CA1069130A - Anthelmintically active 2-carbalkoxyamino benzimidazolyl-5(6) sulfonic acid phenyl esters and process for their manufacture - Google Patents
Anthelmintically active 2-carbalkoxyamino benzimidazolyl-5(6) sulfonic acid phenyl esters and process for their manufactureInfo
- Publication number
- CA1069130A CA1069130A CA314,151A CA314151A CA1069130A CA 1069130 A CA1069130 A CA 1069130A CA 314151 A CA314151 A CA 314151A CA 1069130 A CA1069130 A CA 1069130A
- Authority
- CA
- Canada
- Prior art keywords
- phenyl ester
- nitro
- diamino
- chloro
- acid
- 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
Links
- 238000000034 method Methods 0.000 title claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 title abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 3
- 150000002367 halogens Chemical class 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims abstract description 3
- 125000003545 alkoxy group Chemical group 0.000 claims abstract 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims abstract 2
- -1 3,4-diamino-benzene sulfonic acid 3-trifluoromethyl phenyl ester Chemical class 0.000 claims description 38
- ROVPGRDMDASARO-UHFFFAOYSA-N phenyl 3,4-diaminobenzenesulfonate Chemical compound C1=C(N)C(N)=CC=C1S(=O)(=O)OC1=CC=CC=C1 ROVPGRDMDASARO-UHFFFAOYSA-N 0.000 claims description 11
- NEZIKMJTIOLUGU-UHFFFAOYSA-N phenyl 4-amino-3-nitrobenzenesulfonate Chemical compound C1=C([N+]([O-])=O)C(N)=CC=C1S(=O)(=O)OC1=CC=CC=C1 NEZIKMJTIOLUGU-UHFFFAOYSA-N 0.000 claims description 9
- 239000007868 Raney catalyst Substances 0.000 claims description 5
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims description 5
- 229910000564 Raney nickel Inorganic materials 0.000 claims description 5
- OEWUTDOUXOVAGR-UHFFFAOYSA-N (3-cyanophenyl) 3,4-diaminobenzenesulfonate Chemical compound C1=C(N)C(N)=CC=C1S(=O)(=O)OC1=CC=CC(C#N)=C1 OEWUTDOUXOVAGR-UHFFFAOYSA-N 0.000 claims description 3
- REDRJDQKXRSTBY-UHFFFAOYSA-N (3-cyanophenyl) 4-amino-3-nitrobenzenesulfonate Chemical compound C1=C([N+]([O-])=O)C(N)=CC=C1S(=O)(=O)OC1=CC=CC(C#N)=C1 REDRJDQKXRSTBY-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 4
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 241000242711 Fasciola hepatica Species 0.000 abstract 1
- 241001465754 Metazoa Species 0.000 abstract 1
- 230000000973 chemotherapeutic effect Effects 0.000 abstract 1
- 201000010099 disease Diseases 0.000 abstract 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 abstract 1
- 208000006275 fascioliasis Diseases 0.000 abstract 1
- 244000000013 helminth Species 0.000 abstract 1
- 244000045947 parasite Species 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- DXNLDBASBALMSX-UHFFFAOYSA-N phenyl 4-chloro-3-nitrobenzenesulfonate Chemical compound C1=C(Cl)C([N+](=O)[O-])=CC(S(=O)(=O)OC=2C=CC=CC=2)=C1 DXNLDBASBALMSX-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 150000004987 o-phenylenediamines Chemical class 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- ZLHORUGUHGSRRM-UHFFFAOYSA-N (2,5-dichlorophenyl) 3,4-diaminobenzenesulfonate Chemical compound C1=C(N)C(N)=CC=C1S(=O)(=O)OC1=CC(Cl)=CC=C1Cl ZLHORUGUHGSRRM-UHFFFAOYSA-N 0.000 description 2
- BGKBIDOMOFMKSU-UHFFFAOYSA-N (3,5-dichlorophenyl) 3,4-diaminobenzenesulfonate Chemical compound C1=C(N)C(N)=CC=C1S(=O)(=O)OC1=CC(Cl)=CC(Cl)=C1 BGKBIDOMOFMKSU-UHFFFAOYSA-N 0.000 description 2
- SEWNAJIUKSTYOP-UHFFFAOYSA-N 4-chloro-3-nitrobenzenesulfonyl chloride Chemical compound [O-][N+](=O)C1=CC(S(Cl)(=O)=O)=CC=C1Cl SEWNAJIUKSTYOP-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- KJOOATXDSQOFPX-UHFFFAOYSA-N [4-(2-methylpropoxy)phenyl] 3,4-diaminobenzenesulfonate Chemical compound C1=CC(OCC(C)C)=CC=C1OS(=O)(=O)C1=CC=C(N)C(N)=C1 KJOOATXDSQOFPX-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- JFIOVJDNOJYLKP-UHFFFAOYSA-N bithionol Chemical compound OC1=C(Cl)C=C(Cl)C=C1SC1=CC(Cl)=CC(Cl)=C1O JFIOVJDNOJYLKP-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- NNBBQNFHCVVQHZ-UHFFFAOYSA-N methyl carbamimidothioate;sulfuric acid Chemical compound CSC(N)=N.OS(O)(=O)=O NNBBQNFHCVVQHZ-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229940086542 triethylamine Drugs 0.000 description 2
- JXCATYHLVAXVEH-UHFFFAOYSA-N (2,4-dimethylphenyl) 2-(methoxycarbonylamino)-3h-benzimidazole-5-sulfonate Chemical compound C1=C2NC(NC(=O)OC)=NC2=CC=C1S(=O)(=O)OC1=CC=C(C)C=C1C JXCATYHLVAXVEH-UHFFFAOYSA-N 0.000 description 1
- ZHGDCLZGIYJAJM-UHFFFAOYSA-N (2,4-dimethylphenyl) 4-amino-3-nitrobenzenesulfonate Chemical compound CC1=CC(C)=CC=C1OS(=O)(=O)C1=CC=C(N)C([N+]([O-])=O)=C1 ZHGDCLZGIYJAJM-UHFFFAOYSA-N 0.000 description 1
- AKWIYEVWEOEZTC-UHFFFAOYSA-N (2,4-dimethylphenyl) 4-chloro-3-nitrobenzenesulfonate Chemical compound CC1=CC(C)=CC=C1OS(=O)(=O)C1=CC=C(Cl)C([N+]([O-])=O)=C1 AKWIYEVWEOEZTC-UHFFFAOYSA-N 0.000 description 1
- PDOHEFDSUYVBHI-UHFFFAOYSA-N (2,5-dichlorophenyl) 2-(methoxycarbonylamino)-3h-benzimidazole-5-sulfonate Chemical compound C1=C2NC(NC(=O)OC)=NC2=CC=C1S(=O)(=O)OC1=CC(Cl)=CC=C1Cl PDOHEFDSUYVBHI-UHFFFAOYSA-N 0.000 description 1
- AWRFXVUKOIBNMG-UHFFFAOYSA-N (2,5-dichlorophenyl) 4-amino-3-nitrobenzenesulfonate Chemical compound C1=C([N+]([O-])=O)C(N)=CC=C1S(=O)(=O)OC1=CC(Cl)=CC=C1Cl AWRFXVUKOIBNMG-UHFFFAOYSA-N 0.000 description 1
- NIVCVAITNATGMG-UHFFFAOYSA-N (2,5-dichlorophenyl) 4-chloro-3-nitrobenzenesulfonate Chemical compound C1=C(Cl)C([N+](=O)[O-])=CC(S(=O)(=O)OC=2C(=CC=C(Cl)C=2)Cl)=C1 NIVCVAITNATGMG-UHFFFAOYSA-N 0.000 description 1
- BQPIDRJNXJZWHZ-UHFFFAOYSA-N (2-bromophenyl) 2-(methoxycarbonylamino)-3h-benzimidazole-5-sulfonate Chemical compound C1=C2NC(NC(=O)OC)=NC2=CC=C1S(=O)(=O)OC1=CC=CC=C1Br BQPIDRJNXJZWHZ-UHFFFAOYSA-N 0.000 description 1
- TZLGLOTZWNAURF-UHFFFAOYSA-N (2-bromophenyl) 3,4-diaminobenzenesulfonate Chemical compound C1=C(N)C(N)=CC=C1S(=O)(=O)OC1=CC=CC=C1Br TZLGLOTZWNAURF-UHFFFAOYSA-N 0.000 description 1
- UOZMDIWCYKFGHF-UHFFFAOYSA-N (2-bromophenyl) 4-amino-3-nitrobenzenesulfonate Chemical compound C1=C([N+]([O-])=O)C(N)=CC=C1S(=O)(=O)OC1=CC=CC=C1Br UOZMDIWCYKFGHF-UHFFFAOYSA-N 0.000 description 1
- VLNPUWGTMAYLQO-UHFFFAOYSA-N (2-bromophenyl) 4-chloro-3-nitrobenzenesulfonate Chemical compound C1=C(Cl)C([N+](=O)[O-])=CC(S(=O)(=O)OC=2C(=CC=CC=2)Br)=C1 VLNPUWGTMAYLQO-UHFFFAOYSA-N 0.000 description 1
- UXSMWEVRCDPXKV-UHFFFAOYSA-N (2-chloro-4-methylphenyl) 2-(methoxycarbonylamino)-3h-benzimidazole-5-sulfonate Chemical compound C1=C2NC(NC(=O)OC)=NC2=CC=C1S(=O)(=O)OC1=CC=C(C)C=C1Cl UXSMWEVRCDPXKV-UHFFFAOYSA-N 0.000 description 1
- CQNCDRXCCSJEPB-UHFFFAOYSA-N (2-chloro-4-methylphenyl) 3,4-diaminobenzenesulfonate Chemical compound ClC1=CC(C)=CC=C1OS(=O)(=O)C1=CC=C(N)C(N)=C1 CQNCDRXCCSJEPB-UHFFFAOYSA-N 0.000 description 1
- WMLWEUMLUGTERN-UHFFFAOYSA-N (2-chloro-4-methylphenyl) 4-amino-3-nitrobenzenesulfonate Chemical compound ClC1=CC(C)=CC=C1OS(=O)(=O)C1=CC=C(N)C([N+]([O-])=O)=C1 WMLWEUMLUGTERN-UHFFFAOYSA-N 0.000 description 1
- HFIUZQSIMIGIOF-UHFFFAOYSA-N (2-chloro-4-methylphenyl) 4-chloro-3-nitrobenzenesulfonate Chemical compound ClC1=CC(C)=CC=C1OS(=O)(=O)C1=CC=C(Cl)C([N+]([O-])=O)=C1 HFIUZQSIMIGIOF-UHFFFAOYSA-N 0.000 description 1
- IGESXLVCVIMMAP-UHFFFAOYSA-N (2-chloro-6-methylphenyl) 2-(methoxycarbonylamino)-3h-benzimidazole-5-sulfonate Chemical compound C1=C2NC(NC(=O)OC)=NC2=CC=C1S(=O)(=O)OC1=C(C)C=CC=C1Cl IGESXLVCVIMMAP-UHFFFAOYSA-N 0.000 description 1
- GVEUYYJRVRFMDS-UHFFFAOYSA-N (2-chloro-6-methylphenyl) 3,4-diaminobenzenesulfonate Chemical compound CC1=CC=CC(Cl)=C1OS(=O)(=O)C1=CC=C(N)C(N)=C1 GVEUYYJRVRFMDS-UHFFFAOYSA-N 0.000 description 1
- QSSHUNNUBJRDLU-UHFFFAOYSA-N (2-chloro-6-methylphenyl) 4-amino-3-nitrobenzenesulfonate Chemical compound CC1=CC=CC(Cl)=C1OS(=O)(=O)C1=CC=C(N)C([N+]([O-])=O)=C1 QSSHUNNUBJRDLU-UHFFFAOYSA-N 0.000 description 1
- CSGBFALEAZRNQN-UHFFFAOYSA-N (2-chloro-6-methylphenyl) 4-chloro-3-nitrobenzenesulfonate Chemical compound CC1=CC=CC(Cl)=C1OS(=O)(=O)C1=CC=C(Cl)C([N+]([O-])=O)=C1 CSGBFALEAZRNQN-UHFFFAOYSA-N 0.000 description 1
- CWTPUEDXFQHLIR-UHFFFAOYSA-N (2-chlorophenyl) 2-(methoxycarbonylamino)-3h-benzimidazole-5-sulfonate Chemical compound C1=C2NC(NC(=O)OC)=NC2=CC=C1S(=O)(=O)OC1=CC=CC=C1Cl CWTPUEDXFQHLIR-UHFFFAOYSA-N 0.000 description 1
- VUPOVZXDFUPZCR-UHFFFAOYSA-N (2-chlorophenyl) 3,4-diaminobenzenesulfonate Chemical compound C1=C(N)C(N)=CC=C1S(=O)(=O)OC1=CC=CC=C1Cl VUPOVZXDFUPZCR-UHFFFAOYSA-N 0.000 description 1
- WOJHQNCMZCQOFK-UHFFFAOYSA-N (2-chlorophenyl) 4-amino-3-nitrobenzenesulfonate Chemical compound C1=C([N+]([O-])=O)C(N)=CC=C1S(=O)(=O)OC1=CC=CC=C1Cl WOJHQNCMZCQOFK-UHFFFAOYSA-N 0.000 description 1
- NXLAPUAKSJCSFS-UHFFFAOYSA-N (2-chlorophenyl) 4-chloro-3-nitrobenzenesulfonate Chemical compound C1=C(Cl)C([N+](=O)[O-])=CC(S(=O)(=O)OC=2C(=CC=CC=2)Cl)=C1 NXLAPUAKSJCSFS-UHFFFAOYSA-N 0.000 description 1
- SGQSDLBDQUTBCP-UHFFFAOYSA-N (2-methoxyphenyl) 3,4-diaminobenzenesulfonate Chemical compound COC1=CC=CC=C1OS(=O)(=O)C1=CC=C(N)C(N)=C1 SGQSDLBDQUTBCP-UHFFFAOYSA-N 0.000 description 1
- PFDGYOJWWONJTA-UHFFFAOYSA-N (2-methoxyphenyl) 4-amino-3-nitrobenzenesulfonate Chemical compound COC1=CC=CC=C1OS(=O)(=O)C1=CC=C(N)C([N+]([O-])=O)=C1 PFDGYOJWWONJTA-UHFFFAOYSA-N 0.000 description 1
- LHNVCIQKOCIAJD-UHFFFAOYSA-N (2-methoxyphenyl) 4-chloro-3-nitrobenzenesulfonate Chemical compound COC1=CC=CC=C1OS(=O)(=O)C1=CC=C(Cl)C([N+]([O-])=O)=C1 LHNVCIQKOCIAJD-UHFFFAOYSA-N 0.000 description 1
- FOPZCEWBOPEBLS-UHFFFAOYSA-N (2-methylphenyl) 3,4-diaminobenzenesulfonate Chemical compound CC1=CC=CC=C1OS(=O)(=O)C1=CC=C(N)C(N)=C1 FOPZCEWBOPEBLS-UHFFFAOYSA-N 0.000 description 1
- UPDSLTBAXXVCPZ-UHFFFAOYSA-N (2-methylphenyl) 4-amino-3-nitrobenzenesulfonate Chemical compound CC1=CC=CC=C1OS(=O)(=O)C1=CC=C(N)C([N+]([O-])=O)=C1 UPDSLTBAXXVCPZ-UHFFFAOYSA-N 0.000 description 1
- TVWLMBSSDIEWJL-UHFFFAOYSA-N (2-methylphenyl) 4-chloro-3-nitrobenzenesulfonate Chemical compound CC1=CC=CC=C1OS(=O)(=O)C1=CC=C(Cl)C([N+]([O-])=O)=C1 TVWLMBSSDIEWJL-UHFFFAOYSA-N 0.000 description 1
- BYGWCYMTSFEQLM-UHFFFAOYSA-N (3,5-dichlorophenyl) 2-(methoxycarbonylamino)-3h-benzimidazole-5-sulfonate Chemical compound C1=C2NC(NC(=O)OC)=NC2=CC=C1S(=O)(=O)OC1=CC(Cl)=CC(Cl)=C1 BYGWCYMTSFEQLM-UHFFFAOYSA-N 0.000 description 1
- WOWQQLGSWXREKK-UHFFFAOYSA-N (3,5-dichlorophenyl) 4-amino-3-nitrobenzenesulfonate Chemical compound C1=C([N+]([O-])=O)C(N)=CC=C1S(=O)(=O)OC1=CC(Cl)=CC(Cl)=C1 WOWQQLGSWXREKK-UHFFFAOYSA-N 0.000 description 1
- BMKAZDKKRQRUDH-UHFFFAOYSA-N (3,5-dichlorophenyl) 4-chloro-3-nitrobenzenesulfonate Chemical compound C1=C(Cl)C([N+](=O)[O-])=CC(S(=O)(=O)OC=2C=C(Cl)C=C(Cl)C=2)=C1 BMKAZDKKRQRUDH-UHFFFAOYSA-N 0.000 description 1
- NXOKKXACBQESEI-UHFFFAOYSA-N (3-bromophenyl) 2-(methoxycarbonylamino)-3h-benzimidazole-5-sulfonate Chemical compound C1=C2NC(NC(=O)OC)=NC2=CC=C1S(=O)(=O)OC1=CC=CC(Br)=C1 NXOKKXACBQESEI-UHFFFAOYSA-N 0.000 description 1
- CGWGGQHTSYXUDD-UHFFFAOYSA-N (3-bromophenyl) 3,4-diaminobenzenesulfonate Chemical compound C1=C(N)C(N)=CC=C1S(=O)(=O)OC1=CC=CC(Br)=C1 CGWGGQHTSYXUDD-UHFFFAOYSA-N 0.000 description 1
- SUVVFPGNNBUFED-UHFFFAOYSA-N (3-bromophenyl) 4-amino-3-nitrobenzenesulfonate Chemical compound C1=C([N+]([O-])=O)C(N)=CC=C1S(=O)(=O)OC1=CC=CC(Br)=C1 SUVVFPGNNBUFED-UHFFFAOYSA-N 0.000 description 1
- BTQROPWNFKTNSO-UHFFFAOYSA-N (3-bromophenyl) 4-chloro-3-nitrobenzenesulfonate Chemical compound C1=C(Cl)C([N+](=O)[O-])=CC(S(=O)(=O)OC=2C=C(Br)C=CC=2)=C1 BTQROPWNFKTNSO-UHFFFAOYSA-N 0.000 description 1
- UFWGRYUVACXAGJ-UHFFFAOYSA-N (3-chloro-4-methylphenyl) 2-(methoxycarbonylamino)-3h-benzimidazole-5-sulfonate Chemical compound C1=C2NC(NC(=O)OC)=NC2=CC=C1S(=O)(=O)OC1=CC=C(C)C(Cl)=C1 UFWGRYUVACXAGJ-UHFFFAOYSA-N 0.000 description 1
- XQYMPPULLSLTTH-UHFFFAOYSA-N (3-chloro-4-methylphenyl) 3,4-diaminobenzenesulfonate Chemical compound C1=C(Cl)C(C)=CC=C1OS(=O)(=O)C1=CC=C(N)C(N)=C1 XQYMPPULLSLTTH-UHFFFAOYSA-N 0.000 description 1
- ZAXZIPLTAJSUOK-UHFFFAOYSA-N (3-chloro-4-methylphenyl) 4-amino-3-nitrobenzenesulfonate Chemical compound C1=C(Cl)C(C)=CC=C1OS(=O)(=O)C1=CC=C(N)C([N+]([O-])=O)=C1 ZAXZIPLTAJSUOK-UHFFFAOYSA-N 0.000 description 1
- ZSVWAAJTTRORET-UHFFFAOYSA-N (3-chloro-4-methylphenyl) 4-chloro-3-nitrobenzenesulfonate Chemical compound C1=C(Cl)C(C)=CC=C1OS(=O)(=O)C1=CC=C(Cl)C([N+]([O-])=O)=C1 ZSVWAAJTTRORET-UHFFFAOYSA-N 0.000 description 1
- ZKHUTBZCEQOSDR-UHFFFAOYSA-N (3-chlorophenyl) 3,4-diaminobenzenesulfonate Chemical compound C1=C(N)C(N)=CC=C1S(=O)(=O)OC1=CC=CC(Cl)=C1 ZKHUTBZCEQOSDR-UHFFFAOYSA-N 0.000 description 1
- MVWMIZKBHIIUJW-UHFFFAOYSA-N (3-chlorophenyl) 4-amino-3-nitrobenzenesulfonate Chemical compound C1=C([N+]([O-])=O)C(N)=CC=C1S(=O)(=O)OC1=CC=CC(Cl)=C1 MVWMIZKBHIIUJW-UHFFFAOYSA-N 0.000 description 1
- NPPCVICNVNTDDO-UHFFFAOYSA-N (3-chlorophenyl) 4-chloro-3-nitrobenzenesulfonate Chemical compound C1=C(Cl)C([N+](=O)[O-])=CC(S(=O)(=O)OC=2C=C(Cl)C=CC=2)=C1 NPPCVICNVNTDDO-UHFFFAOYSA-N 0.000 description 1
- UMRIXOOKYJPSSR-UHFFFAOYSA-N (3-ethoxyphenyl) 2-(methoxycarbonylamino)-3h-benzimidazole-5-sulfonate Chemical compound CCOC1=CC=CC(OS(=O)(=O)C=2C=C3NC(NC(=O)OC)=NC3=CC=2)=C1 UMRIXOOKYJPSSR-UHFFFAOYSA-N 0.000 description 1
- BVDJGIMOJFTONF-UHFFFAOYSA-N (3-ethoxyphenyl) 3,4-diaminobenzenesulfonate Chemical compound CCOC1=CC=CC(OS(=O)(=O)C=2C=C(N)C(N)=CC=2)=C1 BVDJGIMOJFTONF-UHFFFAOYSA-N 0.000 description 1
- KRCUXSWQRHFAKL-UHFFFAOYSA-N (3-ethoxyphenyl) 4-amino-3-nitrobenzenesulfonate Chemical compound CCOC1=CC=CC(OS(=O)(=O)C=2C=C(C(N)=CC=2)[N+]([O-])=O)=C1 KRCUXSWQRHFAKL-UHFFFAOYSA-N 0.000 description 1
- ORCRRODNPXBNEA-UHFFFAOYSA-N (3-ethoxyphenyl) 4-chloro-3-nitrobenzenesulfonate Chemical compound CCOC1=CC=CC(OS(=O)(=O)C=2C=C(C(Cl)=CC=2)[N+]([O-])=O)=C1 ORCRRODNPXBNEA-UHFFFAOYSA-N 0.000 description 1
- MHCALCDTVWGUHT-UHFFFAOYSA-N (3-methoxyphenyl) 2-(methoxycarbonylamino)-3h-benzimidazole-5-sulfonate Chemical compound C1=C2NC(NC(=O)OC)=NC2=CC=C1S(=O)(=O)OC1=CC=CC(OC)=C1 MHCALCDTVWGUHT-UHFFFAOYSA-N 0.000 description 1
- KKQNCKWAALXEKI-UHFFFAOYSA-N (3-methoxyphenyl) 3,4-diaminobenzenesulfonate Chemical compound COC1=CC=CC(OS(=O)(=O)C=2C=C(N)C(N)=CC=2)=C1 KKQNCKWAALXEKI-UHFFFAOYSA-N 0.000 description 1
- GUSLKHUEMKHWEG-UHFFFAOYSA-N (3-methoxyphenyl) 4-amino-3-nitrobenzenesulfonate Chemical compound COC1=CC=CC(OS(=O)(=O)C=2C=C(C(N)=CC=2)[N+]([O-])=O)=C1 GUSLKHUEMKHWEG-UHFFFAOYSA-N 0.000 description 1
- QCCQKSLEMRUDGL-UHFFFAOYSA-N (3-methylphenyl) 2-(methoxycarbonylamino)-3h-benzimidazole-5-sulfonate Chemical compound C1=C2NC(NC(=O)OC)=NC2=CC=C1S(=O)(=O)OC1=CC=CC(C)=C1 QCCQKSLEMRUDGL-UHFFFAOYSA-N 0.000 description 1
- XFMINSQCONUQCO-UHFFFAOYSA-N (3-methylphenyl) 3,4-diaminobenzenesulfonate Chemical compound CC1=CC=CC(OS(=O)(=O)C=2C=C(N)C(N)=CC=2)=C1 XFMINSQCONUQCO-UHFFFAOYSA-N 0.000 description 1
- HMEHAKJPTXFDAV-UHFFFAOYSA-N (3-methylphenyl) 4-amino-3-nitrobenzenesulfonate Chemical compound CC1=CC=CC(OS(=O)(=O)C=2C=C(C(N)=CC=2)[N+]([O-])=O)=C1 HMEHAKJPTXFDAV-UHFFFAOYSA-N 0.000 description 1
- AGSDJTRUYDYOKC-UHFFFAOYSA-N (3-methylphenyl) 4-chloro-3-nitrobenzenesulfonate Chemical compound CC1=CC=CC(OS(=O)(=O)C=2C=C(C(Cl)=CC=2)[N+]([O-])=O)=C1 AGSDJTRUYDYOKC-UHFFFAOYSA-N 0.000 description 1
- WBFISFJOSLSQET-UHFFFAOYSA-N (4-bromophenyl) 2-(methoxycarbonylamino)-3h-benzimidazole-5-sulfonate Chemical compound C1=C2NC(NC(=O)OC)=NC2=CC=C1S(=O)(=O)OC1=CC=C(Br)C=C1 WBFISFJOSLSQET-UHFFFAOYSA-N 0.000 description 1
- IDECGGBOCHQSGR-UHFFFAOYSA-N (4-bromophenyl) 3,4-diaminobenzenesulfonate Chemical compound C1=C(N)C(N)=CC=C1S(=O)(=O)OC1=CC=C(Br)C=C1 IDECGGBOCHQSGR-UHFFFAOYSA-N 0.000 description 1
- SVNOIDOQRCXHJT-UHFFFAOYSA-N (4-bromophenyl) 4-chloro-3-nitrobenzenesulfonate Chemical compound C1=C(Cl)C([N+](=O)[O-])=CC(S(=O)(=O)OC=2C=CC(Br)=CC=2)=C1 SVNOIDOQRCXHJT-UHFFFAOYSA-N 0.000 description 1
- HZLRYBRIYTWVJI-UHFFFAOYSA-N (4-butoxyphenyl) 2-(methoxycarbonylamino)-3h-benzimidazole-5-sulfonate Chemical compound C1=CC(OCCCC)=CC=C1OS(=O)(=O)C1=CC=C(N=C(NC(=O)OC)N2)C2=C1 HZLRYBRIYTWVJI-UHFFFAOYSA-N 0.000 description 1
- UBQZRGHBKMEVEX-UHFFFAOYSA-N (4-butoxyphenyl) 3,4-diaminobenzenesulfonate Chemical compound C1=CC(OCCCC)=CC=C1OS(=O)(=O)C1=CC=C(N)C(N)=C1 UBQZRGHBKMEVEX-UHFFFAOYSA-N 0.000 description 1
- GKOBHQPNYFCMJB-UHFFFAOYSA-N (4-butoxyphenyl) 4-amino-3-nitrobenzenesulfonate Chemical compound C1=CC(OCCCC)=CC=C1OS(=O)(=O)C1=CC=C(N)C([N+]([O-])=O)=C1 GKOBHQPNYFCMJB-UHFFFAOYSA-N 0.000 description 1
- UIIWKMJBGFSXLA-UHFFFAOYSA-N (4-butoxyphenyl) 4-chloro-3-nitrobenzenesulfonate Chemical compound C1=CC(OCCCC)=CC=C1OS(=O)(=O)C1=CC=C(Cl)C([N+]([O-])=O)=C1 UIIWKMJBGFSXLA-UHFFFAOYSA-N 0.000 description 1
- XUMBWVTXGBAVHY-UHFFFAOYSA-N (4-chloro-2-methylphenyl) 2-(methoxycarbonylamino)-3h-benzimidazole-5-sulfonate Chemical compound C1=C2NC(NC(=O)OC)=NC2=CC=C1S(=O)(=O)OC1=CC=C(Cl)C=C1C XUMBWVTXGBAVHY-UHFFFAOYSA-N 0.000 description 1
- WSVZNWBBCBGZLW-UHFFFAOYSA-N (4-chloro-2-methylphenyl) 3,4-diaminobenzenesulfonate Chemical compound CC1=CC(Cl)=CC=C1OS(=O)(=O)C1=CC=C(N)C(N)=C1 WSVZNWBBCBGZLW-UHFFFAOYSA-N 0.000 description 1
- MWPLAFPYVHBZOY-UHFFFAOYSA-N (4-chloro-2-methylphenyl) 4-amino-3-nitrobenzenesulfonate Chemical compound CC1=CC(Cl)=CC=C1OS(=O)(=O)C1=CC=C(N)C([N+]([O-])=O)=C1 MWPLAFPYVHBZOY-UHFFFAOYSA-N 0.000 description 1
- VOPRPWUYSNRGEP-UHFFFAOYSA-N (4-chloro-2-methylphenyl) 4-chloro-3-nitrobenzenesulfonate Chemical compound CC1=CC(Cl)=CC=C1OS(=O)(=O)C1=CC=C(Cl)C([N+]([O-])=O)=C1 VOPRPWUYSNRGEP-UHFFFAOYSA-N 0.000 description 1
- BHRFFHMJAHRLEX-UHFFFAOYSA-N (4-chloro-3,5-dimethylphenyl) 2-(methoxycarbonylamino)-3h-benzimidazole-5-sulfonate Chemical compound C1=C2NC(NC(=O)OC)=NC2=CC=C1S(=O)(=O)OC1=CC(C)=C(Cl)C(C)=C1 BHRFFHMJAHRLEX-UHFFFAOYSA-N 0.000 description 1
- HFMMTBBMICTONS-UHFFFAOYSA-N (4-chloro-3,5-dimethylphenyl) 3,4-diaminobenzenesulfonate Chemical compound CC1=C(Cl)C(C)=CC(OS(=O)(=O)C=2C=C(N)C(N)=CC=2)=C1 HFMMTBBMICTONS-UHFFFAOYSA-N 0.000 description 1
- FIOWISRTPJTJGI-UHFFFAOYSA-N (4-chloro-3,5-dimethylphenyl) 4-amino-3-nitrobenzenesulfonate Chemical compound CC1=C(Cl)C(C)=CC(OS(=O)(=O)C=2C=C(C(N)=CC=2)[N+]([O-])=O)=C1 FIOWISRTPJTJGI-UHFFFAOYSA-N 0.000 description 1
- IYNUFNUTBFRYRP-UHFFFAOYSA-N (4-chloro-3,5-dimethylphenyl) 4-chloro-3-nitrobenzenesulfonate Chemical compound CC1=C(Cl)C(C)=CC(OS(=O)(=O)C=2C=C(C(Cl)=CC=2)[N+]([O-])=O)=C1 IYNUFNUTBFRYRP-UHFFFAOYSA-N 0.000 description 1
- JHKXGBVWAIEDJW-UHFFFAOYSA-N (4-chloro-3-methylphenyl) 2-(methoxycarbonylamino)-3h-benzimidazole-5-sulfonate Chemical compound C1=C2NC(NC(=O)OC)=NC2=CC=C1S(=O)(=O)OC1=CC=C(Cl)C(C)=C1 JHKXGBVWAIEDJW-UHFFFAOYSA-N 0.000 description 1
- ZDDCKEGFMIZQEA-UHFFFAOYSA-N (4-chloro-3-methylphenyl) 4-amino-3-nitrobenzenesulfonate Chemical compound C1=C(Cl)C(C)=CC(OS(=O)(=O)C=2C=C(C(N)=CC=2)[N+]([O-])=O)=C1 ZDDCKEGFMIZQEA-UHFFFAOYSA-N 0.000 description 1
- UIAHQKITDVGGAX-UHFFFAOYSA-N (4-chloro-3-methylphenyl) 4-chloro-3-nitrobenzenesulfonate Chemical compound C1=C(Cl)C(C)=CC(OS(=O)(=O)C=2C=C(C(Cl)=CC=2)[N+]([O-])=O)=C1 UIAHQKITDVGGAX-UHFFFAOYSA-N 0.000 description 1
- SWXAXGYVTNHQPF-UHFFFAOYSA-N (4-chlorophenyl) 3,4-diaminobenzenesulfonate Chemical compound C1=C(N)C(N)=CC=C1S(=O)(=O)OC1=CC=C(Cl)C=C1 SWXAXGYVTNHQPF-UHFFFAOYSA-N 0.000 description 1
- VOJGRWFRPRCNEI-UHFFFAOYSA-N (4-chlorophenyl) 4-amino-3-nitrobenzenesulfonate Chemical compound C1=C([N+]([O-])=O)C(N)=CC=C1S(=O)(=O)OC1=CC=C(Cl)C=C1 VOJGRWFRPRCNEI-UHFFFAOYSA-N 0.000 description 1
- ZROLXLXBAHGRFM-UHFFFAOYSA-N (4-chlorophenyl) 4-chloro-3-nitrobenzenesulfonate Chemical compound C1=C(Cl)C([N+](=O)[O-])=CC(S(=O)(=O)OC=2C=CC(Cl)=CC=2)=C1 ZROLXLXBAHGRFM-UHFFFAOYSA-N 0.000 description 1
- XSFRDQWLPLGEPZ-UHFFFAOYSA-N (4-methoxyphenyl) 2-(methoxycarbonylamino)-3h-benzimidazole-5-sulfonate Chemical compound C1=C2NC(NC(=O)OC)=NC2=CC=C1S(=O)(=O)OC1=CC=C(OC)C=C1 XSFRDQWLPLGEPZ-UHFFFAOYSA-N 0.000 description 1
- PMVPZZFOLSZEBG-UHFFFAOYSA-N (4-methoxyphenyl) 3,4-diaminobenzenesulfonate Chemical compound C1=CC(OC)=CC=C1OS(=O)(=O)C1=CC=C(N)C(N)=C1 PMVPZZFOLSZEBG-UHFFFAOYSA-N 0.000 description 1
- WNCWVTRWQJIRLO-UHFFFAOYSA-N (4-methoxyphenyl) 4-amino-3-nitrobenzenesulfonate Chemical compound C1=CC(OC)=CC=C1OS(=O)(=O)C1=CC=C(N)C([N+]([O-])=O)=C1 WNCWVTRWQJIRLO-UHFFFAOYSA-N 0.000 description 1
- ZWEXWSDQKSCGJA-UHFFFAOYSA-N (4-methoxyphenyl) 4-chloro-3-nitrobenzenesulfonate Chemical compound C1=CC(OC)=CC=C1OS(=O)(=O)C1=CC=C(Cl)C([N+]([O-])=O)=C1 ZWEXWSDQKSCGJA-UHFFFAOYSA-N 0.000 description 1
- JJIXFYOIJWXMEQ-UHFFFAOYSA-N (4-methylphenyl) 3,4-diaminobenzenesulfonate Chemical compound C1=CC(C)=CC=C1OS(=O)(=O)C1=CC=C(N)C(N)=C1 JJIXFYOIJWXMEQ-UHFFFAOYSA-N 0.000 description 1
- QTBFCLOPCUGTCG-UHFFFAOYSA-N (4-methylphenyl) 4-amino-3-nitrobenzenesulfonate Chemical compound C1=CC(C)=CC=C1OS(=O)(=O)C1=CC=C(N)C([N+]([O-])=O)=C1 QTBFCLOPCUGTCG-UHFFFAOYSA-N 0.000 description 1
- SDPFJPNTJUILAT-UHFFFAOYSA-N (4-methylphenyl) 4-chloro-3-nitrobenzenesulfonate Chemical compound C1=CC(C)=CC=C1OS(=O)(=O)C1=CC=C(Cl)C([N+]([O-])=O)=C1 SDPFJPNTJUILAT-UHFFFAOYSA-N 0.000 description 1
- FXOSNEJPMIYUAG-UHFFFAOYSA-N (4-propan-2-yloxyphenyl) 4-amino-3-nitrobenzenesulfonate Chemical compound C1=CC(OC(C)C)=CC=C1OS(=O)(=O)C1=CC=C(N)C([N+]([O-])=O)=C1 FXOSNEJPMIYUAG-UHFFFAOYSA-N 0.000 description 1
- ZKSNEZQDTZWKLS-UHFFFAOYSA-N (4-propan-2-yloxyphenyl) 4-chloro-3-nitrobenzenesulfonate Chemical compound C1=CC(OC(C)C)=CC=C1OS(=O)(=O)C1=CC=C(Cl)C([N+]([O-])=O)=C1 ZKSNEZQDTZWKLS-UHFFFAOYSA-N 0.000 description 1
- SKPPEFZOZSCEKW-UHFFFAOYSA-N (4-propoxyphenyl) 2-(methoxycarbonylamino)-3h-benzimidazole-5-sulfonate Chemical compound C1=CC(OCCC)=CC=C1OS(=O)(=O)C1=CC=C(N=C(NC(=O)OC)N2)C2=C1 SKPPEFZOZSCEKW-UHFFFAOYSA-N 0.000 description 1
- PRBTULNBUPMFAB-UHFFFAOYSA-N (4-propoxyphenyl) 3,4-diaminobenzenesulfonate Chemical compound C1=CC(OCCC)=CC=C1OS(=O)(=O)C1=CC=C(N)C(N)=C1 PRBTULNBUPMFAB-UHFFFAOYSA-N 0.000 description 1
- NHXNXUMBZYJLLG-UHFFFAOYSA-N (4-propoxyphenyl) 4-amino-3-nitrobenzenesulfonate Chemical compound C1=CC(OCCC)=CC=C1OS(=O)(=O)C1=CC=C(N)C([N+]([O-])=O)=C1 NHXNXUMBZYJLLG-UHFFFAOYSA-N 0.000 description 1
- YVUHNROMLBDQEV-UHFFFAOYSA-N (4-propoxyphenyl) 4-chloro-3-nitrobenzenesulfonate Chemical compound C1=CC(OCCC)=CC=C1OS(=O)(=O)C1=CC=C(Cl)C([N+]([O-])=O)=C1 YVUHNROMLBDQEV-UHFFFAOYSA-N 0.000 description 1
- UGCJSPQIFWNLLQ-UHFFFAOYSA-N (5-chloro-2-methylphenyl) 2-(methoxycarbonylamino)-3h-benzimidazole-5-sulfonate Chemical compound C1=C2NC(NC(=O)OC)=NC2=CC=C1S(=O)(=O)OC1=CC(Cl)=CC=C1C UGCJSPQIFWNLLQ-UHFFFAOYSA-N 0.000 description 1
- BRUHGWKEMUAJNB-UHFFFAOYSA-N (5-chloro-2-methylphenyl) 3,4-diaminobenzenesulfonate Chemical compound CC1=CC=C(Cl)C=C1OS(=O)(=O)C1=CC=C(N)C(N)=C1 BRUHGWKEMUAJNB-UHFFFAOYSA-N 0.000 description 1
- YBTLISXPQPVFSN-UHFFFAOYSA-N (5-chloro-2-methylphenyl) 4-amino-3-nitrobenzenesulfonate Chemical compound CC1=CC=C(Cl)C=C1OS(=O)(=O)C1=CC=C(N)C([N+]([O-])=O)=C1 YBTLISXPQPVFSN-UHFFFAOYSA-N 0.000 description 1
- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- FKSRSWQTEJTBMI-UHFFFAOYSA-N 3,4-diaminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1N FKSRSWQTEJTBMI-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- AVZKTUHIRRBENN-UHFFFAOYSA-N [4-(2-methylpropoxy)phenyl] 2-(methoxycarbonylamino)-3h-benzimidazole-5-sulfonate Chemical compound C1=C2NC(NC(=O)OC)=NC2=CC=C1S(=O)(=O)OC1=CC=C(OCC(C)C)C=C1 AVZKTUHIRRBENN-UHFFFAOYSA-N 0.000 description 1
- VEGMDECTEDZPRA-UHFFFAOYSA-N [4-(2-methylpropoxy)phenyl] 4-amino-3-nitrobenzenesulfonate Chemical compound C1=CC(OCC(C)C)=CC=C1OS(=O)(=O)C1=CC=C(N)C([N+]([O-])=O)=C1 VEGMDECTEDZPRA-UHFFFAOYSA-N 0.000 description 1
- CUDIMFTVMLHAPR-UHFFFAOYSA-N [4-(2-methylpropoxy)phenyl] 4-chloro-3-nitrobenzenesulfonate Chemical compound C1=CC(OCC(C)C)=CC=C1OS(=O)(=O)C1=CC=C(Cl)C([N+]([O-])=O)=C1 CUDIMFTVMLHAPR-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 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
- 239000003054 catalyst Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- SURLGNKAQXKNSP-DBLYXWCISA-N chlorin Chemical compound C\1=C/2\N/C(=C\C3=N/C(=C\C=4NC(/C=C\5/C=CC/1=N/5)=CC=4)/C=C3)/CC\2 SURLGNKAQXKNSP-DBLYXWCISA-N 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- BTLAMBOZGAZYLW-UHFFFAOYSA-N ethyl 2-chloro-4-(3,4-diaminophenyl)sulfonyloxybenzoate Chemical compound C1=C(Cl)C(C(=O)OCC)=CC=C1OS(=O)(=O)C1=CC=C(N)C(N)=C1 BTLAMBOZGAZYLW-UHFFFAOYSA-N 0.000 description 1
- XIMRNNFPWCYGHU-UHFFFAOYSA-N ethyl 2-chloro-4-(4-chloro-3-nitrophenyl)sulfonyloxybenzoate Chemical compound C1=C(Cl)C(C(=O)OCC)=CC=C1OS(=O)(=O)C1=CC=C(Cl)C([N+]([O-])=O)=C1 XIMRNNFPWCYGHU-UHFFFAOYSA-N 0.000 description 1
- MIAISPAAIYBOBH-UHFFFAOYSA-N ethyl 2-chloro-4-[[2-(methoxycarbonylamino)-3h-benzimidazol-5-yl]sulfonyloxy]benzoate Chemical compound C1=C(Cl)C(C(=O)OCC)=CC=C1OS(=O)(=O)C1=CC=C(N=C(NC(=O)OC)N2)C2=C1 MIAISPAAIYBOBH-UHFFFAOYSA-N 0.000 description 1
- RJGOUJDYLYFROB-UHFFFAOYSA-N ethyl 4-(4-amino-3-nitrophenyl)sulfonyloxy-2-chlorobenzoate Chemical compound C1=C(Cl)C(C(=O)OCC)=CC=C1OS(=O)(=O)C1=CC=C(N)C([N+]([O-])=O)=C1 RJGOUJDYLYFROB-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000012458 free base Substances 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- FNKPQMSVJJSRBP-UHFFFAOYSA-N phenyl 2-(butoxycarbonylamino)-3h-benzimidazole-5-sulfonate Chemical compound C1=C2NC(NC(=O)OCCCC)=NC2=CC=C1S(=O)(=O)OC1=CC=CC=C1 FNKPQMSVJJSRBP-UHFFFAOYSA-N 0.000 description 1
- YVPYMPMYOGQFIW-UHFFFAOYSA-N phenyl 2-(ethoxycarbonylamino)-3h-benzimidazole-5-sulfonate Chemical compound C1=C2NC(NC(=O)OCC)=NC2=CC=C1S(=O)(=O)OC1=CC=CC=C1 YVPYMPMYOGQFIW-UHFFFAOYSA-N 0.000 description 1
- BWJKYQSSWVHQEG-UHFFFAOYSA-N phenyl 2-(propan-2-yloxycarbonylamino)-3h-benzimidazole-5-sulfonate Chemical compound C1=C2NC(NC(=O)OC(C)C)=NC2=CC=C1S(=O)(=O)OC1=CC=CC=C1 BWJKYQSSWVHQEG-UHFFFAOYSA-N 0.000 description 1
- ZHGXTLXTHYOYDW-UHFFFAOYSA-N phenyl 2-(propoxycarbonylamino)-3h-benzimidazole-5-sulfonate Chemical compound C1=C2NC(NC(=O)OCCC)=NC2=CC=C1S(=O)(=O)OC1=CC=CC=C1 ZHGXTLXTHYOYDW-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 1
- 239000012258 stirred mixture Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
Landscapes
- Coloring (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
ABSTRACT
New carbalkoxyamino-benzimidazolyl-5(6)-sulfonic acid phenyl ester of the formula I
New carbalkoxyamino-benzimidazolyl-5(6)-sulfonic acid phenyl ester of the formula I
Description
10~;9130 deri~a-iveR of th L re o pheny 4n- diamine ~ O-So ~ INH2 R2 ~ INH2 Rl and R2~ independently of :
hYdrogen hyd each other, each t . yl ha~ing 1 to 4 ha~ing l to 4 ` carbon atoms c b opropyl, butyl Y ~11 and R2 ~ are ented by Rl and R are me.th ~ Y
b R utXY- The halOgen ? e fluorine, chlorin ~ atms represented ups represented b , ne, and;iodine p y or carbobutoxy.l '` ~ thoxy, tho8e i ompound- Qf the f ; hiCh Rl stands for hydr ; rmula~ )i3are ' chlorine, bromine trifl and R2 stands for hydro etDoxy the eXpecially preferred position of.tho ~ Further~object f; n~,o~ ~ phony~
,~-'~ 106gl30 above, which comprises reducing an amino-nitro derivative of formula II
R2 ~ -S2 ~ N02 ~II), .
in which R1 and R2 are as defined in formula I.
The reduction may be carried out, for example by hydrogenation in the presence of Raney nickel and a solvent, such as methanol or dimethylformamide, at a temperature of from 20 to 60C, or by a treatment with reducing agents, such as sodium dithionite.
The amino-nitro derivatives of formula II in turn are obtained by reacting the corresponding chloro-nitro compounds of formula ' III, in which R1 and R2 are defined as in formula I , , Rl ~ -52 ~ No2 ~III), ~
Cl with ammonia in a suitable solvent, such as dioxan or methanol, at an elevated temperature and under elevated pressure.
The chloro-nitro compounds of formula III again are obtained by reacting 3-nitro-4-chloro-benzene-sulfonic acid chloride of formula V with a phenol or formula IV , in which R1 and R2 are defined as in formula I
~ .
;1 ~ 0-iI + Cl-S02 ~ No2 (IV) (V)
hYdrogen hyd each other, each t . yl ha~ing 1 to 4 ha~ing l to 4 ` carbon atoms c b opropyl, butyl Y ~11 and R2 ~ are ented by Rl and R are me.th ~ Y
b R utXY- The halOgen ? e fluorine, chlorin ~ atms represented ups represented b , ne, and;iodine p y or carbobutoxy.l '` ~ thoxy, tho8e i ompound- Qf the f ; hiCh Rl stands for hydr ; rmula~ )i3are ' chlorine, bromine trifl and R2 stands for hydro etDoxy the eXpecially preferred position of.tho ~ Further~object f; n~,o~ ~ phony~
,~-'~ 106gl30 above, which comprises reducing an amino-nitro derivative of formula II
R2 ~ -S2 ~ N02 ~II), .
in which R1 and R2 are as defined in formula I.
The reduction may be carried out, for example by hydrogenation in the presence of Raney nickel and a solvent, such as methanol or dimethylformamide, at a temperature of from 20 to 60C, or by a treatment with reducing agents, such as sodium dithionite.
The amino-nitro derivatives of formula II in turn are obtained by reacting the corresponding chloro-nitro compounds of formula ' III, in which R1 and R2 are defined as in formula I , , Rl ~ -52 ~ No2 ~III), ~
Cl with ammonia in a suitable solvent, such as dioxan or methanol, at an elevated temperature and under elevated pressure.
The chloro-nitro compounds of formula III again are obtained by reacting 3-nitro-4-chloro-benzene-sulfonic acid chloride of formula V with a phenol or formula IV , in which R1 and R2 are defined as in formula I
~ .
;1 ~ 0-iI + Cl-S02 ~ No2 (IV) (V)
- 2 -.
, . . .
- . .
- ' ' : , . . .
- ~
~ , - . .
.. . .. . .
1069i30 in an inert solvent in the presence of a base, such as triethyl-amine.
The o-phenylene diamine derivatives of the formula I
are valuable intermediates, preferably for the manufacture of anthelmintically active 2-carbalkoxyamino-benzimidazolyl-5(6)-sulfonic acid phenyl esters of the formula VI
RI ~ -SO2 ~ / C-N~-COOR3 (VI) in which Rl and R2 are as defined in formula I and R3 stands for alkyl having 1 to 4 carbon atoms, by a process, which comprises condensing an o-phenylene diamine derivative of the formula I
Rl ~
2 ~ -S2 ~ ~NH2 NH2 (I) in which Rl and R2 are defined as above, with an alkyl-S-methyl-thiourea carboxylate of formula VII
HN = f-N-COOR3 H (VII) in which R3 is defined as in formula VI.
For carrying out this reaction, S-methyl-thiourea sulfate ffl formula VIII is first mixed with a chloroformiate of formula IX, in which R3 is defined as in formula VI
[H2N-C = NH] H SO Cl-COOR3 (VIII) (IX)
, . . .
- . .
- ' ' : , . . .
- ~
~ , - . .
.. . .. . .
1069i30 in an inert solvent in the presence of a base, such as triethyl-amine.
The o-phenylene diamine derivatives of the formula I
are valuable intermediates, preferably for the manufacture of anthelmintically active 2-carbalkoxyamino-benzimidazolyl-5(6)-sulfonic acid phenyl esters of the formula VI
RI ~ -SO2 ~ / C-N~-COOR3 (VI) in which Rl and R2 are as defined in formula I and R3 stands for alkyl having 1 to 4 carbon atoms, by a process, which comprises condensing an o-phenylene diamine derivative of the formula I
Rl ~
2 ~ -S2 ~ ~NH2 NH2 (I) in which Rl and R2 are defined as above, with an alkyl-S-methyl-thiourea carboxylate of formula VII
HN = f-N-COOR3 H (VII) in which R3 is defined as in formula VI.
For carrying out this reaction, S-methyl-thiourea sulfate ffl formula VIII is first mixed with a chloroformiate of formula IX, in which R3 is defined as in formula VI
[H2N-C = NH] H SO Cl-COOR3 (VIII) (IX)
3 --- - .
, ~ , - . ~.
.
- - . - .. . :': : . .... . :.
.
in water, then a strong base is added dropwise, for example a 25%
sodium hydroxide solution, while maintaining the temperature low, preferably at about 0C. The alkyl-S-methyl-thiourea carboxylate of formula VII which has formed need not be isolated.
As chloroformiates of formula IX, there may be mentioned, for example, methyl chloroformiate, ethyl chloroformiate, propyl chloroformiate, isopropyl chloroformiate, butyl chloroformiate, isobutyl chloroformiate, tert. butyl chloroformiate.
The pH-value of the above-cited reaction mixture is then advantageously adjusted to a range of from 2 to 5, suitably by adding an organic acid, such as acetic acid or lactic acid.
The o-phenylene diamine derivative of formula I is then added, either in the form of a free base or of the acid addition salt, for example hydrochloride. In this latter case, it may be advantageous to add an alkali metal salt of an organic acid as a buffer.
As o-phenylene diamine derivatives of formula I, there are mentioned, for example 3,4-diamino-benzene sulfonic acid phenyl ester 3,4-diamino-benzene sulfonic acid-4-chloro-phenyl ester 3,4-diamino-benzene sulfonic acid-3-chloro-phenyl ester 3,4-diamino-benzene sulfonic acid-2-chloro-phenyl ester 3,4-diamino-benzene sulfonic acid-2,5-dichloro-phenyl ester `~29 3,4-diamino-benzene sulfonic acid-3,5-dichloro-phenyl ester .,. ., - . . -- ~ .
. ' ' - ' '' :
- , : . - -:
. -. ~ . , . : . : , .:: .~ .
- - \
3,4-diamino-benzene sulfonic acid-4-bromo-phenyl ester 3,4-diamino-benzene sulfonic acid-3-bromo-phenyl ester 3,4-diamino-benzene sulfonic acid-2-bromo-phenyl ester 3,4-diamino-benzene sulfonic acid-4-methyl-phenyl ester 3,4-diamino-benzene sulfonic acid-3-methyl-phenyl ester 3,4-diamino-benzene sulfonic acid-2-methyl-phenyl ester 3,4-diamino-benzene sulfonic acid-4-tert.butyl-phenyl ester 3,4-diamino-benzene sulfonic acid-2,4-dimethyl-phenyl ester 3,4-diamino-benzene sulfonic acid-2-chloro-4-methyl-phenyl ester 3,4-diamino-benzene sulfonic acid-2-chloro-6-methyl-phenyl ester 3,4-diamino-benzene sulfonic acid-3-chloro-4-methyl-phenyl ester 3,4-diamino-benzene sulfonic acid-3-chloro-6-methyl-phenyl ester 3,4-diamino-benzene sulfonic acid-3-chloro-4-carbethoxy-phenylester 3,4-diamino-benzene sulfonic acid-4-chloro-2-methyl-phenyl ester 3,4-diamino-benzene sulfonic acid-4-chloro-3-methyl-phenyl ester 3,4-diamino-benzene sulfonic acid-4-chloro-3,5-dimethyl-phenylester 3,4-diamino-benzene sulfonic acid-3,5-bistrifluormethyl-phenylester 3,4-diamino-benzene sulfonic acid-4-methoxy-phenyl ester 3,4-diamino-benzene sulfonic acid-3-methoxy-phenyl ester 3,4-diamino-benzene sulfonic acid-2-methoxy-phenyl ester 3,4-diamino-benzene sulfonic acid-4-propoxy-phenyl ester 3,4-diamino-benzene sulfonic acid-4-isopropoxy-phenyl ester 3,4-diamino-benzene sulfonic acid-4-butoxy-phenyl ester 3,4-diamino-benzene sulfonic acid-4-isobutoxy-phenyl ester The following Examples illustrate the invention.
E X A M P L E 1:
60 grams of a 25% sodium hydroxide solution were added dropwise while cooling with ice at a temperature not exceeding 10C to a 29 thoroughly stirred mixture of 27.8 g of S-methyl-thiourea sulfate .
- . . .
.. : : : : . .:: : . : - .- . : . ..
: . . ., .. : :...... - ::
- ' . . . ' : : , :: , :
.. .. : . . - - . .
~ '~ 1()69130 in 44 ml of water and 13 ml of methyl chloroformiate. Stirring was continued for half an hour, and then a mixture of 10 ml of glacial acetic acid and 100 ml of water was added. Subsequently, 24.2 g of 3,4-diamino-benzene-sulfonic acid phenyl ester dissolved in 100 ml of isopropanol were added, and the mixture was refluxed for 2 hours, whereupon a solid began to precipitate. The solid was suctionfiltered, carefully washed with methanol and then with water and, after drying, l9g of 2-carbomethoxyamino-5-benzimida-zolyl sulfonic acid phenyl ester were obtained. The crude product was purified by dissolving it in 250 ml of dioxan, filtering it with charcoal and adding 50 ml of water to the filtrate. The yield of the analytically pure product was 14 g, having a decompo-sition point of 242C.
3,4-diamino-benzene-sulfonic acid phenyl ester was prepared by hydrogenating 27 g of 3-nitro-4-amino-benzene-sulfonic acid phenyl ester in 300 ml of.methyl glycol with Raney nickel at atmospheric pressùre and room temperature. The catalyst was separated by suction-filtration, and upon concentration, the 3,4-diamino-benzene sulfonic acid phenyl ester was obtained as a crude product in the form of 25 g of a dark-coloured oil which could directly be used for ring closure.
To prepare 3-nitro-4-amino-benzene sulfonic acid phenyl ester 54 g of 3-nitro-4-chloro-benzene sulfonic acid phenyl ester in 500 ml of dioxan were maintained at 50C for 5 hours at an excess pressure of 5 atmospheres of gaseous ammonia, then the solvent was removed in vacuo. The residue was combined with 200 ml of a mixture of equal parts of methanol and water, whereupon a solid precipitated after a short time, which was suction-filtered.
After repeated recrystallization from methanol and then from 29 benzene, 28 g of 3-nitro-4-amino-benzene sulfonic acid phenyl ester ., . .. . ,. - . : :.
,, ~ :
- . . . ~ :
"' - , , `' ~ . ' , , ^~ 1069130 were obtained, m.p. 104C.
3-Nitro-4-chlorobenzene sulfonic acid phenyl ester was obtained by mixing 51 g of 3-nitro-4-chlorobenzene sulfonic acid chloride with 18.8 g of phenol in 120 ml of acetone, and 28 ml of triethylamine were added dropwise while cooling at an internal temperature not exceeding 10C. Stirring was continued for some hours at room temperature, and water was then added, whereupon an oil separted which was worked up with ether.
Upon recyrstallization from methanol, 54 g of 3-nitro-4-chloro-benzene sulfonic acid phenyl ester were obtained, m.p. 71C.
Using correspondingly modified starting products, the following compounds were prepared in an analogous manner:
2) Via 3-nitro-4-chloro-benzenesulfonic acid-4-chloro-phenyl ester, m.p. 84C, and 3-nitro-4- amino -benzenesulfonic acid-4-- chloro-phenyl ester, m.p. 156C, and 3,4-diamino-benzenesulfonic acid-4-chloro-phenyl ester, the 2-carbomethoxyamino-5-benzimadazolylsulfonic acid-4-chloro-phenyl ester, m.p. 250C (decomp.).
3) Via 3-nitro-4-chloro-benzenesulfonic acid-3-chloro-phenyl ester, m.p. 68C, and 3-nitro-4-amino-benzenesulfonic acid-3-chloro-phenyl ester, m.p. 138C, and 3,4-diamino-benzenesulfonic acid-3-chloro-phenyl ester, m.p. 84C, the 2-carbomethoxyamino-5-benzimidazolylsulfonic 28 acid-3-chloro-phenyl ester, m.p. 234C, (decomp.).
. , .
: . ... : .. .. - . . : : , .,, - , , . : , . ~ :, ~ : , : : -1069~30
, ~ , - . ~.
.
- - . - .. . :': : . .... . :.
.
in water, then a strong base is added dropwise, for example a 25%
sodium hydroxide solution, while maintaining the temperature low, preferably at about 0C. The alkyl-S-methyl-thiourea carboxylate of formula VII which has formed need not be isolated.
As chloroformiates of formula IX, there may be mentioned, for example, methyl chloroformiate, ethyl chloroformiate, propyl chloroformiate, isopropyl chloroformiate, butyl chloroformiate, isobutyl chloroformiate, tert. butyl chloroformiate.
The pH-value of the above-cited reaction mixture is then advantageously adjusted to a range of from 2 to 5, suitably by adding an organic acid, such as acetic acid or lactic acid.
The o-phenylene diamine derivative of formula I is then added, either in the form of a free base or of the acid addition salt, for example hydrochloride. In this latter case, it may be advantageous to add an alkali metal salt of an organic acid as a buffer.
As o-phenylene diamine derivatives of formula I, there are mentioned, for example 3,4-diamino-benzene sulfonic acid phenyl ester 3,4-diamino-benzene sulfonic acid-4-chloro-phenyl ester 3,4-diamino-benzene sulfonic acid-3-chloro-phenyl ester 3,4-diamino-benzene sulfonic acid-2-chloro-phenyl ester 3,4-diamino-benzene sulfonic acid-2,5-dichloro-phenyl ester `~29 3,4-diamino-benzene sulfonic acid-3,5-dichloro-phenyl ester .,. ., - . . -- ~ .
. ' ' - ' '' :
- , : . - -:
. -. ~ . , . : . : , .:: .~ .
- - \
3,4-diamino-benzene sulfonic acid-4-bromo-phenyl ester 3,4-diamino-benzene sulfonic acid-3-bromo-phenyl ester 3,4-diamino-benzene sulfonic acid-2-bromo-phenyl ester 3,4-diamino-benzene sulfonic acid-4-methyl-phenyl ester 3,4-diamino-benzene sulfonic acid-3-methyl-phenyl ester 3,4-diamino-benzene sulfonic acid-2-methyl-phenyl ester 3,4-diamino-benzene sulfonic acid-4-tert.butyl-phenyl ester 3,4-diamino-benzene sulfonic acid-2,4-dimethyl-phenyl ester 3,4-diamino-benzene sulfonic acid-2-chloro-4-methyl-phenyl ester 3,4-diamino-benzene sulfonic acid-2-chloro-6-methyl-phenyl ester 3,4-diamino-benzene sulfonic acid-3-chloro-4-methyl-phenyl ester 3,4-diamino-benzene sulfonic acid-3-chloro-6-methyl-phenyl ester 3,4-diamino-benzene sulfonic acid-3-chloro-4-carbethoxy-phenylester 3,4-diamino-benzene sulfonic acid-4-chloro-2-methyl-phenyl ester 3,4-diamino-benzene sulfonic acid-4-chloro-3-methyl-phenyl ester 3,4-diamino-benzene sulfonic acid-4-chloro-3,5-dimethyl-phenylester 3,4-diamino-benzene sulfonic acid-3,5-bistrifluormethyl-phenylester 3,4-diamino-benzene sulfonic acid-4-methoxy-phenyl ester 3,4-diamino-benzene sulfonic acid-3-methoxy-phenyl ester 3,4-diamino-benzene sulfonic acid-2-methoxy-phenyl ester 3,4-diamino-benzene sulfonic acid-4-propoxy-phenyl ester 3,4-diamino-benzene sulfonic acid-4-isopropoxy-phenyl ester 3,4-diamino-benzene sulfonic acid-4-butoxy-phenyl ester 3,4-diamino-benzene sulfonic acid-4-isobutoxy-phenyl ester The following Examples illustrate the invention.
E X A M P L E 1:
60 grams of a 25% sodium hydroxide solution were added dropwise while cooling with ice at a temperature not exceeding 10C to a 29 thoroughly stirred mixture of 27.8 g of S-methyl-thiourea sulfate .
- . . .
.. : : : : . .:: : . : - .- . : . ..
: . . ., .. : :...... - ::
- ' . . . ' : : , :: , :
.. .. : . . - - . .
~ '~ 1()69130 in 44 ml of water and 13 ml of methyl chloroformiate. Stirring was continued for half an hour, and then a mixture of 10 ml of glacial acetic acid and 100 ml of water was added. Subsequently, 24.2 g of 3,4-diamino-benzene-sulfonic acid phenyl ester dissolved in 100 ml of isopropanol were added, and the mixture was refluxed for 2 hours, whereupon a solid began to precipitate. The solid was suctionfiltered, carefully washed with methanol and then with water and, after drying, l9g of 2-carbomethoxyamino-5-benzimida-zolyl sulfonic acid phenyl ester were obtained. The crude product was purified by dissolving it in 250 ml of dioxan, filtering it with charcoal and adding 50 ml of water to the filtrate. The yield of the analytically pure product was 14 g, having a decompo-sition point of 242C.
3,4-diamino-benzene-sulfonic acid phenyl ester was prepared by hydrogenating 27 g of 3-nitro-4-amino-benzene-sulfonic acid phenyl ester in 300 ml of.methyl glycol with Raney nickel at atmospheric pressùre and room temperature. The catalyst was separated by suction-filtration, and upon concentration, the 3,4-diamino-benzene sulfonic acid phenyl ester was obtained as a crude product in the form of 25 g of a dark-coloured oil which could directly be used for ring closure.
To prepare 3-nitro-4-amino-benzene sulfonic acid phenyl ester 54 g of 3-nitro-4-chloro-benzene sulfonic acid phenyl ester in 500 ml of dioxan were maintained at 50C for 5 hours at an excess pressure of 5 atmospheres of gaseous ammonia, then the solvent was removed in vacuo. The residue was combined with 200 ml of a mixture of equal parts of methanol and water, whereupon a solid precipitated after a short time, which was suction-filtered.
After repeated recrystallization from methanol and then from 29 benzene, 28 g of 3-nitro-4-amino-benzene sulfonic acid phenyl ester ., . .. . ,. - . : :.
,, ~ :
- . . . ~ :
"' - , , `' ~ . ' , , ^~ 1069130 were obtained, m.p. 104C.
3-Nitro-4-chlorobenzene sulfonic acid phenyl ester was obtained by mixing 51 g of 3-nitro-4-chlorobenzene sulfonic acid chloride with 18.8 g of phenol in 120 ml of acetone, and 28 ml of triethylamine were added dropwise while cooling at an internal temperature not exceeding 10C. Stirring was continued for some hours at room temperature, and water was then added, whereupon an oil separted which was worked up with ether.
Upon recyrstallization from methanol, 54 g of 3-nitro-4-chloro-benzene sulfonic acid phenyl ester were obtained, m.p. 71C.
Using correspondingly modified starting products, the following compounds were prepared in an analogous manner:
2) Via 3-nitro-4-chloro-benzenesulfonic acid-4-chloro-phenyl ester, m.p. 84C, and 3-nitro-4- amino -benzenesulfonic acid-4-- chloro-phenyl ester, m.p. 156C, and 3,4-diamino-benzenesulfonic acid-4-chloro-phenyl ester, the 2-carbomethoxyamino-5-benzimadazolylsulfonic acid-4-chloro-phenyl ester, m.p. 250C (decomp.).
3) Via 3-nitro-4-chloro-benzenesulfonic acid-3-chloro-phenyl ester, m.p. 68C, and 3-nitro-4-amino-benzenesulfonic acid-3-chloro-phenyl ester, m.p. 138C, and 3,4-diamino-benzenesulfonic acid-3-chloro-phenyl ester, m.p. 84C, the 2-carbomethoxyamino-5-benzimidazolylsulfonic 28 acid-3-chloro-phenyl ester, m.p. 234C, (decomp.).
. , .
: . ... : .. .. - . . : : , .,, - , , . : , . ~ :, ~ : , : : -1069~30
4) Via 3-nitro-4-chloro-benzenesulfonic acid-2-chloro-phenyl ester, and 3-nitro-4-amino-benzenesulfonic acid-2-chloro-phenyl ester, and 3,4-diamino-benzenesulfonic acid-2-chloro-phenyl ester, the 2-carbomethoxyamino-5-benzimidazolylsulfonic acid-2-chloro-phenyl ester.
5) Via 3-nitro-4-chloro-benzenesulfonic acid-2,5-dichloro-phenyl ester, and 3-nitro-4-amino-benzenesulfonic acid-2,5-dichloro-phenyl ester, and 3,4-diamino-benzenesulfonic acid-2,5-dichloro-phenyl-ester, ~ the 2-carbomethoxyamino-5-benzimidazolylsulfonic acid-2,5-dichloro-phenyl ester.
6) Via 3-nitro-4-chloro-benzenesulfonic acid-3,5-dichloro-phenyl ester, m.p. 104C, and 3-nitro-4-amino-benzenesulfonic acid-3,5-dichloro-phenyl ester, m.p. 164C, and 3,4-diamino-benzenesulfonic acid-3,5-dichloro-phenyl ester, m.p. 116C, the 2-carbomethoxyamino-5-benzimidazolylsulfonic acid-3,5-dichloro-phenyl ester, m.p. 250C (decomp.).
7) Via 3-nitro-4-chloro-benzenesulfonic acid-4-bromo-phenyl ester, and 3-nitro-4-amino-benzenesulfonic acid-4-bromo-28 phenyl ester,
- 8 -' ' ' ', , ' : " '' :. ~ ` '' ' ' : . , :' , ' - . ' . . ' : , ~ ,.
. , . . ., ~ : : - . . -': - . : . , : . -. ~' -' :. , -: ' ' ' -, ,: ::' :' - . . . .
-- . . .
~. : . , - ~, : :
~-, and 3,4-diamino-benzenesulfonic acid-4-bromo-phenyl ester, the 2-carbomethoxyamino-5-benzimidazolylsulfonic acid-4-bromo-phenyl ester.
8) Via 3-nitro-4-chloro-benzenesulfonic acid-3-bromo-phenyl ester, m.p. 72C, and 3-nitro-4-amino-benzenesulfonic acid-3-bromo-phenyl ester, m.p. 141C, and 3,4-diamino-benzenesulfonic acid-3-bromo-phenyl ester, m.p. 94C, the 2-carbomethoxyamino-5-benzimidazolylsulfonic acid-3-bromo-phenyl ester, m.p. 242C (decomp.).
. , . . ., ~ : : - . . -': - . : . , : . -. ~' -' :. , -: ' ' ' -, ,: ::' :' - . . . .
-- . . .
~. : . , - ~, : :
~-, and 3,4-diamino-benzenesulfonic acid-4-bromo-phenyl ester, the 2-carbomethoxyamino-5-benzimidazolylsulfonic acid-4-bromo-phenyl ester.
8) Via 3-nitro-4-chloro-benzenesulfonic acid-3-bromo-phenyl ester, m.p. 72C, and 3-nitro-4-amino-benzenesulfonic acid-3-bromo-phenyl ester, m.p. 141C, and 3,4-diamino-benzenesulfonic acid-3-bromo-phenyl ester, m.p. 94C, the 2-carbomethoxyamino-5-benzimidazolylsulfonic acid-3-bromo-phenyl ester, m.p. 242C (decomp.).
9) Via 3-nitro-4-chloro-benzenesulfonic acid-2-bromo-phenyl ester, and 3-nitro-4-amino-benzenesulfonic acid-2-bromo-phenyl ester, and 3,4-diamino-benzenesulfonic acid-2-bromo-phenyl ester, the 2-carbomethoxyamino-5-benzimidazolyl-sulfonic acid-2-bromo-phenyl ester.
10) Via 3-nitro-4-chloro-benzenesulfonic acid-4-methyl-phenyl-ester, m.p. 68C, and 3-nitro-4-amino-benzenesulfonic acid-4-methyl-phenyl ester, m.p. 135C, and 3,4-diamino-benzenesulfonic acid-4-methyl-phenyl ester, the 2-carbomethoxyamino-5-benzimidazolylsulfonic 28 acid-4-methyl-phenyl ester, m.p. 240C, (decomp.).
~, g _ '~:
.. . . . .. . . . . . . ..... .. ... . .
: :- . : . : - ,: - . . :, ~ . : - . . . - : . .
... ~ ' ' , . ' ., , ! ,,, , . . , :, , ' -~ " ~ . ' , . ' ' , ' ' , , . ' , ' . ' ' ' . ' . . ' : ' ' ' . ' , . ., ' . ' , - . . . ' . . .
~~, :~069130
~, g _ '~:
.. . . . .. . . . . . . ..... .. ... . .
: :- . : . : - ,: - . . :, ~ . : - . . . - : . .
... ~ ' ' , . ' ., , ! ,,, , . . , :, , ' -~ " ~ . ' , . ' ' , ' ' , , . ' , ' . ' ' ' . ' . . ' : ' ' ' . ' , . ., ' . ' , - . . . ' . . .
~~, :~069130
11) Via 3-nitro-4-chloro-benzenesulfonic acid-3-methyl-phenyl-ester, m.p. 60C, and 3-nitro-4-amino-benzenesulfonic acid-3-methyl-phenyl-ester, m.p. 138C, and 3,4-diamino-benzenesulfonic acid-3-methyl-phenyl-ester, m.p. 84C, the 2-carbomethoxyamino-5-benzimidazolylsulfonic acid-3-methyl-phenyl ester, m.p. 234C (decomp.).
12) Via 3-nitro-4-chloro-benzenesulfonic acid-2-methyl-phenyl ester, and 3-nitro-4-amino-benzenesulfonic acid-2-methyl-phenyl ester, and 3,4-diamino-benzenesulfonic acid-2-methyl-phenyl ester, the 2-carbomethoxyamino-5-benzimidazolylsulfonic acid-2-methyl-phenyl`ester.
13) Via 3-nitro-4-chloro-benzenesulfonic acid-4-tert.
butyl-phenyl ester, and 3-nitro-4-amino-benzenesulfonic acid-4-tert.
butyl-phenyl ester, and 3,4-diamino-benzenesulfonic acid-4-tert.butyl-phenyl ester,-the 2-carbomethoxyamino-5-benzimidazolylsulfonic acid-tert.butyl-phenyl ester.
butyl-phenyl ester, and 3-nitro-4-amino-benzenesulfonic acid-4-tert.
butyl-phenyl ester, and 3,4-diamino-benzenesulfonic acid-4-tert.butyl-phenyl ester,-the 2-carbomethoxyamino-5-benzimidazolylsulfonic acid-tert.butyl-phenyl ester.
14) Via 3-nitro-4-chloro-benzenesulfonic acid-2,4-dimethyl-phenyl ester, and 3-nitro-4-amino-benzenesulfonic acid-2,4-dimethyl-phenyl ester, and 3,4-diamino-benzenesulfonic acid-2,4-dimethyl phenyl ester, :; . . - , .
: . . ,.:
the 2-carbomethoxyamino-5-benzimidazolylsulfonic acid-2,4-dimethyl-phenyl ester.
: . . ,.:
the 2-carbomethoxyamino-5-benzimidazolylsulfonic acid-2,4-dimethyl-phenyl ester.
15) Via 3-nitro-4-chloro-benzenesulfonic acid-2-chloro-4-methyl-phenyl ester, and 3-nitro-4-amino-benzenesulfonic acid-2-chloro-4-methyl-phenyl ester, and 3,4-diamino-benzenesulfonic acid-2-chloro-4-methyl-phenyl ester, the 2-carbomethoxyamino-5-benzimidazolylsulfonic acid-2-chloro-4-methyl-phenyl ester.
16) Via 3-nitro-4-chloro-benzenesulfonic acid-2-chloro-6-methyl-phenyl ester, and 3-nitro-4-amino-benzenesulfonic acid-2-chloro-6-methyl-phenyl ester, and 3,4-diamino-benzenesulfonic acid-2-chloro-6-methyl-phenyl ester, the 2-carbomethoxyamino-5-benzimidazolylsulfonic acid-2-chloro-6-methyl-phenyl ester.
17) Via 3-nitro-4-chloro-benzenesulfonic acid-3-chloro-4-methyl-phenyl ester, and 3-nitro-4-amino-benzenesulfonic acid-3-chloro-4-methyl-phenyl ester, and 3,4-diamino-benzenesulfonic acid-3-chloro-4-methyl-phenyl ester, the 2-carbomethoxyamino-5-benzimidazolylsulfonic acid-3-chloro-4-methyl-phenyl ester.
18) Via 3-nitro-4-chloro-benzenesulfonic acid-3-chloro-28 6-methyl-phenyl ester, . .
. ., ~ . .. , . .: . - ... . .. .
. :- . . . ~
,, - , ' ' ~.~. ' ,' ~
. . - ., : . . . - : , ~069130 and 3-nitro-4-amino-benzenesulfonic acid-3-chloro-6-methyl-phenyl ester, and 3,4-diamino-benzenesulfonic acid-3-chloro-6-methyl-phenyl ester, the 2-carbomethoxyamino-5-benzimidazolylsulfonic acid-3-chloro-6-methyl-phenyl ester.
. ., ~ . .. , . .: . - ... . .. .
. :- . . . ~
,, - , ' ' ~.~. ' ,' ~
. . - ., : . . . - : , ~069130 and 3-nitro-4-amino-benzenesulfonic acid-3-chloro-6-methyl-phenyl ester, and 3,4-diamino-benzenesulfonic acid-3-chloro-6-methyl-phenyl ester, the 2-carbomethoxyamino-5-benzimidazolylsulfonic acid-3-chloro-6-methyl-phenyl ester.
19) Via 3-nitro-4-chloro-benzenesulfonic acid-3-chloro-4-carbethoxy-phenyl ester, and 3-nitro-4-amino-benzenesulfonic acid-3-chloro-4-carbethoxy-phenyl ester, and 3,4-diamino-benzenesulfonic acid-3-chloro-4-carbethoxy-phenyl ester, the 2-carbomethoxyamino-5-benzimidazolylsulfonic acid-3-chloro-4-carbethoxy-phenyl ester.
20) Via 3-nitro-4-chloro-benzenesulfonic acid-4-chloro-2-methyl-phenyl ester, and 3-nitro-4-amino-benzenesulfonic acid-4-chloro-2-methyl-phenyl ester, and 3,4-diamino-benzenesulfonic acid-4-chloro-2-methyl-phenyl ester, the 2-carbomethoxyamino-5-benzimidazolylsulfonic acid-4-chloro-2-methyl-phenyl ester.
21) Via 3-nitro-4-chloro-benzenesulfonic acid-4-chloro-3- methyl-phenyl ester, and 3-nitro-4-amino-benzenesulfonic acid-4-chloro-3-methyl-phenyl ester, and 3,4-diamino-benzenesulfonic acid-4-chloro-3-28 methyl-phenyl ester, .~ - -- - ~ ~' '' ' , , - ' ' :' ' .
- . , - : ~ - -..
- .
- ~ 1069130 the 2-carbomethoxyamino-5-benzimidazolylsulfonic acid-4-chloro-3-methyl-phenyl ester.
- . , - : ~ - -..
- .
- ~ 1069130 the 2-carbomethoxyamino-5-benzimidazolylsulfonic acid-4-chloro-3-methyl-phenyl ester.
22) Via 3-nitro-4-chloro-benzenesulfonic acid-4-chloro-3,5-dimethyl-phenyl ester, and 3-nitro-4-amino-benzenesulfonic acid-4-chloro-3,5-dimethyl-phenyl ester, and 3,4-diamino-benzenesulfonic acid-4-chloro-3,5-dimethyl-phenyl ester, the 2-carbomethoxyamino-5-benzimidazolylsulfonic acid-4-chloro -3,5-dimethyl-phenyl ester.
23) Via 3-nitro-4-chloro-benzenesulfonic acid-3,5-bistrifluoroimethyl-phenyl ester, and 3-nitro-4-amino-benzenesulfonic acid-3,5-bistrifluoro~methyl-phenyl ester, and 3,4-diamino-benzenesulfonic acid-3,5-bistri-fluoroimethyl-phenyl ester, the 2-carbomethoxyamino-5-benzimidazolylsulfonic acid-3,5-bistrifluoxo-methyl-phenyl ester.
24) Via 3-nitro-4-chloro-benzenesulfonic acid-4-methoxy-phenyl ester, m.p. 88C, and 3-nitro-4-amino-benzenesulfonic acid-4-methoxy-phenyl ester, m.p. 140C, and 3,4-diamino-benzenesulfonic acid-4-methoxy-phenyl ester, the 2-carbomethoxyamino-5-benzimidazolylsulfonic acid-4-methoxy-phenyl ester, m.p. 228C, (decomp.).
25) Via 3-nitro-4-chloro-benzenesulfonic acid-3-28 methoxy-phenyl ester (oil), . . . - .. : .
.. . . ~. . .
.
. . , . , - ,, : .
. .
~--~ 1069130 and 3-nitro-4-amino-benzenesulfonic acid-3-methoxy-phenyl-ester, m.p. 116C, and 3,4-diamino-benzenesulfonic acid-3-methoxy-phenyl ester (oil), S the 2-carbomethoxyamino-5-benzimidazolylsulfonic acid-3-methoxy-phenyl ester, m.p. 227C (decomp.).
.. . . ~. . .
.
. . , . , - ,, : .
. .
~--~ 1069130 and 3-nitro-4-amino-benzenesulfonic acid-3-methoxy-phenyl-ester, m.p. 116C, and 3,4-diamino-benzenesulfonic acid-3-methoxy-phenyl ester (oil), S the 2-carbomethoxyamino-5-benzimidazolylsulfonic acid-3-methoxy-phenyl ester, m.p. 227C (decomp.).
26) Via 3-nitro-4-chloro-benzenesulfonic acid-2-methoxy-phenyl ester, and 3-nitro-4-amino-benzenesulfonic acid-2-methoxy-phenyl ester, and 3,4-diamino-benzenesulfonic acid-2-methoxy-phenyl ester, the 2-carbomethoxyamino-S-benzimidazolylsulfonic acid-2-methoxy-phenyl ester.
27) Via 3-nitro-4-chloro-benzenesulfonic acid-4-propoxy-phenyl ester, and 3-nitro-4-amino-benzenesulfonic acid-4-propoxy-phenyl ester, and 3,4-diamino-benzenesulfonic acid-4-propoxy-phenyl ester, the 2-carbomethoxyamino-5-benzimidazolylsulfonic acid-4-propoxy-phenyl ester.
28) Via 3-nitro-4-chloro-benzenesulfonic acid-4-isopropoxy-phenyl ester, and 3-nitro-4-amino-benzenesulfonic acid-4-isopropoxy-phenyl ester, and 3,4-diamino-benzenesulfonic acid-4-isopropoxy-2a phenyl ester, .. . . .
' .
- . . ~ '' :.:. : : .
: ' -, ~ , ,' ' -~ 1069~30 the 2-carbomethoxyamino-5-benzimidazolylsulfonic acid-4-isopropoxy phenyl ester.
' .
- . . ~ '' :.:. : : .
: ' -, ~ , ,' ' -~ 1069~30 the 2-carbomethoxyamino-5-benzimidazolylsulfonic acid-4-isopropoxy phenyl ester.
29) Via 3-nitro-4-chloro-benzenesulfonic acid-4-butoxy-phenyl ester, S and 3-nitro-4-amino-benzenesulfonic acid-4-butoxy-phenyl ester, and 3,4-diamino-benzenesulfonic acid-4-butoxy-phenyl ester, the 2-carbomethoxyamino-5-benzimidazolylsulfonic acid-4-butoxy-phenyl ester.
30) Via 3-nitro-4-chloro-benzenesulfonic acid-3-ethoxy-phenyl ester (oil), and 3-nitro-4-amino-benzenesulfonic acid-3-ethoxy-phenyl ester, m.p. 86C, and 3,4-diamino-benzenesulfonic acid-3-ethoxy-phenyl ester (oil), the 2-carbomethoxyamino-5-benzimidazolylsulfonic acid 3-ethoxy-phenyl ester, m.p. 212C, (decomp.).
31) Via 3-nitro-4-chloro-benzenesulfonic acid-4-isobutoxy-phenyl ester, and 3-nitro-4-amino-benzenesulfonic acid-4-isobutoxy-phenyl ester, and 3,4-diamino-benzenesulfonic acid-4-isobutoxy-phenyl ester, the 2-carbomethoxyamino-5-benzimidazolylsulfonic acid-4-isobutoxy-phenyl ester.
32) Via 3-nitro-4-chIoro-benzenesulfonic acid-3-cyano-28 phenyl ester, m.p. 118C, :. .. ' : . - :. . -. .. . , . - ~ - ' . :
- . . , .. - : . .
: - , - . . ~ .
. ~ . , -- .
and 3-nitro-4-amino-benzenesulfonic acid-3-cyano-phenyl ester, m.p. 1~3 ~ ~
and 3,4-diamino-benzenesulfonic acid-3-cyano-phenyl ester, the 2-carbomethoxyanino-5-benzimidazolylsulfonic acid-3-cyano-phenyl ester, m.p. 265C, (decomp.).
- . . , .. - : . .
: - , - . . ~ .
. ~ . , -- .
and 3-nitro-4-amino-benzenesulfonic acid-3-cyano-phenyl ester, m.p. 1~3 ~ ~
and 3,4-diamino-benzenesulfonic acid-3-cyano-phenyl ester, the 2-carbomethoxyanino-5-benzimidazolylsulfonic acid-3-cyano-phenyl ester, m.p. 265C, (decomp.).
33) Via 3-nitro-4-chloro-benzenesulfonic acid-phenyl ester, and 3-nitro-4-amino-benzenesulfonic acid-phenyl ester, and 3,4-diamino-benzenesulfonic acid-phenyl ester, the 2-carbethoxyamino-5-benzimidazolylsulfonic acid phenyl ester.
34) Via 3-nitro-4-chloro-benzenesulfonic acid-phenyl ester, and 3-nitro-4-amino-benzenesulfonic acid-phenyl ester, and 3,4-diamino-benzenesulfonic acid-phenyl ester, the 2-carbopropoxyamino-5-benzimidazolylsulfonic acid-phenyl ester.
35) Via 3-nitro-4-chloro-benzenesulfonic acid-phenyl ester, and 3-nitro-4-amino-benzenesulfonic acid-phenyl ester, and 3,4-diamino-benzenesulfonic acid-phenyl ester, the 2-carboisopropoxyamino-5-benzimidazolylsulfonic acid-phenyl ester.
36) Via 3-nitro-4-chIoro-benzenesulfonic acid-phenyl ester, and 3-nitro-4-amino-benzenesulfonic acid-phenyl - 2~ ester, . ' , . . ~' ' . .
-- ~069130 and 3,4-diamino-benzenesulfonic acid-phenyl ester, the 2-carbobutoxyamino-5-benzimidazolylsulfonic acid-phenyl ester.
-- ~069130 and 3,4-diamino-benzenesulfonic acid-phenyl ester, the 2-carbobutoxyamino-5-benzimidazolylsulfonic acid-phenyl ester.
37) Via 3-nitro-4-chloro-benzenesulfonic acid-phenyl ester, and 3-nitro-4-amino-benzenesulfonic acid-phenyl - -ester, and 3,4-diamino-benzenesulfonic acid-phenyl ester, the 2-carboisobutoxyamino-5-benzimidazolylsulfonic acid-phenyl ester.
38) Via 3-nitro-4-chloro-benzenesulfonic acid-phenyl ester, and 3-nitro-4-amino-benzenesulfonic acid-phenyl ester, and 3,4-diamino-benzenesulfonic acid-phenyl ester, the 2-carbo-tert.butoxyamino-5-benzimidazolyl-sulfonic acid-phenyl ester.
39) Via 3-nitro-4-chloro-benzenesulfonic acid 3-trifluoromethyl phenyl ester, m.p. 65C, and 3-nitro-4-amino-benzenesulfonic acid 3-trifluoromethyl phenyl ester, m.p. 132C, and 3,4-diamino-benzenesulfonic acid 3-trifluoro-methyl phenyl ester, the 2-carbomethoxyamino-5-benzimidazolyl-sulfonic acid 3-trifluoromethyl phenyl ester, m.p. 250C (with decomposition).
This application is a divisional of Canadian Application 28 Serial No. 234,273, filed August 27, 1975.
,, , ~ , , - ., ' ~' ' : . - - . . : . - -. . . .: - . . -: ' . . .- . .
- ,, . , . :, .. ~ , . . . :
~ : ' . - . . ,
This application is a divisional of Canadian Application 28 Serial No. 234,273, filed August 27, 1975.
,, , ~ , , - ., ' ~' ' : . - - . . : . - -. . . .: - . . -: ' . . .- . .
- ,, . , . :, .. ~ , . . . :
~ : ' . - . . ,
Claims (8)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the preparation of an o-phenyl diamine derivative of the formula I
(I) wherein R1 and R2, independently of each other, each represents hydrogen, hydroxy, alkoxy of 1 to 4 carbon atoms, halogen, tri-fluoromethyl, alkyl of 1 to 4 carbon atoms, carbalkoxy of 1 to 4 carbon atoms in the alkoxy moiety or cyano, in which an amino-nitro-derivative of the formula II
(II) wherein R1 and R2 are as defined for the formula I, is reduced.
(I) wherein R1 and R2, independently of each other, each represents hydrogen, hydroxy, alkoxy of 1 to 4 carbon atoms, halogen, tri-fluoromethyl, alkyl of 1 to 4 carbon atoms, carbalkoxy of 1 to 4 carbon atoms in the alkoxy moiety or cyano, in which an amino-nitro-derivative of the formula II
(II) wherein R1 and R2 are as defined for the formula I, is reduced.
2. An o-phenyl diamine derivative of the formula I as defined in claim 1, whenever obtained according to a process as claimed in claim 1 or by an obvious chemical equivalent thereof.
3. A process for the preparation of 3,4-diamino-benzene sulfonic acid phenyl ester in which 3-nitro-4-amino-benzene sulfonic acid phenyl ester is hydrogenated in solution in the presence of Raney nickel and the resultant product is sub-sequently isolated.
4. 3,4-Diamino-benzene sulfonic acid phenyl ester, whenever obtained according to a process as claimed in claim 3 or by an obvious chemical equivalent thereof.
5. A process for the preparation of 3,4-diamino-benzene sulfonic acid-3-cyano-phenyl ester in which 3-nitro-4-amino-benzene sulfonic acid-3-cyano-phenyl ester is hydrogenated in the presence of Raney nickel and the resultant product is subsequently isolated.
6. 3,4-Diamino-benzene sulfonic acid-3-cyano-phenyl ester whenver obtained according to a process as claimed in claim 5 or by an obvious chemical equivalent thereof.
7. A process for the preparation of 3,4-diamino-benzene sulfonic acid 3-trifluoromethyl phenyl ester in which 3-nitro-4-amino-benzene sulfonic acid 3-trifluoromethyl phenyl ester is hydrogenated in solution in the presence of Raney nickel and the resultant product is subsequently isolated.
8. 3,4-Diamino-benzene sulfonic acid 3-trifluoromethyl phenyl ester, whenever obtained according to a process as claimed in claim 7 or by an obvious chemical equivalent thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA314,151A CA1069130A (en) | 1974-08-28 | 1978-10-24 | Anthelmintically active 2-carbalkoxyamino benzimidazolyl-5(6) sulfonic acid phenyl esters and process for their manufacture |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2441202A DE2441202C2 (en) | 1974-08-28 | 1974-08-28 | 2-Carbalkoxyamino-benzimidazolyl-5 (6) -sulfonic acid-phenyl ester, process for their preparation and anthelmintic compositions containing them |
| CA234,273A CA1059136A (en) | 1974-08-28 | 1975-08-27 | Anthelmintically active 2-carbalkoxyamino benzimidazolyl-5 (6) sulfonic acid phenyl esters and process for their manufacture |
| CA314,151A CA1069130A (en) | 1974-08-28 | 1978-10-24 | Anthelmintically active 2-carbalkoxyamino benzimidazolyl-5(6) sulfonic acid phenyl esters and process for their manufacture |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1069130A true CA1069130A (en) | 1980-01-01 |
Family
ID=27164086
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA314,151A Expired CA1069130A (en) | 1974-08-28 | 1978-10-24 | Anthelmintically active 2-carbalkoxyamino benzimidazolyl-5(6) sulfonic acid phenyl esters and process for their manufacture |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1069130A (en) |
-
1978
- 1978-10-24 CA CA314,151A patent/CA1069130A/en not_active Expired
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