JP5928149B2 - Method for producing imido acid compound - Google Patents
Method for producing imido acid compound Download PDFInfo
- Publication number
- JP5928149B2 JP5928149B2 JP2012114706A JP2012114706A JP5928149B2 JP 5928149 B2 JP5928149 B2 JP 5928149B2 JP 2012114706 A JP2012114706 A JP 2012114706A JP 2012114706 A JP2012114706 A JP 2012114706A JP 5928149 B2 JP5928149 B2 JP 5928149B2
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- JP
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- Prior art keywords
- organic base
- salt
- carbonate
- group
- complex
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000002253 acid Substances 0.000 title claims description 60
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 150000001875 compounds Chemical class 0.000 title claims description 10
- 150000007530 organic bases Chemical class 0.000 claims description 98
- 238000006243 chemical reaction Methods 0.000 claims description 68
- 150000003839 salts Chemical class 0.000 claims description 62
- 238000005406 washing Methods 0.000 claims description 51
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 44
- 238000000034 method Methods 0.000 claims description 36
- 238000011084 recovery Methods 0.000 claims description 33
- -1 sulfuryl halide Chemical class 0.000 claims description 31
- 150000003949 imides Chemical class 0.000 claims description 25
- 229910021529 ammonia Inorganic materials 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 20
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 17
- 239000011541 reaction mixture Substances 0.000 claims description 14
- 229910052731 fluorine Inorganic materials 0.000 claims description 13
- 239000011737 fluorine Substances 0.000 claims description 13
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 11
- 239000000460 chlorine Substances 0.000 claims description 11
- 229910052801 chlorine Inorganic materials 0.000 claims description 11
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 238000005341 cation exchange Methods 0.000 claims description 10
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 8
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 8
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052794 bromium Inorganic materials 0.000 claims description 8
- 239000011630 iodine Substances 0.000 claims description 8
- 229910052740 iodine Inorganic materials 0.000 claims description 8
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 7
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 7
- 150000003512 tertiary amines Chemical class 0.000 claims description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 6
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 150000003335 secondary amines Chemical class 0.000 claims description 3
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000001188 haloalkyl group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 4
- CEIPQQODRKXDSB-UHFFFAOYSA-N ethyl 3-(6-hydroxynaphthalen-2-yl)-1H-indazole-5-carboximidate dihydrochloride Chemical compound Cl.Cl.C1=C(O)C=CC2=CC(C3=NNC4=CC=C(C=C43)C(=N)OCC)=CC=C21 CEIPQQODRKXDSB-UHFFFAOYSA-N 0.000 claims 1
- 125000000879 imine group Chemical group 0.000 claims 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 57
- 239000010410 layer Substances 0.000 description 53
- 239000012043 crude product Substances 0.000 description 23
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 21
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 18
- 238000005481 NMR spectroscopy Methods 0.000 description 18
- 239000000047 product Substances 0.000 description 18
- 238000000926 separation method Methods 0.000 description 18
- 239000002904 solvent Substances 0.000 description 16
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 15
- 239000012044 organic layer Substances 0.000 description 12
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- 239000003960 organic solvent Substances 0.000 description 10
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 10
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 description 8
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 8
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 7
- 239000005935 Sulfuryl fluoride Substances 0.000 description 7
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical compound FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 description 7
- BWZVCCNYKMEVEX-UHFFFAOYSA-N 2,4,6-Trimethylpyridine Chemical compound CC1=CC(C)=NC(C)=C1 BWZVCCNYKMEVEX-UHFFFAOYSA-N 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 6
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 6
- HPYNZHMRTTWQTB-UHFFFAOYSA-N dimethylpyridine Natural products CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 description 6
- 239000012433 hydrogen halide Substances 0.000 description 6
- 229910000039 hydrogen halide Inorganic materials 0.000 description 6
- 239000007858 starting material Substances 0.000 description 6
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 5
- 229910000024 caesium carbonate Inorganic materials 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 description 5
- 235000011181 potassium carbonates Nutrition 0.000 description 5
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 description 5
- 229910000026 rubidium carbonate Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 5
- JYYNAJVZFGKDEQ-UHFFFAOYSA-N 2,4-Dimethylpyridine Chemical compound CC1=CC=NC(C)=C1 JYYNAJVZFGKDEQ-UHFFFAOYSA-N 0.000 description 4
- NURQLCJSMXZBPC-UHFFFAOYSA-N 3,4-dimethylpyridine Chemical compound CC1=CC=NC=C1C NURQLCJSMXZBPC-UHFFFAOYSA-N 0.000 description 4
- HWWYDZCSSYKIAD-UHFFFAOYSA-N 3,5-dimethylpyridine Chemical compound CC1=CN=CC(C)=C1 HWWYDZCSSYKIAD-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 4
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 4
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-Me3C6H3 Natural products CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 229910000792 Monel Inorganic materials 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 3
- 229910000856 hastalloy Inorganic materials 0.000 description 3
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 150000002466 imines Chemical group 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 150000002825 nitriles Chemical class 0.000 description 3
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 3
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910000018 strontium carbonate Inorganic materials 0.000 description 3
- 125000005463 sulfonylimide group Chemical group 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- RXYPXQSKLGGKOL-UHFFFAOYSA-N 1,4-dimethylpiperazine Chemical compound CN1CCN(C)CC1 RXYPXQSKLGGKOL-UHFFFAOYSA-N 0.000 description 2
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 2
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 2
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- NBPGPQJFYXNFKN-UHFFFAOYSA-N 4-methyl-2-(4-methylpyridin-2-yl)pyridine Chemical group CC1=CC=NC(C=2N=CC=C(C)C=2)=C1 NBPGPQJFYXNFKN-UHFFFAOYSA-N 0.000 description 2
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 description 2
- ZMCUDHNSHCRDBT-UHFFFAOYSA-M caesium bicarbonate Chemical compound [Cs+].OC([O-])=O ZMCUDHNSHCRDBT-UHFFFAOYSA-M 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
- 229940043279 diisopropylamine Drugs 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 2
- KEDRKJFXBSLXSI-UHFFFAOYSA-M hydron;rubidium(1+);carbonate Chemical compound [Rb+].OC([O-])=O KEDRKJFXBSLXSI-UHFFFAOYSA-M 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 229910000032 lithium hydrogen carbonate Inorganic materials 0.000 description 2
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- KTQDYGVEEFGIIL-UHFFFAOYSA-N n-fluorosulfonylsulfamoyl fluoride Chemical class FS(=O)(=O)NS(F)(=O)=O KTQDYGVEEFGIIL-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000010702 perfluoropolyether Substances 0.000 description 2
- RDOWQLZANAYVLL-UHFFFAOYSA-N phenanthridine Chemical compound C1=CC=C2C3=CC=CC=C3C=NC2=C1 RDOWQLZANAYVLL-UHFFFAOYSA-N 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 229960003975 potassium Drugs 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 description 2
- 239000011736 potassium bicarbonate Substances 0.000 description 2
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 2
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 2
- GFYHSKONPJXCDE-UHFFFAOYSA-N sym-collidine Natural products CC1=CN=C(C)C(C)=C1 GFYHSKONPJXCDE-UHFFFAOYSA-N 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
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- CQXADFVORZEARL-UHFFFAOYSA-N Rilmenidine Chemical compound C1CC1C(C1CC1)NC1=NCCO1 CQXADFVORZEARL-UHFFFAOYSA-N 0.000 description 1
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- 239000003377 acid catalyst Substances 0.000 description 1
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- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
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- 238000004811 liquid chromatography Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 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 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- DTKANQSCBACEPK-UHFFFAOYSA-N n',n'-bis[3-(dimethylamino)propyl]-n,n-dimethylpropane-1,3-diamine Chemical compound CN(C)CCCN(CCCN(C)C)CCCN(C)C DTKANQSCBACEPK-UHFFFAOYSA-N 0.000 description 1
- SWVGZFQJXVPIKM-UHFFFAOYSA-N n,n-bis(methylamino)propan-1-amine Chemical compound CCCN(NC)NC SWVGZFQJXVPIKM-UHFFFAOYSA-N 0.000 description 1
- MXHTZQSKTCCMFG-UHFFFAOYSA-N n,n-dibenzyl-1-phenylmethanamine Chemical compound C=1C=CC=CC=1CN(CC=1C=CC=CC=1)CC1=CC=CC=C1 MXHTZQSKTCCMFG-UHFFFAOYSA-N 0.000 description 1
- YWWNNLPSZSEZNZ-UHFFFAOYSA-N n,n-dimethyldecan-1-amine Chemical compound CCCCCCCCCCN(C)C YWWNNLPSZSEZNZ-UHFFFAOYSA-N 0.000 description 1
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 1
- LFSXCDWNBUNEEM-UHFFFAOYSA-N phthalazine Chemical compound C1=NN=CC2=CC=CC=C21 LFSXCDWNBUNEEM-UHFFFAOYSA-N 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- CPNGPNLZQNNVQM-UHFFFAOYSA-N pteridine Chemical compound N1=CN=CC2=NC=CN=C21 CPNGPNLZQNNVQM-UHFFFAOYSA-N 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- NVBFHJWHLNUMCV-UHFFFAOYSA-N sulfamide Chemical compound NS(N)(=O)=O NVBFHJWHLNUMCV-UHFFFAOYSA-N 0.000 description 1
- NBNBICNWNFQDDD-UHFFFAOYSA-N sulfuryl dibromide Chemical compound BrS(Br)(=O)=O NBNBICNWNFQDDD-UHFFFAOYSA-N 0.000 description 1
- TWPVZKPFIMFABN-UHFFFAOYSA-N sulfuryl diiodide Chemical compound IS(I)(=O)=O TWPVZKPFIMFABN-UHFFFAOYSA-N 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- ABVVEAHYODGCLZ-UHFFFAOYSA-N tridecan-1-amine Chemical compound CCCCCCCCCCCCCN ABVVEAHYODGCLZ-UHFFFAOYSA-N 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- RKBCYCFRFCNLTO-UHFFFAOYSA-N triisopropylamine Chemical compound CC(C)N(C(C)C)C(C)C RKBCYCFRFCNLTO-UHFFFAOYSA-N 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/086—Compounds containing nitrogen and non-metals and optionally metals containing one or more sulfur atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は、電池電解質、酸触媒、イオン液体として有用なイミド酸化合物、具体的にはビス（ハロゲン化スルホニル）イミド酸化合物の工業的な製造方法に関する。 The present invention relates to an industrial production method for imido acid compounds useful as battery electrolytes, acid catalysts, and ionic liquids, specifically, bis (halogenated sulfonyl) imidic acid compounds.
ビス（フルオロスルホニル）イミド塩は電池電解質溶媒やイオン液体、帯電防止剤としても有用な化合物である。 Bis (fluorosulfonyl) imide salts are useful compounds as battery electrolyte solvents, ionic liquids, and antistatic agents.
ビス（フルオロスルホニル）イミド酸化合物の製造方法として、特許文献１に尿素とフルオロスルホン酸とを反応させて、ビス（フルオロスルホニル）イミド酸を得る方法が、非特許文献１には、ビス（クロロスルホニル）イミド酸に金属フッ化物を反応させて、ビス（フルオロスルホニル）イミド酸を得る製造法が知られている。 As a method for producing a bis (fluorosulfonyl) imidic acid compound, Patent Document 1 discloses a method in which urea and fluorosulfonic acid are reacted to obtain bis (fluorosulfonyl) imide acid. A production method is known in which a metal fluoride is reacted with (sulfonyl) imidic acid to obtain bis (fluorosulfonyl) imidic acid.
しかしながら、特許文献１の方法では、毒性・腐食性の高いフルオロスルホン酸を使用しており、さらにこの反応で得られるビス（フルオロスルホニル）イミド酸とフルオロスルホン酸の分離が困難なため低収率となることから、工業的な製造法として採用するには難がある。また、非特許文献１の方法は、毒性が高く、高価である三フッ化砒素や三フッ化アンチモンを使用することから、工業的に量産を行うには不利である。 However, in the method of Patent Document 1, fluorosulfonic acid having high toxicity and corrosivity is used, and furthermore, it is difficult to separate bis (fluorosulfonyl) imidic acid and fluorosulfonic acid obtained by this reaction, so that the yield is low. Therefore, it is difficult to adopt as an industrial manufacturing method. The method of Non-Patent Document 1 is disadvantageous for industrial mass production because it uses arsenic trifluoride or antimony trifluoride, which is highly toxic and expensive.
本出願人らは、ビス（フルオロスルホニル）イミド酸化合物のより大量規模製造に適した方法として、ハロゲン化スルフリルとアンモニアを反応させて、ビス（ハロゲン化スルホニル）イミド酸誘導体を得る方法を提案している（特許文献２）。 The present applicants proposed a method for obtaining a bis (halogenated sulfonyl) imidic acid derivative by reacting sulfuryl halide with ammonia as a method suitable for larger-scale production of a bis (fluorosulfonyl) imidic acid compound. (Patent Document 2).
特許文献２の方法は、高収率で高純度なビス（ハロゲン化スルホニル）イミド酸化合物が得られる有用な製法であるが、工業的スケールでは、反応後の後処理での水洗操作において、目的物の一部が水層に溶解し大幅に収率が低下する場合があり、改善の余地があった。 The method of Patent Document 2 is a useful production method for obtaining a high-yield and high-purity bis (halogenated sulfonyl) imidic acid compound, but on an industrial scale, in the water washing operation in the post-treatment after the reaction, Part of the product was dissolved in the aqueous layer, and the yield could be significantly reduced, leaving room for improvement.
そこで、本発明は、ハロゲン化スルフリルとアンモニアを反応させて、ビス（ハロゲン化スルホニル）イミド酸誘導体を得る方法において、従来よりも収率が向上し工業的に有効な方法を提供することを課題とする。 Therefore, the present invention has an object to provide an industrially effective method in which the yield is improved as compared with the conventional method in a method for obtaining a bis (halogenated sulfonyl) imidic acid derivative by reacting sulfuryl halide with ammonia. And
発明者らは、上記課題に鑑み、鋭意検討したところ、ハロゲン化スルフリルとアンモニアを反応させて、ビス（ハロゲン化スルホニル）イミド酸誘導体を得る方法において、「イミド酸と有機塩基Ｂからなる塩又は錯体」（以下、単に「目的物」ということがある）を含む水層と有機塩基Ａとを接触させることで、水層に溶解した目的物を効率的に回収でき、目的物の収率が向上することを見出した。 The inventors of the present invention have intensively studied in view of the above problems. In a method of obtaining a bis (halogenated sulfonyl) imidic acid derivative by reacting a sulfuryl halide with ammonia, a “salt composed of imido acid and an organic base B or By contacting the aqueous layer containing the “complex” (hereinafter sometimes simply referred to as “target product”) with the organic base A, the target product dissolved in the aqueous layer can be efficiently recovered, and the yield of the target product is increased. I found it to improve.
すなわち、本発明は、式［１］で表される「イミド酸と有機塩基Ｂからなる塩又は錯体」
［式中、Ｒはそれぞれ独立してハロスルホニル基（−ＳＯ２Ｘ１；Ｘ１はＸ2又はＸ3を表し、Ｘ2、Ｘ3は同一、又は異なるハロゲン（フッ素、塩素、臭素、ヨウ素））を表す。Ｂは有機塩基を表す。］
の製造方法であって、以下の工程を含むことを特徴とする方法を提供するものである。
[In the formula, each R independently represents a halosulfonyl group (—SO 2 X 1 ; X 1 represents X 2 or X 3 , and X 2 and X 3 are the same or different halogens (fluorine, chlorine, bromine, iodine )). B represents an organic base. ]
The manufacturing method of this, Comprising: The method characterized by including the following processes is provided.
有機塩基Ｂ存在下、ハロゲン化スルフリル（ＳＯ２Ｘ2Ｘ3；Ｘ2、Ｘ3は同一、又は異なるハロゲン（フッ素、塩素、臭素、ヨウ素）を表す。）とアンモニアとを反応させ、反応混合物を得る工程（以下、「反応工程」ということもある）
前記反応混合物に水を添加し、「イミド酸と有機塩基Ｂからなる塩又は錯体」を含む有機混合物と、「イミド酸と有機塩基Ｂからなる塩又は錯体」を含む水層とに分離する工程（以下、「洗浄工程」ということもある）
前記洗浄工程において分離された水層と有機塩基Ａとを接触させ、「イミド酸と有機塩基Ｂからなる塩又は錯体」を有機塩基Ａに抽出する工程（以下、「回収工程」ということもある）
また、本発明は、前記方法であって、式［１］で表される「イミド酸と有機塩基Ｂからなる塩又は錯体」中のＸ１、及び、ハロゲン化スルフリルのＸ２、Ｘ３がそれぞれフッ素又は塩素のいずれかであることを特徴とする方法を提供するものである。
In the presence of the organic base B, sulfuryl halide (SO 2 X 2 X 3 ; X 2 and X 3 represent the same or different halogen (fluorine, chlorine, bromine, iodine)) and ammonia are reacted, and the reaction mixture (Hereinafter sometimes referred to as “reaction process”)
Step of adding water to the reaction mixture and separating into an organic mixture containing “salt or complex consisting of imide acid and organic base B” and an aqueous layer containing “salt or complex consisting of imide acid and organic base B” (Hereafter, sometimes referred to as “cleaning process”)
A step of bringing the aqueous layer separated in the washing step into contact with the organic base A and extracting the “salt or complex comprising imide acid and the organic base B” into the organic base A (hereinafter, also referred to as “recovery step”). )
Further, the present invention is the above method, X 1 in the formula "salt or complex composed of an imide acid and an organic base B" represented by [1], and, the X 2, X 3 halogenated sulfuryl The present invention provides a method characterized in that each is either fluorine or chlorine.
また、本発明は、前記方法において、反応工程で用いる有機塩基Ｂが、式［２］で表される３級アミン
［式［２］中、Ｒ１、Ｒ２、Ｒ３は同一、又は異なり、炭素数１〜６の直鎖又は分岐のアルキル基、炭素数３〜８のシクロアルキル基、又はアリール基（アリール基の水素原子の一部又は全てが、ハロゲン（フッ素、塩素、臭素、ヨウ素）、炭素数１〜１０のアルキル基、炭素数１〜１０のハロアルキル基、炭素数３〜８のシクロアルキル基、アミノ基、ニトロ基、アセチル基、シアノ基もしくはヒドロキシル基で置換されていても良い。）を示す。］、含窒素芳香族複素環式化合物、又はイミン骨格（−Ｃ＝Ｎ−Ｃ−）を有する化合物であることを特徴とする「イミド酸と有機塩基Ｂからなる塩または錯体」の製造方法を提供するものである。 [In the formula [2], R 1 , R 2 , and R 3 are the same or different, and a linear or branched alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or an aryl group (aryl Some or all of the hydrogen atoms in the group are halogen (fluorine, chlorine, bromine, iodine), an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, And may be substituted with an amino group, a nitro group, an acetyl group, a cyano group, or a hydroxyl group. A method for producing a “salt or complex comprising imido acid and organic base B”, which is a nitrogen-containing aromatic heterocyclic compound or a compound having an imine skeleton (—C═N—C—) It is to provide.
また、本発明は、前記回収工程において、前記洗浄工程で分離された水層と有機塩基Ａとを接触させる際に、アルカリ金属の炭酸塩もしくは炭酸水素塩、又は、アルカリ土類金属の炭酸塩を存在させることを特徴とする方法を提供するものである。 Further, the present invention provides an alkali metal carbonate or hydrogen carbonate or an alkaline earth metal carbonate when the aqueous layer separated in the washing step and the organic base A are brought into contact in the recovery step. The present invention provides a method characterized in that
また、本発明は、前記の何れかに記載の方法で得られた「イミド酸と有機塩基Ｂからなる塩または錯体」に、アルカリ金属の水酸化物もしくは炭酸塩、又はアルカリ土類金属の水酸化物もしくは炭酸塩を反応させカチオン交換を行うことを特徴とする、式［３］で表されるイミド酸金属塩
［式［３］中、Ｒは前記に同じ。Ｍはアルカリ金属又はアルカリ土類金属を示す。ｎはＭの価数と同数の整数を示す。］の製造方法を提供するものである。 [In the formula [3], R is the same as defined above. M represents an alkali metal or an alkaline earth metal. n represents an integer having the same number as the valence of M. ] Is provided.
特許文献３には、クロロスルホニルイミド又はその塩を原料とするフルオロスルホニルイミド塩の製造において、精製工程の分液抽出を行う際に水層に流出するフルオロスルホニルイミド塩の一部を有機溶媒で回収する方法が開示されているが、本発明とは反応原料や条件が異なるものである。 In Patent Document 3, in the production of a fluorosulfonylimide salt using chlorosulfonylimide or a salt thereof as a raw material, a part of the fluorosulfonylimide salt that flows out to the aqueous layer when performing liquid separation extraction in the purification step is used as an organic solvent. Although a method for recovery is disclosed, the reaction raw materials and conditions are different from those of the present invention.
本発明によれば、水層に溶解した「イミド酸と有機塩基Ｂからなる塩又は錯体」を効率的に回収でき、工業スケールにおいても、高純度な「イミド酸と有機塩基Ｂからなる塩又は錯体」を高収率で製造できる。 According to the present invention, the “salt or complex comprising imide acid and organic base B” dissolved in the aqueous layer can be efficiently recovered, and even on an industrial scale, the highly pure “salt comprising imide acid and organic base B or "Complex" can be produced in high yield.
本発明は、式［１］で表される「イミド酸と有機塩基Ｂからなる塩又は錯体」
［式中、Ｒはそれぞれ独立してハロスルホニル基（−ＳＯ２Ｘ１；Ｘ１はＸ2又はＸ3を表し、Ｘ2、Ｘ3は同一、又は異なるハロゲン（フッ素、塩素、臭素、ヨウ素））を表す。Ｂは有機塩基を表す。］
の製造方法であって、以下の工程を含むことを特徴とする。
[In the formula, each R independently represents a halosulfonyl group (—SO 2 X 1 ; X 1 represents X 2 or X 3 , and X 2 and X 3 are the same or different halogens (fluorine, chlorine, bromine, iodine )). B represents an organic base. ]
This manufacturing method includes the following steps.
有機塩基Ｂの存在下、ハロゲン化スルフリル（ＳＯ２Ｘ2Ｘ3；Ｘ2、Ｘ3は同一、又は異なるハロゲン（フッ素、塩素、臭素、ヨウ素）を表す）とアンモニアとを反応させ、反応混合物を得る工程（反応工程）
前記反応混合物に水を添加し、「イミド酸と有機塩基Ｂからなる塩又は錯体」を含む油分と、「イミド酸と有機塩基Ｂからなる塩又は錯体」を含む水層とに分離する工程（洗浄工程）
前記洗浄工程において分離された水層と有機塩基Ａとを接触させ、「イミド酸と有機塩基Ｂからなる塩又は錯体」を有機塩基Ａに抽出する工程（回収工程）
［反応工程］
まずは、本発明の反応工程について説明する。
In the presence of the organic base B, sulfuryl halide (SO 2 X 2 X 3 ; X 2 and X 3 represent the same or different halogens (fluorine, chlorine, bromine, iodine)) and ammonia are reacted, and the reaction mixture Process (reaction process)
A step of adding water to the reaction mixture and separating it into an oil containing “salt or complex consisting of imido acid and organic base B” and an aqueous layer containing “salt or complex consisting of imido acid and organic base B” ( Cleaning process)
The step of bringing the aqueous layer separated in the washing step into contact with the organic base A, and extracting the “salt or complex comprising imide acid and the organic base B” into the organic base A (recovery step)
[Reaction process]
First, the reaction process of this invention is demonstrated.
反応工程で用いるハロゲン化スルフリルとしては、フッ化スルフリル、塩化スルフリル、臭化スルフリル、ヨウ化スルフリルが挙げられるが、これらの中で、フッ化スルフリル、塩化スルフリルは工業的規模での入手がしやすいため好ましく、特にフッ化スルフリルが好ましい。よって、式［１］におけるＸ１（つまり、ハロゲン化スルフリルにおけるＸ２、Ｘ３）は、フッ素又は塩素である場合が好ましく、特にフッ素が好ましい。 Examples of the sulfuryl halide used in the reaction step include sulfuryl fluoride, sulfuryl chloride, sulfuryl bromide, and sulfuryl iodide. Of these, sulfuryl fluoride and sulfuryl chloride are easily available on an industrial scale. Therefore, sulfuryl fluoride is particularly preferable. Therefore, X 1 in Formula [1] (that is, X 2 and X 3 in the sulfuryl halide) is preferably fluorine or chlorine, and fluorine is particularly preferable.
ハロゲン化スルフリルの量が、アンモニア１モルに対して、通常、１〜１０モルで行い、好ましくは１〜８モル、より好ましくは２〜５モルで行う。 The amount of the sulfuryl halide is usually 1 to 10 mol, preferably 1 to 8 mol, more preferably 2 to 5 mol per mol of ammonia.
反応工程で使用する有機塩基（本明細書では、反応工程で使用する有機塩基を「有機塩基Ｂ」、後述する回収工程で使用する有機塩基を「有機塩基Ａ」と記載し区別することもある。）は、式［２］で表される３級アミン、含窒素芳香族複素環式化合物、又は次のイミン骨格
−Ｃ＝Ｎ−Ｃ−
を有する化合物（以下、「イミン系塩基」ということもある）であるが、それぞれの化合物の具体的な例を、以下、明示する。
Organic base used in the reaction step (In this specification, the organic base used in the reaction step is sometimes referred to as “organic base B”, and the organic base used in the recovery step described later is sometimes referred to as “organic base A”. .) Is a tertiary amine represented by the formula [2], a nitrogen-containing aromatic heterocyclic compound, or the following imine skeleton —C═N—C—
In the following, specific examples of each compound will be clarified.
（ａ）３級アミン：トリメチルアミン、トリエチルアミン、ジイソプロピルエチルアミン、トリ−ｎ−プロピルアミン、トリイソプロピルアミン、トリ−ｎ−ブチルアミン、トリオクチルアミン、トリデシルアミン、トリフェニルアミン、トリベンジルアミン、トリス（２−エチルへキシル）アミン、Ｎ，Ｎ−ジメチルデシルアミン、Ｎ−ベンジルジメチルアミン、Ｎ−ブチルジメチルアミン、Ｎ，Ｎ−ジメチルシクロヘキシルアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルエチレンジアミン、Ｎ，Ｎ−ジメチルアニリン、Ｎ，Ｎ−ジエチルアニリン、１，４−ジアザビシクロ［２．２．２］オクタン、Ｎ−メチルピロリジン、Ｎ−メチルピペリジン、Ｎ−メチルモルホリン、Ｎ−エチルモルホリン、Ｎ，Ｎ′−ジメチルピペラジン、Ｎ−メチルピペコリン、Ｎ−メチルピロリドン、Ｎ−ビニル−ピロリドン、ビス（２−ジメチルアミノ−エチル）エーテル、Ｎ，Ｎ，Ｎ，Ｎ'，Ｎ''−ペンタメチル−ジエチレントリアミン、トリエタノールアミン、トリプロパノールアミン、ジメチルエタノールアミン、ジメチルアミノエトキシエタノール、Ｎ，Ｎ−ジメチルアミノプロピルアミン、Ｎ，Ｎ，Ｎ'，Ｎ'，Ｎ''−ペンタメチルジプロピレントリアミン、トリス（３−ジメチルアミノプロピル）アミン、テトラメチルイミノ−ビス（プロピルアミン）、Ｎ−ジエチル−エタノールアミンなど。 (A) Tertiary amine: trimethylamine, triethylamine, diisopropylethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, trioctylamine, tridecylamine, triphenylamine, tribenzylamine, tris (2 -Ethylhexyl) amine, N, N-dimethyldecylamine, N-benzyldimethylamine, N-butyldimethylamine, N, N-dimethylcyclohexylamine, N, N, N ', N'-tetramethylethylenediamine, N , N-dimethylaniline, N, N-diethylaniline, 1,4-diazabicyclo [2.2.2] octane, N-methylpyrrolidine, N-methylpiperidine, N-methylmorpholine, N-ethylmorpholine, N, N '-Dimethylpiperazine, N-methyl Pipecoline, N-methylpyrrolidone, N-vinyl-pyrrolidone, bis (2-dimethylamino-ethyl) ether, N, N, N, N ′, N ″ -pentamethyl-diethylenetriamine, triethanolamine, tripropanolamine, dimethyl Ethanolamine, dimethylaminoethoxyethanol, N, N-dimethylaminopropylamine, N, N, N ′, N ′, N ″ -pentamethyldipropylenetriamine, tris (3-dimethylaminopropyl) amine, tetramethylimino -Bis (propylamine), N-diethyl-ethanolamine and the like.
（ｂ）含窒素芳香族複素環式化合物：ピリジン、２，４，６−トリメチルピリジン、４−ジメチルアミノピリジン、ルチジン、ピリミジン、ピリダジン、ピラジン、オキサゾール、イソオキサゾール、チアゾール、イソチアゾール、イミダゾール、１，２−ジメチルイミダゾール、３−（ジメチルアミノ）プロピルイミダゾール、ピラゾール，フラザン、ピラジン、キノリン、イソキノリン、プリン、１Ｈ−インダゾール、キナゾリン、シンノリン、キノキサリン、フタラジン、プテリジン、フェナントリジン、２，６−ジ−ｔ−ブチルピリジン、２，２'−ビピリジン、４，４'−ジメチル−２，２'−ビピリジル、４，４'−ジメチル−２，２'−ビピリジル、５，５'−ジメチル−２，２'−ビピリジル、６，６'−ｔ−ブチル−２，２'−ジピリジル、４，４'−ジフェニル−２，２'−ビピリジル、１，１０−フェナントロリン、２，７−ジメチル−１，１０−フェナントロリン、５，６−ジメチル−１，１０−フェナントロリン、４，７−ジフェニル−１，１０−フェナントロリンなど。 (B) Nitrogen-containing aromatic heterocyclic compounds: pyridine, 2,4,6-trimethylpyridine, 4-dimethylaminopyridine, lutidine, pyrimidine, pyridazine, pyrazine, oxazole, isoxazole, thiazole, isothiazole, imidazole, 1 , 2-dimethylimidazole, 3- (dimethylamino) propylimidazole, pyrazole, furazane, pyrazine, quinoline, isoquinoline, purine, 1H-indazole, quinazoline, cinnoline, quinoxaline, phthalazine, pteridine, phenanthridine, 2,6-di -T-butylpyridine, 2,2'-bipyridine, 4,4'-dimethyl-2,2'-bipyridyl, 4,4'-dimethyl-2,2'-bipyridyl, 5,5'-dimethyl-2, 2'-bipyridyl, 6,6'-t-butyl-2,2'-dipyri 4,4′-diphenyl-2,2′-bipyridyl, 1,10-phenanthroline, 2,7-dimethyl-1,10-phenanthroline, 5,6-dimethyl-1,10-phenanthroline, 4,7- Diphenyl-1,10-phenanthroline and the like.
（ｃ）イミン系塩基：１，８−ジアザビシクロ［５．４．０］ウンデカ−７−エン、１，５−ジアザビシクロ［４．３．０］ノン−５−エンなど。 (C) Imine base: 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] non-5-ene and the like.
これらの中でもトリメチルアミン、トリエチルアミン、ジイソプロピルエチルアミン、トリ−ｎ−プロピルアミン、トリ−ｎ−ブチルアミン等の３級アミン、ジイソプロピルアミン等の２級アミン、ピリジン、２，３−ルチジン、２，４−ルチジン、２，６−ルチジン、３，４−ルチジン、３，５−ルチジン、２，４，６−コリジン、３，５，６−コリジン等の含窒素芳香族複素環式化合物が好ましい。さらに、トリメチルアミン、トリエチルアミン、ジイソプロピルエチルアミン、トリ−ｎ−プロピルアミン、トリ−ｎ−ブチルアミン、ピリジン等がより好ましい。 Among these, tertiary amines such as trimethylamine, triethylamine, diisopropylethylamine, tri-n-propylamine, tri-n-butylamine, secondary amines such as diisopropylamine, pyridine, 2,3-lutidine, 2,4-lutidine, Nitrogen-containing aromatic heterocyclic compounds such as 2,6-lutidine, 3,4-lutidine, 3,5-lutidine, 2,4,6-collidine, and 3,5,6-collidine are preferred. Furthermore, trimethylamine, triethylamine, diisopropylethylamine, tri-n-propylamine, tri-n-butylamine, pyridine and the like are more preferable.
前記有機塩基Ｂの使用量は、化学量論的には、アンモニア１モルに対して３モルであり、ハロゲン化スルフリル１モルに対して１．５モルであるが、反応を円滑に進行させる為には、化学量論量より多く用いることが好ましい。 The amount of the organic base B used is stoichiometrically 3 moles per mole of ammonia and 1.5 moles per mole of sulfuryl halide. In order to facilitate the reaction, It is preferable to use more than the stoichiometric amount.
従って、前記有機塩基Ｂの使用量として、アンモニア１モルに対し１〜５０モル（好ましくは１〜１０モル）であり、又、該スルフリル１モルに対して１．５〜１０モル（好ましくは２〜５モル）である。 Therefore, the amount of the organic base B used is 1 to 50 mol (preferably 1 to 10 mol) with respect to 1 mol of ammonia, and 1.5 to 10 mol (preferably 2 with respect to 1 mol of sulfuryl). ~ 5 mol).
なお、有機塩基Ｂが該スルフリル１モルに対して１．５モル未満の場合、反応自体は進行するが、この場合、反応系内にアンモニアの割合が多くなり、スルファミドが多く生成し、変換率が低下することもあるので、前述の当量で反応を行うことが好ましい。 In addition, when the organic base B is less than 1.5 mol with respect to 1 mol of the sulfuryl, the reaction itself proceeds, but in this case, the proportion of ammonia increases in the reaction system, so that a large amount of sulfamide is generated and the conversion rate is increased. In some cases, the reaction is preferably carried out at the above-mentioned equivalent.
また、本工程は、有機溶媒又は水を共存させて反応を行うこともできる。ここで有機溶媒とは、本発明の反応に直接関与しない不活性な有機化合物のことを言う。反応溶媒としては、ｎ−ヘキサン、シクロヘキサン、ｎ−ヘプタン等の脂肪族炭化水素類、ベンゼン、トルエン、キシレン、メシチレン等の芳香族炭化水素類、塩化メチレン、クロロホルム、１，２−ジクロロエタン等のハロゲン化炭化水素類、ジエチルエーテル、テトラヒドロフラン、ｔｅｒｔ−ブチルメチルエーテル等のエーテル類、酢酸エチル、酢酸ブチル等のエステル類、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチルピロリドン等のアミド類、アセトニトリル、プロピオニトリル等のニトリル類、ジメチルスルホキシド等が挙げられる。 Moreover, this process can also react by coexisting an organic solvent or water. Here, the organic solvent means an inert organic compound that does not directly participate in the reaction of the present invention. Reaction solvents include aliphatic hydrocarbons such as n-hexane, cyclohexane and n-heptane, aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene, halogens such as methylene chloride, chloroform and 1,2-dichloroethane. Hydrocarbons, ethers such as diethyl ether, tetrahydrofuran and tert-butyl methyl ether, esters such as ethyl acetate and butyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like Examples include amides, nitriles such as acetonitrile and propionitrile, and dimethyl sulfoxide.
その中でも酢酸エチル、酢酸ブチル等のエステル類、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチルピロリドン等のアミド類、アセトニトリル、プロピオニトリル等のニトリル類、ジメチルスルホキシドが好ましく、アセトニトリル、プロピオニトリル等のニトリル類がより好ましい。これらの反応溶媒は単独又は組み合わせて使用することができる。 Among them, esters such as ethyl acetate and butyl acetate, amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone, nitriles such as acetonitrile and propionitrile, and dimethyl sulfoxide are preferable. Nitriles such as acetonitrile and propionitrile are more preferable. These reaction solvents can be used alone or in combination.
有機溶媒又は水の使用量としては、特に制限はないが、アンモニア１モルに対して０．１Ｌ（リットル）以上を使用すればよく、通常は０．１〜２０Ｌが好ましく、特に０．１〜１０Ｌがより好ましい。 Although there is no restriction | limiting in particular as the usage-amount of an organic solvent or water, 0.1 L (liter) or more should just be used with respect to 1 mol of ammonia, and 0.1-20L is preferable normally, Especially 0.1-L is preferable. 10L is more preferable.
なお、上述の有機塩基Ｂが液体である場合には、これら有機塩基Ｂ（例えばトリエチルアミンなど）が溶媒としての役割も兼ねるため、これらを過剰に用いて溶媒として機能させることもできる。 In addition, when the above-mentioned organic base B is liquid, since these organic bases B (for example, triethylamine etc.) also serve as a solvent, they can be used in excess to function as a solvent.
温度条件としては、特に制限はないが、−５０〜＋１５０℃の範囲で行えばよい。通常は−２０〜＋１００℃が好ましく、特に−１０〜＋７０℃がより好ましい。−５０℃よりも低い温度であれば反応速度が遅くなり、＋１５０℃を超える温度であれば、生成物の分解等が生じることもある。 Although there is no restriction | limiting in particular as temperature conditions, What is necessary is just to carry out in the range of -50- + 150 degreeC. Usually, −20 to + 100 ° C. is preferable, and −10 to + 70 ° C. is more preferable. If the temperature is lower than −50 ° C., the reaction rate is slow, and if it is higher than + 150 ° C., decomposition of the product may occur.
圧力条件としては、特に制限はなく、常圧条件（０．１ＭＰａ（絶対圧。以下同じ。））、又は圧力に耐えられる反応器を用いて減圧条件もしくは加圧条件の下で行うことができる。すなわち、０〜５ＭＰａの範囲で行えば良いが、０．０１〜２ＭＰａが好ましく、０．０２〜１ＭＰａがより好ましい。 The pressure condition is not particularly limited, and can be performed under normal pressure conditions (0.1 MPa (absolute pressure; the same applies hereinafter)) or under reduced pressure conditions or pressurized conditions using a reactor that can withstand the pressure. . That is, it may be performed in the range of 0 to 5 MPa, but 0.01 to 2 MPa is preferable, and 0.02 to 1 MPa is more preferable.
反応工程に使われる反応容器としては、ステンレス鋼、モネル、ハステロイ、ニッケル、又はこれらの金属やポリテトラフルオロエチレン、パーフルオロポリエーテル樹脂などのフッ素樹脂でライニングされた耐圧反応容器などが挙げられる。 Examples of the reaction vessel used in the reaction process include a pressure-resistant reaction vessel lined with stainless steel, monel, hastelloy, nickel, or a fluororesin such as these metals, polytetrafluoroethylene, and perfluoropolyether resin.
反応時間としては、特に制限はない。反応に必要な時間は、基質および反応条件により異なるため、ガスクロマトグラフィー、液体クロマトグラフィー、ＮＭＲ等の分析手段により、反応の進行状況を追跡して原料が殆ど消失した時点を終点とすることが好ましい。例えば、反応開始直後に原料が消失しているのであれば、その時点で反応を終わらせて良いし、逆に一週間程度反応を続けても良い。 There is no restriction | limiting in particular as reaction time. Since the time required for the reaction varies depending on the substrate and the reaction conditions, the progress of the reaction can be traced by an analytical means such as gas chromatography, liquid chromatography, NMR, etc. preferable. For example, if the raw material disappears immediately after the start of the reaction, the reaction may be terminated at that point, or the reaction may be continued for about one week.
以下、［反応工程］において好ましい条件を述べる。 Hereinafter, preferable conditions in the [reaction step] will be described.
有機塩基Ｂの存在下、ハロゲン化スルフリル、及びアンモニアを反応させることで、式［ １ ］ で表される、「イミド酸と有機塩基Ｂからなる塩又は錯体」が得られるが、例えば、反応器への仕込みの順番として、オートクレーブ等の耐圧反応容器に有機溶媒、有機塩基Ｂ、ハロゲン化スルフリルを加えた後に、アンモニアを加えた後、容器を密閉して反応させることが好ましい。また、反応させる際、アンモニア１モルに対して、ハロゲン化スルフリルが２〜５ モル、有機塩基Ｂが２〜５モルで行うのが好ましい。 By reacting sulfuryl halide and ammonia in the presence of the organic base B, a “salt or complex composed of imidic acid and the organic base B” represented by the formula [1] can be obtained. It is preferable to add the organic solvent, the organic base B, and the sulfuryl halide to a pressure-resistant reaction vessel such as an autoclave, and then add ammonia, and then close the vessel for the reaction. Moreover, when making it react, it is preferable to carry out by 2-5 mol of halogenated sulfuryl, and 2-5 mol of organic base B with respect to 1 mol of ammonia.
また、有機溶媒の使用量として、アンモニア１モルに対して０．１〜２０Ｌ が好ましく、温度条件として、０〜１００℃が好ましい。また、圧力条件としては、０．０２〜１ＭＰａが好ましい。 Moreover, 0.1-20L is preferable with respect to 1 mol of ammonia as the usage-amount of an organic solvent, and 0-100 degreeC is preferable as temperature conditions. Moreover, as pressure conditions, 0.02-1 MPa is preferable.
前記反応工程を経ることで、「イミド酸と有機塩基Ｂからなる塩又は錯体」を含む反応混合物が得られる。該反応混合物中には、以下の副生成物（以下、単に「副生成物」ということもある）、
ＸＳＯ2ＮＨＳＯ2ＮＨＳＯ2Ｘ
が微量、生成することがある（スキーム１参照）。
XSO 2 NHSO 2 NHSO 2 X
May form in trace amounts (see Scheme 1).
該副生成物は、水洗などの簡便な操作により除去することが可能である。本発明で後述する洗浄工程のように、水を添加して洗浄する工程を経ることは、該目的物である「イミド酸と有機塩基Ｂからなる塩又は錯体」の化学純度を向上させるという点でも、好ましいものである。 The by-product can be removed by a simple operation such as washing with water. The point of passing through the step of washing by adding water as in the washing step described later in the present invention improves the chemical purity of the “salt or complex comprising imide acid and organic base B” which is the target product. However, it is preferable.
［洗浄工程］
次に、得られた反応混合物を水洗し、「イミド酸と有機塩基Ｂからなる塩又は錯体」を含む水層を得る工程（洗浄工程）について説明する。
[Washing process]
Next, the process (washing | cleaning process) which wash | cleans the obtained reaction mixture and obtains the water layer containing "the salt or complex which consists of an imide acid and the organic base B" is demonstrated.
洗浄工程は、前記反応混合物に水を添加して洗浄し（以下、単に「水洗浄」ということもある）、分離操作によって「イミド酸と有機塩基Ｂからなる塩又は錯体」を含む有機混合物（以下、これを「有機混合物」ということもある）、及び、「イミド酸と有機塩基Ｂからなる塩又は錯体」を含む水層（以下、単に「塩又は錯体を含む水層」ということもある）を得る工程である。洗浄工程は、特にその操作は限定されないが、主な方法について以下に記載する。 In the washing step, water is added to the reaction mixture for washing (hereinafter, sometimes simply referred to as “water washing”), and an organic mixture containing a “salt or complex composed of imide acid and organic base B” by a separation operation ( Hereinafter, this may also be referred to as “organic mixture”) and an aqueous layer containing “salt or complex comprising imide acid and organic base B” (hereinafter, simply referred to as “aqueous layer containing salt or complex”). ). The operation of the washing step is not particularly limited, but the main method is described below.
まず、反応混合物にアセトニトリルやテトラヒドロフラン等の水に可溶な溶媒が含まれる場合、水を添加する前に、該溶媒を蒸留等で濃縮することが好ましい。濃縮の際に蒸留等で留去した該溶媒は再度反応に使用することも出来る。濃縮により残った「イミド酸と有機塩基Ｂからなる塩又は錯体」を含む残渣に、水を添加し、水洗浄した後に、分離操作により有機混合物と塩又は錯体を含む水層とがそれぞれ得られる（スキーム２の（ｂ）参照）。この時、水と共に、水に不溶・難溶な溶媒を添加し、水洗浄・分離操作を行い、有機溶媒で希釈された有機混合物としても良い（スキーム２の（ａ）参照）。 First, when a water-soluble solvent such as acetonitrile or tetrahydrofuran is contained in the reaction mixture, it is preferable to concentrate the solvent by distillation or the like before adding water. The solvent removed by distillation or the like during concentration can be used again for the reaction. Water is added to the residue containing “salt or complex consisting of imido acid and organic base B” remaining after concentration, and after washing with water, an organic mixture and an aqueous layer containing the salt or complex are obtained by separation operation, respectively. (See (b) of Scheme 2). At this time, a solvent insoluble or hardly soluble in water may be added together with water, followed by washing with water and separation operation to obtain an organic mixture diluted with an organic solvent (see (a) of Scheme 2).
次に、反応混合物中に水に不溶・難溶な溶媒が含まれる場合、前記のように濃縮を行っても良いし、そのまま水を添加して、水洗浄・分離によって有機混合物と塩又は錯体を含む水層とを得ても良い（スキーム２の（ｃ）参照）。反応工程において、無溶媒で反応を行った場合も同様である。
前記水洗浄で用いられる水の量は特に限定されないが、通常、反応混合物中の「イミド酸と有機塩基Ｂからなる塩又は錯体」に対して、５０〜３００質量％程度を用いることが好ましい。また、前記の量の水を数回に分けて洗浄・分離を繰り返すことも好ましい操作の一つである。 The amount of water used in the water washing is not particularly limited, but it is usually preferable to use about 50 to 300% by mass with respect to the “salt or complex consisting of imide acid and organic base B” in the reaction mixture. It is also a preferable operation to repeat the washing / separation by dividing the amount of water into several times.
前記水洗浄は通常は常温行うことが好ましいが、温度条件に特に制限はなく、加温してもよい。また、水洗浄に使われる反応容器としては、ステンレス鋼、モネル、ハステロイ、ニッケル、又はこれらの金属やポリテトラフルオロエチレン、パーフルオロポリエーテル樹脂などのフッ素樹脂でライニングされた耐圧反応容器などが挙げられる。 The washing with water is usually preferably performed at room temperature, but the temperature condition is not particularly limited and may be heated. Examples of the reaction vessel used for water washing include a pressure-resistant reaction vessel lined with stainless steel, monel, hastelloy, nickel, or a fluorine resin such as these metals, polytetrafluoroethylene, and perfluoropolyether resin. It is done.
洗浄工程において、水洗浄した後の分離操作とは、有機混合物と、塩又は錯体を含む水層とを分けられる方法であれば特に限定はない。一般的には簡便な分液やろ過、遠心分離等で行うことが出来る。 In the washing step, the separation operation after washing with water is not particularly limited as long as it is a method capable of separating an organic mixture and an aqueous layer containing a salt or a complex. In general, it can be carried out by simple separation, filtration, centrifugation or the like.
洗浄工程によって得られた有機混合物は、さらにアルカリ金属の炭酸塩もしくは炭酸水素塩、又は、アルカリ土類金属の炭酸塩による洗浄・分離操作を行うことが好ましい。該有機混合物には、反応工程で生成した、有機塩基Ｂとハロゲン化水素とからなる塩が含まれる（スキーム１参照）。そのため、該炭酸塩もしくは該炭酸水素塩による洗浄・分離操作を行うことで、有機塩基Ｂとハロゲン化水素とからなる塩が効果的に除かれ、目的物である「イミド酸と有機塩基Ｂからなる塩又は錯体」の粗体を得ることが出来る（スキーム２（ｄ）参照。該有機混合物が溶媒で希釈されている場合、さらに濃縮を行うことで粗体が得られる）。該粗体は、溶媒濃縮や洗浄等の操作によって精製を行うことができる。また、後述する［カチオン交換工程］に用いることで、式［３］で表されるビスハロゲン化スルホニルイミド酸金属塩に変換することが出来る。カチオン交換工程へは、アルカリ金属の炭酸塩もしくは炭酸水素塩又はアルカリ土類金属の炭酸塩による洗浄・分離を経ずに有機混合物のまま用いることも出来る（スキーム２（ｅ））が、有機塩基Ｂとハロゲン化水素とからなる塩を取り除いた粗体を用いる（スキーム２（ｆ））方が、カチオン工程における、アルカリ金属の水酸化物もしくは炭酸塩、又はアルカリ土類金属の水酸化物もしくは炭酸塩の使用量を抑えることが出来るため、好ましいといえる。また、該分離操作によって得られた水層は、微量の「イミド酸と有機塩基Ｂからなる塩又は錯体」を含むことがあるため、洗浄工程で得られた塩又は錯体を含む水層に混ぜて回収工程に用いることも本発明の好ましい形態といえる（スキーム２（ｇ））。 The organic mixture obtained by the washing step is preferably further subjected to a washing / separation operation with an alkali metal carbonate or hydrogen carbonate or an alkaline earth metal carbonate. The organic mixture includes a salt formed from the organic base B and hydrogen halide formed in the reaction step (see Scheme 1). Therefore, by performing washing / separation operation with the carbonate or the hydrogen carbonate, the salt composed of the organic base B and the hydrogen halide is effectively removed, and the target product “from imidic acid and the organic base B is obtained. (Refer to Scheme 2 (d). When the organic mixture is diluted with a solvent, the crude product is obtained by further concentration). The crude product can be purified by operations such as solvent concentration and washing. Moreover, it can convert into the bis halogenated sulfonyl imide acid metal salt represented by Formula [3] by using for the [cation exchange process] mentioned later. For the cation exchange step, the organic mixture can be used as it is without washing and separation with an alkali metal carbonate or hydrogen carbonate or an alkaline earth metal carbonate (Scheme 2 (e)), but an organic base The method of using a crude product from which a salt composed of B and a hydrogen halide is removed (Scheme 2 (f)) is an alkali metal hydroxide or carbonate, or an alkaline earth metal hydroxide or Since the amount of carbonate used can be suppressed, it can be said to be preferable. In addition, since the aqueous layer obtained by the separation operation may contain a trace amount of “salt or complex consisting of imide acid and organic base B”, it is mixed with the aqueous layer containing the salt or complex obtained in the washing step. It can also be said that it is a preferred embodiment of the present invention to be used in the recovery step (Scheme 2 (g)).
前記アルカリ金属の炭酸塩としては炭酸リチウム（Ｌｉ２ＣＯ３）、炭酸ナトリウム（Ｎａ２ＣＯ３）、炭酸カリウム（Ｋ２ＣＯ３）、炭酸ルビジウム（Ｒｂ２ＣＯ３）、炭酸セシウム（Ｃｓ２ＣＯ３）が、アルカリ金属の炭酸水素塩としては炭酸水素リチウム（ＬiＨＣＯ３）、炭酸水素ナトリウム（ＮａＨＣＯ３）、炭酸水素カリウム（ＫＨＣＯ３）、炭酸水素ルビジウム（ＲｂＨＣＯ３）、炭酸水素セシウム（ＣｓＨＣＯ３）アルカリ土類金属の炭酸塩としては炭酸マグネシウム（ＭｇＣＯ３）、炭酸カルシウム（ＣａＣＯ３）、炭酸バリウム（ＢａＣＯ３）、炭酸ストロンチウム（ＳｒＣＯ３）が挙げられる。中でも炭酸リチウム（Ｌｉ２ＣＯ３）、炭酸ナトリウム（Ｎａ２ＣＯ３）、炭酸カリウム（Ｋ２ＣＯ３）、炭酸ルビジウム（Ｒｂ２ＣＯ３）、炭酸セシウム（Ｃｓ２ＣＯ３）が好ましい。 Examples of the alkali metal carbonate include lithium carbonate (Li 2 CO 3 ), sodium carbonate (Na 2 CO 3 ), potassium carbonate (K 2 CO 3 ), rubidium carbonate (Rb 2 CO 3 ), and cesium carbonate (Cs 2 CO 3 ) are alkali metal hydrogen carbonates such as lithium hydrogen carbonate (LiHCO 3 ), sodium hydrogen carbonate (NaHCO 3 ), potassium hydrogen carbonate (KHCO 3 ), rubidium hydrogen carbonate (RbHCO 3 ), cesium hydrogen carbonate (CsHCO 3 ) Alkaline earth metal carbonates include magnesium carbonate (MgCO 3 ), calcium carbonate (CaCO 3 ), barium carbonate (BaCO 3 ), and strontium carbonate (SrCO 3 ). Among these, lithium carbonate (Li 2 CO 3 ), sodium carbonate (Na 2 CO 3 ), potassium carbonate (K 2 CO 3 ), rubidium carbonate (Rb 2 CO 3 ), and cesium carbonate (Cs 2 CO 3 ) are preferable.
［回収工程］
回収工程は、洗浄工程によって得られた「イミド酸と有機塩基Ｂからなる塩又は錯体」を含む水層から、目的物である「イミド酸と有機塩基Ｂからなる塩又は錯体」を回収するものである。回収工程では、塩又は錯体を含む水層と有機塩基Ａとを接触させることで、目的物である「イミド酸と有機塩基Ｂからなる塩又は錯体」を効率よく選択的に有機塩基Ａに抽出することが出来る（スキーム３（ｈ）参照）。この際、水層中には目的物と共に、反応工程において生成した前記副生成物が含まれていることがあるが、回収工程によって得られた目的物を含む有機塩基Ａ中には前記副生成物が混入することはなく、高純度で目的物を回収することができる。
[Recovery process]
The recovery step recovers the target “salt or complex consisting of imido acid and organic base B” from the aqueous layer containing “salt or complex consisting of imido acid and organic base B” obtained in the washing step. It is. In the recovery step, the aqueous layer containing the salt or complex is brought into contact with the organic base A to efficiently and selectively extract the target “salt or complex consisting of imide acid and organic base B” into the organic base A. (See Scheme 3 (h)). At this time, the by-product generated in the reaction step may be contained together with the target product in the aqueous layer, but the by-product is contained in the organic base A containing the target product obtained in the recovery step. The product is not mixed, and the target product can be recovered with high purity.
水層と接触させる有機塩基Ａは、水と混合した時に２層に分離するものであれば特に限定はされない。具体的には、トリメチルアミン、トリエチルアミン、ジイソプロピルエチルアミン、トリプロピルアミン、トリブチルアミン等の３級アミン、ジイソプロピルアミン等の２級アミン、ピリジン、２，３−ルチジン、２，４−ルチジン、２，６−ルチジン、３，４−ルチジン、３，５−ルチジン、２，４，６−コリジン、３，５，６−コリジン等の含窒素芳香族複素環式化合物等が挙げられる。中でもトリエチルアミン、ジイソプロピルエチルアミン、トリブチルアミンは、工業的規模での入手がし易く且つ、安価である点で好ましい。 The organic base A brought into contact with the aqueous layer is not particularly limited as long as it is separated into two layers when mixed with water. Specifically, tertiary amines such as trimethylamine, triethylamine, diisopropylethylamine, tripropylamine and tributylamine, secondary amines such as diisopropylamine, pyridine, 2,3-lutidine, 2,4-lutidine, 2,6- Examples thereof include nitrogen-containing aromatic heterocyclic compounds such as lutidine, 3,4-lutidine, 3,5-lutidine, 2,4,6-collidine, and 3,5,6-collidine. Among these, triethylamine, diisopropylethylamine, and tributylamine are preferable because they are easily available on an industrial scale and are inexpensive.
該水層には、反応工程で生成した有機塩基Ｂとハロゲン化水素とからなる塩が含まれていることがある（スキーム１参照）。そこで、回収工程において、該水層と有機塩基Ａとを接触させる際に、アルカリ金属の炭酸塩もしくは炭酸水素塩又はアルカリ土類金属の炭酸塩を添加し、該有機塩基Ｂとハロゲン化水素からなる塩を取り除くことは好ましい操作の一つである（スキーム３（ｉ））。この際、ハロゲン化水素と塩をなしていた有機塩基Ｂが遊離する。遊離した有機塩基Ｂは目的物抽出用の有機塩基Ａとして機能するため、該水層に添加する有機塩基Ａの量を低減させる効果があり、その点でも好ましい。また、前記遊離した有機塩基Ｂのみを回収工程の有機塩基Ａとして用いることも可能であり、この場合、追加の有機塩基Ａを添加せずに分離操作を行ってよい（スキーム３（ｊ））
前記アルカリ金属の炭酸塩としては炭酸リチウム（Ｌｉ２ＣＯ３）、炭酸ナトリウム（Ｎａ２ＣＯ３）、炭酸カリウム（Ｋ２ＣＯ３）、炭酸ルビジウム（Ｒｂ２ＣＯ３）、炭酸セシウム（Ｃｓ２ＣＯ３）が、アルカリ金属の炭酸水素塩としては炭酸水素リチウム（ＬiＨＣＯ３）、炭酸水素ナトリウム（ＮａＨＣＯ３）、炭酸水素カリウム（ＫＨＣＯ３）、炭酸水素ルビジウム（ＲｂＨＣＯ３）、炭酸水素セシウム（ＣｓＨＣＯ３）アルカリ土類金属の炭酸塩としては炭酸マグネシウム（ＭｇＣＯ３）、炭酸カルシウム（ＣａＣＯ３）、炭酸バリウム（ＢａＣＯ３）、炭酸ストロンチウム（ＳｒＣＯ３）が挙げられる。中でも炭酸リチウム（Ｌｉ２ＣＯ３）、炭酸ナトリウム（Ｎａ２ＣＯ３）、炭酸カリウム（Ｋ２ＣＯ３）、炭酸ルビジウム（Ｒｂ２ＣＯ３）、炭酸セシウム（Ｃｓ２ＣＯ３）が好ましい。 Examples of the alkali metal carbonate include lithium carbonate (Li 2 CO 3 ), sodium carbonate (Na 2 CO 3 ), potassium carbonate (K 2 CO 3 ), rubidium carbonate (Rb 2 CO 3 ), and cesium carbonate (Cs 2 CO 3 ) are alkali metal hydrogen carbonates such as lithium hydrogen carbonate (LiHCO 3 ), sodium hydrogen carbonate (NaHCO 3 ), potassium hydrogen carbonate (KHCO 3 ), rubidium hydrogen carbonate (RbHCO 3 ), cesium hydrogen carbonate (CsHCO 3 ) Alkaline earth metal carbonates include magnesium carbonate (MgCO 3 ), calcium carbonate (CaCO 3 ), barium carbonate (BaCO 3 ), and strontium carbonate (SrCO 3 ). Among these, lithium carbonate (Li 2 CO 3 ), sodium carbonate (Na 2 CO 3 ), potassium carbonate (K 2 CO 3 ), rubidium carbonate (Rb 2 CO 3 ), and cesium carbonate (Cs 2 CO 3 ) are preferable.
前記有機塩基Ａの量は、水層中に含まれる目的物の含有量に合わせて適宜検討すればよいが、通常、目的物に対して０．１〜５質量％であることが好ましい。より好ましくは０．３〜３質量％であり、特に好ましくは０．５〜２質量％である。水層中の目的物の含有量については、１９Ｆ−ＮＭＲ測定によって確認することができる。 The amount of the organic base A may be appropriately determined in accordance with the content of the target product contained in the aqueous layer, but it is usually preferably 0.1 to 5% by mass with respect to the target product. More preferably, it is 0.3-3 mass%, Most preferably, it is 0.5-2 mass%. The content of the target product in the aqueous layer can be confirmed by 19 F-NMR measurement.
該水層と有機塩基Ａとの接触時間は特に限定されないが、通常０．５〜１２時間程度で充分である。好ましくは０．５〜５時間であり、さらに好ましくは０．５〜３時間がよい。また、接触方法は特に限定はなく、通常、反応器内にて水層と有機塩基Ａとの混合溶液を攪拌すればよい。 The contact time between the aqueous layer and the organic base A is not particularly limited, but usually about 0.5 to 12 hours is sufficient. Preferably it is 0.5-5 hours, More preferably, 0.5-3 hours are good. Further, the contact method is not particularly limited, and usually, the mixed solution of the aqueous layer and the organic base A may be stirred in the reactor.
水層と有機塩基Ａとを接触させた後、分離を行うことで、目的物である「イミド酸と有機塩基Ｂからなる塩又は錯体」を含む有機層が得られる。該有機層を濃縮することで、「イミド酸と有機塩基Ｂからなる塩又は錯体」の粗体を得ることが出来る。該粗体は、そのまま単独で再結晶などの精製に用いてもよく、単独で、又は洗浄工程で得られた有機混合物又は「イミド酸と有機塩基Ｂからなる塩又は錯体」の粗体と混合して、［カチオン交換工程］に使用してもよい。また、前記の量の有機塩基Ａを数回に分けて抽出・分離を繰り返して該粗体を得ることも好ましい操作の一つである。また、抽残液である水層を分析し、目的物が残っていた場合は、注残液にさらに有機塩基Ａを加えて抽出・分離を行うことも好ましい。 After the aqueous layer and the organic base A are brought into contact with each other, separation is performed to obtain an organic layer containing the target “salt or complex composed of imido acid and organic base B”. By concentrating the organic layer, a crude product of “salt or complex composed of imido acid and organic base B” can be obtained. The crude product may be used alone for purification such as recrystallization, alone or mixed with an organic mixture obtained in the washing step or a crude product of “salt or complex comprising imido acid and organic base B”. Then, it may be used in the [cation exchange step]. Further, it is one of preferable operations to obtain the crude product by repeating the extraction and separation by dividing the amount of the organic base A into several times. In addition, when the aqueous layer that is the extracted residual liquid is analyzed and the target product remains, it is also preferable to add the organic base A to the poured residual liquid for extraction / separation.
［カチオン交換工程］
本工程は、洗浄工程及び回収工程において得られた有機混合物又は「イミド酸と有機塩基Ｂからなる塩又は錯体」の粗体を用いて、アルカリ金属の水酸化物もしくは炭酸塩、又はアルカリ土類金属の水酸化物もしくは炭酸塩を反応させ、式［３］で表されるビスハロゲン化スルホニルイミド酸金属塩を得る工程である。
[Cation exchange process]
In this step, the organic mixture obtained in the washing step and the recovery step, or a crude product of “salt or complex consisting of imido acid and organic base B” is used, alkali metal hydroxide or carbonate, or alkaline earth In this step, a metal hydroxide or carbonate is reacted to obtain a metal salt of a bishalogenated sulfonylimide acid represented by the formula [3].
アルカリ金属の水酸化物としては、水酸化リチウム（ＬｉＯＨ）、水酸化ナトリウム（ＮａＯＨ）、水酸化カリウム（ＫＯＨ）、水酸化ルビジウム（ＲｂＯＨ）、水酸化セシウム（ＣｓＯＨ）が、アルカリ金属の炭酸塩としては炭酸リチウム（Ｌｉ２ＣＯ３）、炭酸ナトリウム（Ｎａ２ＣＯ３）、炭酸カリウム（Ｋ２ＣＯ３）、炭酸ルビジウム（Ｒｂ２ＣＯ３）、炭酸セシウム（Ｃｓ２ＣＯ３）が、アルカリ土類金属の水酸化物としては、水酸化マグネシウム（Ｍｇ（ＯＨ）２）、水酸化カルシウム（Ｃａ（ＯＨ）２）、水酸化バリウム（Ｂａ（ＯＨ）２）、水酸化ストロンチウム（Ｓｒ（ＯＨ）２）、アルカリ土類金属の炭酸塩としては炭酸マグネシウム（ＭｇＣＯ３）、炭酸カルシウム（ＣａＣＯ３）、炭酸バリウム（ＢａＣＯ３）、炭酸ストロンチウム（ＳｒＣＯ３）が挙げられ、好ましくは水酸化リチウム（ＬｉＯＨ）、水酸化カリウム（ＫＯＨ）、水酸化ルビジウム（ＲｂＯＨ）、水酸化セシウム（ＣｓＯＨ）、水酸化マグネシウム（Ｍｇ（ＯＨ）２）、水酸化カルシウム（Ｃａ（ＯＨ）２）、水酸化バリウム（Ｂａ（ＯＨ）２）、水酸化ストロンチウム（Ｓｒ（ＯＨ）２）が挙げられる。また、これらのアルカリ金属の水酸化物もしくは炭酸塩、又はアルカリ土類金属の水酸化物もしくは炭酸塩は１種または２種以上を組み合わせて用いることもできる。２種以上を用いる場合、同一のアルカリ金属の水酸化物と炭酸塩（例えば、水酸化カリウムと炭酸カリウム）の組み合わせ、又は同一のアルカリ土類金属の水酸化物と炭酸塩（例えば、水酸化マグネシウムと炭酸マグネシウム）の組み合わせを用いることが好ましい。 Examples of the alkali metal hydroxide include lithium hydroxide (LiOH), sodium hydroxide (NaOH), potassium hydroxide (KOH), rubidium hydroxide (RbOH), and cesium hydroxide (CsOH). As lithium carbonate (Li 2 CO 3 ), sodium carbonate (Na 2 CO 3 ), potassium carbonate (K 2 CO 3 ), rubidium carbonate (Rb 2 CO 3 ), cesium carbonate (Cs 2 CO 3 ), alkaline earth Examples of metal hydroxides include magnesium hydroxide (Mg (OH) 2 ), calcium hydroxide (Ca (OH) 2 ), barium hydroxide (Ba (OH) 2 ), and strontium hydroxide (Sr (OH)). 2), magnesium carbonate as the alkaline earth metal carbonate (MgCO 3), calcium carbonate (CaCO 3), carbonate Bali Beam (BaCO 3), can be mentioned strontium carbonate (SrCO 3), preferably lithium hydroxide (LiOH), potassium hydroxide (KOH), rubidium hydroxide (RbOH), cesium hydroxide (CsOH), magnesium hydroxide ( Mg (OH) 2 ), calcium hydroxide (Ca (OH) 2 ), barium hydroxide (Ba (OH) 2 ), and strontium hydroxide (Sr (OH) 2 ). These alkali metal hydroxides or carbonates, or alkaline earth metal hydroxides or carbonates may be used alone or in combination of two or more. When two or more are used, a combination of the same alkali metal hydroxide and carbonate (for example, potassium hydroxide and potassium carbonate), or the same alkaline earth metal hydroxide and carbonate (for example, hydroxide) It is preferable to use a combination of magnesium and magnesium carbonate.
アルカリ金属の水酸化物もしくは炭酸塩、又はアルカリ土類金属の水酸化物もしくは炭酸塩の使用量は、「イミド酸と有機塩基Ｂからなる塩又は錯体」１モルあたり１〜５モルが好ましく、より好ましくは１〜３モルである。５モルを超える量、すなわち過剰量の塩基を反応させた場合、反応は進行するが、「イミド酸と有機塩基Ｂからなる塩又は錯体」が分解してしまい、収率が低下してしまうことがある為、過剰量の塩基を用いることは好ましくない。また、１モルよりも少ないと、変換率が低下することからも、好ましくない。 The amount of alkali metal hydroxide or carbonate, or alkaline earth metal hydroxide or carbonate used is preferably 1 to 5 mol per mol of "salt or complex consisting of imide acid and organic base B" More preferably, it is 1-3 mol. When the amount exceeds 5 mol, that is, when an excess amount of base is reacted, the reaction proceeds, but the “salt or complex composed of imido acid and organic base B” is decomposed, resulting in a decrease in yield. Therefore, it is not preferable to use an excessive amount of base. On the other hand, when the amount is less than 1 mol, the conversion rate decreases, which is not preferable.
アルカリ金属の水酸化物もしくは炭酸塩、又はアルカリ土類金属の水酸化物もしくは炭酸塩を反応させる際、溶媒を用いることができる。例えば水を溶媒として用いた場合、塩基の濃度を、通常１０〜７０質量％、好ましくは２０〜６０質量％、より好ましくは２０〜４０質量％となるように水を加えると良い。水の量が少なすぎると反応系内における攪拌が困難になり、また多すぎる場合は、反応後の処理が煩雑になることや、通常よりも大きな反応容器が必要となる。 When reacting an alkali metal hydroxide or carbonate, or an alkaline earth metal hydroxide or carbonate, a solvent can be used. For example, when water is used as a solvent, water is preferably added so that the concentration of the base is usually 10 to 70% by mass, preferably 20 to 60% by mass, more preferably 20 to 40% by mass. If the amount of water is too small, stirring in the reaction system becomes difficult, and if it is too large, processing after the reaction becomes complicated and a reaction container larger than usual is required.
なお、水以外の有機溶媒を用いることもできる。ジエチルエーテル、ジオキサン、テトラヒドロフラン、エチレングリコールジメチルエーテルなどのエーテル類等の溶媒が使用できる。また、水と共に組み合わせて使用することもできる。溶媒の使用量としては、「イミド酸と有機塩基Ｂからなる塩又は錯体」に対して通常０．５〜１０倍容量、好ましくは１〜７倍容量の範囲から適宜選択される。しかしながら、水を用いても十分反応が進行する為、水以外の有機溶媒を特に用いるメリットは少ない。 An organic solvent other than water can also be used. Solvents such as ethers such as diethyl ether, dioxane, tetrahydrofuran and ethylene glycol dimethyl ether can be used. It can also be used in combination with water. The amount of the solvent to be used is appropriately selected from the range of usually 0.5 to 10 times, preferably 1 to 7 times the capacity of “a salt or complex comprising imide acid and organic base B”. However, since the reaction proceeds sufficiently even if water is used, there is little merit in using an organic solvent other than water.
反応温度に特別に制限はないが、通常−１０℃〜＋１１０℃、好ましくは＋２５〜＋８０℃である。−１０℃未満であると反応が充分に進行せず、収率低下の原因となり、経済的に不利となる、あるいは、反応速度が低下して反応終了までに長時間を要するなどの問題を生ずる場合がある。一方、＋１１０℃を超えると、副生物が生じやすく、また過剰な加熱はエネルギー効率が悪い。 The reaction temperature is not particularly limited, but is usually −10 ° C. to + 110 ° C., preferably +25 to + 80 ° C. If the temperature is lower than -10 ° C, the reaction does not proceed sufficiently and causes a decrease in yield, which is economically disadvantageous, or causes a problem that the reaction rate decreases and it takes a long time to complete the reaction. There is a case. On the other hand, if it exceeds + 110 ° C., by-products are likely to be generated, and excessive heating is not energy efficient.
反応時間としては、特に制限はないが、通常は２４時間以内の範囲で行えばよく、イオンクロマトグラフィー、ＮＭＲ等の分析手段により反応の進行状況を追跡し、原料基質が殆ど消失した時点を終点とするのが好ましい。 The reaction time is not particularly limited, but it may usually be within a range of 24 hours. The progress of the reaction is traced by an analytical means such as ion chromatography or NMR, and the end point when the raw material substrate has almost disappeared. Is preferable.
カチオン交換工程に用いられる反応器は、ステンレス鋼、ハステロイ、モネルなどの金属製容器や、四フッ化エチレン樹脂、クロロトリフルオロエチレン樹脂、フッ化ビニリデン樹脂、ＰＦＡ樹脂、ポリプロピレン樹脂、ポリエチレン樹脂、そしてガラスなどを内部にライニングしたもの等、常圧又は加圧下で十分反応を行うことができる反応器を使用することができる。 The reactor used for the cation exchange process is made of metal containers such as stainless steel, hastelloy, monel, tetrafluoroethylene resin, chlorotrifluoroethylene resin, vinylidene fluoride resin, PFA resin, polypropylene resin, polyethylene resin, and A reactor that can sufficiently react at normal pressure or under pressure, such as glass lined inside, can be used.
本工程で得られた反応混合物は、中和や再結晶等の簡便な操作によって、精製された高純度のビスハロゲン化スルホニルイミド酸金属塩を得ることが出来る。この際、得られる水を含む有機塩基Ｂは、蒸留等の脱水操作を行うことにより再度反応に使用することができる。 From the reaction mixture obtained in this step, a purified high-purity bishalogenated sulfonylimide acid metal salt can be obtained by a simple operation such as neutralization or recrystallization. At this time, the obtained organic base B containing water can be used again for the reaction by performing a dehydration operation such as distillation.
次に本発明を実施例に基づき詳細に説明する。なお、本発明はかかる実施例に限定されるものではない。 Next, the present invention will be described in detail based on examples. In addition, this invention is not limited to this Example.
［実施例１］
[反応工程]
１Lオートクレーブにアセトニトリルを１８６ｇ、トリエチルアミンを１８６ｇ（１．８４ ｍоｌ）仕込み、氷水で５℃に冷却し、フッ化スルフリルを１２９ｇ(１．２７ ｍоｌ)導入した。フッ化スルフリルを導入した後、続いて、無水アンモニアを９．８ｇ(０．５８ｍоｌ)、３時間掛けて導入した。反応器を室温まで昇温させ、１２時間攪拌した。この反応における目的物の生成比は、９９.９％であり、ＦＳＯ2ＮＨＳＯ2ＮＨＳＯ2Ｆが０．１％であった。この反応液を１９Ｆ−ＮＭＲにより定量を行ったところ出発原料のアンモニアに対するビスフルオロスルホニルイミドトリエチルアンモニウム塩の収率は１００．３％であった。
[Example 1]
[Reaction process]
A 1 L autoclave was charged with 186 g of acetonitrile and 186 g (1.84 mol) of triethylamine, cooled to 5 ° C. with ice water, and 129 g (1.27 mol) of sulfuryl fluoride was introduced. After the introduction of sulfuryl fluoride, 9.8 g (0.58 mole) of anhydrous ammonia was subsequently introduced over 3 hours. The reactor was warmed to room temperature and stirred for 12 hours. The production ratio of the target product in this reaction was 99.9%, and FSO 2 NHSO 2 NHSO 2 F was 0.1%. When this reaction solution was quantified by 19 F-NMR, the yield of bisfluorosulfonylimide triethylammonium salt relative to the starting material ammonia was 100.3%.
[洗浄工程]
上記反応工程で得られた反応液の溶媒を留去し、残渣に水を加え、水洗浄・分離を行い、トリエチルアンモニウム塩を含む有機混合物とトリエチルアンモニウム塩を含む水層とを得た。得られた有機混合物を２０％炭酸カリウム水溶液で洗浄し、ビスフルオロスルホニルイミドトリエチルアンモニウム塩の粗体を１５０ｇ得た。この粗体を１９Ｆ−ＮＭＲにより定量を行ったところ出発原料のアンモニアに対する収率は７４．３％（０．４３１ｍｏｌ）であった（なお、粗体をここでは単離精製せずに、このままカチオン交換反応に用いた）。水洗浄で得られた水層に、２０％炭酸カリウム水溶液洗浄にて得られた水層を加えて１９Ｆ−ＮＭＲにより定量を行ったところ、出発原料のアンモニアに対する収率は２０．９％（０．１１４ｍоｌ）であった。
[Washing process]
The solvent of the reaction solution obtained in the above reaction step was distilled off, and water was added to the residue, followed by washing with water and separation to obtain an organic mixture containing triethylammonium salt and an aqueous layer containing triethylammonium salt. The obtained organic mixture was washed with 20% aqueous potassium carbonate solution to obtain 150 g of a crude product of bisfluorosulfonylimide triethylammonium salt. When this crude product was quantified by 19 F-NMR, the yield relative to the starting material ammonia was 74.3% (0.431 mol). Used for cation exchange reaction). When the aqueous layer obtained by washing with 20% aqueous potassium carbonate was added to the aqueous layer obtained by washing with water and quantitatively determined by 19 F-NMR, the yield relative to ammonia of the starting material was 20.9% ( 0.114 mol).
[回収工程]
上記、洗浄工程における水洗浄および、２０％炭酸カリウム水溶液洗浄にて、分離した水層に対し攪拌下、炭酸カリウムを２３ｇ添加した。その後、トリエチルアミンを７０ｇ添加し、水層と有機層を分離した。得られた有機層を濃縮し、ビスフルオロスルホニルイミドトリエチルアンモニウム塩の粗体を３３．２ｇ得た。この水層から回収した粗体を１９Ｆ−ＮＭＲにより定量を行ったところ、出発原料のアンモニアに対するビスフルオロスルホニルイミドトリエチルアンモニウム塩の収率は１９．５％（０．１１２ｍоｌ）であり、回収工程における回収率は９８．２％であった。回収後の抽残液についても同様に１９Ｆ−ＮＭＲにより定量を行ったところ出発原料のアンモニアに対するビスフルオロスルホニルイミドトリエチルアンモニウム塩の収率は０．４％（０．００２４ｍоｌ）であった。回収工程を経ることで、洗浄工程で水層に溶解したビスフルオロスルホニルイミドトリエチルアンモニウム塩を効率的に回収できた。
[Recovery process]
23 g of potassium carbonate was added to the separated aqueous layer with stirring in the water washing in the washing step and the 20% potassium carbonate aqueous solution washing. Thereafter, 70 g of triethylamine was added, and the aqueous layer and the organic layer were separated. The obtained organic layer was concentrated to obtain 33.2 g of a crude product of bisfluorosulfonylimide triethylammonium salt. When the crude product recovered from this aqueous layer was quantified by 19 F-NMR, the yield of bisfluorosulfonylimide triethylammonium salt relative to the starting ammonia was 19.5% (0.112 mol), and the recovery step The recovery rate was 98.2%. The amount of the extracted residual liquid after recovery was similarly determined by 19 F-NMR. As a result, the yield of bisfluorosulfonylimide triethylammonium salt relative to the starting material ammonia was 0.4% (0.0024 mol). By passing through the recovery step, the bisfluorosulfonylimide triethylammonium salt dissolved in the aqueous layer in the washing step could be recovered efficiently.
[カチオン交換工程]
次に、洗浄工程及び回収工程で得られたビスフルオロスルホニルイミドトリエチルアンモニウム塩の粗体を混合し、水酸化カリウム３１．８ｇを含む水溶液を１時間、室温で混合した。反応混合物のトリエチルアミンおよび水を留去して、ビスフルオロスルホニルイミドカリウムを得た。さらにこれにイソプロパノールを加え、６０℃に加温し未溶解成分を濾別後、冷却することで結晶を析出させて、分離、乾燥後、純度９９％以上のビスフルオロスルホニルイミドカリウムを１０７．３ｇ、収率８５．１％（０．４６９ｍоｌ）であった。
[Cation exchange process]
Next, the crude product of bisfluorosulfonylimide triethylammonium salt obtained in the washing step and the recovery step was mixed, and an aqueous solution containing 31.8 g of potassium hydroxide was mixed for 1 hour at room temperature. Triethylamine and water of the reaction mixture were distilled off to obtain potassium bisfluorosulfonylimide. Further, isopropanol was added thereto, and the mixture was heated to 60 ° C., and the undissolved components were separated by filtration and cooled to precipitate crystals. After separation and drying, 107.3 g of bisfluorosulfonylimide potassium having a purity of 99% or more was obtained. The yield was 85.1% (0.469 mol).
［実施例２］
実施例１と同様の手法により反応および洗浄を行ったところ水層のビスフルオロスルホニルイミドトリエチルアンモニウム塩の１９Ｆ−ＮＭＲによる定量値は０．０７４ｍｏｌであった。
[Example 2]
When the reaction and washing were carried out in the same manner as in Example 1, the quantitative value by 19 F-NMR of the bisfluorosulfonylimide triethylammonium salt in the aqueous layer was 0.074 mol.
[回収工程]
上記、洗浄工程で分離した水層に対し攪拌下、ジイソプロピルエチルアミンを１００ｇ添加し、水層と有機層を分離した。得られた有機層を濃縮し、ビスフルオロスルホニルイミドトリエチルアンモニウム塩の粗体を２１．３ｇ得た。この粗体を１９Ｆ−ＮＭＲにより定量を行ったところ、回収工程における回収率は８２．４％（０．０６１ｍоｌ）であった。
[Recovery process]
While stirring, 100 g of diisopropylethylamine was added to the aqueous layer separated in the washing step, and the aqueous layer and the organic layer were separated. The obtained organic layer was concentrated to obtain 21.3 g of a crude product of bisfluorosulfonylimide triethylammonium salt. When this crude product was quantified by 19 F-NMR, the recovery rate in the recovery step was 82.4% (0.061 mol).
［実施例３］
トリエチルアミンの代わりにジイソプロピルエチルアミンを２３８ｇ（１．８４ ｍоｌ）用いた以外は実施例１と同様の手法により反応および洗浄を行ったところ水層のビスフルオロスルホニルイミドジイソプロピルエチルアンモニウム塩の１９Ｆ−ＮＭＲによる定量値は０．０５２ｍｏｌであった。
[Example 3]
According to 19 F-NMR of bisfluorosulfonylimide diisopropylethyl ammonium salt of the aqueous layer was subjected to reaction and washed in the same manner except for using 238g (1.84 mоl) diisopropylethylamine to Example 1 in place of triethylamine The quantitative value was 0.052 mol.
[回収工程]
上記、洗浄工程で分離した水層に対し攪拌下、トリエチルアミンを１００ｇ添加し、水層と有機層を分離した。得られた有機層を濃縮し、ビスフルオロスルホニルイミドジイソプロピルエチルアンモニウム塩の粗体を１３．７ｇ得た。この粗体を１９Ｆ−ＮＭＲにより定量を行ったところ、回収工程における回収率は８８．８％（０．０４６ｍоｌ）であった。
[Recovery process]
While stirring, 100 g of triethylamine was added to the aqueous layer separated in the washing step, and the aqueous layer and the organic layer were separated. The obtained organic layer was concentrated to obtain 13.7 g of a crude product of bisfluorosulfonylimide diisopropylethylammonium salt. When this crude product was quantified by 19 F-NMR, the recovery rate in the recovery step was 88.8% (0.046 mol).
［実施例４］
トリエチルアミンの代わりにジイソプロピルエチルアミンを２３８ｇ（１．８４ ｍоｌ）用いた以外は実施例１と同様の手法により反応および洗浄を行ったところ水層のビスフルオロスルホニルイミドジイソプロピルエチルアンモニウム塩の１９Ｆ−ＮＭＲによる定量値は０．０５２ｍｏｌであった。
[Example 4]
According to 19 F-NMR of bisfluorosulfonylimide diisopropylethyl ammonium salt of the aqueous layer was subjected to reaction and washed in the same manner except for using 238g (1.84 mоl) diisopropylethylamine to Example 1 in place of triethylamine The quantitative value was 0.052 mol.
[回収工程]
上記、洗浄工程で分離した水層に対し攪拌下、ジイソプロピルエチルアミンを１００ｇ添加し、水層と有機層に分離した。得られた有機層を濃縮し、ビスフルオロスルホニルイミドトリエチルアンモニウム塩の粗体を１６．７ｇ得た。この粗体を１９Ｆ−ＮＭＲにより定量を行ったところ、回収工程における回収率は７５．４％（０．０３９ｍоｌ）であった。
[Recovery process]
With stirring, 100 g of diisopropylethylamine was added to the aqueous layer separated in the washing step, and the aqueous layer and the organic layer were separated. The obtained organic layer was concentrated to obtain 16.7 g of a crude product of bisfluorosulfonylimide triethylammonium salt. When this crude product was quantified by 19 F-NMR, the recovery rate in the recovery step was 75.4% (0.039 mol).
［比較例１］
[反応工程]
１Lオートクレーブにアセトニトリルを１２１ｇ、トリエチルアミンを１２１ｇ（１．２０ ｍоｌ）仕込み、氷水で５℃に冷却し、フッ化スルフリルを８４．７ｇ(０．８３ ｍоｌ)導入した。フッ化スルフリルを導入した後、続いて、無水アンモニアを６．５ｇ(０．３８ｍоｌ)、３時間掛けて導入した。反応器を室温まで昇温させ、１２時間攪拌した。この反応における目的物の生成比は、９９.９％であり、ＦＳＯ2ＮＨＳＯ2ＮＨＳＯ2Ｆが０．１％であった。この反応液を１９Ｆ−ＮＭＲにより定量を行ったところ出発原料のアンモニアに対するビスフルオロスルホニルイミドトリエチルアンモニウム塩の収率は９９．３％であった。
[Comparative Example 1]
[Reaction process]
A 1 L autoclave was charged with 121 g of acetonitrile and 121 g (1.20 mol) of triethylamine, cooled to 5 ° C. with ice water, and 84.7 g (0.83 mol) of sulfuryl fluoride was introduced. After introducing sulfuryl fluoride, 6.5 g (0.38 mol) of anhydrous ammonia was introduced over 3 hours. The reactor was warmed to room temperature and stirred for 12 hours. The production ratio of the target product in this reaction was 99.9%, and FSO 2 NHSO 2 NHSO 2 F was 0.1%. When this reaction solution was quantified by 19 F-NMR, the yield of bisfluorosulfonylimide triethylammonium salt relative to the starting material ammonia was 99.3%.
[洗浄工程]
上記反応工程で得られた反応液の溶媒を留去し、残渣に水を加え、水洗浄・分離を行い、トリエチルアンモニウム塩を含む有機混合物とトリエチルアンモニウム塩を含む水層とを得た。得られた有機混合物を２０％炭酸カリウム水溶液で洗浄し、ビスフルオロスルホニルイミドトリエチルアンモニウム塩の粗体を１００ｇ得た。この粗体を１９Ｆ−ＮＭＲにより定量を行ったところ出発原料のアンモニアに対する収率は７３．７％（０．２８０ｍｏｌ）であった（なお、粗体をここでは単離精製せずに、このままカチオン交換反応に用いた）。水洗浄で得られた水層に、２０％炭酸カリウム水溶液洗浄にて得られた水層を加えて１９Ｆ−ＮＭＲによりビスフルオロスルホニルイミドトリエチルアンモニウム塩の定量を行ったところ、出発原料のアンモニアに対する収率は１９．５％（０．０７４ｍоｌ）であった。
[Washing process]
The solvent of the reaction solution obtained in the above reaction step was distilled off, and water was added to the residue, followed by washing with water and separation to obtain an organic mixture containing triethylammonium salt and an aqueous layer containing triethylammonium salt. The obtained organic mixture was washed with a 20% aqueous potassium carbonate solution to obtain 100 g of a crude product of bisfluorosulfonylimide triethylammonium salt. When this crude product was quantified by 19 F-NMR, the yield relative to the starting material ammonia was 73.7% (0.280 mol). Used for cation exchange reaction). The aqueous layer obtained by washing with 20% aqueous potassium carbonate was added to the aqueous layer obtained by washing with water, and bisfluorosulfonylimide triethylammonium salt was quantified by 19 F-NMR. The yield was 19.5% (0.074 mol).
[回収工程]
上記、洗浄工程で分離した水層に対しジイソプロピルエーテル１００ｇを添加し、水層と有機層に分離した。得られた有機層を濃縮し、ビスフルオロスルホニルイミドトリエチルアンモニウム塩の粗体を１４．１ｇ得た。この水層から回収した粗体を１９Ｆ−ＮＭＲにより定量を行ったところ、回収工程における回収率は５４．１％（０．０４０ｍоｌ）であった。
[Recovery process]
100 g of diisopropyl ether was added to the aqueous layer separated in the washing step, and the aqueous layer and the organic layer were separated. The obtained organic layer was concentrated to obtain 14.1 g of a crude product of bisfluorosulfonylimide triethylammonium salt. When the crude product recovered from the aqueous layer was quantified by 19 F-NMR, the recovery rate in the recovery step was 54.1% (0.040 mol).
実施例及び比較例の結果を表１に示す。
このように、エーテルなどの有機溶媒を用いても該イミド酸塩は回収可能であるが、有機塩基Ａを用いることでより効率的に回収が行えることがわかる。 Thus, it can be seen that the imidoate can be recovered using an organic solvent such as ether, but the organic base A can be recovered more efficiently.
Claims (5)
の製造方法であって、以下の３工程を含むことを特徴とする製造方法。
有機塩基Ｂの存在下、ハロゲン化スルフリル（ＳＯ2Ｘ2Ｘ3；Ｘ2、Ｘ3は同一、又は異なるハロゲン（フッ素、塩素、臭素、ヨウ素）を表す。）とアンモニアとを反応させ、反応混合物を得る工程（反応工程）
前記反応混合物に水を添加し、「イミド酸と有機塩基Ｂからなる塩又は錯体」を含む有機混合物と、「イミド酸と有機塩基Ｂからなる塩又は錯体」を含む水層とに分離する工程（洗浄工程）
前記洗浄工程において分離された水層と、
３級アミン、２級アミン、及び含窒素芳香族複素環式化合物からなる群より選ばれる少なくとも１種の有機塩基Ａとを接触させ、「イミド酸と有機塩基Ｂからなる塩又は錯体」を該有機塩基Ａに抽出する工程（回収工程） "Salt or complex consisting of imide acid and organic base B" represented by formula [1]
A manufacturing method comprising the following three steps:
In the presence of the organic base B, sulfuryl halide (SO 2 X 2 X 3 ; X 2 and X 3 represent the same or different halogens (fluorine, chlorine, bromine, iodine)) and ammonia are reacted. Step of obtaining a mixture (reaction step)
Step of adding water to the reaction mixture and separating into an organic mixture containing “salt or complex consisting of imide acid and organic base B” and an aqueous layer containing “salt or complex consisting of imide acid and organic base B” (Washing process)
An aqueous layer separated in the washing step ;
Tertiary amines, secondary amines, and contacting the at least one organic bases A selected from the group consisting of nitrogen-containing aromatic heterocyclic compound, a "salt or complex composed of an imide acid and an organic base B" the Extraction process to organic base A (recovery process)
An alkali metal hydroxide or carbonate, or an alkaline earth metal hydroxide is added to the “salt or complex comprising imide acid and organic base B” obtained by the method according to claim 1. Alternatively, the imidate metal salt represented by the formula [3], wherein the cation exchange is performed by reacting the carbonate
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