JP5979633B2 - エポキシ化合物の製造方法 - Google Patents
エポキシ化合物の製造方法 Download PDFInfo
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- JP5979633B2 JP5979633B2 JP2012116391A JP2012116391A JP5979633B2 JP 5979633 B2 JP5979633 B2 JP 5979633B2 JP 2012116391 A JP2012116391 A JP 2012116391A JP 2012116391 A JP2012116391 A JP 2012116391A JP 5979633 B2 JP5979633 B2 JP 5979633B2
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- Prior art keywords
- compound
- epoxy compound
- carbon
- solid catalyst
- hydrogen peroxide
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- 150000001875 compounds Chemical class 0.000 title claims description 100
- 239000004593 Epoxy Substances 0.000 title claims description 61
- 238000004519 manufacturing process Methods 0.000 title claims description 39
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 57
- 239000011949 solid catalyst Substances 0.000 claims description 54
- 239000000843 powder Substances 0.000 claims description 46
- 239000007787 solid Substances 0.000 claims description 42
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 31
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 29
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 25
- 229910052721 tungsten Inorganic materials 0.000 claims description 25
- 239000010937 tungsten Substances 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 23
- 239000003960 organic solvent Substances 0.000 claims description 21
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 12
- 229910052586 apatite Inorganic materials 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 239000000376 reactant Substances 0.000 claims description 10
- 239000011541 reaction mixture Substances 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 239000005909 Kieselgur Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 5
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 235000021317 phosphate Nutrition 0.000 claims description 4
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 4
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 150000002825 nitriles Chemical class 0.000 claims description 3
- 150000003457 sulfones Chemical class 0.000 claims description 3
- 239000004927 clay Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 29
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 17
- 229910052750 molybdenum Inorganic materials 0.000 description 17
- 239000011733 molybdenum Substances 0.000 description 17
- 239000000047 product Substances 0.000 description 16
- UFERIGCCDYCZLN-UHFFFAOYSA-N 3a,4,7,7a-tetrahydro-1h-indene Chemical compound C1C=CCC2CC=CC21 UFERIGCCDYCZLN-UHFFFAOYSA-N 0.000 description 14
- 239000012043 crude product Substances 0.000 description 12
- 230000007423 decrease Effects 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 11
- 229910052720 vanadium Inorganic materials 0.000 description 11
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 238000000605 extraction Methods 0.000 description 8
- -1 olefin compound Chemical class 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 125000003545 alkoxy group Chemical group 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 4
- CTMHWPIWNRWQEG-UHFFFAOYSA-N 1-methylcyclohexene Chemical compound CC1=CCCCC1 CTMHWPIWNRWQEG-UHFFFAOYSA-N 0.000 description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 238000006735 epoxidation reaction Methods 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 229910052707 ruthenium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 150000004965 peroxy acids Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- GRWFGVWFFZKLTI-IUCAKERBSA-N (-)-α-pinene Chemical compound CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- VQOXUMQBYILCKR-UHFFFAOYSA-N 1-Tridecene Chemical compound CCCCCCCCCCCC=C VQOXUMQBYILCKR-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- PJLHTVIBELQURV-UHFFFAOYSA-N 1-pentadecene Chemical compound CCCCCCCCCCCCCC=C PJLHTVIBELQURV-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 2
- WGLLSSPDPJPLOR-UHFFFAOYSA-N 2,3-dimethylbut-2-ene Chemical compound CC(C)=C(C)C WGLLSSPDPJPLOR-UHFFFAOYSA-N 0.000 description 2
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 2
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 2
- JMMZCWZIJXAGKW-UHFFFAOYSA-N 2-methylpent-2-ene Chemical compound CCC=C(C)C JMMZCWZIJXAGKW-UHFFFAOYSA-N 0.000 description 2
- IBVJWOMJGCHRRW-UHFFFAOYSA-N 3,7,7-Trimethylbicyclo[4.1.0]hept-2-ene Chemical compound C1CC(C)=CC2C(C)(C)C12 IBVJWOMJGCHRRW-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- BQOFWKZOCNGFEC-UHFFFAOYSA-N carene Chemical compound C1C(C)=CCC2C(C)(C)C12 BQOFWKZOCNGFEC-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 229960004830 cetylpyridinium Drugs 0.000 description 2
- RLGQACBPNDBWTB-UHFFFAOYSA-N cetyltrimethylammonium ion Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)C RLGQACBPNDBWTB-UHFFFAOYSA-N 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
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- 125000003700 epoxy group Chemical group 0.000 description 2
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- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
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- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
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- 239000011574 phosphorus Substances 0.000 description 2
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- 238000000746 purification Methods 0.000 description 2
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- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
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- 239000005770 Eugenol Substances 0.000 description 1
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- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
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- VHVOLFRBFDOUSH-UHFFFAOYSA-N Isosafrole Natural products CC=CC1=CC=C2OCOC2=C1 VHVOLFRBFDOUSH-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
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- QROGIFZRVHSFLM-QHHAFSJGSA-N [(e)-prop-1-enyl]benzene Chemical compound C\C=C\C1=CC=CC=C1 QROGIFZRVHSFLM-QHHAFSJGSA-N 0.000 description 1
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- 238000004458 analytical method Methods 0.000 description 1
- YOUGRGFIHBUKRS-UHFFFAOYSA-N benzyl(trimethyl)azanium Chemical compound C[N+](C)(C)CC1=CC=CC=C1 YOUGRGFIHBUKRS-UHFFFAOYSA-N 0.000 description 1
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- HQABUPZFAYXKJW-UHFFFAOYSA-O butylazanium Chemical compound CCCC[NH3+] HQABUPZFAYXKJW-UHFFFAOYSA-O 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
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- 239000003795 chemical substances by application Substances 0.000 description 1
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- BJIOGJUNALELMI-ARJAWSKDSA-N cis-isoeugenol Chemical compound COC1=CC(\C=C/C)=CC=C1O BJIOGJUNALELMI-ARJAWSKDSA-N 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- UCIYGNATMHQYCT-OWOJBTEDSA-N cyclodecene Chemical compound C1CCCC\C=C\CCC1 UCIYGNATMHQYCT-OWOJBTEDSA-N 0.000 description 1
- HYPABJGVBDSCIT-UPHRSURJSA-N cyclododecene Chemical compound C1CCCCC\C=C/CCCC1 HYPABJGVBDSCIT-UPHRSURJSA-N 0.000 description 1
- ZXIJMRYMVAMXQP-UHFFFAOYSA-N cycloheptene Chemical compound C1CCC=CCC1 ZXIJMRYMVAMXQP-UHFFFAOYSA-N 0.000 description 1
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 description 1
- 239000004913 cyclooctene Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- UURSXESKOOOTOV-UHFFFAOYSA-N dec-5-ene Chemical compound CCCCC=CCCCC UURSXESKOOOTOV-UHFFFAOYSA-N 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
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- PROQIPRRNZUXQM-ZXXIGWHRSA-N estriol Chemical compound OC1=CC=C2[C@H]3CC[C@](C)([C@H]([C@H](O)C4)O)[C@@H]4[C@@H]3CCC2=C1 PROQIPRRNZUXQM-ZXXIGWHRSA-N 0.000 description 1
- LDLDYFCCDKENPD-UHFFFAOYSA-N ethenylcyclohexane Chemical compound C=CC1CCCCC1 LDLDYFCCDKENPD-UHFFFAOYSA-N 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229960002217 eugenol Drugs 0.000 description 1
- 229910052587 fluorapatite Inorganic materials 0.000 description 1
- 229940077441 fluorapatite Drugs 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- LCWMKIHBLJLORW-UHFFFAOYSA-N gamma-carene Natural products C1CC(=C)CC2C(C)(C)C21 LCWMKIHBLJLORW-UHFFFAOYSA-N 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000011964 heteropoly acid Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 229910001411 inorganic cation Inorganic materials 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 1
- YULMNMJFAZWLLN-UHFFFAOYSA-N methylenecyclohexane Chemical compound C=C1CCCCC1 YULMNMJFAZWLLN-UHFFFAOYSA-N 0.000 description 1
- WPHGSKGZRAQSGP-UHFFFAOYSA-N methylenecyclohexane Natural products C1CCCC2CC21 WPHGSKGZRAQSGP-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- YCBSHDKATAPNIA-UHFFFAOYSA-N non-3-ene Chemical compound CCCCCC=CCC YCBSHDKATAPNIA-UHFFFAOYSA-N 0.000 description 1
- KPADFPAILITQBG-UHFFFAOYSA-N non-4-ene Chemical compound CCCCC=CCCC KPADFPAILITQBG-UHFFFAOYSA-N 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- IRUCBBFNLDIMIK-UHFFFAOYSA-N oct-4-ene Chemical compound CCCC=CCCC IRUCBBFNLDIMIK-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 229930015698 phenylpropene Natural products 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- GRWFGVWFFZKLTI-UHFFFAOYSA-N rac-alpha-Pinene Natural products CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- BJIOGJUNALELMI-UHFFFAOYSA-N trans-isoeugenol Natural products COC1=CC(C=CC)=CC=C1O BJIOGJUNALELMI-UHFFFAOYSA-N 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical class [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/04—Ortho-condensed systems
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Epoxy Compounds (AREA)
Description
工程(1):(a)炭素−炭素二重結合を有する化合物、(b)過酸化水素水、(c)固体担体の粉末及び(d)固体触媒の粉末、あるいはさらに(e)有機溶媒の共在下に、炭素−炭素二重結合を有する化合物と過酸化水素を反応させてエポキシ化合物を製造する工程。
工程(2):前記工程(1)の反応混合物から反応物であるエポキシ化合物を分離する工程。
工程(3):前記工程(2)で反応物を分離した後の固体担体及び固体触媒からなる粉末の混合物に、(d)固体触媒の粉末を添加するとともに、(a)炭素−炭素二重結合を有する化合物及び(b)過酸化水素水、あるいはさらに(e)有機溶媒を添加する工程。
工程(1):(a)炭素−炭素二重結合を有する化合物、(b)過酸化水素水、(c)固体担体の粉末及び(d)固体触媒の粉末、あるいはさらに(e)有機溶媒の共在下に、炭素−炭素二重結合を有する化合物と過酸化水素を反応させてエポキシ化合物を製造する工程。
工程(2):前記工程(1)の反応混合物から反応物であるエポキシ化合物を分離する工程。
工程(3):前記工程(2)で反応物を分離した後の固体担体及び固体触媒からなる粉末の混合物に、(d)固体触媒の粉末を添加するとともに、(a)炭素−炭素二重結合を有する化合物及び(b)過酸化水素水、あるいはさらに(e)有機溶媒を添加する工程。
アルコキシ基としては、炭素数1〜10のアルコキシ基が好ましく、炭素数1〜4のアルコキシ基がより好ましい。アルコキシ基が置換基を有するとき、当該置換基としては、ハロゲン原子、アルコキシ基等が挙げられる。
固体触媒の量は、固体担体の5〜60質量%であることが好ましく、より好ましくは10〜50質量%である。5質量%未満では反応速度が低下するため式(1)の化合物を収率よく得られない。60質量%を超えて用いても収率は向上せず、工業的に不利となる。
固体担体及び固体触媒は、(a)1mmolに対して、0.01〜0.4g程度の範囲で用いることができるが、0.05〜0.2gが望ましい。
また、反応時間は一般に1〜24時間が好ましく、1〜12時間がより好ましい。1時間未満では反応の進行が十分でないため収率が低下し、24時間を超えると生産性が低下する。
反応物の分離方法は特に限定されるものではなく、例えばろ過や遠心分離、溶剤抽出等が挙げられる。分離された固相は水や有機溶剤を用いて洗浄してもよい。一般的には反応後の(a)〜(e)及び反応物を含む混合物のろ過を行い、有機溶剤を用いて残渣(主に固体担体及び固体触媒を含む粉末の混合物)を洗浄する方法が簡便で有利である。
エポキシ化合物の塩素含量は、蒸留精製で低減することもでき、アルカリ水溶液洗浄、吸着剤処理等の方法で低減することもできる。
エポキシ化合物の金属含量は、蒸留精製で低減することもでき、アルカリ水溶液洗浄、吸着剤処理等の方法で低減することもできる。
固体触媒の粉末(d)および原料(a)、(b)、(e)の添加の順序は特に限定されず、例えば、工程(2)で反応物を分離した後の固体担体及び固体触媒からなる粉末の混合物に、(d)、(a)、(b)、(e)を同時に添加しても良いし、(d)を加えたのち、(a)、(b)、(e)を加えても良いし、あるいは、(a)、(b)、(e)を加えたのち、(d)を加えても良い。一般的には、スラリーを形成させるのが容易であることから、(a)、(b)、(e)を加えたのち、(d)を加える方が好ましい。
工程(3)での固体触媒の粉末の添加量については、工程(3)で添加する(a)炭素−炭素二重結合を有する化合物の重量に対して1質量%以上20質量%以下であることが好ましく、より好ましくは2質量%以上14質量%以下である。1質量%未満では活性が低く、20質量%を超えると、スラリーを形成させるのが難しい場合がある。
ねじ口試験管に、固体担体であるアパタイト0.50g及び固体触媒である(Cety1Py)9(NH4)[H2W12O42]0.085g(0.015mmol)を秤取り、よく混合した。これらの混合物に、テトラヒドロインデン0.60g(5.0mmol)、35%過酸化水素水0.87g(9.0mmol)を加えた。20℃で6時間攪拌した後、反応混合物をトルエン(1mL×3回)で抽出した。抽出液から溶媒を留去し、粗生成物を得た。粗生成物を蒸留器に仕込み、圧力2mmHgで蒸留を行った。塔頂温度90℃の留分として、テトラヒドロインデンジエポキシド0.43gを得た。生成物の収率(ジエポキシド収率)は57%であった。また、抽出における残渣として固体担体及び固体触媒の混合物0.56gを得た。
固体触媒である(Cety1Py)9(NH4)[H2W12O42]0.028g(0.0050mmol)を秤取り、抽出における残渣0.56gとよく混合した。これらの混合物に、テトラヒドロインデン0.60g(5.0mmol)、35%過酸化水素水0.87g(9.0mmol)を加えた。20℃で6時間攪拌した後、反応混合物をトルエン(1mL×3回)で抽出した。抽出液から溶媒を留去し、粗生成物を得た。粗生成物を蒸留器に仕込み、圧力2mmHgで蒸留を行った。塔頂温度90℃の留分として、テトラヒドロインデンジエポキシド0.43gを得た。生成物の収率(ジエポキシド収率)は57%であった。抽出における残渣である固体担体及び固体触媒を同様にしてさらに繰り返し使用しても、テトラヒドロインデンジエポキシドの収量と収率の低下は見られなかった。
ねじ口試験管に、固体担体であるアパタイト0.50g及び固体触媒である(Cety1Py)9(NH4)[H2W12O42]0.085g(0.015mmol)を秤取り、よく混合した。これらの混合物に、テトラヒドロインデン0.60g(5.0mmol)、トルエン0.31g、35%過酸化水素水0.87g(9.0mmol)を加えた。20℃で6時間攪拌した後、反応混合物をトルエン(1mL×3回)で抽出し、抽出液から溶媒を留去し、粗生成物を得た。粗生成物を蒸留器に仕込み、圧力2mmHgで蒸留を行った。塔頂温度90℃の留分として、テトラヒドロインデンジエポキシド0.40gを得た。生成物の収率(ジエポキシド収率)は53%であった。また、抽出における残渣として固体担体及び固体触媒の混合物0.56gを得た。
固体触媒である(Cety1Py)9(NH4)[H2W12O42]0.028g(0.0050mmol)を秤取り、抽出における残渣0.56gとよく混合した。これらの混合物に、テトラヒドロインデン0.60g(5.0mmol)、35%過酸化水素水0.87g(9.0mmol)を加えた。20℃で6時間攪拌した後、反応混合物をトルエン(1mL×3回)で抽出した。抽出液から溶媒を留去し、粗生成物を得た。粗生成物を蒸留器に仕込み、圧力2mmHgで蒸留を行った。塔頂温度90℃の留分として、テトラヒドロインデンジエポキシド0.43gを得た。生成物の収率(ジエポキシド収率)は56%であった。抽出における残渣である固体担体及び固体触媒を同様にしてさらに繰り返し使用しても、テトラヒドロインデンジエポキシドの収量と収率の低下は見られなかった。
ねじ口試験管に、固体担体であるアパタイト0.50g及び固体触媒である(Cety1Py)9(NH4)[H2W12O42]0.085g(0.015mmol)を秤取り、よく混合した。これらの混合物に、テトラヒドロインデン0.60g(5.0mmol)、35%過酸化水素水0.87g(9.0mmol)を加えた。20℃で6時間攪拌した後、反応混合物をトルエン(1mL×3回)で抽出した。抽出液から溶媒を留去し、粗生成物を得た。粗生成物を蒸留器に仕込み、圧力2mmHgで蒸留を行った。塔頂温度90℃の留分として、テトラヒドロインデンジエポキシド0.43gを得た。生成物の収率(ジエポキシド収率)は57%であった。また、抽出における残渣として固体担体及び固体触媒の混合物0.56gを得た。
抽出における残渣0.56gに、テトラヒドロインデン0.57g(4.8mmol)、35%過酸化水素水0.83g(8.6mmol)を加えた。20℃で6時間攪拌した後、反応混合物をトルエン(1mL×3回)で抽出した。抽出液から溶媒を留去し、粗生成物を得た。粗生成物を蒸留器に仕込み、圧力2mmHgで蒸留を行った。塔頂温度90℃の留分として、テトラヒドロインデンジエポキシド0.094gを得た。生成物の収率(ジエポキシド収率)は13%であった。
Claims (6)
- 炭素−炭素二重結合を有する化合物と過酸化水素を反応させてエポキシ化合物を製造する方法であって、以下の工程(1)、(2)および(3)の工程を繰返しあるいは連続的に行うことを特徴とするエポキシ化合物の製造方法。
工程(1):(a)炭素−炭素二重結合を有する化合物、(b)過酸化水素水、(c)固体担体の粉末及び(d)固体触媒の粉末、あるいはさらに(e)有機溶媒の共在下に、炭素−炭素二重結合を有する化合物と過酸化水素を反応させてエポキシ化合物を製造する工程であって、前記(c)及び(d)の重量の合計が、(a)、(b)及び(e)の重量の合計に対して100質量%以下であり、前記固体担体がリン酸塩類、珪藻土、シリカ、アルミナ、白陶土、シリカアルミナ及びフッ化カルシウムからなる群から選択されるものであり、前記固体触媒がタングステンを含有するイソポリ酸類であり、前記の(a)〜(d)成分、あるいはさらに(e)成分を混合してスラリーとし、前記スラリー中で各成分を接触させる工程。
工程(2):前記工程(1)の反応混合物から反応物であるエポキシ化合物を分離する工程。
工程(3):前記工程(2)で反応物を分離した後の固体担体及び固体触媒からなる粉末の混合物に、(d)固体触媒の粉末を添加するとともに、(a)炭素−炭素二重結合を有する化合物及び(b)過酸化水素水、あるいはさらに(e)有機溶媒を添加する工程であって前記の添加する(d)固体触媒の粉末の量が、前記の添加する(a)炭素―炭素二重結合を有する化合物の質量に対して1質量%以上20質量%以下である工程。 - 前記タングステンを含有するイソポリ酸類が、(NH 4 ) 6 W 7 O 24 、(NH 4 ) 10 [H 2 W 12 O 42 ]、(CetylNMe 3 ) 7 (NH 4 ) 3 [H 2 W 12 O 42 ]、(CetylNMe 3 ) 10 [H 2 W 12 O 42 ]、(CetylPy) 9 (NH 4 )[H 2 W 12 O 42 ]、(CetylPy) 10 [H 2 W 12 O 42 ]、(CetylPy) 4 [W 10 O 32 ]、およびK 4 [W 10 O 32 ]からなる群から選択されるイソポリタングステン酸類であることを特徴とする請求項1に記載のエポキシ化合物の製造方法。
- 前記有機溶媒が、脂肪族炭化水素、芳香族炭化水素、アルコール、エーテル、エステル、アミド、ケトン、ニトリル、スルホン、エポキシ又はこれらの混合物であることを特徴とする請求項1または2に記載のエポキシ化合物の製造方法。
- 前記有機溶媒の量が、炭素−炭素二重結合を有する化合物の重量に対して0質量%ないし500質量%であることを特徴とする請求項1〜3の何れかに記載のエポキシ化合物の製造方法。
- 前記固体担体が、アパタイトであることを特徴とする請求項1〜4の何れかに記載のエポキシ化合物の製造方法。
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