JP6941918B2 - Method for Producing Alkali Metal Salt of Sulfonimide - Google Patents
Method for Producing Alkali Metal Salt of Sulfonimide Download PDFInfo
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- JP6941918B2 JP6941918B2 JP2016015214A JP2016015214A JP6941918B2 JP 6941918 B2 JP6941918 B2 JP 6941918B2 JP 2016015214 A JP2016015214 A JP 2016015214A JP 2016015214 A JP2016015214 A JP 2016015214A JP 6941918 B2 JP6941918 B2 JP 6941918B2
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- Prior art keywords
- group
- carbon atoms
- linear
- general formula
- alkyl group
- Prior art date
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- -1 Alkali Metal Salt Chemical class 0.000 title claims description 26
- JHRWWRDRBPCWTF-OLQVQODUSA-N captafol Chemical compound C1C=CC[C@H]2C(=O)N(SC(Cl)(Cl)C(Cl)Cl)C(=O)[C@H]21 JHRWWRDRBPCWTF-OLQVQODUSA-N 0.000 title claims description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- 229910052783 alkali metal Inorganic materials 0.000 title claims description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 25
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 14
- 125000001424 substituent group Chemical group 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- 229940124530 sulfonamide Drugs 0.000 claims description 10
- 150000003456 sulfonamides Chemical class 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- 125000000304 alkynyl group Chemical group 0.000 claims description 9
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 8
- 125000003342 alkenyl group Chemical group 0.000 claims description 7
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 229910000103 lithium hydride Inorganic materials 0.000 claims description 5
- 150000003461 sulfonyl halides Chemical class 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- ONWRSBMOCIQLRK-UHFFFAOYSA-N 2-phenylethenesulfonyl chloride Chemical compound ClS(=O)(=O)C=CC1=CC=CC=C1 ONWRSBMOCIQLRK-UHFFFAOYSA-N 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- SIAPCJWMELPYOE-UHFFFAOYSA-N lithium hydride Chemical compound [LiH] SIAPCJWMELPYOE-UHFFFAOYSA-N 0.000 claims 2
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 150000002367 halogens Chemical class 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000002994 raw material Substances 0.000 description 14
- 150000003949 imides Chemical class 0.000 description 13
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 13
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 229910003002 lithium salt Inorganic materials 0.000 description 9
- 159000000002 lithium salts Chemical class 0.000 description 9
- 159000000000 sodium salts Chemical class 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 5
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 5
- 150000003512 tertiary amines Chemical class 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 4
- 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 4
- 239000012776 electronic material Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 3
- 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 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 3
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 125000006431 methyl cyclopropyl group Chemical group 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 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 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 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 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 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 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N 2-Methylpentane Chemical compound CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
- GXDHCNNESPLIKD-UHFFFAOYSA-N 2-methylhexane Chemical compound CCCCC(C)C GXDHCNNESPLIKD-UHFFFAOYSA-N 0.000 description 2
- VLJXXKKOSFGPHI-UHFFFAOYSA-N 3-methylhexane Chemical compound CCCC(C)CC VLJXXKKOSFGPHI-UHFFFAOYSA-N 0.000 description 2
- PFEOZHBOMNWTJB-UHFFFAOYSA-N 3-methylpentane Chemical compound CCC(C)CC PFEOZHBOMNWTJB-UHFFFAOYSA-N 0.000 description 2
- VHEKFTULOYIMSU-UHFFFAOYSA-N 4-ethenylbenzenesulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=C(C=C)C=C1 VHEKFTULOYIMSU-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- DIKBFYAXUHHXCS-UHFFFAOYSA-N bromoform Chemical compound BrC(Br)Br DIKBFYAXUHHXCS-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- NDJKXXJCMXVBJW-UHFFFAOYSA-N heptadecane Chemical compound CCCCCCCCCCCCCCCCC NDJKXXJCMXVBJW-UHFFFAOYSA-N 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 2
- YCOZIPAWZNQLMR-UHFFFAOYSA-N pentadecane Chemical compound CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 description 2
- KAKQVSNHTBLJCH-UHFFFAOYSA-N trifluoromethanesulfonimidic acid Chemical compound NS(=O)(=O)C(F)(F)F KAKQVSNHTBLJCH-UHFFFAOYSA-N 0.000 description 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- APQIUTYORBAGEZ-UHFFFAOYSA-N 1,1-dibromoethane Chemical compound CC(Br)Br APQIUTYORBAGEZ-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- WQONPSCCEXUXTQ-UHFFFAOYSA-N 1,2-dibromobenzene Chemical compound BrC1=CC=CC=C1Br WQONPSCCEXUXTQ-UHFFFAOYSA-N 0.000 description 1
- CZWSZZHGSNZRMW-UHFFFAOYSA-N 1,2-dibromobutane Chemical compound CCC(Br)CBr CZWSZZHGSNZRMW-UHFFFAOYSA-N 0.000 description 1
- XFNJYAKDBJUJAJ-UHFFFAOYSA-N 1,2-dibromopropane Chemical compound CC(Br)CBr XFNJYAKDBJUJAJ-UHFFFAOYSA-N 0.000 description 1
- PQBOTZNYFQWRHU-UHFFFAOYSA-N 1,2-dichlorobutane Chemical compound CCC(Cl)CCl PQBOTZNYFQWRHU-UHFFFAOYSA-N 0.000 description 1
- KNKRKFALVUDBJE-UHFFFAOYSA-N 1,2-dichloropropane Chemical compound CC(Cl)CCl KNKRKFALVUDBJE-UHFFFAOYSA-N 0.000 description 1
- JSRLURSZEMLAFO-UHFFFAOYSA-N 1,3-dibromobenzene Chemical compound BrC1=CC=CC(Br)=C1 JSRLURSZEMLAFO-UHFFFAOYSA-N 0.000 description 1
- XZNGUVQDFJHPLU-UHFFFAOYSA-N 1,3-dibromobutane Chemical compound CC(Br)CCBr XZNGUVQDFJHPLU-UHFFFAOYSA-N 0.000 description 1
- VEFLKXRACNJHOV-UHFFFAOYSA-N 1,3-dibromopropane Chemical compound BrCCCBr VEFLKXRACNJHOV-UHFFFAOYSA-N 0.000 description 1
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 description 1
- QBGVARBIQGHVKR-UHFFFAOYSA-N 1,3-dichlorobutane Chemical compound CC(Cl)CCCl QBGVARBIQGHVKR-UHFFFAOYSA-N 0.000 description 1
- YHRUOJUYPBUZOS-UHFFFAOYSA-N 1,3-dichloropropane Chemical compound ClCCCCl YHRUOJUYPBUZOS-UHFFFAOYSA-N 0.000 description 1
- SWJPEBQEEAHIGZ-UHFFFAOYSA-N 1,4-dibromobenzene Chemical compound BrC1=CC=C(Br)C=C1 SWJPEBQEEAHIGZ-UHFFFAOYSA-N 0.000 description 1
- ULTHEAFYOOPTTB-UHFFFAOYSA-N 1,4-dibromobutane Chemical compound BrCCCCBr ULTHEAFYOOPTTB-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- KJDRSWPQXHESDQ-UHFFFAOYSA-N 1,4-dichlorobutane Chemical compound ClCCCCCl KJDRSWPQXHESDQ-UHFFFAOYSA-N 0.000 description 1
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 description 1
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 description 1
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 1
- BXXWFOGWXLJPPA-UHFFFAOYSA-N 2,3-dibromobutane Chemical compound CC(Br)C(C)Br BXXWFOGWXLJPPA-UHFFFAOYSA-N 0.000 description 1
- RMISVOPUIFJTEO-UHFFFAOYSA-N 2,3-dichlorobutane Chemical compound CC(Cl)C(C)Cl RMISVOPUIFJTEO-UHFFFAOYSA-N 0.000 description 1
- UPSXAPQYNGXVBF-UHFFFAOYSA-N 2-bromobutane Chemical compound CCC(C)Br UPSXAPQYNGXVBF-UHFFFAOYSA-N 0.000 description 1
- NAMYKGVDVNBCFQ-UHFFFAOYSA-N 2-bromopropane Chemical compound CC(C)Br NAMYKGVDVNBCFQ-UHFFFAOYSA-N 0.000 description 1
- BSPCSKHALVHRSR-UHFFFAOYSA-N 2-chlorobutane Chemical compound CCC(C)Cl BSPCSKHALVHRSR-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- BJEMXPVDXFSROA-UHFFFAOYSA-N 3-butylbenzene-1,2-diol Chemical compound CCCCC1=CC=CC(O)=C1O BJEMXPVDXFSROA-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229950005228 bromoform Drugs 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 1
- 229940078552 o-xylene Drugs 0.000 description 1
- 229940038384 octadecane Drugs 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Description
本発明は、電子材料等の原料あるいは合成中間体として工業的に重要なスルホンイミドのアルカリ金属塩の製造方法に関するものである。 The present invention relates to a method for producing an alkali metal salt of sulfonimide, which is industrially important as a raw material for electronic materials or a synthetic intermediate.
従来、スルホンイミドのアルカリ金属塩を製造する方法としては、以下の二工程よりなる方法が知られている。すなわち、スルホニルクロリド、スルホンアミドと三級アミンを反応させてスルホンイミドのアミン塩を得る工程と、得られたアミン塩にアルカリ金属塩を反応させることでスルホンイミドのアルカリ金属塩を得る工程からなる製造方法である（例えば特許文献１参照）。また、スルホニルクロリドとスルホンアミドを、塩基を使わずに反応させる方法についても例示されている（例えば特許文献２参照）。 Conventionally, as a method for producing an alkali metal salt of sulfonimide, a method including the following two steps is known. That is, it comprises a step of reacting a sulfonyl chloride or sulfonamide with a tertiary amine to obtain an amine salt of sulfonimide, and a step of reacting the obtained amine salt with an alkali metal salt to obtain an alkali metal salt of sulfonimide. This is a manufacturing method (see, for example, Patent Document 1). Further, a method of reacting a sulfonyl chloride with a sulfonamide without using a base is also exemplified (see, for example, Patent Document 2).
特許文献１において、原料である三級アミンは、スルホンイミドのアミン塩を形成させるだけでなく、副生する塩化水素を捕捉する為に用いられている。しかしながら、発生する塩化水素を三級アミンにより完全に除去することは容易とは言えず、生成する塩化水素および三級アミンの塩化水素塩は反応系に残存する可能性がある。この点は、スルホンイミドのアルカリ金属塩が多用される電子材料分野において好ましくない。一般に、塩化水素および三級アミンの塩化水素塩についてはできる限り除去されること、更には塩化水素を発生させないことが望まれる。 In Patent Document 1, the tertiary amine as a raw material is used not only for forming an amine salt of sulfonimide but also for capturing hydrogen chloride produced as a by-product. However, it is not easy to completely remove the generated hydrogen chloride with a tertiary amine, and the produced hydrogen chloride and the hydrogen chloride salt of the tertiary amine may remain in the reaction system. This point is not preferable in the field of electronic materials in which alkali metal salts of sulfonimide are often used. In general, it is desired that hydrogen chloride and hydrogen chloride salts of tertiary amines be removed as much as possible, and that hydrogen chloride is not generated.
また特許文献２において、原料にスチレンスルホン酸を用いた反応式の例示があるものの、該化合物は極めて重合しやすいため取り扱いが容易ではなく、この反応を実際に工業的に利用することは現実的ではない。
従って、スルホンイミドのアルカリ金属塩を製造するにあたり、効率的に実施可能な製造方法が求められていた。
Further, although Patent Document 2 exemplifies a reaction formula using styrene sulfonic acid as a raw material, the compound is extremely easy to polymerize and is not easy to handle, and it is practical to actually use this reaction industrially. is not it.
Therefore, in producing an alkali metal salt of sulfonimide, an efficiently feasible production method has been required.
本発明の目的は、かかる従来の実状に鑑みて提案されたものであり、従来の方法では製造が困難であったスルホンイミドのリチウム塩またはナトリウム塩を、工業的規模においても安定して得るための製造方法を提供することにある。また本発明は、アミン類を原料に用いずに簡便且つ効率よくスルホンイミドのリチウム塩またはナトリウム塩、殊にリチウム塩を工業的スケールで製造し得る製造方法を提供することも目的とする。 An object of the present invention has been proposed in view of the conventional circumstances, and is for stably obtaining a lithium salt or a sodium salt of sulfonimide, which has been difficult to produce by a conventional method, even on an industrial scale. To provide a manufacturing method for. Another object of the present invention is to provide a production method capable of easily and efficiently producing a lithium salt or a sodium salt of sulfonimide, particularly a lithium salt, on an industrial scale without using amines as a raw material.
本発明者らは、アミン類を原料に用いずに簡便且つ効率よくスルホンイミドのリチウム塩またはナトリウム塩を工業的スケールで製造し得る製造方法を提供することを目的とし、鋭意研究を行った。その結果、原料にスルホンアミドとリチウム塩またはナトリウム塩を用いてスルホンアミドのリチウム塩またはナトリウム塩を取得後、得られたものを更にスルホニルハライドと反応させることにより、スルホンイミドのリチウム塩またはナトリウム塩を製造できることを見出し、本発明を完成するに至った。 The present inventors have conducted intensive studies with the aim of providing a production method capable of easily and efficiently producing a lithium salt or a sodium salt of sulfonimide on an industrial scale without using amines as a raw material. As a result, after obtaining the lithium salt or sodium salt of sulfonamide using sulfonamide and lithium salt or sodium salt as raw materials, the obtained product is further reacted with sulfonyl halide to obtain the lithium salt or sodium salt of sulfonamide. We have found that we can manufacture the above, and have completed the present invention.
すなわち本発明は、下記一般式（１） That is, the present invention has the following general formula (1).
（式（１）中、Ｒ1はフッ素、任意の数の置換基を有する炭素数１〜１０の直鎖もしくは分岐状アルキル基、炭素数２〜１０の直鎖もしくは分岐状アルケニル基、炭素数２〜１０の直鎖もしくは分岐状アルキニル基、または炭素数３〜１０の環状アルキル基を示す。）で表されるスルホンアミドと、下記一般式（２） (In the formula (1), R 1 is fluorine, a linear or branched alkyl group having 1 to 10 carbon atoms having an arbitrary number of substituents, a linear or branched alkenyl group having 2 to 10 carbon atoms, and a carbon number of carbon atoms. A sulfonamide represented by 2 to 10 linear or branched alkynyl groups or a cyclic alkyl group having 3 to 10 carbon atoms) and the following general formula (2).
（式（２）中、Ｍ+はリチウムイオンまたはナトリウムイオンを示し、Ｘn-はｎ価の陰イオンを示し、ｎは１または２である。）で表されるリチウム塩またはナトリウム塩と、を反応させて下記一般式（３） (In the formula (2), M + represents a lithium ion or a sodium ion, X n- represents an n-valent anion, and n is 1 or 2). To react with the following general formula (3)
（式（３）中、Ｒ1及びＭ+は前記式（１）および（２）に同じ。）を得る工程と、上記一般式（３）と下記一般式（４） (In the formula (3), R 1 and M + are the same as those in the formulas (1) and (2)), and the general formula (3) and the following general formula (4).
（式（４）中、Ｒ2、Ｒ3およびＲ4はそれぞれ独立して、水素、任意の数の置換基を有する炭素数１〜１０の直鎖もしくは分岐状アルキル基、炭素数２〜１０の直鎖もしくは分岐状アルケニル基、炭素数２〜１０の直鎖もしくは分岐状アルキニル基、または炭素数３〜１０の環状アルキル基を示し、Ｒ5、Ｒ6、Ｒ7およびＲ8はそれぞれ独立して、水素、任意の数の置換基を有する炭素数１〜１０の直鎖もしくは分岐状アルキル基、炭素数２〜１０の直鎖もしくは分岐状アルケニル基、炭素数２〜１０の直鎖もしくは分岐状アルキニル基、または炭素数３〜１０の環状アルキル基を示し、それぞれが環状構造を形成しても構わない。また、Ｙはハロゲン原子を示す。）で表されるスルホニルハライドと、を反応させて下記一般式（５） (In formula (4), R 2 , R 3 and R 4 are independently hydrogen, a linear or branched alkyl group having 1 to 10 carbon atoms having an arbitrary number of substituents, and 2 to 10 carbon atoms. , A linear or branched alkynyl group having 2 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms, and R 5 , R 6 , R 7 and R 8 are independent of each other. Then, hydrogen, a linear or branched alkyl group having 1 to 10 carbon atoms having an arbitrary number of substituents, a linear or branched alkenyl group having 2 to 10 carbon atoms, a linear or branched alkyl group having 2 to 10 carbon atoms. It may represent a branched alkynyl group or a cyclic alkyl group having 3 to 10 carbon atoms, each of which may form a cyclic structure. Y represents a halogen atom) and reacts with a sulfonyl halide. Let me do the following general formula (5)
（式（５）中、Ｒ1及びＭ+は前記式（１）および（２）に同じ。）で表されるスルホンイミドのリチウム塩またはナトリウム塩を得る工程よりなる、スルホンイミドのリチウム塩またはナトリウム塩の製造方法に係る。 (In the formula (5), R 1 and M + are the same as those in the formulas (1) and (2)). It relates to a method for producing a sodium salt.
本発明の方法によれば、電子材料等の原料あるいは合成中間体として工業的に重要な化合物であるスルホンイミドのリチウム塩またはナトリウム塩を高収率かつ高純度で効率よく得ることができるため、本製造法は工業的製造方法として有用である。 According to the method of the present invention, a lithium salt or a sodium salt of sulfonimide, which is an industrially important compound as a raw material for electronic materials or the like or as a synthetic intermediate, can be efficiently obtained in high yield and with high purity. This manufacturing method is useful as an industrial manufacturing method.
本発明を実施するに当たり、原料として用いられるスルホンアミドは上記一般式（１）で表される。
一般式（１）中、Ｒ1はフッ素、任意の数の置換基を有する炭素数１〜１０の直鎖もしくは分岐状アルキル基、炭素数２〜１０の直鎖もしくは分岐状アルケニル基、炭素数２〜１０の直鎖もしくは分岐状アルキニル基、または炭素数３〜１０の環状アルキル基を示す。Ｒ1は具体的に、フッ素、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、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−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、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、メチルシクロプロピル基、１’−メチルシクロブチル基、２’−メチルシクロブチル基、１’−メチルシクロペンチル基、２’−メチルシクロペンチル基、１’−メチルシクロヘキシル基、２’−メチルシクロヘキシル基、３’−メチルシクロヘキシル基、１’，１’−ジメチルシクロプロピル基、１’，２’−ジメチルシクロプロピル基、１’，１’−ジメチルシクロブチル基、１’ ，２’−ジメチルシクロブチル基、１’，３’−ジメチルシクロブチル基、２’，２’−ジメチルシクロブチル基等が挙げられ、反応を阻害しない範囲で任意の位置に置換基を有していてもよい。これらの内でも、トリフルオロメチル基を有するものが好ましく用いられる。
In carrying out the present invention, the sulfonamide used as a raw material is represented by the above general formula (1).
In the general formula (1), R 1 is fluorine, a linear or branched alkyl group having 1 to 10 carbon atoms having an arbitrary number of substituents, a linear or branched alkenyl group having 2 to 10 carbon atoms, and a carbon number of carbon atoms. It represents a linear or branched alkynyl group of 2 to 10 or a cyclic alkyl group having 3 to 10 carbon atoms. R 1 is specifically a fluorine, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group and a 1-methylbutyl group. , 2-Methylbutyl group, 3-Methylbutyl group, 1-ethylpropyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group , Cyclohexyl group, methylcyclopropyl group, 1'-methylcyclobutyl group, 2'-methylcyclobutyl group, 1'-methylcyclopentyl group, 2'-methylcyclopentyl group, 1'-methylcyclohexyl group, 2'-methyl Cyclohexyl group, 3'-methylcyclohexyl group, 1', 1'-dimethylcyclopropyl group, 1', 2'-dimethylcyclopropyl group, 1', 1'-dimethylcyclobutyl group, 1', 2'-dimethyl Cyclobutyl group, 1', 3'-dimethylcyclobutyl group, 2', 2'-dimethylcyclobutyl group and the like can be mentioned, and a substituent may be provided at an arbitrary position as long as the reaction is not inhibited. Among these, those having a trifluoromethyl group are preferably used.
一般式（２）中、Ｍ+はアルカリ金属イオンのうちリチウムイオンまたはナトリウムイオンを示し、さらにリチウムイオンが好ましい。
一般式（２）中、Ｘn-はｎ価の陰イオンを示し、具体的に、ヒドリドイオン、水酸化物イオン、フッ素イオン、塩素イオン、臭素イオン、ヨウ素イオン、炭酸イオン、硫酸イオン等が挙げられる。なお、本発明に係る反応を阻害しない範囲で制限されないが、ヒドリドイオン、水酸化物イオン、炭酸イオンであることが好ましい。これらはリチウム塩またはナトリウム塩である化合物であれば使用できる。例えば化合物として、水素化リチウム、水酸化リチウム、炭酸ナトリウムを挙げることができる。
In the general formula (2), M + represents lithium ion or sodium ion among alkali metal ions, and lithium ion is more preferable.
In the general formula (2), X n- indicates an n-valent anion, and specifically, hydride ion, hydroxide ion, fluorine ion, chlorine ion, bromine ion, iodine ion, carbonate ion, sulfate ion and the like. Can be mentioned. The reaction is not limited as long as it does not inhibit the reaction according to the present invention, but hydride ion, hydroxide ion, and carbonate ion are preferable. These can be used as long as they are compounds that are lithium salts or sodium salts. For example, examples of the compound include lithium hydride, lithium hydroxide, and sodium carbonate.
一般式（４）中、Ｒ2、Ｒ3およびＲ4はそれぞれ独立して水素、任意の数の置換基を有する炭素数１〜１０の直鎖もしくは分岐状アルキル基、炭素数２〜１０の直鎖もしくは分岐状アルケニル基、炭素数２〜１０の直鎖もしくは分岐状アルキニル基、または炭素数３〜１０の環状アルキル基を示す。Ｒ2、Ｒ3およびＲ4は具体的に、水素、フッ素、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、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−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、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、メチルシクロプロピル基、１’−メチルシクロブチル基、２’−メチルシクロブチル基、１’−メチルシクロペンチル基、２’−メチルシクロペンチル基、１’−メチルシクロヘキシル基、２’−メチルシクロヘキシル基、３’−メチルシクロヘキシル基、１’，１’−ジメチルシクロプロピル基、１’，２’−ジメチルシクロプロピル基、１’，１’−ジメチルシクロブチル基、１’，２’−ジメチルシクロブチル基、１’，３’−ジメチルシクロブチル基、２’，２’−ジメチルシクロブチル基等が挙げられ、反応を阻害しない範囲で任意の位置に置換基を有していてもよい。 In the general formula (4), R 2 , R 3 and R 4 are independently hydrogen, a linear or branched alkyl group having 1 to 10 carbon atoms having an arbitrary number of substituents, and 2 to 10 carbon atoms. A linear or branched alkenyl group, a linear or branched alkynyl group having 2 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms is shown. Specifically, R 2 , R 3 and R 4 are hydrogen, fluorine, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-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, cyclo Propyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, methylcyclopropyl group, 1'-methylcyclobutyl group, 2'-methylcyclobutyl group, 1'-methylcyclopentyl group, 2'-methylcyclopentyl group, 1'- Methylcyclohexyl group, 2'-methylcyclohexyl group, 3'-methylcyclohexyl group, 1', 1'-dimethylcyclopropyl group, 1', 2'-dimethylcyclopropyl group, 1', 1'-dimethylcyclobutyl group , 1', 2'-dimethylcyclobutyl group, 1', 3'-dimethylcyclobutyl group, 2', 2'-dimethylcyclobutyl group and the like, and substituents at arbitrary positions within a range that does not inhibit the reaction. May have.
一般式（４）中、Ｒ5、Ｒ6、Ｒ7およびＲ8はそれぞれ独立して水素、任意の数の置換基を有する炭素数１〜１０の直鎖もしくは分岐状アルキル基、炭素数２〜１０の直鎖もしくは分岐状アルケニル基、炭素数２〜１０の直鎖もしくは分岐状アルキニル基、または炭素数３〜１０の環状アルキル基を示す。Ｒ5、Ｒ6、Ｒ7およびＲ8は具体的に、水素、フッ素、塩素、臭素、ヨウ素、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、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−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、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、メチルシクロプロピル基、１’−メチルシクロブチル基、２’−メチルシクロブチル基、１’−メチルシクロペンチル基、２’−メチルシクロペンチル基、１’−メチルシクロヘキシル基、２’−メチルシクロヘキシル基、３’−メチルシクロヘキシル基、１’，１’−ジメチルシクロプロピル基、１’，２’−ジメチルシクロプロピル基、１’，１’−ジメチルシクロブチル基、１’，２’−ジメチルシクロブチル基、１’，３’−ジメチルシクロブチル基、２’，２’−ジメチルシクロブチル基等が挙げられ、反応を阻害しない範囲で任意の位置に置換基を有していてもよい。さらに、Ｒ5、Ｒ6、Ｒ7およびＲ8はそれぞれが環状構造を形成しても構わない。 In the general formula (4), R 5 , R 6 , R 7 and R 8 are each independently hydrogen, a linear or branched alkyl group having 1 to 10 carbon atoms having an arbitrary number of substituents, and 2 carbon atoms. A linear or branched alkenyl group having 10 to 10 carbon atoms, a linear or branched alkynyl group having 2 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms is shown. R 5 , R 6 , R 7 and R 8 are specifically hydrogen, fluorine, chlorine, bromine, iodine, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec- Butyl group, tert-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, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, methylcyclopropyl group, 1'-methylcyclobutyl group, 2'-methylcyclobutyl group, 1'-methylcyclopentyl group, 2 '-Methylcyclopentyl group, 1'-methylcyclohexyl group, 2'-methylcyclohexyl group, 3'-methylcyclohexyl group, 1', 1'-dimethylcyclopropyl group, 1', 2'-dimethylcyclopropyl group, 1 ', 1'-dimethylcyclobutyl group, 1', 2'-dimethylcyclobutyl group, 1', 3'-dimethylcyclobutyl group, 2', 2'-dimethylcyclobutyl group and the like, which inhibit the reaction. It may have a substituent at any position as long as it does not. Further, R 5 , R 6 , R 7 and R 8 may each form an annular structure.
また、Ｙは反応を阻害しない範囲で特に制限されるものではないが、ハロゲン原子が好ましく、フッ素原子であることが特に好ましい。 Further, Y is not particularly limited as long as it does not inhibit the reaction, but a halogen atom is preferable, and a fluorine atom is particularly preferable.
一般式（４）で表されるスルホニルハライドは以上の通りであり、これらの内でも、スチレンスルホン酸クロライドが好ましく用いられる。 The sulfonyl halide represented by the general formula (4) is as described above, and among these, styrene sulfonic acid chloride is preferably used.
本発明の製造方法に係る反応は、溶媒の存在下において実施するか、あるいは溶媒を用いずに実施しても構わない。用いられる溶媒としては、具体的に、ペンタン、ヘキサン、ヘプタン、オクタン、ノナン、デカン、ウンデカン、ドデカン、トリデカン、テトラデカン、ペンタデカン、ヘキサデカン、ヘプタデカン、オクタデカン等の直鎖状脂肪族炭化水素類、２−メチルブタン、２−メチルペンタン、３−メチルペンタン、２−メチルヘキサン、３−メチルヘキサン等の分岐状脂肪族炭化水素類、ベンゼン、トルエン、ｏ−キシレン、ｍ−キシレン、ｐ−キシレン等の芳香族炭化水素類、塩化メチレン、クロロホルム、四塩化炭素、１，２−ジクロロエタン、１−クロロプロパン、１，２−ジクロロプロパン、１，３−ジクロロプロパン、１−クロロブタン、２−クロロブタン、１，２−ジクロロブタン、１，３−ジクロロブタン、１，４−ジクロロブタン、２，３−ジクロロブタン、ジブロモメタン、ブロモホルム、四臭化炭素、１，１−ジブロモエタン、１−ブロモプロパン、２−ブロモプロパン、１，２−ジブロモプロパン、１，３−ジブロモプロパン、１−ブロモブタン、２−ブロモブタン、１，２−ジブロモブタン、１，３−ジブロモブタン、１，４−ジブロモブタン、２，３−ジブロモブタン等の脂肪族ハロゲン化合物類、クロロベンゼン、ｏ−ジクロロベンゼン、ｍ−ジクロロベンゼン、ｐ−ジクロロベンゼン、ブロモベンゼン、ｏ−ジブロモベンゼン、ｍ−ジブロモベンゼン、ｐ−ジブロモベンゼン等の芳香族ハロゲン化合物類、テトラヒドロフラン、アセトン、アセトニトリル、酢酸エチル、Ｎ，Ｎ−ジメチルホルムアミド、ジメチルスルホキシド等の非プロトン性の極性の溶媒を用いることができ、中でも非プロトン性の極性の溶媒を用いるのが好ましく、アセトニトリルもしくは酢酸エチル、Ｎ，Ｎ−ジメチルホルムアミドを用いるのがさらに好ましい。また、本製造方法に係る溶媒の使用量は特に制限されないが、一般式（１）に示されるスルホンアミドに対して重量比で１から１００にするのが好ましく、重量比で１から３０がさらに好ましい。 The reaction according to the production method of the present invention may be carried out in the presence of a solvent or may be carried out without using a solvent. Specific examples of the solvent used include linear aliphatic hydrocarbons such as pentane, hexane, heptane, octane, dichloromethane, dichloromethane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane and octadecane, 2-. Branched aliphatic hydrocarbons such as methylbutane, 2-methylpentane, 3-methylpentane, 2-methylhexane and 3-methylhexane, and aromatics such as benzene, toluene, o-xylene, m-xylene and p-xylene. Hydrocarbons, methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1-chloropropane, 1,2-dichloropropane, 1,3-dichloropropane, 1-chlorobutane, 2-chlorobutane, 1,2-dichloro Butane, 1,3-dichlorobutane, 1,4-dichlorobutane, 2,3-dichlorobutane, dibromomethane, bromoform, carbon tetrabromide, 1,1-dibromoethane, 1-bromopropane, 2-bromopropane, 1,2-Dibromopropane, 1,3-dibromopropane, 1-bromobutane, 2-bromobutane, 1,2-dibromobutane, 1,3-dibromobutane, 1,4-dibromobutane, 2,3-dibromobutane, etc. Hydrocarbon compounds such as chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, bromobenzene, o-dibromobenzene, m-dibromobenzene, p-dibromobenzene and other aromatic halogen compounds, tetrahydrofuran. , Aprotonic polar solvents such as acetone, acetonitrile, ethyl acetate, N, N-dimethylformamide, and dimethylsulfoxide can be used, and among them, aprotonic polar solvents are preferably used, and acetonitrile or ethyl acetate is preferable. , N, N-dimethylformamide is more preferred. The amount of the solvent used in the present production method is not particularly limited, but it is preferably 1 to 100 by weight with respect to the sulfonamide represented by the general formula (1), and 1 to 30 by weight is further used. preferable.
本発明のスルホンイミドのアルカリ金属塩に用いられる一般式（２）の使用量は特に制限するものではないが、反応を定量的に進行させる為には原料であるスルホンアミド類に対して２当量〜１０当量使用するのが好ましく、さらに好ましくは２当量〜３当量である。 The amount of the general formula (2) used for the alkali metal salt of the sulfonimide of the present invention is not particularly limited, but is equivalent to 2 equivalents with respect to the sulfone amides as raw materials in order to proceed the reaction quantitatively. It is preferably used in an amount of 10 to 10 equivalents, more preferably 2 equivalents to 3 equivalents.
本発明のスルホンイミドのアルカリ金属塩を合成する際の反応温度は０℃〜８０℃で実施可能であるが、０℃〜６０℃で実施するのが好ましい。なお、一般式（３）を得た後においては特に低温を必要とすることはなく、２０℃〜６０℃で反応を実施することが可能である。 The reaction temperature for synthesizing the alkali metal salt of the sulfonimide of the present invention can be carried out at 0 ° C. to 80 ° C., but is preferably carried out at 0 ° C. to 60 ° C. After obtaining the general formula (3), a low temperature is not particularly required, and the reaction can be carried out at 20 ° C to 60 ° C.
また、本発明のスルホンイミドのアルカリ金属塩を合成する際に使用する反応器は、大気開放型の反応器、またはオートクレーブ等の密閉系の反応器のいずれも可能であり、反応圧力は、大気圧下、または加圧下のいずれも可能である。
本発明のスルホンイミドのアルカリ金属塩の製造方法にて合成されたスルホンイミドのアルカリ金属塩は、反応終了後の反応液から、ろ過、抽出、晶析など常法により分離、精製することができる。
Further, the reactor used for synthesizing the alkali metal salt of the sulfonimide of the present invention can be either an open-air reactor or a closed reactor such as an autoclave, and the reaction pressure is large. It can be under pressure or under pressure.
The alkali metal salt of sulfoneimide synthesized by the method for producing an alkali metal salt of sulfonimide of the present invention can be separated and purified from the reaction solution after completion of the reaction by a conventional method such as filtration, extraction and crystallization. ..
以下、実施例により本発明を説明するが、それらは本発明を限定するものではない。
なお、本発明により得られる化合物については、核磁気共鳴分析（以下、「ＮＭＲ分析」と示す）により反応系中における目的化合物の生成、および反応生成物を同定した。
［ＮＭＲ分析］
装置：ブルカー・バイオスピン社製、 ＡＶ−４００Ｍ
測定サンプルの調製方法：内部標準物質として約０．０５％のテトラメチルシランを含むジメチルスルホキシド−ｄ６（９９．５％）約０．７ｍＬに試料を溶解し、1Ｈ−ＮＭＲおよび19Ｆ−ＮＭＲを測定した。
Hereinafter, the present invention will be described with reference to examples, but they are not limited to the present invention.
For the compound obtained by the present invention, the production of the target compound in the reaction system and the reaction product were identified by nuclear magnetic resonance analysis (hereinafter referred to as “NMR analysis”).
[NMR analysis]
Equipment: Bruker Biospin, AV-400M
Method for preparing measurement sample: Dissolve the sample in about 0.7 mL of dimethyl sulfoxide-d6 (99.5%) containing about 0.05% tetramethylsilane as an internal standard, and 1 H-NMR and 19 F-NMR. Was measured.
（実施例１）リチウム ４−スチレンスルホニル（トリフルオロメチルスルホニル）イミドの合成
１００ｍＬの四口フラスコに撹拌子と温度計を装着し、水素化リチウム０．２１ｇ（２６．８ｍｍｏｌ）、無水アセトニトリル９．５０ｇを入れた後に撹拌しながら０℃に冷却した。次に、トリフルオロメタンスルホンアミド２．００ｇ（１３．４ｍｍｏｌ）を無水アセトニトリル ９．５０ｇに溶解したものを滴下した。続いて、３４％４−スチレンスルホニルクロリド／トルエン溶液８．００ｇ（１３．４ｍｍｏｌ）を滴下し、さらに室温で撹拌を１７時間継続した。得られた反応液にトルエン２０．００ｇを加え、３０分間撹拌した後に、ろ過により無機塩を除去した。ロータリーエバポレータで溶媒を留去したところ、目的化合物であるリチウム ４−スチレンスルホニル（トリフルオロメチルスルホニル）イミドが７８％の収率で得られた。
1Ｈ−ＮＭＲ （４００ ＭＨｚ， ＤＭＳＯ−ｄ６）： δ （ｐｐｍ） ７．７０ （ｄ， Ｊ ＝ ８．０ Ｈｚ， ２Ｈ）， ７．５５ （ｄ， Ｊ ＝ ８．０ Ｈｚ， ２Ｈ）， ７．２４−７．１０ （ｄｄ， Ｊ ＝ １２．０ Ｈｚ， ２０．０ Ｈｚ， １Ｈ）， ５．９３ （ｄ， Ｊ ＝ ２０．０ Ｈｚ， １Ｈ）， ５．３７ （ｄ， Ｊ ＝ １２．０ Ｈｚ， １Ｈ）
19Ｆ−ＮＭＲ （３７６ ＭＨｚ， ＤＭＳＯ−ｄ６）： δ （ｐｐｍ）−７７．８９（ｓ）．
(Example 1) Synthesis of lithium 4-styrene sulfonyl (trifluoromethylsulfonyl) imide A stirrer and a thermometer were attached to a 100 mL four-necked flask, and 0.21 g (26.8 mmol) of lithium hydride and anhydrous acetonitrile 9. After adding 50 g, the mixture was cooled to 0 ° C. with stirring. Next, 2.00 g (13.4 mmol) of trifluoromethanesulfonamide dissolved in 9.50 g of anhydrous acetonitrile was added dropwise. Subsequently, 8.00 g (13.4 mmol) of a 34% 4-styrenesulfonyl chloride / toluene solution was added dropwise, and stirring was further continued at room temperature for 17 hours. Toluene (20.00 g) was added to the obtained reaction solution, and the mixture was stirred for 30 minutes, and then the inorganic salt was removed by filtration. When the solvent was distilled off with a rotary evaporator, the target compound, lithium 4-styrenesulfonyl (trifluoromethylsulfonyl) imide, was obtained in a yield of 78%.
1 1 H-NMR (400 MHz, DMSO-d6): δ (ppm) 7.70 (d, J = 8.0 Hz, 2H), 7.55 (d, J = 8.0 Hz, 2H), 7 .24-7.10 (dd, J = 12.0 Hz, 20.0 Hz, 1H), 5.93 (d, J = 20.0 Hz, 1H), 5.37 (d, J = 12. 0 Hz, 1H)
19 F-NMR (376 MHz, DMSO-d6): δ (ppm) -77.89 (s).
（実施例２）リチウム ４−スチレンスルホニル（トリフルオロメチルスルホニル）イミドの合成
実施例１の原料である水素化リチウムを水酸化リチウム０．６４ｇ（２６．８ｍｍｏｌ）、反応溶媒である無水アセトニトリルをＮ，Ｎ−ジメチルホルムアミドに変え、６０℃で反応を行ったところ、目的化合物であるリチウム４−スチレンスルホニル（トリフルオロメチルスルホニル）イミドが６６％の収率で得られた。
(Example 2) Synthesis of lithium 4-styrene sulfonyl (trifluoromethylsulfonyl) imide 0.64 g (26.8 mmol) of lithium hydride, which is the raw material of Example 1, and N anhydrous acetonitrile, which is the reaction solvent, are used. , N-Dimethylformamide was changed and the reaction was carried out at 60 ° C., and the target compound, lithium 4-styrenesulfonyl (trifluoromethylsulfonyl) imide, was obtained in a yield of 66%.
（実施例３）リチウム ４−スチレンスルホニル（トリフルオロメチルスルホニル）イミドの合成
実施例１の反応溶媒である無水アセトニトリルを酢酸エチルに変え、６０℃で反応を行ったところ、目的化合物であるリチウム ４−スチレンスルホニル（トリフルオロメチルスルホニル）イミドが４８％の収率で得られた。
(Example 3) Synthesis of lithium 4-styrene sulfonyl (trifluoromethylsulfonyl) imide When anhydrous acetonitrile, which is the reaction solvent of Example 1, was changed to ethyl acetate and the reaction was carried out at 60 ° C., the target compound, lithium 4 -Stylonylsulfonyl (trifluoromethylsulfonyl) imide was obtained in a yield of 48%.
（実施例４）ナトリウム ４−スチレンスルホニル（トリフルオロメチルスルホニル）イミドの合成
１００ｍＬの四口フラスコに撹拌子と温度計を装着し、炭酸ナトリウム２．９７ｇ（２８．１ｍｍｏｌ）、酢酸エチル２０．００ｇ、トリフルオロメタンスルホンアミド２．０９ｇ（１４．０ｍｍｏｌ）、４１％４−スチレンスルホニルクロリド／トルエン溶液７．００ｇ（１４．０ｍｍｏｌ）、４−ターシャリブチルカテコール０．１０ｇ（０．６ｍｍｏｌ）を入れた後に撹拌しながら６０℃に加熱し、さらに撹拌を１７時間継続した。その後、反応液に水２０．００ｇを加えて分液し、得られた有機層を２０％食塩水で洗浄した。トルエンを加えて、濃縮したところ、目的化合物であるナトリウム ４−スチレンスルホニル（トリフルオロメチルスルホニル）イミドが７７％の収率で得られた。
1Ｈ−ＮＭＲ （４００ ＭＨｚ， ＤＭＳＯ−ｄ６）： δ （ｐｐｍ） ７．７０ （ｄ， Ｊ ＝ ８．０ Ｈｚ， ２Ｈ）， ７．５５ （ｄ， Ｊ ＝ ８．０ Ｈｚ， ２Ｈ）， ７．２４−７．１０ （ｄｄ， Ｊ ＝ １２．０ Ｈｚ， ２０．０ Ｈｚ， １Ｈ）， ５．９３ （ｄ， Ｊ ＝ ２０．０ Ｈｚ， １Ｈ）， ５．３７ （ｄ， Ｊ ＝ １２．０ Ｈｚ， １Ｈ）
19Ｆ−ＮＭＲ （３７６ ＭＨｚ， ＤＭＳＯ−ｄ６）： δ （ｐｐｍ）−７７．８９（ｓ）．
(Example 4) Synthesis of sodium 4-styrenesulfonyl (trifluoromethylsulfonyl) imide A stirrer and a thermometer were attached to a 100 mL four-necked flask, and 2.97 g (28.1 mmol) of sodium carbonate and 20.00 g of ethyl acetate were attached. , 2.09 g (14.0 mmol) of trifluoromethanesulfonamide, 7.00 g (14.0 mmol) of 41% 4-styrenesulfonyl chloride / toluene solution, and 0.10 g (0.6 mmol) of 4-tarsial butyl catechol. After that, the mixture was heated to 60 ° C. with stirring, and the stirring was continued for 17 hours. Then, 20.00 g of water was added to the reaction solution to separate the layers, and the obtained organic layer was washed with 20% saline solution. When toluene was added and concentrated, the target compound sodium 4-styrenesulfonyl (trifluoromethylsulfonyl) imide was obtained in a yield of 77%.
1 1 H-NMR (400 MHz, DMSO-d6): δ (ppm) 7.70 (d, J = 8.0 Hz, 2H), 7.55 (d, J = 8.0 Hz, 2H), 7 .24-7.10 (dd, J = 12.0 Hz, 20.0 Hz, 1H), 5.93 (d, J = 20.0 Hz, 1H), 5.37 (d, J = 12. 0 Hz, 1H)
19 F-NMR (376 MHz, DMSO-d6): δ (ppm) -77.89 (s).
（比較例１）（アルカリ金属塩の有無に関する検討）
実施例４の原料である炭酸ナトリウムを加えず、反応溶媒である酢酸エチルをテトラヒドロフランに変え、反応を行ったところ、目的化合物であるナトリウム ４−スチレンスルホニル（トリフルオロメチルスルホニル）イミドは得られなかった。
(Comparative Example 1) (Examination of presence / absence of alkali metal salt)
When the reaction was carried out by changing ethyl acetate as a reaction solvent to tetrahydrofuran without adding sodium carbonate as a raw material of Example 4, sodium 4-styrenesulfonyl (trifluoromethylsulfonyl) imide as a target compound could not be obtained. rice field.
（比較例２）カルシウム ４−スチレンスルホニル（トリフルオロメチルスルホニル）イミドの合成
実施例４の原料である炭酸ナトリウムを炭酸カルシウム２．６９ｇ（２８．１ｍｍｏｌ）に変え、反応を行ったところ、目的化合物であるカルシウム ４−スチレンスルホニル（トリフルオロメチルスルホニル）イミドは得られなかった。
(Comparative Example 2) Synthesis of calcium 4-styrene sulfonyl (trifluoromethylsulfonyl) imide When sodium carbonate, which is the raw material of Example 4, was changed to 2.69 g (28.1 mmol) of calcium carbonate and a reaction was carried out, the target compound was obtained. Calcium 4-styrene sulfonyl (trifluoromethylsulfonyl) imide was not obtained.
（比較例３）マグネシウム ４−スチレンスルホニル（トリフルオロメチルスルホニル）イミドの合成
実施例４の原料である炭酸ナトリウムを炭酸マグネシウム２．２６ｇ（２８．１ｍｍｏｌ）に変え、反応を行ったところ、目的化合物であるマグネシウム ４−スチレンスルホニル（トリフルオロメチルスルホニル）イミドは得られなかった。
(Comparative Example 3) Synthesis of magnesium 4-styrenesulfonyl (trifluoromethylsulfonyl) imide When sodium carbonate, which is the raw material of Example 4, was changed to 2.26 g (28.1 mmol) of magnesium carbonate and a reaction was carried out, the target compound was obtained. Magnesium 4-styrene sulfonyl (trifluoromethylsulfonyl) imide was not obtained.
本発明により得られるスルホンイミドのアルカリ金属塩は、電子材料等の原料あるいは合成中間体として、工業的に極めて有用である。 The alkali metal salt of sulfonimide obtained by the present invention is extremely useful industrially as a raw material for electronic materials or the like or as a synthetic intermediate.
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