ZA200300643B

ZA200300643B - Pyridinyl amides and imides for use as fungicides.

Info

Publication number: ZA200300643B
Application number: ZA200300643A
Authority: ZA
Inventors: Timothy Donald Neubert; David Walter Piotrowski; Michael Paul Walker
Original assignee: Du Pont
Priority date: 2000-09-18
Filing date: 2003-01-23
Publication date: 2004-02-19
Also published as: CN1688546A

Description

TITLE

PYRIDINYL AMIDES AND IMIDES FOR USE AS FUNGICIDES

BACKGROUND OF THE INVENTION

This invention relates to certain pyridinyl amides and imides, their N-oxides, agriculturally suitable salts and compositions, and methods of their use as fungicides.

The control of plant diseases caused by fungal plant pathogens is extremely important in achieving high crop efficiency. Plant disease damage to ornamental, vegetable, field, cereal, and fruit crops can cause significant reduction in productivity and thereby result in increased costs to the consumer. Many products are commercially available for these purposes, but the need continues for new compounds, which are more effective, less costly, less toxic, environmentally safer or have different modes of action.

WO 99/42447 discloses certain benzamides of formula i as fungicides

R3 XN 5 wherein, among others, ¥ R4 R'is H, alkyl or acyl; _ N__ R? is H or alkyl; and

L is «(C=0)-, -SO5- or -(C=S)-.

Rl . : 1

SUMMARY OF THE INVENTION

This invention pertains to compounds of Formula I or Formula IT including all geometric and stereoisomers, N-oxides, and agriculturally suitable salts thereof:

R3

Se? . SONY

RI' R2 RI" RZ xX 1 II wherein

A is a substituted pyridinyl ring;

B is a substituted pyridinyl ring;

Wis C=L or SO;

LisOorS;

R1 and R? are each independently H; or C;-Cg alkyl, C,-Cg alkenyl, C,-Cg alkynyl or

C3-Cg cycloalkyl, each optionally substituted;

R3 is H; or C;-Cg alkyl, C-Cg alkenyl, C»-Cg alkynyl or C3-Cg cycloalkyl, C»-Cg alkylcarbonyl, C»-Cg alkoxycarbonyl, C»-Cgq alkylaminocarbonyl or C3-Cg dialkylaminocarbonyl;

R# is C1-Cg alkyl, C,-Cg alkenyl, C,-Cg alkynyl or C3-Cg cycloalkyl, each optionally substituted;

Xis OorS; and nis 1 or 2; provided that when W is C=0 and R1, R2 and R3 are H; then B is other than 4-trifluoromethyl-3-pyridinyl, 2-chloro-4-pyridinyl and 2,6-dihalo-4-pyridinyl.

This invention also relates to fungicidal compositions comprising fungicidally effective amounts of the compounds of the invention and at least one additional component selected from the group consisting of surfactants, solid diluents or liquid diluents and/or at least one other fungicide having a different mode of action.

This invention also relates to a method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof, or to the plant seed or seedling, a fungicidally effective amount of the compounds of the invention (e.g., as a composition described herein).

DETAILS OF THE INVENTION

As noted above, A and B are each independently a substituted pyridinyl ring. The term “substituted” in connection with these A or B groups refers to groups that have at least one non-hydrogen substituent that does not extinguish the fungicidal activity. Examples of

Formula I and Formula II incorporating said pyridinyl rings in which A is substituted with 1 to 4 R3, B is substituted with 1 to 4 R6 include the rings illustrated in Exhibit 1 wherein m and p are independently integers from 1 to 4. Note that the attachment point between (R53), and A and (RS), and B is illustrated as floating, and (R)y, and (RS), can be attached to any available carbon atom of the pyridinyl rings.

Exhibit 1

AN R3 AN A R3 X

Fm I} JS ® ni _ Je

ZZ Sw ZZ Sw Z

RY R2 RI' R2 1-1 12

AN R3 XN 6 X R3 XN 6 ® ur x Cr ®) ®u a 1 | P ®p

ZZ ~wW ZZ Pe w rRY R2 RI' R2 1-3 1-4

EAN R3 XN 6 A R3 NN = Sw Pp Pa Ww rR R2 RI" R2

I-5 I-6 2 R3 A R3 =

Rh L i$; ®)p ® i L JS

PP ~ Ww 2 Sw ZZ

RY R2 RI' R2 1-7 I-8

A R3 SN wo LF = Sw

RI' R2 1-9

XX NR RAN X rf JL a LF SOSU EL

PZ ~ SZ Y 1 2 1 2

R

11-1 1-2 ®t | ®) ®n | ®p = YZ NA Z

RI R2 RI' R2

Apt LN 11-3 11-4 nn = EN NN ®p @iy ®p

Ry

N= a ZN NA Z : rR R2 rRI' RZ xX Np4 ms R me =X

A x =

LF > A J “ = Z Zz

I 2 RY 2

R. R: Xo of R AN 1-7 I-8

AS AY

J JF ®p pr =

RI R2

Xe 11-9 : 5

Examples of RS when attached to A and RS when attached to B include:

RS and RO are each independently Cy-Cg alkyl, C-Cg alkenyl, C»-Cg alkynyl, C3-Cg cycloalkyl, C;-Cg haloalkyl, C,-Cg haloalkenyl, C,-Cg haloalkynyl, C3-Cq halocycloalkyl, halogen, CN, CO,H, CONH,, NO,, hydroxy, C{-C4 alkoxy,

C1-C4 haloalkoxy, C;-C4 alkylthio, C;-C4 alkylsulfinyl, C;-C, alkylsulfonyl,

C;-C,4 haloalkylthio, C1~C4 haloalkylsulfinyl, C1-Cy4 haloalkylsulfonyl, C;-C4 alkoxycarbonyl, C{-C4 alkylamino, C,-Cg dialkylamino, C3-Cg cycloalkylamino, C»-Cg alkylcarbonyl, C»-Cg alkoxycarbonyl, C»-Cg alkylaminocarbonyl, C3-Cg dialkylaminocarbonyl, C3-Cg trialkylsilyl; or

R5 and RS are each independently phenyl, benzyl or phenoxy, each optionally substituted with C;-C4 alkyl, C,-C4 alkenyl, C,-C4 alkynyl, C3-Cg cycloalkyl, 5 C;-C4 haloalkyl, Co-C4 haloalkenyl, C,-C4 haloalkynyl, C3-Cg halocycloalkyl, halogen, CN, NO,, C,-C4 alkoxy, C;-Cy4 haloalkoxy, C;-C4 alkylthio, C;-C4 alkylsulfinyl, C;-C4 alkylsulfonyl C;-C4 alkoxycarbonyl, C{-C4 alkylamino,

C,-Cg dialkylamino, C3-C¢ cycloalkylamino, C3-Cg (alkyl)cycloalkylamino,

C,-C4 alkylcarbonyl, C,-Cg alkoxycarbonyl, C,-Cg alkylaminocarbonyl, C3-Cg dialkylaminocarbonyl or C3-Cg trialkylsilyl.

Other R5 and R6 groups will be evident to one of ordinary skill. For example, each RS and/or R6 can be NH,, NHCO(C1-C;4 alkyl) or NHCO(C-C,4 haloalkyl); or each RS and/or

RO can be phenyl, benzyl or phenoxy, each substituted with Cs-Cyg trialklylsilylalkynyl.

Of note are compounds of Formula I wherein

RA and RO are each independently C,-Cg alkyl, C,-Cg alkenyl, Co-Cg alkynyl, C3-Cg cycloalkyl, C;-Cg haloalkyl, C»-Cg haloalkenyl, C5-Cg haloalkynyl, C3-Cg halocycloalkyl, halogen, CN, CO,H, CONH,, NO,, hydroxy, C;-C4 alkoxy,

C1-C4 haloalkoxy, C;-C4 alkylthio, C;-Cy4 alkylsulfinyl, C;-Cy4 alkylsulfonyl,

C;-C4 haloalkylthio, C{-C4 haloalkylsulfinyl, C{-C4 haloalkylsulfonyl, C;-C4 alkoxycarbonyl, C,-C, alkylamino, C,-Cg dialkylamino, C3-Cg cycloalkylamino, C,-Cg alkylcarbonyl, C»-Cg4 alkoxycarbonyl, Co-Cg alkylaminocarbonyl, C3-Cg dialkylaminocarbonyl, C3-Cy trialkylsilyl; or

RS and RO are each independently phenyl, benzyl or phenoxy, each optionally substituted with C;-C4 alkyl, C,-C4 alkenyl, C,-Cy4 alkynyl, C3-Cg cycloalkyl,

C,-C4 haloalkyl, C,-C4 haloalkenyl, C,-C4 haloalkynyl, C3-Cg4 halocycloalkyl, halogen, CN, NO,, C;-C4 alkoxy, C;-C4 haloalkoxy, C;-C4 alkylthio, C{-C4 alkylsulfinyl, C;-C, alkylsulfonyl C;-C, alkoxycarbonyl, C{-C4 alkylamino,

C,-Cg dialkylamino, C3-Cg4 cycloalkylamino, C3-Cg (alkylcycloalkylamino,

C,-C4 alkylcarbonyl, C,-Cg4 alkoxycarbonyl, C,-Cg4 alkylaminocarbonyl, C3-Cg dialkylaminocarbonyl, Cs-Cg trialklylsilylalkynyl or C3-Cg trialkylsilyl.

As noted above, R! and R2 are each independently H; or C;-Cg alkyl, C,-Cg alkenyl,

Cy-Cg alkynyl or C3-Cg cycloalkyl, each optionally substituted; and R4 is C;-Cg alkyl, C,-

Cg alkenyl, C»-Cg4 alkynyl or C3-Cg¢ cycloalkyl, each optionally substituted. The term “optionally substituted” in connection with these R1, R2 and R4 groups refers to groups which are unsubstituted or have at least one non-hydrogen substituent that does not extinguish the fungicidal activity possessed by the unsubstituted analog. Examples of optionally substituted R1, R2 and R4 groups are those that are optionally substituted with one . or more substituents selected from the group consisting of halogen, CN, NO», hydroxy,

C1-C4 alkoxy, C;-C4 alkylthio, C{-C4 alkylsulfinyl, C;-C, alkylsulfonyl, C»-Cy4 alkoxycarbonyl, C1-Cy4 alkylamino, C»-Cg dialkylamino and C3-Cg cycloalkylamino.

Although these substituents are listed in the examples above, it is noted that they do not need to be present since they are optional substituents. :

Examples of N-oxides of Formula I or Formula II are illustrated as I-10 through I-16 and as II-10 through II-16, respectively, in Exhibit 2, wherein R!, RZ, R3, R4, R5, R6, W, X, m and p are as defined above.

Exhibit 2

ES 3 AS Xx R3 NX 5 Fol ®p & ®p ®)nr N Pe mn pp NO ZN

SZ Sw Ww

I rY ‘R2 | rR R2

I-10 I-11

AS R3 SN 6 ® ys IN Te p = Ww = o RR?

I-12

R3 N A R3 xX ®t ll ®% @y ll ®p

ZZ Nw — p> NQ Ww =

Il RI R2 I RI’ R2 1S

I-13 I-14

AS R3 ~~ x R3 x > | | &p > | yp

RI R2 0 RI R2 I

I-15 I-16

EN X A

®p & ®p ll rRI' R2 il rRI' R2 : 1-10 I-11 = NN 6 5 ®)p ®

LJ

Ir Re 0) Age

I-12

A X EN 2 wf ue; © kL J 5

Z Z YZ = ll rl’ R2 I rRI' R2 Il 'e) XX ” 0 XX ” oO

I-13 11-14

X A A NX

Bm | ®p @y | ®p

N_ =~ ZF Z &

I

RI' R2 RI R2

X< pa © gt © 11-15 11-16 5 In the above recitations, the term “alkyl”, used either alone or in compound words such as “alkylthio” or “haloalkyl” includes straight-chain or branched alkyl, such as, methyl, ethyl, n-propyl, i-propyl, or the different butyl, pentyl or hexyl isomers. The term “1-2 alkyl” indicates that one or two of the available positions for that substituent may be alkyl which are independently selected. “Alkeny!l” includes straight chain or branched alkenes such as ethenyl, 1-propenyl, 2-propenyl, and the different butenyl, pentenyl and hexenyl isomers. “Alkenyl” also includes polyenes such as 1,2-propadienyl and 2,4-hexadienyl. “Alkyny!” includes straight chain or branched alkynes such as ethynyl, 1-propynyl, 2-propynyl and the different butynyl, pentyny! and hexynyl isomers. “Alkynyl” can also include moieties comprised of multiple triple bonds such as 2,5-hexadiynyl. “Alkoxy” includes, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy,

pentoxy and hexyloxy isomers. “Alkoxyalkyl” denotes alkoxy substitution on alkyl.

Examples of “alkoxyalkyl” include CH30CH,, CH30CH,CH,, CH3;CH,OCHj,,

CH;3CH,CH,CH,0CH, and CH;CH,0CH,CH,. “Alkoxyalkoxy” denotes alkoxy substitution on alkoxy. The term “Alkenyloxy” includes straight chain or branched alkenyloxy moieties. Examples of “alkenyloxy” include H,C=CHCH,O, (CHj3),C=CHCH,0, (CH3)CH=CHCH,0, (CH3)CH=C(CH3)CH,0 and

CH)=CHCH,CH,0. “Alkynyloxy” includes straight chain or branched alkynyloxy moieties. Examples of “alkynyloxy” include HC=CCH,0, CH;C=CCH,0 and

CH;3C=CCH,CH,0. “Alkylthio” includes branched or straight chain alkylthio moieties such as methylthio, ethylthio, and the different propylthio, butylthio, pentylthio and hexylthio isomers. “Alkylthioalkyl” denotes alkylthio substitution on alkyl. Examples of “alkylthioalkyl” include CH3SCH,, CH3SCH,CH,, CH3CH,SCH,, CH3CH,CH,CH,SCH, and CH3CH,SCH,CH,. “Alkylthioalkoxy” denotes alkylthio substitution on alkoxy. “Alkylsulfinyl” includes both enantiomers of an alkylsulfinyl group. Examples of “alkylsulfinyl” include CH3S(O), CH3CH,S(0), CH3CH,CH,S(0), (CH3),CHS(O) and the different butylsulfinyl, pentylsulfinyl and hexylsulfinyl isomers. Examples of “alkylsulfonyl” include CH3S(0),, CH3CH,S(0),, CH;CH,CH,S(0),, (CH3),CHS(0O), and the different butylsulfonyl, pentylsulfonyl and hexylsulfonyl isomers. “Cyanoalkyl” denotes an alkyl group substituted with one cyano group. Examples of “cyanoalkyl” include

NCCHj, NCCH,CH, and CH3CH(CN)CH,. “Alkylamino”, “dialkylamino”, “alkenylthio”, “alkenylsulfinyl”, “alkenylsulfonyl”, “alkynylthio”, “alkynylsulfinyl”, “alkynylsulfonyl”, and the like, are defined analogously to the above examples. “Cycloalkyl” includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. The term “cycloalkoxy” includes the same groups linked through an oxygen atom such as cyclopentyloxy and cyclohexyloxy.

The term “halogen”, either alone or in compound words such as “haloalkyl”, includes fluorine, chlorine, bromine or iodine. The term “1-2 halogen” indicates that one or two of the available positions for that substituent may be halogen which are independently selected.

Further, when used in compound words such as “haloalkyl”, said alkyl may be partially or fully substituted with halogen atoms which may be the same or different. Examples of “haloalkyl” include F3C, CICH,, CF3CH, and CF;CCl,. The terms “haloalkenyl”, “haloalkynyl”, “haloalkoxy”, “haloalkylthio”, and the like, are defined analogously to the term “haloalkyl”. Examples of “haloalkenyl” include (C1),C=CHCH; and

CF;CH,CH=CHCH,. Examples of “haloalkyny!l” include HC=CCHCI, CF3C=C, CC3,C=C and FCH,C=CCH,. Examples of “haloalkoxy” include CF30, CC13CH,0, HCF,CH,CH,0 and CF3CH,0. Examples of “haloalkylthio” include CCl3S, CF3S, CC CH,S and

CICH,CH,CH,S. Examples of “haloalkylsulfinyl” include CF35(0), CCl35(0),

CF3CH,S(0) and CF3CF,S(0). Examples of “haloalkylsulfony!” include CF3S(0),,

CCLS(0),, CF3CH,S(0), and CF3CF,S(0),. Examples of “haloalkoxyalkoxy” include

CF30CH,0, CICH,CH,0CH,CH,0, Cl3CCH,OCH,0 as well as branched alkyl derivatives. Examples of “alkylcarbonyl” include C(O)CH3, C(O)CH,CH,CHj; and

C(O)CH(CH3);. Examples of “alkoxycarbonyl” include CH;0C(=0), CH3CH,0C(=0), CH3CH,;CH,0C(=0), (CH3),CHOC(=0) and the different butoxy- or pentoxycarbonyl isomers.

One skilled in the art will appreciate that not all nitrogen containing heterocycles can form N-oxides since the nitrogen requires an available lone pair for oxidation to the oxide; one skilled in the art will recognize those nitrogen containing heterocycles which can form

N-oxides. One skilled in the art will also recognize that tertiary amines can form N-oxides.

Synthetic methods for the preparation of N-oxides of heterocycles and tertiary amines are very well known by one skilled in the art including the oxidation of heterocycles and tertiary amines with peroxy acids such as peracetic and m-chloroperbenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as t-butyl hydroperoxide, sodium perborate, and dioxiranes such as dimethydioxirane. These methods for the preparation of N-oxides have been extensively described and reviewed in the literature, see for example:

T. L. Gilchrist in Comprehensive Organic Synthesis, vol. 7, pp 748-750, S. V. Ley, Ed.,

Pergamon Press; M. Tisler and B. Stanovnik in Comprehensive Heterocyclic Chemistry, vol. 3, pp 18-20, A. J. Boulton and A. McKillop, Eds., Pergamon Press; M. R. Grimmett and B. R.T. Keene in Advances in Heterocyclic Chemistry, vol. 43, pp 149-161, A. R. Katritzky,

Ed., Academic Press; M. Tisler and B. Stanovnik in Advances in Heterocyclic Chemistry, vol. 9, pp 285-291, A. R. Katritzky and A. J. Boulton, Eds., Academic Press; and

G. W. H. Cheeseman and E. S. G. Werstiuk in Advances in Heterocyclic Chemistry, vol. 22, pp 390-392, A. R. Katritzky and AT Boulton, Eds., Academic Press.

The total number of carbon atoms in a substituent group is indicated by the “Ci-Cy” prefix where i and j are numbers from 1 to 8. For example, C;-Cj alkylsulfonyl designates methylsulfonyl through propylsulfonyl; C, alkoxyalkyl designates CH3OCH,; C, alkoxyalkyl designates, for example, CH; CH(OCHj3), CH3;OCH;CH, or CH3CH,OCH,; and C4 alkoxyalkyl designates the various isomers of an alkyl group substituted with an alkoxy group containing a total of four carbon atoms, examples including

CH;CH,CH,0CH, and CH3CH,OCH,CH,.

When a compound is substituted with a substituent bearing a subscript that indicates the number of said substituents can exceed 1, said substituents (when they exceed 1) are independently selected from the group of defined substituents. Further, when the subscript indicates a range, e.g. (R);j, then the number of substituents may be selected from the integers between i and j inclusive.

When a group contains a substituent which can be hydrogen, for example R1 or R2 then, when this substituent is taken as hydrogen, it is recognized that this is equivalent to said group being unsubstituted.

Compounds of this invention can exist as one or more stereoisomers. The various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers. One skilled in the art will appreciate that one stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to the other stereoisomer(s) or when separated from the other stereoisomer(s). Additionally, the skilled artisan knows how to separate, enrich, and/or to selectively prepare said stereoisomers. Accordingly, the present invention comprises compounds selected from Formula I, N-oxides and agriculturally suitable salts thereof. The compounds of the invention may be present as a mixture of stereoisomers, individual stereoisomers, or as an optically active form. In particular, when

Rl and R? of Formula I and Formula II are different, then said formulas possess a chiral center at the carbon to which they are commonly bonded. This invention comprises racemic mixtures. In addition, this invention includes compounds that are enriched compared to the racemic mixture in an enantiomer of the formulas 3 “x he WB N° rf R2 rf R2 X

NR4

T nr

Included are the essentially pure enantiomers of Formula I’ and Formula II’. This invention also includes compounds that are enriched compared to the racemic mixture in an enantiomer of the formulas

R3

Nt we SOY rE R2 RE R2 X

I" a

Included are the essentially pure enantiomers of Formula I’” and Formula II”.

When enantiomerically enriched, one enantiomer is present in greater amounts that the other and the extent of enrichment can be defined by an expression of enantiomer excess(“ee”), which is defined as 100(2x-1) where x is the mole fraction of the dominant enantiomer in the mixture. (e.g., an ee of 20% corresponds to a 60:40 ratio of enantiomers).

The more active enantiomer with respect to the relative positions of R1, R2, A and the rest of the molecule bonded through nitrogen corresponds to the configuration of the enantiomer of 2,4-dichloro-N-[(1R)-1-[3-chloro-5-(trifluoromethyl)-2-pyridinyljethyl]-3- pyridinecarboxamide that, when in a solution of CDCl3, rotates plane polarized light in the (+) or dextro direction (i.e. the predominant enantiomer of Compound 31 of Index Table B).

Preferably the compositions of this invention have at least a 50 % enantiomeric excess; more preferably at least a 75 % enantiomeric excess; still more preferably at least a 90 % enantiomeric excess; and the most preferably at least a 94 % enantiomeric excess of the more active isomer. Of particular note are enantiomerically pure embodiments of the more active isomer.

Compounds of Formula II can also exist as (E)- or (Z)-isomers , or as a mixture of (E)- and (Z)-isomers with respect to the C=N bond shown in the structure. This invention comprises mixtures of geometric isomers as well as the individual isomers.

The salts of the compounds of the invention include acid-addition salts with inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric acids. The salts of the compounds of the invention also include those formed with organic bases (e.g., pyridine, ammonia, or triethylamine) or inorganic bases (e.g., hydrides, hydroxides, or carbonates of sodium, potassium, lithium, calcium, magnesium or barium) when the compound contains an acidic group such as a carboxylic acid or phenol.

Preferred compounds for reasons of better activity and/or ease of synthesis are:

Preferred 1. Preferred are compounds of Formula I or Formula IT wherein

A is a pyridinyl ring substituted with from 1 to 4 R3;

B is a pyridinyl ring substituted with from 1 to 4 RS;

R1 and R2 are each independently H; or C{-Cg alkyl, C,-Cg alkenyl, C»-Cg alkynyl or C3-Cg4 cycloalkyl, each optionally substituted with one or more substituents selected from the group consisting of halogen, CN,

NO,, hydroxy, C;-C4 alkoxy, C;-C4 alkylthio, C;-Cy alkylsulfinyl,

C;-C4 alkylsulfonyl, C,-C4 alkoxycarbonyl, C;-C,4 alkylamimo, C,-Cg dialkylamino and C3-Cg cycloalkylamino;

R# is C1-Cg alkyl, C,-Cg alkenyl, C-Cg alkynyl or C3-Cg cycloalkyl, each optionally substituted with one or more substituents selected from the group consisting of halogen, CN, NO,, hydroxy, C;-C, alkoxy, C;-C,4 alkylthio, C;-C,4 alkylsulfinyl, C;-Cy4 alkylsulfonyl, C»-Cy alkoxycarbonyl, C1-C, alkylamino, C»-Cg dialkylamino and C3-Cg cycloalkylamino; and

RJ and RS are each independently C1-Cg alkyl, C,-Cg alkenyl, C,-Cg alkynyl,

C3-Cg cycloalkyl, C{-Cg haloalkyl, C,-Cg haloalkenyl, C5-Cg haloalkynyl, C3-Cg4 halocycloalkyl, halogen, CN, CO,H, CONH,, NO», hydroxy, C;-C4 alkoxy, C;-C4 haloalkoxy, C;-C4 alkylthio, C1-Cy alkylsulfinyl, C;-C4 alkylsulfonyl, C;-C4 haloalkylthio, C;-C4 haloalkylsulfinyl, C;-C4 haloalkylsulfonyl, C;-C4 alkoxycarbonyl,

C;-C4 alkylamino, C,-Cg dialkylamino, C3-Cg cycloalkylamino, Co-Cg alkylcarbonyl, C,-Cg¢ alkoxycarbonyl, C,-Cg alkylaminocarbonyl,

C3-Cg dialkylaminocarbonyl, C3-Cg4 trialkylsilyl; or

R3 and RY are each independently phenyl, benzyl or phenoxy, each optionally substituted with C;-C4 alkyl, C,-C, alkenyl, C,-C, alkynyl, C3-Cq cycloalkyl, C;-C4 haloalkyl, C,-C4 haloalkenyl, C,-C4 haloalkynyl,

C3-Cg halocycloalkyl, halogen, CN, NO,, C;-C4 alkoxy, C{-C4 haloalkoxy, C-Cy4 alkylthio, C;-C,4 alkylsulfinyl, C;-C4 alkylsulfonyl

C1-C4 alkoxycarbonyl, C;-Cy4 alkylamino, C,-Cg dialkylamino, C3-Cg cycloalkylamino, C3-C4 (alkyl)cycloalkylamino, C5-C4 alkylcarbonyl,

C,-Cg alkoxycarbonyl, Co-Cg alkylaminocarbonyl, C3-Cg dialkylaminocarbonyl or C3-Cg trialkylsilyl.

Of note are compounds of Preferred 1 wherein each R3 is independently C;-Cg alkyl, C,-Cg alkenyl, C,-Cg alkynyl, C3-Cg4 cycloalkyl, C1-Cg haloalkyl, C,-Cg haloalkenyl, C,-Cg haloalkynyl,

C3-Cg halocycloalkyl, halogen, CN, CO,H, CONH,, NO,, hydroxy,

C1-C4 alkoxy, C{-Cy4 haloalkoxy, C;-C4 alkylthio, C;-C, alkylsulfinyl,

C1-C4 alkylsulfonyl, C-C4 haloalkylthio, C;-C4 haloalkylsulfinyl,

C;-C4 haloalkylsulfonyl, C;-C,4 alkoxycarbonyl, C{-C, alkylamino,

C,-Cyg dialkylamino, C3-Cg cycloalkylamino, C,-Cg alkylcarbonyl,

C,-Cg alkoxycarbonyl, C»-Cg alkylaminocarbonyl, C3-Cg dialkylaminocarbonyl, C3-Cg trialkylsilyl; provided that when A is 2-pyridinyl, then RS is other than C; to Cg haloalkyl; and each RO is independently C;-Cg alkyl, Co-Cg alkenyl, C,-Cg alkynyl, C3-Cg4 cycloalkyl, C{-Cg haloalkyl, C,-Cg haloalkenyl, C,-Cg4 haloalkynyl,

C3-Cg halocycloalkyl, halogen, CN, CO,H, CONH;, NO, hydroxy,

C;-C4 alkoxy, C1-C4 haloalkoxy, C-Cy alkylthio, C;-C, alkylsulfinyl,

C;-C4 alkylsulfonyl, C;-C4 haloalkylthio, C;-C, haloalkylsulfinyl,

C1-C4 haloalkylsulfonyl, C;-C4 alkoxycarbonyl, C1-C,4 alkylamino,

C,-Cg dialkylamino, C3-Cg cycloalkylamino, C,-Cg alkylcarbonyl,

Cy-Cg alkoxycarbonyl, Co-Cg alkylaminocarbonyl, C3-Cg dialkylaminocarbonyl, C3-Cg trialkylsilyl; or

R3 and RO are each independently phenyl, benzyl or phenoxy, each optionally substituted with Cy-Cy4 alkyl, C,-Cy4 alkenyl, C,-C4 alkynyl, C3-Cg cycloalkyl, C;-Cy4 haloalkyl, Co~Cy haloalkenyl, C,-C4 haloalkynyl,

C5-Cg halocycloalkyl, halogen, CN, NO,, C4-C4 alkoxy, C1-C4 haloalkoxy, C{-Cy4 alkylthio, C;-C4 alkylsulfinyl, Cy-Cy4 alkylsulfonyl

C,-C4 alkoxycarbonyl, C;-C4 alkylamino, C,-Cg dialkylamino, C3-Cg cycloalkylamino, C3-Cg (alkyl)cycloalkylamino, C,-Cy alkylcarbonyl,

C,-C¢ alkoxycarbonyl, C,-Cg¢ alkylaminocarbonyl, C3-Cg dialkylaminocarbonyl or C3-Cg trialkylsilyl.

Preferred 2. Compounds of Preferred 1 of Formula I wherein W is C=0.

Of note are compounds of Preferred 2 wherein A is a substituted 3-pyridinyl ring.

Also of note are compounds of Preferred 2 wherein each R? is independently C;-Cg alkyl, C5-Cg alkenyl, C,-Cg alkynyl, C3-Cg cycloalkyl, C{-Cg haloalkyl, C,-C¢ haloalkenyl, C,-Cg¢ haloalkynyl, C3-Cy halocycloalkyl, halogen, CN, CO,H, CONH,, NO,, hydroxy, C;-C4 alkoxy,

C,-C4 haloalkoxy, C1-C4 alkylthio, C;-Cy4 alkylsulfinyl, C{-C4 alkylsuifonyl,

C;-C4 haloalkylthio, C1-Cy4 haloalkylsulfinyl, C;-C4 haloalkylsulfonyl, C;-C4 alkoxycarbonyl, C{-Cy4 alkylamino, C,-Cq dialkylamino, C3-Cg cycloalkylamino, C,-Cg alkylcarbonyl, C,-C¢ alkoxycarbonyl, C»-Cg alkylaminocarbonyl, C3-Cg dialkylaminocarbonyl, C3-Cg trialkylsilyl; provided that when A is 2-pyridinyl, then RS is other than C; to Cg haloalkyl.

Preferred 3. Compounds of Preferred 2 wherein

A is a 2-pyridinyl ring substituted with from 1 to 4 RS; and

B is substituted with from 1 to 4 RS, with at least one RS located in a position ortho to the link with W.

Of note are compounds of Preferred 3 wherein RS is Cl, Br, CH, OCF3, OCHF,,

OCH, CFj3, OCF,CF;, OCF,CF,H, OCHFCF;, SCF3, SCHF,, SCH,CF3, SCF,CF;j,

SCF,CF,H, SCHFCF3, SOCF3, SOCHF,, SOCH,CF3, SOCF,CF3, SOCF,CFH,

SOCHFCF;, SO,CF;, SO,CHF,, SO,CH,CF3, SO,CF,CF3, SO,CF,CF,H or

SO,CHFCF3. Also of note are compounds of Preferred 3 wherein B is either a 3-pyridinyl or 4-pyridinyl ring having an R9 at each position ortho to the link with W (and optionally 1 to 2 additional RS),

Preferred 4. Compounds of Preferred 3 wherein B is either a 3-pyridinyl or 4-pyridinyl ring having an R6 at each position ortho to the link with W, and optionally 1 to 2 additional RS and RO is either halogen or methyl.

Preferred 5. Compounds of Preferred 4 wherein B is a 3-pyridinyl ring wherein one R® is Cl and is located at the 2-position ortho to the link with W, another R6 is selected from Cl or methyl and is located at the 4-position ortho to the link with

W and a third optional R is methy! at the 6-position.

Preferred 6. Compounds of Preferred 5 wherein A is 3-chloro-5-CF3-2-pyridinyl.

Preferred 7. Compounds of Preferred 3, but especially Preferred 4, wherein R1 is H and

R2 is CH.

Preferred 8. Compounds of Preferred 1 of Formula II wherein

A is a 2-pyridinyl ring substituted with from 1 to 4 R5; and

B is substituted with from 1 to 4 RS, with at least one RO located in a position ortho to the link with the carbon that is bonded to both X and B.

Preferred 9. Compounds of Preferred 5 wherein X is S.

Preferred compounds of this invention include those of Preferred 1 through Preferred 9 wherein R! is H or CHz, R? is H and (in Formula I) R3 is H.

Specifically preferred are the compounds selected from the group consisting of 2,4-Dichloro-N-[[3-chloro-5-(trifluoromethyl)-2-pyridinylmethyl}-3- pyridinecarboxamide, 2,4-Dichloro-N-[1-[3-chloro-5-(trifluoromethyl)-2-pyridinyl]ethyl]-3- pyridinecarboxamide, 2,4-Dichloro-N-{[3-chloro-5-(trifluoromethyl)-2-pyridinyljmethyl}-6-methyl-3- pyridinecarboxamide, and 2,4-Dichloro-N-[1-[3-chloro-5-(trifluoromethyl)-2-pyridinyl]ethyl]-6-methyl-3- pyridinecarboxamide.

Also specifically preferred are the compounds selected from the group consisting of 2,4-Dichloro-N-[(3,5-dichloro-2-pyridinyl)methyl]-3-pyridinecarboxamide, 2,4-Dichloro-N-[1-(3,5-dichloro-2-pyridinyl)ethyl]-3-pyridinecarboxamide, 2,4-Dichloro-N-[(3,5-dichloro-2-pyridinyl)methyl]-6-methyl-3- pyridinecarboxamide, 2,4-Dichloro-N-[1-(3,5-dichloro-2-pyridinyl)ethyl]-6-methyl-3- pyridinecarboxamide,

N-[(5-bromo-3-chloro-2-pyridinyl)methyl]}-2 4-dichloro-3-pyridinecarboxamide,

N-[1-(5-bromo-3-chloro-2-pyridinyl)ethyl]-2,4-dichloro-3-pyridinecarboxamide,

N-[(5-bromo-3-chloro-2-pyridinyl)methyl]-2,4-dichloro-6-methyl-3- pyridinecarboxamide, and

N-[1-(5-bromo-3-chloro-2-pyridinyl)ethyl]-2,4-dichloro-6-methyl-3- pyridinecarboxamide.

This invention also relates to fungicidal compositions comprising fungicidally effective amounts of the compounds of the invention and at least one additional component selected from the group consisting of surfactants, solid diluents or liquid diluents. The preferred compositions of the present invention are those which comprise the above preferred compounds.

This invention also relates to a method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof, or to the plant seed or seedling, a fungicidally effective amount of the compounds of the invention (e.g., as a composition described herein). The preferred methods of use are those involving the above- preferred compounds.

The compounds of Formula I and Formula II can be prepared by one or more of the following methods and variations as described in Schemes 1-6. The definitions of A, B, L, W, RI! through RS, X and n in the compounds of Formulas 1-4 below are as defined above.

Compounds of Formula la, 1b and 1c are subsets of Formula 1. Compounds of Formulae Ia,

Ib and Ic are subsets of the compounds of Formula I, and all substituents for Formulae Ia, Ib and Ic are as defined above for Formula I. Compounds of Formula Ila are a subset of the compounds of Formula II, and all substituents for Formula Ila are as defined above for

Formula II.

The compounds of Formula I can be prepared as described below in Schemes 1-5. The compounds of Formula Ic and Ila can be prepared as described below in Scheme 6.

The compounds of Formula Ia are prepared by treating amine salts of Formula 1 with an appropriate acid chloride in an inert solvent with two molar equivalents of a base (e.g. triethylamine or potassium carbonate) present. Suitable solvents are selected from the group consisting of ethers such as tetrahydrofuran, dimethoxyethane, or diethyl ether; hydrocarbons such as toluene or benzene; and halocarbons such as dichloromethane or chloroform.

Scheme 1

Rr3 R3 oan J 2 SN

RE RrR2 a B 2 RE RZ 10] 1 Ia

Alternatively, compounds of Formula Ia can be synthesized by reacting the amine salts of Formula 1 with an appropriate carboxylic acid in the presence of an organic dehydrating reagent such as 1,3-dicyclohexylcarbodiimide (DCC) or 1-[3-(Dimethylamino)propyl]-3- ethylcarbodiimide hydrochloride (EDC) as depicted in Scheme 2. Suitable solvents are selected from the group consisting of ethers such as tetrahydrofuran, dimethoxyethane, or diethyl ether; hydrocarbons such as toluene or benzene; and halocarbons such as dichloromethane or chloroform.

Scheme?2 3 la \ MI DCC or EDC f . >< R2 H H B Solvent <a

Oo 1 Ia

Intermediate salt 1a, wherein A is 2-pyridyl bearing the indicated substituents and R1,

R2, and R3 are hydrogen, can be prepared by reacting the commercially available imine ester shown in Scheme 3 with a 2,3-dichloro-pyridine substituted with RS (of Formula 4) in the 5 presence of a strong base such as sodium hydride in a polar, aprotic solvent such as N,N- dimethylformamide followed by heating in acidic medium in a procedure analogous to those found in W099/42447. Compounds of Formula 1b can be prepared by similar procedures in which the intermediate anion resulting from step 1 is treated with an alkylating agent such as methyl iodide prior to heating in an acidic medium. Of note are compounds wherein R3 is

CF;.

Claims

1. A fungicidal composition comprising: (1) at least one compound selected from Formula I and Formula II, N-oxides and agriculturally suitable salts thereof, RrR3 hr RI R2 rR R2 Xs I 1I wherein: oo A is a substituted pyridinyl ring; B is a substituted pyridinyl ring; W is C=L or SO; LisOorS; R! and R? are each independently H; or C;-Cg alkyl, C,-Cg alkenyl, C,-C¢ alkynyl or C3-Cg¢ cycloalkyl, each optionally substituted; : R3 is H; or C;-Cg alkyl, C,-Cg alkenyl, C;-Cg alkynyl or C3-Cg cycloalkyl, C,-Cg alkylcarbonyl, C,-Cg4 alkoxycarbonyl, C,-Cg alkylaminocarbonyl or C3-Cg dialkylaminocarbonyl; R4 is C;-Cg alkyl, C,-Cg alkenyl, C,-Cg alkynyl or C3-C¢ cycloalkyl, each optionally substituted, XisOorS; and : : nis 1 or 2; provided that when W is C=0 and R!, R2 and R3 are H; then B is other than 4-trifluoromethyl-3-pyridinyl, 2-chloro-4-pyridinyl and 2,6-dihalo-4- pyridinyl; and : (2) at least one other fungicide having a different mode of action.

2. A fungicidal composition of Claim 1 wherein A is a pyridinyl ring substituted with from 1 to 4 R5; B is a pyridinyl ring substituted with from 1 to 4 RS; ~ R! and R2 are each independently H; or C-Cg alkyl, C;-Cg alkenyl, C,-Cg4 alkynyl or C3-Cg cycloalkyl, each optionally substituted with one or more substituents selected from the group consisting of halogen, CN, NO», Amended Sheet - 2004-04-06 hydroxy, Cy-C4 alkoxy, C;-C4 alkylthio, C;-C,4 alkylsulfinyl, C;{-C4 alkylsulfonyl, C,-C4 alkoxycarbonyl, C,-C4 alkylamino, C,-Cg dialkylamino and C3-Cg cycloalkylamino; R4 is C;-Cg alkyl, C,-Cg alkenyl, C,-C¢ alkynyl or C3-Cg cycloalkyl, each optionally substituted with one or more substituents selected from the group consisting of halogen, CN, NO,, hydroxy, C;-C4 alkoxy, C;-C4 alkylthio, : Ci-C4 alkylsulfinyl, C,-C4 alkylsulfonyl, C,-C4 alkoxycarbonyl, C;-Cy4 alkylamino, C,-Cg dialkylamino and C3-Cg4 cycloalkylamino; RS and RO are each independently C;-Cg alkyl, C,-Cg alkenyl, C»-Cg alkynyl, C5- : Cg cycloalkyl, C;-Cg4 haloalkyl, C,-Cg haloalkenyl, C,-Cg haloalkynyl, Cs- Cg halocycloalkyl, halogen, CN, CO,H, CONH,;, NO,, hydroxy, C;-C4 alkoxy, C;-C4 haloalkoxy, C-Cy4 alkylthio, Ci-C4 alkylsulfinyl, Cy-C4 alkylsulfonyl, C;-C4 haloalkylthio, C,-C4 haloalkylsulfinyl, C;-C4 : * haloalkylsulfonyl, C;-C4 alkoxycarbonyl, C;-C4 alkylamino, C,-Cg : dialkylamino, C3-Cg cycloalkylamino, C,-Cg4 alkylcarbonyl, C,-Cg oo : alkoxycarbonyl, C,-Cg alkylaminocarbonyl, C4-Cg dialkylaminocarbonyl, C3-Cg trialkylsilyl; or : RS and RS are each independently phenyl, benzyl or phenoxy, each optionally substituted with C;-Cy alkyl, C,-C4 alkenyl, C,-Cy4 alkynyl, C5-Cg¢ cycloalkyl, C;-C4 haloalkyl, C5-C4 haloalkenyl, C,-C4 haloalkynyl, C3-Cg : : halocycloalkyl, halogen, CN, NO,, C,-C4 alkoxy, C,-C4 haloalkoxy, C{-C4 alkylthio, C-C, alkylsulfinyl, C;-C4 alkylsulfonyl C;-C4 alkoxycarbonyl, C;-C4 alkylamino, C,-Cg dialkylamino, C3-Cg cycloalkylamino, C3-Cg (alkyl)cycloalkylamino, Cp-Cy4 alkylcarbonyl, C,-Cg alkoxycarbonyl, Cy-Cg alkylaminocarbonyl, C3-Cg dialkylaminocarbonyl or C3-Cg trialkylsilyl.

3. A fungicidal composition of Claim 2 wherein for Formula I W is C=0.

4. A fungicidal composition of Claim 3 wherein A is a 2-pyridinyl ring substituted with from 1 to 4 R3; and B is substituted with from 1 to 4 RS, with at least one RO located in a position ortho to the link with W.

: 5. A fungicidal composition of Claim 1 wherein the at least one other fungicide having a different mode of action is selected from the group consisting of fungicides inhibiting mitochondrial respiration, fungicides inhibiting protein synthesis by interference of the synthesis of ribosomal RNA, and fungicides inhibiting beta-tubulin synthesis. Amended Sheet — 2004-04-06

6. A compound selected from Formula I and Formula II, N-oxides and agriculturally suitable salts thereof, R3 : St SOY RI' RZ RI" RZ Xs 1 II wherein:

A is a 3-pyridinyl ring substituted with from 1 to 4 R3;

B is a pyridinyl ring substituted with from 1 to 4 RS;

Wis C=0;

~ Rl and R? are each independently H; or C;-Cg alkyl, C,-Cg alkenyl, C,-Cg alkynyl or C3-Cg cycloalkyl, each optionally substituted with one or more substituents selected from the group consisting of halogen, CN, NO,, hydroxy, C,-C4 alkoxy, C;-Cy alkylthio, Cy-C4 alkylsulfinyl, C;-Cy alkylsulfonyl, C,-C,4 alkoxycarbonyl, C;-C4 alkylamino, C,-Cg dialkylamino and C3-Cy4 cycloalkylamino;

R3 is H; or C;-Cg alkyl, C;-Cg alkenyl, C;-Cg alkynyl or C53-Cg cycloalkyl, Co-Cg alkylcarbonyl, C,-Cg alkoxycarbonyl, C,-Cg alkylaminocarbonyl or C5-Cg dialkylaminocarbonyl,

R% is C;-Cg alkyl, C,-Cg alkenyl, C,-Cg alkynyl or C3-Cg cycloalkyl, each optionally substituted with one or more substituents selected from the group consisting of halogen, CN, NO, hydroxy, C;-C4 alkoxy, C,-C4 alkylthio,

C,-C4 alkylsulfinyl, C;-Cy4 alkylsulfonyl, C,-C4 alkoxycarbonyl, C;-Cy4 alkylamino, C,-Cg dialkylamino and C3-Cg cycloalkylamino;

R3 and RY are each independently C,-Cg alkyl, C,-Cg alkenyl, C,-Cg alkynyl, C3-

Cg cycloalkyl, Ci-Cg¢ haloalkyl, C,-Cg haloalkenyl, C,-Cg4 haloalkynyl, Cs- Cg halocycloalkyl, halogen, CN, CO,H, CONH,, NO,, hydroxy, C;-C4 alkoxy, C,-C4 haloalkoxy, C;-C4 alkylthio, C;-C4 alkylsulfinyl, C,-C4 alkylsulfonyl, C;-Cy4 haloalkylthio, C;-C4 haloalkylsulfinyl, C|-C4 haloalkylsulfonyl, C;-Cy4 alkoxycarbonyl, C;-C4 alkylamino, C,-Cg ~~ dialkylamino, C3-Cg4 cycloalkylamino, C,-Cg alkylcarbonyl, C,-Cg Amended Sheet — 2004-04-06 alkoxycarbonyl, C,-Cg4 alkylaminocarbonyl, C3-Cg dialkylaminocarbonyl, C3-Cg trialkylsilyl; or RS and RS are each independently phenyl, benzyl or phenoxy, each optionally substituted with C-Cy alkyl, C,-C4 alkenyl, C,-C4 alkynyl, C3-Cgq cycloalkyl, C;-C4 haloalkyl, C,-C4 haloalkenyl, C,-C4 haloalkynyl, C5-Cg halocycloalkyl, halogen, CN, NO,, C;-Cy4 alkoxy, C;-C, haloalkoxy, C;-C4 alkylthio, C;-C4 alkylsulfinyl, C,-C, alkylsulfonyl C;-C4 alkoxycarbonyl, C,-C4 alkylamino, C,-Cg dialkylamino, C3-Cg cycloalkylamino, C3-Cg : (alkyl)cycloalkylamino, C,-Cy4 alkylcarbonyl, C,-Cgq alkoxycarbonyl, C,-Cg alkylaminocarbonyl, C3-Cg dialkylaminocarbonyl or C3-Cg trialkylsilyl; and X is O or S; provided that when R!, R? and R3 are H; then B is other than 4- trifluoromethyl-3-pyridinyl, 2-chloro-4-pyridinyl and 2,6-dihalo-4-pyridinyl.

7. A compound selected from Formula I and Formula II, N-oxides and agriculturally suitable salts thereof, R3 Se _B SN 1 2 1 2 : . R © | RI" R X_ y wherein: : A is a 2-pyridinyl ring substituted with from 1 to 4 R5; B is a 3-pyridinyl ring or 4-pyridinyl ring substituted with from 2 to 4 RS; having an R® at each position ortho to the link with W and optionally 1 to 2 additional R6; Wis C=0; R! and RZ are each independently H; or C-Cg alkyl, C,-Cg alkenyl, C,-Cg alkynyl or C3-Cg cycloalkyl, each optionally substituted with one or more substituents selected from the group consisting of halogen, CN, NO,, hydroxy, C;-C4 alkoxy, C;-Cy4 alkylthio, C;-C4 alkylsulfinyl, C{-C4 alkylsulfonyl, C,-C4 alkoxycarbonyl, C;-Cy4 alkylamino, C,-Cg dialkylamino and C3-Cgq cycloalkylamino; : Amended Sheet — 2004-04-06

R3 is H; or C;-Cg alkyl, C,-Cg alkenyl, C,-Cg alkynyl or C3-Cg cycloalkyl, C;-Cg alkylcarbonyl, C,-Cg alkoxycarbonyl, C,-Cg alkylaminocarbonyl or C4-Cg dialkylaminocarbonyl; R# is C;-Cg alkyl, C5-Cg alkenyl, C,-Cg alkynyl or C3-Cg cycloalkyl, each optionally substituted with one or more substituents selected from the group consisting of halogen, CN, NO,, hydroxy, C;-C4 alkoxy, C;-Cy4 alkylthio, C1-Cy alkylsulfinyl, C,-C4 alkylsulfonyl, C,-C4 alkoxycarbonyl, C;-Cy4 alkylamino, C,-Cg dialkylamino and C3-Cg cycloalkylamino; R53 and R® are each independently C;-Cg alkyl, C,-Cg alkenyl, C,-C¢ alkynyl, Cs- Cg cycloalkyl, Cy-Cg¢ haloalkyl, C,-Cg haloalkenyl, C,-Cg haloalkynyl, Cs- Cg halocycloalkyl, halogen, CN, CO,H, CONH,, NO,, hydroxy, C;-C4 alkoxy, Cy-C4 haloalkoxy, C;-C4 alkylthio, C;-C4 alkylsulfinyl, C;-C4 alkylsulfonyl, Cy-C4 haloalkylthio, C{-Cy4 haloalkylsulfinyl, C;-C4 haloalkylsulfonyl, C|-Cy4 alkoxycarbonyl, C|-C, alkylamino, C,-Cg dialkylamino, C3-Cg cycloalkylamino, C,-C¢ alkylcarbonyl, C,-Cg alkoxycarbonyl, C,-Cg4 alkylaminocarbonyl, C3-Cg dialkylaminocarbonyl, C;-Cg trialkylsilyl; or R> and R® are each independently phenyl, benzyl or phenoxy, each optionally : substituted with C,-Cy4 alkyl, C,-C4 alkenyl, C,-C4 alkynyl, C3-Cq cycloalkyl, C;-C4 haloalkyl, C,-C4 haloalkenyl, C,-C,4 haloalkynyl, C3-Cg halocycloalkyl, halogen, CN, NO,, C;-C4 alkoxy, C-C4 haloalkoxy, C;-C4 alkylthio, C;-C4 alkylsulfinyl, C,-C, alkylsulfonyl C,-C4 alkoxycarbonyl, - C,-C4 alkylamino, C,-Cg dialkylamino, C3-Cg cycloalkylamino, C3-Cg (alkyl)cycloalkylamino, C,-Cy4 alkylcarbonyl, C,-Cq alkoxycarbonyl, C5-Cg alkylaminocarbonyl, C3-Cg dialkylaminocarbonyl or C3-Cgy trialkylsilyl; and XisOorS.

8. A compound of Claim 7 wherein each R is either halogen or methyl.

9. A compound of Claim 8 wherein B is a 3-pyridinyl ring wherein one R is Cl and is located at the 2-position ortho to the link with W, another RO is selected from Cl or methyl and is located at the 4-position ortho to the link with W and a third optional R6 is methyl at the 6-position. :

10. A compound of Claim 9 wherein A is 3-chloro-5-CF3-2-pyridinyl. .

11. A compound of Claim 8 wherein R! is H and R? is CH;.

12. A compound of Claim 9 selected from the group consisting of Amended Sheet — 2004-04-06

2,4-Dichloro-N-[[3-chloro-5-(trifluoromethyl)-2-pyridinyl]methyl]-3- pyridinecarboxamide, and 2,4-Dichloro-N-[[3-chloro-5-(triflucromethyl)-2-pyridinylJmethyl]-6-methyl-3- pyridinecarboxamide.

13. A compound selected from Formula I and Formula II, N-oxides and : agriculturally suitable salts thereof, : : RI tt | SON Rl" R2 RI RZ 0 pd 1 I wherein: A is a 2-pyridinyl ring substituted with from 1 to 4 R5; B is a pyridinyl ring substituted with from 1 to 4 RS, with at least one R® located in a position ortho to the link with W; : Wis C=0; R!is H; : R2 is CHj; R3 is H; or C;-Cg alkyl, C;-Cg alkenyl, C,-Cg alkynyl or C3-Cg cycloalkyl, C-Cg alkylcarbonyl, C,-Cg alkoxycarbonyl, C,-Cg alkylaminocarbonyl or C3-Cg dialkylaminocarbonyl, R# is Cy-Cg alkyl, C,-Cg alkenyl, C,-Cg alkynyl or C3-Cg cycloalkyl, each optionally substituted with one or more substituents selected from the group consisting of halogen, CN, NO,, hydroxy, C;-C4 alkoxy, C;-C4 alkylthio, C,-C4 alkylsulfinyl, C;-C4 alkylsulfonyl, C,-C, alkoxycarbonyl, C;-C4 alkylamino, C;-Cg dialkylamino and C3-Cg cycloalkylamino; RS5 and R® are each independently C-Cg alkyl, C,-Cg alkenyl, C,-Cg alkynyl, C3- Cg cycloalkyl, C;-Cg4 haloalkyl, C,-Cg¢ haloalkenyl, C,-Cg haloalkynyl, Cs- Cg halocycloalkyl, halogen, CN, CO,H, CONH,, NO,, hydroxy, C;-C4 alkoxy, C|-C4 haloalkoxy, C-C4 alkylthio, C;-C4 alkylsulfinyl, C;-C4 alkylsulfonyl, C;-C4 haloalkylthio, C;-C4 haloalkylsulfinyl, C,-C4 haloalkylsulfonyl, C;-C4 alkoxycarbonyl, C;-C,4 alkylamino, C-Cg dialkylamino, C3-Cg cycloalkylamino, C,-Cg alkylcarbonyl, C,-Cg Amended Sheet — 2004-04-06 alkoxycarbonyl, C,-Cg alkylaminocarbonyl, C3-Cg dialkylaminocarbonyl, C3-Cg trialkylsilyl; or R5 and R® are each independently phenyl, benzyl or phenoxy, each optionally : substituted with C;-C4 alkyl, C,-C4 alkenyl, C,-Cy4 alkynyl, C3-Cq : cycloalkyl, C{-C4 haloalkyl, C5-C, haloalkenyl, C,-C4 haloalkynyl, C3-Cq halocycloalkyl, halogen, CN, NO,, C;-C4 alkoxy, C;-C4 haloalkoxy, C{-C4 alkylthio, C,-C, alkylsulfinyl, C;-Cy4 alkylsulfonyl C;-C4 alkoxycarbonyl, C,-C4 alkylamino, C,-Cg dialkylamino, C;-Cg4 cycloalkylamino, C5-Cg (alkyl)cycloalkylamino, C,-C4 alkylcarbonyl, C,-Cg alkoxycarbonyl, C,-Cg - alkylaminocarbonyl, C5-Cg dialkylaminocarbonyl or C3-Cg trialkylsilyl; and XisOorS.

14. A compound of Claim 13 selected from the group consisting of 2,4-Dichloro-N-{1-[3-chloro-5-(trifluoromethyl)-2-pyridinyl]ethyl]-3- pyridinecarboxamide, and 2,4-Dichloro-N-{1-[3-chloro-5-(trifluoromethyl)-2-pyridinyl]ethyl}-6-methyl-3- pyridinecarboxamide.

15. A compound selected from Formula I, N-oxides and agriculturally suitable salts thereof, 3 he RI Rr? 1 wherein: A is a pyridinyl ring substituted with from 1 to 4 R5; B is a pyridinyl ring substituted with from 1 to 4 RS; ’ Wis C=L or SO; LisOorS; R! and R2 are each independently H; or C;-Cg alkyl, C5-Cg alkenyl, C,-Cg alkynyl or C3-Cg cycloalkyl, each optionally substituted with one or more substituents selected from the group consisting of halogen, CN, NO,, hydroxy, C;-C4 alkoxy, C;-C4 alkylthio, C;-C4 alkylsulfinyl, C;-C4 alkylsulfonyl, C,-Cy4 alkoxycarbonyl, C;-Cy4 alkylamino, C,-Cg dialkylamino and C5-Cg cycloalkylamino; Amended Sheet — 2004-04-06

R3 is H; or C;-Cg alkyl, C,-Cg alkenyl, C,-Cg alkynyl or C3-Cg4 cycloalkyl, C,-Cg alkylcarbonyl, C,-C¢ alkoxycarbonyl, C,-C¢ alkylaminocarbonyl or C3-Cg dialkylaminocarbonyl; R# is C;-Cg alkyl, C,-Cg alkenyl, C,-Cg alkynyl or C3-C¢ cycloalkyl, each optionally substituted with one or more substituents selected from the group consisting of halogen, CN, NO», hydroxy, C;-C4 alkoxy, C-Cy4 alkylthio, C,-C4 alkylsulfinyl, C;-C4 alkylsulfonyl, C,-C4 alkoxycarbonyl, C;-Cy4 alkylamino, C,-Cg dialkylamino and C3-Cg cycloalkylamino; each RS is independently Cy-Cg alkyl, C,-Cg alkenyl, C,-Cg alkynyl, C3-Cg cycloalkyl, C;-Cg¢ haloalkyl, C,-Cg haloalkenyl, C,-Cg haloalkynyl, C5-Cg halocycloalkyl, halogen, CN, CO,H, CONH,, NO,, hydroxy, C,-C, alkoxy, C-Cy4 haloalkoxy, C,-C4 alkylthio, C;-C4 alkylsulfinyl, C,-C4 alkylsulfonyl, C,-C4 haloalkylthio, C;-Cy4 haloalkylsulfinyl, C;-C4 haloalkylsulfonyl, C,-

C4 alkoxycarbonyl, C;-C4 alkylamino, C,-Cg dialkylamino, C3-Cg cycloalkylamino, C,-Cg alkylcarbonyl, C,-Cg alkoxycarbonyl, C,-Cg alkylaminocarbonyl, C4-Cg dialkylaminocarbonyl, C3-Cg trialkylsilyl; provided that when A is 2-pyridinyl, then R3 is other than C; to Cg haloalkyl;

and each RO is independently C;-Cg alkyl, C5-Cg alkenyl, C,-Cg alkynyl, C3-Cg cycloalkyl, C,-Cg¢ haloalkyl, C,-Cg haloalkenyl, C,-Cg4 haloalkynyl, C4-Cg halocycloalkyl, halogen, CN, CO,H, CONHj, NO,, hydroxy, C;-C4 alkoxy, C4-C4 haloalkoxy, C;-Cy4 alkylthio, Ci-Cy4 alkylsulfinyl, C,-C4 alkylsulfonyl, C1-Cy4 haloalkylthio, C;-C4 haloalkylsulfinyl, C;-C4 haloalkylsulfonyl, C;- C4 alkoxycarbonyl, C;-C4 alkylamino, C,-Cg dialkylamino, C5-Cg ~~ cycloalkylamino, C,-Cg alkylcarbonyl, C,-Cg¢ alkoxycarbonyl, C,-Cg : alkylaminocarbonyl, C3-Cg dialkylaminocarbonyl, C3-Cq trialkylsilyl; or R3 and R6 are each independently phenyl, benzyl or phenoxy, each optionally substituted with C,-C4 alkyl, C,-C, alkenyl, C,-C4 alkynyl, C3-Cgq : cycloalkyl, C;-C4 haloalkyl, C5-C4 haloalkenyl, C,-C4 haloalkynyl, C3-Cgq halocycloalkyl, halogen, CN, NO,, C;-C, alkoxy, Cy-C4 haloalkoxy, C;-C4 alkylthio, C;-C4 alkylsulfinyl, C;-C,4 alkylsulfonyl C;-C4 alkoxycarbonyl, C;-C4 alkylamino, C,-Cg dialkylamino, C3-Cg cycloalkylamino, C3-Cg (alkyl)cycloalkylamino, C,-C4 alkylcarbonyl, C,-Cq alkoxycarbonyl, C,-Cg alkylaminocarbonyl, C3-Cg dialkylaminocarbonyl or C3-Cg trialkylsilyl; and Amended Sheet — 2004-04-06 nis 1 or 2; provided that when W is C=0 and R!, R2 and R3 are H; then B is other than 4-trifluoromethyl-3-pyridinyl, 2-chloro-4-pyridinyl and 2,6-dihalo-4- pyridinyl.

16. A compound of Claim 15 wherein Wis C=0; each R? is independently Cy-Cg alkyl, C,-Cg alkenyl, C;-C¢ alkynyl, C3-Cg cycloalkyl, C;-Cg4 haloalkyl, C,-Cg haloalkenyl, C,-C¢ haloalkynyl, C5-Cg halocycloalkyl, halogen, CN, CO,H, CONH,, NO,, hydroxy, C;-C4 alkoxy, C-C4 haloalkoxy, C;-Cy4 alkylthio, Cy-Cy alkylsulfinyl, C,-C4 alkylsulfonyl, : C,-C4 haloalkylthio, C;-C4 haloalkylsulfinyl, C;-Cy4 haloalkylsulfonyl, C,- C4 alkoxycarbonyl, C;-C,4 alkylamino, C,-Cg dialkylamino, C5-Cg cycloalkylamino, C,-Cg4 alkylcarbonyl, C,-Cg alkoxycarbonyl, C,-Cg alkylaminocarbonyl, C3-Cg dialkylaminocarbonyl, C3-Cg trialkylsilyl; provided that when A is 2-pyridinyl, then R3 is other than C; to Cg haloalkyl.

17. A compound of Claim 16 wherein RS is Cl, Br, CHj, OCF,, OCHF,, OCH, CF3, OCF,CF;, OCF,CF,H, OCHFCF3, SCF;, SCHF,, SCH, CF5, SCF,CF;, SCF,CF,H, SCHFCF3, SOCF;, SOCHF,, SOCH,CF3, SOCF,CF3, SOCF,CF,H, SOCHFCF;, SO,CF5, SO,CHF,, SO,CH,CF;, SO,CF,CF5, SO,CF,CF,H or SO,CHFCEF;.

18. A compound of Claim 17 selected from the group consisting of 2,4-Dichloro-N-[(3,5-dichloro-2-pyridinyl)methyl]-3-pyridinecarboxamide, 2,4-Dichloro-N-[1-(3,5-dichloro-2-pyridinyl)ethyl]-3-pyridinecarboxamide, 2,4-Dichloro-N-[(3,5-dichloro-2-pyridinyl)methyl]-6-methyl-3- pyridinecarboxamide, 2,4-Dichloro-N-[1-(3,5-dichloro-2-pyridinyl)ethyl]-6-methyl-3- pyridinecarboxamide, ' N-[(5-bromo-3-chloro-2-pyridinyl)methyl]-2,4-dichloro-3-pyridinecarboxamide, N-[1-(5-bromo-3-chloro-2-pyridinyl)ethyl]-2,4-dichloro-3-pyridinecarboxamide, N-[(5-bromo-3-chloro-2-pyridinyl)methyl}-2,4-dichloro-6-methyl-3- : pyridinecarboxamide, and Co : N-[1-(5-bromo-3-chloro-2-pyridinyl)ethyl]-2,4-dichloro-6-methyl-3- pyridinecarboxamide.

19. A fungicidal composition comprising a fungicidally effective amount of a compound of Claim 6, Claim 7, Claim 13, or Claim 15 and at least one additional Amended Sheet ~ 2004-04-06 component selected from the group consisting of surfactants, solid diluents and liquid diluents.

20. A method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof, or to the plant seed or seedling, a ~ fungicidally effective amount of a compound of Claim 6, Claim 7, Claim 13, or Claim

15. : Amended Sheet — 2004-04-06