slide 1

Back to the List of the Granted Patents                                                                        Click here to download KE000403 PDF

(51) lnt.O.7:C 07C 233/03, C 070 207/34,211/45, 213/82, 231/14,231116, 237124, 239128, 239/30, 263/34, 277/56, 307/68, 309128, 327/06, 333/38

(21) Application Number: KElP/ 2003/ 000314

(22) Filing Date: 15/1212003

(30) Priority data: 0230155.4  24/1212002  GB

(86) PCTdata PCf/EP03/014248    15/1212003 WO 2004/058723 AI    15/07/2004

(54) Title:
 
(73)0wner:SYNGENTA PARTICIPATIONS AG of Sch.wazwaldallee 215,CH-4058 Basel, Switzerland

(72) Ioventor:WALTER, HARALD of 215, CH-4058, Switzerland;

EHRENFREUND, JOSEF of 215, CH-4058 BASEL, Switzerland; LAMBERTI!, CLEMENS of 215, CH-4058 BASEL, Switzerland wtd TOBLER, HANS of 215, CH-4058, Switzerland.

(74)    Agent/address for correspondence:

Hwnilton Harrison & Mathews, ICEA Building, Kenyatta Avenue, P.O. Box 30333-00100, Nairobi
 
BIPHENYL DERIVATIVES AND THEIR USE AS FUNGICIDES

(~7)Abstrad:
A  fungicidally  active  compound of formula  (1): where  Het is  a  substituted  5-  or  6-membered  heterocyclic  ring;  R 1  is
hydrogen,  formyl,  CQ-C1-4 alkyl,  COO-C1-4  alkyl,  Ct-4 alkoxy(C1-4)alkylene,  CQ-Cl-4 alkylenoxy(C1-4)alkyl, propargyl  or
~=~~; !2'c~;; R;7~d (~~~~~\~~;:q~~(~~f)n~ h~i~~~:):Y:~:Y~~ iF~~ ~c:r R:; i~~~~peS:~:r•~~~

independently, hydrogen, halogen, C1-{i alkyl [optionally substituted by one or more substituents each independently selected from halogen, hydroxy, C 1-4 alkoxy, C 1-4 haloalkoxy, C1-4 alkylthio, C1-4 haloalkylthio, C1-4 alkylarnino, d.i(C1-4)alkylarnino, C 1-4 alk.oxycarbonyl, C 1-4 alkylcarbonyloxy and tri(C 1-4)alkylsilyl], C2-4 alkenyl [optionally substituted by one or more substituents each independently selected from halogen], C2-4 alkynyl [optionally substituted by one or more substituents each independently selected from halogen], C3•7 cycloalkyl [optionally substituted by one or more substituents each independently selected from halogen, C1-4 alkyl and C1-4 haloalkyl] or tri(C 14)alkylsilyl; Z is C 1-4 alkylene [optionally substituted by one or more substituents each independently selected from hydroxy, cyano, C1-4 alkoxy, halogen, C1-4 haloalkyl, C 1-4 haloalkoxy, C 1-4 alkylthio, COOH and COO-Cl-4 alkyl]; m is 0 or 1; and n is 0, 1 or 2; the invention also relates to novel intermediates used in the preparation of these compounds, to agrochemical oompositions which oomprise at least one of the novel compounds as active ingredient and to the use of the active ingredients or oompositions in agriculture or horticulture for controlling or preventing infestation of plants by phytopathogenic microorganisms, preferably fungi.

BIPHENYL DERIVATIVES AND THEIR USE AS FUNGICIDES

The present invention relates to novel carboxamide derivatives as active ingredients which have microbiocidai activity, in particular fungicidaJ activity. The invention also rdates to preparation of these active ingredients, to novel diphenyl derivatives used as intermediates

5    in the preparation of these active ingredients, to preparation of these novel intermediates, to agrochemica1 compositions which comprise at least one of the novel active ingredients, to preparation of these compositions and to use of the active ingredients or compositions in agriculture or horticulture for controlling or preventing infestation of plants by phytopathogenic microorganisms, preferably fungi.

10 Fungicidally active carboxamide derivatives are disclosed in JP2001 072510, JP2001072508, JP2001072507 and JP2001302605.

Certain amino- or halo-substituted diphenyl derivatives are disclosed in DE2205732 and JP2001302605.

The present invention provides a compound of formula (I):

where Het is a 5- or 6-membered heterocyclic ring containing one to three heteroatomst each independently selected from oxygen, nitrogen and suphur, provided that the ring is not 1,2,3-triazole, the ring being substituted by one, two or three groups RY; R1 is hydrogen.
formyl, CO-Ct 4 alkyl, COO-Ct-< alkyl, c, .. alkoxy(C,4)alkylene,

20CO-Cr4  alkylenoxy(Ct4)alkyl, prupargyl or allenyl; R    2    3    5   
        , R    , R' and R  are each,   

independently, hydrogen, halogen, methyl or•CF,; each R6 is, independently, halogen, methyl or CF,; R7 is (Z)mCsC(Y'), (Z)mC(Y1)=C(Y2)(Y3) or tri(C1,.)alkylsilyl; each R' is, independently, halogen, c,_,alkyl, C,.,haloalkyl, C,., allwxy(Cr.,)alkylene or cyano; X is 0 or S; Y1, Y2 "'!d Y3 are each, independently, hydrogen, halogen, Cr.o alkyl [optionally

substituted by one or more substituents each independently selected from halogen, hydroxy,

C14 alkoxy, C14 haloalkoxy, c,_. alkylthio, c,_. haloalkylthio, C14 alkylamino,

di(C1_.)alkylamino, c,_. alkoxycarbonyl, c,_.a!kylcarbonyloxy and tri(C,_.)alkylsilyl], c,_. alkenyl [optionally substituted by one or more substituents each independently selected from halogen], C24 alkynyl [optionally substituted by one or more substituents each independently selected from halogen], c,_, cycloalkyl [optionally substituted by one or more substituents each independently selected from halogen, c,_. alkyl and c,_. haloalkyl] or tri(C 14)alkylsilyl;

Z is Ct-4 alkylene {optionally substituted by one or more substituents each independently

selected from hydroxy, cyano, c, .. alkoxy, halogen, cl-4 haloalkyl, c, .. haloalkoxy,

10    C14 alkylthio, COOH and COO-C,_.alkyl]; m is 0 or I; and n is 0, I or2.

In one particular aspect, the present invention provides a compound of formula (I) as

defined above where Y1' Y2 and Y3 are each, independently, hydrogen, halogen, cl-4 alkyl [optionally substituted by one or more substituents each independently selected from halogen, hydroxy, cl-4 alkoxy, c, .. haloalkoxy, cl-4 alkylthio, c, .. haloalkylthio, cl-4 alkylamino,

15    di(C14)alkylamino, C, 4 alkoxycarbonyl and tri(C14)alkylsilyl], C24 alkenyl [optionally substituted by one or more substituents each independently selected from halogen], C2-4 alkynyl [optionally substituted by one or more substituents each independently selected from halogen], C,., cycloalkyl [optionally substituted by one or more substituents each

independently selected from halogen, c,_. alkyl and C14 haloalkyl] or tri(C1-,)alkylsilyl.

20    In one aspect, the present invention provides a compound of formula (I) as defined

above where Z is Ct-4 alkylene [optionally substituted by one or more substituents each

independently selected from hydroxy, cyano, c,_. alkoxy, cl-4 haloalkoxy, cl-4 alkylthio,

COOH and COO-C1_.alkyl].

In one aspect, the present invention provides a compound of formula (I) as defined

25    above provided that R7 is not Cz-6 alkenyl when X is 0; R1 is hydrogen; one ofR2 , R3, R4 and R5 is fluorine and the others are all hydrogen; n is 1; and Het is
F  H
F~v) {
or    NQ
I
CH3


In another aspect, the present invention provides a compound of formula (1) as defined above provided that R7 is not C2-6 alkenyl when X is 0; R1, R2, R3, R4 and R5 are all hydrogen; and Het is
In a further aspect, the present invention provides a compound of formula (1) as defined above provided that R7 is not c,_. alkenyl when X is 0; R1, R2 , R3 , R4 and R5 are all hydrogen; n is I; and Het is

In yet another aspect, the present invention provides a compound of fonnula (I) as

10    defined above provided that R7 is not C2-6 alkenyl in the 4' position when X is 0; R1, R3 and

R5 are all hydrogen; R2 and R4 are each, independently, hydrogen or fluorine; n is 0; or n is 1; or n is 2 and the two independent R 6 substituents are in positions 2',3' or 2',5' or 3',5'; and Het is



15 Halogen is fluorine, chlorine, bromine or iodine [preferably fluorine, chlorine or bromine].

Each alkyl moiety is a straight or branched chain and is, for example, methyl, ethyl, n-prupyl, n-butyl, iso-propyl, n-butyl, sec-butyl, iso-butyl or tert-butyl. Likewise, each alkylene moiety is a straight or branched chain.
Haloalkyl moieties are alkyl moieties which are substituted by one or more of the same

or different halogen atoms and are, for example, CF,, CF2CI, CHF2,  CH2F, CCI,, CF3CH2,

CHF2CH2, CH2FCH,, CH,CHF or CH3CF,.

Alkenyl and alkynyl moieties can be in the form of straigbt or branched chains. The alkenyl moieties, where appropriate, can be of either the®- or (Z)-<:onfiguration. Examples are vinyl, allyl, ethynyl and pmpargyl.

Cycloalkyl includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl.
In tri(C14)alkylsilyl and in di(C 14)alkylarnino, each alkyl moiety is selected independently.

10    Throughout this description, Me stands for methyl and Et stands for ethyl.

It is preferred that Het is pyrazole, pyrrole, thiophene, furan, thiazole, isothiazole,

oxazole, isoxazole, pyridine, pyrazine, pyrimidine, pyridazine, 5.6-dihydropyran or

5.6-dihydro-1.4-oxathiine [more preferably pyrazole, pyrrole, thiophene, furan, thiazole, oxazole, pyridine, pyrimidine, pyridazine or 5.6-dihydmpyran; yet more preferably pyrazole,
15    pyrrole, pyridine or thiazole; and even more preferably pyrazole, pyrrole or thiazole].

In one aspect it is preferred that Het is pyrazole, pyrrole, thiophene, furan, thiazole,

isothiazole, oxazole, isoxazole, pyrazine, pyrimidine, pyridazine, 5.6-dihydropyran or

5.6-dihydro-1.4-oxathiine [more preferably pyrazole, pyrrole, thiophene, furan, thia:zole, oxazole, pyrimidine, pyridazine or 5.6-dihydropyran and even more preferably pyrazole,
20    pyrrole or thiazole].

Preferably R1 is hydrogen, propargyl, allenyl, formyl, COMe, COEt or COCH20Me. More preferably R1 is hydrogen.

Preferably R2 is hydrogen. Preferably R3 is hydrogen.
25    Preferably R4 is hydrogen.

Preferably R5 is hydrogen or halogen. More preferably R5 is hydrogen or fluorine. Even more preferably R5 is hydrogen.
In one aspect of the invention R7 is tri(C,4)alkylsilyl.
30 Preferably Y1, Y2 and Y3 are, independently, hydrogen, halogen, c,_. alkyl, C1.3 haloalkyl, C,4(haloalkoxy)C,4alkyl, C1..,(haloalkylthio)C, 4 alkyl, trimethylsilyl, C24 alkenyl,

5

C24 haloalkenyl or C3_. cycloalkyl (optionally substituted by one or more substituents each independently selected from halogen and C 1-2 alkyl).

Preferably Z is C1., alkylene [which may be optionally substituted by one or more substituents each independently selected from halogen, C14 haloalkyl and C1 4 haloalkoxy].
5    PreferablyR7 is in the 4' position.

Preferably R7 is vinyl [optionally substituted by one to three substituents each
independently selected from halogen, C1_. alkyl, C1., haloalkyl, c,_. cycloalkyl (optionally

substituted by one to five substituents each independently selected from halogen, CH3 and

c,.,haloalkyl) and trimethylsilyl], ethynyl [optionally substituted by one substituent selected

10    from cyclopropyl, cyclopentyl and cyclohexyl (each optionally substituted by one to five

substituents each independently selected from halogen, CH, and C1.2 haloalkyl), halogen,
C 1-6 alkyl, C 14 haloalkyl, c,_. alkenyl, c,_. haloalkenyl and tri(C 14)alkylsilyl], allyl [optionally substituted by one to tlrree substituents each independently selected from halogen, CH,,
Cl-2 haloalkyl and trimethylsilyl], propargyl [optionally substituted by one to tlrree substituents

15    each independently selected from halogen, C1-4 alkyl, C1-2 haloalkyl and trimethylsilyl] or

tri(C1 4 )alkylsilyl.

In one particular aspect R7 is preferably vinyl [optionally substituted by one to three substituents each independently selected from halogen, c, .. alkyl, Cl.] haloalkyl, c,_.

cycloalkyl and trimethylsilyl], ethynyl [optionally substituted by one substituent selected from

20    halogen, cl-4 alkyl, Cl-2 haloalkyl, cyclopropyl (optionally substituted by one to five substituents each independently selected from halogen, CH,, c,., haloalkyl and trimethylsilyl)

and trimethylsilyl), allyl [optionally substituted by one to three substituents each independently selected from halogen, CH,, C1., haloalkyl and trimethylsilyl], propargyl

[optionally substituted by one to three substituents each independently selected from halogen,

25    CH3,  C1.2 haloalkyl and trimethylsilyl] or tri(CI_.)alkylsilyL

In another particular aspect R 7 is preferably vinyl [optionally substituted by one to three substituents each independently selected from halogen, c,.., alkyl, c,., haloalkyl, c,_. cycloalkyl and trimethylsilyl], ethynyl [optionally substituted by one substituent selected from halogen, C14 alkyl, C1., haloalkyl and trimethylsilyl], allyl [optionally substituted by one to

30    three substituents each independently selected from halogen, CH,, C 1-2 haloalkyl and trimethylsilyl], propargyl [optionally substituted by one to three substituents each
independently selected from halogen, CH,, C1., haloalkyl and trimethylsilyl] or

tri(C,~)alkylsilyl.

More preferably R7 is CH~H,, CH~H(CH,), CH=CHSiMe,, CH=CF,, CH~CI,,

C(CH3)'=CC!,, CH=CBr,, C(CH,)=CBr,, C(CH,)'=CF,, CH~FCI, CH~FBr, C(CH3)'=CFCI,

C(CH,)~r, CH~FMe, CH=CBrMe, CH=CCIMe, CH~HBr, CH=CHF, CH=CHCI,

CF~F2, CCI=CF,, CCI=CH,, CBr=CH1 , CF=CH,, C(CF,)'=CFBr, C(CF,)'=CFCI, C(CF3)'=CBr2, C(CF,)'=CCI,, C(CF,)'=CF,, C(CF,)~H2, CF=CHF, CH=CHCF3,
CH=CFCF2CI, CH=CCICF,CI, CH=CBrCF,CI, CH~(CF,h, CH=CHC,Fs,

CH=CHCF(CF3J, C(CH,)~HCF,, C(CH,)~FCF,, C(CH,)'=CCICF,, C(CH3)=CBrCF3,

10    CH=CCICF, CH~ClC,F5, CH=CBrCF, CH~FC,F5, CH~FCF3, CH,CH~H2,

CH1CH~F, CH,CH~CI2, CH,CH~Br,, CH,CH=CFBr, CH,CH=CFCI, CH2CH=CCICF3 , CH2CH~HSiMe,, C-=CH, CsCSiMe3, CsCSiEt3, C=CSiMe2C(CH,)3, CsCCI, CsCBr, C=CF, CsCCF,, CsCCF,H, CsCCF,CI, CsCCF,Me, CsCCF,Et,

CsCCHFCI, CsCCF2Br, CsCC,F5, CsCCF(CF,)2,  CsCCHF(CF3), C=CCH,F,

15    CsCCH(Me)F, C=CCH(Et)F, CsCMe, CsCCH,Me, C-~CHMe2, CsCCH,CHMe2, CsCCMe3, CsCCH2CMe3 , CsCCH,SiMe,, CsCCMe2CI, CsCCMe,F, C-~CH20Me, CsCCH2CF3, C-..CCMe,OMe, CsCCMe,OH, CsCCMe20COMe, C"CC(Me)'=CH2, CsCCF=CF,, CsC(cyclopropyl), C=C(cyclopentyl), CsC(l-F-cyclopentyl), CH2CsCH,

CF2CsCH, CHFCsCH, CH(CF,)CsCH, SiMe,, CH,CsCCMe3 or CH,CsCSiMe,.

20    In one particular aspect R7 is more preferably CH..CH,, CH~H(CH3), CH~HSiMe3,

CH=CF2, CH~CI,, C(CH,)=CCI,, CH=CBr,, CF=CF,, CCI~H,, CBr=CH,, CF~H,,

CF~, CH=CHCF3, CH..CCICF,, CH=CBrCF3, CH2CH=CH2, CH2CH=CHSiMe3, C=CH, C=-{;SiMe3, CsCSiEt3, CsCSiMe,C(CH,),, CsCCI, CsCBr, CsCCF,, C-..CCF2H, CsCCF2CI, CsCCF2Br, CsCCF(CF,),CsCMe, CsCCHMe,, CsCCMe,, CsCCMe2CI, CsCCH20Me,

25    CsC(cycloC,Hs), CsC(cycloC,H,), CH,CsCH, SiMe, or CH,CsCSiMe,.

Even more preferably R7 is CH..CF,, CH=CCI,, C(CH3)'=CCI,, CH..CBr2,

C(CH,)'=CBr2, C(CH3)'=CF2, CH..CFCI, CH..CFBr, C(CH,)'=CFCI, C(CH,)'=CFBr,

CH~r, CH=CHF, CH..CHCI, CCI~H2, CH=CHCF,, CH..CFCF2CI, CH~CICF,CI, CH~BrCF,CI, CH~(CF,)l, CH~HC,F,, CH=CHCF(CF,),, C(CH,)'=CHCF,,

30    CH..CCICF,, CH=CCIC,Fs, CH=CFC,Fs, CH..CBrCF,, CH=CFCF,, CH,CH~CICF,,
CH,CH={;C!,, CH,CH~CBr,, C"CH, C..CSiMe,, C"CSiEt,, C"CSiMe,C(CH,j,, C..CCI, C..CCF,, C..CCF,H, C"CCF,Cl, C"CCHFCI, C"CCF,Me, C..CCF2Et, C..CCHFEt, C"CCF,Br, C..CCF(CF,j,, C..CCF,CF,, C"CCHF(CF,), C"CCH,F, C..CCH(Me)F, C"CMe, C"CCHMe,, C..CCH,Me, C..CCH,CHMe,, C"CCMe,, C..CCH,CMe,,

5    C"CCMe,F, C..CCH,CF,, C"C(cyclopropyl), C..C(cyclopentyl), C"C(l-F-cyclopentyl), C"CC(MeFCH,, C"CCF~CF,, C..CCH,SiMe,, CH2C,rn, CF2C,rn or CHFC..CH.

In one particular aspect R7 is even more preferably CH={;H,, CH~SiMe,, CH={;F2 ,
CH={;C!,, CH~CBr,, CF~CF,, CCI~CH,, CBPCH,, CF={;HF, CH~CF,, CH~CCICF3,

C..CH, C..CSiMe3, C"CCI, C"CBr, C"CCF,, C"CMe, C..CCMe3, C..CCHMe2,

10    C..C(cycloC,H5), CH2C,CH, SiMe, or CH,C,CSiMe3.

Yet more preferablyR7 is CH~CF,, CH={;CJ,, CH~r2,CH={;FCI, CH={;FBr,
CH~CHBr, CH~CHF, CH~CHCI, CCJ~CH,, CH~CF,, CH={;FCF,CI, CH~CCICF2CI,

CH={;BrCF,CI, CH~C(CF,j,, CH~CHC,Fs, CH~CCICF,, CH~rCF,, CH~CF,, C"CH,

C..CSiMe,, C..CCI, C"CCF,, C..CCF,H, C"CCHFCI, C"CCHF(CF,), C..CCF,Cl,

15    C"CCF,Me, C..CCF2Br, C"CCF,CF,, C..CCH,F, C"CCH(Me)F, C"CMe, C..CCHMe2, C..CCH,CHMe,, C"CCMe,, C"CCCH,CMe,, C"CCMe,F, C"CCH2CF3, C..C(cyclopropyl),

C"C(cyclopentyl), C..C(l-F-cyclopentyl), CH,C"CH, CF,c,rn, CHfC,CH or C"CCH2Me. In one particular aspect R7 is yet more preferably CH~CHSiMe3, CH~CF,, CH~CClz,
CH~r,, CF~CF2, CCI~,, CBPCH,, CF~CHF, CH~CHCF3, CH={;CICF3,  C..CH,

20    C..CSiMe,, C"CCI, C"CBr, C..CCF,, C"CMe, C"CCMe,, C..CCHMe2, C..C(cycloC3H5), CH2C..CH, SiMe, or CH,C..CSiMe,.

Preferably nitrogen atoms in the Het ring are, independently, either unsubstituted or

substituted by R'-

When RY is a substituent on a nitrogen atom it is preferably C1_3 alkyl, C1-J ha1oalkyl or

25    metboxymethylene; more preferably C1., alkyl, CF3, CF2CI, CHF2, CH2F or methoxymethylene; even more preferably methyl, CHFz or methoxymethylene; yet more preferably methyl or metboxymetbylene; and most preferably methyl.

Preferably carbon atoms in the Het ring which are not bonded to the atom substituted by

CXNR1 are, independently, eitherunsubstituted or substituted byR'.
 
When RY is a substituent on a carbon atom which is not bonded to the atom substituted by CXNR I it is preferably halogen, c,_, alkyl, c,_, haloalkyl or methoxymethylene; more preferably chloro, methoxymethylene, CH,, CHFz or CF3; yet more preferably chloro, CH,, CHF2 or CF3; and even more preferably CH3 or CF3.There may be one or two carbon atoms in

5    the Ret ring bonded to the atom substituted by CXNR1; preferably such carbon atoms are, independently, either unsubstituted or substituted by RY.

When RY is a substituent on a carbon atom bonded to the atom substituted by CXNR1 it is preferably halogen, CJ-3 alkyl or Cl-3 haloalkyl; more preferably chloro, fluoro, bromo,

C 1•2 alkyl, CF3, CF,CI, CHF2, CH,F; and even more preferably chloro, fluoro, bromo, methyl, 10 CF,, CHF,orCHzF.

More preferably, when there is only one carbon atom in the Het ring bonded to the atom substituted by CXNR1 that carbon atom is substituted by RY .

More preferably, when there are two carbon atoms in the Het ring bonded to the atom substituted by CXNR1 one such carbon atom is substituted by RY and the other carbon atom is

15 either unsubstituted or is substituted by fluoro, chloro or methyl. Preferably m is 0.

Preferably n is 0. Preferably X is 0.

Compounds offormula (II):

20

R'
R'    R'

R'' -N    R5
I    (II)
H
where R\ R2 , R3, R4, R\ R6,R7 and n are as defined above for a compound of formula (I), are also novel [except for the compound offonnula (II) where R 1, R 2, R3, R4 and R 5 are each

    Compoond C according    Compound 2•91 according   
    to the present invention    to document {A)           
Action aaainst Puccinia recondita (Brown rust)•                           
                                           
    Compound No.                    ppm           
                                           
                    200        I    60    I    20   
    C (present invention)        1o0%    1    sO%    1    20%   
    2-91 (prior art)        2o%    1    o%    I    0%   
Action aaainst Monooraohella nivalis (Snow mould)                   
    Compound No.                        ppm           
                                       
                                           
                    20        I    6    I    2   
    C (present invention)            1oo%    1    1oo%    1    0%   
    2-91 (prior art)            o%    I    0%    I    0%   

Also the third example shows the superior fungicidal activity of the compound according to the present invention: (1) compound Cis able to control Puccinia recondita at application
rates of 200 ppm and 60 ppm, whereas compound no. 2-91 is Ineffective at these concentrations; (2) compound Cis able to control Monographella nivalis at concentrations of 20 ppm and 6 ppm, whereas compound no. 2-91 is totally ineffective at these concentrations. Also for the tested thiazolyl-compounds, the only structural differences between these compounds are: the alkinyl vs alkyl substituent at the second phenyl and the fluorine vs chlorine substituent at the first phenyl.

Conclusion:

These results are indicative of the superior fungicidal activity of the three compounds according to the present invention when compared with compounds described In document

(A) against Puccinia recondite (on wheat leaf segments) and MonographeUa nivalis (in liquid culture tests) at the tested application rates. In the light of the structural similarities of the tested compounds, this surprising improvement of the fungicidal properties is completely

unexpected Blld cannot be derived from what is known from prior art. This superior

performance is important because it allows a more efficient disease control of these plant

diseases at significantly lower application rates.
 
hydrogen, n is 0 and R7 is CH~CHCH,CO,H] and are useful as intermediates in the

preparation of compounds of formula (I).

Therefore, in another aspect the present invention provides a compound of formula (D), where R1, R2, R3 ,R4, RS. R6, R7 and n are as defined above for a compound offommJa(I)
5    provided that when R1, R2, R3, R4 and R5 are each hydrogen and n is 0 then R7 is not

CH~HCH,C02H

The preferred values forR 1,R2, R3 , R4, R', R6, R7 and n for a compound offormula(m

are as defined above for a compound of formula (I).

Many compounds of formula (ill):

10

R'

Hal    (Ill)




where R2 , R3, R\ R5, R6, R7 and n are as defined above for a compound of formula (I) and Hal is bromo, chloro or iodo, are also novel and are useful as intermediates in the preparation of

compounds of formula (I).

15    Certain compounds of formula (lll) are already known; Table 0 shows known

compounds of formula (IDa) where Hal, R 2, R3, R4 and R7 are as defined in Table 0.
R~R' R'
""I
Hal    ~

(lila)

""I
"'
R'

    Hal    R'    R'    R    R   
    Cl    Cl    H    H    C(CH,)=CH-CH,-OH   
    Br    H    Me    H    C(CF,f=CF,   
    Br    H    Me    Br    C(CF, =CF,   
    Cl    H    H    H    C=CH   
    Cl    H    H    H    CH=CH-CH,-CH,-OH   
    Cl    H    H    H    C(CH,FCH-CH,-OH   
    Cl    H    H    H    C(CH,}=CH-C(~O)-OC,Hs   
                       
    Cl    H    H    H    C(CH,)~CH-CH(OH)CH,   
    Cl    H    H    H    CH-CH-CH(OH)C H,   

Therefore, in a further aspect the present invention provides a compound of fonnula

(III), where R\ R\ R4 , R5, R6 , R1 and n are as defined above for a compound offonnula (I) and Hal is bromo, chloro or iodo; provided that the compound is not a compound of formula (IDa) according to Table 0.

The preferred values for R2, R3, R4, R5, R6, R7 and n for a compound of formula (III) are as defined above for a compound offormula (1).

Preferably Hal is bromo or chloro. More preferably Hal is bromo.

10 The compounds of formulae (1), (ll) and (III) may exist as different geometric or optical isomers or in different tautomeric forms. For each formu1a, this invention covers ali such isomers and tautomers and mixtures thereof in all proportions as well as isotopic forms such

as deuterated compounds.

The compounds in Tables 1 to 13 below illustrate compounds of the invention.

The compounds according to the present invention may be prepared according to the following reaction schemes, in which, unless otherwise stated, the definition of each variable
5    is as defined above for a compound of formula (!).

There are a number of alternative methods for preparing a compound of formula (1).

Method A

A compound of formula (I) may be prepared by reacting a compound of formula (II)
with a compound of formula Het-C(~Q)OR' [where R' is C1.5 alkyl] in the presence of strong

10    base [for example NaH or sodium hexamethyldisilazane], in a dry polar solvent (preferably TIIF] and at a temperature between -10'C and the boiling point of the solvent [preferably at ambient temperature]. The article by J.Wang et al, Syn!ett 2001,1485 provides details of analogous preparations.

MethodB

15 A compound of formula (I) may be prepared by reacting a compound of formula (II) with a compound of formula Het-C(~)R" [where R" is OH or a leaving group, such as Cl, Br, for OC(~)C1~ alkyl] in an inert organic solvent [such as ethylacetate, dichloromethane, dioxane or DMF] and at a temperature between -IO'C and the boiling point of the solvent

[preferably at ambient temperature].  lfR" is OH, the reaction is carried out in the presence of

20    an activating agent [for example BOP-CI] and two equivalents of a base [such as a tertiary

amine~ an inorganic carbonate or a hydrogen carbonate]. Alternatively, ifR" is a leaving group, the reaction is carried out in the presence of at least one equivalent of base [such as pyridine, a tertiary amine, an inorganic carbonate or a hydrogen carbonate].

Methode

5 A compound of formula (l) [where R 1 is as defined ahnve but is not hydrogen] maybe prepared by reacting a compound of formula (l) [where R 1 is hydrogen] with a compound of

formula R1 ~L1 [where R1 is as defined above but is not hydrogen; and L1 is a leaving group

such as Cl, Br, I, a sulfonate (for example a mesylate or a tosylate) or OC(O)C 14 alkyl] in a

solvent [such as a halogenated solvent (for example dichloromethane), an ether, ethylacetate,

10    DMF or even water (as a biphasic mixture, optionally in the presence of a phase transfer catalyst such as tetrabutylammonium hydrogeosulfate)] and in the presence of a base [such as a tertiary amine, an alkali carbonate, an alkali bicarbonate, an alkali hydroxide or NaH; though ifL1 is O(CO) C,-4 alkyl then simply heating without base is possible].

15    A compound of formula (l) may be prepared by reacting a compound of formula (III)

[where Hal is preferably bromo or iodoJ with a compound of formula Het-C(=O)NH2 in the

presence of a Cu(I) compound and an aprotic solvent [such as a cyclic ether, for example dioxane] at an elevated temperature and preferably at reflux . The preferred conditions are Cui used at 2% to IOO%mole/mole, relative to the compound of formula (Ill), in the presence

20    of a 1,2-diamine as a ligand-forming substance (such as 1,2-diamino cyclohexane or ethylene diarnine) and at least 1 equivalent of a base (such as an alkali carbonate or an alkali phosphate.
The article by A.Klapars et al. J.Am.Cbern.Soc. 123,7727 (2001) provides details of analogous preparations.

25    A compound of formula (l) may be prepared by conversion of a compound of formula

(N)


    R>           
R'        R•       
R\_        R5       
N            (IV)   
j_    lj    (R\       
X    He!           
        FG       

[where FG is a functional group which is convertible to R7 in one or more synthetic steps]. Functional group interconversions are standard procedures for a person skilled in the art.
There are many methods described in the literature, which can be used as such or with modifications according to the functionalities present; Table A gives literature references (some of which also cite further appropriate references) which are specifically relevant to the
preparation of a compound of formula (I) by the interconversion ofFG to R7 • It is apparent to

the person skilled in the art that the literature examples given in Table A are not necessarily

10    limited to the preparation of the specifically mentioned R7 but can be also applied by analogy to the preparation of other structurally related R7

Table A

    Reference    .FG    R   
               
    Synthesis 2001,2081    CHO    CH-CBr,   
               
               
    Tetrahedron 58, 1491 (2002)        CH=CHBr   
               
            C=CBr   
               
               
    Russ. Chern. Bull. 50 (6), I 047 (2001)    CHO    CH-CCI,   
               
    Tetrahedron 57,7519 (2001)    CHO    CH-CCICF,   
               
            CH=CFCF,CI   
               
    Bull.Cbem.Soc.Jpn. 73, 1691 (2000)    CHO    CF=CBrF   
    Bull.Chem.Soc.Jpn. 71,2903 (1998-)           
               
               
               
               
    J. Cbem.Soc.Perkin I 2002, 883    COCH3    C(CH3)=CHBr   
               
            C(CH,)=CCh   
               
               
    J.Fiuorine Cbern. I, 381 (1972)    COCH,    C(CH3)=CBr,   

    ).fluorine Chern. 23, 339 (1983)        COCF,    C(CH,)=CFBr   
                C(CH,)~CFCI   
                C(CF,)=CFBr   
                C(CF,)=CFCI   
                C(CF,)=CF2   
                   
    Tetrahedron Letters 41, 8045 (2000)        Hal    CF=CHF   
    J.Org.Chem. 62,9217 (1997)               
                   
    Tetrahedron Letters 37,8799 (1996)        Hal    CH=CF,   
                   
    JP 09278688        Hal    CF-CF,   
    ).Fluorine Chern. 31, 115 (1986)               
                   
                   
    Zh.Org.Khim. 25, 1451 (1989)        Hal    CF-CFCI   
                   
    J.Org.Chem. 53,2714 (1988)        Hal       
                CF~CFCF,   
                   
                   
    J.Org.Chem. 56,7336 (1991)        Hal    C(CF,)=CH,   
    Tetrahedron Letters 42,4083 (2001)               
                   
                   
    Ukr.Khim.Zh. 32,996 (1966)        CHBrCH,CF,    CH-CHCF,   
                   
                   
    Buli.Chem.Soc.Jap. 62,1352        CH-CC1CF,    C..CCF,   
            CH=CFCF,CI    C..CCF,CI   
                   
    J.Org.Chem. 54, 5856 (1989)        Hal ortriflate    C..CH   
    J.Am.Chem.Soc. 109,2138 (1987)            C..CSiMe,   
                   
    Tetrahedron 45,6511 (1989)            C..CCH,   
    J.Orgmet.Chem.549,127 (1997)            C..CCMe3   
                   
    Tetrahedron 56, 10075 (2000)            C..CCH,OH   
                   
                   
    Tetrahedron Asymmetry  6, 245 (1995)            C..CCHMeOH   
                C..CCMe,OH   
                C..CCHO   
                C..CC(O)Me   
                   
    J.Org.Chem. 32, 1674 (1967)        C..CCH,    CH,C..CH   
                   
                   
    Synth.Conun.l989,561        CHO    C..CH   
                   
            CH2CHO    CH,C=CH   
                   
                   
                   
 





            WOOl 092563    CHO    CH-CH,   
                       
            J.Am.Chem.Soc. 123,4155 (2001)    Hal ortriflate    CH-CH,   
            Org.Lett. 2,3703 (2000)           
            J.Org.Chem. 57,3558 (1992)           
            Synthesis 2001,893           
                       
            GB 2 183 639    C=CH    CH-CH,   
                       
            Synthesis 1996, 1494    CHO    C=CCl   
                       
            J.Org.Chem.49, 294 (1984)        C=CH   
                    C=CBr   
                       
                       
            us 6159956    CH2Br    CH2CF~F2   
                       
            Liebigs Ann.Chem. 1995, 2027    CH,Br    CH~(CF,),   
                       
                       
            J.Am.Chem.Soc. 123,4155 (2001)    CH,Br    CH,C =CSiMe3   
                       
            lnorg.Chim.Acta 296, 37 (1999)    Hal    CH,C=CMe,   
                       
            !.Fluorine Chem.lll, 185 (2001)    CH~CHBr       
                    CH~HCF,   
            I.Chem.Soc. Perkin I 1988,  921    CH~CFBr    CH~CFCF,   
                       
                       
                CH~r,    CH~C(CF,),   
                       
                       
            DE4417441    C=CCH,OH    C=CCH,F   
            US3976691    C=CCHMeOH    C=CCHMeF   
            J. Org. Chern. 64, 7048 (1999)    C=CCMe,OH    C=CCMe2F   
                       
                C=CCHO    C=CCHF2   
                       
                       
                C=CC(O)Me    C=CCF,Me   
                       
                       
            J.Cbem.Soc. Perkin I 1994,  725    C=CCH,OH    C=CCH,CF,   
                       
            Synthesis 1997, 1489    C=CH    C=CCF,CF,   
            Angew.Chem.Int.Ed. 39, 2481 (2000)        CH~HCF2CF,   
            J.Org.Chem. 47,2255 (1982)           
                       
            J.Fluorine.Chem.ll3, 55 (2002)           
                       
                       
                       
            J.Fluorine.Chem.64, 61 (1993)    C=CH    C=CCHFCJ   
            J.Am.Chem.Soc. 109,3492 (1987)        C=CCF,Br   
                       
            J.Am.Chem.Soc. 107,5186 (1985)    CH~HBr    CH=CHCF,CF,   

There are a number of alternative methods for preparing a compound of formula (II),

(ill)or(N).

Method F- preparation of a comoound offonnula (ill or (ill).

R'~R'IR'    functional1nterconversiongroup    •XX:        deprotectJon or   
T""'-.    R'                    II(T=NH2)   
                    FG interconversion       
1        (R\    . Q(R\    (if T not NH,)   
                       
    FG    R'           
(V)            • II (ifT=NHR1l   
            Ill (ifT= HaloQen}   
VI (ifT=T'or T"}
5

A compound of formula (II), (ill) or (VI) may be prepared, by functional group

interconversion, from a compound of formula (V) [where FG is as defined above for a compound of formula (IV) and Tis either halogen, amino, NHR1, a protected amino group T'

10    (for example a carbamate, an amide, a cyclic imide, anN-alkyl-, N-alkenyl-, N-benzyl-, N-diphenylmethyl- or N-trityl-derivative, an imine derivative or an N-silyl- or N-disilyl-derivative) or a group T''(that is, a group which may be converted to NH2 or NHR1 by applying synthetic methodology described in the literature; T" being preferably azido, nitro,
halogen, triflate, CONH2, COOH, COCI or NCO)].  Starting from a compound of formula (V)

15    the functional group FG may be converted to R7 by applyiog a method analogous to methodE above. This conversion leads directJy to a compound offonnu1a (II) [when Tis NHR1], to a compound of formula (ill) [when Tis halogen (preferably chloro, bromo oriodo)] or to a compound of formula (VI) [when T is T' or T"].

In a second step a compound of formula (VI) or (II) [when R1 is other than H] can be

20    converted to a compound of formula (II) [where R1 isH] by either applyiog the methods [that is, deprotection or conversion ofT'' to NHz] as generically described above.

Examples of versatile values forT' plus methods for deprotection are given in

T.W.Green and P. Wuts, Protective Groups in Organic Synthesis, 3"' edition (John Wiley &

Sons 1999), Chapter 7.

Compilations of useful values forT'' plus literature to convert T''into NHz, T'or

5    NHR1 can be found in M.B. Smith, Compendium of Organic Synthetic Methods, Vols. 1-10, Chapter 7 (Wiley, Vol.IO: 2002).

4    +RaQ'Ij(R\  ~R:~:,    .,__ .,   
R*R'           
?'I    ------        FG interconversion   
T   :::,-._R5    -    lj    (R\  (i!T not NH2)   
Ra    R'    -       
               
(VII)    (VIII)    R'   
        II (ifT=NHR1)       
               
Ill (if T= Halogen)

VI (ifT=T'or T")

10 A compound of formula (IT), (III) or (VI) may be prepared by a coupling reaction between a compound of formula (VIT) and a compound of formula (VIII) [where Ra and Ra' are each, independently, halogen (preferably Cl, Br or I), triflate or a metal-containing
functionality containing, for example, B, Sn, Mg, Zn or Cu as 1he metal; examples are

B(OH),, esters ofboronic acid (preferably esters derived from 1,2- or 1,3-diols), trialkyltin

15    (preferably Sn(CH3) 3 or Sn(nBu)3), a halogen salt ofMg, a halogen salt ofZn or Cu.  If either

Ra or Ra' is a metal containing functionality, the other substituent must be halogen or triflate. Such coupling reactions are widely known in the literature. Especially suitable are the
Pd(O) ,Ni(O), or copper catalysed couplings which are well known to the person skilled in the

art as Stille coupling, Suzuki coupling, Negishi coupling or Ulhnann reaction.  A

20    comprehensive review of these reactions can be found in Metal-Catalysed Cross-Coupling

Reactions; F.Diederich and P.Stang (eds.); Wiley-VCH; Weinheim 1998.
In a second step a compound of fonnula (VI) or (ll) [when R 1 is other than H] can be converted to a compound offonnula (II) [where R1 isH] by either applying the methods [that is, deprotection or conversion ofT'' to NH2] as generically described above.

5    Surprising]y, it has now been found that the novel compounds of fonnula (I) have, for

practical purposes, a very advantageous spectrum of activities for protecting plants against diseases that are caused by fungi as well as by bacteria and viruses.

The compounds offonnula (I) can be used in the agricultural sector and related fields of use as active ingredients for controlling plant pests. The novel compounds are distinguished

10    by excellent activity at low rates of application, by being well tolerated by plants and by being environmentally safe. They have very useful curative, preventive and systemic properties and

are used for protecting numerous cultivated plants. The compounds of fonnula I can be used

to inhibit or destroy the pests that occur on plants or parts of plants (fruit, blossoms, leaves, stems, tubers, roots) of different crops of useful plants, while at the same time protecting also

15    those parts of the plants that grow later e.g. from phytopathogenic microorganisms.

It is also possible to use compounds of fonnula (I) as dressing agents for the treatment of plant propagation material, in particular of seeds (fruit, tubers, grains) and plant cuttings (e.g. rice), for the protection against fungal infections as well as against phytopathogenic fungi occurring in the soil

20 Furthennore the compounds according to present invention may be used for controlling fungi in related areas, for example in the protection oftechnical materials, including wood and wood related technical products, in food storage, in hygiene management, etc.

The compounds of formula (I) are, for example, effective against the phytopathogenic fungi of the following classes: Fungi imperfecti (e.g. Botrytis, P}ricularia, Helminthosporium,

25    Fusarium, Septoria, Cercospora and Alternaria) and Basidiomycetes (e.g. Rhizoctonia, Hemileia, Puccinia). Additionally, they are also effective against the Ascomycetes classes (e.g. Venturia and Erysiphe, Podosphaera, Monilinia, Uncinula) and of the Oomycetes classes
(e.g. Phytophthora, Pythium, Plasmopara). Outstanding activity has been observed against powdery mildew (Erysiphe spp.) and rust ( Puccinia spp.). Furthermore, the novel compounds

30    offonnula I are effective against phytopathogenic bacteria and viruses (e.g. against

Xanthomonas spp, Pseudomonas spp, Erwinia amylovora as well as against the tobacco mosaic virus).
Within the scope of present invention, target crops to be protected typical1y comprise the fol1owing species of plants: cereal (wheat, barley, rye, oat, rice, maize, sorghum and related

5    species); beet (sugar beet and fodder beet); pomes, drupes and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawbenies, raspbenies and blackberries); leguminous plants (beans, lentils, peas, soybeans); oil plants (rape, mustard, poppy, olives, sunflowers, coconut,

castor oil plants, cocoa beans, groundnuts); cucumber plants (pumpkins, cucumbers, melons); fibre plants (cotton, flax, hemp, jute); citrus fruit (oranges, lemons, grapefruit, mandarins);

10    vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika); lauraceae (avocado, cinnarnomum, camphor) or plants such as tobacco, nuts, coffee, eggplants, sugar cane, tea, pepper, vines, hops, bananas and natura] rubber plants, as well as
ornamentals.

The compounds of formula (I) are used in unmodified fonn or, preferably, together with

15    the adjuvants conventionally employed in the art of formulation. To this end they are conve-niently formulated in known manner to emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations e.g. in polymeric substances. As with the type of the

compositions, the methods of application, such as spraying, atomising, dusting, scattering,

20    coating or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances. The compositions may also contain further adjuvants such as stabilizers, antifoams, viscosity regulators, binders or t~lcifiers as well as fertilizers, micronutrient donors or other formulations for obtaining special effects.

Suitable carriers and adjuvants can be solid or Jiquid and are substances useful in

25    formulation technology, e.g. natural or regenerated mineraJ substances, solvents, dispersants, wetting agents, tacki:fiers, thickeners, binders or fertilizers. Such carriers are for example described in WO 97/33890.

The compounds of formula (I) are normally used in the form of compositions and can be applied to the crop area or plant to be treated, simultaneously or in succession with further

30    compounds. These further compounds can be e.g. fertilizers or micronutrient donors or other preparations which influence the growth of plants. They can also be selective herbicides as

well as insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or application promoting adjuvants customarily employed in the art offonnulation.
The compounds offonnula (I) can be mixed with other fungicides, resuJting in some cases in unexpected synergistic activities. Mixing components which are particularly preferred are azoles, such as azaconazole, BAY 14120, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imazalil, imibenconazole, ipconazole, metconazole, myclobutanil, pefurazoate, penconazole, pyrifenox, prochloraz, propiconazole: simeconazole, tebuconazole,

10    tetraconazole, triadimefon, triadimenol, triflumizole, triticonazole; pyrimidinyl carbinole, such as ancymidol, fenarimol, nuarimol; 2-amino-pyrimidines, such as bupirimate, dimethirimol, ethirimol; morpholines, such as dodemorph, fenpropidine, fenpropimorph, spiroxamine, tridemorph; anilinopyrimidines, such as cyprodinil, mepanip}Tim, pyrimethanil; pyrro1es, such as fenpicloni1, fludioxoni1; phenylamides, such as benalaxy1, furalaxy1, meta-

15    laxy1, R-metalaxyl, ofurace, oxadixyl; benzimidazoles, such as benomyl, carbendazim, debacarb, fuberidazole, thiabendazole; dicarboximides, such as chlozolinate, dichlozoline, iprodione, myclozoline, procymidone, vinclozoline; carboxamides, such as carboxin, fenfuram, flutolanil, mepronil, oxycarboxin, thifluzamide; guanidines, such as guazatine,

dodine, iminoctadine; strobilurines, such as azoxystrobin, kresoxim-methyl, metominostrobin,

20    SSF-129, trifloxystrobin, picoxystrobin, BAS 500F (proposed name pyrac1ostrobin), BAS 520; dithiocarbamates, such as ferbarn, mancozeb, maneb, metirarn, propineb, thiram, zineb, zirnm; N-ha1omethy1thiotetrahydrophthalimides, such as captafo1, captan, dich1ofluanid,

fluoromides, folpet, tolyfluanid; Co-compounds, such as Bordeaux mixture, copper

hydroxide, copper oxychloride, copper sulfate, cuprous oxide, mancopper, oxine-copper;

25    nitrophenol-derivatives, such as dinocap, nitrothal-isopropyl; organo-p-derivatives, such as edifenphos, iprobenphos, isoprothiolane, phosdiphen, p)T3ZOphos, tolclofos-methyl; various others, such as acibenzolar-S-methyl, anilazine, benthiavalicarb, blasticidin-S, chinomethio-

nate, chloroneb, chlorothalonil, cyflufenamid, cymoxanil, dichlone, diclomezine, didoran,

diethofencarb, dimethomorph, SYP-LI90 (proposed name: flumorph), dithianon, ethaboxaru,

30    etridiazole, farnoxadone, fenamidone, fenoxanil, fentin, ferimzone, fluazinam, flusulfarnide, fenhexarnid, fusety1-aluminium, hyrnexazo1, iprova1icarb, IKF-916 (cyazofarnid),


kasugamycin, methasulfocarb, metrafenone, nicobifen, pencycuron, phthalide, polyoxins,

probenazo]e, propamocarb, pyroquilon, quinoxyfen, quintozene, sulfur, triaz.oxide,

tricyc]azole, triforine, validamycin, wxamide (RH7281).

A preferred method of applying a compound of formula (1), or an agrochemical

5    composition which contains at least one of said compounds, is foliar application. The frequency of application and the rate of application will depend on the risk of infestation by the corresponding pathogen. However, the compounds of formula I can a] so penetrate the plant through the roots via the soil (systemic action) by drenching the locus of the plant with a

liquid formulation, or by applying the compounds in solid form to the soil, e.g. in granular

10    fonn (soil application).ln crops of water rice such granulates can be applied to the flooded rice field. The compounds of formula I may also be applied to seeds (coating) by impregnating the seeds or tubers either with a liquid formulation of the fungicide or coating them with a solid formulation.
A fonnulation [that is, a composition containing the compound of fonnula (I)] and, if

15    desired, a solid or liquid adjuvant, is prepared in a known manner, typically by intimately mixing and/or grinding the compound with extenders, for example solvents, solid caniers and, optiona1ly, surface active compounds (surfactants).

The agrocbemical fonnulations will usually contain from 0.1 to 99% by weight,

preferably from 0.1 to 95% by weight, of the compound ofrormula 1, 99.9«> 1% by weight,

20    preferably 99.8 to 5% by weight, of a solid or liquid adjuvant, and fiom 0 to 25% by weight, preferably fiom 0.1 to 25% by weight, of a surfactant.

Advantageous rates of application are normally from 5g to 2kg of active ingredient (a.i.) per hectare (ha), preferably fiom lOg to !kg a.i.lha, most preferably fiom 2{}g to 600g a.i.!ha.

When used as seed drenching agent, convenient dosages are from 1Omg to lg of active

25    substance per kg of seeds.

Whereas it is preferred to formulate commercial products as concentrates, the end user

will normally use dilute formulations.

The following non-limiting Examples illustrate the above-described invention in more

detail.

30    EXAMPLE l

This Example illustrates the preparation ofComponnd No. l.Ol.

2-Amino-4' -ethinyl-biphenyl (0.30g) and 1-methyl-3-trifluoromethyl-4-chlorocaroonyl-

pyrazol (0.33g) were combined in TilF under cooling with ice and then pyridine (0.12ml) was

added. After wanning to ambient temperature the suspension was stirred for 3.5hours, poured into water and extracted twice with ethylacetate. Separation of the organic phase, drying with sodium sulfate and evaporation of the solvent and chromatographic purification on silica gel
(solvent: hexane:ethylacetate 2:1) yielded 0.4g (70.2%) of Compound No. 1.01. EXAMPLE2

This Example illustrates the preparation of Compound No. 2.01.

To 1-methyl-3-trifluoromethyl-4-pyrrol carooxylic acid (0.22g) dissolved in !Om!

10    dichloromethane were added triethylamine (0.32ml) and 2-amino-4'-trimethylsilylethinyl-biphenyl (0.3g) and finally, under cooling with ice, bis(2-oxo-3-oxazolidinyl) chlorophosphinic acid (0.29g). After stirring for 18hours the solvents were removed under reduced pressure and the residue was taken up with ethylacetate. Washing with water and

brine, drying with sodiwnsulfate and evaporation of the solvent yielded 0.45g of a yellow oil

15    which was chromatographed on silica gel (eluent: hexane:ethylacetate 2:1) to yield 0.13g (26%) of Compound No. 2.01.

EXAMPLE3

This Example illustrates the preparation of Compound No. I. 72.

To  Nail (46mg) in Sml dry TilF at 0-S'C was added 2-N-formylantino-4'-(propin-1-yl)-

20    biphenyl (0.3g) in !Om! dry THF. The reaction was kept at this temperature for !hour and afterwards 1-methyl-3-trifluoromethyl-4-chlorocaroonyl-pyrazol (0.372g) was added. The resultant suspension was stirred at room temperature overnight, poured into brine and extracted with ethylacetate. The solvent was evaporated and the the residue was taken into

methanol and sodiummethylate (1Om g) was added.  After 30minutes the mixture was

25    neutralised with diluted HCI, extracted with ethylacetate and washed until neutral. Chromatographic putification on silica gel (eluent: ethylacetate:hexane 1 :2) and recrystallisation from toluene:hexane (4:1) yielded 0.!69g of Compound No. 1.72.

EXAMPLE4

This Example illustrates the preparation of2- amino-4' -{trimethylsilyl)ethinyl-biphenyl

30    (Compound No.l2.02) and 2-amino-4' -ethinyl-biphenyl (Compound No.l2.01) using a preparation according to Method F above.

To 2.5g 2-amino-4'-bromo-biphenyl (W00264562) in piperidine (25m!) under nitrogen

were added in sequence Cui (O.lg), bis(triphenylphosphino)palladium dichloride (0.35g) and

trimethylsilylacetylene (2.8ml).  The mixture was stirred for 22hours at room temperature and

for a further 26hours at 60°C. After cooling the reaction mixture was diluted with water and extracted with ethylacetate. Then the organic phase was washed with water and dried over sodium sulfate. After evaporation of the solvents in vacuum the mixture was

chromatographed  on silica gel (hexane:ethylacetate 9:1) to yield 2- amino-4'-

(trimethylsilyl)ethinyl-biphenyl (2g) (Compound No.l2.02).

1.4g of this compound was dissolved in methanol (40ml) and potassium carbonate (0.9g)

10    was added with cooling. The resultant suspension was stirred for 2hours, poured on ice-water and the precipitate fonned was filtered off, washed thoroughly with water and dried to obtain
2-amino-4'-ethinyl-biphenyl (0.9g) (Compound No.l2.01) as light tan crystals.

EXAMPLES

This Example illustrates the preparation of2-N-formylamino-4'-(propin-l-yl)-biphenyl

15    (Compound No.l2.16)

N-formylarnino-4'bromo-biphenyl (3.5g) (J.Chem.Soc. 1957, 4), tributyltin(propinyl-1)

(5g) (commercial from Aldrich), tetrakis(triphenylphosphine)palladium (0.37g) were

combined in toluene (200ml) under nitrogen and heated to reflux for 16hours. The resultant dark mixtw-e was diluted with water and extracted with ethyl acetate. The organic phase was

20    washed with water, dried over sodium sulfate and the solvents were evaporated at reduced pressure. The residue was taken into acetonitrile and washed repeatedly with hexane. After removal of the acetonitrile at reduced pressure and chromatography of the residue with silicagel (eluent:hexane ethylacetate 2: I) 2-N-formylarnino-4' -(propin-1-yl)-biphenyl (Compound No.l2.16) (!.57 g) was obtained as a light yellow powder.

25    EXAMPLE6
This Example illustrates the preparation of2-arnino-4'(2,2-dichloro)ethylene-biphenyl
(Compound No.l2.07) and 2-arnino-4'(chloroethinyl)-biphenyl (Compound No 12.04.
a)    Preparation of2-nitro-4'(2,2-dichloro)ethylene-biphenyl.

To 2-nitro-4 'formyl-biphenyl (2g) (WO 95 03290) (prepared by Pd-catalysed coupling of

30    2-bromonnitrobenzene with 4-formyl-phenyl-boronic acid) in ethanol (?Om!) was added hydrazine hydrate (95%) (L32g) and the resultant mixture was then refluxed for 5hours. The


solvent was evaporated to di)'Jless under reduced pressure, the residue was suspended in

DMSO (30m!) and then ammonia (25%) (3m!) and freshly prepared CuC! (80mg) were sequentially added and finally tetrnchlorometane (3.8g) was dropped in under cooling with
water.  The mixture was stirred at room temperature for 24hourS and the resultant green

5    suspension was poured into water, extracted with dichloromethane, washed with water and dried over sodium sulfate. Evaporation of the solvent and chromatography of the residue over silicagel (e!uent:hexane:ethy!acetate 4:1) yielded 2-nitro-4'(2,2-<lichloro)ethylene-biphenyl (O.Sg), m.p. 58-59"C.
b)  Preparation of 2-amino-4'(2,2-<lich!oro)ethylene-biphenyl.

10 2-Nitr<>-4'(2,2-<lichloro)ethylene-biphenyl (0.76g) from step (a) was dissolved in 50% ethanol (30m!) and heated to reflux. Then 2N HCI (0.3ml) in 50% ethanol(! Om!) was added

dropwise. The reaction mixture was held at reflux for 4hours, cooled to room temperature and filtered. The filtrate was neutralised with sodiwn bicarbonate, extracted twice with ethylacetate and the organic phase was dried over sodiwn sulfate. Evaporation of the solvent
15    under reduced pressure yielded 2-amino-4'(2,2-dichloro)ethylene-bipheny! (0.62g)

(Compound No.l2.07).

c)  2-Amino-4'(2,2-dich!oro)ethylene-biphenyl (3g) was dissolved in 150m!  dimethyl

sulfoxide in which 0.9g KOH (85%, powder) has been suspended. The mixture was stirred

over night at room temperature, diluted with excess of water and extracted twice with ethyl

20    acetate and the organic phase was dried over sodium sulfate. Evaporation of the solvent under reduced pressure and chromatography of the residue over silicagel (eluent:hexane:ethylacetate

4: I) yielded 2.5 g 2-amino-4'(2,2-dich!oro)ethylene-biphenyl as a tan coloured solid. EXAMPLE?

This Example illustrates the preparation of Compound Number 12.!8. 25 Step A: 2-Nitro-(4'-trimethylsily!l-biphenyl

2-Bromo-nitrobenzene (0.86g), 4-(trimethylsilyl)pbenylboronic acid (!g) and bis-(triphenylpbosphine}-palladiumdichloride (0.3g) were dissolved in dimethoxyetane (35m!) and then a solution of sodium bicarbonate (1.3g) dissoved in water (5ml) was added dropwise. The mixture was heated for 3 hours (80°C bath temperature), cooled to room temperature,
30    poured on to ethyl acetate:water::l:l (300m!) and suction filtered. The organic phase was separated, dried over sodium sulfate and the solvent was removed. The resultant residue

(1.58g of a dark oil) was chromatographed on silica gel (eluenthexane:ethyl acetate::4: I) to yield a yellow oil (1.12g). This compound was used in Step 8.

Step 8: 2-Amino-(4'-trimethylsilyll-biphenyl [Compound 12.18]

The compound obtainedfrom step A above (0.955g) and ammonium fonniate (1.86g) were dissolved in methanol (30m!) and purged with nitrogen. To this solution, Pd (I OOmg; 10% on carbon) was added, in 2 portions. After stirring at room temperature for 15 hours, the

reaction mixture was filtered and the solvent was evaporated.

FORMULATION EXAMPLES FOR COMPOUNDS OF FORMULA (I)

10    Working procedures for preparing formulations of the compounds offomula I such as

Emulsifiable Concentrates, Solutions, Granules, Dusts and Wettable Powders are described in

W097/33890.

BIOLOGICAL EJSAMPLES: FUNGICIDAL ACTIONS

15    Example B-1: Action against Puccinia recondita I wheat (Brownrust on wheat)

I week old wheat plants cv. Arina are treated with the foiTIIulated test compound

(0.02% active ingredient) in a spray chamber. One day after application, the wheat plants are inoculated by spraying a spore suspension (lxl05uredospores/ml) on the test plants. After an incubation period of2 days at 20°C and 95o/or.h. the plants are kept in a greenhouse for 8days

20    at 20°C and 60%r.h.  The disease incidence is assessed I Odays after inoculation.

Infestation is prevented virtually completely (0-5% infestation) with each of compounds 1.01, 1.03, 1.08, 1.10, 1.12, 1.13, 1.15, 1.16, 1.18, 1.19, 1.22, 1.24, 1.33, 1.56, 1.57, 1.60, 1.66, 1.67, 1.69, 1.70, 1.77, 1.78, 1.81, 1.106, 1.107, 1.138, 1.139, 1.151, 1.152, 1.154, 1.155, 1.182, 1.185, 1.251, I. 252, 2.01, 2.08, 2.66, 3.01, 3.08, 3.12, 3.18, 3.32, 3.56, 3.66, 3.69,

25    3.250,  9.01, 9.06,9.15, 9.21, 9.41, 9.50, 9.53, 9.59, 15.25,15.26 and 15.28.

Example B-2: Action against Podosohaeca leucolricha I apple (Powderv mildew on l!J!Ple)

5 week old apple seedlings cv. Mcintosh are treated with the formulated test compound

(0.02% active ingredient) in a spray chamber.  One day after, the application apple plants are

30    inoculated by shaking plants infected with apple powdery mildew above the test plants.  After
 





an incubation period of12 days at 22'C and 60%r.h. under a light regime ofl4110hours

(light/dark) the disease incidence is assessed.

Infestation is prevented virtuaHy completely (0-5% infestation) with each of

compounds. 1.01, 1.03, 1.08, 1.10, 1.12, 1.13, l.l5, l.l6, l.l8, l.l9, 1.24,1.33, 1.35, 1.36,

5    1.56, 1.57, 1.66, 1.67, 1.70, 1.77, 1.78, 1.81, 1.106, l.I07, l.l39, l.l51, l.l52, 1.154, l.l55, l.l82, l.l85, 1.251, I. 252, 2.01, 2.08,2.66, 3.01, 3.08, 3.12, 3.18, 3.32, 3.35, 3.56, 3.66, 3.69, 3.250, 9.01, 9.06,9.15, 9.21, 9.41, 9.50, 9.53, 9.59, 9.62, 15.25, 15.26 and 15.28.

Example B-3: Action against Venturia inaeaualis I apple (Scab on apple)

10    4 week old apple seedlings cv. Mcintosh are treated with the formulated test compound

(0.02% active ingredient) in a spray chamber. One day after application, the apple plants are inoculated by spraying a spore suspension (4xl05conidialml) on the test plants. After an incubation period of 4 days at 21 °C and 95%r.h. the plants are placed for 4 days at 21 °C and 60%r .h. in a greenhouse. After another 4 day incubation period at 21°C and 95%r.h. the

15    disease incidence is assessed.

Infestation is prevented virtually completely (0-5% infestation) with each of

compounds. 1.01, 1.03, 1.08, 1.10, 1.12, 1.13, l.l8, l.l9, 1.24, 1.33, 1.56, 1.57, 1.66, 1.67, 1.69,1.70, 1.77, 1.78, 1.81, 1.106, 1.107, 1.138, 1.152, 1.154, 1.155, 1.251, I. 252, 2.01, 2.08, 2.66, 3.01, 3.08, 3.12, 3.18, 3.32, 3.56, 3.66, 3.69, 9.01, 9.06,9.15, 9.21, 9.50 and 9.59.

20

Example B-4: Action against Erysiphe graminis I barley (Powderv mildew on barley)

I week old barley plants cv. Regina are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. One day after application, the barley plants are inoculated by shaking powdery mildew infected plants above the test plants. After an
25    incubation period of 6 days at 20•c I 18'C (day/night) and 60%r.h. in a greenhouse the disease incidence is assessed.

Infestation is prevented virtually completely (0-5% infestation) with each of compounds 1.01, 1.03, 1.08, 1.10, 1.12, 1.13, l.l5, 1.16, 1.18, 1.19, 1.24, 1.33, 1.35, 1.36, !.56, 1.57,

1.66, 1.67, 1.70, 1.77, 1.78, 1.106, 1.107, 1.152, 1.155, 1.251, I. 252, 2.01, 2.08, 2.66, 3.01, 30 3.08, 3.12, 3.18, 3.32, 3.35, 3.56, 3.66, 3.69, 3.250, 9.01, 9.06,9.15, 9.21, 9.41, 9.50 and 9.59.
 


Example B-5: Action against Botrytis cinerea/ grape ffiotrvtis on grapes)

5 week old grape seedlings cv. Gutedel are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. Two days after application, the grape plants are inoculated by spraying a spore suspension (Ixlrf conidia!mJ) on the test plants. After an

5    incubation period of 4 days at 21°C and 95%r.h. in a greenhouse the disease incidence is assessed.

Infestation is prevented virtua1ly completely (0-5% infestation) with each of compounds 1.01, 1.03, 1.08 and 1.10.

10    Example B-6: Action against Botrvtis cinerea I tomato <Botrytis on tomatoes)

4 week old tomato plants cv. Roter Gnom are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. Two days after application, the tomato plants are inoculated by spraying a spore suspension (lxl05conidia/ml) on the test plants. After an incubation period of 4 days at 20°C and 95%r.h. in a growth chamber the disease incidence is
15    assessed.

Infestation is prevented virtuaHy completely (0-5% infestation) with each of compounds 1.01, 1.03, 1.08, 1.10, 1.12, 1.13, 1.15, 1.16, 1.18, 1.19, 1.24, 1.33, 1.36, 1.56, 1.57, 1.66,

1.67, 1.69, 1.70, 1.77, 1.78, 1.106, 1.107, 1.138, 1.139, 1.152, 1.155, 1.251, I. 252, 2.01, 2.66, 3.01, 3.08, 3.12, 3.66, 3.69, 3250, 9.06,9.15, 9.21, 9.41, 9.50 and 9.59.

20

Example B-7: Action against Septoria nodorum I wheat fSeptoria leaf spot on wheat) 1 week old wheat plants cv. Arina are treated with the formulated test compound

(0.02% active ingredient) in a spray chamber. One day after application, the wheat plants are inoculated by spraying a spore suspension (5xl 05conidia!ml) on the test plants. After an

25    incubation period of I day at 20'C and 95o/or.h. the plants are kept for 10 days at 20'C and 60%r.h. in a greenhouse. The disease incidence is assessed 11 days after inoculation.

Infestation is prevented virtually completely (0-5% infestation) with each of compounds 1.01, 1.03, 1.08 and 1.10.

30    Example B-8:  Action against Helminthosporium teres I barley INet blotch on barley)

1 week old barley plants cv. Regina are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. Two days after application, the barley plants are inoculated by spraying a spore suspension (3xl04conidia/ml) on the test plants. After an
incubation period of 4 days at 20°C and 95%r.h. in a greenhouse the disease incidence is

5    assessed.

Infestation is prevented virtually completely (0-5% infestation} wilh each of compounds 1.01, 1.03, 1.08, l.IO, 1.12, 1.13, 1.15, 1.16, l.l8, !.19, 1.22, 1.24, 1.33, 1.36, 1.35, 1.56, 1.57, 1.60, 1.66, 1.67, 1.69, 1.70, 1.77, !.78, 1.81, !.106, 1.107, l.l38, l.l39, l.l51, 1.152, 1.154, 1.155, 1.182, 1.185, 1.251, 1. 252, 2.01, 2.08, 2.66, 3.01, 3.08, 3.12, 3.18, 3.32, 3.35,

10    3.56, 3.66, 3.69,  9.01, 9.06,9.15, 9.21, 9.41, 9.50, 9.53, 9.59, 9.62, 15.25, 15.26 aml15.28.

Example B-9:  Action against Alternaria solani I tomato (Early blight on tomatoes)

4 week old tomato plants cv. Roter Gnom are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. Two days after application, the tomato plants

15    are inoculated by spraying a spore suspension (2xlflconidia/ml) on the test plants. After an incubation period of 3 days at 20°C and 95%r.h. in a growth chamber the disease incidence is assessed.

Infestation is prevented virtually completely (0-5% infestation) with each of compounds

1.01, 1.03, 1.08, 1.10, 1.13, 1.15, 1.16, 1.19, 1.22, 1.24, 1.33, !.35, 1.36, !.56, 1.57, !.67,

20    1.69, 1.70, 1.77, 1.78, 1.81, l.l07, Ll51, l.l52, l.l54, l.l55, l.l82, l.l85, 1.251, 1. 252, 2.01, 3.01, 3.08, 3.12, 3.32, 3.35, 3.56, 3.69, 9.01, 9.06,9.15, 9.41, 9.50, 9.62 and 15.26.

Example B-1 0:  Action against Uncinula necator I grape fPowdenr mildew on grapes)

5 week old grape seedlings cv. Gutede] are treated with the formulated test compound

25    (0.02% active ingredient} in a spray chamber. One day after application, the grape plants are inoculated by shaking plants infected with grape powdery mildew above the test plants. After an incubation period of? days at 26°C and 600/or.h. nnder a light regime of14110bours (ligbVdarl<) the disease incidence is assessed.

Infestation is prevented virtually completely (0-5% infestation) with each of compounds

30    1.01, 1.03, 1.08, l.IO, l.l2, 1.13, l.l8, 1.19, 1.24, 1.33, 1.56, 1.57, 1.60, 1.66, 1.67, 1.70, 1.77, 1.78, 1.81, 1.106, 1.107, l.l38, 1.139, l.I51, 1.152, 1.154, 1.155, l.l82, 1.185, 1.251, l.

252, 2.01, 2.08, 2.66, 3.01, 3.08, 3.12, 3.32, 3.56, 3.66, 3.69, 3.250,  9.01, 9.06,9.15, 9.41,

9.50, 9.53 and 9.59.

Example B-11: Action against Septoria tritici I wheat <Seotoria leaf snot on wheat)

5    2 week old wheat plants cv. Riband are treated with the formulated test compound

(0.2% active ingredient) in a spray chamber.  One day after application, wheat plants are

inoculated by spraying a spore suspension (!Oxl05conidia/ml) on the test plaots. After an incubation period of I day at 23'C and 95% r.h., the plants are kept for 16 days at 23'C and

60% r.h. in a greenhouse. The disease incidence is assessed 18 days after inoculation.

Compounds 1.10, 1.03, 1.09, 1.70, 1.69, 3.01, 1.67, 1.66, 3.66, 9.59, 3.69, 1.33, 2.66, 9.06, 3.08, 1.77, 1.78, 1.56, 1.57, 1.138, 1.139, 1.12, 1.18, 1.106, 1.107, 9.53, 3.32, 1.151, 1.152, 1.252, 1.155, 9.41, 3.56, 1.13, 3.12, 9.21, 1.250, 1.19 and 3.18. each show good

activity in this test (<20% disease incidence).

I.    A compound of formula (I):

R'

                            R'    (I)   
                                   
                            (R\       
    where Ret is a pyrazole, pyrrole or thiazole ring, the ring being substitutecrny one, two   
    or three groups RY;       
    R 1 is hydrogen;       
    R    2    , R    3    and R    4    are each, independently, hydrogen, halogen, methyl or CF3;   
                               
    R 5 is hydrogen or fluorine;       
10    each R6 is, independently, halogen, methyl or CF3;       
    R    7    is                1       
                (Z)mC=C(Y );       

each RY is, independently, halogen, C1-J alkyl, C 1.3 haloalkyl, C1-J alkoxy(C 1•3)alkylene or cyano;
XisO;

15    Y1 is hydrogen, halogen, C 1-4 alkyl [optionally substituted by one or more substituents each independently selected from halogen, hydroxy, C1 4 alkoxy, C 14 haloalkoxy,

C1•4 alkylthlo, C 14 haloalkylthio, C14  alkylamino, di(C1_4)alkylamino,

C 1•4 alkoxycarbonyl and tri(C 14)alkylsilyl], C24 alkenyl [optionally substituted by one or more substituents each independently selected from halogen], C24 alkynyl [optionally

20    substituted by one or more substituents each independently selected from halogen], C3 _7 cycloalkyl [optionally substituted by one or more substituents each independently
selected from halogen, C1-4  alkyl and C1-4 haloalkyl] or tri(C 1- 4)alkylsilyl;

z is C 1-4 alkylene [optionally substituted by one or more substituents each independently

selected from hydroxy, cyano, C 1-4  alkoxy, C 1•4 haloalkoxy, C 1-4  alkylthio, COOH and

25    coo-c,~ alkyl];


m is 0 or I; and

n is 0, 1 or2.

2.    A compound of formula (I) as claimed in claim 1 where m = 0.

3.    A compound of formula (I) as claimed in claim 1 where R7 is in the 4' position.

4.    A compound of formula (I) as claimed in claim I where R5 is hydrogen.

10    5. A compound of formula (I) as claimed in claim 4 where R2 , R3 and R4 are hydrogen. 6. A compound of formula (I) _as claimed in claim 1 where n = 0.

7.    A compound selected from 3-difluoromethyl-1-methyl-tH-pyrazole-4-carboxylic acid

15    [ 4'-(3,3-dimethyl-but-1-ynyl)-biphenyl-2-ylJ-amide and 3-difluoromethyl-1-methyl-IH-pyrazole-4-carboxylic acid (4'-prop-1-ynyl-biphenyl-2-yl)-amide.

8.    A compound of formula Cm:


9.    A compound of formula (III):
 

where R2, R3 , R4, R5, R6 , R7 and n are as defined in claim 1 and Hal is bromo, chloro or iodo; provided that the compound is not a compound of formula {illa)

H:~?R'I R'

(Ilia)

"'I
""
R'

wherein Hal is Cl; R2, R 3 and R4 are each hydrogen and R7 is -C=CH.

10.    A composition for controlling microorganisms and preventing attack and infestation of

plants therewith, wherein the active ingredient is a compound of formula (I) as claimed

10    in claim I together with a suitable carrier.

II.    A method of controlling or preventing infestation of cultivated plants by phytopathogenic microorganisms by application of a compound of formula (I) as claimed in claim 1 to plants, to parts thereof or the locus thereof.

Comparison of the biological activity of the compounds according to Kenya Patent

Application No. PCT/EP03114248 with the pr1or art:

In the following tests, the biological activity of a representative number of compounds of

formula I according to the present invention is compared with the structurally closest

compounds described in document (A) (JP-A-2001-302605). Compounds A (1-methyl-3-trifluoromethyl-1 H-pyrazole-4-carboxylic acid (4'-ethynyl-6-fluoro-biphenyi-2-yl)-amide),8 (1-rnethyl-3-trifluoromethyl-1 H-pyrazole-4-carboxylic acid (4'-chloro-3'-ethynyl-6-fluoro-biphenyt-
2-yl}-amide) and C (2-Methy1-4-trifluoromethyl-thiazole-5-carboxylic acid (4'-ethyny1-6-fluoro-biphenyl-2-yl)-amide) are encompassed by the scope of the present invention. Compounds

no. 1-91, 1-97 and 2-91 according to the prior art are disclosed in tables 1 and 2 of document (A). The method employed was as follows:

Action against Puccinia recondite lBrown rust) on wheat

Wheat leaf disks (cv Kanzler) were placed on agar in multiwell plates (24-well format). The leaf disks were inoculated with a spore suspension of the fungus (45.000 conidia/ml) and one day after the inoculation the leaf disks were treated with the the formulated (2 % Dimethylsulfoxid, 0,025 % Tween 20) test compounds by spraying. The compounds were tested at a variety of application rates; these rates are shown in parts per million (ppm) In the table. After an incubation period of 8 days at 19 oc and 75-90 % relative humidity the disease incidence was assessed as % disease control (0 "" no control of Puccinla recondita, ratings of 80 % to 99 % mean good to very good control, 100 % ::: complete control).

Action aaainst Monographella nivalls lanamomh: Fusarium nivale Microdochium nivaie• Snow mould)

After placing a DMSO-solution (2% Dimethylsulfoxid, 0,025 % Tween 20) of the test compounds into a microliter plate (96-well format) the nutrient broth containing the fungal spores was added. 40.000 conidia/ml of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). The compounds were tested at a variety of application rates; these rates are shown in parts per million (ppm) in the table. The test plates were incubated at 24°C and the inhibition of growth was measured photometrically after 72 hrs (0 "" no growth inhibition of Monographella nivalis, ratings of 80 %to 99% mean good to very good inhibition, 100%"" complete inhibition).

Comparative example 1 fpyrazolyl compounds):

Comparison of compound A of the present invention with compound no. 1-91 according to

document (A).

Compound A according    Compound 1-91 according
to the present invention    todocument(A)

Ao't1on aga1nst  ucc1ma recon 1a   rown rust:

    Compound No.            I    ppm           
            2oo        60    I    20   
    A (present invention)    1oo%    1    so%    1    BO"k   
    1-91  (prior art)    o<r.    I    0%    I    0%   
Action aaainst Monoaraohella nivalis fSnow mould)•                   
    Compound No.                    ppm           
                                   
                                   
            20        I    6    I    2   
    A (present invention)        100""'    I 1ooo/o    I 1o0""'   
    1-91 (prior art)        100%    1    100""'    1    0%   
                                   

This example shows the superior fungicidal activity of the compound according to the present invention: (1) compound A is able to control Puccinia recondita at application rates of 200 ppm and 60 ppm, whereas compound no. 1-91 is totally Ineffective at these concentrations; (2) compound A is able to control Monographella nivalis at application rates as low as 2 ppm, whereas compound no. 1-91 is totally Ineffective at this low concentration. The only structural difference between this pair of compounds is: the alkinyl vs alkyl substituent at the second phenyl of the biphenyl system and the fluorine vs chlorine substituent at the first phenyl of the biphenyl system.

Comparative example 2 fpyrazolyl comooundsl:

Comparison of compound B of the present invention with compound no. 1-97 according to document (A).

Newsletter

Join our newsletter for CIPIT news through subscriptions!

SEND

Social Media

    

Contact Us

TEL : (254) 703 034 612