WO2000011954A1 - Herbicidal method - Google Patents

Abstract

The invention relates to a method of reducing phytotoxicity to crop plants caused by a herbicidal cyclic amide derivative; which comprises applying to the locus of the crop plant an antidotally effective amount of an antidote; wherein said antidote is antidotally effective to said cyclic amide derivative.

Description

HERBICIDAL METHOD

Field of the Invention

The present invention relates to the safening of herbicidal compounds, in particular the safening of herbicidal cyclic amide derivatives which are useful for the growing of crops (particularly for rice and cereal crops such as wheat and barley) and to the compositions of matter useful for such treatment .

Description of the Related Art It is known that many herbicides injure crop plants at herbicide application rates needed to control weed growth. This renders many herbicides unsuitable for controlling weeds in the presence of certain crops. Where weed growth in crops is uncontrolled however, this results in lower crop yield and reduced crop quality, as weeds will compete with crops for nutrients, light and water. Reduction in herbicidal injury to crops without an unacceptable reduction in the herbicidal action can be accomplished by use of crop protectants known as " antidotes ", also sometimes referred to as " safeners " or "antagonists". The safening effect of a compound is generally specific to the herbicidal partner and the crop where the active ingredients are applied.

Certain types of herbicidal cyclic amide derivatives are disclosed in for example International Patent Publication Numbers WO 93/15064, WO 95/18113, WO 97/00865, WO 95/22523 and WO 96/38413; European Patent Publication Number EP 557691; German Patent Publication Number DE 19535842; and Japanese Patent Publication Number J8-311026.

Surprisingly the applicants have found that the presence of certain antidotes (known for other herbicides and/or other crops) with certain cyclic amide derivatives (optionally in admixture with a partner herbicide) , under certain conditions, allows any crop phytotoxicity in rice or in cereal crops such as wheat or barley to be reduced, while maintaining a good level of weed control.

DESCRIPTION OF THE INVENTION

The present invention provides a method of reducing phytotoxicity to crops (especially rice or cereal crops such as wheat or barley) caused by a herbicidal cyclic amide derivative of formula (I) :

(I) wherein:

R^ and R5 independently represent alkyl; and i) -X-Y- represents -C (R^la) =C (R² ) -0-; W represents NHR- or R^³; R^^a represents phenyl or thienyl optionally substituted by one to five groups which may be the same or different selected from halogen, hydroxy, alkyl, haloalkyl, alkoxy, haloalkoxy, -S(0)_nR⁶, -C0₂R⁶, -COR⁶, cyano, nitro, -0 (CH₂ ) q^~C0₂R⁶ and phenoxy; or represents R^lbS(0)_x;

R b represents alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl or cycloalkyl;

R² represents hydrogen, alkyl, haloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, alkoxyalkenyl, -CHO, -COR⁶, -CO2R⁶, -CH₂N0 , or alkyl which is substituted by a group selected from -S(0)_nR⁶, OH, -OCOR⁶ and -NR⁷R⁸; or a group selected from cyano, -CHO, -COR⁶,

-C0 H, -C0₂R⁶, -COSR⁶, -CONR⁷R⁸, -CH=N0H, -CH=NOR⁶, -CH=NOCOR⁶, -CH=NNR⁷R⁸, -CH₂CN,

-CH₂N0₂ and oxiranyl;

R3 represents phenyl optionally substituted by from one to five groups which may be the same or different selected from halogen, hydroxy, alkyl, haloalkyl, alkoxy, haloalkoxy, -S(0)_nR⁶, -C0₂R⁶, -COR⁶, cyano, nitro, -NR⁷R⁸, phenoxy, alkoxycarbonylalkoxy and -SF5;

R^^a represents - (CH₂ ) _r- (phenyl or naphthyl) which is optionally substituted by from one to five groups which may be the same or different selected from halogen, hydroxy, alkyl, haloalkyl, alkoxy, haloalkoxy,

-S(0)_nR⁶, -C0 R⁶, -COR⁶, cyano, nitro, -0 (CH₂) qC0₂R⁶, phenoxy and -SF5; or substituted by a group selected from -0C0R⁶, NR⁹R¹⁰, NHR^6a, -CH₂NR⁹R¹⁰, -CONR⁹R¹⁰,

-CONHR^6a, -OS0₂R⁶, -OS0₂R^6a, -0C0R^6a, -OCH₂COR^6a, -OCH₂R^6a, -S(0)_mR^6a, R^6a, -P(=0) (OR⁶) (OR^6b) , -P (=0) (OR⁶)R^6b ,

-CH₂P(=0) (OR⁶) (OR^6b) , -CH₂P(=0) (OR⁶)R^6b , -C0 R^6a, -CH₂S(0)_nR⁶, -CH₂S (0)_mR^6a, -CH₂OR⁶,

-CH₂OR^6a, -CH₂OCOR^6a, -CH₂OS0 R^6a and alkenyl

(the phenyl and naphthyl rings may be additionally substituted by one or more halogen or R⁶ groups) ) ; or represents a phenyl ring optionally substituted by from one to five groups which may be the same or different selected from halogen, alkyl, haloalkyl, alkoxy, haloalkoxy,

-S(0)_nR⁶, CN and N0 , and which is fused to a second five or six membered cycloalkyl or cycloalkenyl ring, or to a saturated five or six membered heterocyclic ring (for example to give a 1 , 3-benzodioxole or 1 , 4-benzodioxane ring) which contains one to three heteroatoms which may be the same or different selected from nitrogen, oxygen and sulphur, said rings being optionally substituted by one or more groups R^² or optionally one of the carbon atoms in the cycloalkyl, cycloalkenyl or saturated five or six membered heterocyclic ring may form a carbonyl group (it is understood that for fused ring systems it is the phenyl ring which is linked to the carbonyl group which forms part of -C(=0)W wherein W is R^^a) ; or represents a phenanthrene or anthracene ring optionally substituted by one or more groups selected from halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, -S(0)_nR⁶, CN and N0₂; or represents - (CH₂ ) _s- ( five to seven membered heteroaromatic ring) wherein the heteroaromatic ring has from one to four ring heteroatoms which may be the same or different selected from nitrogen, oxygen and sulphur, said ring being optionally fused to a phenyl ring or to a second five to seven membered heteroaromatic ring having from one to four heteroatoms which may be the same or different selected from nitrogen, oxygen and sulphur, to form a bicyclic ring system, the monocyclic ring or either ring in the bicyclic system being optionally substituted by from one to four groups which may be the same or different selected from halogen, hydroxy, alkyl, cyano, haloalkyl, alkoxy, haloalkoxy, -S(0)_nR⁶,

-C0₂R⁶, -COR⁶, nitro, -0 (CH₂ ) _qC0₂R⁶ and phenoxy; or represents an optionally halogenated alkyl, alkenyl or alkynyl group containing up to ten carbon atoms; or represents an optionally halogenated alkyl, alkenyl or alkynyl group containing up to ten carbon atoms which is substituted by cycloalkyl containing from three to six carbon atoms (the cycloalkyl ring may be optionally substituted by one or more halogen or alkyl groups) ; or represents cycloalkyl containing from three to six carbon atoms or cycloalkenyl containing five or six carbon atoms, the ring systems of which are optionally substituted by a group R⁶ or one or more halogen atoms which may be the same or different; or represents cycloalkyl containing from three to eight carbon atoms or cycloalkenyl containing four to eight carbon atoms, wherein the ring systems are substituted by a group E which is selected from C0₂H, C0₂R⁶, alkenyl, haloalkenyl, R^6a, NR⁹R¹⁰, alkoxy, haloalkoxy, S(0)_nR⁶, COR⁶, COR^6a, CH₂C0R^6a, COCH R^6a,

C0₂CH₂R^6a, S(0)_mR^6a, CN, S(0)_tCH₂R^6a,

S(0)_uR¹⁴, CH₂OR⁶, CHO, COR¹¹, N0₂ , CONHR^6a,

CONR⁶R^6a, CH₂OH and -CH(OR¹³) (OR^13a)

(optionally the group -CH(OR¹³) (OR^13a) . represents a five or six membered cyclic acetal optionally substituted by one or more

R⁶ groups), or one of the cycloalkyl carbon atoms forms part of a carbonyl group (optionally the above defined cycloalkyl or cycloalkenyl rings may contain in addition to

E one or more halogen or R⁶ groups), and preferably the substituent E is attached to the carbon atom by which the cycloalkyl or cycloalkenyl group is attached to the carbonyl group which forms part of the -C(=0)W group wherein W is R^3a; or represents cycloalkyl containing from five to seven carbon atoms or cycloalkenyl containing five or six carbon atoms, the rings of which are optionally substituted by one or more groups R¹², and wherein the ring systems are fused to a phenyl ring (for example to form indanyl) optionally substituted by from one to four groups which may be the same or different selected from halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, -S(0)_nR⁶, cyano and nitro (it is understood that for fused ring systems it is the cycloalkyl or cycloalkenyl ring which is linked to the carbonyl group which forms part of the -C(=0)W group wherein W is R^3a) ; or represents alkyl or haloalkyl either of which is substituted by one or two R¹^ groups, optionally together with an R¹⁶ group; or represents alkenyl or haloalkenyl either of which is substituted by one or two R¹^ groups, optionally together with a group selected from R^6a, R¹⁷ and R¹⁸; or represents alkynyl substituted by a group

R¹^ (preferably an R¹^ group in the above definitions is located on the carbon atom of R^3a which is alpha or beta to the carbonyl group which forms part of -C(=0)W wherein W is

R^3a) ; R⁶ and R⁶ represent alkyl or haloalkyl;

R^6a represents phenyl optionally substituted by one or more groups which may be the same or different selected from halogen, alkyl, haloalkyl, alkoxy, haloalkoxy,

-S(0)_nR⁶, cyano and nitro;

R ,R⁸,R⁹ and R¹^ independently represent hydrogen, alkyl or haloalkyl;

R¹¹ represents cycloalkyl containing from three to seven carbon atoms or cycloalkenyl containing five or six carbon atoms, wherein the ring systems are optionally substituted by one or more groups R ²;

R¹² represents halogen, alkyl or haloalkyl

R¹³ and R ^3a represent alkyl, or the group -C(OR¹³) (OR^13a)- represents a five or^' six membered cyclic ketal, namely a 1,3- dioxolane or 1,3-dioxane ring of formula -C(OR^13b) (OR^13c)- wherein R^13b and R^13c together represent a C2 or C3 alkylene chain which is optionally substituted by alkyl;

R ⁴ represents cycloalkyl containing from three to seven carbon atoms optionally substituted by one or more groups R¹²;

R¹⁵ represents -OH, -OR⁶, -S(0)_nR⁶,

-S(0)_mR^6a, -C0₂R⁶, -C0₂CH₂R^6a, CN, N0 , CHO,

COR⁶, COR^6a, COCH₂R^6a, -C0 H, -CONR⁹R¹⁰,

-S (0) _tCH₂R^6a, -S(0)pR¹⁸ or a five or six membered cyclic acetal group optionally substituted by one or more R⁶ groups; R¹⁶ represents R^6a, alkynyl, or a three to six membered cycloalkyl ring optionally substituted by one or more R⁶ or halogen groups ; R¹⁷ represents a thienyl or furyl ring optionally substituted by one or more groups

Rl2;

R¹⁸ represents cycloalkyl containing from three to seven carbon atoms optionally substituted by one or more groups R¹²; m, n, p, t, u and x represent zero, one or two; q represents one or two; and r and s represent zero or one; or

ii) -X-Y- represents -C (R¹ ) =C (R^2a) -;

R represents phenyl optionally substituted by halogen, alkyl, haloalkyl, alkoxy or haloalkoxy; R^2a represents alkyl; and

W represents -NHR^3c, wherein R ^c represents phenyl, naphthyl or a five or six membered heterocyclic ring containing one to three heteroatoms selected from oxygen, nitrogen and sulphur, the ring systems of which are optionally substituted by halogen, alkyl, haloalkyl, alkoxy, haloalkoxy,

-S(0)_nR⁶, -C0₂R⁶, nitro, cyano or -C0₂H; or

W represents R , wherein R represents alkyl, haloalkyl; phenyl optionally substituted by halogen, alkyl, haloalkyl or alkoxy; benzyl, alkenyl, haloalkenyl, alkynyl; C3-7 cycloalkyl optionally substituted by halogen or alkyl; or alkyl substituted by C3-7 cycloalkyl; or

R^2a represents hydroxy, alkoxy, haloalkoxy, -S(0)_nR⁶, amino, alkylamino or dialkylamino; and

W represents R^3c wherein R^3c^ represents alkyl, alkenyl, alkynyl, or benzyl or phenyl optionally substituted by halogen, alkyl, haloalkyl or -S(0)_nR⁶; or

iii) -X-Y- represents -N (R¹) -CH (R^2a) - or -N(R¹)-CH(R^2a)-CH₂-; wherein R^2a represents alkyl; and

W represents -NHR^3c or R^3b; or

iv) -X-Y- represents -N (R¹ ) -N (Me) -CH - or

-H { R¹ ) -0- ; and W represents NHR^3e or R³ ; and

R ^e represents phenyl optionally substituted by halogen, alkyl, haloalkyl, alkoxy, haloalkoxy or -S(0)_nR⁶; or

v) -X-Y- represents -C (R¹ ) =C (R^2a) -CH -;

-CH(R¹)-N(R^2a)- or -CH (R¹ ) -S (0) _v-; and

W represents NHR^3c; and v represents zero, one or two; or an agriculturally acceptable salt thereof; which method comprises applying to - li the locus of the crop an antidotally effective amount of an antidote compound wherein the said antidote is antidotally effective to said cyclic amide derivative, optionally with a partner herbicide .

The present invention also provides compositions which comprise:

(a) a herbicidally effective amount of a cyclic amide compound of formula (I) or an agriculturally acceptable salt thereof, optionally in combination with a partner herbicide; and

(b) an antidotally effective amount of an antidote compound; in association with a herbicidally acceptable diluent or carrier and/or surface active agent.

It will be understood that antidotes used in the method of the invention may form for example salts, and that the use of such salts is also embraced by the invention.

It will be appreciated that certain substituents in the compounds of formula (I) may contribute to optical and/or stereoisomerism. All such forms and mixtures thereof are embraced by the present invention. In this patent specification and accompanying claims it is understood that the term 'agriculturally acceptable salts' is meant salts the cations or anions of which are known and accepted in the art for the formation of salts for agricultural or horticultural use. Preferably the salts are water-soluble. Suitable salts with bases include alkali metal (e.g. sodium and potassium), alkaline earth metal (e.g. calcium and magnesium), ammonium and amine (e.g. diethanolamine, triethanolamine, octylamine, morpholine and dioctylmethylamine) salts.

Suitable acid addition salts, e.g. formed by compounds of formula (I) containing an amino group, include salts with inorganic acids, for example hydrochlorides , sulphates, phosphates and nitrates and salts with organic acids for example acetic acid.

In this specification and accompanying claims unless otherwise specified, alkyl groups and alkyl moieties contain from one to six carbon atoms and are straight- or branched-chain; alkenyl groups and alkenyl moieties contain from two to six carbon atoms and are straight- or branched-chain; alkynyl groups and alkynyl moieties contain from two to six carbon atoms and are straight- or branched-chain.

Compounds of formula (I) above in which -X-Y- represents -C (R^la) =C (R² ) -0- are preferred.

Compounds of formula (I) above in which

R^la represents phenyl or thienyl which are optionally substituted by one to three groups which may be the same or different selected from halogen, alkyl, haloalkyl and alkoxy; or represents alkylthio are preferred ( compounds in which R ^a represents phenyl optionally substituted by a group selected from halogen, methyl and methoxy are particularly preferred) .

Especially preferred compounds of formula (I) above are those in which R¹ represents phenyl optionally substituted by fluorine, chlorine or methyl.

Compounds of formula (I) above in which R² represents alkyl, haloalkyl or hydrogen are preferred. Most preferably R² represents methyl, ethyl, fluoromethyl or hydrogen .

Compounds of formula (I) above in which W represents R ^a are also preferred (most preferably R^3a represents cycloalkyl containing from three to six carbon atoms or cycloalkenyl containing five or six carbon atoms, the ring systems of which are optionally substituted by a group R⁶ or one or more halogen atoms which may be the same or different; or R^3a represents an optionally halogenated alkyl group containing up to four carbon atoms which is substituted by cycloalkyl containing from three to six carbon atoms (the cycloalkyl ring may be optionally substituted by one or more halogen or alkyl groups) .

Compounds of formula (I) above in which W represents NHR³ and R³ represents phenyl substituted by from one to three groups which are the same or different selected from halogen, alkyl, haloalkyl and haloalkoxy are also preferred (compounds in which R³ represents 3-halophenyl, 2 , 5-dihalophenyl, 3, 5-dihalophenyl, 2-halo-5-haloalkoxyphenyl, 3-haloalkylphenyl or 3-halo-5-alkylphenyl are especially preferred) . Compounds of formula (I) above in which R⁴ and R5 represent methyl are particularly preferred.

A preferred class of compounds of formula (I) above are those wherein: -X-Y- represents -C (R^la) =C (R² ) -0-;

R ^a represents phenyl or thienyl each of which is optionally substituted by one to three groups which may be the same or different selected from halogen, alkyl, haloalkyl and alkoxy; or represents alkylthio;

R² represents alkyl, haloalkyl or hydrogen;

W represents NHR³ or R ^a;

R³ represents phenyl substituted by from one to three groups which are the same or different selected from halogen, alkyl, haloalkyl and haloalkoxy;

R^3a represents R^3a represents cycloalkyl containing from three to six carbon atoms or cycloalkenyl containing five or six carbon atoms, the ring systems of which are optionally substituted by a group R⁶ or one or more halogen atoms which may be the same or different; or R^3a represents an optionally halogenated alkyl group containing up to four carbon atoms which is substituted by cycloalkyl containing from three to six carbon atoms (the cycloalkyl ring may be optionally substituted by one or more halogen or alkyl groups ) ; and

R and R^ represent methyl. A more preferred class of compounds of formula (I) above are those having one or more of the following features:

-X-Y- represents -C (R^la) =C (R² ) -0-;

R^la represents phenyl, 2-chlorophenyl, 2- fluorophenyl, 2-methylphenyl or alkylthio ;

R² represents methyl, ethyl or fluoromethyl ;

W represents NHR³ or NHR ^a;

R³ represents 3-halophenyl, 2,5- dihalophenyl, 3, 5-dihalophenyl, 2-halo-5- haloalkoxyphenyl, 3-haloalkylphenyl or 3-halo- 5-alkylphenyl;

R^3a represents cyclopentyl or cyclopentenyl optionally substituted by a group R⁶ or one or more halogen atoms which may be the same or different; or R^3a represents methyl which is substituted by cyclopentyl or cyclopentenyl optionally substituted by one or more halogen or alkyl groups; or R^3a represents an alkyl group containing up to four carbon atoms which is substituted by cyclopropyl unsubstituted or substituted by alkyl ; and

R⁴ and R^ represent methyl. Particularly preferred compounds of formula (I) are: l-cyclopentyl-2- (2, 3-dihydro-6-methyl-4- oxo-5-phenyl-4H-l, 3-oxazin-3-yl) -2- methylpropan-1-one; l-cyclobutyl-3- (2, 3-dihydro-6-methyl-4- oxo-5-phenyl-4H-l , 3-oxazin-3-yl) -3- methylbutan-2-one; l-cyclopentyl-2- (2, 3-dihydro-6-ethyl-4- oxo-5-phenyl-4H-l, 3-oxazin-3-yl) -2- methylpropan-1-one; N- (2, 5-difluorophenyl) -2-methyl-2- [6- methyl-5- (2-fluorophenyl ) -2, 3-dihydro-4-oxo- 4H-1, 3-oxazin-3-yl] propanamide;

N- (3-iodophenyl) -2-methyl-2- [ 6-methyl-5- (2 -fluorophenyl) -2 , 3-dihydro-4-oxo-4H-l, 3- oxazin-3-yl] propanamide;

2- (2, 3-dihydro-6-methyl-4-oxo-5-phenyl- 4H-l,3-oxazin-3-yl) -2-methyl-4- (1- methylcyclopropyl) butan-3-one;

4-cyclopropyl-2- (2, 3-dihydro- 6-methyl-4- oxo-5-phenyl-4H-l, 3-oxazin-3-yl) -2- methylpentan-3-one;

N- (2-fluoro-5-trifluoromethoxyphenyl) -2- methyl-2- ( 6-methyl-5-phenyl-2 , 3-dihydro-4-oxo- 4H-1, 3-oxazin-3-yl) propanamide; N- (3-fluoromethylphenyl) -2-methyl-2- ( 6- methyl-5-phenyl-2 , 3-dihydro-4-oxo-4H-l, 3- oxazin-3-yl) propanamide;

N- (3-trifluoromethylphenyl) -2-methyl-2- [5- (2-fluorophenyl) -2, 3-dihydro-4-oxo-4H-l , 3- oxazin-3-yl] propanamide;

N- (3-fluoro-5-methylphenyl) -2-methyl-2- [5- (2-fluorophenyl) -6-methyl-2 , 3-dihydro-4- OXO-4H-1 , 3-oxazin-3-yl] propanamide; and N- (3, 5-difluorophenyl) -2-methyl-2- (5- isopropylthio-6-methy1-2 ,3-dihydro-4-oxo-4H- 1, 3-oxazin-3-yl) propanamide .

The most particularly preferred compounds of formula (I) are:

N- (2, 5-difluorophenyl) -2-methyl-2- [ 6- methyl-5- (2-fluorophenyl) -2, 3-dihydro-4-oxo- 4H-1, 3-oxazin-3-yl] propanamide; and N- (3-iodophenyl) -2-methyl-2- [6-methyl-5-

(2-fluorophenyl) -2 , 3-dihydro-4-oxo-4H-l, 3- oxazin-3-yl] propanamide .

Certain compounds of formula (I) have not been previously described and may be prepared as illustrated in the following example. Example 1

Oxalyl chloride (0.2ml) in dichloromethane was added to a solution of 2-methyl-2- ( 6- methyl-5-phenyl-2, 3-dihydro-4-oxo-4H-l , 3- oxazin-3-yl) propanoic acid (0.55g) in dichloromethane containing 1 drop of N,N- dimethylformamide , and the mixture stirred at

20°C for 10 minutes and cooled to 15°C. A solution of 2-fluoro-5-trifluoromethoxyaniline (0.41g) in dichloromethane was added during 1 minute followed by triethylamine (0.63ml) in dichloromethane. After 2.5 hours the mixture was washed with hydrochloric acid (2M) , sodium carbonate solution and water, dried (magnesium sulphate) and evaporated. After purification by chromatography on silica gel eluting with ethyl acetate/isohexane there was obtained N- (2-fluoro-5-trifluoromethoxyphenyl) -2-methyl- 2- (6-methyl-5-phenyl-2, 3-dihydro-4-oxo-4H-l, 3- oxazin-3-yl ) propanamide (O.lg), mpl01.5-

102.5°C.

By proceeding in a similar manner the following compounds were obtained:

N- (3-fluoromethylphenyl) -2-methyl-2- (6- methyl-5-phenyl-2, 3-dihydro-4-oxo-4H-l , 3- oxazin-3-yl) propanamide, NMR 1.62 (s,6H), 1.88(s,3H), 5.23(s,2H), 5.2 and 5.35(d,2H), 7.0(d,lH), 7.25(m,7H), 7,5(s,lH), 8.4 (brs, IH) ; N- (3-trifluoromethylphenyl) -2-methyl-2- [5- (2-fluorophenyl) -2, 3-dihydro-4-oxo-4H-l, 3- oxazin-3-yl] propanamide, NMR 1.7(s,6H), 5.4(s,2H), 7.0-7.4 (m,7H) , 7.65(d,lH), 7.8(s,lH), 8.43 (brs, IH) ;

N- (2, 5-difluorophenyl) -2-methyl-2- [ 6- methyl-5- (2-fluorophenyl) -2, 3-dihydro-4-oxo-

4H-1, 3-oxazin-3-yl] propanamide, mpl06-107.5°C; N- (3-iodophenyl ) -2-methyl-2- [6-methyl-5- (2-fluorophenyl) -2 , 3-dihydro-4-oxo-4H-l , 3- oxazin-3-yl] propanamide, mpl53-154°C;

N- (3-fluoro-5-methylphenyl) -2-methyl-2-

[5- (2-fluorophenyl) -6-methyl-2 , 3-dihydro-4- oxo-4H-l, 3-oxazin-3-yl] propanamide, NMR 1.7(s,6H), 1.9(s,3H), 2.3(s,3H), 5.35(s,2H),

6.6(d,lH), 7.0-7.3(m, 6H) , 8.5(brs,lH); and N- (3, 5-difluorophenyl) -2-methyl-2- (5- isopropylthio-6-methyl-2 , 3-dihydro-4-oxo-4H-

1, 3-oxazin-3-yl) propanamide, NMR l.l(d,6H), 1.6(s,6H), 2.3(s,3H), 3.2(m,lH), 5.1(s,2H),

6.4(t,lH), 7.0(d,2H), 8.6(s,lH). It has been found that such antidote compounds can be selected from a wide range of chemical substances. The preferred compositions of this invention may include any one or more of such antidotes with the herbicides. Some of the more important types of antidotes are amides of haloalkanoic acids, aromatic oxime derivatives, thiazole carboxylic acids and derivatives, and 1,8- naphthalic anhydride.

Examples of the antidotes suitable for use are :

(i) a compound of the formula (II) :

(II) wherein R 70 is selected from the group consisting of haloalkyl; haloalkenyl; alkyl; alkenyl; cycloalkyl; cycloalkylalkyl; halogen; hydrogen; carboalkoxy; N-N- alkynylcarbamylalkyl; N- alkenylcarbamylalkoxyalkyl ; N-alkyl-N- alkynylcarbamylalkoxyalkyl ; alkynyloxy; haloalkoxy; thiocyanatoalkyl; alkenylaminoalkyl; alkylcarboalkyl; cyanoalkyl; cyanatoalkyl; a1keny1aminosulfonalkyl; alkylthioalkyl; haloalkylcarbonyloxyalkyl; alkoxycarboalkyl; haloalkenylcarbonyloxyalkyl; hydroxyhaloaIkyloxyalkyl ; hydroxyalkylcarboalkyloxyalkyl ; hydroxyalkyl; alkoxysulfonoalkyl; furyl; thienyl; alkyldithiolenyl; thienalkyl; phenyl; substituted phenyl wherein the substitutents can be selected from halogen, alkyl, haloalkyl, alkoxy, carbamyl, nitro, carboxy and salts thereof, and haloalkylcarbamyl; phenylalkyl; phenylhaloalkyl; phenylalkenyl; substituted phenylalkenyl wherein the substituents can be selected from halogen, alkyl, alkoxy, and halophenoxy, phenylalkoxy; phenylalkylcarboxyalkyl; phenylcycloalkyl; halophenylalkenoxy; halothiophenylalkyl; halophenoxyalkyl; bicycloalkyl ; alkenylcarbamylpyridinyl ; alkynylcarbamylpyridinyl; dialkenylcarbamylbicycloalkenyl and alkynylcarbamylbicycloalkenyl; R 71 and R72 , which may be the same or different, are selected from the group consisting of alkenyl; haloalkenyl; hydrogen; alkyl; haloalkyl; alkynyl; cyanoalkyl; hydroxyalkyl; hydroxyhaloalkyl; haloalkylcarboxyalkyl; alkylcarboxyalkyl; alkoxycarboxyalkyl; thioalkylcarboxyalkyl ; alkoxycarboalkyl; aIkylcarbamyloxyalkyl; amino; formyl; haloalkyl-N-alkylamido; haloalkylamido; haloalkylamidoalkyl; haloalkyl-N-alkylamidoalkyl; haloalkylamidoalkenyl; alkylimino; cycloalkyl; alkylcycloalkyl; alkoxyalkyl; alkylsulfonyloxyalkyl; mercaptoalkyl; alkylaminoalkyl; alkoxycarboalkenyl ; haloalkylcarbonyl; alkylcarbonyl; alkenylcarbamyloxyalkyl ; cycloaIkylcarbamyloxyalkyl ; alkoxycarbonyl ; haloalkoxycarbonyl ; halophenylcarbamyloxyalkyl; cycloalkenyl; phenyl; substituted phenyl wherein said substitutents can be selected from alkyl, halogen, haloalkyl, alkoxy, haloalkylamido, phthalimido, hydroxy, alkylcarbamyloxy, alkenylcarbamyloxy, alkylamido, haloalkylamido and alkylcarboalkenyl; phenylsulfonyl; substituted phenylalkyl wherein said substituents can be selected from halogen or alkyl; dioxyalkylene; halophenoxyalkylamido-alkyl; alkylthiodiazolyl; piperidyl; piperidylalkyl; dioxolanylalkyl; thiazolyl; alkylthiazolyl; benzothiazolyl; halobenzothiazolyl; furyl; alkyl-substituted furyl; furylalkyl; pyridyl; alkylpyridyl; alkoxyazolyl; tetrahydrofurylalkyl; 3-cyano-thienyl; alkyl substituted thienyl; 4 , 5-polyalkylene thienyl; α-haloalkylacetamidophenylalkyl; α- haloalkylacetamidonitrophenylalkyl; α- haloalkylacetamidohalopheny1alkyl ; cyanoalkenyl; and naphthyl (as in for example naptalan) or R 71 and R72 when taken together can form a structure consisting of piperidinyl; alkylpiperidinyl; pyridyl; di- or tetrahydropyridinyl; alkyltetrahydropyridyl; morpholyl; 2,3-dihydro-l,4-benzoxazine, azabicyclononyl; diazacycloalkanyl; benzoalkylpyrrolidinyl; oxazolidinyl ; perhydrooxazolidinyl; alkyloxazolidinyl; furyloxazolidinyl; thienyloxazolidinyl; pyridyloxazolidinyl; pyrimidinyloxazolidinyl; benzooxazolidinyl; C3.7 spirocycloalkyl- oxazolidinyl; alkylaminoalkenyl; alkylideneimino; pyrrolidinyl; piperidonyl; perhydroazepinyl; perhydroazocinyl; pyrazolyl;

-tetrahydro- or perhydroquinolyl or isoquinolyl; indolyl or di- or perhydroindolyl; and which combined R 71and R72 members can be substituted with those independent R 71 and R72 radicals enumerated above; or (ii) one of the following compounds: α - [ (cyanomethoxy) imino] benzeneacetonitrile; α- [ (1, 3-dioxolan-2- ylmethoxy) imino] -benzeneacetonitrile; 0- [3-dioxolan-2-ylmethyl] -2,2,2- trifluoromethyl-4 ' -chloroacetophenone oxime; benzenemethamine, N-[4- ( dichloromethylene) -l,3-dithiolan-2-ylidene]-α -methyl, hydrochloride; diphenylmethoxy acetic acid methyl ester;

1, 8-naphthalic anhydride; cloquintocet ( 5-chloroquinoline-8-yloxy acid) or a salt or ester thereof such as cloquintocet-mexyl ( 1-methylhexyl (5-chloroquinoline-8-yloxy) acetate);

4 , 6-dichloro-2-phenylpyrimidine;

2-chloro-N-[l- (2, 4, 6-trimethylphenyl) ethenyl] acetamide; ethylene glycol acetal of 1 , 1-dichloroacetone; fenchlorazole (1- (2, 4-dichlorophenyl) - 5-trichloromethyl) -1H- 1 , 2 , 4-triazole- 3-carboxylic acid) , or a salt or ester thereof such as fenchlorazole-ethyl (ethyl 1- (2, 4-dichlorophenyl) -5-trichloromethyl ) - lff-1 , 2 , 4-triazole-3-carboxylate) ; benoxacor; dichlormid; fenclorim; furilazole or mefenpyr diethyl (diethyl (RS) -1- (2 , 4-dichlorophenyl) - 5-methyl-2-pyrazoline-3, 5-dicarboxylate) ; flurazole; 5, 5-diphenylisoxazolinone-3- carboxylic acid and ethyl 5,5- diphenylisoxazolinone-3-carboxylate (AEF- 129431); CMPI (N- (4-chlorophenyl) maleimide) ;

4-hydroxy-l-methyl-3- (1-1 H-tetrazol-5- ylmethanoyl) -lH-quinolin-2-one; or

3- (5-tetrazolylcarbonyl) -2-quinolones of formula (III ) :

(III) wherein A_-A3 represent a direct bond,

-C(=Q)-, -C(=Q)-T-, -SO-, -S0₂- or -S0₂NR⁸⁶-;

Q represents 0 or S; T = 0; S; or NR⁸⁶; R⁸³-

R⁸⁶ independently represent H, optionally substituted phenyl, optionally substituted phenyl-Cl-6 alkyl, optionally substituted C2-6 alkenyl, optionally substituted C2-6 alkynyl, optionally substituted C3-9 cycloalkyl; or alkyl optionally substituted by 1 or more halo, N0₂, CN, SCN, Cl-4 alkoxy, Cl-4 alkylthio, Cl-4 alkylsulphinyl , Cl-4 alkylsulphonyl, C2-4 alkenyl and C2-4 alkynyl or optionally substituted C3-9 cycloalkyl, optionally substituted phenyl and/or optionally substituted 3-6 membered heterocyclyl containing 1-3N, 0 and/or S atoms; R⁷⁹-R⁸² represent H, NH₂, COOH, CHO,

OH, halo, N0₂, CN, SCN, J-R⁸⁷, J-R⁸⁸; or 2 of

R⁷ -R⁸² on adjacent C atoms form together with these C atoms a 5- or 6-membered unsaturated or partly saturated ring optionally containing 1-3 0, S and/or N atoms and optionally substituted by 1 or more halo, Cl-4 alkyl and/or oxo; or -A^-R⁸³ and R⁸² together with their associated ring atoms form a 5- to 7- membered unsaturated or partly saturated ring optionally containing 1-3 0, S and/or N atoms and optionally substituted by 1 or more halo, Cl-4 alkyl and/or oxo; J = direct bond, S(=0)_w, S(=0)_w-0, C(=Q), C(=Q)-Q, 0-C0₂, NR⁸⁹,

NR⁸⁹-0, NR⁸⁹ -(C=0), NR⁸⁹ C0₂, NR⁸⁹-CO-NR⁹⁰ or

0; R⁸⁷ represents optionally substituted Cl-6 alkyl, C2-6 alkenyl or C2-6 alkynyl; R⁸⁸ represents optionally substituted unsaturated or partly saturated carbocyclyl, C3-8 cycloalkyl, phenyl or heterocyclyl; R⁸⁹ and

R⁹⁰ represent H, Cl-6 alkyl, C3-6 cycloalkyl, Cl-5 alkylcarbonyl, phenyl or benzyl; w represents 0,1 or 2; or iii) N-phenyl-N' -alkylureas such as daimuron [1- ( 1-methyl-l-phenylethyl) -3-p- tolylurea] or (S ) -1- (alpha-methylbenzyl ) -3-p- tolylurea [(S)-MBU]; or thiocarbamates such as dimepiperate ( S-l-methyl-1- phenylethylpiperidine-1-carbothioate) , and agriculturally acceptable salts of the compounds defined above under (i) , (ii) and

(iii) •

Antidotal amides of haloalkanoic acids of formula (II), which include those in which the nitrogen forms a portion of a heterocyclic ring with substituents, are described in a number of publications such as U.S. Patent Nos. 4,021,224, 4,256,481, 4,294,764, and 5,201,933 and British Patent 1,521,540. U.S. Patent No 4,021,224 contains a broad disclosure of such types of compounds and indicates a great many possibilities for mono- or di-substitution on the nitrogen atom.

One group of preferred antidotal compounds includes those according to formula (II) wherein R is C1-3 haloalkyl, R and R are independently C₂-4 alkenyl or haloalkenyl or

2, 3-dioxolan-2-yl-methyl and R and R - when combined form a C4-10 saturated or unsaturated heterocyclic ring containing 0, S and/or N atoms and which mav be substituted with C1-5 alkyl, haloalkyl, alkoxy, alkoxyalkyl or haloacvl groups. The preferred haloalkyl R 70 member in formula (II) is dichloromethyl . Preferred species in this group of antidotal compounds are

N, N-diallyl-dichloroacetamide and

N- (2-propenyl) -N- (1, 3-dioxolan-2-yl-methyl) dichloroacetamide . Still more preferred antidotal compounds according to formula (II) is a group of substituted 1, 3-oxazolidinyl or thiazolidinyl dichloroacetamides having the formula (IV) :

(IV) wherein : Z is oxygen or sulfur;

R⁷³, R⁷⁴, R⁷⁵, R^7β, R⁷⁷ and R⁷⁸ independently represent hydrogen; C1-4 alkyl, hydroxyalkyl, haloalkyl or alkoxy; C₂-6 alkoxyalkyl; C1-4 alkylthio (C1-4 ) alkyl ; C1-4 alkylsulfonylmethyl; a bicyclic hydrocarbon radical having up to 10 carbon atoms; phenyl; or a saturated or unsaturated heterocyclic radical having C4-.10 ring atoms and containing 0, S and/or N atom(s); wherein the phenyl and heterocyclic radicals are optionally substituted with one or more C1-4 alkyl, C1-4 haloalkyl, Cχ_4 alkoxy, C ₂-ς alkoxyalkyl, halogen or nitro radicals; or R 73 and R74 together with the carbon atom to which they are attached form a C3-7 spiro cycloalkyl group optionally substituted by one or two methyl groups.

Preferred members according to formula

(IV) are those wherein R⁷⁶, R⁷⁷ and R⁷⁸ are hydrogen; R 75 is hydrogen, methyl, phenyl or a heterocyclic radical; and R73 and R74 independently represent methyl or trifluoromethyl, or when taken together with the carbon atom to which they are attached form a C5 or Cζ cycloalkyl radical. An important example is R29148, which is 2,2- dichloro-1- (2,2, 5-trimethyloxazolidin-3-yl) - ethanone .

Oxime derivatives which are suitable for use as antidotes with herbicides are disclosed, for instance, in U.S. Patent Nos.

4,070,389 and 4,269,775 and have the general formula :

Ar (NC)C=NOCH₂R⁹¹ in which Ar is a phenyl or substituted phenyl radical where the substituents are optionally methyl, methoxy, chlorine, cyano or trifluoromethyl, or Ar is a naphthyl radical;

R⁹¹ is cyano, -C (NH ) (OR_e) (ORf ) , -C(=0)NHNH₂, -C(=0)N(R_c) (R_d) , or -CN (R_g) (R_h) , where R_e and Rf independently represent alkyl, or together with the carbon form an oxygen or sulfur containing 5- or 6- membered heterocyclic ring which is unsubstituted or substituted by lower alkyl, halogen and/or nitro; (Re) nd (Rd) are independently hydrogen, alkyl, cycloalkyl, which are unsubstituted or further substituted with one or more halogen, alkoxy and/or cyano; (Rg) and (Rh) together with the nitrogen form a 5- or 6-membered ring which is unsubstituted or mono- or polysubstituted by halogen, cyano and/or alkyl and which can be interrupted by a nitrogen, oxygen or sulfur atom.

Representative compounds of this type are those in which R 91 is cyano, and in which R91 is 1 , 3-dioxolan-2-yl , such as oxabetrinil (0-

[2- (1, 3-dioxolanyl) methyl] -alpha- cyanobenzaldoxime) .

Thiazole carboxylic acids and derivatives suitable for use as antidotes are disclosed generally in U.S. Patent No. 4,199,506.

A representative of this class is the compound benzyl-2-chloro-4- trifluoromethyl-5-thiazole carboxylate .

Another useful herbicide antidote compound is disclosed in European Patent No.0104495 as having the formula:

wherein R 98 is C1-C3 haloalkyl containing from 1 to 3 halogen atoms or a phenyl group optionally substituted; R 96 represents a hydrogen atom, a methyl or a phenyl; R 97 represents a hydrogen atom, a methyl or a phenyl; R 97 represents a Ci -Cβ alkyl group, a

C5 -Cβ cycloalkyl group, a cyclohexylmethyl group, a phenyl group optionally substituted, a benzyl group optionally substituted, an allyl or propargyl group; and z is zero or one . A representative antidote of that group would be:

Especially preferred antidotes for use in the present invention include: 2,2,5- trimethyl-N-dichloroacetyl oxazolidine; 2,2- dimethyl-5-phenyl-N-dichloroacetyl oxazolidine; 2 , 2-dimethyl-5- (2-furanyl) -N- dichloroacetyl oxazolidine; 2 , 2-dimethyl-5- (2- thienyl)- N-dichloroacetyl oxazolidine; N,N- diallyl dichloroacetamide; 2.2-spirocyclohexane-N-dichloroacetyl oxazolidine; 2 , 2-dimethyl-N-dichloroacetyl oxazolidine; 4- (dichloroacetyl) -3 , 4-dihydro-3- methyl-2H-l, -benzoxazine; 3- [3- ( dichloroacetyl) -2, 2-dimethyl-5- oxazolidinyl] pyridine;

4- (dichloroacetyl) -l-oxa-4-azaspiro- (4,5)- decane; 2 , 2-dichloro-l- ( 1 , 2,3, 4-tetrahydro - l-methyl-2-isoquinolyl) ethanone : cis/trans- 1, -bis (dichloroacetyl) -2, 5- dimethylpiperazine; N- (dichloroacetyl) -1, 2, 3, 4-tetrahydroquinaldine; 1,5- bis (dichloroacetyl ) -1, 5-diaza cyclononane; 1- (dichloroacetyl)-l-azaspiro[4,4]nonane; α t (cyanomethoxy) imino] benzeneacetonitrile; α- [( 1, 3-dioxolan-2- ylmethoxy) imino] benzeneacetonitrile; 0- [ 1, 3- dioxolan-2-ylmethyl] -2 , 2, 2-trifluoromethyl- 4 ' -chloroacetophenone oxime; benzenemethamine;

N- [4- (dichloromethylene) -l,3-dithiolan-2- ylidene] -α-methyl hydrochloride; diphenylmethoxy acetic acid methyl ester; 1,8- naphthalic anhydride; 4 , 6-dichloro-2- phenylpyrimidine; 2-chloro-N- [1- (2, 4 , 6- trimethylphenyl) ethenyl] -acetamide; cloquintocet-mexyl; and ethylene glycol acetal of 1 , 1-dichloroacetone . The most preferred antidotes in this invention for use in rice are daimuron, dimepiperate, fenclorim, fenchlorazole ethyl, cloquintocet-mexyl, 1 , 8-naphthalic anhydride, mefenpyr diethyl, benoxacor and (S) -1- (alpha- methylbenzyl) -3-p-tolylurea [(S)-MBU].

The most preferred antidotes in this invention for use in cereal crops such as wheat and barley are mefenpyr diethyl, fenchlorazole ethyl, cloquintocet-mexyl, oxabetrinil, flurazole, fenclorim and naptalam.

Herbicidal compositions according to this invention may also contain one or more additional pesticidally active ingredients such as herbicides .

The preferred crops which may be protected by the method of the invention are rice, wheat and barley.

The mixtures of the invention may be used to obtain selective weed control with low crop injury in various crop plants such as rice, maize, sorghum, soybeans, cotton, or cereals such as wheat, barley, oats and rye. Effective weed control coupled with low crop injury is a result of treatment of a plant locus with a combination of a herbicidal cyclic amide compound and an antidote compound in accordance with the present invention. By application to the "plant locus" is meant application, for example, to the plant growing medium, such as soil, as well as to the seeds, emerging seedlings, roots, stems, leaves, or other plant parts.

The phrase "combination of a herbicidal cyclic amide compound and an antidote compound" includes various methods of treatment. For example, the soil of a plant locus may be treated with a "tank-mix" composition containing a mixture of the herbicide and the antidote which is "in combination" , or the soil may be treated with the herbicide and antidote compounds separately so that the "combination" is made on, or in the soil. After such treatments of the soil with a mixture of herbicide and antidote or by separate or sequential application of the herbicide and the antidote to the soil, the herbicide and antidote may be mixed into or incorporated into the soil either by mechanical mixing of the soil with implements or by "watering in" by rainfall or irrigation. The soil of a plant locus may also be treated with antidote by application of the antidote in a dispersible-concentrate form such as a granule. The granule may be applied to a furrow which is prepared for receipt of the crop seed and the herbicide may be applied to the plant locus either before or after in-- furrow placement of the antidote-containing granule so that the herbicide and antidote form a "combination" . Crop seed may be treated or coated with the antidote compound either while the crop seed is in-furrow just after seeding or, more commonly, the crop seed may be treated or coated with antidote prior to seeding into a furrow. The herbicide may be applied to the soil plant locus before or after seeding and a "combination" is made when both herbicide and an antidote-coated seed are in the soil. In one embodiment the method of the invention is preferably performed by applying the antidote directly to the seed before planting. This is generally effected by coating a quantity of crop seed with the antidote and thereafter planting the coated seed.

In the foregoing description of various modes of application of the herbicide-antidote combinations, it is inherent that each form of application requires that in some manner, the herbicide and antidote will physically combine to form a "composition" of those agents.

The amount of a particular cyclic amide herbicide to be applied to the plant locus or crop-growing area will depend upon the nature of the weeds, the particular herbicide used, the time of application, the climate and the nature of the crop. Application rates of from about Ig/ha to lOOOg/ha herbicide are generally suitable, with a rate of about 25g/ha to 250g/ha being preferred. The amount of antidote used in the method of the invention varies according to a number of parameters including the particular antidote employed, the crop to be protected, the amount and rate of herbicide applied, and the edaphic and climatic conditions prevailing. Also, the selection of the specific antidotes for use in the method of the invention, the manner in which it is to be applied and the determination of the activity which is non-phytotoxic but antidotally effective, can be readily performed in accordance with common practice in the art.

The antidote is applied in combination with the herbicide in a non-phytotoxic antidotally effective amount. By "non- phytotoxic" is meant an amount of the antidote which causes at most minor or no injury to the desired crop species. By "antidotally- effective" is meant an antidote used in an amount which is effective as an antidote with the herbicide to decrease the extent of injury caused by the herbicide to the desired crop species .

The ratio of herbicide to antidote may vary depending upon the crop to be protected, weed to be inhibited, herbicide used, etc., but normally an herbicide-to-antidote ratio ranging from 1:25 to 60:1 parts by weight may be employed, although much higher rates of antidote may be used, e.g., 1:100 to 1:300 parts by weight of herbicide to-antidote. The preferred weight ratio of herbicide-to- antidote is from about 1:20 to about 30:1 (for example from about 1:2 to about 1:20) .

In field applications, the herbicide, antidote, or a mixture thereof, may be applied to the plant locus without any adjuvants other than a solvent. Usually, the herbicide, antidote, or mixture thereof, is applied in conjunction with one or more adjuvants in liquid or solid form. Compositions or formulations containing mixtures of an appropriate herbicide and antidote usually are prepared by admixing the herbicide and antidote with one or more adjuvants such as diluents, solvents, extenders, carriers, conditioning agents, water, wetting agents, dispersing agents, or emulsifying agents, or any suitable combination of these adjuvants. These mixtures can be in the form of particulate solids, granules, pellets, wettable powders, dusts, solutions, aqueous dispersions, or emulsions.

Application of the herbicide, antidote, or mixture thereof, can be carried out by conventional techniques utilizing, for example, hand-carried or tractor-mounted spreaders, power dusters, boom and hand sprayers, spray dusters, and granular applicators. If desired, application of the compositions of the invention to plants can be accomplished by incorporating the compositions in the soil or other media.

The optional partner herbicides which may be combined with the compound of formula (I) and antidote when used for rice culture are preferably selected from pyrazosulfuron ethyl, bensulfuron methyl, ethoxysulfuron, benzofenap, oxadiargyl, cinosulfuron, azimsulfuron, cyclosulfamuron, metsulfuron- methyl, imazasulfuron (which is 1- (2- chloroimidazo [1, 2-a] pyridin-3-ylsulphonyl) -3- (4 , 6-dimethoxypyrimidin-2-yl) urea) , clomeprop, pyrazolynate, pyrazoxyfen, cumyluron (which is 1- (2-chlorobenzyl) -3- ( 1-methyl-l-phenylethyl) - urea), daimuron, dimepiperate, oxadiazon, 2,4- D, MCPA, simetryn, bromobutide, naproanilide, benfuresate, bentazone, acifluorfen and bifenox, mefenacet, cafenstrole, pretilachlor , thiobencarb, MY-100 (which is 6-methyl-3- [ 1- methyl-1- (3, 5-dichlorophenyl ) ethyl] -5-phenyl- 2, 3-dihydro-4H-l , 3-oxazin-4-one) , pentoxazone, anilofos, thenylchlor, pyributicarb, esprocarb, quinclorac, cinmethylin, cyhalofop- butyl, pyriminobac-methyl , etobenzanid, molinate, propanil, fenoxaprop-P-ethyl and butachlor .

The optional partner herbicides which may be combined with the compound of formula (I) and antidote when used in cereal culture are preferably selected from quizalofop; clodinafop; cyhalofop; diclofop; fenoxaprop; fenthiaprop-ethyl ; fluazifop; haloxyfop; propaquizafop-P; trifluralin; pendimethalin; chlorsulfuron; tribenuron-methyl; thifensulfuron methyl; metsulfuron; triasulfuron; prosulfuron; nicosulfuron; primisulfuron; rimsulfuron; sulfosulfuron; flupyrsulfuron methyl; (EPTC) ; butylate; vernolate; triallate; simazine, cyanazine; atrazine; ametryn; metribuzin; imazapyr; imazaquin; imazethapyr; imazamethabenz; imazamox; imazameth; isoxaflutole; mesotrione; alloxydim; clethodim; cycloxydim; sethoxydim; tralkoxydim; tepraloxydim; diflufenican; flurtamone; isoproturon; aclonifen; diuron; bromoxynil; ioxynil; isoxaben and metosulam.

According to a further feature of the present invention there is provided a product comprising :

(a) a herbicidally effective amount of a cyclic amide compound of formula (I), or an agriculturally acceptable salt thereof; and

(b) an antidotally effective amount of an antidote; and wherein said antidote is antidotally effective to said cyclic amide compound; as a combined preparation for separate, simultaneous or sequential use in the control of weeds at a locus.

The following non-limiting Examples illustrate the invention. The antidotes used were as follows: Bl = daimuron B2 = dimepiperate B3 = fenclorim

B4 = fenchlorazole ethyl

B5 = cloquintocet-mexyl

B6 = naphthalic anhydride B7 = mefenpyr diethyl

B8 = benoxacor

B9 = (S) -1- (alpha-methylbenzyl) -3-p- tolylurea [(S)-MBU]

BIO = fenchlorazole Bll = oxabetrinil

B12 = flurazole

B13 = Naptalam

The compounds of formula (I) used were as follows : Al = l-cyclopentyl-2- (2, 3-dihydro-6- methyl-4-oxo-5-phenyl-4H-l, 3-oxazin-3-yl) -2- methylpropan-1-one

A2 = N- (2, 5-difluorophenyl) -2-methyl-2- [6-methyl-5- (2-fluorophenyl) -2, 3-dihydro-4- oxo-4H-l, 3-oxazin-3-yl] propanamide

A3 = N- (3-iodophenyl) -2-methyl-2- [ 6- methyl-5- (2-fluorophenyl) -2, 3-dihydro-4-oxo- 4H-l,3-oxazin-3-yl] propanamide

A4 = 4-cyclopropyl-2- (2, 3-dihydro-6- methyl-4-oxo-5-phenyl-4H-l, 3-oxazin-3-yl) -2- methylpentan-3-one .

Example 1A (Transplanted rice)

Seeds of Japonica rice were sown in compost in a glasshouse with supplementary illumination (14 hours). Rice plants at the 2- 3 leaf stage were transplanted into paddy pots containing puddled clay loam (3 plants per pot) . After 2 days the paddies were treated with compound Al dissolved in 0.5ml acetone, applied at three dose rates, and the antidotes (dissolved in 0.5ml acetone added prior to compound Al) at dose rates which gave herbicide : antidote ratios of 1:1 and 1:2. The paddies were watered as necessary and the rice visually assessed for the % reduction in growth 6 weeks after treatment.

Table 1 shows the percentage rice damage (three replicate values are given) following treatment with compound Al alone or in combination with an antidote compound Bl, B2, B3, B4 or B5.

Table 1

The results show that there was a significant antidote effect produced by the antidotes Bl to B5.

A similar experiment showed that no antidote effect was obtained when the rice was replaced by the weed species echinochloa crus- qalli . Example 2A (Rice Seed pre-treatment with antidote)

Japonica rice seed was shaken with antidote B6 powder to give known weight coatings of seed. The seed was germinated in the dark for five days and sown into pots containing a puddled loam/sand mixture. The pots was kept in a glasshouse with supplementary illumination (14 hours). After eleven days the soil surface was treated with an acetone solution of compound Al to give dose rates of 3-25g/ha. The pots were flooded and at 27 days were assessed for % growth reduction .

Table 2 shows the percentage rice damage following treatment with compound Al alone or in combination with antidote B6.

Table 2

antidotal effect was produced by the antidote B6 when applied as a seed pre-treatment .

Example 3A

Rice ( Oryza sa tiva ) var Ariete seeds were pre-germinated on filter paper soaked with water before being sown in tubes containing 20 ml 1% agar supplemented with Compound A2 or A3, with or without an antidote in solution in dimethylsulphoxide (0.2%). After 6 days growth in the dark at 26°C, the percentage inhibition of the root lengths (in mm) of the rice seedlings treated with A2 or A3 with or without antidote were compared to control values, as shown in Tables 3 and 4.

Table 3

Table 4

An excellent antidotal effect was produced by the antidotes Bl, B7 , B8 and B9.

Example 4A (Water seeded rice test in glasshouse)

Pre-germinated seeds of rice ( Oryza sa tiva ) var Ariete having roots of up to 5mm in length were sown onto the surface of a clay loam soil in paddy pots watered just to saturation, and the pots kept in a polythene tent in a glasshouse. When the plants were at about the half leaf growth stage the pots were sprayed with acetone solutions of compound A3 (30g/ha) and antidote Bl . Three days later the pots were flooded to a depth of about 2cm with water. A month after treatment the rice plant shoots were assessed for reduction of shoot growth as a % compared to that of untreated plants. Table 5 shows an antidote effect for Bl.

Table 5

Example 5A (Water seeded rice under field conditions)

A field trial was performed using water seeded rice and the plot sprayed with compound A4 at 60g/ha and antidotes Bl and B3. Table 6 shows the percentage reduction in growth of the rice compared to that of the untreated control when assessed 35 days after treatment. An antidote effect was observed for Bl and B3.

Table 6

Example 6A (an Imbibition method in Wheat)

A stack of microscope slides was placed on a filter paper which lined a petri dish base. A filter paper was positioned above the stack so that both filter papers joined to make a continuous absorption surface. Winter wheat seeds (variety Rialto) were placed on the raised bed of filter paper and microscope slides. A total of 6 ml of dosing solution of antidote was placed within the petri dish and the seeds imbibed with antidote at various rates. The lid of the petri dish was replaced, sealed and stored in darkness at 24°C for 16 hours, and the seeds then sown into a pot of loam and compound A2 applied at various rates. Treated pots were placed in a glasshouse under normal conditions and an assessment of the percentage reduction in growth of each plant compared to the untreated control plants was made 21 days after treatment.

Table 7

Table 8

Tables 7 and 8 show an antidote effect for B7, B10, B5, Bll, B12, B3 and B13.

Example 7A (In wheat using a tank mixture of A2 + antidote)

Winter wheat seeds (variety Rialto) were sown into pots of loam and sprayed with various antidotes at several application rates and then with compound A2. The pots were placed in a glasshouse under normal conditions, and the percentage reduction in growth of each plant was assessed compared to the untreated control plants at 21 days after treatment .

Table 9

Table 10

r B7, B4, B5, Bll, B12 and B3.

Claims

1. A method of reducing phytotoxicity to crops caused by a herbicidal cyclic amide derivative of formula (I):

( I ) wherein :

R4 and R^ independently represent alkyl; and i) -X-Y- represents -C (R^la) =C (R² ) -0-;

W represents NHR³ or R ^a;

R^la represents phenyl or thienyl optionally substituted by one to five groups which may be the same or different selected from halogen, hydroxy, alkyl, haloalkyl, alkoxy, haloalkoxy, -S(0)_nR⁶, -C0₂R⁶, -COR⁶, cyano, nitro, -0 (CH₂ ) q-C0 R⁶ and phenoxy; or represents R¹^^lS(0)_x; R^k represents alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl or cycloalkyl ;

R2 represents hydrogen, alkyl, haloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, alkoxyalkenyl, -CHO, -COR⁶, -C0₂R⁶, -CH₂N0₂, or alkyl which is substituted by a group selected from -S(0)_nR⁶, OH, -OCOR⁶ and -NR⁷R⁸; or a group selected from cyano, -CHO, -COR⁶, -C0₂H, -C0₂R⁶, -COSR⁶, -CONR⁷R⁸, -CH=NOH, -CH=NOR⁶, -CH=NOCOR⁶, -CH=NNR⁷R⁸, -CH₂CN,

-CH₂N0₂ and oxiranyl;

R³ represents phenyl optionally substituted by from one to five groups which may be the same or different selected from halogen, hydroxy, alkyl, haloalkyl, alkoxy, haloalkoxy, -S(0)_nR⁶, -C0₂R⁶, -COR⁶, cyano, nitro, -NR⁷R⁸, phenoxy, alkoxycarbonylalkoxy and -SF5;

R^3a represents - (CH₂ ) _r- (phenyl or naphthyl) which is optionally substituted by from one to five groups which may be the same or different selected from halogen, hydroxy, alkyl, haloalkyl, alkoxy, haloalkoxy,

-S(0)_nR⁶, -C0₂R⁶, -COR⁶, cyano, nitro, -0 (CH₂) _qC0₂R⁶, phenoxy and -SF5; or substituted by a group selected from -OCOR⁶, NR⁹R¹⁰, NHR^6a, -CH₂NR⁹R¹⁰, -CONR⁹R¹⁰,

-C0NHR^6a, -OS0₂R⁶, -OS0₂R^6a, -OCOR^6a,

-OCH₂COR^6a, -OCH₂R^6a, -S(0)_mR^6a, R^6a, -P(=0) (OR⁶) (OR^6b) , -P(=0) (OR⁶)R^6b ,

-CH₂P(=0) (OR⁶) (OR^6b) , -CH₂P(=0) (OR⁶)R^6b ,

-C0₂R^6a, -CH₂S(0)_nR⁶, -CH₂S(0)_mR^6a, -CH₂OR⁶,

-CH₂OR^6a, -CH₂OCOR^6a, -CH OS0₂R^6a and alkenyl (the phenyl and naphthyl rings may be additionally substituted by one or more halogen or R⁶ groups) ); or represents a phenyl ring optionally substituted by from one to five groups which may be the same or different selected from halogen, alkyl, haloalkyl, alkoxy, haloalkoxy,

-S(0)_nR⁶, CN and N0 , and which is fused to a second five or six membered cycloalkyl or cycloalkenyl ring, or to a saturated five or six membered heterocyclic ring (for example to give a 1 , 3-benzodioxole or 1 , 4-benzodioxane ring) which contains one to three heteroatoms which may be the same or different selected from nitrogen, oxygen and sulphur, said rings being optionally substituted by one or more groups R^-2 _or optionally one of the carbon atoms in the cycloalkyl, cycloalkenyl or saturated five or six membered heterocyclic ring may form a carbonyl group (it is understood that for fused ring systems it is the phenyl ring which is linked to the carbonyl group which forms part of -C(=0)W wherein W is R^3a); or represents a phenanthrene or anthracene ring optionally substituted by one or more groups selected from halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, -S(0)_nR⁶, CN and N0₂ ; or represents - (CH ) _s- ( five to seven membered heteroaromatic ring) wherein the heteroaromatic ring has from one to four ring heteroatoms which may be the same or different selected from nitrogen, oxygen and sulphur, said ring being optionally fused to a phenyl ring or to a second five to seven membered heteroaromatic ring having from one to four heteroatoms which may be the same or different selected from nitrogen, oxygen and sulphur, to form a bicyclic ring system, the monocyclic ring or either ring in the bicyclic system being optionally substituted by from one to four groups which may be the same or different selected from halogen, hydroxy, alkyl, cyano, haloalkyl, alkoxy, haloalkoxy, -S(0)_nR⁶,

-C0₂R⁶, -COR⁶, nitro, -0 (CH₂ ) _qC0₂R⁶ and phenoxy; or represents an optionally halogenated alkyl, alkenyl or alkynyl group containing up to ten carbon atoms; or represents an optionally halogenated alkyl, alkenyl or alkynyl group containing up to ten carbon atoms which is substituted by cycloalkyl containing from three to six carbon atoms (the cycloalkyl ring may be optionally substituted by one or more halogen or alkyl groups) ; or represents cycloalkyl containing from three to six carbon atoms or cycloalkenyl containing five or six carbon atoms, the ring systems of which are optionally substituted by a group R⁶ or one or more halogen atoms which may be the same or different; or represents cycloalkyl containing from three to eight carbon atoms or cycloalkenyl containing four to eight carbon atoms, wherein the ring systems are substituted by a group E which is selected from C0₂H, C0₂R⁶, alkenyl, haloalkenyl, R^6a, NR⁹R¹⁰, alkoxy, haloalkoxy, S(0)_nR⁶, COR⁶, COR^6a, CH₂COR^6a, COCH₂R^6a, C0₂CH₂R^6a, S(0)_mR^6a, CN, S(0)_tCH₂R^6a,

S(0)_uR¹⁴, CH₂OR⁶, CHO, COR¹¹, N0₂ , CONHR^6a,

CONR⁶R^6a, CH₂OH and -CH(OR¹³) (OR^13a)

(optionally the group -CH(OR¹³) (OR^13a) represents a five or six membered cyclic acetal optionally substituted by one or more

R⁶ groups), or one of the cycloalkyl carbon atoms forms part of a carbonyl group (optionally the above defined cycloalkyl or cycloalkenyl rings may contain in addition to E one or more halogen or R⁶ groups), and preferably the substituent E is attached to the carbon atom by which the cycloalkyl or cycloalkenyl group is attached to the carbonyl group which forms part of the -C(=0)W group wherein W is R^3a; or represents cycloalkyl containing from five to seven carbon atoms or cycloalkenyl containing five or six carbon atoms, the rings of which are optionally substituted by one or more groups R¹², and wherein the rings are fused to a phenyl ring (for example to form indanyl) optionally substituted by from one to four groups which may be the same or different selected from halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, -S(0)_nR⁶, cyano and nitro

(it is understood that for fused ring systems it is the cycloalkyl or cycloalkenyl ring which is linked to the carbonyl group which forms part of the -C(=0)W group wherein W is

R^3a); or represents alkyl or haloalkyl either of which is substituted by one or two R¹^ groups, optionally together with an R ⁶ group; or represents alkenyl or haloalkenyl either of which is substituted by one or two R ^ groups, optionally together with a group selected from R^6a, R¹⁷ and R¹⁸; or represents alkynyl substituted by a group

R¹^ (preferably an R¹^ group in the above definitions is located on the carbon atom of R ^a which is alpha or beta to the carbonyl group which forms part of -C(=0)W wherein W is

R^3a) ;

R⁶ and R^6b represent alkyl or haloalkyl;

R a represents phenyl optionally substituted by one or more groups which may be the same or different selected from halogen, alkyl, haloalkyl, alkoxy, haloalkoxy,

-S(0)_nR⁶, cyano and nitro;

R⁷,R⁸,R⁹ and R¹*-¹ independently represent hydrogen, alkyl or haloalkyl;

R¹ represents cycloalkyl containing from three to seven carbon atoms or cycloalkenyl containing five or six carbon atoms, wherein the ring systems are optionally substituted by one or more groups R¹²; R¹² represents halogen, alkyl or haloalkyl

R¹³ and R^13a represent alkyl, or the group -C(0R¹³) (OR^13a)- represents a five or six membered cyclic ketal, namely a 1,3- dioxolane or 1,3-dioxane ring of formula

-C(OR^13b) (OR^13c)- wherein R^13b and R^13c together represent a C2 or C3 alkylene chain which is optionally substituted by alkyl; R¹⁴ represents cycloalkyl containing from three to seven carbon atoms optionally substituted by one or more groups R¹²;

R¹⁵ represents -OH, -OR⁶, -S(0)_nR⁶,

-S(0)_mR^6a, -C0₂R⁶, -C0₂CH₂R^6a, CN, N0₂ , CHO, COR⁶, COR^6a, COCH R^6a, -C0 H, -CONR⁹R¹⁰,

-S (0) _tCH₂R^6a, -S(0)_pR¹⁸ or a five or six membered cyclic acetal group optionally substituted by one or more R⁶ groups;

R¹⁶ represents R^6a, alkynyl, or a three to six membered cycloalkyl ring optionally substituted by one or more R⁶ or halogen groups;

R¹⁷ represents a thienyl or furyl ring optionally substituted by one or more groups R¹²;

R ⁸ represents cycloalkyl containing from three to seven carbon atoms optionally substituted by one or more groups R¹²; m, n, p, t, u and x represent zero, one or two; q represents one or two; and r and s represent zero or one; or

ii) -X-Y- represents -C (R¹ ) =C (R^2a) -; R¹ represents phenyl optionally substituted by halogen, alkyl, haloalkyl, alkoxy or haloalkoxy;

R^2a represents alkyl; and

W represents -NHR^3c, wherein R^3c represents phenyl, naphthyl or a five or six membered heterocyclic ring containing one to three heteroatoms selected from oxygen, nitrogen and sulphur, the ring systems of which are optionally substituted by halogen, alkyl, haloalkyl, alkoxy, haloalkoxy,

-S(0)_nR⁶, -C0₂R⁶, nitro, cyano or -C0₂H; or

W represents R^3b, wherein R^3b represents alkyl, haloalkyl; phenyl optionally substituted by halogen, alkyl, haloalkyl or alkoxy; benzyl, alkenyl, haloalkenyl, alkynyl; C3-7 cycloalkyl optionally substituted by halogen or alkyl; or alkyl substituted by C3-7 cycloalkyl; or

R^2a represents hydroxy, alkoxy, haloalkoxy, -S(0)_nR⁶, amino, alkylamino or dialkylamino; and

W represents R³^ wherein R^3c represents alkyl, alkenyl, alkynyl, or benzyl or phenyl optionally substituted by halogen, alkyl, haloalkyl or -S(0)_nR⁶; or iii) -X-Y- represents -N (R¹ ) -CH (R^2a) - or -N (R¹) -CH(R^2a) -CH₂-; wherein R ^a represents alkyl; and W represents -NHR ^c or R^3b; or

iv) -X-Y- represents -N (R¹ ) -N (Me) -CH₂- or

-N(R¹)-0-; and

W represents NHR^3e or R^3b; and

R^3e represents phenyl optionally substituted by halogen, alkyl, haloalkyl, alkoxy, haloalkoxy or -S(0)_nR⁶; or

v) -X-Y- represents -C (R¹ ) =C (R^2a) -CH -;

-CH(R¹) -N(R^2a) - or -CH (R¹ ) -S (0) _v-; and W represents NHR^3c; and v represents zero, one or two; or an agriculturally acceptable salt thereof; which method comprises applying to the locus of the crop an antidotally effective amount of an antidote compound wherein the said antidote is antidotally effective to said cyclic amide derivative, optionally with a partner herbicide .

2. A method according to claim 1 in which the crop is a rice crop, and wherein, in formula (I) :

R⁴ and R^ independently represent alkyl; and i) -X-Y- represents -C (R^la) =C (R² ) -0-;

W represents NHR³ or R^3a; R^la represents phenyl or thienyl optionally substituted by one to five groups which may be the same or different selected from halogen, hydroxy, alkyl, haloalkyl, alkoxy, haloalkoxy, -S(0)_nR⁶, -C0₂R⁶, -COR⁶, cyano, nitro, -0 (CH₂ ) q-C0₂R⁶ and phenoxy;

R² represents hydrogen, alkyl, haloalkyl, alkoxyalkyl, haloalkoxyalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, alkoxyalkenyl, -CHO, -COR⁶, -C0₂R⁶, -CH₂N0 , or alkyl which is substituted by a group selected from -S(0)_nR⁶, OH, -OCOR⁶ and -NR⁷R⁸; or a group selected from cyano, -CHO, -COR⁶, -C0₂H, -C0₂R⁶, -COSR⁶, -CONR⁷R⁸, -CH=NOH,

-CH=NOR⁶, -CH=NOCOR⁶, -CH=NNR⁷R⁸, -CH₂CN, -CH₂N0₂ and oxiranyl;

R³ represents phenyl optionally substituted by from one to five groups which may be the same or different selected from halogen, hydroxy, alkyl, haloalkyl, alkoxy, haloalkoxy, -S(0)_nR⁶, -C0₂R⁶, -COR⁶, cyano, nitro, -NR R⁸, phenoxy, alkoxycarbonylalkoxy and -SF5; R^3a represents - (CH₂ ) _r- (phenyl or naphthyl) which is optionally substituted by from one to five groups which may be the same or different selected from halogen, hydroxy, alkyl, haloalkyl, alkoxy, haloalkoxy, -S(0)_nR⁶, -C0 R⁶, -COR⁶, cyano, nitro, -0 (CH₂) _qC0₂R⁶, phenoxy and -SF5; or substituted by a group selected from -OCOR⁶, NR⁹R¹⁰, NHR^6a, -CH₂NR⁹R¹⁰, -CONR⁹R¹⁰,

-CONHR^6a, -OS0₂R⁶, -OS0₂R^6a, -OCOR^6a, -0CH₂C0R^6a, -OCH₂R^6a, -S(0)_mR^6a, R^6a,

-P(=0) (OR⁶) (OR^6b) , -P(=0) (OR⁶)R^6b , -CH₂P(=0) (OR⁶) (OR^6b) , -CH₂P(=0) (OR⁶)R^6b ,

-C0₂R^6a, -CH₂S(0)_nR⁶, -CH₂S (0)_mR^6a, -CH₂OR⁶,

-CH₂OR^6a, -CH OCOR^6a, -CH₂OS0₂R^6a and alkenyl (the phenyl and naphthyl rings may be additionally substituted by one or more halogen or R⁶ groups) ); or represents a phenyl ring optionally substituted by from one to five groups which may be the same or different selected from halogen, alkyl, haloalkyl, alkoxy, haloalkoxy,

-S(0)_nR⁶, CN and N0₂ , and which is fused to a second five or six membered cycloalkyl or cycloalkenyl ring, or to a saturated five or six membered heterocyclic ring (for example to give a 1 , 3-benzodioxole or 1 , 4-benzodioxane ring) which contains one to three heteroatoms which may be the same or different selected from nitrogen, oxygen and sulphur, said rings being optionally substituted by one or more groups R¹² or optionally one of the carbon atoms in the cycloalkyl, cycloalkenyl or saturated five or six membered heterocyclic ring may form a carbonyl group (it is understood that for fused ring systems it is the phenyl ring which is linked to the carbonyl group which forms part of -C(=0)W wherein W is R ^a) ; or represents a phenanthrene or anthracene ring optionally substituted by one or more groups selected from halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, -S(0)_nR⁶, CN and N0₂ ; or represents - (CH₂ ) _s- (five to seven membered heteroaromatic ring) wherein the heteroaromatic ring has from one to four ring heteroatoms which may be the same or different selected from nitrogen, oxygen and sulphur, said ring being optionally fused to a phenyl ring or to a second five to seven membered heteroaromatic ring having from one to four heteroatoms which may be the same or different selected from nitrogen, oxygen and sulphur, to form a bicyclic ring system, the monocyclic ring or either ring in the bicyclic system being optionally substituted by from one to four groups which may be the same or different selected from halogen, hydroxy, alkyl, cyano, haloalkyl, alkoxy, haloalkoxy, -S(0)_nR⁶,

-C0₂R⁶, -COR⁶, nitro, -0 (CH₂) _qC0₂R⁶ and phenoxy) ; or represents an optionally halogenated alkyl, alkenyl or alkynyl group containing up to ten carbon atoms; or represents an optionally halogenated alkyl, alkenyl or alkynyl group containing up to ten carbon atoms which is substituted by cycloalkyl containing from three to six carbon atoms (the cycloalkyl ring may be optionally substituted by one or more halogen or alkyl groups ) ; or represents cycloalkyl containing from three to six carbon atoms or cycloalkenyl containing five or six carbon atoms, the ring systems of which are optionally substituted by a group R⁶ or one or more halogen atoms which may be the same or different; or represents cycloalkyl containing from three to eight carbon atoms or cycloalkenyl containing four to eight carbon atoms, wherein the ring systems are substituted by a group E which is selected from C0 H, C0₂R⁶, alkenyl, haloalkenyl, R^6a, NR⁹R¹⁰, alkoxy, haloalkoxy, S(0)_nR⁶, COR⁶, C0R^6a, CH₂COR^6a, COCH₂R^6a,

C0₂CH₂R^6a, S(0)_mR^6a, CN, S(0)_tCH₂R^6a,

S(0)_uR¹⁴, CH₂OR⁶, CHO, COR¹¹, N0₂, CONHR^6a,

CONR⁶R^6a, CH OH and -CH (OR¹³ ) (OR^13a) (optionally the group -CH (OR¹³ ) (0R^13a) represents a five or six membered cyclic acetal optionally substituted by one or more

R⁶ groups), or one of the cycloalkyl carbon atoms forms part of a carbonyl group (optionally the above defined cycloalkyl or cycloalkenyl rings may contain in addition to

E one or more halogen or R⁶ groups) , and preferably the substituent E is attached to the carbon atom by which the cycloalkyl or cycloalkenyl group is attached to the carbonyl group which forms part of the -C(=0)W group wherein W is R^3a; or represents cycloalkyl containing from five to seven carbon atoms or cycloalkenyl containing five or six carbon atoms, the rings of which are optionally substituted by one or more groups R¹², and wherein the ring systems are fused to a phenyl ring (for example to form indanyl) optionally substituted by from one to four groups which may be the same or different selected from halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, -S(0)_nR⁶, cyano and nitro (it is understood that for fused ring systems it is the cycloalkyl or cycloalkenyl ring which is linked to the carbonyl group which forms part of the -C(=0)W group wherein W is R ^a) ; or represents alkyl or haloalkyl either of which is substituted by one or two R¹^ groups, optionally together with an R¹⁶ group; or represents alkenyl or haloalkenyl either of which is substituted by one or two R¹^ groups, optionally together with a group selected from R^6a, R¹⁷ and R¹⁸; or represents alkynyl substituted by a group

R ^ (preferably an R¹^ group in the above definitions is located on the carbon atom of

R^3a which is alpha or beta to the carbonyl group which forms part of -C(=0)W wherein W is R^3a) ;

R⁶ and R ^b represent alkyl or haloalkyl; R^6a represents phenyl optionally substituted by one or more groups which may be the same or different selected from halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, -S(0)_nR⁶, cyano and nitro;

R⁷,R⁸,R⁹ and R '-' independently represent hydrogen, alkyl or haloalkyl;

R ¹ represents cycloalkyl containing from three to seven carbon atoms or cycloalkenyl containing five or six carbon atoms, wherein the ring systems are optionally substituted by one or more groups R¹²;

R¹² represents halogen, alkyl or haloalkyl

R¹³ and R^13a represent alkyl, or the group -C(OR¹³) (OR^{1 a})- represents a five or six membered cyclic ketal, namely a 1,3- dioxolane or 1,3-dioxane ring of formula

-C(OR^13b) (OR^13c)- wherein R^13b and R^13c together represent a C2 or C3 alkylene chain which is optionally substituted by alkyl;

R¹⁴ represents cycloalkyl containing from three to seven carbon atoms optionally substituted by one or more groups R¹²; R¹⁵ represents -OH, -OR⁶, -S(0)_nR⁶,

-S(0)_mR^6a, -C0₂R⁶, -C0 CH₂R^6a, CN, N0 , CHO,

COR⁶, COR^6a, COCH₂R^6a, -C0₂H, -CONR⁹R¹⁰,

-S (0) _tCH R^6a, -S(0)_pR¹⁸ or a five or six membered cyclic acetal group optionally substituted by one or more R⁶ groups; R¹⁶ represents R^6a, alkynyl, or a three to six membered cycloalkyl ring optionally substituted by one or more R⁶ or halogen groups ; R¹⁷ represents a thienyl or furyl ring optionally substituted by one or more groups

R¹²;

R¹⁸ represents cycloalkyl containing from three to seven carbon atoms optionally substituted by one or more groups R¹²; m, n, p, t and u represent zero, one or two; q represents one or two; and r and s represent zero or one; or

ii) -X-Y- represents -C (R¹ ) =C (R^2a) -;

R¹ represents phenyl optionally substituted by halogen, alkyl, haloalkyl, alkoxy or haloalkoxy; R ^a represents alkyl; and

W represents -NHR ^c, wherein R^3c represents phenyl, naphthyl or a five or six membered heterocyclic ring containing one to three heteroatoms selected from oxygen, nitrogen and sulphur, the ring systems of which are optionally substituted by halogen, alkyl, haloalkyl, alkoxy, haloalkoxy,

-S(0)_nR⁶, -C0₂R⁶, nitro, cyano or -C0₂H; or

W represents R ^b, wherein R ^b represents alkyl, haloalkyl; phenyl optionally substituted by halogen, alkyl, haloalkyl or alkoxy; benzyl, alkenyl, haloalkenyl, alkynyl; C3-7 cycloalkyl optionally substituted by halogen or alkyl; or alkyl substituted by C3-7 cycloalkyl; or

R ^a represents hydroxy, alkoxy, haloalkoxy, -S(0)_nR⁶, amino, alkylamino or dialkylamino; and

W represents R^3c wherein R ^c represents alkyl, alkenyl, alkynyl, or benzyl or phenyl optionally substituted by halogen, alkyl, haloalkyl or -S(0)_nR⁶; or

iii) -X-Y- represents -N (R¹ ) -CH (R^2a) - or -N(R¹) -CH(R^2a)-CH₂-; and R^2a represents alkyl;

W represents -NHR^3c or R^3b; or

iv) -X-Y- represents -N (R¹ ) -N (Me) -CH₂- or

-N(R¹)-0-; and W represents NHR^3e or R^3b; and

R^3e represents phenyl optionally substituted by halogen, alkyl, haloalkyl, alkoxy, haloalkoxy or -S(0)_nR⁶; or

v) -X-Y- represents -C (R¹ ) =C (R^2a) -CH₂-;

-CH(R¹) -N(R^2a) - or -CH (R¹ ) -S (0) _v-; and

W represents NHR^3c; and v represents zero, one or two; or an agriculturally acceptable salt thereof; which method comprises applying to the locus of the rice crop an antidotally effective amount of an antidote compound wherein the said antidote is antidotally effective to said cyclic amide derivative.

3. A method according to claim 1 wherein the crop is rice, wheat or barley.

4. A method according to claim 1 or 3 wherein, in formula (I):

-X-Y- represents -C (R^la) =C (R² ) -0-;

R^la represents phenyl or thienyl each of which is optionally substituted by one to three groups which may be the same or different selected from halogen, alkyl, haloalkyl and alkoxy; or represents alkylthio;

R² represents alkyl, haloalkyl or hydrogen; W represents NHR³ or R^3a;

R³ represents phenyl substituted by from one to three groups which are the same or different selected from halogen, alkyl, haloalkyl and haloalkoxy; R^3a represents cycloalkyl containing from three to six carbon atoms or cycloalkenyl containing five or six carbon atoms, the ring systems of which are optionally substituted by a group R⁶ or one or more halogen atoms which may be the same or different; or R^3a represents an optionally halogenated alkyl group containing up to four carbon atoms which is substituted by cycloalkyl containing from three to six carbon atoms (the cycloalkyl ring may be optionally substituted by one or more halogen or alkyl groups) ; and

R⁴ and R represent methyl.

5. A method according to claim 1 or 3 wherein -X-Y- represents -C (R^la) =C (R² ) -0-;

R^la represents phenyl, 2-chlorophenyl, 2- fluorophenyl, 2-methylphenyl or alkylthio ; R² represents methyl, ethyl or fluoromethyl;

W represents NHR³ or NHR^3a;

R³ represents 3-halophenyl, 2,5- dihalophenyl, 3, 5-dihalophenyl, 2-halo-5- haloalkoxyphenyl, 3-haloalkylphenyl or 3-halo- 5-alkylphenyl;

R^3a represents cyclopentyl or cyclopentenyl optionally substituted by a group R⁶ or one or more halogen atoms which may be the same or different; or R^3a represents methyl which is substituted by cyclopentyl or cyclopentenyl optionally substituted by one or more halogen or alkyl groups; or R^3a represents an alkyl group containing up to four carbon atoms which is substituted by cyclopropyl unsubstituted or substituted by alkyl ; and

R⁴ and R^ represent methyl.

6. A method according to claim 1 wherein the said derivative of formula (I) is selected from: N- (2, 5-difluorophenyl) -2-methyl-2- [6- methyl-5- (2-fluorophenyl) -2, 3-dihydro-4-oxo- 4H-1 , 3-oxazin-3-yl] propanamide; and

N- (3-iodophenyl) -2-methyl-2- [6-methyl-5- (2-fluorophenyl) -2, 3-dihydro-4-oxo-4H-l , 3- oxazin-3-yl] propanamide .

7. A method according to Claim 1 or 3 wherein the antidote is selected from: (i) a compound of the formula (II) :

R ⁰-CO-NR⁷²R⁷¹

(ID wherein R 70 is selected from the group consisting of haloalkyl; haloalkenyl; alkyl; alkenyl; cycloalkyl; cycloalkylalkyl; halogen; hydrogen; carboalkoxy; N-N- alkynylcarbamylalkyl; N- alkenylcarbamylalkoxyalkyl ; N-alkyl-N- alkynylcarbamylalkoxyalkyl ; alkynyloxy; haloalkoxy; thiocyanatoalkyl; alkenylaminoalkyl; alkylcarboalkyl; cyanoalkyl; cyanatoalkyl; alkenylaminosulfonalkyl; alkylthioalkyl; haloalkylcarbonyloxyalkyl; alkoxycarboalkyl; haloalkenylcarbonyloxyalkyl; hydroxyhaloalkyloxyalkyl ; hydroxyaIkylcarboaIkyloxyalkyl ; hydroxyalkyl; alkoxysulfonoalkyl; furyl; thienyl; alkyldithiolenyl ; thienalkyl; phenyl; substituted phenyl wherein the substitutents can be selected from halogen, alkyl, haloalkyl, alkoxy, carbamyl, nitro, carboxy and salts thereof, and haloalkylcarbamyl; phenylalkyl; phenylhaloalkyl; phenylalkenyl; substituted phenylalkenyl wherein the substituents can be selected from halogen, alkyl, alkoxy, and halophenoxy, phenylalkoxy; phenylalkylcarboxyalkyl; phenylcycloalkyl; halophenylalkenoxy; halothiophenylalkyl ; halophenoxyalkyl; bicycloalkyl; alkenylcarbamylpyridinyl; alkynylcarbamylpyridinyl ; dialkenylcarbamylbicycloalkenyl and alkyny1carbamylbicycloalkenyl; R 71 and R72 , which may be the same or different, are selected from the group consisting of alkenyl; haloalkenyl; hydrogen; alkyl; haloalkyl; alkynyl; cyanoalkyl; hydroxyalkyl; hydroxyhaloalkyl ; haloalkylcarboxyalkyl; alkylcarboxyalkyl ; alkoxycarboxyalkyl; thioalkylcarboxyalkyl; alkoxycarboalkyl; alkylcarbamyloxyalkyl ; amino; formyl; haloalkyl-N-alkylamido; haloalkylamido; ha1oalkylamidoalkyl ; haloalkyl-N-alkylamidoalkyl; haloalkylamidoalkenyl; alkylimino; cycloalkyl; alkylcycloalkyl; alkoxyalkyl; alkylsulfonyloxyalkyl; mercaptoalkyl; alkylaminoalkyl; alkoxycarboalkenyl; haloalkylcarbonyl; aIky1carbonyl ; alkenylcarbamyloxyalkyl; cycloaIkylcarbamyloxyalkyl; alkoxycarbonyl ; haloalkoxycarbonyl; halophenylcarbamyloxyalkyl; cycloalkenyl; phenyl; substituted phenyl wherein said substitutents can be selected from alkyl, halogen, haloalkyl, alkoxy, haloalkylamido, phthalimido, hydroxy, alkylcarbamyloxy, alkenylcarbamyloxy, alkylamido, haloalkylamido and alkylcarboalkenyl; phenylsulfonyl ; substituted phenylalkyl wherein said substituents can be selected from halogen or alkyl; dioxyalkylene; halophenoxyalkylamido-alkyl ; alkylthiodiazolyl; piperidyl; piperidylalkyl; dioxolanylalkyl; thiazolyl; alkylthiazolyl; benzothiazolyl; halobenzothiazolyl; furyl; alkyl-substituted furyl; furylalkyl; pyridyl; alkylpyridyl; alkoxyazolyl ; tetrahydrofurylalkyl ; 3-cyano-thienyl; alkyl substituted thienyl; , 5-polyalkylene thienyl; ╬▒-haloalkylacetamidophenylalkyl; ╬▒- haloalky1acetamidonitrophenylalkyl; ╬▒- ha1oalkylacetamidohalopheny1alkyl; cyanoalkenyl; and naphthyl (as in for example naptalan) or R 71 and R72 when taken together can form a structure consisting of piperidinyl; alkylpiperidinyl; pyridyl; di- or tetrahydropyridinyl; alkyltetrahydropyridyl; morpholyl; 2,3-dihydro-l, 4-benzoxazine, azabicyclononyl; diazacycloalkanyl; benzoalkylpyrrolidinyl; oxazolidinyl; perhydrooxazolidinyl; alkyloxazolidinyl ; furyloxazolidinyl; thienyloxazolidinyl; pyridyloxazolidinyl; pyrimidinyloxazolidinyl; benzooxazolidinyl; C3.7 spirocycloalkyl- oxazolidinyl; alkylaminoalkenyl; alkylideneimino; pyrrolidinyl ; piperidonyl; perhydroazepinyl; perhydroazocinyl; pyrazolyl; -tetrahydro- or perhydroquinolyl or isoquinolyl; indolyl or di- or perhydroindolyl; and which combined R 71and R72 members can be substituted with those independent R 71 and R72 radicals enumerated above; or

(ii) one of the following compounds: ╬▒ - [ (cyanomethoxy) imino] benzeneacetonitrile; - [ (1, 3-dioxolan-2- ylmethoxy) imino] -benzeneacetonitrile;

0- [3-dioxolan-2-ylmethyl] -2,2,2- trifluoromethyl-4 ' -chloroacetophenone oxime; benzenemethamine, N-[4- (dichloromethylene) -1, 3-dithiolan-2-ylidene] -╬▒ -methyl, hydrochloride; diphenylmethoxy acetic acid methyl ester;

1, 8-naphthalic anhydride; cloquintocet (5-chloroquinoline-8-yloxy acid) or a salt or ester thereof such as cloquintocet-mexyl ( 1-methylhexyl (5-chloroquinoline-8-yloxy) acetate) ;

4 , 6-dichloro-2-phenylpyrimidine;

2-chloro-N-[l- (2, 4, 6-trimethylphenyl ) ethenyl] acetamide; ethylene glycol acetal of 1, 1-dichloroacetone; fenchlorazole (l-(2, 4-dichlorophenyl ) - 5-trichloromethyl) -1if-1, 2, 4-triazole- 3-carboxylic acid) , or a salt or ester thereof such as fenchlorazole-ethyl (ethyl 1- (2, 4-dichlorophenyl) -5-trichloromethyl) - lJi-1, 2, 4-triazole-3-carboxylate) ; benoxacor; dichlormid; fenclorim; furilazole or mefenpyr diethyl (diethyl (RS ) -1- (2 , 4-dichlorophenyl) - 5-methyl-2-pyrazoline-3 , 5-dicarboxylate) ; flurazole; 5, 5-diphenylisoxazolinone-3- carboxylic acid and ethyl 5,5- diphenylisoxazolinone-3-carboxylate (AEF- 129431); CMPI (N- ( 4-chlorophenyl ) maleimide) ; 4-hydroxy-l-methyl-3- (l-lf-tetrazol-5- ylmethanoyl ) -lH-quinolin-2-one;or

3- (5-tetrazolylcarbonyl) -2-quinolones of formula (III ) :

( III ) wherein A -A3 repre sent a direct bond ,

-C ( =Q ) - , -C ( =Q ) -T- , - SO- , -S0₂ - or -S0₂NR^{8 6}- ;

Q represents 0 or S; T = 0; S; or NR⁸⁶; R⁸³-

R⁸⁶ independently represent H, optionally substituted phenyl, optionally substituted phenyl-Cl-6 alkyl, optionally substituted C2-6 alkenyl, optionally substituted C2-6 alkynyl, optionally substituted C3-9 cycloalkyl; or alkyl optionally substituted by 1 or more halo, N0₂, CN, SCN, Cl-4 alkoxy, Cl-4 alkylthio, Cl-4 alkylsulphinyl, Cl-4 alkylsulphonyl, C2-4 alkenyl and C2-4 alkynyl or optionally substituted C3-9 cycloalkyl, optionally substituted phenyl and/or optionally substituted 3-6 membered heterocyclyl containing 1-3N, 0 and/or S atoms; R⁷⁹-R⁸² represent H, NH₂, COOH, CHO, OH, halo, N0₂ , CN, SCN, J-R⁸⁷, J-R⁸⁸; or 2 of

R⁷⁹-R⁸² on adjacent C atoms form together with these C atoms a 5- or 6-membered unsaturated or partly saturated ring optionally containing 1-3 0, S and/or N atoms and optionally substituted by 1 or more halo, Cl-4 alkyl and/or oxo; or -A]_-R⁸³ and R⁸² together with their associated ring atoms form a 5- to 7- membered unsaturated or partly saturated ring optionally containing 1-3 0, S and/or N atoms and optionally substituted by 1 or more halo, Cl-4 alkyl and/or oxo; J = direct bond,

S(=0)_w, S(=0)_w-0, C(=Q), C(=Q)-Q, 0-C0₂, NR⁸⁹, NR⁸⁹-0, NR⁸⁹ -(C=0), NR⁸⁹ C0₂, NR⁸⁹-CO-NR⁹⁰ or

0; R⁸⁷ represents optionally substituted Cl-6 alkyl, C2-6 alkenyl or C2-6 alkynyl; R⁸⁸ represents optionally substituted unsaturated or partly saturated carbocyclyl, C3-8 cycloalkyl, phenyl or heterocyclyl; R⁸⁹ and

R⁹⁰ represent H, Cl-6 alkyl, C3-6 cycloalkyl, Cl-5 alkylcarbonyl, phenyl or benzyl; w represents 0,1 or 2; or iii) N-phenyl-N' -alkylureas such as daimuron [1- (1-methyl-l-phenylethyl) -3-p- tolylurea] or (S) -1- (alpha-methylbenzyl ) -3-p- tolylurea [(S)-MBU]; or thiocarbamates such as dimepiperate (S-l-methyl-1- phenylethylpiperidine-1-carbothioate) ; or (iv)oximes having the general formula: Ar (NC)C=N0CH₂R⁹¹ in which Ar is phenyl which is unsubstituted or substituted by, for example, methyl, methoxy, chlorine, cyano or trifluoromethyl, or Ar is a naphthyl radical;

R⁹¹ is cyano, -C (NH ) (OR_e) (OR_f) , -C(=0)NHNH₂, -C(=0)N(R_c) (R_d) , or -CN(R_g) (R_h), where R_e and Rf independently represent alkyl, or together with the carbon form an oxygen or sulfur containing 5- or 6- membered heterocyclic ring which is unsubstituted or substituted by lower alkyl, halogen and/or nitro; (R_c) and (Rd) are independently hydrogen, alkyl or cycloalkyl, which are unsubstituted or further substituted with one or more halogen, alkoxy and/or cyano groups; (Rq) and (Rh) together with the nitrogen form a 5- or 6-membered ring which is unsubstituted or mono- or polysubstituted by halogen, cyano and/or alkyl and which can be interrupted by a nitrogen, oxygen or sulfur atom, representative compounds of this type being those in which R 91 is cyano, and in which R91 is 1 , 3-dioxolan-2-yl, such as oxabetrinil (0-

[2- (1, 3-dioxolanyl ) methyl] -alpha- cyanobenzaldoxime) ; or

(v) thiazole carboxylic acids and derivatives including benzyl-2-chloro-4- trifluoromethyl-5-thiazole carboxylate;

(vi) compounds having the formula:

wherein R 98 is C1-C3 haloalkyl containing from 1 to 3 halogen atoms or a phenyl group which is optionally substituted; R 96 represents a hydrogen atom, methyl or phenyl; R 97 represents a hydrogen atom, methyl or phenyl; R 97 represents a C]_ -C╬▓ alkyl group, a

C5 -Cg cycloalkyl group, a cyclohexylmethyl group, a phenyl group which is optionally substituted, a benzyl group which is optionally substituted, an allyl or propargyl group; and z is zero or one, such as:

8. A method according to Claim 1 or 3 wherein the antidote is selected from daimuron, dimepiperate, fenclorim, fenchlorazole ethyl, cloquintocet-mexyl, 1,8- naphthalic anhydride, mefenpyr diethyl, benoxacor, (S) -1- (alpha-methylbenzyl) -3-p- tolylurea [(S)-MBU], oxabetrinil, flurazole and naptalam.

9. A method according to Claim 1, 2 or 3 in which the weight ratio of the cyclic amide derivative of formula (I): antidote is from about 1:20 to about 30:1.

10. A herbicidal composition comprising:

(a) a herbicidally effective amount of a cyclic amide derivative of formula (I) as defined in claim 1 or an agriculturally acceptable salt thereof, and optionally a partner herbicide; and

(b) an antidotally effective amount of an antidote as defined in claim 7; in association with an agriculturally acceptable diluent or carrier and/or surface active agent.

11. A composition according to Claim 10 in which the said cyclic amide derivative is selected from:

N- (2, 5-difluorophenyl) -2-methyl-2- [6- methyl-5- (2-fluorophenyl) -2, 3-dihydro-4-oxo- 4H-l,3-oxazin-3-yl] propanamide; and

N- (3-iodophenyl) -2-methyl-2- [ 6-methyl-5- (2-fluorophenyl) -2 , 3-dihydro-4-oxo-4H-l , 3- oxazin-3-yl] propanamide .

12. A composition according to Claim 10 or 11 in which the antidote is selected from daimuron, dimepiperate, fenclorim, fenchlorazole ethyl, cloquintocet-mexyl, 1,8- naphthalic anhydride, mefenpyr diethyl, benoxacor and (S) -1- (alpha-methylbenzyl) -3-p- tolylurea [ (S) -MBU] .

13. A composition according to Claim 10 or 11 in which the antidote is selected from mefenpyr diethyl, fenchlorazole ethyl, cloquintocet-mexyl, oxabetrinil, flurazole, fenclorim and naptalam.

14. A composition according to any one of Claims 10 to 13 for application at a rate of the cyclic amide derivative of formula (I) of from 1 g/ha to 1000 g/ha.

15. A composition according to any one of Claims 10 to 13 for application at a rate of the cyclic amide derivative of formula (I) of from 25 g/ha to 250 g/ha.

16. A composition according to any one of Claims 10, 11, 12, 14 and 15 which is suitable for application to rice.

17. A composition according to any one of Claims 10, 11, 13, 14 and 15 which is suitable for application to wheat or barley.

18. A product comprising:

(a) a herbicidally effective amount of a cyclic amide derivative as defined in any one of claims 1 to 6, or an agriculturally acceptable salt thereof; and

(b) an antidotally effective amount of an antidote as defined in claim 7 or 8; and wherein said antidote is antidotally effective to said cyclic amide derivative; for separate, simultaneous or sequential use in the control of weeds at a crop locus with reduced phytotoxicity.