CA1242722A - Substituted phenoxypropionyl-isourea derivatives, a process for their preparation and their use in plant protection - Google Patents
Substituted phenoxypropionyl-isourea derivatives, a process for their preparation and their use in plant protectionInfo
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- CA1242722A CA1242722A CA000467443A CA467443A CA1242722A CA 1242722 A CA1242722 A CA 1242722A CA 000467443 A CA000467443 A CA 000467443A CA 467443 A CA467443 A CA 467443A CA 1242722 A CA1242722 A CA 1242722A
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C275/04—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms
- C07C275/20—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms of an unsaturated carbon skeleton
- C07C275/24—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing six-membered aromatic rings
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/32—Ingredients for reducing the noxious effect of the active substances to organisms other than pests, e.g. toxicity reducing compositions, self-destructing compositions
-
- 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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
- A01N47/42—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides containing —N=CX2 groups, e.g. isothiourea
-
- 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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
- A01N47/42—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides containing —N=CX2 groups, e.g. isothiourea
- A01N47/44—Guanidine; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C275/70—Compounds containing any of the groups, e.g. isoureas
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- 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
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- 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
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
- C07D277/68—Benzothiazoles 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
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- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Environmental Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Zoology (AREA)
- Plant Pathology (AREA)
- Toxicology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Thiazole And Isothizaole Compounds (AREA)
- Pyridine Compounds (AREA)
- Detergent Compositions (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Compounds of the formula I
wherein X denotes O or -CH2-, Y denotes O, S or NR5, A denotes a direct bond, -CH2-CH2- or -CH=CH-, R1 denotes (substituted) phenyl, pyridyl, benzoxazolyl, benzothiazolyl or quinazolyl, R2 denotes alkyl or, together with NR5, denotes a heterocyclic ring, R3 and R4 denote H, alkyl or, together, the =CH-N(CH3)2 group and, if R3 = H, R4 also denotes an acyl, carboxylic acid ester or carbamoyl group, and R5 denotes H or alkyl, areactive herbicides, growth regulators and antidotes.
Compounds of the formula I
wherein X denotes O or -CH2-, Y denotes O, S or NR5, A denotes a direct bond, -CH2-CH2- or -CH=CH-, R1 denotes (substituted) phenyl, pyridyl, benzoxazolyl, benzothiazolyl or quinazolyl, R2 denotes alkyl or, together with NR5, denotes a heterocyclic ring, R3 and R4 denote H, alkyl or, together, the =CH-N(CH3)2 group and, if R3 = H, R4 also denotes an acyl, carboxylic acid ester or carbamoyl group, and R5 denotes H or alkyl, areactive herbicides, growth regulators and antidotes.
Description
~ 2 - HOE 83/F 236 The present ;nvention relates to novel conpounds of the general formula I
R l _x~ O-CH-A~C-N-C-N
- ~Ra in which S X denotes O or -CH~-, Y denotes 0~ S or NR ;
A1 denotes a direct bond, -CH2-CH2- or -CH=CH-;
R denotes the radical ~ or R ~ N
~here ~ = CH or N, a - u or S and n = O or 1;
R2 denotes ~C1-C~)-alkyl, ~here~ if y a NRS~ R~ and R5~ togeth~r Yith the nitrogen a~om, can ~orm a 5-me~b~red or 6-membered ring, in ~h;ch one -CH-group oay be repl~ced by O or NH;
R3 and R4 independently of one another denote hydrogen or ~C1-C4)-alkyl, or together denote the group /t~3 =CH-N ~ and, if R3 - hydrogen, R4 also \CH3 denotes the group -CO-R8, -COOR8 or -CO-NHR ;
R5 denotes hydrogen or ~C1-C4)-alkyL;
R6 and R7 independently of one another denote ~, F, Cl, ~r, CH~ CF3, N02 or CN; and R denotes (C1-C83-alkyl, (C3 C6) alk y , optionally ~ono- or di-subs~ituted by halogen, ~z~
or CF3 or (c1-c~)-alkyln Preferred compounds of the general for~ula I here are çompounds in which X and Y denote oxygen, A denotes a direct bond, R2 denotes methyl or ethyl and R3 3nd R4 each denote hydrogen or together denote the dimethyl-aminomethylene radical; R6 denotes CF3, F, Cl or Br; R7 denotes H, Cl or er; Z denotes CH or N; n denotes zero and Q denotes a or S.
The invention also relates to a process for th~
preparation of the compounds of the general formula I, which comprises reacting compounds of the general Formula II
Rl-X~O CH-A~C~' I I
;n which "Hal" denotes chlorine or bromine, with com-pounds of the general ~ormula IlI
R ;
N-CcNH II
R~ y ~2 The compounds of the general formula II are known, or they can be prepared by kno~n processes, such ~s those described, for example, in 6er~an Offenlegungsschrift
R l _x~ O-CH-A~C-N-C-N
- ~Ra in which S X denotes O or -CH~-, Y denotes 0~ S or NR ;
A1 denotes a direct bond, -CH2-CH2- or -CH=CH-;
R denotes the radical ~ or R ~ N
~here ~ = CH or N, a - u or S and n = O or 1;
R2 denotes ~C1-C~)-alkyl, ~here~ if y a NRS~ R~ and R5~ togeth~r Yith the nitrogen a~om, can ~orm a 5-me~b~red or 6-membered ring, in ~h;ch one -CH-group oay be repl~ced by O or NH;
R3 and R4 independently of one another denote hydrogen or ~C1-C4)-alkyl, or together denote the group /t~3 =CH-N ~ and, if R3 - hydrogen, R4 also \CH3 denotes the group -CO-R8, -COOR8 or -CO-NHR ;
R5 denotes hydrogen or ~C1-C4)-alkyL;
R6 and R7 independently of one another denote ~, F, Cl, ~r, CH~ CF3, N02 or CN; and R denotes (C1-C83-alkyl, (C3 C6) alk y , optionally ~ono- or di-subs~ituted by halogen, ~z~
or CF3 or (c1-c~)-alkyln Preferred compounds of the general for~ula I here are çompounds in which X and Y denote oxygen, A denotes a direct bond, R2 denotes methyl or ethyl and R3 3nd R4 each denote hydrogen or together denote the dimethyl-aminomethylene radical; R6 denotes CF3, F, Cl or Br; R7 denotes H, Cl or er; Z denotes CH or N; n denotes zero and Q denotes a or S.
The invention also relates to a process for th~
preparation of the compounds of the general formula I, which comprises reacting compounds of the general Formula II
Rl-X~O CH-A~C~' I I
;n which "Hal" denotes chlorine or bromine, with com-pounds of the general ~ormula IlI
R ;
N-CcNH II
R~ y ~2 The compounds of the general formula II are known, or they can be prepared by kno~n processes, such ~s those described, for example, in 6er~an Offenlegungsschrift
2,623,55R, G~rman Offenlegungsschrift 2,914,300, European Otfenlegungsschrift 50,019 and Belgian Pat~nt ~89,7~3.
Th~ co~pounds of the general formula III are like~ise kno~n; their preparation i-~ described~ for example, in German O~fenlegungsschrift 2,353,~04.
The compounds of the formula llI are preferably employed in the process according ~o the in~ention in the form of their hydrochloric acid or sulfur;c acid saLts.
The reactions are carried out in the presence of inorgan;c or organic bases~ the alkali ~etal hydroxides being preferred here.
~r Suitable solvents are hydrocarbons or halogeno-,~.
~Z4!2~
~, hydrocarbons which are ;nert under the reaction condi-tions, such as, for example, toluene, xylene or methylene chloride.
If the reaction is carr;ed out in methylene chlor;de, it i5 advisable to add ~ater. A procedure is then preferably follQwed in ~hich, for examp!e, the sul-fur;c dcid salts of the compounds III are initially intro-dused into a mixture of ~ater and methylene chlorlde at temperatures of -10C to +40C and the compounds II and and t~ice the molar a~ount of aqueous sodium hydroxide solution are added dropwise from separate vessels. De-pending on their solubility, the compounds accord;ng to the ;nvention are worked up and isolated by filtrat;on with suc~ion or by evaporation of the methylene chloride phase.
The compounds of the general formula I according to the inYention have a center of asymmetry and are usually present in racemic form. Ho~ever, it is also possible to use optically active starting substances of the g~neral formula II in the preparation process des-cribed, the preparation of these subst~nces being des-cribed, ~or example, in Europ~an Pat~nt 2,800. The des-ired isom~rs are thereby obtained in high optical purity.
On the basis of biological activity, the D-isomers are preferred. The general formuLa I thus comprises both the race~ates and the D-iso~ers o~ the compounds accord-ing to th~ invention.
The compounds of the formula I exhibit a good herbicidal action and good s~lectivity in important large-scale crops. They are suitable for ~electively combat-ing broad-leav~d and graminaceous annual and perennial ~eeds in agriculturally i~portant crops~ such as, for example, ~heat, rice, mai~e, sugar be~t, ~oybean and cotton) by the pre-e~ergence and post-emergence ~ethod.
Moreover, the s~bst~nces according to the invention e~-hibit good gro~th-regul3ting properties on crop plants.
They have a reguLating effect on the endogenous ~etabol-ism of plants and can thus be used for controlled infLu-encing of the contenes of plants and for facilitating z%
harvesting, such as~ for example, for des;ccation, abs-ciss;on or growth compression. Furthermore, they are also suitable for general control and inhibition of un-desirable vegeta~ive growth, without thereby destroying the plants. Inhibi~ion of vegetative gro~th is of great i~portance in many monocotyledonous and dicotyledonous crops, since lodging can thereby be reduced or completely prevented.
The compounds according to the invention also exhibit a surprising activity as herbicide antidotes (safeners). They can thus antagonize, that is to say completely eliminate, phytotoxic effects arising from the use of various herbicides on crop plants. It is thereby possible to use known herbicides selectively in crops where use ~as not hitherto possible.
The agents according to the invention can be appLied as ~ettable powders, emulsifiable concentrates, solutions ~hich can be sprayed, dusting agents, dressing agents, dispersions, granules or microgranules in the usual formulations.
~ ettable po~ders are products wh;ch are uniformly dispersible in ~ater and ~h;cho in addition to the active substance and ~part from a diluent or inert substance, if appropriate, also contain wetting agents, for example polyoxyethylated alkylphenols, polyoxyethylated fatty alcohols and ~lkyl- or alkylphenyl-sulfonates, and dis-persing ~gents, for example sodium lignin-sulfonate~
sodiu~ 2,2'-dinaphthylmethane-6,6'-disulfona~e, sodium dibutylnaphthaleneswlfonate or sodium oleyl-methyl-taur-ide. ~hey are prepared in the customary manner, ~forexample by grinding and mixing the comPonents.
E~ulsifiable concentrates can be pr~pared~ for example, by diss~lving the ac~ive substance ;n an inert organic solvent, for example butanol, cyclohexanone, dimethylfor0amide, xylene or higher-boiling aro~atics or hydrocarbons, w;th the addition of one or mor~ emulsi-fiers. In the cas@ of l;qu;d active subs~ances, all or some of this solven~ content can also be dispensed with.
Examples of em~lsifiers which can be used: calcium alkyl--- 6 --arylsulfonat2s, such as Ca dodecylbenzenesulfonate, or non-ionic e~ulsifiers, such as fatty acid polyglycol esters, aLkylaryl polyglycol ethers, fatty alcohol poly-glycol ethers, propyl2ne o~ide/ethylene oxide condens-ation products, fatty alcohol/propylene oxide/ethyleneoxide condensation products, alkyl polyglycol ethers, sorbitan fa~ty acid esters, polyoxyethyLene sorbitan fatty acid esters or polyoxyethylene sorbi~ol esters~
Dusting agents can be obtained by grinding the active substance with finely divided, solid substances, for exa~ple ealc or natural clays, such as kaolin, bentonite, pyrophiLite or diatomaceous earth.
Granules can be prepared either by spraying the active substance onto adsorbent, granular inert material or by applyiny active substance concentrates to the sur-face of carriers, such as sand or kaolinites, or granular inert material by means of binders, for example Polyvinyl alcohol, sodium polyacrylate or mineral oils. Suitable act;ve substances can al50 be granulated in the usual ~anner for the prepara~ion of fertilizer granules, if desired mixed with fertilizers~
~ he active substance concentration in wettable pouders is, tor ~xample, about 10 to 90X by ~eight~ the remainder to ~ake up to 100X by ~eight consisein~ of the usual formuLaeion constituents. The active substance concen~ra~ion in emulsifiable concentrates can be about 10 to ~OX by ~ight. Dust-like formulations usually con-tain 5 to 20~ by ~eight of active substance~ and solut;ons ~hich can be sprayed contain about 2 to 20X by ~eight.
The active substance content in granules parely depends on whether the aceive compound is presen~ in li~uid or solid for~ and ~hich granulaeion auxiliaries, fill2rs and the like are used.
The active substance for~ulations mentioned also contain, if appropriate, the particular customary ~acki-fiers, ~etting agents, dispersing ayents~ e~ulsif;ers, penetration agents, solvents~ fillers or carriers.
For use, the concentrates in the commercially avaiLable form are diluted~ if appropria~e, in the cus-~ >~ ~ g ~
-- 7 --tomary manner, ~or example by means of hater in the case of wettable powders, emulsifiable concentrates, disper-sions and somet;mes also microgranules. Dust-like and granular formulations and solutions which can sprayed are usually not further diluted with additional inert substances before use.
Mixtures or mixed formulations with other act;ve substances, such as, for example, insecticides, acari-cides~ herbicides, fertili~ers, growth regulators or fungicides, are also possible, where relevant.
Some formulation examples are described below:
Example A
_ _ A dust;ng agent is obtained by ~ixing 10 parts by ~eight of active substance and 90parts by weight of talc, as the ;nert substance, and comminut;ng the ~ix-ture in an impact mill.
Example 3 A powder wh;ch is read;ly dispersible and ~et-table in water is obtained by mixing ZS parts by weight o~ active substance, ~4 parts by ~eight of kaolin-contain-ing quartx, as ~he inert substance, 10 parts by weight of potassium lignin-sulfonat~ and 1 part by ~eight of sodium ol~yl-methyl t~uride, as the ~etting agent and dispersing agent, and grinding the mixtur~ in a pinned disc mill.
A dispersion concentration which is readily dis-persi~le in water is obtained by mixing 20 parts by ~eight of active ~ubstance with 6 parts by ~eight of alkylphenol polyglycol ether tTriton X 207), 3 parts by ~eight o~ isotridecanol polyglycol ether t8 moles of ethylene oxide) and 71 parts by ~eight of paraffinic mineral oil tboil;ng range, for example, about 255 to above 377C), and grinding the ~ixture to a fineness of less than S microns i~ a balL mill.
Example D
An emulsifiable concentrate ;s ob~ained trom 15 parts by ~eight of active substance, 75 parts by weight of cyclohexanone9 as the solvent, and 10 parts by ~eight ~Z~7~
of oxyethylated nonylphenol, as the emulsif;er.
A~ Preparation Exa~ples xample 1 N-(2-[4-(2,4-Dichlorophenoxy)-phenoxy]-propionyl)-0-methyl-isourea 6.2 9 (0.05 mole) of methylisourea sulfate are dissolved in 50 ml of water and 100 ml of methylene chlor-ide and the solution is cooled to 0C. At 0C, 8 9 of 50%
~trength aqueous sodium hydroxide solution (0.1 mole) 10 and 17.3 9 (O.OS ~ole) of 2-[4-(2,4-dichlorophenoxy)-phenoxyJ-propionyl chloride, dissolved in sa ml of tolu-ene, are simultaneously added dropwise. The mixture is stirred at 0C for 1 hour and at 30C for 3 hours. The organic phase is separ~ted off, washed with 100 ml of water and dried over sodium sulfate. The solvent is dis-tilled off under reduced pressure. 17.5 9 (95~ of theory) of N-(2-t4-(2,4-dichlorophenoxy)-phenoxy]-propionyl)-0-methyl-isourea are obtained as the residue in the form of colorless crystals of melting point 9~-97C.
~0 Cl~ ~O-CH-C-N= -NH~
Example 2 N-~2-C4-t4-Chloroben2yl)-Phenoxy]-Propionyl)-0-methyl-__ isourea _._ 6.2 g (0.05 ~ol~) of methylisourea sulfate are 25 dissoLved in 100 ml of methylene chLoride and 50 ml of water at 0C. 15.4 g (O.OS mole) of 2-t4-(4-rhloro-benzyl~-phenoxy] propionyl chloride, dissolved in 50 ml of toluene, and 8 9 of SOZ strength aqueous sodium hy-droxide solution (D.1 mole) are simultaneously ~dded drop~ise. The mixture is stirred at 0C for 1 hour and at 40C for 2 hours and the organic phase ;s separated off. After drying over sod;um sulfate, the solvent is distilled off under redured pressure. 13 g (75~ of th~ory) of N-(~-t4-~4-chlorobenYyl)-phenoxy]-propionyl-0-~ethyl-isourea are obtained in the form of a light bro~n oil.
~2~
_ 9 _ t: 1~ CH 2 ~ O- CH-C-N=C -NH 2 O OC~ 3 E x a N-(Z-t4 (~-Trifluoromethylphenoxy)-phenoxy]-propionyl)-0-methyl-isourea 1Z.3 9 tO~1 mole) of methylisourea sul~ate are dissolved ;n 80 ml of water and 150 mL of methylene chlor-ide at 0C. 34.4 9 (0.1 mole) of 2-C4-(4-trifluoromethyl-phenoxy)-phenoxy~-propionyl chloride, dissolved in 70 ml of toLuene, and 16 9 of 50g strength aqueous sodium hyd-1D roxide solution (0.2 mole) are simultaneously added drop-~ise, ~hile cooling with ice~ The mixture is stirred at 0C for 1 hour and at 40C for 3 hours and the organic phase is separated off~ ~ashed with 200 ml of water and dried over soclium sulfate. After the solvent has be~n distilled off under reduced pressure, 35 9 (92% of theory) of N-(2-~4-~4-trifluoromethylphenoxy)-phenoxy3-propionyl)-0-methyl-isourea are obtained in the form of a yello~
o i ~ .
F 3 ~ ~ O-CH C-N=C-NH 2 O OC~ 3 t :~a~p~e 1 N-~2-C4-(6-Chlorobenzothiazol-2-yloxy) ~henoxy~-propionyl)-O~methyl- _ourea_ 12.3 9 (0.1 ~ole) of methylisourea sulfate are dissolved in 80 ml of ~a~er and 150 ml of methylene chloride at O~C. 36.7 g (0.1 mole) of ~t4-~6 chloro-benzothiazol-2-ylo~y)-phenoxy3-propionyl chloride, dis-soLved in 70 ml of toluene, and 16 g of ~0~ strength aqueous sodium hydroxide solution ~0.2 moLe) are simul-taneously added drop~ise at 0C, with vigorous stirring.
The mixture is stirred at 0C for 1 hour and at 40C
~or 2 hours. The precipitate ~hich has separated out is Z~2~
filtered off ~ith suction and washed with 50 ml of ether.
27 9 of N-(2-[4-~6-chlorobenzothiazol-Z-yloxy)-phenoxy]-propionyl)-O~methyl-isourea are obtained in the form of colorless crystals of melting point 142C. The organic phase is separated off from the mother liquor, washed with 200 m! of ~ater and dried over sodium sulfate. After the solvent has been distilled off under reduced pressure, a light brown solid is obtained, which is bsiled up with 100 ml of e~her. After cooling, ~he solid is filtered off ~ith suction to give a further 8.5 9 of N-(2-~4-(6-chlorobenzothiazol-2-yloxy)-phenoxy]-propionyl)-0-methyl-isourea in the form of colorless crystals of melting point 141-142C. Total yield: 35.5 9 ~88X of theory).
O'`~)-O~CH~-N=~-~H 2 The follo~ing compounds listed in Table 1 can be obtained in ~n analogous manner.
Table 1 R1-X ~ o-8H-C-N=C-N
~R2 __ ___ ~__ ___ _ _- Boiling point ~NxOample IFI.l X Y R~ R~ Rd ~lting point __ ~ __ . ~- __ _~
S ! 1~ O O OH3 ~H 11 i!i n O O C2Hs H
7 n O S CH3 H H
8 C~ O S C~13 ~1 ~1 Table 1 ( cont inued) ___ __ _ _ _~
ExarnpleR' X ~! R2 R~ R~ (C) ' _ __ __ _ ___ _ _ 9 F 9 C n C1 O S) ~ 2H3 ~H H
F3C ~ O O CH3 H H
11 Cl Cl O O CH3 H H
1 2 ~ O O CH 3 H ~1 13 ~ O O CH 3 ~I H
Cl 4 ~ O O C2H5 lI ~I
E~r 1 5 Cl~l O O C ~H 5 }I H
'l 6 C:l~ O S CH3 H
17 F 3 C ~ -CH 2 ~ -NH CH, }I
18 F ~ O O CH3 H H
19 F ~7 O O CH, H H
Example 20 N-(2-t4-(2,~-Dichlorophenoxy)-phenoxy]-propionyl)-N'-dimethylaminomethylene-0-methyL-isourea __ _ 19.2 9 (0.05 mole) of N-(2-[4-(2,4-dichlorophen-oxy)-phenoxy]-propionyl)-0-methyl-isourea ~Example 1) and 9 9 (0.06 mole~ of dimethylfrJrmamide diethyl acetal are mixed ~ith one another. After addition of 1/~ ml of concentrated sulfuric acid, the mixture is heated rapidly to 100CO It is stirred at 100C for 3 m;nutes and allowed to cool to room temperature. The resulting light brown oil is freed from all the volatile consti~u-ents under an oil pump at 60-70C/0.01 bar. 19.5 9 (88%
of theory) of N-(2-t4-(2~4-dichlorophenoxy)-phenoxy]-propionyl)-N'-dimethylaminomethylene-0-methyl-isourea are obtained in the form of a light bro~n viscous oil.
Cl Cl ~ O ~ H-C-N=C N=CH-N ~
O C~3 ~ CH 3 The following compvunds listed in Table 2 can be prepared in an analogous manner.
Table 2 __ Rl~-X~ ~R~
, . ~ __ . . . _ ,, , EX- 2 Boiling point I~O.le Rl X Y R meOting point ~ ~ - - - ~ -21 F3C~ O O C~3 2 2 ~ CH a O CH J
;2 3 Cl~ O ~; CH3 . . .
~z~
T a b l e 2 t c o n t i n u e d ) _ _ Boiling point E~)le R ~ X Y R 2 ( t' ) ' nD
r Br ___~_ 24 1:1~ O O ~
Cl~ O O ~ 2H 5 N
26 C~S~ O O CH3 2 7 C~ O O CH 3 28 ~ O O CH3 B. ~iolog;cal ExamPles 1. Herbicidal action The present compounds according to the invention exhibit a good herbicidal activity against a broad spec-trum of economically ;mpor~ant monocotyledonous and di-coeyledonous harmful plants. The active substances also have a good action against perennial species which are difficult to combat. It is irrelevant here whether the su~stances are applied by pre-sow;ng, pre-emergence or 1D post-emergence spraying. If the compounds according to the invention are applied to the soil surface by the pre-so~ing or pre-emergence method befors germination of the ~eeds, the emergence of seedlings is not completely pre-vented. The weeds grow to the cotyledon stage, but their growth then stops and they finally die completely after
Th~ co~pounds of the general formula III are like~ise kno~n; their preparation i-~ described~ for example, in German O~fenlegungsschrift 2,353,~04.
The compounds of the formula llI are preferably employed in the process according ~o the in~ention in the form of their hydrochloric acid or sulfur;c acid saLts.
The reactions are carried out in the presence of inorgan;c or organic bases~ the alkali ~etal hydroxides being preferred here.
~r Suitable solvents are hydrocarbons or halogeno-,~.
~Z4!2~
~, hydrocarbons which are ;nert under the reaction condi-tions, such as, for example, toluene, xylene or methylene chloride.
If the reaction is carr;ed out in methylene chlor;de, it i5 advisable to add ~ater. A procedure is then preferably follQwed in ~hich, for examp!e, the sul-fur;c dcid salts of the compounds III are initially intro-dused into a mixture of ~ater and methylene chlorlde at temperatures of -10C to +40C and the compounds II and and t~ice the molar a~ount of aqueous sodium hydroxide solution are added dropwise from separate vessels. De-pending on their solubility, the compounds accord;ng to the ;nvention are worked up and isolated by filtrat;on with suc~ion or by evaporation of the methylene chloride phase.
The compounds of the general formula I according to the inYention have a center of asymmetry and are usually present in racemic form. Ho~ever, it is also possible to use optically active starting substances of the g~neral formula II in the preparation process des-cribed, the preparation of these subst~nces being des-cribed, ~or example, in Europ~an Pat~nt 2,800. The des-ired isom~rs are thereby obtained in high optical purity.
On the basis of biological activity, the D-isomers are preferred. The general formuLa I thus comprises both the race~ates and the D-iso~ers o~ the compounds accord-ing to th~ invention.
The compounds of the formula I exhibit a good herbicidal action and good s~lectivity in important large-scale crops. They are suitable for ~electively combat-ing broad-leav~d and graminaceous annual and perennial ~eeds in agriculturally i~portant crops~ such as, for example, ~heat, rice, mai~e, sugar be~t, ~oybean and cotton) by the pre-e~ergence and post-emergence ~ethod.
Moreover, the s~bst~nces according to the invention e~-hibit good gro~th-regul3ting properties on crop plants.
They have a reguLating effect on the endogenous ~etabol-ism of plants and can thus be used for controlled infLu-encing of the contenes of plants and for facilitating z%
harvesting, such as~ for example, for des;ccation, abs-ciss;on or growth compression. Furthermore, they are also suitable for general control and inhibition of un-desirable vegeta~ive growth, without thereby destroying the plants. Inhibi~ion of vegetative gro~th is of great i~portance in many monocotyledonous and dicotyledonous crops, since lodging can thereby be reduced or completely prevented.
The compounds according to the invention also exhibit a surprising activity as herbicide antidotes (safeners). They can thus antagonize, that is to say completely eliminate, phytotoxic effects arising from the use of various herbicides on crop plants. It is thereby possible to use known herbicides selectively in crops where use ~as not hitherto possible.
The agents according to the invention can be appLied as ~ettable powders, emulsifiable concentrates, solutions ~hich can be sprayed, dusting agents, dressing agents, dispersions, granules or microgranules in the usual formulations.
~ ettable po~ders are products wh;ch are uniformly dispersible in ~ater and ~h;cho in addition to the active substance and ~part from a diluent or inert substance, if appropriate, also contain wetting agents, for example polyoxyethylated alkylphenols, polyoxyethylated fatty alcohols and ~lkyl- or alkylphenyl-sulfonates, and dis-persing ~gents, for example sodium lignin-sulfonate~
sodiu~ 2,2'-dinaphthylmethane-6,6'-disulfona~e, sodium dibutylnaphthaleneswlfonate or sodium oleyl-methyl-taur-ide. ~hey are prepared in the customary manner, ~forexample by grinding and mixing the comPonents.
E~ulsifiable concentrates can be pr~pared~ for example, by diss~lving the ac~ive substance ;n an inert organic solvent, for example butanol, cyclohexanone, dimethylfor0amide, xylene or higher-boiling aro~atics or hydrocarbons, w;th the addition of one or mor~ emulsi-fiers. In the cas@ of l;qu;d active subs~ances, all or some of this solven~ content can also be dispensed with.
Examples of em~lsifiers which can be used: calcium alkyl--- 6 --arylsulfonat2s, such as Ca dodecylbenzenesulfonate, or non-ionic e~ulsifiers, such as fatty acid polyglycol esters, aLkylaryl polyglycol ethers, fatty alcohol poly-glycol ethers, propyl2ne o~ide/ethylene oxide condens-ation products, fatty alcohol/propylene oxide/ethyleneoxide condensation products, alkyl polyglycol ethers, sorbitan fa~ty acid esters, polyoxyethyLene sorbitan fatty acid esters or polyoxyethylene sorbi~ol esters~
Dusting agents can be obtained by grinding the active substance with finely divided, solid substances, for exa~ple ealc or natural clays, such as kaolin, bentonite, pyrophiLite or diatomaceous earth.
Granules can be prepared either by spraying the active substance onto adsorbent, granular inert material or by applyiny active substance concentrates to the sur-face of carriers, such as sand or kaolinites, or granular inert material by means of binders, for example Polyvinyl alcohol, sodium polyacrylate or mineral oils. Suitable act;ve substances can al50 be granulated in the usual ~anner for the prepara~ion of fertilizer granules, if desired mixed with fertilizers~
~ he active substance concentration in wettable pouders is, tor ~xample, about 10 to 90X by ~eight~ the remainder to ~ake up to 100X by ~eight consisein~ of the usual formuLaeion constituents. The active substance concen~ra~ion in emulsifiable concentrates can be about 10 to ~OX by ~ight. Dust-like formulations usually con-tain 5 to 20~ by ~eight of active substance~ and solut;ons ~hich can be sprayed contain about 2 to 20X by ~eight.
The active substance content in granules parely depends on whether the aceive compound is presen~ in li~uid or solid for~ and ~hich granulaeion auxiliaries, fill2rs and the like are used.
The active substance for~ulations mentioned also contain, if appropriate, the particular customary ~acki-fiers, ~etting agents, dispersing ayents~ e~ulsif;ers, penetration agents, solvents~ fillers or carriers.
For use, the concentrates in the commercially avaiLable form are diluted~ if appropria~e, in the cus-~ >~ ~ g ~
-- 7 --tomary manner, ~or example by means of hater in the case of wettable powders, emulsifiable concentrates, disper-sions and somet;mes also microgranules. Dust-like and granular formulations and solutions which can sprayed are usually not further diluted with additional inert substances before use.
Mixtures or mixed formulations with other act;ve substances, such as, for example, insecticides, acari-cides~ herbicides, fertili~ers, growth regulators or fungicides, are also possible, where relevant.
Some formulation examples are described below:
Example A
_ _ A dust;ng agent is obtained by ~ixing 10 parts by ~eight of active substance and 90parts by weight of talc, as the ;nert substance, and comminut;ng the ~ix-ture in an impact mill.
Example 3 A powder wh;ch is read;ly dispersible and ~et-table in water is obtained by mixing ZS parts by weight o~ active substance, ~4 parts by ~eight of kaolin-contain-ing quartx, as ~he inert substance, 10 parts by weight of potassium lignin-sulfonat~ and 1 part by ~eight of sodium ol~yl-methyl t~uride, as the ~etting agent and dispersing agent, and grinding the mixtur~ in a pinned disc mill.
A dispersion concentration which is readily dis-persi~le in water is obtained by mixing 20 parts by ~eight of active ~ubstance with 6 parts by ~eight of alkylphenol polyglycol ether tTriton X 207), 3 parts by ~eight o~ isotridecanol polyglycol ether t8 moles of ethylene oxide) and 71 parts by ~eight of paraffinic mineral oil tboil;ng range, for example, about 255 to above 377C), and grinding the ~ixture to a fineness of less than S microns i~ a balL mill.
Example D
An emulsifiable concentrate ;s ob~ained trom 15 parts by ~eight of active substance, 75 parts by weight of cyclohexanone9 as the solvent, and 10 parts by ~eight ~Z~7~
of oxyethylated nonylphenol, as the emulsif;er.
A~ Preparation Exa~ples xample 1 N-(2-[4-(2,4-Dichlorophenoxy)-phenoxy]-propionyl)-0-methyl-isourea 6.2 9 (0.05 mole) of methylisourea sulfate are dissolved in 50 ml of water and 100 ml of methylene chlor-ide and the solution is cooled to 0C. At 0C, 8 9 of 50%
~trength aqueous sodium hydroxide solution (0.1 mole) 10 and 17.3 9 (O.OS ~ole) of 2-[4-(2,4-dichlorophenoxy)-phenoxyJ-propionyl chloride, dissolved in sa ml of tolu-ene, are simultaneously added dropwise. The mixture is stirred at 0C for 1 hour and at 30C for 3 hours. The organic phase is separ~ted off, washed with 100 ml of water and dried over sodium sulfate. The solvent is dis-tilled off under reduced pressure. 17.5 9 (95~ of theory) of N-(2-t4-(2,4-dichlorophenoxy)-phenoxy]-propionyl)-0-methyl-isourea are obtained as the residue in the form of colorless crystals of melting point 9~-97C.
~0 Cl~ ~O-CH-C-N= -NH~
Example 2 N-~2-C4-t4-Chloroben2yl)-Phenoxy]-Propionyl)-0-methyl-__ isourea _._ 6.2 g (0.05 ~ol~) of methylisourea sulfate are 25 dissoLved in 100 ml of methylene chLoride and 50 ml of water at 0C. 15.4 g (O.OS mole) of 2-t4-(4-rhloro-benzyl~-phenoxy] propionyl chloride, dissolved in 50 ml of toluene, and 8 9 of SOZ strength aqueous sodium hy-droxide solution (D.1 mole) are simultaneously ~dded drop~ise. The mixture is stirred at 0C for 1 hour and at 40C for 2 hours and the organic phase ;s separated off. After drying over sod;um sulfate, the solvent is distilled off under redured pressure. 13 g (75~ of th~ory) of N-(~-t4-~4-chlorobenYyl)-phenoxy]-propionyl-0-~ethyl-isourea are obtained in the form of a light bro~n oil.
~2~
_ 9 _ t: 1~ CH 2 ~ O- CH-C-N=C -NH 2 O OC~ 3 E x a N-(Z-t4 (~-Trifluoromethylphenoxy)-phenoxy]-propionyl)-0-methyl-isourea 1Z.3 9 tO~1 mole) of methylisourea sul~ate are dissolved ;n 80 ml of water and 150 mL of methylene chlor-ide at 0C. 34.4 9 (0.1 mole) of 2-C4-(4-trifluoromethyl-phenoxy)-phenoxy~-propionyl chloride, dissolved in 70 ml of toLuene, and 16 9 of 50g strength aqueous sodium hyd-1D roxide solution (0.2 mole) are simultaneously added drop-~ise, ~hile cooling with ice~ The mixture is stirred at 0C for 1 hour and at 40C for 3 hours and the organic phase is separated off~ ~ashed with 200 ml of water and dried over soclium sulfate. After the solvent has be~n distilled off under reduced pressure, 35 9 (92% of theory) of N-(2-~4-~4-trifluoromethylphenoxy)-phenoxy3-propionyl)-0-methyl-isourea are obtained in the form of a yello~
o i ~ .
F 3 ~ ~ O-CH C-N=C-NH 2 O OC~ 3 t :~a~p~e 1 N-~2-C4-(6-Chlorobenzothiazol-2-yloxy) ~henoxy~-propionyl)-O~methyl- _ourea_ 12.3 9 (0.1 ~ole) of methylisourea sulfate are dissolved in 80 ml of ~a~er and 150 ml of methylene chloride at O~C. 36.7 g (0.1 mole) of ~t4-~6 chloro-benzothiazol-2-ylo~y)-phenoxy3-propionyl chloride, dis-soLved in 70 ml of toluene, and 16 g of ~0~ strength aqueous sodium hydroxide solution ~0.2 moLe) are simul-taneously added drop~ise at 0C, with vigorous stirring.
The mixture is stirred at 0C for 1 hour and at 40C
~or 2 hours. The precipitate ~hich has separated out is Z~2~
filtered off ~ith suction and washed with 50 ml of ether.
27 9 of N-(2-[4-~6-chlorobenzothiazol-Z-yloxy)-phenoxy]-propionyl)-O~methyl-isourea are obtained in the form of colorless crystals of melting point 142C. The organic phase is separated off from the mother liquor, washed with 200 m! of ~ater and dried over sodium sulfate. After the solvent has been distilled off under reduced pressure, a light brown solid is obtained, which is bsiled up with 100 ml of e~her. After cooling, ~he solid is filtered off ~ith suction to give a further 8.5 9 of N-(2-~4-(6-chlorobenzothiazol-2-yloxy)-phenoxy]-propionyl)-0-methyl-isourea in the form of colorless crystals of melting point 141-142C. Total yield: 35.5 9 ~88X of theory).
O'`~)-O~CH~-N=~-~H 2 The follo~ing compounds listed in Table 1 can be obtained in ~n analogous manner.
Table 1 R1-X ~ o-8H-C-N=C-N
~R2 __ ___ ~__ ___ _ _- Boiling point ~NxOample IFI.l X Y R~ R~ Rd ~lting point __ ~ __ . ~- __ _~
S ! 1~ O O OH3 ~H 11 i!i n O O C2Hs H
7 n O S CH3 H H
8 C~ O S C~13 ~1 ~1 Table 1 ( cont inued) ___ __ _ _ _~
ExarnpleR' X ~! R2 R~ R~ (C) ' _ __ __ _ ___ _ _ 9 F 9 C n C1 O S) ~ 2H3 ~H H
F3C ~ O O CH3 H H
11 Cl Cl O O CH3 H H
1 2 ~ O O CH 3 H ~1 13 ~ O O CH 3 ~I H
Cl 4 ~ O O C2H5 lI ~I
E~r 1 5 Cl~l O O C ~H 5 }I H
'l 6 C:l~ O S CH3 H
17 F 3 C ~ -CH 2 ~ -NH CH, }I
18 F ~ O O CH3 H H
19 F ~7 O O CH, H H
Example 20 N-(2-t4-(2,~-Dichlorophenoxy)-phenoxy]-propionyl)-N'-dimethylaminomethylene-0-methyL-isourea __ _ 19.2 9 (0.05 mole) of N-(2-[4-(2,4-dichlorophen-oxy)-phenoxy]-propionyl)-0-methyl-isourea ~Example 1) and 9 9 (0.06 mole~ of dimethylfrJrmamide diethyl acetal are mixed ~ith one another. After addition of 1/~ ml of concentrated sulfuric acid, the mixture is heated rapidly to 100CO It is stirred at 100C for 3 m;nutes and allowed to cool to room temperature. The resulting light brown oil is freed from all the volatile consti~u-ents under an oil pump at 60-70C/0.01 bar. 19.5 9 (88%
of theory) of N-(2-t4-(2~4-dichlorophenoxy)-phenoxy]-propionyl)-N'-dimethylaminomethylene-0-methyl-isourea are obtained in the form of a light bro~n viscous oil.
Cl Cl ~ O ~ H-C-N=C N=CH-N ~
O C~3 ~ CH 3 The following compvunds listed in Table 2 can be prepared in an analogous manner.
Table 2 __ Rl~-X~ ~R~
, . ~ __ . . . _ ,, , EX- 2 Boiling point I~O.le Rl X Y R meOting point ~ ~ - - - ~ -21 F3C~ O O C~3 2 2 ~ CH a O CH J
;2 3 Cl~ O ~; CH3 . . .
~z~
T a b l e 2 t c o n t i n u e d ) _ _ Boiling point E~)le R ~ X Y R 2 ( t' ) ' nD
r Br ___~_ 24 1:1~ O O ~
Cl~ O O ~ 2H 5 N
26 C~S~ O O CH3 2 7 C~ O O CH 3 28 ~ O O CH3 B. ~iolog;cal ExamPles 1. Herbicidal action The present compounds according to the invention exhibit a good herbicidal activity against a broad spec-trum of economically ;mpor~ant monocotyledonous and di-coeyledonous harmful plants. The active substances also have a good action against perennial species which are difficult to combat. It is irrelevant here whether the su~stances are applied by pre-sow;ng, pre-emergence or 1D post-emergence spraying. If the compounds according to the invention are applied to the soil surface by the pre-so~ing or pre-emergence method befors germination of the ~eeds, the emergence of seedlings is not completely pre-vented. The weeds grow to the cotyledon stage, but their growth then stops and they finally die completely after
3-S weeks.
~ hen the active substances are applied to the green parts of plants by the post-emergence ~ethod, a drastic stop to gro~th likewise occurs very rap;dly after the treatment and the ~eeds remain at the gro~h stage of the time of application or die rompletely after a certain period, so that ~eed competition, wh;ch is harm-ful to the crop plants, can in this ~ay be eliminated very early and permanently by using the nov~l agents according to the invention. Although the compounds acçording to the invention also exhibit an excellen~
herbicidal ~ctivity, ~specially a~ainst monocotyledon-ous ~eeds, plants in ~conomically important crops9 such as, for example, ~heat, barley~ rye, rice~ maize, sugar ~eet, cotton and soybean, are damaged only partly or in significantly, or not at all. Compared with the prior art, the present substances according to the invention therefore have a substantialLy improved selectiYity to-~ards crop plants. For these reasons, the present com-pounds are particularly suitable for co~bating undesir-able plant gro~th in agricultural~y useful pl~nts. The damage to the ~eeds and the tol~rance by the crsP plants has been rated ;n a key ~rom 0 to 5.
In this key:
~z~
0 = no action ~damage) 1 = 0 - 20% act;on 2 = 20 - 40% ac~ion 3 = 40 - 60% action
~ hen the active substances are applied to the green parts of plants by the post-emergence ~ethod, a drastic stop to gro~th likewise occurs very rap;dly after the treatment and the ~eeds remain at the gro~h stage of the time of application or die rompletely after a certain period, so that ~eed competition, wh;ch is harm-ful to the crop plants, can in this ~ay be eliminated very early and permanently by using the nov~l agents according to the invention. Although the compounds acçording to the invention also exhibit an excellen~
herbicidal ~ctivity, ~specially a~ainst monocotyledon-ous ~eeds, plants in ~conomically important crops9 such as, for example, ~heat, barley~ rye, rice~ maize, sugar ~eet, cotton and soybean, are damaged only partly or in significantly, or not at all. Compared with the prior art, the present substances according to the invention therefore have a substantialLy improved selectiYity to-~ards crop plants. For these reasons, the present com-pounds are particularly suitable for co~bating undesir-able plant gro~th in agricultural~y useful pl~nts. The damage to the ~eeds and the tol~rance by the crsP plants has been rated ;n a key ~rom 0 to 5.
In this key:
~z~
0 = no action ~damage) 1 = 0 - 20% act;on 2 = 20 - 40% ac~ion 3 = 40 - 60% action
4 = 60 - 80X action
5 = 80 - 100% action.
a) Action against weeds Seeds of monocotyLedonous and dicotyledonous ~eeds ~ere placed in loam soil in plastic pots ( 9 cm) and covered with soil. The compounds according to the invention, formulated as we~tabLe powders or as e~ulsion concentrates, ~ere sprayed onto the soiL surface ~pre-emergence method) or onto the pLants which had developed to the 4-leaf stage (post-emergence method) in the form of aqueous suspensions or emulsions. The amount of water appLied per pot corresponded, ~hen converted, to 60n liters/
ha~ After the treatment, the test pots ~ere placed in a greenhouse and the test pLants were gro~n under good growing conditions (temperature: 23 ~ 1C; relative atmospheric humidity 60-B0%). After aboue 3 ~eeks, the damage to the ~Lants was rated visually. Untreated con-~rols were used for comparison.
As can be seen from thQ values in Tables 3 and 4, the compounds according to the invention exhibi~ a Z5 very ~ood herbicidal activity against economically impor-tan~ monocotyLedonous and dicotyl~donous harmful plants when applied by the pr~-~mergence or ~ost-emergence method.
Table 3 Herbicidal ~ctivity in the pr~emer~ence method ___ __ _~_ __ Example No! EC6 L~M ALM STM
_________ __ ___ 1 2 .b 5 S _ 4 ~ 0.~ 5 5 3 2 ~.4 ~ 5 5 2 0"6 S 5 ~ 4 3 2.~ 5 5 5 5 3 0.6 5 ~!i 5 ~ __ __ __ _ _ ~r ,~;29L;Z~t~ %
ECG = Echinochloa crus gall;
LOM = Lolium multiflorum ALM = Alopecurus myosuroides STM = St~llaria media Selectivity Compounds 1, 2~ 3 and ~ according to the inven-tion are comple~ely ~olerated by soybean, cotton and sugar beet crop plan~s and other dicotyledonous crop plants, ~ithout a harmful effece being observed, ~hen 1û applied in amounts of 2.4 kg of active substance. Com-pounds 1, ~ and 2 are also completely selective in cereal varieties (wheat and rice).
Table 4 _ .
Herbicidal activity by the post-emergence method _, _ _ _ __ Exsmple Nol EC6 LOM AL~
_ ___ __ L~
2. ~
~ ane sugar plants ~re grown under greenhouse condi~ions at 25-35~C and about 65% atmospheric humidity.
Various amounts of the formuLated agents were suspended in water, ~hich addi~iQnally ~oneained about 0.25X by ~eighe o~ a surface-active agent (nonylphenol).
In each case û.~ ml of ~he suspensions ~ere 7'~2 ~ f.o applied ~ith the aid of a syringe in the sp;ndle region at ~he height of last visible leaf blade ("dewlap") (10 plants per test group). The plants ~ere 6 months old at the time of application.
After 5 ~eeks, the Plants were harvested~ the foliage was re~oved and the 14 upper internodes ~ere analyzed ;n each case together in groups for sucrose con-Sent and juice purity by means of the so-called "press method" (T. Tanimoto, Hawaiin Planters Record, 57, 133 ~1964]).
The sugar content here is determined polarimet-rically and expressed in "pol~ percentage of cane"; this figure corresponds to the percentage of sucrose in the solution, under the assumption that sucrose is the only substance in the sugar soLution ~hich rotates the plane of polarized light. The determination of the "pol. per-centage of cane" ;s a recognized method for determin;ng the sugar content of sugar cane~
The results are shown ;n Table S.
Table S
___, __ ~ount oppli~d Ju;ce putity Sucro~e content ~/pl~nt) (X) ~pol. X r~ne) ~__ _ __ __ Control ~.8 ~.9 ~ample 3 10 75 11.5 '?4 1 1 n2 Ex~ple 4 10 72 lû.2 71 10.1
a) Action against weeds Seeds of monocotyLedonous and dicotyledonous ~eeds ~ere placed in loam soil in plastic pots ( 9 cm) and covered with soil. The compounds according to the invention, formulated as we~tabLe powders or as e~ulsion concentrates, ~ere sprayed onto the soiL surface ~pre-emergence method) or onto the pLants which had developed to the 4-leaf stage (post-emergence method) in the form of aqueous suspensions or emulsions. The amount of water appLied per pot corresponded, ~hen converted, to 60n liters/
ha~ After the treatment, the test pots ~ere placed in a greenhouse and the test pLants were gro~n under good growing conditions (temperature: 23 ~ 1C; relative atmospheric humidity 60-B0%). After aboue 3 ~eeks, the damage to the ~Lants was rated visually. Untreated con-~rols were used for comparison.
As can be seen from thQ values in Tables 3 and 4, the compounds according to the invention exhibi~ a Z5 very ~ood herbicidal activity against economically impor-tan~ monocotyLedonous and dicotyl~donous harmful plants when applied by the pr~-~mergence or ~ost-emergence method.
Table 3 Herbicidal ~ctivity in the pr~emer~ence method ___ __ _~_ __ Example No! EC6 L~M ALM STM
_________ __ ___ 1 2 .b 5 S _ 4 ~ 0.~ 5 5 3 2 ~.4 ~ 5 5 2 0"6 S 5 ~ 4 3 2.~ 5 5 5 5 3 0.6 5 ~!i 5 ~ __ __ __ _ _ ~r ,~;29L;Z~t~ %
ECG = Echinochloa crus gall;
LOM = Lolium multiflorum ALM = Alopecurus myosuroides STM = St~llaria media Selectivity Compounds 1, 2~ 3 and ~ according to the inven-tion are comple~ely ~olerated by soybean, cotton and sugar beet crop plan~s and other dicotyledonous crop plants, ~ithout a harmful effece being observed, ~hen 1û applied in amounts of 2.4 kg of active substance. Com-pounds 1, ~ and 2 are also completely selective in cereal varieties (wheat and rice).
Table 4 _ .
Herbicidal activity by the post-emergence method _, _ _ _ __ Exsmple Nol EC6 LOM AL~
_ ___ __ L~
2. ~
~ ane sugar plants ~re grown under greenhouse condi~ions at 25-35~C and about 65% atmospheric humidity.
Various amounts of the formuLated agents were suspended in water, ~hich addi~iQnally ~oneained about 0.25X by ~eighe o~ a surface-active agent (nonylphenol).
In each case û.~ ml of ~he suspensions ~ere 7'~2 ~ f.o applied ~ith the aid of a syringe in the sp;ndle region at ~he height of last visible leaf blade ("dewlap") (10 plants per test group). The plants ~ere 6 months old at the time of application.
After 5 ~eeks, the Plants were harvested~ the foliage was re~oved and the 14 upper internodes ~ere analyzed ;n each case together in groups for sucrose con-Sent and juice purity by means of the so-called "press method" (T. Tanimoto, Hawaiin Planters Record, 57, 133 ~1964]).
The sugar content here is determined polarimet-rically and expressed in "pol~ percentage of cane"; this figure corresponds to the percentage of sucrose in the solution, under the assumption that sucrose is the only substance in the sugar soLution ~hich rotates the plane of polarized light. The determination of the "pol. per-centage of cane" ;s a recognized method for determin;ng the sugar content of sugar cane~
The results are shown ;n Table S.
Table S
___, __ ~ount oppli~d Ju;ce putity Sucro~e content ~/pl~nt) (X) ~pol. X r~ne) ~__ _ __ __ Control ~.8 ~.9 ~ample 3 10 75 11.5 '?4 1 1 n2 Ex~ple 4 10 72 lû.2 71 10.1
Claims (11)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A compound of the formula I
I
in which X denotes O or -CH2-;
Y denotes O, S or NR5;
A denotes a direct bond, -CH2-CH2- or -CH=CH-;
R1 denotes the radical or where Z = CH or N, Q = O or S and n = 0 or 1;
R2 denotes (C1-C4)-alkyl, where, if Y = NR5, R2 and R5, together with the nitrogen atom, can form a 5-membered or 6-membered ring, in which one -CH-group may be re-placed by O or NH;
- 18a -R3 and R4 independently of one another denote hydrogen or (Cl-C4) alkyl, or together denote the group , and, if R3 = hydrogen, R4 also denotes the group - CO-R8, -COOR8 or -CO-NHR8;
R5 denotes hydrogen or (C1-C4)-alkyl;
R6 and R7 independently of one another denote H, F, C1, Br, CH3, CF3, NO2 or CN; and R8 denotes (C1-C8)-alkyl, (C3-C6)-alkenyl, phenyl, optionally mono-or di-substituted by halogen, or CF3 or (C1-C4)-alkyl.
I
in which X denotes O or -CH2-;
Y denotes O, S or NR5;
A denotes a direct bond, -CH2-CH2- or -CH=CH-;
R1 denotes the radical or where Z = CH or N, Q = O or S and n = 0 or 1;
R2 denotes (C1-C4)-alkyl, where, if Y = NR5, R2 and R5, together with the nitrogen atom, can form a 5-membered or 6-membered ring, in which one -CH-group may be re-placed by O or NH;
- 18a -R3 and R4 independently of one another denote hydrogen or (Cl-C4) alkyl, or together denote the group , and, if R3 = hydrogen, R4 also denotes the group - CO-R8, -COOR8 or -CO-NHR8;
R5 denotes hydrogen or (C1-C4)-alkyl;
R6 and R7 independently of one another denote H, F, C1, Br, CH3, CF3, NO2 or CN; and R8 denotes (C1-C8)-alkyl, (C3-C6)-alkenyl, phenyl, optionally mono-or di-substituted by halogen, or CF3 or (C1-C4)-alkyl.
2. A compound as claimed in Claim 1, in which, if X and Y denote oxygen, A denotes a direct bond, R2 denotes methyl or ethyl and R3 and R4 each denote hydrogen or together denote the dimethylaminomethylene radical, R6 denotes CF3, F, Cl or Br; R7 denotes H, C1 or Br; Z denotes CH or N; n denotes zero; and Q denotes O or S.
3. A process for the preparation of a compound of the formula I as claimed in claim 1, which comprises reacting a compound of the formula (II) in which X, R1 and A have the abovementioned meaning, with a compound of the general formula in which R2, R3, R4 and Y have the abovementioned meaning.
4. A process for the preparation of a compound as claimed in either claim 1 or 2, which comprises reacting a compound of the formula with a dimethylformamide dialkyl acetal in the presence of an acid catalyst.
5. A herbicidal agent containing a compound as claimed in either claim 1 or 2, in admixture with a diluent.
6. A method of combating weeds in agricultural crops and of influencing plant growth, which comprises applying an active amount of a compound of the formula I as defined in claim 1 to the areas or plants to be treated.
7. A method of protecting crop plants from phytotoxic side effects of herbicides, which comprises treating the plants, parts of plants or soil with a compound as claimed in either claim 1 or 2 in subtoxic concentrations, before, after or at the same time as the treatment with herbicides.
A compound of the formula:
9. A compound of the formula:
10. A compound of the formula:
11. A compound of the formula:
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19833340771 DE3340771A1 (en) | 1983-11-11 | 1983-11-11 | SUBSTITUTED PHENOXYPROPIONYL ISO-UREA DERIVATIVES, METHOD FOR THEIR PRODUCTION AND THEIR USE IN PLANT PROTECTION |
| DEP3340771.1 | 1983-11-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1242722A true CA1242722A (en) | 1988-10-04 |
Family
ID=6214031
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000467443A Expired CA1242722A (en) | 1983-11-11 | 1984-11-09 | Substituted phenoxypropionyl-isourea derivatives, a process for their preparation and their use in plant protection |
Country Status (14)
| Country | Link |
|---|---|
| EP (1) | EP0144001B1 (en) |
| JP (1) | JPS60116662A (en) |
| KR (1) | KR850004104A (en) |
| CN (1) | CN85101144A (en) |
| AT (1) | ATE26975T1 (en) |
| AU (1) | AU572224B2 (en) |
| BR (1) | BR8405722A (en) |
| CA (1) | CA1242722A (en) |
| DE (2) | DE3340771A1 (en) |
| ES (1) | ES537503A0 (en) |
| GR (1) | GR80899B (en) |
| HU (1) | HU193235B (en) |
| IL (1) | IL73468A (en) |
| ZA (1) | ZA848758B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102004023332A1 (en) * | 2004-05-12 | 2006-01-19 | Bayer Cropscience Gmbh | Quinoxaline-2-one derivatives, crop protection agents containing them, and processes for their preparation and their use |
| JP2011193857A (en) * | 2010-03-24 | 2011-10-06 | Sumitomo Chemical Co Ltd | Method for producing n-carbamoylamino compound |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3064249D1 (en) * | 1979-07-03 | 1983-08-25 | Ciba Geigy Ag | Thio-urea derivatives and isothio-urea derivatives, process for their preparation, compositions containing these compounds and their use in combating pests |
| US4330321A (en) * | 1981-03-16 | 1982-05-18 | The Dow Chemical Company | Compounds and method for selectively controlling grassy weeds in broadleaved crops |
| DE3340770A1 (en) * | 1983-11-11 | 1985-05-23 | Hoechst Ag, 6230 Frankfurt | PHENOXYALKANOYL DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE IN PLANT PROTECTION |
-
1983
- 1983-11-11 DE DE19833340771 patent/DE3340771A1/en not_active Withdrawn
-
1984
- 1984-11-02 HU HU844074A patent/HU193235B/en unknown
- 1984-11-03 EP EP84113235A patent/EP0144001B1/en not_active Expired
- 1984-11-03 DE DE8484113235T patent/DE3463501D1/en not_active Expired
- 1984-11-03 AT AT84113235T patent/ATE26975T1/en active
- 1984-11-08 ES ES537503A patent/ES537503A0/en active Granted
- 1984-11-09 IL IL73468A patent/IL73468A/en unknown
- 1984-11-09 ZA ZA848758A patent/ZA848758B/en unknown
- 1984-11-09 AU AU35290/84A patent/AU572224B2/en not_active Expired - Fee Related
- 1984-11-09 JP JP59235340A patent/JPS60116662A/en active Pending
- 1984-11-09 GR GR80899A patent/GR80899B/en unknown
- 1984-11-09 BR BR8405722A patent/BR8405722A/en unknown
- 1984-11-09 CA CA000467443A patent/CA1242722A/en not_active Expired
- 1984-11-10 KR KR1019840007055A patent/KR850004104A/en not_active Application Discontinuation
-
1985
- 1985-04-01 CN CN198585101144A patent/CN85101144A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| ATE26975T1 (en) | 1987-05-15 |
| IL73468A (en) | 1988-06-30 |
| IL73468A0 (en) | 1985-02-28 |
| JPS60116662A (en) | 1985-06-24 |
| DE3340771A1 (en) | 1985-05-23 |
| EP0144001B1 (en) | 1987-05-06 |
| AU3529084A (en) | 1985-05-16 |
| CN85101144A (en) | 1987-01-17 |
| ES8600283A1 (en) | 1985-10-16 |
| HUT36681A (en) | 1985-10-28 |
| KR850004104A (en) | 1985-07-01 |
| ZA848758B (en) | 1985-06-26 |
| DE3463501D1 (en) | 1987-06-11 |
| AU572224B2 (en) | 1988-05-05 |
| EP0144001A1 (en) | 1985-06-12 |
| ES537503A0 (en) | 1985-10-16 |
| GR80899B (en) | 1985-02-26 |
| HU193235B (en) | 1987-08-28 |
| BR8405722A (en) | 1985-09-17 |
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