CN114981482A - Method for producing epoxy compound - Google Patents
Method for producing epoxy compound Download PDFInfo
- Publication number
- CN114981482A CN114981482A CN202080075921.8A CN202080075921A CN114981482A CN 114981482 A CN114981482 A CN 114981482A CN 202080075921 A CN202080075921 A CN 202080075921A CN 114981482 A CN114981482 A CN 114981482A
- Authority
- CN
- China
- Prior art keywords
- epoxy compound
- ion
- formula
- olefin
- ions
- 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.)
- Pending
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 104
- 239000004593 Epoxy Substances 0.000 title claims abstract description 98
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 31
- -1 peracid ion Chemical class 0.000 claims abstract description 74
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 65
- 150000001336 alkenes Chemical class 0.000 claims abstract description 63
- 150000003839 salts Chemical class 0.000 claims abstract description 56
- 239000008346 aqueous phase Substances 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 32
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 35
- 150000004696 coordination complex Chemical class 0.000 claims description 29
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- 239000012071 phase Substances 0.000 claims description 21
- 230000003647 oxidation Effects 0.000 claims description 20
- 230000001590 oxidative effect Effects 0.000 claims description 19
- 239000003960 organic solvent Substances 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 14
- 150000001768 cations Chemical class 0.000 claims description 11
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 9
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 abstract description 2
- 229910052783 alkali metal Inorganic materials 0.000 abstract 1
- 150000001340 alkali metals Chemical class 0.000 abstract 1
- 238000002848 electrochemical method Methods 0.000 abstract 1
- 229910021645 metal ion Inorganic materials 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 27
- 125000004432 carbon atom Chemical group C* 0.000 description 21
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 20
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 20
- 239000003446 ligand Substances 0.000 description 19
- 239000000460 chlorine Substances 0.000 description 14
- 229910052801 chlorine Inorganic materials 0.000 description 14
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 13
- 239000003792 electrolyte Substances 0.000 description 12
- 125000000623 heterocyclic group Chemical group 0.000 description 11
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 10
- 235000017557 sodium bicarbonate Nutrition 0.000 description 10
- 239000011780 sodium chloride Substances 0.000 description 10
- VEUMANXWQDHAJV-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VEUMANXWQDHAJV-UHFFFAOYSA-N 0.000 description 9
- 238000004817 gas chromatography Methods 0.000 description 9
- 229910052748 manganese Inorganic materials 0.000 description 8
- 239000011572 manganese Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 150000002430 hydrocarbons Chemical group 0.000 description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 7
- 239000003566 sealing material Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 125000002723 alicyclic group Chemical group 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- 125000004423 acyloxy group Chemical group 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 150000001805 chlorine compounds Chemical class 0.000 description 4
- 150000001925 cycloalkenes Chemical group 0.000 description 4
- 229910003460 diamond Inorganic materials 0.000 description 4
- 239000010432 diamond Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- ITWBWJFEJCHKSN-UHFFFAOYSA-N 1,4,7-triazonane Chemical compound C1CNCCNCCN1 ITWBWJFEJCHKSN-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-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
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- QROGIFZRVHSFLM-KXFIGUGUSA-N [(z)-prop-1-enyl]benzene Chemical compound C\C=C/C1=CC=CC=C1 QROGIFZRVHSFLM-KXFIGUGUSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 125000005647 linker group Chemical group 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 2
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- 150000004032 porphyrins Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 229910052702 rhenium Inorganic materials 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910052706 scandium Inorganic materials 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 2
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 125000006661 (C4-C6) heterocyclic group Chemical group 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical group CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical group OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 241001590997 Moolgarda engeli Species 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical group CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000000392 cycloalkenyl group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 description 1
- 239000004913 cyclooctene Substances 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- HRGDZIGMBDGFTC-UHFFFAOYSA-N platinum(2+) Chemical compound [Pt+2] HRGDZIGMBDGFTC-UHFFFAOYSA-N 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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Abstract
Provided is a method for efficiently producing an epoxy compound by an electrochemical method. Disclosed is a method for producing an epoxy compound, wherein a salt represented by the following formula (a) is electrolytically oxidized in an aqueous phase to form a peracid ion represented by the following formula (b), and an olefin is oxidized by the peracid ion represented by the following formula (b) to obtain the corresponding epoxy compound. In the formula, R d Represents a group selected from a single bond, SO 2 A divalent radical of CO and P (═ O) OH, A + Represents an ion selected from alkali metal ionsAlkaline earth metal ions, ammonium ions, phosphonium ions and sulfonium ions.
Description
Technical Field
The present disclosure relates to a method of oxidizing an olefin to produce an epoxy compound using an electrochemical process. The present disclosure claims priority from Japanese patent application No. 2019-196508, filed in Japan on 10/29/2019, the contents of which are incorporated herein by reference.
Background
The epoxy compound reacts with various curing agents and curing catalysts to form a cured product having high strength, heat resistance, transparency, and the like. Therefore, the resin composition is extremely useful as a raw material for sealing materials, coating materials, adhesives, inks, sealing materials, and the like.
As a method for producing such an epoxy compound, non-patent document 1 describes that an organic layer-aqueous phase two-phase solvent containing a salen manganese complex and cis- β -methylstyrene as a matrix, dichloromethane and an aqueous sodium chloride solution is charged into an electrolytic cell provided with a pair of platinum electrodes, and the following reactions 1 to 3 are continuously performed by applying electricity, whereby an epoxy compound can be produced stereoselectively.
1. Hypochlorous acid is generated by electrolytic oxidation of sodium chloride in the aqueous phase.
2. Hypochlorous acid generated in the aqueous phase moves to the organic layer and oxidizes the salen manganese complex.
3. The oxidized salen manganese complex oxidizes cis-beta-methylstyrene to produce a cis-epoxy compound corresponding to cis-beta-methylstyrene.
Documents of the prior art
Non-patent literature
Non-patent document 1: tanaka, m.kuroboshi, h.takeda, h.kanda, s.torii, j.electroananal.chem.2001, 507,75-81.
Disclosure of Invention
Problems to be solved by the invention
However, in the above reaction, the epoxy compound is obtained in a yield of 80% or more, but it takes 16 hours or more, and therefore, it is necessary to increase the reaction rate.
In addition, since sodium chloride is used as an electrolyte in the above method, a chloride of olefin is by-produced. Therefore, it is inevitable to mix a chlorine compound into the epoxy compound, and for example, when a substance in which a chlorine compound is mixed into the epoxy compound is used for a sealing material of a printed circuit board or the like, the wiring (particularly copper wiring) of the printed circuit board is corroded by the chlorine compound, and thus there is a problem that long-term reliability is lowered. Further, the above problem is remarkable with the miniaturization and high density of electronic parts. In addition, chlorides of olefins have a large environmental burden, which is also a problem.
Accordingly, it is an object of the present disclosure to provide a method for efficiently manufacturing an epoxy compound using an electrochemical process.
It is another object of the present disclosure to provide a method for efficiently manufacturing an epoxy compound having a low chlorine content using an electrochemical process.
Technical scheme
As a result of intensive studies to solve the above problems, the present inventors have found that an olefin can be produced by subjecting a salt represented by the following formula (a) to electrolytic oxidation in water to oxidize the olefin using a generated peracid ion represented by the following formula (b), or by subjecting a salt represented by the following formula (a) to electrolytic oxidation in water to oxidize a metal complex using a generated peracid ion represented by the following formula (b) and oxidize the olefin using a metal oxo complex generated by oxidizing the metal complex, whereby the oxidation reaction of the olefin can be more efficiently carried out, the corresponding epoxy compound can be produced in a higher yield, and the epoxy compound having a low chlorine content can be produced without using sodium chloride in the reaction. The present disclosure has been completed based on these findings.
That is, the present disclosure provides a method for producing an epoxy compound, comprising electrolytically oxidizing a salt represented by the following formula (a) in an aqueous phase to generate a peracid ion represented by the following formula (b), and oxidizing an olefin with the generated peracid ion represented by the following formula (b) to obtain the corresponding epoxy compound.
[ chemical formula 1]
(in the formula, R d Represents a group selected from a single bond, SO 2 A divalent radical of CO and P (═ O) OH, A + Represents a cation selected from the group consisting of an alkali metal ion, an alkaline earth metal ion, an ammonium ion, a phosphonium ion and a sulfonium ion)
The present disclosure also provides a method for producing an epoxy compound, comprising electrolytically oxidizing a salt represented by the following formula (a) in an aqueous phase to generate a peracid ion represented by the following formula (b), oxidizing a metal complex with the generated peracid ion represented by the following formula (b) to generate a metal oxo complex, and oxidizing an olefin with the generated metal oxo complex to obtain a corresponding epoxy compound.
[ chemical formula 2]
(in the formula, R d Represents a group selected from a single bond, SO 2 A divalent radical of CO and P (═ O) OH, A + Represents a cation selected from the group consisting of an alkali metal ion, an alkaline earth metal ion, an ammonium ion, a phosphonium ion and a sulfonium ion)
The present disclosure also provides a method for producing the epoxy compound, wherein a metal complex, an olefin, a salt represented by the following formula (a), and water are charged in an electrolytic bath and an electric current is applied.
[ chemical formula 3]
(wherein R is d Represents a group selected from a single bond, SO 2 Divalent radicals of CO and P (═ O) OH, A + Represents a cation selected from the group consisting of an alkali metal ion, an alkaline earth metal ion, an ammonium ion, a phosphonium ion and a sulfonium ion)
The present disclosure also provides a method for producing the epoxy compound, wherein the concentration of the salt represented by the following formula (a) in the aqueous phase is 0.1 to 5 mol/L.
[ chemical formula 4]
(in the formula, R d Represents a group selected from a single bond, SO 2 A divalent radical of CO and P (═ O) OH, A + Represents a cation selected from the group consisting of an alkali metal ion, an alkaline earth metal ion, an ammonium ion, a phosphonium ion and a sulfonium ion)
The present disclosure also provides a method for producing the epoxy compound, wherein the electrolytic oxidation is performed in a two-phase solvent of an aqueous phase and an organic solvent phase.
Effects of the invention
According to the method for producing an epoxy compound of the present disclosure, the oxidation reaction rate of olefin can be increased as compared with the case of using the conventional method, and the corresponding epoxy compound can be efficiently produced.
In addition, in the method for producing an epoxy compound of the present disclosure, since sodium chloride is not required to be used as an electrolyte, the chlorine content of the obtained epoxy compound can be made extremely low. Therefore, the epoxy compound can be preferably used as a sealing material for a semiconductor or the like, and a semiconductor sealed with the epoxy compound can prevent corrosion of wiring due to chlorine, and thus can prevent occurrence of disconnection, insulation failure, and the like due to corrosion of wiring.
Therefore, the use of the epoxy compound can realize further miniaturization, higher density, higher reliability, and longer life of electronic parts.
Drawings
FIG. 1 is a diagram 1- (I) showing the results of gas chromatography analysis of the epoxy compound obtained in example 1 and a diagram 1- (II) showing the results of gas chromatography analysis of the epoxy compound obtained in comparative example 1.
FIG. 2 is a graph (2- (I) showing the results of gas chromatography analysis of the epoxy compound obtained in example 2 and a graph (2- (II) showing the results of gas chromatography analysis of the epoxy compound obtained in comparative example 2.
Detailed Description
[ Process for producing epoxy Compound ]
The method for producing an epoxy compound of the present disclosure is characterized by obtaining an epoxy compound through the following steps [1] and [2 ].
[1] Subjecting a salt represented by the following formula (a) (hereinafter, sometimes referred to as "salt (a)") to electrolytic oxidation in an aqueous phase to obtain a peracid ion represented by the following formula (b) (hereinafter, sometimes referred to as "peracid ion (b)");
[2] oxidizing the olefin with the generated peracid ion (b).
In addition, electrolytic oxidation is a method of obtaining an oxide by utilizing an anode reaction in electrolysis.
[ chemical formula 5]
(in the formula, R d Represents a group selected from a single bond, SO 2 A divalent radical of CO and P (═ O) OH, A + Is selected from alkali metal ions (such as sodium ion, potassium ion, etc.), alkaline earth metal ions (such as magnesium ion, calcium ion, etc.), ammonium ions (such as ammonium ion shown in the following formula (c) ("wherein four R's are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms)]) Phosphonium and sulfonium cations. )
[ chemical formula 6]
Examples of the salt (a) include sodium hydrogen carbonate, sodium hydrogen sulfate, and disodium hydrogen phosphate.
Examples of the peracid ion (b) include a percarbonate ion, a persulfate ion, and a perphosphate ion.
Comprising the step [1]And [2]]The following reaction is carried out in the method for producing an epoxy compound of (1). In addition, in the following reaction system, the olefin is represented by formula(s), and the corresponding epoxy compound is represented by formula (p). R in the formula d As described above.
[ chemical formula 7]
R in the above formula(s) 11 ～R 14 The same or different, represent a hydrogen atom, a hydrocarbon group or a heterocyclic group. R 11 And R 12 Or may be linked to each other to form a ring together with the adjacent carbon atoms. R is 13 And R 14 The same applies.
R in the above formula (p) 11 ～R 14 And R in the above formula(s) 11 ～R 14 And (7) corresponding.
The hydrocarbon group includes a saturated or unsaturated aliphatic hydrocarbon group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group. Among the aliphatic hydrocarbon groups, a saturated or unsaturated aliphatic hydrocarbon group having 1 to 10 carbon atoms is preferable. Examples of the aliphatic hydrocarbon group include: alkyl groups having 1 to 10 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, decyl, and dodecyl groups; alkenyl groups having 1 to 10 carbon atoms such as vinyl, allyl, and 1-butenyl groups.
As the alicyclic hydrocarbon group, C is preferred 3-10 Examples of the alicyclic hydrocarbon group of (2) include: cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl; cycloalkenyl groups such as cyclopentenyl and cyclohexenyl; decahydronaphthalen-1-yl, norbornyl, adamantyl, tricyclo [5.2.1.0 2,6 ]Bridged hydrocarbon groups such as a decane-8-yl group.
As the aromatic hydrocarbon group, C is preferred 6-14 (particularly C) 6-10 ) Examples of the aromatic hydrocarbon group in (b) include a phenyl group and a naphthyl group.
The heterocyclic ring constituting the heterocyclic group includes aromatic heterocyclic rings and non-aromatic heterocyclic rings. Examples of such heterocyclic rings include 3 to 10-membered heterocyclic rings (preferably 4 to 6-membered heterocyclic rings) having carbon atoms and at least one kind of hetero atoms (for example, oxygen atom, sulfur atom, nitrogen atom, etc.) among atoms constituting the ring, and condensed rings thereof. The heterocyclic group is a group obtained by removing one hydrogen atom from the structural formula of the above-mentioned heterocycle.
As R 11 And R 12 Or R 13 And R 14 Rings which may be linked to each other and which form together with adjacent carbon atoms, for example C 3-10 Cycloolefin ring, C 6-14 Aromatic rings, heterocycles, and the like.
The olefin is a compound represented by the formula(s) wherein R is 11 And R 12 Is a hydrogen atom and R 13 And R 14 The compound which is bonded to each other and forms a cycloolefin ring together with the adjacent carbon atoms, that is, a cyclic olefin is preferable, a 3 to 10-membered cyclic olefin is particularly preferable, and a 5 to 8-membered cyclic olefin is particularly preferable.
In general, it is very difficult to directly electrolytically oxidize olefins by means of electrodes. Further, even if the olefin is oxidized, only radicals are generated, and an epoxy compound cannot be obtained. However, in the present disclosure, a salt (a) that is more easily oxidized than an olefin is electrolytically oxidized through an electrode to generate a peracid ion (b), and the olefin is oxidized using the generated peracid ion (b). Therefore, the progress of the oxidation reaction of the olefin can be promoted, and the corresponding epoxy compound can be efficiently produced.
In the present disclosure, since the oxidation reaction of the olefin proceeds as described above, the oxidation reaction rate of the olefin can be adjusted by adjusting the concentration of the salt (a) (or the cation represented by the above formula (a')) in the system (particularly in the aqueous system), and the reaction can be easily controlled. In addition, the peracid ion (b) is reduced by oxidizing the olefin, and the cation represented by the above formula (a ') is regenerated, but the regenerated cation represented by the above formula (a') can be used again for electrolytic oxidation. Therefore, the salt (a) is used only in an amount of the catalyst level relative to the olefin, contributing to a reduction in environmental load.
In the step [1], for example, an aqueous solution of the salt (a) is fed as an electrolytic solution to an electrolytic cell (preferably a non-diaphragm electrolytic cell) provided with a pair of electrodes, and the cell is energized (specifically, a voltage is applied and a current is applied).
Examples of the electrode include a platinum electrode, a conductive diamond (e.g., boron-doped diamond, nitrogen-doped diamond, etc.) electrode, and a graphite electrode.
The applied voltage is, for example, 5 to 10V. Under the condition of constant current, the applied voltage is 3-30 mA/cm 2 。
For example, when an electrolytic cell charged with an aqueous solution of sodium bicarbonate as the aqueous solution of the salt (a) is energized, sodium bicarbonate is electrolyzed at the anode (the electrode where electrochemical oxidation occurs, i.e., the anode). Then, a percarbonate ion is generated by the reaction shown in the following formula (1). The percarbonate ion corresponds to the peracid ion (b).
NaHCO 3 +H 2 O→HCO 4 - +Na + +2H + +2e - (1)
The electrolyte solution of the present disclosure contains at least a salt (a) as an electrolyte. The concentration of the salt (a) in the aqueous phase is, for example, 0.1 to 5mol/L, preferably 0.1 to 2.8mol/L, more preferably 0.5 to 2mol/L, particularly preferably 0.8 to 1.4mol/L, and most preferably 1.0 to 1.2 mol/L.
The supply molar ratio (former/latter) of the olefin and the salt (a) to the reaction system is, for example, 1/1000 to 1000/1, preferably 1/100 to 100/1, and particularly preferably 1/10 to 10/1.
The electrolyte solution may contain other electrolytes (for example, carbonates such as sodium carbonate or halides such as sodium chloride) in addition to the salt (a), and the content of the other electrolytes (the total content thereof in the case of containing 2 or more species) is, for example, 95 mol% or less of the total amount of electrolytes contained in the electrolyte solution, and is preferably 80 mol% or less, more preferably 70 mol% or less, more preferably 60 mol% or less, further preferably 50 mol% or less, particularly preferably 40 mol% or less, most preferably 20 mol% or less, and particularly preferably 15 mol% or less, from the viewpoint of excellent effect of promoting the oxidation reaction of olefins.
The electrolyte can be produced by mixing the salt (a), an acid, and water, for example. Examples of the acid include nitric acid, sulfuric acid, and phosphoric acid. The mixing amount of the acid is within the range of about 0 to 12 of the pH value of the electrolyte.
The pH of the electrolyte is preferably appropriately changed depending on the kind of the salt (a). For example, in the use of carbonWhen sodium hydrogen carbonate is used as the salt (a), the pH is preferably set to bicarbonate ion (HCO) in the electrolyte 3 - ) The concentration of (3) is in a range of 4 to 12, preferably 5 to 11, more preferably 6 to 11, and most preferably 6.3 to 10.5.
By the above-mentioned step [1]Generated peracid ion (b) [ for example, in the case of using sodium hydrogencarbonate as the salt (a), percarbonate ion (HCO) 4 - )]In the step [2]Is used as an oxidizing agent. Then, the peracid ion (b) oxidizes an olefin (compound represented by formula (s)) to generate a corresponding epoxy compound (compound represented by formula (p)).
In the reaction system, the olefin may be dispersed in an aqueous solution containing the salt (a). The olefin may be mixed with the aqueous solution containing the salt (a) in a state of being dissolved in the solvent, or the solvent in which the olefin is dissolved may be separated from the aqueous solution containing the salt (a).
Examples of the solvent for dissolving the olefin include: halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1, 2-dichloroethane, dichlorobenzene, and the like; hydrocarbons such as hexane and toluene; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; nitriles such as acetonitrile, propionitrile, and benzonitrile; and esters such as ethyl acetate and butyl acetate. These may be used singly or in combination of two or more.
For example, when a water-insoluble organic solvent (i.e., an organic solvent insoluble in water) is used as the solvent for dissolving the olefin, the aqueous solution containing the salt (a) and the water-insoluble organic solvent are separated without mixing to form a two-phase system, but when electrolytic oxidation is performed in the two-phase system, the reaction in the step [1] proceeds in the aqueous phase. Then, the peracid ion (b) generated in the step [1] is transferred to a water-insoluble organic solvent phase, and the reaction in the step [2] is carried out in the water-insoluble organic solvent phase. Therefore, by bringing the electrode into contact with only the aqueous phase, the oxidation reaction can be carried out only in the aqueous phase, and a side reaction in which the organic compound is oxidized on the electrode surface can be suppressed.
As described above, the reaction in the steps [1] and [2] is preferably carried out in a two-phase solvent of an aqueous phase containing the salt (a) and an aqueous phase/organic solvent phase of a water-insoluble organic solvent for dissolving the olefin, whereby a high-purity epoxy compound can be produced.
The method for producing an epoxy compound of the present disclosure may be a method in which a salt (a) which is more easily oxidized than an olefin is electrolytically oxidized using an electrode to generate a peracid ion (b), the generated peracid ion (b) is used to first oxidize a metal complex to generate a metal oxo complex, and then the generated metal oxo complex is used to oxidize the olefin. That is, a method of obtaining an epoxy compound by oxidizing an olefin in the following step [4] using a metal oxo complex produced in the following steps [1] and [3 ].
[1] The salt (a) is electrolytically oxidized in the aqueous phase to form the peracid ion (b).
[3] Oxidizing the metal complex with the generated peracid ion (b) to generate a metal oxo complex.
[4] The resulting metal oxo complex is used to oxidize an olefin.
Comprises the following step [1]、[3]And [4]The process for producing an epoxy compound according to (1), wherein the following reaction is carried out. In the following reaction system, the olefin is represented by formula(s) and the corresponding epoxy compound is represented by formula (p). In addition, R in the following formula d 、R 11 ～R 14 As described above.
[ chemical formula 8]
In the above reaction system, the salt (a) releases electrons on the electrode surface to generate the peracid ion (b), and the metal complex (L-M) is oxidized by the generated peracid ion (b) to generate the metal oxo complex (L-M ═ O). Then, the generated metal oxo complex (L-M ═ O) accelerates the oxidation reaction of the olefin represented by the formula(s).
Then, the metal oxo complex (L-M ═ O) is reduced by oxidizing the olefin, and the metal oxo complex (L-M) is regenerated, but the regenerated metal oxo complex (L-M) can be reused for electrolytic oxidation in the same manner as the salt (a). Therefore, the amount of the metal complex to be used may be an amount of the olefin to the extent of the catalyst, and this contributes to reduction of the environmental load.
In the process for producing an epoxy compound through the above steps [1] and [2], if the concentration of the salt (a) in the aqueous phase is increased, the rate of progress of the olefin oxidation reaction can be increased. However, if the concentration of the salt (a) is increased, the concentration of the peracid ion (b) increases, and the risk of explosion or the like increases. Therefore, there is a limit to increase the salt (a) concentration to increase the oxidation reaction rate of the olefin. On the other hand, in the method for producing an epoxy compound through the steps [1], [3] and [4], by using the salt (a) and the metal complex in combination, the oxidation reaction rate of the olefin can be increased by the catalytic action of the metal complex without excessively increasing the concentration of the salt (a), and the yield of the epoxy compound can be safely increased.
Examples of the metal complex include metal complexes containing a ligand selected from the group consisting of salen-based ligands, 1,4, 7-triazacyclononane-based ligands, porphyrin-based ligands, quinoline-based ligands, pyridine-based ligands, and acyloxy groups. When the ligand has a stereoisomer, it may be either of S type or R type.
Examples of the metal element constituting the metal complex include Sc, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, Ru, Rh, Pd, W, Re, Ir, and Pt. Among them, from the viewpoint of excellent effect of promoting the oxidation reaction of the olefin, a metal element selected from Ti, Cr, Mn, Fe, Co, Mo, and W is preferable, and a metal element selected from Ti, Mn, Mo, and W is particularly preferable.
Among these ligands, from the viewpoint of excellent effect of promoting the oxidation reaction of an olefin, a Salen-based ligand or a 1,4, 7-triazacyclonane-based ligand is preferable, and a Salen-based ligand is particularly preferable.
The metal complex containing a salen-based ligand is represented by the following formula (L-1), for example.
[ chemical formula 9]
(in the formula, R 1 ～R 10 The same or different, and is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Is selected from R 1 ～R 4 The 2 groups (2) may be bonded to each other to form a ring together with the adjacent carbon atom. R is 5 、R 6 Or may be linked to each other to form a ring together with the adjacent carbon atoms. Is selected from R 7 ～R 10 The 2 groups (2) may be bonded to each other to form a ring together with the adjacent carbon atoms. M represents a metal element, and X represents a halogen atom or an acyloxy group. )
Examples of the alkyl group having 1 to 5 carbon atoms include: and linear or branched alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, and pentyl.
As selected from R 1 ～R 4 Or R 7 ～R 10 The two groups (a) may be bonded to each other to form a ring together with adjacent carbon atoms, for example, a cycloolefin ring having 3 to 8 carbon atoms such as a cyclopentene ring and a cyclohexene ring. Further, as R 5 、R 6 And a ring which is formed together with adjacent carbon atoms and can be linked to each other, for example, a cycloalkane ring having 3 to 8 carbon atoms such as a cyclopentane ring or a cyclohexane ring.
The halogen atom in X is, for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.
Examples of the acyloxy group include a group represented by an [ R 'COO group ] (wherein R' is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms) such as a formate group, an acetate group, a propionate group, and a butyrate group.
The 1,4, 7-triazacyclononane-based ligand is represented by the following formula (L-2), for example.
[ chemical formula 10]
(in the formula, R 20 ～R 22 The same or different may have a substituent, and represents a monovalent hydrocarbon groupA monovalent heterocyclic group, or a monovalent group in which two or more of the above groups are bonded via a linking group. R 23 ～R 25 The monovalent hydrocarbon group may have a substituent, a monovalent heterocyclic group, or a monovalent group in which two or more of the above groups are bonded via a linking group. Is selected from R 20 ～R 25 May be bonded to each other to form a ring together with the nitrogen or carbon atom to which they are attached. )
At R 20 ～R 22 The hydrocarbon group in (1) includes a linear or branched aliphatic hydrocarbon group, alicyclic hydrocarbon group and aromatic hydrocarbon group.
Examples of the substituent which the group may have include a halogen atom, a hydroxyl group, a carboxyl group, a sulfo group, a nitro group, a phosphoric acid group and the like.
Examples of the linking group include: carbonyl (-CO-), ether bond (-O-), thioether bond (-S-), ester bond (-COO-), amide bond (-CONH-), and the like.
As selected from the group consisting of the R 20 ～R 25 A ring which is bonded to each other and may be formed together with the nitrogen atom or the carbon atom to which they are bonded, and examples thereof include alicyclic rings such as cyclopentane ring and cyclohexane ring; heterocyclic rings containing nitrogen atoms or the like as hetero atoms, and the like.
In the reaction system, the above metal complex may be present as a heterogeneous catalyst or may be present as a homogeneous catalyst. That is, the metal complex may be dispersed in a solvent (in an organic solvent in the case of electrolytic oxidation in a two-phase solvent of an aqueous phase and an organic solvent phase), and may be present as a homogeneous catalyst in a state of being supported on a carrier (for example, silica, alumina, zeolite, activated carbon, or the like) or in a state of being held on an electrode.
When the salt (a) and the metal complex are used together, the supply molar ratio (former/latter) of the olefin and the salt (a) in the reaction system is, for example, 1/1000 to 1000/1, preferably 1/100 to 100/1, and particularly preferably 1/10 to 10/1.
When the salt (a) and the metal complex are used together, the supply molar ratio (former/latter) of the olefin and the metal complex to the reaction system is, for example, 1/10 to 100000/1, preferably 1/1 to 1000/1, and particularly preferably 10/1 to 1000/1.
For example, when the reaction through the steps [1], [3] and [4] is performed by electrolytic oxidation in a two-phase solvent comprising an aqueous phase of the salt (a) and a water-insoluble organic solvent containing a metal complex, the reaction of the step [1] proceeds in the aqueous phase. Then, the peracid ion (b) generated in the step [1] is transferred to a water-insoluble organic solvent phase, and the reactions in the steps [3] to [4] are carried out in the organic solvent phase. Therefore, by bringing the electrode into contact with only the aqueous phase, the oxidation reaction can be carried out only in the aqueous phase, and a side reaction in which the organic compound is oxidized on the electrode surface can be suppressed.
As described above, the reaction through steps [1], [3] and [4] is preferably carried out in a two-phase solvent comprising an aqueous phase of the salt (a) and a water-insoluble organic solvent containing a metal complex, from the viewpoint of producing a high-purity epoxy compound.
According to the method for producing an epoxy compound of the present disclosure, an olefin can be efficiently oxidized to selectively produce a corresponding epoxy compound. For example, the yield of the epoxy compound when a voltage of 2.5V (vs. ag/AgCl) is applied for 30 minutes is, for example, 3% or more, preferably 4% or more. The yield of the epoxy compound when a voltage of 2.5V (vs. ag/AgCl) is applied for 14 hours is, for example, 30% or more.
Further, according to the method for producing an epoxy compound of the present disclosure, an epoxy compound having a low chlorine content can be produced. The chlorine content is, for example, 3000ppm or less, preferably 100ppm or less, particularly preferably 50ppm or less, and most preferably 1ppm or less, based on the total amount of the epoxy compound.
The epoxy compound obtained by the method for producing an epoxy compound of the present disclosure has a low chlorine content as described above, and thus can be preferably used as a sealing material for a printed circuit board or the like.
Further, when the epoxy compound obtained by the production method of the present disclosure is used as a sealing material, the problem of corrosion of wiring due to chlorine does not occur, and therefore, further downsizing, high density, high reliability, and long life of electronic parts can be achieved.
As described above, the respective configurations and combinations of the respective configurations of the present disclosure are examples, and addition, omission, replacement, and change of appropriate configurations may be made within the scope not departing from the gist of the present disclosure. The present disclosure is not limited by the embodiments, but is limited only by the description of the patent claims.
Examples
Hereinafter, the present disclosure will be described more specifically with reference to examples, but the present disclosure is not limited to these examples.
Example 1
In a one-compartment type electrolytic cell without a diaphragm, a two-phase solvent was added, which was added as an aqueous phase 84.01g of NaHCO 3 2.25mL of an aqueous sodium bicarbonate solution (1mol/L) obtained by dissolving the aqueous sodium bicarbonate solution in 1000mL of water was added CH as an organic phase 2 Cl 2 0.75mL, 32mg (0.05mmol) of Salen manganese complex (represented by the following formula (L-1-1), (S, S) - (+) -N, N' -bis (3, 5-di-t-butylsalicylidene) -1, 2-cyclohexanediaminommanganese (III) chloride) and 110mg (1mmol) of cyclooctene as a substrate were further added, and electrolytic oxidation was carried out under the following conditions under the application of a voltage of 2.5V for 30 minutes. The identification of the reaction products and the determination of the product yields were carried out using gas chromatography. Nitrobenzene was used as the internal standard substance (IS). The results of gas chromatography are shown in FIG. 1- (I).
< electrolytic Oxidation conditions >
Reference electrode: silver/silver chloride
Anode: boron-doped diamond
Cathode: platinum (II)
[ chemical formula 11]
Comparative example 1
The procedure of example 1 was repeated, except that an aqueous sodium chloride solution (1mol/L) was used instead of the aqueous sodium hydrogencarbonate solution. The results of the gas chromatography are shown in FIG. 1- (II).
The results are shown in the following table.
[ Table 1]
| Aqueous phase | Yield of epoxy Compound (%) | Chlorine content (ppm) | |
| Example 1 | NaHCO 3 | 3.4 | 0 |
| Comparative example 1 | NaCl | 2.5 | 5000 |
Example 2
The procedure of example 1 was repeated except that the substrate was changed to cyclohexene 82mg (1 mmol). The results of the gas chromatography are shown in FIG. 2- (I).
Comparative example 2
The procedure of example 2 was repeated, except that an aqueous sodium chloride solution (1mol/L) was used in place of the aqueous sodium hydrogencarbonate solution. The results of the gas chromatography are shown in FIG. 2- (II).
The results are shown in the following table.
[ Table 2]
| Aqueous phase | Yield of epoxy Compound (%) | Chlorine content (ppm) | |
| Example 2 | NaHCO 3 | 4.1 | 0 |
| Comparative example 2 | NaCl | 2.5 | 8000 |
Example 3
The reaction was carried out in the same manner as in example 1, except that the reaction time was changed to 14 hours.
The results are shown in the following table.
[ Table 3]
| Application time (h) | Yield of epoxy Compound (%) | Chlorine content (ppm) | |
| Example 1 | 0.5 | 3.4 | 0 |
| Example 3 | 14 | 34 | 0 |
As a summary of the above, the following description will be given of the configuration of the present disclosure and its variations.
[1] A process for producing an epoxy compound, which comprises subjecting a salt represented by the formula (a) to electrolytic oxidation in an aqueous phase to form a peracid ion represented by the formula (b), and oxidizing an olefin with the formed peracid ion represented by the formula (b) to obtain the corresponding epoxy compound.
[2] The process for producing an epoxy compound according to [1], wherein the olefin is a cyclic olefin.
[3] A process for producing an epoxy compound, which comprises subjecting a salt represented by the formula (a) to electrolytic oxidation in an aqueous phase to form a peracid ion represented by the formula (b), and oxidizing an olefin represented by the formula(s) with the peracid ion represented by the formula (b) to obtain an epoxy compound represented by the formula (p).
[4]According to [3]The process for producing an epoxy compound, wherein the olefin represented by the formula(s) is a compound represented by the formula(s) wherein R is 11 And R 12 Is a hydrogen atom, and R 13 And R 14 A compound bonded to each other to form a cycloolefin ring together with an adjacent carbon atom.
[5] A process for producing an epoxy compound, which comprises subjecting a salt represented by the formula (a) to electrolytic oxidation in an aqueous phase to produce a peracid ion represented by the formula (b), oxidizing a metal complex with the produced peracid ion represented by the formula (b) to produce a metal oxo complex, and oxidizing an olefin with the produced metal oxo complex to obtain the corresponding epoxy compound.
[6] The process for producing an epoxy compound according to [5], wherein the olefin is a cyclic olefin.
[7] The method for producing an epoxy compound according to [5] or [6], wherein the metal complex contains at least one metal element selected from Sc, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, Ru, Rh, Pd, W, Re, Ir, and Pt, and at least one ligand selected from a Salen-based ligand, a 1,4, 7-triazacyclononane-based ligand, a porphyrin-based ligand, a quinoline-based ligand, a pyridine-based ligand, and an acyloxy group.
[8] The process for producing an epoxy compound according to [5] or [6], wherein the metal complex is a metal complex represented by the formula (L-1) or (L-2).
[9] The method for producing an epoxy compound according to any one of [5] to [8], wherein the metal complex, the olefin, the salt represented by the formula (a), and water are charged into an electrolytic cell and electrified.
[10] The process for producing an epoxy compound according to any one of [1] to [9], wherein the concentration of the salt represented by the formula (a) in the aqueous phase is 0.1 to 5 mol/L.
[11] The process for producing an epoxy compound according to any one of [1] to [10], wherein the content of the electrolyte other than the salt represented by the formula (a) in the aqueous phase is 40 mol% or less of the total amount of the electrolyte contained in the aqueous phase.
[12] The method for producing an epoxy compound according to any one of [1] to [11], wherein the salt represented by the formula (a) is at least one salt selected from sodium hydrogencarbonate, sodium hydrogensulfate and disodium hydrogenphosphate.
[13] The method for producing an epoxy compound according to any one of [1] to [12], wherein the peracid ion represented by the formula (b) is at least one ion selected from the group consisting of a percarbonate ion, a persulfate ion and a perphosphate ion.
[14] The process according to any one of [1] to [13], which comprises subjecting the epoxy compound to electrolytic oxidation in a two-phase solvent comprising an aqueous phase and an organic solvent phase.
[15] The method for producing an epoxy compound according to any one of [1] to [14], wherein the salt represented by the formula (a) is electrolytically oxidized in an aqueous phase to generate a peracid ion represented by the formula (b), and an olefin is oxidized in an organic solvent phase by the peracid ion represented by the formula (b) to obtain the corresponding epoxy compound.
[16] The process for producing an epoxy compound according to any one of [1] to [15], wherein the molar ratio (former/latter) of the olefin to the salt represented by the formula (a) in the reaction system is 1/1000 to 1000/1.
[17] The process for producing an epoxy compound according to any one of [5] to [16], wherein a supply molar ratio (former/latter) of the olefin to the metal complex in the reaction system is 1/10 to 100000/1.
[18] The process for producing an epoxy compound according to any one of [1] to [17], wherein the chlorine content of the obtained epoxy compound is 3000ppm or less.
Industrial applicability of the invention
According to the method for producing an epoxy compound of the present disclosure, the oxidation reaction rate of an olefin can be increased, and a corresponding epoxy compound can be efficiently produced.
Therefore, the epoxy compound obtained by the above-mentioned production method has an extremely low chlorine content and can be suitably used as a sealing material for semiconductors and the like.
Claims (5)
1. A process for producing an epoxy compound, which comprises subjecting a salt represented by the following formula (a) to electrolytic oxidation in an aqueous phase to form a peracid ion represented by the following formula (b), oxidizing an olefin with the peracid ion represented by the following formula (b) to obtain a corresponding epoxy compound,
[ chemical formula 1]
In the formula, R d Represents a group selected from a single bond, SO 2 CO and P (═ O) OH, a + represents a cation selected from the group consisting of alkali metal ions, alkaline earth metal ions, ammonium ions, phosphonium ions and sulfonium ions.
2. A process for producing an epoxy compound, which comprises subjecting a salt represented by the following formula (a) to electrolytic oxidation in an aqueous phase to form a peracid ion represented by the following formula (b), oxidizing a metal complex with the generated peracid ion represented by the following formula (b) to form a metal oxo complex, and oxidizing an olefin with the formed metal oxo complex to obtain a corresponding epoxy compound,
[ chemical formula 2]
In the formula, R d Represents a group selected from a single bond, SO 2 CO and P (═ O) OH, a + represents a cation selected from the group consisting of alkali metal ions, alkaline earth metal ions, ammonium ions, phosphonium ions and sulfonium ions.
3. The method for producing an epoxy compound according to claim 2, wherein the metal complex, the olefin, the salt represented by the following formula (a), and water are charged in an electrolytic bath and an electric current is applied,
[ chemical formula 3]
In the formula, R d Represents a group selected from a single bond, SO 2 CO and P (═ O) OH, a + represents a cation selected from the group consisting of alkali metal ions, alkaline earth metal ions, ammonium ions, phosphonium ions and sulfonium ions.
4. The method for producing an epoxy compound according to any one of claims 1 to 3, wherein the concentration of the salt represented by the following formula (a) in the aqueous phase is 0.1 to 5mol/L,
[ chemical formula 4]
In the formula, R d Represents a group selected from a single bond, SO 2 A divalent radical of CO and P (═ O) OH, A + Represents a cation selected from the group consisting of an alkali metal ion, an alkaline earth metal ion, an ammonium ion, a phosphonium ion and a sulfonium ion.
5. The method for producing an epoxy compound according to any one of claims 1 to 4, wherein the electrolytic oxidation is performed in a two-phase solvent of an aqueous phase and an organic solvent phase.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2019196508A JP7327758B2 (en) | 2019-10-29 | 2019-10-29 | Method for producing epoxy compound |
| JP2019-196508 | 2019-10-29 | ||
| PCT/JP2020/039561 WO2021085268A1 (en) | 2019-10-29 | 2020-10-21 | Method for producing epoxy compound |
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| CN114981482A true CN114981482A (en) | 2022-08-30 |
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| CN202080075921.8A Pending CN114981482A (en) | 2019-10-29 | 2020-10-21 | Method for producing epoxy compound |
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| JP (1) | JP7327758B2 (en) |
| CN (1) | CN114981482A (en) |
| TW (1) | TW202124402A (en) |
| WO (1) | WO2021085268A1 (en) |
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| JPS496285A (en) * | 1972-05-22 | 1974-01-19 | ||
| JPH05213919A (en) * | 1992-02-04 | 1993-08-24 | Tosoh Corp | Epoxidization of alicyclic olefin |
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| JP4306859B2 (en) * | 1999-03-02 | 2009-08-05 | ペルメレック電極株式会社 | Process for producing 1,2-diols and equivalents thereof |
| JP5506074B2 (en) * | 2008-06-20 | 2014-05-28 | 国立大学法人大阪大学 | Method for producing epoxy compound |
| EP3024581B1 (en) * | 2013-07-24 | 2023-11-15 | Basf Se | Regeneration of a titanium containing zeolite |
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- 2019-10-29 JP JP2019196508A patent/JP7327758B2/en active Active
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- 2020-10-21 WO PCT/JP2020/039561 patent/WO2021085268A1/en active Application Filing
- 2020-10-27 TW TW109137200A patent/TW202124402A/en unknown
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| JP2021070835A (en) | 2021-05-06 |
| TW202124402A (en) | 2021-07-01 |
| JP7327758B2 (en) | 2023-08-16 |
| WO2021085268A1 (en) | 2021-05-06 |
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