The present invention relates to microbiocidal benzoxaboroles derivatives, e.g., as active ingredients, which have microbiocidal activity, in particular fungicidal activity. The invention also relates to the preparation of these benzoxaboroles derivatives. The invention also relates to agrochemical compositions which comprise at least one of these benzoxaboroles derivatives and to uses of the benzoxaboroles derivatives or compositions thereof in agriculture or horticulture for controlling or preventing the infestation of plants, harvested food crops, seeds or non-living materials by phytopathogenic microorganisms, preferably fungi.

The present invention accordingly relates to substituted benzoxaboroles of formula (I)

wherein

R ^a is fluorine, chlorine, bromine, cyano, unsubstituted Ci-C4alkyl, Ci-C4alkyl substituted by one to three R , unsubstituted Ci-C4haloalkyl, Ci-C4haloalkyl substituted by one to three R ² , unsubstituted Ci-C4alkoxy, Ci-C4alkoxy substituted by one to three R , unsubstituted Ci-C4haloalkoxy, Ci-

C4haloalkoxy substituted by one to three R ² , unsubstituted C2-C6alkynyl, or C2-C6alkyny substituted by one to three R ;

R is unsubstituted Ci-C4alkyl, Ci-C4alkyl substituted by one to three R , unsubstituted Ci-C4haloalkyl, Ci-C4haloalkyl substituted by one to three R ² , unsubstituted Ci-C4alkoxy, Ci-C4alkoxy substituted by one to three R , unsubstituted Ci-C4haloalkoxy, Ci-C4haloalkoxy substituted by one to three R ² , unsubstituted C2-C6alkenyl, C2-C6alkenyl substituted by one to three R , unsubstituted C2-C6alkynyl, C2-C6alkynyl substituted by one to three R , unsubstituted phenyl, phenyl substituted by one to three R ³ , unsubstituted phenyl-Ci-C4alkyl, phenyl-Ci-C4alkyl substituted by one to three R ³ , unsubstituted 5- 6 membered heteroaryl, 5-6 membered heteroaryl substituted by one to three R ³ , unsubstituted d- C6cycloalkyl, or C3-C6cycloalkyl substituted by one to three R ;

R is independently halogen, cyano, nitro, amino, hydroxy, oxo, Ci-dalkylamino, hydroxyimino, Ci- Csalkyloxyimino, N.N-C-i-Csdialkylamino, d-dalkoxy, acetyloxy, formyloxy, d-Cshaloalkoxy, Ci- C4alkylthio or (Ci-C4alkyl)o-3silyl;

R ² is independently cyano, nitro, amino, hydroxy, oxo, Ci-Csalkylamino, hydroxyimino, Ci- dalkyloxyimino, N.N-Ci-Csdialkylamino, Ci- alkoxy, acetyloxy, formyloxy, Ci- haloalkoxy, Ci- C4alkylthio or (Ci-C4alkyl)o-3silyl;

R ³ is independently halogen, cyano, nitro, d-dalkyl, d-dhaloalkyl, Ci-dalkoxy, or Ci-dhaloalkoxy; n is an interger 0 to 2;

or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide of thereof.

As used herein, the term "halogen" refers to fluorine, chlorine, bromine or iodine.

As used herein, the term "cyano" means a -CN group.

As used herein, the term "hydroxyl" or "hydroxy" stands for a -OH group. „

- 2 -

As used herein, oxo means a =0 group.

As used herein, amino means an -NH2 group.

As used herein, nitro means an -NO2 group.

As used herein, the term "d-Csalkyl" refers to a straight or branched hydrocarbon chain radical consisting solely of carbon and hydrogen atoms, containing no unsaturation, having from one to eight carbon atoms, and which is attached to the rest of the molecule by a single bond. Examples of Ci- Csalkyl include, but are not limited to, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl and the isomers thereof, for example, iso-propyl, iso-butyl, sec-butyl, tert-butyl or iso-amyl.

As used herein, the term "d-Cshaloalkyl" refers to a straight or branched hydrocarbon chain radical consisting solely of carbon, hydrogen and halogen atoms, containing no unsaturation, having from one to eight carbon atoms, and which is attached to the rest of the molecule by a single bond. Examples of d-Cshaloalkyl include, but are not limited to, CH2CI, CHCI2, CCI ₃ , CH2F, CHF2, CF ₃ , CF3CH2, CH3CF2, CF3CF2 or CCI3CCI2.

As used herein, the term "d-Cealkenyl" refers to a straight or branched hydrocarbon chain radical group consisting solely of carbon and hydrogen atoms, containing at least one double bond that can be of either the (E)- or (Z)-configuration, having from two to six carbon atoms, which is attached to the rest of the molecule by a single bond. Examples of d dalkenyl include, but are not limited to, prop-1-enyl, allyl (prop-2-enyl), but-1-enyl.

As used herein, the term "d-Cealkynyl" refers to a straight or branched hydrocarbon chain radical group consisting solely of carbon and hydrogen atoms, containing at least one triple bond, having from two to six carbon atoms, and which is attached to the rest of the molecule by a single bond. Examples of d dalkynyl include, but are not limited to, prop-1-ynyl, propargyl (prop-2-ynyl), but-1-ynyl.

As used herein, the term "Ci-Csalkoxy" refers to a radical of the formula -OR _a where R _a is a Ci- Csalkyl radical as generally defined above. Examples of Ci-Cs alkoxy include, but are not limited to, methoxy, ethoxy, 1-methylethoxy (iso-propoxy), propoxy, butoxy, 1-methylpropoxy and 2- methylpropoxy.

As used herein, the term "d-Cshaloalkoxy" refers to a radical of the formula -OR _a where R _a is a d-Cshaloalkyl radical as generally defined above. Examples of d-Cshaloalkoxy include, but are not limited to, CH2CIO, CHCI2O, CCI3O, CH2FO, CHF2O-, CF3O-, CF3CH2O-, CH3CF2O, CF3CF2O- or

As used herein, the term "acetyloxy" refers to a group of the formula -OC(0)CH3.

As used herein, the term "formyloxy" refers to a group of the formula -OC(0)H.

As used herein, the term "hydroxyimino" refers to a group of the formula =NOH.

As used herein, the term "Ci Csalkyloxyimino" refers to a radical of the formula =NOR _a where R _a is a Ci-Csalkyl radical as generally defined above. Examples of Ci Csalkyloxyimino include, but are not limited to methoxyimino or ethoxyimino.

As used herein, the term "Ci-dalkylthio" refers to a radical of the formula -SR _a where R _a is a Ci- dalkyl radical as generally defined above. Examples of Ci-dalkylthio include, but are not limited to, methylthio, ethylthio, propylthio or butylthio. As used herein, the term "C3-C6cycloalkyl" refers to a radical which is a mono- or bicyclic saturated ring system and which contains 3 to 6 carbon atoms. Examples of C3-C6cycloalkyl include, but are not limited to, cyclopropyl, 1-methylcyclopropyl, 2-methylcyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

As used herein, the term "Ci Csalkylamino" refers to a radical of the formula -NHR _a where R _a is a d-Csalkyl radical as generally defined above.

As used herein, the term "N.N-Ci Csdialkylamino" refers to a radical of the formula -N(R _a )R _a where each R _a independently of each other is a d-Csalkyl radical as generally defined above.

As used herin, the term "(Ci-C4alkyl)o-3silyl" refers to a radical of the formula -Si(R _a )o-3, where each R _a is independently of each other a Ci-C4alkyl radical as generally defined above. Examples of (Ci-C4alkyl)o-3silyl include but are not limited to, trimethylsilyl or dimethylsilyl.

As used herein, the term "phenyld dalkyl" refers to a phenyl ring attached to the rest of the molecule by a d-4alkylene radical as defined above. Examples of phenyld-4alkyl include, but are not limited to, benzyl.

As used herein, the term "heteroaryl" refers to a 5- or 6-membered monocyclic aromatic ring, which comprises 1 , 2, 3 or 4 heteroatoms individually selected from nitrogen, oxygen and sulfur. The heteroaryl radical is bonded to the rest of the molecule via a carbon atom or a heteroatom. Examples of heteroaryl include, furyl, pyrrolyl, thienyl, pyrazolyl, imidazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, tetrazolyl, pyrazinyl, pyridazinyl, pyrimidyl, pyridyl, or indolyl. The presence of an acyclic C=N double bond in the compounds of formula I means that they may occur as E-isomer, as Z-isomer or as mixture of E and Z isomers. Also enantiomers may occur as a result of the presence of a possible asymmetric carbon atom. Furthermore also atropisomers may occur as a result of restricted rotation about a single bond. Formula I is intended to include all those possible isomeric forms, enantiomers, diastereomers and atropisomers, and mixtures thereof. The present invention includes all those possible isomeric forms and mixtures thereof for a compound of formula I.

In each case, the compounds of formula I according to the invention are in free form, in oxidized form as a N-oxide or in salt form, e.g. an agronomically usable salt form.

N-oxides are oxidized forms of tertiary amines or oxidized forms of nitrogen containing heteroaromatic compounds. They are described for instance in the book "Heterocyclic N-oxides" by A. Albini and S. Pietra, CRC Press, Boca Raton 1991.

The following list provides definitions, including preferred definitions, for substituents R, R ^a , R , R ² and R ³ , with reference to compounds of formula (I). For any one of these substituents, any of the definitions given below may be combined with any definition of any other substituent given below or elsewhere in this document.

Preferably R ^a is fluorine, chlorine, or Ci-C4alkyl; More preferably R ^a is fluorine, chlorine, or methyl; Most preferably R ^a is fluorine, or chlorine.

Preferably R is unsubstituted Ci-C4alkyl, Ci-C4alkyl substituted by one to three R , unsubstituted d- C4haloalkyl, Ci-C4haloalkyl substituted by one to three R ² , unsubstituted C2-C6alkenyl, C2-C6alkenyl substituted by one to three R , unsubstituted phenyl-Ci-C4alkyl, phenyl-Ci-C4alkyl substituted by one to three R ³ , unsubstituted C3-C6cycloalkyl, or C3-C6cycloalkyl substituted by one to three R ; More preferably R is unsubstituted Ci-C4alkyl, Ci-C4alkyl substituted by one to three R\ unsubstituted Ci- C4haloalkyl, Ci-C4haloalkyl substituted by one to three R ² , unsubstituted C2-C6alkenyl, C2-C6alkenyl substituted by one to three R\ unsubstituted C3-C6cycloalkyl, or C3-C6cycloalkyl substituted by one to three R ; Most preferably R is unsubstituted Ci-C4alkyl, Ci-C4alkyl substituted by one to three R\ unsubstituted Ci-C4haloalkyl, Ci-C4haloalkyl substituted by one to three R ² , unsubstituted C2- Cealkenyl, C2-C6alkenyl substituted by one to three R\ unsubstituted C3-C6cycloalkyl, or C3- C6cycloalkyl substituted by one to three R .

Preferably R is independently halogen, cyano, nitro, amino, hydroxy, oxo, d-Csalkoxy, acetyloxy, formyloxy, Ci-Cshaloalkoxy, or (Ci-C4alkyl)o-3silyl; More preferably R is independently halogen, cyano, nitro, amino, hydroxy, oxo, Ci-Csalkoxy, acetyloxy, formyloxy, Ci-Cshaloalkoxy, or (Ci-C4alkyl)o-3silyl; Preferably R ² is independently cyano, nitro, amino, hydroxy, oxo, Ci-Csalkoxy, acetyloxy, formyloxy, Ci-Cshaloalkoxy, or (Ci-C4alkyl)o-3silyl; More preferably R ² is independently cyano, nitro, amino, hydroxy, oxo, Ci-Csalkoxy, acetyloxy, formyloxy, Ci-Cshaloalkoxy, or (Ci-C4alkyl)o-3silyl.

Preferably R ³ is independently halogen, cyano, nitro, Ci-Csalkyl, Ci-Cshaloalkyl, Ci-Csalkoxy, or Ci- Cshaloalkoxy; More preferably R ³ is independently halogen, cyano, nitro, Ci-Csalkyl, Ci-Cshaloalkyl, Ci-Csalkoxy, or Ci-Cshaloalkoxy.

Preferably n is an interger 0 or 1.

Preferably R ^a is fluorine, chlorine, or Ci-C4alkyl;

R is unsubstituted Ci-C4alkyl, Ci-C4alkyl substituted by one to three R , unsubstituted Ci-C4haloalkyl, Ci-C4haloalkyl substituted by one to three R ² , unsubstituted C2-C6alkenyl, C2-C6alkenyl substituted by one to three R , unsubstituted phenyl-Ci-C4alkyl, phenyl-Ci-C4alkyl substituted by one to three R ³ , unsubstituted C3-C6cycloalkyl, or C3-C6cycloalkyl substituted by one to three R ;

R is independently halogen, cyano, nitro, amino, hydroxy, oxo, Ci-Csalkoxy, acetyloxy, formyloxy, Ci- Cshaloalkoxy, or (Ci-C4alkyl)o-3silyl;

R ² is independently cyano, nitro, amino, hydroxy, oxo, Ci-Csalkoxy, acetyloxy, formyloxy, Ci- Cshaloalkoxy, or (Ci-C4alkyl)o-3silyl;

R ³ is independently halogen, cyano, nitro, Ci-Csalkyl, Ci-Cshaloalkyl, Ci-Csalkoxy, or Ci-Cshaloalkoxy; n is an interger 0 to 2, preferably 0 or 1.

More preferably R ^a is fluorine, chlorine, or methyl;

R is unsubstituted Ci-C4alkyl, Ci-C4alkyl substituted by one to three R , unsubstituted Ci-C4haloalkyl, Ci-C4haloalkyl substituted by one to three R ² , unsubstituted C2-C6alkenyl, C2-C6alkenyl substituted by one to three R , unsubstituted C3-C6cycloalkyl, or C3-C6cycloalkyl substituted by one to three R ; R is independently halogen, cyano, nitro, amino, hydroxy, oxo, Ci-Csalkoxy, acetyloxy, formyloxy, Ci- Cshaloalkoxy, or (Ci-C4alkyl)o-3silyl;

R ² is independently cyano, nitro, amino, hydroxy, oxo, Ci-Csalkoxy, acetyloxy, formyloxy, Ci- Cshaloalkoxy, or (Ci-C4alkyl)o-3silyl;

R ³ is independently halogen, cyano, nitro, Ci-Csalkyl, Ci-Cshaloalkyl, Ci-Csalkoxy, or Ci-Cshaloalkoxy; n is an interger 0 to 2, preferably 0 or 1.

Most preferably R ^a is fluorine, or chlorine; R is unsubstituted Ci-C4alkyl, Ci-C4alkyl substituted by one to three R\ unsubstituted Ci-C4haloalkyl, Ci-C4haloalkyl substituted by one to three R ² , unsubstituted C2-C6alkenyl, C2-C6alkenyl substituted by one to three R\ unsubstituted C3-C6cycloalkyl, or C3-C6cycloalkyl substituted by one to three R ; R is independently halogen, cyano, nitro, amino, hydroxy, oxo, d-Csalkoxy, acetyloxy, formyloxy, Ci- Cshaloalkoxy, or (Ci-C4alkyl)o-3silyl;

R ² is independently cyano, nitro, amino, hydroxy, oxo, Ci-Csalkoxy, acetyloxy, formyloxy, Ci- Cshaloalkoxy, or (Ci-C4alkyl)o-3silyl;

R ³ is independently halogen, cyano, nitro, Ci-Csalkyl, Ci-CshaloalkyI, Ci-Csalkoxy, or Ci-Cshaloalkoxy; n is an interger 0 to 2, preferably 0 or 1.

According to the present invention there is further provided a method for controlling or preventing infestation of plants or plant propagation material and/or harvested food crops susceptible to microbial attack by treating plants or plant propagation material and/or harvested food crops with an effective amount of a benzoxaboroles of general formula (Γ)

wherein

R ^a is hydrogen, fluorine, chlorine, bromine, cyano, unsubstituted Ci-C4alkyl, Ci-C4alkyl substituted by one to three R , unsubstituted Ci-C4haloalkyl, Ci-C4haloalkyl substituted by one to three R ² ,

unsubstituted Ci-C4alkoxy, Ci-C4alkoxy substituted by one to three R , unsubstituted Ci-C4haloalkoxy, Ci-C4haloalkoxy substituted by one to three R ² , unsubstituted C2-C6alkynyl, or C2-C6alkynyl substituted by one to three R ;

R is unsubstituted Ci-C4alkyl, Ci-C4alkyl substituted by one to three R , unsubstituted Ci-C4haloalkyl, Ci-C4haloalkyl substituted by one to three R ² , unsubstituted Ci-C4alkoxy, Ci-C4alkoxy substituted by one to three R , unsubstituted Ci-C4haloalkoxy, Ci-C4haloalkoxy substituted by one to three R ² , unsubstituted C2-C6alkenyl, C2-C6alkenyl substituted by one to three R , unsubstituted C2-C6alkynyl, C2-C6alkynyl substituted by one to three R , unsubstituted phenyl, phenyl substituted by one to three R ³ , unsubstituted phenyl-Ci-C4alkyl, phenyl-Ci-C4alkyl substituted by one to three R ³ , unsubstituted 5- 6 membered heteroaryl, 5-6 membered heteroaryl substituted by one to three R ³ , unsubstituted C3- C6cycloalkyl, or C3-C6cycloalkyl substituted by one to three R ;

R is independently halogen, cyano, nitro, amino, hydroxy, oxo, Ci-Csalkylamino, hydroxyimino, Ci- Csalkyloxyimino, N,N-Ci-Csdialkylamino, Ci-Csalkoxy, acetyloxy, formyloxy, Ci-Cshaloalkoxy, Ci- C4alkylthio or (Ci-C4alkyl)o-3silyl;

R ² is independently cyano, nitro, amino, hydroxy, oxo, Ci-Csalkylamino, hydroxyimino, Ci- Csalkyloxyimino, N,N-Ci-Csdialkylamino, Ci-Csalkoxy, acetyloxy, formyloxy, Ci-Cshaloalkoxy, Ci- C4alkylthio or (Ci-C4alkyl)o-3silyl;

R ³ is independently halogen, cyano, nitro, Ci-Csalkyl, Ci-Cshaloalkyl, Ci-Csalkoxy, or Ci-Cshaloalkoxy; n is an interger 0 to 2;

or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide of thereof. Preferably the method comprises treating plants or plant propagation material and/or harvested food crops with an effective amount of a benzoxaboroles of general formula (Γ) wherein

R ^a is hydrogen, fluorine, chlorine, or Ci-C4alkyl;

R is unsubstituted Ci-C4alkyl, Ci-C4alkyl substituted by one to three R , unsubstituted Ci-C4haloalkyl, Ci-C4haloalkyl substituted by one to three R ² , unsubstituted C2-C6alkenyl, C2-C6alkenyl substituted by one to three R , unsubstituted phenyl-Ci-C4alkyl, phenyl-Ci-C4alkyl substituted by one to three R ³ , unsubstituted C3-C6cycloalkyl, or C3-C6cycloalkyl substituted by one to three R ;

R is independently halogen, cyano, nitro, amino, hydroxy, oxo, Ci-Csalkoxy, acetyloxy, formyloxy, Ci- Cshaloalkoxy, or (Ci-C4alkyl)o-3silyl;

R ² is independently cyano, nitro, amino, hydroxy, oxo, Ci-Csalkoxy, acetyloxy, formyloxy, Ci- Cshaloalkoxy, or (Ci-C4alkyl)o-3silyl;

R ³ is independently halogen, cyano, nitro, Ci-Csalkyl, Ci-Cshaloalkyl, Ci-Csalkoxy, or Ci-Cshaloalkoxy; n is an interger 0 to 2, preferably 0 or 1.

The following list provides definitions, including preferred definitions, for substituents R, R ^a , R , R ² and R ³ , with reference to compounds of formula (Γ). For any one of these substituents, any of the definitions given below may be combined with any definition of any other substituent given below or elsewhere in this document.

In the benzoxaboroles of general formula (Γ) preferably R ^a is hydrogen, fluorine, chlorine, or Ci- C4alkyl; More preferably R ^a is fluorine, chlorine, or methyl; Most preferably R ^a is fluorine, or chlorine. Preferably R is unsubstituted Ci-C4alkyl, Ci-C4alkyl substituted by one to three R , unsubstituted Ci- C4haloalkyl, Ci-C4haloalkyl substituted by one to three R ² , unsubstituted C2-C6alkenyl, C2-C6alkenyl substituted by one to three R , unsubstituted phenyl-Ci-C4alkyl, phenyl-Ci-C4alkyl substituted by one to three R ³ , unsubstituted C3-C6cycloalkyl, or C3-C6cycloalkyl substituted by one to three R ; In the benzoxaboroles of general formula (Γ) more preferably R is unsubstituted Ci-C4alkyl, Ci-C4alkyl substituted by one to three R , unsubstituted Ci-C4haloalkyl, Ci-C4haloalkyl substituted by one to three R ² , unsubstituted C2-C6alkenyl, C2-C6alkenyl substituted by one to three R , unsubstituted C3- C6cycloalkyl, or C3-C6cycloalkyl substituted by one to three R ; Most preferably R is unsubstituted Ci- C4alkyl, Ci-C4alkyl substituted by one to three R , unsubstituted Ci-C4haloalkyl, Ci-C4haloalkyl substituted by one to three R ² , unsubstituted C2-C6alkenyl, C2-C6alkenyl substituted by one to three R\ unsubstituted C3-C6cycloalkyl, or C3-C6cycloalkyl substituted by one to three R .

In the benzoxaboroles of general formula (Γ) preferably R is independently halogen, cyano, nitro, amino, hydroxy, oxo, Ci-Csalkoxy, acetyloxy, formyloxy, Ci-Cshaloalkoxy, or (Ci-C4alkyl)o-3silyl; More preferably R is independently halogen, cyano, nitro, amino, hydroxy, oxo, Ci-Csalkoxy, acetyloxy, formyloxy, Ci-Cshaloalkoxy, or (Ci-C4alkyl)o-3silyl;

In the benzoxaboroles of general formula (Γ) preferably R ² is independently cyano, nitro, amino, hydroxy, oxo, Ci-Csalkoxy, acetyloxy, formyloxy, Ci-Cshaloalkoxy, or (Ci-C4alkyl)o-3silyl; More preferably R ² is independently cyano, nitro, amino, hydroxy, oxo, Ci-Csalkoxy, acetyloxy, formyloxy, Ci-Cshaloalkoxy, or (Ci-C4alkyl)o-3silyl.

In the benzoxaboroles of general formula (Γ) preferably R ³ is independently halogen, cyano, nitro, Ci- Csalkyl, Ci-Cshaloalkyl, Ci-Csalkoxy, or Ci-Cshaloalkoxy; More preferably R ³ is independently halogen, cyano, nitro, Ci-Csalkyl, Ci-Cshaloalkyl, Ci-Csalkoxy, or Ci-Cshaloalkoxy. In the benzoxaboroles of general formula (Γ) n is an interger 0 to 2, preferably 0 or 1.

More preferably the method comprises treating plants or plant propagation material and/or harvested food crops with an effective amount of a benzoxaboroles of general formula (Γ) wherein

R ^a is hydrogen, fluorine, chlorine, or methyl;

R is unsubstituted Ci-C4alkyl, Ci-C4alkyl substituted by one to three R , unsubstituted Ci-C4haloalkyl, Ci-C4haloalkyl substituted by one to three R ² , unsubstituted C2-C6alkenyl, C2-C6alkenyl substituted by one to three R , unsubstituted C3-C6cycloalkyl, or C3-C6cycloalkyl substituted by one to three R ; R is independently halogen, cyano, nitro, amino, hydroxy, oxo, Ci-Csalkoxy, acetyloxy, formyloxy, Ci- Cshaloalkoxy, or (Ci-C4alkyl)o-3silyl;

R ² is independently cyano, nitro, amino, hydroxy, oxo, Ci-Csalkoxy, acetyloxy, formyloxy, Ci- Cshaloalkoxy, or (Ci-C4alkyl)o-3silyl;

R ³ is independently halogen, cyano, nitro, Ci-Csalkyl, Ci-Cshaloalkyl, Ci-Csalkoxy, or Ci-Cshaloalkoxy; n is an interger 0 to 2, preferably 0 or 1.

Most preferably the method comprises treating plants or plant propagation material and/or harvested food crops with an effective amount of a benzoxaboroles of general formula (Γ) wherein

R ^a is hydrogen, fluorine, or chlorine;

R is unsubstituted Ci-C4alkyl, Ci-C4alkyl substituted by one to three R , unsubstituted Ci-C4haloalkyl, Ci-C4haloalkyl substituted by one to three R ² , unsubstituted C2-C6alkenyl, C2-C6alkenyl substituted by one to three R , unsubstituted C3-C6cycloalkyl, or C3-C6cycloalkyl substituted by one to three R ; R is independently halogen, cyano, nitro, amino, hydroxy, oxo, Ci-Csalkoxy, acetyloxy, formyloxy, Ci- Cshaloalkoxy, or (Ci-C4alkyl)o-3silyl;

R ² is independently cyano, nitro, amino, hydroxy, oxo, Ci-Csalkoxy, acetyloxy, formyloxy, Ci- Cshaloalkoxy, or (Ci-C4alkyl)o-3silyl;

R ³ is independently halogen, cyano, nitro, Ci-Csalkyl, Ci-Cshaloalkyl, Ci-Csalkoxy, or Ci-Cshaloalkoxy; n is an interger 0 to 2, preferably 0 or 1.

The present invention accordingly further relates to a method for controlling or preventing of infestation of plants or plant propagation material and/or harvested food crops susceptible to microbial attack, preferably susceptible to fungicidal attack, by treating plants or plant propagation material and/or harvested food crops with an effective amount of of benzoxaborole derivatives according to formula (I) or formula (Γ).

The present invention accordingly further relates to the use of benzoxaborole derivatives according to formula (I) or formula (Γ) for controlling or preventing infestation of plants or plant propagation material and/or harvested food crops susceptible to microbial attack, preferably susceptible to fungicidal attack.

The present invention accordingly further relates to the use of benzoxaborole derivatives according to formula (I) or formula (Γ) and salts thereof for controlling or preventing infestation of plants or plant propagation material and/or harvested food crops by treating plants or plant propagation material and/or harvested food crops with an effective amount of an benzoxaborole of general formula (I) or formula (Γ).

Accordingly the present invention also relates to a method of protecting plant propagation material and organs that grow at a later point in time against damage phytopathogenic diseases, which method comprises applying to said propagation material a fungicidally effective amount of a compound of formula I.

In yet a further aspect of the invention, the invention provides plant propagation material treated with a plant propagation material protecting composition comprising a compound of formula (I) or formula (Γ).

A preferred embodiment of the invention relates to a method of controlling or preventing damage by phytopathogenic diseases in a growing plant or growing plant tissue said method comprising: applying onto the plant propagation material, before planting or sowing thereof a fungicidial effective amount of a compound of formula (I) or formula (Γ).

A method of controlling or preventing fungal diseases in a growing plant or growing plant tissue said method comprising: applying onto the plant propagation material before planting or sowing thereof a fungicidial effective amount of a compound of formula (I) or formula (Γ).

In a preferred embodiment the plant propagation material is a seed or a tuber. In a further preferred embodiment the plant propagation material is a seed. In a further preferred embodiment the plant propagation material is a tuber. Preferably the seeds and tubers (stem tubers and root tubers) according to this application are alive. Preferably the seeds and tubers according to this application are able to germinate.

In a further aspect of the invention, the invention provides a method of controlling or preventing damage by phytopathogenic diseases in a growing plant said method comprising applying onto the seed, before planting or sowing thereof a compound of formula (I) or formula (Γ).

In a further aspect of the invention, the invention provides a method of protecting plant propagation material and organs that grow at a later point in time against damage by phytopathogenic diseases, which method comprises applying to said propagation material a fungicidally effective amount of a compound of formula (I) or formula (Γ).

In a further aspect of the invention, the invention provides a plant propagation material comprising compound a compound of formula (I) or formula (Γ). Preferably the plant propargation material comprising a fungicidial effective amount of a compound of formula (I) or formula (Γ).

In a further aspect of the invention, the invention provides a coated plant propagation material coated with a compound of formula (I) or formula (Γ).

In a further aspect of the invention, the invention provides a coated plant propagation material coated with coating comprising a compound of formula (I) or formula (Γ) as defined in claim 1.

In a further aspect of the invention, the invention provides a plant propagation material comprising an outer coating characterized that the outer coating comprises a compound according to formula (I) or formula (Γ), preferably a seed comprising an outer coating characterized that the outer coating comprises a compound according to formula (I) or formula (Γ).

In a further aspect of the invention, the invention relates to the use of a compound of formula (I) or formula (Γ) in the preparation of a composition for coating a plant propagation material for the prevention or control of plant pathogenic fungi.

In a further aspect of the invention, the invention relates to a method of controlling or preventing infestation of plants or plant propagation material and/or harvested food crops susceptible to microbial attack by providing in a first step a agrochemical compositions according to the present invention comprising a compound of formula (I) or formula (Γ) and in a second step applying said composition to the plants or the locus thereof.

The compounds of formula (I) or formula (Γ) are applied by treating plant propagation material with a fungicidally effective amount of a compound of formula I. Preferably, compounds of formula (I) or formula (Γ) are applied by adhering compounds of formula (I) or formula (Γ) to plant propagation material in a fungicidally effective amount.

The compounds of formula (I)

may be prepared by coupling the compound of formula III

wherein R ^a is as defined under formula I; with a compound of formula IV or the salts thereof such as the sodium salt of compound IV

R- ^{S H} (IV)

wherein R is as defined under formula (I), in the presence of a palladium or copper catalyst and further hydrolysis of the obtained product to cleave the N1 ,N1 ,N8-trimethylnaphthalene-1 ,8-diamine group under acidic conditions.

Compounds of formula (III) can be advantageously prepared in analogy to known methods published in RSC Adv., 2013, 3, 2131-2133 or US 20140275601.

Scheme-1

A cross coupling reaction of the intermediate III with the compound (IV) (mercaptan) or its salt such as the sodium salt of RSH under catalytic conditions may provide intermediates of formula V.

The cross-coupling reactions between intermediate III and mercaptan compound IV may be carried out in the presence of a palladium catalyst such as Tris(dibenzylideneacetone) dipalladium or tetrakis(triphenylphosphine)-palladium(0) and suitable ligand for example 4,5-Bis(diphenylphosphino)- 9,9-dimethylxanthene, in a suitable solvent for example dioxane or tetrahydrofuran under reflux conditions for about 1 hour to 24 hours.

Intermediates of formula V may be oxidised using oxidising agents such as sodium periodate or metacholorperbenzoic acid or oxone in suitable solvent, such as alcohol for example methanol or ethanol to obtain compounds of formula V. It will be appreciated by those skilled in the art that the above mentioned oxidation reaction can be carried out with a number of different conditions.

Compound I may be obtained by reacting Intermediates of formula V with suitable acids, such as Hydrochloric acid, Trifluoroacetic acid, Acetic acid etc in a suitable solvent such as tetrahydrofuran, acetonitrile, dioxane and water or a combination thereof. Compound of formula I" may be obtained by reacting intermediates of formula V with suitable acids, such as Hydrochloric acid, Trifluoroacetic acid, Acetic acid etc in a suitable solvent such as tetrahydrofuran, acetonitrile, dioxane and water or a combination thereof. _ _

- 1 1 -

Compounds of formula I" may be oxidised to give the corresponding compound I wherein n=1 . Oxidation may be carried out using conventional oxidising agents, such as sodium periodate or oxone, in a suitable solvent, for example an alcohol such as ethanol at ambient temperature.

The sulfoxide product thus obtained and the compound I" can be converted to compound I wherein n=2 by oxidation with a peracid, for example metachloroperbenzoic acid in a suitable.

It will be appreciated by those skilled in the art that the above mentioned oxidation reaction can be carried out with a number of different conditions.

The compounds of formula (I) and the respective starting materials may also be obtained according to the processes of Schemes 2, 3 and 4.

Scheme-3 Compounds of formula V and VIII are either commercially available or can be prepared by those skilled in the art with a number of different conditions already known.

Intermediates of the formula (VI) can be prepared by methods known in the art by reacting compounds of formula V with Triflic anhydride in presence of a base, for example pyridine in a suitable 5 solvent, such as dichloromethane at about 0°C to ambient temperatures.

Intermediates of formula VII can be prepared from either compounds of formula VI as described in scheme I or from compound VIII as in scheme 2 via palladium catalysed Miyaura cross coupling reactions for the introduction of boron atom. It will be appreciated by those skilled in the art that this reaction can be carried out with a number of different conditions.

10 Compound of formula I can be produced by the reduction of compound of formula VII, as

described in scheme 2 and scheme 3, by reacting with reducing agents such as sodium borohydride or Lithium aluminum hydride in an inert solvent. Inert solvent is chosen from methanol, ethanol and tetrahydrofuran. The reaction is carried out at about 0°C to ambient temperatures for about 1 hour to 24 hours. The reaction mass is acidified with suitable acids like dilute HCI, prior to the extraction and 15 isolation of the compound I.

1. C11SO4.5H2O, bipyridine,

IX

I

Scheme-4

Compound of Formula I" can be advantageously also prepared from amino intermediates (IX) as described in scheme-4, in analogy to the known method published in Org. Lett. 2014, 16,

20 2692-2695 by Jiang et.al. using sodium thiosulfate as a sulfurating reagent

The intermediates of formula IX

wherein R ^a is defined under formula I, preferably wherein R ^a is F (CAS Registry Number:

94331 1-50-0), R ^a is CI, (CAS Registry Number: 947165-43-7), are known, and described in the literature, for example in Bioorganic & Medicinal Chemistry Letters, 20(24), 7317-7322; 2010, or Journal of Molecular Biology, 390(2), 196-207; 2009 or Bioorganic & Medicinal Chemistry Letters, 21 (7), 2048-2054; 201 1.

The compounds of formula (I) of this invention are useful as plant disease control agents. The present invention therefore further comprises a method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof to be protected, or to the plant seed to be protected, an effective amount of a compound of the invention or a fungicidal composition containing said compound.

Compounds of formula (I) and fungicidal compositions containing them may be used to control plant diseases caused by a broad spectrum of fungal plant pathogens in the Basidiomycete,

Ascomycete, Oomycete and/or Deuteromycete, Blasocladiomycete, Chrytidiomycete, Glomeromycete and/or Mucoromycete classes.

They are effective in controlling a broad spectrum of plant diseases, such as foliar, seed- and soilborne pathogens of ornamental, turf, vegetable, field, cereal, and fruit crops.

These pathogens may include:

Oomycetes, including Phytophthora diseases such as those caused by Phytophthora capsici, Phytophthora infestans, Phytophthora sojae, Phytophthora fragariae, Phytophthora nicotianae, Phytophthora cinnamomi, Phytophthora citricola, Phytophthora citrophthora and Phytophthora erythroseptica; Pythium diseases such as those caused by Pythium aphanidermatum, Pythium arrhenomanes, Pythium graminicola, Pythium irregulare and Pythium ultimum; diseases caused by Peronosporales such as Peronospora destructor, Peronospora parasitica, Plasmopara viticola, Plasmopara halstedii, Pseudoperonospora cubensis, Albugo Candida, Sclerophthora macrospora and Bremia lactucae; and others such as Aphanomyces cochlioides, Labyrinthula zosterae,

Peronosclerospora sorghi and Sclerospora graminicola.

Ascomycetes, including blotch, spot, blast or blight diseases and/or rots for example those caused by Pleosporales such as Stemphylium solani, Stagonospora tainanensis, Spilocaea oleaginea, Setosphaeria turcica, Pyrenochaeta lycoperisici, Pleospora herbarum, Phoma destructiva,

Phaeosphaeria herpotrichoides, Phaeocryptocus gaeumannii, Ophiosphaerella graminicola,

Ophiobolus graminis, Leptosphaeria maculans, Hendersonia creberrima, Helminthosporium triticirepentis, Setosphaeria turcica, Drechslera glycines, Didymella bryoniae, Cycloconium

oleagineum, Corynespora cassiicola, Cochliobolus sativus, Bipolaris cactivora, Venturia inaequalis, Pyrenophora teres, Pyrenophora tritici-repentis, Alternaria alternata, Alternaria brassicicola, Alternaria solani and Alternaria tomatophila, Capnodiales such as Septoria tritici, Septoria nodorum, Septoria glycines, Cercospora arachidicola, Cercospora sojina, Cercospora zeae-maydis, Cercosporella capsellae and Cercosporella herpotrichoides, Cladosporium carpophilum, Cladosporium effusum, Passalora fulva, Cladosporium oxysporum, Dothistroma septosporum, Isariopsis clavispora,

Mycosphaerella fijiensis, Mycosphaerella graminicola, Mycovellosiella koepkeii, Phaeoisariopsis bataticola, Pseudocercospora vitis, Pseudocercosporella herpotrichoides, Ramularia beticola, Ramularia collo-cygni, Magnaporthales such as Gaeumannomyces graminis, Magnaporthe grisea, Pyricularia oryzae, Diaporthales such as Anisogramma anomala, Apiognomonia errabunda, Cytospora platani, Diaporthe phaseolorum, Discula destructiva, Gnomonia fructicola, Greeneria uvicola, Melanconium juglandinum, Phomopsis viticola, Sirococcus clavigignenti-juglandacearum, Tubakia dryina, Dicarpella spp. , Valsa ceratosperma, and others such as Actinothyrium graminis, Ascochyta pisi, Aspergillus flavus, Aspergillus fumigatus, Aspergillus nidulans, Asperisporium caricae, Blumeriella jaapii, Candida spp. , Capnodium ramosum, Cephaloascus spp., Cephalosporium gramineum, Ceratocystis paradoxa, Chaetomium spp., Hymenoscyphus pseudoalbidus, Coccidioides spp., Cylindrosporium padi, Diplocarpon malae, Drepanopeziza campestris, Elsinoe ampelina, Epicoccum nigrum, Epidermophyton spp., Eutypa lata, Geotrichum candidum, Gibellina cerealis, Gloeocercospora sorghi, Gloeodes pomigena, Gloeosporium perennans; Gloeotinia temulenta, Griphospaeria corticola, Kabatiella lini, Leptographium microsporum, Leptosphaerulinia crassiasca, Lophodermium seditiosum, Marssonina graminicola, Microdochium nivale, Monilinia fructicola, Monographella albescens, Monosporascus cannonballus, Naemacyclus spp., Ophiostoma novo-ulmi, Paracoccidioides brasiliensis, Penicillium expansum, Pestalotia rhododendri, Petriellidium spp., Pezicula spp.,

Phialophora gregata, Phyllachora pomigena, Phymatotrichum omnivora, Physalospora abdita, Plectosporium tabacinum, Polyscytalum pustulans, Pseudopeziza medicaginis, Pyrenopeziza brassicae, Ramulispora sorghi, Rhabdocline pseudotsugae, Rhynchosporium secalis, Sacrocladium oryzae, Scedosporium spp., Schizothyrium pomi, Sclerotinia sclerotiorum, Sclerotinia minor,

Sclerotium spp., Typhula ishikariensis, Seimatosporium mariae, Lepteutypa cupressi, Septocyta ruborum, Sphaceloma perseae, Sporonema phacidioides, Stigmina palmivora, Tapesia yallundae, Taphrina bullata, Thielviopsis basicola, Trichoseptoria fructigena, Zygophiala jamaicensis; powdery mildew diseases for example those caused by Erysiphales such as Blumeria graminis, Erysiphe polygoni, Uncinula necator, Sphaerotheca fuligena, Podosphaera leucotricha, Podospaera macularis Golovinomyces cichoracearum, Leveillula taurica, Microsphaera diffusa, Oidiopsis gossypii,

Phyllactinia guttata and Oidium arachidis; molds for example those caused by Botryosphaeriales such as Dothiorella aromatica, Diplodia seriata, Guignardia bidwellii, Botrytis cinerea, Botryotinia allii, Botryotinia fabae, Fusicoccum amygdali, Lasiodiplodia theobromae, Macrophoma theicola,

Macrophomina phaseolina, Phyllosticta cucurbitacearum; anthracnoses for example those caused by Glommerelales such as Colletotrichum gloeosporioides, Colletotrichum lagenarium, Colletotrichum gossypii, Glomerella cingulata, and Colletotrichum graminicola; and wilts or blights for example those caused by Hypocreales such as Acremonium strictum, Claviceps purpurea, Fusarium culmorum, Fusarium graminearum, Fusarium virguliforme, Fusarium oxysporum, Fusarium subglutinans, Fusarium oxysporum f.sp. cubense, Gerlachia nivale, Gibberella fujikuroi, Gibberella zeae,

Gliocladium spp., Myrothecium verrucaria, Nectria ramulariae, Trichoderma viride, Trichothecium roseum, and Verticillium theobromae.

Basidiomycetes, including smuts for example those caused by Ustilaginales such as

Ustilaginoidea virens, Ustilago nuda, Ustilago tritici, Ustilago zeae, rusts for example those caused by Pucciniales such as Cerotelium fici, Chrysomyxa arctostaphyli, Coleosporium ipomoeae, Hemileia vastatrix, Puccinia arachidis, Puccinia cacabata, Puccinia graminis, Puccinia recondita, Puccinia sorghi, Puccinia hordei, Puccinia striiformis f.sp. Hordei, Puccinia striiformis f.sp. Secalis,

Pucciniastrum coryli, or Uredinales such as Cronartium ribicola, Gymnosporangium juniperi- viginianae, Melampsora medusae, Phakopsora pachyrhizi, Phragmidium mucronatum, Physopella ampelosidis, Tranzschelia discolor and Uromyces viciae-fabae; and other rots and diseases such as _ _.

- 15 - those caused by Cryptococcus spp., Exobasidium vexans, Marasmiellus inoderma, Mycena spp., Sphacelotheca reiliana, Typhula ishikariensis, Urocystis agropyri, Itersonilia perplexans, Corticium invisum, Laetisaria fuciformis, Waitea circinata, Rhizoctonia solani, Thanetephorus cucurmeris, Entyloma dahliae, Entylomella microspora, Neovossia moliniae and Tilletia caries.

Blastocladiomycetes, such as Physoderma maydis.

Mucoromycetes, such as Choanephora cucurbitarum.; Mucor spp.; Rhizopus arrhizus, As well as diseases caused by other species and genera closely related to those listed above. In addition to their fungicidal activity, the compounds and compositions comprising them may also have activity against bacteria such as Erwinia amylovora, Erwinia caratovora, Xanthomonas campestris, Pseudomonas syringae, Strptomyces scabies and other related species as well as certain protozoa.

Compounds of formula (I) may be mixed with one or more of compounds selected from those in the following chemical or functional classes:- 1 ,2,4-thiadiazoles, 2,6-dinitroanilines, acylalanines, aliphatic nitrogenous compounds, amidines, aminopyrimidinols, anilides, anilino-pyrimidines, anthraquinones, antibiotics, aryl-phenylketones, benzamides, benzene-sulfonamides, benzimidazoles, benzothiazoles, benzothiodiazoles, benzothiophenes, benzoylpyridines, benzthiadiazoles, benzylcarbamates, butylamines, carbamates, carboxamides, carpropamids, chloronitriles, cinnamic acid amides, copper containing compounds, cyanoacetamideoximes, cyanoacrylates,

cyanoimidazoles, cyanomethylene-thiazolidines, dicarbonitriles, dicarboxamides, dicarboximides, dimethylsulphamates, dinitrophenol carbonates, dinitrophenysl, dinitrophenyl crotonates, diphenyl phosphates, dithiino compounds, dithiocarbamates, dithioethers, dithiolanes, ethyl-amino-thiazole carboxamides, ethyl-phosphonates, furan carboxamides, glucopyranosyls, glucopyranoxyls, glutaronitriles, guanidines, herbicides/plant growth regulatosr, hexopyranosyl antibiotics, hydroxy(2- amino)pyrimidines, hydroxyanilides, hydroxyisoxazoles, imidazoles, imidazolinones, insecticides/plant growth regulators, isobenzofuranones, isoxazolidinyl-pyridines, isoxazolines, maleimides, mandelic acid amides, mectin derivatives, morpholines, norpholines, n-phenyl carbamates, organotin compounds, oxathiin carboxamides, oxazoles, oxazolidine-diones, phenols, phenoxy quinolines, phenyl-acetamides, phenylamides, phenylbenzamides, phenyl-oxo-ethyl-thiophenes amides, phenylpyrroles, phenylureas, phosphorothiolates, phosphorus acids, phthalamic acids, phthalimides, picolinamides, piperazines, piperidines, plant extracts, polyoxins, propionamides, pthalimides, pyrazole-4-carboxamides, pyrazolinones, pyridazinones, pyridines, pyridine carboxamides, pyridinyl- ethyl benzamides, pyrimdinamines, pyrimidines, pyrimidine-amines, pyrimidione-hydrazone, pyrrolidines, pyrrolquinoliones, quinazolinones, quinolines, quinoline derivatives, quinoline-7- carboxylic acids, quinoxalines, spiroketalamines, strobilurins, sulfamoyl triazoles, sulphamides, tetrazolyloximes, thiadiazines, thiadiazole carboxamides, thiazole carboxanides, thiocyanates, thiophene carboxamides, toluamides, triazines, triazobenthiazoles, triazoles, triazole-thiones, triazolo- pyrimidylamine, valinamide carbamates, ammonium methyl phosphonates, arsenic-containing compounds, benyimidazolylcarbamat.es, carbonitriles, carboxanilides, carboximidamides, carboxylic phenylamides, diphenyl pyridines, furanilides, hydrazine carboxamides, imidazoline acetates, isophthalates, isoxazolones, mercury salts, organomercury compounds, organophosphates, oxazolidinediones, pentylsulfonyl benzenes, phenyl benzamides, phosphonothionates, phosphorothioates, pyridyl carboxamides, pyridyl furfuryl ethers, pyridyl methyl ethers, SDHIs, thiadiazinanethiones, thiazolidines.

Particularly preferred fungicidal combinations include the following where "I" designates compounds of formula (I): I + (.+/-.)-cis-1-(4-chlorophenyl)-2-(1 H-1 ,2,4-triazol-1-yl)-cycloheptanol (huanjunzuo), I + (2RS)-2-bromo-2-(bromomethyl)glutaronitrile (bromothalonil), I + (E)-N-methyl-2- [2- (2, 5-dimethylphenoxymethyl) phenyl]-2-methoxy-iminoacetamide, (mandestrobin), I + 1-(5-bromo-2- pyridyl)-2-(2,4-difluorophenyl)-1 , 1-difluoro-3-(1 ,2,4-triazol-1-yl)propan-2-ol, I + 1-methylcyclopropene, I + 2-m ethyl-[[4-m ethoxy-2-[[[(3S, 1R, 8R, 9S)-9-methyl-8-(2-m ethyl- 1 -oxopropoxy)-2 , 6-dioxo-7- (phenylmethyl)-1 ,5-dioxonan-3-yl]amino]carbonyl]-3-pyridinyl]oxy]propanoic acid methyl ester, I + 2-(1- tert-butyl)-1-(2-chlorophenyl)-3-(1 ,2,4-triazol-1-yl)-propan-2-ol (TCDP), I + 2,4-D, I + 2,4-DB, I + 2,6- dichloro-N-(4-trifluoromethylbenzyl)-benzamide, I + 2,6-dimethyl-[1 ,4]dithiino[2,3-c:5,6-c']dipyrrole- 1 ,3,5J(2H,6H)-tetraone, I + 2-[[(1 R,5S)-5-[(4-fluorophenyl)methyl]-1-hydroxy-2,2-dimethyl- cyclopentyl]methyl]-4H-1 ,2,4-triazole-3-thione I + 2-[[3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2- yl]methyl]-4H-1 ,2,4-triazole-3-thione I + ametoctradin (imidium), I + 2-[2-[(7,8-difluoro-2-methyl-3- quinolyl)oxy]-6-fluoro-phenyl]propan-2-ol I + 2-[2-fluoro-6-[(8-fluoro-2-methyl-3- quinolyl)oxy]phenyl]propan-2-ol I + cyflufenamid, I + 2-benzyl-4-chlorophenol (Chlorophene), I + 3- (difluoromethyl)-N-(7-fluoro-1 , 1 ,3,3-tetramethyl-indan-4-yl)-1-methyl-pyrazole-4-carboxamide I + diclocymet, I + 3-(difluoromethyl)-N-methoxy-1-methyl-N-[1-methyl-2-(2,4,6- trichlorophenyl)ethyl]pyrazole-4-carboxamide, I + 3'-chloro-2-methoxy-N-[(3RS)-tetrahydro-2-oxofuran- 3-yl]acet-2',6'-xylidide (clozylacon), I + 3-iodo-2-propinyl n-butylcarbamate (IPBC), I + 4,4,5-trifluoro- 3,3-dimethyl-1-(3-quinolyl)isoquinoline I + 4,4-difluoro-3,3-dimethyl-1-(3-quinolyl)isoquinoline I + 5- fluoro-3,3,4,4-tetramethyl-1-(3-quinolyl)isoquinoline I + 9-fluoro-2,2-dimethyl-5-(3-quinolyl)-3H-1 ,4- benzoxazepine I + tebufloquin, I + 4-CPA, I + 5-fluoro-2-(p-tolylmethoxy)pyrimidin-4-amine I + ferimzone, I + acibenzolar, I + acibenzolar-S-methyl, I + allyl alcohol, I + ametoctradin, I + amisulbrom, I + anilazine, I + aureofungin, I + azaconazole, I + azafenidin, I + azithiram, I + azoxystrobin, I + benalaxyl, I + benalaxyl-M, I + benalaxyl-M (kiralaxyl), I + benomyl, I + benthiavalicarb, I + benthiazole (TCMTB), I + benzalkonium chloride, I + benzamorf, I + benzovindiflupyr (solatenol), I + bethoxazin, I + biphenyl, I + bitertanol (biloxazol), I + bixafen, I + BLAD, I + blasticidin-S, I + Bordeaux mixture, I + boscalid, I + bromuconazole, I + bupirimate, I + but-3-ynyl N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl- methylene]amino]oxymethyl]-2-pyridyl]carbamate I + dazomet, I + butylamine, I + calcium polysulfide, I + captafol, I + captan, I + carbaryl, I + carbendazim, I + carbendazim chlorhydrate, I + carboxin, I + CAS 517875-34-2 (DAS777), I + chinomethionate, I + chinomethionate (oxythioquinox,

quinoxymethionate), I + chitosan, I + chlobenthiazone, I + chlorfenazole, I + chlormequat, I + chloroneb, I + chloropicrin, I + chlorothalonil, I + chlozolinate, I + climbazole, I + clofencet, I + copper acetate, I + copper carbonate, I + copper hydroxide, I + copper naphthenate, I + copper oleate, I + copper oxychloride, I + copper oxyquinolate, I + copper silicate, I + copper sulphate, I + copper tallate, I + coumoxystrobin, I + cresol, I + cuprous oxide, I + cyazofamid, I + cyclafuramid, I + cymoxanil, I + cyproconazole, I + cyprodinil, I + daracide, I + dichlofluanid, I + dichlorophen (dichlorophene), I + dichlorprop, I + diclomezine, I + dicloran, I + diethofencarb, I + difenoconazole, I + difenzoquat, I + diflumetorim, I + dimetachlone (dimethaclone), I + dimetconazole, I + dimethipin, I + dimethirimol, I + dimethomorph, I + dimoxystrobin, I + dingjunezuo (Jun Si Qi), I + diniconazole, I + diniconazole-M, I +, I + dinobuton, I + dinocap, I + dinocton, I + dinopenton, I + diphenylamine, I + dipyrithione, I + ditalimfos, I + dithianon, I + dithioether, I + dodemorph, I + dodicin, I + dodine, I + doguadine, I + drazoxolon, I + edifenphos, I + endothal, I + enestroburin, enoxastrobin I + fenamistrobin, I + epoxiconazole, I + etaconazole, I + etem, I + ethaboxam, I + ethephon, I + ethoxyquin, I +

famoxadone, I + fenamidone, I + fenarimol, I + fenbuconazole, I + fenfuram, I + fenhexamid, I + fenoxanil, I + fenpiclonil, I + fenpropidin, I + fenpropimorph, I + fenpyrazamine, I + fentin acetate, I + fentin hydroxide, I + ferbam, I + fluazinam, I + fludioxonil, I + flufenoxystrobin, I + flumetralin, I + flumorph, I + fluopicolide, I + fluopicolide (flupicolide), I + fluopyram, I + fluoroimide, I + fluoxastrobin, I + fluquinconazole, I + flusilazole, I + flusulfamide, I + flutianil, I + flutolanil, I + flutriafol, I +

fluxapyroxad, I + folpet, I + forchlorfenuron, I + fosetyl, I + fuberidazole, I + furalaxyl, I + furametpyr, I + gibberellic acid, I + gibberellins, I + guazatine, I + hexachlorobenzene, I + hexaconazole, I + hymexazol, I + hymexazole, hydroxyisoxazole I + imazalil, I + I + etridiazole, I + imazalil, I + imazalil sulphate, I + imibenconazole, I + iminoctadine, I + iminoctadine triacetate, I + iodocarb (isopropanyl butylcarbamate), I + ipconazole, I + iprobenfos, I + iprodione, I + iprovalicarb, I + isofetamid, I + isopropanyl butylcarbamate (iodocarb), I + isoprothiolane, I + isopyrazam, I + isotianil, I +

kasugamycin, I + kresoxim-methyl, I + KSF-1002, I + maleic hydrazide, I + mancozeb, I +

mandestrobin, I + mandipropamid, I + maneb, I + mepanipyrim, I + mepiquat, I + mepronil, I + meptyldinocap, I + metalaxyl, I + metalaxyl-M (mefenoxam), I + metam, I + metaminostrobin, I + metconazole, I + methyl bromide, I + methyl iodide, I + methyl isothiocyanate, I + metiram (polyram), I + metiram-zinc, I + metominostrobin, I + metrafenone, I + m-phenylphenol, I + myclobutanil, I + N'- (2,5-Dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine , I + N'-[4-(4,5-Dichloro-thiazol-2- yloxy)-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine, I + N'-[4-[[3-[(4-chlorophenyl)methyl]-1 ,2,4- thiadiazol-5-yl]oxy]-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-f ormamidine, I + ethirimol, I + N-(2-p- chlorobenzoylethyl)-hexaminium chloride, I + N-[(5-chloro-2-isopropyl-phenyl)methyl]-N-cyclopropyl-3- (difluoromethyl)-5-fluoro-1-methyl-pyrazole-4-carboxamide I + N-cyclopropyl-3-(difluoromethyl)-5- fluoro-N-[(2-isopropylphenyl)methyl]-1-methyl-pyrazole-4-car boxamide I + carpropamid, I + nabam, I + naphthalene acetamide, I + NNF-0721 , I + octhilinone, I + ofurace, I + orysastrobin, I + osthol, I + oxadixyl, I + oxasulfuron, I + oxathiapiprolin, I + oxine-copper, I + oxolinic acid, I + oxpoconazole, I + oxycarboxin, I + paclobutrazol, I + pefurazoate, I + penconazole, I + pencycuron, I + penflufen, I + penthiopyrad, I + phenamacril, I + phosdiphen, I + phosetyl-AI, I + phosetyl-AI (fosetyl-al), I + phosphorus acids, I + phthalide (fthalide), I + picarbutrazox, I + picoxystrobin, I + piperalin, I + polycarbamate, I + polyoxin D (polyoxrim), I + p-phenylphenol, I + probenazole, I + prochloraz, I + procymidone, I + prohexadione, I + prohexadione-calcium, I + propamidine, I + propamocarb, I + propiconazole, I + propineb, I + propionic acid, I + proquinazid, I + prothioconazole, I + pyraclostrobin, I + pyrametostrobin, I + pyraoxystrobin, I + pyrazophos, I + pyribencarb (KIF-7767), I + pyrifenox, I + pyrimethanil, I + pyriofenone (IKF-309), I + pyroquilon, I + quinoxyfen, I + quintozene, I + sedaxane, I + silthiofam, I + simeconazole, I + spiroxamine, I + streptomycin, I + sulphur, I + tebuconazole, I + tebufloquin, I + tecloftalam, I + tecnazene, (TCNB), I + tetraconazole, I + thiabendazole, I + thicyofen, I + thidiazuron, I + thifluzamide, I + thiophanate-methyl, I + thiram, I + tiadinil, I + tioxymid, I + tolclofos- methyl, I + tolprocarb, I + tolylfluanid, I + triadimefon, I + triadimenol, I + triazoxide, I + tribromophenol (TBP), I + tribufos (tributyl phosphorotrithioate), I + triclopyricarb, I + tricyclazole, I + tridemorph, I + _„

- 18 - trifloxystrobin, I + triflumizole, I + triforine, I + trinexapac, I + triticonazole, I + uniconazole, I + validamycin, I + valifenalate, I + vapam, I + vapam (metam sodium), I + vinclozolin, I + zineb, I + ziram, I + zoxamide, I + onaphthalene acetic acid.

Compounds of this invention can also be mixed with one or more further pesticides including insecticides, nematocides, bactericides, acaricides, growth regulators, chemosterilants,

semiochemicals, repellents, attractants, pheromones, feeding stimulants or other biologically active compounds to form a multi-component pesticide giving an even broader spectrum of agricultural protection.

Examples of such agricultural protectants with which compounds of this invention can be formulated are:

Insecticides such as abamectin, acephate, acetamiprid, amidoflumet (S-1955), avermectin, azadirachtin, azinphos-methyl, bifenthrin, bifenazate, buprofezin, carbofuran, cartap,

chlorantraniliprole (DPX-E2Y45), chlorfenapyr, chlorfluazuron, chlorpyrifos, chlorpyrifos-methyl, chromafenozide, clothianidin, cyflumetofen, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, cypermethrin, cyromazine, deltamethrin, diafenthiuron, diazinon, dieldrin, diflubenzuron, dimefluthrin, dimethoate, dinotefuran, diofenolan, emamectin, endosulfan, esfenvalerate, ethiprole, fenothiocarb, fenoxycarb, fenpropathrin, fenvalerate, fipronil, flonicamid, flubendiamide, flucythrinate, tau-fluvalinate, flufenerim (UR-50701 ), flufenoxuron, fonophos, halofenozide, hexaflumuron, hydramethylnon, imidacloprid, indoxacarb, isofenphos, lufenuron, malathion, metaflumizone, metaldehyde,

methamidophos, methidathion, methomyl, methoprene, methoxychlor, metofluthrin, monocrotophos, methoxyfenozide, nitenpyram, nithiazine, novaluron, noviflumuron (XDE-007), oxamyl, parathion, parathion-methyl, permethrin, phorate, phosalone, phosmet, phosphamidon, pirimicarb, profenofos, profluthrin, pymetrozine, pyrafluprole, pyrethrin, pyridalyl, pyrifluquinazon, pyriprole, pyriproxyfen, rotenone, ryanodine, spinetoram, spinosad, spirodiclofen, spiromesifen (BSN 2060), spirotetramat, sulprofos, tebufenozide, teflubenzuron, tefluthrin, terbufos, tetrachlorvinphos, thiacloprid,

thiamethoxam, thiodicarb, thiosultap-sodium, tralomethrin, triazamate, trichlorfon and triflumuron;

Bactericides such as streptomycin;

Acaricides such as amitraz, chinomethionat, chlorobenzilate, cyenopyrafen, cyhexatin, dicofol, dienochlor, etoxazole, fenazaquin, fenbutatin oxide, fenpropathrin, fenpyroximate, hexythiazox, propargite, pyridaben and tebufenpyrad; and

Biological agents such as Bacillus thuringiensis, Bacillus thuringiensis delta endotoxin, baculovirus, and entomopathogenic bacteria, virus and fungi.

Plant disease control is ordinarily accomplished by applying an effective amount of a compound of this invention either pre- or post-infection, to the portion of the plant to be protected such as the roots, stems, foliage, fruit, seeds, tubers or bulbs, or to the media (soil or sand) in which the plants to be protected are growing. The compounds may also be applied to seeds to protect the seeds and seedlings developing from the seeds. The compounds may also be applied through irrigation water to treat plants.

The present invention envisages application of the compounds of the invention to plant propagation material prior to, during, or after planting, or any combination of these. Although active ingredients can be applied to plant propagation material in any physiological state, a common approach is to use seeds in a sufficiently durable state to incurr no damage during the treatment process. Typically, seed would have been harvested from the field; removed from the plant; and separated from any cob, stalk, outer husk, and surrounding pulp or other non-seed plant material. Seed would preferably also be biologically stable to the extent that treatment would not cause biological damage to the seed. It is believed that treatment can be applied to seed at any time between seed harvest and sowing of seed including during the sowing process.

Methods for applying or treating active ingredients on to plant propagation material or to the locus of planting are known in the art and include dressing, coating, pelleting and soaking as well as nursery tray application, in furrow application, soil drenching, soil injection, drip irrigation, application through sprinklers or central pivot, or incorporation into soil (broad cast or in band).

Alternatively or in addition active ingredients may be applied on a suitable substrate sown together with the plant propagation material.

Rates of application for these compounds can be influenced by many factors of the environment and should be determined under actual use conditions. Foliage can normally be protected when treated at a rate of from less than about 1 g/ha to about 5,000 g/ha of active ingredient. Seed and seedlings can normally be protected when seed is treated at a rate of from about 0.1 to about 10g per kilogram of seed.

Crops of useful plants in which the composition according to the invention can be used include perennial and annual crops, such as berry plants for example blackberries, blueberries, cranberries, raspberries and strawberries; cereals for example barley, maize (corn), millet, oats, rice, rye, sorghum triticale and wheat; fibre plants for example cotton, flax, hemp, jute and sisal; field crops for example sugar and fodder beet, coffee, hops, mustard, oilseed rape (canola), poppy, sugar cane, sunflower, tea and tobacco; fruit trees for example apple, apricot, avocado, banana, cherry, citrus, nectarine, peach, pear and plum; grasses for example Bermuda grass, bluegrass, bentgrass, centipede grass, fescue, ryegrass, St. Augustine grass and Zoysia grass; herbs such as basil, borage, chives, coriander, lavender, lovage, mint, oregano, parsley, rosemary, sage and thyme; legumes for example beans, lentils, peas and soya beans; nuts for example almond, cashew, ground nut, hazelnut, peanut, pecan, pistachio and walnut; palms for example oil palm; ornamentals for example flowers, shrubs and trees; other trees, for example cacao, coconut, olive and rubber; vegetables for example asparagus, aubergine, broccoli, cabbage, carrot, cucumber, garlic, lettuce, marrow, melon, okra, onion, pepper, potato, pumpkin, rhubarb, spinach and tomato; and vines for example grapes.

Crops are to be understood as being those which are naturally occurring, obtained by conventional methods of breeding, or obtained by genetic engineering. They include crops which contain so-called output traits (e.g. improved storage stability, higher nutritional value and improved flavour).

Crops are to be understood as also including those crops which have been rendered tolerant to herbicides like bromoxynil or classes of herbicides such as ALS-, EPSPS-, GS-, HPPD- and PPO- inhibitors. An example of a crop that has been rendered tolerant to imidazolinones, e.g. imazamox, by conventional methods of breeding is Clearfield® summer canola. Examples of crops that have been rendered tolerant to herbicides by genetic engineering methods include e.g. glyphosate- and „„

- 20 - glufosinate-resistant maize varieties commercially available under the trade names RoundupReady®, Herculex I® and LibertyLink®.

Crops are also to be understood as being those which naturally are or have been rendered resistant to harmful insects. This includes plants transformed by the use of recombinant DNA techniques, for example, to be capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria. Examples of toxins which can be expressed include δ-endotoxins, vegetative insecticidal proteins (Vip), insecticidal proteins of bacteria colonising nematodes, and toxins produced by scorpions, arachnids, wasps and fungi.

An example of a crop that has been modified to express the Bacillus thuringiensis toxin is the Bt maize KnockOut® (Syngenta Seeds). An example of a crop comprising more than one gene that codes for insecticidal resistance and thus expresses more than one toxin is VipCot® (Syngenta Seeds). Crops or seed material thereof can also be resistant to multiple types of pests (so-called stacked transgenic events when created by genetic modification). For example, a plant can have the ability to express an insecticidal protein while at the same time being herbicide tolerant, for example Herculex I® (Dow AgroSciences, Pioneer Hi-Bred International).

The compounds according to the invention can be used as pesticidal agents in unmodified form, but they are generally formulated into compositions in various ways using formulation adjuvants, such as carriers, solvents and surface-active substances. The formulations can be in various physical forms, e.g. in the form of dusting powders, gels, wettable powders, water-dispersible granules, water- dispersible tablets, effervescent pellets, emulsifiable concentrates, microemulsifiable concentrates, oil- in-water emulsions, oil-flowables, aqueous dispersions, oily dispersions, suspo-emulsions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (with water or a water- miscible organic solvent as carrier), impregnated polymer films or in other forms known e.g. from the Manual on Development and Use of FAO and WHO Specifications for Pesticides, United Nations, First Edition, Second Revision (2010). Such formulations can either be used directly or diluted prior to use. The dilutions can be made, for example, with water, liquid fertilisers, micronutrients, biological organisms, oil or solvents.

The formulations can be prepared e.g. by mixing the active ingredient with the formulation adjuvants in order to obtain compositions in the form of finely divided solids, granules, solutions, dispersions or emulsions. The active ingredients can also be formulated with other adjuvants, such as finely divided solids, mineral oils, oils of vegetable or animal origin, modified oils of vegetable or animal origin, organic solvents, water, surface-active substances or combinations thereof.

The active ingredients can also be contained in very fine microcapsules. Microcapsules contain the active ingredients in a porous carrier. This enables the active ingredients to be released into the environment in controlled amounts (e.g. slow-release). Microcapsules usually have a diameter of from 0.1 to 500 microns. They contain active ingredients in an amount of about from 25 to 95 % by weight of the capsule weight. The active ingredients can be in the form of a monolithic solid, in the form of fine particles in solid or liquid dispersion or in the form of a suitable solution. The encapsulating membranes can comprise, for example, natural or synthetic rubbers, cellulose, styrene/butadiene copolymers, polyacrylonitrile, polyacrylate, polyesters, polyamides, polyureas, polyurethane or chemically modified polymers and starch xanthates or other polymers that are known to the person _

- 21 - skilled in the art. Alternatively, very fine microcapsules can be formed in which the active ingredient is contained in the form of finely divided particles in a solid matrix of base substance, but the microcapsules are not themselves encapsulated.

The formulation adjuvants that are suitable for the preparation of the compositions according to the invention are known per se. As liquid carriers there may be used: water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid, diacetone alcohol, 1 ,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, A/,A/-dimethylformamide, dimethyl sulfoxide, 1 ,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkylpyrrolidone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1 ,1 , 1- trichloroethane, 2-heptanone, alpha-pinene, d-limonene, ethyl lactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma-butyrolactone, glycerol, glycerol acetate, glycerol diacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropylbenzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxypropanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol, propionic acid, propyl lactate, propylene carbonate, propylene glycol, propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylenesulfonic acid, paraffin, mineral oil, trichloroethylene,

perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, ethanol, isopropanol, and alcohols of higher molecular weight, such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, A/-methyl-2-pyrrolidone and the like.

Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed husks, wheat flour, soybean flour, pumice, wood flour, ground walnut shells, lignin and similar substances.

A large number of surface-active substances can advantageously be used in both solid and liquid formulations, especially in those formulations which can be diluted with a carrier prior to use. Surface-active substances may be anionic, cationic, non-ionic or polymeric and they can be used as emulsifiers, wetting agents or suspending agents or for other purposes. Typical surface-active substances include, for example, salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; salts of alkylarylsulfonates, such as calcium dodecylbenzenesulfonate; alkylphenol/alkylene oxide addition products, such as nonylphenol ethoxylate; alcohol/alkylene oxide addition products, such as tridecylalcohol ethoxylate; soaps, such as sodium stearate; salts of alkylnaphthalenesulfonat.es, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2- ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryltrimethylammonium chloride, polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono- and di- alkylphosphate esters; and also further substances described e.g. in McCutcheon's Detergents and Emulsifiers Annual, MC Publishing Corp., Ridgewood New Jersey (1981 ).

Further adjuvants that can be used in pesticidal formulations include crystallisation inhibitors, viscosity modifiers, suspending agents, dyes, anti-oxidants, foaming agents, light absorbers, mixing auxiliaries, antifoams, complexing agents, neutralising or pH-modifying substances and buffers, corrosion inhibitors, fragrances, wetting agents, take-up enhancers, micronutrients, plasticisers, glidants, lubricants, dispersants, thickeners, antifreezes, microbicides, and liquid and solid fertilisers.

The compositions according to the invention can include an additive comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters of such oils or mixtures of such oils and oil derivatives. The amount of oil additive in the composition according to the invention is generally from 0.01 to 10 %, based on the mixture to be applied. For example, the oil additive can be added to a spray tank in the desired concentration after a spray mixture has been prepared. Preferred oil additives comprise mineral oils or an oil of vegetable origin, for example rapeseed oil, olive oil or sunflower oil, emulsified vegetable oil, alkyl esters of oils of vegetable origin, for example the methyl derivatives, or an oil of animal origin, such as fish oil or beef tallow. Preferred oil additives comprise alkyl esters of C8-C22 fatty acids, especially the methyl derivatives of C12-C18 fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid (methyl laurate, methyl palmitate and methyl oleate, respectively). Many oil derivatives are known from the Compendium of Herbicide Adjuvants, 10 ^th Edition, Southern Illinois University, 2010.

The inventive compositions generally comprise from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of compounds of the present invention and from 1 to 99.9 % by weight of a formulation adjuvant which preferably includes from 0 to 25 % by weight of a surface-active substance. Whereas commercial products may preferably be formulated as concentrates, the end user will normally employ dilute formulations.

The rates of application vary within wide limits and depend on the nature of the soil, the method of application, the crop plant, the pest to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop. As a general guideline compounds may be applied at a rate of from 1 to 2000 l/ha, especially from 10 to 1000 l/ha.

Preferred formulations can have the following compositions (weight %):

Emulsifiable concentrates:

active ingredient: 1 to 95 %, preferably 60 to 90 %

surface-active agent: 1 to 30 %, preferably 5 to 20 %

liquid carrier: 1 to 80 %, preferably 1 to 35 %

Dusts:

active ingredient: 0.1 to 10 %, preferably 0.1 to 5 %

solid carrier: 99.9 to 90 %, preferably 99.9 to 99 %

Suspension concentrates:

active ingredient: 5 to 75 %, preferably 10 to 50 %

water: 94 to 24 %, preferably 88 to 30 %

surface-active agent: 1 to 40 %, preferably 2 to 30 % Wettable powders:

active ingredient: 0.5 to 90 %, preferably 1 to 80 %

surface-active agent: 0.5 to 20 %, preferably 1 to 15 %

solid carrier: 5 to 95 %, preferably 15 to 90 %

Granules:

active ingredient: 0.1 to 30 %, preferably 0.1 to 15 %

solid carrier: 99.5 to 70 %, preferably 97 to 85 %

The following Examples further illustrate, but do not limit, the invention.

The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground a suitable mill, affording wettable powders that can be diluted with water to give suspensions of the desired concentration.

The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording powders that can be used directly for seed treatment.

Emulsions of any required dilution, which can be used in plant protection, can be obtained from this concentrate by dilution with water. Dusts a) b) c)

Active ingredients 5 % 6 % 4 %

Talcum 95 % - -

Kaolin - 94 % - mineral filler - - 96 %

Ready-for-use dusts are obtained by mixing the combination with the carrier and grinding the mixture in a suitable mill. Such powders can also be used for dry dressings for seed.

The combination is mixed and ground with the adjuvants, and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air.

The finely ground combination is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.

Suspension concentrate

The finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.

Flowable concentrate for seed treatment

active ingredients 40 % propylene glycol 5 % copolymer butanol PO/EO 2 %

Tristyrenephenole with 10-20 moles EO 2 %

1 ,2-benzisothiazolin-3-one (in the form of a 20% solution in water) 0.5 % monoazo-pigment calcium salt 5 %

Silicone oil (in the form of a 75 % emulsion in water) 0.2 % Water 45.3 %

The finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.

Slow Release Capsule Suspension

28 parts of the combination are mixed with 2 parts of an aromatic solvent and 7 parts of toluene diisocyanate/polymethylene-polyphenylisocyanate-mixture (8: 1 ). This mixture is emulsified in a mixture of 1 .2 parts of polyvinylalcohol, 0.05 parts of a defoamer and 51 .6 parts of water until the desired particle size is achieved. To this emulsion a mixture of 2.8 parts 1 ,6-diaminohexane in 5.3 parts of water is added. The mixture is agitated until the polymerization reaction is completed. The obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent. The capsule suspension formulation contains 28% of the active ingredients. The medium capsule diameter is 8-15 microns. The resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable for that purpose.

The Examples which follow serve to illustrate the invention. The compounds of the invention can be distinguished from known compounds by virtue of greater efficacy at low application rates, which can be verified by the person skilled in the art using the experimental procedures outlined in the Examples, using lower application rates if necessary, for example 60 ppm, 20 ppm, 6 ppm, 2 ppm or 0.6 ppm.

Preparation examples:

The following non-limiting examples illustrate the above-described invention in greater detail without limiting it.

Synthesis of 5-fluoro-1 -hydroxy-6-iodo-3H-2,1 -benzoxaborole

To a solution of PTSA monohydrate (3 equiv., 35.9396 mmol, 100 mass%) in acetonitrile (25.0 mL, 99.5 mass%) was added 5-fluoro-1-hydroxy-3H-2,1-benzoxaborol-6-amine (2.0 g, 1 1.9798 mmol, 100 mass%) and the grey suspension obtained was stirred for 10min at 20°C. The mixture was cooled to 0°C and a solution of sodium nitrite (2.0 equiv., 23.9597 mmol, 99 mass%) and potassium iodide (2.5 equiv., 29.9496 mmol, 99 mass%) in water (5 mL, 100 mass%) was added drop wise (1 h) via dropping funnel. During addition the mixture turned dark brown quickly, gas release was observed and mixture became thicker (stirring to be increased a lot). The mixture was stirred 1 h at 20°C. Water (50ml_), sat. sodium hydrogen carbonate (25ml_), 2M sodium thiosulfate (25ml_) was added to the stirred mixture. The crude was extracted three times with ethyl acetate. Combined organics were washed with water, dried over sodium sulfate, evaporated under reduced pressure to afford the crude as red solid. The crude was subject to flash chromatography over silicagel (1 10g prepacked column) „„

- 26 - with Cyclohexane/Ethylacetate 99.5:0.5 to 20:80 as eluent to obtain 5-fluoro-1-hydroxy-6-iodo-3H-2, 1- benzoxaborole (1.4 g, 5 mmol, 100 mass%, 42% Yield) was obtained as a white solid.

Ή NMR (400 MHz, DMSO-de) δ ppm 4.94 (s, 2 H), 7.36 (s, 1 H), 8.16 (s, 1 H), 9.32 (s, 1 H)

LCMS : rt 1.72 min 276.8 -ESI

Synthesis of N8-(5-fluoro-6-iodo-3H-2,1 -benzoxaborol-1 -yl)-N1 ,N1 ,N8-trimethyl- naphthalene-1 ,8-diamine

To a stirred solution of 5-fluoro-1-hydroxy-6-iodo-3H-2,1-benzoxaborole (1.38g 4.9 mmol, 95 mass%) in toluene (100 mL, 99.9 mass%) was added N1 ,N1 ,N8-trimethylnaphthalene-1 ,8-diamine (1.0 equiv., 4.9 mmol, 99.8 mass%) at 23°C under argon. The reaction mass was stirred for 1 h at 120°C accompanied by azeotropic removal of water. Toluene was distilled to obtain the crude. The crude mass was washed with ethyl acetate to afford (N8-(5-fluoro-6-iodo-3H-2, 1 -benzoxaborol-1 -yl)- N1 ,N1 ,N8-trimethyl-naphthalene-1 ,8-diamine (1.6 g, 3.5 mmol, 95 mass%, 70% Yield) as a pale yellow solid.

Ή NMR (400 MHz, DMSO-c/6) δ ppm 2.68 - 2.75 (m, 6 H) 2.80 (s, 3 H) 5.01 (s, 2 H) 6.18 (br. s., 1 H) 6.53 (d, J=7.78 Hz, 1 H) 7.07 (d, J=8.78 Hz, 1 H) 7.16 (d, J=7.53 Hz, 1 H) 7.40 - 7.56 (m, 3 H) 7.85 (dd, J=7.78, 1.25 Hz, 1 H)

LC-MS: rt 2.19-2.32 min - 460.9

Synthesis of N8-(6-methylsulfanyl-5-fluoro-3H-2,1 -benzoxaborol-1 -yl)-N1 ,N1 ,N8-trimethyl- naphthalene-1 ,8-diamine.

To a stirred solution of N8-(5-fluoro-6-iodo-3H-2, 1 -benzoxaborol-1 -yl)-N1 ,N 1 , N8-trimethyl- naphthalene-1 ,8-diamine (0.5 g, 1 mmol) in 1 ,4-doxane (15 mL) was added,

Tris(dibenzylideneacetone)dipalladium (0.05 g, 0.05 mmol), 4,5-Bis(diphenylphosphino)-9,9- dimethylxanthene (0.06 g 0.1 mmol) and stirred for 10 minutes under nitrogen. At the end was added methylsulfanylsodium (0.08 g, 1 mmol) and the reaction mixture was heated at 105°C for 1 hour. The reaction mixture was allowed to cool down to RT and was diluted with water; extracted thrice with ethyl acetate, washed with water, dried over sodium sulfate and concentrated under reduced pressure. The crude material was purified by flash chromatography to give N8-(6-methylsulfanyl-5-fluoro-3H-2, 1- benzoxaborol-1-yl)-N1 ,N1 ,N8-trimethyl-naphthalene-1 ,8-diamine (0.3 g, 80% Yield).

Ή NMR (400 MHz, DMSO-d6) δ ppm 1.82 (s, 3H) 2.67-2.73 (m, 3H) 2.73-2.77 (m, 3H) 2.79- 2.84 (m, 3H), 5.00 (s, 2H) 5.67-5.81 (m, 1 H) 6.45-6.56 (m, 1 H) 6.95-7.03 (m, 1 H) 7.12-7.19 (m, 1 H) 7.36-7.45 (m, 1 H) 7.44-7.56 (m, 2H) 7.80-7.86 (m, 1 H)

Synthesis of 6-methylsulfanyl-5-fluoro-1 -hydroxy-3H-2,1 -benzoxaborole

To a solution of N8-(5-fluoro-6-methylsulfanyl-3H-2, 1-benzoxaborol-1-yl)-N1 ,N 1 ,N8-trimethyl- naphthalene-1 ,8-diamine (0.2 g, 0.53 mmol) in tetrahydrofuran (1 mL) were added hydrochloric acid (2N) (2 mL) and two drops of trifluoroacetic acid. The reaction mixture was stirred at room temperature for 18 hrs. The reaction mixture was extracted with ethyl acetate/water. The combined organic layers were dried over sodium sulfate, filtered and concentrated under reduced pressure. The crude was purified by chromatography to give 5-fluoro-1-hydroxy-6-methylsulfanyl-3H-2, 1 -benzoxaborole (0.05 g, 50%) as a off white solid.

mp: 144-146°C

Ή NMR (400 MHz, DMSO-d6) δ ppm 2.48 (s, 3H) 5.01 (s, 2H) 7.40 (d, 1 H) 7.76 (d, 1 H), 9.36 (s, 1 H)

Synthesis of 6-(chloromethylsulfinyl)-5-fluoro-1 -hydroxy-3H-2,1 -benzoxaborole and 6-

(dichloromethylsulfinyl)-5-fluoro-1 -hydroxy-3H-2,1 -benzoxaborole

To a stirred solution of 5-fluoro-1-hydroxy-6-methylsulfanyl-3H-2, 1 -benzoxaborole (0.12 g, 0.61 mmol) in dichloromethane (4 mL) were added, 4-methyl benzenesu Ifonic acid (0.052 g, 0.3 mmol) and 1-chloropyrrolidine-2,5-dione (0.097 g 0.73 mmol) and stirred for 1 hour. The reaction mixture was diluted with water; extracted thrice with dichlorromethane, washed with water, dried over sodium sulfate and concentrated under reduced pressure. The crude mixture thus obtained was subject to column chromatography. Two products were obtained:

Compound No.20: 6-(chloromethylsulfinyl)-5-fluoro-1-hydroxy-3H-2,1 -benzoxaborole (0.03 g, 0.1 mmol, 100 mass%, 20% Yield) as a solid compound

1 H NMR (400 MHz, DMSO-d6) δ ppm 4.89 (d, J=12 Hz, 1 H) 5.07 (s, 2H) 5.17 (d, J=12 Hz, 1 H) 7.40 (d, 1 H) 8.18 (d, 1 H) 9.52 (s, 1 H) „„

- 28 -

LC-MS: RT 0.33 Min 249.25/251.17 [M+H]+

Compound No.22: 6-(dichloromethylsulfinyl)-5-fluoro-1-hydroxy-3H-2, 1-benzoxaborole (O, 0.028 g, 0.099 mmol, 100 mass%, 16% Yield) as a solid.

1 H NMR (400 MHz, DMSO-d6) δ ppm 5.09 (s, 2H) 7.54 (d, 1 H) 7.55 (s, 1 H), 8.26 (d, 2H) 9.5 (s, 1 H)

LC-MS: RT 0.59 Min 283.23/285.15 [M+H]+

Synthesis of 6-Benzylsulfanyl-5-chloro-1 -hydroxy-3H-2,1 -benzoxaborole

A mixture of anhydrous sodium thiosulfate (2.26 g, 14.0 mmol), benzyl bromide (1.71 mL, 14.0 mmol), copper sulfate pentahydrate (0.050 g, 0.20 mmol and 2,2'-dipyridyl (0.031 g, 0.20 mmol) in water (5.0 mL) and methanol (5.0 mL) was stirred at 75°C for 2 hours under nitrogen. The light yellow mixture was cooled to 10°C and 5-chloro-1-hydroxy-3H-2, 1-benzoxaborol-6-amine (0.386 g, 2.00 mmol) was added followed by drop wise addition of tert-butyl nitrite (0.40 mL, 3.00 mmol). The mixture was stirred for 10 minutes at 25°C and another for 4.5 hours at 80°C.

The mixture was cooled down to 23°C and the organic phase evaporated under reduced pressure. The resulting aqueous phase was extracted three times with ethyl acetate. Combined organic layers were dried over magnesium sulfate, filtrated over celite and evaporated under reduced pressure to afford the crude as orange resin. The crude was subject to flash chromatography over silicagel 40g column (heptane/ethyl acetate) eluent gradient 95:5 to 60:40 to afford 6-Benzylsulfanyl-5- chloro-1-hydroxy-3H-2, 1 -benzoxaborole (0.18 g, 5.14% Yield) as a white solid

mp: 135-145°C.

LC/MS (Method A) retention time = 1 .04 minutes, 290.0 (M+H)

Synthesis of 2-r(5-chloro-1 -hydroxy-3H-2,1 -benzoxaborol-6-yl)sulfanyl1ethyl-trimethyl- silane.

Under N2, to a 50 ml flask equipped with a condenser was added 5-chloro-1-hydroxy-6-iodo-3H- 2, 1 -benzoxaborole (1.70 mmol, 0.500 g), Tris(dibenzylideneacetone)dipalladium(0) (0.0850 mmol, 0.0802 g), 4,5-Bis(diphenylphosphino)-9,9-dimethylxanthene (0.170 mmol, 0.101 g) in 1 ,4-dioxane (12.5 mL). At the end was added sodium 2-trimethylsilylethanethiolate (2.38 mmol, 2.4 mL) and the reaction mixture was heated at 105°C for 1 hour. The reaction mixture was allowed to cool down to RT _

- 29 - and was diluted with water; extracted thrice with ethyl acetate, washed with water, dried over sodium sulfate and concentrated under reduced pressure. The crude material was purified by flash chromatography to give 2-[(5-chloro-1-hydroxy-3H-2,1-benzoxaborol-6-yl)sulfanyl]eth yl-trimethyl-silane (0.258 g, 50.5% Yield).

LC-MS: t _R = 1.19 min, m/z = 299 [M-1], 301 [M+1 ].

Ή NMR (400 MHz, DMSO-d6) δ ppm -0.01 - 0.01 (m, 9 H) 0.83 - 0.87 (m, 2 H) 2.92 - 2.97 (m, 2 H) 4.88 (s, 2 H) 7.48 (s, 1 H) 7.63 (s, 1 H) 9.23 (s, 1 H).

Preparation of 6-ethylsulfanyl-1 -hvdroxy-5-methyl-3H-2,1 -benzoxaborole.

Synthesis of methyl 2-chloro-4-hydroxy-5-iodo-benzoate.

Methyl 2-chloro-4-hydroxy-5-iodo-benzoate (cas: 195250-54-5) was prepared as described in WO2015121442.

(b) Synthesis of methyl 2-chloro-4-hvdroxy-5-methyl-benzoate.

Methyl 2-chloro-4-hydroxy-5-methyl-benzoate (cas: 195250-54-5) was prepared as described in WO2015121442, using methyl 2-chloro-4-hydroxy-5-iodo-benzoate as starting material.

(c) Synthesis of methyl 2-chloro-4-(dimethylcarbamothioyloxy)-5-methyl- benzoate.

To a solution of methyl 2-chloro-4-hydroxy-5-methyl-benzoate (1.85 g, 9.22 mmol) in N-methyl- 2-pyrrolidone (5 ml, 1.4 mol/L) was added 1 ,4-diazabicyclo[2.2.2]octane (1.29 g, 1 1.5 mmol), the resulting mixture was heated up to 50°C; then a solution of Ν,Ν-dimethylcarbamothioyl chloride (1.20 5 g, 9.68 mmol) in N-methyl-2-pyrrolidone (1 .6 ml, 1.4 mol/L) was added dropwise. The reaction mixture was stirred at 50°C till completion (3 hrs), water was added at 50°C. The reaction mixture was cooled down to room temperature and the aqueous layer was extracted twice with ethyl acetate. The organic layer was dried over sodium sulfate and concentrated under reduced pressure. The crude was purified by chromatography to give methyl 2-chloro-4-(dimethylcarbamothioyloxy)-5-methyl-benzoate (2.146 g, 10 80%).

LC-MS: iR = 0.99 min, m/z = 288 [M+1 ].

Ή NMR (400 MHz, CDCIs) δ ppm 2.19 (s, 3 H) 3.35 (m, 3 H) 3.46 (m, 3 H) 3.92 (s, 3 H) 7.12 (s, 1 H) 7.77 (s, 1 H).

(d) Synthesis of methyl 2-chloro-4-(dimethylcarbamoylsulfanyl)-5-methyl- 15 benzoate

A solution of methyl 2-chloro-4-(dimethylcarbamothioyloxy)-5-methyl-benzoate (200 mg, 0.6949 mmol) in N-methyl-2-pyrrolidone (0.6949 mmol, 0.189 mol/L, 3.68 mL) was irradiated by microwaves at 220°C for 20 min. Water was added and the aqueous layer was extracted thrice with methyl fert- 20 butyl ether. The organic layers were combined, dried over sodium sulfate and concentrated under reduced pressure. The resulting crude was purified by chromatography to give methyl 2-chloro-4- (dimethylcarbamoylsulfanyl)-5-methyl-benzoate (159 mg, 79%).

LC-MS: iR = 0.99 min, m/z = 288 [M+1 ].

Ή NMR (400 MHz, CDCI3) δ ppm 2.39 (s, 3 H) 3.00 - 3.19 (m, 6 H) 3.90 (m, 3 H) 7.60 (s, 1 H) 25 7.74 (s, 1 H).

(e) Synthesis of methyl 2-chloro-5-methyl-4-sulfanyl-benzoate.

To a solution of methyl 2-chloro-4-(dimethylcarbamoylsulfanyl)-5-methyl-benzoate (1.435 g, 4.986 mmol) in methanol (20 mL) was added sodium methoxide (4.5M in MeOH) (1 .3 mL, 5.983 mmol, 4.5 mol/L). The reaction mixture was stirred at room temperature for 18 hrs. Then, additional sodium methoxide in methanol (0.2 mL ) was added slowly. The reaction mixture was further stirred for 4 hrs. Hydrochloride acid (1 N) was added and the aqueous layer was extracted thrice with dichloromethane. The organic layers were combined, dried over sodium sulfate and concentrated under reduced pressure. The crude was purified by chromatography to give methyl 2-chloro-5-methyl-4-sulfanyl- benzoate (855 mg, 79%).

LC-MS: iR = 0.99 min, m/z = 215 [M-1].

Ή NMR (400 MHz, CDCIs) δ ppm 2.30 (s, 3 H) 3.51 (s, 1 H) 3.88 (s, 3 H) 7.33 (s, 1 H) 7.66 (s, 1

H).

(f) Synthesis of methyl 2-chloro-4-ethylsulfanyl-5-methyl-benzoate

To a solution of methyl 2-chloro-5-methyl-4-sulfanyl-benzoate (740 mg, 3.4152 mmol) in DMF

(23 mL) was added at 0°C potassium carbonate (0.75522 g, 5.4643 mmol) then bromoethane

(0.44659 g, 4.0982 mmol). The reaction mixture was stirred 10 min. at 0°C then at room temperature for 3 hrs. Ethyl acetate and water were added and the two layers were separated. The aqueous layer was extracted twice with ethyl acetate. The organic layers were combined, washed twice with water, once with brine, dried over sodium sulfate and concentrated under reduced pressure. The crude was purified by chromatography to give 2-chloro-4-ethylsulfanyl-5-methyl-benzoate (751 mg, 90%) as a white solid.

LC-MS: iR = 1.12 min, m/z = 245 [M+1 ].

Ή NMR (400 MHz, CDCI3) δ ppm 1.40 (t, 3 H) 2.28 (s, 3 H) 2.99 (q, 2 H) 3.90(s, 3 H) 7.17 (s, 1 H) 7.65 (d, 1 H).

(g) Synthesis of methyl 4-ethylsulfanyl-5-methyl-2-(4,4,5,5-tetramethyl-1 ,3,2- dioxaborolan-2-yl)benzoate.

Methyl 2-chloro-4-ethylsulfanyl-5-methyl-benzoate (240 mg, 0.9808 mmol) was dissolved in 1 ,4- dioxane (6.5 mL) in a microwave tube and Argon was bubbled through the solution for few minutes. Tricyclohexylphosphane (0.04401 g, 0.1569 mmol), Bis(pinacolato)diborane (0.3736 g, 1 .471 mmol), potassium acetate (0.1444 g, 1.471 mmol) and Tris(dibenzylideneacetone)dipalladium (0) (0.03593 g, 0.03924 mmol) were added. The mixture was irradiated by the microwaves at 150°C for 50 minutes. The reaction mixture was filtered and the filtrate was concentrated. The crude was purified by chromatography to give methyl 4-ethylsulfanyl-5-methyl-2-(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2- yl)benzoate (175 mg, 53%).

LC-MS: t _R = 1.19 min, m/z = 337 [M+1 ].

(h) Synthesis of 6-ethylsulfanyl-1 -hvdroxy-5-methyl-3H-2,1 -benzoxaborole.

To a solution of methyl 4-ethylsulfanyl-5-methyl-2-(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2- yl)benzoate (175 mg, 0.5205 mmol) in ethanol (5 ml) was added portionwise sodium borohydride (0.02950 g, 0.7798 mmol) at 0°C. The reaction mixture was stirred at room temperature for 2 hrs. Water was added, and then ethanol was evaporated under reduced pressure. Then hydrochloric acid 4N (4ml_) was added and the mixture was stirred for 18 hrs. Ethyl acetate and water were added, the two layers were separated. The aqueous layer was extracted twice with ethyl acetate and the organic layers were combined, dried over sodium sulfate and concentrated under reduced pressure. The crude was purified by chromatography to give 6-ethylsulfanyl-1-hydroxy-5-methyl-3H-2,1- benzoxaborole (57 mg, 5.3%) as a white solid,

mp: 89-92°C.

Synthesis of 6-ethylsulfanyl-5-fluoro-1 -hydroxy-3H-2,1 -benzoxaborole

Under Argon to a 100 ml flask equipped with a condenser were added 5-fluoro-1-hydroxy-6- iodo-3H-2, 1 -benzoxaborole (49.30 g, 177.4 mmol), sodium ethanethiol (23.50 g, 248.4 mmol,), Xantphos (2.646 g, 4.436 mmol,) in 1 ,4-dioxane (739.5 mL) . At the end, was added Pd ₂ (dba) ₃ (1.675 g, 1.774 mmol) and the reaction mixture was heated at 105°C for 30 min. The reaction mixture was cooled down to room temperature and the solvent was evaporated under reduced pressure. The crude was extracted with ethyl acetate/water. The combined organic layers were combined and dried with sodium sulfate, filtered and evaporated under reduced pressure. The crude (41.5g) was recrystallized under reflux in toluene. The solid was filtered off and washed with 15ml of cold toluene and 20 ml of cold n-Hexane to give 19.7g of 6-ethylsulfanyl-5-fluoro-1-hydroxy-3H-2, 1-benzoxaborole. The mother liquor was evaporated under reduced pressure and purified by chromatography to give an additional batch (7.7 g) of 6-ethylsulfanyl-5-fluoro-1-hydroxy-3H-2,1-benzoxaborole. Combined batches gave 27.4 g, (73%) of 6-ethylsulfanyl-5-fluoro-1-hydroxy-3H-2, 1-benzoxaborole.

LC-MS: iR = 0.89 min, m/z = 21 1 [M-1], 213 [M+1 ].

Ή NMR (400 MHz, DMSO-d6) δ ppm 1.23 (t, 3 H) 2.96 (q, 2 H) 4.96 (s, 2 H) 7.30 (d, 1 H) 7.78 (d, 1 H) 9.25 (s, 1 H).

Synthesis of N8-(6-ethylsulfanyl-5-fluoro-3H-2,1 -benzoxaborol-1 -yl)-N1 ,N1 ,N8-trimethyl- naphthalene-1 ,8-diamine.

To a stirred solution of 6-ethylsulfanyl-5-fluoro-1-hydroxy-3H-2, 1-benzoxaborole (2.00 g, 9.43 mmol) in toluene (20.0 mL) was added N1 ,N1 ,N8-trimethylnaphthalene-1 ,8-diamine (1.89 g, 9.43 mmol). The reaction mixture was heated to reflux overnight with a Dean-Stark apparatus. The reaction mixture was concentrated under reduced pressure and purified by chromatography to give N8-(6- ethylsulfanyl-5-fluoro-3H-2, 1 -benzoxaborol-1 -yl)-N1 ,N 1 ,N8-trimethyl-naphthalene-1 ,8-diamine (3.52 g, 94.6 %).

LC-MS: t _R = 1.25 min, m/z = 395 [M+1 ].

Synthesis of N8-(6-ethylsulfinyl-5-fluoro-3H-2,1 -benzoxaborol-1 -yl)-N1 ,N1 ,N8-trimethyl- naphthalene-1 ,8-diamine.

To a solution of N8-(6-ethylsulfanyl-5-fluoro-3H-2, 1-benzoxaborol-1-yl)-N1 ,N1 ,N8-trimethyl- naphthalene-1 ,8-diamine (0.500 g, 1.27 mmol) in methanol (12.7 mL) was added portionwise Oxone (Potassium monopersulfate triple salt) (1 .17 g, 1.90 mmol) at 0°C. Then, the reaction mixture was stirred at room temperature for 2 hrs and then, extracted with ethylacetate/water. The combined organic layers were dried over sodium sulfate, filtered and concentrated under reduced pressure. The crude was purified by chromatography to give N8-(6-ethylsulfinyl-5-fluoro-3H-2, 1-benzoxaborol-1-yl)- N1 ,N1 ,N8-trimethyl-naphthalene-1 ,8-diamine (0.168 g, 32%).

LC-MS: t _R = 1.03 min, m/z = 401 [M+1 ].

Synthesis of 6-ethylsulfinyl-5-fluoro-1 -hydroxy-3H-2,1 -benzoxaborole

To a solution of N8-(6-ethylsulfinyl-5-fluoro-3H-2, 1-benzoxaborol-1-yl)-N1 ,N1 ,N8-trimethyl- naphthalene-1 ,8-diamine (0.168 g, 0.409 mmol) in tetrahydrofurane (1.68 mL) were added hydrochloric acid (1 N) (3.36 mL) and two drops of trifluoroacetic acid. The reaction mixture was stirred at room temperature for 16 hrs. The reaction mixture was extracted with ethyl acetate/water. The combined organic layers were dried over sodium sulfate, filtered and concentrated under reduced pressure. The crude was purified by chromatography to give 6-ethylsulfinyl-5-fluoro-1-hydroxy-3H-2, 1- benzoxaborole (0.021 g, 22%) as a white solid.

mp: 145-170°C

LC-MS: t _R = 0.66 min, m/z = 229 [M+1 ].

1 H NMR (400 MHz, Acetone) δ ppm 1.17 (t, 3 H) 2.85 (m, 1 H) 3.10 (m, 1 H) 5.12 (s, 2 H) 7.37 (d, 1 H) 8.14 (d, 11-1) 8.39 (s, 1 H).

Table T1 : Characterising data:

Table 4 shows All the prepared examples with selected melting point and selected NMR data for prepared compounds. CDCI3/D2O and DMSO are used as solvents for NMR 400 MHz

measurements. No attempt is made to list all characterising data in all cases.

In Table 4 and throughout the description that follows, temperatures are given in degrees Celsius; "NMR" means nuclear magnetic resonance spectrum; MS stands for mass spectrum; "%" is percent by weight, unless corresponding concentrations are indicated in other units. The following abbreviations are used throughout this description: melting point boiling point,

S = singlet broad

d = doublet doublet of doublets

t = triplet quartet

m = multiplet parts per million

The following LC-MS methods were used to characterize the compounds:

Method -A

The description of the LC/MS apparatus and the method A is:

SQ Detector 2 from Waters

lonisation method: Electrospray

Polarity: positive and negative ions

Capillary (kV) 3.0, Cone (V) 30.00, Extractor (V) 2.00, Source Temperature (°C) 150, Desolvation

Temperature (°C) 350, Cone Gas Flow (L/Hr) 0, Desolvation Gas Flow (L/Hr) 650

Mass range: 100 to 900 Da

DAD Wavelength range (nm): 210 to 500

Method Waters ACQUITY UPLC with the following HPLC gradient conditions:

(Solvent A: Water/Methanol 20: 1 + 0.05% formic acid and Solvent B: Acetonitrile+ 0.05% formic acid)

Time (minutes) A (%) B (%) Flow rate (ml/min)

0 100 0 0.85

1.2 0 100 0.85

1.5 0 100 0.85

Type of column: Waters ACQUITY UPLC HSS T3; Column length: 30 mm; Internal diameter of column: 2.1 mm; Particle Size: 1 .8 micron; Temperature: 60°C.

Method -B

ACQUITY SQD Mass Spectrometer from Waters (Single quadrupole mass spectrometer) lonisation method: Electrospray

Polarity: positive ions

Capillary (kV) 3.00, Cone (V) 20.00, Extractor (V) 3.00, Source Temperature (°C) 150,

Desolvation Temperature (°C) 400, Cone Gas Flow (L/Hr) 60, Desolvation Gas Flow (L/Hr) 700 Mass range: 100 to 800 Da

DAD Wavelength range (nm): 210 to 400 Method Waters ACQUITY UPLC with the following HPLC gradient conditions

(Solvent A: Water/Methanol 9:1 ,0.1 % formic acid and Solvent B: Acetonitrile,0.1 % formic acid ) Time (minutes) A (%) B (%) Flow rate (ml/min)

0 100 0 0.75

2.5 0 100 0.75

2.8 0 100 0.75

3.0 100 0 0.75

Type of column: Waters ACQUITY UPLC HSS T3; Column length: 30 mm; Internal diameter of column: 2.1 mm; Particle Size: 1.8 micron; Temperature: 60°C.

The characteristic values obtained for each compound were the retention time ("Rt", recorded in minutes) and the molecular ion as listed in Table 3.

Method- C

Instrumentation :-

Mass Spectrometer : 6410 Triple quadrupole Mass Spectrometer from Agilent Technologies HPLC : Agilent 1200 Series HPLC

Optimized Mass Parameter :- lonisation method : Electrospray (ESI)

Polarity : positive and Negative Polarity Switch

Scan Type : MS2 Scan

Capillary (kV) : 4.00

Fragmentor (V) : 100.00

Gas Temperature (°C) : 350

Gas Flow (L/min) : 1 1

Nebulizer Gas (psi) : 35

Mass range : 1 10 to 1000 Da

DAD Wavelength range (nm): 190 to 400

Optimized Chromatographic parameter :-

Gradient conditions

(Solvent A: Water, 0.1 % formic acid and Solvent B: Acetonitrile, 0.1 % formic acid)

Time (minutes) A (%) B (%) Flow rate (ml/min)

0 90 10 1.8

2.0 0 100 1.8

3.0 0 100 1.8

3.2 90 10 1.8

4.0 90 10 1.8

Type of column: Waters Xterra MS C18; Column length: 30 mm; Internal diameter of column: 4.6 mm; Particle Size: 3.5 μ; Temperature: 30°C.

Table of examples prepared

Table T2 18 Me 0 89-92 209 0.91 A

19 F Me 1 157-159

20 F 1 177-179

21 F 1 145-170

22 F 1 156-158

CI'^^ ^* CI

BIOLOGICAL EXAMPLES: FUNGICIDAL ACTION:

Alternaria solani / tomato / leaf disc (early blight)

Tomato leaf disks cv. Baby are placed on agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water. The leaf disks are inoculated with a spore suspension of the fungus 2 days after application. The inoculated leaf disks are incubated at 23 °C / 21 °C (day/night) and 80% rh under a light regime of 12/12 h (light/dark) in a climate cabinet and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears on untreated check disk leaf disks (5 - 7 days after application).

The following compounds gave at least 80% control of Alternaria solani at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development: 17 Botrvotinia fuckeliana (Botrvtis cinerea) / liquid culture (Gray mould)

Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (Vogels broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24 °C and the inhibition of growth is determined photometrically 3-4 days after application. „„

- 40 -

The following compounds gave at least 80% control of Botryotinia fuckeliana at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: 2, 5, 7, 8, 10, 1 1 , 18

Glomerella laqenarium (Colletotrichum laqenarium) / liquid culture (Anthracnose)

Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24 °C and the inhibition of growth is measured photometrically 3-4 days after application.

The following compounds gave at least 80% control of Glomerella lagenarium at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: 2, 3, 4, 6, 7, 8, 9, 1 1 , 13, 14, 15, 16, 17, 18

Blumeria qraminis f. sp. tritici (Ervsiphe qraminis f. sp. tritici) / wheat / leaf disc preventative (Powdery mildew on wheat)

Wheat leaf segments cv. Kanzler are placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water. The leaf disks are inoculated by shaking powdery mildew infected plants above the test plates 1 day after application. The inoculated leaf disks are incubated at 20 °C and 60% rh under a light regime of 24 h darkness followed by 12 h light / 12 h darkness in a climate chamber and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears on untreated check leaf segments (6 - 8 days after application).

The following compounds gave at least 80% control of Blumeria graminis f. sp. tritici at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development: 1 1

Fusarium culmorum / liquid culture (Head blight)

Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24 °C and the inhibition of growth is determined photometrically 3-4 days after application.

The following compounds gave at least 80% control of Fusarium culmorum at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: 2, 5, 7, 8, 9, 10, 1 1 , 13, 14, 15, 17, 18

Gaeumannomvces qraminis / liquid culture (Take-all of cereals)

Mycelial fragments of the fungus from cryogenic storage were directly mixed into nutrient broth

(PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores iss added. The test plates are incubated at 24 °C and the inhibition of growth is determined photometrically 4-5 days after application.

The following compounds gave at least 80% control of Gaeumannomyces graminis at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: 1 , 2, 3, 4, 5, 6, 7, 8, 10, 1 1 , 12, 13, 14, 15, 17, 18

Phaeosphaeria nodorum (Septoria nodorum) / wheat / leaf disc preventative (Glume blotch) _

- 41 -

Wheat leaf segments cv. Kanzler are placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water. The leaf disks are inoculated with a spore suspension of the fungus 2 days after application. The inoculated test leaf disks are incubated at 20 °C and 75% rh under a light regime of 12 h light / 12 h darkness in a climate cabinet and the activity of a 5 compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf disks (5 - 7 days after application).

The following compounds gave at least 80% control of Phaeosphaeria nodorum at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development: 1 1 , 17

10 Monoqraphella nivalis (Microdochium nivale) / liquid culture (foot rot cereals)

Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24 °C and the inhibition of growth is determined photometrically 4-5 days after application.

15 The following compounds gave at least 80% control of Monographella nivalis at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: 1 , 2, 3, 4, 5, 6, 7, 8, 10, 1 1 , 12, 13, 14, 15, 16, 17, 18

Mvcosphaerella arachidis (Cercospora arachidicola) / liquid culture (early leaf spot)

Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato 20 dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24 °C and the inhibition of growth is determined photometrically 4-5 days after application.

The following compounds gave at least 80% control of Mycosphaerella arachidis at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease 25 development: 2, 4, 5, 6, 7, 8, 10, 1 1 , 13, 14, 15, 17, 18

Phvtophthora infestans / tomato / leaf disc preventative (late blight)

Tomato leaf disks are placed on water agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water. The leaf disks are inoculated with a spore suspension of the fungus 1 day after application. The inoculated leaf disks are incubated at 16 °C and 75% rh under a 30 light regime of 24 h darkness followed by 12 h light / 12 h darkness in a climate cabinet and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf disks (5 - 7 days after application).

The following compounds gave at least 80% control of Phytophthora infestans at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease 35 development: 2, 21

Plasmopara viticola / grape / leaf disc preventative (late blight)

Grape vine leaf disks are placed on water agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water. The leaf disks are inoculated with a spore suspension of the fungus 1 day after application. The inoculated leaf disks are incubated at 19 °C and 40 80% rh under a light regime of 12 h light / 12 h darkness in a climate cabinet and the activity of a „„

- 42 - compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf disks (6 - 8 days after application).

The following compounds gave at least 80% control of Plasmopara viticola at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development: 3, 4, 5, 6, 7, 8, 9, 15, 16, 17, 20, 22

Puccinia recondita f. sp. tritici / wheat / leaf disc curative (Brown rust)

Wheat leaf segments cv. Kanzler are placed on agar in multiwell plates (24-well format). The leaf segments are inoculated with a spore suspension of the fungus. Plates are stored in darkness at 19 °C and 75% rh. The formulated test compound diluted in water is applied 1 day after inoculation. The leaf segments are incubated at 19 °C and 75% rh under a light regime of 12 h light / 12 h darkness in a climate cabinet and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf segments (6 - 8 days after application).

The following compounds gave at least 80% control of Puccinia recondita f. sp. tritici at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development: 9, 15, 16, 20

Puccinia recondita f. sp. tritici / wheat / leaf disc preventative (Brown rust)

Wheat leaf segments cv. Kanzler are placed on agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water. The leaf disks are inoculated with a spore suspension of the fungus 1 day after application. The inoculated leaf segments are incubated at 19 °C and 75% rh under a light regime of 12 h light / 12 h darkness in a climate cabinet and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf segments (7 - 9 days after application).

The following compounds gave at least 80% control of Puccinia recondita f. sp. tritici at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development: 3, 4, 5, 6, 9, 1 1 , 13, 16, 17

Pvthium ultimum / liquid culture (seedling damping off)

Mycelia fragments and oospores of a newly grown liguid culture of the fungus are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal mycelia/spore mixture is added. The test plates are incubated at 24 °C and the inhibition of growth is determined photometrically

2-3 days after application.

The following compounds gave at least 80% control of Pythium ultimum at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 13, 14, 15, 16, 17, 18, 19, 20, 21 , 22

Thanatephorus cucumeris (Rhizoctonia solani) / liguid culture (foot rot, damping-off)

Mycelia fragments of a newly grown liguid culture of the fungus are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96-well format), the nutrient broth containing the fungal material is added. The test plates are incubated at 24 °C and the inhibition of growth is determined photometrically 3-4 days after application. „„

- 43 -

The following compounds gave at least 80% control of Thanatephorus cucumeris at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: 1 , 5, 6, 7, 8, 9, 10, 1 1 , 13, 14, 15, 16, 17, 22

Sclerotinia sclerotiorum / liquid culture (cottony rot)

Mycelia fragments of a newly grown liquid culture of the fungus are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format) the nutrient broth containing the fungal material is added. The test plates are incubated at 24 °C and the inhibition of growth is determined photometrically 3-4 days after application.

The following compounds gave at least 80% control of Sclerotinia sclerotiorum at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 13, 14, 17, 18

Mvcosphaerella qraminicola (Septoria tritici) / liquid culture (Septoria blotch)

Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24 °C and the inhibition of growth is determined photometrically 4-5 days after application.

The following compounds gave at least 80% control of Mycosphaerella graminicola at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: 1 , 2, 4, 5, 6, 7, 8, 10, 1 1 , 12, 13, 14, 15, 17, 18