EP0000852A1 - Treatment of herbicid containing cultures with derivatives of dichloroacetamide or of thrichloroacetamide, novel derivatives of dichloroacetamide or trichloroacetamide and process for their preparation - Google Patents
Treatment of herbicid containing cultures with derivatives of dichloroacetamide or of thrichloroacetamide, novel derivatives of dichloroacetamide or trichloroacetamide and process for their preparation Download PDFInfo
- Publication number
- EP0000852A1 EP0000852A1 EP7878400063A EP78400063A EP0000852A1 EP 0000852 A1 EP0000852 A1 EP 0000852A1 EP 7878400063 A EP7878400063 A EP 7878400063A EP 78400063 A EP78400063 A EP 78400063A EP 0000852 A1 EP0000852 A1 EP 0000852A1
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- EP
- European Patent Office
- Prior art keywords
- formula
- group
- compounds
- chlorine
- ethyl
- 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.)
- Granted
Links
- WCGGWVOVFQNRRS-UHFFFAOYSA-N dichloroacetamide Chemical class NC(=O)C(Cl)Cl WCGGWVOVFQNRRS-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 20
- UPQQXPKAYZYUKO-UHFFFAOYSA-N 2,2,2-trichloroacetamide Chemical compound OC(=N)C(Cl)(Cl)Cl UPQQXPKAYZYUKO-UHFFFAOYSA-N 0.000 title abstract description 12
- 239000004009 herbicide Substances 0.000 claims abstract description 57
- 239000000729 antidote Substances 0.000 claims abstract description 45
- 230000002363 herbicidal effect Effects 0.000 claims abstract description 39
- 229940075522 antidotes Drugs 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 74
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 58
- -1 arylhaloalkyl Chemical group 0.000 claims description 28
- 229910052801 chlorine Inorganic materials 0.000 claims description 20
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 18
- 239000000460 chlorine Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- 125000001153 fluoro group Chemical group F* 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 229910052731 fluorine Inorganic materials 0.000 claims description 12
- 125000001188 haloalkyl group Chemical group 0.000 claims description 12
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 11
- 150000001408 amides Chemical class 0.000 claims description 10
- 125000003342 alkenyl group Chemical group 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- 125000005347 halocycloalkyl group Chemical group 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 125000004994 halo alkoxy alkyl group Chemical group 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 5
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 125000003277 amino group Chemical group 0.000 claims description 5
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 5
- 125000004772 dichloromethyl group Chemical group [H]C(Cl)(Cl)* 0.000 claims description 5
- 125000000262 haloalkenyl group Chemical group 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 4
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical group 0.000 claims description 3
- 239000012442 inert solvent Substances 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 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 claims description 2
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- 230000000295 complement effect Effects 0.000 claims 2
- 125000004201 2,4-dichlorophenyl group Chemical group [H]C1=C([H])C(*)=C(Cl)C([H])=C1Cl 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 230000010933 acylation Effects 0.000 claims 1
- 238000005917 acylation reaction Methods 0.000 claims 1
- 150000001768 cations Chemical class 0.000 claims 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- 150000007529 inorganic bases Chemical class 0.000 claims 1
- 241000196324 Embryophyta Species 0.000 abstract description 19
- 231100000674 Phytotoxicity Toxicity 0.000 abstract description 7
- 239000003815 herbicide antidote Substances 0.000 abstract description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 42
- 239000000047 product Substances 0.000 description 21
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 21
- 238000002844 melting Methods 0.000 description 17
- 230000008018 melting Effects 0.000 description 17
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 238000001914 filtration Methods 0.000 description 11
- 239000002689 soil Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- RBGDLYUEXLWQBZ-UHFFFAOYSA-N 2-chlorobenzamide Chemical compound NC(=O)C1=CC=CC=C1Cl RBGDLYUEXLWQBZ-UHFFFAOYSA-N 0.000 description 8
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 7
- 240000008042 Zea mays Species 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- GUVLYNGULCJVDO-UHFFFAOYSA-N EPTC Chemical compound CCCN(CCC)C(=O)SCC GUVLYNGULCJVDO-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- 238000005292 vacuum distillation Methods 0.000 description 5
- ONIKNECPXCLUHT-UHFFFAOYSA-N 2-chlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1Cl ONIKNECPXCLUHT-UHFFFAOYSA-N 0.000 description 4
- 235000019270 ammonium chloride Nutrition 0.000 description 4
- 235000013877 carbamide Nutrition 0.000 description 4
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- 125000004189 3,4-dichlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(Cl)C([H])=C1* 0.000 description 3
- 241000209219 Hordeum Species 0.000 description 3
- 235000007340 Hordeum vulgare Nutrition 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- FBCCMZVIWNDFMO-UHFFFAOYSA-N dichloroacetyl chloride Chemical compound ClC(Cl)C(Cl)=O FBCCMZVIWNDFMO-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 3
- NWQWQKUXRJYXFH-UHFFFAOYSA-N 2,2-Dichloroacetaldehyde Chemical compound ClC(Cl)C=O NWQWQKUXRJYXFH-UHFFFAOYSA-N 0.000 description 2
- BMTAFVWTTFSTOG-UHFFFAOYSA-N Butylate Chemical compound CCSC(=O)N(CC(C)C)CC(C)C BMTAFVWTTFSTOG-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- QTSULTYGMHMUPB-UHFFFAOYSA-N ClC(C(=O)NCC(Cl)(Cl)Cl)Cl Chemical compound ClC(C(=O)NCC(Cl)(Cl)Cl)Cl QTSULTYGMHMUPB-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- XCSGPAVHZFQHGE-UHFFFAOYSA-N alachlor Chemical compound CCC1=CC=CC(CC)=C1N(COC)C(=O)CCl XCSGPAVHZFQHGE-UHFFFAOYSA-N 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 235000005822 corn Nutrition 0.000 description 2
- 150000004292 cyclic ethers Chemical class 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229940047889 isobutyramide Drugs 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- MFOUDYKPLGXPGO-UHFFFAOYSA-N propachlor Chemical compound ClCC(=O)N(C(C)C)C1=CC=CC=C1 MFOUDYKPLGXPGO-UHFFFAOYSA-N 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 2
- JVTSHOJDBRTPHD-UHFFFAOYSA-N 2,2,2-trifluoroacetaldehyde Chemical compound FC(F)(F)C=O JVTSHOJDBRTPHD-UHFFFAOYSA-N 0.000 description 1
- VONWPEXRCLHKRJ-UHFFFAOYSA-N 2-chloro-n-phenylacetamide Chemical class ClCC(=O)NC1=CC=CC=C1 VONWPEXRCLHKRJ-UHFFFAOYSA-N 0.000 description 1
- DGMOBVGABMBZSB-UHFFFAOYSA-N 2-methylpropanoyl chloride Chemical compound CC(C)C(Cl)=O DGMOBVGABMBZSB-UHFFFAOYSA-N 0.000 description 1
- GUCPYIYFQVTFSI-UHFFFAOYSA-N 4-methoxybenzamide Chemical compound COC1=CC=C(C(N)=O)C=C1 GUCPYIYFQVTFSI-UHFFFAOYSA-N 0.000 description 1
- XKJMBINCVNINCA-UHFFFAOYSA-N Alfalone Chemical compound CON(C)C(=O)NC1=CC=C(Cl)C(Cl)=C1 XKJMBINCVNINCA-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 0 C*(C)*[N+](C)[O-] Chemical compound C*(C)*[N+](C)[O-] 0.000 description 1
- DFCAFRGABIXSDS-UHFFFAOYSA-N Cycloate Chemical compound CCSC(=O)N(CC)C1CCCCC1 DFCAFRGABIXSDS-UHFFFAOYSA-N 0.000 description 1
- 241001057636 Dracaena deremensis Species 0.000 description 1
- WARIWGPBHKPYON-UHFFFAOYSA-N Ethiolate Chemical compound CCSC(=O)N(CC)CC WARIWGPBHKPYON-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000005573 Linuron Substances 0.000 description 1
- BYUKRKALWSMYBW-UHFFFAOYSA-N O.[F] Chemical compound O.[F] BYUKRKALWSMYBW-UHFFFAOYSA-N 0.000 description 1
- 241000209504 Poaceae Species 0.000 description 1
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 229940095054 ammoniac Drugs 0.000 description 1
- MXMOTZIXVICDSD-UHFFFAOYSA-N anisoyl chloride Chemical compound COC1=CC=C(C(Cl)=O)C=C1 MXMOTZIXVICDSD-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- MXWJVTOOROXGIU-UHFFFAOYSA-N atrazine Chemical compound CCNC1=NC(Cl)=NC(NC(C)C)=N1 MXWJVTOOROXGIU-UHFFFAOYSA-N 0.000 description 1
- MCOQHIWZJUDQIC-UHFFFAOYSA-N barban Chemical compound ClCC#CCOC(=O)NC1=CC=CC(Cl)=C1 MCOQHIWZJUDQIC-UHFFFAOYSA-N 0.000 description 1
- SLUNEGLMXGHOLY-UHFFFAOYSA-N benzene;hexane Chemical compound CCCCCC.C1=CC=CC=C1 SLUNEGLMXGHOLY-UHFFFAOYSA-N 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- CWJSHJJYOPWUGX-UHFFFAOYSA-N chlorpropham Chemical compound CC(C)OC(=O)NC1=CC=CC(Cl)=C1 CWJSHJJYOPWUGX-UHFFFAOYSA-N 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 125000000031 ethylamino group Chemical group [H]C([H])([H])C([H])([H])N([H])[*] 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- GTVRLHPVICIJFQ-UHFFFAOYSA-N hexane;tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl.CCCCCC GTVRLHPVICIJFQ-UHFFFAOYSA-N 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 235000009973 maize Nutrition 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- DEDOPGXGGQYYMW-UHFFFAOYSA-N molinate Chemical compound CCSC(=O)N1CCCCCC1 DEDOPGXGGQYYMW-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 231100000208 phytotoxic Toxicity 0.000 description 1
- 230000000885 phytotoxic effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- VXPLXMJHHKHSOA-UHFFFAOYSA-N propham Chemical compound CC(C)OC(=O)NC1=CC=CC=C1 VXPLXMJHHKHSOA-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- PVFOMCVHYWHZJE-UHFFFAOYSA-N trichloroacetyl chloride Chemical compound ClC(=O)C(Cl)(Cl)Cl PVFOMCVHYWHZJE-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/32—Ingredients for reducing the noxious effect of the active substances to organisms other than pests, e.g. toxicity reducing compositions, self-destructing compositions
Definitions
- the subject of the present invention is new derivatives of dichloroacetamide and trichloroacetamide, their methods of preparation and their application as herbicide antidotes.
- herbicide antidote products which have the property of giving herbicides increased selectivity or new selectivities, without harming their herbicidal quality.
- the antidote makes disappear completely or at least in large part, the phytotoxicity of the herbicide with respect to the cultivated plant without reducing its phytotoxicity with regard to undesirable plants.
- herbicide antidote products have for example been described in French patents Nos. 2,133,793, 2,212,336, 2,215,170, 2,228,065, 2,309,546 and 2,310,348 and in US'Nos patents 3,867,444 ; 3,923,494, 3,931,313 and 3,959,304.
- the present invention aims to obtain chemically new and active compounds also as antidotes to herbicides.
- R 1 represents a dichloromethyl or trichloromethyl group
- X 1 represents a chlorine or fluorine atom
- X 2 represents a chlorine or fluorine atom
- X 3 represents a hydrogen, chlorine or fluorine atom
- R 2 represents an amino group HH 2 or a group in which R 3 is a hydrogen atom or an alkyl, haloalkyl, alkenyl, haloalkenyl, arylalkyl, arylhaloalkyl, cycloalkyl, halocycloalkyl, alkoxyalkyl, haloalkoxyalkyl or aryl group, the latter optionally being substituted by one or two halogen atoms or by an alkyl, alkoxy, nitro or haloalkyl group.
- the alkyl, alkenyl, alkoxy chains of the alkyl, haloalkyl, alkenyl, haloalkenyl, arylalkyl, arylhaloalkyl, alkoxyalkyl and haloalkoxyalkyl groups preferably have 1 to 5 carbon atoms
- the cycloalkyl and halocycloalkyl groups preferably have 3 to 6 carbon atoms
- aryl and aryl preferably denote phenyl and phenyl respectively and the halogen substituent of the aryl group is preferably a chlorine atom.
- the present invention relates to all of the compounds of formula (I), it relates more particularly to those of these compounds for which R 2 is NH 2 or a group wherein R ' 3 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, a haloalkyl group having 1 to 5 carbon atoms and 1 to 7 d atoms 'halogen, or a phenyl group substituted by one or two chlorine atoms.
- R ' 3 is a haloalkyl group, it is preferably a group wherein Y 1 is a chlorine or fluorine atom, Y 2 is a chlorine or fluorine atom and Y 3 is a hydrogen, chlorine or fluorine atom.
- the reactions (1), (2), (3), (4) are preferably carried out in an inert solvent such as for example a linear or cyclic ether, an aliphatic or aromatic hydrocarbon or a chlorinated derivative of an aliphatic or aromatic hydrocarbon , at a temperature between -30 ° C and + 60 ° C and preferably between - 15 ° C and + 30 ° C.
- the hydrochloric acid formed in the reaction is neutralized, as it is formed, by a mineral base such as for example an alkali or alkaline earth metal hydroxide or by a tertiary amine such as for example triethylamine or pyridine.
- the product of formula (I) formed is isolated in the brot state by elimination of the solvent by distillation. It can be purified, for example by recrystallization, or used as it is.
- the compounds of formula (I) for which R 2 is an NH 2 group, which are identical to the compounds of formula (II), and the compounds of formula (III) can be prepared by the action of ammonia on the chlorinated derivatives of formulas (IV) and (V).
- the reaction is carried out in the same solvents as those used for reactions (1) to (4) and preferably in a cyclic ether such as, for example, tetrahydrofuran.
- the chlorinated derivative of formula (IV) or (V) is introduced into the solvent saturated with am oniac, at a temperature of between -30 ° C. and + 30 ° C.
- the ammonium chloride formed is removed by filtration and the compound of formula (II) or (III) is isolated in the raw state by elimination of the solvent. It can be purified by recrystallization or used as such, in particular for carrying out reactions (1) or (2).
- the compounds of formula (IV) and (V) can be prepared by the action of thionyl chlorur on the hydroxylated compounds of formulas: in which R 1 , R 3 , X 1 , X 2 , X 3 have the same meanings as in formula (I).
- the reaction can be carried out, in the presence or not of a solvent, with an excess of thionyl chloride, at a temperature between 50 ° C. and 80 ° C.
- the solvent used can be identical to those used to carry out reactions (1) to (4). In the case where one operates without solvent, and also when one operates with certain solvents such as CCl 4 or hexane, the compound of formula (IV) or (V) precipitates and can be isolated by filtration.
- the compound of formula (IV) or (V) does not precipitate. It is then possible either to isolate the product by evaporating the solvent under vacuum, or to directly use the medium obtained at the end of the reaction for the continuation of the process leading to the compounds (I), without isolating the products (IV) or (V).
- the hydroxylated compounds of formulas (VI) or (VII) can be prepared by the action of an amide of formula on a halogenated aldehyde of formula following the procedures described by Joseph P.LAROCCA, John. M. LEONARD, Warren. E. WEAVER [Journal of Organic Chemistry 16, 47-50, (1951)] and by A. BOUCHERLE, G. CARRAZ, J. VIGIER [Bull. Trav. Soc. Pharm. Lyon 10 (1), 3-10, (1966)].
- the compounds of formula (I) can be used, as herbicide antidotes, for the treatment of crops. They protect cultivated plants against damage caused by herbicides, and this at doses of herbicides effective against undesirable plants.
- the compounds of formula (I) can in particular be used in combination with herbicides belonging to the families of chloroacetanilides, ureas, triazines, carbamates, uracils and more especially thiolcarbamates.
- herbicides belonging to the families of chloroacetanilides, ureas, triazines, carbamates, uracils and more especially thiolcarbamates.
- EPTC N-dipropyl thiolcarbamate
- butylate ethyl N, N-diisobutyl thiolcarbamate (butylate)
- the compounds of formula (I) can be incorporated, jointly with the herbicide or separately, in compositions which contain, in addition to the active material (that is to say the antidote compound and optionally the herbicide ), inert additives usually used in agriculture to facilitate the conservation, implementation and penetration into plants of active products, such as mineral fillers (talc, silica, kieselguhr, diatomaceous earth, clay, etc.), diluents various organic (mineral oils, organic solvents), surfactants, antioxidants and stabilizers.
- active material that is to say the antidote compound and optionally the herbicide
- inert additives usually used in agriculture to facilitate the conservation, implementation and penetration into plants of active products, such as mineral fillers (talc, silica, kieselguhr, diatomaceous earth, clay, etc.), diluents various organic (mineral oils, organic solvents), surfactants, antioxidants and stabilizers.
- Such com p OSi tions can be in the form of
- the content of antidote compound can vary from 10% to 90% by weight.
- the content of antidote compound can vary from 0.09% to 50% by weight, that in herbicide from 1% to 90% by weight, the ratio by weight of antidote products being between 0.001 and 10.
- the antidote compounds according to the invention can be applied to the soil at the same time as the herbicide, pre-emergence or post-emergence of the crop.
- the dose of antidote product provided can vary from 100 g to 5000 g per hectare.
- compositions containing the antidote product and the herbicide simultaneously such as those mentioned above.
- the antidote compounds according to the invention can also be applied to the soil at a time different from that of the treatment with the herbicide, pre-emergence or post-emergence of the crop, the dose of antidote product provided being the same as above. They can in particular be applied to soils containing herbicide residues in order to protect crops against the residual activity of these residues.
- the antidote compounds according to the invention can also be applied to the seed of the crop to be protected, said seed then being sown in soil already treated with the herbicide or which will be treated with the herbicide.
- the dose of antidote provided can vary from 10 g to 500 g per quintal of seed.
- a brown solid is obtained which is recrystallized from a 50/50 carbon tetrachloride-hexane mixture. 15.3 g are thus obtained (ie a yield of 40.4%) of N - [(2,2-dichloroacetamido-1) ethyl] o-chlorobenzamide, melting point 179-180 ° C.
- N - [(2,2-dichloro-1 amino-1) ethyl] dichloroacetamide used as starting material can be prepared as indicated in Example 14.
- N - [(2,2,2-amino-trichloro-1) ethyl] formamide By replacing the N - [(2,2,2-amino-trichloro-1) ethyl] formamide by the N - [(2,2,2-amino-trichloro-1) ethyl] acetamide, N - [(2,2-trichloro-2,2,2, dichloroacetamido-1) ethyl] acetamide is obtained, with a yield of 61.5%, of melting point 239-240 ° C.
- the N - [(2,2,2-trichlora-1 amino-1) ethyl] acetamide used as starting material is prepared according to the method used to prepare the N - [(trichlbro-2,2,2 amino-1) ethyl] trichloroacetamide, but by replacing the 100 g of N - [(tetrachloro-1,2,2,2) ethyl] trichloroacetamide with 320 g of N - [(tetrachloro-1,2,2,2) ethyl] acetamide (1, 42 mole). The addition to THF saturated with ammonia is carried out in 1 h 45 '.
- N - [(2,2-dichloro-1-hydroxy) ethyl] dichloroacetamide (0.87 mole) prepared as indicated above and 300 g of thionyl chloride are introduced into a 500 ml reactor, with stirring. (2.5 moles). We bring to reflux for 2 h 3D. 300 ml of hexane are added to facilitate precipitation during cooling. After filtration, 175 g of N - [(2,2,2-trichloro) ethyl] dichloroacetamide are obtained (ie a yield of 77.5 in the form of a white solid with melting point 77-78 ° C.
- a soil consisting of two parts by weight of clay and three parts by weight of sand, is spread in plastic trays of dimensions 18 x 12 x 5 cm. On this soil we sow, in 4 furrows of 0.5 cm deep, 10 corn seeds, variety "Sandrina”, and 10 barley seeds, variety "Rika”.
- the seedlings thus produced are separated into 3 batches, each batch containing 5 trays.
- On the 1st batch spread a layer, 2 cm thick, of soil that has not undergone any treatment.
- On the 2nd batch spread a layer, 2 cm thick, of soil in which a naturally phytotoxic herbicide has been incorporated by careful mixing. corn but at the dose where it is applied.
- the herbicide and the antidote are formulated in the form of aqueous suspensions.
- the quantities of herbicide applied correspond to doses of herbicides of 5 kg and 10 kg / ha.
- the amounts of antidote product provided correspond to doses equal to one tenth of the doses of the herbicide, ie 0.5 and 1 kg g / ha.
- the herbicide used is EPTC or ethyl N, N-dipropyl thiolcarbamate.
- the antidote products tested are the compounds of Examples 1 to 15.
- the batches of trays, once treated, are placed in a greenhouse maintained at 20 ° C and at a humidity rate of 70%. 12 and 20 days after treatment (D + 12; D + 20), the batches are examined and the herbicidal efficacy of the "antidote + .herbicide" combination is determined on the one hand, and the efficacy on the other hand antidote for the compound according to the invention tested.
- the antidote E efficacy is evaluated by measuring the average height of the maize plants in the three batches.
- A denotes the average size of the maize plants in the untreated control lots
- B the average size of the maize plants in the lots treated with the herbicide alone
- C the average size of the corn plants in the lots treated with l herbicide and antidote.
- Example 1 the product of Example 1 was tested according to the method described in the previous example, but by varying the dose of the antidote product relative to that of the associated herbicide (E P T C).
- the herbicide was applied at a dose of 5 kg / ha and the product of Example 1 at the doses 0 kg / ha (tests with herbicide alone), 0.312 kg / ha, 0.625 kg / ha, 1.250 kg / ha and 2,500 kg / ha.
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Abstract
La présente invention a pour objet de nouveaux dérivés de dichloroacétamide et trichloroacétamide, leurs procédés de préparation et leur application en tant qu'antidotes d'herbicides. Les herbicides existant actuellement peuvent être classés en deux catégories : les herbicides totaux, qui détruisent toutes le plantes, et les herbicides sélectifs. Ces derniers, qui sont les plus précieux en agriculture, permettent de détruire les mauvaises herbes présentes dans les cultures sans nuire à la plante cultivée et sont dits, pour cette raison, sélectifs de la plante cultivée. Malheureusement il arrive que cette sélectivité ne soit pas parfaite à la dose d'emploi et que les herbicides sélectifs présentent une certaine phytotoxicité vis-à-vis de la plante cultivée. Aussi utilise-t-on, en association avec les herbicides, des produits dits antidotes d'herbicides qui ont la propriété de conférer aux herbicides une sélectivité accrue ou des sélectivités nouvelles, sans nuire à leur qualité herbicide. Autrement dit l'antidote fait disparaitre totalement ou tout au moins en grande partie, la phytotoxicité de l'herbicide vis-à-vis de la plante cultivée sans réduire sa phytotoxicité vis-à-vis des plantes indésirables.The subject of the present invention is new derivatives of dichloroacetamide and trichloroacetamide, their methods of preparation and their application as antidotes for herbicides. Currently existing herbicides can be classified into two categories: total herbicides, which destroy all the plants, and selective herbicides. The latter, which are the most precious in agriculture, allow to destroy the weeds present in the crops without harming the cultivated plant and are said, for this reason, selective of the cultivated plant. Unfortunately it sometimes happens that this selectivity is not perfect at the dose of use and that the selective herbicides present a certain phytotoxicity with respect to the cultivated plant. So we use, in combination with herbicides, so-called herbicide antidote products which have the property of giving herbicides increased selectivity or new selectivities, without harming their herbicidal quality. In other words, the antidote makes disappear completely or at least in large part, the phytotoxicity of the herbicide with respect to the cultivated plant without reducing its phytotoxicity with regard to undesirable plants.
Description
Le présente invention a pour objet de nouveaux dérivés de dichloroacétamide et trichloroacétamide, leurs procédés de préparation et leur application en tant qu'antidotes d'herbicides.The subject of the present invention is new derivatives of dichloroacetamide and trichloroacetamide, their methods of preparation and their application as herbicide antidotes.
Les herbicides existant actuellement peuvent être classés en deux catégories : les herbicides totaux, qui détruisent toutes les plantes, et les herbicides sélectifs. Ces derniers, qui sont les plus précieux en agriculture, permettent de détruire les mauvaises herbes présentes dans les cultures sans nuire à la plante cultivée et sont dits, pour cette raison, sélectifs de la plante cultivée. Malheureusement il arrive que cette sélectivité ne soit pas parfaite à la dose. d'emploi et que les herbicides sélectifs présentent une certaine phytotoxicité vis-à-vis de la plante cultivée.Currently existing herbicides can be classified into two categories: total herbicides, which destroy all plants, and selective herbicides. The latter, which are the most precious in agriculture, allow to destroy the weeds present in the crops without harming the cultivated plant and are said, for this reason, selective of the cultivated plant. Unfortunately it sometimes happens that this selectivity is not perfect at the dose. of use and that the selective herbicides have a certain phytotoxicity with respect to the cultivated plant.
Aussi utilise-t-on, en association avec les herbicides, des produits dits antidotes d'herbicides qui ont la propriété de conférer aux herbicides une sélectivité accrue ou des sélectivités nouvelles, sans nuire à leur qualité herbicide. Autrement dit l'antidote fait disparaitre totalement ou tout au moins en grande partie, la phytotoxicité de l'herbicide vis-à-vis de la plante cultivée sans réduire sa phytotoxicité vis-à-vis des plantes indésirables.So we use, in combination with herbicides, so-called herbicide antidote products which have the property of giving herbicides increased selectivity or new selectivities, without harming their herbicidal quality. In other words, the antidote makes disappear completely or at least in large part, the phytotoxicity of the herbicide with respect to the cultivated plant without reducing its phytotoxicity with regard to undesirable plants.
De tels produits antidotes d'herbicides ont par exemple été décrits dans les brevets français Nos 2.133.793, 2.212.336, 2.215.170, 2.228.065, 2.309.546 et 2.310.348 et dans les brevets US'Nos 3.867.444; 3.923.494, 3.931.313 et 3.959.304.Such herbicide antidote products have for example been described in French patents Nos. 2,133,793, 2,212,336, 2,215,170, 2,228,065, 2,309,546 and 2,310,348 and in US'Nos patents 3,867,444 ; 3,923,494, 3,931,313 and 3,959,304.
La présente invention a pour but l'obtention de composés chimiquement nouveaux et actifs eux aussi comme antidotes d'herbicides.The present invention aims to obtain chemically new and active compounds also as antidotes to herbicides.
* Les composés selon l'invention peuvent être représentés par la formule générale :* The compounds according to the invention can be represented by the general formula:
Dans les définitions données ci-dessus pour R3, les chaînes alkyle, alkényle, alcoxy des groupes alkyle, haloalkyle, alkényle, haloalkényle, arylalkyle, arylhaloalkyle, alcoxyalkyle et haloalcoxyalkyle ont de préférence 1 à 5 atomés de carbone, les groupes cycloalkyle et halocycloalkyle ont de préférence 3 à 6 atomes de carbone, les groupes haloal- kyle, haloalkényle, arylhaloalkyle, halocycloalkyle, haloalcoxyalkyle pnt de préférence 1 à 7 atomes d'halogène pris parmi les atomes de chlore, brome ou fluor, aryl et aryle désignent de préférence respectivement phényl et phényle et le substituant halogène du groupe aryle est de préférence un atome de chlore.In the definitions given above for R 3 , the alkyl, alkenyl, alkoxy chains of the alkyl, haloalkyl, alkenyl, haloalkenyl, arylalkyl, arylhaloalkyl, alkoxyalkyl and haloalkoxyalkyl groups preferably have 1 to 5 carbon atoms, the cycloalkyl and halocycloalkyl groups preferably have 3 to 6 carbon atoms, haloalkyl, haloalkenyl, arylhaloalkyl, halocycloalkyl, haloal coxyalkyle p nt preferably 1 to 7 halogen atoms taken from the chlorine, bromine or fluorine atoms, aryl and aryl preferably denote phenyl and phenyl respectively and the halogen substituent of the aryl group is preferably a chlorine atom.
Bien que la présente invention concerne l'ensemble des composés de formule (I), elle a plus particulièrement pour objet ceux de ces composés pour lesquels R2 est NH2 ou un groupe
Les composée de formule (I) pour lesquels R2 est un groupe
- 1) action d'un chlorure d'acide de formule
- 2) action d'un chlorure d'acide de formule
- 1) action of an acid chloride of formula
- 2) action of an acid chloride of formula
. Dans les formules (II), (III), (IV), (V) ci-dessus ainsi que dans celles des chlorures d'acide et amides, X1, X2, X3, R1 et R3 ont les mêmes significations que dans la formule (I).. In formulas (II), (III), (IV), (V) above as well as in those of acid chlorides and amides, X 1 , X 2 , X 3 , R 1 and R 3 have the same meanings as in formula (I).
Les réactions (1), (2), (3), (4) sont effectuées de préférence dans un solvant inerte tel par exemple un éther linéaire ou cyclique, un hydrocarbure aliphatique ou aromatique ou un dérivé chloré d'un hydrocarbure aliphatique ou aromatique, à une température comprise entre -30°C et + 60°C et de préférence entre - 15°C et + 30°C. L'acide chlorhydrique formé dans la réaction est neutralisé, au fur et à mesure de sa formation, par une base minérale comme par exemple un hydroxyde de métal alcalin ou alcalino-terreux ou par une amine tertiaire comme par exemple la triéthylamine ou la pyridine. Après séparation par extraction à l'eau ou par fil- tration du chlorure de la base minérale ou du chlorhydrate de l'smine, le produit de formule (I) formé est isolé à l'état brot par élimination du solvant par distillation. Il peut être purifié, par exemple par recristallisation, ou utilisé tel quel.The reactions (1), (2), (3), (4) are preferably carried out in an inert solvent such as for example a linear or cyclic ether, an aliphatic or aromatic hydrocarbon or a chlorinated derivative of an aliphatic or aromatic hydrocarbon , at a temperature between -30 ° C and + 60 ° C and preferably between - 15 ° C and + 30 ° C. The hydrochloric acid formed in the reaction is neutralized, as it is formed, by a mineral base such as for example an alkali or alkaline earth metal hydroxide or by a tertiary amine such as for example triethylamine or pyridine. After separation by extraction with water or by filtration of the chloride of the mineral base or of the hydrochloride of the mine, the product of formula (I) formed is isolated in the brot state by elimination of the solvent by distillation. It can be purified, for example by recrystallization, or used as it is.
Les composés de formule (I) pour lesquels R2 est un groupe NH2, qui sont identiques aux composés de formule (II), et les composés de formule (III) peuvent être préparés par action de l'ammoniac sur les dérivés chlorés de formules (IV) et (V). La réaction est réalisée dans les mêmes solvants que ceux utilisés pour les réactions (1) à (4) et de préférence dans un éther cyclique come par exemple le tétrahydrofuranne. Le dérivé chloré de formule (IV) ou (V) est introduit dans le solvant saturé en am oniac, à une température comprise -entre -30°C et + 30°C. Le chorure d'ammonium formé est éliminé par filtration et le composé de formule (II) ou (III) est isolé à l'état brut par éimination du solvant. Il peut être purifié par recristallistion ou utilisé tel quel, en particulier pour effectuer le réactions (1) ou (2).The compounds of formula (I) for which R 2 is an NH 2 group, which are identical to the compounds of formula (II), and the compounds of formula (III) can be prepared by the action of ammonia on the chlorinated derivatives of formulas (IV) and (V). The reaction is carried out in the same solvents as those used for reactions (1) to (4) and preferably in a cyclic ether such as, for example, tetrahydrofuran. The chlorinated derivative of formula (IV) or (V) is introduced into the solvent saturated with am oniac, at a temperature of between -30 ° C. and + 30 ° C. The ammonium chloride formed is removed by filtration and the compound of formula (II) or (III) is isolated in the raw state by elimination of the solvent. It can be purified by recrystallization or used as such, in particular for carrying out reactions (1) or (2).
Les pomposés de formule (IV) et (V) peuvent être préparés par action du chlorur de thionyle sur les composés hydroxylés de formules :
Les composés hydroxylés de formules (VI) ou (VII) peuvent être préparés par action d'un amide de formule
Les composés de formule (III) pour lesquels R3 est autre qu'un atome d'hydrogène sont nouveaux et font partie en tant que tels de l'invention. Comme exemples de composés de formule (III) nouveaux on peut citer en particulier ceux pour lesquels on a simultanément X1 = X2 = X3 = Cl et R3 = monochlorométhyl, trichlorométhyl, pentachloro-1,2,3,3,3 propyl, trifluorométhyl, méthyl, o-chlorophényl, p-chlorophényl, p-méthylphényl, m-trifluorométhylphényl, dichloro-2,4 phényl ou dichloro-3,4 phényl.The compounds of formula (III) for which R 3 is other than a hydrogen atom are new and form part of the invention as such. As examples of new compounds of formula (III), mention may be made in particular of those for which there is simultaneously X 1 = X 2 = X 3 = Cl and R 3 = monochloromethyl, trichloromethyl, 1,2,3,3,3,3-pentachloro, propyl, trifluoromethyl, methyl, o-chlorophenyl, p-chlorophenyl, p-methylphenyl, m-trifluoromethylphenyl, 2,4-dichloro or 3,4-dichloro-phenyl .
Certains des composés de formules (IV), (V), (VI), (VII) sont aussi des produits nouveaux. Comme tels on peut citer en particulier les composés répondant à la formule :
Les composés de formule (I) peuvent être utilisés, en tant qu'antidotes d'herbicides, pour le traitement des cultures. Ils protègent les plantes cultivées contre les dommages occasionnés par les herbicides, et ce aux doses d'herbicides efficaces vis-à-vis des plantes indésirables.The compounds of formula (I) can be used, as herbicide antidotes, for the treatment of crops. They protect cultivated plants against damage caused by herbicides, and this at doses of herbicides effective against undesirable plants.
Les composés de formule (I) peuvent en particulier être employés en association avec les herbicides appartenant aux familles des chloroacétanilides, urées, triazines, carbamates, uraciles et plus spécialement des thiolcarbamates. Comme tels on peut citer par exemple le N,N-dipropyl thiolcarbamate d'éthyle (EPTC), le N,N-diisobutyl thiolcarbamate d'éthyle (butylate), le N,N-dipropyl thiolcarbamate de propyle, le N,N-diéthyl thiolcarbamate d'éthyle (éthiolate), le N,N-cy- clohexaméthylène thiolcarbamate d'éthyle (molinate), le N-éthyl N-cyclohexyl thiolcarbamate d'éthyle (cycloate), le N,N-diisopropyl thiolcarbamate de dichloro-2,3 propényle (dial- late), le N,N-diisopropyl thiolcarbamate d'éthyle, le N-(chloro-3 phényl) carbamate de chloro-4 butynyle-2 (barban), la (chloro-3 méthyl-4 phényl)-3 diméthyl-1,1 urée (chiobitruron), la (dichloro-3,4 phényl)-3 méthoxy-1 méthyl-1 urée (linuron), la (dichloro-3,4 phényl)-3 diméthyl-1,1 urée, la N-chloroacétyl N-isopropyl aniline (propachlor), la diéthyl-2,6 N-chloroacétyl N-méthoxyméthyl aniline (alachlor), la chloro-2 éthylamino-4 isopropylamino-6 triazina-1,3,5 (atrazine), la chloro-2 bis (éthylamino)-4,6 triazine-1,3,5 la chloro-2 cyclopropylamino-4 isopropylamino-6 triazine-1,3,5 et leurs combinaisons. Le rapport en poids produit antidote à employer herbicide peut varier beaucoup selon la nature de l'herbicide concerné. Ce rapport est en général compris entre 0,001 et 10, et le plus souvent entre 0,01 et 5.The compounds of formula (I) can in particular be used in combination with herbicides belonging to the families of chloroacetanilides, ureas, triazines, carbamates, uracils and more especially thiolcarbamates. As such there may be mentioned for example ethyl N, N-dipropyl thiolcarbamate (EPTC), ethyl N, N-diisobutyl thiolcarbamate (butylate), N, N, N-dipropyl thiolcarbamate propyl, N, N- ethyl diethyl thiolcarbamate (ethiolate), ethyl N, N-cyclohexamethylene thiolcarbamate (molinate), ethyl N-ethyl N-cyclohexyl thiolcarbamate (cycloate), dichloro- N, N-diisopropyl thiolcarbamate 2,3 propenyl (dialate), ethyl N, N-diisopropyl thiolcarbamate, chloro-4-butynyl-2 (barban) N- (3-chloro-phenyl) carbamate, (3-chloro-4-methyl-phenyl) -3 dimethyl-1,1 urea (chiobitruron), (3,4-dichloro phenyl) -3 methoxy-1 methyl-1 urea (linuron), (3,4-dichloro phenyl) -3 dimethyl-1,1 urea, N-chloroacetyl N-isopropyl aniline (propachlor), 2,6-diethyl N-chloroacetyl N-methoxymethyl aniline (alachlor), 2-chloro-4-ethylamino isopropylamino-6 triazina-1,3,5 (atrazine), chloro-2 bis (ethylamino) -4,6 triazine-1,3,5 chloro-2 cyclopropylamino-4 isopropylamino-6 triazine-1,3,5 and combinations thereof . The weight ratio of the antidote product to be used as a herbicide can vary greatly depending on the nature of the herbicide concerned. This ratio is generally between 0.001 and 10, and most often between 0.01 and 5.
Pour leur mise en oeuvre les composés de formule (I) peuvent être incorporés, conjointement avec l'herbicide ou séparément, dans des compositions qui contiennent, outre la matière active (c'est-à-dire le composé antidote et éventuellement l'herbicide), les additifs inertes habituellement utilisés en agriculture pour faciliter la conservation, la mise en oeuvre et la pénétration dans les plantes des produits actifs, tels que charges minérales (talc, silice, kieselguhr, terre de diatomées, argile etc..), diluants organiques divers (huiles minérales, solvants organiques), tensioactifs, antioxydants et stabilisants. De telles composi- tions peuvent se présente sous la forme de poudres mouillables, solutions émulsifiables dans l'eau, granulés ou toute autre forme en usage dans le domaine des herbicides. Dans les compositions contenant seulement un composé antidote selon l'invention et des additifs inertes, la teneur en compo- sé antidote peut varier de 10 % à 90 % en poids. Dans les compositions contenant un composé antidote selon l'invention, un herbicide et des additifs inertes, la teneur en composé antidote peut varier de 0,09 % à 50 % en poids, celle en herbicide de 1 % à 90 % en poids, le rapport en poids produits antidote étant compris entre 0,001 et 10. herbicideFor their use, the compounds of formula (I) can be incorporated, jointly with the herbicide or separately, in compositions which contain, in addition to the active material (that is to say the antidote compound and optionally the herbicide ), inert additives usually used in agriculture to facilitate the conservation, implementation and penetration into plants of active products, such as mineral fillers (talc, silica, kieselguhr, diatomaceous earth, clay, etc.), diluents various organic (mineral oils, organic solvents), surfactants, antioxidants and stabilizers. Such com p OSi tions can be in the form of wettable powders, emulsifiable solutions in water, granules or any other form in use in the field of herbicides. In the compositions containing only an antidote compound according to the invention and inert additives, the content of antidote compound can vary from 10% to 90% by weight. In the compositions containing an antidote compound according to the invention, a herbicide and inert additives, the content of antidote compound can vary from 0.09% to 50% by weight, that in herbicide from 1% to 90% by weight, the ratio by weight of antidote products being between 0.001 and 10. herbicide
Les composés antidotes selon l'invention peuvent être appliqués sur le sol en même temps que l'herbicide, en prélevée ou en post-levée de la culture. La dose en produit antidote apportée peut varier de 100 g à 5000 g par hectare. Pour une telle application il est avantageux d'utiliser des compositions contenant simultanément le produit antidote et l'herbicide, telles que celles citées précédemment.The antidote compounds according to the invention can be applied to the soil at the same time as the herbicide, pre-emergence or post-emergence of the crop. The dose of antidote product provided can vary from 100 g to 5000 g per hectare. For such an application, it is advantageous to use compositions containing the antidote product and the herbicide simultaneously, such as those mentioned above.
Les composés antidotes selon l'invention peuvent aussi être appliqués sur le sol à une époque différente de celle du traitement par l'herbicide, en pré-levée ou en post-levée de la culture, la dose en produit antidote apportée étant la même que ci-dessus. Ils peuvent en particulier être appliqués sur des sols contenant des résidus d'herbicide afin de protéger les cultures contre l'activité rémanente de ces résidus.The antidote compounds according to the invention can also be applied to the soil at a time different from that of the treatment with the herbicide, pre-emergence or post-emergence of the crop, the dose of antidote product provided being the same as above. They can in particular be applied to soils containing herbicide residues in order to protect crops against the residual activity of these residues.
Enfin les composés antidotes selon l'invention peuvent aus'si être appliqués sur la semence de la culture à protéger, ladite semence étant ensuite semée dans une terre déjà traitée avec l'herbicide ou qui sera traitée avec l'herbicide. Pour le traitement des semences la dose en produit antidote apportée peut varier de 10 g à 500 g par quintal de semence.Finally, the antidote compounds according to the invention can also be applied to the seed of the crop to be protected, said seed then being sown in soil already treated with the herbicide or which will be treated with the herbicide. For the treatment of seeds, the dose of antidote provided can vary from 10 g to 500 g per quintal of seed.
Les exemples suivants illustrent l'invention sans la limiter.The following examples illustrate the invention without limiting it.
On dissout 19,15 g (0,1 mole) de N-[trichloro-2,2,2 amino-1) ethyl] formamide dans 200 ml de tétrahydrofuranne (THF). On ajoute 10,1 g de triéthylamine (0,1 mole). En maintenant la température à 15°C, on ajoute sous agitation, en environ 30 minutes, 14,75 g de chlorure de dichloroacétyle (0,1 mole) dissous dans 100 ml de THF. On maintient ensuite 1/2 heure sous agitation en laissant revenir à la température ambiante. On filtre le précipité de chlorhydrate de triéthylamine. On élimine le THF par distillation sous vide. Au cours de la distillation, il se forme un produit cristallisé qui est séparé. Ce produit est recristallisé dans un mélange benzène-hexane 50-50. On obtient ainsi 24,5 g (soit un rendement de 81 %) de N-[trichloro-2,2,2 dichloroacétamido-1) éthyl]formamide, de point de fusion 141-142°C.19.15 g (0.1 mol) of N- [2,2,2-trichloro-1) ethyl] formamide are dissolved in 200 ml of tetrahydrofuran (THF). 10.1 g of triethylamine (0.1 mole) are added. Maintaining the temperature at 15 ° C., 14.75 g of dichloroacetyl chloride (0.1 mol) dissolved in 100 ml of THF are added with stirring over approximately 30 minutes. Then maintained for 1/2 hour with stirring, leaving to return to the ambient temperature. The precipitate of triethylamine hydrochloride is filtered. THF is removed by vacuum distillation. During distillation, a crystallized product is formed which is separated. This product is recrystallized from a benzene-hexane mixture 50-50. 24.5 g are thus obtained (ie a yield of 81%) of N- [2,2,2-trichloro-dichloroacetamido-1) ethyl] formamide, with a melting point of 141-142 ° C.
On dissout 10,2 g de dichloroacétamide (0,08 mole) dans 150 ml de chloroforme. On ajoute 10 g de triéthylamine (0,1 mole). En maintenant la température au voisinage de 0°C, on ajoute sous agitation, en environ 1 h, 23,5 g de N-[(tétrachloro-1,2,2,2) éthyl]dichloroacétamide (0,08 mole) dissous dans 150 ml de chloroforme. On laisse revenir à température ambiante sous agitation, puis on reprend par 1 litre d'eau. Après décantation, la phase organique est séparée et lavée deux fois avec 500 ml d'eau, puis séchée sur sulfate de magnésium. Le chloroforme est distillé sous vide et on obtient un solide qui est recristallisé dans l'hexane. On obtient ainsi 24,5 g de N-[(trichloro-2,2,2 dichloroacétemido-1) éthyl]dichloroecétemide (soit un rendement de 79,5 %), de point de fusion 249-250°C.10.2 g of dichloroacetamide (0.08 mole) are dissolved in 150 ml of chloroform. 10 g of triethylamine (0.1 mol) are added. Maintaining the temperature in the region of 0 ° C., 23.5 g of dissolved N - [(tetrachloro-1,2,2,2) ethyl] dichloroacetamide (0.08 mol) are added with stirring over approximately 1 hour. in 150 ml of chloroform. The mixture is allowed to return to ambient temperature with stirring, then it is taken up in 1 liter of water. After decantation, the organic phase is separated and washed twice with 500 ml of water, then dried over magnesium sulfate. The chloroform is distilled under vacuum and a solid is obtained which is recrystallized from hexane. 24.5 g of N - [(2,2,2-dichloroacetemido-1) ethyl] dichloroecetemide (ie a yield of 79.5%), with a melting point of 249 ° -250 ° C., are thus obtained.
En opérant comme dans l'exemple n° 3, mais en remplaçant les 10,2 g de dichloroacétamide par 6,96 g d'iso- butyramide (0,08 mole), on obtient 21 g (soit un rendement de 76,3 %) de N-[(trichloro-2,2,2 dichloroacétamido-1) éthyl]isobutyramide de point de fusion 264-265°C.By operating as in Example No. 3, but replacing the 10.2 g of dichloroacetamide with 6.96 g of isobutyramide (0.08 mole), 21 g are obtained (ie a yield of 76.3 %) of N - [(2,2,2-trichloro-dichloroacetamido-1) ethyl] isobutyramide, mp 264-265 ° C.
On opère comme dans l'exemple 1, en remplaçant les 19,15 g de N-[(trichloro-2,2,2 amino-1) éthyl] formamide par 24,7 g de N- [(trichloro-2,2,2 amino-1),éthyl] trichloroacétamide (0,08 mole). On obtient ainsi 21,8 g (soit un rendement de 65 %)de N-[(trichloro-2,2,2 dichloroacétamido-1) éthyl]trichloroacétamide de point de fusion 184-185°C.The procedure is as in Example 1, replacing the 19.15 g of N - [(2,2,2-trichloro-1 amino-1) ethyl] formamide with 24.7 g of N- [(2,2-trichloro) , 2 amino-1), ethyl] trichloroacetamide (0.08 mole). 21.8 g are thus obtained (ie a yield of 65%) of N - [(2,2,2-trichloro-dichloroacetamido-1) ethyl] trichloroacetamide with melting point 184-185 ° C.
Le N-[(trichlorc-2,2,2 amino-1) éthyl]trichloroacétamide utilisé comme produit de départ peut être préparé comme suit :
- On sature 300 ml de THF par de l'ammoniac gazeuxtet on maintient cette saturation pendant toute la durée de l'opération. En maintenant la température à 0°C, on ajoute sous agitation, en environ 1 h, 100 g de N-[(tétra- chloro-1,2,2,2) éthyl]trichloroacétamide (0,3 mole). Le précipité de chlorure d'ammonium qui s'est formé est séparé par filtration. Le THF est ensuite séparé par distillation sous vide. On obtient ainsi 59 g de N- [(trichloro-2,2,2 amino-1) éthyl]trichloroacétamide (soit un rendement de 62,7 %) sous la forme d'un solide blanc de point de fusion 132-133°C. EXEMPLE N° 7 - Préparation du composé:
- 300 ml of THF are saturated with gaseous ammonia and this saturation is maintained throughout the duration of the operation. Maintaining the temperature at 0 ° C., 100 g of N - [(tetra-chloro-1,2,2,2) ethyl] trichloroacetamide (0.3 mole) are added, with stirring, in approximately 1 hour. The precipitate of ammonium chloride which has formed is separated by filtration. THF is then separated by vacuum distillation. 59 g of N- [(2,2,2-amino-1 trichloro) ethyl] trichloroacetamide are thus obtained (ie a yield of 62.7%) in the form of a white solid with melting point 132-133 ° vs. EXAMPLE N ° 7 - Preparation of the compound:
On opère comme dans l'exemple 1, en remplaçant les 19,15 g de N-[(trichlorc-2,2,2 amino-1) éthyl]formamide par 18,2 g de N-[(trichlorc-2,2,2 amino-1) éthyl] o-chlorobenzamide (0,06 mole) et en utilisant 10,3 g de chlorure de dichloroacétyle (0,07 mole) au lieu de 14,75 g. On obtient ainsi, après évaporation du solvant, 23 g (soit un rendement de 79,5 %) de N-[(trichlorc-2,2,2 dichloroacétamido-1) éthyl] o-chlorobenzamide de point de fusion 214-215°C.The procedure is as in Example 1, replacing the 19.15 g of N - [(trichlorc-2,2,2 amino-1) ethyl] formamide with 18.2 g of N - [(trichlorc-2,2 , 2 amino-1) ethyl] o-chlorobenzamide (0.06 mole) and using 10.3 g of dichloroacetyl chloride (0.07 mole) instead of 14.75 g. 23 g (ie a yield of 79.5%) of N - [(trichlorc-2,2,2 dichloroacétamido-1) ethyl] o-chlorobenzamide, melting point 214-215 °, are thus obtained, after evaporation of the solvent. vs.
Le N- [(trichloro-2,2,2 amino-1) éthyl]o-chlorobenzamide utilisé comme produit de départ peut être préparé comme suit :
- On opère comme pour la préparàtion du N-[(trichloro-2,2,2 amino-1) éthyl]trichloroacétamide Mais en remplaçant les 100 g de N-[(tétrachloro-1,2,2,2) éthyl]trichloroacétamide par 100 g de N-[(tétrachloro-1,2,2,2) éthyl] o-chlorobenzamide (0,31 mole). On obtient 89 g (soit un rendement de 94,7 %) de N- [(trichloro-2,2,2 emino-1) éthyl] o-chlorobenzamide, solide blanc de point de fusion 169-170°C.
- The procedure is as for the preparation of N - [(2,2,2,2-amino-1-amino) ethyl] trichloroacetamide But replacing the 100 g of N - [(1,2,2,2-tetrachloroethyl) trichloroacetamide by 100 g of N - [(tetrachloro-1,2,2,2) ethyl] o-chlorobenzamide (0.31 mole). 89 g (a yield of 94.7%) of N- [(2,2,2-trichloro-1 emino) ethyl] o-chlorobenzamide, a white solid with a melting point of 169-170 ° C., are obtained.
Cl
On dissout 24 g de N-[dichloro-2,2 amino-1) éthyl]dichloroacétamide (0,1 mole) dans 300 ml de tétrahydrofuranne (THF). On ajoute 10,1 g de triéthylamine (0,1 mole). En maintenant la température à 20-25°C, on ajoute sous agitation, en environ 15 minutes, 17,5 g de chlorure d'o-chlo- robenzoyle (0,1 mole) dissous dans 50 ml de THF. On maintient ensuite 1 heure sous agitation en laissant revenir à la température ambiante. On filtre le précipité de chlorhydrate de triéthylamine. On sépare le THF par distillation sous vide. On obtient un solide brun qui est recristallisé dans un mélange tétrachlorure de carbone-hexane 50/50. On obtient ainsi 15,3 g (soit un rendement de 40,4 %) de N-[(dichloro-2,2 dichloroacétamido-1) éthyl] o-chlorobenzamide de point de fusion 179-180°C.24 g of N- [2,2-dichloro-1 amino-1) ethyl] dichloroacetamide (0.1 mol) are dissolved in 300 ml of tetrahydrofuran (THF). 10.1 g of triethylamine (0.1 mole) are added. Maintaining the temperature at 20-25 ° C., 17.5 g of o-chlorobenzoyl chloride (0.1 mol) dissolved in 50 ml of THF are added with stirring over about 15 minutes. Then maintained for 1 hour with stirring while allowing to return to room temperature. The precipitate of triethylamine hydrochloride is filtered. The THF is separated by vacuum distillation. A brown solid is obtained which is recrystallized from a 50/50 carbon tetrachloride-hexane mixture. 15.3 g are thus obtained (ie a yield of 40.4%) of N - [(2,2-dichloroacetamido-1) ethyl] o-chlorobenzamide, melting point 179-180 ° C.
Le N-[(dichloro-2,2 amino-1) éthyl]dichloroacétamide utilisé comme produit de départ peut être préparé comme indiqué à l'exemple 14.The N - [(2,2-dichloro-1 amino-1) ethyl] dichloroacetamide used as starting material can be prepared as indicated in Example 14.
On opère comme dans l'exemple 8, en remplaçant les 17,5 g de chlorure d'o-chlorobenzoyle par 11 g de chlorure d'isobutyryle (0,103 mole). On obtient ainsi 17,7 g (soit un rendement de 57,1 %) de N-[(dichloro-2,2-isobutyramido-1) éthy]dichloracétamide de point de fusion 189-190°C. EXEMPLE N° 10 - Préparation du composé de formule
On opère comme dans l'exemple B, en remplaçant les 17,5 g de chlorure d'o-chlorobenzoyle par 10 g de chlorure d'acryloyle (0,11 mole). On obtient ainsi 12,8 g (soit un rendement de 43,5 %) de N -[(dichloro-2,2 acrylamido-1) éthyl]dichlcroacétamide.The procedure is as in Example B, replacing the 17.5 g of o-chlorobenzoyl chloride with 10 g of acryloyl chloride (0.11 mole). 12.8 g are thus obtained (ie a yield of 43.5%) of N - [(2,2-dichloro-1 acrylamido-1) ethyl] dichlcroacetamide.
On dissout 6,4 g de dichlnroacétamide (0,05 mole) dans 50 ml de THF. On ajoute 7 g de triéthylamine (0,07 mole). En maintenant la température à 0°C, on ajoute sous agitation, en environ 15 minutes, 12,3 g de N-[(trifluoro-2,2,2 chloro-1) éthy]dichloroacétamide (0,05 mole) dissous dans 20 ml de THF. On maintient ensuite trois heures sous agitation en laissant revenir à la température ambiante. On filtre le chlorhydrate de triéthylamine. Le THF est éliminé par distillation sous vide. On obtient ainsi 15 g (soit un rendement de 89 %) de N-[(trifluoro-2,2,2 dichloroacétamido-1) éthyl]dichloroacétamide sous la forme d'un liquide visqueux brun.6.4 g of dichloroacetamide (0.05 mole) are dissolved in 50 ml of THF. 7 g of triethylamine (0.07 mole) are added. Keeping the temperature at 0 ° C., 12.3 g of N - [(trifluoro-2,2,2 chloro-1) ethyl] dichloroacetamide (0.05 mol) dissolved in about 15 minutes are added with stirring. 20 ml of THF. Then stirred for three hours while allowing to return to room temperature. The triethylamine hydrochloride is filtered. THF is removed by vacuum distillation. 15 g (a yield of 89%) of N - [(2,2,2-trifluoro-dichloroacetamido-1) ethyl] dichloroacetamide are thus obtained in the form of a brown viscous liquid.
Le N- [(trifluoro-2,2,2 chloro-1) éthyl]dichloroacétamide utilisé comme produit de départ peut être préparé comme suit :
- On dissout dans 150 ml de benzène 19,2 g de dichloroacétamide (0,15 mole) et on ajoute, en 15 minutes environ, 22 g d'hydrate de fluoral (0,2 mole) et 1 ml d'acide sulfurique. On porte à reflux pendant 6 h sous agitation. Après refroidissement et filtration, on obtient 26,5 g de N-[(trifluoro-2,2,2 hydroxy-1) éthyl] dichloroacétamide (soit un rendement de 78 %), sous la forme d'un solide blanc de point de fusion 70-71°C.
- 19.2 g of dichloroacetamide (0.15 mole) are dissolved in 150 ml of benzene and 22 g of fluorine hydrate (0.2 mole) and 1 ml of sulfuric acid are added over approximately 15 minutes. The mixture is brought to reflux for 6 h with stirring. After cooling and filtration, 26.5 g of N - [(2,2,2-trifluoro-1-hydroxy) ethyl] dichloroacetamide are obtained (ie a yield of 78%), in the form of a white solid with a point of melting 70-71 ° C.
Dans un réacteur de 100 ml, on introduit sous agitation 5,5 g de N-[(trifluoro-2,2,2 hydroxy-1) éthyl] dichloroacétamide (0,025 mole) et 7,5 g de chlorure de thionyle (0,06 mole). On porte à reflux pendant 3 heures, puis on ajoute 30 ml d'hexane pour faciliter la précipitation au cours du refroidissement. Après filtratinn, nn obtient 4,4 g de N[(trifluoro-2,2,2 chloro-1) éthyl]dichloroacétamide (soit un rendement de 72 %), sous la forme d'un solide blanc de point de fusion 54-55°C.5.5 g of N - [(2,2,2-trifluoro-1) ethyl] dichloroacetamide (0.025 mol) and 7.5 g of chloride are introduced into a 100 ml reactor. thionyl (0.06 mole). The mixture is refluxed for 3 hours, then 30 ml of hexane are added to facilitate precipitation during cooling. After filtration, nn obtains 4.4 g of N [(2,2,2-trifluoro-1,2 chloro-1) ethyl] dichloroacetamide (ie a yield of 72%), in the form of a white solid with melting point 54- 55 ° C.
En opérant cnmme à l'exemple 1, mais en remplaçant le N-[(trichloro-2,2,2 amino-1) éthy] formamide par le N-[(trichloro-2,2,2 amino-1) éthyl]acétamide, on obtient, avec un rendement de 61,5 %, le N-[(trichloro-2,2,2, dichloroacétamido-1) éthyl]acétamide, de point de fusion 239-240° C.By operating as in Example 1, but by replacing the N - [(2,2,2-amino-trichloro-1) ethyl] formamide by the N - [(2,2,2-amino-trichloro-1) ethyl] acetamide, N - [(2,2-trichloro-2,2,2, dichloroacetamido-1) ethyl] acetamide is obtained, with a yield of 61.5%, of melting point 239-240 ° C.
Le N-[(trichlora-2,2,2 amino-1) éthyl]acétamide utilisé comme produit de départ est préparé suivant la méthode employée pour préparer le N-[(trichlbro-2,2,2 amino-1) éthyl]trichloroacétamide, mais en remplaçant les 100 g de N-[(tétrachloro-1,2,2,2) éthyl] trichloroacétamide par 320 g de N-[(tétrachloro-1,2,2,2) éthyl]acétamide (1,42 mole). L'addition au THF saturé d'ammoniac s'effectue en 1 h 45'. On obtient 262 g de N-[(trichloro-2,2,2 amino-1) éthyl]acé - tamide (soit un rendement de 89,6 %), sous la forme d'un solide blanc de point de fusion 134-135°C.The N - [(2,2,2-trichlora-1 amino-1) ethyl] acetamide used as starting material is prepared according to the method used to prepare the N - [(trichlbro-2,2,2 amino-1) ethyl] trichloroacetamide, but by replacing the 100 g of N - [(tetrachloro-1,2,2,2) ethyl] trichloroacetamide with 320 g of N - [(tetrachloro-1,2,2,2) ethyl] acetamide (1, 42 mole). The addition to THF saturated with ammonia is carried out in 1 h 45 '. 262 g of N - [(2,2,2-trichloro-1-amino) ethyl] acetamide are obtained (ie a yield of 89.6%), in the form of a white solid with melting point 134- 135 ° C.
En opérant comme à l'exemple 0, mais en remplaçant le chlorure d'o-chlorobenzoyle par le chlorure de p-mé- thoxybenzoyle, on obtient, avec un rendement de 70,9 %, le N-[(dichloro-2,2 dichloroacétamido-1) éthyl]p-mtthoxy- benzamide, de point de fusion 171-172°C.By operating as in Example 0, but replacing the o-chlorobenzoyl chloride by the p-methoxybenzoyl chloride, the N - [(2-dichloro, 2 dichloroacetamido-1) ethyl] p-methoxybenzamide, mp 171-172 ° C.
On dissout dans 60 ml de benzène 64 g de dichloroacétamide (0,5 mole) et on ajoute, en 10 minutes environ,'68 g de dichloroacétaldéhyde (0,6 mole) et 1 ml d'acide sulfurique. On porte à reflux pendant 5 heures et on évapore le solvant et l'excès de dichloroacétaldéhyde sous vide. On obtient ainsi 118 g de N -[(dichloro-2,2 hydroxy-1) éthyl]dichloroacétamide brut (soit un rendement de 98 %), sous la forme d'un liquide visqueux pratiquement incolore.
'Dans un réacteur de 500 ml, on introduit sous agitation 210 g de N-[(dichloro-2,2 hydroxy-1) éthyl] dichloroacétamide (0,87 mole) préparé comme indiqué ci-dessus et 300 g de chlorure de thionyle (2,5 moles). On por- 'te à reflux pendant 2 h 3D'. On ajoute 300 ml d'hexane pour faciliter la précipitation au cours du refroidissement. Après filtration, on obtient 175 g de N-[(trichloro-2,2,1) éthyl]dichloroacétamide (soit un rendement de 77,5 sous la forme d'un solide blanc de point de fusion 77-78°C.'' 210 g of N - [(2,2-dichloro-1-hydroxy) ethyl] dichloroacetamide (0.87 mole) prepared as indicated above and 300 g of thionyl chloride are introduced into a 500 ml reactor, with stirring. (2.5 moles). We bring to reflux for 2 h 3D. 300 ml of hexane are added to facilitate precipitation during cooling. After filtration, 175 g of N - [(2,2,2-trichloro) ethyl] dichloroacetamide are obtained (ie a yield of 77.5 in the form of a white solid with melting point 77-78 ° C.
On sature 600 ml de THF par de l'ammoniac gazeux et on maintient cette saturation pendant toute la durée de l'opération suivante. En maintenant la température à 0°C, on ajoute sous agitation, en environ 1 heure, 130 g de N-[(trichloro-2,2,1) éthyl]dichloroacétamide (0,5 mole) préparé comme indiqué ci-dessus. Le chlorure d'ammonium formé est séparé par filtration. Le THF est ensuite évaporé sous vide. On obtient ainsi 95,4 g de N-[(dichloro-2,2 amino-1) éthyl dichlornacétamide (soit un rendement de 79,5 %) sous la forme d'un solide blanc de point de fusion 96-97°C. EXEMPLE N° 15 - Préparation du composé de formule :
En-opérant comme à l'exemple 3, mais en remplaçant le dichloroacétamide et le N-[(tétrachloro-1,2,2,2) éthyl]dichloroacétamide par respectivement le formamide et le N-[(trichloro-1,2,2) éthyl]dichloroacétamide, on obtient, avec un rendement de 74,6 %, le N-[(dichloro-2,2 dichloroacétamido-1) éthyl]formamide, de point de fusion 79-80°C.By operating as in Example 3, but replacing the dichloroacetamide and the N - [(tetrachloro-1,2,2,2) ethyl] dichloroacetamide by respectively the formamide and the N - [(1,2-trichloro, 2) ethyl] dichloroacetamide, N - [(2,2-dichloroacetamido-1) ethyl] formamide, with melting point 79-80 ° C., is obtained with a yield of 74.6%.
En opérant comme à l'exemple 3, mais en remplaçant le dichloroacétamide et le N-[(tétrachloro-1,2,2,2) éthyl] dichloroecétamide par respectivement l'acétamide et le N -[(trichloro-1,2,2) éthyl]dichloroacétamide, on obtient, avec un rendement de 78 %, le N-[(dichlorc-2,2 dichloroacétamido-1) éthyl]acétamide, de point de fusion 63-64°C.By operating as in Example 3, but replacing the dichloroacetamide and the N - [(tetrachloro-1,2,2,2) ethyl] dichloroecetamide by acetamide and the N - [(1,2-trichloro, respectively, 2) ethyl] dichloroacetamide, N - [(2,2-dichloroacetamido-1) ethyl] acetamide, melting point 63-64 ° C., is obtained with a yield of 78%.
Un sol, constitué de deux parties en poids d'argile et trois parties en poids de sable, est épandu dans des .barquettes en plastique de dimensions 18 x 12 x 5 cm. Sur ce sol on sème, selon 4 sillons de 0,5 cm de profondeur, 10 graines de mais, variété "Sandrina", et 10 graines d'orge, variété "Rika".A soil, consisting of two parts by weight of clay and three parts by weight of sand, is spread in plastic trays of dimensions 18 x 12 x 5 cm. On this soil we sow, in 4 furrows of 0.5 cm deep, 10 corn seeds, variety "Sandrina", and 10 barley seeds, variety "Rika".
Les semis ainsi réalisés sont séparés en 3 lots, chaque lot contenant 5 barquettes. Sur le ler lot on répand une couche, de 2 cm d'épaisseur, d'une terre n'ayant subi aucun traitement. Sur le 2ème lot on répand une couche, d'épaisseur 2 cm, d'une terre dans laquelle on a incorporé par brassage soigné un herbicide naturellement phytotoxique pour le mais à la dose où il est appliqué. Enfin, sur le 3ème lot, on répand une couche, d'épaisseur 2 cm, d'une terre dans laquelle on a incorporé le même herbicide que pour le 2ème lot, à la même dose, et un produit antidote selon l'invention.The seedlings thus produced are separated into 3 batches, each batch containing 5 trays. On the 1st batch spread a layer, 2 cm thick, of soil that has not undergone any treatment. On the 2nd batch spread a layer, 2 cm thick, of soil in which a naturally phytotoxic herbicide has been incorporated by careful mixing. corn but at the dose where it is applied. Finally, on the 3rd batch, spread a layer, 2 cm thick, of soil in which the same herbicide has been incorporated as for the 2nd batch, at the same dose, and an antidote product according to the invention.
Pour leur incorporation dans la terre l'herbicide et le produit antidote sont formulés sous forme de suspensidns aqueuses. Les quantités d'herbicide apportées correspondent à des doses d'herbicides de 5 kg et 10 kg/ha. Les quantités de produit antidote apportées correspondent à des doses égales au dixième des doses de l'herbicide, soit 0,5 et 1 kg/ha. L'herbicide utilisé est l'E.P.T.C. ou N,N-dipropyl thiolcarbamate d'éthyle. Les produits antidote testés sont les composés des exemples 1 à 15.For their incorporation into the soil, the herbicide and the antidote are formulated in the form of aqueous suspensions. The quantities of herbicide applied correspond to doses of herbicides of 5 kg and 10 kg / ha. The amounts of antidote product provided correspond to doses equal to one tenth of the doses of the herbicide, ie 0.5 and 1 kg g / ha. The herbicide used is EPTC or ethyl N, N-dipropyl thiolcarbamate. The antidote products tested are the compounds of Examples 1 to 15.
Les lots de barquettes, une fois traités, sont placés dans une serre maintenue à 20°C et à un taux d'hygrométrie de 70 %. 12 et 20 jours après le traitement (J + 12; J + 20), les lots sont examinés et on détermine d'une part l'efficacité herbicide de l'association "antidote +.herbicide", d'autre part l'efficacité antidote du composé selon l'invention testé. L'efficacité antidote E est évaluée en mesurant la hauteur moyenne des plants de mais dans les trois lots. Elle est donnée par la formule :
On constate que, dans tous les essais réalisés avec les associations "antidote + herbicide" à faible dose ou à forte dose, les orges, qui servent ici de plantes adventices de référence, sont détruite à 100 %, ce qui prouve ,que l'efficacité herbicide vis-à-vis des graminacées n'est pas réduite par les produits selon l'invention.It can be seen that, in all the tests carried out with the low-dose or high-dose “antidote + herbicide” associations, the barley, which is used here as reference weed plants, is 100% destroyed, which proves , that the herbicidal efficiency with respect to gramineae is not reduced by the products according to the invention.
Les résultats concernant l'efficacité antidote E sont rassemblés dans le tableau de la page 20.The results concerning the antidote E efficacy are collated in the table on page 20.
On voit que les composés des exemples 1, 3, 4, 9, 11 et 14, associés à l'E.P.T.C., ont une efficacité antidote particulièrement marquée.It can be seen that the compounds of Examples 1, 3, 4, 9, 11 and 14, associated with the E.P.T.C., have a particularly marked antidote efficacy.
Dans le présent essai, le produit de l'exemple 1 a été testé suivant la méthode décrite dans l'exemple précédent, mais en faisant varier la dose du produit antidote par rapport à celle de l'herbicide associé (E P T C).In the present test, the product of Example 1 was tested according to the method described in the previous example, but by varying the dose of the antidote product relative to that of the associated herbicide (E P T C).
L'herbicide a été appliqué à la dose de 5 kg/ha et le produit de l'exemple 1 aux doses 0 kg/ha (essais avec herbicide seul), 0,312 kg/ha, 0, 625 kg/ha, 1,250 kg/ha et 2,500 kg/ha.The herbicide was applied at a dose of 5 kg / ha and the product of Example 1 at the doses 0 kg / ha (tests with herbicide alone), 0.312 kg / ha, 0.625 kg / ha, 1.250 kg / ha and 2,500 kg / ha.
Les notations, effectuées au jour_J + 20, ont donné pour l'efficatité antidote E les résultats du tableau ci-dessous :
Ce tableau montre que l'efficacité antidote croit avec la dose du composé de l'exemple 1 et que ce composé ne présente pas de phytotoxicité vis-à-vis du mais, même à la dose la plus élevée.This table shows that the antidote efficacy increases with the dose of the compound of Example 1 and that this compound does not exhibit phytotoxicity with respect to maize, even at the highest dose.
Quant au pouvoir herbicide de ltE P T C vis-à-vis des plantes adventices (orge), il n'est pas réduit par les doses croissantes de composé antidote.
Claims (23)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR7723866A FR2399408A1 (en) | 1977-08-03 | 1977-08-03 | DICHLOROACETAMIDE AND TRICHLOROACETAMIDE DERIVATIVES HERBICIDE ANTIDOTES |
FR7723866 | 1977-08-03 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0000852A1 true EP0000852A1 (en) | 1979-02-21 |
EP0000852B1 EP0000852B1 (en) | 1982-08-25 |
Family
ID=9194171
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP78400063A Expired EP0000852B1 (en) | 1977-08-03 | 1978-07-21 | Treatment of herbicid containing cultures with derivatives of dichloroacetamide or of thrichloroacetamide, novel derivatives of dichloroacetamide or trichloroacetamide and process for their preparation |
Country Status (11)
Country | Link |
---|---|
US (1) | US4330323A (en) |
EP (1) | EP0000852B1 (en) |
BR (1) | BR7804963A (en) |
CA (1) | CA1116632A (en) |
DE (1) | DE2862004D1 (en) |
DK (1) | DK314678A (en) |
ES (1) | ES472304A1 (en) |
FR (1) | FR2399408A1 (en) |
IT (1) | IT1172893B (en) |
PT (1) | PT68222A (en) |
RO (1) | RO76179A (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
HU183997B (en) * | 1982-07-14 | 1984-06-28 | Noevenyvedelmi Kutato Intezet | Herbicide and antidote composition resp. containing thiolcarba mate derivative and/or chloroacetanilide derivatives as herbicide and/or substituted acetamide antidote |
JPS61293956A (en) * | 1985-06-21 | 1986-12-24 | Tokuyama Soda Co Ltd | Chloroacetamide compound and production thereof |
US5201933A (en) * | 1988-08-01 | 1993-04-13 | Monsanto Company | Safening herbicidal benzoic acid derivatives |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2742501A (en) * | 1951-06-11 | 1956-04-17 | Glanzstoff Ag | Method of producing alkylidene bis-amides |
DE1186467B (en) * | 1963-01-25 | 1965-02-04 | Bayer Ag | Process for the preparation of acylated beta, beta, beta-trichloroacetaldehyde aminals |
DE1617459A1 (en) * | 1966-03-18 | 1971-04-08 | Bayer Ag | Amidal halogenated aliphatic aldehydes |
DE2047258A1 (en) * | 1970-03-18 | 1971-10-07 | VEB Chemiekombinat Bitterfeld, χ 4400 Bitterfeld | Unsymmetrical n,n-trichloroethylidene-bis-amides |
US3923494A (en) * | 1973-05-24 | 1975-12-02 | Stauffer Chemical Co | Gem-bis amide herbicide antidote compositions and methods of use |
FR2340927A1 (en) * | 1976-02-12 | 1977-09-09 | Fisons Ltd | NEW CHLORAL DERIVATIVES, THEIR PREPARATION PROCESS AND THEIR APPLICATION AS FUNGICIDES |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1617457U (en) | 1950-11-07 | 1950-12-14 | Anton Grimm | CLOTHING HANGER. |
GB1054347A (en) * | 1964-10-29 | |||
BE756062A (en) * | 1969-09-11 | 1971-03-11 | Boehringer Sohn Ingelheim | 1,1,1-TRICHLORETHANE DERIVATIVES THEIR MANUFACTURING PROCESSES AND THEIR USE AS BIOCIDAL SUBSTANCES |
DD105113A1 (en) | 1973-01-31 | 1974-04-12 | ||
DE2358592A1 (en) | 1973-11-24 | 1975-06-05 | Bayer Ag | ANTIMICROBIAL AGENTS |
-
1977
- 1977-08-03 FR FR7723866A patent/FR2399408A1/en active Granted
-
1978
- 1978-06-27 PT PT68222A patent/PT68222A/en unknown
- 1978-07-13 DK DK314678A patent/DK314678A/en unknown
- 1978-07-21 EP EP78400063A patent/EP0000852B1/en not_active Expired
- 1978-07-21 DE DE7878400063T patent/DE2862004D1/en not_active Expired
- 1978-07-28 IT IT68804/78A patent/IT1172893B/en active
- 1978-08-02 ES ES472304A patent/ES472304A1/en not_active Expired
- 1978-08-02 RO RO7894872A patent/RO76179A/en unknown
- 1978-08-02 BR BR7804963A patent/BR7804963A/en unknown
- 1978-08-03 CA CA000308656A patent/CA1116632A/en not_active Expired
-
1979
- 1979-05-25 US US06/042,478 patent/US4330323A/en not_active Expired - Lifetime
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2742501A (en) * | 1951-06-11 | 1956-04-17 | Glanzstoff Ag | Method of producing alkylidene bis-amides |
DE1186467B (en) * | 1963-01-25 | 1965-02-04 | Bayer Ag | Process for the preparation of acylated beta, beta, beta-trichloroacetaldehyde aminals |
DE1617459A1 (en) * | 1966-03-18 | 1971-04-08 | Bayer Ag | Amidal halogenated aliphatic aldehydes |
DE2047258A1 (en) * | 1970-03-18 | 1971-10-07 | VEB Chemiekombinat Bitterfeld, χ 4400 Bitterfeld | Unsymmetrical n,n-trichloroethylidene-bis-amides |
US3923494A (en) * | 1973-05-24 | 1975-12-02 | Stauffer Chemical Co | Gem-bis amide herbicide antidote compositions and methods of use |
FR2340927A1 (en) * | 1976-02-12 | 1977-09-09 | Fisons Ltd | NEW CHLORAL DERIVATIVES, THEIR PREPARATION PROCESS AND THEIR APPLICATION AS FUNGICIDES |
Also Published As
Publication number | Publication date |
---|---|
DK314678A (en) | 1979-02-04 |
EP0000852B1 (en) | 1982-08-25 |
IT7868804A0 (en) | 1978-07-28 |
IT1172893B (en) | 1987-06-18 |
ES472304A1 (en) | 1979-10-01 |
RO76179A (en) | 1982-04-12 |
FR2399408A1 (en) | 1979-03-02 |
DE2862004D1 (en) | 1982-10-21 |
FR2399408B1 (en) | 1980-03-21 |
CA1116632A (en) | 1982-01-19 |
BR7804963A (en) | 1979-03-13 |
US4330323A (en) | 1982-05-18 |
PT68222A (en) | 1978-07-01 |
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