を行ったが、２，５−ジメトキシ−２，５−ジヒドロフランは得られなかった。
(Comparative Example 1)
The same operation as in Example 1 was carried out except that a non-visible light responsive TiO 2 photoanode electrode carrying no N719 dye was used, but 2,5-dimethoxy-2,5-dihydrofuran was obtained. I couldn't.
（実施例２）
アルゴン置換したグローブバッグ中で０.５０Ｍ、および０.２５Ｍの六塩化タングステンのジメチルホルムアミド溶液を調製した。導電性基板のＦＴＯ膜の表面に０.５０Ｍの六塩化タングステン溶液２００μＬを２０００ｒｐｍでスピンコートした後５００℃にて空気中で焼成し、０.２５Ｍの六塩化タングステン溶液２００μＬを２０００ｒｐｍで再度スピンコートした後５００℃にて空気中で焼成しＷＯ３膜を作製した。そして、ビスマス前駆体塗布液（高純度化学研究所製、ＥＭＯＤ塗布型材料）、バナジウム前駆体塗布液（高純度化学研究所製、ＥＭＯＤ塗布型材料）、および増粘剤としてエチルセルロースを溶解した酢酸ブチルからなる溶液（Ｂｉ、Ｖ濃度各０.０４Ｍ）４００μＬを、ＷＯ3膜の表面に５００ｒｐｍでスピンコートした。これを５５０℃にて空気中で焼成し、ＷＯ3とＢｉＶＯ4が積層したＷＯ3／ＢｉＶＯ4可視光応答性光アノード電極を作製した。
(Example 2)
A dimethylformamide solution of 0.50 M and 0.25 M tungsten hexachloride was prepared in an argon-substituted glove bag. 200 μL of 0.50 M tungsten hexachloride solution was spin-coated on the surface of the FTO film of the conductive substrate at 2000 rpm, then fired in air at 500 ° C., and 200 μL of 0.25 M tungsten hexachloride solution was spin-coated again at 2000 rpm. Then, it was fired in air at 500 ° C. to prepare a WO 3 film. Then, a bismuth precursor coating solution (manufactured by High Purity Chemical Laboratory, EMOD coating type material), a vanadium precursor coating solution (manufactured by High Purity Chemical Laboratory, EMOD coating type material), and acetic acid in which ethyl cellulose is dissolved as a thickener. 400 μL of a solution consisting of butyl (Bio, V concentration 0.04 M each) was spin-coated on the surface of the WO 3 film at 500 rpm. This was fired in air at 550 ° C. to prepare a WO 3 / BiVO 4 visible light responsive photoanode electrode in which WO 3 and BiVO 4 were laminated.
アルコールとしてエタノール（Ｃ2Ｈ5ＯＨ）、及びＷＯ3／ＢｉＶＯ4可視光応答性光アノード電極を用いたことを除いて実施例１と同様の操作を行ったところ、下記式（５）
（実施例３）
アルコールとしてｎ−ブタノール（ｎ−Ｃ4Ｈ9ＯＨ）、およびＷＯ3／ＢｉＶＯ4可視光応答性光アノード電極を用いたことを除いて実施例１と同様の操作を行ったところ、下記式（６）
The same operation as in Example 1 was carried out except that n-butanol (n-C 4 H 9 OH) and WO 3 / BiVO 4 visible light responsive photoanode electrode were used as the alcohol. 6)
（実施例４）
フラン０.８ｍＬ、アルコールとしてメタノール２.２ｍＬ、および支持電解質としてテトラエチルアンモニウムブロミド（濃度０.１Ｍ）を１２ｍＬのアセトニトリルに溶解させ、電解液を調製した。
(Example 4)
An electrolytic solution was prepared by dissolving 0.8 mL of furan, 2.2 mL of methanol as an alcohol, and tetraethylammonium bromide (concentration 0.1 M) as a supporting electrolyte in 12 mL of acetonitrile.
次に、一室型電解槽にＷＯ3／ＢｉＶＯ4可視光応答性光アノード電極、白金からなるカソード電極、および銀からなる参照電極を設置し、直流電源のポテンシオ／ガルバノスタットを介してこれらの電極を電気的に接続した。この電解槽に電解液を注入し、ソーラーシュミレーターを用いて疑似太陽光（ＡＭ１.５）を照射して１.０Ｖ（ＳＨＥ）の一定電位で５Ｃの電気量を流した。光照射下では、光非照射下と比較して必要な印加電圧が１.５Ｖ低減された。 Next, a WO 3 / BiVO 4 visible light responsive photoanode electrode, a cathode electrode made of platinum, and a reference electrode made of silver were installed in a one-chamber electrolytic cell, and these were installed via a DC power supply potentio / galvanostat. The electrodes were electrically connected. An electrolytic solution was injected into this electrolytic cell, and pseudo-sunlight (AM1.5) was irradiated using a solar simulator to pass an electric amount of 5C at a constant potential of 1.0V (SHE). Under light irradiation, the required applied voltage was reduced by 1.5 V as compared with under non-light irradiation.
電解液２００μＬを採取し、ジエチルエーテルとイオン交換水にて分液処理を行い、有機層をガスクロマトグラフ（島津製作所社製、ＧＣ−２０１４）により分析したところ、２，５−ジメトキシ−２，５−ジヒドロフランが得られたことを確認した。 200 μL of the electrolytic solution was collected, separated with diethyl ether and ion-exchanged water, and the organic layer was analyzed by a gas chromatograph (manufactured by Shimadzu Corporation, GC-2014). As a result, 2,5-dimethoxy-2,5 was obtained. -It was confirmed that dihydrofuran was obtained.
（実施例５）
支持電解質としてテトラブチルアンモニウムブロミド０.１Ｍを用いたことを除いて実施例４と同様の操作を行ったところ、２，５−ジメトキシ−２，５−ジヒドロフランが得られた。
(Example 5)
When the same operation as in Example 4 was carried out except that tetrabutylammonium bromide 0.1M was used as the supporting electrolyte, 2,5-dimethoxy-2,5-dihydrofuran was obtained.
（実施例６）
支持電解質としてテトラエチルアンモニウムブロミド０.０５Ｍとテトラフルオロほう酸テトラエチルアンモニウム０.０５Ｍを用いたことを除いて実施例４と同様の操作を行ったところ、２，５−ジメトキシ−２，５−ジヒドロフランが得られた。
(Example 6)
When the same operation as in Example 4 was carried out except that tetraethylammonium bromide 0.05M and tetraethylammonium tetraethylammonium tetrafluoroborate were used as supporting electrolytes, 2,5-dimethoxy-2,5-dihydrofuran was obtained. Obtained.
（実施例７）
支持電解質としてテトラエチルアンモニウムブロミド０.０５Ｍとトリフルオロメタンスルホン酸テトラエチルアンモニウム０.０５Ｍを用いたことを除いて実施例４と同様の操作を行ったところ、２，５−ジメトキシ−２，５−ジヒドロフランが得られた。
(Example 7)
When the same operation as in Example 4 was carried out except that tetraethylammonium bromide 0.05M and tetraethylammonium trifluoromethanesulfonate 0.05M were used as supporting electrolytes, 2,5-dimethoxy-2,5-dihydrofuran was carried out. was gotten.
（実施例８）
支持電解質としてテトラエチルアンモニウムブロミド０.０５Ｍと過塩素酸テトラエチルアンモニウム０.０５Ｍを用いたことを除いて実施例４と同様の操作を行ったところ、２，５−ジメトキシ−２，５−ジヒドロフランが得られた。
(Example 8)
When the same operation as in Example 4 was carried out except that tetraethylammonium bromide 0.05M and tetraethylammonium perchlorate 0.05M were used as the supporting electrolytes, 2,5-dimethoxy-2,5-dihydrofuran was obtained. Obtained.
（比較例２）
支持電解質としてテトラフルオロほう酸テトラエチルアンモニウム０.１Ｍを用いたことを除いて実施例４と同様の操作を行ったが、２，５−ジメトキシ−２，５−ジヒドロフランは得られなかった。
(Comparative Example 2)
The same procedure as in Example 4 was carried out except that tetraethylammonium tetraethylammonium tetrafluoroborate was used as the supporting electrolyte, but 2,5-dimethoxy-2,5-dihydrofuran was not obtained.
（比較例３）
電圧を印加しないことを除いて実施例４と同様の操作を行ったが、２，５−ジメトキシ−２，５−ジヒドロフランは得られなかった。
(Comparative Example 3)
The same operation as in Example 4 was carried out except that no voltage was applied, but 2,5-dimethoxy-2,5-dihydrofuran was not obtained.
（比較例４）
電圧を印加しないこと、及び光を照射しないことを除いて実施例４と同様の操作を行ったが、２，５−ジメトキシ−２，５−ジヒドロフランは得られなかった。
(Comparative Example 4)
The same operation as in Example 4 was carried out except that no voltage was applied and no light was applied, but 2,5-dimethoxy-2,5-dihydrofuran was not obtained.
本発明は、医農薬原料、ポリマー原料、香料などの合成の中間体として重要である２，５−ジアルコキシ−２，５−ジヒドロフランやその誘導体を、安価に効率よく製造する技術に適用できる。 The present invention can be applied to a technique for inexpensively and efficiently producing 2,5-dialkoxy-2,5-dihydrofuran and its derivatives, which are important as intermediates for the synthesis of medical and agricultural chemical raw materials, polymer raw materials, fragrances and the like. ..
Claims (8)
Ｒ３ＯＨ
（式中、Ｒ３は炭素数４以下のアルキル基を示す）で表されるアルコールから、臭素の酸化還元系を含む支持電解質と、直流電圧が印可された可視光応答性光アノード電極を用い、可視光応答性光アノード電極表面に光を照射して光電解酸化反応により次の一般式（２）
(In the formula, R 3 represents an alkyl group having 4 or less carbon atoms), using a supporting electrolyte containing a redox system of bromine and a visible light responsive photoanode electrode to which a DC voltage is applied. , Visible light responsive photoAnode electrode surface is irradiated with light and subjected to photoelectrolyte oxidation reaction by the following general formula (2)
Ｒ3ＯＨ
（式中、Ｒ3は炭素数４以下のアルキル基を示す）で表されるアルコールとを供給する供給装置とを具備する、次の一般式（２）
(In the formula, R 3 represents an alkyl group having 4 or less carbon atoms), which comprises a supply device for supplying the alcohol represented by the following general formula (2).
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