JPH0584291B2 - - Google Patents
Info
- Publication number
- JPH0584291B2 JPH0584291B2 JP63202954A JP20295488A JPH0584291B2 JP H0584291 B2 JPH0584291 B2 JP H0584291B2 JP 63202954 A JP63202954 A JP 63202954A JP 20295488 A JP20295488 A JP 20295488A JP H0584291 B2 JPH0584291 B2 JP H0584291B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- general formula
- represented
- chloride
- reaction
- 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.)
- Expired - Fee Related
Links
- -1 alkyl nitrite Chemical compound 0.000 claims description 96
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 46
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 21
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 16
- 150000004982 aromatic amines Chemical class 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 239000005749 Copper compound Substances 0.000 claims description 9
- 150000001880 copper compounds Chemical class 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 4
- CPZPJCBMTQJVEF-UHFFFAOYSA-N 1h-pyrazole-5-sulfonyl chloride Chemical compound ClS(=O)(=O)C=1C=CNN=1 CPZPJCBMTQJVEF-UHFFFAOYSA-N 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 47
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 45
- 238000006243 chemical reaction Methods 0.000 description 44
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 36
- 238000003756 stirring Methods 0.000 description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 25
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 17
- 239000007789 gas Substances 0.000 description 15
- 239000007787 solid Substances 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 229910001873 dinitrogen Inorganic materials 0.000 description 13
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 12
- 230000020169 heat generation Effects 0.000 description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- IOGXOCVLYRDXLW-UHFFFAOYSA-N tert-butyl nitrite Chemical compound CC(C)(C)ON=O IOGXOCVLYRDXLW-UHFFFAOYSA-N 0.000 description 12
- 238000009835 boiling Methods 0.000 description 11
- 238000001914 filtration Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 240000002380 Rosa carolina Species 0.000 description 9
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 9
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 9
- 239000002808 molecular sieve Substances 0.000 description 9
- 125000001624 naphthyl group Chemical group 0.000 description 9
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 8
- 229960003280 cupric chloride Drugs 0.000 description 8
- 238000000605 extraction Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 5
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 150000001500 aryl chlorides Chemical class 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 239000012954 diazonium Substances 0.000 description 3
- 150000001989 diazonium salts Chemical class 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 3
- 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 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 2
- YIGAWISCEHGPRK-UHFFFAOYSA-N 2,2-dimethylpropyl nitrite Chemical compound CC(C)(C)CON=O YIGAWISCEHGPRK-UHFFFAOYSA-N 0.000 description 2
- SEHRYTWQMFUOBZ-UHFFFAOYSA-N 3-bromo-1,4-dimethylpyrazole Chemical group CC1=CN(C)N=C1Br SEHRYTWQMFUOBZ-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000012024 dehydrating agents Substances 0.000 description 2
- 238000006193 diazotization reaction Methods 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 150000002431 hydrogen Chemical group 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- 150000003613 toluenes Chemical class 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- UCCYKZGOGQZMMX-UHFFFAOYSA-N 1,4-diethylpyrazole Chemical class CCC=1C=NN(CC)C=1 UCCYKZGOGQZMMX-UHFFFAOYSA-N 0.000 description 1
- PCDSBHWKDOKENY-UHFFFAOYSA-N 1,4-dimethyl-3-nitropyrazole Chemical group CC1=CN(C)N=C1[N+]([O-])=O PCDSBHWKDOKENY-UHFFFAOYSA-N 0.000 description 1
- SZQCPPRPWDXLMM-UHFFFAOYSA-N 1,4-dimethylpyrazole Chemical class CC=1C=NN(C)C=1 SZQCPPRPWDXLMM-UHFFFAOYSA-N 0.000 description 1
- FLNMQGISZVYIIK-UHFFFAOYSA-N 1-ethylpyrazole Chemical class CCN1C=CC=N1 FLNMQGISZVYIIK-UHFFFAOYSA-N 0.000 description 1
- KQCMTOWTPBNWDB-UHFFFAOYSA-N 2,4-dichloroaniline Chemical compound NC1=CC=C(Cl)C=C1Cl KQCMTOWTPBNWDB-UHFFFAOYSA-N 0.000 description 1
- FDTPBIKNYWQLAE-UHFFFAOYSA-N 2,4-dichlorobenzenesulfonyl chloride Chemical compound ClC1=CC=C(S(Cl)(=O)=O)C(Cl)=C1 FDTPBIKNYWQLAE-UHFFFAOYSA-N 0.000 description 1
- UETNOXJRYZSQRA-UHFFFAOYSA-N 3-chloro-1,4-dimethylpyrazole Chemical group CC1=CN(C)N=C1Cl UETNOXJRYZSQRA-UHFFFAOYSA-N 0.000 description 1
- DZKLEICJWIZWGU-UHFFFAOYSA-N 3-iodo-1,4-dimethylpyrazole Chemical group CC1=CN(C)N=C1I DZKLEICJWIZWGU-UHFFFAOYSA-N 0.000 description 1
- QSNSCYSYFYORTR-UHFFFAOYSA-N 4-chloroaniline Chemical compound NC1=CC=C(Cl)C=C1 QSNSCYSYFYORTR-UHFFFAOYSA-N 0.000 description 1
- ZLYBFBAHAQEEQQ-UHFFFAOYSA-N 4-chlorobenzenesulfonyl chloride Chemical compound ClC1=CC=C(S(Cl)(=O)=O)C=C1 ZLYBFBAHAQEEQQ-UHFFFAOYSA-N 0.000 description 1
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 description 1
- JXRGUPLJCCDGKG-UHFFFAOYSA-N 4-nitrobenzenesulfonyl chloride Chemical compound [O-][N+](=O)C1=CC=C(S(Cl)(=O)=O)C=C1 JXRGUPLJCCDGKG-UHFFFAOYSA-N 0.000 description 1
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- JQJPBYFTQAANLE-UHFFFAOYSA-N Butyl nitrite Chemical compound CCCCON=O JQJPBYFTQAANLE-UHFFFAOYSA-N 0.000 description 1
- CEDNGVLTWMMUII-UHFFFAOYSA-N CCCOC(=O)C=1C=NN(C)C=1 Chemical class CCCOC(=O)C=1C=NN(C)C=1 CEDNGVLTWMMUII-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- QQZWEECEMNQSTG-UHFFFAOYSA-N Ethyl nitrite Chemical compound CCON=O QQZWEECEMNQSTG-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methyl-N-phenylamine Natural products CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 1
- UQFQONCQIQEYPJ-UHFFFAOYSA-N N-methylpyrazole Chemical class CN1C=CC=N1 UQFQONCQIQEYPJ-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- PWUBONDMIMDOQY-UHFFFAOYSA-N acetonitrile;hydrochloride Chemical compound Cl.CC#N PWUBONDMIMDOQY-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- CSKNSYBAZOQPLR-UHFFFAOYSA-N benzenesulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=CC=C1 CSKNSYBAZOQPLR-UHFFFAOYSA-N 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
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229940108928 copper Drugs 0.000 description 1
- RFKZUAOAYVHBOY-UHFFFAOYSA-M copper(1+);acetate Chemical compound [Cu+].CC([O-])=O RFKZUAOAYVHBOY-UHFFFAOYSA-M 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- WIVXEZIMDUGYRW-UHFFFAOYSA-L copper(i) sulfate Chemical compound [Cu+].[Cu+].[O-]S([O-])(=O)=O WIVXEZIMDUGYRW-UHFFFAOYSA-L 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- QUQFTIVBFKLPCL-UHFFFAOYSA-L copper;2-amino-3-[(2-amino-2-carboxylatoethyl)disulfanyl]propanoate Chemical compound [Cu+2].[O-]C(=O)C(N)CSSCC(N)C([O-])=O QUQFTIVBFKLPCL-UHFFFAOYSA-L 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- BUPSXJWSGYSVFL-UHFFFAOYSA-N ethyl 1,5-dimethylpyrazole-4-carboxylate Chemical group CCOC(=O)C=1C=NN(C)C=1C BUPSXJWSGYSVFL-UHFFFAOYSA-N 0.000 description 1
- XDGRKQJBBYAGQA-UHFFFAOYSA-N ethyl 1-ethylpyrazole-4-carboxylate Chemical class CCOC(=O)C=1C=NN(CC)C=1 XDGRKQJBBYAGQA-UHFFFAOYSA-N 0.000 description 1
- GXKQVOXCQOQZED-UHFFFAOYSA-N ethyl 1-methylpyrazole-4-carboxylate Chemical class CCOC(=O)C=1C=NN(C)C=1 GXKQVOXCQOQZED-UHFFFAOYSA-N 0.000 description 1
- ZYSGPOXVDOROJU-UHFFFAOYSA-N ethyl 2,5-dimethylpyrazole-3-carboxylate Chemical group CCOC(=O)C1=CC(C)=NN1C ZYSGPOXVDOROJU-UHFFFAOYSA-N 0.000 description 1
- DDADHABILFWYRA-UHFFFAOYSA-N ethyl 3-bromo-1-methylpyrazole-4-carboxylate Chemical group CCOC(=O)C1=CN(C)N=C1Br DDADHABILFWYRA-UHFFFAOYSA-N 0.000 description 1
- KADJPZFGDNHJES-UHFFFAOYSA-N ethyl 3-chloro-1-methylpyrazole-4-carboxylate Chemical group CCOC(=O)C1=CN(C)N=C1Cl KADJPZFGDNHJES-UHFFFAOYSA-N 0.000 description 1
- VKQPNWRQKHYCFP-UHFFFAOYSA-N ethyl 3-iodo-1-methylpyrazole-4-carboxylate Chemical group CCOC(=O)C1=CN(C)N=C1I VKQPNWRQKHYCFP-UHFFFAOYSA-N 0.000 description 1
- BXPQVOSHELHKSE-UHFFFAOYSA-N ethyl 5-chlorosulfonyl-1-methylpyrazole-4-carboxylate Chemical compound CCOC(=O)C=1C=NN(C)C=1S(Cl)(=O)=O BXPQVOSHELHKSE-UHFFFAOYSA-N 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- IFTFDQGCTIBBPM-UHFFFAOYSA-N methyl 1,5-dimethylpyrazole-4-carboxylate Chemical group COC(=O)C=1C=NN(C)C=1C IFTFDQGCTIBBPM-UHFFFAOYSA-N 0.000 description 1
- YJOLQLMJAZKELN-UHFFFAOYSA-N methyl 1-methyl-3-nitropyrazole-4-carboxylate Chemical group COC(=O)C1=CN(C)N=C1[N+]([O-])=O YJOLQLMJAZKELN-UHFFFAOYSA-N 0.000 description 1
- HGQQQXMARFJNCP-UHFFFAOYSA-N methyl 1-methylpyrazole-4-carboxylate Chemical class COC(=O)C=1C=NN(C)C=1 HGQQQXMARFJNCP-UHFFFAOYSA-N 0.000 description 1
- KYQGPXFQWUSRMY-UHFFFAOYSA-N methyl 2,5-dimethylpyrazole-3-carboxylate Chemical group COC(=O)C1=CC(C)=NN1C KYQGPXFQWUSRMY-UHFFFAOYSA-N 0.000 description 1
- OFJONVVSTNCLRM-UHFFFAOYSA-N methyl 3-chloro-1-methylpyrazole-4-carboxylate Chemical group COC(=O)C1=CN(C)N=C1Cl OFJONVVSTNCLRM-UHFFFAOYSA-N 0.000 description 1
- ZLYOYYFLZIJDJN-UHFFFAOYSA-N methyl 3-iodo-1-methylpyrazole-4-carboxylate Chemical group COC(=O)c1cn(C)nc1I ZLYOYYFLZIJDJN-UHFFFAOYSA-N 0.000 description 1
- CRMIQSQQCPLMIJ-UHFFFAOYSA-N methyl 5-methyl-1h-pyrazole-4-carboxylate Chemical group COC(=O)C=1C=NNC=1C CRMIQSQQCPLMIJ-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- CSDTZUBPSYWZDX-UHFFFAOYSA-N n-pentyl nitrite Chemical compound CCCCCON=O CSDTZUBPSYWZDX-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- KAOQVXHBVNKNHA-UHFFFAOYSA-N propyl nitrite Chemical compound CCCON=O KAOQVXHBVNKNHA-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- 239000000273 veterinary drug Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
(イ) 産業上の利用分野
本発明で得られる一般式〔〕で表されるアリ
ールスルホニルクロライドは医薬、農薬及び動物
薬等の中間体として有用である。
(ロ) 従来の技術
アリールスルホニルクロライドの製法として
は、二つの方法が実施されている。
第１の方法は、アリール化合物の大過剰のクロ
ルスルホン酸を反応させ、水中で処理してアリー
ルスルホニルクロライドを得る方法である。
この方法は、クロルスルホン酸を大過剰に使用
するため危険である上、アリール化合物の種類に
よつては反応が進行しない場合がある。
又、目的とするアリールスルホニルクロライド
と置換位置が異なるアリールスルホニルクロライ
ド等の副生成物が生成し、複雑なアリールスルホ
ニルクロライドの製造には適用できない場合があ
る。
第２の方法は、硫酸水溶液中、アリールアミン
塩素塩を亜硝酸ナトリウムでジアゾ化後、この水
溶液を二酸化硫黄及び銅化合物が存在する酢酸等
の溶液へ低温で滴下して、アリールスルホニルク
ロライドを得る方法である。〔ジヤーナル、ヘテ
ロサイクリツク、ケミストリイ（Ｊ of
Heterocyclic chemistry）、第21巻、４号、1017
頁、1984年、オルガニツク、シンセシス
（Organic Synsesis）、第60巻、121頁〕。
この方法は適用範囲が広く、複雑なアリールス
ルホニルクロライドの製法として有用であるが、
工業的実施に際しては、次のようなジアゾ化反応
特有の欠点を有している。
(1) ジアゾ化反応の反応熱が大きく、ジアゾニウ
ム塩の安定性が低いため、反応温度を０℃程度
の低温に保つ必要がある。
従つて、工業規模になると冷却が充分できず
反応時間が長くなり、しばしばアリールスルホ
ニルクロライドの収率が低下する。
(2) 多量の溶媒を必要とする上、反応操作が煩雑
であるため、アリールスルホニルクロライドの
製造の効率が非常に悪い。
又、廃酸が大量に生成しその処理に困る。
(ハ) 問題点を解決する為の手段
本発明者等は、上記２法の欠点を改良すべく鋭
意検討の結果本発明を完成するに至つた。
即ち、本発明は一般式〔〕
ArNH2 〔〕
（Arは置換又は未置換のアリール基を示す。）
で表されるアリールアミンを
塩化水素、二酸化硫黄及び銅化合物の存在下、
一般式〔〕
R1YNOa 〔〕
（R1は炭素数２〜10のアルキル基、Ｙは酸素原
子又は硫黄原子、ａは１又は２の整数を示す。）
で表されるアルキルナイトライトと反応させるこ
とを特徴とする
一般式〔〕
ArSO2Cl 〔〕
で表されるアリールスルホニルクロライドの製法
に関するものである。
特に、本発明は一般式〔〕
(a) Industrial application field The arylsulfonyl chloride represented by the general formula [] obtained by the present invention is useful as an intermediate for pharmaceuticals, agricultural chemicals, veterinary drugs, etc. (b) Prior Art Two methods have been used to produce arylsulfonyl chloride. The first method is to react an aryl compound with a large excess of chlorosulfonic acid and treat it in water to obtain an arylsulfonyl chloride. This method is dangerous because it uses a large excess of chlorosulfonic acid, and the reaction may not proceed depending on the type of aryl compound. Furthermore, by-products such as arylsulfonyl chloride having a substitution position different from that of the target arylsulfonyl chloride are produced, and this method may not be applicable to the production of complex arylsulfonyl chloride. The second method is to diazotize an arylamine chloride salt with sodium nitrite in an aqueous sulfuric acid solution, and then dropwise drop this aqueous solution into a solution of acetic acid or the like containing sulfur dioxide and a copper compound at a low temperature to obtain an arylsulfonyl chloride. It's a method. [Journal, Heterocyclics, Chemistry (J of
Heterocyclic chemistry), Volume 21, No. 4, 1017
Page, 1984, Organic Synthesis, Vol. 60, p. 121]. This method has a wide range of applicability and is useful as a method for producing complex arylsulfonyl chlorides.
In industrial implementation, the diazotization reaction has the following disadvantages. (1) Since the reaction heat of the diazotization reaction is large and the stability of the diazonium salt is low, the reaction temperature must be kept at a low temperature of about 0°C. Therefore, on an industrial scale, cooling is not sufficient and the reaction time becomes long, often resulting in a decrease in the yield of arylsulfonyl chloride. (2) Since a large amount of solvent is required and the reaction operation is complicated, the efficiency of producing arylsulfonyl chloride is very low. In addition, a large amount of waste acid is generated, making it difficult to dispose of it. (c) Means for solving the problems The inventors of the present invention have completed the present invention as a result of intensive studies to improve the drawbacks of the above two methods. That is, the present invention provides an arylamine represented by the general formula [] ArNH 2 [] (Ar represents a substituted or unsubstituted aryl group) in the presence of hydrogen chloride, sulfur dioxide, and a copper compound. R 1 YNO a [ ] (R 1 is an alkyl group having 2 to 10 carbon atoms, Y is an oxygen atom or a sulfur atom, and a is an integer of 1 or 2.) This invention relates to a method for producing arylsulfonyl chloride represented by the general formula [] ArSO 2 Cl []. In particular, the present invention relates to the general formula []
【化】 （R2は炭素数１〜10のアルキル基を示す。） で表されるピラゾールアミンより 一般式〔〕[Chemical formula] (R 2 represents an alkyl group having 1 to 10 carbon atoms.) From the general formula []
【化】
（R2は炭素数１〜10のアルキル基を示す。）
で表されるピラゾールスルホニルクロライドの製
法として特に有用である。
炭素数２〜10のアルキル基であるR1としては、
エチル基、ｎ−プロピル基、ｉ−プロピル基、ｎ
−ブチル基、ｉ−ブチル基、ｔ−ブチル基、ｎ−
ペンチル基、ｉ−ペンチル基、ｎ−ヘキシル基、
ｉ−ヘキシル基、ｎ−ヘプチル基、ｉ−ヘプチル
基、ｎ−オクチル基、ｉ−オクチル基、ｎ−ノニ
ル基、ｉ−ノニル基、ｎ−デシル基、ｉ−デシル
基等が挙げられる。
炭素数１〜10のアルキル基であるR2としては、
メチル基、エチル基、ｎ−プロピル基、ｉ−プロ
ピル基、ｎ−ブチル基、ｉ−ブチル基、ｔ−ブチ
ル基、ｎ−ペンチル基、ｉ−ペンチル基、ｎ−ヘ
キシル基、ｉ−ヘキシル基、ｎ−ヘプチル基、ｉ
−ヘプチル基、ｎ−オクチル基、ｉ−オクチル
基、ｎ−ノニル基、ｉ−ノニル基、ｎ−デシル
基、ｉ−デシル基等が挙げられる。
置換又は未置換のアリール基であるArとして
は、フエニル基、ナフチル基、アントラセニル
基、アルキル基置換フエニル基、アルキル基置換
ナフチル基、アルキル基置換アントラセニル基、
ハロゲン置換フエニル基、ハロゲン置換ナフチル
基、ハロゲン置換アントラセニル基、ニトロ基置
換フエニル基、ニトロ基置換ナフチル基、ニトロ
基置換アントラセニル基、１−アルキルピラゾー
ル、１，４−ジアルキルピラゾール、１−アルキ
ル−４−アルコキシカルボニルピラゾール基、１
−アルキル−４−アルコキシカルボニル−５−ア
ルキルピラゾール基、１，３−ジアルキル−５−
アルコキシカルボニルピラゾール基、３−ハロゲ
ノ−１，４−ジアルキルピラゾール基、３−ハロ
ゲノ−１−アルキル−４−アルコキシカルボニル
ピラゾール基、３−ニトロ−１，４−ジアルキル
ピラゾール基、３−ニトロ−１−アルキル−４−
アルコキシカルボニルピラゾール基等が挙げられ
る。
上記置換基のアルキル基としては、メチル基、
エチル基、ｎ−プロピル基、ｉ−プロピル基、ｎ
−ブチル基、ｉ−ブチル基、ｔ−ブチル基、ｎ−
ペンチル基、ｉ−ペンチル基、ｎ−ヘキシル基、
ｉ−ヘキシル基、ｎ−ヘプチル基、ｉ−ヘプチル
基、ｎ−オクチル基、ｉ−オクチル基、ｎ−ノニ
ル基、ｉ−ノニル基、ｎ−デシル基、ｉ−デシル
基等が挙げられる。
ハロゲンとしては、塩素、臭素、妖素等が挙げ
られる。
置換又は未置換のアリール基であるArの具体
例としては、フエニル基、ナフチル基、アントラ
セニル基、メチル基置換フエニル基、エチル基置
換フエニル基、ｎ−プロピル基置換フエニル基、
ｉ−プロピル基置換フエニル基、ｎ−ブチル基置
換フエニル基、ｉ−ブチル基置換フエニル基、メ
チル基置換ナフチル基、エチル基置換ナフチル
基、ｎ−プロピル基置換ナフチル基、ｉ−プロピ
ル基置換ナフチル基、ｎ−ブチル基置換ナフチル
基、ｉ−ブチル基置換ナフチル基、メチル基置換
アントラセニル基、エチル基置換アントラセニル
基、ｎ−プロピル基置換アントラセニル基、ｉ−
プロピル基置換アントラセニル基、ｎ−ブチル基
置換アントラセニル基、ｉ−ブチル基置換アント
ラセニル基、塩素置換フエニル基、臭素置換フエ
ニル基、沃素置換フエニル基、塩素置換ナフチル
基、臭素置換ナフチル基、沃素置換ナフチル基、
塩素置換アントラセニル基、臭素置換アントラセ
ニル基、沃素置換アントラセニル基、ニトロ基置
換フエニル基、ニトロ基置換ナフチル、ニトロ基
置換アントラセニル基、１−メチルピラゾール、
１−エチルピラゾール、１，４−ジメチルピラゾ
ール、１，４−ジエチルピラゾール、１−メチル
−４−メトキシカルボニルピラゾール基、１−メ
チル−４−エトキシカルボニルピラゾール基、１
−メチル−４−ブトキシカルボニルピラゾール
基、１−メチル−４−オクタオキシカルボニルピ
ラゾール基、１−メチル−４−デシロキシカルボ
ニルピラゾール基、１−エチル−４−メトキシカ
ルボニルピラゾール基、１−エチル−４−エトキ
シカルボニルピラゾール基、１−メチル−４−プ
ロポキシカルボニルピラゾール基、１−メチル−
４−ヘプタオキシカルボニルピラゾール基、１−
メチル−４−ノナキシカルボニルピラゾール基、
１−メチル−４−メトキシカルボニル−５−メチ
ルピラゾール基、１−メチル−４−エトキシカル
ボニル−５−メチルピラゾール基、１−メチル−
４−エトキシカルボニル−５−エチルピラゾール
基、１，３−ジメチル−５−メトキシカルボニル
ピラゾール基、１，３−ジエチル−５−メトキシ
カルボニルピラゾール基、１，３−ジメチル−５
−エトキシカルボニルピラゾール基、３−クロロ
−１，４−ジメチルピラゾール基、３−クロロ−
１，４−ジエチルルピラゾール基、３−ブロモ−
１，４−ジメチルピラゾール基、３−ブロモ−
１，４−ジメチルピラゾール基、３−ヨード−
１，４−ジメチルピラゾール基、３−ヨード−
１，４−ジエチルピラゾール基、３−クロロ−１
−メチル−４−メトキシカルボニルピラゾール
基、３−ブロモ−１−メチル−４−メトキシカル
ボニルピラゾール基、３−ヨード−１−メチル−
４−メトキシカルボニルピラゾール基、３−クロ
ロ−１−エチル−４−メトキシカルボニルピラゾ
ール基、３−ブロモ−１−エチル−４−メトキシ
カルボニルピラゾール基、３−ヨード−１−エチ
ル−４−メトキシカルボニルピラゾール基、３−
クロロ−１−メチル−４−エトキシカルボニルピ
ラゾール基、３−ブロモ−１−メチル−４−エト
キシカルボニルピラゾール基、３−ヨード−１−
メチル−４−エトキシカルボニルピラゾール基、
３−ニトロ−１，４−ジメチルピラゾール基、３
−ニトロ−１，４−ジエチルピラゾール基、３−
ニトロ−１−メチル−４−メトキシカルボニルピ
ラゾール基、３−ニトロ−１−エチル−４−メト
キシカルボニルピラゾール基、３−ニトロ−１−
メチル−４−メトキシカルボニルピラゾール基等
が挙げられる。
以下、本発明について詳細に説明する。
一般式〔〕で表されるアルキルナイトライト
としては、ｔ−ブチルナイトライト、ネオペンチ
ルナイトライト等の第３級アルキルナイトライト
を使用することが望ましい。
一般式〔〕で表されるアルキルナイトライト
が、エチルナイトライト、ｎ−プロピルナイトラ
イト、ｎ−ブチルナイトライト、ｎ−アルミナイ
トライト、ｉ−アルミナイトライト等の第１級ア
ルキルナイトライトの場合、一般式〔〕で表さ
れるアリールアミンのアミン基が水素に置換され
たアリール化合物ArHが生成し易いからである。
尚、第１級アルキルナイトライトを使用する場
合、反応系に無水酢酸を添加するとアリール化合
物ArHの副生を抑制することができる。
一般式〔〕で表されるアルキルナイトライト
の量は、一般式〔〕で表されるアリールアミン
に対して通常１〜５（モル比）の範囲、望ましく
は１〜２（モル比）の範囲が良い。
一般式〔〕で表されるアルキルナイトライト
の製法としては、例えば亜硝酸ナトリウム水溶液
に硫酸とアルキルアルコールの混合物を低温で滴
下する方法等が挙げられる。
塩化水素としては、塩素水素ガス及び塩酸を使
用することができるが、塩素水素ガスが望まし
い。
塩化水素の量は、一般式〔〕で表されるアリ
ールアミンに対して通常１〜1.5（モル比）の範囲
が良い。
塩化水素の量が１（モル比）未満であると、一
般式〔〕で表されるアリールアミンのアミノ基
が水素に置換されたアリール化合物ArHの生成
が増加する。
塩素水素の量が1.5（モル比）を越えると、一般
式〔〕で表されるアリールアミンのアミノ基が
塩素に置換されたアリールクロライドArClの生
成が増加する。
二酸化硫黄は、液状でもガス状でも使用するこ
とができる。
二酸化硫黄の量は、一般式〔〕で表されるア
リールアミンに対して１〜20（モル比）の範囲、
望ましくは２〜８（モル比）の範囲が良い。
銅化合物としては、硫酸第１銅、硫酸第２銅、
硝酸第１銅、硝酸第２銅、塩化第１銅、塩化第２
銅、酢酸第１銅、酢酸第２銅、塩基性酢酸第２
銅、酸化第１銅、酸化第２銅、ビスアセチルアセ
トナト第２銅が挙げられ、望ましくは硫酸第２銅
が良い。
銅化合物の量は、一般式で表されるアリールア
ミンに対して0.1〜100重量％の範囲、望ましくは
２〜10重量％の範囲が良い。
銅化合物の量が0.1重量％未満では、上記アリ
ール化合物ArH及びアリールクロライドArClの
生成が増加し、100重量％と越えるとアリールク
ロライドArClの生成が増加する。
本発明には溶媒を使用することもできる。
溶媒としては、一般式〔〕で表されるアリー
ルアミン、その塩酸塩、二酸化硫黄、銅化合物を
溶解する溶媒が望ましい。
溶媒としては、有機酸、その酸無水物、有機酸
エステル、第３級アルコール、ケトン、ハロゲン
化炭化水素、低級アルキルニトリル等が挙げられ
る。
その具体例としては、例えば酢酸、酢酸エチ
ル、無水酢酸、ｔ−ブチルアルコール、アセト
ン、メチルエチルケトン、エチレンジクロライ
ド、クロロホルム、アセトニトリル、プロピオニ
トリル等が挙げられる。
又、反応試剤である二酸化硫黄も溶媒として使
用することができる。
一般式〔〕で表されるアルキルナイトライト
として第１級ナイトライトを使用する場合、上述
のようにアリール化合物ArHが生成し易いので
上記溶媒と無水酢酸の混合溶媒を使用することが
望ましい。
反応温度は、通常０〜50℃の範囲、望ましくは
０〜25℃の範囲が良い。
温度が50℃を越えると、副反応が起こり一般式
〔〕で表されるアリールスルホニルクロライド
の収率が低下する。
本発明反応は、常圧でも加圧でも行うことがで
きる。
本発明反応では反応中に水が生成するが、この
水を除去するために反応系に脱水剤を添加する
と、一般式〔〕で表されるアリールスルホニル
クロライドの収率が向上する場合がある。
脱水剤としては、シリカゲル、モレキユラーシ
ーブ等を挙げることができる。
本発明の実施態様の具体例を挙げると
第１の方法は、一般式〔〕で表されるアリー
ルアミンと塩化水素の存在下、一般式〔〕で表
されるアルキルナイトライトを低温、例えば０〜
５℃で反応させ、一般式〔〕で表されるアリー
ルアミンのジアゾニウム塩を生成させた後、二酸
化硫黄、銅化合物及び必要なら溶媒からなる分解
液に添加することにより、一般式〔〕で表され
るアリールスルホニルクロライドを得る方法であ
る。
第２の方法は、一般式〔〕で表されるアリー
ルアミン、塩化水素、二酸化硫黄、銅化合物及び
必要なら溶媒の存在下、一般式〔〕で表される
アルキルナイトライトを添加し、一般式〔〕で
表されるアリールスルホニルクロライドを得る方
法である。
上記の方法において、どちらかと言えば第２の
方法の方が一般式〔〕で表されるアリールスル
ホニルクロライドの収率及び反応操作面で好まし
い。
(ニ) 発明の効果
一般式〔〕で表されるアルキルナイトライト
を使用することにより、一般式〔〕で表される
アリールアミンから一般式〔〕で表されるアリ
ールスルホニルクロライドが工業規模でも容易に
高収率で得られ、又廃酸の生成がない。
(ホ) 実施例
次に実施例を挙げて、本発明について更に詳し
く説明するが本発明はこれらに限定されるもので
はない。
実施例 １It is particularly useful as a method for producing pyrazolesulfonyl chloride represented by: (R 2 represents an alkyl group having 1 to 10 carbon atoms). As R 1 which is an alkyl group having 2 to 10 carbon atoms,
Ethyl group, n-propyl group, i-propyl group, n
-butyl group, i-butyl group, t-butyl group, n-
pentyl group, i-pentyl group, n-hexyl group,
Examples include i-hexyl group, n-heptyl group, i-heptyl group, n-octyl group, i-octyl group, n-nonyl group, i-nonyl group, n-decyl group, i-decyl group, and the like. R2, which is an alkyl group having 1 to 10 carbon atoms, is
Methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, n-pentyl group, i-pentyl group, n-hexyl group, i-hexyl group , n-heptyl group, i
-heptyl group, n-octyl group, i-octyl group, n-nonyl group, i-nonyl group, n-decyl group, i-decyl group and the like. Ar, which is a substituted or unsubstituted aryl group, includes a phenyl group, a naphthyl group, an anthracenyl group, an alkyl group-substituted phenyl group, an alkyl group-substituted naphthyl group, an alkyl group-substituted anthracenyl group,
Halogen-substituted phenyl group, halogen-substituted naphthyl group, halogen-substituted anthracenyl group, nitro-substituted phenyl group, nitro-substituted naphthyl group, nitro-substituted anthracenyl group, 1-alkylpyrazole, 1,4-dialkylpyrazole, 1-alkyl-4 -alkoxycarbonylpyrazole group, 1
-Alkyl-4-alkoxycarbonyl-5-alkylpyrazole group, 1,3-dialkyl-5-
Alkoxycarbonylpyrazole group, 3-halogeno-1,4-dialkylpyrazole group, 3-halogeno-1-alkyl-4-alkoxycarbonylpyrazole group, 3-nitro-1,4-dialkylpyrazole group, 3-nitro-1- Alkyl-4-
Examples include alkoxycarbonylpyrazole groups. As the alkyl group of the above substituent, methyl group,
Ethyl group, n-propyl group, i-propyl group, n
-butyl group, i-butyl group, t-butyl group, n-
pentyl group, i-pentyl group, n-hexyl group,
Examples include i-hexyl group, n-heptyl group, i-heptyl group, n-octyl group, i-octyl group, n-nonyl group, i-nonyl group, n-decyl group, i-decyl group, and the like. Examples of the halogen include chlorine, bromine, and atomic. Specific examples of Ar, which is a substituted or unsubstituted aryl group, include phenyl group, naphthyl group, anthracenyl group, methyl group-substituted phenyl group, ethyl group-substituted phenyl group, n-propyl group-substituted phenyl group,
i-propyl-substituted phenyl group, n-butyl-substituted phenyl group, i-butyl-substituted phenyl group, methyl-substituted naphthyl group, ethyl-substituted naphthyl group, n-propyl-substituted naphthyl group, i-propyl-substituted naphthyl group group, n-butyl-substituted naphthyl group, i-butyl-substituted naphthyl group, methyl-substituted anthracenyl group, ethyl-substituted anthracenyl group, n-propyl-substituted anthracenyl group, i-
Propyl-substituted anthracenyl group, n-butyl-substituted anthracenyl group, i-butyl-substituted anthracenyl group, chlorine-substituted phenyl group, bromine-substituted phenyl group, iodine-substituted phenyl group, chlorine-substituted naphthyl group, bromine-substituted naphthyl group, iodine-substituted naphthyl group basis,
Chlorine-substituted anthracenyl group, bromine-substituted anthracenyl group, iodine-substituted anthracenyl group, nitro-substituted phenyl group, nitro-substituted naphthyl, nitro-substituted anthracenyl group, 1-methylpyrazole,
1-ethylpyrazole, 1,4-dimethylpyrazole, 1,4-diethylpyrazole, 1-methyl-4-methoxycarbonylpyrazole group, 1-methyl-4-ethoxycarbonylpyrazole group, 1
-Methyl-4-butoxycarbonylpyrazole group, 1-methyl-4-octoxycarbonylpyrazole group, 1-methyl-4-desyloxycarbonylpyrazole group, 1-ethyl-4-methoxycarbonylpyrazole group, 1-ethyl-4 -Ethoxycarbonylpyrazole group, 1-methyl-4-propoxycarbonylpyrazole group, 1-methyl-
4-heptaoxycarbonylpyrazole group, 1-
methyl-4-nonoxycarbonylpyrazole group,
1-methyl-4-methoxycarbonyl-5-methylpyrazole group, 1-methyl-4-ethoxycarbonyl-5-methylpyrazole group, 1-methyl-
4-ethoxycarbonyl-5-ethylpyrazole group, 1,3-dimethyl-5-methoxycarbonylpyrazole group, 1,3-diethyl-5-methoxycarbonylpyrazole group, 1,3-dimethyl-5
-Ethoxycarbonylpyrazole group, 3-chloro-1,4-dimethylpyrazole group, 3-chloro-
1,4-diethyllupyrazole group, 3-bromo-
1,4-dimethylpyrazole group, 3-bromo-
1,4-dimethylpyrazole group, 3-iodo-
1,4-dimethylpyrazole group, 3-iodo-
1,4-diethylpyrazole group, 3-chloro-1
-Methyl-4-methoxycarbonylpyrazole group, 3-bromo-1-methyl-4-methoxycarbonylpyrazole group, 3-iodo-1-methyl-
4-methoxycarbonylpyrazole group, 3-chloro-1-ethyl-4-methoxycarbonylpyrazole group, 3-bromo-1-ethyl-4-methoxycarbonylpyrazole group, 3-iodo-1-ethyl-4-methoxycarbonylpyrazole group, 3-
Chloro-1-methyl-4-ethoxycarbonylpyrazole group, 3-bromo-1-methyl-4-ethoxycarbonylpyrazole group, 3-iodo-1-
methyl-4-ethoxycarbonylpyrazole group,
3-nitro-1,4-dimethylpyrazole group, 3
-nitro-1,4-diethylpyrazole group, 3-
Nitro-1-methyl-4-methoxycarbonylpyrazole group, 3-nitro-1-ethyl-4-methoxycarbonylpyrazole group, 3-nitro-1-
Examples include methyl-4-methoxycarbonylpyrazole group. The present invention will be explained in detail below. As the alkyl nitrite represented by the general formula [], it is desirable to use tertiary alkyl nitrite such as t-butyl nitrite and neopentyl nitrite. When the alkyl nitrite represented by the general formula [] is a primary alkyl nitrite such as ethyl nitrite, n-propyl nitrite, n-butyl nitrite, n-aluminum nitrite, i-aluminum nitrite, etc. This is because an aryl compound ArH, in which the amine group of the arylamine represented by the general formula [] is substituted with hydrogen, is likely to be produced. In addition, when using primary alkyl nitrite, adding acetic anhydride to the reaction system can suppress the by-product of the aryl compound ArH. The amount of alkyl nitrite represented by the general formula [] is usually in the range of 1 to 5 (molar ratio), preferably in the range of 1 to 2 (molar ratio), relative to the arylamine represented by the general formula [] is good. Examples of the method for producing the alkyl nitrite represented by the general formula [] include a method in which a mixture of sulfuric acid and alkyl alcohol is dropped into an aqueous sodium nitrite solution at a low temperature. As hydrogen chloride, chlorine-hydrogen gas and hydrochloric acid can be used, but chlorine-hydrogen gas is preferable. The amount of hydrogen chloride is usually in the range of 1 to 1.5 (molar ratio) to the arylamine represented by the general formula []. When the amount of hydrogen chloride is less than 1 (molar ratio), the production of aryl compound ArH, in which the amino group of the arylamine represented by the general formula [] is substituted with hydrogen, increases. When the amount of chlorine hydrogen exceeds 1.5 (molar ratio), the production of aryl chloride ArCl, in which the amino group of the arylamine represented by the general formula [] is substituted with chlorine, increases. Sulfur dioxide can be used in liquid or gaseous form. The amount of sulfur dioxide is in the range of 1 to 20 (molar ratio) to the arylamine represented by the general formula [],
Desirably, the range is 2 to 8 (molar ratio). Copper compounds include cuprous sulfate, cupric sulfate,
Cuprous nitrate, cupric nitrate, cuprous chloride, dichloride
Copper, cuprous acetate, cupric acetate, basic acetic acid 2
Examples include copper, cuprous oxide, cupric oxide, and cupric bisacetylacetonate, with cupric sulfate being preferred. The amount of the copper compound is preferably in the range of 0.1 to 100% by weight, preferably in the range of 2 to 10% by weight, based on the arylamine represented by the general formula. When the amount of the copper compound is less than 0.1% by weight, the production of the aryl compound ArH and the aryl chloride ArCl increases, and when it exceeds 100% by weight, the production of the aryl chloride ArCl increases. Solvents can also be used in the present invention. The solvent is preferably a solvent that dissolves the arylamine represented by the general formula [], its hydrochloride, sulfur dioxide, and the copper compound. Examples of the solvent include organic acids, their acid anhydrides, organic acid esters, tertiary alcohols, ketones, halogenated hydrocarbons, lower alkyl nitriles, and the like. Specific examples include acetic acid, ethyl acetate, acetic anhydride, t-butyl alcohol, acetone, methyl ethyl ketone, ethylene dichloride, chloroform, acetonitrile, propionitrile, and the like. Moreover, sulfur dioxide, which is a reaction reagent, can also be used as a solvent. When primary nitrite is used as the alkyl nitrite represented by the general formula [], it is desirable to use a mixed solvent of the above solvent and acetic anhydride because the aryl compound ArH is likely to be formed as described above. The reaction temperature is usually in the range of 0 to 50°C, preferably in the range of 0 to 25°C. When the temperature exceeds 50°C, side reactions occur and the yield of the arylsulfonyl chloride represented by the general formula [] decreases. The reaction of the present invention can be carried out at normal pressure or under increased pressure. In the reaction of the present invention, water is produced during the reaction, and if a dehydrating agent is added to the reaction system to remove this water, the yield of the arylsulfonyl chloride represented by the general formula [] may be improved. Examples of the dehydrating agent include silica gel and molecular sieve. To give specific examples of the embodiments of the present invention, the first method involves alkyl nitrite represented by the general formula [] in the presence of an arylamine represented by the general formula [] and hydrogen chloride at a low temperature, e.g. ~
After reacting at 5°C to produce a diazonium salt of the arylamine represented by the general formula [], the diazonium salt represented by the general formula [] is added to the decomposition solution consisting of sulfur dioxide, a copper compound and, if necessary, a solvent. This is a method for obtaining arylsulfonyl chloride. The second method involves adding an alkyl nitrite represented by the general formula [] in the presence of an arylamine represented by the general formula [], hydrogen chloride, sulfur dioxide, a copper compound, and a solvent if necessary, and This is a method for obtaining arylsulfonyl chloride represented by []. Among the above methods, the second method is preferable in terms of the yield of the arylsulfonyl chloride represented by the general formula [] and the reaction operation. (d) Effect of the invention By using the alkyl nitrite represented by the general formula [], the arylsulfonyl chloride represented by the general formula [] can be easily produced from the arylamine represented by the general formula [] even on an industrial scale. It can be obtained in high yield and there is no generation of waste acid. (e) Examples Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto. Example 1
【化】
１−メチル−４−エトキシカルボニル−５−ア
ミノピラゾール−（以下、MPAと略称する。）
5.07ｇ（0.03モル）、塩化水素1.1ｇ（0.03モル
比）、塩化第２銅２水塩0.5ｇ及び酢酸50ｇを反応
器に仕込んだ後、亜硫酸ガス８ｇを吹込んだ。
次に、撹拌しながらｔ−ブチルナイトライト６
mlを10℃での溶液に10分間で滴下した。滴下と同
時に、発熱と窒素ガスの発生があり温度は15〜20
℃に上昇した。15〜20℃で撹拌しながら１時間反
応させた。
固形分を濾過後、反応液について内部標準法で
液クロマトグラフイ分析したところ、１−メチル
−４−エトキシカルボニル−５−クロロスルホニ
ルピラゾール（以下、PSClと略称する。）4.1ｇ
（収率54％）が得られた。
実施例 ２
MPA5.07ｇ（0.03モル）、塩化水素1.1ｇ（0.03
モル）、酢酸50ｇ、塩化第２銅２水塩0.5ｇ及びモ
レキユラーシーブ10ｇを反応器に仕込んだ後、亜
硫酸ガス８ｇを吹込んだ。
次に、撹拌しながらｔ−ブチルナイトライト６
mlを10℃の溶液に10分間で滴下した。滴下と同時
に、発熱と窒素ガスの発生があり温度は15〜20℃
に上昇した。15〜20℃で撹拌しながら１時間反応
させた。
実施例１と同様に操作を行い反応液について分
析を行つたところ、PSCl5.0ｇ（収率66％）が得
られた。
実施例 ３
MPA5.07ｇ（0.03モル）、アセトニトリル30
ｇ、塩化水素1.1ｇ（0.03モル）のアセトニトリ
ル溶液4.85ｇ、硫酸第２銅５水塩0.5ｇ及びモレ
キユラーシーブ10ｇを反応器に仕込んだ後、亜硫
酸ガス12ｇを吹込んだ。
次に、撹拌しながらｔ−ブチルナイトライト６
mlを10℃の溶液に10分間で滴下した。滴下と同時
に、発熱と窒素ガスの発生があり温度は20〜25℃
に上昇した。15〜20℃で撹拌しながら１時間反応
させた。
固形分を濾過後、反応液中の低沸物を減圧下で
留去し、残留物に加え、トルエン抽出を行つた。
実施例１と同様に抽出液について分析を行つた
ところ、PSCl5.8ｇ（収率76％）が得られた。
実施例 ４
アセトニトリル30ｇ、硫酸第２銅５水塩0.5ｇ
及びモレキユラーシーブ10ｇを反応器に仕込み、
亜硫酸ガス８ｇを吹込んだ。
次に、MPA5.07ｇ（0.03モル）、アセトニトリ
ル30ｇ及び塩化水素1.1ｇ（0.03モル）のアセト
ニトリル溶液4.85ｇの混合液に、ｔ−ブチルナイ
トライト６mlを撹拌しながら０℃で10分間で滴下
した溶液を、上記反応器中の溶液に０〜10℃で30
分間で滴下した。更に、15〜20℃で撹拌しながら
１時間反応させた。
固形分を濾過後、反応液中の低沸物を減圧下60
℃以下で留去し、水を加えトルエン抽出を行つ
た。
実施例１と同様に抽出液について分析を行つた
ところ、PSCl4.0ｇ（収率53％）が得られた。
実施例 ５
アセトニトリル30ｇ、硫酸第２銅５水塩0.5ｇ
及びモレキユラーシーブ10ｇを反応器に仕込み、
亜硫酸ガス８ｇを吹込んだ。
次に、MPA5.07ｇ（0.03モル）、アセトニトリ
ル30ｇ及び塩化水素1.1ｇ（0.03モル）のアセト
ニトリル溶液4.85ｇの混合液に、ネオペンチルナ
イトライト７mlを撹拌しながら０℃で10分間で滴
下した溶液を、上記反応器中の溶液に０〜10℃で
30分間で滴下した。更に、15〜20℃で撹拌しなが
ら１時間反応させた。
固形分を濾過後、反応液中の低沸物を減圧下60
℃以下で留去し、水を加えトルエン抽出を行つ
た。
実施例１と同様に抽出液について分析を行つた
ところ、PSCl4.7ｇ（収率62％）が得られた。
実施例 ６
MPA50.7ｇ（0.3モル）、塩化水素10.95ｇ（0.3
モル）、酢酸250ｇ、塩化第２銅２水塩５ｇ及びモ
レキユラーシーブ50ｇを反応器に仕込んだ後、亜
硫酸ガスを80ｇ吹込んだ。
次に、撹拌しながらｔブチルナイトライト60ml
を10℃の溶液に30分間で滴下した。滴下と同時
に、発熱と窒素ガスの発生があり温度は15〜20℃
に上昇した。15〜20℃で撹拌しながら１時間反応
させた。
固形分を濾過後、反応液中の低沸物を減圧下30
℃以下で留去し、残留物に水300ｇを加え、ジク
ロロエチレン500ｇで抽出を行つた。
更に、ジクロロエチレン層を水300ｇで洗浄し、
ジクロロエチレンを減圧下留去後、残渣について
真空蒸留を行つたところ、PSCl42ｇ（沸点110
℃／0.3mmHg、収率55％）が得られた。
実施例 ７
MPA5.07ｇ（0.03モル）、塩化水素1.1ｇ（0.03
モル）、酢酸20ｇ、塩化第２銅２水塩0.5ｇ及び無
水酢酸25ｇを反応器に仕込んだ後、亜硫酸ガスを
８ｇ吹込んだ。
次に、撹拌しながら、ｎ−アミルナイトライト
６mlを20℃の溶液に10分間で滴下した。滴下と同
時に、発熱と窒素ガスの発生があり温度は20〜20
℃に上昇した。15〜20℃で撹拌しながら１時間反
応させた。
実施例１と同様に操作を行い反応液について分
析を行つたところ、PSCl4.2ｇ（収率55％）が得
られた。
実施例 ８
酢酸25ｇ、塩化第２銅２水塩0.5ｇ、モレキユ
ラーシーブ10ｇを反応器に仕込んだ後、亜硫酸ガ
スを８ｇ吹込んだ。
次に、撹拌しながらMPA5.07ｇ（0.03モル）、
塩化水素1.1ｇ（0.03モル）及び酢酸25ｇよりな
る溶液を10℃の溶液に30分間で滴下した。滴下と
同時に、窒素ガスの発生があり温度は15〜20℃に
上昇した。15〜20℃で撹拌しながら１時間反応さ
せた。
次に、実施例１と同様に操作を行い反応液につ
いて分析を行つたところ、PSCl4.0ｇ（収率53
％）が得られた。
実施例 ９
MPA5.7ｇ（0.03モル）、アセトニトリル30ｇ、
塩化水素1.1ｇ（0.03モル）を含むアセトニトリ
ル溶液4.85ｇ及び硫酸第２銅５水塩0.5ｇを反応
器に仕込んだ後、亜硫酸ガス12ｇを吹込んだ。
次に、撹拌しながらｔ−ブチルナイトライト60
mlを10℃の溶液に10分間で滴下した。滴下と同時
に、発熱と窒素ガスの発生があり温度は20〜25℃
に上昇した。15〜20℃で撹拌しながら１時間反応
させた。この反応の間、圧力は５Kg／cm2に維持し
た。
固形分を濾過後、反応液中の低沸物を減圧下60
℃以下で留去し、水を加え、トルエン抽出を行つ
た。
次に、実施例１と同様に操作を行い反応液につ
いて分析を行つたところ、PSCl5.6ｇ（収率74
％）が得られた。
実施例 10
MPA5.7ｇ（0.03モル）、塩化水素1.1ｇ（0.03
モル）を含むアセトニトリル溶液4.85ｇ及び硫酸
第２銅５水塩0.5ｇを反応器に仕込んだ後、亜硫
酸ガス25ｇを吹込んだ。
次に、撹拌しながら５−ブチルナイトライト60
mlを10℃の溶液に10分間で滴下した。滴下と同時
に、発熱と窒素ガスの発生があり温度は20〜25℃
に上昇した。15〜20℃で撹拌しながら１時間反応
させた。この反応の間、圧力は５Kg／cm2に維持し
た。
固形分を濾過後、反応液中の低沸物を減圧下60
℃以下で留去し、水を加え、トルエン抽出を行つ
た。
次に、実施例１と同様に操作を行い反応液につ
いて分析を行つたところ、PSCl3.8ｇ（収率50
％）が得られた。
実施例 11
アニリン2.79ｇ（0.03モル）、塩化水素1.1（0.03
モル）、酢酸50ｇ、塩化第２銅２水塩0.5ｇ及びモ
レキユラーシーブ10ｇを反応器に仕込んだ後、亜
硫酸ガス８ｇを吹込んだ。
次に、撹拌しながら、ｔ−ブチルナイトライト
６mlを10℃の溶液に10分間で滴下した。滴下と同
時に、発熱と窒素ガスの発生があり温度は15〜20
℃に上昇した。15〜20℃で撹拌しながら１時間反
応させた。
実施例１と同様に操作を行い反応液について分
析を行つたところ、ベンゼンスルホニルクロライ
ド2.1ｇ（収率45％）が得られた。
実施例 12
ｐ−ニトロアニリン4.14ｇ（0.03モル）、塩化
水素1.1ｇ（0.03モル）、酢酸80ｇ及び塩化第２銅
２水塩0.5ｇを反応器に仕込んだ後、亜硫酸ガス
８ｇを吹込んだ。
次に、撹拌しながらｔ−ブチルナイトライト６
mlを10℃の溶液に10分間で滴下した。滴下と同時
に、発熱と窒素ガスの発生があり温度は20〜25℃
に上昇した。15〜20℃で撹拌しながら１時間反応
させた。
固形分を濾過後、反応液中の低沸物を減圧下60
℃以下で留去し、残留物に氷水を加えたところオ
レンジ色の固体が析出した。
この固体を乾燥後、実施例１と同様に分析を行
つたところ、ｐ−ニトロベンゼンスルホニルクロ
ライド4.9ｇ（収率73％）が得られた。
実施例 13
ｐ−クロルアニリン3.83ｇ（0.03モル）、塩化
水素1.1ｇ（0.03モル）、酢酸80ｇ及び塩化第２銅
２水塩0.5ｇ及びモレキユラーシーブ10ｇを反応
器に仕込んだ後、亜硫酸ガス８ｇを吹込んだ。
次に、撹拌しながらｔ−ブチルナイトライト６
mlを10℃の溶液に10分間で滴下した。滴下と同時
に、発熱と窒素ガスの発生があり温度は20〜25℃
に上昇した。15〜20℃で撹拌しながら１時間反応
させた。
固形分を濾過後、反応液中の低沸物を減圧下60
℃以下で留去し、残留物に氷水を加えたところ淡
橙色の固体が析出した。
この固体を乾燥後、実施例１と同様に分析を行
つたところ、ｐ−クロルベンゼンスルホニルクロ
ライド6.1ｇ（収率96％）が得られた。
実施例 14
ｐ−トルイジン3.2ｇ（0.03モル）、塩化水素1.1
ｇ（0.03モル）を含むアセトニトリル溶液4.85
ｇ、硫酸第２銅５水塩0.5ｇ及びアセトニトリル
30ｇを反応器に仕込んだ後、亜硫酸ガス８ｇを吹
込んだ。
次に、撹拌しながらｔ−ブチルナイトライト６
mlを10℃の溶液に10分間で滴下した。滴下と同時
に、発熱と窒素ガスの発生があり温度は20〜25℃
に上昇した。15〜20℃で撹拌しながら１時間反応
させた。
固形分を濾過後、反応液中の低沸物を減圧下60
℃以下で留去し、水を加えトルエン抽出を行つ
た。
このトルエン溶液を乾燥後、実施例１と同様に
分析を行つたところ、ｐ−メチルベンゼンスルホ
ニルクロライド3.4ｇ（収率50％）が得られた。
実施例 15
２，４−ジクロロアニリン4.9ｇ（0.03モル）、
塩化水素1.1ｇ（0.03モル）を含むアセトニトリ
ル溶液4.85ｇ、硫酸第２銅５水塩0.5ｇ及びアセ
トニトリル30ｇを反応器に仕込んだ後、亜硫酸ガ
ス12ｇを吹込んだ。
次に、撹拌しながらｔ−ブチルナイトライト６
mlを10℃を溶液に10分間で滴下した。滴下と同時
に、発熱と窒素ガスの発生があり温度は20〜25℃
に上昇した。15〜20℃で撹拌しながら１時間反応
させた。
固形分を濾過後、反応液中の低沸物を減圧下60
℃以下で留去し、水を加えトルエン抽出を行つ
た。
このトルエン溶液を乾燥後、実施例１と同様に
分析を行つたところ、２，４−ジクロロベンゼン
スルホニルクロライド6.0ｇ（収率83％）が得ら
れた。[Chemical formula] 1-Methyl-4-ethoxycarbonyl-5-aminopyrazole- (hereinafter abbreviated as MPA)
After charging 5.07 g (0.03 mol), 1.1 g (0.03 molar ratio) of hydrogen chloride, 0.5 g of cupric chloride dihydrate, and 50 g of acetic acid into a reactor, 8 g of sulfur dioxide gas was blown into the reactor. Next, while stirring, t-butyl nitrite 6
ml was added dropwise over 10 minutes to the solution at 10°C. At the same time as dropping, heat generation and nitrogen gas are generated, and the temperature is 15 to 20.
The temperature rose to ℃. The reaction was allowed to proceed for 1 hour while stirring at 15-20°C. After filtering the solid content, liquid chromatography analysis of the reaction solution using an internal standard method revealed 4.1 g of 1-methyl-4-ethoxycarbonyl-5-chlorosulfonylpyrazole (hereinafter abbreviated as PSCl).
(Yield 54%) was obtained. Example 2 MPA5.07g (0.03mol), hydrogen chloride 1.1g (0.03mol)
After charging 50 g of acetic acid, 0.5 g of cupric chloride dihydrate, and 10 g of molecular sieve into a reactor, 8 g of sulfur dioxide gas was blown into the reactor. Next, while stirring, t-butyl nitrite 6
ml was added dropwise to the solution at 10°C over 10 minutes. At the same time as dropping, heat generation and nitrogen gas are generated, and the temperature is 15 to 20℃.
rose to The reaction was allowed to proceed for 1 hour while stirring at 15-20°C. When the reaction solution was analyzed in the same manner as in Example 1, 5.0 g of PSCl (yield: 66%) was obtained. Example 3 MPA5.07g (0.03mol), acetonitrile 30
After charging a reactor with 4.85 g of an acetonitrile solution containing 1.1 g (0.03 mol) of hydrogen chloride, 0.5 g of cupric sulfate pentahydrate, and 10 g of molecular sieve, 12 g of sulfur dioxide gas was blown into the reactor. Next, while stirring, t-butyl nitrite 6
ml was added dropwise to the solution at 10°C over 10 minutes. At the same time as dropping, heat generation and nitrogen gas are generated, and the temperature is 20 to 25℃.
rose to The reaction was allowed to proceed for 1 hour while stirring at 15-20°C. After filtering the solid content, low-boiling substances in the reaction solution were distilled off under reduced pressure, added to the residue, and extracted with toluene. When the extract was analyzed in the same manner as in Example 1, 5.8 g of PSCl (yield 76%) was obtained. Example 4 30 g of acetonitrile, 0.5 g of cupric sulfate pentahydrate
and 10g of molecular sieve into the reactor,
8 g of sulfur dioxide gas was blown into the tank. Next, 6 ml of t-butyl nitrite was added dropwise to a mixture of 4.85 g of an acetonitrile solution containing 5.07 g (0.03 mol) of MPA, 30 g of acetonitrile, and 1.1 g (0.03 mol) of hydrogen chloride at 0°C for 10 minutes with stirring. Add the solution to the solution in the above reactor at 0-10℃ for 30 minutes.
It was dripped in minutes. Furthermore, the mixture was reacted for 1 hour while stirring at 15 to 20°C. After filtering the solid content, remove low-boiling substances from the reaction solution under reduced pressure at 60°C.
The residue was distilled off at a temperature below 0.degree. C., water was added, and extraction with toluene was performed. When the extract was analyzed in the same manner as in Example 1, 4.0 g of PSCl (yield 53%) was obtained. Example 5 Acetonitrile 30g, cupric sulfate pentahydrate 0.5g
and 10g of molecular sieve into the reactor,
8 g of sulfur dioxide gas was blown into the tank. Next, 7 ml of neopentyl nitrite was added dropwise to a mixture of 4.85 g of an acetonitrile solution containing 5.07 g (0.03 mol) of MPA, 30 g of acetonitrile, and 1.1 g (0.03 mol) of hydrogen chloride at 0°C with stirring. into the solution in the above reactor at 0-10℃
It was added dropwise over 30 minutes. Furthermore, the mixture was reacted for 1 hour while stirring at 15 to 20°C. After filtering the solid content, remove low-boiling substances from the reaction solution under reduced pressure at 60°C.
The residue was distilled off at a temperature below 0.degree. C., water was added, and extraction with toluene was performed. When the extract was analyzed in the same manner as in Example 1, 4.7 g of PSCl (yield 62%) was obtained. Example 6 MPA50.7g (0.3mol), hydrogen chloride 10.95g (0.3mol)
After charging 250 g of acetic acid, 5 g of cupric chloride dihydrate, and 50 g of molecular sieve into a reactor, 80 g of sulfur dioxide gas was blown into the reactor. Next, while stirring, add 60ml of t-butyl nitrite.
was added dropwise to the solution at 10°C over 30 minutes. At the same time as dropping, heat generation and nitrogen gas are generated, and the temperature is 15 to 20℃.
rose to The reaction was allowed to proceed for 1 hour while stirring at 15-20°C. After filtering the solid content, remove low-boiling substances from the reaction solution under reduced pressure for 30 minutes.
The residue was distilled off at a temperature below 0.degree. C., and 300 g of water was added to the residue, followed by extraction with 500 g of dichloroethylene. Furthermore, the dichloroethylene layer was washed with 300 g of water,
After dichloroethylene was distilled off under reduced pressure, the residue was vacuum distilled, resulting in 42 g of PSCl (boiling point 110
°C/0.3 mmHg, yield 55%). Example 7 MPA5.07g (0.03mol), hydrogen chloride 1.1g (0.03mol)
After charging a reactor with 20 g of acetic acid, 0.5 g of cupric chloride dihydrate, and 25 g of acetic anhydride, 8 g of sulfur dioxide gas was blown into the reactor. Next, 6 ml of n-amyl nitrite was added dropwise to the 20° C. solution over 10 minutes while stirring. At the same time as dropping, heat generation and nitrogen gas are generated, and the temperature is 20 to 20.
The temperature rose to ℃. The reaction was allowed to proceed for 1 hour while stirring at 15-20°C. When the reaction solution was analyzed in the same manner as in Example 1, 4.2 g of PSCl (yield 55%) was obtained. Example 8 After charging 25 g of acetic acid, 0.5 g of cupric chloride dihydrate, and 10 g of molecular sieve into a reactor, 8 g of sulfur dioxide gas was blown into the reactor. Next, while stirring, MPA5.07g (0.03mol),
A solution consisting of 1.1 g (0.03 mol) of hydrogen chloride and 25 g of acetic acid was added dropwise to the solution at 10° C. over 30 minutes. Simultaneously with the dropping, nitrogen gas was generated and the temperature rose to 15-20°C. The reaction was allowed to proceed for 1 hour while stirring at 15-20°C. Next, the same operation as in Example 1 was carried out and the reaction solution was analyzed, and it was found that PSCl4.0g (yield 53
%)was gotten. Example 9 MPA5.7g (0.03mol), acetonitrile 30g,
After charging 4.85 g of an acetonitrile solution containing 1.1 g (0.03 mol) of hydrogen chloride and 0.5 g of cupric sulfate pentahydrate into a reactor, 12 g of sulfur dioxide gas was blown into the reactor. Next, while stirring, add t-butyl nitrite 60
ml was added dropwise to the solution at 10°C over 10 minutes. At the same time as dropping, heat generation and nitrogen gas are generated, and the temperature is 20 to 25℃.
rose to The reaction was allowed to proceed for 1 hour while stirring at 15-20°C. During this reaction, the pressure was maintained at 5 Kg/cm 2 . After filtering the solid content, remove low-boiling substances from the reaction solution under reduced pressure at 60°C.
The residue was distilled off at a temperature below 0.degree. C., water was added, and extraction with toluene was performed. Next, the same operation as in Example 1 was carried out and the reaction solution was analyzed, and it was found that 5.6 g of PSCl (yield 74
%)was gotten. Example 10 MPA5.7g (0.03mol), hydrogen chloride 1.1g (0.03mol)
After charging 4.85 g of an acetonitrile solution containing mol) and 0.5 g of cupric sulfate pentahydrate into a reactor, 25 g of sulfur dioxide gas was blown into the reactor. Next, while stirring, 5-butyl nitrite 60
ml was added dropwise to the solution at 10°C over 10 minutes. At the same time as dropping, heat generation and nitrogen gas are generated, and the temperature is 20 to 25℃.
rose to The reaction was allowed to proceed for 1 hour while stirring at 15-20°C. During this reaction, the pressure was maintained at 5 Kg/cm 2 . After filtering the solid content, remove low-boiling substances from the reaction solution under reduced pressure at 60°C.
The residue was distilled off at a temperature below 0.degree. C., water was added, and extraction with toluene was performed. Next, the same operation as in Example 1 was carried out and the reaction solution was analyzed, and it was found that 3.8 g of PSCl (yield: 50
%)was gotten. Example 11 2.79 g (0.03 mol) of aniline, 1.1 (0.03 mol) of hydrogen chloride
After charging 50 g of acetic acid, 0.5 g of cupric chloride dihydrate, and 10 g of molecular sieve into a reactor, 8 g of sulfur dioxide gas was blown into the reactor. Next, 6 ml of t-butyl nitrite was added dropwise to the 10° C. solution over 10 minutes while stirring. At the same time as dropping, heat generation and nitrogen gas are generated, and the temperature is 15 to 20.
The temperature rose to ℃. The reaction was allowed to proceed for 1 hour while stirring at 15-20°C. The reaction solution was analyzed in the same manner as in Example 1, and 2.1 g (yield: 45%) of benzenesulfonyl chloride was obtained. Example 12 After charging 4.14 g (0.03 mol) of p-nitroaniline, 1.1 g (0.03 mol) of hydrogen chloride, 80 g of acetic acid, and 0.5 g of cupric chloride dihydrate into a reactor, 8 g of sulfur dioxide gas was blown into the reactor. . Next, while stirring, t-butyl nitrite 6
ml was added dropwise to the solution at 10°C over 10 minutes. At the same time as dropping, heat generation and nitrogen gas are generated, and the temperature is 20 to 25℃.
rose to The reaction was allowed to proceed for 1 hour while stirring at 15-20°C. After filtering the solid content, remove low-boiling substances from the reaction solution under reduced pressure at 60°C.
The residue was distilled off at a temperature below 0.degree. C., and ice water was added to the residue to precipitate an orange solid. After drying this solid, it was analyzed in the same manner as in Example 1, and 4.9 g (yield: 73%) of p-nitrobenzenesulfonyl chloride was obtained. Example 13 After charging 3.83 g (0.03 mol) of p-chloroaniline, 1.1 g (0.03 mol) of hydrogen chloride, 80 g of acetic acid, 0.5 g of cupric chloride dihydrate, and 10 g of molecular sieve into a reactor, sulfurous acid 8g of gas was injected. Next, while stirring, t-butyl nitrite 6
ml was added dropwise to the solution at 10°C over 10 minutes. At the same time as dropping, heat generation and nitrogen gas are generated, and the temperature is 20 to 25℃.
rose to The reaction was allowed to proceed for 1 hour while stirring at 15-20°C. After filtering the solid content, remove low-boiling substances from the reaction solution under reduced pressure at 60°C.
The residue was distilled off at a temperature below 0.degree. C., and ice water was added to the residue to precipitate a pale orange solid. After drying this solid, it was analyzed in the same manner as in Example 1, and 6.1 g (yield: 96%) of p-chlorobenzenesulfonyl chloride was obtained. Example 14 3.2 g (0.03 mol) p-toluidine, 1.1 hydrogen chloride
Acetonitrile solution containing 4.85 g (0.03 mol)
g, cupric sulfate pentahydrate 0.5 g and acetonitrile
After charging 30 g into the reactor, 8 g of sulfur dioxide gas was blown into the reactor. Next, while stirring, t-butyl nitrite 6
ml was added dropwise to the solution at 10°C over 10 minutes. At the same time as dropping, heat generation and nitrogen gas are generated, and the temperature is 20 to 25℃.
rose to The reaction was allowed to proceed for 1 hour while stirring at 15-20°C. After filtering the solid content, remove low-boiling substances from the reaction solution under reduced pressure at 60°C.
The residue was distilled off at a temperature below 0.degree. C., water was added, and extraction with toluene was performed. After drying this toluene solution, it was analyzed in the same manner as in Example 1, and 3.4 g (yield: 50%) of p-methylbenzenesulfonyl chloride was obtained. Example 15 2,4-dichloroaniline 4.9 g (0.03 mol),
After charging 4.85 g of an acetonitrile solution containing 1.1 g (0.03 mol) of hydrogen chloride, 0.5 g of cupric sulfate pentahydrate, and 30 g of acetonitrile into a reactor, 12 g of sulfur dioxide gas was blown into the reactor. Next, while stirring, t-butyl nitrite 6
ml was added dropwise to the solution at 10°C for 10 minutes. At the same time as dropping, heat generation and nitrogen gas are generated, and the temperature is 20 to 25℃.
rose to The reaction was allowed to proceed for 1 hour while stirring at 15-20°C. After filtering the solid content, remove low-boiling substances from the reaction solution under reduced pressure at 60°C.
The residue was distilled off at a temperature below 0.degree. C., water was added, and extraction with toluene was performed. After drying this toluene solution, it was analyzed in the same manner as in Example 1, and 6.0 g (yield: 83%) of 2,4-dichlorobenzenesulfonyl chloride was obtained.
Claims (1)
子又は硫黄原子、ａは１又は２の整数を示す。） で表されるアルキルナイトライトと反応させるこ
とを特徴とする 一般式〔〕 ArSO2Cl 〔〕 で表されるアリールスルホニルクロライドの製
法。 ２ 一般式〔〕で表されるアルキルナイトライ
トが第３級アルキルナイトライトである請求項１
記載のアリールスルホニルクロライドの製法。 ３ 一般式〔〕で表されるアリールスルホニル
クロライドが 一般式〔〕 【化】 （R2は炭素数１〜10のアルキル基を示す。） で表されるピラゾールスルホニルクロライドであ
ることを特徴とする請求項１記載のアリールスル
ホニルクロライドの製法。[Claims] 1. An arylamine represented by the general formula [] ArNH 2 [] (Ar represents a substituted or unsubstituted aryl group) in the presence of hydrogen chloride, sulfur dioxide and a copper compound, [] R 1 YNO a [] (R 1 is an alkyl group having 2 to 10 carbon atoms, Y is an oxygen atom or a sulfur atom, and a is an integer of 1 or 2.) React with alkyl nitrite represented by A method for producing arylsulfonyl chloride represented by the general formula [] ArSO 2 Cl []. 2 Claim 1 wherein the alkyl nitrite represented by the general formula [] is a tertiary alkyl nitrite.
Process for producing the described arylsulfonyl chloride. 3 The arylsulfonyl chloride represented by the general formula [] is a pyrazolesulfonyl chloride represented by the general formula [] [C] (R 2 represents an alkyl group having 1 to 10 carbon atoms) A method for producing arylsulfonyl chloride according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63202954A JPH0253738A (en) | 1988-08-15 | 1988-08-15 | Production of arylsulfonyl chloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63202954A JPH0253738A (en) | 1988-08-15 | 1988-08-15 | Production of arylsulfonyl chloride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0253738A JPH0253738A (en) | 1990-02-22 |
| JPH0584291B2 true JPH0584291B2 (en) | 1993-12-01 |
Family
ID=16465916
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63202954A Granted JPH0253738A (en) | 1988-08-15 | 1988-08-15 | Production of arylsulfonyl chloride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0253738A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3599537B2 (en) * | 1997-08-29 | 2004-12-08 | 株式会社ニデック | Eye refractive power measuring device |
-
1988
- 1988-08-15 JP JP63202954A patent/JPH0253738A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0253738A (en) | 1990-02-22 |
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