WO2013147092A1 - エポキシ化合物の製造方法及びエポキシ化反応用触媒組成物 - Google Patents
エポキシ化合物の製造方法及びエポキシ化反応用触媒組成物 Download PDFInfo
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- 238000007796 conventional method Methods 0.000 description 1
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- UVJHQYIOXKWHFD-UHFFFAOYSA-N cyclohexa-1,4-diene Chemical compound C1C=CCC=C1 UVJHQYIOXKWHFD-UHFFFAOYSA-N 0.000 description 1
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 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
- UYDJAHJCGZTTHB-UHFFFAOYSA-N cyclopentane-1,1-diol Chemical compound OC1(O)CCCC1 UYDJAHJCGZTTHB-UHFFFAOYSA-N 0.000 description 1
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000010908 decantation Methods 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
- 238000000151 deposition Methods 0.000 description 1
- 206010012601 diabetes mellitus Diseases 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical group C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 1
- 229940008406 diethyl sulfate Drugs 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 235000019797 dipotassium phosphate Nutrition 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
- AAQNGTNRWPXMPB-UHFFFAOYSA-N dipotassium;dioxido(dioxo)tungsten Chemical compound [K+].[K+].[O-][W]([O-])(=O)=O AAQNGTNRWPXMPB-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical group [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
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- 238000006911 enzymatic reaction Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- QJZTYUWSTSEBDG-UHFFFAOYSA-N ethyl 6-(dioctylamino)hexanoate Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCC(=O)OCC QJZTYUWSTSEBDG-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229930182470 glycoside Natural products 0.000 description 1
- 150000002338 glycosides Chemical class 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000001976 hemiacetal group Chemical group 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002400 hexanoic acid esters Chemical class 0.000 description 1
- YWGHUJQYGPDNKT-UHFFFAOYSA-N hexanoyl chloride Chemical compound CCCCCC(Cl)=O YWGHUJQYGPDNKT-UHFFFAOYSA-N 0.000 description 1
- FXXZWXTZEYMGGZ-UHFFFAOYSA-N hexyl 12-bromododecanoate Chemical compound CCCCCCOC(=O)CCCCCCCCCCCBr FXXZWXTZEYMGGZ-UHFFFAOYSA-N 0.000 description 1
- RKBWYQMWDPLYPG-UHFFFAOYSA-N hexyl 2-bromododecanoate Chemical compound CCCCCCCCCCC(Br)C(=O)OCCCCCC RKBWYQMWDPLYPG-UHFFFAOYSA-N 0.000 description 1
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 150000002440 hydroxy compounds Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- CAAULPUQFIIOTL-UHFFFAOYSA-N methyl dihydrogen phosphate Chemical compound COP(O)(O)=O CAAULPUQFIIOTL-UHFFFAOYSA-N 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 1
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 235000019691 monocalcium phosphate Nutrition 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 1
- 125000000466 oxiranyl group Chemical group 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000004675 pentylcarbonyl group Chemical group C(CCCC)C(=O)* 0.000 description 1
- CMPQUABWPXYYSH-UHFFFAOYSA-N phenyl phosphate Chemical compound OP(O)(=O)OC1=CC=CC=C1 CMPQUABWPXYYSH-UHFFFAOYSA-N 0.000 description 1
- BCTWNMTZAXVEJL-UHFFFAOYSA-N phosphane;tungsten;tetracontahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.P.[W].[W].[W].[W].[W].[W].[W].[W].[W].[W].[W].[W] BCTWNMTZAXVEJL-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000007867 post-reaction treatment Methods 0.000 description 1
- 229960003975 potassium Drugs 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000003132 pyranosyl group Chemical group 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000005730 ring rearrangement reaction Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- LPSXSORODABQKT-UHFFFAOYSA-N tetrahydrodicyclopentadiene Chemical compound C1C2CCC1C1C2CCC1 LPSXSORODABQKT-UHFFFAOYSA-N 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 150000007970 thio esters Chemical group 0.000 description 1
- 125000001382 thioacetal group Chemical group 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- VYGSFTVYZHNGBU-UHFFFAOYSA-N trichloromethanesulfonic acid Chemical compound OS(=O)(=O)C(Cl)(Cl)Cl VYGSFTVYZHNGBU-UHFFFAOYSA-N 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical class C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- 238000004704 ultra performance liquid chromatography Methods 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0239—Quaternary ammonium compounds
-
- 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
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
- C07D303/28—Ethers with hydroxy compounds containing oxirane rings
- C07D303/30—Ethers of oxirane-containing polyhydroxy compounds in which all hydroxyl radicals are etherified with oxirane-containing hydroxy compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/27—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a liquid or molten state
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C219/00—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C219/02—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C219/04—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C219/06—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having the hydroxy groups esterified by carboxylic acids having the esterifying carboxyl groups bound to hydrogen atoms or to acyclic carbon atoms of an acyclic saturated carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C219/00—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C219/26—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
- C07C219/28—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton having amino groups bound to acyclic carbon atoms of the carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
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- 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
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- 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
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
- C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
- C07D303/24—Ethers with hydroxy compounds containing no oxirane rings with polyhydroxy compounds
- C07D303/27—Ethers with hydroxy compounds containing no oxirane rings with polyhydroxy compounds having all hydroxyl radicals etherified with oxirane containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/027—Polycondensates containing more than one epoxy group per molecule obtained by epoxidation of unsaturated precursor, e.g. polymer or monomer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/223—Di-epoxy compounds together with monoepoxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
- C08G59/245—Di-epoxy compounds carbocyclic aromatic
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
- B01J2231/72—Epoxidation
Definitions
- the present invention relates to a method for producing a novel epoxy compound and a novel catalyst composition for epoxidation reaction used therefor.
- Epoxy compounds are widely used as epoxy monomers as raw materials for epoxy resins and as raw materials for various chemical products.
- the epoxy resin is a resin obtained by curing an epoxy monomer using various curing agents.
- Epoxy resin is a resin that excels in mechanical properties, water resistance, chemical resistance, heat resistance, electrical properties, etc., and is used in electronic materials, optical materials, building materials, adhesives, paints, laminates, molding materials, It is used in a wide range of fields such as mold materials and resists.
- semiconductor encapsulants, printed wiring boards, build-up wiring boards, solder resists, etc. with higher integration, packaging materials represented by epoxy resins are required to be highly purified. ing.
- technologies that make use of optical signals are being developed to smoothly transmit and process vast amounts of information. Development of this resin is desired.
- Typical epoxy monomer glycidyl ether compounds such as phenols, naphthols, bisphenol A, etc., condensed with glycidyloxy groups are heat resistant, adhesive, chemical resistant, electrical properties, mechanical properties Therefore, it is an industrial material that has many uses such as an adhesive, a molding material, a sealant, and a paint by being cross-linked and cured by a curing agent.
- a method for producing a glycidyl ether compound when phenols are used as a raw material, a method of reacting epichlorohydrin with a raw material phenols is most widely used.
- a specific synthesis method of glycidyl ether using epichlorohydrin is represented, for example, by the following reaction formula.
- This epoxidation reaction is a clean reaction with less waste compared to an epoxidation reaction with an organic peroxide typified by peracetic acid because the by-product is only water. Further, since 30% to 45% hydrogen peroxide water is used, it is easily available and easy to handle.
- an ammonium salt having a long-chain alkyl group such as methyltrioctylammonium chloride or a pyridinium salt having a long-chain alkyl group such as cetylpyridinium salt is used as an onium salt that usually coexists as a catalyst.
- An oxidant is prepared.
- the onium salt having a long-chain alkyl group has a high distribution ratio to an organic solvent, an epoxy compound dissolved in an organic phase after the reaction, a component derived from the catalyst composition, specifically tungsten or an onium salt.
- a component derived from the catalyst composition specifically tungsten or an onium salt.
- separation and purification from onium salt-derived nitrogen-containing compounds are extremely difficult.
- tungsten, nitrogen-containing compounds, and the like are removed by a method such as recrystallization or hanging washing, there is a problem that the purification yield (recovery rate) of the epoxy compound is low.
- catalyst-derived heavy metal components such as tungsten and molybdenum and ionic compounds such as onium salts remain in the resulting epoxy compound. These remain even when an epoxy resin is produced from an epoxy compound, and adversely affect the product.
- Patent Document 5 or 6 discusses a method of adsorbing and removing an ammonium salt using an ion exchange resin or a metal oxide as an adsorbent after the epoxidation reaction.
- Patent Documents 7 and 8 or Non-Patent Document 4 discusses a method in which an ammonium salt used as an epoxidizing agent is supported on a resin or silica gel and then separated and recovered by filtration.
- Patent Document 9 discusses a method of depositing an ammonium salt used as a catalyst after the epoxidation reaction.
- Patent Document 10 discusses a method for making the catalyst non-uniform.
- Patent Document 11 discusses a method of binding and removing a magnetic substance from an ammonium salt.
- the adsorbent must be added in an amount of 15% by weight or more of the epoxy compound, and an operation for separating the adsorbent is required. Further, when an adsorbent is used, there is a concern that productivity decreases due to an adsorption loss of the epoxy compound to the adsorbent, organic impurities derived from the ion exchange resin, and metals derived from the metal oxide are eluted and mixed.
- Patent Documents 7 and 8 Used when the catalyst component is immobilized on a carrier as described in Patent Documents 7 and 8, or Non-Patent Document 4, because the activity of the catalyst is reduced and a large amount of catalyst is required. New problems arise, such as the limitation of the solvent that can be produced or the deterioration of the thermal stability of the catalyst.
- Patent Document 9 describes that the amount of tungsten can be reduced only to about 600 ppm by only the precipitation operation.
- the reaction rate decreases due to non-uniformization, and that the method cannot be applied to monomers having good crystallinity.
- the method described in Patent Document 11 has a problem that the synthesis of the catalyst is complicated.
- the content of heavy metals such as tungsten is extremely small, preferably the amount of nitrogen-containing compounds derived from onium salts (hereinafter simply referred to as nitrogen content), more preferably the content of chlorine. It is an object of the present invention to provide a method for producing an epoxy compound having a small amount without requiring a complicated purification step.
- the inventors incorporated a new concept of introducing a structure that can be converted into an easily removable compound into the onium salt that coexists as a catalyst, designed the compound, and used it in the epoxidation reaction. Specifically, the reaction was carried out in the presence of an onium salt having at least one substituent in the molecule that can be converted into a functional group containing active hydrogen or a salt thereof. As a result, the desired epoxy compound is obtained and converted to a functional group containing active hydrogen or a salt thereof after the epoxidation reaction. The epoxy compound and the component derived from the epoxidizing agent are separated and removed, and the epoxy compound has high purity. Has been found, and the present invention has been completed.
- the gist of the present invention is as follows.
- a method for producing an epoxy compound wherein a compound having a carbon-carbon double bond has at least one of a tungsten compound and a molybdenum compound, and a substituent that can be converted into a functional group containing active hydrogen or a salt thereof.
- a method for producing an epoxy compound comprising reacting hydrogen peroxide in the presence of an onium salt having one or more and containing 20 or more carbon atoms.
- any one or more of R 1 to R 4 , any one or more of R 5 to R 10 , and any of R 11 to R 15 is independently —Y—CO—O—Z or —Y—O—CO—Z (where Y is a direct bond or a part of carbon atoms is substituted with a hetero atom) And represents a divalent aliphatic hydrocarbon group having 1 to 25 carbon atoms which may have a substituent, and Z is a group in which some carbon atoms are substituted with heteroatoms.
- R 1 to R 5 , R 11 and R 13 are not the above-mentioned —Y—CO—O—Z and —Y—O—CO—Z, some carbon atoms are independently heteroatoms.
- R 6 to R 10 , R 12 , R 14, and R 15 are each independently a hydrogen atom, a halogen atom, or a group other than —Y—CO—O—Z and —Y—O—CO—Z
- R 1 to R 15 may combine with each other in the same compound to form a ring.
- the total number of carbon atoms contained in R 1 to R 4 in the above formula (1) is 20 or more
- the total number of carbon atoms contained in R 5 to R 10 in the above formula (2) is 15 or more
- the total number of carbon atoms contained in R 11 to R 15 in the above formula (3) is 17 or more.
- X ⁇ represents a monovalent anion.
- [12] A method of producing an epoxy resin by polymerizing an epoxy compound, the step of producing an epoxy compound by the method described in [1] to [11] above, and the polymerization of the epoxy compound obtained in the step The manufacturing method of the epoxy resin including the process to do.
- Epoxidation reaction comprising at least one of a tungsten compound and a molybdenum compound, and an onium salt having 20 or more carbon atoms having at least one functional group containing active hydrogen or a substituent that can be converted to a salt thereof. Catalyst composition.
- the onium salt is an ammonium salt, a pyridinium salt, an imidazolinium salt, or a phosphonium salt.
- any one or more of R 1 to R 4 , any one or more of R 5 to R 10 , and any of R 11 to R 15 is independently —Y—CO—O—Z or —Y—O—CO—Z (where Y is a direct bond or a part of carbon atoms is substituted with a hetero atom) And represents a divalent aliphatic hydrocarbon group having 1 to 25 carbon atoms which may have a substituent, and Z is a group in which some carbon atoms are substituted with heteroatoms.
- R 1 to R 5 , R 11 and R 13 are not the above-mentioned —Y—CO—O—Z and —Y—O—CO—Z, some carbon atoms are independently heteroatoms.
- R 6 to R 10 , R 12 , R 14, and R 15 are each independently a hydrogen atom, a halogen atom, or a group other than —Y—CO—O—Z and —Y—O—CO—Z
- R 1 to R 15 may combine with each other in the same compound to form a ring.
- the total number of carbon atoms contained in R 1 to R 4 in the above formula (1) is 20 or more
- the total number of carbon atoms contained in R 5 to R 10 in the above formula (2) is 15 or more
- the total number of carbon atoms contained in R 11 to R 15 in the above formula (3) is 17 or more.
- X ⁇ represents a monovalent anion.
- R 20 represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, or a part of carbon atoms substituted with a hetero atom.
- R 21 to R 23 each independently represents one Represents an alkyl group having 1 to 25 carbon atoms or a benzyl group, in which part of the carbon atoms may be substituted with a hetero atom, and R 20 to R 23 may combine within the same compound to form a ring.
- K represents an integer of 1 to 4.
- R 31 and R 32 each independently represents a divalent aliphatic hydrocarbon group having 1 to 25 carbon atoms in which some carbon atoms may be substituted with heteroatoms.
- R 33 represents a monovalent aliphatic hydrocarbon group having 1 to 25 carbon atoms in which some of the carbon atoms may be substituted with hetero atoms, or 4 to 25 carbon atoms that may have a substituent. Represents a monovalent aromatic hydrocarbon group.
- a plurality of k, R 20 and R 31 present in the same compound may be the same or different. The total number of carbon atoms contained in the cation moiety in the formula is 20 or more.
- X ⁇ represents a monovalent anion
- G represents a glycidyl group (2,3-epoxypropanyl group), and the glycidyl group may be substituted with an alkyl group, a phenyl group or an alkoxycarbonyl group.
- a 201 represents a (m201 + 1) -valent aromatic or aliphatic hydrocarbon group which may have a substituent
- a 202 represents a divalent aromatic or aliphatic hydrocarbon which may have a substituent.
- a 203 represents a (m203 + 2) -valent aromatic or aliphatic hydrocarbon group which may have a substituent.
- X 201 and X 202 each independently represent a divalent linking group which may have a direct bond or a substituent.
- p201 represents 0 or 1.
- m201 and m203 each independently represent an integer of 1 or more.
- n201 represents an integer of 1 or more, n202 represents 0 or an integer of 1 or more, and n203 represents 0 or 1.
- a plurality of G, A 201 , A 202 , X 201 , X 202 , m201 and p201 contained in one molecule may be the same or different.
- Z is a monovalent aliphatic hydrocarbon group having 1 to 25 carbon atoms in which some of the carbon atoms may be substituted with heteroatoms, or 4 to 25 carbon atoms that may have a substituent.
- R 35 represents a group represented by any of the following formulas (18) to (20).
- R 41 represents a direct bond or a divalent aliphatic hydrocarbon group having 1 to 25 carbon atoms in which some of the carbon atoms may be substituted with heteroatoms.
- R 42 to R 44 each independently represents an alkyl group having 1 to 25 carbon atoms or a benzyl group in which some carbon atoms may be substituted with heteroatoms.
- Any one of R 45 to R 50 represents a divalent aliphatic hydrocarbon group having 1 to 25 carbon atoms which may be a direct bond or a part of carbon atoms may be substituted with a hetero atom.
- R 46 to R 50 are each independently In addition, a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 25 carbon atoms in which some carbon atoms may be substituted with a hetero atom, a phenyl group, a phenoxy group, an N-alkylcarbamoyl group Or represents an N-alkylsulfamoyl group,
- Each of the four is independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group having 1
- any one of R 51 to R 55 represents a direct bond or a divalent aliphatic hydrocarbon group having 1 to 25 carbon atoms in which some carbon atoms may be substituted with hetero atoms.
- the other is one Represents an alkyl group having 1 to 25 carbon atoms or a benzyl group, in which part of the carbon atoms may be substituted with a hetero atom
- R 52 , R 54 and R 55 each independently represents a hydrogen atom, a halogen atom or a cyano group , A nitro group, an alkyl group having 1 to 25 carbon atoms in which some carbon atoms may be substituted with a hetero atom, a phenyl group, a phenoxy group, a benzyl group,
- R 52 , R 54 and R 55 are a direct bond or a divalent aliphatic hydrocarbon group having 1 to 25 carbon atoms in which some carbon atoms may be substituted with heteroatoms
- the other two are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 25 carbon atoms in which some carbon atoms may be substituted with a hetero atom, a phenyl group, Represents a phenoxy group, a benzyl group, an N-alkylcarbamoyl group or an N-alkylsulfamoyl group, and R 51 and R 53 each independently represents a carbon atom in which some of the carbon atoms may be substituted with a heteroatom.
- G represents a glycidyl group (2,3-epoxy-propanyl group), the glycidyl group is an alkyl group, optionally .
- a 1 be phenyl or substituted alkoxycarbonyl group
- M1 represents an aromatic or aliphatic hydrocarbon group which may have a substituent
- m1 represents an integer of 1 or more, and plural Gs contained in one molecule may be the same or different.
- G represents a glycidyl group, and this glycidyl group may be substituted with an alkyl group, a phenyl group or an alkoxycarbonyl group.
- a 21 may have a substituent ( m @ 2 + 1) valent aromatic or aliphatic hydrocarbon group, a 22 is connected via a .
- X 2 representing an aromatic or aliphatic hydrocarbon group which may be divalent to have a substituent group a 21 and A 22 , or a plurality of adjacent A 22 may be bonded to each other to form a ring
- X 2 is a divalent bond that may have a direct bond or a substituent.
- a plurality of G, A 21 , A 22 , X 2 , and m2 contained in one molecule are the same.
- G represents a glycidyl group, and the glycidyl group may be substituted with an alkyl group, a phenyl group or an alkoxycarbonyl group.
- a 3 may have a substituent ( m3 + 2) represents a valent aromatic or aliphatic hydrocarbon group, X 3 represents a direct bond, an alkylene group which may have a substituent, or —R 41 -phenylene-R 42 —, wherein R 41 and R 42 represents an alkylene group independently, m3 represents an integer of 1 or more, n3 represents an integer of 2 or more, and a plurality of G, A 3 , X 3 , and m3 contained in one molecule are the same Or different.) [23] The composition according to [21] or [22] above, wherein an abundance ratio of the compound ⁇ to the epoxy compound ⁇ is 0.05 mol% or more and 10.0 mol% or less. object.
- R 35 represents a group represented by any one of the formulas (18) to (20).
- Z may have a monovalent aliphatic hydrocarbon group having 1 to 25 carbon atoms in which some carbon atoms may be substituted with heteroatoms, or a substituent. It represents a monovalent aromatic hydrocarbon group having 4 to 25 carbon atoms.
- an epoxy compound having a very small content of heavy metals such as tungsten can be obtained. Further, it is possible to produce a high-purity epoxy compound having an extremely small content of onium salt and chlorine by a simple method without requiring complicated steps such as purification. Furthermore, it can be applied to the production of epoxy compounds that cannot be distilled or crystallized and is excellent in versatility.
- the epoxy compound obtained by the method of the present invention is used as a raw material for electronic materials, optical materials, and medical and agricultural chemicals, problems due to impurities are reduced, and a product with high purity and high quality can be obtained.
- the method for producing an epoxy compound of the present invention includes a compound having a carbon-carbon double bond (hereinafter sometimes referred to as “olefin compound”) containing at least one of a tungsten compound and a molybdenum compound and active hydrogen. It is characterized by reacting hydrogen peroxide in the presence of an onium salt having at least one functional group or a substituent that can be converted into a salt thereof and containing 20 or more carbon atoms.
- tungsten compound and molybdenum compound at least one of tungsten compound and molybdenum compound is referred to as “catalytic metal component”, and “having one or more substituents that can be converted into a functional group containing active hydrogen or a salt thereof,
- the “onium salt containing 20 or more carbon atoms” is simply referred to as “onium salt”, and the one containing the above “catalyst metal component” and “onium salt” is referred to as “catalyst composition for epoxy reaction” or simply “catalyst composition”.
- the catalyst composition oxidized with hydrogen peroxide may be referred to as a “reactive active species composition”.
- hydrogen peroxide serves as an oxidizing agent that oxidizes the catalyst composition.
- Hydrogen peroxide is usually hydrogen peroxide, and commercially available hydrogen peroxide can be used as it is or diluted with water.
- concentration of the hydrogen peroxide solution is usually 1% by weight or more, preferably 20% by weight or more and usually 60% by weight or less, and more preferably, considering availability, safety issues, productivity, etc. 30 wt% or more and 45 wt% or less.
- the amount of hydrogen peroxide used is usually 0.5 moles or more, preferably 1 moles or more, usually 10 moles or less, preferably 3 moles per mole of the double bond in the olefin compound used as a raw material. Use below.
- the catalyst composition of the present invention refers to a mixture of a catalytic metal component and an onium salt described later.
- the method for preparing the catalyst composition can be appropriately selected according to the reaction substrate and the reactivity thereof, and is not particularly limited. However, a method of mixing the catalyst metal component and the onium salt in the reaction system, or in advance Any method of mixing the catalyst metal component and the onium salt outside the reaction system and then using it for the reaction may be used. Further, the method for adding phosphoric acids described later may be either a method of mixing in the reaction system or a method of mixing outside the reaction system in advance.
- the mixing method and mixing order are not particularly limited, but specifically, the catalytic metal component and the onium salt described later are usually included in the reaction system containing the olefin compound. It can be prepared by adding. The order of addition is not particularly limited, and either the catalytic metal component or the onium salt may be added first, or may be added simultaneously.
- the catalyst metal component and the onium salt can be mixed before use outside the reaction system.
- the mixing method, the mixing order, and the use mode of the mixture are not particularly limited, but the catalyst metal component and the onium salt may be mixed in the catalyst composition even if the catalyst metal component and the onium salt are used as they are.
- the complex may be isolated and used. Among them, it is convenient and preferable to mix a catalytic metal component and an onium salt and use them as they are without isolation or activation.
- the catalytic metal component and the onium salt in the catalyst composition of the present invention form a complex, and preferably further form a complex with at least one of phosphoric acids and phosphonic acids described later.
- the body is oxidized by hydrogen peroxide to become a “reactive active species composition”, which is considered to be a reactive active species in the epoxidation reaction in the present invention.
- the reactive active species composition can be added to the reaction system after being partially activated by adding hydrogen peroxide to the mixture of the catalytic metal component and the onium salt (that is, the “catalyst composition”). .
- tungstic acid or a tungstic acid salt hereinafter referred to as tungstic acid
- molybdic acid or molybdic acid salt hereinafter referred to as molybdic acid
- tungstic acids are preferred because of their price and availability.
- tungstic acids include, for example, tungstic acid; tungstates such as sodium tungstate, potassium tungstate, calcium tungstate, ammonium tungstate; hydrates of the tungstates; Acid, phosphotungstic acid such as 18-tungstophosphoric acid; silicotungstic acid such as 12-tungstosilicic acid; 12-tungstoboric acid or metallic tungsten etc., tungstic acid, tungstate and phosphotungstic acid are preferred In terms of ease, tungstic acid, sodium tungstate, calcium tungstate, and 12-tungstophosphoric acid are more preferable.
- molybdic acids examples include molybdic acid; molybdates such as sodium molybdate, potassium molybdate, and ammonium molybdate; and hydrates of the molybdates.
- molybdic acids and molybdic acids tungstic acid or sodium tungstate and its hydrate, calcium tungstate and its hydrate are preferable in terms of availability, and from the ease of recovery and regeneration. Tungstic acid is more preferable.
- the catalyst metal components can be used alone or in combination of two or more.
- the amount of the catalytic metal component used in the present invention can be appropriately adjusted depending on the properties of the substrate used and the like, and is not particularly limited. It is usually 0.001 mol or more, preferably 0.005 mol or more, more preferably 0.01 mol or more, and usually 1.0 mol or less, preferably in terms of atoms (for example, in the case of tungstic acids in terms of tungsten atoms). Is 0.50 mol or less, more preferably 0.10 mol or less. If the amount is less than the lower limit, the reaction may not proceed. If the amount is more than the upper limit, the cost may be disadvantageous.
- the onium salt used in the present invention has 20 or more carbon atoms and one or more functional groups containing active hydrogen or a substituent that can be converted to a salt thereof.
- the onium salt is fat-soluble during the epoxidation reaction, is soluble in the reaction solvent, and is distributed on the organic phase side separated into an aqueous phase and an organic phase, and is stable under epoxidation reaction conditions or epoxidized. Even if the structure changes during the reaction, the catalytic ability is not significantly lowered. In order to be soluble in the reaction solvent and to be distributed to the organic phase, high fat solubility is required, and thus the onium salt needs to contain 20 or more carbon atoms.
- the onium salt is converted into a water-soluble compound having a functional group containing active hydrogen or a salt thereof by a simple method under mild conditions in which the epoxy group of the epoxy compound generated by the reaction is not decomposed after the epoxidation reaction. It has the feature of having a substituent that can be converted.
- onium Cation species (hereinafter simply referred to as “onium”) of the onium salt used in the present invention are not particularly limited as long as the above conditions are satisfied. That is, it is an onium having 20 or more carbon atoms and one or more functional groups containing active hydrogen or one or more substituents that can be converted to a salt thereof. Specific examples of onium include usually ammonium, pyridinium, imidazolinium. Quaternary cations of nitrogen-containing heterocycles such as phosphonium, and the like.
- onium salts include ammonium salts, pyridinium salts, imidazolinium salts, and phosphonium salts.
- imidazolinium is used as ammonium and pyridinium because they are easily synthesized.
- the anion species of the onium salt used in the present invention is not particularly limited, but is a monovalent anion. Specific examples include hydrogen sulfate ion, monomethyl sulfate ion, halide ion, nitrate ion, acetate ion, hydrogen carbonate ion, dihydrogen phosphate ion, sulfonate ion, carboxylate ion, hydroxide ion, and the like.
- Monomethyl sulfate ion, hydrogen sulfate ion, acetate ion from the point that the seed is not added to the epoxy group of the epoxy compound that is the reaction product or the carbon-carbon double bond of the olefin compound that is the raw material compound, and because it is easy to prepare.
- Dihydrogen phosphate ions or hydroxide ions are preferred.
- the onium salt used in the present invention has one or more functional groups containing active hydrogen in the onium moiety or a substituent that can be converted into a salt thereof.
- a functional group containing active hydrogen represents a functional group capable of dissociating and releasing hydrogen ions, and a salt thereof is a compound in which another cation species becomes a counter anion instead of the dissociated hydrogen ion.
- the functional group containing active hydrogen is not particularly limited, but is preferably a hydroxyl group, a carboxyl group, an amino group, a mercapto group, a sulfonic acid group, a phosphoric acid group, or a salt thereof, more preferably a carboxyl group. Or it is a hydroxyl group, Especially preferably, it is a hydroxyl group.
- a substituent that can be converted into a functional group containing active hydrogen or a salt thereof is a substituent that can be converted into a functional group containing active hydrogen or a salt thereof by performing at least one of a physical operation and a chemical operation. Means. Specifically, it refers to a substituent that can be converted by a base reaction, an acid reaction, a chemical reaction such as catalytic hydrogenation, heating, a photoreaction, an enzyme reaction, microwave irradiation, or the like.
- a substituent that can be converted under mild conditions is preferable, and a substituent that can be converted under conditions that do not react with an epoxy group is more preferable.
- Examples thereof include a carbamate group, a thioacetal group, a phosphate ester group, and a benzyl ether group.
- a functional group containing active hydrogen or a salt thereof is generated from a substituent that can be converted into the functional group containing active hydrogen or a salt thereof in the process of reacting the reactive species composition containing the onium salt with an olefin compound.
- a ketone group ketone structure
- a nitrile group a benzyl group, or the like that is converted into an ester group by a buyer-Billiger oxidation reaction during the reaction
- Examples of convertible substituents are mentioned.
- the alkoxycarbonyl group and the acyloxy group can be converted into a hydroxyl group, a carboxylic acid group, and a salt thereof by being contacted with a basic aqueous solution, easily and without decomposing the epoxy group,
- the synthesis is also preferable because it is simple. More preferred is an alkoxycarbonyl group.
- the number of the substituents is one or more, but is preferably two or more from the viewpoint of removal efficiency in washing.
- the reactive species composition containing an onium salt used in the present invention is preferably dissolved in at least one of an olefin compound as a reaction raw material and a solvent used in the epoxidation reaction. Therefore, it is necessary to have a highly lipophilic portion in the onium salt structure.
- the specific structure and shape are not particularly limited as long as they do not inhibit the reaction and are stable with respect to the epoxidation reaction, or retain catalytic activity even if the structure changes during the epoxidation reaction.
- the structure may be any of an aliphatic group, an aromatic group, and a compound having both, and the shape may be any of a linear, branched, or cyclic structure.
- onium salt used in the present invention an onium salt represented by any one of the following general formulas (1) to (3) is preferably used.
- any one or more of R 1 to R 4 , any one or more of R 5 to R 10 , and any of R 11 to R 15 is independently —Y—CO—O—Z or —Y—O—CO—Z (where Y is a direct bond or a part of carbon atoms is substituted with a hetero atom) And represents a divalent aliphatic hydrocarbon group having 1 to 25 carbon atoms which may have a substituent, and Z is a group in which some carbon atoms are substituted with heteroatoms.
- R 1 to R 5 , R 11 and R 13 are not the above-mentioned —Y—CO—O—Z and —Y—O—CO—Z, some carbon atoms are independently heteroatoms.
- R 6 to R 10 , R 12 , R 14, and R 15 are each independently a hydrogen atom, a halogen atom, or a group other than —Y—CO—O—Z and —Y—O—CO—Z
- R 1 to R 15 may combine with each other in the same compound to form a ring.
- R 1 to R 15 are, in the case of an alkyl group having 1 to 25 carbon atoms, in which some of the carbon atoms may be substituted with heteroatoms and may have a substituent, You may have another onium salt represented by either of Formula (1) thru
- the total number of carbon atoms contained in R 1 to R 4 in the above formula (1) is 20 or more, and the total number of carbon atoms contained in R 5 to R 10 in the above formula (2) is 15 or more.
- the total number of carbon atoms contained in R 11 to R 15 in the above formula (3) is 17 or more.
- X ⁇ represents a monovalent anion.
- any one or more of R 1 to R 4 represents —Y—CO—O—Z or —Y—O—CO—Z.
- the total number of carbon atoms contained in R 1 to R 4 is 20 or more.
- any one or more of R 5 to R 10 in Formula (2) represents —Y—CO—O—Z or —Y—O—CO—Z.
- the total number of carbon atoms contained in R 5 to R 10 is 15 or more.
- any one or more of R 11 to R 15 in Formula (3) represents —Y—CO—O—Z or —Y—O—CO—Z.
- the total number of carbon atoms contained in R 11 to R 15 is 17 or more.
- Y is a direct bond, or a divalent aliphatic hydrocarbon group having 1 to 25 carbon atoms in which some carbon atoms may be substituted with heteroatoms and may have a substituent.
- the aliphatic hydrocarbon group may be linear, branched or cyclic.
- a linear aliphatic hydrocarbon group such as methylene, ethylene, tetramethylene, hexamethylene, etc.
- a branched aliphatic hydrocarbon group having an alkyl chain bonded thereto and
- cyclic aliphatic hydrocarbon groups such as cyclohexene.
- Y is a divalent aliphatic hydrocarbon group having 1 to 25 carbon atoms
- the carbon atom may be partially substituted with a hetero atom.
- the methylene group in the structure of these divalent aliphatic hydrocarbon groups is —O—, —S—, —SO—, —SO 2 —, —NH—, —NR 16 —
- R 16 is A monovalent aliphatic hydrocarbon group having 1 to 25 carbon atoms or a monovalent aromatic hydrocarbon group
- —CONR 17 — R 17 is a hydrogen atom, monovalent aliphatic carbon having 1 to 25 carbon atoms
- —NHCONH—, —CONHCO—, —SO 2 NR 17 — (R 17 is as defined above) Good.
- a hydrocarbon group in which some of the carbon atoms may be substituted with heteroatoms has the same meaning as described above.
- Y is preferably ethylene, propylene, tetramethylene, hexamethylene and —CH 2 CH 2 —O—CH 2 CH 2 —.
- Y is a divalent aliphatic hydrocarbon group having 1 to 25 carbon atoms in which some of the carbon atoms may be substituted with heteroatoms and may have a substituent
- Examples of the group include —O—CO—Z or —CO—O—Z (wherein Z is as defined in the above formulas (1) to (3)).
- any one of R 1 to R 15 is —Y—CO—O—Z or —Y—O—CO—Z.
- R 1 to R 15 is —Y—CO—O—Z or —Y—O—CO—Z.
- —O—CO—Z or —CO—O—Z also having —O—CO—Z or —CO—O—Z as a substituent of the aliphatic hydrocarbon group in Y become.
- Z represents a monovalent aliphatic hydrocarbon group having 1 to 25 carbon atoms or a monovalent aromatic hydrocarbon group having 4 to 25 carbon atoms in which some carbon atoms may be substituted with heteroatoms.
- the monovalent aliphatic hydrocarbon group having 1 to 25 carbon atoms may be linear, branched or cyclic. Specifically, straight chain aliphatic hydrocarbon groups such as methyl, ethyl, propyl, butyl, hexyl, butyl and octyl, branched aliphatic hydrocarbons having an alkyl chain bonded thereto, and cyclic aliphatic carbon groups such as cyclohexyl.
- a hydrogen group is mentioned.
- Examples of the monovalent aromatic hydrocarbon group having 4 to 25 carbon atoms include a monovalent benzene ring and a naphthalene ring which may have an alkyl group or a halogen atom as a substituent.
- the monovalent aliphatic hydrocarbon group having 1 to 25 carbon atoms may have a carbon atom in its structure partially substituted with a heteroatom, specifically, a methylene group in the structure of an aliphatic hydrocarbon group.
- a heteroatom specifically, a methylene group in the structure of an aliphatic hydrocarbon group.
- R 17 represents a family hydrocarbon group), - CONR 17 - (R 17 represents a hydrogen atom, a monovalent aliphatic hydrocarbon group or a monovalent aromatic hydrocarbon group having 1 to 25 carbon atoms), - -NHCONH-, It may be substituted with a structure containing a heteroatom such as —CONHCO— or —SO 2 NR 17 — (R 17 has the same meaning as described above).
- Examples of the monovalent aromatic hydrocarbon group having 4 to 25 carbon atoms include a phenyl group, a benzyl group, and a naphthyl group. These include a halogen atom, a cyano group, a nitro group, and some carbon atoms are heteroatoms. Have an optionally substituted alkyl group having 1 to 25 carbon atoms, phenyl group, phenoxy group, benzyl group, alkoxycarbonyl group, N-alkylcarbamoyl group, N-alkylsulfamoyl group, etc. Also good. Of these, a phenyl group is preferable because of the productivity of the onium salt.
- Y represents a hydrocarbon group in the formula —Y—CO—O—Z
- the number of carbon atoms is preferably 3 or more from the viewpoint of stability during the epoxidation reaction of the onium salt.
- R 1 to R 15 are not —Y—CO—O—Z or —Y—O—CO—Z.
- R 1 to R 15 R 1 to R 5 , R 11, and R 13 are each independently selected when they are not —Y—CO—O—Z and —Y—O—CO—Z.
- a part of carbon atoms may be substituted with a heteroatom, and an optionally substituted alkyl group having 1 to 25 carbon atoms or a benzyl group;
- R 6 to R 10 , R 12 , R 14, and R 15 are each independently a hydrogen atom, a halogen atom, or a group other than —Y—CO—O—Z and —Y—O—CO—Z,
- a cyano group, a nitro group, a part of carbon atoms may be substituted with a heteroatom, and an optionally substituted alkyl group having 1 to 25 carbon atoms, phenyl group, phenoxy group, N— Represents an alkylcarbamoyl group or an N-alkylsulfamoyl group;
- R 1 to R 15 may combine with each other in the same compound to form a ring.
- R 1 to R 15 are, in the case of an alkyl group having 1 to 25 carbon atoms, in which some of the carbon atoms may be substituted with heteroatoms and may have a substituent.
- the structures of the plurality of onium salts may be the same or different. Specific examples include 1,2-ethanediaminium salt and 4,4′-bipyridinium salt.
- R 1 to R 15 are alkyl groups having 1 to 25 carbon atoms, carbon atoms in the structure may be partially substituted with heteroatoms.
- a methylene group may be —O—, — S—, —SO—, —SO 2 —, —NH—, —NR 16 — (R 16 represents a monovalent aliphatic hydrocarbon group having 1 to 25 carbon atoms or a monovalent aromatic hydrocarbon group. ), —CONR 17 — (R 17 represents a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 25 carbon atoms, or a monovalent aromatic hydrocarbon group), —NHCONH—, —CONHCO—, — It may be substituted with a structure containing a heteroatom such as SO 2 NR 17 — (R 17 is as defined above).
- R 1 to R 5 , R 11 and R 13 are preferably methyl, ethyl, propyl, isopropyl, t-butyl, octyl, octadecyl or benzyl, and more preferably A methyl group or an ethyl group.
- R 6 to R 10 , R 12 , R 14 and R 15 are preferably hydrogen atoms, chlorine atoms, methyl groups, ethyl groups, propyl groups, isopropyl groups, t-butyl groups, octyl groups, octadecyl groups, halogen atoms.
- X ⁇ represents an anionic species of the onium salt and is a monovalent anion.
- hydrogen sulfate ion, monomethyl sulfate ion, halide ion, nitrate ion, acetate ion, hydrogen carbonate ion, dihydrogen phosphate ion, sulfonate ion, carboxylate ion, hydroxide ion preferably From the viewpoint that the anion is not added to an epoxy group or a carbon-carbon double bond and is easy to prepare, it is a monomethyl sulfate ion, a hydrogen sulfate ion, a chlorine ion, an acetate ion, a dihydrogen phosphate ion, or a hydroxide ion. .
- specific compounds that can be suitably used as the onium salt of the present invention include the following general formulas (8) to (11), (34) and (35). ).
- the compounds represented by the following general formulas (8) to (10) are novel compounds suitable as the onium salt of the present invention. These compounds are preferable in that they have a plurality of ester structures in the molecule and can be converted into water-soluble compounds after hydrolysis, and can be easily synthesized from readily available raw materials.
- Items (11) to (11) are preferable in terms of easy adjustment of production in terms of easy instrumental analysis such as a high performance liquid chromatograph.
- R 20 represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, or a part of carbon atoms substituted with a hetero atom.
- each of R 21 to R 23 is independently Represents an alkyl group or a benzyl group having 1 to 25 carbon atoms in which part of the carbon atoms may be substituted with a hetero atom, and R 24 represents 1 carbon atom in which some of the carbon atoms may be substituted with hetero atoms.
- R 31 and R 32 each independently represents a divalent aliphatic hydrocarbon group having 1 to 25 carbon atoms in which some carbon atoms may be substituted with heteroatoms.
- a plurality of k, R 20 and R 31 present in the same compound may be the same or different.
- the total number of carbon atoms contained in the cation moiety in the formula is 20 or more.
- X ⁇ represents a monovalent anion
- specific compounds that can be suitably used as the onium salt of the present invention include compounds represented by the following general formulas (12) and (31). .
- the compounds represented by the following general formulas (12) and (31) are novel compounds suitable as the onium salt of the present invention.
- R 20 represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 25 carbon atoms in which some carbon atoms may be substituted with hetero atoms, a phenyl group, Represents a phenoxy group, a benzyl group, an alkoxycarbonyl group, an N-alkylcarbamoyl group or an N-alkylsulfamoyl group, and R 20 may combine within the same compound to form a ring. To an integer of 4 to 4. A plurality of k and R 20 present in the same compound may be the same or different.
- R 31 and R 32 each independently represents a divalent aliphatic hydrocarbon group having 1 to 25 carbon atoms in which some carbon atoms may be substituted with heteroatoms. The total number of carbon atoms contained in the cation moiety in the formula is 20 or more.
- X ⁇ represents a monovalent anion
- R 20 represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 25 carbon atoms in which some carbon atoms may be substituted with a hetero atom, a phenyl group, Represents a phenoxy group, a benzyl group, an alkoxycarbonyl group, an N-alkylcarbamoyl group or an N-alkylsulfamoyl group, which may be bonded together in the same compound to form a ring.
- R 31 represents a divalent aliphatic hydrocarbon group having 1 to 25 carbon atoms in which a part of carbon atoms may be substituted with a hetero atom.
- R 33 represents a monovalent aliphatic hydrocarbon group having 1 to 25 carbon atoms in which some of the carbon atoms may be substituted with hetero atoms, or 4 to 25 carbon atoms that may have a substituent.
- the total number of carbon atoms contained in the cation moiety in the formula is 20 or more.
- R 20 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
- R 21 to R 23 Is preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms
- R 24 is preferably an alkyl group having 1 to 8 carbon atoms
- R 31 and R 32 are Independently, an alkylene group having 1 to 11 carbon atoms is preferable, an alkylene group having 1 to 5 carbon atoms is more preferable, and an ethylene group substituted with an ethylene group or a propane-1,2-diyl group is more preferable.
- R 31 and R 32 may be bonded to each other to form a cyclic structure such as a pyranose ring.
- R 33 is preferably an alkyl group having 1 to 16 carbon atoms.
- k is preferably 1
- X ⁇ is preferably monomethyl sulfate ion, hydrogen sulfate ion, dihydrogen phosphate ion or chlorine ion.
- the onium salts may be used alone or in combination of two or more.
- the amount of the onium salt used relative to the catalyst metal component can be appropriately adjusted depending on the properties of the substrate used and the like, and is not particularly limited.
- the molar ratio is preferably 0.3 times to 5.0 times mole, more preferably 0.2 times to 2.0 times mole.
- the above onium salts can be synthesized by alkylating the corresponding tertiary amines, pyridines, imidazoles and the like.
- the reagent used for alkylation is not particularly limited, but R 18 -A (wherein A is a halogen atom such as chlorine, bromine or iodine, or aromatic sulfonyl such as p-toluenesulfonyl or methanesulfonyl, aliphatic sulfonyl, etc.)
- R 18 represents R 1 to R 4 , R 5 , R 11 or R 13 in the above formulas (1) to (3), or R 1 to R 4 , R 5 , R 11 or R 13 represents a substituent convertible).
- R 18 -A include halogenated alkyl compounds such as methyl iodide, ethyl iodide, ethyl bromide, octyl chloride and cetyl chloride; sulfonyl such as octyl ester of methanesulfonic acid and benzyl ester of p-toluenesulfonic acid.
- halogenated alkyl compounds such as methyl iodide, ethyl iodide, ethyl bromide, octyl chloride and cetyl chloride
- sulfonyl such as octyl ester of methanesulfonic acid and benzyl ester of p-toluenesulfonic acid.
- Compounds sulfate esters such as dimethyl sulfate and diethyl sulfate
- carbonate esters such as dimethyl carbonate
- a base may be used in the alkylation reaction.
- Specific examples of the base used include inorganic bases such as potassium carbonate, sodium carbonate, cesium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydroxide and potassium hydroxide: organic bases such as ammonia, methylamine and ethylamine.
- inorganic bases such as potassium carbonate, sodium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, and potassium carbonate are preferable, and potassium carbonate is more preferable.
- an organic solvent may be used.
- the solvent used for the reaction may be distilled off after the reaction or after the post-reaction treatment described later, or may be subjected to the epoxidation reaction as a solution after the post-treatment.
- Specific examples of the organic solvent to be used include esters such as ethyl acetate, aliphatic hydrocarbons such as heptane, hexane and cyclohexane, aromatic hydrocarbons such as benzene, toluene, xylene and pyridine, acetonitrile, tetrahydrofuran, dioxane, 1 , 2-dimethoxyethane and other aprotic solvents, acetone and methyl ethyl ketone and other ketones, N, N'-dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide and other aprotic polar solvents, chloroform, dichloromethane, 1,2 -H
- the inorganic substance produced by the reaction can be removed by operations such as filtration and washing as appropriate.
- the produced onium often forms a salt with A ⁇ as a counter ion.
- a salt is often formed with hydroxide ions in water or ions in washing water.
- These counter ions can be exchanged for desired counter ions by operations such as washing and ion exchange resin treatment. For example, when methylation is carried out using dimethyl sulfate, monomethyl sulfate is formed, but it can be converted to hydrogen sulfate by washing with sulfuric acid water.
- Method introduced by 2) A method in which amines having —Y—CO 2 H, pyridines, and imidazoles are esterified to give —Y—CO—OZ, and then alkylated to give an onium salt as described above;
- amines, pyridines, and imidazoles having —Y—CO—O—R 19 R 19 represents an alkyl group having 1 to 12 carbon atoms) are converted to —Y—CO—O—Z by transesterification.
- a method of esterifying —Y—OH a method of reacting it with a corresponding acid chloride Z—CO—T (T represents a halogen atom), and dehydration condensation of Z—CO—OH with an acid catalyst. Or condensation using a condensing agent such as DCC or CDI.
- Examples of the method of transesterifying —Y—CO—O—R 19 include a method of reacting the corresponding alcohol Z—OH in the presence of an acid catalyst. At this time, it is preferable to carry out the transesterification while removing the produced R 19 —OH by a method such as distillation or adsorption.
- a method of introducing an ester group by dehydration condensation or transesterification under an acid catalyst is preferable.
- the acid catalyst used is a mineral acid such as sulfuric acid, nitric acid and hydrochloric acid, benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, trichloromethanesulfonic acid, trifluoroacetic acid.
- Organic acids such as trichloroacetic acid and acetic acid, H 3 PW 12 O 40 , H 4 SiW 12 O 40 , H 4 TiW 12 O 40 , H 5 CoW 12 O 40 , H 5 FeW 12 O 40 , H 6 P 2 W 18 O 62, H 7 PW 11 O 33, H 4 TiMo 12 O 40, H 3 PMo 12 O 40, H 7 PMo 11 O 39, H 6 P 2 Mo 18 O 62, H 4 PMoW 11 O 40, H 4 PVMo 11 O 40, H 4 SiMo 12 O 40, H 5 PV 2 Mo 10 O 40, H 3 PM 6 W 6 O 40, H 0.5 Cs 2.5 PW 12 O 40 , and tungstic acid, such as hydrates thereof, molybdenum acid or these heteropolyacids; cation exchange resin such as Amberlyst IR120, H-ZSM H type zeolite such as ⁇ 5 can be used.
- cation exchange resin such as Amberlyst IR120, H
- sulfuric acid is preferable from the viewpoint of cost.
- an organic acid such as p-toluenesulfonic acid or methanesulfonic acid as necessary.
- These catalysts can be used in an amount of 0.1 to 100% by weight, preferably 1 to 20% by weight, based on the substrate.
- the solvent to be used is not particularly limited, but is not particularly limited as long as it does not participate in the reaction, and aromatic hydrocarbons such as benzene, toluene, and xylene, hexane, heptane, octane, dodecane, Aliphatic hydrocarbons are mentioned.
- the amount of the solvent to be used is not particularly limited, but when the substrate and the salt of the acid catalyst are precipitated from the system, the reaction rate may be lowered. Therefore, it is preferable to appropriately adjust the amount according to the properties of the substrate and the acid.
- the onium salt obtained through the above steps may be isolated and purified and then used for the epoxidation reaction or may be used without isolation or purification, but is advantageous in terms of production efficiency. Moreover, it is preferable to use for epoxidation reaction, without isolating and refine
- the “functional group containing active hydrogen” is an alkoxycarbonyl group or an acyloxy group, it may contain a carboxylic acid or an alcohol which is a decomposition product of an onium salt.
- the catalyst composition of the present invention may contain at least one of phosphoric acids and phosphonic acids (excluding onium salts), and it is preferable in view of reactivity. At least one of phosphoric acids and phosphonic acids only needs to coexist with the catalyst metal component and the onium salt during the production reaction of the epoxy compound. Good.
- phosphoric acids include inorganic phosphoric acid such as phosphoric acid, polyphosphoric acid, and pyrophosphoric acid; sodium phosphate, potassium phosphate, ammonium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, hydrogen phosphate Inorganic phosphates such as ammonium, sodium dihydrogen phosphate, potassium dihydrogen phosphate, and calcium dihydrogen phosphate; phosphoric acids such as monomethyl phosphate, dimethyl phosphate, trimethyl phosphate, triethyl phosphate, triphenyl phosphate Esters; and the like.
- inorganic phosphoric acid such as phosphoric acid, polyphosphoric acid, and pyrophosphoric acid
- Inorganic phosphates such as ammonium, sodium dihydrogen phosphate, potassium dihydrogen phosphate, and calcium dihydrogen phosphate
- phosphate esters In the case of phosphate esters, phosphate esters other than onium salts having a phosphate ester group as “a functional group containing active hydrogen or a substituent that can be converted to a salt thereof” are used.
- phosphoric acids inorganic phosphoric acid is preferable, and phosphoric acid is preferable.
- phosphonic acids include aminomethylphosphonic acid and phenylphosphonic acid. Of these, inexpensive phosphoric acid is preferred.
- the amount used of at least one of phosphoric acids and phosphonic acids is not particularly limited, and the appropriate amount used varies depending on at least one type of phosphoric acids and phosphonic acids used and the type of catalytic metal component.
- the amount used is adjusted so that the pH of the reaction system aqueous phase described below is in an appropriate range.
- the equivalent amount of phosphorus contained in at least one of the phosphoric acids and phosphonic acids is the catalyst used.
- the amount is usually 0.1 times to 10 times mol, preferably 0.2 times to 5.0 times mol, more preferably 0.2 times to 3.0 times mol per metal atom in the metal component.
- the form of the reaction for producing an epoxy compound from an olefin compound (hereinafter sometimes referred to as “the epoxidation reaction of the present invention”) is not particularly limited, but is usually a two-phase system of an aqueous phase and an organic phase. This is done in the reaction system.
- the epoxy compound produced by the reaction of the present invention quickly dissolves in the organic phase, and as described later, the aqueous phase usually exhibits acidity. This is because it is possible to suppress decomposition due to ring opening and rearrangement.
- a reaction solvent can be used as necessary.
- the olefin compound used in the reaction or the epoxy compound to be produced is liquid under the reaction conditions, it can be used in the reaction without using a reaction solvent. This is because hydrogen peroxide usually contains water, so that a two-phase reaction system can be formed by mixing.
- a reaction solvent which may be dissolved in a solvent or in a suspended state, but is usually preferably dissolved in a reaction solvent under reaction temperature conditions. .
- the reaction solvent to be used is not particularly limited as long as it does not participate in the reaction, and an organic solvent that forms a two-phase system with water is preferable.
- Aromatic hydrocarbons such as benzene, toluene, xylene, hexane, Aliphatic hydrocarbons such as heptane, octane and dodecane, alcohols such as methanol, ethanol, isopropanol, butanol, hexanol and cyclohexanol, halogenated solvents such as chloroform, dichloromethane and dichloroethane, ethers such as tetrahydrofuran and dioxane, methyl ethyl ketone , Ketones such as methyl isobutyl ketone, cyclopentanone and anone, nitriles such as acetonitrile and butyronitrile, ester compounds such as ethyl acetate, buty
- the amount used when using the reaction solvent depends on the solubility of the compound, but the reaction rate may decrease as the amount of the reaction solvent increases.
- the amount is preferably 5 times or less, more preferably 3 times or less.
- water may be further added during the reaction. Since hydrogen peroxide to be added usually contains water, an aqueous phase is formed without adding water, but it may be added as necessary.
- the amount of water added is usually 0.1 to 10 times, preferably 0.1 to 5 times, more preferably 0.1 to 3 times the amount of the olefin compound. Amount.
- the use amount of at least one of the catalyst metal component, onium salt, phosphoric acid and phosphonic acid is as described above, but the molar ratio of the catalyst metal component / onium salt is usually 0.2 or more, Preferably it is 0.3 or more, More preferably, it is 0.5 or more, Usually, 4 or less, Preferably it is 3 or less, More preferably, it is 2 or less.
- the molar ratio of catalyst metal component / (at least one of phosphoric acids and phosphonic acids) is usually 0.2 or more, preferably 0.3 or more, more preferably 0.5 or more, usually 4 or less, preferably 3 or less. More preferably, it is 2 or less.
- At least one of phosphoric acids and phosphonic acids is preferably added so that the pH of the aqueous phase of the reaction solution is in an appropriate range, but an acid or base is added as necessary to adjust the pH.
- the structure of the catalytic metal component such as tungstic acid in the present invention changes depending on its pH, and the reaction activity changes. Therefore, it is preferable to adjust the pH appropriately depending on the reactivity of the olefin compound, the stability of the epoxy group, the distribution and solubility of the compound in water, and the like.
- the pH of the aqueous phase of the reaction solution varies depending on the stability of the epoxy compound and the solubility in water, but is usually 2 or more, preferably 2.5 or more, usually 6 or less, preferably 5 or less.
- the reaction solution is a two-phase system of an aqueous phase and an organic phase
- the pH of the aqueous phase is excessively acidic
- the ring-opening reaction or transfer reaction of the epoxy group is likely to proceed
- the onium salt is an alkoxycarbonyl group or
- an acyloxy group or the like is included, such a group may be hydrolyzed to cause problems such as reduced reactivity.
- problems such as extremely slow reaction, hydrogen peroxide decomposition, and alkoxycarbonyl group or acyloxy group hydrolysis may occur.
- acids such as phosphoric acid, aminomethylphosphonic acid, phenylphosphonic acid, sulfuric acid, nitric acid, hydrochloric acid, perchloric acid; sodium hydroxide, potassium hydroxide, sodium carbonate as necessary
- Inorganic bases such as potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, phosphoric acid, disodium hydrogen phosphate and dipotassium hydrogen phosphate: organic bases such as ammonia, methylamine and ethylamine may be added.
- the production method of the present invention is specifically described below.
- ⁇ Raw material> The compound having a carbon-carbon double bond used as a raw material in the present invention is not particularly limited as long as it is a compound having one or more carbon-carbon double bonds in the molecule. 30) and the like.
- R represents an allyl group, and the allyl group may be substituted with an alkyl group, a phenyl group or an alkoxycarbonyl group.
- a 201 represents a (m201 + 1) -valent aromatic or aliphatic hydrocarbon group which may have a substituent
- a 202 represents a divalent aromatic or aliphatic hydrocarbon which may have a substituent.
- a 203 represents a (m203 + 2) -valent aromatic or aliphatic hydrocarbon group which may have a substituent.
- aromatic or aliphatic hydrocarbon group includes those having both hydrocarbon skeletons, for example, those containing both structures of an aromatic ring and an aliphatic ring in the molecule.
- X 201 and X 202 each independently represent a divalent linking group which may have a direct bond or a substituent.
- p201 represents 0 or 1.
- m201 and m203 each independently represent an integer of 1 or more.
- a plurality of R, A 201 , A 202 , X 201 , X 202 , m201 and p201 contained in one molecule may be the same or different.
- compounds represented by the above formula (30) compounds represented by the following general formulas (4) to (6) are preferable.
- R represents an allyl group, and the allyl group may be substituted with an alkyl group, a phenyl group or an alkoxycarbonyl group.
- a 1 is an m1-valent aromatic or aliphatic hydrocarbon group.
- M1 represents an integer of 1 or more, and a plurality of R contained in one molecule may be the same or different.
- Examples of the aromatic hydrocarbon group represented by A 1 include an m1-valent group obtained by removing m1 hydrogen from an aromatic hydrocarbon having 6 to 14 carbon atoms such as a benzene ring, a naphthalene ring, and an anthracene ring, A benzene ring having 6 carbon atoms is preferred.
- the corresponding hydroxy compound (that is, (A 1 )-(OH) m1 ) is a straight chain such as diethylene glycol, propane-1,3-diol, butane-1,4-diol, polyvinyl alcohol or the like.
- Fatty acid polyhydric alcohols linear polyhydric alcohols having branched substituents such as neopentyl glycol, 2-methylpropanediol, 2,2-dimethylpropanediol, pentaerythritol; diethylene glycol, triethylene glycol, polytetramethylene glycol (PTMG) Polyhydric alcohols having an ether group in the molecular chain; carbonate polyols such as ethanediol carbonate, butanediol carbonate, ethanediol polycarbonate, butanediol polycarbonate, cyclopentanediol Cycloaliphatic diols such as cyclopentanedimethanol, cyclopentanediethanol, cyclohexanediol, cyclohexanedimethanol, cyclohexanediethanol, norbornanediol, norbornanedimethanol, norbornaned
- Examples of the substituent other than the OR group that the aromatic or aliphatic hydrocarbon group represented by A 1 may have include an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, and a propyl group; Group, an ethoxy group, a propyloxy group and the like, an alkyloxy group having 1 to 4 carbon atoms; a nitro group and the like.
- the upper limit of the number thereof is usually 4 or less, preferably 3 or less, and usually 1 or more, which the group represented by A 1 can have.
- m1 represents an integer of 1 or more, 2 or more preferably an integer, the upper limit on the number of replaceable hydrogen atoms on the group represented by A 1 is determined but is usually 4 or less, particularly preferably 2 is there.
- the compound represented by the general formula (4) include those represented by any of the general formula groups (7) below.
- On the benzene ring for example, a t-butyl group other than the OR group It may have a substituent.
- a nuclear hydrogenated product in which part or all of the aromatic ring is reduced may be used.
- Examples of the compound in which A 1 is an aliphatic hydrocarbon group include isosorbide, 1,4-cyclohexanedimethanol, and 2,3-norbornanediol.
- R represents an allyl group, and the allyl group may be substituted with an alkyl group, a phenyl group or an alkoxycarbonyl group.
- a 21 may have a substituent ( m @ 2 + 1) valent aromatic or aliphatic hydrocarbon group, a 22 is connected via a .
- X 2 representing an aromatic or aliphatic hydrocarbon group which may be divalent to have a substituent group a 21 and A 22 , or a plurality of adjacent A 22 may be bonded to each other to form a ring
- X 2 is a divalent bond that may have a direct bond or a substituent.
- M2 represents an integer of 1 or more
- n2 represents an integer of 0 or 1.
- a plurality of R, A 21 , A 22 , X 2 and m2 contained in one molecule are the same. It may or may not be.
- a 21 and A 22 each represent a (m1 + 2) -valent or divalent aromatic or aliphatic hydrocarbon group, and they may have a substituent.
- Examples of the aromatic or aliphatic hydrocarbon group represented by A 21 and A 22 include groups derived from the same hydrocarbon as A 1 in the general formula (4), and the number of carbon atoms is also the same.
- Examples of the substituent that the group represented by A 21 or A 22 may have include an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, and a propyl group; a methoxy group, an ethoxy group, and a propyloxy group An alkyloxy group having 1 to 4 carbon atoms such as nitro group and the like, among which an alkyl group is preferable.
- the upper limit of the number is the upper limit of the number of substituents that the group represented by A 21 can have, but usually 4 or less, preferably 3 or less.
- X 2 represents a divalent linking group which may have a direct bond or a substituent, and examples of the divalent linking group include a methylene group, a dimethylmethylene group, a ditrifluoromethylmethylene group, an ethylene group, and a propylene group.
- the divalent linking group may have an arbitrary substituent.
- a (RO) m2- (A 21 ) group (provided that R, A 21 and m2 have the same meanings as those in formula (5), and preferred ones are also the same) May be included). That compound represented by Formula (5), the two as specified in the formula (RO) m2 - (A 21 ) - in addition to groups, further (RO) m2 - (A 21 ) - have a group May be.
- X 2 is a direct bond, a divalent alkylene group having 1 to 4 carbon atoms (provided that it may be substituted with an aromatic hydrocarbon group, and the aromatic hydrocarbon group preferably has 6 to 10), and alicyclic hydrocarbons having 7 to 10 carbon atoms having a bridged condensed ring structure, particularly direct bonds, alkylene groups having 1 to 2 carbon atoms (however, an aromatic hydrocarbon group) It may be substituted, and the aromatic hydrocarbon group preferably has 6 to 8 carbon atoms).
- adjacent A 21 and A 22 connected via X 2 or a plurality of adjacent A 22 may be bonded to each other to form a ring.
- the ring includes a 5- to 6-membered hydrocarbon ring or an oxygen atom. Examples thereof include 6-membered rings.
- n2 represents an integer of 1 or more, its upper limit is determined by the number of replaceable hydrogen atoms of the group represented by A 21, is generally 4 or less, preferably 2 or less.
- n2 represents 0 or an integer of 1 or more, and the upper limit thereof is usually 5 and preferably 2.
- a compound represented by the following general formula (5-1) is particularly preferable.
- R 100 represents an allyl group which may have a substituent, and the substituent is an alkyl group having 1 to 6 carbon atoms, a phenyl group, or an alkoxy group having 2 to 7 carbon atoms. It is a carbonyl group.
- a 121 represents an optionally substituted ⁇ (m102) +1 ⁇ -valent aromatic hydrocarbon group having 6 to 14 carbon atoms
- a 122 represents a divalent optionally substituted substituent. Represents an aromatic hydrocarbon group having 6 to 14 carbon atoms.
- a 121 and A 122 connected through X 102 , or a plurality of A 122 may be bonded to each other to form a ring.
- X 102 is substituted with a direct bond, a methylene group, a dimethylmethylene group, a ditrifluoromethylmethylene group, an ethylene group, —C (CH 3 ) ⁇ CH—, a phenyl group, or (R 100 O) m2 — (A 121 ) —.
- a plurality of R 100 , A 121 , A 122 , X 102 and m102 contained in one molecule may be the same or different.
- m102 represents an integer of 1 to 4
- n102 represents an integer of 0 to 5.
- R 100 may have, a methyl group, a phenyl group, a methoxycarbonyl group, and an ethoxycarbonyl group are more preferable, and R 100 is an unsubstituted allyl group. Is particularly preferred.
- X 102 is more preferably a direct bond, a divalent alkylene group having 1 to 4 carbon atoms (which may be substituted with an aromatic hydrocarbon group, and the aromatic hydrocarbon group preferably has 6 to 10 carbon atoms).
- alicyclic hydrocarbons having 7 to 10 carbon atoms having a bridged condensed ring structure, particularly direct bonds, alkylene groups having 1 to 2 carbon atoms (provided that they are substituted with aromatic hydrocarbon groups).
- aromatic hydrocarbon group preferably has 6 to 8 carbon atoms). More preferable m102 is 1 or 2, and more preferable n102 is 0, 1 or 2.
- Specific examples of the compound represented by the general formula (5) include those represented by the following structural formula (n represents an integer of 1 or more), and part or all of these aromatic rings. And a hydrogenated hydrogenated product in which is reduced.
- the benzene ring may have a substituent other than the —OR group and the specified methyl.
- R represents an allyl group, and the allyl group may be substituted with an alkyl group, a phenyl group or an alkoxycarbonyl group.
- a 3 may have a substituent (m3 + 2).
- X 3 represents a direct bond, an alkylene group which may have a substituent, or —R 61 -phenylene-R 62 —, wherein R 61 and R 62 each represents Independently represents an alkylene group, m3 represents an integer of 1 or more, n3 represents an integer of 2 or more, and a plurality of G, A 3 , X 3 , and m3 contained in one molecule may be the same May be different.
- Examples of the aromatic or aliphatic hydrocarbon group represented by A 3 include groups derived from the same hydrocarbon as A 1 in formula (4), and the number of carbon atoms is also the same.
- X 3 represents a direct bond, an alkylene group which may have a substituent, or —R 61 -phenylene-R 62 —, wherein R 61 and R 62 each independently represents an alkylene group.
- Examples of the alkylene group which may have a substituent represented by X 3 include those similar to X 2 in the general formula (5). Among them, the number of carbon atoms is 1 to 4, preferably 1 carbon atoms. Or the alkylene group of 2 is mentioned.
- R 61 and R 62 in —R 61 -phenylene-R 62 — each independently represents an alkylene group having 1 to 4 carbon atoms, preferably 1 or 2 carbon atoms.
- n3 represents an integer of 1 or more, its upper limit is determined by the number of replaceable hydrogen atoms of the group represented by A 3, is generally 4 or less, preferably 2 or less.
- n3 represents an integer of 2 or more, and is usually 20 or less, preferably 10 or less.
- Specific examples of the compound represented by the general formula (6) include compounds represented by the following structural formula (wherein n and n ′ are the same as n3) and a part or all of these aromatic rings are reduced. And nuclear hydrogenated materials.
- the benzene ring may have a substituent other than the —OR group and the methyl group specified.
- Another example of the compound having a carbon-carbon double bond used as a raw material in the present invention includes a cyclic olefin compound represented by the following general formula (36).
- i and j each independently represent an integer of 1 to 4
- R 64 to R 71 each independently represents a hydrogen atom, a halogen atom, or an optionally substituted alkyl.
- R 64 to R 71 are each independently a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an aromatic hydrocarbon group which may have a substituent, a nitro group, an alkoxyl group, a carbonyl Represents a group, an alkoxycarbonyl group, an acyloxy group, a carboxyl group or a salt thereof.
- the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
- the alkyl group an alkyl group having 1 to 20 carbon atoms is preferable.
- substituents include halogen atoms such as fluorine atom, chlorine atom and bromine atom; methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group.
- substituents include alkoxyl groups such as nitro groups; carboxyl groups; alkoxycarbonyl groups such as methoxycarbonyl groups and ethoxycarbonyl groups; acyloxy groups such as acetyloxy groups and propionyloxy groups.
- aromatic hydrocarbon group include a phenyl group and a naphthyl group. The aromatic hydrocarbon group may have a substituent.
- substituents include halogen atoms such as fluorine atom, chlorine atom and bromine atom; methoxy group, ethoxy group, propoxy group, isopropoxy group, Alkoxy group such as butoxy group; nitro group; carboxyl group; alkoxycarbonyl group such as methoxycarbonyl group and ethoxycarbonyl group; acyl group such as acetyl group, propionyl group and benzoyl group; acyloxy group such as acetyloxy group and propionyloxy group Etc.
- alkoxyl group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and a butoxy group.
- acyloxy group examples include an acetyloxy group, a propionyloxy group, and a benzoyloxy group.
- carboxyl group salt examples include alkali metal salts such as sodium salt and potassium salt. Any two or more of R 64 to R 71 may be bonded to each other to form a ring.
- i and j each independently represents an integer of 1 to 4, preferably 1 to 3, more preferably 1 or 2, and most preferably 2.
- the cyclic olefin represented by the general formula (36) include 1,4-cyclohexadiene, 1,5-cyclooctadiene, 1,5,9-cyclododecatriene, 1,5-dimethyl-1,5-cyclohexane. Examples thereof include cyclic non-conjugated olefins such as octadiene, dicyclopentadiene, and 2,5-norbornadiene.
- R 72 to R 76 are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a carbon number of 3
- R 77 and R 78 are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, carbon A cycloalkyl group having a number of 3 to 7, an aromatic hydrocarbon group, an aralkyl group, an acyl group, a carboxyl group, or an acyloxy group.
- any two or more of R 72 to R 78 may be bonded to each other to form a ring.
- Specific examples of the styrene represented by the general formula (37) include styrene, 4-methylstyrene, 4-fluorostyrene, 2,4-difluorostyrene, 3-chlorostyrene, 4-chlorostyrene, and 4-bromostyrene. 4-nitrostyrene, 4-vinylbenzoic acid, ⁇ -methylstyrene, ⁇ -methylstyrene, 1-phenyl-1-cyclohexene, indene, dihydronaphthalene and the like.
- the olefin compound in the present invention may be used after pretreatment such as removing impurities as necessary.
- the epoxidation reaction using hydrogen peroxide affected by foreign materials such as metal, activated carbon, silica gel, glass fragments, etc. mixed from raw materials, solvents, reaction vessels and auxiliary equipment such as pipes and liquid pumps There is. Oxides such as hydrogen peroxide are decomposed by contact with the aforementioned foreign substances, and may generate reaction heat and oxygen, which may be dangerous. It is preferable that these foreign substances do not enter or are not affected by the reaction solution.
- the olefin compound is filtered, the olefin compound is washed with an acidic aqueous solution, and the olefin compound is a chelating agent (a compound capable of forming a chelate with a metal. Is preferably washed with a metal masking agent) or in the presence of a chelating agent in the epoxidation reaction.
- a chelating agent a compound capable of forming a chelate with a metal. Is preferably washed with a metal masking agent or in the presence of a chelating agent in the epoxidation reaction.
- the type of acid used in the acidic aqueous solution for washing the olefin compound used as a raw material is not particularly limited, and specific examples include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid; and organic acids such as acetic acid and citric acid. It is done.
- the pH of the acidic aqueous solution is not particularly limited, and varies depending on the stability of the olefin compound to be used. For the purpose of adjusting pH, various salts may be added. For example, sodium sulfate, sodium acetate, sodium phosphate, disodium hydrogen phosphate, sodium citrate and the like may be added.
- a mixed aqueous solution of acetic acid and sodium sulfate is preferable.
- an aqueous solution containing 4% acetic acid and 1% sodium sulfate and having a pH of about 4 is more preferable.
- the aqueous solution containing a chelating agent is not particularly limited as long as it is an aqueous solution containing a compound having a chelating ability with a metal, but an aqueous solution containing a so-called metal mask agent is preferable.
- Examples thereof include ethylenediaminetetraacetic acid and pyrophosphoric acid described in Japanese Patent Special Publication 2002-501005.
- a method of washing with water containing at least one of ethylenediaminetetraacetic acid and pyrophosphoric acid is preferred. By performing these treatments, the metal is solubilized in water and removed together with the aqueous phase.
- the chelating agent can be used by adding it to the reaction system, and a method of adding at least one of ethylenediaminetetraacetic acid and pyrophosphoric acid to the reaction solution is preferable. This is because these chelating agents, which are metal masking agents, can suppress decomposition of peroxides by chelating metals.
- the specific reaction operation method in the production method of the present invention is not particularly limited, but the olefin compound includes at least one of hydrogen peroxide, a tungsten compound and a molybdenum compound, an onium salt, and optionally phosphorus. At least one of acids and phosphonic acids is added, and the aforementioned organic solvent and buffer are added as necessary.
- the order of addition and mixing of each component is not limited as long as the reaction is not hindered, but since it generates heat during the epoxidation reaction and decomposition of hydrogen peroxide, from the viewpoint of controlling reaction progress and heat generation, Hydrogen peroxide is gradually added after the components are added, or an amount of hydrogen peroxide necessary to oxidize at least one of the tungsten compound and the molybdenum compound is added in advance, and the tungsten and molybdenum peroxide are added.
- a method of gradually adding the remaining hydrogen peroxide after at least one is preferred.
- As a method for adding hydrogen peroxide it may be added in divided portions or may be added gradually and continuously. From the viewpoint of safety, it is preferable to add it according to the progress of the reaction so that unreacted hydrogen peroxide does not stay in the reaction system.
- the reaction temperature in the production method of the present invention is not particularly limited as long as the reaction is not hindered. Below, more preferably 75 ° C. or less. If the amount is less than the lower limit, the reaction rate may be slow, and if the upper limit is exceeded, it may not be preferable from the viewpoint of safety.
- the reaction time can be appropriately selected depending on the reaction temperature, the amount of catalyst, the type of raw material, and the like, and is not particularly limited. Hereinafter, it is preferably 36 hours or less, more preferably 24 hours or less.
- the reaction in the production method of the present invention is preferably carried out under normal pressure and a nitrogen stream from the viewpoint of safety.
- the production method of the present invention is not particularly limited, but is usually performed in a two-phase reaction system of an aqueous phase and an organic phase.
- the pH during the reaction varies depending on the structure of the reaction raw material. For example, while cyclic olefins are easily epoxidized, the resulting epoxy tends to transfer or cleave, so reaction under conditions close to neutrality is preferable. In the case of allyloxyether, epoxy is more preferable than cyclic olefins. There is a tendency that it is more acidic than the case of a cyclic olefin because it is difficult to be converted and is difficult to cleave.
- the pH is not particularly limited, but usually the pH of the aqueous phase is 2 or more, preferably 2.5 or more, and usually 6 or less.
- the pH changes depending on the amount of hydrogen peroxide in the aqueous phase, and in the latter half of the reaction, the generated epoxy is cleaved under acidic conditions, so an acid or base is added as appropriate depending on the progress of the reaction.
- a buffer solution can also be used.
- the type of the buffer any buffer that matches the target pH can be used as long as it does not inhibit the reaction.
- the buffer solution include citric acid and sodium citrate, acetic acid and sodium acetate, and the like as a combination of an aqueous phosphate solution, hydrogen phosphate, dihydrogen phosphate, or phenyl phosphate.
- the above tungstic acids may be combined to form a buffer solution.
- the catalyst composition may contain a carboxylic acid, preferably an aliphatic carboxylic acid having 1 to 10 carbon atoms.
- the co-oxidant may be added to the composition.
- the co-oxidant may be generated by hydrolysis of the ester group.
- a nitrogen-containing compound such as a surfactant, amines and pyridine ring compound may be included in the oxidizing agent composition.
- ⁇ Reactant removal step post-treatment step>
- post-treatment is performed to convert a substituent of the onium salt into a functional group having active hydrogen or a salt thereof. Since the onium salt converted from the substituent moves from the organic phase in the reaction system to the aqueous phase, it can be easily separated from the epoxy compound present in the organic phase. The product epoxy compound may be further purified as necessary.
- the method for converting a substituent of an onium salt into a functional group having active hydrogen or a salt thereof is not limited as long as the object of the present invention is not impaired.
- an acidic aqueous solution in a range in which an epoxy compound is not decomposed Conversion method by adding basic aqueous solution, conversion method by catalytic hydrogenation, conversion method by heating, conversion method using an auxiliary or enzyme capable of selectively converting substituents, conversion by photoreaction And a method of converting by microwave irradiation.
- the onium salt After conversion to a functional group having active hydrogen or a salt thereof, the onium salt has moved into the water of the reaction system.
- the onium salt can be separated as long as the epoxy compound is not decomposed.
- a separation method according to physical properties is used. Examples of the separation method include liquid separation, washing, hanging washing, adsorption, filtration, and distillation. The case where an onium salt having an alkoxycarbonyl group or an acyloxy group is used will be specifically described below.
- the aqueous phase is discarded, washed with water, and if necessary, a reducing agent is added to quench excess hydrogen peroxide.
- a reducing agent Sodium sulfite, sodium thiosulfate, hydrazine, oxalic acid, etc. are mentioned.
- the onium salt is converted to water-soluble.
- the hydrolysis method is not particularly limited, but a method using a basic compound is usually performed, and specific examples of the basic compound include metal hydroxides such as sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, Examples thereof include metal carbonates such as sodium carbonate and potassium carbonate, phosphates such as sodium phosphate and sodium hydrogen phosphate, ion exchange resins, and basic solids such as alumina.
- hydrolysis with a basic aqueous solution is preferable, and specific examples include hydrolysis with a sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution.
- the base treatment operation is carried out after or after the reaction solvent is distilled off. This is preferable because the product can be easily separated.
- the concentration, pH, and temperature of the basic aqueous solution are not particularly limited, but can be selected within a range where the epoxy compound is not decomposed. Specifically, a basic aqueous solution having an aqueous solution concentration of usually 0.1 N to 5 N, preferably 0.3 N to 3 N, and more preferably 0.5 N to 2 N is used.
- the pH of the aqueous solution is usually 10-12.
- the temperature of the aqueous solution is usually 0 ° C. or higher, preferably 20 ° C. or higher, usually 60 ° C. or lower, preferably 45 ° C. or lower.
- the water-soluble onium salt is removed by washing.
- the catalytic metal component is also removed by washing.
- the epoxy compound thus obtained has a low content of metals derived from the catalytic metal component, such as tungsten and onium salts. Although it depends on the chlorine content of the compound subjected to the reaction, it generally has a feature that the chlorine content is small as compared with an epoxy compound synthesized using epichlorohydrin.
- a specific purification method is not particularly limited, and a known method can be appropriately used.
- the epoxy compound is a solid, crystallization, hanging washing, liquid separation, adsorption and the like can be mentioned, and when the epoxy compound is a liquid, liquid separation, washing, adsorption and distillation can be mentioned.
- Purification by separation and washing may be performed by combining water and an organic solvent that is insoluble or hardly soluble in water, or combining a plurality of organic solvents that are not mixed with each other.
- Examples of the combination of water and an organic solvent insoluble or hardly soluble in water include a combination of an organic solvent such as ethyl acetate, toluene, diethyl ether, diisopropyl ether, n-hexane, and water.
- combinations of a plurality of organic solvents that are not mixed with each other include, for example, a combination of N, N′-dimethylformamide and at least one of n-heptane, n-hexane, n-pentane, diisopropyl ether, xylene, dimethyl sulfoxide, n-heptane, n-hexane, n-pentane, diisopropyl ether, diethyl ether, combination with at least one of xylene, acetonitrile and n-heptane, n-hexane, n-pentane, cyclohexane, cyclopentane There is a combination with at least one of them, and a combination with methanol and at least one of n-heptane, n-hexane and n-pentane.
- the solvent is distilled off under reduced pressure, or it is cooled and crystallized without distilling off, a solvent having a low solubility of the compound, a method of adding a so-called poor solvent to precipitate, and a compound having a high solubility. Any of a method of precipitating by combining a solvent, a so-called easy solvent and a poor solvent, and a method of adding water to crystallize after completion of the reaction may be used.
- the solvent may be any organic solvent, water or a mixture thereof, a combination of organic solvents, and the like, and an appropriate one is selected depending on the solubility of the compound.
- organic solvent examples include esters such as ethyl acetate, aliphatic hydrocarbons such as heptane, hexane and cyclohexane, aromatic hydrocarbons such as benzene, toluene and xylene, acetonitrile, tetrahydrofuran, dioxane, 1,2-dimethoxyethane and the like.
- Aprotic solvents examples include polar solvents.
- alcohols such as methanol, ethanol, 2-propanol and n-butanol
- ketones such as acetone and methyl ethyl ketone
- aprotic such as N, N′-dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide
- Examples include polar solvents.
- a solvent having a low compound solubility For purification by hanging washing, a solvent having a low compound solubility, a so-called poor solvent is used. Although a preferable poor solvent changes with compounds, highly polar things, such as alcohols, such as methanol, and low polarity aliphatic hydrocarbons, such as a pentane, hexane, and a cyclohexane, are raised conversely.
- the water-soluble solvent include tetrahydrofuran, 1,3-dioxolane, N, N, N-dimethylformamide, dimethyl sulfoxide and the like, and these can be used by mixing with water. When the amount of the solvent is too small, the purification effect is not sufficient, and when it is too large, the recovery rate is lowered. After completion of the hanging washing, the target product can be obtained by collecting the solid by filtration and drying.
- Purification by adsorption includes activated carbon, activated clay, molecular sieves, activated alumina, zeolite, ion exchange resin and the like as chlorine-containing impurities and adsorbents.
- the liquid separation method is preferable from the viewpoint of the operation method regardless of the properties of the epoxy compound.
- the crystallization method is effective.
- Epoxy composition An epoxy compound is obtained through the above epoxidation reaction, a separation / removal step of the catalytic metal component and the onium salt, and a purification step as necessary.
- the epoxy composition obtained by the production method of the present invention is obtained as a composition having a very low content of metal derived from a catalyst metal, and the content of the metal is usually 200 ppm or less, preferably 100 ppm or less, more preferably Is 10 ppm or less, more preferably 1 ppm or less.
- the epoxy composition obtained by the production method of the present invention has a low nitrogen content derived from the onium salt, and the content is usually 500 ppm or less, preferably 200 ppm or less, more preferably 10 ppm or less. Become.
- the epoxy composition obtained by the production method of the present invention has a low halogen atom content, and the content is usually 200 ppm or less, preferably 50 ppm or less, more preferably 10 ppm or less.
- the manufacturing method of this invention can be used for manufacture of the pharmaceutical intermediate etc. which have an epoxy structure other than the epoxy resin mentioned later.
- the epoxy composition of this invention can be used as a pharmaceutical intermediate etc. which have an epoxy structure other than the epoxy resin mentioned later.
- production of an antifungal agent having a halogen-substituted styrene oxide structure, an intermediate of a diabetic drug, and the like can be raised. Since the epoxy composition obtained by the method of the present invention has few impurities, the concern about toxicity derived from impurities is reduced.
- the epoxy compound in the present invention (hereinafter sometimes referred to as an epoxy compound ⁇ ) is not particularly limited as long as it is a compound having one or more epoxy groups in the molecule.
- the compound represented by (32) is mentioned.
- G represents a glycidyl group (2,3-epoxypropanyl group), and the glycidyl group may be substituted with an alkyl group, a phenyl group or an alkoxycarbonyl group.
- a 201 represents a (m201 + 1) -valent aromatic or aliphatic hydrocarbon group which may have a substituent
- a 202 represents a divalent aromatic or aliphatic hydrocarbon which may have a substituent.
- a 203 represents a (m203 + 2) -valent aromatic or aliphatic hydrocarbon group which may have a substituent.
- X 201 and X 202 each independently represent a divalent linking group which may have a direct bond or a substituent.
- p201 represents 0 or 1.
- m201 and m203 each independently represent an integer of 1 or more.
- n201 represents an integer of 1 or more, n202 represents 0 or an integer of 1 or more, and n203 represents 0 or 1.
- a plurality of G, A 201 , A 202 , X 201 , X 202 , m201 and p201 contained in one molecule may be the same or different.
- G in the general formula (32) represents a glycidyl group (2,3-epoxypropanyl group).
- the glycidyl group may be substituted with an alkyl group, a phenyl group or an alkoxycarbonyl group, and among these substituents, a methyl group, a phenyl group, a methoxycarbonyl group and an ethoxycarbonyl group are more preferable.
- An unsubstituted glycidyl group is particularly preferred.
- a 201 to A 203 , X 201 , X 202 , n201 to n203, m201, m203, and p201 in the general formula (32) have the same meanings as in the general formula (30), and preferable ones are also the same. .
- compounds represented by the general formula (32) compounds represented by the following general formulas (13) to (15) are preferable.
- G represents a glycidyl group (2,3-epoxy-propanyl group), the glycidyl group is an alkyl group, optionally .
- a 1 be phenyl or substituted alkoxycarbonyl group
- M1 represents an aromatic or aliphatic hydrocarbon group which may have a substituent
- m1 represents an integer of 1 or more
- plural Gs contained in one molecule may be the same or different. May be.
- Specific examples and preferred ranges of G are the same as those in the general formula (32), and specific examples and preferred ranges of A 1 are the same as those in the general formula (4).
- G represents a glycidyl group, and this glycidyl group may be substituted with an alkyl group, a phenyl group or an alkoxycarbonyl group.
- a 21 may have a substituent ( m @ 2 + 1) valent aromatic or aliphatic hydrocarbon group, a 22 is connected via a .
- X 2 representing an aromatic or aliphatic hydrocarbon group which may be divalent to have a substituent group a 21 and A 22 , or a plurality of adjacent A 22 may be bonded to each other to form a ring
- X 2 is a divalent bond that may have a direct bond or a substituent.
- a plurality of G, A 21 , A 22 , X 2 , and m2 contained in one molecule are the same.
- G is the same as those in the general formula (32).
- a 21 , A 22 , X 2 , m2 and n2 and preferred ranges thereof are the same as those in the general formula ( Same as in 5).
- G represents a glycidyl group, and the glycidyl group may be substituted with an alkyl group, a phenyl group or an alkoxycarbonyl group.
- a 3 may have a substituent ( m3 + 2) represents a valent aromatic or aliphatic hydrocarbon group, X 3 represents a direct bond, an alkylene group which may have a substituent, or —R 61 -phenylene-R 62 —, wherein R 61 and R 62 independently represents an alkylene group, m3 represents an integer of 1 or more, n3 represents an integer of 2 or more, and a plurality of G, A 3 , X 3 , and m3 contained in one molecule are the same Or different.) Specific examples and preferred ranges of G are the same as those in the general formula (32), and specific examples and preferred ranges of A 3 , X 3 , m3 and n3 are the same as those in the general formula (6). It is.
- the epoxy compound ⁇ obtained by the production method of the present invention is generally a compound ⁇ having a structure in which one or more glycidyl groups of the epoxy compound ⁇ are substituted with 3-acyloxy-2-hydroxypropyl groups (provided that the acyl compound The group is obtained as a composition containing —CO—R 35 or a group represented by —CO—Z.
- These compounds are mainly produced by the reaction of an onium salt with an epoxy compound under basic conditions during a post-treatment step after the reaction.
- Z is a monovalent aliphatic hydrocarbon group having 1 to 25 carbon atoms in which some carbon atoms may be substituted with hetero atoms, or 4 to 25 carbon atoms that may have a substituent.
- R 35 represents any of (18) to (20) below.
- R 41 represents a direct bond or a divalent aliphatic hydrocarbon group having 1 to 25 carbon atoms in which some of the carbon atoms may be substituted with heteroatoms.
- R 42 to R 44 each independently represents an alkyl group having 1 to 25 carbon atoms or a benzyl group in which some carbon atoms may be substituted with heteroatoms.
- Any one of R 45 to R 50 represents a divalent aliphatic hydrocarbon group having 1 to 25 carbon atoms which may be a direct bond or a part of carbon atoms may be substituted with a hetero atom.
- R 46 to R 50 are each independently
- Each of the four is independently a hydrogen atom, a halogen atom, a cyano group, a
- any one of R 51 to R 55 represents a direct bond or a divalent aliphatic hydrocarbon group having 1 to 25 carbon atoms in which some carbon atoms may be substituted with hetero atoms.
- the other is one Represents an alkyl group having 1 to 25 carbon atoms or a benzyl group, in which part of the carbon atoms may be substituted with a hetero atom
- R 52 , R 54 and R 55 each independently represents a hydrogen atom, a halogen atom or a cyano group , A nitro group, an alkyl group having 1 to 25 carbon atoms in which some carbon atoms may be substituted with a hetero atom, a phenyl group, a phenoxy group, a benzyl group,
- R 52 , R 54 and R 55 are a direct bond or a divalent aliphatic hydrocarbon group having 1 to 25 carbon atoms in which some carbon atoms may be substituted with heteroatoms
- the other two are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 25 carbon atoms in which some carbon atoms may be substituted with a hetero atom, a phenyl group, Represents a phenoxy group, a benzyl group, an N-alkylcarbamoyl group or an N-alkylsulfamoyl group, and R 51 and R 53 each independently represents a carbon atom in which some of the carbon atoms may be substituted with a heteroatom.
- R 41 to R 44 in the above formula (18) is 20 or more, and the total number of carbon atoms contained in R 45 to R 50 in the above formula (19) is 15 or more.
- the total number of carbon atoms contained in R 51 to R 55 is 17 or more.
- R 41 to R 55 may combine with each other in the same compound to form a ring.
- the groups represented by the general formulas (18) to (20) correspond to the onium portion of the onium salt represented by the general formulas (1) to (3).
- R x not bonded to —CO— of —CO—R 35 (x represents any of 42 to 55) is Of R 1 to R 15 in the general formulas (1) to (3), these are synonymous with groups other than —Y—CO—O—Z or —Y—O—CO—Z, and preferred groups are also the same.
- R y (y represents any of 42 to 55) and R 41 bonded to —CO— of —CO—R 35. Is synonymous with —Y— in the general formulas (1) to (3), and preferred groups are also the same.
- one or more —OG groups are substituted with a group represented by the following formula (16) or (17),
- one or more —OG groups may be substituted with a group represented by the following formula (33).
- R 35 represents a group represented by any one of the above formulas (18) to (20).
- Z represents a part of carbon atoms being heterogeneous. It represents a monovalent aliphatic hydrocarbon group having 1 to 25 carbon atoms which may be substituted with an atom, or a monovalent aromatic hydrocarbon group having 4 to 25 carbon atoms which may have a substituent.
- Z has the same meaning as Z in formulas (1) to (3).
- an epoxy compound ⁇ represented by the following structural formula (21) (hereinafter sometimes referred to as “compound (21)”),
- a compound ⁇ represented by the following general formula (22) (hereinafter sometimes referred to as “compound (22)”) or a compound ⁇ represented by the following general formula (23) (hereinafter referred to as “compound (23)”). And a composition containing the same).
- Q represents R 35 or —Z in the above general formula (16) or (17).
- the compound ⁇ may be a compound in which the glycidyl ether group of the compound represented by the general formula (22) is substituted with the group represented by the general formula (33).
- the epoxy composition includes a compound in which one or both of the glycidyl ether groups of the compound represented by the structural formula (21) are ring-opened and changed to the group represented by the general formula (33). Also good.
- the amount of compound ⁇ (ester) produced varies depending on the structure of the compound, reaction conditions and post-treatment conditions, but is usually 0.05 mol% or more and 10 mol% or less, preferably 5 mol% or less with respect to compound ⁇ . is there.
- the amount of compound ⁇ (diol body) produced varies depending on the structure of the compound, reaction conditions, and post-treatment conditions, but is usually 0.05 mol% or more and 10 mol% or less with respect to compound ⁇ .
- the abundance ratio of compound ⁇ to compound ⁇ can be determined by NMR. Specifically, it can be obtained by comparing the proton integrated value of a peak that is easy to specify and integrate with the peak integrated value of the epoxy compound ⁇ . For example, in the case of the ester compound ⁇ , it can be obtained by comparing the proton integrated value of the peak derived from the alcohol or carboxylic acid forming the ester with the integrated value of the peak of the epoxy compound ⁇ .
- the abundance ratio of compound ⁇ to compound ⁇ can be determined by LC (liquid chromatograph) analysis.
- the weight ratio is obtained by correcting the LC area ratio of compound ⁇ and compound ⁇ determined by LC analysis in consideration of the difference between the factors of compound ⁇ and compound ⁇ , that is, the difference in UV absorption. Or converted into a molar ratio. If the LC analysis is difficult because the compound ⁇ or the compound ⁇ is weak in UV absorption and difficult to measure accurately, or it is difficult to measure accurately at the same UV wavelength, the GC (gas chromatogram) G) analysis. Specifically, the weight ratio and molar ratio are corrected by taking into account the difference in factor of compound ⁇ and compound ⁇ , that is, the difference in sensitivity, with respect to the GC area ratio of compound ⁇ and compound ⁇ determined by GC analysis. Can be converted to
- the compound ⁇ has one or more hydroxyl groups obtained by adding one or more epoxy groups to a carboxylic acid and opening the ring. It is known that the hydroxyl group contained in the epoxy compound contributes to the adhesiveness of the epoxy resin. It is known that the epoxy compound produced from the epichlorohydrin method contributes to adhesiveness because it contains approximately 10% of a hydroxyl group. In a conventional epoxidation reaction using an onium salt, since a compound corresponding to the compound ⁇ cannot be produced, there are very few components having a hydroxyl group in the obtained epoxy composition, and there is a concern of insufficient adhesion. However, since the epoxy composition obtained by the production method of the present invention contains a certain amount of the compound ⁇ , it is excellent in that there is no concern.
- the epoxy compound obtained by the production method of the present invention and the epoxy composition of the present invention can produce an epoxy resin by polymerization.
- a known method can be applied to the polymerization reaction. Specifically, the polymerization reaction can be performed by a method described in JP-A No. 2007-246819.
- the high-purity epoxy resin obtained by the method of the present invention can be used in electronic materials, optical materials, adhesives, construction fields and the like.
- an electronic component material such as semiconductor encapsulant, printed wiring board, build-up wiring board, solder resist, etc.
- optical material such as lighting sealant for wiring corrosion and short circuit caused by impurities In this case, it is possible to reduce or avoid coloring and deterioration.
- the catalyst composition for epoxidation reaction of the present invention can also be used as an oxidant other than the epoxidation reaction, preferably an oxidant for oxidizing an olefin.
- LC device SPD-10Avp manufactured by Shimadzu Corporation Temperature: 35 ° C
- Column Mightysil RP-18GP aqua 150-4.6 (5 ⁇ m) (manufactured by Kanto Chemical Co., Inc.)
- ⁇ GC analysis conditions Equipment: GC-1700, manufactured by Shimadzu Corporation Column: ZB-5 (30mx0.25mm ⁇ , 0.25 ⁇ m) manufactured by phenomenex Detector: Hydrogen flame ion detector (FID) Carrier gas (nitrogen flow rate): 28 ml / min Column temperature: Increased from 100 ° C to 300 ° C at 10 ° C / min INJ temperature: 250 ° C DET temperature: 300 ° C
- GC device GC-2010 manufactured by Shimadzu Corporation
- MS equipment GCMS-QP2010Plus manufactured by Shimadzu Corporation
- Column DB-5 25M ⁇ 0.25 (0.25 ⁇ )
- Ionization method EI method and CI method
- RI analysis conditions > RI apparatus: JASCO's JASCO RI-930 Temperature: 35 ° C Column: ODS-3 150-4.6 (5 ⁇ m) (manufactured by GL Sciences) Eluent: Acetonitrile flow rate: 0.5 ml / min
- the chlorine content (ppm by weight) was measured by the following method for the total amount of chlorine combined with inorganic and organic.
- the sample was burned and absorbed in the absorbing solution, and then measured with an ion chromatograph.
- AQF-100 manufactured by Mitsubishi Chemical Corporation was used as the combustion apparatus, and DX-500 manufactured by DIONEX was used as the ion chromatograph apparatus.
- Dionex Ion Pac AS12A was used for the column, and the detection was performed based on the electric conductivity.
- the tungsten content (ppm by weight) was measured by the following method. 0.1 to 0.5 g of the sample was weighed, 2 ml of sulfuric acid was added and heated and carbonized, and nitric acid and hydrogen peroxide were further added and heated, followed by wet decomposition. To this was added 2 ml of hydrogen peroxide and heated, and the volume was increased to about 40 ml with pure water. Further, 2 ml of hydrogen peroxide solution was added, and the volume was made up to 50 ml with pure water. The solution was analyzed by ICP-AES (ULTIMA 2C manufactured by HORIBA Jobin Yvon).
- the nitrogen content was measured by the following method. A sample of 8 mg was combusted in an oxygen and argon atmosphere, and the generated decomposition gas was measured with a trace nitrogen analyzer (TN-10 model, manufactured by Mitsubishi Chemical Analytech Co., Ltd.) using combustion and reduced pressure chemiluminescence method. Further, aniline was dissolved in toluene and used as a standard sample. The pH of the aqueous phase was measured using pH test paper Comparator (manufactured by Johnson Test Papers) pH 1.0 to 3.5 and pH 3.6 to 5.1.
- the diol compound ⁇ (compound 23) contained in the epoxy compound (compound 21) was synthesized by the method described in Reference Example 1, and using this, the NMR peak assignment, retention time by LC analysis, and UV The absorption intensity was confirmed and used for quantification of the content of compound 23 in compound 21.
- the ester compound ⁇ (compound 22) in Examples 12, 14, 16, 18, 20, 22, 25, and 26 was synthesized according to the method described in Reference Example 2, and subjected to NMR analysis of the sample. Identification of each NMR peak was confirmed. By performing NMR analysis of Compound 21 with reference to this, the content of Compound 22 in Compound 21 was used for quantification. In other examples, the content of compound 22 in compound 21 was quantified by analogy with NMR of the compound obtained in Reference Example 2.
- the molecular weight of the ester compound ⁇ (Compound 22) in Examples 2, 8, and 9 was confirmed by LC-Mass. m / z 470.3.
- LC analysis Example 28 is GC analysis
- LC area% of each component was measured.
- the abundance ratio of compound ⁇ to compound ⁇ was converted to a molar ratio by correcting the detection sensitivity of each compound to the ratio of the peak area of compound ⁇ to compound ⁇ determined by LC analysis (Example 28 was GC analysis). .
- each compound As for the detection sensitivity of each compound, a preparation of each compound having a purity of 95% or more is prepared in advance, and an approximate value of the net number of moles of the compound (purity estimated from the number of moles XLC area% / 100) and its LC It was calculated from the peak area.
- the abundance ratio of the compound ⁇ is the integrated value of the proton peak of the epoxy compound ⁇ , such as the terminal methyl group of hexanoic acid ester, the t-butyl group of t-butylbenzoic acid ester, etc. It was calculated by comparing with.
- the contents of the compounds ⁇ and ⁇ were represented by the molar ratio (mol%) when the abundance ratio with respect to the epoxy compound ⁇ , that is, the epoxy compound ⁇ was 100.
- -Mass compound with m / z 370.2
- This compound and compound ⁇ are both more polar than epoxy compound ⁇ (21), and give a faster retention time than compound ⁇ (21) in LC analysis.
- the compounds that give a faster retention time than these epoxy compounds ⁇ (21) may be collectively referred to as “polar compounds” in the examples.
- LC area refers to the peak area of the target compound obtained by liquid chromatography (LC) analysis
- LC area% refers to the ratio of the peak area of the target compound to the peak area of the total amount of the composition.
- the toluene phase was analyzed by NMR and the onium salt [1] was hydrolyzed by the disappearance of the peak of the ethylene portion of N-methyl-N, N, N-tri [2- (pentylcarbonyloxy) ethyl] ammonium hydrogen sulfate. It was confirmed that it was decomposed.
- the same sodium hydroxide aqueous solution washing and NMR analysis were repeated three times, followed by washing with 10 ml of water.
- the obtained toluene phase was concentrated to obtain 3.8 g of 3,3 ′, 5,5′-tetramethylbiphenyl-4,4′-diglycidyl ether (compound 21) as crude crystals. The purity was 86.4% and the yield was 60%.
- the crude crystals contained 2.7 mol% of the ester compound ⁇ (Compound 22) and 5.2 mol% of the diol compound ⁇ (Compound 23).
- the aqueous phase was discharged and concentrated, and N- (6-ethoxy-6-oxohexyl) -N-methyl-N, N-dioctylammonium sulfate 1.0 g of hydrogen salt (hereinafter referred to as onium salt [2]) was obtained. This was subjected to an epoxidation reaction without purification.
- Example 4 (Epoxidation reaction using onium salt [2])
- N-methyl-N, N, N-tri [2- (pentylcarbonyloxy) ethyl] ammonium hydrogen sulfate as the ammonium salt
- N- (6-ethoxy-6- The reaction was carried out in the same manner using oxohexyl) -N-methyl-N, N-dioctylammonium hydrogen sulfate (5% mol / substrate). Reaction yield 80% (LC area%).
- the crude crystal of Compound 21 obtained contained 1.1 mol% of ester compound ⁇ (Compound 22).
- the content of tungsten in the compound was measured by the above method. The measurement results are shown in Table 1.
- N, N, N-trioctyl-N- (2-methoxy-2-oxoethyl) ammonium phosphate 0.88 (9H, t, —CH3), 1.20-1.40 (30H, m, —CH2 -), 1.76 (6H, m, -CH2-), 3.60-3.67 (6H, m, -CH2-), 3.81 (3H, s, -CH3), 4.85 (2H , SN-CH2-)
- Example 6 Epoxidation reaction using onium salt [3]
- the reaction was conducted in the same manner as in Example 2, except that N, N, N-trioctyl-N- (2-methoxy-2-oxoethyl) ammonium phosphate (5% mol / substrate) was used as the ammonium salt. It was. The progress of the reaction stopped 4 hours after the start of the reaction, and the reaction yield was 23% (LC area%). NMR analysis of the reaction mixture was conducted in the same manner as in Example 2.
- Example 7 (Synthesis method of onium salt [1 ′] (monomethyl sulfate as counter ion))
- a mixture of 20.0 g (207 mmol) of triethanolamine hydrochloride, 60 ml of octane, 43.3 g of hexanoic acid (3.0 times mol / substrate), and 5.28 g of sulfuric acid is heated in an oil bath at 135 ° C. to produce. It reacted for 61 hours, distilling off water.
- Example 8 Epoxidation reaction using onium salt [1 ']
- 5.0 g (15.5 mmol) of 3,3 ′, 5,5-tetramethyl-4,4′-bis (2-propen-1-yloxy) -1,1′-biphenyl was dissolved in 6.3 ml of toluene.
- the solution was washed with 15 ml of an aqueous solution containing 1% by weight of anhydrous sodium sulfate and 1% by volume of acetic acid, and then a mixed solution of 0.23 ml of 3% by weight sodium pyrophosphate aqueous solution, 0.06 ml of 10% by weight ethylenediaminetetraacetic acid solution and 15 ml of water.
- the aqueous phosphoric acid solution added at that time was 0.5 ml (3% mol / substrate).
- This mixture was heated to 65 ° C., and under a nitrogen stream at an internal temperature of 65-68 ° C., 0.5 ml of 45% hydrogen peroxide (0.5 mol / substrate) was started at 1 hour after that. After 2 hours, 3 hours, and 6 hours, a total of 5 times was added. After 1.5 hours from the start of the reaction, 0.4 ml of 1N aqueous sodium hydroxide solution was added, 0.1 ml after 4.5 hours, and 0.1 ml after 6.5 hours, and the pH of the aqueous phase was adjusted to 3.0-3. Adjusted to 5.
- the reaction was carried out at an internal temperature of 65-68 ° C. for a total of 8 hours. According to the above LC analysis, 3,3 ′, 5,5′-tetramethylbiphenyl-4,4′-diglycidyl was obtained with a reaction yield of 82% (LC area%). It was confirmed that ether was formed. In addition, it was confirmed that 11% (LC area%) of a monoepoxy compound as a reaction intermediate and 6% (LC area%) of a polar compound were produced.
- the ester compound ⁇ (compound 22) was 2.4 mol%, and the diol compound ⁇ (compound 23) was 3.5 mol%.
- the chlorine, tungsten and nitrogen contents in the compound were analyzed by the above method. The measurement results are shown in Table 1.
- Example 9 15 g of methanol was added to 2.0 g of 3,3 ′, 5,5′-tetramethylbiphenyl-4,4′-diglycidyl ether obtained by the above method, followed by rinsing at 50 ° C. for 1 hour. As a result, 1.8 g of 91% (LC area%) of 3,3 ′, 5,5′-tetramethylbiphenyl-4,4′-diglycidyl ether (Compound 21) was obtained. Recovery rate 98%. This crystal contained 0.3 mol% of the ester compound ⁇ (Compound 22).
- Example 10 Synthesis of onium salt [4]
- the reaction was carried out in the same manner as in Example 8 without adding an aqueous sodium hydroxide solution. It was confirmed that 3,3 ′, 5,5′-tetramethylbiphenyl-4,4′-diglycidyl ether was produced at a reaction yield of 77% (LC area%). In addition, it was confirmed that 9% (LC area%) of the monoepoxy compound as a reaction intermediate and 12% (LC area%) of compound ⁇ in which the epoxy ring was opened with an acid were confirmed.
- R 25 represents a C8 to C18 alkyl group.
- Esocard C / 12 N-alkyl (C8-C18) -N, N-bis (2-hydroxyethyl) -N-methylammonium chloride, containing about 20% isopropanol
- Lion Akzo 200 ml of toluene 50 ml of toluene and isopropanol were distilled off while heating the mixed solution, and then 5.0 g of triethylamine was added, 6.7 g of benzoic acid chloride was added at an internal temperature of 60 to 80 ° C., and an internal temperature of 65 The reaction was carried out at 30 ° C for 30 minutes and at 80 ° C for 2 hours.
- the reaction system was changed over time by dissolving about 0.1 ml of the reaction mixture in 1 ml of methanol, converting unreacted benzoic acid chloride into benzoic acid methyl ester, and then performing LC analysis under analytical condition 2.
- Triethylamine and benzoic acid chloride were gradually added at 80 ° C., and the point where the consumption of benzoic acid chloride ceased was regarded as the end point of the reaction.
- the added triethylamine was 4.8 g, and benzoic acid chloride was 3.6 g.
- N-alkyl-N, N-bis [2- (phenylcarbonyloxy) ethyl] -N-methylammonium chloride 0.88 (3H, —CH3), 1.0-1.4 (about 20H, br, — CH2-), 1.76 (2H, m, -CH2-), 2.00 (2H, m, -CH2-), 3.63 (3H, s, N-CH3), 3.63 (2H, m -CH2-), 4.38 (4H, m, N-CH2-), 4.91 (4H, m, -CH2-CO), 7.42 (4H, dd, -Ph), 7.56 (2H , Dd, -Ph), 8.00 (4H, d, -Ph)
- Example 12 (Epoxidation reaction using onium salt [4]) A solution of 10.0 g (31.0 mmol) of 3,3 ′, 5,5-tetramethyl-4,4′-bis (2-propen-1-yloxy) -1,1′-biphenyl dissolved in 10 ml of toluene After washing with 30 ml of an aqueous solution containing 1% by weight of anhydrous sodium sulfate and 1% by volume of acetic acid, it was washed with a mixed solution of 0.26 ml of 3% by weight sodium pyrophosphate aqueous solution, 0.12 ml of 10% ethylenediaminetetraacetic acid solution and 30 ml of water. .
- the aqueous phase was discharged, washed twice with 20 ml of water and 2 ml of saturated brine, and twice with 20 ml of water, and then cooled to room temperature to precipitate the reaction contents as a solid. After draining the supernatant water and toluene mixed solution by decantation, nitrogen was blown in and the remaining solvent was distilled off to obtain a solid of the reaction contents. To the obtained solid, 20 ml of 1N aqueous sodium hydroxide solution was added and stirred for 1 hour, and the aqueous phase was discharged.
- Example 14 Epoxidation reaction using onium salt [5]
- 5.0 g of 3,3 ′, 5,5-tetramethyl-4,4′-bis (2-propen-1-yloxy) -1,1′-biphenyl pretreated in the same manner as described above (15 0.5 mmol), toluene 3.8 ml, sodium tungstate dihydrate 512 mg (10% mol / substrate), 8.5% (weight / volume) phosphoric acid aqueous solution 1.61 ml (9% mol / substrate), water 3 4 ml and the above N-methyl-N, N, N-tri [2- (4-tert-butylphenylcarbonyloxy) ethyl] ammonium monomethyl sulfate toluene solution were added and stirred.
- the NMR data of the obtained onium salt [6] were as follows. 2,3-bis (4-t-butyl-phenyloxy) -N, N-diethyl-N-methyl-1-propaneammonium monomethyl sulfate: 1.37 (18H, s, t-Bu), 1.43 (6H, s, -CH3), 3.26 (3H, s, CH3-N), 3.56 (4H, m, N- CH2- CH3), 3.73 (3H, s, CH3OSO2-), 4 .36 (2H, m, —CH 2 —O—CO), 4.58 (1H, dd, —CH 2 —N), 4.78 (1H, dd, —CH 2 —N), 6.03 (1 H, m , -CH-), 7.41 (2H, dd, -Ar), 7.46 (2H, dd, -Ar), 7.87 (2H, dd, -Ar), 7.96 (2H, dd, -A
- Example 16 (Epoxidation reaction using onium salt [6]) 2.0 g of 3,3 ′, 5,5-tetramethyl-4,4′-bis (2-propen-1-yloxy) -1,1′-biphenyl pretreated in the same manner as described above ( 6.2 mmol), toluene 1.4 ml, sodium tungstate dihydrate 204 mg (10% mol / substrate), 8.5% (weight / volume) phosphoric acid aqueous solution 0.36 ml (5% mol / substrate), water 3.6 ml of the toluene solution of 2,3-bis (4-tert-butyl-phenyloxy) -N, N-diethyl-N-methyl-1-propaneammonium monomethyl sulfate described above was added and stirred.
- This mixture was heated to 65 ° C., and under a nitrogen stream at an internal temperature of 65-68 ° C., 0.1 ml of 45% hydrogen peroxide (0.5-fold mol / substrate) was started at 1 hour. After 2 hours, 3 hours, and 6 hours, a total of 5 times was added. The reaction was conducted at an internal temperature of 65-68 ° C. for a total of 7 hours. According to the LC analysis, 3,3 ′, 5,5′-tetramethylbiphenyl-4,4 was obtained with a reaction yield of 77% (LC area%, analysis condition 1). It was confirmed that '-diglycidyl ether was formed. In addition, 11% (LC area%) of a monoepoxy compound as a reaction intermediate and 8% (LC area%) of a polar compound were produced.
- the NMR data of the obtained onium salt [7] are as follows. 2,3-bis (4-t-butyl-phenyloxy) -N, N, N-triethyl-1-propaneammonium hydrogen sulfate: 1.32 (18H, s, t-Bu), 1.47 (9H , S, —CH3), 3.59 (6H, m, N—CH2—CH3), 4.29 (1H, m, HSO4), 4.37 (2H, m, —CH2—O—CO), 4 .64 (1H, dd, -CH2-N), 4.82 (1H, dd, -CH2-N), 6.00 (1H, m, -CH-), 7.42 (4H, dd, -Ar ), 7.90 (4H, dd, -Ar)
- Example 18 (Epoxidation reaction using onium salt [7]) 5.0 g of 3,3 ′, 5,5-tetramethyl-4,4′-bis (2-propen-1-yloxy) -1,1′-biphenyl pretreated in the same manner as described above (15 0.5 mmol), 3.8 ml of toluene, 51.2 mg of sodium tungstate dihydrate (10% mol / substrate), 1.25 ml of 8.5% (weight / volume) aqueous phosphoric acid solution (7% mol / substrate), Add 3.4 ml of water and 0.46 g (5% mol / substrate) of the above 2,3-bis (4-tert-butyl-phenyloxy) -N, N, N-triethyl-1-propaneammonium sulfate.
- onium salt [8] 1- [2,3-bis [(4-tert-butylphenylcarbonyloxy) propyl] pyridinium chloride (hereinafter referred to as onium salt [8]) was added to 0. .32 g was obtained. Purity 92.9% (LC area%, LC analysis condition 2). Yield 28%.
- NMR data of the obtained onium salt [8] are as follows: 1- [2,3-bis [(4-tert-butylphenylcarbonyloxy) propyl] pyridinium chloride: 1.32 (18H, d, t-Bu ), 4.91 (2H, m, -CH2-O-CO), 5.38 (2H, m, -CH2-N), 5.93 (1H, m, -CH-), 6.22 (1H , M, -CH2-N), 6.03 (1H, m, -CH-), 7.42 (2H, dd, -Ar), 7.45 (2H, dd, -Ar), 7.82 ( 2H, dd, -Ar), 7.97 (2H, dd, -Ar), 8.40 (1H, m, Py), 9.61 (2H, m, Py)
- 12-bromododecanoic acid 5 g (18.8 mmol), 2.35 ml of hexanol (1 mol / substrate), 100 ml of toluene, 0.2 ml of sulfuric acid are produced for 4 hours while azeotropically distilling off water with toluene. did. 0.47 ml of hexanol (0.2-fold mol / substrate) was added, and the reaction was further continued for 2.5 hours.
- N, N-diethyl-N-methyl-1-dodecanoic acid hexyl ester ammonium methyl sulfate 0.85-1.10 (9H, m, -CH3), 1.25-1.80 (34H, m,- CH2-CH2-CH2-), 2, 38 (2H, m, -CO-CH2-), 3.07 (3H, s, N-CH3), 3.21 (6H, m, N-CH2-), 3.83 (3H, s, CH3S02-), 4.12 (2H, m, -COO-CH2)
- Example 22 (Epoxidation reaction using onium salt [9]) 2.0 g of 3,3 ′, 5,5-tetramethyl-4,4′-bis (2-propen-1-yloxy) -1,1′-biphenyl pretreated in the same manner as described above (6 0.2 mmol), toluene 1.2 ml, sodium tungstate dihydrate 0.205 g (10% mol / substrate), 8.5% (weight / volume) phosphoric acid aqueous solution 0.64 ml (9% mol / substrate), 1.4 ml of water and the above 12-N, N-dibutyldodecanoic acid hexyl ester ammonium monomethyl sulfate solution in toluene were added and stirred.
- This mixture was heated to 65 ° C., and under a nitrogen stream at an internal temperature of 65-68 ° C., 0.1 ml of 45% hydrogen peroxide (0.5-fold mol / substrate) was started at 1 hour. After 2 hours, 3 hours, 4 hours, and 6 hours, 6 times in total were added. The pH of the aqueous phase during the reaction was 2.0. The mixture was reacted at an internal temperature of 65-68 ° C. for a total of 6 hours. According to the above LC analysis, 3,3 ′, 5,5′-tetramethylbiphenyl-4,4′- was obtained with a reaction yield of 81.3% (LC area%). It was confirmed that diglycidyl ether was produced.
- Example 24 (Epoxidation reaction using onium salt [10]) 1.5 g of 3,3 ′, 5,5-tetramethyl-4,4′-bis (2-propen-1-yloxy) -1,1′-biphenyl pretreated in the same manner as described above (4 0.7 mmol), toluene 1 ml, octane 1 ml, sodium tungstate dihydrate 0.154 g (10% mol / substrate), 8.5% (weight / volume) phosphoric acid aqueous solution 0.48 ml (9% mol / substrate) Then, 1.0 ml of water and 0.106 g (5% mol / substrate) of the above 1-[(hexadecyloxycarbonyl) oxy] butyl] pyridinium chloride were added and stirred.
- Example 25 14 ml of methanol was added to 2.0 g of the crude 3,3 ′, 5,5′-tetramethylbiphenyl-4,4′-diglycidyl ether obtained in Example 14, followed by rinsing at 50 ° C. for 3 hours. . After cooling to 6 ° C., the crystals were collected by filtration and 3,3 ′, 5,5′-tetramethylbiphenyl-4,4′-diglycidyl ether having a purity of 90.9% (LC area%, LC analysis condition 2) 1.55 g was obtained. Recovery rate 79%. The hanging crystal contained 2.6 mol% of ester compound ⁇ (Compound 22) and 0.6 mol% of diol compound ⁇ (Compound 23). The nitrogen and chlorine contents in the compound were analyzed by the above method. The measurement results are shown in Table 1.
- Example 26 3 ml of methanol was added to 0.69 g of the crude 3,3 ′, 5,5′-tetramethylbiphenyl-4,4′-diglycidyl ether obtained in Example 16, and the suspension was washed at 50 ° C. for 1 hour. . After cooling to 6 ° C., the crystals were collected by filtration and 3,3 ′, 5,5′-tetramethylbiphenyl-4,4′-diglycidyl ether having a purity of 90.4% (LC area%, LC analysis condition 2) 0.52 g was obtained. Recovery rate 80%. The hanging crystal contained 2.0 mol% of the ester compound ⁇ (Compound 22) and 1.2 mol% of the diol compound ⁇ (Compound 23). The nitrogen content in the compound was analyzed by the above method. The measurement results are shown in Table 1.
- Example 27 3 g of toluene was added to 2.0 g of 3,3 ′, 5,5′-tetramethylbiphenyl-4,4′-diglycidyl ether crude crystals obtained in Example 18 and dissolved by heating to 50 ° C. 14 ml was added. After cooling to 6 ° C., the precipitated crystals were collected by filtration and 3,3 ′, 5,5′-tetramethylbiphenyl-4,4′-di having a purity of 96.1% (LC area%, LC analysis condition 2). 1.38 g of glycidyl ether was obtained. 71% recovery. This crystal contained an ester compound ⁇ of 0.2 mol% and a diol compound ⁇ of 0.5 mol%. The nitrogen content in the compound was analyzed by the above method. The measurement results are shown in Table 1.
- Example 28 Epoxidation reaction of 1,5-cyclooctadiene using onium salt [7]) 1,5-cyclooctadiene 3.0 g (27.7 mmol; manufactured by Tokyo Chemical Industry Co., Ltd.), toluene 9 ml, sodium tungstate dihydrate 0.183 g (2% mol / substrate), 8.5% (weight / volume) ) 0.32 ml of phosphoric acid aqueous solution (1% mol / substrate), 3.4 ml of water and the above 2,3-bis (4-tert-butyl-phenyloxy) -N, N, N, N-triethyl-1-propaneammonium 0.16 g (1% mol / substrate) of sulfate (onium salt [7]) was added and stirred.
- This mixture was heated to 50 ° C., and then under a nitrogen stream, 0.9 ml of 45% hydrogen peroxide (0.5-fold mol / substrate) was started at the time, 1 hour later, 2 hours later, 3 hours later. 5 hours later and 7 hours later, 6 times in total.
- the pH of the aqueous phase for 2 hours after the start of the reaction was 4.8.
- the reaction was conducted at an internal temperature of 50-51 ° C. for a total of 9 hours, and 1,2,5,6-diepoxycyclooctane was produced with a reaction yield of 90.2% (GC area%) by the above GC analysis. confirmed.
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Abstract
Description
エポキシ樹脂は、エポキシモノマーを、種々の硬化剤を用いて硬化させることにより得られる樹脂である。エポキシ樹脂は、機械的性質、耐水性、耐薬品性、耐熱性、電気的性質などに優れた樹脂であり、電子材料、光学材料、建築材料、接着剤、塗料、積層板、成形材料、注型材料、レジストなどの幅広い分野に利用されている。
近年、電子材料分野、例えば半導体封止材、プリント配線基板、ビルドアップ配線板、ソルダーレジストなどの分野では、その高集積化に伴いエポキシ樹脂に代表されるパッケージ材料にも高純度化が要求されている。また、オプトエレクトロニクス関連分野では、近年の高度情報化に伴い、膨大な情報を円滑に伝送、処理するために、光信号を生かした技術が開発されていく中で、透明性に優れた高純度の樹脂の開発が望まれている。
代表的なエポキシモノマーであるグリシジルエーテル化合物、例えば、フェノール類、ナフトール類、又はビスフェノールA等に、グリシジルオキシ基を縮合させた化合物は、耐熱性、接着性、耐薬品性、電気特性、機械特性等に優れるため、硬化剤により架橋硬化させ接着剤、成型材、封止剤、塗料等の多くの用途を有する工業材料である。グリシジルエーテル化合物の製造法としては、フェノール類を原料に用いる場合には、原料のフェノール類にエピクロルヒドリンを反応させる方法が最も広く用いられている。エピクロルヒドリンを用いたグリシジルエーテルの具体的な合成法は、例えば下記反応式で表される。
この製造方法において用いられるエポキシ化反応には、アンモニウム塩等のオニウム塩類と、タングステン化合物及びモリブデン化合物類のうち少なくとも一方を触媒組成物として共存させ、過酸化水素を酸化剤(エポキシ化剤)として用いるのが一般的である(例えば、非特許文献1~3参照)。
しかしながら、このエポキシ化反応では、通常触媒として共存させるオニウム塩として、塩化メチルトリオクチルアンモニウム塩等の長鎖アルキル基を有するアンモニウム塩や、セチルピリジニウム塩等の長鎖アルキル基を有するピリジニウム塩を使用して酸化剤を調製している。しかし前記長鎖アルキル基を有するオニウム塩は、有機溶媒への分配率が高く、反応後に有機相に溶解しているエポキシ化合物と、触媒組成物由来の成分、具体的にはタングステンや、オニウム塩、オニウム塩由来の含窒素化合物との分離、精製が極めて困難であるという問題がある。さらにタングステンや含窒素化合物等を、再結晶や懸洗といった方法により除去をすると、エポキシ化合物の精製収率(回収率)が低いという問題がある。
そのため、得られるエポキシ化合物中に、タングステンやモリブデンといった触媒由来の重金属成分や、オニウム塩等のイオン性化合物が残留する。これらは、エポキシ化合物からエポキシ樹脂を製造した際にも残留し、製品に悪影響を及ぼす。
例えば特許文献5または6では、エポキシ化反応後、イオン交換樹脂や金属酸化物等を吸着剤として用いてアンモニウム塩を吸着除去する方法が検討されている。
また特許文献7、8、または非特許文献4には、エポキシ化剤に用いるアンモニウム塩を、樹脂やシリカゲル等に担持させて用いた後、ろ過によって分離回収する方法が検討されている。
また特許文献10には、触媒を不均一化する方法が検討されている。
さらに特許文献11にはアンモニウム塩に磁性体を結合し、除去する方法が検討されている。
また、吸着剤を使用した場合には、吸着剤へのエポキシ化合物の吸着ロスによる生産性低下や、イオン交換樹脂由来の有機不純物や、金属酸化物由来の金属の溶出、混入の懸念がある。
特許文献10に記載の方法では、不均一化することにより、反応速度が低下する、また結晶性の良いモノマーには適用ができない等の問題がある。
特許文献11に記載の方法では、触媒の合成が煩雑という問題がある。
また過酸化水素等の酸化物は、金属、活性炭、シリカゲル、ガラス片等の異物との接触により、分解、発熱、酸素の発生等を起こすため、エポキシ化反応液中にこれらの異物の混入を避けることが好ましいが、製造プロセスにおいて異物の混入を完全に防ぐことは困難であり、安全面での対策を講じる必要があった。
本発明は、エポキシ化合物の製造において、タングステン等の重金属含有量が極めて少ない、好ましくはさらにオニウム塩由来の含窒素化合物量(以下、単に窒素含有量という)の少ない、より好ましくはさらに塩素含有量の少ないエポキシ化合物を、煩雑な精製工程等を要さずに製造する方法を提供することを課題とする。
具体的には、活性水素を含む官能基またはその塩に変換可能な置換基を、分子内に少なくとも1つ以上有しているオニウム塩を共存させて反応を行った。その結果、目的とするエポキシ化合物が得られ、エポキシ化反応後に活性水素を含む官能基またはその塩に変換したところ、エポキシ化合物とエポキシ化剤由来成分とが分離、除去され、純度の高いエポキシ化合物が得られることを見出し、本発明を完成させるに至った。
[1]エポキシ化合物の製造方法であって、炭素-炭素二重結合を有する化合物に、タングステン化合物及びモリブデン化合物のうち少なくとも一方と、活性水素を含む官能基またはその塩に変換可能な置換基を1つ以上有し、かつ炭素原子を20以上含むオニウム塩との存在下、過酸化水素を反応させる、エポキシ化合物の製造方法。
[2]前記活性水素を含む官能基が、水酸基、カルボキシル基、アミノ基、メルカプト基、スルホン酸基又はリン酸基である上記[1]に記載のエポキシ化合物の製造方法。
[3]前記反応時に、さらにリン酸類及びホスホン酸類(但しオニウム塩を除く)のうち少なくとも一方を共存させる上記[1]または[2]に記載のエポキシ化合物の製造方法。
[4]前記反応が水相と有機相の二相系反応であり、かつ前記水相のpHが2以上6以下である、上記[1]~[3]のいずれか1に記載のエポキシ化合物の製造方法。
[5]前記オニウム塩が、アンモニウム塩、ピリジニウム塩、イミダゾリニウム塩又はホスホニウム塩である上記[1]~[4]のいずれか1に記載のエポキシ化合物の製造方法。
[6]前記活性水素を含む官能基またはその塩に変換可能な置換基が、アルコキシカルボニル基又はアシルオキシ基である上記[1]~[5]のいずれか1に記載のエポキシ化合物の製造方法。
[7]前記オニウム塩が、下記一般式(1)~(3)のいずれかで表される化合物である上記[1]~[6]のいずれか1に記載のエポキシ化合物の製造方法。
R1~R5、R11及びR13は、前記-Y-CO-O-Z及び-Y-O―CO-Zではない場合は、それぞれ独立して、一部の炭素原子がへテロ原子で置換されていてもよく、かつ置換基を有していてもよい炭素数1~25のアルキル基又はベンジル基を表し、
R6~R10、R12、R14及びR15は、前記-Y-CO-O-Z及び-Y-O―CO-Zではない場合は、それぞれ独立して、水素原子、ハロゲン原子、シアノ基、ニトロ基、一部の炭素原子がへテロ原子で置換されていてもよく、かつ置換基を有していてもよい炭素数1~25のアルキル基、フェニル基、フェノキシ基、ベンジル基、N-アルキルカルバモイル基又はN-アルキルスルファモイル基を表す。
R1~R15は同一化合物内で結合して環を形成していてもよい。
なお、上記式(1)におけるR1~R4に含まれる炭素原子数の合計は20以上であり、上記式(2)におけるR5~R10に含まれる炭素原子数の合計は15以上であり、上記式(3)におけるR11~R15に含まれる炭素原子数の合計は17以上である。
X-は、1価のアニオンを表す。)
[8]前記製造方法において、反応後に、前記活性水素を含む官能基またはその塩に変換可能な置換基を、塩基性化合物で加水分解する上記[1]~[7]のいずれか1に記載のエポキシ化合物の製造方法。
[9]前記炭素-炭素二重結合を有する化合物を、酸性水溶液で洗浄した後に反応に供する、上記[1]~[8]のいずれか1に記載のエポキシ化合物の製造方法。
[10]前記炭素-炭素二重結合を有する化合物を、キレート化剤水溶液で洗浄した後に反応に供する上記[1]~[8]のいずれか1に記載のエポキシ化合物の製造方法、
[11]前記製造方法において、キレート化剤を反応時に共存させる、上記[1]~[10]のいずれか1に記載のエポキシ化合物の製造方法。
[12]エポキシ化合物を重合してエポキシ樹脂を製造する方法であって、上記[1]~[11]に記載の方法でエポキシ化合物を製造する工程と、前記工程で得られたエポキシ化合物を重合する工程を含むエポキシ樹脂の製造方法。
[13]タングステン化合物及びモリブデン化合物のうち少なくとも一方と、活性水素を含む官能基またはその塩に変換可能な置換基を1つ以上有する、炭素数が20以上のオニウム塩と、を含むエポキシ化反応用触媒組成物。
[14]前記活性水素を含む官能基が、水酸基、カルボキシル基、アミノ基、メルカプト基、スルホン酸基又はリン酸基である上記[13]に記載のエポキシ化反応用触媒組成物。
[15]前記組成物が、さらにリン酸類及びホスホン酸類(但しオニウム塩を除く)のうち少なくとも一方を含む上記[13]または[14]に記載のエポキシ化反応用触媒組成物。
[16]前記オニウム塩が、アンモニウム塩、ピリジニウム塩、イミダゾリニウム塩又はホスホニウム塩である上記[13]~[15]のいずれか1に記載のエポキシ化反応用触媒組成物。
[17]前記活性水素を含む官能基またはその塩に変換可能な置換基がアルコキシカルボニル基又はアシルオキシ基である上記[13]~[16]のいずれか1に記載のエポキシ化反応用触媒組成物、
[18]更にカルボン酸(但し、カルボキシ基を有するオニウム塩を除く)を含有する上記[13]~[17]のいずれか1に記載のエポキシ化反応触媒組成物、
[19]前記オニウム塩が、下記一般式(1)~(3)のいずれかで表される化合物である上記[13]~[18]のいずれか1に記載のエポキシ化反応用触媒組成物、
R1~R5、R11及びR13は、前記-Y-CO-O-Z及び-Y-O―CO-Zではない場合は、それぞれ独立して、一部の炭素原子がへテロ原子で置換されていてもよく、かつ置換基を有していてもよい炭素数1~25のアルキル基又はベンジル基を表し、
R6~R10、R12、R14及びR15は、前記-Y-CO-O-Z及び-Y-O―CO-Zではない場合は、それぞれ独立して、水素原子、ハロゲン原子、シアノ基、ニトロ基、一部の炭素原子がへテロ原子で置換されていてもよく、かつ置換基を有していてもよい炭素数1~25のアルキル基、フェニル基、フェノキシ基、ベンジル基、N-アルキルカルバモイル基又はN-アルキルスルファモイル基を表す。
R1~R15は同一化合物内で結合して環を形成していてもよい。
なお、上記式(1)におけるR1~R4に含まれる炭素原子数の合計は20以上であり、上記式(2)におけるR5~R10に含まれる炭素原子数の合計は15以上であり、上記式(3)におけるR11~R15に含まれる炭素原子数の合計は17以上である。
X-は、1価のアニオンを表す。)
[20]下記一般式(8)~(10)、(12)又は(31)で表されるオニウム塩。
R31及びR32は、それぞれ独立に、一部の炭素原子がへテロ原子で置換されていてもよい炭素数1~25の2価の脂肪族炭化水素基を表わす。
R33は、一部の炭素原子がへテロ原子で置換されていてもよい炭素数1~25の1価の脂肪族炭化水素基、又は置換基を有していてもよい炭素数4~25の1価の芳香族炭化水素基を表す。
なお、同一化合物中に存在する複数のk、R20及びR31は、同一であっても異なっていてもよい。また式中のカチオン部分に含まれる炭素原子数の合計は20以上である。
X-は、1価のアニオンを表す)
[21]下記式(32)で表されるエポキシ化合物αと、
該エポキシ化合物αが有するグリシジル基の1つ以上が3-アシルオキシ-2-ヒドロキシプロピル基に置換された構造を有する化合物β(但し、該アシル基は-CO-R35、又は-CO-Zで表される基)、とを含む組成物。
A201は置換基を有していてもよい(m201+1)価の芳香族または脂肪族炭化水素基を表し、A202は置換基を有していてもよい2価の芳香族または脂肪族炭化水素基を表し、A203は置換基を有していてもよい(m203+2)価の芳香族または脂肪族炭化水素基を表す。
X201及びX202は、各々独立に、直接結合又は置換基を有していてもよい2価の連結基を表す。
p201は0又は1を表す。
m201及びm203は、各々独立に、1以上の整数を表す。
n201は1以上の整数を表し、n202は0又は1以上の整数を表し、n203は0又は1を表す。
但しn202=n203=0の場合、p201=0であればA201はm201価となり、p201=1であればX201は水素原子または1価の基となる。
なお1分子中に含まれる複数のG、A201、A202、X201、X202、m201及びp201は、同じであっても異なっていてもよい。)
なお、-CO-R35及び-CO-Zにおいて、
Zは、一部の炭素原子がへテロ原子で置換されていてもよい炭素数1~25の1価の脂肪族炭化水素基、又は置換基を有していてもよい炭素数4~25の1価の芳香族炭化水素基を表わし、
R35は、下記式(18)~(20)のいずれかで表される基を表す。
R41は直接結合又は一部の炭素原子がへテロ原子で置換されていてもよい炭素数1~25の2価の脂肪族炭化水素基を表す。
R42~R44は各々独立に、一部の炭素原子がへテロ原子で置換されていてもよい炭素数1~25のアルキル基又はベンジル基を表す。
上記式(19)において、
R45~R50のいずれか1つは、直接結合又は一部の炭素原子がへテロ原子で置換されていてもよい炭素数1~25の2価の脂肪族炭化水素基を表わす。
なおR45が、直接結合又は一部の炭素原子がへテロ原子で置換されていてもよい炭素数1~25の2価の脂肪族炭化水素基である場合、R46~R50は各々独立に、水素原子、ハロゲン原子、シアノ基、ニトロ基、一部の炭素原子がへテロ原子で置換されていてもよい炭素数1~25のアルキル基、フェニル基、フェノキシ基、N-アルキルカルバモイル基又はN-アルキルスルファモイル基を表し、
R46~R50のいずれか1つが、直接結合又は一部の炭素原子がへテロ原子で置換されていてもよい炭素数1~25の2価の脂肪族炭化水素基である場合、他の4つは各々独立に、水素原子、ハロゲン原子、シアノ基、ニトロ基、一部の炭素原子がへテロ原子で置換されていてもよい炭素数1~25のアルキル基、フェニル基、フェノキシ基、ベンジル基、N-アルキルカルバモイル基又はN-アルキルスルファモイル基を表し、R45は一部の炭素原子がへテロ原子で置換されていてもよい炭素数1~25のアルキル基又はベンジル基を表す。
上記式(20)において、
R51~R55のいずれか1つは、直接結合又は一部の炭素原子がへテロ原子で置換されていてもよい炭素数1~25の2価の脂肪族炭化水素基を表わす。
なおR51及びR53の一方が、直接結合又は一部の炭素原子がへテロ原子で置換されていてもよい炭素数1~25の2価の脂肪族炭化水素基である場合、他方は一部の炭素原子がへテロ原子で置換されていてもよい炭素数1~25のアルキル基又はベンジル基を表し、R52、R54及びR55は各々独立に、水素原子、ハロゲン原子、シアノ基、ニトロ基、一部の炭素原子がへテロ原子で置換されていてもよい炭素数1~25のアルキル基、フェニル基、フェノキシ基、ベンジル基、N-アルキルカルバモイル基又はN-アルキルスルファモイル基を表す。
R52、R54及びR55のいずれか1つが、直接結合又は一部の炭素原子がへテロ原子で置換されていてもよい炭素数1~25の2価の脂肪族炭化水素基である場合、他の2つは各々独立に、水素原子、ハロゲン原子、シアノ基、ニトロ基、一部の炭素原子がへテロ原子で置換されていてもよい炭素数1~25のアルキル基、フェニル基、フェノキシ基、ベンジル基、N-アルキルカルバモイル基又はN-アルキルスルファモイル基を表し、R51及びR53は、各々独立に、一部の炭素原子がへテロ原子で置換されていてもよい炭素数1~25のアルキル基又はベンジル基を表す。
上記式(18)におけるR41~R44に含まれる炭素原子数の合計は20以上、上記式(19)におけるR45~R50に含まれる炭素原子数の合計は15以上、上記式(20)におけるR51~R55に含まれる炭素原子数の合計は17以上である。
なおR41~R55は同一化合物内で結合して環を形成していてもよい。)
[22]前記エポキシ化合物αが、下記式(13)~(15)のいずれかで表される化合物である上記[21]に記載の組成物。
(A1)-(OG)m1 (13)
(上記式(13)において、Gはグリシジル基(2,3-エポキシプロパニル基)を表し、該グリシジル基はアルキル基、フェニル基又はアルコキシカルボニル基で置換されていてもよい。A1は、置換基を有していてもよいm1価の芳香族又は脂肪族炭化水素基を表す。m1は1以上の整数を表す。なお1分子中に含まれる複数のGは同じであっても異なっていてもよい。)
(GO)m2-(A21)-[X2-(A22)]n2-X2-(A21)-(OG)m2 (14)
(上記式(14)において、Gはグリシジル基を表し、該グリシジル基はアルキル基、フェニル基又はアルコキシカルボニル基で置換されていてもよい。A21は、置換基を有していてもよい(m2+1)価の芳香族又は脂肪族炭化水素基を表し、A22は、置換基を有していてもよい2価の芳香族又は脂肪族炭化水素基を表す。X2を介して連結するA21とA22、又は隣接する複数のA22は、その置換基同士が結合して環を形成していてもよい。X2は、直接結合又は置換基を有していてもよい2価の連結基を表す。m2は1以上の整数を表し、n2は0又は1以上の整数を表す。なお1分子中に含まれる複数のG、A21、A22、X2、及びm2は同じであっても異なっていてもよい。)
H-[(A3(OG)m3)―X3]n3-H (15)
(上記式(15)において、Gはグリシジル基を表し、該グリシジル基はアルキル基、フェニル基又はアルコキシカルボニル基で置換されていてもよい。A3は、置換基を有していてもよい(m3+2)価の芳香族又は脂肪族炭化水素基を表す。X3は、直接結合、置換基を有していてもよいアルキレン基又は-R41-フェニレン-R42-を表し、R41及びR42は、夫々独立にアルキレン基を表す。m3は1以上の整数を表す。n3は2以上の整数を表す。なお1分子中に含まれる複数のG、A3、X3、及びm3は同じであっても異なっていてもよい。)
[23]前記組成物中の含まれる、前記エポキシ化合物αに対する前記化合物βの存在比が、0.05モル%以上10.0モル%以下である上記[21]または[22]に記載の組成物。
[24]前記化合物βが、前記一般式(13)~(15)又は(32)において、1以上の-OG基が下記式(16)または(17)で表される基で置換され、かつ1以上の-OG基が下記式(33)で表される基で置換されていてもよい化合物である、上記[21]~[23]のいずれか1に記載の組成物。
上記式(17)において、Zは、一部の炭素原子がへテロ原子で置換されていてもよい炭素数1~25の1価の脂肪族炭化水素基、又は置換基を有していてもよい炭素数4~25の1価の芳香族炭化水素基を表す。)
更には、蒸留や結晶化精製ができないようなエポキシ化合物の製造にも適用でき、汎用性に優れる。本発明の方法で得られたエポキシ化合物を電子材料、光学材料等および医農薬の原料として使用した場合、不純物に起因する問題が低減し、高純度、高品質な製品を得ることができる。
本発明のエポキシ化合物の製造方法は、炭素-炭素二重結合を有する化合物(以下、「オレフィン化合物」と称することがある。)に、タングステン化合物及びモリブデン化合物のうち少なくとも一方と、活性水素を含む官能基またはその塩に変換可能な置換基を1つ以上有し、炭素原子を20以上含むオニウム塩との存在下、過酸化水素を反応させることに特徴をもつものである。なお、本明細書において、「タングステン化合物及びモリブデン化合物のうち少なくとも一方」を「触媒金属成分」といい、「活性水素を含む官能基またはその塩に変換可能な置換基を1つ以上有し、炭素原子を20以上含むオニウム塩」を単に「オニウム塩」といい、前記「触媒金属成分」と「オニウム塩」を含むものを「エポキシ反応用触媒組成物」又は単に「触媒組成物」といい、前記触媒組成物が、過酸化水素により酸化されたものを、「反応活性種組成物」と言うことがある。
過酸化水素は、通常は過酸化水素水を用い、市販の過酸化水素水をそのまま、あるいは水で希釈して用いることができる。過酸化水素水の濃度は、通常1重量%以上、好ましくは20重量%以上、通常60重量%以下であり、より好ましくは、入手のしやすさや、安全性の問題、生産性等を考慮すると、30重量%以上、45重量%以下である。
過酸化水素の使用量は、原料として使用するオレフィン化合物中の二重結合1モルに対し、通常0.5倍モル以上、好ましくは1倍モル以上、通常10倍モル以下、好ましくは3倍モル以下用いる。
本発明の触媒組成物は、後述する触媒金属成分とオニウム塩との混合物をいう。触媒組成物の調製方法は、反応基質やその反応性に応じて適宜選択することができ、特に制限されるものではないが、反応系内で触媒金属成分とオニウム塩を混合する方法、又は予め反応系外で触媒金属成分とオニウム塩を混合してから反応に用いる方法のいずれの方法でもよい。また、後述のリン酸類の添加方法も反応系内で混合する方法、予め反応系外で混合する方法のいずれの方法でもよい。
また反応活性種組成物は前記の触媒金属成分とオニウム塩の混合物(すなわち「触媒組成物」)に、過酸化水素を一部添加して、活性化させてから反応系に添加することもできる。
本発明の触媒金属成分として、タングステン化合物及びモリブデン化合物のうち少なくとも一方を用いる。具体的にはタングステン酸あるいはタングステン酸の塩(以下、タングステン酸類という)、モリブデン酸あるいはモリブデン酸の塩(以下、モリブデン酸類という)、またはそれらの混合物を用いる。このうち価格や入手のしやすさからタングステン酸類が好ましい。
上記タングステン酸類およびモリブデン酸類の中でも、入手しやすさの点で、タングステン酸、またはタングステン酸ナトリウム及びその水和物、タングステン酸カルシウム及びその水和物が好ましく、回収、再生のしやすさからは、タングステン酸がより好ましい。
本発明における触媒金属成分の使用量は、使用する基質等の性質により適宜調節することができ、特に制限されないが、原料として使用するオレフィン化合物中に含まれる二重結合1モルに対して触媒金属原子換算(例えばタングステン酸類の場合には、タングステン原子換算)で通常0.001モル以上、好ましくは0.005モル以上、より好ましくは0.01モル以上であり、通常1.0モル以下、好ましくは0.50モル以下、より好ましくは0.10モル以下である。前記下限値より少なすぎる場合、反応が進行しない場合があり、前記上限値よりも多すぎる場合は、コスト的に不利になる場合がある。
本発明において用いられるオニウム塩は、炭素原子を20以上有し、かつ活性水素を含む官能基またはその塩に変換可能な置換基を1つ以上有するものである。
前記オニウム塩は、エポキシ化反応時には脂溶性であり、反応溶媒に可溶であり、かつ水相と有機相に分離した有機相側に分配し、エポキシ化反応条件下で安定、または、エポキシ化反応中に構造が変化しても触媒能が著しく低下しない性質を有する。反応溶媒に可溶で、かつ有機相に分配するためには、高い脂溶性が必要であるため、オニウム塩は炭素原子を20個以上含むことが必要である。
このうち、アルコキシカルボニル基及びアシルオキシ基は、塩基性水溶液と接触させることで、簡便に、且つ、エポキシ基を分解することなく、加水分解され、水酸基やカルボン酸基およびそれらの塩に変換でき、合成も簡便であるため好ましい。より好ましくはアルコキシカルボニル基である。
前記置換基の数は、1つ以上であるが、洗浄での除去効率の観点から、好ましくは2個以上である。
本発明において用いられるオニウム塩として、好ましくは下記一般式(1)から(3)のいずれかで表されるオニウム塩が用いられる。
R1~R5、R11及びR13は、前記-Y-CO-O-Z及び-Y-O―CO-Zではない場合は、それぞれ独立して、一部の炭素原子がへテロ原子で置換されていてもよく、かつ置換基を有していてもよい炭素数1~25のアルキル基又はベンジル基を表し、
R6~R10、R12、R14及びR15は、前記-Y-CO-O-Z及び-Y-O―CO-Zではない場合は、それぞれ独立して、水素原子、ハロゲン原子、シアノ基、ニトロ基、一部の炭素原子がへテロ原子で置換されていてもよく、かつ置換基を有していてもよい炭素数1~25のアルキル基、フェニル基、フェノキシ基、ベンジル基、N-アルキルカルバモイル基又はN-アルキルスルファモイル基を表す。
R1~R15は同一化合物内で結合して環を形成していてもよい。
またR1~R15は、一部の炭素原子がヘテロ原子で置換されていてもよく、かつ置換基を有していてもよい炭素数1~25のアルキル基の場合、該置換基として上記式(1)ないし(3)のいずれかで表される別のオニウム塩を有していてもよい。
なお、上記式(1)におけるR1~R4に含まれる炭素原子数の合計は20以上であり、上記式(2)におけるR5~R10に含まれる炭素原子数の合計は15以上であり、上記式(3)におけるR11~R15に含まれる炭素原子数の合計は17以上である。
X-は、1価のアニオンを表す。)
式(1)において、R1~R4のうちのいずれか1つ以上は、-Y-CO-O-Z、または-Y-O―CO-Zを表す。またR1~R4に含まれる合計の炭素原子数の合計が20以上である。
また同様に、式(3)のR11~R15のうちのいずれか1つ以上は、-Y-CO-O-Z、または-Y-O―CO-Zを表す。またR11~R15に含まれる炭素原子数の合計が17以上である。
2価の脂肪族炭化水素基として、具体的には、メチレン、エチレン、テトラメチレン、ヘキサメチレン等の直鎖脂肪族炭化水素基、これらに更にアルキル鎖が結合した分岐脂肪族炭化水素基、及びシクロヘキセン等の環状脂肪族炭化水素基が挙げられる。Yが炭素数1~25の2価の脂肪族炭化水素基である場合は、その炭素原子がヘテロ原子で一部置換されていてもよい。具体的にはこれら2価の脂肪族炭化水素基の構造中のメチレン基が、-O-、-S-、-SO-、-SO2-、-NH-、-NR16-(R16は炭素数1~25の1価の脂肪族炭化水素基又は1価の芳香族炭化水素基を表す)、-CONR17-(R17は水素原子、炭素数1~25の1価の脂肪族炭化水素基又は1価の芳香族炭化水素基を表す)、―NHCONH-、―CONHCO-、-SO2NR17-(R17は前述と同義)等のヘテロ原子を含む構造に置換されていてもよい。なお、本明細書における「一部の炭素原子がヘテロ原子で置換されていてもよい炭化水素基」は、いずれも上述と同義である。Yとして好ましくは、エチレン、プロピレン、テトラメチレン、ヘキサメチレン及び-CH2CH2-O-CH2CH2-が挙げられる。
また、Yが一部の炭素原子がヘテロ原子で置換されていてもよく、かつ置換基を有していてもよい炭素数1~25の2価の脂肪族炭化水素基である場合、該置換基としては、例えば-O-CO-Z又は-CO-O-Z(但し、Zは前記式(1)ないし(3)におけると同義)が挙げられる。この場合、前記一般式(1)ないし(3)で表される化合物は、R1~R15のいずれかが-Y-CO-O-Z、または-Y-O―CO-Zであり、-O-CO-Z又は-CO-O-Zを有していることに加え、Yにおける脂肪族炭化水素基の置換基としても-O-CO-Z又は-CO-O-Zを有することになる。
上記式中の-Y-CO-O-ZでYが炭化水素基を表す場合、オニウム塩のエポキシ化反応中の安定性の観点から、炭素数が3以上であることが好ましい。
R1~R15のうち、R1~R5、R11及びR13は、前記-Y-CO-O-Z及び-Y-O―CO-Zではない場合は、それぞれ独立して、一部の炭素原子がへテロ原子で置換されていてもよく、かつ置換基を有していてもよい炭素数1~25のアルキル基又はベンジル基を表し、
R6~R10、R12、R14及びR15は、前記-Y-CO-O-Z及び-Y-O―CO-Zではない場合は、それぞれ独立して、水素原子、ハロゲン原子、シアノ基、ニトロ基、一部の炭素原子がへテロ原子で置換されていてもよく、かつ置換基を有していてもよい炭素数1~25のアルキル基、フェニル基、フェノキシ基、N-アルキルカルバモイル基又はN-アルキルスルファモイル基を表す。
R1~R15は同一化合物内で結合して環を形成していてもよい。
またR1~R15は、一部の炭素原子がヘテロ原子で置換されていてもよく、かつ置換基を有していてもよい炭素数1~25のアルキル基の場合、該置換基として上記式(1)ないし(3)のいずれかで表される別のオニウム塩を有していてもよい。すなわちR1~R15を介し上記式(1)ないし(3)のいずれかで表される化合物が複数個結合してなる化合物であってもよい。このとき該複数のオニウム塩の構造は、同一であっても、異なっていてもよい。具体的には1,2-エタンジアミニウム塩、4,4’-ビピリジニウム塩等が挙げられる。
R1~R15が、炭素数1~25のアルキル基の場合、その構造中の炭素原子がヘテロ原子で一部置換されていてもよく、具体的にはメチレン基が、-O-、-S-、-SO-、-SO2-、-NH-、-NR16-(R16は炭素数1~25の1価の脂肪族炭化水素基、又は1価の芳香族炭化水素基を表す)、-CONR17-(R17は水素原子、炭素数1~25の1価の脂肪族炭化水素基、又は1価の芳香族炭化水素基を表す)、―NHCONH-、―CONHCO-、-SO2NR17-(R17は前述と同義)等のヘテロ原子を含む構造に置換されていてもよい。
またR6~R10、R12、R14及びR15として好ましくは、水素原子、塩素原子、メチル基、エチル基、プロピル基、イソプロピル基、t-ブチル基、オクチル基、オクタデシル基、ハロゲン原子又はフェニル基であり、更に好ましくは、水素原子、t-ブチル基、又はフェニル基である。
X-は、オニウム塩のアニオン種を表し、1価のアニオンである。具体的には硫酸水素イオン、モノメチル硫酸イオン、ハロゲン化物イオン、硝酸イオン、酢酸イオン、炭酸水素イオン、リン酸二水素イオン、スルホン酸イオン、カルボン酸イオン、水酸化物イオンであり、好ましくは、該アニオンがエポキシ基や炭素-炭素二重結合に付加しない点、調製が容易である点からモノメチル硫酸イオン、硫酸水素イオン、塩素イオン、酢酸イオン、リン酸二水素イオン、水酸化物イオンである。
これらの化合物は、分子内にエステル構造を複数個有し、加水分解後に水溶性の化合物に変換できる上、入手が容易な原料から簡便に合成が可能である点で好ましく、このうち(8)~(11)は、高速液体クロマトグラフのような機器分析が容易な点で製造の調節が容易である点で好ましい。
R31及びR32は、それぞれ独立に、一部の炭素原子がへテロ原子で置換されていてもよい炭素数1~25の2価の脂肪族炭化水素基を表わす。
なお、同一化合物中に存在する複数のk、R20及びR31は、同一であっても異なっていてもよい。また式中のカチオン部分に含まれる炭素原子数の合計は20以上である。X-は、1価のアニオンを表す)
R31及びR32は、それぞれ独立に、一部の炭素原子がへテロ原子で置換されていてもよい炭素数1~25の2価の脂肪族炭化水素基を表わす。また式中のカチオン部分に含まれる炭素原子数の合計は20以上である。X-は、1価のアニオンを表す)
R31は、一部の炭素原子がへテロ原子で置換されていてもよい炭素数1~25の2価の脂肪族炭化水素基を表わす。
R33は、一部の炭素原子がへテロ原子で置換されていてもよい炭素数1~25の1価の脂肪族炭化水素基、又は置換基を有していてもよい炭素数4~25の1価の芳香族炭化水素基を表す。
また式中のカチオン部分に含まれる炭素原子数の合計は20以上である。X-は、1価のアニオンを表す)
なお、前記式(8)~(12)、(31)、(34)及び(35)において、R20としては、水素原子または炭素数1~4のアルキル基、が好ましく、R21~R23としては、炭素数1~18のアルキル基が好ましく、炭素数1~8のアルキル基がより好ましく、R24としては、炭素数1~8のアルキル基が好ましく、R31及びR32としては、各々独立に、炭素数1~11のアルキレン基が好ましく、炭素数1~5のアルキレン基がより好ましく、エチレン基またはプロパン-1,2-ジイル基で置換されたエチレン基が更に好ましい。また、R31とR32は結合し、ピラノース環などの環状構造を形成していてもよい。R33としては、炭素数1~16のアルキル基が好ましい。kとしては、1が好ましく、X-としては、モノメチル硫酸イオン、硫酸水素イオン、リン酸二水素イオン又は塩素イオンが好ましい。
触媒金属成分に対するオニウム塩の使用量は、使用する基質等の性質により適宜調節することができ、特に制限されないが、通常、使用する触媒金属成分の1原子に対して0.1倍モル~10倍モルであり、好ましくは0.3倍モル~5.0倍モルであり、より好ましくは0.2倍モル~2.0倍モルである。
上記のオニウム塩は、それぞれ対応する3級アミン類、ピリジン類、イミダゾール類等をアルキル化することにより合成できる。アルキル化に用いる試剤は、特に制限されないが、R18-A(式中Aは、塩素、臭素、ヨウ素等のハロゲン原子、または、p-トルエンスルホニル、メタンスルホニル等の芳香族スルホニル、脂肪族スルホニル、硫酸エステル、炭酸エステルまたはオキシラニル基を表す。R18は前記式(1)~(3)におけるR1~R4、R5、R11又はR13、或いはR1~R4、R5、R11又はR13に変換可能な置換基を表す)を用いる。
R18-Aを用いてアルキル化を行った場合、生成したオニウムはA-を対イオンとした塩を形成する場合が多い。また、洗浄操作を行った場合、水中の水酸化物イオンや洗浄水中のイオンと塩を形成する場合が多い。これらの対イオンは、洗浄やイオン交換樹脂処理等の操作により、所望の対イオンに交換することができる。例えば、硫酸ジメチルを用いてメチル化を行った場合は、モノメチル硫酸塩を形成するが、硫酸水で洗浄することにより、硫酸水素塩とすることができる。
1)A-Y-CO-O-ZまたはA-Y-O―CO-Z(Aは前述と同義)をオニウム塩の原料となる前記3級アミン類、ピリジン類、イミダゾール類と反応することにより導入する方法;
2)-Y-CO2Hを有するアミン類、ピリジン類、イミダゾール類をエステル化して-Y-CO-O-Zとした後、前述のようにこれをアルキル化してオニウム塩とする方法;
-Y-OHを有するアミン類、ピリジン類、イミダゾール類をエステル化して-Y-O-CO-Zとした後、前述のようにこれをアルキル化してオニウム塩とする方法;
または-Y-CO-O-R19(R19は炭素数1~12のアルキル基を表す)を有するアミン類、ピリジン類、イミダゾール類をエステル交換反応により-Y-CO-O-Zとした後、前述のようにこれをアルキル化してオニウム塩とする方法;
3)-Y-CO2Hを有するオニウム塩をエステル化して-Y-CO-O-Zとする方法;
-Y-OHを有するオニウム塩をエステル化して-Y-O-CO-Zとする方法;
-Y-CO-O-R19を有するオニウム塩をエステル交換反応により-Y-CO-O-Zとする方法
4)-Y-CO-O-Zまたは-Y-O―CO-Zを有するアミン類、ピリジン類、イミダゾール類をアルキル化してオニウム塩とする方法、あるいは -Y-CO-O-Z、または -Y-O―CO-Zを有するアンモニウム塩、ピリジニウム塩、イミダゾリニウム塩を原料として用いる方法、等の方法が挙げられる。
この際、用いる酸触媒としては、硫酸、硝酸および塩酸等の鉱酸、ベンゼンスルホン酸、p-トルエンスルホン酸、メタンスルホン酸、エタンスルホン酸、トリフルオロメタンスルホン酸、トリクロロメタンスルホン酸、トリフルオロ酢酸、トリクロロ酢酸および酢酸等の有機酸、H3PW12O40、H4SiW12O40、H4TiW12O40、H5CoW12O40、H5FeW12O40、H6P2W18O62、H7PW11O33、H4TiMo12O40、H3PMo12O40、H7PMo11O39、H6P2Mo18O62、H4PMoW11O40、H4PVMo11O40、H4SiMo12O40、H5PV2Mo10O40、H3PMo6W6O40、H0.5Cs2.5PW12O40およびこれらの水和物等のタングステン酸、モリブデン酸或いはこれらのヘテロポリ酸;アンバーリストIR120等の陽イオン交換樹脂、H-ZSM-5等のH型ゼオライト等を使用することができる。これらのうち、コストの面からは硫酸が好ましいが、硫酸塩が析出し反応性が低下する場合には、必要に応じてp-トルエンスルホン酸、メタンスルホン酸等の有機酸を用いることが好ましい。これらの触媒の使用量は、基質に対して0.1~100重量%の範囲で、好ましくは1~20重量%の範囲で使用することができる。
用いる溶媒の量は特に限定されないが、基質と酸触媒の塩が系から析出した場合、反応速度が低下することがあるため、基質や酸の性質に応じ、適宜量を調整することが好ましい。
本発明の触媒組成物には、リン酸類及びホスホン酸類のうち少なくとも一方(但しオニウム塩を除く)を含んでいてもよく、含んでいることが、反応性の面で好ましい。リン酸類及びホスホン酸類のうち少なくとも一方は、エポキシ化合物の製造反応時に、触媒金属成分及びオニウム塩と共存していればよく、反応系内で混合しても、予め反応系外で混合してもよい。
リン酸類としては、無機リン酸が好ましく、リン酸が好ましい。
ホスホン酸類としては、アミノメチルホスホン酸、フェニルホスホン酸などが挙げられる。
これらのうち安価なリン酸が好ましい。
本発明においてオレフィン化合物からエポキシ化合物を製造する反応(以下、「本発明のエポキシ化反応」と称することがある)の形態は特に限定はされないが、通常、水相と有機相の二相系での反応系でおこなう。二相系で反応をすることにより、本発明の反応により生成したエポキシ化合物が、有機相にすみやかに溶解し、また後述する通り、水相が通常酸性を呈するため、生成したエポキシ化合物のエポキシ環が開環、転移などで分解することを抑えることができるためである。
また反応時には、さらに水を添加してもよい。添加する過酸化水素は通常水を含むため、水を添加しなくても、水相は形成されるが、必要に応じて添加してもよい。水を添加する場合の水の添加量は、通常オレフィン化合物の0.1倍量~10倍量、好ましくは0.1倍量~5倍量、更に好ましくは、0.1倍量~3倍量である。
触媒金属成分/(リン酸類及びホスホン酸類のうち少なくとも一方)のモル比率は通常0.2以上、好ましくは0.3以上、より好ましくは0.5以上であり、通常4以下、好ましくは3以下、より好ましくは2以下である。
リン酸類及びホスホン酸類のうち少なくとも一方は、反応液の水相のpHが適切な範囲になるように添加するのが好ましいが、必要に応じて酸や塩基を添加し、pHの調整を行う。
反応液の水相のpHは、エポキシ化合物の安定性や水への溶解度により異なるが、通常2以上、好ましくは2.5以上であり、通常6以下であり、好ましくは5以下である。
反応液の水相のpH調節のために、必要に応じてリン酸、アミノメチルホスホン酸、フェニルホスホン酸、硫酸、硝酸、塩酸、過塩素酸などの酸;水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、炭酸水素カリウム、リン酸、リン酸水素二ナトリウム、リン酸水素二カリウムなどの無機塩基:アンモニア、メチルアミン、エチルアミンなどの有機塩基を添加してもよい。
以下に具体的に本発明の製造方法について記載する。
<原料>
本発明において原料として使用する炭素-炭素二重結合を有する化合物としては、分子中に炭素-炭素二重結合を一つ以上有する化合物であれば、特に限定はされないが、例えば、下記一般式(30)で表される化合物などが挙げられる。
A201は置換基を有していてもよい(m201+1)価の芳香族または脂肪族炭化水素基を表し、A202は置換基を有していてもよい2価の芳香族または脂肪族炭化水素基を表し、A203は置換基を有していてもよい(m203+2)価の芳香族または脂肪族炭化水素基を表す。
なお、以下において「芳香族または脂肪族炭化水素基」には、両方の炭化水素骨格を有する物、例えば芳香族環と脂肪族環の双方の構造を分子内に含むものなども含まれる。
X201及びX202は、各々独立に、直接結合又は置換基を有していてもよい2価の連結基を表す。
p201は0又は1を表す。
m201及びm203は、各々独立に、1以上の整数を表す。
n201は1以上の整数を表し、n202は0又は1以上の整数を表し、n203は0又は1を表す。
但しn202=n203=0の場合、p201=0であればA201はm201価となり、p201=1であればX201は水素原子または1価の基となる。
なお1分子中に含まれる複数のR、A201、A202、X201、X202、m201及びp201は、同じであっても異なっていてもよい。)
上記式(30)で表される化合物の中でも、下記一般式(4)~(6)で表される化合物が好ましい。
(上記式(4)において、Rはアリル基を表し、該アリル基はアルキル基、フェニル基又はアルコキシカルボニル基で置換されていてもよい。A1はm1価の芳香族又は脂肪族炭化水素基を表す。m1は1以上の整数を表す。なお1分子中に含まれる複数のRは、同じであっても異なっていてもよい。)
一般式(4)で表される化合物の好ましい例としては、以下、一般式群(7)のいずれかで示すものが挙げられ、ベンゼン環上にはOR基以外の例えば、t-ブチル基などの置換基を有していてもよい。また、芳香族環の一部あるいは全部が還元された核水添体でもよい。またA1が脂肪族炭化水素基である化合物の例としては、イソソルビド、1,4-シクロヘキサンジメタノール、2,3-ノルボルナンジオールが挙げられる。
(上記式(5)において、Rはアリル基を表し、該アリル基はアルキル基、フェニル基又はアルコキシカルボニル基で置換されていてもよい。A21は、置換基を有していてもよい(m2+1)価の芳香族又は脂肪族炭化水素基を表し、A22は、置換基を有していてもよい2価の芳香族又は脂肪族炭化水素基を表す。X2を介して連結するA21とA22、または隣接する複数のA22は、その置換基同士が結合して環を形成していてもよい。X2は、直接結合又は置換基を有していてもよい2価の連結基を表す。m2は1以上の整数を表し、n2は0又は1以上の整数を表す。なお1分子中に含まれる複数のR、A21、A22、X2及びm2は、同じであっても異なっていてもよい。)
A21及びA22で表される芳香族又は脂肪族炭化水素基としては、一般式(4)におけるA1と同様の炭化水素に由来する基が挙げられ、その炭素数も同様である。A21又はA22で表される基が有していてもよい置換基としては、メチル基、エチル基、プロピル基等の炭素数1~4のアルキル基;メトキシ基、エトキシ基、プロピルオキシ基等の炭素数1~4のアルキルオキシ基;ニトロ基等が挙げられ、中でもアルキル基が好ましい。
また、X2を介して連結する隣接するA21とA22、又は隣接する複数のA22は、その置換基同士が更に結合して環を形成していてもよい。具体的には、例えばA21とA22、又は2つのA22がメチレン基又はエーテル基を介して結合する例が挙げられ、該環としては、5~6員の炭化水素環又は酸素原子を含む6員環等が挙げられる。
n2は0又は1以上の整数を表すが、その上限は、通常、5であり、好ましくは2である。
前記一般式(5)で表される化合物の中でも、特に下記一般式(5-1)で表される化合物が好ましい。
A121は、置換基を有していてもよい{(m102)+1}価の炭素数6~14の芳香族炭化水素基を表し、A122は、置換基を有していてもよい2価の炭素数6~14の芳香族炭化水素基を表す。X102を介して連結するA121とA122、または複数のA122は、その置換基同士が結合して環を形成していてもよい。X102は、直接結合、メチレン基、ジメチルメチレン基、ジトリフルオロメチルメチレン基、エチレン基、―C(CH3)=CH-、フェニル基又は(R100O)m2-(A121)-で置換されていてもよいメチレン基、シクロへキシレン基、-CO-、-O-、-SO2-、-COO-、-N=CH-或いはテトラヒドロジシクロペンタジエニレン基を表す。なお1分子中に含まれる複数のR100、A121、A122、X102及びm102は、同じであっても異なっていてもよい。m102は1~4の整数を表し、n102は0~5の整数を表す。)
X102として、より好ましくは直接結合、炭素数1~4の2価アルキレン基(芳香族炭化水素基で置換されていてもよく、該芳香族炭化水素基の炭素数は、好ましくは6~10である)、及び架橋縮合環構造を有する炭素数7~10の脂環式炭化水素が好ましく、特に、直接結合、炭素数1~2のアルキレン基(但し、芳香族炭化水素基で置換されていてもよく、該芳香族炭化水素基の炭素数は、好ましくは6~8である)が好ましい。
より好ましいm102は1又は2であり、より好ましいn102は0、1又は2である。
(式中、Rはアリル基を表し、該アリル基はアルキル基、フェニル基又はアルコキシカルボニル基で置換されていてもよい。A3は、置換基を有していてもよい(m3+2)価の芳香族又は脂肪族炭化水素基を表す。X3は、直接結合、置換基を有していてもよいアルキレン基又は-R61-フェニレン-R62-を表し、R61及びR62は、夫々独立にアルキレン基を表す。m3は1以上の整数を表す。n3は2以上の整数を表す。なお1分子中に含まれる複数のG、A3、X3、及びm3は同じであっても異なっていてもよい。)
A3で表される芳香族又は脂肪族炭化水素基としては、一般式(4)におけるA1と同様の炭化水素に由来する基が挙げられ、その炭素数も同様である。
一般式(6)で表される化合物の具体例としては、以下の構造式で示されるもの(式中n及びn’はn3と同義)およびこれらの芳香族環の一部あるいは全部が還元された核水添体などが挙げられる。また、ベンゼン環上には-OR基及び明記されているメチル基以外の置換基を有していてもよい。
なお、R64~R71のうち、いずれか2以上が互いに結合して、環を形成していてもよい。)
R64~R71はそれぞれ独立に、水素原子、ハロゲン原子、置換基を有していてもよいアルキル基、置換基を有していてもよい芳香族炭化水素基、ニトロ基、アルコキシル基、カルボニル基、アルコキシカルボニル基、アシルオキシ基、カルボキシル基もしくはその塩を表す。
ハロゲン原子としては、例えばフッ素原子、塩素原子、臭素原子などが挙げられる。
アルキル基としては、炭素数1~20のアルキル基が好ましく、例えば、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、sec-ブチル基、t-ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、セチル基、ステアリル基などの直鎖状または分岐状のアルキル基;シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロオクチル基などのシクロアルキル基などが挙げられる。これらのアルキル基は置換基を有していてもよく、該置換基としては、例えば、フッ素原子、塩素原子、臭素原子などのハロゲン原子;メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、ブトキシ基などのアルコキシル基;ニトロ基;カルボキシル基;メトキシカルボニル基、エトキシカルボニル基などのアルコキシカルボニル基;アセチルオキシ基、プロピオニルオキシ基などのアシルオキシ基などが挙げられる。
芳香族炭化水素基としては、例えばフェニル基、ナフチル基などが挙げられる。
芳香族炭化水素基は置換基を有していてもよく、その置換基としては、例えば、フッ素原子、塩素原子、臭素原子などのハロゲン原子;メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、ブトキシ基などのアルコキシル基;ニトロ基;カルボキシル基;メトキシカルボニル基、エトキシカルボニル基などのアルコキシカルボニル基;アセチル基、プロピオニル基、ベンゾイル基などのアシル基;アセチルオキシ基、プロピオニルオキシ基などのアシルオキシ基などが挙げられる。
アルコキシル基としては、例えばメトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、ブトキシ基などが挙げらる。
またアシルオキシ基としては、例えば、アセチルオキシ基、プロピオニルオキシ基、ベンゾイルオキシ基などが挙げられる。
カルボキシル基の塩としては、例えばナトリウム塩、カリウム塩などのアルカリ金属塩を挙げることができる。
なお、R64~ R71のうちいずれか2以上が互いに結合して、環を形成していてもよい。
i及びjは各々独立に、1~4の整数を表し、好ましくは1~3、より好ましくは1又は2、最も好ましくは2である。
一般式(36)で示される環状オレフィンとしては、例えば1,4-シクロヘキサジエン、1,5-シクロオクタジエン、1,5,9-シクロドデカトリエン、1,5-ジメチル-1,5-シクロオクタジエン、ジシクロペンタジエン、2,5-ノルボルナジエンなどの環状非共役オレフィン類などを挙げることができる。
R77及びR78はそれぞれ独立して、水素原子、炭素数1~8の直鎖状又は分岐状のアルキル基、炭素数1~8のアルコキシ基、炭素数2~8のアルコキシカルボニル基、炭素数3~7のシクロアルキル基、芳香族炭化水素基、アラルキル基、アシル基、カルボキシル基又はアシルオキシ基を示す。
なお、R72~R78のうちいずれか2つ以上が互いに結合し、環を形成していてもよい。)
一般式(37)で表されるスチレン類の具体例としては、スチレン、4-メチルスチレン、4-フルオロスチレン、2,4-ジフルオロスチレン、3-クロロスチレン、4-クロロスチレン、4-ブロモスチレン、4-ニトロスチレン、4-ビニル安息香酸、α-メチルスチレン、β-メチルスチレン、1-フェニル-1-シクロヘキセン、インデン、ジヒドロナフタレン等が挙げられる。
過酸化水素を用いたエポキシ化反応において、原料や溶媒、反応容器および配管や送液ポンプなどの付帯設備などから混入してくる異物、例えば金属や活性炭、シリカゲル、ガラス片等の影響を受ける場合がある。過酸化水素などの酸化物は、前記の異物と接触することで分解し、反応熱や酸素を発生することがあり、危険を伴う場合がある。反応液中にこれらの異物が混入しない、または影響を受けないようにすることが好ましい。具体的には、前記の異物を除去するために、オレフィン化合物の濾過を行なう、オレフィン化合物を酸性水溶液で洗浄する、オレフィン化合物をキレート化剤(金属とのキレートを形成しうる化合物。具体的には金属マスク剤)で洗浄する、又はエポキシ化反応時にキレート化剤を共存させて反応させることが好ましい。
酸性水溶液のpHは特に限定はされず、用いるオレフィン化合物の安定性により異なるが、通常pH1以上、好ましくは3以上、通常5以下、好ましくは4以下で行う。pHの調整の目的で、各種の塩を加えてもよく、例えば硫酸ナトリウム、酢酸ナトリウム、リン酸ナトリウム、リン酸水素二ナトリウム、クエン酸ナトリウム等を添加してもよい。
キレート化剤を含む水溶液としては、金属とのキレート能力を有する化合物を含む水溶液であれば、特に限定はされないが、好ましくは、いわゆる金属マスク剤を含む水溶液が好ましい。例えば日本国特表2002-501005号公報に記載のエチレンジアミン四酢酸や、ピロリン酸等が挙げられる。エチレンジアミン四酢酸及びピロリン酸のうち少なくとも一方を含む水で洗浄する方法が好ましい。これらの処理を行なうことで金属が水に可溶化し、水相と共に除去される。
本発明の製造方法における具体的な反応操作方法としては、特に限定されるものではないが、オレフィン化合物に、過酸化水素、タングステン化合物及びモリブデン化合物のうち少なくとも一方、オニウム塩、必要に応じてリン酸類及びホスホン酸類のうち少なくとも一方を加え、必要に応じ前述の有機溶媒、緩衝液を加える。
各成分の添加、混合順序は、反応が阻害されない限り限定されるものではないが、エポキシ化反応および過酸化水素分解の際に発熱を伴うため、反応の進行や発熱のコントロールする観点から、各成分を添加した後に過酸化水素を徐々に添加する、または、予めタングステン化合物及びモリブデン化合物のうち少なくとも一方を酸化するのに必要な量の過酸化水素を添加し、タングステン及びモリブデン過酸化物のうち少なくとも一方とした後、残りの過酸化水素を徐々に添加する方法が好ましい。過酸化水素の添加方法としては、分割して添加しても、連続で除々に添加してもよい。安全上の観点から、未反応の過酸化水素が反応系中に滞留しないように、反応の進行具合に応じて、追加するのが好ましい。
本発明の製造方法における反応温度は、反応が阻害されない限り、特に限定されないが、通常10℃以上、好ましくは35℃以上、より好ましくは60℃以上であり、通常90℃以下、好ましくは80℃以下、より好ましくは75℃以下である。前記下限未満では反応速度が遅くなる場合があり、前記上限超過では安全上の観点で好ましくない場合があるためである。
本発明の製造方法における反応は、安全上の観点から、常圧、窒素気流下で行うことが好ましい。
本発明の製造方法は、特に限定されないが、通常は水相と有機相の二相反応系で行なわれる。
また同様に界面活性剤やアミン類、ピリジン環化合物等の含窒素化合物を酸化剤組成物中に含んでいてもよい。
本発明の製造方法においては、エポキシ化反応終了後に後処理を行ない、オニウム塩が有する置換基を活性水素を有する官能基またはその塩に変換する。置換基を変換したオニウム塩は、反応系中の有機相から水相に移動するため、有機相中に存在するエポキシ化合物との分離が容易に行なえる。生成物であるエポキシ化合物は、必要に応じ、更に精製を行なってもよい。
アルコキシカルボニル基又はアシルオキシ基を有するオニウム塩を使用する場合を例に挙げ、以下具体的に説明する。
上記の方法で得られたエポキシ化合物は、必要に応じて更に精製してもよい。具体的な精製方法は、特に限定されるものではなく、公知の方法を適宜使用することができる。エポキシ化合物が固体の場合は晶析、懸洗、分液、吸着等が挙げられ、エポキシ化合物が液体の場合は分液、洗浄、吸着、蒸留が挙げられる。
お互いに混合しない複数の有機溶媒同士の組合せとしては例えばN,N’-ジメチルホルムアミドとn-ヘプタン、n-へキサン、n-ペンタン、ジイソプロピルエーテル、キシレンのうち少なくともひとつとの組合せ、ジメチルスルホキシドとn-ヘプタン、n-へキサン、n-ペンタン、ジイソプロピルエーテル、ジエチルエーテル、キシレンのうち少なくともひとつとの組合せ、アセトニトリルとn-ヘプタン、n-へキサン、n-ペンタン、シクロへキサン、シクロペンタンのうち少なくともひとつとの組合せ、メタノールとn-ヘプタン、n-へキサン、n-ペンタンのうち少なくともひとつとの組合せがある。
水溶性の溶媒としては、テトラヒドロフラン、1,3-ジオキソラン、N,N,N-ジメチルホルムアミド、ジメチルスルホキサイド等が挙げられ、これらは水と混合して用いることができる。溶媒量は少なすぎる場合は精製効果が十分ではなく、多すぎる場合には、回収率の低下につながる。懸洗終了後、固形物をろ過回収し、乾燥することによって目的物を得ることができる。
上記精製法の中でも、操作法の点からは、エポキシ化合物の性状に関わらず分液法が好ましい。エポキシ化合物が固体の場合は晶析法が有効である。
上記エポキシ化反応、触媒金属成分やオニウム塩等の分離・除去工程、必要に応じ精製工程を経て、エポキシ化合物を得る。
本発明の製造方法により得られたエポキシ組成物は、触媒金属由来の金属の含有量が極めて少ない組成物として得られ、該金属の含有量は通常200ppm以下に、好ましくは100ppm以下に、より好ましくは10ppm以下に、更に好ましくは1ppm以下になる。
同様に、本発明の製造方法により得られたエポキシ組成物は、オニウム塩由来の窒素含有量が少ないものとなり、その含有量は通常500ppm以下に、好ましくは200ppm以下に、より好ましくは10ppm以下になる。
A201は置換基を有していてもよい(m201+1)価の芳香族または脂肪族炭化水素基を表し、A202は置換基を有していてもよい2価の芳香族または脂肪族炭化水素基を表し、A203は置換基を有していてもよい(m203+2)価の芳香族または脂肪族炭化水素基を表す。
X201及びX202は、各々独立に、直接結合又は置換基を有していてもよい2価の連結基を表す。
p201は0又は1を表す。
m201及びm203は、各々独立に、1以上の整数を表す。
n201は1以上の整数を表し、n202は0又は1以上の整数を表し、n203は0又は1を表す。
但しn202=n203=0の場合、p201=0であればA201はm201価となり、p201=1であればX201は水素原子または1価の基となる。
なお1分子中に含まれる複数のG、A201、A202、X201、X202、m201及びp201は、同じであっても異なっていてもよい。)
前記一般式(32)におけるGは、グリシジル基(2,3-エポキシプロパニル基)を表す。該グリシジル基はアルキル基、フェニル基又はアルコキシカルボニル基で置換されていてもよく、これら置換基のうち、より好ましくはメチル基、フェニル基、メトキシカルボニル基及びエトキシカルボニル基が挙げられるが、Gは無置換のグリシジル基が特に好ましい。
なお、前記一般式(32)におけるA201~A203、X201、X202、n201~n203、m201、m203及びp201は、前記一般式(30)におけると同義であり、好ましいものも同様である。
一般式(32)で表される化合物の中でも、下記一般式(13)~(15)で表される化合物が好ましい。
(上記式(13)において、Gはグリシジル基(2,3-エポキシプロパニル基)を表し、該グリシジル基はアルキル基、フェニル基又はアルコキシカルボニル基で置換されていてもよい。A1は、置換基を有していてもよいm1価の芳香族又は脂肪族炭化水素基を表す。m1は1以上の整数を表す。なお1分子中に含まれる複数のGは同じであっても異なっていてもよい。)
なお、Gの具体例および好ましい範囲は前記一般式(32)におけると同様であり、A1の具体例およびその好ましい範囲については、上記一般式(4)におけると同じである。
(上記式(14)において、Gはグリシジル基を表し、該グリシジル基はアルキル基、フェニル基又はアルコキシカルボニル基で置換されていてもよい。A21は、置換基を有していてもよい(m2+1)価の芳香族又は脂肪族炭化水素基を表し、A22は、置換基を有していてもよい2価の芳香族又は脂肪族炭化水素基を表す。X2を介して連結するA21とA22、又は隣接する複数のA22は、その置換基同士が結合して環を形成していてもよい。X2は、直接結合又は置換基を有していてもよい2価の連結基を表す。m2は1以上の整数を表し、n2は0又は1以上の整数を表す。なお1分子中に含まれる複数のG、A21、A22、X2、及びm2は同じであっても異なっていてもよい。)
なお、Gの具体例及び好ましい範囲は前記一般式(32)におけると同様であり、A21、A22、X2、m2およびn2の具体例、並びにそれらの好ましい範囲については、上記一般式(5)におけると同じである。
(上記式(15)において、Gはグリシジル基を表し、該グリシジル基はアルキル基、フェニル基又はアルコキシカルボニル基で置換されていてもよい。A3は、置換基を有していてもよい(m3+2)価の芳香族又は脂肪族炭化水素基を表す。X3は、直接結合、置換基を有していてもよいアルキレン基又は-R61-フェニレン-R62-を表し、R61及びR62は、夫々独立にアルキレン基を表す。m3は1以上の整数を表す。n3は2以上の整数を表す。なお1分子中に含まれる複数のG、A3、X3、及びm3は同じであっても異なっていてもよい。)
なお、Gの具体例及び好ましい範囲は前記一般式(32)におけると同様であり、A3、X3、m3及びn3の具体例、並びに好ましい範囲については、上記一般式(6)におけると同じである。
これらの化合物は、主に反応後の後処理工程時、塩基条件下でオニウム塩がエポキシ化合物と反応することにより生成する。
R35は以下(18)~(20)のいずれかを表す。
R41は直接結合又は一部の炭素原子がへテロ原子で置換されていてもよい炭素数1~25の2価の脂肪族炭化水素基を表す。
R42~R44は各々独立に、一部の炭素原子がへテロ原子で置換されていてもよい炭素数1~25のアルキル基又はベンジル基を表す。
上記式(19)において、
R45~R50のいずれか1つは、直接結合又は一部の炭素原子がへテロ原子で置換されていてもよい炭素数1~25の2価の脂肪族炭化水素基を表わす。
なおR45が、直接結合又は一部の炭素原子がへテロ原子で置換されていてもよい炭素数1~25の2価の脂肪族炭化水素基である場合、R46~R50は各々独立に、水素原子、ハロゲン原子、シアノ基、ニトロ基、一部の炭素原子がへテロ原子で置換されていてもよい炭素数1~25のアルキル基、フェニル基、フェノキシ基、ベンジル基、N-アルキルカルバモイル基又はN-アルキルスルファモイル基を表し、
R46~R50のいずれか1つが、直接結合又は一部の炭素原子がへテロ原子で置換されていてもよい炭素数1~25の2価の脂肪族炭化水素基である場合、他の4つは各々独立に、水素原子、ハロゲン原子、シアノ基、ニトロ基、一部の炭素原子がへテロ原子で置換されていてもよい炭素数1~25のアルキル基、フェニル基、フェノキシ基、ベンジル基、N-アルキルカルバモイル基又はN-アルキルスルファモイル基を表し、R45は一部の炭素原子がへテロ原子で置換されていてもよい炭素数1~25のアルキル基又はベンジル基を表す。
上記式(20)において、
R51~R55のいずれか1つは、直接結合又は一部の炭素原子がへテロ原子で置換されていてもよい炭素数1~25の2価の脂肪族炭化水素基を表わす。
なおR51及びR53の一方が、直接結合又は一部の炭素原子がへテロ原子で置換されていてもよい炭素数1~25の2価の脂肪族炭化水素基である場合、他方は一部の炭素原子がへテロ原子で置換されていてもよい炭素数1~25のアルキル基又はベンジル基を表し、R52、R54及びR55は各々独立に、水素原子、ハロゲン原子、シアノ基、ニトロ基、一部の炭素原子がへテロ原子で置換されていてもよい炭素数1~25のアルキル基、フェニル基、フェノキシ基、ベンジル基、N-アルキルカルバモイル基又はN-アルキルスルファモイル基を表す。
R52、R54及びR55のいずれか1つが、直接結合又は一部の炭素原子がへテロ原子で置換されていてもよい炭素数1~25の2価の脂肪族炭化水素基である場合、他の2つは各々独立に、水素原子、ハロゲン原子、シアノ基、ニトロ基、一部の炭素原子がへテロ原子で置換されていてもよい炭素数1~25のアルキル基、フェニル基、フェノキシ基、ベンジル基、N-アルキルカルバモイル基又はN-アルキルスルファモイル基を表し、R51及びR53は、各々独立に、一部の炭素原子がへテロ原子で置換されていてもよい炭素数1~25のアルキル基又はベンジル基を表す。
上記式(18)におけるR41~R44に含まれる炭素原子数の合計は20以上、上記式(19)におけるR45~R50に含まれる炭素原子数の合計は15以上、上記式(20)におけるR51~R55に含まれる炭素原子数の合計は17以上である。
なおR41~R55は同一化合物内で結合して環を形成していてもよい。)
なお、前記一般式(18)~(20)で表される基は、前記一般式(1)~(3)で表されるオニウム塩のオニウム部分に対応する。
一方、前記一般式(18)~(20)におけるR42~R55のうち、-CO-R35の-CO-に結合するRy(yは42~55のいずれかを表す)及びR41は、前記一般式(1)~(3)における-Y-と同義であり、好ましい基も同様である。
なおZは、前記一般式(1)~(3)におけるZと同義である。
化合物γ(ジオール体)の生成量は、化合物の構造、反応条件および後処理条件により異なるが、化合物αに対して通常0.05モル%以上、10モル%以下である。
これらの化合物は、上記の後処理や精製工程において低減することが可能であるが、微量エポキシ化合物α中に残存する。
前記下限値よりも少なすぎる場合は、該エポキシ組成物から得られるエポキシ樹脂の接着性が低下するおそれがあり、前記上限値よりも多すぎる場合は、該エポキシ組成物を重合させる際の反応点が少ないことになるため、エポキシ樹脂の生産性の低下を招く場合がある。
具体的には特定および積算が容易なピークのプロトン積算値を、エポキシ化合物αのピークの積算値と比較することにより求めることができる。例えば、エステル化合物βであれば、エステルを形成するアルコールまたはカルボン酸由来のピークのプロトン積算値を、エポキシ化合物αのピークの積算値と比較することより求めることができる。
また化合物γの化合物αに対する存在比率は、LC(液体クロマトグラフ)分析で求めることができる。
具体的には、LC分析で求めた化合物αと化合物γのLC面積比に対し、化合物αと、化合物γのファクターの差、即ちUV吸収量の差を考慮して補正することにより、重量比率やモル比率に換算し、求めることができる。
なお、化合物αや化合物γのUV吸収が弱く正確に測定することが困難であったり、同一のUV波長で正確に測定することが困難等の理由でLC分析が困難な場合にはGC(ガスクロマトグラフ)分析で求めればよい。具体的にはGC分析で求めた化合物αと化合物γのGC面積比に対し、化合物αと、化合物γのファクターの差、即ち感度の差を考慮して補正することにより、重量比率やモル比率に換算し、求めることができる。
本発明の製造方法によって得られたエポキシ化合物、及び本発明のエポキシ組成物は、重合することによりエポキシ樹脂を製造することができる。重合反応は、公知の方法を適用することができ、具体的には日本国特開2007-246819号公報等に記載の方法等により行なうことができる。
本発明の方法で得られた高純度エポキシ樹脂は、電子材料、光学材料、接着剤、建築分野等で用いることができる。半導体封止材、プリント配線基板、ビルドアップ配線板、ソルダーレジスト等の電子部品材料として用いた場合、不純物が原因で起きる配線の腐食や短絡の、照明の封止剤等の光学材料として用いた場合、着色や劣化の低減や回避が可能となる。
なお本発明のエポキシ化反応用触媒組成物は、エポキシ化反応以外の酸化反応、好ましくは、オレフィンを酸化する際の酸化剤としても利用可能である。
<1H-NMR分析条件>
装置:BRUKER社製 AVANCE400, 400MHz
溶媒:0.03体積%テトラメチルシラン含有重クロロホルム
積算回数:128回
実施例中のデータは、1H-NMR(400MHz、CDCl3)におけるδ値を表す。
また実施例に記載のNMRデータにおける下線は、同定されたプロトンの位置を表す。
LC装置:島津製作所製 SPD-10Avp
温度:35℃
カラム:Mightysil RP-18GP aqua 150-4.6(5μm)(関東化学社製)
検出器:UV 280nm
溶離液:アセトニトリル/0.1%トリフルオロ酢酸水溶液=90/10(vol%)
流量:0.5ml/min
(以下、分析条件2とする。)
検出器:UV 254nm
溶離液:アセトニトリル/0.1%トリフルオロ酢酸水溶液60/40→100/0 (vol%)、20分間、その後100/0 (vol%)で10分間保持
流量:0.5ml/min
LC装置:Waters Acquity
温度:40℃
カラム:UPLC BEH C18 2.1X100mm(1.7μm)
溶離液:アセトニトリル/20mM酢酸アンモニウム水溶液=50/50(vol%)→10minで100/0、100/0で10min保持
流量:0.25ml/min
MS装置:Waters LCT Premier XE
イオン化法:ESI(+)法
装置:島津製作所製 GC-1700
カラム:phenomenex社製 ZB-5(30mx0.25mmφ、0.25μm)
検出器:水素炎イオン検出器 (FID)
キャリヤーガス(窒素流量):28ml/min
カラム温度:100℃より、10℃/minで300℃まで昇温
INJ温度:250℃
DET温度:300℃
GC装置:島津製作所製 GC-2010
MS装置:島津製作所製 GCMS-QP2010Plus
カラム:DB-5 25M×0.25(0.25μ)
イオン化法 :EI法及びCI法
RI装置:日本分光製 JASCO RI-930
温度:35℃
カラム:ODS-3 150-4.6(5μm)(GLサイエンス製)
溶離液:アセトニトリル
流量:0.5ml/min
水相のpHは、pH試験紙 Comparator(Johnson Test Papers社製) pH1.0~3.5 およびpH3.6~5.1を用いて測定した。
3,3’,5,5-テトラメチル-4,4’-ビス(2-プロペン-1-イルオキシ)-1,1’-ビフェニル(別名称:3,3’,5,5’-テトラメチルビフェニル-4,4’-ジアリルエーテル)は、日本国特開2011-213716号公報実施例2に準ずる方法で合成したものを用いた。塩素23ppmを含む。純度99.9%(LC面積%、上記分析条件1)であった。
1,5-シクロオクタジエンは東京化成社製の試薬を用いた。
実施例12、14、16、18、20、22、25、26中のエステル化合物β(化合物22)は、参考例2記載の方法に従い標品を合成し、この標品のNMR分析を行い、NMRの各ピークの帰属の確認を行った。これを参考に化合物21のNMR分析を行うことにより、化合物21中の化合物22の含有量の定量に用いた。それ以外の実施例では、参考例2で得られた化合物のNMRより類推し、化合物21中の化合物22の含有量の定量を行った。
尚、実施例2、8、9中のエステル化合物β(化合物22)は、LC-Massにて分子量を確認した。m/z 470.3。
化合物αに対する化合物β及び化合物γの存在比率を求めるため、まずはエポキシ化反応にて得られた組成物につきLC分析(実施例28はGC分析)を行ない、各成分のLC面積%を測定した。
化合物αに対する化合物γの存在比率は、LC分析(実施例28はGC分析)によって求められた化合物γの化合物αに対するピーク面積の比に、各化合物の検出感度を補正してモル比率に換算した。各化合物の検出感度は、予め、純度95%以上のそれぞれの化合物の標品を用意し、化合物の正味のモル数の近似値(モル数XLC面積%より推定される純度/100)とそのLCのピーク面積より算出した。
化合物βの存在比率は、へキサン酸エステルの末端メチル基、t-ブチル安息香酸エステルのt-ブチル基等の特定および積算が容易なピークのプロトン積算値を、エポキシ化合物αのピークの積算値と比較することより求めた。
化合物βおよびγの含有量は、エポキシ化合物αに対する存在比率、すなわちエポキシ化合物αを100とした場合の、モル比率(mol%)で表した。
実施例において、エポキシ化反応により(21)を合成する工程中には、上記化合物βおよびγ以外に、反応中にエポキシ環が熱または酸によりアルデヒド異性化後、酸化されたと考えられる成分(LC-Massにおいて、m/z 370.2の化合物)が微量生成する。この化合物、および化合物γはいずれもエポキシ化合物α(21)より極性が高く、LC分析で化合物α(21)より早い保持時間を与える。これらのエポキシ化合物α(21)より早い保持時間を与える化合物を総称して、実施例中で「極性化合物」と称することがある。
(オニウム塩[1]の合成)
トリエタノールアミントリへキサン酸エステルのNMRデータは以下の通りであった。
0.90(9H,t,-CH3),1.30(12H,m,CH3-CH2-CH2-),1.61(6H,m,-CH2-CH2-CO),2.30(6H,t,J=7.56,-CH2-CH2-CO),2.83(6H,t,J=6.08,N-CH2-),4.12(6H,t,J=6.08,-CH2-O-CO-)
上記トリエタノールアミントリへキサン酸エステル1.63gにトルエン4ml、硫酸ジメチル0.46g(1.0倍mol/基質)、炭酸カリウム0.51g(1.0倍mol/基質)を加え、80℃にて5.5時間反応した。NMR分析にてトリエタノールアミントリへキサン酸エステルのエチレン部分のピークの消失により、原料が転化したことを確認した後、5mlの水で洗浄、20%硫酸水5mlで3回洗浄した。さらに水5mlで洗浄後、濃縮し、粗なN-メチル-N,N,N-トリ[2-(ペンチルカルボニルオキシ)エチル]アンモニウム硫酸水素塩2.1gを得た。m/z 458.3(LC-Mass)、純度75%(RI)。これを精製することなく、エポキシ化反応に供した。
なお以下で「N-メチル-N,N,N-トリ[2-(ペンチルカルボニルオキシ)エチル]アンモニウム硫酸水素塩」を「オニウム塩[1]」ということがある。
N-メチル-N,N,N-トリ[2-(ペンチルカルボニルオキシ)エチル]アンモニウム硫酸水素塩:
0.90(9H,t,-CH3),1.31(12H,m,CH3-CH2-CH2-), 1.61(6H,m-CH2-CH2-CO),2.33(6H,t,-CH2-CO),3.38(3H,s,N-CH3),3.92(6H,br,N-CH2-),4.60(6H,br,-CH2-O-CO-),5,78(1H,br,HO-SO2)
(オニウム塩[1]を用いたエポキシ化反応)
その他に反応中間体である3,3’,5,5’-テトラメチルビフェニル-4,4’-モノアリルエーテルモノグリシジルエーテル(以降この化合物をモノエポキシ化合物と称することがある)を7.0%、前述のジオール化合物γを含む極性化合物が9.5%(いずれもLC面積%)生成していた。
なお「LC面積」とは、液体クロマトグラフ(LC)分析で得られた分析対象化合物のピーク面積をいい、「LC面積%」とは、組成物全量のピーク面積に対する対象化合物のピーク面積の割合をいう。
3,3’,5,5-テトラメチル-4,4’-ビス(2-プロペン-1-イルオキシ)-1,1’-ビフェニル:2.32(12H,s,-CH3),4.34(4H,dt,O-CH2-),5.27(2H,ddd,-CH=CH2),5.44(2H,ddd,-CH=CH2),6.13(2H,m,-CH=CH2),7.18(4H,s,-C6H2(Me)2-)
3,3’,5,5’-テトラメチルビフェニル-4,4’-ジグリシジルエーテル(化合物21):2.34(12H,s,-CH3),2.75(2H,dd,-CH2-),2.90(2H,dd,-CH2-),3.38(2H,m,-CH-),3.73(2H,dd,-CH2-),4.07(2H,dd,-CH2-),7.18(4H,s,-C6H2(Me)2-)
(オニウム塩[2]の合成)
N-(6-エトキシ-6-オキソヘキシル)-N-メチル-N,N-ジオクチルアンモニウム硫酸水素塩:0.90(6H,m,-CH3),1.15-1.5(25H,m,-CH2-+-CH3),1.5-1.8(8H,m,-CH2-),2.3-2.4(2H,m,-CH2-CO-),3.23(3H,s,N-CH3),3.2-3.4(6H,m,N-CH2-),4.12(2H,dd,-CH2-O-CO-),5.66(1H,br,HO-SO2)
(オニウム塩[2]を用いたエポキシ化反応)
実施例2と同様の方法で、アンモニウム塩としてN-メチル-N,N,N-トリ[2-(ペンチルカルボニルオキシ)エチル]アンモニウム硫酸水素塩の代わりに、N-(6-エトキシ-6-オキソヘキシル)-N-メチル-N,N-ジオクチルアンモニウム硫酸水素塩(5%mol/基質)を用い、同様に反応を行った。反応収率80%(LC面積%)。得られた化合物21の粗結晶中には中にはエステル化合物β(化合物22)が1.1mol%含まれていた。上記の方法にて化合物中のタングステンの含有量を測定した。測定結果を表1に示した。
(オニウム塩[3]の合成)
得られたオニウム塩[3]のNMRデータは以下の通り。
N,N,N-トリオクチル-N-(2-メトキシ-2-オキソエチル)アンモニウムリン酸塩:0.88(9H,t,-CH3),1.20-1.40(30H,m,-CH2-),1.76(6H,m,-CH2-),3.60-3.67(6H,m,-CH2-),3.81(3H,s,-CH3),4.85(2H,s-N-CH2-)
(オニウム塩[3]のを用いたエポキシ化反応)
実施例2と同様の方法で、アンモニウム塩としてN,N,N-トリオクチル-N-(2-メトキシ-2-オキソエチル)アンモニウムリン酸塩(5%mol/基質)を用い、同様に反応を行った。反応開始後4時間で反応の進行が停止し、反応収率23%(LC面積%)であった。実施例2と同様の方法で、反応混合物のNMR分析を行ったところ、N,N,N-トリオクチル-N-(2-メトキシ-2-オキソエチル)アンモニウム塩の2-メトキシ-2-オキソエチル部分の消失が確認され、オニウム塩[3]の分解がおきていることが示唆された。
(メチルトリオクチルアンモニウム硫酸水素塩を用いたエポキシ化反応)
実施例2と同様の方法で、3,3’,5,5-テトラメチル-4,4’-ビス(2-プロペン-1-イルオキシ)-1,1’-ビフェニル150.0g(0.47mol)をアンモニウム塩としてメチルトリオクチルアンモニウム硫酸水素塩(5%mol/基質)を用いて反応した。3,3’,5,5’-テトラメチルビフェニル-4,4’-ジグリシジルエーテルの反応収率は84%(LC面積%)であった。反応終了後、同様の方法で処理し、3,3’,5,5’-テトラメチルビフェニル-4,4’-ジグリシジルエーテルを粗結晶として147gを得た。収率76%、純度91.2%(LC面積%、LC分析条件2)。この粗結晶にはメチルトリオクチルアンモニウム塩が含まれていたおり、NMR分析でオクチル基の末端メチルのプロトン積算比より6mol%(3,3’,5,5’-テトラメチルビフェニル-4,4’-ジグリシジルエーテルを100とした場合の比率で表す)と推定された。無機分析にて窒素およびタングステンの残存量をそれぞれ測定した。分析結果を表1に示した。
比較例1の方法で得られた3,3’,5,5’-テトラメチルビフェニル-4,4’-ジグリシジルエーテル1.5gにメタノール10.5mlを加え、50℃にて2時間懸洗後、6℃まで冷却し、懸洗結晶0.89gを濾取した。回収率62%。純度95.2%(LC面積%、LC分析条件2)。この懸洗結晶にはメチルトリオクチルアンモニウム塩が含まれていたおり、含有率は1.75mol%(上記と同様のNMR分析、窒素残存量690ppmに相当)であった。
(オニウム塩[1’](モノメチル硫酸を対イオンとする)の合成法)
トリエタノールアミン塩酸塩20.0g(207mmol)、オクタン60ml、ヘキサン酸43.3g(3.0倍mol/基質)、硫酸5.28gの混合液を135℃のオイルバスで加温し、生成する水を留去しながら61時間反応した。反応系を放冷した後、酢酸エチル200ml、飽和重曹水400mlを加えて攪拌した後、水相を排出し、有機相を水100mlで洗浄した。得られた化合物は、ヘキサン酸モノエステル、ジエステル、トリエステルの混合物であり、エステル化率(NMR分析のH積算比より求めたエステル化された水酸基の比率)は79%であった。
(オニウム塩[1’])を用いたエポキシ化反応)
3,3’,5,5-テトラメチル-4,4’-ビス(2-プロペン-1-イルオキシ)-1,1’-ビフェニル5.0g(15.5mmol)をトルエン6.3mlに溶解した溶液を、無水硫酸ナトリウム1重量%および酢酸を1体積%含む水溶液15mlで洗浄した後、3重量%ピロリン酸ナトリウム水溶液0.23ml、10重量%エチレンジアミン四酢酸溶液0.06ml、水15mlの混合液で洗浄した。更に水10mlで洗浄した後、得られたトルエン層にタングステン酸ナトリウム二水和物511mg(10%mol/基質)、8.5%(重量/体積)りん酸水溶液0.9ml(5%mol/基質)、水2mlおよび上記のN-メチル-N,N,N-トリ[2-(ペンチルカルボニルオキシ)エチル]アンモニウムメチル硫酸水素塩のトルエン溶液を添加し攪拌した。更にこの混合液にりん酸水溶液を加え、混合液の水相のpHを4.8とした。その際に添加したリン酸水溶液は0.5ml(3%mol/基質)であった。この混合液を65℃に加温した後、窒素気流下、内温65-68℃で、45%過酸化水素0.5ml(0.5倍モル/基質)を反応開始時、その1時後、2時間後、3時間後、6時間後に計5回添加した。反応開始後、1.5時間後に1N水酸化ナトリウム水溶液を0.4ml、4.5時間後に0.1ml、6.5時間後に0.1mlを加え、水相のpHを3.0~3.5に調整した。内温65-68℃で計8時間反応し、上記LC分析により、反応収率82%(LC面積%)で3,3’,5,5’-テトラメチルビフェニル-4,4’-ジグリシジルエーテルが生成していることを確認した。その他に、反応中間体であるモノエポキシ化合物が11%(LC面積%)、極性化合物が6%(LC面積%)生成していることを確認した。
上記の方法にて得られた、3,3’,5,5’-テトラメチルビフェニル-4,4’-ジグリシジルエーテル2.0gにメタノール15mlを加え、50℃で1時間懸洗し、純度91%(LC面積%)の3,3’,5,5’-テトラメチルビフェニル-4,4’-ジグリシジルエーテル(化合物21)の結晶を1.8g得た。回収率98%。この結晶にはエステル化合物β(化合物22)が0.3mol%含まれていた。
(オニウム塩[4]の合成)
反応中、水酸化ナトリウム水溶液の添加を行うことなく、上記実施例8と同様な方法で反応をおこなった。反応収率77%(LC面積%)で3,3’,5,5’-テトラメチルビフェニル-4,4’-ジグリシジルエーテルが生成していることを確認した。その他に、反応中間体であるモノエポキシ化合物が9%(LC面積%)、エポキシ環が酸により開環した化合物γが12%(LC面積%)生成していることを確認した。
ライオン・アクゾ社製エソカードC/12(N-アルキル(C8~C18)-N,N-ビス(2-ヒドロキシエチル)-N-メチルアンモニウムクロライド、イソプロパノールを約20%含む)12.0g、トルエン200mlの混合液を加熱しながら、トルエンとイソプロパノールの混合液を50ml留去した後、トリエチルアミン5.0gを添加し、内温60~80℃で安息香酸クロライド6.7gを添加した後、内温65℃で30分間、80℃で2時間反応した。反応系の経時変化は、反応混合液約0.1mlをメタノール1mlに溶解し、未反応の安息香酸クロライドを安息香酸メチルエステルに変換後、LC分析を、分析条件2にて行った。80℃でトリエチルアミンと安息香酸クロライドを徐々に添加し、安息香酸クロライドの消費が止まったところを反応の終点とした。追加したトリエチルアミンは4.8g、安息香酸クロライドは3.6gであった。
N-アルキル-N,N-ビス[2-(フェニルカルボニルオキシ)エチル]-N-メチルアンモニウムクロライド:0.88(3H,-CH3),1.0-1.4(約20H,br,-CH2-),1.76(2H,m,-CH2-),2.00(2H,m,-CH2-),3.63(3H,s,N-CH3),3.63(2H,m-CH2-),4.38(4H,m,N-CH2-),4.91(4H,m,-CH2-CO),7.42(4H,dd,-Ph),7.56(2H,dd,-Ph),8.00(4H,d,-Ph)
(オニウム塩[4]を用いたエポキシ化反応)
3,3’,5,5-テトラメチル-4,4’-ビス(2-プロペン-1-イルオキシ)-1,1’-ビフェニル10.0g(31.0mmol)をトルエン10mlに溶解した溶液を、無水硫酸ナトリウム1重量%および酢酸を1体積%含む水溶液30mlで洗浄した後、3重量%ピロリン酸ナトリウム水溶液0.26ml、10%エチレンジアミン四酢酸溶液0.12ml、水30mlの混合液で洗浄した。水30mlで洗浄した後、得られた有機相にタングステン酸ナトリウム二水和物1.02g(10%mol/基質)、8.5%(重量/体積)りん酸水溶液1.79ml(5%mol/基質)、水2mlおよび上記のエソカードC/12の安息香酸エステル体をA-14を1.0g添加し攪拌した。窒素気流下、内温65~68℃で、45%過酸化水素0.5ml(0.5倍モル/基質)を添加後、更にこの混合液にりん酸水溶液を1.79ml(5%mol/基質)加え、混合液の水相のpHを3.5とした。この混合液を65℃に加温しながら、その1時間後、2時間後、3時間後、6時間後に45%過酸化水素0.5ml(0.5倍モル/基質)を計5回添加し、また8時間後にエソカードC/12の安息香酸エステル体を0.1g対添加した。内温65~68℃で計12時間反応し、上記LC分析により、反応収率82%(LC面積%)で3,3’,5,5’-テトラメチルビフェニル-4,4’-ジグリシジルエーテルが生成していることを確認した。その他に、反応中間体であるモノエポキシ化合物が8%(LC面積%)、極性化合物が5%(LC面積%)生成していることを確認した。
得られた固体に1N水酸化ナトリウム水溶液20mlを加え1時間攪拌し、水相を排出した。同様の操作を3回繰り返した後、5%チオ硫酸ナトリウム水溶液2ml、水20mlで洗浄、水20mlで洗浄し、得られた固体を乾燥し、純度94%(LC面積%)の3,3’,5,5’-テトラメチルビフェニル-4,4’-ジグリシジルエーテル(化合物21)を粗結晶として8.2g得た。(収率70%) この粗結晶にはエステル化合物β(化合物22)0.6mol%、ジオール化合物γ(化合物23)6.8mol%が含まれていた。
上記の方法にて化合物中のタングステンの含有量を分析した。測定結果を表1に示した。
(オニウム塩[5]の合成)
N-メチル-N,N,N-トリ[2-(4-t-ブチルフェニルカルボニルオキシ)エチル]アンモニウムモノメチル硫酸塩:1.28(27H,s,t-Bu),3.58(3H,s,-CH3),3.67(3H,s,CH3OSO2-),4.26(6H,br,N-CH2-),4.92(6H,br,-CH2-CO),7.38(6H,dd,-Ar),7.88(6H,dd,-Ar)
(オニウム塩[5]を用いたエポキシ化反応)
予め、上記と同様の方法で前処理した3,3’,5,5-テトラメチル-4,4’-ビス(2-プロペン-1-イルオキシ)-1,1’-ビフェニル5.0g(15.5mmol)、トルエン3.8ml、タングステン酸ナトリウム二水和物512mg(10%mol/基質)、8.5%(重量/体積)りん酸水溶液1.61ml(9%mol/基質)、水3.4mlおよび上記N-メチル-N,N,N-トリ[2-(4-t-ブチルフェニルカルボニルオキシ)エチル]アンモニウムモノメチル硫酸塩トルエン溶液を添加し攪拌した。この混合液を65℃に加温した後、窒素気流下、45%過酸化水素0.5ml(0.5倍モル/基質)を反応開始時、その1時後、2時間後、3時間後、4時間後の計5回添加し、7時間反応した。途中1N水酸化ナトリウム水溶液を0.5ml添加し水層のpHを2.5に調整した。反応収率78%(LC面積%、分析条件1)で3,3’,5,5’-テトラメチルビフェニル-4,4’-ジグリシジルエーテルが生成していることを確認した。その他に、反応中間体であるモノエポキシ化合物が8.2%(LC面積%)、極性化合物が10.7%(LC面積%)生成していた。
上記の方法にて化合物中のタングステンおよび窒素の含有量を分析した。測定結果を表1に示した。
(オニウム塩[6]の合成)
エポキシ化反応に供した。
2,3-ビス(4-t-ブチル-フェニルオキシ)-N、N-ジエチル-N-メチル-1-プロパンアンモニウムモノメチル硫酸塩:1.37(18H,s,t-Bu),1.43(6H,s,-CH3),3.26(3H,s,CH3-N),3.56(4H,m,N-CH2-CH3),3.73(3H,s,CH3OSO2-),4.36(2H,m,-CH2-O-CO),4.58(1H,dd,-CH2-N),4.78(1H,dd,-CH2-N),6.03(1H,m,-CH-),7.41(2H,dd,-Ar),7.46(2H,dd,-Ar),7.87(2H,dd,-Ar),7.96(2H,dd,-Ar)
(オニウム塩[6]を用いたエポキシ化反応)
予め、上記と同様の方法で前処理をした3,3’,5,5-テトラメチル-4,4’-ビス(2-プロペン-1-イルオキシ)-1,1’-ビフェニル2.0g(6.2mmol)、トルエン1.4ml、タングステン酸ナトリウム二水和物204mg(10%mol/基質)、8.5%(重量/体積)りん酸水溶液0.36ml(5%mol/基質)、水3.6mlおよび上記の2,3-ビス(4-t-ブチル-フェニルオキシ)-N、N-ジエチル-N-メチル-1-プロパンアンモニウムモノメチル硫酸塩のトルエン溶液を添加し攪拌した。この混合液を65℃に加温した後、窒素気流下、内温65-68℃で、45%過酸化水素0.1ml(0.5倍モル/基質)を反応開始時、その1時後、2時間後、3時間後、6時間後に計5回添加した。内温65-68℃で計7時間反応し、上記LC分析により、反応収率77%(LC面積%、分析条件1)で3,3’,5,5’-テトラメチルビフェニル-4,4’-ジグリシジルエーテルが生成していることを確認した。その他に、反応中間体であるモノエポキシ化合物が11%(LC面積%)、極性化合物が8%(LC面積%)生成していた。
上記の方法にて化合物中のタングステンおよび窒素の含有量を分析した。測定結果を表1に示した。
(オニウム塩[7]の合成)
上記の方法で得られたアンモニウムクロライド2gをダイヤイオンHP120(三菱化学製)100mlにて精製し(展開溶媒:エタノール)、濃縮した。得られた残渣を酢酸エチル30mlに溶解し、10%(v/v)硫酸水で5mlで2回洗浄後濃縮し、2,3-ビス(4-t-ブチル-フェニルオキシ)-N、N、N-トリエチル-1-プロパンアンモニウム硫酸水素塩(以下、オニウム塩[7])を1.42g得た。純度98%(LC面積%、LC分析条件2)。
2,3-ビス(4-t-ブチル-フェニルオキシ)-N、N、N-トリエチル-1-プロパンアンモニウム硫酸水素塩:1.32(18H,s,t-Bu),1.47(9H,s,-CH3),3.59(6H,m,N-CH2-CH3),4.29(1H,m,HSO4),4.37(2H,m,-CH2-O-CO),4.64(1H,dd,-CH2-N),4.82(1H,dd,-CH2-N),6.00(1H,m,-CH-),7.42(4H,dd,-Ar),7.90(4H,dd,-Ar)
(オニウム塩[7]を用いたエポキシ化反応)
予め、上記と同様の方法で前処理した3,3’,5,5-テトラメチル-4,4’-ビス(2-プロペン-1-イルオキシ)-1,1’-ビフェニル5.0g(15.5mmol)、トルエン3.8ml、タングステン酸ナトリウム二水和物51.2mg(10%mol/基質)、8.5%(重量/体積)りん酸水溶液1.25ml(7%mol/基質)、水3.4mlおよび上記の2,3-ビス(4-t-ブチル-フェニルオキシ)-N、N、N-トリエチル-1-プロパンアンモニウム硫酸塩0.46g(5%mol/基質)を添加し攪拌した。この混合液を65℃に加温した後、窒素気流下、45%過酸化水素0.5ml(0.5倍モル/基質)を反応開始時、その1時後、2時間後、3時間後、4時間後、6時間後に計6回添加した。内温65~66℃で4時間、内温68~69℃で6時間、計10時間反応し、上記LC分析により、反応収率82%(LC面積%、分析条件1)で3,3’,5,5’-テトラメチルビフェニル-4,4’-ジグリシジルエーテルが生成していることを確認した。その他に、反応中間体であるモノエポキシ化合物が5.4%(LC面積%)、極性化合物が10.7%(LC面積%)生成していた。
上記の方法にて化合物中の窒素およびタングステンの含有量を分析した。測定結果を表1に示した。
(オニウム塩[8]の合成)
1-[2,3-ビス[(4-t-ブチルフェニルカルボニルオキシ)プロピル]ピリジニウムクロライド:1.32(18H,d,t-Bu),4.91(2H,m,-CH2-O-CO),5.38(2H,m,-CH2-N),5.93(1H,m,-CH-),6.22(1H,m,-CH2-N),6.03(1H,m,-CH-),7.42(2H,dd,-Ar),7.45(2H,dd,-Ar),7.82(2H,dd,-Ar),7.97(2H,dd,-Ar),8.40(1H,m,Py),9.61(2H,m,Py)
オニウム塩[8]を用いたエポキシ化反応
予め、上記と同様の方法で無水硫酸ナトリウム1重量%および酢酸を1体積%含む水溶液、次に3重量%ピロリン酸ナトリウム水溶液と10重量%エチレンジアミン四酢酸溶液の混合溶液、更に水で洗浄した3,3’,5,5-テトラメチル-4,4’-ビス(2-プロペン-1-イルオキシ)-1,1’-ビフェニル1.0g(3.1mmol)、トルエン1.0ml、タングステン酸ナトリウム二水和物102mg(10%mol/基質)、8.5%(重量/体積)りん酸水溶液0.36ml(5%mol/基質)、水1mlおよび上記の1-[2,3-ビス[(4-t-ブチルフェニルカルボニルオキシ)プロピル]ピリジニウムクロライド81mg(5%mol/基質)を添加し攪拌した。この混合液を65℃に加温した後、窒素気流下、内温65-68℃で、45%過酸化水素0.1ml(0.5倍モル/基質)を反応開始時、その1時後、2時間後、3時間後、4時間後に計5回添加し、各添加後1時間ずつ反応した。その後りん酸水溶液0.10mlを加え、水層のpHを2.5に調整し、さらに45%過酸化水素0.1ml(0.5倍モル/基質)を1時間ごとに2回添加しながら内温68℃で反応し、計9時間反応した。反応収率68%で3,3’,5,5’-テトラメチルビフェニル-4,4’-ジグリシジルエーテルが生成していることを確認した。その他に、反応中間体であるモノエポキシ化合物が13.7%、極性化合物が10.2%(LC面積%)生成していた。
上記の方法にて化合物中のタングステンの含有量を分析した。測定結果を表1に示した。
(オニウム塩[9]の合成)
上記の方法で得られた12-ブロモドデカン酸ヘキシルエステル2.20g(6.1mmol)、ジブチルアミン0.78g(1.0倍モル/基質)を加え、途中ジブチルアミン0.31g(0.4倍モル/基質)を2回追加しながら、110℃にて19時間攪拌反応した。反応終了後、酢酸エチル20mlを加え、水10mlで2回洗浄した。得られた有機層を濃縮後、カラム精製し(Silica60N 100g、展開溶媒:ヘキサン/酢酸エチル=4/1→2/1)12-N,N-ジブチルドデカン酸ヘキシルエステル1.68gを得た。収率67%。
上記の方法で得られた12-N,N-ジブチルドデカン酸ヘキシルエステル0.165g(0.4mmol)にトルエン1.2ml、硫酸ジメチル57.5mg(1.5倍mol/基質)を加え、70℃にて3時間反応した。NMR分析にて転化率99%以上で、N、N-ジエチル-N-メチル-1-ドデカン酸ヘキシルエステルアンモニウムメチル硫酸塩(以下オニウム塩[9]とする)の生成を確認した。この反応溶液を精製することなくそのまま酸化反応に供した。
得られたオニウム塩[9]のNMRデータは以下の通り。
N、N-ジエチル-N-メチル-1-ドデカン酸ヘキシルエステルアンモニウムメチル硫酸塩:0.85-1.10(9H,m,-CH3),1.25-1.80(34H,m,-CH2-CH2-CH2-),2,38(2H,m,-CO-CH2-),3.07(3H,s,N-CH3),3.21(6H,m,N-CH2-),3.83(3H,s,CH3S02-),4.12(2H,m,-COO-CH2)
(オニウム塩[9]を用いたエポキシ化反応)
予め、上記と同様の方法で前処理した3,3’,5,5-テトラメチル-4,4’-ビス(2-プロペン-1-イルオキシ)-1,1’-ビフェニル2.0g(6.2mmol)、トルエン1.2ml、タングステン酸ナトリウム二水和物0.205g(10%mol/基質)、8.5%(重量/体積)りん酸水溶液0.64ml(9%mol/基質)、水1.4mlおよび上記の12-N,N-ジブチルドデカン酸ヘキシルエステルアンモニウムモノメチル硫酸塩のトルエン溶液を添加し攪拌した。この混合液を65℃に加温した後、窒素気流下、内温65-68℃で、45%過酸化水素0.1ml(0.5倍モル/基質)を反応開始時、その1時後、2時間後、3時間後、4時間後、6時間後に計6回添加した。反応時の水相のpHは2.0であった。内温65-68℃で計6時間反応し、上記LC分析により、反応収率81.3%(LC面積%)で3,3’,5,5’-テトラメチルビフェニル-4,4’-ジグリシジルエーテルが生成していることを確認した。その他に、モノエポキシ化合物が10.7%、極性化合物が7.4%(LC面積%)生成していた。
反応終了後、トルエン20mlを追加した後、水層を排出し、有機相を5%チオ硫酸ナトリウム水溶液10mlで洗浄した。さらに1N水酸化ナトリウム水溶液10mlを加え1時間攪拌し、水層を排出した。同様の水酸化ナトリウム水溶液洗浄を3回繰り返した後、水8mlで洗浄した。得られた有機相を濃縮し、3,3’,5,5’-テトラメチルビフェニル-4,4’-ジグリシジルエーテルを粗結晶として2.08g得た。純度86.4%(LC面積%、LC分析条件2)収率82%。
得られた上記粗結晶1g(2.4mmol)にトルエン3mlを加え50℃に加温し溶解した後、メタノール7mlを加え、6℃に冷却し、析出した結晶を濾取し、3,3’,5,5’-テトラメチルビフェニル-4,4’-ジグリシジルエーテルの結晶を0.52g得た。NMRでオニウム塩(10)および、オニウム塩の分解物が結晶中に含まれないことを確認した。純度95.6%(LC面積%、LC分析条件2)。回収率58%。エステル化合物β(化合物22)が0.7mol%、ジオール化合物γ(化合物23)が6.9mol%含まれていた。
(オニウム塩[10]の合成)
得られたオニウム塩[10]のNMRデータは以下の通り。
1-[(ヘキサデシルオキシカルボニル)オキシ]ブチル]ピリジニウムクロライド:
0.88(3H,dd,-CH3),1.2-1.4(26H,m,-CH2-),1.66(2H,m,-CH2-),1.85(2H,m,-CH2-),2.20(2H,m,-CH2-),4.11(2H,dd,-CH2-),4.20(2H,dd,-CH2-),5.20(2H,dd,N-CH2-),8.09(2H,dd,Py),8.46(1H,dd,Py),9.53(2H,dd,Py)
(オニウム塩[10]を用いたエポキシ化反応)
予め、上記と同様の方法で前処理した3,3’,5,5-テトラメチル-4,4’-ビス(2-プロペン-1-イルオキシ)-1,1’-ビフェニル1.5g(4.7mmol)、トルエン1ml、オクタン1ml、タングステン酸ナトリウム二水和物0.154g(10%mol/基質)、8.5%(重量/体積)りん酸水溶液0.48ml(9%mol/基質)、水1.0mlおよび上記の1-[(ヘキサデシルオキシカルボニル)オキシ]ブチル]ピリジニウムクロライド0.106g(5%mol/基質)を添加し攪拌した。この混合液を65℃に加温した後、窒素気流下、45%過酸化水素0.5ml(0.5倍モル/基質)を反応開始時、その1時後、2時間後、3時間後、4時間後、6時間後に計6回添加した。反応中の水相のpHは約3.0であった。内温65-66℃で7時間、内温68-69℃で10時間、計17時間反応し、上記LC分析により、反応収率53.7%(LC面積%、分析条件1)で3,3’,5,5’-テトラメチルビフェニル-4,4’-ジグリシジルエーテルが生成していることを確認した。その他に、反応中間体であるモノエポキシ化合物が10.3%(LC面積%)、極性化合物が22.0%(LC面積%)生成していた。
反応終了後、トルエン7.5mlを追加した後、水層を排出し、水7.5mlで2回洗浄後、5%チオ硫酸ナトリウム水溶液7.5mlで洗浄した。さらに1N水酸化ナトリウム水溶液7.5mlを加え25℃で1時間攪拌し、水層を排出した。水酸化ナトリウム水溶液洗浄を内温30℃で30分間3回繰り返し処理し、オニウム塩[11]が加水分解され消失したことをLCおよびNMRにて確認し、水25mlで洗浄した。得られた有機相を濃縮し、3,3’,5,5’-テトラメチルビフェニル-4,4’-ジグリシジルエーテルを粗結晶として0.94g得た。純度63.0%(LC面積%、LC分析条件2)、収率36%。
実施例14で得られた3,3’,5,5’-テトラメチルビフェニル-4,4’-ジグリシジルエーテル粗結晶2.0gにメタノール14mlを加え、50℃で3時間懸洗を行った。6℃まで冷却後、結晶を濾取し、純度90.9%(LC面積%、LC分析条件2)の3,3’,5,5’-テトラメチルビフェニル-4,4’-ジグリシジルエーテルを1.55g得た。回収率79%。この懸洗結晶中にはエステル化合物β(化合物22)2.6mol%、ジオール化合物γ(化合物23)0.6mol%が含まれていた。上記の方法にて化合物中の窒素及び塩素の含有量を分析した。測定結果を表1に示した。
実施例16で得られた3,3’,5,5’-テトラメチルビフェニル-4,4’-ジグリシジルエーテル粗結晶0.69gにメタノール3mlを加え、50℃で1時間懸洗を行った。6℃まで冷却後、結晶を濾取し、純度90.4%(LC面積%、LC分析条件2)の3,3’,5,5’-テトラメチルビフェニル-4,4’-ジグリシジルエーテルを0.52g得た。回収率80%。この懸洗結晶中にはエステル化合物β2.0mol%(化合物22)、ジオール化合物γ(化合物23)1.2mol%が含まれていた。上記の方法にて化合物中の窒素の含有量を分析した。測定結果を表1に示した。
実施例18で得られた3,3’,5,5’-テトラメチルビフェニル-4,4’-ジグリシジルエーテル粗結晶2.0gにトルエン3mlを加え50℃に加温し溶解した後、メタノール14mlを加えた。6℃まで冷却後、析出した結晶を濾取し、純度96.1%(LC面積%、LC分析条件2)の3,3’,5,5’-テトラメチルビフェニル-4,4’-ジグリシジルエーテルを1.38g得た。回収率71%。この結晶中にはエステル化合物β0.2mol%、ジオール化合物γ0.5mol%が含まれていた。
上記の方法にて化合物中の窒素の含有量を分析した。測定結果を表1に示した。
(オニウム塩[7]を用いた1,5-シクロオクタジエンのエポキシ化反応)
1,5-シクロオクタジエン3.0g(27.7mmol;東京化成社製)、トルエン9ml、タングステン酸ナトリウム二水和物0.183g(2%mol/基質)、8.5%(重量/体積)りん酸水溶液0.32ml(1%mol/基質)、水3.4mlおよび上記の2,3-ビス(4-t-ブチル-フェニルオキシ)-N、N、N-トリエチル-1-プロパンアンモニウム硫酸塩(オニウム塩[7])0.16g(1%mol/基質)を添加し攪拌した。この混合液を50℃に加温した後、窒素気流下、45%過酸化水素0.9ml(0.5倍モル/基質)を反応開始時、その1時後、2時間後、3時間後、5時間後、7時間後に計6回添加した。反応開始後2時間の水相のpHは4.8であった。内温50-51℃で計9時間反応し、上記GC分析により、反応収率90.2%(GC面積%)で1,2,5,6-ジエポキシシクロオクタンが生成していることを確認した。その他に、反応中間体であるモノエポキシ化合物が6.6%(LC面積%)、エポキシが開環した化合物が3.2%(GC面積%)生成していた。
反応終了後、トルエン10mlを追加した後、水層を排出し、水3mlで洗浄後、5%チオ硫酸ナトリウム水溶液10mlで洗浄した。さらに1N水酸化ナトリウム水溶液10mlを加え25℃で15分間攪拌し、水層を排出した。水酸化ナトリウム水溶液洗浄を内温30℃で30分間3回繰り返し処理し、オニウム塩[7]が加水分解され消失したこと、およびオニウム塩[7]の加水分解物であるt-ブチル安息香酸が有機相に残存していないことをLCおよびNMRにて確認した。有機相を更に水4mlで2回洗浄した後、得られた有機相を濃縮し、液状の1,2,5,6-ジエポキシシクロオクタンを1.0g得た。純度97%(GC面積%)収率26%。この化合物はエステル化合物βを1.8mol%を含有していた。
上記の方法にて化合物中のタングステンおよび窒素の含有量を分析した。測定結果を表1に示した。
1,2,5,6-ジエポキシシクロオクタンのNMRデータは以下の通り。
1,2,5,6-ジエポキシシクロオクタン:
1.82-2.05(8H,m,-CH2-),3.00(4H,m,-CH-O-)
3-[[3,3’,5,5’-テトラメチル-4’-(2-オキシラニルメトキシ)[1,1’-ビフェニル]-4-イル]オキシ]-1,2-プロパンジオール(化合物γ)の合成
3,3’,5,5’-テトラメチルビフェニル-4,4’-ジグリシジルエーテル(0.028mol)10gに酢酸50mlを加え、内温約85℃で9時間反応した。酢酸をトルエンと共沸しながら減圧で留去し、16.1gの残渣を得た。これに1N水酸化ナトリウム水溶液60mlを加え室温で2時間反応した。析出した[[3,3’,5,5’-テトラメチル-[1,1’-ビフェニル]-4,4’-イル]オキシ]ビス-(1,2-プロパンジオール)を主成分とする固体を濾別し、濾物を酢酸エチル100mlで洗浄した。洗液の酢酸エチルと水相を合わせて分液し、得られた有機相を濃縮、得られた残渣をカラムクロマトグラフィー(silica60N 300g、展開溶媒:ヘキサン/酢酸エチル=1/1~1/2)で精製し、3-[[3,3’,5,5’-テトラメチル-4’-(2-オキシラニルメトキシ)[1,1’-ビフェニル]-4-イル]オキシ]-1,2-プロパンジオールを結晶として3.8g得た。収率36%。純度95.5%(LC面積%、LC分析条件2)
得られたジオール化合物γのNMRデータは以下の通り。
3-[[3,3’,5,5’-テトラメチル-4’-(2-オキシラニルメトキシ)[1,1’-ビフェニル]-4-イル]オキシ]-1,2-プロパンジオール:2.34(12H,s,-CH3),2.72(1H,dd,-CH2-),2.91(1H,dd,-CH2-),3.44(1H,m,-CH-),3.76(1H,dd,-CH2-),3.79(2H,m,-CH2-OH),3.90(2H,d,O-CH2-CH(OH)),4.08(1H,dd,-CH2-),4.09(1H,m,CH-OH),7.18(4H,s,-C6H2(Me)2-)
4-t-ブチル安息香酸-2-ヒドロキシ-3-[[3,3’,5,5’-テトラメチル-4’-(2-オキシラニルメトキシ)[1,1’-ビフェニル]-4-イル]オキシ]プロピルエステル(化合物β)の合成
上記の方法で得られたジオール化合物0.1g(0.3mmol)、トルエン2ml、トリエチルアミン0.11ml(3倍mol/基質)の混合液中に上記の方法で得られたt-ブチル安息香酸クロライド0.08g(1.5倍mol/基質)を加え、室温にて5時間反応した。反応後、酢酸エチル6ml、水2mlを加え攪拌し、得られた有機相をカラムクロマトグラフィー(silica60N 30g、展開溶媒:ヘキサン/酢酸エチル=4/1)で精製し、4-t-ブチル安息香酸-2-ヒドロキシ-3-[[3,3’,5,5’-テトラメチル-4’-(2-オキシラニルメトキシ)[1,1’-ビフェニル]-4-イル]オキシ]プロピルエステルを約50mg(化合物β)を約50mg得た。純度96.3%(LC面積%、LC分析条件2)
得られた化合物βのNMRデータは以下の通り。
4-t-ブチル安息香酸-2-ヒドロキシ-3-[[3,3’,5,5’-テトラメチル-4’-(2-オキシラニルメトキシ)[1,1’-ビフェニル]-4-イル]オキシ]プロピルエステル:
1.32(9H,s,t-Bu),2.34(12H,s,-CH3),2.73(1H,dd,-CH2-),2.90(1H,dd,-CH2-),3.40(1H,m,-CH-),3.78(1H,dd,-CH2-),3.95(2H,m,O-CH2-CH(OH)),4.10(1H,m,-CH2-),4.39(1H,m,CH-OH),4.60(2H,m,-CH2-OCO-),7.18(4H,s,-C6H2(Me)2-),7.49(2H,d,t-Bu-C6H4-),7.99(2H,d,t-Bu-C6H4-)
Claims (24)
- エポキシ化合物の製造方法であって、
炭素-炭素二重結合を有する化合物に、
タングステン化合物及びモリブデン化合物のうち少なくとも一方と、
活性水素を含む官能基またはその塩に変換可能な置換基を1つ以上有し、かつ炭素原子を20以上含むオニウム塩との存在下、
過酸化水素を反応させる、エポキシ化合物の製造方法。 - 前記活性水素を含む官能基が、水酸基、カルボキシル基、アミノ基、メルカプト基、スルホン酸基又はリン酸基である請求項1に記載のエポキシ化合物の製造方法。
- 前記反応時に、さらにリン酸類及びホスホン酸類(但しオニウム塩を除く)のうち少なくとも一方を共存させる請求項1または2に記載のエポキシ化合物の製造方法。
- 前記反応が水相と有機相の二相系反応であり、かつ前記水相のpHが2以上6以下である、請求項1~3のいずれか1項に記載のエポキシ化合物の製造方法。
- 前記オニウム塩が、アンモニウム塩、ピリジニウム塩、イミダゾリニウム塩又はホスホニウム塩である請求項1~4のいずれか1項に記載のエポキシ化合物の製造方法。
- 前記活性水素を含む官能基またはその塩に変換可能な置換基が、アルコキシカルボニル基又はアシルオキシ基である請求項1~5のいずれか1項に記載のエポキシ化合物の製造方法。
- 前記オニウム塩が、下記一般式(1)~(3)のいずれかで表される化合物である請求項1~6のいずれか1項に記載のエポキシ化合物の製造方法。
R1~R5、R11及びR13は、前記-Y-CO-O-Z及び-Y-O―CO-Zではない場合は、それぞれ独立して、一部の炭素原子がへテロ原子で置換されていてもよく、かつ置換基を有していてもよい炭素数1~25のアルキル基又はベンジル基を表し、
R6~R10、R12、R14及びR15は、前記-Y-CO-O-Z及び-Y-O―CO-Zではない場合は、それぞれ独立して、水素原子、ハロゲン原子、シアノ基、ニトロ基、一部の炭素原子がへテロ原子で置換されていてもよく、かつ置換基を有していてもよい炭素数1~25のアルキル基、フェニル基、フェノキシ基、ベンジル基、N-アルキルカルバモイル基又はN-アルキルスルファモイル基を表す。
R1~R15は同一化合物内で結合して環を形成していてもよい。
なお、上記式(1)におけるR1~R4に含まれる炭素原子数の合計は20以上であり、上記式(2)におけるR5~R10に含まれる炭素原子数の合計は15以上であり、上記式(3)におけるR11~R15に含まれる炭素原子数の合計は17以上である。
X-は、1価のアニオンを表す。) - 前記製造方法において、反応後に、前記活性水素を含む官能基またはその塩に変換可能な置換基を、塩基性化合物で加水分解する請求項1~7のいずれか1項に記載のエポキシ化合物の製造方法。
- 前記炭素-炭素二重結合を有する化合物を、酸性水溶液で洗浄した後に反応に供する、請求項1~8のいずれか1項に記載のエポキシ化合物の製造方法。
- 前記炭素-炭素二重結合を有する化合物を、キレート化剤水溶液で洗浄した後に反応に供する請求項1~8のいずれか1項に記載のエポキシ化合物の製造方法。
- 前記製造方法において、キレート化剤を反応時に共存させる、請求項1~10のいずれか1項に記載のエポキシ化合物の製造方法。
- エポキシ化合物を重合してエポキシ樹脂を製造する方法であって、請求項1~11のいずれか1項に記載の方法でエポキシ化合物を製造する工程と、前記工程で得られたエポキシ化合物を重合する工程を含むエポキシ樹脂の製造方法。
- タングステン化合物及びモリブデン化合物のうち少なくとも一方と、
活性水素を含む官能基またはその塩に変換可能な置換基を1つ以上有する、炭素数が20以上のオニウム塩と、を含むエポキシ化反応用触媒組成物。 - 前記活性水素を含む官能基が、水酸基、カルボキシル基、アミノ基、メルカプト基、スルホン酸基又はリン酸基である請求項13に記載のエポキシ化反応用触媒組成物。
- 前記組成物が、さらにリン酸類及びホスホン酸類(但しオニウム塩を除く)のうち少なくとも一方を含む請求項13または14に記載のエポキシ化反応用触媒組成物。
- 前記オニウム塩が、アンモニウム塩、ピリジニウム塩、イミダゾリニウム塩又はホスホニウム塩である請求項13~15のいずれか1項に記載のエポキシ化反応用触媒組成物。
- 前記活性水素を含む官能基またはその塩に変換可能な置換基が、アルコキシカルボニル基又はアシルオキシ基である請求項13~16のいずれか1項に記載のエポキシ化反応用触媒組成物。
- 更にカルボン酸(但し、カルボキシ基を有するオニウム塩を除く)を含有する請求項13~17のいずれか1項に記載のエポキシ化反応触媒組成物。
- 前記オニウム塩が、下記一般式(1)~(3)のいずれかで表される化合物である請求項13~18のいずれか1項に記載のエポキシ化反応用触媒組成物。
R1~R5、R11及びR13は、前記-Y-CO-O-Z及び-Y-O―CO-Zではない場合は、それぞれ独立して、一部の炭素原子がへテロ原子で置換されていてもよく、かつ置換基を有していてもよい炭素数1~25のアルキル基又はベンジル基を表し、
R6~R10、R12、R14及びR15は、前記-Y-CO-O-Z及び-Y-O―CO-Zではない場合は、それぞれ独立して、水素原子、ハロゲン原子、シアノ基、ニトロ基、一部の炭素原子がへテロ原子で置換されていてもよく、かつ置換基を有していてもよい炭素数1~25のアルキル基、フェニル基、フェノキシ基、ベンジル基、N-アルキルカルバモイル基又はN-アルキルスルファモイル基を表す。
R1~R15は同一化合物内で結合して環を形成していてもよい。
なお、上記式(1)におけるR1~R4に含まれる炭素原子数の合計は20以上であり、上記式(2)におけるR5~R10に含まれる炭素原子数の合計は15以上であり、上記式(3)におけるR11~R15に含まれる炭素原子数の合計は17以上である。
X-は、1価のアニオンを表す。) - 下記一般式(8)~(10)、(12)又は(31)で表されるオニウム塩。
R31及びR32は、それぞれ独立に、一部の炭素原子がへテロ原子で置換されていてもよい炭素数1~25の2価の脂肪族炭化水素基を表わす。
R33は、一部の炭素原子がへテロ原子で置換されていてもよい炭素数1~25の1価の脂肪族炭化水素基、又は置換基を有していてもよい炭素数4~25の1価の芳香族炭化水素基を表す。
なお、同一化合物中に存在する複数のk、R20及びR31は、同一であっても異なっていてもよい。また式中のカチオン部分に含まれる炭素原子数の合計は20以上である。
X-は、1価のアニオンを表す) - 下記式(32)で表されるエポキシ化合物αと、
該エポキシ化合物αが有するグリシジル基の1つ以上が3-アシルオキシ-2-ヒドロキシプロピル基に置換された構造を有する化合物β(但し、該アシル基は-CO-R35、又は-CO-Zで表される基)、とを含む組成物。
A201は置換基を有していてもよい(m201+1)価の芳香族または脂肪族炭化水素基を表し、A202は置換基を有していてもよい2価の芳香族または脂肪族炭化水素基を表し、A203は置換基を有していてもよい(m203+2)価の芳香族または脂肪族炭化水素基を表す。
X201及びX202は、各々独立に、直接結合又は置換基を有していてもよい2価の連結基を表す。
p201は0又は1を表す。
m201及びm203は、各々独立に、1以上の整数を表す。
n201は1以上の整数を表し、n202は0又は1以上の整数を表し、n203は0又は1を表す。
但しn202=n203=0の場合、p201=0であればA201はm201価となり、p201=1であればX201は水素原子または1価の基となる。
なお1分子中に含まれる複数のG、A201、A202、X201、X202、m201及びp201は、同じであっても異なっていてもよい。)
なお、-CO-R35及び-CO-Zにおいて、
Zは、一部の炭素原子がへテロ原子で置換されていてもよい炭素数1~25の1価の脂肪族炭化水素基、又は置換基を有していてもよい炭素数4~25の1価の芳香族炭化水素基を表わし、
R35は、下記式(18)~(20)のいずれかで表される基を表す。
R41は直接結合又は一部の炭素原子がへテロ原子で置換されていてもよい炭素数1~25の2価の脂肪族炭化水素基を表す。
R42~R44は各々独立に、一部の炭素原子がへテロ原子で置換されていてもよい炭素数1~25のアルキル基又はベンジル基を表す。
上記式(19)において、
R45~R50のいずれか1つは、直接結合又は一部の炭素原子がへテロ原子で置換されていてもよい炭素数1~25の2価の脂肪族炭化水素基を表わす。
なおR45が、直接結合又は一部の炭素原子がへテロ原子で置換されていてもよい炭素数1~25の2価の脂肪族炭化水素基である場合、R46~R50は各々独立に、水素原子、ハロゲン原子、シアノ基、ニトロ基、一部の炭素原子がへテロ原子で置換されていてもよい炭素数1~25のアルキル基、フェニル基、フェノキシ基、N-アルキルカルバモイル基又はN-アルキルスルファモイル基を表し、
R46~R50のいずれか1つが、直接結合又は一部の炭素原子がへテロ原子で置換されていてもよい炭素数1~25の2価の脂肪族炭化水素基である場合、他の4つは各々独立に、水素原子、ハロゲン原子、シアノ基、ニトロ基、一部の炭素原子がへテロ原子で置換されていてもよい炭素数1~25のアルキル基、フェニル基、フェノキシ基、ベンジル基、N-アルキルカルバモイル基又はN-アルキルスルファモイル基を表し、R45は一部の炭素原子がへテロ原子で置換されていてもよい炭素数1~25のアルキル基又はベンジル基を表す。
上記式(20)において、
R51~R55のいずれか1つは、直接結合又は一部の炭素原子がへテロ原子で置換されていてもよい炭素数1~25の2価の脂肪族炭化水素基を表わす。
なおR51及びR53の一方が、直接結合又は一部の炭素原子がへテロ原子で置換されていてもよい炭素数1~25の2価の脂肪族炭化水素基である場合、他方は一部の炭素原子がへテロ原子で置換されていてもよい炭素数1~25のアルキル基又はベンジル基を表し、R52、R54及びR55は各々独立に、水素原子、ハロゲン原子、シアノ基、ニトロ基、一部の炭素原子がへテロ原子で置換されていてもよい炭素数1~25のアルキル基、フェニル基、フェノキシ基、ベンジル基、N-アルキルカルバモイル基又はN-アルキルスルファモイル基を表す。
R52、R54及びR55のいずれか1つが、直接結合又は一部の炭素原子がへテロ原子で置換されていてもよい炭素数1~25の2価の脂肪族炭化水素基である場合、他の2つは各々独立に、水素原子、ハロゲン原子、シアノ基、ニトロ基、一部の炭素原子がへテロ原子で置換されていてもよい炭素数1~25のアルキル基、フェニル基、フェノキシ基、ベンジル基、N-アルキルカルバモイル基又はN-アルキルスルファモイル基を表し、R51及びR53は、各々独立に、一部の炭素原子がへテロ原子で置換されていてもよい炭素数1~25のアルキル基又はベンジル基を表す。
上記式(18)におけるR41~R44に含まれる炭素原子数の合計は20以上、上記式(19)におけるR45~R50に含まれる炭素原子数の合計は15以上、上記式(20)におけるR51~R55に含まれる炭素原子数の合計は17以上である。
なおR41~R55は同一化合物内で結合して環を形成していてもよい。) - 前記エポキシ化合物αが、下記式(13)~(15)のいずれかで表される化合物である請求項21に記載の組成物。
(A1)-(OG)m1 (13)
(上記式(13)において、Gはグリシジル基(2,3-エポキシプロパニル基)を表し、該グリシジル基はアルキル基、フェニル基又はアルコキシカルボニル基で置換されていてもよい。A1は、置換基を有していてもよいm1価の芳香族又は脂肪族炭化水素基を表す。m1は1以上の整数を表す。なお1分子中に含まれる複数のGは同じであっても異なっていてもよい。)
(GO)m2-(A21)-[X2-(A22)]n2-X2-(A21)-(OG)m2(14)
(上記式(14)において、Gはグリシジル基を表し、該グリシジル基はアルキル基、フェニル基又はアルコキシカルボニル基で置換されていてもよい。A21は、置換基を有していてもよい(m2+1)価の芳香族又は脂肪族炭化水素基を表し、A22は、置換基を有していてもよい2価の芳香族又は脂肪族炭化水素基を表す。X2を介して連結するA21とA22、又は隣接する複数のA22は、その置換基同士が結合して環を形成していてもよい。X2は、直接結合又は置換基を有していてもよい2価の連結基を表す。m2は1以上の整数を表し、n2は0又は1以上の整数を表す。なお1分子中に含まれる複数のG、A21、A22、X2、及びm2は同じであっても異なっていてもよい。)
H-[(A3(OG)m3)―X3]n3-H (15)
(上記式(15)において、Gはグリシジル基を表し、該グリシジル基はアルキル基、フェニル基又はアルコキシカルボニル基で置換されていてもよい。A3は、置換基を有していてもよい(m3+2)価の芳香族又は脂肪族炭化水素基を表す。X3は、直接結合、置換基を有していてもよいアルキレン基又は-R41-フェニレン-R42-を表し、R41及びR42は、夫々独立にアルキレン基を表す。m3は1以上の整数を表す。n3は2以上の整数を表す。なお1分子中に含まれる複数のG、A3、X3、及びm3は同じであっても異なっていてもよい。) - 前記組成物中の含まれる、前記エポキシ化合物αに対する前記化合物βの存在比が、0.05モル%以上10.0モル%以下である請求項21または22に記載の組成物。
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CN107082870A (zh) | 2017-08-22 |
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KR20150002630A (ko) | 2015-01-07 |
TW201348220A (zh) | 2013-12-01 |
US20170204077A1 (en) | 2017-07-20 |
JP2018199829A (ja) | 2018-12-20 |
KR102049711B1 (ko) | 2019-11-28 |
TW201815775A (zh) | 2018-05-01 |
US10730846B2 (en) | 2020-08-04 |
US20150018515A1 (en) | 2015-01-15 |
JP6233303B2 (ja) | 2017-11-22 |
CN104203933A (zh) | 2014-12-10 |
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JPWO2013147092A1 (ja) | 2015-12-14 |
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