AU608700B2 - Thiazol-5-carboxamides for protecting cultivated plants from the phytotoxic action of highly effective herbicides - Google Patents

Description

Lii~ .ivetu1L.ounsLie suojecT or mne application.

DECLARED at Basle, Switzerland on January 24, 1989 CIBA-GEIGY AG Werner Waldegg Single Signature, by special power To: The Commissioner of Patents 2.88 521 WW i I .1 1 II I v" 44 4r

IL

417 S F Ref: 85300 FORM COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952 COMPLETE SPECIFICATION

(ORIGINAL)

FOR OFFICE USE: Class Int Class '0o *r Complete Specification Lodged: Accepted: Published: Priority: Related Art: This document contains th1 amendments made under Section 49 and is correct fur prin ting.

S Name and Address of Applicant: Ciba-Geigy AG Klybeckstrasse 141 4002 Basle

SWITZERLAND

Spruson Ferguson, Patent Attorneys Level 33 St Martins Tower, 31 Market Street Sydney, New South Wales, 2000, Australia Address for Service: J Complete Specification for the invention entitled: for Protecting Cultivated Plants from the Phytotoxic Action of Highly Effective Herbicides The following statement is a full description of this invention, including the best method of performing it known to me/us 5845/3 5-16942/1+2/= for protecting cultivated plants from the phytotoxic action of highly effective herbicides Abstract amides of the formula I below are useful as counter-agents ("safeners" or "antidotes") for protecting cultivated plants, especially maize, sorghum, rice, cereal and soya from the phytotoxic effects of herbicidally active agrochemicals, especially of herbicides.

The thiazol-5-carboxamides correspond to the formula I

CF

3

*-COA

wherein A is an anidorest -NRjR 2 or a hydrazidorest -NR 3

-NR

4 (CO) mR 5 wherein m is zero or one and RI, R2, R 3 R4, R 5 have the meaning given in the description.

9* 40*4 *444 4 *0 a 4* 4

S

*0 9*4 0* 44 4 1

S

*44S 04 a.

*4 *4 0 as" 4s 4 6 41

U

IA-

5-16942/1+2/= for protecting cultivated plants from 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 agrochemicals, especially herbicides, which composition contains as herbicide a antagonist, and also to compositions which, in addition to containing said antagonist (also called antidote or safener), already contain the herbicide, and to a method of selectively controlling weeds, which comprises the use of these herbicides and said safener.

Ir I If I I

I

i-

I

It js known that herbicides belonging to a very wide range of compound classes such as triazines, urea derivatives, carbamates, thiocarbamates, 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.

SThe climatic conditions or the nature of the soil may be such that the S 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 Sharmful action of the herbicide on the cultivated plant, i.e. to protect t t L the cultivated plant without noticeably influencing the herbicidal action t 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.

a

I~

i 2 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 phytotoxically 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 S overdose occasionally occurs, e.g. whenever peripheral spraying zones overlap. In view of the possibility of such occasional unintentional 2d overdosage, for technical application it is desirable, for example in zones to be treated which overlap, to protect the seeds against approximately i' twice the intended concentration of herbicide.

m acid derivatives are known from the literature.

2,4-Dimethylthiazol-5-carboxaiides are disclosed as fungicides in US patent 3,725,427; 2-chloro-4-trifluoromethylthiazol-5-carbonic acid derivatives S are disclosed as antidotes (safeners) to reduce the phytotoxic action of 0oo strong herbicides on cultivated plants in US patents 4,199,506, 4,251,261, in the published European patent applications 27,018, 44,201 and 63,353.

According to a broad form of the present invention there is provided a composition for protecting cultivated plants from the phytotoxic action of highly effective agrochemicals, which contains inert carrier material, additives and as herbicide-antagonistically active component a carboxamide of the formula I CF3-*. -COA k 4'M. W:1148y /V r 0 -2Awherein A is a group -NR, R 2 or -NR 3 NR 4 (CO) mR 5 s whereinR,

R

2 1 R 3

R

4 R 5 independently of each other are hydrogen, C 1 8 alkyl or C 3

C

8 cycloalkyl which is unsubstituted or substituted by C 1 -C 8 alkoxy, C 2 8 alkoxyalkoxy, CG 1 -C 8 alkylthio, cyano, a group -COOR 6

G

1 -C 4 alkylcarbamoyl, di-C 1

-GC

4 alkylcarbamoyl, C 1 -C 4 alkylamino, di-C 1 -C 4 alkylamino, piperidinocarbonyl, pyrrolidinocarbonyl, piperidino or pyrrolidino; R 1 R 2 R 3

R

4 and F jfurther r~present C 3 -C 8 alkenyl or C 3 -C 8 cycloalkenyl which is unsubstituted or substituted by halogen, CI- C 8 alkoxy, C 3 8 cycloalkyl, or a group cyano, -GOOR 6 CI- C 4 alkylcarbamoyl, di-C 1 -C 6 alkylcarbamoyl, U, pyrrolidinocarbamoyl or piperidinocarbamoyl; RP, R 2 9 R 3 9 R 4 and R 5 represent further CG 3 -C 8 alkynyl, which is unsubstituted or substituted by U; R 1 R 2 R 3

R

4 and R 5 represent also a racidal m-U or m-Q; R 1 and R2or R4and R 5 together with the nitrogen atom, to which they are bound form a saturated or unsaturated h eterocycle with 5 to 9 ring members which may include one or more oxygen, sulfur, nitrogen, -NC 1

-C

4 alkyl, -CO- or -G(0R 7 )0R 8 and which may be substituted by halogen, cyano, C C alkoxy, amino, C -G alkylamino, di-C 1 -C 4 alkylamino, or a group -GOOR 6 R 6 is hydrogen, G 1

-C

8 o alkyl, C 3 -C 8 cycloalkyl, C 3

-G

8 alkenyl, C 3 -C 8 cycloalkenyl, C -G alkynyl, C -C alkoxyalkyl, C 3 -G alkoxyalkoxyalkyl, C 1 4 haloalkyl, -(C 1

-C

3 alkylene) mU, -(CG 1 -C 3 alkylene) MQ G 1 -C 4 haloalkoxy; R 7 and R8are independently of each other C-Gaklo and Rform together a 2 to 4 membered alkylene S chain, U is phenyl or naphthyl, which is unsubstituted or substituted by 004" one or more halogen, C 1

-G

4 alkyl, -Y-G 1 4 alkyl, C 1 4 haloalkyl, G 1 -C 4 haloalkoxy, cyano, nitro, carboxyl, -COOR 7 -CONH 2 -GONHR 7 a -CON(R 7 2 1 -so 2 NHR 7 so 2 N(R 7 2 pyrrolidino, piperidino, pyrrolidinocarbonyl or piperidinocarbonyl; E is a C 1 8 alkylene or

C

2 8 alkylene chain, which is unsubstituted or substituted by halogen, C~ C 1 -C 4 alkoxy, CG 1

-G

4 alkylthio, C 1

-C

4 haloalkoxy or by a group -CO(O) m R 6 1(O mNH 2 1 mNHR 7 1 (C)mNR 7 RP~ and which may be interrupted by -GO- or -C(OR 7 )OR 8 Q is a saturated or unsaturated heterocycle with 5 to 12 ring members which may contain 1 to 4 heteroatoms or 1 to 2 heteroatoms in combination with a sulfinyl or sulfonyl group or which may be interrupted by 1 to 2 carbonyl groups and which may be benzannelated and m is zero or 1; with the proviso that when one of Rand R2is hydrogen or unsubstituted C -G alkyl the other 1 8i -2B is different from hydrogen or unsubstituted CI- C 8 alkyl.

It has surprisingly been found that the thiazol-5-carboxamides of formula I are excellently suited for protecting cultivated plants from the damaging action of agrochemicals, such as e.g. haloacyl-herbicides. The are therefore in the following text also referred to as "counter-agents", "antidotes" or "safeners".

t C t W118 0 0, -3- The thiazol-5-carboxamides correspond to formula I

CF

3 -i *-COA wherein A is a Eerovp jR or -N3N4C)R5, wherein RI, R 2

R

3

R

4

R

m independently of each other are hyc~rogen, CI-C 8 alkyl or C3-C8cycloalkyl which is unsubstituted or substituted by C 1 -Csalkoxy, G 2

-C

8 alkoxyalkoxy, 3 ,q up Cl-Csalkylthio, cyano, a .r.es&t- -COOR6, Cl-Ci~alkylcarbamoyl, di-Cl-C+alkylcarbamoyl, CI-C~alkylamino, di-Cl-Ci~alkylamino, piperidinocarbor-1, pyrrolidinocarbonyl, piperidino or pyrrolidino; R 1 R2, R 3 R4+ and R further represent C 3 -Csalkenyl or C3-C 8 cycloalkenyl which is unsubstituted or substituted by halogen, CI-C 8 alkoxy, C3-C8cycloalkyl, or a .9tOUp r-astf-cyano, -COOR 6 Ca-CL~alkylcarbamoyl, di-Cl-C 6 alkylcarbamoyl, U, pyrrolidinocarbamoyl or piperidinocarbamoyl; RI, R2, R31 R4~ and R represent further C 3 -C~alkinyl, which is unsubstituted or substituted by RI, R2, R 3 R4. and R 5 represent also a radical M-U or m-Q; R 1

L

and R 2 or R4. and R5 together with the nitrogen atom, to which they are *..:bound form a saturated or unsaturated heterocycle with 5 to 9 ring members which may include once or several times oxygen, sulfur, nitrogen,

-NCI-C

4 alkyl, -CO-or -C(0R 7 )0R 8 and which may be substituted by halogen, cyano, Cl-Csalkoxy, amino, CI-Ci~alkylamino, di-Cl-Ci.-alkylamino, 9O4P .or arcztk -COOR 6 R6 is hydrogen, CI-Csalkyl, C3-C~cycloalkyl, C 3 -C8alkenyl, C3-C~cycloalkenyl, C 3 -Caalkinyl, C 2 -Csalkoxyalkyl, C 3 -Csalkoxy- 0 0 alkoxyalkyl, C 1 -Ci~haloalkyl, -(Cl-C3alkylene) U, -(Cl-C3alkylene)

Q,

in m C-Ci~haioalkoxy; R 7 and Ra are independently of each other C-Ci~alkyl or

R

7 and R 8 form together a 2 to 4 membered alkylene chain, 0000 O.Jd U is phenyl or naphthyl, which is unsubstituted or substituted once or several times by halogen, Cl-Ci~alkyl, -Y-CI-Ci~alkyl, Ci-Ci~haloalkyl, CI-Ci~haloalkoxy, cyano, nitro, carboxyl, -COOR 7

-CONH

2

-CONHR

7

-CON(R

7 2

-SO

2

NHR

7

-SO

2

N(R

7 2 pyrrolidino, piperidino, pyrrolidinocarbonyl or piperidinocarbonyl; E is a CI-Caalkylene or C2-Csalkylene chain, which is unsubstituted or substituted by halogen, Cl-Ci~alkoxy, Cl-Ci~alkylthio, Cl-Ci~haloalkoxy or by aFest -CO(O) in, mNH 2 mNHR7, NR 7 R8, and which may be interrupted by -GO- or -C(0R 7

)ORB-;

FIFMM

-4- Q is a saturated or unsaturated heterocycle with 5 to 12 ring members which may contain 1 to 4 heteroatoms or 1 to 2 heteroatoms in combination with a sulfinyl or sulfonyl group or which may be interrupted by 1 to 2 carbonyl groups and which may be benzannelated and m is zero or 1.

Because of their herbicide-antagonistic activity the acid aoides corresponding to formula Ia are to be emphazised CF 3 R 1 (Ia) wherein the radicals R, and R 2 inde endently of each other are a Ca C! c- coo t hydrogen, CI-C 8 alkyl or G5C unsubsttu ted or substituted by halogen, cyano, Cl-Ct~alkoxy or -COORG; C2-C~alkenyl, unsubstituted by halogen, cyano, CI-Ci~alkoxy or -COOR 6 or C3-Cealkynyl, R2 Rmay also be-(E)mU or mQ, RI and R 2 together form also a 4- to 5-membered alkylene chain, which may be interrupted by oxygen, sulfur, -NH- or -NR 7 and/or substituted by a. E is CI-C~alkylene, C3-C4cycloalkylene, C2-C~alkenylene or C 2 -G4alkynylene, U is phenyl, unsubstituted or substituted by halogen, cyano, CI-Cz~alkyl, a Cl-C~+alkoxy, CI-Ci~haloalkyl, CI-C~haloalkoxy, COOR6, -SO 2

NH

2 -S0 2 11HR 7

-SO

2

N(R

7 2 -CONH2, -CONHR 7 or -CON(R 7 2 Q is a 5 to 6 membered heterocycle which is unsubstituted or substituted oaa by halogen, CI-Ci~alkyl, CI-Ci~alkoxy, Cl-C~+haloalkyl or CI-C~haloalkoxy and R6 and R 7 have the meaning given above.

The amides are especially active, wherein R, is hydrogen, C:-C 8 alkyl or C 3 -Cealkynyl and

R

2 is Cl-C 8 cyanoalkyl, C3-Cscyanocycloalkyl, C3-C~alkynyl, phenyl, halophenyl, Ci-Ct~alkylphenyl, Ci-C~alkylhalophenyl, phenylamino, halophenylamino or furyl, especially those wherein the radical -NRjR 2 is represented by N-methyl-N-( 1-cyanopentyl) amine or -N-methyl-N-( 2,6dichlorobenzyl) amine.

IV

/V1 1 II Another group of very active herbizid-antagonists is represented by the acid hydrazides of the formula Ib CF3- R 0 3 k4(Ib) wherein R 3 R4 and Rs independently of each other are hydrogen, C 1 -C8alkyl, C3-Cscycloalkyl, phenyl or benzyl, the phenyl ring being unsubstituted or substituted by halogen, Ci-C4alkyl, C 1 -C4haloalkyl, C 1 -C4alkoxy, C 1 -Cshaloalkoxy, -COORs, -CONH 2

-CONHR

7

-CON(R

7 2

-SONH

2

-SONHR

7

-SON(R

7 2 and R4 and Rs together can also form a 4 5 membered alkylene chain that may be interrupted by oxygen, sulfur, -NR 7 and/or substituted by

CI-C

4 alkyl.

When the compounds of formula I exist in optically isomeric forms, the S* present invention includes the optical isomers as well as racemic S mixtures as active ingredients.

In these definitions halogen by itself or as part of a definition, such as haloalkoxy, haloalkyl oc haloalkenyl includes fluorine, chlorine, bromine and iodine preferably fluorine, chlorine and bromine, especially chlvrine.

*a P~ Alkoxy rest include e.g. methoxy, ethoxy, n-propoxy, isopropoxy or the S isomeric forms of butyloxy, pentyloxy, heptyloxy or octyloxy, especially methoxy, ethoxy or isopropoxy.

Examples for unsubstituted substituents or parts of unsubstituted substituents are e.g. allyl, allyloxy, propynyl, propynyloxy, methallyl, methallyloxy, butenyl, butenyloxy, butynyl, butynyloxy, 3,3,3-trifluoro- 1-propenyl, 3,3,3-trifluoro-1-propynyl or 2,3-dichloropropen-1-yl.

Alkoxyalkylrests are represented by e.g. methoxymethyl, ethoxymethyl, methoxyethyl and ethoxyethyl, propoxyethyl, isopropoxyethyl, butoxyethyl, allyloxyethyl, especially by methoxyethyl.

6 -6- Haloalkyl in itself or as part of haloalkoxy or haloalkylthio stands as a rule for the radicals chloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, dichloromethyl, trichloromethyl, 2-chloroethyl, 2,2,2trifluoroethyl, 1,1,2,2-tetrafluoroethyl, pentafluoroethyl, 1,1,2-trifluoro-2-chloroethyl, 2,2,2,-trifluoro-2,2-dichloroethyl, pentachloroethyl, 3,3,3-trifluoropropyl, 2,3-dichloropropyl, 2,2,2-trichloroehtyl and 1-chloroethyl, especially chloromethyl, dichloromethyl, trichloromethyl and 1-chloroethyl.

In these definitions, the alkyl rests are understood to have 1 to 18 carbon atoms. They can be straight-chained or branched. The most usual rest are e.g. methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec.butyl, tert.butyl, n-pentyl, isopentyl, n-hexyl and n-octyl. The alkenyl and alkynyl rest can also be straight-chained or branched and contain 3 to 18 carbon atoms. The most used rest are e.g. allyl, S methallyl, butene, butadiene, propynyl, methylpropynyl, 1-butynyl and 2-butynyl. Cycloalkyl or cycloalkenyl rest have preferably 3 to 13 carbon 9 o* atoms and can also be benzannellated. Typical representatives are e.g.

cyclopropyl, cyclopentyl, cyclohexyl, cyclohexenyl, indan, tetrahydronaphthalin, decalin. Halogen stands for fluorine, chlorine, bromine and iodine atoms, especially fluorine and chlorine. Haloalkyl and haloalkenyl rests are mono- or polysubstituted with halogen atoms.

4, 94 4 The above-mentioned rest can be unsubstituted or substituted, typical substituents of such rests are halogen or alkyl, alkenyl, alkynyl, cycloalkyl, aryl or aralkyl rests which are bound via oxygen, sulfur or an imino group. The aryl rests can be substituted in turn. These rests can also be bound via a sulfinyl-, sulfonyl-, carbonyl-, carbonyloxy-, carbamoyl-, sulfamoyl- or an amino-oxy-bridge to the alicyclic hydrocarbon rest.

The substituent Q, as well as the rests RI and R 2 or R4 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 carbonyl groups and be benzannellated unsubstituted or substituted.

-7- Possible heteroatoms are in this context one, two or three additional nitrogen atoms, up to two oxygen or sulfur atoms,-whereby two oxygen atoms cannot be in vicinal position.

Examples for such heterocycles are listed below: pyrroline, pyrrolidine, imidazoline, imidazolidine, pyrazoline, pyrazolidine, isazoline, isazolidine, oxazoline, oxazolidine, isothiazolidine, thiazoline, thiazolidine, diathiazolidine, oxadiazolidine, piperidine, piperazine, tetrahydropyrimidine and pyrazine, morpholine, thiomorpholine, thiazine, hexahydrotriazine, tetrahydropyrazine, oxadiazine, oxatriazine, hexahydroazepine, hexahydrodiazepine, diazepine, hexahydrodiazepine, azacyclooctan, indoline, isoindoline, benzimidazoline, benzindazoline, benzoxazoline, benzthiazoline, benzisooxazoline, benzthiazole, tetrahydrochinoline, tetrahydroisochinoline, tetrahydrochinazoline, tetrahydrochinoxaline, tetrahydrophthalazine, benzomorpholine, benzothiomorpholine, tetrahydrobenzazepine, tetrahydrobenzdiazepine, tetrahydrobenzoxazepine, 1,5-diabicyclo[4.3.O1nonane, dihydrobenzoxazepine, 1,6-diabicyclo[5.3.O]decane, 1,4-diabicyclo- [3.3.O]octane, 1,5-diazabicyclo[4.4.O0decane.

The above heterocycles can also be substituents. Further examples of heterocyclic systems which may occur as substituents are e.g. pyrrole, s inidazole, pyrazole, isoxazole, thiazole, triazole, oxadiazole, thiadiazole, tetrazole, oxatriazole, thiatriazole, furan, tetrahydrofuran, dioxole, dioxolane, oxathiole, oxathiolane, thiophen, tetrahydrothiophen, dithiolan, dithiazole, pyridine, pyran, thiopyran, pyridazine, pyrimidine, pyrazine, tetrahydropyran, tetrahydrothiopyran, dioxin, dioxan, dithiin, dithian, oxazine, thiazine, oxathii,.-, oxathiane, 4;.4 triazine, oxadiazine, thiadiazine, oxathiazine, dioxazine, azepine, oxepin, thiepin, diazepine, oxazepine, indole, benzofuran, benzothiophen, indazole, benzimidazole, benzdioxol, benzdithiol, benzisoxazole, benzthiazole, benzoxazole, benzoxathiole, benztriazole, benzoxadiazole, benzofurazame, benzothiadiazole, quinolin, isoquinolin, chromene, chromane, isochromene, isochromane, thiochromene, isothiochromene, thiochromane, isothiochromane, cinnoline, chinazoline, chinoxaline, -8phtalazine, benzdioxin, benzdithiin, benzoxazine, benzdioxan, benzoxathiane, benzotriazine, benzazepine, benzdilazepine, benzoxazepine, purine, pteridine, phenoxazine, phenothiazine.

The heterocyclic rests can be substituted as mentioned above.

Some derivatives of the formula I are known from the published European patent application EP-A 279,239 and can be produced by known methods.

The thiazol derivatives of formula 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 formula III, according to the reaction scheme

F

3 C- CN--A' Cl--S-Cl

H

2 H S(III(Ic) I. 4 r 4, S The 2-oxo-4-trifluoromethyl-thiazol-5-carbonic acid derivative otained is U" heated with phcsphoroxychloride whereby 2-chloto-4-trifluoromethylacid derivative of the formula I is produced

F

3 F C- 'F POC1 3 (Ic) (I) S Acrylic acid derivatives of the formula II can be prepared according to a J. Het. Chem. 9 (1972) p 13 by condensing an acetoacetic ester with trifluoromethylnitril in a boiling solvent in the presence of sodium acetate, according to the reaction scheme

F

3 C-CN CH 3

-CH

2 -CA' Na- F3C-CHIA' NIH2

(II)

r3 a 9- 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: F3C-*- C+ amine F3C-

HA

~1 ~1 (Id) (I) In these formulae A and R 1 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: siCtr halohydrocarbons, especially'chlorohydrocarbons, such as tetrachlorost i t ethylene, tetrachloroethane, dichloropropane, methylene chloride, S dichlorobutane, chloroform, chloronaphthalene, dichloronaphthalene, i t1 S carbon tetrachloride, trichloroethane, trichloroethylene, pentachlorocr t ethane, difluo-obenzene, 1,2-dichloroethane, 1,1-dichloroethane, V 9 1,2-cis-dichloroethylene, chlorobenzene, fluorobenzene, bromobenzene, iodobenzene, dichlorobenzene, dibromobenzene, chlorotoluene and tri- S chlorobenzene; ethers, such as ethyl propyl ether, methyl tert.-butyl S ether, n-butyl ethyl ether, di-n-butyl ether, diisobutyl ether, diisoamyl t Ltt ether, diisopropyl ether, anisole, phenetole, cyclohexyl methyl ether, diethyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxan, thioanisole and dichlorodiethyl ether; nitrohydrocarbons, such as nitromethane, nitroethane, nitrobenzene, chloronitrobenzene and o-nitrotoluene; nitriles, such as acetonitrile, butyronitrile, isobutyronitrile, benzonitrile and m-chlorobenzonitrile; aliphatic or S cycloaliphatic hydrocarb6ns, such as heptane, pinane, nonane, cymol, petroleum fractions within a boiling range 7f from 700 to 190 0

C,

cyclohexane, methylcyclohexane, decaline, petroleum ether, hexane, ligroin, trimethylpentane, 2,3,3-trimethylpentane and octane- esters, such as ethyl acetate, ethyl acetoacetate and isobutyl acetate; amides, for example formamide, methylformamide and dimethylformamide.

I

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 formula I can be used, according to the desired application, for pretreating seeds of the culture plant (seed dressing and impregnation 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 the plants or the seed with the antidot can be done in principle independently of the application of the phytotoxic chemical substance.

T1,i treatment of the plant can also be done by simultaneous application of phytotoxic chemical substance and the antidote (tank-mixture). The pre-emergent treatment includes the application onto the cultivation area before sowing (ppi, pre plant incorporation) as well as the treatment of the sown cultivation area before emergence of the crop.

The amount of antidote of the formula I necessary to achieve the desired S" safening effect can vary to a large extent depending on the method and the moment 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 agrochemicals.

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 S* additionally those agrochemicals, form 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, I P)l: i

T

11 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-carboxamide of formula I have become known recently in large numbers. Form a multiplicity of publication devoted to the disclosure of herbicidally active sulfonyla urea-derivatives shall be cited as examples 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-derivatives are embraced by formula IV

E-(CH

2

)-SO

2 -NH-CO-N-- Y n S \N= wherein E is a group /Rll or S\ \s R 1 S-I *l II i -12n is zero or one, G is hydrogen or methyl, X is methoxy, ethoxy, difluoromethoxy or chlorine, Y nitrogen or methine Z is methyl, methoxy, difluoromethoxy, cyclopropyl or methylamino,

R

10 is C 2 -Csalkoxyalkoxy, Cl-C~haloalkoxy, Cl-C 4 haloalkylthio, C 2 -C4.haloalkenyl, chlorine or Cl-C~.alkoxycarbonyl,

R

11 is trifluoronethyl or di(CI-Ci.-alkyl)carbamoyl,

R

1 2 is Ci-Ckalkoxycarbonyl,

R

13 is Cl-G4alkoxycarbonyl and

R

1 4 is Cl-C4alkyl.

The following compounds are encompassed by the active substances of formula IV: N-(3-trifluoromethylpyridin-2-ylsulfonyl)-N'-(4,6-dimethoxypyrinidin- 2-yl) -urea, 3-dinethylcarbamoylpyridin-2-ylsulfonyl)-N'-(4,6-dinethoxy- ,7 pyrimidin-2-yl)-urea, N-(lI-methyl-4-ethoxycarbonylpyrazol-2-ylsulf onyl) 6-dimethoxypyrimidin-2-yl)-urea, N-(2-methoxycarbonylthien-3-ylsulfonyl)-N'-(4-methoxy-6-methyl-1 triazin-2-yl)-urea, N-(2-methoxycarbonylbenzylsulfonyl)-N'-(4,6-dimethoxypyrimidin-2-yl)urea, N-(2-methoxycarbonylphenylsulfonyl)-N'-(4,6-bis-difluormethoxypyrimidin-2-yl)-urea, N-(2-methoxycarbonylphenylsulfonyl)-N'-(4-ethoxy-6-methylamino-l triazin-2-yl)-urea, 2-nethoxycarbonylphenylsulfonyl) -(4-nethoxy-6-methyl- triazin-2-yl)-urea, 2-ethoxycarbonylphenylsulfonyl)-N'-(4-chlor-6-methoxypyrimidin- 2-yl)-urea, N-(2-nethoxycarbonylphenylsulfonyl)-N' -(4-methoxy-6-methyl-1 triazin-2-yl)-N' -methylurea, -13 N-(2-methoxycarbonylphenylsulfonyl)-N'-(4,6-dimethoxypyrimidin-2-yl)urea, N-(2-chlorophenylsulfonyl)-N'-(4-methoxy-6-methyl-1 ,3,5-triazin-2-yl)urea, N-12-(2-chloroethoxy)-phenylsulfonyl]-N'-(4-methoxy-6-methyl-1,3,5triazin-2-yl)-urea, and N-[2-(2--methoxyethoxy)-phenylsulfonyl]-N'-(4,6-dimethoxy-1 2-yl)-urea.

H-alogenacetanilides, whose phytotoxic effect on culture plants can be reduced or cancelled by the thiazol-5-carboxamides of formula I are also known in great numbers. They can be characterized by the following generic formula V: *tt*& t*t 4* 4~ \R16 wherein L is a CI-C4-alkylen bridge,

R

15

R

16 and R 17 independently of each other hydrogen, halogen, Cl-C4-alkyl, CI-C4-alkoxy, Cl-C4-haloalkyl, C 2

-C

5 alkoxyalkyl or C2-Cs-alkylthioalkyl, and

R

18 CI-C4--alkoxy, -COON, CI-C4-alkoxycarbonyl, -CONH 2 Cl-C4-alkylcarbanoyl, di-C 1 C-alkylcarbamoyl, cyano, Cl-C4-alkylcarbonyl, optionally substituted benzoyl, optionally substituted furyl, optionally substituted thienyl, optionally substituted pyrrolyl, optionally substituted pyrazolyl, optionally substituted 1, 3,4-oxadiazol-2-yl, opts )nally substituted 1,3,4-thiadiazol-2-yl, opt inally substituted 1,2,4-triazol-3-yl, optionally substituted dioxolanyl, optionally substituted dioxanyl, optionally substituted 1,3, 4 -triazol-2-yl or optionally substituted tetrahydrofuryl.

-14- The following chloroacetanilide derivatives are typical representatives of the active substances according to formula V: N-ethoxymethyl-N-chloroacetyl-2-ethyl-6-methylaniline, N-chloroacetyl-N-methoxymethyl-2 ,6-diethylaniline, N-chloroacetyl-N-( 2-inethoxyethyl) -2 ,6-dimethylaniline, N-chloroacetyl-N-(2-n-propoxyethyl)-2 ,6-dimethylaniline, N-chloroacetyl-N-(2--isopropoxyethyl)-2 ,6-dimethylaniline, N-chloroacetyl-N-(2-methoxyethyl)-2-ethyl-6-methylaniline, N-chloroacetyl-N-(methoxyethyl) 6-diethylaniline, 2-ethoxyethyl) -N-chloroacetyl-2-ethyl-6-methylaniline, N-chloroacetyl-N-( 2-methoxy-1 -methylethyl) -2-methylaniline, N-chloroacetyl-N-(2-methoxy-1-methylethyl)-2 ,6-dimethylaniline, N-chloroacetyl-N-(2-methoxy-l-methylethyl)-2 ,6-diethylaniline, S N-chloroacetyl-N-(2-methoxy-1-methylethyl)-2-ethyl-6-methylaniline, a* N-(2-ethoxyethyl)-N-chloroacetyl-2,6-diethylaniline, N-chloroacetyl-N-(2-n-propoxyethyl)-2-ethyl-6-methylaniline, 4at N-chloroacetyl-N-(2-n-propoxyethyl)-2,6-diethylaniline, CCC N-chloroacetyl-N-(2-isopropoxyethyl)-2-ethyl-6-methylaniline, N-ethoxycarbonylmethyl-N-chloroacetyl-2, 6-dimethylaniline N-ethoxycarbonylmethyl-N-chloroacetyl-2 ,6-diethylaniline ccC N-chloroacetyl-N-methoxycarbonylmethyl-2 ,6-dimethylaniline, a **4cty--22ditoytyl-,-ietyaiie g. N-chloroacetyl-N-(2,-detoxyehl-thylety)23mthylaniline, N-chloroacetyl-N-(2-methoxy-2-methylethyl)-2, 3-dimethylaniline, a 2-ethoxyethyle-N-loroa)-Nctl-2aetlety--methylaniline, N -chloroacetyl-N-(l2-ethy-ethoxy-2-ethyl26dtyaniline, N-chloroacetyl-N-(2-eoyethyl)-2ehyethy-,6-diethylaniline, N--uoymty1-blraey4*tr.btyaiie N-(2-ethoxy-2-methylethylet)-N-chloroacetyl-2h,6-dmetylaniline, N-chloroacetyl-N-(-2-metoxyetyl) -2-ehlory-6-methylaniline, N-n2-utoxyethyl-N-cloroacetyl-2-ero6-btylanli, Nl-(2-ethoxyehl2tyethyl)-N-chloroacetyl-2,3, 6-dimethylaniline, N-chloroacetyl-N-(-2-methoxyethyl)-2-chlotro-metylaniline, N-chloroacetyl-N-cyanomethyl-2 ,6-dimethylaniline, N-chloroacetyl-N-( 3-dioxolan-2-ylmethyl)-2 ,6-dimethylaniline, N-chloroacetyl-N-(1 ,3-dioxolan-2-ylmethyl)-2-ethyl-6-methylaniline, N-chloroacetyl-N-(1 ,3-dioxan-2-ylmethyl)-2-ethyl-6-methylaniline, N-chloroacetyl-N-(2-furylmethyl)-2,6-dimethylaniline, N-chloroacetyl-N-( 2-furylmethyl)-2-ethyl-6-methylaniline, N-chloroacetyl--N-(2-tetrahydrofurylmethyl)-2,6-dimethylaniline, N-chloroacetyl-N-(N,N-dimethylcarbamoylmethyl)-2 ,6-dimethylaniline, N-(n-butoxymethyl).-N-chloroacetyl-2 ,6-diethylaniline, 2-n-butoxyethyl) -N-chloroacetyl-2, 6-diethylaniline, N-chloroacetyl-N-(2-metoxy-1 ,2-dimethylethyl)-2 ,6-dimethylaniline, N-chloroacetyl-N-isopropyl-2, 3-dimethylaniline, N-chloroacetyl-N-isopropyl-2-chloroaniline, N-chloroacetyl-N--(1H--pyrazol-1-ylmethyl)-2 ,6-dimethylaniline, woo#.: N-chloroacetyl-N-(1H-pyrazol--1-ylmethyl)-2-ethyl-6-methylaniline, N-hooctlN*H1,,-rao- 4ehl)26dmtyaiie 44 N-chloroacetyl-N--(lH-1,2,4-triazol-1-ylmethyl)-2,6-dimethylaniline, N-benzoylmethyl-N-chloroacetyl-2, 6-diethylaniline, N-benzoylmethyl-N--chloroacetyl-2-ethyl-6-methylaniline, N-hoocty.-5mthl134oxdao0*y)26detyaiie N-chloroacetyl--N-(5-methyl-1 ,3,4-oxadiazol-2-yl)-2,-diyl-ethylaniline, N-chloroacetyl-N-(5-methyl-1,3,4-oxadiazol-2-yl)-2-ety-6rthylaniline, N-chloroacetyl-N-(4-chlorobenzoylmethyl)-2,6-dimethylaniline and N-chloroacetyl-N-(l-methyl-5-methylthio-1 ,3,4-triazol-2-ylmethyl)-2,6die thylaniline.

Further haloacetanilides, whose phytotoxic effect on culture plants is reduced or cancelled by the thiazol-5-carboxamides of formula I are disclosed in R. Wegler, Chemie der Pflanzenschutz- und Sch~dlingsbe- S k~mpfungsmittel, Vol. 8,.pages 90-93 and pages 322-327.

Aryloxyphenoxy-propionic acid herbicides, whose phytotoxic effect on culture plants is reduced or cancelled by the thiazol-5-carboxamides of formula I are known in great numbers. Such aryloxyphenoxypropionic acid derivatives can be characterised by the generic formula VI 16- H3

(VI)

H-CO-T

wherein Q is a radical RRi 9 *i /l

R

2 0\ 0N I ior R 2

NI

wherein T is

-NR

21

R

22

-N(GN)R

2 1, -OR 2 2

SR

2 2 or -0-N=CR 23

R

2 Rig is halogen or trifluoromethyl,

SR

2 0 is hydrogen or halogen,

R

21 and R2 2 independently of each other hydrogen, G 1 -Caalkoxy, CI-C~alkyl, phenyl or benzyl, R 21 and R 22 together with the nitrogen atom, to which they are bound also form a saturated 5- to 6-membered 0 nitrogen-heterocyclus, which may contain an oxygen or sulfur atom,

R

2 3 is Cl-CL~alkyl, C 3 -Ci~alkenyl, C 3 -Ci~alkynyl or C 2

-C

4 alkoxyalkyl R24. is hydrogen or the cation-equivalent of an alkali metal, an alkaline earth metal of copper or iron; of a quaternary Cl-C 4 alkylammonium 0 00 or Cl-C4-hydroxyalkylammonium radical; Cl-Cgalkyl unsubstituted or mono- or polysubstituted by amino, halogen, hydroxyl, cyano, nitro, 0 S phenyl, Cl-C4alkoxy, polyethoxy with 2 to 6 ethyleneoxy-units, -C00R 27 -COSR2 7

-CONH

2 -CON(C1-C4ralkoxy)-CI-C4-alkyl, -CQ-N-di-Cl-C 4 -alkyl, CONH-Ci--C4-alkyl, -N(CI-C 4 -alkoxy)-C1-C 4 -alkyl or di-C 1 -Ci.-alkylamino; C3Caknl nusiutdo usiue yhaoe rC0~loy C3-Cgalkenyl, unsubstituted or substituted by halogen or C 1 -C~.alkoxy; C3-Cgcycloalkylphenyl unsubstituted or substituted by cyano.

CI-Ci~alkyl, CI-Ci~alkoxy, acetyl, -COOR 2

COSR

27

-CON-

2 -CON(C1-CL.-alkoxy)-Gl-C 4 -alkyl, -CO-N-di-C 1 -C4-alkyl oder -CONH-Ca-CL.-alkyl;

R

2 s and R 26 are independently of each other CI-Ci~alkyl or together a 3to 6-membered alkylene chain and i: i i -17-

R

27 hydrogen, Ci-C 6 alkyl, Cl-Cshaloalkyl, Cz-C 6 alkoxyalkyl, C 3 -C6alkenyl,

C

3 -Cshaloalkenyl, C 3

-C

6 alkynyl or C 3 -Cshaloalkynyl.

Under the formula VI fall especially the following herbicidally active aryloxyphenoxypropionic acid derivatives: 2-[4-(3,5-dichloropyridin-2-yfoxy)-phenoxy]-propionic acid-propynyl ester, 2-[4-(3,5-dichloropyridin-2-yloxy)-pheno::y]-thiopropionic acid-propynyl ester, 2-[4-(5-chloro-3-fluorpyridin-2-yloxy)-phenoxy]-propionic acid-methyl ester, 2-[4-(5-chloro-3-fluorpyridin-2-yloxy)-phenoxy]-propionic acid-butyl ester, 2-[4-(5-trifluoromethylpyridin-2-yloxy)-phenoxy]-propionic acid-butyl ester, 2-[4-(5-trifluoromethylpyridin-2-yloxy)-phenoxy]-propionic acid-methylester, 2-[4-(6-chlorochinoxalin-2-yloxy)-phenoxy]-propionic acid-ethyl ester and 2-[4-(6-chlorobenzoxazolin-2-yloxy)-phenoxy]-propionic acid-ethyl ester.

The antidotes of the formula I are especially suitable for protecting cultivated plants from the phytotoxic effects of the herbicides of the formulae IV, V and VI.

Agrochemical compositions which contain in a common formulation the antidote of formula 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 formula I and one of the sulfonylureas of formula IV, the chloroacetanilides of formula V or the aryloxyphenoxy propionic acid derivatives of formula VI.

j. halophenylamino or furyl, especially those wherein the radical -NR 1

R

2 is represented by N-methyl-N-(l-cyanopentyl)amine or -N-methyl-N-(2,6dichlorobenzyl)amine.

I I 18 Unless it is used to dress seed, the amount varies between about 0.01 and about 5 parts of herbicide. The most suitable ratio based particular cultivated plant is determind on depending on the type of herbicide used.

of the counter-agent applied by weight per part by weight on optimum action on the a case by case basis, i.e.

The invention also relates to a process for selectively controlling weeds in crops of cultivated plants, whereby the crops of cultivated plants, parts of the cultivated plants or areas cultivated for cultivated plants are treated with a herbicide and the compound of the formula I or a composition containing this combination. The compositions containing the herbicide/antidote combination also form a part of the present invention.

The weeds to be controlled can be either monocotyledonous or dicotyledonous weeds.

Various methods and techniques are suitable for using the compound of the formula I or compositions containing it in order to protect cultivated plants against the harmful effects of agricultural chemicals, for example the following methods and techniques: i) Seed dressing *0 a) Dressing the seed with an active substance, formulated as a wettable powder, by shaking in a vessel until uniform distribution over the surface of the seed is achieved (dry dressing). In this procedure, about S 10 to 500 g of active substance of the formula I (40 g to 2 kg of wettable powder) are used per 100 kg of seed.

4.i, .7 S, A b) Dressing the seed with an emulsion concentrate of the active substance formula I by method a) (wet dressing).

c) Dressing by immersing the seed in a liquor containing 50 3,200 ppm of an active substance of the formula I for 1 to 72 hours and, if desired, subsequently drying the seed (immersion dressing).

i-?i r L i" Alkoxyalkylrests are represented by e.g. methoxymethyl, ethoxymethyl, methoxyethyl and ethoxyethyl, propoxyethyl, isopropoxyethyl, butoxyethyl, allyloxyethyl, especially by methoxyethyl.

19 Dressing the seed or treating the sprouted seedling are, of course, the preferred methods of application, because the treatment with active substance is directed entirely towards the target crop. As a rule, 10 g to 500 g, preferably 50 to 250 g, of active substance are used per 100 kg of seed, and, depending on the method employed, which also enables other active substances or micro-nutrients to be added, it is possible to exceed or to use less than the limiting concentrations indicated (repeat dressing).

ii) Application from a tank mixture A liquid formulation of a mixture of counter-agent and herbicide (ratio of the one to the other between 10:1 and 1:30) is used, the application rate of herbicide being 0.1 to 10 kg per hectare. A tank mixture of this type is preferably applied before or immediately after sowing or is worked 5 to 10 cm deep into the soil before sowing.

t t iii) Application to the seed furrow 1 The counter-agent is introduced, in the form of an emulsion concentrate, t wettable powder or granules, into the open, sown seed furrow and then, after the seed furrow has been covered in a normal manner, the herbicide is applied by the pre-emergence process.

iv) Controlled release of active substance A solution of the active substance is absorbed onto mineral granular carriers or polymerised granules (urea/formaldehyde) and is allowed to S dry. If desired, it is possible to apply a coating (coated granules) which enables the active substance to be released in a metered manner over a specific period of time.

The compound of the formula I is employed in an unaltered form or, preferably, together with the adjuncts conventionally used in the art of formulation and are, therefore, processed in a known manner to give, for example, emulsion concentrates, solutions which can be atomised or diluted without further treatment, dilute emulsions, wettable powders, soluble powders, dusts, granules and also encapsulations in, for example, polymeric substances. The application processes, such as atomising, I..1 -1 20 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 example 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 from Cs to C 1 2 for example 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 N-methyl-2-pyrrolidone, dimethyl sulfoxido or dimethylformamide, and epoxidised 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 calcite, talc, kaolin, montmorillonite or attapulgite. It is also possible to add highly S, disperse silica or highly disperse absorbent polymers in order to improve the physical properties. Suitable particulate, adsorptive granular carriers are porous types, for example pumice stone, broken brick, S sepiolite or bentonite, while examples of suitable non-sorptive carriers are calcite or sand. In addition, it is possible to use a large number of pregranulated materials of an inorganic or organic nature, such as, in particular, dolomite or comminuted plant residues.

Suitable surface-active compounds are nonionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties.

Surfactants are also to be understood as meaning mixtures of surfactants.

7 21 Suitable anionic surfactants can be so-called watersoluble soaps as well as water-soluble synthetic surface-active compounds.

Examples of soaps are the alkali metal salts, alkaline earth metal salts or substituted or unsubstituted ammonium salts of higher fatty acids

(C

10

-C

22 for example the Na or K salts of oleic or stearic acid, or of natural mixtures of fatty acids, which can be obtained, for example, from coconut oil or tallow oil. Furthermore, mention should also be made of the salts of fatty acid methyltaurides.

More 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 metal salts, alkaline earth metal 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 Na or Ca salt of ligninsulfonic acid, of dodecylsulfuric acid aster or of a mixture of fatty alcohol sulfates prepared from a.

natural fatty acids. Included under this heading are also the salts of a the sulfuric acid esters and sulfonic acids or fatty alcohol/ethylene S oxide acducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and a fatty acid radical having 8-22 C atoms. Examples of alkylarylsulfonates are the Na, Ca or triethanolamine salts of dodecylbenzenesulfonic acid, of dibutylnaphthalene- *a sulfonic acid or of a naphthalenesulfonic acid/formaldehyde condensation product.

Furthermore, corresponding 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 cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols; these derivatives can contain 3 to 30 glycol 22 ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to 18 carbon atoms in the alkyl radical of the alkylphenols.

Further suitable nonionic surfactants are the watersoluble 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 compounds usually contain 1 to 5 ethylene glycol units per unit of propylene glycol.

Examples of nonionic surfactants which may be mentioned are nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.

*Furthermore, fatty acid esters of polyoxyethylenesorbitan, such as polyoxyethylenesorbitan trioleate, are also suitable.

e 4

O

S 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 substituents, lower, halogenated or unhalogenated alkyl radicals, benzyl radicals or lower hydroxyalkyl radicals. The salts are preferably in the form of halides, methylsulfates S or ethylsulfates, for example stearyltrimethylammoniumchloride or benzyldi-(2-chloroethyl)ethylammonium bromide.

94 The surfactants which are conventional in the art of formulation are described, inter alia, in the following publications: S "McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., Ridgewood, New Jersey, 1981; H. Stache, "Tensid-Taschenbuch" ("Surfactants Manual"), 2nd edition, C. E .er Verlag, Munich, Vienna, 1981; M. and J. Ash, "Encyclopedia of Surfactants", vol. I-III, Chemical Publishing Co., New York, 1980-1981.

I ,d ,-LMImIIY.iypencane ana octane: esters, such as ethyl acetate, ethyl acetoacetate and isobutyl acetate; amides, for example formamide, methylformamide and dimethylformamide.

i.

1.1: .aal~« i iisif~fi 23 The agrochemical preparations contain, as a rule, 0.1 to 95 in particular 0.1 to 80 of active substance, 1 to 99.9 of a solid or liquid adjuvant and 0 to 25 in particular 0.1 to 25 of a surfactant.

In particular, the composition per cent by weight) Emulsifiable concentrates Active substance: Surface-active agent: Liquid carrier: Dusts: Active substance: Solid carrier: of preferred formulations is as follows: 1 to 20 preferably 5 to 5 to 30 preferably 10 to 50 to 94 preferably 70 to 0.1 to 10 preferably 0.1 99.9 to 90 preferably 99.9 10 20 85 to 1 to 99 Suspension concentrates: Active substance: SWater: Surface active agent: 0 Wettable powders Active substance: Surface-active agent: Solid carrier: 0 Granules Active substance: Solid carrier: 5 to 75 preferably 10 to 94 to 25 preferably 90 to 1 to 40 preferably 2 to 0.5 to 90 preferably 1 to 80 0.5 to 20 preferably 1 to 15 5 to 95 preferably 15 to 90 0.5 to 30 preferably 3 to 15 99.5 to 70 preferably 97 to 85 0 Whereas concentrated compositions are more likely to be preferred as commercial products, the final consumer as a rule uses dilute compositions. The application forms can be diluted down to 0,001 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.

4 1, Si 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, i "i i 24 The compositions can also contain further adjuvants, such as stabilisers, anti-foaming agents, viscosity regulators, binders, tackifiers and fertilisers or other active substances for achieving special effects.

The following examples serve to explain further the invention, without limiting it. Temperatures are given in these examples and in the following tables in degrees centigrade, OC, the pressures are given in millibar (mbar), indication of percent or parts relate to weight.

Example 1: Preparation of carbamoyl]-3-trifluoromethyl-thiazol CF3-* \CN N H 3 81 To a solution of 112.5 g of 2-chloro-4-trifluoromethyl-thiazol-5carbonic acid chloride in 200 ml of acetonitrile is added dropwise at 00 Sc temperature, while stirring, a mixture of 55.9 g of 1-cyano-l-methyl- S amino-cyclopentene (0.45 mole) and 46.0 g of triethylamine (0.45 mole).

Ammonium hydrochloride precipitates during this addition. The suspension is stirred overnight at room temperature and then poured while stirring into 2 litres of water. The oil that separates is extruded with ethyl acetale, dried over sodium 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. Melting point 134 1360: Yield 125 g (83 of the theory).

According to this example, the thiazol-5-carboxamides listed in Table 1 are obtained.

*I

ii "4

Q

25 Table 1 CF3- CO-N/ (Id) 1.001 1.002 1.003 1.004 1.005 1.006 1.007 1.008 1.009 1.010 1.011 1.012 1.013 1.014 1.015 1.01 1.016 1.018 1.019 1.020 1.021 1.022 1.023 1.024 1.025 1.026 1.027 1.028 1.029 v. 1.030 1.031 1.032 1.033 1.034 1.035 1.036 S1.037 1.03 1.038 1.039 1.040 1.041 1.043 1.043 allyl allyl allyl 2-methyl-2-propen-1 -yl 2-methyl-2-propen-1-yl 2-chloro-2-propen-1 -yl 2-chloro-2-propen-1 -yl 2-chloro-2-propen-1 -yl 2-chloro-2-propen-1 -yl 3-chloro-2-propen-1 -yl propyl methyl methyl methyl isopropyl isopropyl

H

H

methyl methyl ethyl ethyl

H

methyl isopropyl cyclopropyl ethyl allyl cyclohexyl phenyl phenyl cyclohexyl 2,6-dime thyl-phenyl phenyl phenyl 4-chlo ro-phenyl 2,4-dichlorophenyl 3, 4-dichlorophenyl 3-t rif luorome thyl-phemyl methyl

H

py~crolidino piperidino 2-me thylpipe ridino allyl 2-methoxy-ethyl isopropyl isopropyl cyclohexyl 2-methoxy-ethyl isopropyl cyclohexyl 2-chloro-2-propen- 1 -yl propyl 2-me thoxy-e thyl cyclohexyl benzyl 2 ,6-dichloro-benzyl benzyl 4-chlorobenzyl benzyl phenyl phenyl 4-chlorophenyl physical. data mp. 38 mp. 70 *.720 mp. 38 -400 n 20 1.5408

D

mp. 118 1200 n 20 1.5333

D

102 137 57 1050 138 590 2- chloro -4-brom-phenyl 3-t rifluoromethyl-phenyl

-CH

2

-COOO

2

-CH

2

-COOCH

3

-CH

2

-CO-NH-C

3

H

7 (i)

-CH

2

-CO-N(C

2

H

5 2

-CH

2

-CH

2

-CN

-CH

2

-CH

2

-CN

-CH

2

-CH

2

-CN

-CH

2

-CH

2

-CN

-OH

2

-OH

2

-COOH

-CH

2

-CH

2

-COOCH

3 nip. 116 1200

-CH(CH

3

)COOCH

3 mp. 120 1230

-CH

2

-COOH

-OH

2

-ON

-CHz -ON

-OH

2

-ON

-CH

2 -CN mp. 128 1310

-OH

2

-ON

1-cyanocyclopent-1-yl nip. 130 1330 3-trifluoromethyl-cyclohexyl -26- Nr. R R 2 physical data 1.1.

.4.4.4 4 4**9 9 4 4 9~ .4 .4 4 9 4 9 4*449S R9 *4 4 4 .444,4 4 9404 o 9 4 *4 4 444 1 .045 1 .046 1 .047 1 .048 1 .049 1 .050 1 .051 1 .052 1 .053 1 .054 1 .055 1 .056 1 .057 1 .058 1 .059 1 .060 1 .061 1 .062 1 .063 1 .064 1 .065 1 .066 1 .067 1 .068 1 .069 1 .070 1 .071 1 .072 1 .073 1 .074 1 .075 1 .076 2-ethylpiperidino hexahydroazepi no morphol ino 2,2,5,5-tetramethyl 1,3-oxazo1idin-3-y1 5,5-dimethyl-2,2-tetra-methylen-1,3-oxazolidin-3-yI 5,5-dimethyl-2,2-pentaiethylen-i ,3-oxazolidin-3-yl 2-phenyl-1 ,3-oxazolidln-3-yl 2,2-tetraniethylen-benzthl azol-3-yl 2-oxo-pyrrol idl no hexahydro-2-oxo-azepl no 3-oxo-thlomorphol ino 2-oxo-1 ,3-oxazoli1n-3-yl 2-trichloromethyl-1 ,3-oxazolidin-3-yl H 2-chlorobenzyl mp. 115 -1160 H 2-hexyl benzyl allyl phenyl ethyl C 2

H

2-chlorobenzyl propargyl,, c4 F,9 allyl -CH 2 -CH(CH 3 2 4-chloro-2-fl uoro-6-i sopropoxyphenyl cyano-di methyl methyl chiorphenyl cyano-di methyl -methyl 2,2-dimethyl indanyl 3,5-.bi s-trifluoromethylphenyl dl phenylmethyl 2, 6-difi uorophenyl 5-trifi uoromethyl -thi azol 2-y 1

H

H

2 ,6-di ch Iorobenzyl

H

propargy 1 2,6-di chlorobenzyl ethoxycroton-2-y 1 2-chioral lyl

H

methoxyethyl

H

mp.

mp.

mp.

mp.

mp.

n20 nD mp.

n20 nD mp.

mp.

mp.

56 580 88 890 89 910 115 1160 100 1010 1 .5491 72 740 1.5027 123 1250 130 1320 125 1260 mp. 174 1750 ,1270 1790 161

H

triethylanimonlum salt mp. 136 1380 :1 148y 27 Nr. nhuciral rlaf;3 Nr.

.077 .078 .079 .080 .081 .082 .083 .084 .085 .086 .087 .088 .089 2-carboxyl -4-chi orphenyl 3-trifi voromethyl cyclohexyl 2,4,6-trichioranilino furfuryl 3,4-methyl endioxybenzyl 4-ami dosulfonyl phenyl 1 ,2-diphenyleth-l-yl ax-methyl benzyl 4-fl uorobenzyl 2,2-diphenyl eth-1-yl 1 -cyano-cyci opent-l -yl 1 -cyano-cyclohex-1-y1 2-methoxycarbonyl -4chiorophenyl 2-methyl ami nocarbonyl 4-chlorophenyl 2-di methyl ami no l-cyanocyclopent-1-yl cyano-di methyl -methyl

H

H

H

H

H

H

H

H

H

H

methoxycarbonyl methyl methyl

H

H

H

CH 3 CH 3 1340 1090 1860 1020 1310 1890 1480 1330 1300 1290 1470 1470 000000 0 0000 0 00 4~ 0 *0 00 00 0 *00000 00 *0 0 0 0 0 1 .090 .091 .092 .093 mp. 78 800 Example 2: Preparation of 2-chloro-4-trifluoromethyl-thiazol-5-carbonic acid-N'-(2.4.6-trichloro-phenyl)-hydrazide 000*~~b 0 0000 00 00 0 0 000000 0 C1\_

CO-NH-NH-*

CF

3 k C1 00 0 0 O 0-0 A solution of 9.3g 2-chloro-4-trifluoromethyl-thiazol-5-carbonic acid chloride (0.037 mole) in 50m1 of acetonitrile is prepared. While stirring it at 00 there is added thereto dropwise another solution of 8.3g of 2,4,6-trichloro-phenylhydrazine 95%. (0.037 mole) and 3.8g triethylamine (0.037 mole) in 50 ml of acetonitrile. A suspension forms, which is :XW:ll 48y ~1 N-chloroacety.-N.Q..2-methoxyethl)- 2 -hoo6-mtyaii

N-(

2 -ethoxyethy >.N..rochioroa 2 -hi 6 -mtyaii Ul-( 2 -ethoxyethyl) N-chloroacetyl-2,3, 6 trimethyianiline, N-cioroacetyl-l..(2methoxyethyl)- 2 6 -trimethylaniline, uI~ 27A stirred overnight, then poured into 1 litre of water. The reaction-mixture crystallizes. The crystals are filtered off and recrystallized in ethanol. Melting point 184 1860, yield 7.2g of the theory).

In a manner analogous to this example, the thiazol-5-carbonic acid hydrazides listed in Table 2 are obtained.

0 *0000* o *000 04 0 0 *0 0* 0 0 0 00 0*000* 0 0* 00 0 0 0 0 *0*000 0 0 00*0 0 0 *0 0 0 0,00000 *0 0 0 *00 SKXW: 1148y 3U AItT us uw i.laimns is reaucea or cancelled by the thiazol-b-carboxamides ot formula I are known in great numbers. Such aryloxyphenoxypropionic acid derivatives can be characterised by the generic formula VI 1 ON-- 11 I. 1 MW AWM ~I 28 Table 2

CF

3 U4 phys. data 2.001 H H H 2.002 H CH 3

CH

3 2.003 CH 3 H CH 3 2.004 H H phenyl 2.005 H H CO phenyl 2.006 H H SOz phenyl 2.007 H H 2-chlorophenyl 2.008 H H 4-chlorophenyl 2.009 H H 2,4,6-trichlorphenyl Formulation Examples for active ingredients of m.p. 137-1380 m.p. 192-1940 m.p. 184-1860 the formula I or mixtures thereof with herbicides per cent by weight) a 6 Example 3: Wettable powders active ingredient from the Tables 1-2 or mixture with herbicide sodium lignosulphonate sodium lauryl sulphate sodium diisobutylnaphthalenesulphonate octylphenolpolyethylene glycol ether (7-8 mol ethylene oxide) 94 highly dispersed silicic acid S kaolin sodium chloride a) b) 0.5 5 6 2 27 59.5 4 9 The active ingredient is mixed well with the adjuvants and ground well in a suitable mill. Wettable powders are obtained that can be diluted with water to give suspensions of any desired concentration.

I$

iJ ie% 1 29 Example 4: Emulsifiable concentrate a) b) active ingredient from the Tables 1-2 or mixture with a herbicide 10 1 octylphenolpolyethylene glycol ether mol ethylene oxide) 3 3 calcium dodecylbenzenesulphonate 3 3 castor oil polyglycol ether mol of ethylene oxide) 4 4 cyclohexanone 30 10 xylene mixture 50 79 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 1 talcum 99.9 kaolin 99 B* S Dusts that are ready for use are obtained by mixing the active ingredient Swith the carriers and grinding in a suitable mill.

Example 6z Extruder granulate a) b) i* active ingredient from the Tables 1-2 or mixture with herbicide of formula V 10 1 sodium lignosulphonate 2 2 S carboxymethylcellulose 1 1 kaolin 87 96 The active ingredient is mixed with the adjuvants, ground and moistened Uu: with water. This mixture is extruded and then dried in a stream of air.

0

I

Example 7: Coated granulate active ingredient from the Tables 1-2 or mixture with a herbicide 3 polyethylene glycol (MW 200) 3 kaolin 94 (MW molecular weight) 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 40 5 ethylene glycol 10 10 nonylphenolpolyethylene glycol ether (15 mol of ethylene oxide) 6 1 Ssodium lignosulphonate 10 5 Scarboxymethylcellulose 1 1 37 aqueous formaldehyde S solution 0.2 0.2 silicone oil in the form of S* S a 75 aqueous emulsion 0.8 0.8 water 32 77 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 6uo active ingredient from Tables 1-2 or mixture with a herbicide of formula IV 5 isopropylamine 1 octylphenolpolyethylenglykol ether (78 mol of ethylene oxide) 3 water 91 of an active substance of the formula I for 1 to 72 hours and, if desired, subsequently drying the seed (immersion dressing).

1

P

n.,.II 31 Biological Examples The following examples 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 formula 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 protection) serve thereby as references.

*4 C S The tested compounds reduced the phytotoxic effect of the herbicide to a t degree, which does not influence the yield of the harvest.

i c Example 11: Test with water-sown rice. Antidote and herbicide are applied pre-emergent as tank-mixture.

4 4 The rice-seeds are pre-soaked during 44 hours in 30 0 C warm water.

S.

I' Plastic containers of 500 ml volume are filled with sandy loam to 2 cm below the upper rim. The herbicide N-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 tank-mixture onto the surface of the soil.

The pre-soaked rice-seeds are then sown onto the swampy surface of the soil.

example, emulsion concentrates, solutions which can be atomised or diluted without further treatment, dilute emulsions, wettable powders, 1 soluble powders, dusts, granules and also encapsulations in, for example, polymeric substances. The application processes, such as atomising, 32 The earth is maintained 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 No. protective action (test without antidote) 0 1.07n 3s 1.080 38 1.08 50 1.093 38 h h Example 12: Test with maYze. The herbicide and the antidote are applied pre-emergent as tank-mixture.

t In order to evaluate the safening activity, seed of maze 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 S light for optimal growth. The plants are fertilized and watered according to their need.

S 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-methoxy-1-methylethyl)-N-chloroacetyl-2-ethyl-6-methylaniline was applied in an amount of 8 kg/ha. The substance to be tested as antidote was added in an application rate 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 phyto no damage growth like untreated control plants; 100 phyto total damage, loss of plant). The difference of the damage on plants, which have been treated with the ,diff t Examplrene of12: Test with damaizge on plants, whThe herbicide and the antidoeate are applied i_ Suitable surface-active compounds are nonionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties.

Surfactants are also to be understood as meaning mixtures of surfactants.

ww V

I~

-33 herbicide alone and those, which have been treated with the combination herbicide and safener gives the amount of protective action, which is indicated in in Table 4.

Table 4 antidote No.

protective action 1.014 37.5 1.017 62.5 1.040 62.5 1.080 37.5 1.084- 62.5 1.088 37.5 1.093 25 Example 13: Test with sorghum and maize. The herbicide and antidote are applied pre-emergent 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 temperature for Soptimal growth. The plants are watered and fertilized according to their a, 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.

f As herbicide N-(2-methoxy-l-methylethyl)-N-chloroacetyl-2-ethyl-6-methyl- I*t, aniline, "metolachlor" and N-(isopropyl)-N-chloroacetyl-3,3,5-trimethyl-cyclohex-1-enamid, "trimexachlor" 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.

4P4 a In order to evaluate the protective action, the general damage (phytotox) done to the plants is assessed in percent (0 phyto no damage, plant grows like untreated plant; 100 phyto total damage). The difference in Suitable nonionic surfactants are primarily polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols; these derivatives can contain 3 to 30 glycol 4 34 the damage rating of plants treated with the herbicide alone and plants treated with the combination of herbicide and safener is calculated and given as protective action in table Table antidote application No. rate herbicide No. application protective action plant rate 1.040 1000 g/ha 1.040 1000 g/ha 1.040 1.040 250 g/ha 250 g/ha 1000 g/ha 1000 g/ha 1000 g/ha 1000 g/ha 1000 g/ha 1000 g/ha 1000 g/ha 1000 g/ha

S(

t Si Sr t£ 4 Si t 'I .it I 1.040 1000 g/ha 1.040 1000 g/ha 1.040 250 g/ha 1.040 250 g/ha 1.040 8000 g/ha 1.040 8000 g/ha 1.040 2000 g/ha 1.040 2000 g/ha 1.040 8000 g/ha 1 040 8000 g/ha 1.040 2000 g/ha 1.040 2000 g/ha sorghum Echinochloa sorghum Echinochloa sorghum Echinochloa sorghum Echinochloa maize Echinochloa maize Echinochloa maize Echinochloa maize Echinochloa 8000 g/ha 8000 g/ha 8000 g/ha 8000 g/ha 35 0% 10 0% 40 0% 20 0% 70 0% 60 0% 40 0% 35 0% 8000 g/ha 8000 g/ha 8000 g/ha 8000 g/ha Example 14: Test with sorghum. The herbicide and antidote are applied pre-emergent as tank-mixture.

In oder to evaluate the safening activity, seeds of sorghum (millet of the variety Funk G-623) 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 watered and fertilized according to their need.

4

.I

35 The herbicide and the substance to be tested as safener were applied pre-emergent together as tank-mixture using 550 1 of water per hectare. As herbicide N-(2-methoxy-l-methylethyl)-N-chloroacetyl-2-ethyl-6-methylaniline (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 phyto no damage, plant grows like untreated control plant.

100 phyto total damage). The difference of the damage done to plants treated with the herbicide alone and to plants, treated with the combination of herbicide ,nd antidote is calculated and given in table 6 as protective action.

Table 6 antidote No. protective action

C

1.014 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-emergent immediately after sowing.

t I t In order to evaluate the safening activity seed of rice (of the Str variety S-201) are pre-soaked in an aqueous solution of the compound to be E tested as safener, during 48 hours. The incubation time of the seed before sowing is 24 hours. The herbicide is applied pre-emergent, by spraying onto the surface of the sown area.

CCEC

CII '(A 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 amount of water corresponding to 550 1 per hectare pre-emergent immediately after sowing onto the pre-soaked seed. The 3 ~1

II

-36 following herbicides were used: N-(n-propoxyethyl)-N-chloroacetyl-2,6diethylanilide, pretilachlor and N-(2-methoxyethylphenyls:,lfonyl)- 4 ,6-dimethoxy-l,3,5-triazin-2-yl)-urea The substance to be tested as antidote was applied in the given concentration during seed-soaking.

In order to evaluate the protective action, the general damage (phytotox) done to the plants was assessed 26 days after the treatment and expressed in percent (0 phyto no damage, like untreated control l.ant; 100 phyto total damage). The difference of the damage 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 4 .4,4 4

CI

a 9 I 9 4 9* 1.014 100 ppm 250 g/ha 37.5 1.017 100 ppm 250 g/ha 37.5 1.018 100 ppm 250 g/ha 62.5 1.040 100 ppm 250 g/ha 37.5 1.064- 100 ppm 250 g/ha 62.5 1.040 150 ppm 30 g/ha 45 1.040 300 ppm 30 g/ha 55 Example 16: Test with rice. The antidote and herbicide are applied pre-emergent as tank-mixture.

In order to evaluate the safening activity, seeds of rice are raised in earth in pots of 9 cm diameter. The plants are cultivated in a greenhouse under adapted conditions of temperature and light for optimal growth.

Watering and fertilizing occurs according to need.

The substance to be tested as safener and the herbicide are applied together as tank mixture pre-emergent with an amount of water corresponding to 550 1 per hectare. As herbicides N-(2-methoxy-l-methylethyl)- N-chloroacetyl-2-ethyl-6-methylanilide, metolachlor and N-(2-methoxyethylphenylsulfonyl)-N'-(4,6-dimethoxy-l,3,5-triazin-2-yl)-urea are i- ^.3Sto 37 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 and 30-60 g/ha for herbizide 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 phyto no damage, as untreated control plant; 100 phyto total damage). The difference in damage rating between plants treated with the herbicide alone and of plants treated with 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 375 g/ha "Starbonnet" 25 1.040 1500 g/ha 375 g/ha "Starbonnet" 12.5 1.040 60 g/ha 30 g/ha S-201 50 1.040 30 g/ha 30 g/ha S-201 35 4: 4 4+ 46 S C Cs Example 17: Test with different varieties of rice and with weeds. The antidote and herbicide are applied together as tank-mixture post-emergent.

8 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 were cultivated S in the greenhouse under adapted conditions of temperature and light for optimal growth. Watering and fertilizing occured according to need. The weeds Echinochloa, Rottboellia and Digitaria are raised in the same manner.

a* The substance to be tested as safener and the herbicide were applied together as tank-mixture, with an amount of water corresponding to 550 1 per hectare post-emergent. As herbicides N-(2-methoxyethylphenylsulfonyl)-N'-( 4 ,6-dimethoxy-1,3,5-triazin-2-yl)-urea and the 2R enantiomer of the propinyl ester of 2-[ 4 -(5-chloro-3-fluoropyridin-2- 1.040 1.041 1.042 1.043 1.044 j- methyl 1-cyanocyclopent-l-yl mp. 130 133° H 3-trifluoromethyl-cyclohexyl pyrrolidino piperidino 2-methylpiperidino a "1 lc" r i 38 yloxy)-phenoxy]-propionic acid 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 phyto total danage). The difference of the damage done to the plants treated with the herbicide alone and to plants, treated with the combination herbicide and ant-dote is calculated and given in Table 9.

Table 9 plant herbicide No. application rate antidote No. application rate protective action ft (af f ft f ft ft oft ft ft ft.

ft...

ii.

ft, ft*V t ft ft rice "S-201" rice "S-201" 30 30 rice rice rice rice rice rice rice rice rice rice rice rice rice rice "New Bonet" "New Bonet" "Balilla" "Balilla" "Jung Weon" "Jung Weon" "PB-56" "PB-56" "IR-54" "IR-54" "Yamabiko" "Yamabiko" "Starbonet" "Starbonet" g/ha g/ha g/ha g/ha g/ha g/ha g/ha g/ha g/ha g/ha g/ha g/ha g/ha g/ha g/ha g/ha g/ha g/ha g/ha g/ha 1.040 60 1.040 30 1.040 1.040 1.040 1.040 1.040 1.040 1.040 1.040 1.040 1.040 1.040 1.040 1.040 1.040 g/ha g/ha g/ha g/ha g/ha g/ha g/ha g/ha g/ha g/ha g/ha g/ha g/ha g/ha g/ha g/ha 55 60 Digitaria sanguinalis Digitaria sanguinalis Rottboellia exaltata Rottboellia exaltata Echinochloa crus galli Echinochloa crus galli 1.040 120 g/ha 1.040 30 g/ha 1.040 120 g/ha 1.040 30 g/ha 0% 0% 0% 0% 0% 0% 60 g/ha 1.040 120 g/ha 60 g/ha 1.040 30 g/ha 2-yi H mp. 136 138* triethylammonium salt r A W:1148y i I "r 0 i L 39 Example 18: Test with rice and maize. The antidote is applied by seed-dre'sing, the herbicide pre-emergent onto the sown area.

In order to evaluate the safening acitvity, seeds of rice of the variety "Starbonet" and maYze seed of the variety "Blizzard" are brought together with antidote No. 1.040 in a glass-container and mixed well by shaking and rotating. The seeds are then raised in earth in pots of 11 cm diameter.

The plants are 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 immediately after sowing in an amount of water corresponding to 550 1 per hectare. As herbicides were sprayed N-(n-propoxyethyl)-N-chloroacetyl-2,6-diethylaniline, pretilachlor N-(isopropyl)-N-chloroacetyl-3,3,5-trimethyl-cyclohex-1-enamid, trimexar chlor and N-(2-methoxyethylphenylsulfonyl)-N'-(4,6-dimethoxy-1,3,5- 4 triazin-2-yl)-urea and N-(methoxymethyl-N-chloroacetyl-2,6-diethylanilin, alachlor in the given application rate.

ft In order to evaluate the protective action, the general damage (phytotox) done to the plants was assessed 25 days after treatment with the herbicide in percent (0 phyto no damage, plant grows like untreated control; 100 phyto total damage). The difference in the damage rating of plants S treated with the herbicide alone and plants, treated with the combination of safener and herbicide is calculated in percent and expressed as protective action expressed in Table 04 o4 a r t

I

I

o aeeradhriie scluae i ecn n epesda prtctv cto xpesd nTbl 0 40 Table antidote application herbicide protective No. rate No. application action rate 1.040 0,5 g/kg rice 1 kg/ha 45 1.040 0,25 g/kg rice 1 kg/ha 40 1.040 0,5 g/kg rice 0,5 kg/ha 40 1.040 0,25 g/kg rice 0,5 kg/ha 35 1.040 0,5 g/kg rice 1 kg/ha 50 1.040 0,25 g/kg rice 1 kg/ha 45 1.040 1 g/kg maize 30 g/ha 45 Example 19: Test with maize. The antidote is applied by seed-dressing, the herbicide is sprayed post-emergent onto the plants.

S In order to evaluate .iie safening activity, maize seed of the variety "Blizzard" are put together with antidote No. 1.040 in a glass container t r and thoroughly mixed by shaking and rotating. The seeds are then raised in "ci earth pots of 11 cm 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 S corresponding to 550 1 of water per hectare. As herbicide N-(2-methoxyethylphenylsulfonyl)-N'-(4,6-dimethoxy-l,3,5-triazin-2-yl)urea was sprayed onto the maize plants, when they had reached the 2-3 leaf stage.

et Ct S 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 phyto no damage, plant grows like untreated control plant; 100 phyto total damage). The difference in S the damage rating between the plants treated with the herbicide alone and those treated ;ith the combination of herbicide and antidote is calculated and given in Table 11 as protective action.

I iI

U

41 Table 11 antidote No.

rapplication rate herbicide No.

application rate protective action 1.040 1 g/kg maize 30 g/ha Example 2Q: The herbicidal properties of herbicide and safener combinations of safeners claimed in the present application and of a compound of similar chemical structure, known from the UK Patent No. 2 020 662 were investigated.

The following compounds were tested: ct t tl t

L

C' r ii

C

2P--R

CFRI

reference 1.014 1.017 1.018 1.040 1.064 1.080 1.084 1.088 1.093

CH

3

H

H

CH

3

CH

2

C=CH

H

H

CH

3

CH

3 2,6-dichlorobenzyl benzyl phenyl 1-cyanocyclopent-l-yl

CH

2

C-CH

furfuryl phenyleth-1-yl l-cyanocyclohex-1-yl l-cyano-isopropyl this this this this this this this this this application application application application application application application application application

CF

3

-N(C

2

H

5 2 C i known from GB-A 2 020 662 11 Rf4 XW:1148y A -z 6-v= upiiLuns or any desired concentration.

Li 41A The herbicide used as N-(n-propoxyethy1)-N-chloroacetyl-2,6-diethylanilide of the formula CzHs These substances, as well as the herbicide were worked up to a wettable powder of the following composition: substance to be tested sodium lignosulfate sodium lauryl sulfate 3% c, highly dispersed silicic acid Kaolin 62% SThe active substance is mixed well with the adjuvants and ground well S in a mill. The obtained wettable powders are then diluted with water until the concentration of active substance desired was achieved.

The test was conducted in the greenhouse as follows: Test with wet-sown rice. Rice seeds are presoaked in water for 24 hours and then sown onto the swampy surface of the soil (sandy loam) in plastic containers (surface 4x9cm; volume 500ml). The herbicide N-chloroacetyl-N-(2-propoxyethyl)-2,6-diethylaniline at a concentration of 500 and O00g active substance per hectare and the substance to be tested as safener in concentrations of 125, 250 and 500, respectively 250, 500 and O00Og active substance per hectare are sprayed together as tank-mixture onto the surface of the soil.

The soil is maintained in a humid state and the water-level is raised according to the growth of the rice plants. The injury to the plants is i evaluated 21 days after the application of the test-substances and recorded in percent. As reference for the evaluation of the protective action serve plants, which have been treated with the herbicide alone and plants, which have not been treated and have suffered no damage. The protective action is the difference 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 the Table below: S LR XW:1148y Ir .0 -41Bcompound tested herbicide amount crop niurv protective action amouint .014 014 .014 .014 .014 .014 1000 500 250 500 250 125 0 00000* 0 0.000 0 00 o 0 00 0 t~ 0 0 0 0 0 00 0 0 0 000000 0 0 00 00 0 0 0 0 0 0 0080*0 0 0 o~o 0 00 08 0 0 0 1 .017 1 .017 1.017 1.017 1 .017 1.017 1 .018 1.018 1 .018 1.018 1 .018 1 .018 1 .040 1 .040 1 .040 1 .040 1 .040 1 .040 1000 500 250 1000 giha 1000 g/ha 1000 g/ha 1000 500 g/ha 500 g/ha 500 g/ha 500 1000 g/ha 1000 g/ha 1000 giha 1000 500 g/ha 500 g/ha 500 g/ha 500 1000 g/ha 1000 g/ha 1000 g/ha 1000 500 g/ha 500 g/ha 500 g/ha 500 1000 g/ha 1000 giha 1000 g/ha 1000 500 g/ha 500 g/ha 500 g/ha 500 giha g /ha g/ha g/ha giha g /ha g/ha g/ha g/ha g /ha g/ha g /ha g/ha g /ha gI ha g /ha g/ha g/ha g /ha g/ha g/ha g/ha g/ha g/ha g/ ha g/ha g/ha g/ha g/ha glha g/ha g/ha 98% 98% 0% 1000 500 250 00 *0 000 1000 500 250 500 250 125 I KXW: 1148y 2 compound tested No 41C herbicide amount amount 1.064 1.064 1.064 1.064 1.064 1.064 1.080 1.080 1.080 1.080 1.080 1.080 1.084 1.084 1.084 1.084 1000 500 250 1000 500 250

I

t t t t 4 1 t o* i c t o t 1 0 44.t 1000 g/ha 1000 g/ha 1000 g/ha 1000 500 g/ha 500 g/ha 500 g/ha 500 1000 g/ha 1000 g/ha 1000 g/ha 1000 500 g/ha 500 g/ha 500 g/ha 500 1000 g/ha 1000 g/ha 1000 g/ha 1000 500 g/ha 500 g/ha 500 g/ha 500 1000 g/ha 1000 g/ha 1000 g/ha 1000 500 g/ha 500 g/ha 500 g/ha 500 g/ha g/ha g/ha g/ha g/ha g/ha g/ha g/ha g/ha g/ha g/ha g/ha g/ha g/ha g/ha g/ha g/ha g/ha g/ha g/ha g/ha g/ha g/ha g/ha g/ha g/ha g/ha g/ha g/ha g/ha g/ha g/ha crop injury 98% 20% 40% 60%7 15% 25% 25% protective action 78% 58% 38% 63% 62% 62% 62% 62% 38% 38% 63% 63% .084 .084 .084 .088 .088 .088 .088 .088 .088 1000 500 250 500 250 125 1000 500 250 500 250 125 :1148y i i compound tested No 41D herbicide amount crop iniurv protective action mmniin actio 1.093 1.093 1.093 1.093 1 .093 1.093 1.093 1000 500 250 500 250 125 1000 500 250 g/ha g/ha g/ha g/ha g/ha g/ha 1000 1000 1000 1000 500 500 500 500 g/ha g/ha g/ha g/ha g/ha g/ha g/ha g/ha g/ha g/ha g/ha g/ha g/ha g/ha g/ha g/ha 100% 50% 50% 38% 88% 38% 25% 13% 100% 88% 88% 88% 63% 63% 88% 62% 63% crrrtr I: L gCtf let r E rr.

re r a c r s t +sri

I

te r r.

P

I

tC':l: rrrs Irr c a r

LCEI

a a r r t g/ha g/ha g/ha g/ha g/ha g/ha 1000 1000 1000 1000 500 500 500 500 Conclusion In these experiments the herbicide is used at dosage rate, which damages the rice to 75-100%. When the antidote is added with the herbicide, the crop injury is much less.

The compounds of the present invention show protective action of 38 to 83% which reduces the crop-injury to an extent which permits the crop rice to survive in spite of the application of the herbicide.

The compound A which was tested along under the same conditions also antagonizes the herbicidal action but only to less than 25%, which does not sufficiently protect the rice.

From a practical point of view the compounds of this application are much better safeners for the use of the herbicide N-(n-propoxyethyl)-Nchloroacetyl-2,6-diethylanilide (pretilachlor) in rice than would be compound A.

1148y

Claims (5)

1. 2. Composition for selectively controlling weeds in areas of cultivated plants, containing besides inert carrier material and additives, a herbicide and a herbicidally-antagonistic component, which is characterised in that the herbicide is a sulfonylurea derivative, a haloacetanilide or an aryloxyphenoxy-propionic acid derivative and the herbicidally-antagonistic component is a thiazol-5-carboxamide according to claim 1.
2. 3. Composition for selectively controlling weeds in areas of cultivated plants, containing besides inert carrier material and additives, a herbicide and a herbicidally-antagonistic component, which is characterised in that the herbicide is a sulfonylurea-derivative of the 1 formula IV, E-(CH2)--S02-NH-CO-N- Y (IV) z\ wherein E is a group :W:1148y -44 I or \Rio /13 n is zero or one, G is hydrogen or methyl, X is methoxy, ethoxy, difluoromethoxy or chlorine, Y nitrogen or meth-ine Z is methyl, methoxy, difluoromethoxy, cyclopropyl or methylamino, Rio is C2-Csalkoxyalkoxy, CI-C~baloalkoxy, Cl-Ci~haloalkylthio, C 2 -C4- haloalkenyl, chlorine or Cl-G4alkoxycarbonyl, SRii is trifluoromethyl or di(Ci-Ci.-alkyl)carbamoyl, o R 12 is Cl-CL~alkoxycarbonyl, R 1 3 is Cl-C~alkoxycarbonyl and o t Ri4 is C 1 -Ci~alkyl, and the herbicidally-antagonistic component is a according to claim
3. 4. Composition for selectively controlling weeds in areas of cultivated 44 s plants, containing besides inert carrier material and additives, a herbicide and a herbicidally-antagonistic component, which is ''characterised that the herbicide is a haloacetanilide of the formula V, R 1 5 N R i s( R 17 \'R6 ~co-cH 2 cl wherein L is a CI-C4-akylenebridge, Ris R 1 6 and R 1 7 independently of each other hydrogen, halogen, Cl-C4-alkyl, CI-C4-alkoxy, Cl-Ci.-haloalkyl, C 2 -C 5 -alkoxyalkyl or C2-Cs-alkylthioalkyl, and RIB Cl-C4ralkoxy, -COOH, Cl-C4-al7koxycarbonyl, -CONH 2 Cl-C4-alkyl- carbamoyl, di-Ci-C4-alkylcarbamoyl, cyano, Cl-Ci.-alkylcarbonyl, optionally substituted benzoyl, optionally substituted furyl, optionally substituted thienyl, optionally substituted pyrrolyl, optionally substituted pyrazolyl, optionally substituted 1 4-oxadiazol-2-yl, optionally substituted 1, 3,4-thiadiazol-2-yl, optionally substituted 1 4-triazol-3-yl, optionally subst~ituted dioxolanyl, optionally substituted dioxanyl, optionally substituted 1,3,4-triazol-2-yl or optionally substituted tetrahydrofuryl, and the herbicidally-antagonistic component is a thiazol-5-carboxamide according to claim 1. 9 AR Composition for selectively controlling weeds in areas of cultivated plants, containing besides inert carrier material and additives, a and a herbicidally-antagonistic component, which is *A characterised that the herbicide is an aryloxyphenoxy-propionic acid t~herbicide of the formula VI, \-H-CO-T (i wherein Q is a radical R 2 0 or wherein T is -NR21R22, -N(CN)R21, -OR 22 SR 22 or -O-N=CR 23 R 22 R 19 is halogen or trifluoromethyl, R 20 is hydrogen or halogen,I sulfonyl)-N'-(4,6-dimethoxy-1,3,5-triazin-2-yl)-urea and the 2R enantiomer of the propinyl ester of 2-[4-(5-chloro-3-fluoropyridin-2 464 R 2 1 and R 2 2 independently of each other hydrogen, C 1 -C~alkoxy, CI-Csalkyl, phenyl or benzyl, R 21 and R 22 together with the nitrogen atom, to which they are bound also form a saturated 5- to 6-membered nitrogen-heterocycle, which may contain am oxygen or sulfur atom, R 23 is Ci-Ct~alkyl, .C 3 -Ci~alkenyl, C3-C4alkynyl or C 2 -Ci~alkoxyalkyl R 24 is hydrogen or the cation-equivalent of an alkali metal, an alkaline earth metal copper or iron; of a quaternary CI-C4alkylammonium or Cl-C4-hydroxyalkylammonium radical; Cl-Cgalkyl unsubstituted or mono- or polysubstituted by amino, halogen, hydroxyl, cyano, nitro, phenyl, CI-Ci~alkoxy, polyethoxy with 2 to 6 ethyleneoxy-units, -C00R 2 7 -COSR27, -CONH 2 -CON(Ca-Ci-alkoxy)-C 1 -C 4 -alkyl, -CO-N-di-Cl-CL.-alkyl-, CONH-C:L-C4-alkyl, -N(C 1 -C 4 -alkoxy)-C 1 -C 4 -alkyl or di-C 1 -C 4 -alkylamino; C 3 -Cgalkenyl, unsubstituted or substituted by halogen or Cl-C~alkoxy; C3-Cgalkynyl, unsubstituted or substituted by halogen or C 1 -C~.alkoxy; C3-Cgcycloalkyliphenyl unsubstituted or substituted by cyano. Ca-C~.alkyl, Ca-C 4 alkoxy, acetyl, -COOR 2 7, COSR 27 at t -CONH 2 -CON(Ci-CL.-alkoxy)-CI-Cc-alkyl, -CO-N-di-Cl-Ci.-alkyl oder -CONH-Ca-Ci.-alkyl; at R 2 s and R 2 6 independently of each other are CI-C4alkyl or together a 3 -to 6-membered alkylene chain and R 27 is hydrogen, Ci-Csalkyl, CI-Gshaloalkyl, C 2 -Csalkoxyalkyl, C 3 -C6- alkenyl, C 3 -Cshaloaikenyl, '3-Csalkynyi or C 3 -C 6 haloalkynyl, 4t and the herbicidally-antagonistic component is a- a t a a according to claim 1. 4 1' 6. Composition according to claim 1 or 2, characterised that it contains as herbicidally-antagonistic component a thiazol-5-carbonic acid amide of the formula Ia, t ~CF 3 R a wheeinth raicls i nd d ndpendently of each other are a hydrogen, CI-Cealkyl or G, Gai- unsub2tituted or substituted by halogen, cyano, C1-C4alkoxy or -COOR 6 C 2 -Csalkenyl, unsubstituted by halogen, cyano, CI-Ci~alkoxy or -COOR6 or C3-Cealkynyl, ~jA~vj 0
4. 47- R 2 may also be -()mUor -E Q RI and R2 together form also a 4- to 5-membered alkylene chain, which may be interrupted by oxygen, sulfur, -NH- or -NR 7 and/or substituted by Cl-C4alkyl, E is C1-Clialkylene, C3-CL~cycloalkylene, C2-C4alkenylene or C 2 -Ci.- alkynylene, U is phenyl, unsubstituted or substituted by halogen, cyano, CI-Ci~alkyl, CI-C~alkoxy, Cl-C4haloalkyl, Cl-C4haloalkoxy, CQOR6, -SO 2 NH 2 _SO 2 NHRis -SOzN(R 7 2 -CONH2, -CONHR 7 or -CON(R 7 )2, Q is a 5 to 6 membered heterocycle which is unsubstituted or substituted by halogen, Cl-C~.alkyl, C 1 -C4alkoxy, Cl-C~haloalkyl or Cl-C~haloalkoxy and R 6 and R7 have the meaning given in claim 1. 7. Composition according to claim 1 or 2, characterised that it contains as herbicidally-antagonistic component a thiazol-5-carbonic acid amide of I the formula Ia, 0 L t ~(Ia) wherein RI is hydrogen, CI-Cealkyl or C 3 -Csalkynyl and SR 2 is CI-Cacyanoalkyl, C3-Cecyanocycloalkyl, C 3 -Caalkynyl, phenyl, 0 X halophenyl, Cl-Ci~alkylphenyl, C 1 -C~.alkylhalophenyl, phenylamino, halo- phenylamino or fr=yl. 8 Composition according to claim 7, wherein -NR R 2 is N-methyl-l-cyano- pentylamine or -N-methyl-N- (2 ,6-dichloro)benizylamin-e. 9. Composition according to claim 1 or 2, characterised that it contains a 7 7 a hericiall-antagonistic component a thiezol-5-carbonic acid hydrazide 4~4: of the formula lb VT 0
5. 48- 4< wherein R 3 R4 and R5 independently of each other are hydrogen, C 1 -C 8 alkyl, C3-Cecycloalkyl, phenyl or benzyl, the phenyl ring being unsub- stituted or substituted by halogen, Cl-C4alkyl, CI-C 4 haloalkyl, C 1 -Caalk- oxy, CI-C 4 haloalkoxy, -COORs, -CONH 2 -CONHR7, -CON(R7) 2 -SONH2, -SONHR7, -SON(R7) 2 and R4 and Rs together can also form a 4 5 membered alkylene chain that may be interrupted by oxygen, sulfur, -NR7 and/or substituted by CI-C4alkyl. Composition according to claim 1 or 2, characterised that it contains as herbicidally-antagonistic component a thiazol-5-carboxamide selected from the group consisting of acid-N-methyl-N-benzylamide, acid-benzylamide, acid-N-methyl-N-(1-cyano-cyclopent-1-yl)amide, acid-N,N-dipropylamide, t thiazol-5-carbonic acid-N'-(2,4,6-trichlorophenyl)hydrazide, I~tL S thiazol-5-carbonic acid furfurylamide, acid(4-amidosulfonyl)anilide, S thiazol-5-carbonic acid-N-methyl-N-(cyano-dimethyl)amide. a r. 11. Method for protecting cultivated plants from the phytotoxic effect of herbicides, characterized by applying to the plants or the area where they .tit are cultivated, a herbicidally-antagonistic effective amount of a composition according to claim 1. S 12. Method for selectively controlling weeds in cultures of useful plants, characterized in that the plants or the area where they are cultivated, are treated with a herbicidally effective amount of a herbicide and with a herbicidally-antagonistic effective amount of a S according to claim 1. a i 4r rV rr" 49 I 13. Method for protecting cultivated plants from damage which might appear during the application of herbicides, which 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, with a herbicidally-antagonistically effective amount of a according to claim 1. 14. Seeds or seedlings of cultivated plants which have been treated with a herbicidally-antagonistic amount of a compound according to claim 1. Composition for protecting cultivated plants from the phytotoxic action of highly effective agrochemicals, which contains inert carrier material, additives and as herbicide-antagonistically active component a which herbicide-antagonistically active compound is substantially as hereinbefore described with reference to any one of Examples 1 or 2 or any one of Compounds 1.001 to 1.093 or 2.001 to 2.009. 16. A composition for protecting cultivated plants from the phytotoxic action of highly effective agrochemicals, substantially as hereinbefore described with reference to any one of Examples 3 to 9. 17. A method for protecting cultivated plants from the phytotoxic effect of herbicides, characterized by applying to the plants or the area where they are cultivated, a herbicidally-antagonistic effective amount of a composition according to claim 15 or claim 16. 18. Method for selectively controlling weeds in cultures of useful plants, characterized in that the plants or the area where they are cultivated are treated with a herbicidally effective amount of a herbicide and with a herbicidally-antagonistic effective amount of a S carboxamide, which thiazol-5-carboxamide is substantially as herein described with reference to Example 1 or 2 or any one of compounds 1.001 to 1.093 or 2.001 to 2.009. 19. Method for protecting cultivated plants from damage which might appear during the application of herbicides, which 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 with a herbicidally-antagonistically effective amount of a which thiazol-5-carboxamide is substantially as herein described with reference to Example 1 or 2 or any one of compounds 1.001 to 1.093 or 2.001 to 2.009. Seeds or seedlings of cultivated plants which have been treated with a herbicidally-antagonistic amount of thiazol-5-carboxamide, which :1148y Ri XW:1I148y <"Vr M4 50 is substantially as herein described with reference to Example 1 or 2 or any one of compounds 1.001 to 1.093 or 2.001 to 2.009. DATED this SEVENTH day of JANUARY 1991 Ciba-Geigy AG Patent Attorneys for the Applicant SPRUSON FERGUSON 6 II 6 6 I' 6 t t 6 ii 1 6 t 1t C JLH/KXW: 1148y