NZ228318A - Herbicidal compositions containing thiazol-5-carboxamides as herbicide antagonists; methods of protection and treated seedlings - Google Patents

Herbicidal compositions containing thiazol-5-carboxamides as herbicide antagonists; methods of protection and treated seedlings

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Publication number
NZ228318A
NZ228318A NZ228318A NZ22831889A NZ228318A NZ 228318 A NZ228318 A NZ 228318A NZ 228318 A NZ228318 A NZ 228318A NZ 22831889 A NZ22831889 A NZ 22831889A NZ 228318 A NZ228318 A NZ 228318A
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NZ
New Zealand
Prior art keywords
alkyl
herbicide
thiazol
substituted
unsubstituted
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NZ228318A
Inventor
Andreas Nyffeler
Werner Topfl
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Ciba Geigy Ag
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Publication of NZ228318A publication Critical patent/NZ228318A/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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
    • C07D277/56—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)

Description

New Zealand Paient Spedficaiion for Paient Number £28318 NO DRAWINGS 22 8 3 1 8 Priority Date(s): . A .O. 2>. ?>%'/ ....\.D:.V?,:S8; Complete Specification Filed: Class: .CnD.l^S/3^; Publication Date: P.O. Journal. No Patents Form No. 5 NEW ZEALAND PATENTS ACT 1953 COMPLETE SPECIFICATION TRIAZOL-5-CARBOXAMIDBS POR PROTBCTING CULTIVATED PLANTS PROM THB PHYTOTOXIC ACTION OP HIGHLY BPPBCTIVB HBRBZCIDBS X/We, CIBA-GBIGY AG# A Svisa Corporation# of Klybeckstrasse 141* 4002 Basle# SWITZERLAND hereby declare the invention, for which Vwe pray that a patent nay be granted to c£/us, and the aethod by which it is to be perforned, to be particularly described in and by the following statement: (followed by page la) "•.♦UMi*-. B-." . !,, ,.,1^. 22 8 3 - la- -169A2/1+2/- Thiazol-5-carboxaaides for protecting cultivated plants froa the phytotoxic action of highly effective herbicides The present invention relates to a composition for protecting cultivated plants from the phytotoxic action of highly effective agrocheaicals, especially herbicides, which composition contains as herbicide a thiazol-5-carboxamide antagonist, and also to compositions which, in addition to containing said antagonist (also called antidote or safener), already contain the herbicide, and to a aethod of selectively controlling weeds, which comprises the use of these herbicides and said safener.
It is known that herbicides belonging to a very wide range of compound classes such as triasines, urea derivatives, carbamates, thiocarbaaates, haloacetanilides, halophenoxyacetic acids etc., when employed in an effective concentration, occasionally also damage cultivated plants to a certain extent in addition to the weeds which it is desired to control. The climatic conditions or the nature of the soil may be sueh that the concentration of herbicide recommended for normal conditions acts as an overdose. The quality of the seeds may also be a factor in the tolerance of the herbicide. To counteract this problem, different compounds have already been proposed which are able specifically to antagonise the harmful action of the herbicide on the cultivated plant, i.e. to protect the cultivated plant without noticeably influencing the herbicidal action on the weeds to be controlled. However* it has been found that the proposed antidotes very often have a species-specific activity both with respect to the cultivated plants and to the herbicide and also, in some cases, contingent on the mode of application, i.e. a specific antidote is often suitable only for a specific cultivated plant and a few classes of herbicides. (followed by page 2) 22 8 3 From an economic point of view, several factors have to be taken into account when using chemical safeners against herbicides. The applied chemical has to be a substance which remains in close contact with the crop plants long enough to be able to afford the emergent plants protection until the concentration of the herbicide is no longer phyto-toxically hazardous. Other compounds have a tendency themselves to exert a phytotoxic action on the crop plants. This may occur in three possible ways: i.e. by preventing the emergence of the crop plants, a consequence of which is dissatisfactory germination; by causing deformations during the growth of the emergent crop plants or by stunting or retarding the growth of the crop plants. In some cases these effects can be eliminated by simply reducing the concentration. However, in other cases it does not seem possible to apply the compounds in a concentration which is sufficiently low to reduce the damage to an economically tolerable degree. In some instances, the chemical safeners protect the crop plants against the usual amounts of herbicides, but can no longer afford protection if overdosage occasionally occurs, e.g. whenever peripheral spraying zones overlap. In view of the possibility of such occasional unintentional overdosage, for technical application it is desirable, for example in zones to be treated which overlap, to protect the seeds against approximately twice the intended concentration of herbicide.
Thiazol-5-carbonic add derivatives are known from the literature. 2,6-Dlaethylthiazol-5-carboxaaldes are disclosed as fungicides in US patent 3,725,427; 2-chloro-4-trifluoroaethylthiazol-5-carbonic add derivatives are disclosed as antidots (safeners) to reduce the phytotoxic action of strong herbicides on cultivated plants in US patents 6,199,506, 4,251,261, in the published European patent applications 27,018, 4&,201 and 63,353.
It has surprisingly been found that the thlazol-5-carboxaaldes of formula I are excellently suited for protecting cultivated plants froa the damaging action of agrocheaicals, such as e.g. haloacyl-herbicides. The thiazol-5-carboxaaides are therefore in the following text also referred to as "counter-agents", "antidots" or "safeners". ' *" jr. ■?,... ..„;w,„. «... „ , ^ ?2C318 - j - The thiazol-5-carboxamides correspond to formula I CFj-;=;-€OA ^ > (i) O h wherein A is a group -MRiRj or -NRj-NRk(CO)BR$. wherein Rx, Rj. Rj. Rfc. Rs independently of «ech other are hydrogen, Ci-Caalkyl or Ci-C«cycloalkyl which is unsubstituted or substituted by Cx-Caalkoxy, Cz-C«alkoxyalkoxy, Ci-C»alkylthio, cyano, a 9*°UP-COORs, Cx-C«,alkylcarbaaoyl, di-Cj-C\-alkylcarbaaoyl. Cx-C^alkylaaino. di-Cx-C*alkylaaino, piperidinocarbonyl, pyrrolidinocarbonyl, piperidino or pyrrolidino: Rx. Ri, Rj, Rw and R» further represent C)-C«alkenyl or Ci-Cscycloalkenyl which is unsub-stituted or substituted by halogen, Cx-Caalkoxy, C]-Cacycloalkyl, or a rest cyano, -COORt, Cx-C«alkylcarbaaoyl, di-Cx-C«alkylcarbaaoyl, U, pyrrolidinocarbaaoyl or piperidinocerbaaoyl; Rx, Rj, Rj. R* and Rs represent further Ci-Csalkinyl, which is unsubstituted or substituted by 0: Ri. Rj, Ri, Rt and Rs represent also a radical -(Ej^-U or -(E)a~Q; Rx and Rx or R* and Rs together with the nitrogen atoa, to which they are bound fora a saturated or unsaturated heterocycle with 5 to 9 ring aeabers which say include once or several tiaes oxygen, sulfur, nitrogen, -MH-, -XCi-Ctalkyl. -CO-or -C(OR;)OR« and which aay be substituted by halogen, cyano, Ci-C«alkoxy, aaino, Ct-Ctalkylaaino, di-ci-ck-alkylaaino.or a aroup -COOR»; R» is hydrogen, Cx-Caalkyl, Cj-Cacycloalkyl, Cj-C«-alkenyl, Cj-Cacycloalkenyl, Cj-Caalkinyl. Ci-C*alkoxyalkyl, Cj-Cialkoxy-alkoxyalkyl, Cx-Cthaloalkyl, -(Cx-CjalkylenaJ^U, -(Cx-Cjalkylene)aQ, Cx-Cthaloalkoxy; R? and R« are independently of each other Ci-Caalkyl or . Ri and Ri fora together a 2 to 4 aeabered alkylene chain.
C U is phenyl or naphthyl. which is unsubstituted or substituted once or several tiaes by halogen, Ct-C*alltyl, -Y-Cx-C»alkyl, Cx-C*haloalkyl, ^ Ci-Cwhaloalkoxy, cyano, nitro, carboxyl, -COOR7, -COKHj, -COXHR?. i . -C0*(R7)i, -SOjKHR?. -S0:M(R7>s, pyrrolidino, piperidino, pyrrolidlno| carbonyl or piperidinocarbonyl; E is a Cx-Caalkylene or Cz-Caalkylene chain, which is unsubstituted or substituted by halogen. Cj-Ctalkoxy. Ci-Ctalkylthio, Cx-C%haloalkox£_or by a group -00(0) It, -(COJ^SHj. -(COJ^XHR?, -(CO^XRjR,. and which aay be interrupted by -CO- or -C(OR7)ORa-*; ™ ^»«><»■Kg'XwJW*' WHWHOww —■» " -i •■»—. . 228318 - & - Q is a saturated or unsaturated heterocycle with 5 to 12 ring aembers which aay contain 1 to 4 heteroatons or 1 to 2 heteroatoas in combination with a sulfinyl or sulfonyl group or which may be interrupted by 1 to 2 carbonyl groups and which nay be benzannelated and a is zero or 1, with the proviso that only one of and Rj is hydrogen or unsubstituted C^-Cg alkyl. Because of their herbicide-antagonistic activity the thiazol-5-carbonic acid aaides corresponding to formula la are to be eaphazised CFj-*«—» j-CO-SJRi M * il (la) wherein the radicals Rx and Rj independently of each other are a hydrogen, Cx-C«alkyl or Cj-C«, unsubstituted or substituted by halogen. cyano. Cx-C»alkoxy or -COOR»; C;-C«alkenyl, unsubstituted by halogen. cyano, Cx-Ctalkoxy or -COOR* or C)-C*alkynyl, Ri aay also be "(E)^ or -(E)^, Rx and Ri together fora also a 4- to 5-aeabered alkylene chain, which aay be interrupted by oxygen, sulfur, -KM- or -MR; and/or substituted by Cx-Ctalkyl, E is Ci-Ckalkylene, Cj-Ctcycloalkylene. Cz-Ctalkenylene or Cj-Ck-alkynylene, U is phenyl, unsubstituted or substituted by halogen, cyano, Cx-Caalkyl, Ci-Ctalkoxy, Cx-Cthaloalkyl, Cx-C*haloalkoxy. COOR«, -SOjSH:. -SOjNHR?. -SO;S(Rj)j. -COKMi, -COKHRt or -COXUj)j, Q is a 5 to 6 aeabered heterocycle which is unsubstituted or substituted by halogen, Cx-Ctalkyl, Cx-Caalkoxy, Cx-C*haloalkyl or Cx-Cthaloalkoxy and R« and R? have the aeaning given above# with the proviso that enly -cna.jgfc. and Rg is hydrogen or unsubstituted C^-Cg alkyl.
The aaides are especially active, wherein Rx is hydrogen, Ci-C«alkyl or Ct-C«alkynyl and Ra is Cx-Cicyanoalkyl, Cs-Caeyanocycloalkyl, Cj-C»alkynyl, phenyl723 AUG 1990' halophenyl, Cx-C*alkylphenyl. Ci-Ckalkylhalophenyl, phenylanino, V ^ halophenylaaino or furyl, especially those wherein the radical -MRxRj iV^ misrepresented by X-aethyl-2f-(l-cyanopentyl)aaine or -S-aethyl-S-( 2,6-dichlorobenzyl)aainer with the proviso that only one of arid hydrogen or ^substituted C^-Cg alkyl.
♦Vfc" -v.- ' ( B" ia^ n 228318 Another group of very active herbizid-antagonists is represented by the thiazol-5-carbonic acid hydrazides of the formula lb ^ cfj-™;-co—ji—r—rj A. i Rj Rw (lb) \.S il wherein Rj, R<» and Rs independently of each other are hydrogen, C'-C»-alkyl, Cj-C»cycloalkyl, phenyl or benzyl, the phenyl ring being unsub-stituted or substituted by halogen. Ci-Ctalkyl, Cx-Cthaloalkyl. Ci-Ctalk-oxy. Cx-Ckhaloalkoxy, -COOR*. -CONHj, -CONHR?, -CON(R7);, -SONHj, -SONHR?, -SOH(R7)i and Rt and Rs together can also form a * - 5 aeebered alkylene chain that aay be interrupted by oxygen, sulfur, -SIH-, -NR? and/or substituted by Ci-C*alkyl.
Uhen the compounds of formula I exist in optically isomeric forms, the present invention includes the optical isomers as well as raceaic aixtures as active ingredients.
Zn these definitions halogen by itself or as part of a definition, such as haloalkoxy, haloalkyl or haloalkenyl Includes fluorine, chlorine, broaine and iodine preferably fluorine, chlorine and broaine. especially ^ chlorine.
Alkoxy groups include e.g. aethoxy. ethoxy. n-propoxy, isopropoxy or the isoaeric foras of butyloxy. pentyloxy, heptyloxy or octyloxy. especially . aethoxy. ethoxy or Isopropoxy.
^ Exaaples for unsubstituted substituents or parts of unsubstituted substituents ere e.g. allyl. allyloxy. propynyl. propynyloxy. aethallyl. aethallyloxy, butenyl. butenyloxy, butynyl. butynyloxy. 3,3.3-trifluoro-1-propenyl, 3,3,3-trif luoro-l-propynyl or 2,3-dichloropropen-l-yl.
AltaxyaUcyl groups are represented by e.g. aethoxyaethyl. ethoxyaethyl, aethoxy ethyl end ethoxyethyl, propoxyethyl. isopropoxyethyl. b«to> allyloxy ethyl, especially by aethoxyethyl. 228318 Haloalkyl in itself or as pare of haloalkoxy or haloalkylchio stands as a rule for the radicals chloromethyl, fluoromethyl, difluoromethyl, tri-fluoromethyl, dichloroaethyl, trichloromethyl, 2-chloroethyl, 2,2,2-trifluoroethyl. 1.1.2,2-tetrafluoroethyl, pentafluoroethyl. 1.1,2-tri-fluoro-2-chloroethy1, 2,2,2.-trifluoro-2,2-dichloroethyl, pentachloro-ethyl, 3,3,3-trifluoropropyl. 2.3-dichloropropyl, 2,2,2-trichloroehtyl and 1-chloroethyl. especially chloromethyl, dichloroaethyl, trichloromethyl and 1-chloroathyl.
In these definitions, the alkyl groups are understood to have 1 to 18 carbon atoms. They can be straight-chained or branched. The most usual groups are e.g. methyl, ethyl, n-propyl, isopropyl, n-butyl, isobucyl, sac.butyl, tert.butyl, n-pentyl, isopentyl, n-hexyl and n-octyl. The alkenyl and alkynyl groups can y^®%e straight-chained or branched and contain 3 to 18 carbon atoms. The most used groups are e.g. allyl, aethallyl, butene, butadiene, propynyl, methylpropynyl. 1-butynyl and 2-butynyl. Cycloalkyl or cycloalkenyl groups have preferably 3 to 13 carton atoms and can also be benzannellated. Typical representatives arm e.g. cyclopropyl, cyclopentyl. cyclohexyl, cyclohaxanyl, indan, tetrahydro-naphthalin, decalin. Halogen stands for fluorine, chlorine, bromine and iodine atoms, especially fluorine and chlorine. Haloalkyl and haloalkenyl groups arm mono- or polysubstituted with halogen atoms. be The above-mentioned groups can /unsubstituted or substituted, typical substituents of such groups are halogen or alkyl, alkenyl, alkynyl, cycloalkyl, aryl or aralkyl groups which y bound via oxygen, sulfur or an laino group.The aryl gxoups can be substituted in turn. Those groups can also be bound via a sulfinyl-, sulfonyl-, earbonyl-, carbonyloxy-. carbamoyl-, sulfamoyl- or an amino-oxy-bridge to the alicyclic hydrocarbon group, groups The substituent Q, as well as the / and Rj or Rk and Rs with the nitrogen atom, to which they are bound can represent unsaturated or saturated heterocycles with 5 to 12 ring members, which may include one two or three additional heteroatoms or a sulfinyl- or sulfonyl group.
They can further contain one or two earbonyl grotips and be" benzaiSmXlggpd unsubstituted or substituted. i-. . n v_. 22 8 3 Possible heteroatons are in this context one, two or three additional nitrogen atons, up to two oxygen or sulfur atoas, whereby two oxygen atoas cannot be in vicinal position.
Exaaples for such heterocycles are listed below: pyrroline, pyrrolidine, iaidazoline, iaidazolidine, pyrazoline, pyrazolidine, isazoline, isazolidine, oxazoline, oxazolidine, isothia-zolidine, thiazoline, thiazolidine, diathiazolidine, oxadiazolidine, piperidino, piperazine, tetrahydropyriaidine and pyrazine, aorpholine, thionorpholine, thiazine, hexahydrotriazine, tetrahydropyrazine, oxadiazine, oxatriazine, hexahydroazepine. hexahydrodiazepine, diazepine, hexahydrodiazepine, azacyclooctan, indoline, isoindoline, benz-iaidazoline, benzindazoline, benzoxazoline, benzthiazoline, benziso-oxazoline, benzthiazole, tetrahydrochinoline, tetrahydroisochinollne, tetrahydrochinazoline, tetrahydrochinoxaline, tetrahydrophthalacine, benzonorpholine, benzothioaorpholine, tetrahydrobenzazepine, tetrahydro-benzdiazepine, tetrahydrobenzoxazepine, 1,5-diabicyclo[4.3.0]nonane, dihydrobenzoxazepine, 1,6-diabicyclo[5.3.0]decane, 1,4-diabicyclo-(3.3.0]octane. 1,5-diazablcyclo[4.&.0]decane.
The above heterocycles can also be substituents. Further exaaples of ^ heterocyclic systeas which aay occur as substituents ara e.g. pyrrols, iaidazole, pyrazole, isoxazole, thiazole, triazole, oxadlazole, thia-diazole, tetrazole, oxatriazole, thiatriazole, furan, tetrahydrofuran, dioxole, dioxolane, oxathiole, oxathiolane, thiophen, tetrahydrothiophen, dithiolan, dithiazole, pyridine, pyran, thlopyran, pyrldazine, pyrlaidine, pyrazine, tetrahydropyran, tetrahydrothiopyran, dioxln, dioxan, dithiin, dithlan, oxazlne, thiazine, oxathline, oxathiane, triazine. oxadiazine, thiadiazine, oxathiazine, dioxazine, azepine, oxepin, thlepin, diazepine, oxazeplne, indole, benzofuran, benzothiophen, indazole, benziaidazole, benzdloxol, benzdithiol, benzisoxazole, benzthiazole, benzoxazole, benzoxathiole, benztriazole, benzoxadiazole, benzofurazane, benzothiadiazole, quinolln, isoqulnolln, chroaene, chroaane, isochroaene, isochroaane, thiochroaene, isothiochroaene, thiochroaane, isothiochroaane, cinnoline, chinazoline, chinoxaline. ■7-7 - - ~ ' " —'V*WH!f'W',.^'^^^L 228318 n n V, phtalazine, benzdioxin, benzdithiin, banzoxazine, banzdioxan, benzoxa-thiane, benzotriazine, benzazepine. benzdilazapine, banzoxazapine, purine, pcaridina. phenoxazine, phenothiazine.
The heterocyclic groups can be substituted as mentioned above.
Some derivatives of tha fornula I are known froa the published European patent application EP-A 279,239 and can ba produced by known aethods.
The thiazol derivatives of foraula I are produced e.g. according to US patent 4,199,506, by condensing an acrylic acid ester of the formula II with chlorocarbonyl-sulfonylchloride of the foraula III, according to the reaction scheae r,CH ♦ Cl-J-S-Cl » FjC—8A' SH; H—^ i (ii) (iii) j (ic) The 2-oxo-4-trifluoroaethyl-thiazol-5-carbonic acid derivative otained is heated with phosphoroxychloride whereby 2-chloro-4-trifluoroaethyl-thiazol-5-carbonic acid derivative of the foraula I is produced r»c—•—?A' rjC ——?A* h-sn i ♦ pocij i Ji I " 6i (Ic) (I) Acrylic acid derivatives of tha foraula II can ba prepared according to J. Met. Chea, 9 (1972) p 13 by condensing an acetoacetic ester with trifluoroaethylnitril in a boiling solvent in the presence of sodiua acetate, according to the reaction scheae FiC-CX ♦ CHi?-C*J ' «"<*»• *- '; y (ii) \*3a0' " c ' r> 22 8 3 1 8 Starting from 2-chloro-4-trifluoromethyl-thiazol-5-carbochloride the following active derivatives of formula I can be prepared according to known methods and to the following reaction scheme: In these formulae A and Ri have the meaning given above.
In these reactions there are used inert solvents and diluents are used to suit the particular reaction conditions. There may be mentioned as examples: halohydrocarbons, especially chlorohydrocarbons. such as tetrachloro-ethylene, tetrachloroethane. dichloropropane. methylene chloride, dichlorobutane, chloroform, chloronaphthalene, dichloronaphthalene, carbon tetrachloride, trichloroethane, trlchloroethylene, pentachloro-ethane. difluorobenzene, 1,2-dichloroethane, 1,l-dichloroethane, 1,2-cis-dichloroethylene, chlorobenzene, fluorobenzene, bromobenzene, lodobenzene, dichlorobenzene, dibromobenzene, chlorotoluene and tri-chlorobenzene; ethers, such as ethyl propyl ether, methyl tert.-butyl •ther, n-butyl ethyl ether, di-n-butyl ether, diisobutyl ethor, dilsoaayl ether, diisopropyl ether, anisole, phenetole, cyclohexyl methyl ether, diethyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxan, thioanisole and dichlorodiethyl ether; nitrohydrocarbons, such as nitromethane, nltroethane, nitrobenzene, chloronitrobenzene and o-nitrotoluene; nitriles, such as acetonitrlle, butyronitrile, iso-butyronitrile, benzonitrile and m-chlorobenzonitrile; aliphatic or cycloaliphatlc hydrocarbons, such as heptane, pinane, nonane, cymol, petroleum fractions within a boiling range of from 70" to 190*C, cyclohexane, methylcyclohexane, decaline, petroleum ether, hexane, ligroln, trlmethylpentane, 2,3,3-trimethylpentane and octane; esters, such as ethyl acetate, ethyl acetoacetate and isobutyl acetate; aaides, for example formamide, mcthylformamide and dimethylformamide. n (Id) (I) 22 8 3 The thiazol-carboxamides of this invention according to formula I show excellent safener activity and are superior in their activity to known compounds.
A counter-agent or antidot of the foraula I can be used, according to the desired application, for pretreating seeds of the culture plant (seed dressing and inpregnation of seedlings) or for application onto the soil before or after sowing. It can be applied alone or together with the herbicide before or after the emergence of the plants. The treatment of tho plants or the seed with the antidot can be done in principle independently of the application of the phytotoxic chemical substance. The treatment of the plant can also be done by simultaneous application of phytotoxic chemical substance and the antidote (tank-mixture). The pre-eaergent treatment Includes the application onto the cultivation area before sowing (ppi, pre plant incorporation) as veil as the treatment of the sown cultivation area before emergence of the crop.
The amount of antidote of the formula 1 necessary to achieve the desired safening effect can vary to a large extent depending on the method and the aoment of application and cannot be determined by simple methods.
As a rule there is a longer laps of time between protective means such as seed-dressing or treatment of seedlings with the counter-agent according to formula I and the optional field treatment thereof with agrocheaicals. Pre-treated seeds, and plant-material can come in contact with the most diverse chemicals during their application in agriculture, horticulture or forestry. The invention therefore also extends on protective compositions for culture plants which contain the antidote of formula I together with usual carrier-material. Such compositions can contain additionally those agrocheaicals, fora the effect of which the culture plants should be protected.
As culture plants are considered in the context of this invention all those plants, which produce in any form useful products, such as seeds, roots, stems, bulbs, leaves, flowers or contents such as oils, sugars, starch, protein etc. and are cultivated for this purpose. Among those plants belonging e.g. every kind of cereal such as wheat, rye, barley. 22 8 3 and oats, further especially culture millet, maize, cotton, sugar-beet, cane-sugar, soya, beans and peas and especially rice.
The counter-agent can be used whereever an above-mentioned culture plant has to be protected from the damaging effect of agrochemicals, primarily of herbicides of the most diverse classes. Excellent protecitve action can be observed when the antidotes of the formula I are used to protect the culture plants against sulfonylurea herbicides, chloracetanilide and aryloxy-phenoxy-propionic acid herbicides, especially in cultures of maize, sorghum and rice.
Sulfonylureas herbicides, whose phytotoxic effect against culture plants can be induced or cancelled with the thiazol-5-carboxaaido of formula I have become known recently in large numbers. Form a multiplicity of publication devoted to the disclosure of herbicidally active sulfonyl-urea-derivatives shall be cited as exaaples US patent 4,127.405 as well as the published European Patent Applications EP-A 7687, EP-A 30,142, EP-A 44,807, EP-A 44,808, EP-A 51,466, EP-A 70,802, EP-A 84,020, EP-A 87,780, EP-A 102,925, EP-A 108,708, EP-A 120,814, EP-A 136,061, EP-A 184,385, EP-A 206,995 and EP-A 237,292.
Typical representatives of herbicidally active sulfonylurea-derivativts are embraced by formula IV E-(CHi)—SOa-NH-CO-M—S n 6 V-/ wherein E is a group I { n > . y'~\_ . i ( \.y w W or 22 8 3 n is zero or one, G is hydrogen or methyl, X is aethoxy, ethoxy, difluoromethoxy or chlorine, Y nitrogen or nethine (-CH-) Z is Methyl, aethoxy, difluoromethoxy. cyclopropyl or aethylanino, Rio is Cs-Csalkoxyalkoxy, Ci-Cthaloalkoxy, Ci-Cthaloalkylthio, Cz-Ct- haloalkenyl, chlorine or Ci-C«alkoxycarbonyl, Rn is trifluoroaethyl or dKCi-Ct-alkyDcarbanoyl, Riz is Ci-Ctalkoxycarbonyl, Ru is Ci-Ctalkoxycarbonyl and Riv is Ci-C%alkyl.
The folloving coapounds are encoapassed by the active substances of foraula IV: N-(3-trifluoroMthylpyridin-2-ylsulfonyl)-N'-(&,6-diMthoxypyriaidin-2-yl)-urea, N-(3-diaethylcarbaaoylpyridin-2-ylsulfonyl)-N'-(4,6-diaethoxy-pyriaidin-2-yl)-urea, N-(1 -aethyl-6-ethoxycarbonylpyrazol-2-ylsulfonyl)-N*-(4,6-diaathoxy-py riaidin-2-y1)-urea, N-(2-aathoxycarbonylthian-3-ylsulfonyl)-)l,-(4-aothoxy-6-aethyl-l,3,5-t rlazin-2-yl)-u rea, N-(2-aethoxycarbonylbenzylsulfonyl)-H'-(4,6-diaethoxypyriaidin-2-yl)-urea, X-( 2-aethoxycarbonylphenylsulf onyl) -H '-(4, 6-bis-dif luoraethoxy-pyriaidin-2-yl)-urea, X-(2-aathoxycarbonylphenylsulfonyl)-X'-(&-«thoxy-6-aethylaaino-l,3,5-triatin-2-y1)-urea, li-(2-»ethoxycarbonylphenylsulfonyl)-K,-(4-»cthoxy-6-s«thyl-l,3,5-t riazin-2-y1)-u rea, X-(2-athoxycarbonylphenylsulfonyl)-N'-(4-chlor-6-«ethoxypyriaidin-2-yD-urea, X-(2-aathoxycarbonylphenylsulfonyl)-N'-(4-aethoxy-6-aethyl-l ,3,5-t riazin-2-yl) -N'-aathylu r ea, .asm:--- ■l^"Wti. -WMr-..!-., v. - Jt n 22 8 3 1 8 N-(2-Bethoxycarbonylphenylsulfonyl)-N'-(&,6-dimethoxypyriBidin-2-yl)-urea, K-(2-chlorophenylsulfonyl)-N,-(4-B«thoxy-6-Bothyl-l,3,5-triazin-2-yl)-urea, H-I2-(2-chloroethoxy)-phonylsulfonyl]-N'-(4-methoxy-6-aethyl-1.3,5-triazin-2-yl)-urea, and K—[2—C2-methoxyethoxy)-phenylsulfonyl]-N'-(4,6-diaethoxy-l.3,5-triazin-2-yl)-uroa.
Halogenacetanilides, whose phytotoxic effect on culture plants can be reduced or cancelled by the thiazol-5-carboxaaides of foraula I are also known in great numbers. They can be characterized by the following generic foraula V: /*»• (V) - ' CO-CHiCl *» wherein L is a Ci-Ct-alkylen bridge, Rtt Ru *nd Rx7 independently of each other hydrogen, halogen, Ci-Ct-alkyl, Cx-Ct-alkoxy. Cx-Ct-haloalkyl, Cj-Cj-alkoxyalkyl or Cj-Cs-alkylthioalkyl, and Ru Cx-Cfc-alkoxy, -COOH, Cj-Ct-alkoxycarbonyl. -COKHj. Cx-Ck-alkyl carbamoyl, di-Cx-Ch-alkylcarbaaoyl, cyano, Cx-Ct-alkylcarbonyl optionally substituted benzoyl. optionally substituted furyl. optionally substituted thienyl. optionally substituted pyrrolyl. optionally substituted pyrazolyl. optionally substituted 1,3,A-oxadiazol-2-yl, optionally substituted 1,3,4-thiadiazol-2-yl. optionally substituted 1,2,4-triazol-3-yl. optionally substituted dloxolanyl. optionally substituted dioxanyl. optionally substituted l,3,4-triazol-2-yl or optionally substituted tetrahydrofuryl.
*** •■'Wl , - m 22 83 18 The following chloroacetanilide derivatives are cypical representatives of the active substances according to formula V: a H-ethoxyaethyl-N-chloroacetyl-2-ethyl-6-aethylaniline, N-chloroacetyl-N-aethoxyaethyl-2,6-diethylaniline, K-chloroacetyl-N-C 2-aethoxyethyl)-2,6-diaethylaniline, K-chloroacetyl-N-(2-n-propoxyethyl)-2,6-diaethylaniline. o N-chloroacetyl-N-(2-isopropoxyethyl)-2.6-diaethylaniline, X-chloroaeetyl-N-(2-aethoxyethyl)-2-ethyl-6-aethylaniline» N-chloroacetyl-N-(aethoxyethyl)-2.6-diethylaniline. X-(2-ethoxyethyl)-M-chloroacetyl-2-ethyl-6-aethylaniline, M-chloroacetyl-N-(2-aethoxy-l-aethylethyl)-2-aethylaniline, N-chloroacetyl-K-(2-ae thoxy-1-aethylethyl)-2,6-diaethylaniline, K-chloroacetyl-X-(2-aothoxy-l-aethylethyl)-2,6-diethylaniline, X-chloroaeetyl-X-(2-aethoxy-l-aethylethyl)-2-ethyl-6-Bethylaniline, H-(2-ethoxyethyl)-N-chloroacety1-2,6-diethylaniline, X-chloroaeetyl-X-(2-n-propoxyethyl)-2-ethyl-6-aethylaniline, K-chloroacetyl-K-C2-n-propoxyethyl)-2,6-diethylaniline, K-chloroacotyl-X-(2-isopropoxyethyl)-2-«thyl-6-aathylaniline, N-ethoxycarbonylaethyl-K-chloroacety1-2,6-diaethylaniline K-ethoxycarbonylaethyl-K-chloroacetyl-2,6-diethylaniline K-chloroacetyl-K-aethoxycarbonylaethyl-2,6-diaethylaniline, X-chloroacetyl-X-(2.2-diethoxyethyl)-2,6-diaethylaniline, H-chloroacetyl-X-(2-a#thoxy-l-aethylethyl)-2,3-diaethylaniline, X-(2-ethoxyethyl)-N-chloroacetyl-2-aethylaniline, K-chloroacetyl-K- (2-ao thoxyethyl)-2-aethylaniline, X-chloroace tyl-X- ( 2-ae thoxy-2-aethyle thyl) -2,6-diaethylaniline * X-(2-ethoxy-2-aethylethyl)-X-chloroacetyl-2-ethyl-6-aethylaniline, H-chloroacety l-X-(l-ethyl-l-aethoxyethyl)-2,6-diaethylaniline, N-chloroacetyl-K-(2-aethoxyethyl)-2-aethoxy-6-aethylanillne, X-n-butoxyaethyl-K-chloroacetyl-2-tert.-butylaniline, X-( 2-ethoxyethyl-2-aethylethyl)-K-chloroacetyl-2,6-diaethylaniline • X-chloroacetyl-X-(-2-aethoxyethyl)-2-chloro-6-aethylaniline, X-(2-ethoxyethyl)-K-chloroacetyl-2-chloro-6-aethylanilin«, X-(2-ethoxyethyl)-N-chloroacetyl-2,3,6-triaethylaniline.
X-chloroacetyl-l-( 2-aethoxyethyl)-2 , 3,6-tria® thyl aniline, „ .... jl. _. 22 83 18 N-chloroacetyl-N-cyanoaethyl-2.6-diaethylaniline, N-chloroacetyl-N-(1,3-dioxolan-2-ylaethyl)-2,6-diaethylaniline, N-chloroacetyl-N-(1,3-dioxolan-2-ylaethyl)-2-ethyl-6-aethylaniline» N-chloroacetyl-N-(l,3-dioxan-2-ylaethyl)-2-ethyl-6-aethylanilina, N-chloroacetyl-N-(2-furylaethyl)-2,6-diaethylaniline, N-chloroacetyl-N-(2-furylaethyl)-2-ethyl-6-aethylaniline, N-chloroacetyl-N-(2-tetrahydrofurylaethyl)-2,6-diaethylaniline, K-chloroace tyl-N-( N, N-diaethylcarbaaoylaethyl )-2,6-diaethylaniline , X-(n-butoxyaethyl)-N-chloroacetyl-2,6-diethylaniline, N-(2-n-butoxyethyl)-N-chloroacatyl-2,6-diethylaniline, N-chloroacetyl-N-(2-aethoxy-l,2-diaethylethyl)-2,6-diaethylaniline, N-chloroacetyl-X-isopropyl-2,3-diaethylaniline, N-chloroacetyl-N-isopropyl-2-chloroaniline, N-chloroacotyl-N-(lH-pyrazol-l-ylnothyl)-2.6-diaathylaniline, N-chloroacetyl-N-(lH-pyrazol-l-ylaothyl)-2-ethyl-6-aethylanilina, N-chloroacetyl-N-(lH-l,2,4-triazol-l-ylaethyl)-2,6-diaathylanilino, N-chloroacetyl-K-(1H-l,2,4-t riazol-1-ylaethyl)-2,6-diethylaniline, K-benzoylaethyl-K-chloroacetyl-2,6-diethylaniline, N-benzoylaethyl-N-chloroacetyl-2-ethyl-6-aethylaniline, N-chloroacetyl-N-( 5-aethyl-l,3.4-oxadiazol-2-yl)-2,6-diothylanilina, N-chloroacetyl-N-(5-aothyl-l,3,4-oxadiazol-2-yl)-2-ethyl-6-aethylaniline, X-chloroacetyl-X-(5-aethyl-l ,3.4-oxadiazol-2-yl)-2-tert.butylaniline, N-chloroacetyl-X-(4-chlorobenzoylaethyl)-2.6-diaethylaniline and X-chloroacetyl-X-O-aathyl-5-aathylthio-l ,3,4-triazol-2-ylaathyl)-2,6-diethylaniline.
Further haloacetanilidos, whosa phytotoxic effect on cultura plants is reduced or cancelled by the thiazol-5-carboxaaides of foraula I are disclosed in R. Vegler, Cheaie der Pflanzenschutz- und Schadlingsba-kaapfungsaittal, Vol, 8, pages 90-93 and pages 322-327.
Aryloxyphenoxy-propionic acid herbicides, whose phytotoxic affect on culture plants is reduced or cancelled by tha thiazol-5-carboxaaides of foraula I are known in great nuabers. Such aryloxyphenoxypropionic acid derivatives can be characterisad by the generic foraula VI 22 8 3 1 8 Q-0 CO-T (VI) wherein Q is a radical ^zo rjo • 0 or R*<\ A • • V v u wheroin T is -NRjiRji, -N(CN)R21. "ORij, SRjj or -O-S-CRjjRjj Rm is halogen or trifluoroaethyl, Rao is hydrogen or halogen, Rn and R:i independently of each other hydrogen, Ci-C»alkoxy, Ci-Ctalkyl. phenyl or benzyl, Rn and Xjt together with the nitrogen atoa, to which they are bound also fora a saturated 5- to 6-aeabered nitrogen-heterocyclus, which aay contain an oxygen or sulfur atoa, Rn is Ci-Ctalkyl, Cj-Ctalkenyl, Ci-Ctalkynyl or Cs-Ctalkoxyalkyl Rit is hydrogen or the cation-equivalent of an alkali aetal, an alkaline earth aetal of copper or iron; of a quaternary Ci-Ctalkylaaaoniua or Ci-Ct-hydroxyalkylaaaoniua radical; Ci-C$alkyl unsubstituted or aono- or polysubstituted by aaino, halogen, hydroxyl, cyano, nitro, phenyl, Ci-C*alkoxy. polyethoxy with 2 to 6 ethyleneoxy-units, -COORjj. -COSRj?, -CONHj, -COX(Ci-Ct-alkoxy)-Ci-Ch-alkyl, -CO-N-di-Ci-Ck-alkyl, COXH-Ci-Ch-alkyl, -K(Cj-Cfc-alkoxy)-Ci-Ck-alkyl or di-Ci-Ck-alkylaaino; Cj-Ctalkenyl, unsubstituted or substituted by halogen or Ci-Ctalkoxy; C)-C*alkynyl, unsubstituted or substituted by halogen or Ci-Ctalkoxy; Cj-C*cycloalkylphenyl unsubstituted or substituted by cyano. Ci-Chalkyl, Ci-Ctalkoxy, acetyl, -COORn« COSRj?, -CONHz, -COK(Cj-C%-alkoxy)-Ci-Cb-alkyl, -CO-H-di-Ci-C*-alkyl oder -COXH-Cx-Cfc-alkyl; Rjs and Ru are independently of each other Cj-Ctalkyl or together a 3-to 6-aeabered alkylene chain and 228318 R27 hydrogen, Ci-C»alkyl, Ci-Cthaloalkyl, Cj-Ctalkoxyalkyl, Cj-Ctalkenyl, Cj-C»haloalkenyl, Cj-Cialkynyl or Cj-Cjhaloalkynyl.
Undor the foraula VI fall especially the following herbicidally active aryloxyphenoxypropionic acid derivatives: 2-[&-(3,5-dichloropyridin-2-yloxy)-phenoxyJ-propionic acid-propynyl ester, 2-[4-(3,5-dichloropyridin-2-yloxy)-phenoxy]-thiopropionic acid-propynyl ester, 2-[6-(5-chloro-3-fluorpyridin-2-yloxy)-phenoxy]-propionic acid-aethyl ester, 2-l4-(5-chloro-3-fluorpyridin-2-yloxy)-phenoxyl-propionic acid-butyl ester, 2-14-(5-trifluoromethylpyridin-2-yloxy)-phenoxy)-propionic acid-butyl ester, 2-(4-(5-trifluoronethylpyridin-2-yloxy)-phenoxyJ-propionic acid-methyl-ester, 2-14-(6-chlorochinoxalin-2-yloxy)-phenoxyl-propionic acid-ethyl ester and 2-[6-(6-chlorobenzoxazolin-2-yloxy)-phenoxy]-propionic acid-ethyl ester.
The antidotes of the foraula I are especially suitable for protecting cultivated plants froa the phytotoxic effects of the herbicides of the foraulae IV, V and VI.
Agrocheaical compositions which contain in a coaaon formulation the antidote of foraula I and a sulfonylurea-herbicide, a chloroacetanilide herbicide or an aryloxyphenoxy propionic acid herbicide are suitable to be used as selective herbicides in crops of cultivated plants. The compositions according to this invention contain preferably the antidote of foraula I and one of the sulfonylureas of foraula IV, the chloro-acetanilides of foraula V or the aryloxyphenoxy propionic acid derivatives of foraula VI. 22 8 3 Unless ic is used to dress seed, the amount of the counter-agent applied varies between about 0.01 and about 5 parts by weight per part by weight of herbicide. The aost suitable ratio based on optiaua action on the particular cultivated plane is deteraind on a case by case basis, i.e. depending on the type of herbicide used.
The invention also relates to a process for selectively controlling weeds in crops of cultivated planes, whereby che crops of cultivated plants, parts of the cultivated plants or areas cultivated for cultivated plants are treated with a herbicide and the coapound of the foraula I or a coaposition containing this coabination. The coapositions containing the herbicide/antidote coabination also fora a part of the present invention.
The weeds to be controlled can be either aonocotyledonous or dicotyledonous weeds.
Various aethods and techniques are suitable for using the coapound of the foraula I or coapositions containing it in order to protect cultivated plants against the haraful effects of agricultural cheaicals, for exaaple the following aethods and techniques: 1) Seed dressing a) Dressing the seed with an active substance, foraulated as a wettable powder, by shaking in a vessel until unifora distribution over the surface of tha seed is achieved (dry dressing). In this procedure, about 10 to 500 g of active substance of the foraula I (40 g to 2 kg of wettable powder) are used per 100 kg of seed. b) Dressing the seed with an eaulsion concentrate of the active substance of the foraula I by aothod a) (wet dressing). c) Dressing by iaaersing the seed in a liquor containing 50 - 3,200 ppa of an active substance of the foraula I for 1 to 72 hours and, if desired, subsequently drying the seed (iaaerslon dressing). 22 8 3 Dressing Che seed or creacing Che sprouCed seedling are, of course, the preferred aechods of applicaCion, because Che creacmenc wich acCive subscance is direcCed enCirely Cowards che targec crop. As a rule, 10 g Co 500 g. preferably 50 Co 250 g, of acCive subscance are used per 100 kg of seed, and, depending on che aechod employed, which also enables other acCive subscances or aicro-nuCrienCs Co be added, ic is possible Co exceed or Co use less Chan che liaicing concencracions indicaced (repeac dressing). ii) Application fro» a cank aixcure A liquid foraulacion of a aixCure of councer-agenc and herbicide (ratio of che one Co che ocher becveen 10:1 and 1:30) is used, che applicaCion race of herbicide being 0.1 Co 10 kg per heccare. A cank aixcure of this type is preferably applied before or iaaediacely afcer sowing or is worked 5 Co 10 ca deep inCo Che soil before sowing* ill) ApplicaCion Co the seed furrow The counter-agenc is introduced, in che fora of an eaulsion concencrace, wetcable powder or granules, lnco che open, sown seed furrow and then, afcer Che seed furrow has been covered in a noraal Banner, che herbicide is applied by che pre-eaergence process. iv) Conerolled release of acclve subscance A solution of che active substance is absorbed onto aineral granular carriers or polyaerised granules (urea/foraaldehyde) and is allowed to dry. If desired, it is possible to apply a coating (coated granules) which enables che active subscance to be released in a aecored Banner over a specific period of Clae.
The coapound of the foraula I is eaployed in an unaltered fora or, preferably, togecher wich che adjunccs convencionally used in the art of foraulation and are* therefore, processed in a known aanner Co give* for exaaple, eaulsion concentraces, solutions which can be atoaised or diluCed without furcher treataent, diluCe eaulsions, wettable powders, soluble powders, dusts, granules and also encapsulations in, for exaaple, polyaerlc substances. The application processes, such as atoaising. o . .. 22 8 3 1 8 > nebulising, dusting, sprinkling or watering, are selected to suit the intended aims and the given circumstances, as is also the type of composition.
The formulations, i.e. the compositions, preparations or combinations containing the active substance of the formula I and, if appropriate, a solid or liquid adjuvant, are prepared in a known manner, for exaaple by intimately mixing and/or grinding the active substances with extenders, (^ for example solvents, solid carriers and, if appropriate, surface-active compounds (surfactants).
The following can be suitable as solvents: aromatic hydrocarbons, preferably the fractions froa C« to Cu. for exaaple mixed xylenes or substituted naphthalenes, phthalic acid esters, such as dibutyl or dioctyl phthalate, aliphatic hydrocarbons, such as cyclohexane or paraffins, alcohols and glycols and also ethers and esters thereof, such as ethanol, ethylene glycol or ethylene glycol monomethyl or monoethyl ether, ketones, such as cyclohexanone, strongly polar solvents, such as H-methyl-2-pyrrolidono, dimethyl sulfoxide or diaethylformaaide, and epoxldised or unepoxidised vegetable oils, such as epoxidised coconut oil or soya oil; or water.
The solid carriers used, for example for dusts and dispersible powders, are, as a rule, natural ground minerals, such as calclte, talc, kaolin, montmorillonite or attapulglte. It is also possible to add highly disperse silica or highly disperse absorbent polyaers in order to iaprovo the physical properties. Suitable particulate, adsorptivo granular carriers are porous types, for exaaple pumice stone, broken brick, sepiolite or bentonite, while examples of suitable non-sorptive carriers are calcite or sand. In addition, it is possible to use a largo nuabor of pregranulated materials of an inorganic or organic nature, such as* in particular, dolomite or comminuted plant residues.
Suitable surface-active compounds are nonlonic, cationic and/Or anionic surfactants having good emulsifying, dispersing and vetting properties. Surfactants are also to be understood as meaning Mixtures of surfactants. 22 8 3 Suitable anionic surfactants can be so-called uatersoluble soaps as well as vater-solubl« synthetic surface-active compounds.
Examples of soaps are the alkali metal salts, alkaline earth aetal salts or substituted or unsubstituted aamoniua salts of higher fatty acids (Cjo-Cji), for exaaple the Na or K salts of oleic or stearic acid, or of natural aixtures of fatty acids, which can be obtained, for exaaple, froa coconut oil or tallow oil. Furthermore, aention should also be made of the salts of fatty acid methyltaurides.
Mora frequently, however, so-called synthetic surfactants are used, in particular fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.
The fatty sulfonates or sulfates are, as a rule, in the form of alkali aetal salts, alkaline earth aetal salts or substituted or unsubstituted ammonium salts and contain an alkyl radical having 8 to 22 C atoms, in which connection alkyl also includes the alkyl moiety of acyl radicals, for example the Ka or Ca salt of ligninsulfonic acid, of dodecylsulfuric acid ester or of a mixture of fatty alcohol sulfates prepared from natural fatty adds. Included under this heading are also the salts of the sulfuric acid esters and sulfonic acids or fatty alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonic add groups and a fatty add radical having 8-22 C atoms. Examples of alkylarylsulfonates are the Ka. Ca or tri-ethanolamlne salts of dodecylbenzonosulfonlc add, of dibutylnaphthalene-sulfonic acid or of a naphthalenesulfonic acidsformaldehyde condensation product.
Furthermore, corrosponding phosphates, for example salts of the phosphoric acid ester of a p-nonylphenol/(4-14)-ethylene oxide adduct. or phospholipids are also suitable.
Suitable nonionic surfactants are primarily polyglycol ether derivatives of aliphatic or cycloallphatic alcohols, saturated or unsaturated fatty acids and alkylphenols; these derivatives can contain 3 to 30 glycol •""ISlOlk* 22 8 3 1 8 22 - ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to 18 carbon atoas in the alkyl radical of the alkyl-phenols.
Further suitable nonionic surfactants are the vatersoluble adducts, containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups, of polyethylene oxide with polypropylene glycol, ethylenediaminopolypropylene glycol and an alkylpolypropylene glycol having 1 to 10 carbon atoms in the alkyl chain. The said conpounds usually contain 1 to 5 ethylene glycol units per unit of propylene glycol.
* Examples of nonionic surfactants which may be mentioned are nonyl-phenolpolyethoxyethanols. castor oil polyglycol others, polypropylene/polyethylene oxide adducts, tributylphenoxypolyothoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.
Furthermore, fatty acid esters of polyoxyethylenosorbitan, such as polyoxyethylenosorbitan trioleate, are also suitable.
The cationic surfactants are, in particular, quaternary ammonium salts which contain, as N-substituents, at least one alkyl radical having 8 to 22 C atoms and, as further substituonts, lower, halogonatod or unhalogenated alkyl radicals, benzyl radicals or lovor hydroxyalkyl radicals. The salts are preferably in the form of halidos, methylsulfates or ethylsulfates, for example stearyltrimethylammoniumchloride or benzyldi-(2-chloroothyl)othylammonium bromide.
The surfactants which are conventional in the art of formulation are described, inter alia, in the following publications: "McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., Rldgewood, Mew Jersey, 1981; H. Stache, "Tensld-Taschenbuch" ("Surfactants Manual"), 2nd edition, C. Hanser Verlag, Munich, Vienna, 1981; M. and J. Ash, "Encyclopedia of Surfactants", vol. I-III, Chemical Publishing Co., Xev York, 1980-1981. 228318 The agrochemical preparations contain, as a rule, 0.1 to 95 X, in particular 0.1 to 80 X, of active substance, 1 to 99.9 X of a solid or liquid adjuvant and 0 to 25 X, in particular 0.1 to 25 X, of a surfactant.
In particular, the coaposition of preferred formulations is as follows: (X ■ per cent by weight) Eaulsifiable concentrates Active substance: Surface-active agent: Liquid carrier: 1 to 20 X, preferably 5 to 10 X 5 to 30 X, preferably 10 to 20 X 50 to 94 X, preferably 70 to 85 X Dusts: Active substance: Solid carrier: 0.1 to 10 X, preferably 0.1 to IX 99.9 to 90 X preferably 99.9 to 99 X Suspension concentrates: Active substance: 5 to 75 X, preferably 10 to 50 X Vater: 94 to 25 X, preferably 90 to 30 X Surface active agent: 1 to 40 X, preferably 2 to 30 X Wettable powders Active substance: 0.5 to 90 X, preferably 1 to 80 X Surface-active agent: 0.5 to 20 X, preferably 1 to 15 X Solid carrier: 5 to 95 X, preferably 15 to 90 X Granules Active substance: 0.5 to 30 X, preferably 3 to 15 X Solid carrier: 99.5 to 70 X, preferably 97 to 85 X.
Whereas concentrated coapositions are more likely to be preferred as coaaercial products, the final consumer as a rule uses dilute coapositions. The application forms can be diluted down to 0,001 X of active substance. The application rates are, as a rule, 0.01 to 10 kg of active substance per hectare* preferably 0.025 to 5 kg of active substance per hectare. 22 8 3 1 8 The compositions can also contain further adjuvants, such as stabilisers, anti-foaaing agents, viscosity regulators, binders, tackifiers and fertilisers or other active substances for achieving special effects.
The following exaaples serve to explain further the invention, without liaiting it. Temperatures are given in these exaaples and in the following tables in degrees centigrade, °C, the pressures are given in aillibar (abar), indication of percent or parts relate to weight.
Exaaple It Preparation of 2-chloro-5-[N-(l-cyano-cvclopentvl)-M-aethvl-carbaaovl1-3-trifluoroaethvl-thiatol To a solution of 112.5 g of 2-chloro-4-trifluoroaethyl-»thiazol-5-carbonic acid chloride in 200 al of acetonitrile is added dropwise at 0* teaperature, while stirring, a aixture of 55.9 g of 1-cyano-1-aethy 1-aaino-cyclopentene (0.45 aole) and 46.0 g of triethylaalne (0.45 aole). Aaaoniua hydrochloride precipitates during this addition. The suspension is stirred overnight at rooa teaperature and then poured while stirring into 2 litres of water. The oil that separates is extruded with ethyl acetale, dried over sodiua sulfate and the solvent is then distilled off under reduced pressure. The residue crystallizes when stirred with ether. Colourless crystals of the title product are thus obtained. Halting point 134 - 136*: Yield 125 g (83 X of the theory).
I \ / il According to this exaaple, the thiazol-5-carboxaaides listed in Table 1 are obtained.
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OOOOOOOOO OOOO OO OOOOOOOOOOOOOOOOOOOOOOOOOOOOO r*aootQ*«r>i<*t««m<or*40»o*«r4 4 4 c 0 t' 22 83 1 Kr. Rl R* physikal. data 1.045 2-othylpiperidino 1.046 hexahydroazepino 1.047 aorpholino 1.048 2,2,5.5-tetranethyl 1,3-oxazolidin-3-yl 1.049 5.5-diaethyl-2,2-tetra-»ethylen-l, 3-oxazolidin-3-yl 1.050 5,5-diaethyl-2,2-pentaaethyl«n-l,3-oxazolidin-3-yl 1.051 2-phenyl-l,3-oxazolidin-3-yl 1.052 2,2-tetraaethylen-benzthiazol-3-yl 1.053 2-oxo-pyrrolidino 1.054 h«xahydro-2-oxo-azepino 1.055 3-oxo-thioBorpholino 1.056 2-oxo-l♦3-oxazolin-3-yl 1.057 2-trichloroaethyl-l,3-oxazolidin-3-yl 1.058 H 2-chlorob«nzyl ap. 115-116° 1.059 H 2-hexylbanzyl 1.060 CzHj CjH» ap. 40 - 41* 1.061 allyl H ap. 56 - 58* 1.062 phanylethyl H ap. 88 - 89° 1.063 CzHs 2,6-dichlorob«nzyl ap. 89- 91° 1.064 2-chlorob«nzyl H ap. 115-116° 1.065 propargyl propargyl ap. 100 - 101° 1.066 CfcH»-n 2,6-dichlorob«nzyl n** 1.5491 1.067 allyl othoxycroton-2-yl ap. 72 - 74* 1.068 -CHi-CH(CHj)2 2-chlorallyl n[* 1.5027 1.069 4-chloro-2-fluoro-6-l»o- propoxyphenyl H ap. 123 - 125* 1.070 cyano-diMthyla«thyl aathoxyathyl ap. 130 - 132* 1.071 chlorphanyl H ap. 125 - 126* 1.072 cyano-diaathyl-aethyl H 1.073 2.2-diaathylindanyl H ap. 174 - 175* 1.074 3.5-bis-trifluoraathyl- phanyl H «p- 125 - 127* 1.075 diphanylaathyl H ap. 177 - 179* 1.076 2»6-dlfluoroph«nyl H ap* 160 - 161* 1.077 5-trifluoroaathyl- thlazol-2-yl H ap. 136 - 138* trlathylaaaonlua salt 1.078 2-earboxyl-4-chlorph«nyl H ap. 132 - 134* 1.079 3-trlfluoroa«thylcyclo- haxyl H ap. 106 - 109* 1.080 2c4,6-trichloranilino H ap. 184 - 186* 1.081 furfuryl H ap. 100 - 102* 1.082 3,4-a*thyl«ndioxyb«nzyl H ap. 129 - 131* 1.083 4-aaidosul£onylph«nyl H «p» 186 - 189* 1.084 1,2-diph*nyl«th-l-yl H ap. 146 - 148* 22 8 3 1 8 Nr.
Rl R* physikal. data 1.085 o-ae thylbenzyl H Dp. 131 - 133° 1.086 4-fluorobenzyl H Bp. 128 - 130° 1.087 2,2-diphenyleth-l-yl H Bp. 127 - 129® 1.088 1-cyano-cyclopent-l-yl methoxycarbonylmethyl ap. 145 - 147° 1.089 1-cyano-cyclohex-l-yl ■ethyl Bp. 145 - 147° 1.090 2-methoxycarbonyl-4- chlorophenyl H 1.091 2-methylaminocarbonyl- 4-chlorophenyl H 1.092 2-diaethylaaino H 1.093 1-cyanocyclopent-l-yl CH) 1.094 cyano-diaethyl-aethyl CH) Bp. 78 - • o CO Exaaple 2: Preparation of 2-chloro- -4-trlfluoroaethvl- ■thlazol- ■5-carbonic acid-N'-(2.4»6-t richloro-phenvl)-hvdrazide C\_.
CO-KH-HH— ' Cl CF)*"*hbb« *ot KJ il A solution of 9*3 g 2-chloro-4-trifluoroaethyl-thiazol-5-carbonic acid chloride (0.037 sole) in SO «1 of acetonitrile is prepared. While stirring it at 0* there is added thereto dropwise another solution of 8.3 g of 2,4,6-trichloro-phenylhydrazine 95 X (0.037 sole) and 3.8 g triethylaaine (0.037 aole) in 50 al of acetonitrile. A suspension fores, which is stirred overnight, then poured into 1 1 of water. The reaction-mixture crystallizes. The crystals are filtered off and recrystallized in ethanol. Melting point 184 - 186°, yield 7.2 g (46 X of the theory).
In a sanner analogous to this exaaple, the thiazol-5-carbonic acid hydraxldes listed in Table 2 are obtained. 22 6318 Table 2 6i Nr.
RJ Rt Rs phys. data 2.001 H H H 2.002 H CH) CH) 2.003 CHj H CH) 2.004 H H phenyl a.p. 137-138® 2.005 H H CO phenyl a.p. 192-194® 2.006 H H SO* phenyl 2.007 H H 2-chlo rophenyl 2.008 H H 4-chlorophenyl 2.009 H H 2,4,6-trichlorphenyl a.p. 184-186® Foraulation Exaaple* for active ingredients of the foraula I or ■lxtur«« tharaof with herbicide* (X ■ par cent bv weight) Exaaple 3: Wettable powder* a) b) c) active Ingredient froa tha Tables 1-2 or aixture with herbicide 20 X 60 X 0.5 X sodiua llgnosulphonate 5 X 5 X 5 X sodiua lauryl sulphate 3 X -sodiua dilsobutylnaphthalane- sulphonate - 6 X 6 X octylphenolpolyethylene glycol ether (7-8 aol athylena oxide) - 2 X 2 X highly dispersed silicic acid 5 X 27 X 27 X kaolin 67 X - - sodiua chloride - - 59.5 X The active ingredient is aixed well with the adjuvants and ground well in m suitable aill. Wettable powders are obtained that can ba diluted with water to give suspensions of any desired concentration. © 22 8 J1g Example 4; Emulsifiable concentrate a) b) active ingredient from the Tables 1-2 or mixture with a herbicide 10 % 1 % C octylphenolpolyethylene glycol ether (4-5 mol ethylene oxide) 3 X 3 X calcium dodecylbenzenesulphonate 3 X 3 X castor oil polyglycol ether (35 mol of ethylene oxide) 4 X 4 X /""N cyclohexanone 30 X 10 X xylene mixture 50 X 79 X Emulsions of any desired concentration can be prepared from this concentrate by dilution with water.
Example 5: Dusts a) b) active Ingredient from the Tables 1-2 or a mixture with herbicide 0.5 X IX talcum 99.9 X kaolin - 99 X Dusts that ar« ready for use are obtained by mixing the active ingredient with the carriers and grinding in a suitable mill.
Example 6: Extruder granulate a) b) active ingredient from the Tables 1-2 or mixture with herbicide of foraula V 10 X 1 X sodium lignosulphonate 2 X 2 X carboxymethylcellulose 1 X 1 X kaolin 87 X 96 % The active ingredient is mixed with the adjuvants, ground and moistened with water. This mixture Is extruded and then dried in a stream of air. 22 8 3 1 8 Example 7: Coated granulate activa ingredient from the Tables 1-2 or mixture with a herbicide polyethylene glycol (KV 200) kaolin (MV - molecular weight) 3 X 3 X 94 X The finely ground active ingredient is uniformly applied in a mixer to the kaolin moistened with polyethylene glycol. A dust-free coated granulate is obtained in this manner.
Example 8: Suspension concentrate a) b) active ingredient from the Tables 1-2 or mixture with herbicide of formula V 60 X 5 X ethylene glycol 10 % 10 % nonylphenolpolyethylene glycol ether (15 mol of ethylene oxide) 6 X 1 X sodium lignosulphonate 10 X 5 X carboxymethylcellulose 1 X IX 37 X aqueous formaldehyde solution 0.2 X 0.2 X silicone oil in the form of a 75 X aqueous emulsion 0.8 X 0.8 X water 32 X 77 X The finely ground active ingredient is intimately mixed with the adjuvants. In this manner, a suspension concentrate is obtained from which suspensions of any desired concentration can be prepared by dilution with water.
Example 9: Salt solution active Ingredient from Tables 1-2 or mixture with a herbicide of formula IV 5 X isopropylamine 1 X octylphenolpolyothylenglykol ether (78 mol of ethylene oxide) 3 X water 91 X. 2283j8 Biological Examples The following exaaples illustrate the capacity of the compounds of formula I to protect cultivated plants from the phytotoxic effect of strong herbicides. In the description of the test, the compounds of foraula I are designated as safener or counter-agents (antidotes).
Example 10; Test with herbicide and antidote in maize. The herbicide and the counter-agent are applied together as tank-mixture.
Plastic containers of the dimensions (25 cm long x 17 cm large x 12 cm high) are filled with sandy, loamy earth and sown with maize seed of the variety LG 5. After the seeds are covered with earth, the substance to be tested as safener is applied, together with the herbicide as tank-mixture onto the surface of the soil. After 21 days the protective action of the safener is evaluated in percent. Plants, which are treated with the herbicide alone (no protective action) and plants which are grown untreated (100 S protection) serve thereby as references.
The tested coapounds reduced the phytotoxic effect of the herbicide to a degree* which does not influence the yield of the harvest.
Example 11: Test with water-sown rice. Antidote and herbicide are applied pre-eaergent as tank-mixture.
The rice-seeds are pre-soaked during 44 hours in 30*C warm water.
Plastic containers of 500 ml volume are filled with sandy loam to 2 cm below the upper rim. The herbicide M-chloroacetyl-N-(2-propoxyethyl) 2,6-diethylaniline at a concentration of 250 g active substance per hectare and the substance to be tested as safener in a concentration of 1500 g active substance per hectare are sprayed together as tmnk-mixture onto the surface of the soil.
The pre-soaked rice-seeds are then sown onto the swampy surface of tha soil. 22 8 3 1 8 The earth is aaintained in a humid state and the water-level is raised according to the growth of the rice plants. The protective action of the safener is evaluated 18 days after the application of the test-substances and recorded in percent. As references for this evaluation serve plants, which have been treated with the herbicide alone and plants, which have not been treated at all. The protective action is the difference (improvement) between the damage done to plants that have been treated with the herbicide alone and the damage done to plants that have been treated with the combination of herbicide and safener. The results are summarized in Table 3: Table 3 antidote Ho. protective action (test without antidote) 0 X 1.080 38 X 1.081 38 X 1.085 50 X 1.094 38 X Example 12t Test with ui'ze. The herbicide and the antidote are applied pre-energont as tank-mixture.
In order to evaluate the safening activity, seed of maSze of the variety LG-9 are raised in earth in pots of 9 cm diameter. The plants are cultivated in the greenhouse under adapted conditions of temperature and light for optimal growth. The plants are fertilized and watered according to their need.
The herbicide and the safener are applied as tank-mixture pre-emergently with an amount corresponding to 550 1 of water per hectare. As herbicide N-(2-Mthoxy-l-methylethyl)-N-chloroacetyl-2-ethyl-6-methylanlllne (1) was applied In an amount of 8 kg/ha. The substance to be tested as antidote was added in an application rata of 1.5 kg/ha thereto. In order to evaluate the protective action, the general damage (phytotoxicity) was assessed after 21 days In percent (0 X phyto • no damage ■ growth like untreated control plants; 100 X phyto ■ total damage, loss of plant). The difference of the damage on plants, which have been treated with the 22 8 3 1 8 herbicide alone and those, which have been treated with the combination herbicide and safener gives the amount of protective action, which is indicated in X in Table 4.
Table 4 antidote No. protective action 1.014 37.5 X 1.017 62.5 X 1.040 62.5 X 1.081 37.5 X 1.085 62.5 X 1.089 37.5 X 1.094 X Example 13: Test with sorghum and maaze. The herbicide and antidote are applied pre-energent as tank-mixture.
In order to evaluate the safening-activity, seeds of sorghum (millet of the variety Funk G-623) and maize (corn of the variety "Blizzard") are reared in earth in pots of 11 cm diameter. The plants are then cultivated in the green-house under adapted conditions for light and teaperature for optimal growth. The plants are watered and fertilized according to their need. The weed Echinochloa crus galli is raised according to the same method.
The herbicide and the safener are applied together pre-emergent as tank-mixture with an amount of water corresponding to 550 1 per hectare. As herbicide X-(2-methoxy-l-methylethyl)-N-chloroacetyl-2-ethyl-6-methyl-aniline, "metolachlor" (1) and X-(lsopropyl)-N-chloroacetyl-3,3,5-tri-methyl-cyclohex-l-enamid, "trlmexachlor" (2) were applied in the application rates listed below. The antidote to be tested was mixed thereto in the same amount and in 1/4 of the herbicide amount.
In order to evaluate the protective action, the general damage (phytotox) done to the plants is assessed in percent (OS phyto ■ no damage, plant grows like untreated plant; 100 X phyto ■ total damage). The difference in the damage rating of plants treated vith the herbicide alone and plants treated with the coabination of herbicide and safener is calculated and given as protective action in table S.
Table 5 antidote application herbicide protective No. rate No. application plant action rate 1.040 1000 /ha (1) 1000 g/ha sorghua X 1.040 1000 /ha (1) 1000 g/ha Echinochloa 0 X 1.040 250 /ha (1) 1000 g/ha sorghua X 1.040 250 /ha (1) 1000 g/ha Echinochloa 0 X 1.040 1000 /ha (2) 1000 g/ha sorghua 40 X 1.040 1000 /ha (2) 1000 g/ha Echinochloa 0 X 1.040 250 /ha (2) 1000 g/ha sorghua X 1.040 250 /ha (2) 1000 g/ha Echinochloa 0 X 1.040 8000 /ha (1) 8000 g/ha aak'ze 70 X 1.040 8000 /ha (1) 8000 g/ha Echinochloa 0 X 1.040 2000 /ha (1) 8000 g/ha aak'ze 60 X 1.040 2000 /ha (1) 8000 g/ha Echinochloa 0 X 1.040 8000 /ha (2) 8000 g/ha aaSze 40 X 1 040 8000 /ha (2) 8000 g/ha Echinochloa 0 X 1.040 2000 /ha (2) 8000 g/ha aaSze X 1.040 2000 /ha (2) 8000 g/ha Echinochloa 0 X Exaaple 14: Te pre-eaergent a In oder to eva variety funk G plants are cul teaperature and fertilized acc t vith sorghua. The herbicide and antidote are applied tank-aixture. uate the safening activity, seeds of sorghua (aillet of the 623) are raised In earth In pots of 9 ea diameter. The lvated In the greenhouse under adapted conditions of light for optlaal growth. The plants are watered and rding to their need. 22 8 3 1 The herbicide and che substance to be tested as safener vere applied pre-eaergent together as tank-mixture using 550 1 of water per hectare. As herbicide N-(2-eethoxy-l-methylethyl)-N-chloroacetyl-2-ethyl-6-methyl-aniline (metolachlor) was used at an application rate of 1,5 kg/ha. The antidote was also applied at an application rate of 1.5 kg/ha.
In order to evaluate the protective action, the general damage (phytotox) done to the plants was assessed 21 days after the treatment in percent (0 X phyto ■ no damage, plant grows like untreated control plant. 100 X phyto ■ total damage). The difference of the daaage done to plants treated with the herbicide alone and to plants, treated with the coabination of herbicide and antidote is calculated and given in table 6 as X protective action.
Table 6 antidote No. protective action t 1.014 50 1.017 37.5 1.085 37.5 Example 15: Test with sown rice. The antidote is applied during seed-soaking onto the rice, the herbicide is applied pre-eaergent immediately after sowing.
In order to evaluate the safening activity seed of rice (of tha variety S-201) are pra-soakad in an aqueous solution of tha compound to ba tested as safener, during 48 hours. The incubation time of tha seed before sowing is 24 hours. The herbicide is applied pre-emergent, by spraying onto the surface of the sown area.
The seeds are planted in pots of 9 x 9 cm onto swampy earth. The plants are then cultivated in the greenhouse under adapted conditions of temperature and light for optimal growth. They are watered and fertilized according to their need. The herbicide is applied in the given application rate and with an aaount of water corresponding to 550 1 per hectare pre-emergent immediately after sowing onto the pre-soaked seed. The f a 22 8 3 1 8 following herbicides were used: N-(n-propoxyethyl)-N-chloroac«tyl-2,6-diethylanilide, pretilachlor (3) and N-(2-aethoxyethylphenylsulfonyl)-N'-(4,6-dim«thoxy-l,3,5-triazin-2-yl)-urea (4). The subscance to be tested as antidote was applied in the given concentration during seed-soaking.
In order to evaluate the protective action, the general daaage (phytotox) done to the plants was assessed 26 days after the treataent and expressed in percent (0 X phyto ■ no daaage, like untreated control plant; 100 X phyto ■ total daaage). The difference of the dasage rating calculated in percent between plants which have been treated with the herbicide alone and of plants treated with the combination of herbicide and antidote is expressed as protective action in Table 7 below.
Table 7 antidote application herbicide application protective No. rate No. rate action 1.014 100 ppa (3) 250 g/ha 37.5 X 1.017 100 PP" (3) 250 g/ha 37.5 X 1.018 100 ppa (3) 250 g/ha 62.5 X 1.040 100 ppa (3) 250 g/ha 37.5 X 1.065 100 ppa (3) 250 g/ha 62.5 X 1.040 150 ppa (4) g/ha 45 X 1.040 300 PP* (4) g/ha 55 X Exaaple 16: Test with rice. The antidote and herbicide are applied pre-eaergent as tank-aixture.
In order to evaluate the safening activity, seeds of rice are raised in earth in pots of 9 ca diaaeter. The plants are cultivated in a greenhouse under adapted conditions of teaperature and light for optiaal growth. Watering and fertilizing occurs according to need.
The substance to be tested as safener and the herbicide are applied together as tank aixture pre-eaergent with an aaount of water corresponding to 550 1 per hectare. As herbicides N-(2-aethoxy-l-aathylothyl)-N-chloroacetyl-2-ethyl-6-aethylanilide, aetolachlor (1) and M-(2-aethoxy-ethylphenylsulfonyl)-N'-(4,6-diaethoxy-l ,3,5-triazin-2-yl)-urea (4) are 22 8 3 1 used in the given application rate. The substance to be tested as safener is added thereto in an amount of 1.5 kg/ha for herbizide (1) and 30-60 g/ha for herbizide (4).
In order to evaluate the protective action, the general damage (phytotox) done to the plants is estimated 26 days after the treatment in percent (0 X phyto ■ no damage, as untreated control plant; 100 X phyto ■ total damage). The difference in damage rating between plants treated vith the herbicide alone and of plants treated vith the combination herbicide and antidote gives the protective action, expressed in Table 8.
Table 8 antidote application herbicide rice protective No. rate No. application variety action rate 1.017 1500 g/ha (1) 375 g/ha "Starbonnet" 25 X 1.040 1500 g/ha (1) 375 g/ha "Starbonnet" 12.5% 1.040 60 g/ha (4) 30 g/ha S-201 50 X 1.040 30 g/ha (4) 30 g/ha S-201 35 X Example 17: Test vith different varieties of rice and vith veeds. The antidote snd herbicide are applied together at tank-mixture post-emergent.
In order to evaluate the safening activity, seeds of 8 varieties of rice are raised in earth in pots of 11 cm diameter. The plants vere cultivated in the greenhouse under adapted conditions of teaperature and light for optimal growth. Watering and fertilizing occured according to need. The veeds Echinochloa, Rottboellia and Digitaria are raised in the saae manner* The substance to be tested as safener and the herbicide vere applied together as tank-mixture, vith an amount of water corresponding to 550 1 per hectare post-emergent. As herbicides N-(2-methoxyethylphenyl-sulfonyl)-H,-(4,6-dieethoxy-l,3,5-triazin-2-yl)-ur«a (4) and the 2R enantiomer of the propinyl ester of 2-t4-(5-chloro-3-fluoropyridin-2- ?2 8 3 1 8 yloxy)-phenoxy]-propionic acid (5), were sprayed onto the plants in the given application rate. Antidot No. 1.040 was applied in the given application rate at the same time.
In order to evaluate the protective action, the general damage (phytotox) done to the plants is assessed 21 days of the herbicide treatment and given in percent (0 % phyto " no damage, the plant grows like untreated control; 100 X phyto ■ total damage). The difference of the damage done to the plants treated vith the herbicide alone and to plants, treated vith the combination herbicide and antidote is calculated and given in Table 9.
Table 9 plant herbicide antidote protective No. application No. application action rate rate rice -S-201" (4 /ha 1.040 60 /ha 55 X rice -S-201" (4 /ha 1.040 /ha 60 X rice "Mev lionet" (5 60 /ha 1.040 120 /ha X rice "Nov Bonet" (5 60 /ha 1.040 /ha X rice "Balilla" (5 60 /ha 1.040 120 /ha X rice "Balilla" (5 60 /ha 1.040 /ha X rice "Jung Veon" (5 60 /ha 1.040 120 /ha 45 X rice "Jung Veon" (5 60 /ha 1.040 /ha X rice "PB-56" (5 60 /ha 1.040 120 /ha 45 X rice "PB-56" (5 60 /ha 1.040 /ha 45 X rice "IR-54" (5 60 /ha 1.040 120 /ha 45 X rice "IR-54" (5 60 /ha 1.040 /ha X rice "Yamabiko" (5 60 /ha 1.040 120 /ha X rice "YamabikoN (5 60 /ha 1.040 /ha X rice "Starbonet" (5 60 /ha 1.040 120 /ha 40 X rice "Starbonet" (5 60 /ha 1.040 60 /ha 45 X Digitaria sanguinalis (5 60 /ha 1.040 120 /ha 0 X Digitaria sanguinalis (5 60 /ha 1.040 /ha 0 X Rottboellia exaltata (5 60 /ha 1.040 120 /ha 0 X Rottboellia exaltata (5 60 /ha 1.040 /ha 0 X Echinochloa crus galli (5 60 /ha 1.040 120 /ha 0 X Echinochloa crus galli (5 60 /ha 1.040 /ha 0 X 22 8 3 1 8 Example 18t TesC with rice and maize. The antidote is applied by seed-dressing, the herbicide pre-emergent onto the sown area.
In order to evaluate the safening acitvity, seeds of rice of the variety "Starbonet" and maize seed of the variety "Blizzard" are brought together vith antidote No. 1.040 in a glass-container and mixed veil by shaking and rotating. The seeds are then raised in earth in pots of 11 ca diameter. The plants are cultivated in the greenhouse under adapted conditions of teaperature and light for optimal growth. Watering and fertilizing occured according to need.
The herbicide was applied iaaediately after soving in an aaount of water corresponding to 550 1 per hectare. As herbicides vere sprayed K-(n>propoxyethyl)-K-chloroacetyl-2,6-diethylaniline, pretilachlor (3), K-(isopropyl)-N-chloroacetyl-3,3,5-trimethyl-cyclohex-1-enamid, triaexa-chlor (2) and N-(2-methoxyothylphenyl«ulfonyl)-N"-(A,6-diaothoxy-l,3,5-triazin-2-yl)-urea (4) and N-(methoxymothyl-N-chloroacetyl-2,6-diethyl-anilin, alachlor (6), in the given application rate.
In order to evaluate the protective action, the general damage (phytotox) done to the plants was assessed 25 days after treataent vith the herbicide in percent (0 % phyto ■ no daaage, plant grovs like untreated control; 100 X phyto • total daaage). Tha difference in the daaage rating of plants treated vith the herbicide alona and plants, treated vith the coabination of safener and herbicide is calculated in percent and expressed as protective action expressed in Table 10. 228318 Table 10 antidote application herbicide protective No. rate No. application action rate 1.040 0,5 g/kg rice (3) 1 kg/ha 45 X 1.040 0.25 g/kg rice (3) 1 kg/ha 40 X 1.040 0.5 g/kg rice (2) 0.5 kg/ha 40 X 1.040 0.25 g/kg rice (2) 0.5 kg/ha X 1.040 0.5 g/kg rice (6) 1 kg/ha 50 X 1.040 0.25 g/kg rice (6) 1 kg/ha 45 X 1.040 1 g/kg maize (4) g/ha 45 X Exaaple 19; Test with maize. The antidote is applied by seed-dressing, the herbicide is sprayed post-emergent onto the plants.
In order to evaluate the safening activity, maize seed of the variety "Blizzard" are put together with antidote No. 1.040 in a glass container and thoroughly mixed by shaking and rotating. The seeds aro then raised in earth pots of 11 ca diameter. The plants were cultivated in the greenhouse under adapted conditions of temperature and light for optimal growth. Watering and fertilizing occured according to need.
The herbicide was applied post-emergent with an amount of water corresponding to 550 1 of water per hectare. As herbicide K-(2-methoxy-ethylphenylsulfonyl)-N'-(4,6-di«ethoxy-l ,3.5-triaxin-2-yl)urea (4) was sprayed onto the maize plants, when they had reached the 2-3 leaf stage. In order to evaluate the protective action, the general damage (phytotox) done to the plants was assessed 25 days after spraying of the herbicide. The damage is given in percent (0 X phyto ■ no damage, plant grows like untreated control plant; 100 X phyto ■ total damage)* The difference in the damage rating between the plants treated with the herbicide alono and those treated with the combination of herbicide and antidote is calculated and given in Table 11 as protective action.

Claims (13)

i - . o | - 41 - ^2 8 3 1 8 Table 11 antidote application herbicide protective No. rate No. application action rate 1.040 I g/kg maize (4) 30 g/ha 15 X i - 42 - 228318 WHAT Tf<WE CLAIM Br-
1. Composition for protecting cultivated plants froa the phytotoxic action of highly effective agrochemicals, which contains besides inert carrier ■aterial and additives a herbicide-antagonistically active component a thiazol-5-carboxamide of the foraula I CF j-'Jssoa.-COA 8, yS (I) £i wherein A is a group-NRxR* or -NRj-WUCCOj^Rs, wherein Rx, Rz. Rj, R%, R* independently of each other are hydrogen, Ci-Ctalkyl or C}-C»cycloalkyl which is unsubstituted or substituted by Cx-C«alkoxy. Cj-Caalkoxyalkoxy, Ci-Caalkylthio, a cyano, ^^cCJORj, Cx-Ctalkylcarbaaoyl, di-Cx-Cw-alkylcarbaaoyl. Cx-C*alkylanino, di-Cx-Ctalkylamino. piperidinocarbonyl. pyrrolidinocarbonyl. piperidino or pyrrolidino; Rx. Rj, Rj. R* and Rs further represent Ci-C«alkenyl or C)-C«cycloalkenyl which is unsubstituted or substituted by halogen. Cx-Ctalkoxy, Cj-Ctcycloalkyl. or a group cyano* -COORc. Cx-Ctalkylcarbaaoyl. di-Cx-Ctalkylcarbaaoyl, U. pyrrolidino-carbaaoyl or piperidlnocarbsmoyl; Rx, Rj, R», Rt and R» represent further C)-C«alkynyl( which is unsubstituted or substituted by U: Rx, Rz. Rj, Rw and Rj represent also a radical or -(E>b-Q; Rx and R; or Rk and Rs together with the nitrogen atoa, to which they are bound fora a saturated or unsaturated heterocycle with 5 to 9 ring members which aay include once or several times oxygen, sulfur, nitrogen. -HH-, -NCi-C*alkyl, -CO-or .-C(OR7)ORs and which aay be substituted by halogen, cyano, Cx-Csalkoxy. amino, Ci-C»alkylaaino, di-Cx-C.-alkylaaino, or a ^^P-COOR*; R« is hydrogen. Cs-Caalkyl, Cj-C«cycloalkyl. C)-C«alkenyl, Cj-C«cycloalkenyl, Cj-C»alkynyl, Ci-Ctalkoxyalkyl, Cj-Cialkoxyalkoxyalkyl, Ci-C.haloalkyl, -(Cx-Cialkylene)aU, -(Cx-Cialkylene)aQ, Cx-Cthaloalkoxy: R? end R« are independently of each other Cx-Chalkyl or ^ R? and Ri form together a 2 to 4 membered alkylene chain. * I a *8 AUGI99Q' 228318 - 43 U is phenyl or naphthyl, which is unsubstituted or substituted once or several tines by halogen. Ci-C*alkyl, -Y-Cj-Cvalkyl, Cj-Cwhaloalkyl, Ci-Cthaloalkoxy, cyano, nitro, carboxyl, -COOR7, -CONHj, -CONHR7, -C0X(R7)2, -S0jKHR7, -S0*N(R?)2, pyrrolidino, piperidino, pyrrolidino-earbonyl or piperidinocarbonyl; E is a Ci-Csalkylene or C2-Cialkylene chain, which is unsubstituted or substituted by halogen, Cx-Ctalkoxy, Ci-Ctalkylthio, Cj-Cvhaloalkoxy or by a group -CO(O) Rt, -(CO) NHj, -(CO) NHR7, -(CO) KR7R». and which aay be ■ MM A interrupted by -CO- or -C(0R»)0R»-; Q is a saturated or unsaturated heterocycle vith 5 to 12 ring members which aay contain 1 to 4 heteroatoas or 1 to 2 heteroatons in coabination vith a sulfinyl or sulfonyl group or vhich aay be interrupted by 1 to 2 earbonyl groups and vhich aay be benzannelated and a is zero or I with the proviso that only one of and ^ is hydrogen or unsubstituted Cj-Cg alkyl.
2. Composition as claiaed in elaia 1, for selectively controlling weeds in areas of cultivated plants, containing besides Inert carrier aaterial and additives, a herbicide and a herbicidally-antagonistic component, which it characterised that the herbicide is a sulfonylurea derivative, a haloacetanilide or an aryloxyphenoxy-propionic acid derivative and the herbicidally-antagonistic component in a thiazol-S-carboxaaide according to claim 1.
3. Ooaposltion as claimed in claim 1, for selectively controlling weeds in areas of cultivated plants, containing besides Inert carrier material and additives, a herbicide and a herbicldally-antagonistic component, which Is characterised that the herbicide Is a sulfonylurea-derivative of the foraula XV, / E-(CH2 )—502-NH-C0-K— \ wherein E is a group (IV) o 228318 44 - / II u • • y v > v \ ^Rio ✓ W • or w, n is zero or one, G is hydrogen or aethyl, X is aethoxy, ethoxy, difluoroaethoxy or chlorine, Y nitrogen or settyne (-CH-) Z is aethyl, aethoxy, difluoroaethoxy, cyclopropyl or aethylaaino, Ru it Cj-C$alkoxyalkoxy. CrCihaloalkoxy, Cj-Ckhaloalkylthio, Cj-C»- haloalkenyl, chlorine or Ci-Ctalkoxycarbonyl, Ru is trifluoroaethyl or di(Ci-Cb-alkyl)carbaaoyl, Rw it Cj-Chalkoxycarbonyl, Ru it Cj-Cbalkoxycarbonyl and Rs* it Ci-Caalkyl, and the herbicidally-antagonistic coaponent is a thiazol-5-carboxaaide according to claia ).
4. Compoaltion as elaiaed in claia 1, for selectively controlling weeds in areas of cultivated plants, containing besides inert carrier material and additives, a herbicide and a herbicidally-antagonistic component, which ia characterised that the herbicide la a haloacetanllide of the formula V, /*■» C wherein L is a Ci-Ct-alkylen* bridge. R}» Rat and R17 independently of each other hydrogen, halogen, •«-<* Cj-Ck-alkyl, Cj-C»-alkoxy, Ci-Ck-haloalkyl, Cj-Ci-alkoxyalkyl or^ Cj-Cs-alkylthioalkyl, and s- o 228318 - &5 - Rj» Cj-Ci.-alkoxy, -COOH, Ci-Ct-alkoxycarbonyl, -COKHjj Cj-C*-alkyl- carbamoyl, di-Ci-Ct-alkylcarbamoyl, cyano, Cj-Cw-alkylcarbonyl, optionally substituted benzoyl, optionally substituted furyl, optionally substituted thienyl, optionally substituted pyrrolyl, optionally substituted pyrazolyl, optionally substituted 1,3,4-oxadiazol-2-yl, optionally substituted 1,3,A-thiadiazol-2-yl, optionally substituted 1,2,4-triazol-3-yl, optionally substituted dioxolanyl, optionally substituted dioxanyl, optionally substituted l,3,4-triazol-2-yl or optionally substituted tetrahydrofuryl, and the herbicidally-antagonistic component is a thiazol-5-carboxamide according to claim 1. C
5. Composition as claimed in>claia 1, for aalectivaly controlling weada in areaa of cultivated plants, containing beaidaa inart carrier Material and additives, a harbicida and a harbicldally-antagonlatic component, which ia charactariaad that tha harbicida ia an aryloxyphenoxy-propionic acid harbicida of tha foraula VZ, / V ✓ CHj CH- CO-T (VI) wherein Q is a radical R»»-« ^Rzo / R AA/" Rzo • » or vherein T is -NRzjRzSt -K(CK)Rji, -ORjj, SRji or -0-K"CRijRj» Rj9 is halogen or trifluoromethyl, Rao is hydrogen or halogen. .>++"*& W** 2283 r> - 46 - Rz: and R{] independently of each other hydrogen, Cj-C»alkoxy. Cx-Caalkyl, phenyl or benzyl. Ru and K22 together with che nitrogen atoa, to which they are bound also form a saturated 5- to 6-aeabered nitrogon-heterocycle, which aay contain an oxygen or sulfur atoa. Ru is Ci-C*alkyl, C)-Ctalkenyl, Ci-Ctalkynyl or Cj-Cvalkoxyalkyl Rj% is hydrogen or the cation-equivalent of an alkali aetal. an alkaline earth aetal of copper or iron; of a quaternary Ci-Ctalkylaaaoniua or Ci-Ct-hydroxyalkylaaaoniua radical; Ci-C«alkyl unsubstituted or n aono- or polysubstituted by aaino, halogen, hydroxyl. cyano. nitro. phenyl, Cx-C*alkoxy. polyethoxy vith 2 to 6 ethyleneoxy-units, -COORj 7, -C0SR;7, -COKHj, -CON(Cx-C%-alkoxy)-Cx-Cfc-«lkyl, -CO-X-di-Cx-Ck-alkyl. CONH-Cx-C*-alkyl, -N(Cx-Cfc-alkoxy)-Cx-Ck-alkyl or di-Cx-Ct-alkylaaino; Cj-C»alkenyl, unsubstituted or substituted by halogen or Cx-Ctalkoxy: Cj-C»alkynyl, unsubstituted or substituted by halogen or Cx-Caalkoxy; Cj-Cicycloalkyl,phenyl unsubstituted or substituted by cyano. Cx-Ctalkyl. Cx-C*alkoxy. acetyl. -COOR27. COSRu. -CONKz. -COS(Cx-Ck-alkoxy)-Cx-Cfc-alkyl, -CO-K-di-Cx-Ck-a1ky1 or -COHH-Cx-C*.-alkyl; Ris and Xji independently of each other are Cx-Ctalkyl or together a 3-to 6-aeabered alkylene chain and Rj7 is hydrogen. Cx-C«alkyl, Cx-C«haloalkyl. Cj-Ctalkoxyalkyl, Cj-Ct- alkenyl. Cj-Cthaloalkenyl. Cj-Ctalkynyl or Ci-Cthaloalkynyl, and the herbicidally-antagonistic eoaponent is a thiazol-5-carboxaaide according to claia 1.
*6. Coaposition according to claias 1 or 2, characterised that it contains as herbicidally-antagonistic eoaponent a thiazol-5-carbonic ac*id"aald9..of the foraula Ia, "•i-rx »•> 6l wherein the radicals Rx and Rs independently of each other are hydrogen, Cx-C«alkyl or C)-Ct. unsubstituted or substituted by halogeilT cyano, Cx-Ckalkoxy or -COOR*; Cj-Caalkenyl, unsubstituted by halo||^ cyano, Cx-Ctalkoxy or -COOR* or C)-Ctalkynyl. «. >v«M 228318 - 47 - c c >«*S W Rj may also be -(E) U or -(E) Q, 81 fll Rx and Rt together form also a 4- to 5-aeabered alkylene chain, which nay be interrupted by oxygen, sulfur. -XH- or -NR7 and/or substituted by Ci-Cwalkyl, E is Cx-Cwalkylene, Cj-Cwcycloalkylene, Cj-Ctalkenylene or C2-C%-alkynylene. U is phenyl, unsubstituted or substituted by halogen, cyano, Cx-Ctalkyl, Cx-C%alkoxy. Cx-Cthaloalkyl, Ci-Cwhaloalkoxy. COORt. -SOjNHz, -SOjNHRj. -S0jK(R7)i, -COHHz. -CONHR7 or -C0M(R7)i. Q is a 5 to 6 aeabered heterocycle which is unsubstituted or substituted by halogen, Cx-Ctalkyl, Cx-Caalkoxy, Ci-Cthaloalkyl or Cx-C^haloalkoxy m is zero or 1 and Rt and R7 have the aeaning given in claia 1, with the proviso that only one of and Rj is hydrogen or unsubstituted C^-Cg alkyl.
7. Coaposition according to claias 1 or 2. characterised that it contains as herbicidally-antagonistic eoaponent a thiazol-5-carbonic acid aaide of the foraula la. CT»-j—r-CO-SRx ii (la) wherein Rx is hydrogen, Cx-C«alkyl or C)-*C«alkynyl and Rj is Cx-Cecyanoalkyl, Cj-C«cyanocycloalkyl, C)-C«alkynyl. phenyl, halophenyl, C x -C » aIky1phenyl, Cx-C»alkylhalophenyl, phenylaaino, halo- phenylaaino or furyl, especially wherein -XRxRj is X-aethyl-l-eyano- pentylaaine or -X-aechyl-X-(2,6-dichloro)benzylaaine# with the proviso that <jnly one of and is hydrogen or unsubstituted C^-C^ alkyl.
8. Coaposition according to claias 1 or 2, characterised that it contains as herbicidally-antagonistic eoaponent a thiazol-5-carbonic acid hydraside of the foraula lb CFj— ii '■—R$ (lb) - 48 - 22 8 3 1 8 wherein Rj, Rt and Rs independently of each other are hydrogen, alkyl, Cj-Cgcycloalkyl, phenyl or benzyl, the phenyl ring being unsubstituted or substituted by halogen, Ci-Ctalkyl, Cj-Cthaloalkyl, Ci-C*alk-O oxy% Ci-Ckhaloalkoxy, -COORt, -COHHx. -CONHR?, -CON<R7)2. -SONHj, -SONHR?. -S0N(R7)z and Rw and Rs together can also fora a 4 - 5 aeabered alkylene chain that aay be interrupted by oxygen, sulfur, -NH-, -NR7 and/or substituted by Ci-Ctalkyl. O
9. Coaposition according to claias 1 or 2, characterised that it contains as herbicidally-antagonistic eoaponent a thiazol-5-carboxaaide selected froa the group consisting of thiazol-5-carbonic acid-N-aethyl-N-benzylaaide, thiazol-5-carbonic acid-benzylaaide, thiazol-5-carbonic acid-K-aethyl-N-(l-cyano-cydopent-l-yl)aaide, thiazol-5-carbonic acid-N.K-dipropylaaide. thiazol-5-carbonic acid-K'-(2,4,6-trichlorophenyl)hydrazide, thlazol-5-carbonic acid furfurylaaide. thiazol-5-carbonic acid(4-aaidosulfonyl)anlllde, thiazol-5-carbonic acid-N-aethyl-K-(cyano-diaethyl)aaide.
10. Hethod for protecting cultivated plants froa tha phytotoxic effect of ^ herbicides, characterized by applying to the plants or the area where they are cultivated, a herbicidally-antagonistic effective aaount of a coaposition according to claia 1.
11. Method for selectively controlling weeds in cultures of useful plants, characterised in that the plants or the area where they are cultivated, are treated with a herbicidally effective aaount of a herbicide and with a herbicidally-antagonistic effective aaount of a thlol-S-carboxaaide according to claia 1. 22 631 - 49 -
12. Method for protecting cultivated plants froa damage vhich might appear during the application of herbicides, vhich consists in treating the cultivation area of the plant before or during the application of the herbicide or the seeds or seedlings or the plants itself,vith a herbicidally-antagonistically effective amount of a thiazol-5-carboxamide according to claim 1.
13. Seeds or seedlings of cultivated plants which have been treated with a herbicidally-antagonistic aaount of a coapound according to claim 1. FO 7.5/XU/ac* CIBA-GBIGY AG I BALDWIN* SOW i CAKBY
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