JP5716483B2 - Method for producing 1,3-difluoroacetone - Google Patents
Method for producing 1,3-difluoroacetone Download PDFInfo
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- JP5716483B2 JP5716483B2 JP2011070389A JP2011070389A JP5716483B2 JP 5716483 B2 JP5716483 B2 JP 5716483B2 JP 2011070389 A JP2011070389 A JP 2011070389A JP 2011070389 A JP2011070389 A JP 2011070389A JP 5716483 B2 JP5716483 B2 JP 5716483B2
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- dfip
- difluoroacetone
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- HKIPCXRNASWFRU-UHFFFAOYSA-N 1,3-difluoropropan-2-one Chemical compound FCC(=O)CF HKIPCXRNASWFRU-UHFFFAOYSA-N 0.000 title claims description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- YRIZYWQGELRKNT-UHFFFAOYSA-N 1,3,5-trichloro-1,3,5-triazinane-2,4,6-trione Chemical compound ClN1C(=O)N(Cl)C(=O)N(Cl)C1=O YRIZYWQGELRKNT-UHFFFAOYSA-N 0.000 claims description 10
- BCJCJALHNXSXKE-UHFFFAOYSA-N azado Chemical group C1C(C2)CC3CC1N([O])C2C3 BCJCJALHNXSXKE-UHFFFAOYSA-N 0.000 claims description 10
- 229950009390 symclosene Drugs 0.000 claims description 9
- PVDLUGWWIOGCNH-UHFFFAOYSA-N 1,3-difluoro-2-propanol Chemical compound FCC(O)CF PVDLUGWWIOGCNH-UHFFFAOYSA-N 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 5
- ZLSDEVRDASOICE-UHFFFAOYSA-N 2-azaadamantane Chemical compound C1C(N2)CC3CC1CC2C3 ZLSDEVRDASOICE-UHFFFAOYSA-N 0.000 claims 1
- -1 polycyclic compound Chemical class 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- 239000002904 solvent Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- 238000004821 distillation Methods 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- 239000007800 oxidant agent Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- JRNVZBWKYDBUCA-UHFFFAOYSA-N N-chlorosuccinimide Chemical compound ClN1C(=O)CCC1=O JRNVZBWKYDBUCA-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
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- 229910052731 fluorine Inorganic materials 0.000 description 4
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- 150000003839 salts Chemical class 0.000 description 4
- IBNXYCCLPCGKDM-UHFFFAOYSA-N 1-me-azado Chemical compound C1C(C2)CC3CC2N([O])C1(C)C3 IBNXYCCLPCGKDM-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 3
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- 239000007858 starting material Substances 0.000 description 3
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- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 2
- CINXLCHKHMLIBB-UHFFFAOYSA-N 1-methyl-2-azatricyclo[3.3.1.13,7]decane Chemical compound C1C(C2)CC3CC2NC1(C)C3 CINXLCHKHMLIBB-UHFFFAOYSA-N 0.000 description 2
- VUZNLSBZRVZGIK-UHFFFAOYSA-N 2,2,6,6-Tetramethyl-1-piperidinol Chemical group CC1(C)CCCC(C)(C)N1O VUZNLSBZRVZGIK-UHFFFAOYSA-N 0.000 description 2
- VCBRTBDPBXCBOR-UHFFFAOYSA-N 2-n,2-n,4-n,4-n,6-n,6-n-hexachloro-1,3,5-triazine-2,4,6-triamine Chemical compound ClN(Cl)C1=NC(N(Cl)Cl)=NC(N(Cl)Cl)=N1 VCBRTBDPBXCBOR-UHFFFAOYSA-N 0.000 description 2
- KEPNSIARSTUPGS-UHFFFAOYSA-N 2-n,4-n,6-n-trichloro-1,3,5-triazine-2,4,6-triamine Chemical compound ClNC1=NC(NCl)=NC(NCl)=N1 KEPNSIARSTUPGS-UHFFFAOYSA-N 0.000 description 2
- 229910020366 ClO 4 Inorganic materials 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 229910018286 SbF 6 Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 2
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- MSWVMWGCNZQPIA-UHFFFAOYSA-N 1-fluoropropan-2-one Chemical compound CC(=O)CF MSWVMWGCNZQPIA-UHFFFAOYSA-N 0.000 description 1
- 125000006432 1-methyl cyclopropyl group Chemical group [H]C([H])([H])C1(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000000354 decomposition reaction 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
- 230000001419 dependent effect Effects 0.000 description 1
- 150000001983 dialkylethers Chemical class 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
- 235000019797 dipotassium phosphate Nutrition 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910003439 heavy metal oxide Inorganic materials 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
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- QENHCSSJTJWZAL-UHFFFAOYSA-N magnesium sulfide Chemical compound [Mg+2].[S-2] QENHCSSJTJWZAL-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
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- 238000012544 monitoring process Methods 0.000 description 1
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- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
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- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 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
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl 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])[H] 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011403 purification operation 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
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 125000002948 undecyl 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])[H] 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/30—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with halogen containing compounds, e.g. hypohalogenation
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/006—Catalysts comprising hydrides, coordination complexes or organic compounds comprising organic radicals, e.g. TEMPO
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Description
本発明は、多環式化合物を触媒とする１，３−ジフルオロイソプロパノール（明細書において、「１，３−ＤＦＩＰ」ということがある。）の酸化による１，３−ジフルオロアセトン（明細書において、「１，３−ＤＦＡ」ということがある。）の製造方法に関する。 The present invention relates to 1,3-difluoroacetone (in the specification, by oxidation of 1,3-difluoroisopropanol (in the specification, sometimes referred to as “1,3-DFIP”) catalyzed by a polycyclic compound. It may be referred to as “1,3-DFA”).
１，３−ジフルオロアセトンは医農薬原料として有用な化合物である。１，３−ジフルオロアセトンは、１，３−ジフルオロイソプロパノールを酸化して製造することができ、ＫＭｎＯ４／ＣｕＳＯ４（非特許文献１）や、Ｎａ２Ｃｒ２Ｏ７・２Ｈ２Ｏ／Ｈ２Ｏ，Ｈ２ＳＯ４（非特許文献２）による方法が知られている。 1,3-difluoroacetone is a useful compound as a raw material for medical and agricultural chemicals. 1,3-difluoroacetone can be produced by oxidizing 1,3-difluoroisopropanol, such as KMnO 4 / CuSO 4 (Non-patent Document 1), Na 2 Cr 2 O 7 .2H 2 O / H 2. A method based on O, H 2 SO 4 (Non-patent Document 2) is known.
アルコールのケトン、アルデヒドなどへの酸化にこれらの重金属を使用する方法は環境への影響が懸念され、最近、触媒として２，２，６，６−テトラメチルピペリジン Ｎ−オキシル （明細書において、「ＴＥＭＰＯ」ということがある。）（非特許文献３）や、２−アザアダマンタン Ｎ−オキシル （明細書において、「ＡＺＡＤＯ」ということがある。）または１−メチル−ＡＺＡＤＯ（明細書において、「１−ｍｅｔｈｙｌ−ＡＺＡＤＯ」ということがある。）などのヘテロ環式化合物を用いる酸化が提案されている。 The use of these heavy metals for the oxidation of alcohols to ketones, aldehydes, etc. is concerned with environmental impacts. Recently, 2,2,6,6-tetramethylpiperidine N-oxyl (in the specification, “ TEMPO ”(non-patent document 3), 2-azaadamantane N-oxyl (sometimes referred to as“ AZADO ”in the specification) or 1-methyl-AZADO (in the specification,“ 1 ”). Oxidation using heterocyclic compounds such as “-methyl-AZADO” has been proposed.
特許文献１、２には、ＡＺＡＤＯまたは１−Ｍｅ−ＡＺＡＤＯなどのヘテロ環多環式化合物を触媒として、アルコール類を酸化する方法が記載されているが、１，３−ＤＦＩＰなどの含フッ素イソプロパノールの酸化に関する記述はない。 Patent Documents 1 and 2 describe a method of oxidizing alcohols using a heterocyclic polycyclic compound such as AZADO or 1-Me-AZADO as a catalyst, but fluorine-containing isopropanol such as 1,3-DFIP. There is no description on the oxidation of.
前記のＴＥＭＰＯを触媒として用いる方法（特開平９−１６９６８５）は、反応が十分には速くなく、触媒量を多く必要とする上に、満足しうる収量を得るには実質的に等モル以上のトリクロロイソシアヌル酸を必要とする。 The method using TEMPO as a catalyst (Japanese Patent Laid-Open No. 9-169585) is not sufficiently fast, requires a large amount of catalyst, and is substantially equimolar or more in order to obtain a satisfactory yield. Trichloroisocyanuric acid is required.
そこで、選択率のよい、効率的のよい１，３−ＤＦＡの製造方法を提供する。 Therefore, an efficient method for producing 1,3-DFA with a high selectivity is provided.
本発明者らは上記課題を解決すべく鋭意検討したところ、分子構造理論からはイソプロパノールのメチル基の水素原子をフッ素原子で置き換えると、ＨＯＭＯ−ＬＵＭＯのエネルギーレベルが低下するので酸化しにくくなると予想されたが、１，３−ＤＦＩＰをＡＺＡＤＯ触媒上で酸化すると、簡便かつ効率的に、１，３−ＤＦＡを合成できることを見出し、本発明を完成するに至った。 The present inventors diligently studied to solve the above-mentioned problems. From the molecular structure theory, it is expected that, when the hydrogen atom of the methyl group of isopropanol is replaced with a fluorine atom, the energy level of HOMO-LUMO is lowered, so that it is difficult to oxidize. However, when 1,3-DFIP was oxidized on an AZADO catalyst, it was found that 1,3-DFA could be synthesized simply and efficiently, and the present invention was completed.
すなわち、本発明は次の通りである。 That is, the present invention is as follows.
［発明１］下記式（１） [Invention 1] The following formula (1)
（式中、Ｒ１は互いに同一でも異なっていてもよい電子供与基を表し、Ｎ−ＯはＮ−Ｏ・を表すか、Ｎ−ＯＨを表すか、またはＮ＋（＝Ｏ）Ｘ−を表し、Ｘ−はＦ−、Ｃｌ−、Ｂｒ−、Ｉ−、ＣｌＯ２ −、ＣｌＯ４ −、ＩＯ４ −、ＮＯ２ −、ＮＯ３ −、ＳＯ４ ２−、ＢＦ４ −、ＰＦ６ −、ＳｂＣｌ５ −、ＳｂＦ６ −、ＸｅＦ２ −、（ＣＦ３ＳＯ２）２Ｎ−、ＣＨ３ＣＯ２ −、ＣＦ３ＣＯ２ −、４−ＣＨ３Ｃ６Ｈ４ＳＯ２Ｏ−またはＣＦ３ＳＯ２Ｏ−を表す。）で表される多環式化合物の存在下、１，３−ジフルオロイソプロパノールを酸化剤で酸化する工程を含む１，３−ジフルオロアセトンの製造方法。 (Wherein R 1 represents an electron donating group which may be the same as or different from each other, N—O represents N—O., N—OH, or N + (═O) X − X − represents F − , Cl − , Br − , I − , ClO 2 − , ClO 4 − , IO 4 − , NO 2 − , NO 3 − , SO 4 2− , BF 4 − , PF 6 − , SbCl 5 -, SbF 6 -, XeF 2 -, (CF 3 SO 2) 2 N -, CH 3 CO 2 -, CF 3 CO 2 -, 4-CH 3 C 6 H 4 SO 2 O - or CF 3 SO 2 O -. a represents the presence of a polycyclic compound represented by), the production method of 1,3-difluoro acetone comprising the step of oxidizing with an oxidizing agent 1,3-difluoro isopropanol.
［発明２］多環式化合物が、２−アザアダマンタン Ｎ−オキシルまたは１−メチル−２−アザアダマンタン Ｎ−オキシルである発明１の１，３−ジフルオロアセトンの製造方法。 [Invention 2] The process for producing 1,3-difluoroacetone according to Invention 1, wherein the polycyclic compound is 2-azaadamantane N-oxyl or 1-methyl-2-azaadamantane N-oxyl.
［発明３］前記酸化剤が、トリクロロイソシアヌル酸、Ｎ−クロロスクシンイミド、トリクロロメラミン、ヘキサクロロメラミン、次亜塩素酸またはその塩、および過硫酸カリウムまたはその複塩から選ばれた１種以上の化合物である発明１または２の１，３−ジフルオロアセトンの製造方法。 [Invention 3] The oxidizing agent is one or more compounds selected from trichloroisocyanuric acid, N-chlorosuccinimide, trichloromelamine, hexachloromelamine, hypochlorous acid or a salt thereof, and potassium persulfate or a double salt thereof. A process for producing 1,3-difluoroacetone according to Invention 1 or 2.
［発明４］前記酸化剤が、トリクロロイソシアヌル酸である発明１〜３の何れかの１，３−ジフルオロアセトンの製造方法。 [Invention 4] The process for producing 1,3-difluoroacetone according to any one of Inventions 1 to 3, wherein the oxidizing agent is trichloroisocyanuric acid.
本発明によれば、有毒な重金属酸化物を必要とせずに、穏和な条件において効率よく酸化し、１，３−ジフルオロアセトンをほぼ選択的に高収率で製造することができる。 According to the present invention, 1,3-difluoroacetone can be produced almost selectively and in high yield by oxidizing efficiently under mild conditions without requiring a toxic heavy metal oxide.
本発明では、多環式化合物を触媒として、１，３−ＤＦＩＰを酸化剤で酸化して１，３−ＤＦＡとすることができる。 In the present invention, 1,3-DFIP can be oxidized to 1, 3-DFA using a polycyclic compound as a catalyst and oxidized with an oxidizing agent.
式（１）で表される化合物は、詳細には次の通りである。 The compound represented by Formula (1) is as follows in detail.
（式中、Ｒ１は互いに同一でも異なっていてもよい電子供与基を表し、Ｎ−ＯはＮ−Ｏ・を表すか、Ｎ−ＯＨを表すか、またはＮ＋（＝Ｏ）Ｘ−を表し、Ｘは一価のアニオンを表す。電子供与基としては、水素原子、フッ素原子、ヒドロキシ基、アルキル基（「Ｒ」と表すことがある。）、アルコキシ基などが挙げられる。Ｘ−はＦ−、Ｃｌ−、Ｂｒ−、Ｉ−、ＣｌＯ２ −、ＣｌＯ４ −、ＩＯ４ −、ＮＯ２ −、ＮＯ３ −、ＳＯ４ ２−、ＢＦ４ −、ＰＦ６ −、ＳｂＣｌ５ −、ＳｂＦ６ −、ＸｅＦ２ −、（ＣＦ３ＳＯ２）２Ｎ−、ＣＨ３ＣＯ２ −、ＣＦ３ＣＯ２ −、４−ＣＨ３Ｃ６Ｈ４ＳＯ２Ｏ−またはＣＦ３ＳＯ２Ｏ−を表す。）で表される多環式化合物。 (Wherein R 1 represents an electron donating group which may be the same as or different from each other, N—O represents N—O., N—OH, or N + (═O) X − represents, X is a electron donating group represents a monovalent anion, a hydrogen atom, a fluorine atom, a hydroxy group, an alkyl group, an alkoxy group is .X. (may be represented as "R".) - is F − , Cl − , Br − , I − , ClO 2 − , ClO 4 − , IO 4 − , NO 2 − , NO 3 − , SO 4 2− , BF 4 − , PF 6 − , SbCl 5 − , SbF 6 -, XeF 2 -, ( CF 3 SO 2) 2 N -, CH 3 CO 2 -, CF 3 CO 2 -, 4-CH 3 C 6 H 4 SO 2 O - represents a - or CF 3 SO 2 O .).
アルキル基は、直鎖状、分岐状または環状のアルキル基をいい、例えばメチル基、エチル基、n-プロピル基、i-プロピル基、n-ブチル基、i-ブチル基、s-ブチル基、t-ブチル基、n-ペンチル基、1-メチルブチル基、2-メチルブチル基、3-メチルブチル基、1-エチルプロピル基、１，１−ジメチルプロピル基、１，２−ジメチルプロピル基、２，２−ジメチルプロピル基、ｎ−ヘキシル基、１−メチルペンチル基、２−メチルペンチル基、１，１−ジメチルブチル基、１，３−ジメチルブチル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基等が具体例として挙げられ、これらのうち炭素数１〜３であるのが好ましく、メチル基であるのがより好ましい。また、環状のアルキル基としては、３員環から６員環までの単環または複合環構造を形成することができる。また、環はアルキル基によって任意に置換されていてもよい。例えば置換基としてシクロプロピル基、１−メチルシクロプロピル基、２−メチルシクロプロピル基、２，２−ジメチルシクロプロピル基、２，２，３，３−テトラメチルシクロプロピル基、シクロブチル基、シクロペンチル基、２−メチルシクロペンチル基、３−メチルシクロペンチル基、シクロヘキシル基、２−メチルシクロヘキシル基、３−メチルシクロヘキシル基、４−メチルシクロヘキシル基、ビシクロ［２．２．１］ヘプタン−２−イル基等が具体例として挙げられ、これらのうち、シクロペンチル環、シクロへキシル環またはノルボルネン環を有するものが好ましい。 The alkyl group refers to a linear, branched or cyclic alkyl group, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, n-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylpropyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2 -Dimethylpropyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 1,1-dimethylbutyl group, 1,3-dimethylbutyl group, heptyl group, octyl group, nonyl group, decyl group, Specific examples include an undecyl group, a dodecyl group, and the like. Among these, a group having 1 to 3 carbon atoms is preferable, and a methyl group is more preferable. Moreover, as a cyclic | annular alkyl group, the monocyclic or complex ring structure from a 3-membered ring to a 6-membered ring can be formed. The ring may be optionally substituted with an alkyl group. For example, as a substituent, cyclopropyl group, 1-methylcyclopropyl group, 2-methylcyclopropyl group, 2,2-dimethylcyclopropyl group, 2,2,3,3-tetramethylcyclopropyl group, cyclobutyl group, cyclopentyl group 2-methylcyclopentyl group, 3-methylcyclopentyl group, cyclohexyl group, 2-methylcyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, bicyclo [2.2.1] heptan-2-yl group, etc. Specific examples thereof include those having a cyclopentyl ring, a cyclohexyl ring or a norbornene ring.
アルコキシ基は、前記アルキル基（Ｒ）を用いてＲＯで表される。好ましいアルコキシ基としては、メトキシ基が挙げられる。 The alkoxy group is represented by RO using the alkyl group (R). A preferable alkoxy group includes a methoxy group.
特に好ましい多環式化合物としては、２−アザアダマンタン Ｎ−オキシル（ＡＺＡＤＯ）または１−メチル−２−アザアダマンタン Ｎ−オキシル（１−メチル−２−ＡＺＡＤＯ）が挙げられる。 Particularly preferred polycyclic compounds include 2-azaadamantane N-oxyl (AZADO) or 1-methyl-2-azaadamantane N-oxyl (1-methyl-2-AZADO).
これらの多環式化合物の製造方法は、国際公開第２００９／１４５３２３号パンフレット等に記載され、例えば、１−Ｍｅ−ＡＺＡＤＯは、国際公開第２００６／００１３８７号パンフレット記載の方法で製造することができる。また、AZADO、１−Ｍｅ−ＡＺＡＤＯ、１，３−ジメチル−AZADOなどは市販品を入手することもできる。 The production method of these polycyclic compounds is described in International Publication No. 2009/145323 pamphlet and the like. For example, 1-Me-AZADO can be produced by the method described in International Publication No. 2006/001387 pamphlet. . Moreover, AZADO, 1-Me-AZADO, 1,3-dimethyl-AZADO, etc. can also obtain a commercial item.
酸化剤としては、トリクロロイソシアヌル酸、Ｎ−クロロスクシンイミド、トリクロロメラミン、ヘキサクロロメラミン、次亜塩素酸またはその塩、過硫酸カリウムまたはその複塩（オキソン（Oxone）デュポン社）、ジクロロジエメチルヒダントイン、または塩素などが挙げられる。これらのうち、トリクロロイソシアヌル酸、ジクロロジエメチルヒダントインが好ましい。 Examples of the oxidizing agent include trichloroisocyanuric acid, N-chlorosuccinimide, trichloromelamine, hexachloromelamine, hypochlorous acid or a salt thereof, potassium persulfate or a double salt thereof (Oxone DuPont), dichlorodimethylhydantoin, or Examples include chlorine. Of these, trichloroisocyanuric acid and dichlorodimethylhydantoin are preferable.
１，３−ジフルオロイソプロパノールは、公知の方法で製造したものが使用でき、例えば、クラウンエーテル溶媒中で、エピクロロヒドリンとＫＦ・ＨＦとを反応させて容易に合成可能である。 As the 1,3-difluoroisopropanol, one produced by a known method can be used. For example, it can be easily synthesized by reacting epichlorohydrin with KF.HF in a crown ether solvent.
本発明の方法は、溶媒の存在下または不存在下で行うが、溶媒の存在下で行うことが好ましい。出発原料である１，３−ＤＦＩＰまたは目的化合物である１，３−ＤＦＡを溶媒として使用することもできる。溶媒は有機溶媒単独、水単独、水と有機の混合系でもよいが、１，３−ＤＦＡと溶媒との分離が容易であるので有機溶媒が好ましい。 The method of the present invention is carried out in the presence or absence of a solvent, but is preferably carried out in the presence of a solvent. The starting material 1,3-DFIP or the target compound 1,3-DFA can also be used as a solvent. The solvent may be an organic solvent alone, water alone, or a mixed system of water and organic, but an organic solvent is preferred because it is easy to separate 1,3-DFA from the solvent.
溶媒としては、原料、触媒の適度な溶解度、生成物との分離性、酸化反応に対する安定性等があれば使用できる。水、セロソルブ類（例えばメトキシエタノール、エトキシエタノール等）、非プロトン性極性有機溶媒類（例えばジメチルホルムアミド、ジメチルスルホキシド、ジメチルアセトアミド、テトラメチルウレア、スルホラン、Ｎ−メチルピロリドン、N,N-ジメチルイミダゾリジノン等）、エーテル類（例えばジエチルエーテル、ジイソプロピルエーテル、ｔ−ブチルメチルエーテル、テトラヒドロフラン、ジオキサン等）、脂肪族炭化水素類（例えばペンタン、ヘキサン、ｃ−ヘキサン、オクタン、デカン、デカリン、石油エーテル等）、芳香族炭化水素類（ベンゼン、クロロベンゼン、ｏ−ジクロロベンゼン、ニトロベンゼン、トルエン、キシレン、メシチレン、テトラリン等）、ハロゲン化炭化水素類（例えばクロロホルム、ジクロロメタン、ジクロロエタン、四塩化炭素等）、フッ素系溶媒（例えばトリフルオロメチルベンゼンまたは（ｏ−、ｍ−またはｐ−）ビストリフルオロベンゼン等）、低級脂肪族酸エステル（例えば酢酸メチル、酢酸エチル、酢酸ブチル、プロピオン酸メチル等）、アルコキシアルカン類（例えばジメトキシエタン、ジエトキシエタン等）及びニトリル類（例えばアセトニトリル、プロピオニトリル、ブチロニトリル等）、カルボン酸（例えば酢酸等）等の溶媒が挙げられる。これらの内で、脂肪族炭化水素類（例えばペンタン、ヘキサン、ｃ−ヘキサン等）、芳香族炭化水素類（トルエン、キシレン、メシチレン、等）、ハロゲン化炭化水素類（例えばクロロホルム、ジクロロメタン、ジクロロエタン等）、フッ素系溶媒（例えばトリフルオロメチルベンゼンまたは（ｏ−、ｍ−またはｐ−）ビストリフルオロベンゼン等）が好ましい。また、その中でも、ジクロロメタンが好ましい。さらに、原料である１，３−ＤＦＩＰ、生成物である１，３−ＤＦＡを使用することもできる。 Any solvent can be used as long as it has an appropriate solubility of the raw materials and catalyst, separability from the product, stability to oxidation reaction, and the like. Water, cellosolves (eg, methoxyethanol, ethoxyethanol, etc.), aprotic polar organic solvents (eg, dimethylformamide, dimethylsulfoxide, dimethylacetamide, tetramethylurea, sulfolane, N-methylpyrrolidone, N, N-dimethylimidazolide) Non), ethers (eg, diethyl ether, diisopropyl ether, t-butyl methyl ether, tetrahydrofuran, dioxane, etc.), aliphatic hydrocarbons (eg, pentane, hexane, c-hexane, octane, decane, decalin, petroleum ether, etc.) ), Aromatic hydrocarbons (benzene, chlorobenzene, o-dichlorobenzene, nitrobenzene, toluene, xylene, mesitylene, tetralin, etc.), halogenated hydrocarbons (eg, chloroform, dichloromethane) , Dichloroethane, carbon tetrachloride, etc.), fluorinated solvents (such as trifluoromethylbenzene or (o-, m- or p-) bistrifluorobenzene), lower aliphatic acid esters (such as methyl acetate, ethyl acetate, butyl acetate) , Methyl propionate etc.), alkoxyalkanes (eg dimethoxyethane, diethoxyethane etc.) and nitriles (eg acetonitrile, propionitrile, butyronitrile etc.), carboxylic acids (eg acetic acid etc.) and the like. Among these, aliphatic hydrocarbons (eg, pentane, hexane, c-hexane, etc.), aromatic hydrocarbons (toluene, xylene, mesitylene, etc.), halogenated hydrocarbons (eg, chloroform, dichloromethane, dichloroethane, etc.) ) Or a fluorine-based solvent (for example, trifluoromethylbenzene or (o-, m- or p-) bistrifluorobenzene). Of these, dichloromethane is preferred. Furthermore, 1,3-DFIP as a raw material and 1,3-DFA as a product can also be used.
出発原料である１，３−ＤＦＩＰの溶媒中の濃度は、１，３−ＤＦＩＰを溶媒として用いる場合以外は、好ましくは１〜９９質量％であり、５〜５０質量％がより好ましい。 The concentration of 1,3-DFIP as a starting material in the solvent is preferably 1 to 99% by mass, and more preferably 5 to 50% by mass, except when 1,3-DFIP is used as the solvent.
本発明の製造方法において、pＨ調整剤を添加することもできる。pＨ調整剤としては、特に限定されないが、炭酸水素ナトリウム、炭酸水素カリウム、リン酸水素ナトリウム、リン酸二水素ナトリウム、リン酸水素カリウム、リン酸二水素カリウム、炭酸カリウム、炭酸ナトリウムなどがあげられる。反応液は酸性から弱アルカリ性にpH制御することが好ましい。強アルカリ条件とするのは、二量体が生成し、または、分子内脱ＨＦ反応が生じてモノフルオロ化合物が副生する虞があるので好ましくない。 In the production method of the present invention, a pH adjusting agent may be added. The pH adjusting agent is not particularly limited, and examples thereof include sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydrogen phosphate, sodium dihydrogen phosphate, potassium hydrogen phosphate, potassium dihydrogen phosphate, potassium carbonate, sodium carbonate and the like. . The pH of the reaction solution is preferably controlled from acidic to weakly alkaline. The strong alkali condition is not preferable because a dimer may be generated or an intramolecular deHF reaction may occur and a monofluoro compound may be by-produced.
反応温度は、−５０℃〜＋１００℃であり、−５０℃〜＋５０℃が好ましく、０℃から２０℃がより好ましい。−５０℃未満では反応が遅くなることがあり、＋１００℃以上では、反応制御が困難となり、または副反応がおこることがあり好ましくない。反応は、常圧（大気圧）で行えるが、必要に応じて、０．００１〜１０ＭＰａでも実施できる。通常は、室温で、常圧が行なうのが好ましい。 The reaction temperature is -50 ° C to + 100 ° C, preferably -50 ° C to + 50 ° C, more preferably 0 ° C to 20 ° C. If it is less than −50 ° C., the reaction may be slow, and if it is + 100 ° C. or more, reaction control becomes difficult or side reaction may occur, which is not preferable. The reaction can be carried out at normal pressure (atmospheric pressure), but can be carried out at 0.001 to 10 MPa as necessary. Usually, normal pressure is preferably performed at room temperature.
反応時間は反応条件により必ずしも一定しないが、通常１分〜１００時間であり、好ましくは５分〜２４時間である。 The reaction time is not necessarily constant depending on the reaction conditions, but is usually 1 minute to 100 hours, preferably 5 minutes to 24 hours.
本発明の製造方法では、反応試剤、副資材の添加の方法は特に限られず、非常に小さなスケールの場合、１，３−ＤＦＩＰ、酸化剤、触媒、溶媒等を同時に仕込んで反応することも可能であるが、反応の進行に応じて、逐次的または連続的に酸化剤を添加することは反応のコントロールができ、安全であるので好ましい。 In the production method of the present invention, the method of adding the reaction reagent and auxiliary materials is not particularly limited. In the case of a very small scale, 1,3-DFIP, an oxidizing agent, a catalyst, a solvent, and the like can be charged and reacted simultaneously. However, it is preferable to add an oxidizing agent sequentially or continuously according to the progress of the reaction because the reaction can be controlled and is safe.
反応の進行はガスクロマトグラフ、１Ｈ−ＮＭＲまたは１９Ｆ−ＮＭＲで出発原料の消費または生成物の増加を監視して知ることができる。反応の完了後、反応器内の反応混合物から１，３−ＤＦＡを取り出すには、一般的な有機化学の手法を用いればよく、溶媒の留去、抽出、蒸留、濾過、デカント、カラムクロマトグラフィー等の通常の精製操作により、単離することができる。 The progress of the reaction can be known by monitoring the consumption of starting materials or the increase in products by gas chromatography, 1 H-NMR or 19 F-NMR. After completion of the reaction, 1,3-DFA can be taken out from the reaction mixture in the reactor by using a general organic chemistry method, such as solvent distillation, extraction, distillation, filtration, decantation, column chromatography. It can be isolated by a conventional purification operation such as
例えば、次の様な蒸留により行うことができる。反応混合物をそのまま、または反応混合物に水を添加したのち減圧条件下で蒸留する。添加する水の量に制限はない。減圧蒸留を行う際の圧力は、蒸留装置に依存するが３０００〜７００００Ｐａで行える。蒸留時の１，３−ＤＦＡ留分の留出温度（蒸留塔の塔頂温度）は前記圧力条件下では、９０℃以下である。蒸留時の圧力を調節して留出温度を３０〜７５℃とすると、１，３−ジフルオロアセトンの分解が十分抑制され、かつ工業的な操作も容易となる。 For example, it can be carried out by the following distillation. The reaction mixture is distilled as it is or after adding water to the reaction mixture under reduced pressure. There is no limit to the amount of water added. Although the pressure at the time of carrying out vacuum distillation is dependent on a distillation apparatus, it can carry out at 3000-70000Pa. The distillation temperature of the 1,3-DFA fraction during distillation (the top temperature of the distillation column) is 90 ° C. or less under the pressure conditions. If the distillation temperature is adjusted to 30 to 75 ° C. by adjusting the pressure during distillation, decomposition of 1,3-difluoroacetone is sufficiently suppressed, and industrial operation is facilitated.
留出物には１，３−ジフルオロアセトンの他に水を含むことがある。この水を除くためには、一般的な有機合成の精製の手法を用いればよく、特に限定されない。例えば固体の乾燥剤を添加して水分を乾燥剤に吸着させる。乾燥剤としては、無水塩化カルシウム、ゼオライト、無水硫化マグネシウムなど、汎用の乾燥剤を用いれば良い。また低沸点溶媒としては、ジエチルエーテル、ターシャリーブチルメチルエーテルなどのエーテル類を使用すると、溶媒留去を行い易く好ましい。 The distillate may contain water in addition to 1,3-difluoroacetone. In order to remove this water, a general organic synthesis purification method may be used, and there is no particular limitation. For example, a solid desiccant is added to adsorb moisture to the desiccant. As the desiccant, a general-purpose desiccant such as anhydrous calcium chloride, zeolite, or anhydrous magnesium sulfide may be used. As the low boiling point solvent, it is preferable to use ethers such as diethyl ether and tertiary butyl methyl ether because the solvent can be easily distilled off.
本発明の方法で用いる触媒（多環式化合物）の量は、１，３−ＤＦＩＰに対して好ましくは０．０１モル％〜５０モル％、より好ましくは０．１モル％〜１０モル％である。 The amount of the catalyst (polycyclic compound) used in the method of the present invention is preferably 0.01 mol% to 50 mol%, more preferably 0.1 mol% to 10 mol%, relative to 1,3-DFIP. is there.
本発明の方法で用いる酸化剤の量としては、１，３−ＤＦＩＰに対して１モル％〜１００モル％、好ましくは、１モル％〜５０モル％である。 The amount of the oxidizing agent used in the method of the present invention is 1 mol% to 100 mol%, preferably 1 mol% to 50 mol% with respect to 1,3-DFIP.
反応時間は反応条件により必ずしも一定しないが、通常１分〜１００時間であり、好ましくは５分〜２４時間である。 The reaction time is not necessarily constant depending on the reaction conditions, but is usually 1 minute to 100 hours, preferably 5 minutes to 24 hours.
以下に、実施例を以て本発明を説明するが、本発明はこれらの実施態様に限られない。 Hereinafter, the present invention will be described by way of examples, but the present invention is not limited to these embodiments.
［実施例１］
ドライアイスで冷却したコンデンサーと温度計を備えた３００ｍL四つ口フラスコに、１，３−ジフルオロイソプロピルアルコール（１，３−ＤＦＩＰ）９．６１ｇ（０．１ｍｏｌ）、ジクロロメタン２００ｍＬ、内部標準物質としてｐ−トリフルオロメチルベンゾトリフルオライド（ＰＴＦ−ＴＦＭ）７．１６ｇ（０．０３ｍｏｌ）を加え、氷水浴に浸して攪拌、冷却した。ＡＺＡＤＯ ０．０２４ｇ（０．１６ｍｏｌ％）を加え均一溶解した時、１９Ｆ−ＮＭＲ測定したところ、１，３−ＤＦＩＰ／ＰＴＦ−ＴＦＭ比（モル比）が０．８４８１であった。その後２．５時間に亘り、トリクロロイソシアヌル酸（ＴＣＣＡ）１７．６１ｇ（０．０７６ｍｏｌ）を１．８０〜２．０８ｇずつ９回に分けて添加した。ＴＣＣＡ添加終了後、室温で３０分熟成したのち、ガスクロマトグラフ分析したところ、１，３−ＤＦＩＰの変換率は９９．３％であった。反応液を１９Ｆ−ＮＭＲ測定したところ、１，３−ＤＦＩＰの変換率は９９．１％であった。１，３−ジフルオロアセトン（１，３−ＤＦＡ）／ＰＴＦ−ＴＦＭ比が０．８２８９で１，３−ＤＦＡ収率が９６．８％であった。モノフルオロアセトンは認められなかった。
[Example 1]
In a 300 mL four-necked flask equipped with a condenser cooled by dry ice and a thermometer, 9.61 g (0.1 mol) of 1,3-difluoroisopropyl alcohol (1,3-DFIP), 200 mL of dichloromethane, p as an internal standard substance -Trifluoromethylbenzotrifluoride (PTF-TFM) 7.16 g (0.03 mol) was added, and the mixture was immersed in an ice-water bath and stirred and cooled. When 0.024 g (0.16 mol%) of AZADO was added and uniformly dissolved, 19 F-NMR measurement revealed that the 1,3-DFIP / PTF-TFM ratio (molar ratio) was 0.8481. Thereafter, over the course of 2.5 hours, 17.61 g (0.076 mol) of trichloroisocyanuric acid (TCCA) was added in 9.80 parts in 1.80 to 2.08 parts. After completion of the TCCA addition, the mixture was aged at room temperature for 30 minutes and analyzed by gas chromatography. As a result, the conversion rate of 1,3-DFIP was 99.3%. When the reaction solution was measured by 19 F-NMR, the conversion of 1,3-DFIP was 99.1%. The 1,3-difluoroacetone (1,3-DFA) / PTF-TFM ratio was 0.8289, and the 1,3-DFA yield was 96.8%. Monofluoroacetone was not observed.
［１９Ｆ−ＮＭＲ（ＣＤＣｌ３、標準物質ＣＣｌ３Ｆ）］
１，３−ＤＦＩＰ −２３４．２ｐｐｍ（２Ｆ、ｄｔ、ＪＦ−Ｈ＝４８．８Ｈｚ、ＪＦ−Ｈ＝１８．３Ｈｚ）、１，３−ＤＦＡ −２３９．６ｐｐｍ（２Ｆ、ｔ、ＪＦ−Ｈ＝４５．８Ｈｚ）、ＰＴＦ−ＴＦＭ −６３．６ｐｐｍ （６Ｆ、ｓ）
［比較例１］
コンデンサーを備えた、５０ｍＬ二口フラスコに、１，３−ＤＦＩＰ０．４８ｇ（０．００５ｍｏｌ）、ジクロロメタン２０ｍＬ、２，２，６，６−テトラメチルピペリジン Ｎ−オキシル（ＴＥＭＰＯ）０．００８ｇ（１ｍｏｌ％）、ＴＣＣＡ１．２２ｇ（０．００５３ｍｏｌ）を添加し、室温下、６時間攪拌したのち、ガスクロマトグラフ分析したところ、１，３−ＤＦＡの収率は６９％であった。
[ 19 F-NMR (CDCl 3 , standard substance CCl 3 F)]
1,3-DFIP-234.2 ppm (2F, dt, JF-H = 48.8 Hz, JF-H = 18.3 Hz), 1,3-DFA-239.6 ppm (2F, t, JF-H = 45) .8 Hz), PTF-TFM-63.6 ppm (6F, s)
[Comparative Example 1]
In a 50 mL two-necked flask equipped with a condenser, 1,3-DFIP 0.48 g (0.005 mol), dichloromethane 20 mL, 2,2,6,6-tetramethylpiperidine N-oxyl (TEMPO) 0.008 g (1 mol%) ), 1.22 g (0.0053 mol) of TCCA was added, and the mixture was stirred at room temperature for 6 hours. After gas chromatographic analysis, the yield of 1,3-DFA was 69%.
本発明の製造方法は、１，３−ＤＦＡの工業的製法に適用できる。 The production method of the present invention can be applied to an industrial production method of 1,3-DFA.
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