PT95503A - PROCESS FOR THE PREPARATION OF DERIVATIVES OF HETEROCYCLICALLY SUBSTITUTED PHENOXIALCANOCARBOXYL ACID ACIDS WITH HERBICIDAL PROPERTIES - Google Patents
PROCESS FOR THE PREPARATION OF DERIVATIVES OF HETEROCYCLICALLY SUBSTITUTED PHENOXIALCANOCARBOXYL ACID ACIDS WITH HERBICIDAL PROPERTIES Download PDFInfo
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- PT95503A PT95503A PT9550390A PT9550390A PT95503A PT 95503 A PT95503 A PT 95503A PT 9550390 A PT9550390 A PT 9550390A PT 9550390 A PT9550390 A PT 9550390A PT 95503 A PT95503 A PT 95503A
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 229940111121 antirheumatic drug quinolines Drugs 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- GRSTVVGJSKHCCS-UHFFFAOYSA-N bis(1h-imidazol-2-yl)methanone Chemical compound N=1C=CNC=1C(=O)C1=NC=CN1 GRSTVVGJSKHCCS-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- VJOCYCQXNTWNGC-UHFFFAOYSA-L calcium;benzenesulfonate Chemical compound [Ca+2].[O-]S(=O)(=O)C1=CC=CC=C1.[O-]S(=O)(=O)C1=CC=CC=C1 VJOCYCQXNTWNGC-UHFFFAOYSA-L 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000000973 chemotherapeutic effect Effects 0.000 description 1
- 101150113676 chr1 gene Proteins 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- QUPDWYMUPZLYJZ-UHFFFAOYSA-N ethyl Chemical group C[CH2] QUPDWYMUPZLYJZ-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000004438 haloalkoxy group Chemical group 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000000266 injurious effect Effects 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- IRDCEJVOXCGYAV-UHFFFAOYSA-M lithium;2-dodecylbenzenesulfonate Chemical compound [Li+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O IRDCEJVOXCGYAV-UHFFFAOYSA-M 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- OKDQKPLMQBXTNH-UHFFFAOYSA-N n,n-dimethyl-2h-pyridin-1-amine Chemical compound CN(C)N1CC=CC=C1 OKDQKPLMQBXTNH-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical class CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 229920002113 octoxynol Polymers 0.000 description 1
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 239000008262 pumice Substances 0.000 description 1
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 1
- 229910052903 pyrophyllite Inorganic materials 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000000284 resting effect Effects 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- UQDJGEHQDNVPGU-UHFFFAOYSA-N serine phosphoethanolamine Chemical compound [NH3+]CCOP([O-])(=O)OCC([NH3+])C([O-])=O UQDJGEHQDNVPGU-UHFFFAOYSA-N 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000009331 sowing Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004192 tetrahydrofuran-2-yl group Chemical group [H]C1([H])OC([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- 239000002023 wood Substances 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
-
- 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
-
- 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
- A01N43/42—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings condensed with carbocyclic rings
-
- 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/60—1,4-Diazines; Hydrogenated 1,4-diazines
-
- 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
- A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
-
- 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
- A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
-
- 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
- C07D213/70—Sulfur atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms 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
- C07D215/20—Oxygen atoms
- C07D215/22—Oxygen atoms attached in position 2 or 4
- C07D215/227—Oxygen atoms attached in position 2 or 4 only one oxygen atom which is attached in position 2
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms 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
- C07D215/36—Sulfur atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
- C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
- C07D241/40—Benzopyrazines
- C07D241/44—Benzopyrazines 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 carbon atoms of the hetero ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
- C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
- C07D263/58—Benzoxazoles; Hydrogenated benzoxazoles 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 in position 2
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
Landscapes
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Environmental Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Plant Pathology (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Plural Heterocyclic Compounds (AREA)
Description
77
/ HOECHST AKTIENGESELLSCHAFT "PROCESSO PARA A PREPARAÇÃO DE DERIVADOS DE ÃCIDOS FENOXIALCANOCARBOXÍLICOS HETEROCICLICAMENTE SUBSTITUÍDOS COM PROPRIEDADES HERBICIDAS" São objecto da presente invenção derivados dos ácidos fenoxi-alcanocarboxílicos heterocíclicos substituídos de fórmula geral/ HOECHST AKTIENGESELLSCHAFT " PROCESS FOR THE PREPARATION OF DERIVATIVES OF HETEROCYCLICALLY REPLACED PHENOXIALCANOCARBOXYLIC ACIDES WITH HERBICIDAL PROPERTIES " The present invention provides derivatives of the substituted heterocyclic phenoxy-alkanecarboxylic acids of the general formula
1 \ 01 \ 0
R 1 (I)R 1 (I)
O-(CH) -W-R 2 m na qual o símbolo Y representa um átomo de oxigénio ou de enxo fre; o símbolo Q representa um grupo de fórmula geral N.Wherein Y is oxygen or oxygen; Q is N.
NN
ouor
XX
em que os símbolos X, representam, cada um, independentemente, átomos de halogineos ou grupos halogeno-alquilo, CN ou N02; o símbolo Z representa um átomo de halogéneo ou de hi-drogéneo; e o símbolo n representa o número 0, 1, 2, 3 ou 4; o símbolo representa um átomo de hidrogénio ou um grupo alquilo C^-C4; o símbolo m representa os números 1, 2, 3 ou 4; o símbolo W representa um substituinte bivalente escolhido entre átomos de oxigénio ou grupos de fórmula -O-, -CO-S-ou -CO-O- o símbolo R2 representa um grupo de fórmula geral -ch2ch=chr3, -ch2c==cr3, -ch2-sí(r4) (R5) (R6) ou -n=cr7r8 ou tetra-hidropiranil-metilo ou tetra-hidrofurfurilo, em que os dois radicais mencionados em último lugar são não substituídos ou são substituídos no núcleo por um grupo alquilo C^-C4; o símbolo Rg representa um átomo de hidrogénio ou um grupo alquilo C^-C4 ou fenilo eventualmente substituído; os símbolos R4, R5 e Rg, representam, cada um, indepen dentemente um grupo alquilo C1-C4 ou fenilo; os símbolos R^ e Rg representam, cada um, independente mente, um átomo de hidrogénio ou um grupo alquilo C^-C4 ou os símbolos R^ e Rg, em conjunto, representam um gru_ po cicloalquilo C^-C^, em que, no caso de o símbolo W representar um radical de fórmula -COO-, o grupo dewherein X, are each independently halogen atoms or haloalkyl groups, CN or NO 2; Z is halogen or hydrogen; and n is 0, 1, 2, 3 or 4; the symbol represents a hydrogen atom or a C1 -C4 alkyl group; m is 1, 2, 3 or 4; W is a divalent substituent selected from oxygen atoms or groups of the formula -O-, -CO-S- or -CO-O- R2 is -CH2CH = CH3, -C2C = -C3 , -CH 2 -S (R 4) (R 5) (R 6) or -n = CR 7 -8 or tetrahydropyranyl-methyl or tetrahydrofurfuryl, wherein the two last-mentioned radicals are unsubstituted or are substituted in the nucleus by a C1 -C4 alkyl; R6 is hydrogen, C1-4 alkyl or optionally substituted phenyl; R 4, R 5 and R 6 are each independently C 1 -C 4 alkyl or phenyl; R1 and R2 are each independently hydrogen or C1 -C4 alkyl or R4 and R6 together represent a C1 -C4 cycloalkyl group, wherein , in the case where W is a radical of the formula -COO-, the
fórmula geral Q4 é inexistente e no caso de o símbolo 1*2 representar um grupo de fórmula geral -N=CR^Rg e W representar um átomo de oxigénio, os grupos de fórmulas gerais e Ç>2 são inexistentes e no caso de o símbolo R2 representar um grupo de fórmula geral -CH2CH=CHR3, -CH2C=CR3 ou tetra-hidrofurfurilo, o símbolo m representar um nú mero de 1 a 3 e o símbolo W representar o grupo -C0-0-, o grupo de fórmula geral Q3 está ausente. São já conhecidos compostos herbicidas com as estruturas indicadas parcialmente modificadas por meio dos pedidos de pa. tente de invenção alemã 29 14 300 (US-A-4 482 373), norte-americana 4 687 849, europeia 0 052 798 (GB-A-2 087 890) e europeia 0 008 624 (CA-A-1 114 382) .general formula Q4 is non-existent and in the case where 1 * 2 is -N = CR3 R8 and W represents an oxygen atom, groups of the general formulas and &> 2 are non-existent and in case the R 2 is -CH 2 CH = CHR 3, -CH 2 C = CR 3 or tetrahydrofurfuryl, m is a number from 1 to 3 and W is -C0 -O-, the group of formula general Q3 is absent. Herbicidal compounds having the indicated structures partially modified are known by means of the application of art. German patent application 29 14 300 (US-A-4 482 373), US 4 687 849, European patent 0 052 798 (GB-A-2 087 890) and European patent 0 008 624 (CA-A-1 114 382 ).
Tem interesse especial os compostos de fórmula geral (I) de acordo com a presente invenção em que o símbolo Y representa um átomo de oxigénio, o símbolo Q representa um grupo de fórmula geral Q^, Ç^, Q3 ou Q4, em que o símbolo X representa um átomo de halogéneo, em especial, um átomo de flúor ou de cloro, ou um grupo tri-flúor-metilo, o símbolo Z representa um átomo de halogéneo, e o símbolo n representa os números 1 ou 2, o símbolo R^ representa um átomo de hidrogénio e o sím bolo m representa um número de 1 a 4 ou o símbolo R^ representa um radical metilo ou etilo e o símbolo m representa o número 1, o símbolo W representa um átomo de oxigénio ou o radical de fórmula -C0-0-, o símbolo 1*2 tem os significados referidos antes, o símbolo representa um átomo de hidrogénio, os símbolos R^, R^ e Rg representam, cada um, um radical metilo, e os símbolos R7 e Rg representam, cada um, independente mente, um grupo metilo ou, em conjunto, representam ci clopeptilo ou ciclo-hexilo.Of particular interest are the compounds of the general formula (I) according to the present invention in which Y is oxygen, Q is Q, Q, Q 3, Q 3 or Q 4, wherein X represents a halogen atom, in particular a fluorine or chlorine atom, or a tri-fluoro-methyl group, Z represents a halogen atom, and n is 1 or 2, the symbol R3 represents a hydrogen atom and the symbol m is a number from 1 to 4 or R4 is a methyl or ethyl radical and m is 1, W is O or the radical of the formula -C0 -O-, 1 * 2 has the meanings given above, the symbol R 1, R 2 and R 3 each represent a methyl radical, and R 7 and Râ,, are independently methyl, or together represent cyclo peptidic or cyclohexyl.
Os radicais alquilo, alcenilo ou alcinilo que podem ter os significados dos símbolos R^, 1*2' R3' R4' R5' Rg e R7 P°^em ser tanto de cadeia linear como de cadeia ramificada. "Halogéneo" si gnifica flúor, cloro, bromo ou iodo e, de preferência, significa flúor, cloro ou bromo. Halogéno-alquilo contém, de preferência, um grupo alquilo C^-C^ monossubstituído ou polissubstituído por átomos de halogéneo, em especial, um grupo trifluorometilo ou tri clorometilo. Fenilo substituído significa de preferência fenilo que é substituído por um ou mais radicais escolhidos entre grupos alquilo C^-C^, halogeno-alquilo, alcoxi, halogeno-alcóxi ou cia-no ou por átomos de halogéneo.The alkyl, alkenyl or alkynyl radicals which may have the meanings of the symbols R 1, R 2, R 3, R 4, R 5, R 6 and R 7 are in both straight and branched chain. " Halogen " fluorine, chlorine, bromine or iodine, and preferably fluorine, chlorine or bromine. Halogen-alkyl preferably contains a C1-4 alkyl group monosubstituted or polysubstituted by halogen atoms, in particular a trifluoromethyl or tri-chloromethyl group. Substituted phenyl means preferably phenyl which is substituted by one or more radicals selected from C 1 -C 4 alkyl, haloalkyl, alkoxy, haloalkoxy or cyano groups or by halogen atoms.
Os compostos de fórmula geral (I) possuem pelo menos um centro de assimetria na parte de ácido propiónico e podem, por tanto, existir sob a forma de mistura enantiomérica, por exemplo, sob a forma racémica ou sob a forma de enantiõmeros puros. Os ra cematos podem separar-se nos enantiõmeros de acordo com métodos usuais. É também igualmente possível preparar os enantiõmeros pu ros directamente com utilização das substâncias de partida opti-camente activas correspondentes. Nas restantes partes da molécula, podem, no caso de significações apropriadas dos substituin-tes, estar contidos outros centros de assimetria, de modo que sãoThe compounds of general formula (I) have at least one center of asymmetry in the part of propionic acid and may therefore exist as enantiomeric mixture, for example in racemic form or as pure enantiomers. The racemates can be separated into the enantiomers according to usual methods. It is also also possible to prepare the pu enantiomers directly using the corresponding optically active starting materials. In the other parts of the molecule, other centers of asymmetry may be contained in the case of appropriate meanings of the substituents, so that they are
possíveis mais diasteriõmeros e enantiómeros. Os compostos de fór mula geral (I) abrangem tanto os diasteriõmeros possíveis, os enan tiómeros e os racematos, como as sua misturas. Em especial, abran gem os compostos sob a forma D na parte do ácido propiónico ou na forma enriquecida em relação à mistura racémica ou sob a forma de enantiómeros puros. É também objecto da invenção um processo para a preparação dos compostos de fórmula geral (I) de acordo com a presente invenção, que se caracteriza pelo facto de a) se fazer reagir um composto de fórmula geral (II) Q " Hal com um composto de fórmula geral HY-Further diastereomers and enantiomers are possible. The compounds of general formula (I) encompass both the possible diastereomers, the enantiomers and the racemates, and mixtures thereof. In particular, the compounds in the D-form are included in the propionic acid part or in the form enriched with the racemic mixture or as pure enantiomers. A process for the preparation of the compounds of the general formula (I) according to the present invention, characterized in that a) reacting a compound of formula (II) Hal with a compound of formula HY-
0 (III) O-(CH) -W-R I m 2 ou b) se fazer reagir um composto de fórmula geralOr (b) reacting a compound of general formula
A (IV) com um composto de fórmula geral HO-(CH) -W-R2 m na qual o símbolo A representa um grupo apropriado facilmente eliminãvel de preferência um átomo de cloro ou de bromo, ou c) se transformar um composto de fórmula geral (IV), na qual o símbolo A representa um grupo OH, de acordo com métodos corihe eidos, por exemplo, por meio de carbonil-di-imidazol, em um composto com o grupo carbonilo activado e de se fazer reagir este com um composto de fórmula HO-tCHR1) -W-R2 de modo a obter-se um composto de fórmula geral (I) ou d) se fazer reagir um composto de fórmula geral (IV), na qual o símbolo A representa um grupo OH, de acordo com métodos conhe_ eidos, com o auxílio de diciclo-hexil-carbo-di-imida (DCC), com um composto de fórmula geral HO-ÍCHR1) -W-R2 em presença de uma amina orgânica, para se obter um composto de fórmula geral (I), ou e) se fazer reagir um composto de fórmula geral (II) antes mencionado, com hidroquinona ou 4-hidroxi-tiofenol, de maneira a obter-se um composto de fórmula geral Q - γ OH (v) que, em seguida, se faz reagir com um éster do ácido 2-cloro -propiónico de fórmula geral CH-jCH (Cl) C0-0- (CHR1) m-WR2 A reacção dos compostos de fórmulas gerais (II) e (III), de acordo com a variante a) do processo realiza-se, de preferência, no seio de dissolventes apróticos inertes como hidrocarbone tos alifáticos ou aromáticos (por exemplo, tolueno/xileno), aceto nitrilo, acetona, sulfóxido de dimetilo ou dimetil-formamida, a temperaturas compreendidas entre 40°C e a temperatura de ebulição do dissolvente. 7- A reacção dos compostos de fórmula geral (XV) de acordo com a variante b) do processo realiza-se, de preferência, no seio de hidrocarbonetos alifáticos ou aromáticos inertes, em especial, de hidrocarbonetos halogenados (por exemplo, CHCl^, CCl^) ou éteres (dioxano, tetra-hidrofurano), em geral â tempera tura de refluxo da mistura reaccional. A reacção dos ácidos heteroariloxi-fenoxi-propiónicos de fórmula geral (IV) com os álcoois de fórmula geral ROH, de acor do com a variante c) do processo realiza-se, de preferência, no seio de dissolventes alifáticos ou aromáticos inertes. A reacção dos ácidos heteroariloxi-carboxi-propiónicos de fórmula geral (IV), com o auxílio de DCC, de acordo com a variante d) do processo, realiza-se, por exemplo, em presença de 4-N,N-dimetilamino-piridina (DMAP) no seio de dissolventes alifã ticos ou aromáticos inertes nas condições de realização da reacção. A reacção dos compostos de fórmulas gerais (II) e (V), de acordo com a variante e) do processo pode realizar-se em condições reaccionais análogas ãs da variante a) do processo; o mes^ mo acontece com a reacção entre o produto intermediário assim obti do com os ésteres do ácido 2-cloro-propiónico.(IV) with a compound of the general formula HO- (CH) -W-R2 m wherein A is a suitable leaving group, preferably chlorine or bromine atom, or c) converting a compound of formula (IV) in which A is OH, according to the methods described, for example by means of carbonyl di-imidazole, in a compound having the activated carbonyl group and reacting the latter with a compound of the formula (IV) in which A is OH, R 2 is hydrogen, halogen, according to known methods, with the aid of dicyclohexylcarbodiimide (DCC), with a compound of the general formula HO-CH 2) -W-R 2 in the presence of an organic amine, to give a compound of formula (I), or (e) reacting a compound of the above-mentioned formula (II) with hydroquinone or 4-hydroxy thiophenol, a compound of the formula Q - γOH (v) which is then reacted with a 2 - chloropropionic acid ester of the general formula CH - (CH) 0 - (CHR1) m-WR2 The reaction of the compounds of general formulas (II) and (III) according to process variant a) is preferably carried out in inert aprotic solvents such as aliphatic or aromatic hydrocarbons (for example, toluene / xylene ), acetonitrile, acetone, dimethylsulfoxide or dimethylformamide, at temperatures ranging from 40Â ° C to the boiling point of the solvent. The reaction of compounds of general formula (XV) according to process variant b) is preferably carried out in inert aliphatic or aromatic hydrocarbons, in particular halogenated hydrocarbons (for example CHCl3, ) Or ethers (dioxane, tetrahydrofuran), in general at the reflux temperature of the reaction mixture. The reaction of the heteroaryloxy-phenoxypropionic acids of the general formula (IV) with the alcohols of the general formula ROH according to process variant c) is preferably carried out in inert aliphatic or aromatic solvents. The reaction of the heteroaryloxy carboxypropionic acids of general formula (IV) with the aid of DCC according to process variant d) is carried out, for example, in the presence of 4-N, N-dimethylamino- pyridine (DMAP) in inert aliphatic or aromatic solvents under the conditions of the reaction. The reaction of the compounds of general formulas (II) and (V) according to process variant e) may be carried out under reaction conditions analogous to that of process variant a); the same occurs with the reaction between the intermediate thus obtained with the 2-chloro-propionic acid esters.
Os compostos heterociclicos de fórmula geral (II) neces_ sários para a preparação dos compostos de fórmula geral (I) de acordo com a presente invenção, significam, de acordo com a def_i nição do símbolo Q, 2-halogeno-quinolinas substituídas, 2-haloge no-piridina, 2-halogeno-benzoxazóis e 2-halogeno-quinoxalinas, que são conhecidas ou podem preparar-se por processos análogos conhe eidos, por exemplo, no caso de Q-Hal em que o símbolo Q represen ta Q^, Q2 ou a partir dos correspondentes compostos de 2-mer-capto ou de compostos de 2-oxo por halogenação [veja-se por -8- exemplo, "Chem. Abstracts"; 59_, 396 f; "American Chem. J."; 21_ (1899) p. 111] ou no caso de Q-Hal em que o símbolo Q representa como se indica na memória descritiva no pedido de patente de invenção europeia 0 248 968 e na literatura aí citada.The heterocyclic compounds of general formula (II) necessary for the preparation of the compounds of formula (I) according to the present invention are, according to the definition of Q, substituted 2-halogeno-quinolines, 2- 2-halogeno-benzoxazoles and 2-halogeno-quinoxalines which are known or can be prepared by known analogous processes, for example in the case of Q-Hal wherein Q is Q, Q2 or from the corresponding 2-mer-capto compounds or 2-oxo compounds by halogenation [see for example, " Chem. Abstracts "; 59, 396 f; " American Chem. J. "; 21_ (1899) p. 111] or in the case of Q-Hal where Q is as indicated in the specification in European Patent Application 0 248 968 and in the literature cited therein.
Os fenóis de fórmula geral (III) (em que o símboloY re presenta um átomo de oxigénio) podem preparar-se, por exemplo, por alquilação de hidroquinona com os ésteres do acido cloropropiõnjl co que correspondem ã fórmula ("J. Org. Chem.", 39_j 1974; p.214.The phenols of formula (III) (wherein Y is an oxygen atom) may be prepared, for example, by the alkylation of hydroquinone with the chloropropionic acid esters corresponding to the formula (" Chem. &Quot;, 39, 1974; p.214.
Os tiofenóis de fórmula geral (III) em que o símbolo Y representa um átomo de enxofre) podem preparar-se, por exemplo, por reacção de 4-hidroxi-tiofenol protegido no grupo SH com os mencionados ésteres do ácido 2-cloropropiónico e subsequente eld. minação do grupo de protecção.Thiophenols of general formula (III) in which Y is sulfur) may be prepared, for example, by reacting protected 4-hydroxy thiophenol in the SH group with said 2-chloropropionic acid esters and subsequent eld. tion of the protection group.
Os compostos de fórmula geral (IV) podem preparar-se por processos em geral conhecidos, por exemplo, por reacção de hidroquinona ou de 4-hidroxi-tiofenol com compostos da referida fórmula geral (II) e subsequente reacção com os correspondentes ésteres de ácido 2-cloropropiónico, em que os produtos se transformam ainda nos derivados dos ácidos carboxílicos com um grupo A facilmente eliminável de acordo com processos conhecidos. antes daCompounds of formula (IV) may be prepared by procedures generally known, for example, by reaction of hydroquinone or 4-hydroxy thiophenol with compounds of said general formula (II) and subsequent reaction with the corresponding 2-chloropropionic acid, wherein the products are further converted to the carboxylic acid derivatives having a group A readily removable according to known procedures. before
Os compostos de fórmula geral (I), de acordo com a pre sente invenção, têm uma excelente actividade herbicida contra um largo espectro de plantas daninhas monocotiledõneas economicamen te importantes em que, regra geral, a actividade da respectiva forma D dos compostos é maior do que a do racemato e a forma L tem uma actividade herbicida menor ou nula. Também ervas daninhas perenes dificilmente combatíveis que possuem rizomas, raízes pro fundas ou outros órgãos perenes são atacadas pelas substâncias activas de acordo com a presente invenção.- Para o efeito, é satis_ fatório aplicar as substâncias antes da sementeira, -9-The compounds of general formula (I) according to the present invention have excellent herbicidal activity against a broad spectrum of economically important monocotyledonous weeds wherein, in general, the activity of the respective D form of the compounds is greater than that of the racemate and the L-form has a minor or no herbicidal activity. Also difficult to combat perennial weeds having rhizomes, deep roots or other perennial organs are attacked by the active substances according to the present invention.- For this purpose, it is satisfactory to apply the substances before sowing,
emergência ou depois da emergência. Pormenorizadamente, referem--se, a título de exemplo, os exemplares da flora de ervas daninhas monocotiledóneas que podem ser controlados pelos compostos de acordo com a presente invenção sem que isso constitua uma limitação das espécies tratadas.emergency or after the emergency. Specimens of the monocotyledonous weed flora which can be controlled by the compounds of the present invention are not mentioned in any way except as a limitation of the species treated.
Relativamente ãs espécies de ervas daninhas monocotile dôneas, são abrangidas, por exemplo, Avena, Apera, Lolium, Alope curus, Phalaria, Echinochloa, Digitaria, Setaria, assim como espécies de Cyperus do grupo das ervas daninhas anuais e das espécies perenes Agropyron, Cynodon, Imperata, Paspalum, assim como Sorghum e também espécies de Cyperus perenes.For species of monocotyledonous weeds, for example, Avena, Apera, Lolium, Alope curus, Phalaria, Echinochloa, Digitaria, Setaria, as well as Cyperus species of the annual weeds and perennial species Agropyron, Cynodon , Imperata, Paspalum, as well as Sorghum and also perennial Cyperus species.
As ervas daninhas existentes nas condições específicas de cultura do arroz são igualmente combatidas pelas substâncias activas de acordo com a presente invenção.The weeds existing under the specific conditions of rice cultivation are also combated by the active substances according to the present invention.
Se os compostos de acordo com a presente invenção forem aplicados antes da germinação sobre a superfície do terreno, então evita-se completamente a germinação das ervas daninhas ou as ervas daninhas desenvolvem-se apenas até à fase das folhas dos germes, muito embora, em seguida, o seu desenvolvimento seja dificultado e morram depois do decurso de três ou quatro semanas com pletamente.If the compounds according to the present invention are applied prior to germination on the soil surface, then germination of weeds is completely avoided or weeds only develop until the leaf stage of the germs, although in then their development is hampered and die after the course of three or four weeks completely.
No caso da aplicação das substâncias activas sobre as partes verdes das plantas no processo de tratamento de põs-emer-gência, verifica-se igualmente muito rapidamente depois do tratamento uma interrupção drástica do crescimento e as plantas daninhas ficam numa fase de desenvolvimento existente no momento da aplicação ou morrem depois de um determinado intervalo de tempo, de modo que, desta forma, pode evitar-se a ocorrência de ervas daninhas preju diciais nas plantas de cultura muito cedo e que se mantém durante bastante tempo.In the case of the application of the active substances to the green parts of the plants in the post-emergence treatment process, a drastic interruption of growth occurs very rapidly after the treatment, and the weeds are in a development phase of the application or die after a certain time, so that in this way, harmful weeds can be prevented from occurring in the crop plants very early and maintained for a long time.
Muito embora os compostos de acordo com a presente invenção apresentem uma actividade herbicida excelente contra ervas daninhas raonocotiledóneas, as plantas de cultura de culturas eco nomicamente significativas como, por exemplo, trigo, cevada, cen teio, arroz, milho, beterraba-açucareira, algodão e soja, são ape nas prejudicadas muito ligeiramente ou completamente nada. Os pre sentes compostos são apropriados para o combate selectivo do desenvolvimento de plantas indesejáveis em plantações de plantas úteis do ponto de vista agronómico.While the compounds according to the present invention exhibit excellent herbicidal activity against ratoon pollinosis, culturing plants of economically significant crops such as wheat, barley, maize, rice, maize, sugar beet, cotton and soybeans, are only slightly impaired or completely nothing. The present compounds are suitable for selectively combating the development of undesirable plants in agronomically useful plant crops.
Os compostos de fórmula geral (I) podem ser formulados de diversas maneiras de acordo com os parâmetros respectivos bio lógicos e/ou quimico-físicos apropriados. Como possibilidades de formulações, interessam, por exemplo, pós molháveis (PM), concen trados emulsionáveis (CE), soluções aquosas (SA), emulsões (EM), como emulsões do tipo óleo em água e do tipo água em óleo, soluções ou emulsões pulverizáveis, dispersões ã base de óleo ou de água (SC), emulsões em suspensão, pós de polvilhação (PP), agentes de incrustração, grânulos (GR) como produtos granulados para aplicação por polvilhação ou no terreno ou grânulos dispersáveis em água (DA), formulações de volume ultrapequeno, microcápsulas ou ceras.The compounds of formula (I) may be formulated in various manners according to their respective bio logical and / or chemotherapeutic parameters. Possible formulations include, for example, wettable powders (PM), emulsifiable concentrates (CE), aqueous solutions (SA), emulsions (EM), oil-in-water and water-in-oil emulsions, solutions or dispersible emulsions, water-based (SC) dispersions, suspension emulsions, dusting powders (PP), inking agents, granules (GR) as granules for application by dusts or on the ground or water-dispersible granules ( DA), ultra-small volume formulations, microcapsules or waxes.
Estes tipos de formulações individuais são em princípio conhecidos e estão descritos, por exemplo, em Winnacker-Kuchler, "Chemische Technologie", Volume 7, C. Hauser Verlag, Munique, 4â Edição , 1986; van Valkenburg, "Pesticides Formulations", Mareei Dekker, N. Y., 2& Edição, 1972-1973; K. Martens, "Spray Drying Handbook", 3§ Edição, 1979, G. Goodwin, Ltd., Londres.These types of individual formulations are in principle known and are described, for example, in Winnacker-Kuchler, " Chemische Technologie ", Volume 7, C. Hauser Verlag, Munich, 4th Edition, 1986; van Valkenburg, " Pesticides Formulations ", Mareei Dekker, N.Y., 2 & Edition, 1972-1973; K. Martens, " Spray Drying Handbook ", 3rd Edition, 1979, G. Goodwin, Ltd., London.
As substâncias auxiliares de formulação necessárias, tais como materiais inertes, agentes tensio-activos, dissolventes e outros aditivos, são bem conhecidos e estão descritos, por exemplo em watkins, "Handbook of Insecticid Dust Diluents and Carriers", 2§ Ed., Darland Books, Caldwell, N. J.; H. van Olphen, "Intro-ductions to Clay Colloid Chemistry", 2i Ed., J. Wiley & Sons, N. Y.; Marsden, "Solvents Guide", 2i Ed., Interscience, N. Y., 1950; McCutcheon, "detergents and Emulsifiers Annual", Mc Publ., Corp., Ridgewood, N. Y.; Sisley e Wood, "Encyclopedia of Surface Active Agents", Chem. Publ. Co., Inc., N. Y. 1964; Schonfeldt, "Grenzflachenaktive Athylenoxidaddukte", Wiss. Verlagsgesell., Estugarda, 1976; Winnacker-Kuchler, "Chemische Technologie", Vol. 7, C. Hauser Verlag, Munique, 4ã Ed., 1986. Ã base dessas formulações, podem também preparar-se com binações com outras substâncias pesticidamente activas, adubos e/ou agentes de regulação do crescimento, por exemplo, sob a for ma de uma formulação pronta ou sob a forma de mistura em tanque.The necessary formulation auxiliaries, such as inert materials, surfactants, solvents and other additives, are well known and are described, for example in watkins, " Handbook of Insecticidal Dust Diluents and Carriers ", 2nd Edition, Darland Books, Caldwell, NJ; H. van Olphen, " Intro-ductions to Clay Colloid Chemistry ", 2nd Ed., J. Wiley & Sons, N.Y .; Marsden, " Solvents Guide ", 2nd Ed., Interscience, N.Y., 1950; McCutcheon, " Detergents and Emulsifiers Annual ", Mc Publ., Corp., Ridgewood, N.Y .; Sisley and Wood, " Encyclopedia of Surface Active Agents ", Chem. Publ. Co., Inc., N.Y. 1964; Schonfeldt, " Grenzflachenaktive Athylenoxidaddukte ", Wiss. Verlagsgesell., Stuttgart, 1976; Winnacker-Kuchler, " Chemische Technologie ", Vol. 7, C. Hauser Verlag, Munich, 4th Ed., 1986. Based on these formulations, they may also be prepared with binders with other pesticidally active substances, fertilizers and / or agents for example, in the form of a ready formulation or as a tank mix.
Os pós molháveis são composições dispersáveis uniforme mente em água que, juntamente com a substância activa contêm também um agente diluente ou inerte e ainda agentes molhantes, por exemplcy alquil-fenóis polioxietilados, álcoois gordos e aminas gordas po lioxietilados, alcano-sulfonatos ou alquil-benzeno-sulfonatos e agentes dispersantes, por exemplo, sal de sódio do ácido ligni-no-sulfónico, sal de sódio do ácido 2,2 1-dinaftil-metano-6,6'-dis sulfónico, sal de sódio de ácido dibutil-naftaleno-sulfónico ou também sal de sódio de oleil-metil-taurina.Wettable powders are compositions dispersible evenly in water which together with the active substance also contain a diluting or inert agent and further wetting agents, for example polyoxyethylated alkyl phenols, fatty alcohols and polyoxyethylated fatty amines, alkanesulphonates or alkyl- benzenesulfonates and dispersing agents, for example, sodium salt of lignosulfonic acid, 2,2-dimethyl-methano-6,6'-disulfonic acid sodium salt, dibutyl- naphthalenesulfonic acid or also oleyl-methyl-taurine sodium salt.
Os concentrados emulsionáveis sao preparados por disso lução da substância activa num dissolvente orgânico, por exemplo, butanol, ciclo-hexanona, dimetilformamida, xileno ou também produtos aromáticos de elevado ponto de ebulição ou hidrocarbonetos com adição de um ou vários agentes emulsionantes. Como agentes emulsionantes, podem utilizar-se, por exemplo, sais de cálcio do -12 >r ácido alquil-aril-sulfõnico, como dodecil-benzeno-sulfonato de cal cio ou agentes emulsionantes não iónicos, como ésteres de poli-glicol de ácidos gordos, éteres alquil-aril-poliglicõlicos, éteres de álcoois gordos e poliglicol, produtos de condensação de óxido de propileno-õxido de etileno, poliéteres alquílicos, éste res de ácidos gordos de sorbitano, ésteres de ácidos gordos de po lioxietileno-sorbitano ou ésters de polioxietileno-sorbite.Emulsifiable concentrates are prepared by addition of the active substance in an organic solvent, for example butanol, cyclohexanone, dimethylformamide, xylene or also high boiling aromatic products or hydrocarbons with the addition of one or more emulsifying agents. As the emulsifying agents, for example, calcium salts of alkyl aryl sulfonic acid, such as lithium dodecyl benzene sulfonate or nonionic emulsifying agents such as polyglycol esters of fatty acids, alkylaryl polyglycol ethers, fatty alcohol ethers and polyglycol ethers, condensation products of propylene oxide-ethylene oxide, alkyl polyethers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters or polyoxyethylene sorbite esters.
Obtêm-se pós para polvilhação por moagem da substância activa com materiais sólidos finamente pulverizados, por exemplo, talco, argilas naturais como caulino, bentonite, pirofilite ou terra de diatomãceas.Dusts are obtained by milling the active substance with finely ground solid materials, for example talc, natural clays such as kaolin, bentonite, pyrophyllite or diatomaceous earth.
Os grânulos para a aplicação por polvilhação no terreno e os grânulos dispersáveis em água podem preparar-se ou porpul verização de substância activa com um material inerte granulado, com capacidade de absorção, ou por aplicação de concentrado da substância activa por meio de agentes adesivos, por exemplo, álcool polivinílico, sal de sódio de ácido poliacrílico ou também de óleos minerais sobre a superfície de substâncias veiculares, como areia, caulinite ou material inerte granulado. Também se po dem granular substâncias activas procedendo de acordo com a manei ra de proceder usual apropriada para a preparação de grânulos de adubos - caso se pretenda - em mistura com adubos.The granules for the application by the field dusting and the water dispersible granules can be prepared or by spraying of active substance with an inert granular material, with absorption capacity, or by application of concentrate of the active substance by means of adhesive agents, for example, polyvinyl alcohol, sodium salt of polyacrylic acid or also of mineral oils on the surface of carrier substances such as sand, kaolinite or granular inert material. Active substances may also be granulated by proceeding according to the usual customary procedure for the preparation of fertilizer granules - if desired - in admixture with fertilizers.
As composições agroquímicas contêm, em geral, 0,1 a 99% em peso, em especial, 2 a 95% em peso de substância activa de fór_ mula geral (I). Neste caso, as concentrações de substância activa podem ser diferentes, dependendo do tipo de formulação.The agrochemical compositions generally contain 0.1 to 99% by weight, in particular 2 to 95% by weight of active compound of general formula (I). In this case, the concentrations of the active ingredient may be different, depending on the type of formulation.
Nos pós molháveis, a concentração de substância activa constitui, por exemplo, cerca de 10 a 95% em peso, sendo a parte restante até perfazer 100% em peso constituída pelos componentes auxiliares de formulação usuais. Nos concentrados emulsionáveis, a concentração de substância activa pode variar entre cerca de 1 a 85% em peso, de preferência, entre 5 e 80% em peso. As formula ções sob a forma de pó contêm cerca de 1 a 25% em peso, na maior parte dos casos 5 a 20% em peso de substância activa. As soluções pulverizáveis contem cerca de 0,2 a 25% em peso, de preferência, 2 a 20% em peso de substância activa. Nos grânulos e especialmen te nos grânulos dispersáveis em água, o teor de substância activa depende, em parte, do facto de o composto activo ser líquido ou sólido. Em geral, nos grânulos dispersáveis em água, está compreendido entre 10 e 90% em peso.In wettable powders, the concentration of the active substance constitutes, for example, about 10 to 95% by weight, the remaining part being up to 100% by weight consisting of the usual formulation auxiliaries. In the emulsifiable concentrates, the concentration of the active ingredient may vary from about 1 to 85% by weight, preferably 5 to 80% by weight. The powder formulations contain about 1 to 25% by weight, in most cases 5 to 20% by weight of active ingredient. The sprayable solutions contain about 0.2 to 25% by weight, preferably 2 to 20% by weight of active substance. In granules and especially in water-dispersible granules, the content of the active substance depends in part on whether the active compound is liquid or solid. In general, in the water dispersible granules, it is comprised between 10 and 90% by weight.
Além disso, as mencionadas formulações das substâncias activas contêm, eventualmente, os respectivos agentes adesivos, molhantes, dispersantes, emulsionantes, auxiliares de penetração, dissolventes, cargas ou veículos usuais.In addition, the said formulations of the active substances optionally contain the respective adhesive, wetting, dispersing, emulsifying, penetration aiding agents, solvents, fillers or carriers.
Para a utilização, as formulações existentes sob a for ma comercial são eventualmente diluídas de acordo com a maneira de proceder usual, por exemplo, no caso dos pós molháveis, concen trados emulsionáveis, dispersões e grânulos dispersáveis em água, por meio de água. As composições sob a forma de pós para polvilhar , grânulos para aplicar no solo ou para polvilhar, assim como soluções pulverizáveis não são diluídas correntemente com substân cias inertes antes da utilização.For use, commercially available formulations are optionally diluted in the usual manner, for example in the case of wettable powders, emulsifiable concentrates, dispersions and granules dispersible in water, by means of water. The compositions in the form of powders for sprinkling, granules for application to the soil or for sprinkling, as well as sprayable solutions are not currently diluted with inert substances prior to use.
As quantidades de utilização dos compostos de fórmula geral (I) necessárias variam com as condições exteriores, como temperatura, humidade, tipo de herbicida utilizado, etc. Elas po dem variar dentro de largos limites, por exemplo, entre 0,01 e 10,0 Kg/ha ou mais de substância activa, ficando, no entanto, com preendida entre 0,015 e 5 Kg/ha.The amounts of use of the required compounds of formula (I) vary with the external conditions, such as temperature, humidity, type of herbicide used, etc. They may vary within wide limits, for example between 0.01 and 10.0 kg / ha or more of active substance, however, ranging between 0.015 and 5 kg / ha.
Os exemplos seguintes servem para esclarecimento da in vençao.The following examples serve to clarify the invention.
EXEMPLOS A) Exemplos de formulações a) Obtém-se um pó para polvilhar misturando 10 partes em peso de um composto de fórmula geral (I) e 90 partes em peso de talco como substância inerte e moendo num moinho de impacto. b) Obtém-se um pó molhável facilmente dispersável em agua mis turando 25 partes em peso de um composto de fórmula geral (I), 64 partes em peso de quartzo contendo caulino como ma téria inerte, 10 partes em peso de sal de potássio do áci do lignino-sulfónico e 1 parte em peso de sal de sódio do ácido oleoil-metil-taurinico como agentes molhantes e dis^ persantes, e moi-se num moinho de martelos. c) Obtém-se um concentrado sob a forma de dispersão facilmen te dispersável em água misturando 20 partes em peso do com posto de fórmula geral (I) com 6 partes em peso de éter al quilfenol-poliglicõlico (Triton^ X 207) , 3 partes em peso de éter isotridecanol-poliglicólico (com oito unidades de óxido de etileno) e 71 partes em peso de óleo mineral pa-rafinico (intervalo de ebulição, por exemplo, desde cerca de 255° até um valor superior a 277° C) e moendo num moinho de bolas até se obter uma finura inferior a 5 micra. d) Obtém-se um concentrado emulsionável a partir de 10 partes em peso de um composto de fórmula geral (I), 75 partes em peso de ciclo-hexano como dissolvente e 10 partes em peso de nonil-fenol oxietilado (10 unidades de óxido de etileno) como agente emulsionante. e) Obtém-se um granulado dispersável em água misturando -15-EXAMPLES A) FORMULATION EXAMPLES a) A powder is obtained by spreading by mixing 10 parts by weight of a compound of formula (I) and 90 parts by weight of talc as an inert substance and grinding in an impact mill. b) A wettable powder which is readily dispersible in water is obtained by mixing 25 parts by weight of a compound of formula (I), 64 parts by weight of kaolin containing kaolin as an inert material, 10 parts by weight of potassium salt of lignin sulfonic acid and 1 part by weight of oleoyl methyl tauronic acid sodium salt as wetting and dispersing agents and ground in a hammer mill. (c) A dispersion concentrate is obtained which is readily dispersible in water by mixing 20 parts by weight of the compound of formula (I) with 6 parts by weight of ether to 1-phenylethylpolyglycol ether (Triton® X 207), 3 parts by weight of isotridecanol-polyglycol ether (with eight units of ethylene oxide) and 71 parts by weight of paraffinic mineral oil (boiling range, for example, from about 255Â ° to above 277Â ° C) and grinding in a ball mill until a fineness of less than 5 microns is obtained. d) An emulsifiable concentrate is obtained from 10 parts by weight of a compound of formula (I), 75 parts by weight of cyclohexane as solvent and 10 parts by weight of oxyethylated nonyl-phenol (10 units of oxide of ethylene) as the emulsifying agent. e) A water dispersible granulate is obtained by mixing
75 partes em peso do composto de fórmula geral (I), 10 partes em peso de sal de cálcio do ácido lignino-sulfó nico, 5 partes em peso de lauril-sulfato de sódio, 3 partes em peso de álcool polivinílico e 7 partes em peso de caulino, moendo num moinho de impacto e granulando o pó em leito fluidizado por pulverização de água como líquido de granu lação. f)75 parts by weight of the compound of formula (I), 10 parts by weight of calcium salt of lignino-sulphonic acid, 5 parts by weight of sodium lauryl sulfate, 3 parts by weight of polyvinyl alcohol and 7 parts by weight of weight of kaolin, grinding in an impact mill and granulating the powder in a fluidized bed by spraying water as the granulating liquid. f)
Obtém-se um produto granulado dispersãvel em água misturan do 25 partes em peso de um composto de fórmula geral (I), 5 partes em peso de sal de sódio do ácido 2,2'-dinaf til-ire tano-6,61-dissulfõnico, 2 partes em peso de sal de sodio do ácido oleoil-metil-tau rínico, 1 parte em peso de álcool polivinílico, 17 partes em peso de carbonato de cálcio e 50 partes em peso de água, homogeneizando num moinho coloidal e triturando, em seguida, moendo num moinho contendo pequenas esferas e polvjl lhando a suspensão assim obtida numa torre de pulverização por meio de um pulverizador e secando. g)A granules dispersible in water is mixed with 25 parts by weight of a compound of formula (I), 5 parts by weight of 2,2'-dimethyl-furan-6,6- 2 parts by weight of sodium oleoylmethyl tauric acid sodium salt, 1 part by weight of polyvinyl alcohol, 17 parts by weight of calcium carbonate and 50 parts by weight of water, homogenizing in a colloidal mill and grinding, then milling in a mill containing small beads and powdering the suspension thus obtained in a spray tower by means of a spray and drying. g)
Um granulado preparado de acordo com os métodos usuais con siste, por exemplo, em 2 a 15 partes em peso de substância activa de fórmula geral (I) e 98 a 85 partes em peso de material granulado inerte como atapulgite, pedra pomes ou areia de quartzo. -16- / h)A granulate prepared according to the usual methods comprises, for example, 2 to 15 parts by weight of active compound of general formula (I) and 98 to 85 parts by weight of inert granular material such as attapulgite, pumice or sand of quartz. -16- / h)
Obtém-se um concentrado emulsionável a partir de 10 partes em peso do composto de fórmula geral (I), CÉb 5 partes em peso de ^Genapol PF 40 (polímero de bloco de óxido de etileno/óxido propileno, 40% de teor de óxido de etileno), 3 partes em peso de fenil-sulfonato de cálcio 70 (sal de cálcio de ácido de ácido alquil-aril-sulfónico), 5 partes em peso de ^Imulsogen EL 360 (éster de poligliccl· de ácido gordo), β) 40 partes em peso de ^Solvesso 200 e 37 partes em peso de N-metil-pirrolidona. B) Exemplos de preparaçãoAn emulsifiable concentrate is obtained from 10 parts by weight of the compound of formula (I), 5 parts by weight of Genapol PF 40 (ethylene oxide / propylene oxide block polymer, 40% oxide content of ethylene), 3 parts by weight of calcium phenyl sulphonate 70 (calcium salt of alkyl aryl sulphonic acid), 5 parts by weight of Imulsogen EL 360 (polyglycol ester of fatty acid), β ) 40 parts by weight of Solubles 200 and 37 parts by weight of N-methylpyrrolidone. B) Preparation Examples
Exemplo 1Example 1
Ester de 2-[4-(cloroquinoxalin-2-il-oxi)-fenoxi]-propionato de 2--(propin-3-iloxi)-etilo2- (propyn-3-yloxy) -ethyl 2- [4- (chloroquinoxalin-2-yloxy) phenoxy] propionate
Misturam-se 2,6 gramas (10 milimole) de éster de 2—(4— -hidroxi-fenoxi)-propionato de 3-propin-3-iloxi-etilo em 50 ml de Ν,Ν-dimetil-formamida com 1,8 gramas (12 milimole) de carbonato de potássio e 1,8 gramas (10 milimole) de 2,6-dicloroquinoxa-lina e aquece-se a 100° C com agitação durante quatro horas. Em seguida, elimina-se a DMF a pressão reduzida, recolhe-se o resíduo em acetato de etilo, lava-se a fase orgânica com uma solução de hidróxido de sódio a 5% e, em seguida, com água. Seca-se a fa se orgânica com sulfato de magnésio e elimina-se por destilação o acetato de etilo. Agita-se o resíduo com éter e seca-se no vácuo.2.6 g (10 mmol) of 3-propyn-3-yloxy-ethyl 2- (4-hydroxy-phenoxy) -propionate ester in 50 ml of N, N-dimethylformamide are mixed with 1, 8 grams (12 millimole) of potassium carbonate and 1.8 grams (10 millimole) of 2,6-dichloroquinoxaine and heated to 100 ° C with stirring for four hours. Thereafter, the DMF is removed under reduced pressure, the residue is taken up in ethyl acetate, the organic phase is washed with 5% sodium hydroxide solution and then with water. The organic phase is dried over magnesium sulfate and ethyl acetate is distilled off. The residue is stirred with ether and dried under vacuum.
Obtêm-se 1,9 gramas (44,5% da teoria) de éster de 2- [A_ -(6-cloro-quinoxalin-2-iloxi)-fenoxi]-propionato de 2-(propin-3--iloxi)-etilo como ponto de fusão igual a 135° - 136° C e a fór mula -17-,Preparation of 2- (propyn-3-yloxy) -2- [6- (6-chloro-quinoxalin-2-yloxy) -phenoxy] -propionate, 1.9 g (44.5% of theory) -ethyl ester as the melting point equal to 135 ° -136 ° and the formula -17-,
Exemplo 2Example 2
Ester etílico de 2-[4-(6-clorobenzoxazol-2-iloxi)- fenoxi]-propio-nato de 2-[(tetra-hidrofuran-2-il)-metoxi]2- [4- (6-Chlorobenzoxazol-2-yloxy) -phenoxy] -propionic acid ethyl ester of 2 - [(tetrahydrofuran-2-yl) methoxy]
Dissolvem-se 3,1 grama (9,5 milimole) de ácido 2— [4—(6— -clorobenzoxazol-2-iloxi)-fenoxi]-propiónico em 150 ml de tolue-no anidro, a 90° C e, em seguida, adicionam-se 1,3 grama (10,9 milimole) de cloreto de tionilo. Agita-se durante uma hora a 70° C e destila-se o cloreto de tionilo em excesso a pressão reduzida. A 40° C, adiona-se gota a gota a esta solução uma mistura de 1,4 grama (9,6 milimole) de 2-[(tetra-hidrofuran-2-il)-metoxi]--etanol e 1,13 grama (11 milimole) de trietilamina, agita-se durante duas horas a 40° C e separa-se por filtração o cloreto de piridínio que precipitou. Lava-se a fase orgânica quatro vezes com uma solução a 5% de hidróxido de sódio, seca-se a solução to luénica sobre sulfato de magnésio e, em seguida, destila-se o to lueno no vácuo.3.1 gram (9.5 millimole) of 2- [4- (6-chlorobenzoxazol-2-yloxy) -phenoxy] -propionic acid are dissolved in 150 ml of dry toluene at 90 ° C and, then 1.3 gram (10.9 mmol) of thionyl chloride is added. Stir for one hour at 70 ° C and dilute the excess thionyl chloride under reduced pressure. At 40 DEG C., a mixture of 1.4 g (9.6 mmol) of 2 - [(tetrahydrofuran-2-yl) methoxy] ethanol and 1.13 g (11 mmol) of triethylamine is stirred for two hours at 40 ° C and the pyridinium chloride precipitated out by filtration. The organic phase is washed four times with a 5% sodium hydroxide solution, the toluene solution is dried over magnesium sulfate, and then the toluene is distilled off in vacuo.
Como resíduo, obtém-se 1*6 grama (36,5% do valor teórico) de 2-[4-(6-clorobenzoxazol-2-iloxi)-fenoxi]-propionato de éster etílico de 2-[(2-tetra-hidrofuranil)-metoxi] sob a forma de um óleo incolor, de fórmulaAs a residue, 1.62 grams (36.5% of theory) of 2 - [(2-tetrahydro-pyrrolidine-1,2-dicarboxylic acid 2- [4- (6-chlorobenzoxazol-2-yloxy) -phenoxy] -hydrofuranyl) -methoxy] as a colorless oil of formula
-18--18-
Exemplo 3Example 3
Ester etílico de 2-[4-(5-clorobenzoxazol-2-iloxi)-fenoxi]-propio-nato de 2-(propin-3-iloxi)2- (propyn-3-yloxy) -2- [4- (5-chlorobenzoxazol-2-yloxy) phenoxy] propionic acid ethyl ester
Dissolvem-se 19,28 gramas (54 milimole) de ácido 2-[4--(5-clorobenzoxazol-2-iloxi)-fenoxi]-propiõnico em 200 ml de te-tra-hidrofurano e, em seguida, adicionam-se 9,12 gramas(53 mili-mole) de 1,11-carbonil-di-imidazol. Agita-se à temperatura ambiente durante quarenta minutos até terminar a libertação de gases, adiciona-se gota a gota 6,17 grama (54 milimole) de 2-(propin-3--iloxi)-etanol, agita-se à temperatura ambiente durante cinco mi nutos e depois adiciona-se 1,0 grama de uma suspensão de hidrato de sódio a 50% em óleo mineral e agita-se à temperatura ambiente durante doze horas. Destila-se o tetra-hidrofurano a pressão reduzida, retoma-se o resíduo em acetato de etilo e lava-se a fase orgânica quatro vezes em solução de hidróxido de sódio a 5%. Seca-se a fracção solúvel em acetato de etilo sobre sulfato de magné sio e destila-se o dissolvente em vácuo. Em seguida, filtra-se o resíduo através de óxido de alumínio com acetato de etilo/diclo-rometano (1 : 8). Desta maneira, obtêm-se 5,3 grama (23,6% da teo ria) de éster etílico de 2-[4-(5-clorobenzoxazol-2-iloxi)-fenoxi]_ -propionato de 2-(propin-3-iloxi) sob a forma de um óleo incolor, com a fórmula C119.28 grams (54 millimole) of 2- [4- (5-chlorobenzoxazol-2-yloxy) -phenoxy] -propionic acid are dissolved in 200 ml of tetrahydrofuran and then added 9.12 grams (53 millimoles) of 1,11-carbonyl-diimidazole. Stir at room temperature for 40 minutes until the gas evolution is complete, 6.17 g (54 mmol) of 2- (propyn-3-yloxy) ethanol are added dropwise, the mixture is stirred at room temperature for five minutes and then 1.0 grams of a 50% sodium hydride suspension in mineral oil is added and stirred at room temperature for twelve hours. The tetrahydrofuran is distilled off under reduced pressure, the residue is taken up in ethyl acetate and the organic phase is washed four times in 5% sodium hydroxide solution. The ethyl acetate-soluble fraction is dried over magnesium sulfate and the solvent is distilled off in vacuo. The residue is then filtered through aluminum oxide with ethyl acetate / dichloromethane (1: 8). In this manner, 5.3 g (23.6% of theory) of 2- (propyn-3-ylmethyl) -2- [4- (5-chlorobenzoxazol-2-yloxy) phenoxy] propionate yloxy) as a colorless oil, of formula C1
-0-CH-C CH0 0 O \-O-CH-
0-CH2-CH2-0-CH2-C=CH -19-0-CH 2 -CH 2 -O-CH 2 -CH = CH-
CW
Exemplo 4 Éster de D-2-[4-(6-clorobenzoxazol-2-iloxi)-fenoxi]-propionato de 2-[(isopropilidenamino)-oxi]-etilo _ tC.Example 4 2 - [(Isopropylideneamino) oxy] ethyl] tC-2-carboxylic acid D-2- [4- (6-chlorobenzoxazol-2-yloxy) phenoxy] propionate.
Dissolvem-se 3,1 gramas(9,5 milimole) de ácido D-2-[4--(6-clorobenzoxazol-2-iloxi)-fenoxi]-propiónico em 70 ml de acetato de etilo e adicionam-se 50 miligramas de 4-Ν,Ν-dimetilamino piridina e 1,11 gramas (9,5 milimole) de 2-(isopropilidenaminoxi^ -etanol. A 0o C, adicionam-se 2,06 gramas (10 milimole) de dici-clo-hexil-carbo-di-imida e, em seguida, agita-se ainda durante mais trinta minutos a 20° C e separa-se por filtração sob sucção a diciclo-hexil-ureia que precipitou. Em seguida, lava-se a fase orgânica duas vezes com ácido clorídrico 0,5 N e com uma solução saturada de hidrogeno-carbonato de sódio. Seca-se a fase orgânica sobre sulfato de magnésio e destila-se o acetato de etilo. Obtém -se assim 1,7 gramas (41,3% da teoria) de éster de D-2-[4-(6-clo robenzoxazol-2-iloxi)-fenoxi]-propionato de 2-[(isopropilidenand no)-oxi]-etilo com o ponto de fusão igual a 73° C e com um valor do poder de rotação de (<V)^ = 22,4° C (c = l,CHClg), com a fórmula3.1 grams (9.5 millimole) of D-2- [4- (6-chlorobenzoxazol-2-yloxy) -phenoxy] -propionic acid are dissolved in 70 ml of ethyl acetate and 50 milligrams of 4-Ν, Ν-dimethylamino pyridine and 1.11 grams (9.5 millimole) of 2- (isopropylideneaminoxy) ethanol. At 0 ° C, 2.06 grams (10 mmol) of dicyclohexyl dicyclohexyl-urea and then stirred for an additional 30 minutes at 20 DEG C. The precipitated dicyclohexyl urea was filtered off under suction and the organic phase was washed twice times with 0.5 N hydrochloric acid and a saturated solution of sodium hydrogen carbonate The organic phase is dried over magnesium sulfate and ethyl acetate is distilled to give 1.7 g (41% 3% of theory) of 2 - [(isopropylidene) oxy] ethyl D-2- [4- (6-chlorobenzoxazol-2-yloxy) phenoxy] propionate having the melting point equal to 73 ° C and having a rotational power value of (<V) = 22.4 ° C (c = 1, CHCl 3), of the formula
(Fórmula D)(Formula D)
No quadro 1 seguinte, estão reunidos os exemplos 1 a 5 juntamente com outros exemplos de compostos de fórmula geral (I), acima mencionada, que se obtêm de maneira análoga. -20- Τ'-"* Μ QUADRO 1 NQ Y Q <x>„ x,zn R1 m W R2 Ponto de fusão e s tereoquimica 1 0 Q2 6-C1 H 2 0 -ch9-c=ch 135-136 2 0 Q3 6-C1 H 2 0 -CH2<0> õleo incolor 3 0 Q3 5-C1 H 2 0 -CH2-CsCH Õleo incolor 4 0 Q3 6-C1 H 2 0 -N=C(CH3)CH3 73°C, Iscmsro D 5 0 Q3 6-C1 H . 2 0 -CH2-CH=CH2 40°C, Iscmero D 6 II II II II 2 0 -CH2-CsCH 71°C, Iscmero D 7 II II 11 II 3 II -CH2-CH=CH2 Õleo 8 II 11 11 II 3 II -CH2C^CH Õleo 9 II II II II 2 11 -CH2SÍ(CH3)3 Õleo 10 II II II II II II -a 85°C, Forma D 11 II 11 II II II II -o 70°C, Forma D 12 II II II II 3 II -CH2Si(CH3)3 13 11 II II II II 11 -N=C(CH3)2 14 II II II II II II -a 15 II II 11 11 II 11 -H-O 16 II II II II 2 II -CÍR-^o-^ ^ OCH, _/ 3 17 II II II II II 11 -N=CH-/0 V"OCH Woch3 3 Õleo, forma D 18 II II 5-C1 II II II -CH2-CH=CH2 Õleo 19 II II 11 11 3 11 II 20 11 II II II II II -CH2CsCH 21 II II « II 2 II -CH0Si(CH-)-In the following Table 1, examples 1 to 5 are combined together with other examples of compounds of the above mentioned general formula (I), which are obtained in an analogous manner. TABLE 1 NQ YQ <x> x, zn R1 m W R2 Melting point is tereoquimic 1 0 Q2 6-C1 H 2 0 -ch9-c = ch 135-136 2 0 Q3 6-C1 H 2 0 -CH 2 < 0 > colorless oil 3 0 Q 3 6-C H 2 O-N = C (CH 3) CH 3 73 ° C, D-isopropanoic acid. 2 0 -CH 2 -CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 -CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 II -CH 2 CH 2 CH 2 CH 2 CH 2 Si (CH 3) 3 oleyl 10 II II II II II a at 85 ° C, Form D 11 II II II II -O 70 ° C, Form D 12 II II II II 3 II -CH 2 Si (CH 3) 3 13 11 II II II II 11 -N-C (CH 3) 2 14 II II II II II II II 2 II -III II -III II II II II II II II II II II II II II II II II II II II II CH 2 CH 2 CH 2 CH 2 SiO 3 CH 2 CH 2 SiO 2 CH 2 SiO 2 CH 2 SiO (CH 2)
QUADRO 1 (CONTINUAÇÃO) N° Y Q (X) n x, z R1 m w R2 22 . 0 Q3 5-C1 H 2 0 -N=C(CH3)2 23 II . II II II II II -n=<L ' 24 II 11 II 11 II II -o 25 II 11 II II 3 11 -CH2Si(CH3) 26 II II II II II II -N=C (CH. 3*2 27 11 11 11 II II II -a 28 II II II II II 11 -o 29 II Q2 6-C1 II II II -CH2-CH= =CH2 30 II 11 II 11 1 coo -CH2C=CH 31 II II II II 2 0 -CH2SÍ(CH3) 32 II II II II 3 11 -CH2CH=CH2 33 11 11 11 II II II -CH2CsCH 34 II Q3 5-C1 II 2 II 35 II 11 11 II 3 11 II 36 II Q2 7-C1 II 2 II -CH2SÍ(CH3) 37 II II 6-C1 II 3 II II 38 11 11 11 CH3 1 coo -CH2CH=CH2 39 II II II II II 11 -CH2CsCH 40 II Q4 3,5-F2 H 2 0 -CH2CH= cn2 41 II 11 II II 11 11 -CH2CH= CH 42 II II II II II II -CH2Si(CH3) -n=c(ch3)2 43 IITABLE 1 (CONTINUATION) No. Y Q (X) n x, z R1 m R2 R2. 0 Q3 5-C1 H 2 0 -N = C (CH 3) 2 II. II II II II -n = < L '24 II 11 II II -o 25 II 11 II II 3 11 -CH 2 Si (CH 3) 26 II II II II II -N = C (CH 3) 2 27 11 11 11 II II II -a 28 II II II II -III II II II II -III II II -III II II -III 2 0 -CH 2 Si (CH 3) 32 II II II II 3 11 -CH 2 CH = CH 2 33 II 11 II II -CH 2 CH 2 CH 3 CH 2 CH 3 II 2 II -CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 CH 2 CH 3 CH 2 CH 3 CH CH 2 CH = CH 2 Si (CH 3) - n = c (ch 3) 2 43 II
Cera Óleo Õleo -22- QUADRO 1 (CONTINUAÇÃO)Wax Oil Oil -22- TABLE 1 (CONTINUED)
N9 Y Q (X) n x,z R1 m w R2 44 0 4 Q 2 3,5-F H 2 0 -a 45 II II II 11 11 II -0 46 II II II 11 3 II -CH2CH=CH2 47 II II 11 II II II -CH2C=CH 48 II II II II II II -n=c(ch3)2 49 II II 11 11 11 II -a 50 II II 11 II 11 11 *0 51 II II II II II II -CH2Sl(CH3)3 52 II II II 1-CH3 2 -CH2CH=CH2 53 II II 11 II II II -CH2C=CH 54 II Q1 6-C1 H 2 0 -CH2CH=CH2 55 II II II II II II -CH2C=CH 56 II II II 11 11 II -CH2SÍ(CH3)3 57 II II II II 1 coo -n=c(ch3)2 58 II II II II 1 coo 59 II II II 11 II II -"O 60 II II II II 3 0 -CH2CH=CH2 61 11 II II II II II -CH2C=CH 62 II II 11 CH3 1 coo -n=c(ch3)2 63 II II II CH3 1 coo -CH2CH=CH2 64 II II II 11 II II -CH2C=CHN9 YQ (X) nx, z R1 mw R2 44 0 4 Q 2 3,5-FH 2 0 -a 45 II II II 11 II -0 46 II II II II 3 II -CH 2 CH = CH 2 47 II II II II II II -CH 2 C = CH 48 II II II II II -n = c (ch 3) 2 49 II II 11 11 11 II -a 50 II II 11 II 11 II II II -CH 2 Si (CH 3) ) 3 52 II II II 1-CH 3 2 -CH 2 CH = CH 2 53 II II II -CH 2 C = CH II II II 11 II -CH 2 Si (CH 3) 3 57 II II II II 1 coo-n = c (ch 3) 2 58 II II II II 1 coo 59 II II II II II - 3 0 -CH 2 CH = CH 2 61 II II II II -CH 2 C = CH 62 II II 11 CH 3 1 coo -n = c (ch 3) 2 63 II II CH 3 1 coo -CH 2 CH = CH 2 64 II II II II II -CH 2 C = CH
QUADRO 1 (CONTINUAÇÃO)TABLE 1 (CONTINUED)
Y Q (X) n x,z R1 m w R2 s Q3 6-C1 H 2 0 -CH2C=CH II 11 11 II 11 11 -CH2CH=CH2 0 Q2 11 CH3 1 cos II II II II II II II -CH2C=CH s Q1 6-C1 H 2 0 -CH2CH=CH2 II II II II II II -CH2C=CH II Q2 6-C1 II 11 11 11 II II 11 II 11 II -CH2CH=CH2 II Q4 3,5-Cl2 II II II II II II II II II II -CH2C=CH 11 Q3 5-CH3 11 II II II II II 5,7-Cl2 11 II II 11 II II 6-CF3 II 11 II -CH2CH=CH2 II II 5-CN II II II II II II 5-N02 II II II II II 11 6-C1 11 1 11 II 11 II 11 II 4 II II II II II II II II -CH2C=CH II 11 11 C2H5 1 II -CH2CH=CH2 II Q2 11 H II coo II II II II II II II -CH2C=CH 11 II 11 11 II cos 11 II II II 1! 4 0 -CH2CH=CH2 II II II ch3 1 coo -CH2CH=CH2 II 11 II II 11 II -CH2C=CH 0 Q4 3-C1,5-F H 2 0 -CH2CH=CH2 II II II II II II -CH^CHsCH -24-YQ (X) nx, z R 1, R 2, R 2, and R 2 are each independently selected from the group consisting of: Q1 6-C1 H 2 O -CH 2 CH = CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH II -III II II II -III II II -III II II -III II II -III II II -III II II II -III II II -III II II II II II II II II II II II II II II II II II II -III II II II II II II II II II II II II II II II II II II II II II II II II II II II II H II co II II II II II II -CH 2 C = CH II II 11 II cos II II II II 1! 4-CH 2 CH = CH 2 CH 2 CH 3 CH 2 CH 3 CH 2 CH 3 CH 2 CH 3 CH 2 CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH CHsCH-24-
-24- NQ Y Q (X) n X, z R1 m w 92 0 Q4 3-Cl,5-F H 2 0 93 II II II II II II 94 II II II II II II 95 II II II II II II 96 II II II II 3 II 97 II II II II II II II II II II II II 99 II II II II II II 100 II II II II II II 101 II II II II II II 102 II II " 1· -ch3 2 II 103 II II II II II II 104 II II. 11 11 11 11 105 II II II II II 11 106 II II II II II II 107 11 11 II II 11 11 108 11 11 " 2 -ch3 II II 109 II II II II II II 110 11 II " 1 -C2H5 11 II 111 II II II II II II 112 II II 3,5-Cl2 H 2 0 113 11 11 11 11 11 11 114 II II II II II II QUADRO 1 (CONTINUAÇÃO) -ch2sí(ch3)3 -n=c(ch3)2 -a -o -CH„CH=CH„ -ch2c=ch -n=c(ch3)2(X) n X, z R 1 mw 92 0 Q 4 3-Cl, 5-FH 2 0 93 II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II II 1 · -ch3 2 II 103 II II II II II II II II. 11 11 11 11 105 II II II II II 11 106 II II II II II II II 11 II II 11 11 108 11 11 " 2 -ch 3 II II 109 II II II II II 110 11 II " (CH 3) 3 -n (CH 3) 2 -CH 2 CH 2 CH 2 CH 3 CH 2 = c (ch3) 2 -a -o -CH "CH = CH" -ch2c = ch -n = c (ch3) 2
-O -CH2Si(CH3)3 -CH2CH=CH2-O -CH 2 Si (CH 3) 3 -CH 2 CH = CH 2
-CH2C=CH -CH2CH=CH2-CH 2 C = CH -CH 2 CH = CH 2
-CH2C5CH -CH2SÍ(CH3)3 -N=C(CH3)2 -CH2-CH=CH2-CH2 C5 CH -CH2 Si (CH3) 3 -N = C (CH3) 2 -CH2 -CH = CH2
-CH2-CsCH -CH2-CH=CH2-CH2-CsCH-CH2-CH = CH2
-CH2-C=CH -CH2CH=CH2-CH 2 -C = CH -CH 2 CH = CH 2
-CH2C=CH -CH2Sí(CH3)2-CH 2 C = CH-CH 2 Si (CH 3) 2
Cera Õleo -25 / % QUADRO 1 (CONTINUAÇÃO) NQ Y Q (X) n x,z R1 m w 2 R 115 0 24 3',5-Cl2 H - 2 0 ~N=C(CH3)2 116 11 11 II II II II -a 117 11 II II II 11 * II -0 118 II II II II 3 11 -CHL, CH=CH2 119 II II II II II II -CH2C=CH 120 II II II 11 II II -N=C(CH 3*2 121 II II II II II II 1 122 II 11 11 II 11 II -n=0 123 11 11 II 11 II 11 -CH2SÍ(CH3)3 124 II II 3-F,5-Cl II 2 II -CH2CH=CH2 125 II II II II II II -ch2c=ch 126 II II 11 11 II 11 -CH2SÍ(CH3)3 127 11 11 II 11 II 11 -N=C(CH 3* 2 128 II II II II II 11 -a 129 II II II II II II »0 130 II II II II 3 II -CH2CH=CH2 131 II II II II II II -CH2C=CH 132 II 11 II II II II -N=C(CH 3^ 2 133 11 II II II II II -a 134 II II II II II II -N=0 135 II II II 11 II II -CH2Si(CH3)3 Óleo incolor -26 *Wax -25 /% TABLE 1 (CONTINUATION) NQ YQ (X) nx, z R1 mw 2 R 115 0 24 3 ', 5-Cl2 H-20 / N = C (CH3) 2 116 11 11 II II II II-a 117 II II II II II -III II -IIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIII IIII 3 * 2 121 II II II II II 1 122 II 11 11 II 11 II -n = 0 123 11 11 II 11 II 11 -CH 2 Si (CH 3) 3 124 II II 3-F, 5-Cl II 2 -CH 2 CH = CH2 125 II II II II II -CH2c = ch 126 II II 11 11 II 11 -CH 2 Si (CH 3) 3 127 11 11 II 11 II 11 -N 11 (II): ## STR1 ## wherein X is as defined for formula (II): ## STR1 ## (CH 3) 3 Colorless oil -26 * II-II
EXEMPLOS BIOLÕGICOS A danificação das ervas daninhas e a compatibilidade com as plantas cultivadas foram classificadas de acordo com uma chave em que a actividade se exprime por números classificativos de 0 a 5. De acordo com essa escala: 0 = ausência de acção e de prejuízo 1 = 0 a 20% de acção ou de prejuízo 2 = 20 a 40% de acção ou de prejuízo 3 = 40 a 60% de acção ou de prejuízo 4 = 60 a 80% de acção ou de prejuízo 5 = 80 a 100% de acção ou de prejuízo. 1. Acção sobre as Ervas Daninhas em Pré-EmergênciaBIOLOGICAL EXAMPLES Weed damage and compatibility with cultivated plants were classified according to a key in which the activity is expressed by the numerical numbers 0 to 5. According to this scale: 0 = absence of action and injury 1 = 0 to 20% of action or of injury 2 = 20 to 40% of action or of injury 3 = 40 to 60% of action or of injury 4 = 60 to 80% of action or of injury 5 = 80 to 100% of action or injury. 1. Action on Pre-Emergency Weeds
Colocaram-se sementes ou peças de rizomas de plantas daninhas monocotiledóneas e dicotiledóneas em vasos de plástico com terra argilo-arenosa e recobriram-se com terra. Os compostos sob a forma de pôs molháveis ou concentrados de emulsão de acordo com a presente invenção foram aplicados sob a forma de suspen sões aquosas ou de emulsões aquosas com uma quantidade de água correspondente a 600 - 800 litros por hectare, com diferentes do sagens, sobre a superfície da terra de cobertura.Seeds or pieces of monocotyledonous and dicotyledonous weed rhizomes were placed in plastic vessels with clay-sandy soil and overlaid with earth. The wettable powder compounds or emulsion concentrates according to the present invention were applied in the form of aqueous suspensions or aqueous emulsions with an amount of water corresponding to 600-800 liters per hectare, other than sieves, on the surface of the land cover.
Depois do tratamento, os vasos foram colocados em estu fa e mantidos em boas condições de desenvolvimento das ervas daninhas. A classificação óptica das plantas e dos prejuízos na ger minação realizou-se depois da emergência das plantas de ensaio ao fim de três a quatro semanas em comparação com controlos não tra tados.After treatment, the vessels were placed in the estuary and maintained in good weed development conditions. Optical classification of plants and losses in germination took place after the emergence of the test plants after three to four weeks compared to untreated controls.
Como os valores da classificação indicados no quadro 2 mostram, os compostos, de acordo com a presente invenção, possuem uma boa actividade herbicida de pré-emergência contra um largo espectro de ervas daninhas. -27As the grading values given in Table 2 show, the compounds according to the present invention have good pre-emergence herbicidal activity against a broad spectrum of weeds. -27
2. Acção sobre as Ervas Daninhas depois da Emergência2. Action on Weeds after Emergence
Colocaram-se sementes ou pedaços de rizoma de ervas da ninhas monocotiledóneas e dicotiledóneas em vasos de plástico ccm terra argilo-arenosa, recobriram-se com terra e colocaram-se em estufa em boas condições de desenvolvimento. Depois de tris sema nas, trataram-se as plantas de ensaio, na fase de desenvolvimento de três folhas.Seeds or pieces of rhizome of monocotyledonous and dicotyledonous herbs were placed in plastic vessels with clay-sandy soil, overlaid with earth and placed in a greenhouse under good developmental conditions. After three weeks, the test plants were treated in the development phase of three leaves.
Os compostos de acordo com a presente invenção, formulados como põs molháveis ou como concentrados de emulsão, foram pulverizados em diversas doses, com uma quantidade de utilização de água de aproximadamente 600 a 800 litros por hectare, sobre as partes verdes das plantas e, depois de três a quatro semanas de repouso das plantas de ensaio em estufa, em condições de desenvol vimento óptimas. Classificou-se a acção das composições opticamen te em comparação com controlos não tratados.The compounds according to the present invention, formulated as wettable powders or as emulsion concentrates, were sprayed in several doses, with a water utilization amount of approximately 600 to 800 liters per hectare, on the green parts of the plants, and then three to four weeks' rest of the greenhouse test plants under optimum development conditions. The action of the compositions optically was compared in comparison with untreated controls.
As composições de acordo com a presente invenção pos^ suem também, no tratamento de pós-emergência, uma boa actividade herbicida contra um largo espectro de ervas daninhas importantes do ponto de vista económico (quadro 3). 3. Compatibilidade com as Plantas de CulturaThe compositions according to the present invention also possess good herbicidal activity against a broad spectrum of economically important weeds in the post-emergence treatment (Table 3). 3. Compatibility with Plants of Culture
Em outros ensaios em estufa, colocaram-se sementes de um grande número de plantas de cultura e de ervas daninhas em ter reno argilo-arenoso e recobriram-se com terra.In other greenhouse experiments, seeds of a large number of crop plants and weeds were harvested in sandy-clay reindeer and overlaid with earth.
Parte dos vasos foi imediatamente tratada como se descreveu em 1, os restantes foram colocados em estufa até as plantas terem desenvolvido duas a três folhas verdadeiras e, em segui^ da, pulverizaram-se com as substâncias de"acordo com a presente in venção, em diversas doses, como se mencionou em 2.Part of the vessels were immediately treated as described in 1, the remainder were placed in an oven until the plants had developed two to three true leaves and were then sprayed with the substances of the present invention, in several doses, as mentioned in 2.
Quatro a cinco semanas depois da aplicação e de um tem po de repouso em estufa, determinou-se, por classificação óptica. -28-/ que os compostos de acordo com a presente invenção, em culturas de plantas dicotiledõneas, como, por exemplo, soja, algodão, col za, beterraba açucareira e batata, tanto no processo de pré-emer gência como no processo de pós-emergência, mesmo no caso de elevadas dosagens de substância activa, não sofreram ataque. Algumas substâncias apresentaram, além disso, também em presença de culturas gramíneas, como, por exemplo, cevada, trigo, centeio, sorgo, milho ou arroz, bons resultados. Os compostos de fórmula geral I apresentam, portanto, uma elevada selectividade quando uti lizados para o combate do desenvolvimento de plantas indesejadas em culturas agrícolas. 4. Acção Herbicida no Caso de Utilização em ArrozFour to five weeks after the application and a resting period in the greenhouse, it was determined, by optical classification. The compounds according to the present invention in dicotyledonous plant cultures, such as soybean, cottonseed, sugar beet and potato, both in the pre-emergence process and in the post-fermentation process even in the case of high dosages of active substance, were not attacked. Some substances have also been present in the presence of grass crops, such as barley, wheat, rye, sorghum, maize or rice, good results. The compounds of formula I therefore have a high selectivity when used to combat the development of unwanted plants in agricultural crops. 4. Herbicide Action in the Rice Use Case
Em vasos de plástico, colocaram-se tubérculos e rizomas ou plantas recentes ou sementes de ervas daninhas do arroz tais como espécies de Cyperus, Eleocharis, Scirpus e Echinochloa, em vasos de plástico fechados recobertos com terra especial para o arroz ou plantaram-se e recobriu-se com água até â altura de 1 centímetro acima da terra. Procedeu-se da mesma forma com plantas de arroz.In plastic pots were placed tubers and rhizomes or fresh plants or seeds of rice weeds such as Cyperus, Eleocharis, Scirpus and Echinochloa species in closed plastic vases coated with special rice soil or planted and covered with water up to 1 cm above the earth. The same was done with rice plants.
Para o ensaio do processo de pré-emergência, quer dizer, três a quatro dias depois da plantação, despejaram-se na água de recobertura compostos de acordo com a presente invenção sob a for ma de suspensões ou emulsões aquosas, sob a forma de grânulos pol^ vilhados na água ou sobre as partes verdes das plantas. Respecti. vamente três semanas depois, classificou-se opticamente a acção herbicida e uma eventual acção prejudicial contra o arroz. Os re sultados mostram que os compostos de acordo com a presente inven ção se caracterizam por um combate selectivo contra ervas dani nhas (quadros 4 e 5). Em comparação com os herbicidas de arroz até agora utilizados, os compostos de acordo com a presente in- -29 vençao caracterizam-se por combaterem inúmeras ervas daninhas que se combatem muito dificilmente como Echinochlos e são bem tolera dos pelo arroz. QUADRO 2That is to say, three to four days after planting, compounds of the present invention were dissolved in the coating water in the form of aqueous suspensions or emulsions in the form of granules polymethylated in water or on green parts of plants. Respecti. three weeks later, the herbicidal action and possible injurious action against rice were optically classified. The results show that the compounds according to the present invention are characterized by selective control against harmful herbs (Tables 4 and 5). In comparison with the rice herbicides hitherto used, the compounds according to the present invention are characterized by combating numerous weeds which are very difficult to combat as Echinochlos and are well tolerated by rice. TABLE 2
Acgão Herbicida dos Compostos de Acordo com a Presente Invengão em Pré-EmergenciaHerbicide Acquisition of Compounds According to the Present Preventive Invention
Exemplo Dose Actividade herbicida (Kq de ingrediente activo/ha) AVFA ALMY SEPU LOMU ECCR 2 1,2 4 4 5 5 5 0,3 3 4 5 3 5 co o o 1 2 5 Q 5 113 1/2 5 5 5 5 5 0,3 3 5 5 5 5 0,08 0 4 5 3 5 54 1/2 5 5 5 5 5 0,3 3 5 5 3 5 0,08 1 3 5 0 3 38 1,2 5 5 5 5 5 0,3 4 5 5 5 5 o o 00 0 3 4 0 3 39 1/2 4 5 5 5 5 0,3 2 5 5 3 5 0,08 2 4 5 0 3 130 1/2 5 5 5 5 5 0,3 5 5 5 5 5 0,08 3 5 5 4 5Example Dose Herbicidal activity (Kg of active ingredient / ha) AVFA ALMY SEPU LOMU ECCR 2 1.2 4 4 5 5 5 0.3 3 4 5 3 5 as 1 2 5 Q 5 113 1/2 5 5 5 5 5 0.3 3 5 5 5 5 0.08 0 4 5 3 5 54 1/2 5 5 5 5 5 0.3 3 5 5 3 5 0.08 1 3 5 0 3 38 1.2 5 5 5 5 5 0.3 4 5 5 5 5 0 00 0 3 4 0 3 39 1/2 4 5 5 5 5 0.3 2 5 5 3 5 0.08 2 4 5 0 3 130 1/2 5 5 5 5 5 0 , 3 5 5 5 5 5 0.08 3 5 5 4 5
Abreviaturas: AVFA = Avena fatua ALMY = Alopecurus myosuroides SEPIJ = Setaria pumila LOMU = Lolium Multiflorum ECCR = Echinochloa crus-galli. QUADRO 3Abbreviations: AVFA = Avena fatua ALMY = Alopecurus myosuroides SEPIJ = Setaria pumila LOMU = Lolium Multiflorum ECCR = Echinochloa crus-galli. TABLE 3
Acção Herbicida dos Compostos de Acordo com a Presente Invenção em Põs-Emergênc: ia Actividade Herbicida Exemplo Dose AVFA ALMY SEPU LOMU ECCR (Kg de ingrediente activo/ha) . 2 1/2 5 5 5 5 5 0,3 4 5 5 3 5 0,08 3 4 5 1 5 113 1/2 5 5 5 5 5 0,3 5 5 5 5 5 0,08 5 5 5 5 5 54 1,2 5 5 5 5 5 0,3 5 5 5 5 5 0,08 4 5 5 5 5 38 1,2 5 5 5 5 5 0,3 5 5 5 5 5 0,08 5 5 5 5 5 39 1,2 5 5 5 5 5 0,3 5 5 5 5 5 0,08 5 5 5 5 5 130 1,2 5 5 5 5 5 0,3 5 5 5 5 5 0,08 5 5 5 5 5Herbicidal Action of Compounds According to the Present Invention in P-Emergence Herbicide Activity Example Dose AVFA ALMY SEPU LOMU ECCR (kg active ingredient / ha). 2 1/2 5 5 5 5 5 0.3 4 5 5 3 5 0.08 3 4 5 1 5 113 1/2 5 5 5 5 5 0.3 5 5 5 5 5 0.08 5 5 5 5 5 54 1.2 5 5 5 5 5 0.3 5 5 5 5 5 0.08 4 5 5 5 5 38 1.2 5 5 5 5 5 0.3 5 5 5 5 5 0.08 5 5 5 5 5 39 1.2 5 5 5 5 5 0.3 5 5 5 5 5 0.08 5 5 5 5 5 130 1.2 5 5 5 5 5 0.3 5 5 5 5 5 0.08 5 5 5 5 5
Abreviaturas: AVFA = Avena fatua ALMY = Alopecurus myosuroides SEPU - Setaria pumila LOMU = Lolium multiflorum ECCR = Echinochloa crus-galli. QUADRO 4Abbreviations: AVFA = Avena fatua ALMY = Alopecurus myosuroides SEPU - Setaria pumila LOMU = Lolium multiflorum ECCR = Echinochloa crus-galli. TABLE 4
Acção dos Compostos de Acordo com a Presente Invenção em Arroz - - Aplicação de Pré-Emergência Exemplo (Kg de Dose ingrediente activo/ha) Actividade ORSA herbicida ECCR 6 0,25 2 5 0,125 2 5 0,06 1 5 0,03 0 4 5 0,25 3 5 0,125 2 4 0,06 1 3 0,03 0 3 4 0,25 3 5 0,125 2 5 0,06 1 5 0,03 0 4 7 0,25 1 5 0,125 1 5 0,06 0 5 0,03 0 3Action of Compounds According to the Present Invention in Rice - - Pre-Emergency Application Example (Kg of active ingredient dose / ha) Activity ORSA herbicide ECCR 6 0.25 2 5 0.125 2 5 0.06 1 5 0.03 0 4 5 0.25 3 5 0.125 2 4 0.06 1 3 0.03 0 3 4 0.25 3 5 0.125 2 5 0.06 1 5 0.03 0 4 7 0.25 1 5 0.125 1 5 0, 06 0 5 0.03 0 3
Abreviaturas: ORSA = Oryza sativa ECCR = Echinochloa crus-galli. -32Abbreviations: ORSA = Oryza sativa ECCR = Echinochloa crus-galli. -32
QUADRO 5 Acção dos Compostos de Acordo com a Presente Invenção em Arroz - - Aplicação de Põs-Emergência Exemplo Dose (Kg de ingrediente activo/ha) Actividade ORSA herbicida ECCR 10 0,25 2 5 0,125 1 5 0,06 0 4 0,03 0 3 11 0,25 2 5 0,125 1 5 0,06 0 3 0,03 0 1 6 0,25 2 5 0,125 2 5 0,06 0 5 0,03 0 3 5 0,25 2 5 0,125 2 5 0,06 0 5 0,03 0 3 4 0,25 2 5 0,125 1 5 0,06 1 5 0,03 0 2 17 0,25 1 5 0,125 1 5 0,06 0 3 0,03 0 1 QUADRO 5 (CONTINUAÇÃO)TABLE 5 Action of Compounds According to the Present Invention in Rice Powder Application Example Dose (kg active ingredient / ha) Herbicidal ORSA activity ECCR 10 0.25 2 5 0.125 1 5 0.06 0 40, 03 0 3 11 0.25 2 5 0.125 1 5 0.06 0 3 0.03 0 1 6 0.25 2 5 0.125 2 5 0.06 0 5 0.03 0 3 5 0.25 2 5 0.125 2 5 0.06 0 5 0.03 0 3 4 0.25 2 5 0.125 1 5 0.06 1 5 0.03 0 2 17 0.25 1 5 0.125 1 5 0.06 0 3 0.03 0 1 TABLE 5 (CONTINUATION)
Acção dos Compostos de Acordo com a Presente Invenção em Arroz - - Aplicação de Põs-Emergência Exemplo Dose (Kg de ingrediente activo/ha) Actividade ORSA herbicida ECCR 9 0,25 2 5 0,125 1 5 0,06 0 5 0,03 0 3 7 0,25 1 5 0,125 0 5 0,06 0 5 0,03 0 5 2 0,25 3 5 0,125 1 5 0,06 0 5 0,03 0 4 113 0,24 1 5 0,125 0 5 0,06 0 5 0,03 0 5Action of the Compounds According to the Present Invention in Rice - Powder Application Example Dose (Kg of active ingredient / ha) ORSA herbicidal activity ECCR 9 0.25 2 5 0.125 1 5 0.06 0 5 0.03 0 3 7 0.25 1 5 0.125 0 5 0.06 0 5 0.03 0 5 2 0.25 3 5 0.125 1 5 0.06 0 5 0.03 0 4 113 0.24 1 5 0.125 0 5 0, 06 0 5 0.03 0 5
Abreviaturas: ORSA = Oryza sativa ECCR = Echinochloa crus-galli.Abbreviations: ORSA = Oryza sativa ECCR = Echinochloa crus-galli.
Claims (4)
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DE3933246 | 1989-10-05 | ||
DE3939095 | 1989-11-25 |
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PT9550390A PT95503A (en) | 1989-10-05 | 1990-10-04 | PROCESS FOR THE PREPARATION OF DERIVATIVES OF HETEROCYCLICALLY SUBSTITUTED PHENOXIALCANOCARBOXYL ACID ACIDS WITH HERBICIDAL PROPERTIES |
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AU (1) | AU6540490A (en) |
PT (1) | PT95503A (en) |
WO (1) | WO1991004969A1 (en) |
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DE4042098C2 (en) * | 1990-12-28 | 1993-10-07 | Hoechst Ag | Process for the preparation of optically active quinoxalinyloxy-phenoxypropionic acid esters |
WO1994013647A1 (en) * | 1992-12-15 | 1994-06-23 | The Du Pont Merck Pharmaceutical Company | (2-quinoxalinyloxy)phenoxypropanoic acids and related derivatives as anticancer agents |
WO2006125337A1 (en) * | 2005-05-23 | 2006-11-30 | Sinochem Corporation | α, β- AND, Ϝ-UNSATURATED CARBOXYLATES AND THE USE AS HERBICIDIDE THEREOF |
IN2015DN02264A (en) | 2012-10-19 | 2015-08-21 | Syngenta Participations Ag | |
CN104649995B (en) * | 2013-11-25 | 2017-06-09 | 沈阳中化农药化工研发有限公司 | A kind of 6 chloro benzo oxazole epoxide phenoxy propionic acid allyl ester type compound and its application as herbicide |
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CA1114382A (en) * | 1978-07-03 | 1981-12-15 | Hermann Rempfler | Esters of 0-(pyridyloxy-phenyl)-lactic acids |
ES490262A0 (en) * | 1979-04-09 | 1981-10-16 | Hoechst Ag | PROCEDURE FOR THE PREPARATION OF HERBICIDIC AGENTS BASED ON HETERO CYCLIC PHENILETERS |
DE3170423D1 (en) * | 1980-11-26 | 1985-06-13 | Hoffmann La Roche | Oxime esters, processes for their preparation, their use and compositions containing these esters |
US4391628A (en) * | 1981-02-16 | 1983-07-05 | Ciba-Geigy Corporation | 2-[4-(6-Haloquinoxalinyl-2-oxy)phenoxy]propionic acid esters |
US4687849A (en) * | 1985-10-04 | 1987-08-18 | Hoffmann-La Roche Inc. | [(Isopropylideneamino)oxy]-ethyl-2-[[6-chloroquinoxalinyl)oxy]phenoxy]propionate postemergent herbicide |
-
1990
- 1990-10-01 WO PCT/EP1990/001647 patent/WO1991004969A1/en unknown
- 1990-10-01 AU AU65404/90A patent/AU6540490A/en not_active Abandoned
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WO1991004969A1 (en) | 1991-04-18 |
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