GB2140417A - A process for the preparation of N-aryloxybenzoyl sulphonamides - Google Patents
A process for the preparation of N-aryloxybenzoyl sulphonamides Download PDFInfo
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- GB2140417A GB2140417A GB08412495A GB8412495A GB2140417A GB 2140417 A GB2140417 A GB 2140417A GB 08412495 A GB08412495 A GB 08412495A GB 8412495 A GB8412495 A GB 8412495A GB 2140417 A GB2140417 A GB 2140417A
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- carbon atoms
- alkyl
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- 238000000034 method Methods 0.000 title claims description 49
- 238000002360 preparation method Methods 0.000 title claims description 8
- 150000003456 sulfonamides Chemical class 0.000 title abstract 3
- 239000002253 acid Substances 0.000 claims abstract description 38
- 150000004820 halides Chemical class 0.000 claims abstract description 29
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 230000002140 halogenating effect Effects 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229940124530 sulfonamide Drugs 0.000 claims abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000005843 halogen group Chemical group 0.000 claims abstract description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 5
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 3
- 125000004076 pyridyl group Chemical group 0.000 claims abstract description 3
- 125000001544 thienyl group Chemical group 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 125000000217 alkyl group Chemical group 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 17
- 229910052801 chlorine Inorganic materials 0.000 claims description 16
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 claims description 14
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 14
- 239000012535 impurity Substances 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 12
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 11
- 125000003545 alkoxy group Chemical group 0.000 claims description 10
- 125000004644 alkyl sulfinyl group Chemical group 0.000 claims description 10
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims description 10
- 229910052794 bromium Inorganic materials 0.000 claims description 10
- 239000000460 chlorine Substances 0.000 claims description 10
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 8
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 8
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- 239000011737 fluorine Substances 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- 125000004414 alkyl thio group Chemical group 0.000 claims description 6
- 125000004663 dialkyl amino group Chemical group 0.000 claims description 6
- 229910052740 iodine Inorganic materials 0.000 claims description 6
- -1 cyanosulphonyl Chemical group 0.000 claims description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 5
- 239000007858 starting material Substances 0.000 claims description 5
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical group ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 4
- 125000004448 alkyl carbonyl group Chemical group 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 125000001188 haloalkyl group Chemical group 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- 239000012429 reaction media Substances 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 3
- 239000012433 hydrogen halide Substances 0.000 claims description 3
- 229910000039 hydrogen halide Inorganic materials 0.000 claims description 3
- 239000012442 inert solvent Substances 0.000 claims description 3
- 239000007791 liquid phase Substances 0.000 claims description 3
- JCXJVPUVTGWSNB-UHFFFAOYSA-N Nitrogen dioxide Chemical group O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims description 2
- 101150081344 PAL3 gene Proteins 0.000 claims description 2
- 229910020667 PBr3 Inorganic materials 0.000 claims description 2
- 101150080283 RIM8 gene Proteins 0.000 claims description 2
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 125000004423 acyloxy group Chemical group 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 125000003806 alkyl carbonyl amino group Chemical group 0.000 claims description 2
- 125000005196 alkyl carbonyloxy group Chemical group 0.000 claims description 2
- 125000005907 alkyl ester group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- 125000005117 dialkylcarbamoyl group Chemical group 0.000 claims description 2
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical group II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- 239000011630 iodine Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- 125000000018 nitroso group Chemical group N(=O)* 0.000 claims description 2
- UXCDUFKZSUBXGM-UHFFFAOYSA-N phosphoric tribromide Chemical compound BrP(Br)(Br)=O UXCDUFKZSUBXGM-UHFFFAOYSA-N 0.000 claims description 2
- IPNPIHIZVLFAFP-UHFFFAOYSA-N phosphorus tribromide Chemical compound BrP(Br)Br IPNPIHIZVLFAFP-UHFFFAOYSA-N 0.000 claims description 2
- 125000005208 trialkylammonium group Chemical group 0.000 claims description 2
- 150000001540 azides Chemical class 0.000 claims 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 claims 1
- 230000002363 herbicidal effect Effects 0.000 abstract description 3
- 125000000304 alkynyl group Chemical group 0.000 abstract 1
- 125000000547 substituted alkyl group Chemical group 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 39
- 239000000047 product Substances 0.000 description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 12
- 239000000203 mixture Substances 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 9
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- HNQIVZYLYMDVSB-UHFFFAOYSA-N methanesulfonimidic acid Chemical compound CS(N)(=O)=O HNQIVZYLYMDVSB-UHFFFAOYSA-N 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000005711 Benzoic acid Substances 0.000 description 4
- NUFNQYOELLVIPL-UHFFFAOYSA-N acifluorfen Chemical compound C1=C([N+]([O-])=O)C(C(=O)O)=CC(OC=2C(=CC(=CC=2)C(F)(F)F)Cl)=C1 NUFNQYOELLVIPL-UHFFFAOYSA-N 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 235000010233 benzoic acid Nutrition 0.000 description 4
- 238000004587 chromatography analysis Methods 0.000 description 4
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 125000000565 sulfonamide group Chemical group 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- PKRSYEPBQPFNRB-UHFFFAOYSA-N 2-phenoxybenzoic acid Chemical class OC(=O)C1=CC=CC=C1OC1=CC=CC=C1 PKRSYEPBQPFNRB-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- PACJZZBTXITTDS-UHFFFAOYSA-N 3-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoic acid Chemical compound OC(=O)C1=CC=CC(OC=2C(=CC(=CC=2)C(F)(F)F)Cl)=C1[N+]([O-])=O PACJZZBTXITTDS-UHFFFAOYSA-N 0.000 description 2
- KGPHNHSAYAXSOW-UHFFFAOYSA-N 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoyl chloride Chemical compound C1=C(C(Cl)=O)C([N+](=O)[O-])=CC=C1OC1=CC=C(C(F)(F)F)C=C1Cl KGPHNHSAYAXSOW-UHFFFAOYSA-N 0.000 description 2
- 230000005526 G1 to G0 transition Effects 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 150000003738 xylenes Chemical class 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- ZYRUSOWDJUBNAI-UHFFFAOYSA-N 2-phenoxy-N-sulfonylbenzamide Chemical class S(=O)(=O)=NC(C1=C(C=CC=C1)OC1=CC=CC=C1)=O ZYRUSOWDJUBNAI-UHFFFAOYSA-N 0.000 description 1
- ZVGWXYRRDWYHQL-UHFFFAOYSA-N 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2,4-dinitrobenzoic acid Chemical compound C1=C([N+]([O-])=O)C(C(=O)O)=CC(OC=2C(=CC(=CC=2)C(F)(F)F)Cl)=C1[N+]([O-])=O ZVGWXYRRDWYHQL-UHFFFAOYSA-N 0.000 description 1
- GLBSCOYWQNMMPR-UHFFFAOYSA-N 5-[2-chloro-5-(trifluoromethyl)phenoxy]-2-nitrobenzoic acid Chemical compound C1=C([N+]([O-])=O)C(C(=O)O)=CC(OC=2C(=CC=C(C=2)C(F)(F)F)Cl)=C1 GLBSCOYWQNMMPR-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004215 Carbon black (E152) Substances 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
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 229910001515 alkali metal fluoride Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- IVRMZWNICZWHMI-UHFFFAOYSA-N azide group Chemical group [N-]=[N+]=[N-] IVRMZWNICZWHMI-UHFFFAOYSA-N 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013058 crude material Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/63—One oxygen atom
- C07D213/64—One oxygen atom attached in position 2 or 6
- C07D213/643—2-Phenoxypyridines; Derivatives thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
Herbicidal N-aryloxybenzoyl sulphonamides are prepared by reacting the aryloxybenzoic acid halide, which may be impure, with a sulphonamide in the presence of a halogenating agent such as P(O)Cl3. The N-aryloxybenzoyl sulphonamides are those of the general formula <IMAGE> in which W is -N= or -C(G)= and A, B, C, D, E and G are various specified groups or halogen atoms or (except D) hydrogen and R<3> is an optionally substituted alkyl, alkenyl, alkynyl, phenyl, pyridyl or thienyl group.
Description
SPECIFICATION
Process for the preparation of aryloxybenzoic acids containing a sulphonamide group
The present invention relates to an improved process for the preparation of certain aryloxybenzoic acid derivatives containing a sulphonamide group and having herbicidal properties.
Herbicidal phenoxybenzoic acid derivatives containing a sulphonamide group (or N-sulphonylphenoxybenzamides) are known from European Patent Applications Nos. 3,416 and 23,392 and Japanese Patent Application No. 82/106,654.
These patent applications disclose a number of products of this type, and particularly products of the general formula:
and their salts, in which:
A is hydrogen; fluorine; chlorine; bromine; iodine; a nitro group; -N = NCF3;H2PO3 and its alkyl esters wherein the alkyl group contains from 1 to 4 carbon atoms; NH2; NHOH; Nt; a carboxy group or one of its functional derivatives (e.g. esters, amides and alkali metal, alkaline earth metal, ammonium and amine salts); a monoalkylamino or dialkylamino group; an
NH-CO-R1 group in which R' is an alkyl or alkoxy or morioalkylamino or dialkylamino group; an alkyl group; trialkylammonium;NHS02 in which R2 is an alkyl group or a phenyl group;
NHCONHSO2R2, in which R2 is as hereinbefore defined; alkylthio; alkylsulphinyl: alkylsulphonyl; dialkylsulphonium; cyanosulphonyl; hydroxy; alkanoyloxy; alkoxy; alkoxy substituted by an alkoxycarbonyl group; SH; nitroso ; -SCN; an azide group; CF3;
or acyl;
B is a hydrogen, fluorine, chlorine, bromine or iodine atom, or an alkyl, alkoxy, alkylsulphinyl.
alkylsulphonyl, CF3, NO2, CN, NH2, NHCOR', wherein R1 is as hereinbefore defined, or CONY, group;
C is a hydrogen or halogen atom or an alkyl or dialkylamino group;
D is a fluorine, chlorine, bromine or iodine atom or a CF3, alkylthio, alkylsulphinyl, alkylsulphonyl, haloalkyl, sulphamoyl, formyl, alkylcarbonyl, CN or dimethylamino group;E is hydrogen or a haloalkyl, alkoxy, alkylsulphinyl, alkylsulphonyl, CN, CF3, NH2, CONY2, or
NH-CO-R1 group, in which R' is as hereinbefore defined;
W is a trivalent nitrogen atom or a -C(G) = group in which
G has one of the meanings given for B;
R3 is a phenyl, pyridyl or thienyl group optionally substituted by one or more halogen atoms, alkyl groups or nitro groups; or an alkenyl or alkynyl radical having 2 to 4 carbon atoms or an alkyl radical containing 1 to 4 carbon atoms optionally substituted by one or more fluorine, chlorine, bromine or iodine atoms, preferably CF3, or by one or more of the following substituents: carboxy, alkoxycarbonyl containing from 2 to 5 carbon atoms, alkylcarbonyl containing from 2 to 5 carbon atoms, monoalkylcarbamoyl or dialkylcarbamoyl in which the alkyl groups contain from 1 to 4 carbon atoms, alkylthio, alkylsulphinyl, alkylsulphonyl, each having from 1 to 4 carbon atoms, alkylcarbonyloxy containing from 2 to 5 carbon atoms, alkylcarbonylamino containing from 2 to 5 carbon atoms, or cyano.
in this specification and the accompanying claims alkyl groups and moieties, unless otherwise specified, are straight- or branched-chain and preferably contain from 1 to 4 carbon atoms.
According to the known processes, the products of general formula (I) can be prepared by reacting, between 25 and 1 40 C, an acid halide intermediate of the general formula:
in which X is chlorine, bromine or iodine, and A, B, C, D, E and W have the meanings already indicated, with a sulphonamide of the general formula:
R 3SO2NH2 (Ill) in which R3 is as hereinbefore defined, generally in the presence of an acid acceptor, especially a tertiary amine such as N,N-dimethylaniline or pyridine, or an alkali metal carbonate such as anhydrous potassium carbonate or an alkali metal fluoride such as caesium fluoride.
The compounds of general formula (I) can then be alkylated in a known manner, for example by reaction with a diazoalkane containing from 1 to 4 carbon atoms, so as to give the corresponding products which are substituted on the nitrogen atom of the sulphonamide group by an alkyl group containing from 1 to 4 carbon atoms; the hydrogen atom of this same nitrogen atom can also be replaced by an alkali metal atom such as, e.g. sodium, for example by reaction with basic alkali metal reagents.
This known process for condensing the compounds of general formulae (Il) (Ill) has various disadvantages, in particular poor yields. It is believed that, in general, it is the presence of an acid acceptor which lowers the yield because it favours the diacylation reaction. Moreover, the use of an acid acceptor makes the isolation and the purification of the final products more difficult and more costly.
An objective of the invention is to remedy these disadvantages of the known processes.
The process of the present invention enables the of general formula (I) to be prepared from reactants of the general formula:
(wherein the various symbols are as hereinbefore defined) of technical or industrial grades.
In practice, the latter problem is all the more important because this type of acid of general formula (IV) is liable to contain a considerable number of impurities as a result of the number and the nature of the reactions used in its manufacture. Thus, by way of a non-limiting example, it may be indicated that acifluorofen of the formula:
i.e. 5-(2'-chloro-4'-(trifluoromethyl)phenoxy]-2-nitrobenzoic acid, can be prepared by coupling an alkali metal meta-cresolate with a 3,4-dihalotrifluoromethylbenzene, followed by oxidation of the
CH3 group to a carboxylic acid group and then nitration.During such a sequence of reactions, the number of isomers and other undesirable compounds progressively increases and a large number of acids is often detected in acifluorfen of ordinary quality, and especially the following acids: 2-nitro-3-[2'-chloro-4'-(trifluoromethyl)phenoxy]benzoic acid in an amount which can easily reach 16% by weight, 2-nitro-5-{2'-chloro-5'-(trifluoromethyl)phenoxy]benzoic acid and 4 nitro-5-[2'-chloro-4'-(trifluoromethyl)phenoxy]benzoic acid, it being easily possible for these two acids to be present in quantities of up to 3% by weight, as well as a series of other acids, in amounts which can also range up to 3%, this amount frequently being lower, however, for example less than 0.5%, such as for example the following acids 3-[2'-chloro-5'-(trifluoromethyl)phenoxy]benzoic acid, 3-2'-chlorn-4'-(trifIuornmethyl)phenoxy]benzoic acid and 2,4-dinitro 5-[2'-chloro-4'-(trifluoromethyl)phenoxy]benzoic acid, as well as 4-[2'-chloro-4'-(trifluromethyl)- phenoxyjnitrobenzene and 2-nitro-5-(2'-chloro-4'-(trifluoromethyl)phenoxy]toluene.
The process of the invention permits the preparation of products of general formula (i) having high purity from starting materials of low purity which comprise impurities in addition to the compound of general formula (IV).
The present invention provides a process for the preparation of a compound of general formula (I) wherein the various symbols are as hereinbefore defined which comprises reacting an acid halide of general formula (II) with a sulphonamide of general formula (Ill), wherein, in both, the various symbols are as defined and X is preferably a chlorine atom in the liquid phase, in the presence of a halogenating agent, preferably a phosphorated chlorinating (or chloride-forming) agent and at a temperature which is such that the hydrogen halide which is formed during the reaction is progressively removed from the reaction medium in a gaseous form as it is formed.
According to a preferred embodiment of the process according to the invention, the acid halide of general formula (II) which is used is one which has been prepared by halogenating an acid of general formula (IV) by means of a known halogenating agent.
According to an embodiment of the invention, there is employed Uor reacting with the sulphonamide of general formula (lIl) an acid halide of general formula (II) of technical or industrial quality, that is to say containing up to 20% by weight and possibly up to, but preferably less than, 30% by weight of impurities. Such impurities are, for example, the impurities derived from the reaction of a halogenating agent with an acid of general formula (IV) of technical or industrial quality, containing up to 20% by weight and possibly up to, but preferably less than, 30% by weight of impurities.These impurities in the acid halide of general formula (II) are, therefore, chiefly products whose formula is similar to that of the compound of general formula (II), but differing particularly in the number and the position of the substituents.
These impurities are therefore essentially compounds containing the group of the formula:
which carries one or more substituents, or specifically the group of the formula:
which carries one or more additional substituents.
The process of the invention comprising the reaction of the compounds of general formulae (II) and (III) is preferably carried out in the absence of an acid acceptor; furthermore, the presence of a solvent is optional.
A sub-group of compounds of general formula (I) for the preparation of which the process according to the invention is especially suitable and advantageous, consists of the compounds of general formula (I) in which A is the NO2 group or a hydrogen or chlorine atom; B is a halogen atom and more particularly a chlorine atom; C and E are hydrogen atoms; D is the CF2 group;R3 is an alkyl group preferably having 1 to 4 carbon atoms, particularly CH3; and W is -CH =, and more especially 5-(2'chloro-4'-(trifluoromethyl)phenoxy].2-nitro-N-methanesulphonylbenzam- ide The preferred reactants of general formula (II) and (III) are naturally chosen so that the symbols which appear in their formula have a meaning which is similar to that just given for the products of general formula (I).
Among the halogenating agents which may be employed there may be mentioned: P(0)CI3, PAL3, P(O)Br3 or PBr3; P(O)CI3 is preferred.
The molar ratio of (II) to (III) is generally between 0.8 and 1.2, preferably btween 0.9 and 1. 1; more especially, these reactants are in stoichiometric proportions.
The molar ratio of the halogenating agent relative to the halide of general formula (II) generally varies between 0.1 and 5. The halogenating agent can be present in large excess, e.g.
the molar ratio relative to the acid halide (II) may exceed 5 and may be as much as 20; it can then serve as a solvent for the reaction. In that case, it can be recovered by distillation from the reaction mixture for the purpose of subsequent recycling.
The reactants can also be dissolved in an inert solvent which has a boiling point above the reaction temperature, for example a liquid aliphatic or aromatic, chlorinated or unchlorinated hydrocarbon such as benzene, toluene, xylenes, mixed xylenes, cumene, 1 ,2ichlornethane, chlorobenzene or, for example, a nitrile such as acetonitrile; a mixture of several solvents can also be employed. The use of an inert solvent has the practical advantage of permitting better heat transfer in a process on an industrial scale; it also makes it possible to avoid local overheating of the reaction medium.
As hereinbefore indicated, the temperature at which the process according to the invention is carried out is such that the hydrogen halide formed during the reaction is removed from the reaction medium in a gaseous form concurrently with its production. This temperature, moreover, lies below the decomposition temperature of the compounds of general formulae (II), (III) and (I) involved in the process; in the case where a solvent is employed, the reaction temperature is advantageously less than or equal to the boiling point of this solvent which can, moreover, consist of an excess of the halogenating agent as has already been indicated.The temperature is therefore generally between 70 and 1 80 C. In the absence of a solvent, the preferred temperature is between 80 and 1 20do; in the presence of a solvent (particularly in the case of cumene which boils at 1 53 C), the temperature is advantageously between 80 and 1 50 C.
At the end of the reaction the product of general formula (I) can be isolated by methods known per se. By the term "methods known per se" as used in the present specification is meant methods heretofore used or described in the chemical literature.
The process according to the invention is distinguished by the simplicity of the method by which the final product is recovered because the latter is insoluble in the halogenating agent with the result that this recovery is usually confined to a filtration. This filtration can also be facilitated by the addition of a non-solvent.
The acid halide of general formula (II) can be prepared by any method known per se from the acid of general formula (IV). In general, the procedure is a reaction of an acid of general formula (IV) with a halogenating agent such as those mentioned hereinbefore. The reaction can, if appropriate, be carried out in situ, and catalysts, e.g. dimethylformamide, can also be employed.
The acid halide of general formula (II) can be: -separated and purified, or -separated in the crude state without purification, or prepared in situ in the reaction solvent, without being separated, before being placed in the presence of the sulphonamide of general formula (III).
The following non-limitative examples illustrate the present invention.
Example 1:
5-[2'-Chloro-4'-(trifluoromethyl)phenoxy]-2-nitrobenzoic acid chloride (16.79; 0.044 mol) and methanesulphonamide (4.2 g; 0 044 mol) are suspended in P(O)C13 i.e. phosphoryl chloride (20 cc). The reaction mixture is heated for 1 hour at 90"C with stirring. After adding toluene (50 cc) the precipitate formed is filtered off and then washed with toluene.
A white solid consisting of 5-[2'-chloro-4'-(trifluoromethyl)phenoxy]-2-nitro-N-methanesulpho- nyl benzamide (16.49; 0.034 mol; yield 85%), of the formula (Vl), m.p. 203"C is thus obtained. The structure of this product is confirmed by infrared and by nuclear magnetic resonance (NMR).
Example 2:
5-[2'-Chloro-4'-(trifluoromethyl)phenoxy]-2-nitrobenzoic acid chloride (19 g; 0.05 mol) and methanesulphonamide (4.759; 0.05 mol) are suspended in a mixture of P(O)C13 (14 cc) and toluene (35 cc). The reaction mixture is heated for 3 hours at 1000"C with stirring. After adding toluene (50 cc) the precipitate formed is filtered off and then washed with toluene.
A white solid consisting of 5-[2'-chloro-4'-(trifluoromethyl)phenoxyj-2-nitro-N-methanesulpho- nyl benzamide (14.7 g; 0.034 mol; yield 67%), of the formula (Vl), m.p. 198"C, is thus obtained. The structure of this product is confirmed by infrared and by NMR.
Example 3:
5-E2'-Chloro-4'-(trifluoromethyl)phenoxy]-2-nitrobenzoic acid chloride (7.6 g; 0.02 mol) and methanesulphonamide (1.9 g; 0.02 mol) are dissolved in a mixture of P(O)CI3 (2 cc) and acetonitrile (20 cc). The reaction mixture is boiled under reflux for 2 hours 30 minutes with stirring, and is then concentrated to dryness. The crude material obtained is recrystallised from a mixture of toluene and ethyl acetate (95/5).
A white solid consisting of 5-[2'-chloro-4'-(trifluoromethyl)phenoxy]-2-nitro-N-methanesulpho- nyl benzamide (7.6 g; 0.0173 mol; yield 87%), of the formula (VI), m.p. 215"C, is thus obtained. The structure of this product is confirmed by infrared and by NMR.
Example 4: 5-[21Chlorn41-(tn'fluornmethyl)phenoxyj2-nitrnbenzoic acid (36.1 g; 0.1 mol) is suspended in a mixture of toluene (60 cc) and dimethylformamide (DMF) (1 cc). The reaction mixture is heated to 55"C with stirring. A solution of thionyl chloride (11.9 g; 0.1 mol) in toluene (15 cc) is then added. When gas ceases to be evolved, the reaction mixture is heated to 90"C, before adding methanesulphonamide (9.5 g; 0.1 mol). P(O)C13 (27 cc) is then run in over a period of 10 minutes, and the reaction mixture is then heated at 105"C for 2 hours. After cooling, the precipitate formed is filtered off and then washed with toluene.
A white solid consisting of 5-[2'-chloro-4'-(trifluoromethyl)phenoxy]-2-nitro-N-methanesulpho- nyl benzamide (23.8 g; 0.054 mol; yield 54%), of the formula (VI), m.p. 200C is thus obtained. The structure of this product is confirmed by infrared and by NMR.
Example 5:
This example illustrates the preparation of benzamide of the formula (VI) starting from impure phenoxybenzoic acid. The purity of the starting phenoxybenzoic acid was determined by high performance liquid phase chromatography (abbreviated to HPLC); this HPLC was performed under the following conditions: column 20 cm in length, 4 mm in diameter,
-packing of silica on which a stationary phase containing an amine group has been grafted (the chromatography takes place by a partition between the stationary phase and the eluant ---eluant: a mixture of 2,2,4-trimethylpentane, 2-propanol and acetic acid in constant volume proportions of 42/40/18 respectively -flow rate 2 cc/min.
The purity of the reaction product was also determined by HPLC under similar conditions except for varying the proportions of the components of the eluant mixture between the outset and the end of the chromatography, from a ratio of 35/50/5 to 56/20/24 (elution gradient).
The accuracy of these chromatographic methods was checked by the use of standards corresponding to the samples of each of the impurities mentioned, taken separately.
The percentages shown below are percentages by weight. The "technical-grade" acid employed contains: 80.9% of 5-[2'-chloro-4'-(trifluoromethyl)phenoxy]-2-nitrobenzoic acid of the formula (V), -8.2% of 3-[2 '-chloro-4'-(trifl uoromethyl)phenoxy]-2-nitrobenzoic acid, 3.3% of 5-E2 '-chloro-4'-(trif luoromethyl)phenoxyl-4-nitrobenzoic acid, ess than 1 % of 5-[2 '-chloro-5'-(trifluoromethyl)phenoxy]-2-nitrobenzoic acid, and -less than 1 % of 3-t2'-chloro-4'-(trifluoromethyl)phenoxy] benzoic acid.
Technical-grade acid (38 g) of the composition specified above is suspended in a mixture of 1,2-dichloroethane (100 cc), thionyl chloride (10.3 cc; 0.109 mol) and dimethylformamide (1 cc). The reaction mixture is heated gradually with stirring to the boil under reflux. Refluxing is continued for 1 hour after gas evolution has ended, and the material is then concentrated to dryness. The residue (40 g) is dissolved in toluene (75 cc), after which methanesulphonamide (10 g; 0.105 mol) and P(O)CI3 (25 cc) are added. The reaction mixture is then heated to the boil under reflux for 3 hours with stirring. After cooling, the precipitate formed is filtered off and then washed with toluene.
A white solid consisting of 5-[2'-chloro-4'-(trifluoromethyl)phenoxy]-2-nitro-N-methanesulpho- nyl benzamide (28 g) of the formula (Vl), m.p. 200'C, is thus obtained. The structure of this product is confirmed by infrared and by NMR. Its purity, as determined by HPLC, is 90%.
Claims (27)
1. A process for the preparation of a compound of the general formula:
in which:
A is hydrogen; fluorine; chlorine; bromine; iodine; a nitro group; -N = NCF3; H2PO3 and its alkyl esters wherein the alkyl group contains from 1 to 4 carbon atoms; NH2; NHOH; N +2; a carboxy group or one of its functional derivatives; a monoalkylamino or dialkylamino group; an
NH-CO-R1 group in which R' is an alkyl or alkoxy or monoalkylamino or dialkylamino group; an alkyl group; trialkylammonium; NHSO2R2 in which R2 is an alkyl group or a phenyl group;
NHCONHSO2R2, in which R2 is as hereinbefore defined; alkylthio; alkylsulphinyl; alkylsulphonyl; dialkylsulphonium; cyanosulphonyl, hydroxy; alkanoyloxy; alkoxy, alkoxy substituted by an alkoxycarbonyl group; SH; nitroso; -SCN; azide;CF3;
or acyl;
B is a hydrogen, fluorine, chlorine, bromine or iodine atom, or an alkyl, alkoxy, alkylsulphinyl, alkylsulphonyl, CF3, NO2, CN, NH2, NHCOR1 wherein Rl is as hereinbefore defined or CONY, group;
C is a hydrogen or halogen atom or an alkyl or dialkylamino group;
D is a fluorine, chlorine, bromine or iodine atom or a CF3, alkylthio, alkylsulphinyl, alkylsulphonyl, haloalkyl, sulphamoyl, formyl, alkylcarbonyl, CN or dimethylamino group;
E is hydrogen or a haloalkyl, alkoxy, alkylsulphinyl, alkylsulphonyl, CN, CF3, NH2. CONH2, or
NH-CO-R1 group, wherein R1 is as hereinbefore defined;
W is a trivalent nitrogen atom or a -C(G) = group in which
G has one of the meanings given for B;;
R3 is a phenyl, pyridyl or thienyl group optionally substituted by one or more halogen atoms, alkyl groups or nitro groups; or an alkenyl or alkynyl radical having 2 to 4 carbon atoms or an alkyl radical containing 1 to 4 carbon atoms optionally substituted by one or more fluorine, chlorine, bromine or iodine atoms, or by one or more of the following substituents: carboxy, alkoxycarbonyl containing from 2 to 5 carbon atoms, alkylcarbonyl containing from 2 to 5 carbon atoms, monoalkylcarbamoyl or dialkylcarbamoyl in which the alkyl groups contain from 1 to 4 carbon atoms, alkylthio, alkylsulphinyl, alkylsulphonyl, each having from 1 to 4 carbon atoms, alkylcarbonyloxy containing from 2 to 5 carbon atoms, alkylcarbonylamino containing from 2 to 5 carbon atoms, or cyano, which comprises reacting an acid halide of the general formula:
with a sulphonamide of the general formula:
R3-SO-2-NH2 (111) in which A, B, C, D, E and W are as hereinbefore defined, and X is chlorine, bromine or iodine, in the liquid phase in the presence of a halogenating agent and at a temperature such that the hydrogen halide formed during the reaction is removed progressively from the reaction medium in a gaseous form as it is formed.
2. A process according to claim 1 wherein R3 represents CF3.
3. A process according to claim 1 or 2 in which A is NO2 or a hydrogen or chlorine atom, B is a halogen atom, C and E are hydrogen atoms, D is a trifluoromethyl group, and W is -CH =
4. A process according to claim 1, 2 or 3, in which B is a chlorine atom and R3 is an alkyl group.
5. A process according to any one of claims 1 to 4 in which R3 is an alkyl group containing from 1 to 4 carbon atoms.
6. A process according to any one of claims 1 to 4 in which R3 is CH2.
7. A process according to any one of claims 1 to 6, wherein X in the compound of general formula (II) is a chlorine atom.
8. A process according to any one of claims 1 to 7, in which the starting material comprises, in addition to the acid halide of general formula (II), up to 30% by weight of impurities.
9. A process according to any one of claims 1 to 7 in which the starting material comprises, in addition to the acid halide of general formula (II), up to 20% by weight of impurities.
10. A process according to any one of claims 1 to 9, wherein the starting material comprises, in addition to the acid halide of general formula (II), impurities which are mainly compounds containing a group of the formula: which carries one or more substituents.
11. A process according to claim 10, in which the starting material comprises, in addition to the acid halide of general formula (II), impurities which are mainly compounds containing a group of the formula:
which carries one or more substituents.
1 2. A process according to any one of claims 1 to 11, in which the halogenating agent is P(O)Cl3, PAL3, P(O)Br3, or PBr3.
1 3. A process according to any one of claims 1 to 11, in which the halogenating agent is P(O)Cl3.
1 4. A process according to any one of claims 1 to 13, which is carried out in the absence of an acid acceptor.
1 5. A process according to any one of claims 1 to 14, in which the molar ratio of the sulphonamide of general formula (III) depicted in claim 1 relative to the acid halide of general formula (II) depicted in claim 1 is between 0.8 and 1.2.
1 6. A process according to any one of claims 1 to 14, in which the molar ratio of the sulphonamide of general formula (III) depicted in claim 1 relative to the acid halide of general formula (II) depicted in claim 1 is between 0.9 and 1.1.
1 7. A process according to one of claims 1 to 1 6 in which the molar ratio of the halogenating agent relative to the acid halide of general formula (II) depicted in claim 1 is between 0.1 and 20.
1 8. A process according to any one of claims 1 to 1 6 in which the molar ratio of the halogenating agent relative to the acid halide of general formula (II) depicted in claim 1 is between 0.1 and 5.
1 9. A process according to any one of claims 1 to 18, which is carried out in the presence of an inert solvent.
20. A process according to claim 19, in which the solvent is a liquid aliphatic or aromatic, chlorinated or non-chlorinated hydrocarbon, or a nitrile.
21. A process according to any one of claims 1 to 20, in which the reaction temperature is below the decomposition temperature of the compounds of general formulae (III), (Il) and (I) and, if appropriate, less than or equal to the boiling point of the solvent used.
22. A process according to claim 21, in which the reaction temperature is between 70 and 180"C.
23. A process according to claim 21 in which the reaction is carried out in the absence of a solvent and the reaction temperature is between 80 and 1 20 C.
24. A process according to claim 21 in which the reaction is carried out in the presence of a solvent and the reaction temperature is between 80 and 1 50 C.
25. A process according to claim 1 substantially as hereinbefore described with special reference to Examples 1 to 5.
26. A compound of general formula (I) depicted in claim 1, wherein A, B, C, D, E, Wand R3 are as defined in claim 1, whenever prepared by a process claimed in any one of claims 1 to 25.
27. 5-(2 '-chloro-4'-(trifluoromethyl)-phenoxy]-2-nitro-N-methanesulphonyl benzamide whenever prepared by a process claimed in any one of claims 1 to 25.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8308338A FR2546165B1 (en) | 1983-05-17 | 1983-05-17 | PROCESS FOR THE PREPARATION OF SULFONAMIDE GROUP PHENOXYBENZOIC ACIDS |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8412495D0 GB8412495D0 (en) | 1984-06-20 |
| GB2140417A true GB2140417A (en) | 1984-11-28 |
| GB2140417B GB2140417B (en) | 1986-12-17 |
Family
ID=9289009
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08412495A Expired GB2140417B (en) | 1983-05-17 | 1984-05-16 | A process for the preparation of n-aryloxybenzoyl sulphonamides |
Country Status (6)
| Country | Link |
|---|---|
| BR (1) | BR8402323A (en) |
| CA (1) | CA1230593A (en) |
| FR (1) | FR2546165B1 (en) |
| GB (1) | GB2140417B (en) |
| HU (1) | HU194539B (en) |
| IL (1) | IL71637A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991004964A1 (en) * | 1989-09-29 | 1991-04-18 | Uniroyal Chemical Company, Inc. | Herbicidal sulfonamide derivatives |
| WO2001046130A1 (en) * | 1999-12-22 | 2001-06-28 | Syngenta Limited | Process for the preparation of diphenyl ether compounds |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0003416B1 (en) * | 1978-01-19 | 1981-08-26 | Imperial Chemical Industries Plc | Diphenyl ether compounds useful as herbicides; methods of using them, processes for preparing them, and herbicidal compositions containing them |
-
1983
- 1983-05-17 FR FR8308338A patent/FR2546165B1/en not_active Expired
-
1984
- 1984-04-25 IL IL71637A patent/IL71637A/en unknown
- 1984-05-15 CA CA000454361A patent/CA1230593A/en not_active Expired
- 1984-05-16 HU HU841891A patent/HU194539B/en not_active IP Right Cessation
- 1984-05-16 BR BR8402323A patent/BR8402323A/en unknown
- 1984-05-16 GB GB08412495A patent/GB2140417B/en not_active Expired
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991004964A1 (en) * | 1989-09-29 | 1991-04-18 | Uniroyal Chemical Company, Inc. | Herbicidal sulfonamide derivatives |
| WO2001046130A1 (en) * | 1999-12-22 | 2001-06-28 | Syngenta Limited | Process for the preparation of diphenyl ether compounds |
| US6790991B2 (en) | 1999-12-22 | 2004-09-14 | Syngenta Limited | Process for the preparation of diphenyl ether compounds |
| KR100733515B1 (en) | 1999-12-22 | 2007-06-28 | 신젠타 리미티드 | Process for preparing diphenyl ether compound |
Also Published As
| Publication number | Publication date |
|---|---|
| HUT34155A (en) | 1985-02-28 |
| CA1230593A (en) | 1987-12-22 |
| IL71637A0 (en) | 1984-07-31 |
| BR8402323A (en) | 1984-12-26 |
| GB2140417B (en) | 1986-12-17 |
| GB8412495D0 (en) | 1984-06-20 |
| HU194539B (en) | 1988-02-29 |
| IL71637A (en) | 1987-08-31 |
| FR2546165B1 (en) | 1985-12-06 |
| FR2546165A1 (en) | 1984-11-23 |
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