CA2024876A1 - Plant-protection agents containing n-arylhydrazones, and novel n-arylhydrazones - Google Patents
Plant-protection agents containing n-arylhydrazones, and novel n-arylhydrazonesInfo
- Publication number
- CA2024876A1 CA2024876A1 CA002024876A CA2024876A CA2024876A1 CA 2024876 A1 CA2024876 A1 CA 2024876A1 CA 002024876 A CA002024876 A CA 002024876A CA 2024876 A CA2024876 A CA 2024876A CA 2024876 A1 CA2024876 A1 CA 2024876A1
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- Prior art keywords
- formula
- alkyl
- halogen
- alkoxy
- phenyl
- Prior art date
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- Abandoned
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Classifications
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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
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/52—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing groups, e.g. carboxylic acid amidines
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C257/00—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines
- C07C257/04—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines without replacement of the other oxygen atom of the carboxyl group, e.g. imino-ethers
- C07C257/06—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines without replacement of the other oxygen atom of the carboxyl group, e.g. imino-ethers having carbon atoms of imino-carboxyl groups bound to hydrogen atoms, to acyclic carbon atoms, or to carbon atoms of rings other than six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C257/00—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines
- C07C257/04—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines without replacement of the other oxygen atom of the carboxyl group, e.g. imino-ethers
- C07C257/08—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines without replacement of the other oxygen atom of the carboxyl group, e.g. imino-ethers having carbon atoms of imino-carboxyl groups bound to carbon atoms of six-membered aromatic rings
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- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Dentistry (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Toxicology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Plant-protection agents containing N-arylhydrazones, and novel N-arylhydrazones The compounds of the formula (I) are suitable for reduc-ing or preventing phytotoxic secondary effects of herbicides on crop plants.
Plant-protection agents containing N-arylhydrazones, and novel N-arylhydrazones The compounds of the formula (I) are suitable for reduc-ing or preventing phytotoxic secondary effects of herbicides on crop plants.
Description
HOECHST A~TIENGESELLSCHAFT - HOE 89/F 297 Dr.WE/St 2a2~7~
Description Plant-protection agents containing N-arylhydrazones, and novel N-arylhydrazones The invention relates to ~afeners or antidotes which, when combined with herbicides, can reduce the phytotoxic-ity of the herbicides in crop piants.
The invention relates to plant-protection agents which contain N-arylhydrazones of the formula (I) or ~alts thereof (Z1)nl ~ A Rl (I) where Z1 is halo~en, nitro, cyano or alkyll alkoxy, alkylthio or cycloalkyl, the last four radicals mentioned being unsubstituted or monosubstituted or polysub6-tituted by alkoxy, hydroxyl or halogen, furthermore is amino, mono- or dialkylamino, phenyl or phenoxy, phenyl or phenoxy being unsubstituted or monosubsti-tuted or polysubstituted by halogen or haloalkyl, Rl is alkyl, alkenyl, alkynyl or cycloalkyl, the last four radicals mentioned being unsubstituted or monosubstituted Dr poly6ubstituted by radical6 from the group comprising alkoxy, alkylthiot ~ono- or di-alkylamino, alkoxycarbonyl, alkylcarbonyloxy, cyano and halogen, i6 furthermore phenylalkyl or phenyl, each of which is unsubstituted or monosl~stituted or polys~b&tituted in t~.~ phenyl radical by r2dicals from the group comprising alkyl, alkoxy, alkylthio, mono- and dialkylamino, alko~ycarbonyl, cyano and halogen, nl is an integ~r from 0 to 5, A i O or S, B is B radical of the formula 2 ~ ~ s ~
-CO - R2 or ~ (Z2)n2 where z2 has the meaning mentioned for 1, and n2 is an integer from 0 to 5, and R2 is OH or alko~y, alkenyloxy, alkynyloxy, alkylthio or cycloalkoxy, the la~t five radicals mentioned being unsubstituted or mon~ub~tituted or polysub-stituted by radicals from the group comprising alkoxy, alkylthio, mono- and dialkylamino, cyano and halogen, is furthermore trialkylsilylmethoxy, a radical of the formula -N- ~ or -C ~ R
R O
where in each case R is hydrogen or al~yl, Z3 has the meaning mentioned for zl, and n3 i~ an integer from 0 to 5, R2 is furthermore mono- or dialkylamino, cycloalkyl-amino, pyridino, morpholino, dimethylmorpholino, a radical of the formula - O - N = C
where R3 and R4 in~ependently of one another are alkyl radicals, or R3 and R4 together with the carbon atom linking them form a cycloalkyl radical, in combination with customary auxiliaries for formula-tions of plant protection agents.
In formula (I), al~yl, alkoxy and alkylthio radicals as _ 3 _ 2.~
well as the corresponding unsaturated radicals can be in each case straight-chain or branched. Halogen iB fluor-ine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, in particular fluorine or chlorine.
In the case where R2 = OH, the compounds of the formula (I) can form salt6. Salts which can be employed according to the invention are those which can be u3ed in agricul-ture. Examples of suitable salts are metal salt~ such as alkali metal salts or ~lkaline earth metal salts, in particular sodium or potassium ~alts, salt~ with am-monium, mono-, di-, tri- or tetra-(Cl-C4)alkylammonium, or with mono-, di-, tri- or tetra-(Cl-C4)alkanolammonium.
Formula (I) furthermore also embraces all stereoisomers and mixtures thereof. Stereoisomers can occur mainly when there is an asymmetrical carbon atom or suitably 6ub-stituted double bonds in the formula (I).
Plant-protection agents according to the inv~ntion which are of particular interest are those containing N-arylhydrazones of the formula (I) or salts thereof, where Z~ radicals independently of one another are halogen, nitro, ~yano, (Cl-C4)alkyl, (C1-C4)slkoxy, (Cl-C4)-alkylthio, the alkyl, alkoxy and alkylthio groups being unsubstituted or monosubstituted or polysub-stituted by halogen atoms, in particular fluorine or chlorine, or are (C3-C6)cycloalkyl which i5 unsub-~tituted or substituted by (Cl-C4)alkyl, or are amino, ( C,-C4 )alkylamino, di(Cl-C4)alkylAmino, hydroxymethyl, (C1-C4)slkoxymethyl, phenyl or phenoxy, phenyl and ~henoxy being unsubstituted or monosubstituted or polysubstituted by halogen or monosubstituted by trifluoromethyl or substituted by one or more halogen substituent~ and one trifluoro-methyl, n1 is 0, 1, 2 or 3, A is S or 0, ~ 4 ~ 2~f~ 37i~
Rl iS ( C3-C~ ) CyC loalkyl, (Cl-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl, the four radicals mentioned being unsubstituted or monosubstituted or polysubstituted by radicals from the group comprising (Cl-C2)alkoxy, mono- or di(Cl-C6)alkylamino, (Cl-Csjalkoxycarbonyl, (Cl-C6)alkylcarbonyloxy, (Cl-C2)alkylthio, cyano and halogen, is ~urthermore phenyl (Cl-C6)alkyl or phenyl, each of which is unsub6tituted or monosub-~tituted or polysubstituted $n ~he phenyl radical by radicals from the group compri ing (Cl-C4)alkyl, (Cl-C4)alkoxy, (Cl-C4)alkylthio, mono- and di(C~-C6)-alkylamino, (Cl-C6)alko~ycarbonyl, cyano and halogen, B is a radical of the formula -co-R2 or (Z )n2 where Z2 has the meaning mentioned above for Zl and n2 is 0, l, 2 or 3, R2 is hydroxyl, -QCH2Si(CH3)3, (C3-C6)cycloalkoxy, phenyl~Cl-C6)alkoxy, phenoxy, (~2-~6 ) alkenyloxy , (C2-C6)alkynyloxy,(Cl-C6)alkoxy,(Cl-C~)alkylthio,the alkoxy or alkylthio group being un~ubstituted or monosubstituted or disubstituted by (Cl-C2)alkoxy, mono- or di(Cl-C6)alkylamino, (Cl-C2jalkylthio or cyano, or monosubstituted or polysubstituted by halogen, or R2 i~ a radical of the formula R ~ or -C ~ R
where in each case R i5 hydrogen or (Cl-C~)alkyl, Z3 has the meaning mentioned for z1, and n3 is o~ l~ 2 or 3, R2 i8 furthermore mono- or ditCl~C4)alkylamino, (C5-C6)-cycloalkylamino, piperidino, morpholino or 2,6-5 - ~ ~ 2 ~
dimethylmorpholino or 8 radical of the formula - O-N = C ~
~ R4 where R3 and R4 independently of one annther are (Cl-C4)-alkyl, or R3 and R4 together with the carbon atom linking them form a 5-, 6- or 7-membered cycloalkyl radical.
Preferred plant-protection agents according to the invention containing N-arylhydrazones of the formula (I) or salts thereof are those where Z1 radicals independently of one another are halogen, in particular fluorine or chlorine, nitro, (C1-C4)alkyl, (Cl-C4)alkoxy or trifluoromethyl, A is oxygen, n1 is 0, 1 or 2, R1 is phenyl which is unsubstituted or monosubstituted to trisubstituted by radical~ from the (Cl-C4)alkyl group, in particular methyl, (Cl-C4)alkoxy and halogen, or is (Cl-C4)alkyl, B is a radical of the formula -CO - R2 or ~
(Z2)n2 where R2 is h~droxy or ( C~-C4 )alkoxy, Z3 iS halogen, in particular chlorine, or (Cl~Cq)~
alkyl, and n3 is O ~ 1 or 2.
Some of the compounds of the formula (I) are known ~rom scientific publications ~Bull. Chem. Soc. Japan 48, 365-366 (1975), J. Chem. S~c. ~C) 368 (1970); Tetrahedron 28, 5903 (1972); Tetrahedron Lett. 31, 3211 (1972); Can. J.
- 6 - 2 Q 2 ~ ~ 7 ~
Chem. 91, 4115 (1973)). However, their ~afener effect has not been recognized to date.
The present invention therefore also relates to the novel compounds of the formula ~I) or salts thereof which have not been described to date. These are the above-defined compounds of the formula (I) or ~alts thereof, with the exception of those compounds in which a) Rl is unsub~tituted or sub6tituted phenyl, A is oxygen and B is a radical of the above-defined formula ~ ~Z2)n2 and with the exception of those compounds in which b) Z1 is 4-CH3, 4-Br, 4-Cl, 4-NO2, 3-CH3, n' is O or 1, Rl is unsub~tituted phenyl, 4-methylphenyl or 3-methylphenyl, A is oxygen and B is CO2C2H5-The present invention al80 relates to a process for the preparation of the novel compounds of the formula (I) and fialts thereof, which comprises reacting a compound of the formula (II) ~ -NH - N ~ (II) (Zl)nl where (Z)nl and B ha~e the meanings given above and ~al is Br, Cl or I, with alcohols or thiol of the formula ~A-Rl where A and R1 have the abovementioned meanings, and with a base ~uch as, for example, NaOEt, ROCzH5~ NH3 and 202~ ~' 7~3 NaOCOCH3.
Suitable solvents are unpolar organic solvents, for example ethers ~uch as diethyl ether or THF, or the alcohols themselves required for the reaction.
The compounds of the formula (II) are known from the literature (for example Bull. Chem. Soc. Jpn 48 365-366 (1975)) or they can be prepared analogously to the known compounds.
The compounds of the formula (I) reduce or prevent phytotoxic secondary effects of plant protection agents, in particular of herbicides, which can occur when these ayents are employed in crops.
The compounds of the formula (I) can be applied in succession or together with the herbicidally active sub-stances. They are then capable of le~sening or completelyelLminating noxious secondary effects of the herbicides in crop plants, without Lmpairing the effectiveness of these herbicides against noxious plants.
By virtue of this, the field of application of conven-tional plant protection agent~ can be widened to a very considerable extent. Such compoundc which pos6ess the property of protecting cr3p plants against phytotoxic damageby herbicides are called "an idotes" or "6afenersN.
Examples of herbicides whose phytotoxic ~econdary effects can be reduced by means of the compounds of the formula (I) are carbamates, thiocarbamates, halo~ tanilîdes, substituted phenoxy-, naphthoxy- and phenoxyphenoxy ~arboxylic acid derivative6 as well as heteroaryloxyphen-oxycarboxylic acid derivati~es, such as quinolyloxy-, quinoxalyloxy-, pyridyloxy-, benzoxazolyloxy- and ben-zothiazolyloxy-phenoxy-carboxylic acid e~ters, and furthermore dimedone oxime derivative~. Preferred com-pounds amongst these are phenoxyphenoxy- and heteroaryl-20~!~,,7~3oxy-phenoxycarboxylic acid esters. Suitable es~ers 1n this connection are, in particular, lower alkyl, alkenyl and alkynyl esters.
The following herbicides may be mentioned by way of example but without impo6ing any restriction:
A) Herbicides of the type of the (Cl-C4)alkyl, (C2-C~)-alkenyl and ( C3-c4 )alkynyl phenoxyphenoxy- and heteroaryl-oxy-phenoxycarboxylates, such as methyl 2-(4-(2,4-dichlorophenoxy)phenoxy)propionate, methyl 2-(4-(4-bromo-2-chlorophenoxy~phenoxy)propionate, methyl 2-(4-(4-trifluoromethylphenoxy~phenoxy)propionate, methyl 2-(4-(2-chloro-4-trifluoromethylphenoxy)phenoxy)-propionate, methyl 2-(4-~2,4-dichlorobenzyl)phenoxy)propionate, ethyl 4-t4-(4-trifluoromethylphenoxy)phenoxy)pent-2-enoate, ethyl 2-(4-(3,5-dichloropyridyl-2-oxy)phenoxy)propionate, propargyl 2-(4-(3,5-dichloropyridyl-2-oxy)phenoxy~propio-nate, ethyl 2-(4-(6-chlorobenzoxazol-2-yloxy)phenoxy)propion-ate, methyl 2-(4-(3~chloro-5-trifluoromethyl-2-pyridyloxy)-phenoxy)propionate, butyl 2-(4-(5-trifluoromethyl-2-pyridyloxy)phenoxy)pro-pionate,methyl 2-(4-(3-fluoro-5-chloropyridyl-2-oxy)phenoxy)pro-pionate, propargyl 2-(4-(3-fluoro-5-chloropyridyl-2-oxy)phenoxy)propionate, methyl 2-(4-(6-chloro-2-quinoxalyloxy)phenoxy)propionate, methyl 2-(4-(6-fluoro-2-quinoxalyloxy)phenoxy~propiona~e, methyl 2-(4-(6-chl~ro-2-quinolyloxy)phenoxy)propionate, B) Chloroacetanilide herbicides, such as N-me*hoxymethyl-2,6-diethylchloroacetanilide, N-(3'-methoxyprop-2'-yl~methyl-6-ethylchloroacetanilide, N-(3-methyl-1,2,4-oxdiazol-5 ylmethyl)-2,6-dimethyl-9 ~ ;7i~
chloxoacetanilide, C) Thiocarbamates, such a~S-ethyl N,N-dipropylthiocarbamate or S-ethyl N,N-diisobutylthiocarbamate D) Dimedone derivatives, such as methyl 3-(1-allylo~yimino)butyl-4-hydroxy-6,6~dimethyl-2-oxocyclohex-3-enecarboxylate 2-tN-etho~ybutyrimidoyl)-5-(2-ethylthiopropyl)-3-hydroxy-2-cyclohexen-1-one, 2-(N-ethoxybutyrLmidoyl)-5-(2-phenylthiopropyl)-3-hyd-roxy-2-cyclohexen-1-one, 2-(1-allyloxyLminobutyl)-4-methoxycarbonyl-5,5-dLmethyl-3-oxocyclohexenol, 2-(1-(3-chloroallyloxy)iminobutyl)-5-(2-ethylthio)-propyl)-3-hydroxycyclohex-2-enone, 2-(1-(ethoxyimino)butyl)-3-hy~roxy-5-(thian-3-yl)cyclo-hex-2-enone or 2-(1-ethoxyiminopropyl)-5-(2,4,6-trimethylphenyl)-3-hydroxy-2-cyclohexen-1-one.
The ratio of ~afener : herbicide can vary within wide lLmits, within the range of between 1 : 10 and 10 : 1, in particular between 2 : 1 and 1 . 10. The amounts of herbicide and safener which are ideal in each case depend on the type of the herbicide used or on the safener used as well as on the nature of the plant stand to be treated, and they can be determined for each individual case by appropriate experiments.
The ~afener~ are mainly employed in particular in cereal crops (whe~t, rye, barley, oats3, rice, maize, sorghum, but also in cotton, ~ugar beet, ~ugar cane and soya bean.
Depending on their properties, the ~afeners of the formula ~I~ can be us0d for pre-treating the seed of the crop plant (seed treatment)~ or ~hey can be incorporated in the seed furrows prior to sowing, or u~ed together with the herbicide prior to, or after, plant emergence.
Pre-emergence ~reatment includes both the ~reatment of the area under cultivation prior to sowing and the treatment of the areas under cultivation where seed has been sown but growth of the crop plants has not yet tsken place. Application together with the herbicide i6 prefer-red. Tank mixes or readymixes can be employed for this purpose.
The application rates which are required of the compounds of the formula (I) can vary within wide limit~, depending on the indication and the herbicide used, and they generally vary between 0.01 and 10 kg of active ~ubstance pex hectare.
The present invention therefore also relates to a method of protecting crop plants against phytotoxic secondary effects of herbicides, which comprises applying an effective amount of a compound of the formula (I) before, after, or simultaneou~ly with, the herbicide.
Moreover, the compounds according to the invention exhibit growth-regulating properties in crop plants. ~hey engage in the plant metabolism in a regulating manner and can thus be employed for facilitating the harvest, for example by provoking desiccation, abscission and stunted growth. Moreover, they are also fiuitable for generally monitoring and inhibiting undesired vegetative growth, without at the same tLme destroying the plants. Inhibi-tion of vegetative growth is very important in many monocotyledon and dicotyledon crops since lodging can be reduced, or completely inhibited, by this means.
The compounds of the formula (I) or a combination thereof with one or more of the mentioned herbicides, or ~roups of herbicides, can be formulated in various ways, depend-ing on the given biological and/or physico~hemical parameters. The following are examples of suitable formulation types: wettable powders (WP), emul~ifiable concentrates (EC), aqueous 801ution5 (SL~, concentra~ed emulsions such as oil-in-water nnd water-in-oil emulsions (EW), sprayable solutions or emulsion6, disper~ions based on oil or water (SC), dusts (DP~, seed-treatment aqents, absorption granules for ground and spreading application (FG), water-dispersible granules (WG), ULV formulation~, micro-capsules or waxes.
These individual types of formulation~ are known in principle and are described, for example, in: Winnacker-Kuchler, ~Chemische ~echnologie" tChemi~al Technology~
Volume 7, C. Hau~er Verlag Munich, 4th Ed. 1986; vsn Valkenbur~, "Pesticides Formulations", ~arcel Dekker N.Y., 2nd Ed. 1972-73; R. Marten~, "Spray Drying Hand-book~, 3rd Ed. 1979, G. Goodwin Ltd. London.
The formulation auxiliaries reguired, such as inert materials, surfactants, solvents and ~urther additives are likewise kr.own and hre des~ribed, for example, in:
Watkins, ~Handbook of Insecticid Du t Diluents and Carriers , 2nd Ed., Darland Books, Caldwell N.J.; H.v.
Olphen, "Introduction to Clsy Colloid Chemi~try"; 2nd Ed., J. Wiley ~ Sons, N.Y.~ ~Solvents Guide~, 2nd Ed., Interscience, N.Y. 1950; ~cCutcheon~s, nDetergents and Emulsifiers Annual", ~C Publ. Corp., Ridgewood N.J.;
Sisley and Wood, "Encyclopedia of Surface Active Agentsn, Chem. Publ. Co. Inc., N.Y. 1964; Sch~nfeldt, ~Grenz-fl~chenaktive ~thylenoxidaddukten ~Surface-active Ethylene Oxide ~dduct6], Wi~. Verlagsge~ell., Stuttgart 1975; Winn~cker-RUchler, ~Chemi~che Technologie"
[chemical Technology], Volume 7, C. ~user Verlag ~unich, 4th Ed. 1986.
On the basi~ of these fonmulation~, it is al~o pos6ible to prepare c~bin~tion~ with other pe~ticidally w tive substance6, fertilizers ~nd/or grow~h regulators, for example in the form of a readymix or as a tankmix.
Wettable powers ar~ preparation~ which are uniformly - 12 - 2~ 3 dispersible in water and which, besides the active substance, also contain wetting agen~s, for example polyoxethylated alkylphenols, polyoxethylated fatty alcohols, alkanesulfonates or alkylarylsulfonates, and S dispersing agents, for example sodium ligninsulfonate, sodium 2,2~-dinaphthylmethane-6,6~-disulfonate, sodium dibutylnaphthalenesulfonate, or alternatively ~odium oleoylmethyltaurinate, in addition to a diluent or inert substance.
Emulsifiable concentrate~ are prepared by dis601ving the active substance in an organic solvent, for exEmple butanol, cyclohexan~ne, dimethylf~rmamide, xylene and also higher-boiling aromatic compounds or hydrocarbons, with the addition of one or more emulsifiers. Examples of emulsifiers which can be used are. calcium salts of an alkylarylsulfonic acid, such as Ca dodecylbenzenesul-fonate, or non-ionic emulsifiers, such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide/ethylene oxide condensation products (for example block polymers), alkyl polyglycol ethers, sorbitan fatty acid esters, polyox-ethylene sorbitan fatty acid esters or polyoxethylene sorbitol esters.
Dusting agents can be obtained by grinding the active 2S substance with finely divided ~olid sub6tance6, for example talc or natural clay~, ~uch as kaolin, bentonite, pyTophyllite or diatomaceous earth.
Adsorption granules for ground and spreadmg application can be produced either by ~praying the active ~ubstance onto adsorpti~e, granulated inert material or by applying active substance concen~rates onto the xurface of car-riers, 6uch as sand, kaolinites or granulated inert material, by means of binders, for example polyvinyl alcohol, sodium polyacrylate or, alternatively, mineral oils. Suitable active substances can also be ~ranulated in the manner which is conventional for the production of - 13 - 2 ~ 2 ~ , 3 ~ ~3 ~ fertilizer granules, if de ired in a mixture with fer-tilizers.
In general, the agrochemical preparations contain 0.1 to 99 percent by weight, in particular 0.1 to 95% by weight, of active substance of the formula (I) or of an antidote/
herbicide mixture of acti~e substance, 1 to 99.9~ by weight, in particular 5 to 99.8% by weight, of a solid or a liquid additive and 0 to 25% by weight, in particular 0.1 to 25~ by weight, of a surfactant.
The active substance concentration in wettable powders is, for example, about 10 to 90~ by weight; the remainder to 100% by weight comprises conventional formulation components. In the ca~e of ~mulsifiable concentrates, the active 6ubstance concentration can be about 1 to 80~ by weight, preferably 5 to 80% by weight. Formulations in the form of dusts usually contain 1 to 25% by weight, preferably 5 to 20% by weight of active substance, spray-able solutions about 0.2 to 25% by weight, preferably 2 to 20% by weight of active ~ubstance. In the case of water-dispersible granules, the active ~ubstance content depends partly on whether the active compound is liquid or 601id. In general the water-di~persible granules have a content of between 10 and 90% by weight.
In addition, the active ~ubstance formulations mentioned contain, if appropriate, the adhesives, wetting agents, disper~ing agentfi, emulsifiers, penetrant , ~olvents, fillers or carriers which are conventional in each case.
For use, the formulations, present in commercially avail-able form, are diluted, if appropriate, in a customary manner, ~or e~.~mple using water in the case of wettable powders, emulsiiiable concentrates, dispersion~ and water-disper~ible granules. Preparations in the form of dusts, or adsorption granules for gra md and spreadin~ application and also sprayable ~olutions are u~ually not further diluted with other inert substances before use.
- 14 _ 2~a~7~
The application rate required, of the compounds of the formula (I), varies with the external conditions, ~uch as, inter alia, temperature, humidity and the type of herbicide used. It can vary within wide limits, for example between 0.005 and 10.0 kg/ha or more of active in~redient; preferably, however, it i8 between 0.01 and 5 kg/ha.
The examples which follow are intended to illustrate the invention:
A. Formulation E~ample~
a) A dustinq agent i8 obtained by mixin~ 10 parts by weight of a compound of ~he formula (I) and 90 parts by weight of talc as inert ~ubstance, and comminut-ing the mixture in a hammer mill.
b) A wettable powder which i~ readily disper~ible in water is obtained by mixing 25 parts by weight of a compound of the formula (I), 64 part~ by weight of kaolin-containing guartz as the inert substance, 10 parts by weight of potas~ium ligninsulfonate and 1 part by weight of sodium oleoylmethyltaurinate as the wetting and dispersing agent, and grinding the mixture in a pinned disk mill.
c) A dispersion concentrate which i8 readily di~persible in water is obtained by mixing 20 parts 2S by weight of a compound of the formula (I) with 6 parts by weight of alkylphenol polyglycol ether (~Triton X 207), 3 part~ by weight of isotridecanol polyylycol ether ~ EO) and 71 parts by weight of paraffinic mineral oil (boiling range, for example, about 255 to above 277C), and grinding the mixture in a ball mill to a fineness of below S microns.
d) An emul~ifiable concentrate is obtained from 15 parts by weight of a compound of the formula (I), 75 ~ 15 -parts by weight of cyclohexanone as the solvent and 10 parts by weight of oxethylated nonylphenol a~ the emul~ifier.
e) Water-dispersible granules are obtained by mixing 75 parts by weight of a compound of the formula I, 10 " of calcium ligninsulfonate, 5 " of sodium lauryl sulfate, 3 ~ of polyvinyl alcohol and 7 " of kaolin, grinding the mixture in a pinned di6k mill, and granulating the powder in a fluidized bed by spray-ing on water as the granulation liquid.
f) Water-dispersible granules are also obtained by homogenizing, in a colloid mill, 25 partC by weight of a compound of the formula ~I), 5 " of sodium 2,2'-dinaphthylmeth-ane-6,6'-disulfonate, 2 ~ of ~odium oleoylmethyltaurinate, 1 part by weight of polyvinyl alcohol, 17 parts by weight of calcium carbonate ~nd 50 " of water, precomminutin~ the mixture, 6ub5eguently grinding the mixture in a bead mill, and atomizing and drying the resulting suspen~ion in a spray tower by means of a single-fluid nozzle.
B. Chemical e~2mple~
~thyl 2~ ~ethylph~nylo~)-2-(4-~itrop~enylhydrazono)-acetate ~Example No. 42) O.69 g of ~odium i~ dissolved in 100 ml of ab801ute e~hanol. To thi~ there are added 3.24 g of 4 methylphenol and stirring is continued for 15 minutes at room - 16 ~ J ~
temperature. The mixture is subsequently cooled to 0C, and 8.16 g of ethyl 2-chloro-2-(4-nitrophenylhydrazono)-acetate are added. Stirring is continued for 18 hours at room temperature. The product is filtered off with ~uction and extracted by stirring with ethyl acetate.
After drying, 7.2 g (70~ of theory) of product of melting point 158~C are obtained.
Ethyl 2-phenylo~y-2-phenylhydrazonoacetate (~sample No.7) To a ~olution of 0.68 g of sodium ethanolate in 40 ml of absolute ethanol there i8 added 0.94 g of phenol, and the mixture is stirred for 15 minutes. 2.26 g of ethyl 2-chloro-2-phenylhydrazonoacetate are subsequently added at 0C, and stirring i8 continued for 18 hours at room temperature. The product is filtered off with suction and recrystallized from ethanol. In this manner, 1.7 g (60%) of product of melting point 82-83C are obtained.
Ethyl 2-methoxy-2-(2,4-dichlorophenylhydrazono)acetate (~xample No. 27) To 147.8 g of ethyl 2-chloro-2-~214-dichlorophenylhydra-zono)acetate in 100 ml of tetrahydrofuran there are added dropwise at 0C 50.59 g of triethylamine. After 15 minutes at 0C, 40 ml of methanol are added, and the mixture is stirred for S hours at room temperature. The mixture is evaporated completely on a rotary evaporator, and the product is subsequently chromatographed on silica gel (eluent: n-heptane/ethyl acetate 1:1). In this m~nner, 21.82 g ~15~ of theory) of product of melting point 119-122C are obtained.
~thyl 2-etho y-2-l2,4-dichlorophenylhydrazo~o)acetate (B~ampl~ 153 29.5 g of ethyl 2-~hloro-2-~2~4-dichlorophenylhydrazono)-acetate and 8.2 g of sodium ~cetate are refluxed for 5 hours in 100 ml of 95% pure ethanol. The reaction mixture is subsequently evaporated on a rotary evapor~tor, the product is taken up in C~2Cl2, a~d the mixture i5 ex-tracted with water. The orqanic phase i~ dried with MgS04 1 7 ~
and evaporated on a rotary evaporator. Subsequent column chromatography gives 13.7 g of product of melting point 47 CC .
Table I which follows lists the abovementioned examples together with further examples which can be prepared in an analogous manner:
18 -- ~ r~
Table I
N ~ ( I ) (Z)nl A Rl No. (Z)nl -A-Rl B ~5.p. C
2- CL - O- C6Hs CO2C2Hs 2 4-Cl 3 2,4-Cl 4 3,5-C
2, 6- C
6 4- N02 17 ~I
7 H ll It 82- 83 2,4- (CH3)2 13 2- Cl - O- C2H5 14 4- Cl l' ll 2,4-C12 ll ll 47 16 2,5-Cl 17 2,6-Cl 4~ OCH3 22 2,4- (CH3)2 24 3- CF3 ~I ll 2 5 2- Cl _ O- CH3 C02C2H5 27 2, 4- Cl2 ~ 119- 122 -- 19 -- ~ r/ ;_7 (Table I, continuation) No. (Z)nl A R1 B M.p. C
_ 28 3,5-C12 " ~
29 2,6-C12 " "
4-NO2 1~ ~
31 H " "
32 4-OCH3 " ~I
33 2-CH3 " "
34 2,4-(CH3)2 4-F " "
36 3-CF3 " n 37 2-Cl -O-C6H4-CH3(P) 38 4-Cl " "
39 2,4-C12 " "
3,5-C12 " "
41 2,6-C12 " "
44 4-OC~3 " "
2-CH3 " "
46 2,4-(CH3)2 47 4-F " "
48 3-CF3 " "
49 2-Cl -C2H5 -&6H5 4-Cl " "
51 2,4-C12 " "
52 3,5-C12 " "
53 2,6-C12 " "
54 4-NO2 " "
H " " 168-169 56 4-OCH3 " "
57 2-CH3 " "
(Table I, ~ontinuation) No. (Z)nl A ~l B M.p. C
58 2,4-~CH3)2C2H5 -C6H5 59 4-F " "
3-CF3 " "
61 2-Cl O-C3H7(n) -CO2Et 62 4-Cl " "
63 2,4-C12 - ,.
64 3,5-Cl2 " "
2,6-Cl2 " "
66 4-NO2 " "
67 H " "
68 4-OCH3 " "
69 2-CH3 " "
2,4-(CH3)2 71 4-F " "
72 3-CF3 " "
73 2-Cl -OCH3 ~6H3-2,4-Cl2 74 4-C1 " "
2,4-Cl2 " "
76 3,5-Cl2 " "
77 2,6-Cl2 " "
79 H " "
4-OCH3 " "
82 2,4-(CH3)2 83 4-F " "
84 3-CF3 ~ " "
2-Cl -C2H5 86 4-Cl " n (Table I, continuation) No. (Z)nl _A R1 B ~l.p. C
87 2, 4- C12 C2HS - C6H3- 2, 4~ C12 88 3, 5- C12 " "
89 ~, 6- C12 " "
9 O ~- NO2 " "
91 H " "
92 4- OCH3 " "
9 3 2 - CH 3 " "
94 2,4- (CH3)2 4-F n Biolt~gical E~amples Example 1 Wheat and barley were grown in plastic pots in a green-house until they had reached the 3-4 leaf tage, and then treated in succession with the compounds according to the invention and the herbicides te~ted, u~ing the post-amergence method. For this purpo , the herbicides and the compounds of the formula (I) were applied in the form of aqueous ~upensions or emulsions, at an application rate of water of 800 l/ha (converted~. 3-4 weeks after the treatment, the plants were scored vi6ually for any type of damage cau~ed by the herbicides applied, the extent of sustained growth inhibition, in particular, being taken into account. The asses~ment wa~ expressed in percentages in comparison with untreated controls.
The results from Table II illustrate that the compounds according to the invention are capable of effecti~ely reducing ~evere herbicidal damage on the crop plants.
2P~ ?i Even when fsr too high doses of the herbicide H had been applied, severe damage which occurs in the crop plants is markedly reduced, and lesser damage is eliminated com-pletely. Mixtures of herbicides and compounds according to the invention are therefore outstandingly suitable for selectively controlling weeds in cereal crops.
Table II
Safener action of the compounds according to the inven-tion Example No. Dose in kg Damage to crop plants (%) of a.i./ha TRAE HOW
, _ H 2.0 75 0.2 - 80 H + 3 2.0 + 2.5 40 0.2 + 2.5 - 35 H ~ 27 2.0 + 1.0 0 2.0 + 0.25 10 0.2 ~ 1.0 - 20 0.2 + 0.25 - 22 Abbreviations:
TRAE - Triticum aestivum HOW = Hordeum ~ulgare a.i. = active ingredient 5 H = ethyl 2-(4-(6-chlorobenzoxazol-2-yloxy)phenoxy propionate (Fenoxaprop-ethyl)
Description Plant-protection agents containing N-arylhydrazones, and novel N-arylhydrazones The invention relates to ~afeners or antidotes which, when combined with herbicides, can reduce the phytotoxic-ity of the herbicides in crop piants.
The invention relates to plant-protection agents which contain N-arylhydrazones of the formula (I) or ~alts thereof (Z1)nl ~ A Rl (I) where Z1 is halo~en, nitro, cyano or alkyll alkoxy, alkylthio or cycloalkyl, the last four radicals mentioned being unsubstituted or monosubstituted or polysub6-tituted by alkoxy, hydroxyl or halogen, furthermore is amino, mono- or dialkylamino, phenyl or phenoxy, phenyl or phenoxy being unsubstituted or monosubsti-tuted or polysubstituted by halogen or haloalkyl, Rl is alkyl, alkenyl, alkynyl or cycloalkyl, the last four radicals mentioned being unsubstituted or monosubstituted Dr poly6ubstituted by radical6 from the group comprising alkoxy, alkylthiot ~ono- or di-alkylamino, alkoxycarbonyl, alkylcarbonyloxy, cyano and halogen, i6 furthermore phenylalkyl or phenyl, each of which is unsubstituted or monosl~stituted or polys~b&tituted in t~.~ phenyl radical by r2dicals from the group comprising alkyl, alkoxy, alkylthio, mono- and dialkylamino, alko~ycarbonyl, cyano and halogen, nl is an integ~r from 0 to 5, A i O or S, B is B radical of the formula 2 ~ ~ s ~
-CO - R2 or ~ (Z2)n2 where z2 has the meaning mentioned for 1, and n2 is an integer from 0 to 5, and R2 is OH or alko~y, alkenyloxy, alkynyloxy, alkylthio or cycloalkoxy, the la~t five radicals mentioned being unsubstituted or mon~ub~tituted or polysub-stituted by radicals from the group comprising alkoxy, alkylthio, mono- and dialkylamino, cyano and halogen, is furthermore trialkylsilylmethoxy, a radical of the formula -N- ~ or -C ~ R
R O
where in each case R is hydrogen or al~yl, Z3 has the meaning mentioned for zl, and n3 i~ an integer from 0 to 5, R2 is furthermore mono- or dialkylamino, cycloalkyl-amino, pyridino, morpholino, dimethylmorpholino, a radical of the formula - O - N = C
where R3 and R4 in~ependently of one another are alkyl radicals, or R3 and R4 together with the carbon atom linking them form a cycloalkyl radical, in combination with customary auxiliaries for formula-tions of plant protection agents.
In formula (I), al~yl, alkoxy and alkylthio radicals as _ 3 _ 2.~
well as the corresponding unsaturated radicals can be in each case straight-chain or branched. Halogen iB fluor-ine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, in particular fluorine or chlorine.
In the case where R2 = OH, the compounds of the formula (I) can form salt6. Salts which can be employed according to the invention are those which can be u3ed in agricul-ture. Examples of suitable salts are metal salt~ such as alkali metal salts or ~lkaline earth metal salts, in particular sodium or potassium ~alts, salt~ with am-monium, mono-, di-, tri- or tetra-(Cl-C4)alkylammonium, or with mono-, di-, tri- or tetra-(Cl-C4)alkanolammonium.
Formula (I) furthermore also embraces all stereoisomers and mixtures thereof. Stereoisomers can occur mainly when there is an asymmetrical carbon atom or suitably 6ub-stituted double bonds in the formula (I).
Plant-protection agents according to the inv~ntion which are of particular interest are those containing N-arylhydrazones of the formula (I) or salts thereof, where Z~ radicals independently of one another are halogen, nitro, ~yano, (Cl-C4)alkyl, (C1-C4)slkoxy, (Cl-C4)-alkylthio, the alkyl, alkoxy and alkylthio groups being unsubstituted or monosubstituted or polysub-stituted by halogen atoms, in particular fluorine or chlorine, or are (C3-C6)cycloalkyl which i5 unsub-~tituted or substituted by (Cl-C4)alkyl, or are amino, ( C,-C4 )alkylamino, di(Cl-C4)alkylAmino, hydroxymethyl, (C1-C4)slkoxymethyl, phenyl or phenoxy, phenyl and ~henoxy being unsubstituted or monosubstituted or polysubstituted by halogen or monosubstituted by trifluoromethyl or substituted by one or more halogen substituent~ and one trifluoro-methyl, n1 is 0, 1, 2 or 3, A is S or 0, ~ 4 ~ 2~f~ 37i~
Rl iS ( C3-C~ ) CyC loalkyl, (Cl-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl, the four radicals mentioned being unsubstituted or monosubstituted or polysubstituted by radicals from the group comprising (Cl-C2)alkoxy, mono- or di(Cl-C6)alkylamino, (Cl-Csjalkoxycarbonyl, (Cl-C6)alkylcarbonyloxy, (Cl-C2)alkylthio, cyano and halogen, is ~urthermore phenyl (Cl-C6)alkyl or phenyl, each of which is unsub6tituted or monosub-~tituted or polysubstituted $n ~he phenyl radical by radicals from the group compri ing (Cl-C4)alkyl, (Cl-C4)alkoxy, (Cl-C4)alkylthio, mono- and di(C~-C6)-alkylamino, (Cl-C6)alko~ycarbonyl, cyano and halogen, B is a radical of the formula -co-R2 or (Z )n2 where Z2 has the meaning mentioned above for Zl and n2 is 0, l, 2 or 3, R2 is hydroxyl, -QCH2Si(CH3)3, (C3-C6)cycloalkoxy, phenyl~Cl-C6)alkoxy, phenoxy, (~2-~6 ) alkenyloxy , (C2-C6)alkynyloxy,(Cl-C6)alkoxy,(Cl-C~)alkylthio,the alkoxy or alkylthio group being un~ubstituted or monosubstituted or disubstituted by (Cl-C2)alkoxy, mono- or di(Cl-C6)alkylamino, (Cl-C2jalkylthio or cyano, or monosubstituted or polysubstituted by halogen, or R2 i~ a radical of the formula R ~ or -C ~ R
where in each case R i5 hydrogen or (Cl-C~)alkyl, Z3 has the meaning mentioned for z1, and n3 is o~ l~ 2 or 3, R2 i8 furthermore mono- or ditCl~C4)alkylamino, (C5-C6)-cycloalkylamino, piperidino, morpholino or 2,6-5 - ~ ~ 2 ~
dimethylmorpholino or 8 radical of the formula - O-N = C ~
~ R4 where R3 and R4 independently of one annther are (Cl-C4)-alkyl, or R3 and R4 together with the carbon atom linking them form a 5-, 6- or 7-membered cycloalkyl radical.
Preferred plant-protection agents according to the invention containing N-arylhydrazones of the formula (I) or salts thereof are those where Z1 radicals independently of one another are halogen, in particular fluorine or chlorine, nitro, (C1-C4)alkyl, (Cl-C4)alkoxy or trifluoromethyl, A is oxygen, n1 is 0, 1 or 2, R1 is phenyl which is unsubstituted or monosubstituted to trisubstituted by radical~ from the (Cl-C4)alkyl group, in particular methyl, (Cl-C4)alkoxy and halogen, or is (Cl-C4)alkyl, B is a radical of the formula -CO - R2 or ~
(Z2)n2 where R2 is h~droxy or ( C~-C4 )alkoxy, Z3 iS halogen, in particular chlorine, or (Cl~Cq)~
alkyl, and n3 is O ~ 1 or 2.
Some of the compounds of the formula (I) are known ~rom scientific publications ~Bull. Chem. Soc. Japan 48, 365-366 (1975), J. Chem. S~c. ~C) 368 (1970); Tetrahedron 28, 5903 (1972); Tetrahedron Lett. 31, 3211 (1972); Can. J.
- 6 - 2 Q 2 ~ ~ 7 ~
Chem. 91, 4115 (1973)). However, their ~afener effect has not been recognized to date.
The present invention therefore also relates to the novel compounds of the formula ~I) or salts thereof which have not been described to date. These are the above-defined compounds of the formula (I) or ~alts thereof, with the exception of those compounds in which a) Rl is unsub~tituted or sub6tituted phenyl, A is oxygen and B is a radical of the above-defined formula ~ ~Z2)n2 and with the exception of those compounds in which b) Z1 is 4-CH3, 4-Br, 4-Cl, 4-NO2, 3-CH3, n' is O or 1, Rl is unsub~tituted phenyl, 4-methylphenyl or 3-methylphenyl, A is oxygen and B is CO2C2H5-The present invention al80 relates to a process for the preparation of the novel compounds of the formula (I) and fialts thereof, which comprises reacting a compound of the formula (II) ~ -NH - N ~ (II) (Zl)nl where (Z)nl and B ha~e the meanings given above and ~al is Br, Cl or I, with alcohols or thiol of the formula ~A-Rl where A and R1 have the abovementioned meanings, and with a base ~uch as, for example, NaOEt, ROCzH5~ NH3 and 202~ ~' 7~3 NaOCOCH3.
Suitable solvents are unpolar organic solvents, for example ethers ~uch as diethyl ether or THF, or the alcohols themselves required for the reaction.
The compounds of the formula (II) are known from the literature (for example Bull. Chem. Soc. Jpn 48 365-366 (1975)) or they can be prepared analogously to the known compounds.
The compounds of the formula (I) reduce or prevent phytotoxic secondary effects of plant protection agents, in particular of herbicides, which can occur when these ayents are employed in crops.
The compounds of the formula (I) can be applied in succession or together with the herbicidally active sub-stances. They are then capable of le~sening or completelyelLminating noxious secondary effects of the herbicides in crop plants, without Lmpairing the effectiveness of these herbicides against noxious plants.
By virtue of this, the field of application of conven-tional plant protection agent~ can be widened to a very considerable extent. Such compoundc which pos6ess the property of protecting cr3p plants against phytotoxic damageby herbicides are called "an idotes" or "6afenersN.
Examples of herbicides whose phytotoxic ~econdary effects can be reduced by means of the compounds of the formula (I) are carbamates, thiocarbamates, halo~ tanilîdes, substituted phenoxy-, naphthoxy- and phenoxyphenoxy ~arboxylic acid derivative6 as well as heteroaryloxyphen-oxycarboxylic acid derivati~es, such as quinolyloxy-, quinoxalyloxy-, pyridyloxy-, benzoxazolyloxy- and ben-zothiazolyloxy-phenoxy-carboxylic acid e~ters, and furthermore dimedone oxime derivative~. Preferred com-pounds amongst these are phenoxyphenoxy- and heteroaryl-20~!~,,7~3oxy-phenoxycarboxylic acid esters. Suitable es~ers 1n this connection are, in particular, lower alkyl, alkenyl and alkynyl esters.
The following herbicides may be mentioned by way of example but without impo6ing any restriction:
A) Herbicides of the type of the (Cl-C4)alkyl, (C2-C~)-alkenyl and ( C3-c4 )alkynyl phenoxyphenoxy- and heteroaryl-oxy-phenoxycarboxylates, such as methyl 2-(4-(2,4-dichlorophenoxy)phenoxy)propionate, methyl 2-(4-(4-bromo-2-chlorophenoxy~phenoxy)propionate, methyl 2-(4-(4-trifluoromethylphenoxy~phenoxy)propionate, methyl 2-(4-(2-chloro-4-trifluoromethylphenoxy)phenoxy)-propionate, methyl 2-(4-~2,4-dichlorobenzyl)phenoxy)propionate, ethyl 4-t4-(4-trifluoromethylphenoxy)phenoxy)pent-2-enoate, ethyl 2-(4-(3,5-dichloropyridyl-2-oxy)phenoxy)propionate, propargyl 2-(4-(3,5-dichloropyridyl-2-oxy)phenoxy~propio-nate, ethyl 2-(4-(6-chlorobenzoxazol-2-yloxy)phenoxy)propion-ate, methyl 2-(4-(3~chloro-5-trifluoromethyl-2-pyridyloxy)-phenoxy)propionate, butyl 2-(4-(5-trifluoromethyl-2-pyridyloxy)phenoxy)pro-pionate,methyl 2-(4-(3-fluoro-5-chloropyridyl-2-oxy)phenoxy)pro-pionate, propargyl 2-(4-(3-fluoro-5-chloropyridyl-2-oxy)phenoxy)propionate, methyl 2-(4-(6-chloro-2-quinoxalyloxy)phenoxy)propionate, methyl 2-(4-(6-fluoro-2-quinoxalyloxy)phenoxy~propiona~e, methyl 2-(4-(6-chl~ro-2-quinolyloxy)phenoxy)propionate, B) Chloroacetanilide herbicides, such as N-me*hoxymethyl-2,6-diethylchloroacetanilide, N-(3'-methoxyprop-2'-yl~methyl-6-ethylchloroacetanilide, N-(3-methyl-1,2,4-oxdiazol-5 ylmethyl)-2,6-dimethyl-9 ~ ;7i~
chloxoacetanilide, C) Thiocarbamates, such a~S-ethyl N,N-dipropylthiocarbamate or S-ethyl N,N-diisobutylthiocarbamate D) Dimedone derivatives, such as methyl 3-(1-allylo~yimino)butyl-4-hydroxy-6,6~dimethyl-2-oxocyclohex-3-enecarboxylate 2-tN-etho~ybutyrimidoyl)-5-(2-ethylthiopropyl)-3-hydroxy-2-cyclohexen-1-one, 2-(N-ethoxybutyrLmidoyl)-5-(2-phenylthiopropyl)-3-hyd-roxy-2-cyclohexen-1-one, 2-(1-allyloxyLminobutyl)-4-methoxycarbonyl-5,5-dLmethyl-3-oxocyclohexenol, 2-(1-(3-chloroallyloxy)iminobutyl)-5-(2-ethylthio)-propyl)-3-hydroxycyclohex-2-enone, 2-(1-(ethoxyimino)butyl)-3-hy~roxy-5-(thian-3-yl)cyclo-hex-2-enone or 2-(1-ethoxyiminopropyl)-5-(2,4,6-trimethylphenyl)-3-hydroxy-2-cyclohexen-1-one.
The ratio of ~afener : herbicide can vary within wide lLmits, within the range of between 1 : 10 and 10 : 1, in particular between 2 : 1 and 1 . 10. The amounts of herbicide and safener which are ideal in each case depend on the type of the herbicide used or on the safener used as well as on the nature of the plant stand to be treated, and they can be determined for each individual case by appropriate experiments.
The ~afener~ are mainly employed in particular in cereal crops (whe~t, rye, barley, oats3, rice, maize, sorghum, but also in cotton, ~ugar beet, ~ugar cane and soya bean.
Depending on their properties, the ~afeners of the formula ~I~ can be us0d for pre-treating the seed of the crop plant (seed treatment)~ or ~hey can be incorporated in the seed furrows prior to sowing, or u~ed together with the herbicide prior to, or after, plant emergence.
Pre-emergence ~reatment includes both the ~reatment of the area under cultivation prior to sowing and the treatment of the areas under cultivation where seed has been sown but growth of the crop plants has not yet tsken place. Application together with the herbicide i6 prefer-red. Tank mixes or readymixes can be employed for this purpose.
The application rates which are required of the compounds of the formula (I) can vary within wide limit~, depending on the indication and the herbicide used, and they generally vary between 0.01 and 10 kg of active ~ubstance pex hectare.
The present invention therefore also relates to a method of protecting crop plants against phytotoxic secondary effects of herbicides, which comprises applying an effective amount of a compound of the formula (I) before, after, or simultaneou~ly with, the herbicide.
Moreover, the compounds according to the invention exhibit growth-regulating properties in crop plants. ~hey engage in the plant metabolism in a regulating manner and can thus be employed for facilitating the harvest, for example by provoking desiccation, abscission and stunted growth. Moreover, they are also fiuitable for generally monitoring and inhibiting undesired vegetative growth, without at the same tLme destroying the plants. Inhibi-tion of vegetative growth is very important in many monocotyledon and dicotyledon crops since lodging can be reduced, or completely inhibited, by this means.
The compounds of the formula (I) or a combination thereof with one or more of the mentioned herbicides, or ~roups of herbicides, can be formulated in various ways, depend-ing on the given biological and/or physico~hemical parameters. The following are examples of suitable formulation types: wettable powders (WP), emul~ifiable concentrates (EC), aqueous 801ution5 (SL~, concentra~ed emulsions such as oil-in-water nnd water-in-oil emulsions (EW), sprayable solutions or emulsion6, disper~ions based on oil or water (SC), dusts (DP~, seed-treatment aqents, absorption granules for ground and spreading application (FG), water-dispersible granules (WG), ULV formulation~, micro-capsules or waxes.
These individual types of formulation~ are known in principle and are described, for example, in: Winnacker-Kuchler, ~Chemische ~echnologie" tChemi~al Technology~
Volume 7, C. Hau~er Verlag Munich, 4th Ed. 1986; vsn Valkenbur~, "Pesticides Formulations", ~arcel Dekker N.Y., 2nd Ed. 1972-73; R. Marten~, "Spray Drying Hand-book~, 3rd Ed. 1979, G. Goodwin Ltd. London.
The formulation auxiliaries reguired, such as inert materials, surfactants, solvents and ~urther additives are likewise kr.own and hre des~ribed, for example, in:
Watkins, ~Handbook of Insecticid Du t Diluents and Carriers , 2nd Ed., Darland Books, Caldwell N.J.; H.v.
Olphen, "Introduction to Clsy Colloid Chemi~try"; 2nd Ed., J. Wiley ~ Sons, N.Y.~ ~Solvents Guide~, 2nd Ed., Interscience, N.Y. 1950; ~cCutcheon~s, nDetergents and Emulsifiers Annual", ~C Publ. Corp., Ridgewood N.J.;
Sisley and Wood, "Encyclopedia of Surface Active Agentsn, Chem. Publ. Co. Inc., N.Y. 1964; Sch~nfeldt, ~Grenz-fl~chenaktive ~thylenoxidaddukten ~Surface-active Ethylene Oxide ~dduct6], Wi~. Verlagsge~ell., Stuttgart 1975; Winn~cker-RUchler, ~Chemi~che Technologie"
[chemical Technology], Volume 7, C. ~user Verlag ~unich, 4th Ed. 1986.
On the basi~ of these fonmulation~, it is al~o pos6ible to prepare c~bin~tion~ with other pe~ticidally w tive substance6, fertilizers ~nd/or grow~h regulators, for example in the form of a readymix or as a tankmix.
Wettable powers ar~ preparation~ which are uniformly - 12 - 2~ 3 dispersible in water and which, besides the active substance, also contain wetting agen~s, for example polyoxethylated alkylphenols, polyoxethylated fatty alcohols, alkanesulfonates or alkylarylsulfonates, and S dispersing agents, for example sodium ligninsulfonate, sodium 2,2~-dinaphthylmethane-6,6~-disulfonate, sodium dibutylnaphthalenesulfonate, or alternatively ~odium oleoylmethyltaurinate, in addition to a diluent or inert substance.
Emulsifiable concentrate~ are prepared by dis601ving the active substance in an organic solvent, for exEmple butanol, cyclohexan~ne, dimethylf~rmamide, xylene and also higher-boiling aromatic compounds or hydrocarbons, with the addition of one or more emulsifiers. Examples of emulsifiers which can be used are. calcium salts of an alkylarylsulfonic acid, such as Ca dodecylbenzenesul-fonate, or non-ionic emulsifiers, such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide/ethylene oxide condensation products (for example block polymers), alkyl polyglycol ethers, sorbitan fatty acid esters, polyox-ethylene sorbitan fatty acid esters or polyoxethylene sorbitol esters.
Dusting agents can be obtained by grinding the active 2S substance with finely divided ~olid sub6tance6, for example talc or natural clay~, ~uch as kaolin, bentonite, pyTophyllite or diatomaceous earth.
Adsorption granules for ground and spreadmg application can be produced either by ~praying the active ~ubstance onto adsorpti~e, granulated inert material or by applying active substance concen~rates onto the xurface of car-riers, 6uch as sand, kaolinites or granulated inert material, by means of binders, for example polyvinyl alcohol, sodium polyacrylate or, alternatively, mineral oils. Suitable active substances can also be ~ranulated in the manner which is conventional for the production of - 13 - 2 ~ 2 ~ , 3 ~ ~3 ~ fertilizer granules, if de ired in a mixture with fer-tilizers.
In general, the agrochemical preparations contain 0.1 to 99 percent by weight, in particular 0.1 to 95% by weight, of active substance of the formula (I) or of an antidote/
herbicide mixture of acti~e substance, 1 to 99.9~ by weight, in particular 5 to 99.8% by weight, of a solid or a liquid additive and 0 to 25% by weight, in particular 0.1 to 25~ by weight, of a surfactant.
The active substance concentration in wettable powders is, for example, about 10 to 90~ by weight; the remainder to 100% by weight comprises conventional formulation components. In the ca~e of ~mulsifiable concentrates, the active 6ubstance concentration can be about 1 to 80~ by weight, preferably 5 to 80% by weight. Formulations in the form of dusts usually contain 1 to 25% by weight, preferably 5 to 20% by weight of active substance, spray-able solutions about 0.2 to 25% by weight, preferably 2 to 20% by weight of active ~ubstance. In the case of water-dispersible granules, the active ~ubstance content depends partly on whether the active compound is liquid or 601id. In general the water-di~persible granules have a content of between 10 and 90% by weight.
In addition, the active ~ubstance formulations mentioned contain, if appropriate, the adhesives, wetting agents, disper~ing agentfi, emulsifiers, penetrant , ~olvents, fillers or carriers which are conventional in each case.
For use, the formulations, present in commercially avail-able form, are diluted, if appropriate, in a customary manner, ~or e~.~mple using water in the case of wettable powders, emulsiiiable concentrates, dispersion~ and water-disper~ible granules. Preparations in the form of dusts, or adsorption granules for gra md and spreadin~ application and also sprayable ~olutions are u~ually not further diluted with other inert substances before use.
- 14 _ 2~a~7~
The application rate required, of the compounds of the formula (I), varies with the external conditions, ~uch as, inter alia, temperature, humidity and the type of herbicide used. It can vary within wide limits, for example between 0.005 and 10.0 kg/ha or more of active in~redient; preferably, however, it i8 between 0.01 and 5 kg/ha.
The examples which follow are intended to illustrate the invention:
A. Formulation E~ample~
a) A dustinq agent i8 obtained by mixin~ 10 parts by weight of a compound of ~he formula (I) and 90 parts by weight of talc as inert ~ubstance, and comminut-ing the mixture in a hammer mill.
b) A wettable powder which i~ readily disper~ible in water is obtained by mixing 25 parts by weight of a compound of the formula (I), 64 part~ by weight of kaolin-containing guartz as the inert substance, 10 parts by weight of potas~ium ligninsulfonate and 1 part by weight of sodium oleoylmethyltaurinate as the wetting and dispersing agent, and grinding the mixture in a pinned disk mill.
c) A dispersion concentrate which i8 readily di~persible in water is obtained by mixing 20 parts 2S by weight of a compound of the formula (I) with 6 parts by weight of alkylphenol polyglycol ether (~Triton X 207), 3 part~ by weight of isotridecanol polyylycol ether ~ EO) and 71 parts by weight of paraffinic mineral oil (boiling range, for example, about 255 to above 277C), and grinding the mixture in a ball mill to a fineness of below S microns.
d) An emul~ifiable concentrate is obtained from 15 parts by weight of a compound of the formula (I), 75 ~ 15 -parts by weight of cyclohexanone as the solvent and 10 parts by weight of oxethylated nonylphenol a~ the emul~ifier.
e) Water-dispersible granules are obtained by mixing 75 parts by weight of a compound of the formula I, 10 " of calcium ligninsulfonate, 5 " of sodium lauryl sulfate, 3 ~ of polyvinyl alcohol and 7 " of kaolin, grinding the mixture in a pinned di6k mill, and granulating the powder in a fluidized bed by spray-ing on water as the granulation liquid.
f) Water-dispersible granules are also obtained by homogenizing, in a colloid mill, 25 partC by weight of a compound of the formula ~I), 5 " of sodium 2,2'-dinaphthylmeth-ane-6,6'-disulfonate, 2 ~ of ~odium oleoylmethyltaurinate, 1 part by weight of polyvinyl alcohol, 17 parts by weight of calcium carbonate ~nd 50 " of water, precomminutin~ the mixture, 6ub5eguently grinding the mixture in a bead mill, and atomizing and drying the resulting suspen~ion in a spray tower by means of a single-fluid nozzle.
B. Chemical e~2mple~
~thyl 2~ ~ethylph~nylo~)-2-(4-~itrop~enylhydrazono)-acetate ~Example No. 42) O.69 g of ~odium i~ dissolved in 100 ml of ab801ute e~hanol. To thi~ there are added 3.24 g of 4 methylphenol and stirring is continued for 15 minutes at room - 16 ~ J ~
temperature. The mixture is subsequently cooled to 0C, and 8.16 g of ethyl 2-chloro-2-(4-nitrophenylhydrazono)-acetate are added. Stirring is continued for 18 hours at room temperature. The product is filtered off with ~uction and extracted by stirring with ethyl acetate.
After drying, 7.2 g (70~ of theory) of product of melting point 158~C are obtained.
Ethyl 2-phenylo~y-2-phenylhydrazonoacetate (~sample No.7) To a ~olution of 0.68 g of sodium ethanolate in 40 ml of absolute ethanol there i8 added 0.94 g of phenol, and the mixture is stirred for 15 minutes. 2.26 g of ethyl 2-chloro-2-phenylhydrazonoacetate are subsequently added at 0C, and stirring i8 continued for 18 hours at room temperature. The product is filtered off with suction and recrystallized from ethanol. In this manner, 1.7 g (60%) of product of melting point 82-83C are obtained.
Ethyl 2-methoxy-2-(2,4-dichlorophenylhydrazono)acetate (~xample No. 27) To 147.8 g of ethyl 2-chloro-2-~214-dichlorophenylhydra-zono)acetate in 100 ml of tetrahydrofuran there are added dropwise at 0C 50.59 g of triethylamine. After 15 minutes at 0C, 40 ml of methanol are added, and the mixture is stirred for S hours at room temperature. The mixture is evaporated completely on a rotary evaporator, and the product is subsequently chromatographed on silica gel (eluent: n-heptane/ethyl acetate 1:1). In this m~nner, 21.82 g ~15~ of theory) of product of melting point 119-122C are obtained.
~thyl 2-etho y-2-l2,4-dichlorophenylhydrazo~o)acetate (B~ampl~ 153 29.5 g of ethyl 2-~hloro-2-~2~4-dichlorophenylhydrazono)-acetate and 8.2 g of sodium ~cetate are refluxed for 5 hours in 100 ml of 95% pure ethanol. The reaction mixture is subsequently evaporated on a rotary evapor~tor, the product is taken up in C~2Cl2, a~d the mixture i5 ex-tracted with water. The orqanic phase i~ dried with MgS04 1 7 ~
and evaporated on a rotary evaporator. Subsequent column chromatography gives 13.7 g of product of melting point 47 CC .
Table I which follows lists the abovementioned examples together with further examples which can be prepared in an analogous manner:
18 -- ~ r~
Table I
N ~ ( I ) (Z)nl A Rl No. (Z)nl -A-Rl B ~5.p. C
2- CL - O- C6Hs CO2C2Hs 2 4-Cl 3 2,4-Cl 4 3,5-C
2, 6- C
6 4- N02 17 ~I
7 H ll It 82- 83 2,4- (CH3)2 13 2- Cl - O- C2H5 14 4- Cl l' ll 2,4-C12 ll ll 47 16 2,5-Cl 17 2,6-Cl 4~ OCH3 22 2,4- (CH3)2 24 3- CF3 ~I ll 2 5 2- Cl _ O- CH3 C02C2H5 27 2, 4- Cl2 ~ 119- 122 -- 19 -- ~ r/ ;_7 (Table I, continuation) No. (Z)nl A R1 B M.p. C
_ 28 3,5-C12 " ~
29 2,6-C12 " "
4-NO2 1~ ~
31 H " "
32 4-OCH3 " ~I
33 2-CH3 " "
34 2,4-(CH3)2 4-F " "
36 3-CF3 " n 37 2-Cl -O-C6H4-CH3(P) 38 4-Cl " "
39 2,4-C12 " "
3,5-C12 " "
41 2,6-C12 " "
44 4-OC~3 " "
2-CH3 " "
46 2,4-(CH3)2 47 4-F " "
48 3-CF3 " "
49 2-Cl -C2H5 -&6H5 4-Cl " "
51 2,4-C12 " "
52 3,5-C12 " "
53 2,6-C12 " "
54 4-NO2 " "
H " " 168-169 56 4-OCH3 " "
57 2-CH3 " "
(Table I, ~ontinuation) No. (Z)nl A ~l B M.p. C
58 2,4-~CH3)2C2H5 -C6H5 59 4-F " "
3-CF3 " "
61 2-Cl O-C3H7(n) -CO2Et 62 4-Cl " "
63 2,4-C12 - ,.
64 3,5-Cl2 " "
2,6-Cl2 " "
66 4-NO2 " "
67 H " "
68 4-OCH3 " "
69 2-CH3 " "
2,4-(CH3)2 71 4-F " "
72 3-CF3 " "
73 2-Cl -OCH3 ~6H3-2,4-Cl2 74 4-C1 " "
2,4-Cl2 " "
76 3,5-Cl2 " "
77 2,6-Cl2 " "
79 H " "
4-OCH3 " "
82 2,4-(CH3)2 83 4-F " "
84 3-CF3 ~ " "
2-Cl -C2H5 86 4-Cl " n (Table I, continuation) No. (Z)nl _A R1 B ~l.p. C
87 2, 4- C12 C2HS - C6H3- 2, 4~ C12 88 3, 5- C12 " "
89 ~, 6- C12 " "
9 O ~- NO2 " "
91 H " "
92 4- OCH3 " "
9 3 2 - CH 3 " "
94 2,4- (CH3)2 4-F n Biolt~gical E~amples Example 1 Wheat and barley were grown in plastic pots in a green-house until they had reached the 3-4 leaf tage, and then treated in succession with the compounds according to the invention and the herbicides te~ted, u~ing the post-amergence method. For this purpo , the herbicides and the compounds of the formula (I) were applied in the form of aqueous ~upensions or emulsions, at an application rate of water of 800 l/ha (converted~. 3-4 weeks after the treatment, the plants were scored vi6ually for any type of damage cau~ed by the herbicides applied, the extent of sustained growth inhibition, in particular, being taken into account. The asses~ment wa~ expressed in percentages in comparison with untreated controls.
The results from Table II illustrate that the compounds according to the invention are capable of effecti~ely reducing ~evere herbicidal damage on the crop plants.
2P~ ?i Even when fsr too high doses of the herbicide H had been applied, severe damage which occurs in the crop plants is markedly reduced, and lesser damage is eliminated com-pletely. Mixtures of herbicides and compounds according to the invention are therefore outstandingly suitable for selectively controlling weeds in cereal crops.
Table II
Safener action of the compounds according to the inven-tion Example No. Dose in kg Damage to crop plants (%) of a.i./ha TRAE HOW
, _ H 2.0 75 0.2 - 80 H + 3 2.0 + 2.5 40 0.2 + 2.5 - 35 H ~ 27 2.0 + 1.0 0 2.0 + 0.25 10 0.2 ~ 1.0 - 20 0.2 + 0.25 - 22 Abbreviations:
TRAE - Triticum aestivum HOW = Hordeum ~ulgare a.i. = active ingredient 5 H = ethyl 2-(4-(6-chlorobenzoxazol-2-yloxy)phenoxy propionate (Fenoxaprop-ethyl)
Claims (10)
1. A plant-protection agent which contains an N-arylhydrazone of the formula (I) or a salt thereof (I), where Z1 is halogen, nitro, cyano or alkyl, alkoxy, alkylthio or cycloalkyl, the last four radicals mentioned being unsubstituted or monosubstituted or polysubs-tituted by alkoxy, hydroxyl or halogen, furthermore is amino, mono- or dialkylamino, phenyl or phenoxy, phenyl or phenoxy being unsubstituted or monosubsti-tuted or polysubstituted by halogen or haloalkyl, R1 is alkyl, alkenyl, alkynyl or cycloalkyl, the last four radicals mentioned being unsubstituted or monosubstituted or polysubstituted by radicals from the group comprising alkoxy, alkylthio, mono- or di-alkylamino, alkoxycarbonyl, alkylcarbonyloxy, cyano and halogen, is furthermore phenylalkyl or phenyl, each of which is unsubstituted or monosubstituted or polysubstituted in the phenyl radical by radicals from the group comprising alkyl, alkoxy, alkylthio, mono- and dialkylamino, alkoxycarbonyl, cyano and halogen, n1 is an integer from 0 to 5, A is O or S, B is a radical of the formula -CO - R2 or , where Z2 has the meaning mentioned for Z1, and n2 is an integer from 0 to 5, and R2 is OH or alkoxy, alkenyloxy, alkynyloxy, alkylthio or cycloalkoxy, the last five radicals mentioned being unsubstituted or monosubstituted or polysubstituted by radicals from the group comprising alkoxy, alkylthio, mono- and dialkyl-amino, cyano and halogen, is furthermore trialkylsilylmethoxy, a radical of the formula or , where in each case R is hydrogen or alkyl, Z3 has the meaning mentioned for Z1, and n3 is an integer from 0 to 5, R2 is furthermore mono- or dialkylamino, cycloalkyl-amino, pyridino, morpholino, dimethylmorpholino, a radical of the formula , where R3 and R4 independently of one another are alkyl radicals, or R3 and R4 together with the carbon atom linking them form a cycloalkyl radical, in combination with customary auxiliaries for formula-tions of plant protection agents.
2. A plant-protection agent as claimed in claim 1, in which Z1 radicals independently of one another are halogen, nitro, cyano, (C1-C4)alkyl, ( C1-C4 )alkoxy, (C1-C4)-alkylthio, the alkyl, alkoxy and alkylthic groups being unsubstituted or monosubstituted or polysub-stituted by halogen atoms, or are (C3-Cs)cycloalkyl which is unsubstituted or substituted by (C1-C4)-alkyl, or are amino, (C1-C4 )alkylamino, di(C1-C4)-alkylhmino, hydroxymethyl, (C1-C4)alkoxymethyl, phenyl or phenoxy, phenyl and phenoxy being unsubstituted or monosubstituted or polysubstituted by halogen or monosubstituted by trifluoromethyl or substituted by one or more halogen substituents and one trifluoromethyl, n1 is 0, 1, 2 or 3, A is S or O, Rl is (C3-C6)cycloalkyl, (C1-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl, the four radicals mentioned being unsubstituted or monosubstituted or polysubstituted by radicals from the group comprising (C1-C2)alkoxy, mono- or di(Cl-C6)alkylamino, (C1-C6)alkoxycarbonyl, (C1-C6)alkylcarbonyloxy, (C1-C2)alkylthiol cyano and halogen, is furthermore phenyl (Cl-C63alkyl or phenyl, each of which is unsubstituted or monosub-stituted or polysubstituted in the phenyl radical by radicals from the group comprising (C1-C4)alkyl, (C1-C4)alkoxy, (C1-C4)alkylthio, mono- and di(C1-C6)-alkylamino, (C1-C6)alkoxycarbonyl, cyano and halogen, B is a radical of the formula -CO R2 or , where Z2 has the meaning mentioned above for Z1 and n2 is 0, 1, 2 or 3, RZ is hydroxyl, -OCH2Si(CH3)3, (C3-C6)cycloalkoxy, phenyl(C1-c6)alkoxy, phenoxy, (C2-C6)alkenyloxy, (C2-C6)alkynyloxy, (C1-C6)alkoxy, (C1-C6)alkylthio, the alkoxy or alkylthio group being unsubstituted or monosubstituted or disubstituted by (C1-C6)alkoxy, mono- or di(C1-C6)alkylamino, (C1-C2)alkylthio or cyano, or mono ubstituted or polysubstituted by halogen, or R2 is a radical of the formula or , where in each case R is hydrogen or (C1-C4)alkyl, Z3 has the meaning mentioned for Z1, and n3 is 0, 1, 2 or 3, R2 is furthermore mono- or di(C1-C4)alkylamino, (C5-C6)-cycloalkylamino, piperidino, morpholino or 2,6-dimethylmorpholino or a radical of the formula where R3 and R4 independently of one another are (C1-C4)alkyl, or R3 and R4 together with the carbon atom linking them form a 5-, 6- or 7-membered cycloalkyl radical.
3. A plant-protection agent as claimed in one or more of claims 1 and 2, in which Z1 radicals independently of one another are halogen, in particular fluorine or chlorine, nitro, (C1-C4)-alkyl, (C1-C4)alkoxy or trifluoromethyl, A is oxygen, n1 is 0, 1 or 2, R1 is phenyl which is unsubstituted or monosubstituted to trisubstituted by radicals from the (C1-C4)alkyl group, in particular methyl, (C1-C4)alkoxy and halogen, or is (C1-C4)alkyl, B is a radical of the formula -CO - R2 or , where R2 is hydroxy or (C1-C4)alkoxy, Z3 is halogen, in particular chlorine, or (C1-C4)-alkyl, and n3 is 0, 1 or 2.
4. A herbicidal agent which contains at least one compound of the formula (I) as claimed in one or more of claims 1 to 3 as a safener, and a herbicide.
5. A herbicidal agent as claimed in claim 4, which contains a herbicide from the group of the carbamates, thiocarbamates, haloacetanilides, substituted phenoxy-, naphthoxy- and phenoxyphenoxycarboxylic acid derivatives, heteroaryloxyphenoxycarboxylic acid derivatives and dimedone-derived substances.
6. A method of protecting crop plants against phytotoxic secondary effects of herbicides, which comprises treating the plants, seeds of plants, or areas under cultilation, with a compound of the formula (I) as defined in one or more of claims 1 to 3, before, after, or simultaneously with, the herbicide.
7. The use of a compound as defined in one or more of claims 1 to 3 as a safener against phytotoxic secondary effects of herbicides.
8. A method of controlling undesired plant growth, which comprises treating the plants, seeds of the plants, or areas under cultivation, with an effective amount of a herbicide in combination with a compound of the formula (I) as defined in one or more of claims 1 to 3, or a salt thereof.
9. A compound of the formula (I), or a salt thereof, (I) where Z1, R1, n1, A and B have the meanings as defined in one or more of claims 1 to 3, with the exception of those com-pounds of the formula (I) or the salts thereof where a) R1 is unsubstituted or substituted phenyl, A is oxygen and B is a radical of the above-defined formula and with the exception of those compounds in which b) Z1 is 4-CH3, 4 Br, 4-C1, 4-NO2, 3-CH3, n' is o or 1, R1 is unsubstituted phenyl, 4-methylphenyl or 3-methylphenyl, A is oxygen and B is CO2C2Hs-
10. A process for preparing a compound of the formula (I) or a salt thereof, as defined in Claim 9, which process comprises reacting a compound of the formula (II) (II) where (Z)D1 and B have the abovementioned meanings and Hal is Br, C1 or I, with alcohols or thiols of the formula HA-R1 where A and R1 have the abovementioned meanings, and with a base such as, for example, NaOEt, ROC2Hs, NH3 and NaOCOCH3.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3930112.5 | 1989-09-09 | ||
| DE3930112A DE3930112A1 (en) | 1989-09-09 | 1989-09-09 | PLANT-PROTECTIVE AGENTS CONTAINING N-ARYLHYDRAZONE AND NEW N-ARYLHYDRAZONE |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2024876A1 true CA2024876A1 (en) | 1991-03-10 |
Family
ID=6389057
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002024876A Abandoned CA2024876A1 (en) | 1989-09-09 | 1990-09-07 | Plant-protection agents containing n-arylhydrazones, and novel n-arylhydrazones |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0417626A3 (en) |
| AU (1) | AU6227690A (en) |
| CA (1) | CA2024876A1 (en) |
| DE (1) | DE3930112A1 (en) |
| ZA (1) | ZA907133B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6242647B1 (en) | 1998-12-03 | 2001-06-05 | American Cyanamid Company | Insecticidal biphenylthiohydrazides |
| EP1406863A4 (en) * | 2001-06-05 | 2005-06-15 | Basf Ag | Insecticidal biphenylthiohydrazides |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2436544A1 (en) * | 1973-08-02 | 1975-02-13 | Montedison Spa | FUNGICIDAL ALPHA, ALPHADI-SUBSTITUTED FORMYLIDEPHENYLHYDRAZINE |
| US4619884A (en) * | 1985-07-29 | 1986-10-28 | Eastman Kodak Company | Photographic products employing nondiffusible N',N'-diaromatic carbocyclic--or diaromatic heterocyclic--sulfonohydrazide compounds capable of releasing photographically useful groups |
-
1989
- 1989-09-09 DE DE3930112A patent/DE3930112A1/en not_active Withdrawn
-
1990
- 1990-09-05 EP EP19900117057 patent/EP0417626A3/en not_active Withdrawn
- 1990-09-07 CA CA002024876A patent/CA2024876A1/en not_active Abandoned
- 1990-09-07 ZA ZA907133A patent/ZA907133B/en unknown
- 1990-09-07 AU AU62276/90A patent/AU6227690A/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| AU6227690A (en) | 1991-03-14 |
| ZA907133B (en) | 1991-06-26 |
| EP0417626A2 (en) | 1991-03-20 |
| EP0417626A3 (en) | 1992-05-27 |
| DE3930112A1 (en) | 1991-03-21 |
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