CN1939901B - 制备4-碘-2-氨基磺酰基苯甲酸甲酯的方法 - Google Patents
制备4-碘-2-氨基磺酰基苯甲酸甲酯的方法 Download PDFInfo
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- CN1939901B CN1939901B CN2006100957988A CN200610095798A CN1939901B CN 1939901 B CN1939901 B CN 1939901B CN 2006100957988 A CN2006100957988 A CN 2006100957988A CN 200610095798 A CN200610095798 A CN 200610095798A CN 1939901 B CN1939901 B CN 1939901B
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- 238000004519 manufacturing process Methods 0.000 title 1
- DZERRHAHFNNWSI-UHFFFAOYSA-N methyl 4-iodo-2-sulfamoylbenzoate Chemical compound COC(=O)C1=CC=C(I)C=C1S(N)(=O)=O DZERRHAHFNNWSI-UHFFFAOYSA-N 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims abstract description 58
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000006193 diazotization reaction Methods 0.000 claims description 7
- -1 iodide ions Chemical class 0.000 abstract description 19
- 239000002253 acid Substances 0.000 abstract description 11
- 150000001450 anions Chemical class 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 150000001989 diazonium salts Chemical class 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- 125000003545 alkoxy group Chemical group 0.000 description 12
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 12
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 229910052740 iodine Inorganic materials 0.000 description 10
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 9
- 239000011630 iodine Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 7
- 239000012954 diazonium Substances 0.000 description 7
- 229910052736 halogen Inorganic materials 0.000 description 7
- 150000002367 halogens Chemical class 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 5
- 235000015320 potassium carbonate Nutrition 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 229940100389 Sulfonylurea Drugs 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 125000000753 cycloalkyl group Chemical group 0.000 description 4
- 125000001188 haloalkyl group Chemical group 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 235000007715 potassium iodide Nutrition 0.000 description 4
- 229960004839 potassium iodide Drugs 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- YROXIXLRRCOBKF-UHFFFAOYSA-N sulfonylurea Chemical class OC(=N)N=S(=O)=O YROXIXLRRCOBKF-UHFFFAOYSA-N 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 125000004414 alkyl thio group Chemical group 0.000 description 3
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 229940095102 methyl benzoate Drugs 0.000 description 3
- HNHVTXYLRVGMHD-UHFFFAOYSA-N n-butyl isocyanate Chemical compound CCCCN=C=O HNHVTXYLRVGMHD-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000009333 weeding Methods 0.000 description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 2
- 125000004765 (C1-C4) haloalkyl group Chemical group 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 2
- 229940006461 iodide ion Drugs 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000003791 organic solvent mixture Substances 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- PQUYRZRVPPYNLI-UHFFFAOYSA-N propan-2-yl 4-chloro-2-sulfamoylbenzoate Chemical compound CC(C)OC(=O)C1=CC=C(Cl)C=C1S(N)(=O)=O PQUYRZRVPPYNLI-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 2
- 125000006700 (C1-C6) alkylthio group Chemical group 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- YIDSTEJLDQMWBR-UHFFFAOYSA-N 1-isocyanatododecane Chemical compound CCCCCCCCCCCCN=C=O YIDSTEJLDQMWBR-UHFFFAOYSA-N 0.000 description 1
- VRVUKQWNRPNACD-UHFFFAOYSA-N 1-isocyanatopentane Chemical group CCCCCN=C=O VRVUKQWNRPNACD-UHFFFAOYSA-N 0.000 description 1
- OQURWGJAWSLGQG-UHFFFAOYSA-N 1-isocyanatopropane Chemical compound CCCN=C=O OQURWGJAWSLGQG-UHFFFAOYSA-N 0.000 description 1
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 description 1
- GSLTVFIVJMCNBH-UHFFFAOYSA-N 2-isocyanatopropane Chemical class CC(C)N=C=O GSLTVFIVJMCNBH-UHFFFAOYSA-N 0.000 description 1
- 125000004179 3-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(Cl)=C1[H] 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 125000004442 acylamino group Chemical group 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 125000004448 alkyl carbonyl group Chemical group 0.000 description 1
- 125000004644 alkyl sulfinyl group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N benzoic acid ethyl ester Natural products CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000002837 carbocyclic group Chemical group 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 125000004473 dialkylaminocarbonyl group Chemical group 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 150000004816 dichlorobenzenes Chemical class 0.000 description 1
- GRWZHXKQBITJKP-UHFFFAOYSA-N dithionous acid Chemical compound OS(=O)S(O)=O GRWZHXKQBITJKP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- WUDNUHPRLBTKOJ-UHFFFAOYSA-N ethyl isocyanate Chemical compound CCN=C=O WUDNUHPRLBTKOJ-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 125000004440 haloalkylsulfinyl group Chemical group 0.000 description 1
- 125000000232 haloalkynyl group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- ANJPRQPHZGHVQB-UHFFFAOYSA-N hexyl isocyanate Chemical group CCCCCCN=C=O ANJPRQPHZGHVQB-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001511 metal iodide Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- HAMGRBXTJNITHG-UHFFFAOYSA-N methyl isocyanate Chemical compound CN=C=O HAMGRBXTJNITHG-UHFFFAOYSA-N 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 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 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- VLYDXDHQGKCGCA-UHFFFAOYSA-N n-iodobenzenesulfonamide Chemical compound INS(=O)(=O)C1=CC=CC=C1 VLYDXDHQGKCGCA-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- CFHIDWOYWUOIHU-UHFFFAOYSA-N oxomethyl Chemical compound O=[CH] CFHIDWOYWUOIHU-UHFFFAOYSA-N 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical group CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 150000003613 toluenes Chemical class 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C311/50—Compounds containing any of the groups, X being a hetero atom, Y being any atom
- C07C311/52—Y being a hetero atom
- C07C311/54—Y being a hetero atom either X or Y, but not both, being nitrogen atoms, e.g. N-sulfonylurea
- C07C311/57—Y being a hetero atom either X or Y, but not both, being nitrogen atoms, e.g. N-sulfonylurea having sulfur atoms of the sulfonylurea groups bound to carbon atoms of six-membered aromatic rings
- C07C311/58—Y being a hetero atom either X or Y, but not both, being nitrogen atoms, e.g. N-sulfonylurea having sulfur atoms of the sulfonylurea groups bound to carbon atoms of six-membered aromatic rings having nitrogen atoms of the sulfonylurea groups bound to hydrogen atoms or to acyclic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C311/30—Sulfonamides, the carbon skeleton of the acid part being further substituted by singly-bound nitrogen atoms, not being part of nitro or nitroso groups
- C07C311/37—Sulfonamides, the carbon skeleton of the acid part being further substituted by singly-bound nitrogen atoms, not being part of nitro or nitroso groups having the sulfur atom of at least one of the sulfonamide groups bound to a carbon atom of a six-membered aromatic ring
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
制备式(IV)化合物的方法，该方法包括：a)在酸H+X-存在下，其中X-是当量的阴离子，将式(II)化合物重氮化，给出式(III)化合物，其中X-是当量的阴离子，和b)在碘离子存在下，使分离后的或未分离的式(III)中间体反应，给出式(IV)化合物。
Description
本申请是申请日为1997年6月18日、申请号为01124562.X、发明创造名称为“5-重氮-2-甲氧基羰基-苯基-磺酰胺盐、其制备方法和由其制备碘代化合物的方法”的申请的分案申请。
本发明涉及制备活性化合物的、特别是除草磺酰胺类的中间体的技术领域。
已知，芳基-SO2-NH-CO-NH-R所示的脲-其中芳基是取代的或未取代的芳基且R是烷基-原则上可以与光气反应，给出相应的芳基-SO2-NCO所示的异氰酸酯，而后者可以被用来制备除草活性的磺酰脲(EP-A-0584043；US-A-4566898).为了能够采用一般的方法来制备芳基＝2-羰基甲氧基-5-碘苯-1-基这一系列的磺酰脲(它是一类有用的除草磺酰脲类(WO-A-92/13845))，提出了提供式(I)的化合物这样一种任务：
其中R是烷基或环烷基，后二个基团中的每一个为未取代或取代的。尤其要完成的任务是提供一种制备式(I)化合物的有效方法。
出人意外的是，如下文所讨论的，由式(II)化合物为起始原料，经由中间体(III)和(IV)，可以以非常高的收率获得式(I)化合物。本发明因此使得有可能有效地制备除草磺酰脲类和其它活性化合物。
本发明涉及制备式(I)的N-取代的4-碘-2-[N-(氨基羰基)氨基磺酰基]苯甲酸甲酯的方法
其中R是烷基或环烷基，后二个基团中的每一个为未取代或取代的，且
优选的是，R是未取代的或由一个或多个选自下列的基团取代的(C1-C12)烷基：卤素、(C1-C6)烷氧基、(C1-C6)烷硫基、(C1-C6)卤代烷氧基和取代或未取代的苯基，或R是未取代的或由一个或多个选自下列的基团取代的(C3-C12)环烷基：卤素、(C1-C4)烷基、(C1-C4)卤代烷基、(C1-C4)烷氧基、(C1-C4)卤代烷氧基和(C1-C4)烷硫基，所述方法的特征在于，
(a)在酸H+X-，其中X-是一个当量的阴离子，例如X-＝Cl-、I-或HSO4 -存在下，将式(II)化合物重氮化，
给出式(III)化合物(重氮盐)
其中X-具有与酸H+X-中一样的含意，和
(b)在碘离子存在下，使分离后的或优选未分离的式(III)化合物反应，给出式(IV)化合物
和
(c)使式(IV)化合物与式(V)的异氰酸酯反应
R-N＝C＝O (V)
其中R如式(I)中所定义，给出式(I)化合物。
本发明还提供此方法的各个单独的步骤。
在式(I)中和在下文所用的化学式中，基团烷基、烷氧基、卤代烷基、卤代烷氧基和烷硫基和相应的取代基团其碳骨架均可以是直链或支链的。除非另有指明，这些基团优选是低级碳骨架，例如具有1至4个碳原子的那些。烷基，以及在组合基团如烷氧基、卤代烷基等中的烷基是，例如，甲基、乙基、正-或异丙基、正-、异-、叔-或2-丁基、戊基类、己基类如正己基、异己基或1，3-二甲基丁基、庚基类如正庚基、1-甲基己基和1，4-二甲基戊基。环烷基是碳环状饱和环系，例如具有3至8个环原子的那些，如环丙基、环丁基、环戊基、环己基等。
卤素是，例如，氟、氯、溴或碘。卤代烷基、卤代链烯基和卤代炔基分别是部分或全部由卤素、优选由氟、氯和/或溴、特别是由氟或氯取代的烷基、链烯基和炔基，例如CF3、CHF2、CH2F、CF3CF2、CH2FCHCl2、CCl3、CHCl2、CH2CH2Cl；卤代烷氧基是例如，OCF3、OCHF2、OCH2F、CF3CF2O、OCH2CF3和OCH2CH2Cl；这点同样适应于卤代链烯基或其它由卤素取代的基团。
如果取代是如“一个或多个选自下列一组基团”所定义，则这点既适用于由一个或多个相同的基团取代，也适用于由不同的基团单-或多取代。
取代或未取代的苯基优选的是未取代的、或由相同或不同的选自下列的基团单-或多取代的苯基：卤素、烷基、卤代烷基、烷氧基、卤代烷氧基、烷硫基、羟基、氨基、硝基、氰基、偶氮基、烷氧羰基、烷基羰基、甲酰基、氨基甲酰基、单-和二烷基氨基羰基、取代的氨基如酰基氨基、单-或二烷基氨基、和烷基亚磺酰基、卤代烷基亚磺酰基、烷基磺酰基、卤代烷基磺酰基，优选由选自下列的相同或不同的基团至多三取代：卤素、(C1-C4)烷基、(C1-C4)烷氧基、(C1-C4)卤代烷基、(C1-C4)卤代烷氧基、CN和硝基，例如邻-、间-和对甲苯基、二甲基苯基类、2-、3-和4-氯苯基、2-、3-和4-三氟-和-三氯苯基、2，4-、3，5-、2，5-和2，3-二氯苯基、邻-、间-和对甲氧基苯基。
本发明还涉及式(I)包括的所有立体异构体及其混合物。这些式(I)化合物含有一个或多个未在式(I)中未特别指明的不对称碳原子。可能的和由其特别空间形式限定的立体异构体如对映体和非对映体，均由式(I)所包括，且可以通过常规方法由立体异构体混合物获得，或通过组合使用立体化学纯的起始原料，由立体选择性反应制备。式(I)还包含提到的化合物的互变异构体，只要它们是通过质子迁移产生且只要它们是化学稳定的。
式(I)化合物可以形成盐，其中-SO2-NH基的氢，或其它酸性氢原子由农业上适合的阳离子替代。这些盐是例如金属盐；优选碱金属盐或碱土金属盐，特别是钠和钾盐，或铵盐或与有机胺形成的盐。同样，盐形成可以通过将酸与碱基团进行加成反应而实施，碱基团如氨基或烷基氨基。适合于此目的的酸是强无机酸或有机酸，例如，HCl、HBr、H2SO4或HNO3。
式(II)化合物是已知的(参见，EP-A-382436、EP-A-382437)，或可以通过常规的方法，由简单的市售可得化合物制备(参见，例如用《有机化学杂志》27(1962)2177页等中的方法制备类似的异丙基酯)。
按照方法步骤(a)，重氮化式(II)化合物可以在对重氮反应本身而言是常规的条件下进行。例如，在酸H+X--其中X-优选是Cl-、I-或HSO4 --存在下重氮化式(II)化合物是在水溶液中进行的，且如果适宜，优选通过加入在此反应条件下是惰性的有机溶剂，和通过使用亚硝酸盐来进行。例如，每摩尔式(II)化合物使用1.0-1.2摩尔的亚硝酸盐，优选1.01-1.05摩尔的亚硝酸盐，亚硝酸金属盐如NaNO2(亚硝酸钠)，来进行重氮化。
适合用于重氮化的酸是无机酸或强有机酸。优选的是氢卤酸如盐酸或氢碘酸，或硫酸。以化学计量为基准，通常过量使用酸H+X-；在n大于1的n价酸的情况下，如硫酸(n＝2)，将单价酸的化学计量除以n，获得n价酸的化学计量。每摩尔的式(II)化合物采用5至15摩尔的单价酸，优选每摩尔的式(II)化合物采用8至12摩尔的H+X-。
用于重氮化的溶剂是水或水与一种在反应条件下是惰性的有机溶剂的混合物，例如有机溶剂选自：
-取代或未取代的芳烃如甲苯、氯苯、二氯苯、氯甲苯或二甲苯，
-卤代脂族烃如二氯甲烷和
-醚类如二乙醚、二噁烷和四氢呋喃。
适合于重氮化给出式(III)化合物的温度可以容易地用预备试验确定；通常，反应是在-5至50℃，优选在10至20℃，特别是15至20℃的范围下进行。
式(III)化合物的重氮盐可以通过常规方法分离，但对低稳定性的重氮基应加以注意；然而，优选的是采用化合物(III)，不经中间分离而制备式(IV)化合物。
式(III)的重氮盐，优选其中X-＝I-(碘阴离子)的那些，是新颖的且同样构成本发明主题的一部分。
按照方法步骤(b)，使化合物(III)反应给出式(IV)化合物是在与方法步骤(a)同样的水溶液或水-有机溶剂或溶剂混合物中进行的，或在相似的改性溶剂(混合物)中进行。在此反应中，重氮基由碘原子替代，且因此碘离子是在反应混合物中所需的。在其中X-＝I-的情况下，这些碘离子可以来源于重氮盐本身。如果X-不是碘阴离子，且例如是Cl-，碘必须以另外的形式加入，例如碱金属碘化物如碘化钠或碘化钾。在此情况下，每摩尔的式(III)用例如1.1至1.5摩尔的碘。另外，碘可以在前一步骤(a)中就已加入式(II)化合物中。
由式(III)化合物形成式(IV)化合物通常在10至40℃，优选15至30℃的范围下进行。
式(IV)化合物的制备是通过先将式(II)化合物加入盐酸水溶液中，并混合入催化量的甲苯，如果适宜，与消泡剂一起来进行。在15至20℃，缓慢加入NaNO2的水溶液，将混合物搅拌一段时间，使用酰氨基磺酸来破坏过量的亚硝酸盐。所得的式(III)重氮盐(其中X-＝Cl-)在15至20℃下以其水溶液形式加入碘化钾水溶液中。混合物搅拌一段时间后滤出沉淀物，用亚硫酸氢盐洗涤(例如NaHSO3)，直到再无碘，并干燥。
出人意外的是，经重氮盐(III)制备碘苯基磺酰胺(IV)给出非常高的收率。可以获得大于理论值90％的收率。
考虑已知的相似方法的收率，如此高的收率是出人意外的。根据《美国化学协会杂志》55(1933)1652，使用亚硝酸钠和盐酸来重氮化4-氨基苯甲酸乙酯、随后与碘化钾反应，给出4-碘苯甲酸乙酯，收率只有理论值的68.5％；与此相比，由于磺基酰氨基使它具有另一个官能基，使得用式(III)化合物的反应进行得出人意外的好。
式(IV)碘苯基化合物迄今只能以不充分的收率制备。因此，在氨存在下，由4-碘-2-氯磺酰基苯甲酸甲酯为起始原料，式(IV)化合物只以约75％的收率获得(参见，WO92/13845，实施例6，第26页)；用这种反应类型，通常观察到由于闭环成多糖衍生物而造成的收率损失。然而，使用本发明的方法，式(IV)化合物是高收率地获得的，且没有不需要的碘多糖。
在方法步骤(c)中，式(IV)化合物与式R-N＝C＝O(V)的异氰酸酯反应给出式(I)化合物。反应优选是用碱催化和在惰性溶剂中进行，针对步骤(a)和(b)已提到的加入的有机溶剂在此同样适合；也可以采用有机溶剂，且适合的溶剂可以通过比较预备实验而容易地找出。
方法(c)的优选溶剂是在此反应条件下是惰性的非含水有机溶剂，例如选自下列：
-取代或未取代的芳族烃如甲苯、氯苯、二氯苯类、氯甲苯类或二甲苯类，
-卤代脂族烃如二氯甲烷、醚类如乙醚、二噁烷和四氢呋喃和
-酮类如丙酮。
优选氯苯。
适合的碱是无机或有机碱，例如，碳酸盐如碳酸钾、碳酸钠，取代的胺类如三乙胺、DBU(1，8-二氮杂二环[5.4.0]十一碳-7-烯)等；优选的是碱如碳酸钾。每摩尔的式(IV)化合物采用例如1摩尔至1.1摩尔、优选1.01至1.05摩尔量的碱。
每摩尔的式(IV)采用例如1.0-2.0摩尔，优选1.01至1.1摩尔量的式(V)异氰酸酯。所用的优选的异氰酸酯是异氰酸甲酯、异氰酸乙酯、异氰酸正丙基酯、异氰酸异丙基酯、异氰酸正丁基酯、异氰酸异-、仲-或叔丁基酯、异氰酸正戊基酯、异氰酸正己基酯、异氰酸环己基酯、异氰酸十二烷基酯，优选R为(C4-C6)烷基的异氰酸酯。
当使用溶剂如甲苯、二甲苯或氯苯时，制备式(I)化合物的方法步骤(c)中的反应温度优选分成二个阶段。首先，例如温度保持在55-60℃2小时，之后在90℃下保持5至10小时，优选6至9小时。在溶剂如丙酮存在下，例如，反应先在室温下搅拌进行，之后搅拌回流4至10小时，优选5至8小时。
式(I)化合物的制备是例如通过将式(IV)的磺基酰胺与碳酸钾和式(V)的异氰酸酯在氯苯中混合，先将反应在55至60℃下进行，之后在90℃下进行。冷却至室温后，将反应混合物与水混合，并用2N盐酸调节至pH为1-2。分离出有机相，洗涤至再无酸，并浓缩。残留物为以高收率与非常高的纯度获得的式(I)化合物。
迄今，式(I)化合物只以不够充分的收率获得。因此，例如通过2-(氨基磺酰基)-4-氯苯甲酸异丙酯与异氰酸丁酯在2-丁酮中反应，只以理论值44％的收率获得所需的丁基磺酰脲2-[N-(N-丁基氨基羰基)氨基磺酰基]-4-氯苯甲酸异丙酯(US-A-4566898，实施例5)。
然而，用根据本发明的方法出人意外地高收率地获得了式(I)化合物。使用此方法只产生少量的废物，且体积收率高。因此，例如，由于上面提到的原因，以式(IV)化合物或式(II)化合物为起始原料，以如此高的收率或经几个步骤以如此高的总收率获得式(I)的化合物，这是不能预料到的。
在下列实施例中，量是指重量，除非另有具体指明。
实施例1
4-碘-2-氨基磺酰基苯甲酸甲酯(IV)
将1000g(4.34mol)4-氨基-2-氨基磺酰基苯甲酸甲酯和3400ml水与3700ml浓盐酸(浓度37％)迅速混合。向此混合物中加入10ml甲苯。混合物冷却至15℃，并在15-20℃下、在1小时的时间内加入315gNaNO2(4.56mol)于1740ml水中的溶液。搅拌继续1小时，使用酰氨基磺酸破坏过量的亚硝酸盐。在第二容器中，先加入1082g碘化钾(6.51mol)和7000ml水。在15至20℃下，经1至2小时的时间加入重氮盐溶液。所得的悬浮液用10升水稀释，抽滤滤除沉淀物。之后将滤饼用435g Na2S2O5于8.5升水中的混合物洗涤至再无碘，之后用25升水洗涤至中性。获得1771g(湿量)的式(IV)化合物。在50℃真空(减压下)干燥后，获得1403g(理论值的94.8％)的4-碘-2-氨基磺酰基苯甲酸甲酯(式V的磺基酰胺)，熔点：175-177℃。
实施例2
4-碘-2-[N-(N-正丁基氨基羰基)氨基磺酰基]苯甲酸甲酯(I)
将由实施例1得到的34.1g(0.1mol)式(IV)的磺基酰胺和14.7g碳酸钾(0.105mol)与于250ml氯苯中的10.6g异氰酸正丁酯(纯度98％)(0.105mol)混合，并将混合物在55至60℃下保持2小时。之后将混合物在90℃下搅拌8.5小时。将混合物冷却至室温，先加入2000ml水，之后加入2N盐酸，直到pH达到1-2。分离出有机相，用50ml水洗涤四次至再无酸。减压去除溶剂，余下43.8g所需的式(I)化合物(理论值的99.3％)，熔点：128-130℃。
对比实施例(US-A-4566898)
将1063.4g 2-(氨基磺酰基)-4-氯苯甲酸异丙酯、590.4g异氰酸正丁酯和590.4g碳酸钾于10.8升2-丁酮中的混合物加热回流过液。在冷却到室温后，将反应混合物每次倒入1O升冰水中。水相用9升二氯甲烷萃取。水相用浓盐酸酸化至pH为1.0，并将所得的沉淀物滤出。在干燥后，获得714.6g2-[N-(N-正丁基氨基羰基)氨基磺酰基]-4-氯苯甲酸异丙酯(理论值的44％)，熔点：129-132℃。
Claims (3)
1.式(III)的化合物
其中X-是Cl-或I-。
2.根据权利要求1的化合物，其中X-＝I-。
3.制备权利要求1或2所定义的式(III)化合物的方法，该方法包括(a)在酸H+X-的存在下，使式(II)的化合物重氮化
其中X-是Cl-或I-，以得到式(III)的化合物。
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| CN97195832A Expired - Lifetime CN1078589C (zh) | 1996-06-28 | 1997-06-18 | 4－碘－2－[n－(n－烷基氨基羰基)－氨基磺酰基]苯甲酸甲酯及其衍生物、和其制备方法 |
| CNB01124562XA Expired - Lifetime CN1300103C (zh) | 1996-06-28 | 2001-08-02 | 5－重氮－2－甲氧基羰基－苯基－磺酰胺盐、其制备方法和由其制备碘代化合物的方法 |
Country Status (18)
| Country | Link |
|---|---|
| US (1) | US6147248A (zh) |
| EP (1) | EP0907638B1 (zh) |
| JP (1) | JP4303787B2 (zh) |
| CN (3) | CN1939901B (zh) |
| AT (1) | ATE228501T1 (zh) |
| AU (1) | AU715308B2 (zh) |
| BR (1) | BR9710056A (zh) |
| CA (1) | CA2259216C (zh) |
| CZ (1) | CZ298782B6 (zh) |
| DE (2) | DE19625831A1 (zh) |
| DK (1) | DK0907638T3 (zh) |
| ES (1) | ES2187784T3 (zh) |
| IL (2) | IL127783A0 (zh) |
| PL (1) | PL193481B1 (zh) |
| PT (1) | PT907638E (zh) |
| RU (1) | RU2309948C2 (zh) |
| TR (1) | TR199802683T2 (zh) |
| WO (1) | WO1998000396A2 (zh) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19625831A1 (de) * | 1996-06-28 | 1998-01-02 | Hoechst Schering Agrevo Gmbh | 4-Jod-2-[N-(N-alkyl-aminocarbonyl)- aminosulfonyl)]-benzoesäuremethylester und -derivate und Verfahren zu deren Herstellung |
| EP2052604A1 (de) | 2007-10-24 | 2009-04-29 | Bayer CropScience AG | Salz des 2-lodo-N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)carbamoyl] benzolsulfonamids,Verfahren zu deren Herstellung, sowie deren Verwendung als Herbizide und Pflanzenwachstumregulatoren |
| JP5776883B2 (ja) | 2011-04-14 | 2015-09-09 | セイコーエプソン株式会社 | インクジェット記録用水性顔料インク |
| CN104628606A (zh) * | 2015-02-06 | 2015-05-20 | 王桦 | 一种磺酰肼化合物的制备方法 |
| US12043593B2 (en) | 2018-09-25 | 2024-07-23 | Arxada Ag | Method for preparation of potassium 5-lodo-2-carboxybenzene sulfonate |
| CN113582847B (zh) * | 2021-07-16 | 2023-09-12 | 湖北工业大学 | 一种改进桑德迈尔反应制备碘代苯甲酸（酯）的方法 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4566898A (en) * | 1984-09-07 | 1986-01-28 | E. I. Du Pont De Nemours And Company | Herbicidal sulfonamides |
| CN86103621A (zh) * | 1985-06-11 | 1986-12-10 | 伊莱利利公司 | 制备农业上有用的磺酰胺的方法 |
| CN1223638A (zh) * | 1996-06-28 | 1999-07-21 | 赫彻斯特-舍林农业发展有限公司 | 4－碘－2－[n－(n－烷基氨基羰基)－氨基磺酰基]苯甲酸甲酯及其衍生物、和其制备方法 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4383113A (en) * | 1978-05-30 | 1983-05-10 | E. I. Du Pont De Nemours And Company | Agricultural sulfonamides |
| ZA806970B (en) * | 1979-11-30 | 1982-06-30 | Du Pont | Agricultural sulfonamides |
| ZA92970B (en) * | 1991-02-12 | 1992-10-28 | Hoechst Ag | Arylsulfonylureas,processes for their preparation,and their use as herbicides and growth regulators |
| BG61805B1 (bg) * | 1992-08-18 | 1998-06-30 | Novartis Ag | Метод за получаване на субституирани бензоли и бензолсулфонова киселина и производните й и метод за получаване на n,n'-субституирани карбамиди |
-
1996
- 1996-06-28 DE DE19625831A patent/DE19625831A1/de not_active Withdrawn
-
1997
- 1997-06-18 DE DE59708832T patent/DE59708832D1/de not_active Expired - Lifetime
- 1997-06-18 CN CN2006100957988A patent/CN1939901B/zh not_active Expired - Lifetime
- 1997-06-18 CA CA002259216A patent/CA2259216C/en not_active Expired - Fee Related
- 1997-06-18 EP EP97928229A patent/EP0907638B1/de not_active Expired - Lifetime
- 1997-06-18 IL IL12778397A patent/IL127783A0/xx active IP Right Grant
- 1997-06-18 US US09/214,041 patent/US6147248A/en not_active Expired - Lifetime
- 1997-06-18 TR TR1998/02683T patent/TR199802683T2/xx unknown
- 1997-06-18 WO PCT/EP1997/003170 patent/WO1998000396A2/de active IP Right Grant
- 1997-06-18 ES ES97928229T patent/ES2187784T3/es not_active Expired - Lifetime
- 1997-06-18 DK DK97928229T patent/DK0907638T3/da active
- 1997-06-18 CZ CZ0433298A patent/CZ298782B6/cs not_active IP Right Cessation
- 1997-06-18 RU RU99102669/04A patent/RU2309948C2/ru not_active Application Discontinuation
- 1997-06-18 AT AT97928229T patent/ATE228501T1/de active
- 1997-06-18 CN CN97195832A patent/CN1078589C/zh not_active Expired - Lifetime
- 1997-06-18 PL PL97330970A patent/PL193481B1/pl not_active IP Right Cessation
- 1997-06-18 JP JP50380198A patent/JP4303787B2/ja not_active Expired - Lifetime
- 1997-06-18 PT PT97928229T patent/PT907638E/pt unknown
- 1997-06-18 BR BR9710056A patent/BR9710056A/pt not_active IP Right Cessation
- 1997-06-18 AU AU32603/97A patent/AU715308B2/en not_active Ceased
-
1998
- 1998-12-28 IL IL127783A patent/IL127783A/en not_active IP Right Cessation
-
2001
- 2001-08-02 CN CNB01124562XA patent/CN1300103C/zh not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4566898A (en) * | 1984-09-07 | 1986-01-28 | E. I. Du Pont De Nemours And Company | Herbicidal sulfonamides |
| CN86103621A (zh) * | 1985-06-11 | 1986-12-10 | 伊莱利利公司 | 制备农业上有用的磺酰胺的方法 |
| CN1223638A (zh) * | 1996-06-28 | 1999-07-21 | 赫彻斯特-舍林农业发展有限公司 | 4－碘－2－[n－(n－烷基氨基羰基)－氨基磺酰基]苯甲酸甲酯及其衍生物、和其制备方法 |
| CN1300103C (zh) * | 1996-06-28 | 2007-02-14 | 赫彻斯特-舍林农业发展有限公司 | 5－重氮－2－甲氧基羰基－苯基－磺酰胺盐、其制备方法和由其制备碘代化合物的方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0907638B1 (de) | 2002-11-27 |
| CA2259216A1 (en) | 1998-01-08 |
| CA2259216C (en) | 2008-03-11 |
| RU99102669A (ru) | 2000-12-20 |
| DE19625831A1 (de) | 1998-01-02 |
| CN1078589C (zh) | 2002-01-30 |
| AU715308B2 (en) | 2000-01-20 |
| AU3260397A (en) | 1998-01-21 |
| PL330970A1 (en) | 1999-06-21 |
| JP2000513369A (ja) | 2000-10-10 |
| TR199802683T2 (zh) | 1999-04-21 |
| PL193481B1 (pl) | 2007-02-28 |
| DE59708832D1 (de) | 2003-01-09 |
| IL127783A (en) | 2006-07-05 |
| CZ298782B6 (cs) | 2008-01-30 |
| CZ433298A3 (cs) | 1999-03-17 |
| EP0907638A2 (de) | 1999-04-14 |
| CN1300103C (zh) | 2007-02-14 |
| WO1998000396A2 (de) | 1998-01-08 |
| DK0907638T3 (da) | 2003-03-17 |
| WO1998000396A3 (de) | 1998-03-05 |
| CN1223638A (zh) | 1999-07-21 |
| ES2187784T3 (es) | 2003-06-16 |
| CN1358711A (zh) | 2002-07-17 |
| US6147248A (en) | 2000-11-14 |
| CN1939901A (zh) | 2007-04-04 |
| BR9710056A (pt) | 1999-08-10 |
| RU2309948C2 (ru) | 2007-11-10 |
| IL127783A0 (en) | 1999-10-28 |
| JP4303787B2 (ja) | 2009-07-29 |
| ATE228501T1 (de) | 2002-12-15 |
| PT907638E (pt) | 2003-04-30 |
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