WO2014130241A1

WO2014130241A1 - Fungicidal pyrazoles

Info

Publication number: WO2014130241A1
Application number: PCT/US2014/014833
Authority: WO
Inventors: Andrew Edmund Taggi; James Francis Bereznak; Jeffrey Keith Long
Original assignee: E. I. Du Pont De Nemours And Company
Priority date: 2013-02-20
Filing date: 2014-02-05
Publication date: 2014-08-28
Also published as: EP3010908A1; AR094840A1

Abstract

Disclosed are compounds of Formula 1, including all geometric and stereoisomers, N-oxides, and salts thereof, wherein Q¹, Q², X, R¹, R^1a and R² are as defined in the disclosure. Also disclosed are compositions containing the compounds of Formula 1 and methods for controlling plant disease caused by a fungal pathogen comprising applying an effective amount of a compound or a composition of the invention.

Description

TITLE

FUNGICIDAL PYRAZOLES

FIELD OF THE INVENTION

This invention relates to certain pyrazoles, their N-oxides, salts and compositions, and methods of their use as fungicides.

BACKGROUND OF THE INVENTION

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 sites of action.

PCT Patent Publications WO 2009/137538, WO 2009/137651, WO 2010/101973, WO 2012/023143 and WO 2012/031061 disclose pyrazole derivatives and their use as fungicides.

SUMMARY OF THE INVENTION

This invention is directed to compounds of Formula 1 (including all stereoisomers), N-oxides, and salts thereof, agricultural compositions containing them and their use as fungicides:

¹

wherein

Q¹ is a phenyl ring or a naphthalenyl ring system, each ring or ring system optionally substituted with up to 5 substituents independently selected from R^3a and R^3b; or a 5- to 6-membered fully unsaturated heterocyclic ring or an 8- to 10-membered heteroaromatic bicyclic ring system, each ring or ring system containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, wherein up to 3 carbon ring members are independently selected from C(=0) and C(=S), and the sulfur atom ring members are independently selected from S(=0)_u(=NR²⁷)_v, each ring or ring system optionally substituted with up to 5 substituents independently selected from R^3a and R³^ on carbon atom ring members and selected from cyano, C1-C3 alkyl, C2-C3 alkenyl, C2-C3 alkynyl, C3-C6 cycloalkyl, C2-C3 alkoxyalkyl, C1-C3 alkoxy, C2-C3 alkylcarbonyl, C2-C3 alkoxycarbonyl, C2-C3 alkylaminoalkyl and C3-C4 dialkylaminoalkyl on nitrogen atom ring members; Q² is a phenyl ring or a naphthalenyl ring system, each ring or ring system optionally substituted with up to 5 substituents independently selected from R^3a and R ^b; or a 5- to 6-membered fully unsaturated heterocyclic ring or an 8- to 10-membered heteroaromatic bicyclic ring system, each ring or ring system containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, wherein up to 3 carbon ring members are independently selected from C(=0) and C(=S), and the sulfur atom ring members are independently selected from S(=0)_u(=NR²⁷)_v, each ring or ring system optionally substituted with up to 5 substituents independently selected from R^3a and R^3b on carbon atom ring members and selected from cyano, C1-C3 alkyl, C2-C3 alkenyl, C2-C3 alkynyl, C3-C6 cycloalkyl, C2-C3 alkoxyalkyl, C1-C3 alkoxy, C2-C3 alkylcarbonyl, C2-C3 alkoxycarbonyl, C2-C3 alkylaminoalkyl and C3-C4 dialkylaminoalkyl on nitrogen atom ring members; X is O, S(=0)_m, NR⁴ or CR^5aOR^5b;

R¹ is H, cyano, halogen, C^-Cg alkyl, C^-Cg haloalkyl, C2-Cg alkenyl, C2-Cg alkynyl, C3-C6 cycloalkyl, C2-C6 alkoxyalkyl, C^-C^ alkoxy, C^-C^ haloalkoxy, C(=0)OR⁶ or C(=0)NR⁷R⁸;

R^la is H; or

R^la and R¹ are taken together with the carbon atom to which they are attached to form a cyclopropyl ring optionally substituted with up to 2 substituents independently selected from halogen and methyl;

R² is H, cyano, halogen, C1-C3 alkyl, C2-C3 alkenyl, C2-C3 alkynyl, C1-C3 haloalkyl,

C2-C3 haloalkenyl, C2-C3 cyanoalkyl, C1-C3 hydroxyalkyl, C1-C3 alkoxy or C1-C3 alkylthio; or cyclopropyl optionally substituted with up to 2 substituents independently selected from halogen and methyl;

each R ^a is independently cyano, halogen, hydroxy, nitro, -C4 alkyl, -C4

haloalkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-C4 cycloalkyl, C3-C7

halocycloalkyl, C4-C6 cycloalkylalkyl, C4-C6 alkylcycloalkyl, C1-C3 alkylthio, C1-C3 haloalkylthio, C1-C3 alkylsulfinyl, C1-C3 haloalkylsulfinyl, C1-C3 alkylsulfonyl, C1-C3 haloalkylsulfonyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C3-C7 cycloalkoxy, C1-C2 alkylsulfonyloxy, -C2 haloalkylsulfonyloxy, C2-C3 alkylcarbonyloxy, C2-C3 alkylcarbonyl, amino, methylamino, C2-C4

dialkylamino, C₂-C₃ alkylcarbonylamino, -CH(=0), -NHCH(=0), -SF₅, -SC≡N, -C(=S)NR^9aR^9b or -U-V-T; each R^3b is independently C5-C8 alkyl, C5-C8 haloalkyl, C5-C8 alkenyl, C5-C8 alkynyl, C2-Cg haloalkenyl, C2-Cg haloalkynyl, C i -Cg nitroalkyl, C2-Cg nitroalkenyl, C5-Cg cycloalkyl, C₇-Cg alkylcycloalkyl, C₇-Cg cycloalkylalkyl, C5-C12 cycloalkylalkenyl, C5-C12 cycloalkylalkynyl, Cg-C^

cycloalkylcycloalkyl, C4-Cg alkylthio, C4-Cg haloalkythio, Cz_j-Cg alkylsulfinyl, C4-Cg haloalkylsulfinyl, C4-Cg alkylsulfonyl, C4-Cg haloalkylsulfonyl, C4-Cg alkoxy, C5-Cg haloalkoxy, C2-Cg alkenyloxy, C2-Cg haloalkenyloxy, C3-Cg alkynyloxy, C3-Cg haloalkynyloxy, C2-Cg cyanoalkoxy, Cg-C^ cycloalkoxy, C3-C12 halocycloalkoxy, C4-C12 cycloalkylalkoxy, C5-C 12

cycloalkylalkenyloxy, C5-C 12 cycloalkylalkynyloxy, C3-Cg alkylsulfonyloxy, C3-Cg haloalkylsulfonyloxy, C4-Cg alkylcarbonyloxy, C4-Cg alkylcarbonyl, C2-Cg alkylamino, C4-Cg alkylcarbonylamino, C3-C12 trialkylsilyl, C4-C12 trialkylsilylalkyl, C₄-C₁₂ trialkylsilylalkoxy, -C(=NR^9a)NR^9aOR^9a,

-CR^10a=NOR^10b, -CR^10c=NNR^9aR^9b, -NR^9aN=CR^{l la}R^{l lb} or -ON=CR^{l la}R^{l lb}; or

each R^3b is independently -A(CR^12aR^12b)_nW;

each A is independently O or a direct bond;

each W is independently a 3- to 7-membered heterocyclic ring containing ring

members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, wherein up to 3 carbon atom ring members are independently selected from C(=0) and C(=S), the ring optionally substituted with up to 3 substituents independently selected from R¹³ on carbon atom ring members and R¹⁴ on nitrogen atom ring members;

R⁴ is H, amino, C2-Cg alkenyl, C3-C6 alkynyl, C3-C6 cycloalkyl, -CH(=0),

-S(=0)₂OM, -S(=0)_mR¹⁵, -(C=Z)R¹⁶ or OR¹⁷; or C_rC₆ alkyl or C_rC₆ haloalkyl, each optionally substituted with up to 2 substituents independently selected from R¹⁸;

R^5a is H or C_rC₆ alkyl;

R^5b is H, -CH(=0), C_rC₆ alkyl, C₂-C₆ alkenyl, C₃-C₆ alkynyl, C_rC₆ haloalkyl,

C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C2-Cg alkoxyalkyl, C2-C6 cyanoalkyl, C2-C6 alkylcarbonyl, C2-C6 alkoxycarbonyl, C2-C6 (alkylthio)carbonyl, C4-Cg cycloalkylcarbonyl, C4-Cg cycloalkoxycarbonyl, C4-Cg

(cycloalkylthio)carbonyl, C2-C6 alkoxy(thiocarbonyl) or C4-Cg

cycloalkoxy(thiocarbonyl);

R⁶ is H, C_rC₆ alkyl or C_rC₆ haloalkyl;

R⁷ and R⁸ are each independently H,

haloalkyl, C3-C6 cycloalkyl, C4-Cg cycloalkylalkyl or C4-Cg alkylcycloalkyl; or R⁷ and R⁸ are taken together with the nitrogen atom to which they are attached to form a 4- to 7-membered nonaromatic heterocyclic ring containing ring members, in addition to the connecting nitrogen atom, selected from carbon atoms and up to 1 ring member selected from O, S(=0)_m and NR¹⁹;

each R^9a and R^9b is independently H or Ci -C4 alkyl;

each R^10a is independently H, C1-C3 alkyl or C1-C3 haloalkyl;

each R^10b and R^10c is independently H, C_rC₃ alkyl, C₂-C₄ alkenyl, C₂-C₄ alkynyl, C1-C3 haloalkyl, C2-C4 haloalkenyl, C3-C4 cycloalkyl, C4-C8 cycloalkylalkyl or C3-C4 halocycloalkyl;

each R^{l l a} and R^{l lb} is independently H, C1-C3 alkyl or C1-C3 haloalkyl;

each R^12a is independently H, halogen, cyano or Ci -C4 alkyl;

each R^12b is independently H or Ci -C4 alkyl;

each R¹³ is independently halogen, cyano, Ci -C2 alkyl, Ci -C2 haloalkyl, Ci -C2 alkoxy or C 1 -C2 haloalkoxy;

each R¹⁴ is independently cyano, Ci -C2 alkyl or Ci -C2 alkoxy;

R¹⁵ is C_rC₆ alkyl or C_rC₆ haloalkyl;

R¹⁶ is Ci -Cg alkyl, C2-Cg alkoxyalkyl, C2-Cg alkylaminoalkyl, C3-C6

dialkylaminoalkyl, Ci -Cg alkoxy, Ci -Cg alkylthio or C2-Cg alkylthioalkyl; R¹⁷ is H, -CH(=0), C₃-C₆ cycloalkyl, -S(=0)₂OM or -(C=Z)R²⁰; or C_rC₆ alkyl or

Ci -Cg haloalkyl, each optionally substituted with up to 2 substituents independently selected from R²¹;

each R¹⁸ and R²¹ is independently cyano, C3-Cg cycloalkyl, Ci -Cg alkoxy, Ci -Cg haloalkoxy, Ci -Cg alkylthio, Ci -Cg alkylsulfinyl or Ci -Cg alkylsulfonyl;

R¹⁹ is H, C_rC₃ alkyl or C₂-C₃ haloalkyl;

R²⁰ is Ci -Cg alkyl, C2-Cg alkoxyalkyl, C2-Cg alkylaminoalkyl, C3-Cg

dialkylaminoalkyl, Ci -Cg alkoxy, Ci -Cg alkylthio or C2-Cg alkylthioalkyl; each U is independently O, S(=0)_m, NR²² or a direct bond;

each V is independently Ci -Cg alkylene, C2-Cg alkenylene, C3-Cg alkynylene, C3-Cg cycloalkylene or C3-Cg cycloalkenylene, wherein up to 3 carbon atoms are C(=0), each optionally substituted with up to 5 substituents independently selected from halogen, cyano, nitro, hydroxy, Ci -Cg alkyl, Ci -Cg haloalkyl, Ci -Cg alkoxy and Ci -Cg haloalkoxy;

each T is independently cyano, NR^23aR^23b, OR²⁴ or S(=0)_mR²⁵;

each R²² is independently H, Ci -Cg alkyl, Ci -Cg haloalkyl, C2-Cg alkylcarbonyl,

C2-Cg alkoxycarbonyl, C2-Cg (alkylthio)carbonyl, C2-Cg alkoxy(thiocarbonyl), C4-C8 cycloalkylcarbonyl, C4-C8 cycloalkoxycarbonyl, C4-C8

(cycloalkylthio)carbonyl or C4-C8 cycloalkoxy(thiocarbonyl); each R^23a and R^23b is independently H, C^-Cg alkyl, C^-Cg haloalkyl, C2-Cg alkenyl, C3-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C2-Cg alkylcarbonyl, C2-C6 alkoxycarbonyl, C2-Cg (alkylthio)carbonyl, C2-Cg alkoxy(thiocarbonyl), Cz Cg cycloalkylcarbonyl, C4-C8 cycloalkoxycarbonyl, C4-C8

(cycloalkylthio)carbonyl or C4-C8 cycloalkoxy(thiocarbonyl); or

a pair of R^23a and R²³^ attached to the same nitrogen atom are taken together with the nitrogen atom to form a 3- to 6-membered heterocyclic ring, the ring optionally substituted with up to 5 substituents independently selected from R²⁶; each R²⁴ and R²⁵ is independently H, C^-Cg alkyl, C^-Cg haloalkyl, C2-Cg alkenyl, C3-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C2-Cg alkylcarbonyl, C2-C6 alkoxycarbonyl, C2-Cg (alkylthio)carbonyl, C4-C8 cycloalkylcarbonyl, C4-C8 cycloalkoxycarbonyl, C4-C8 (cycloalkylthio)carbonyl, C2-Cg alkoxy(thiocarbonyl) or C4-C8 cycloalkoxy(thiocarbonyl);

each R²⁶ is independently halogen, C^-Cg alkyl, C^-Cg haloalkyl or C^-Cg alkoxy; each R²⁷ is independently H, cyano, Ci -C3 alkyl or C1-C3 haloalkyl;

Z is O or S;

M is K, Na or Li;

each m is independently 0, 1 or 2;

each n is independently 0, 1, 2 or 3; and

each u and v are independently 0, 1 or 2 in each instance of S(=0)_u(=NR²⁷)_v;

provided that:

(a) the sum of u and v is 0, 1 or 2;

(b) when Q¹ and Q² are each an optionally substituted phenyl ring, an optionally

substituted naphthalenyl ring system, an optionally substituted 5- to 6-membered fully unsaturated heterocyclic ring or an optionally substituted 8- to

10-membered heteroaromatic bicyclic ring system, then at least one of Q¹ or Q² is substituted with at least one R^3b substituent; and

(c) when n is 1, 2, or 3, then W is linked through a carbon atom to the remainder of

Formula 1.

More particularly, this invention pertains to a compound selected from compounds of Formula 1 (including all stereoisomers) and N-oxides and salts thereof.

This invention also relates to a fungicidal composition comprising (a) a compound of the invention (i.e. in a fungicidally effective amount); and (b) at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents.

This invention also relates to a fungicidal composition comprising (a) a compound of the invention; and (b) at least one other fungicide (e.g., at least one other fungicide having a different site of action). This invention further 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, a fungicidally effective amount of a compound of the invention (e.g., as a composition described herein).

This invention also relates to a composition comprising a compound of Formula 1, an

N-oxide, or a salt thereof, and at least one invertebrate pest control compound or agent.

DETAILS OF THE INVENTION

As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having," "contains", "containing," "characterized by" or any other variation thereof, are intended to cover a non-exclusive inclusion, subject to any limitation explicitly indicated. For example, a composition, mixture, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, mixture, process, method, article, or apparatus.

The transitional phrase "consisting of excludes any element, step, or ingredient not specified. If in the claim, such would close the claim to the inclusion of materials other than those recited except for impurities ordinarily associated therewith. When the phrase "consisting of appears in a clause of the body of a claim, rather than immediately following the preamble, it limits only the element set forth in that clause; other elements are not excluded from the claim as a whole.

The transitional phrase "consisting essentially of is used to define a composition, method or apparatus that includes materials, steps, features, components, or elements, in addition to those literally disclosed, provided that these additional materials, steps, features, components, or elements do not materially affect the basic and novel characteristic(s) of the claimed invention. The term "consisting essentially of occupies a middle ground between "comprising" and "consisting of.

Where applicants have defined an invention or a portion thereof with an open-ended term such as "comprising," it should be readily understood that (unless otherwise stated) the description should be interpreted to also describe such an invention using the terms "consisting essentially of or "consisting of."

Further, unless expressly stated to the contrary, "or" refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).

Also, the indefinite articles "a" and "an" preceding an element or component of the invention are intended to be nonrestrictive regarding the number of instances (i.e. occurrences) of the element or component. Therefore "a" or "an" should be read to include one or at least one, and the singular word form of the element or component also includes the plural unless the number is obviously meant to be singular.

As referred to in the present disclosure and claims, "plant" includes members of Kingdom Plantae, particularly seed plants (Spermatopsida), at all life stages, including young plants (e.g., germinating seeds developing into seedlings) and mature, reproductive stages (e.g., plants producing flowers and seeds). Portions of plants include geotropic members typically growing beneath the surface of the growing medium (e.g., soil), such as roots, tubers, bulbs and corms, and also members growing above the growing medium, such as foliage (including stems and leaves), flowers, fruits and seeds.

As referred to herein, the term "seedling", used either alone or in a combination of words means a young plant developing from the embryo of a seed.

As referred to herein, the term "broadlea ' used either alone or in words such as "broadleaf crop" means dicot or dicotyledon, a term used to describe a group of angiosperms characterized by embryos having two cotyledons.

As used herein, the term "alkylating agent" refers to a chemical compound in which a carbon-containing radical is bound through a carbon atom to a leaving group such as halide or sulfonate, which is displaceable by bonding of a nucleophile to said carbon atom. Unless otherwise indicated, the term "alkylating agent" or "alkylating reagent" does not limit the carbon-containing radical to alkyl; the carbon-containing radicals in alkylating agents include the variety of carbon-bound substituent radicals specified, for example, for R².

Generally when a molecular fragment (i.e. radical) is denoted by a series of atom symbols (e.g., C, H, N, O, S) the implicit point or points of attachment will be easily recognized by those skilled in the art. In some instances herein, particularly when alternative points of attachment are possible, the point or points of attachment may be explicitly indicated by a hyphen ("-"). For example, "-SC≡N" indicates that the point of attachment is the sulfur atom (i.e. thiocyanato, not isothiocyanato).

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, /-propyl, or the different butyl, pentyl or hexyl isomers. "Alkenyl" 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. "Alkynyl" includes straight-chain or branched alkynes such as ethynyl, 1-propynyl, 2-propynyl and the different butynyl, pentynyl and hexynyl isomers. "Alkynyl" can also include moieties comprised of multiple triple bonds such as 2,5-hexadiynyl. "Alkylene" denotes a straight-chain or branched alkanediyl. Examples of "alkylene" include CH₂, CH₂CH₂, CH(CH₃), CH₂CH₂CH₂, CH₂CH(CH₃), and the different butylene, pentylene or hexylene isomers. "Alkenylene" denotes a straight-chain or branched alkenediyl containing one olefmic bond. Examples of "alkenylene" include CH=CH, CH₂CH=CH and CH=C(CH₃). "Alkynylene" denotes a straight-chain or branched alkynediyl containing one triple bond. Examples of "alkynylene" include CH₂C≡C, C≡CCH₂, and the different butynylene, pentynylene or hexynylene isomers.

"Alkylamino" includes an NH radical substituted with straight-chain or branched alkyl. Examples of "alkylamino" include CH₃CH₂NH, CH₃CH₂CH₂NH and (CH₃)₂CHNH. Examples of "dialkylamino" include (CH₃)₂N, (CH₃CH₂)₂N and CH₃CH₂(CH₃)N. "Alkylaminoalkyl" denotes alkylamino substitution on alkyl. Examples of "alkylaminoalkyl" include CH₃NHCH₂, CH₃NHCH₂CH₂ and CH₃CH₂NHCH₂. Examples of "dialkylaminoalkyl" include (CH₃)₂NCH₂, CH₃CH₂(CH₃)NCH₂ and (CH₃)₂NCH₂CH₂.

"Alkoxy" includes, for example, methoxy, ethoxy, n-propyloxy, z^'-propyloxy and the different butoxy, pentoxy and hexyloxy isomers. "Alkoxyalkyl" denotes alkoxy substitution on alkyl. Examples of "alkoxyalkyl" include CH₃OCH₂, CH₃OCH₂CH₂, CH₃CH₂OCH₂, CH₃CH₂CH₂CH₂OCH₂ and CH₃CH₂OCH₂CH₂. "Alkenyloxy" includes straight-chain or branched alkenyl attached to and linked through an oxygen atom. Examples of "alkenyloxy" include H₂C=CHCH₂0, (CH₃)₂C=CHCH₂0, CH₃CH=CHCH₂0, CH₃CH=C(CH₃)CH₂0 and CH₂=CHCH₂CH₂0. "Alkynyloxy" includes straight-chain or branched alkynyl attached to and linked through an oxygen atom. Examples of "alkynyloxy" include HC≡CCH₂0, CH₃C≡CCH₂0 and CH₃C≡CCH₂CH₂0. The term "alkylsulfonyloxy" denotes alkylsulfonyl attached to and linked through an oxygen atom. Examples of "alkylsulfonyloxy" include CH₃S(=0)₂0, CH₃CH₂S(=0)₂0, CH₃CH₂CH₂S(=0)₂0 and (CH₃)₂CHS(=0)₂0.

"Alkylthio" includes branched or straight-chain alkylthio moieties such as methylthio, ethylthio, and the different propylthio isomers. "Alkylthioalkyl" denotes alkylthio substitution on alkyl. Examples of "alkylthioalkyl" include CH₃SCH₂, CH₃SCH₂CH₂, CH₃CH₂SCH₂, CH₃CH₂CH₂CH₂SCH₂ and CH₃CH₂SCH₂CH₂. "Alkylsulfmyl" includes both enantiomers of an alkylsulfmyl group. Examples of "alkylsulfmyl" include CH₃S(=0), CH₃CH₂S(=0), CH₃CH₂CH₂S(=0) and (CH₃)₂CHS(=0). Examples of "alkylsulfonyl" include CH₃S(=0)₂, CH₃CH₂S(=0)₂, CH₃CH₂CH₂S(=0)₂ and (CH₃)₂CHS(=0)₂.

The term "cycloalkyl" denotes a saturated carbocyclic ring consisting of between 3 to 8 carbon atoms linked to one another by single bonds. Examples of "cycloalkyl" include cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. The term "cycloalkylalkyl" denotes cycloalkyl substitution on an alkyl group. Examples of "cycloalkylalkyl" include cyclopropylmethyl, cyclopentylethyl, and other cycloalkyl moieties bonded to straight-chain or branched alkyl groups. "Alkylcycloalkyl" denotes alkyl substitution on a cycloalkyl moiety. Examples include 4-methylcyclohexyl and 3-ethylcyclopentyl. The term "cycloalkylcycloalkyl" denotes cycloalkyl substitution on another cycloalkyl ring. Examples of cycloalkylcycloalkyl include cyclopropylcyclopropyl (such as l,l'-bicyclopropyl-l-yl, l,l'-bicyclopropyl-2-yl), cyclohexylcyclopentyl (such as 4-cyclopentylcyclohexyl) and cyclohexylcyclohexyl (such as Ι,Γ-bicyclohexyl-l-yl), and the different cis- and trans- cycloalkylcycloalkyl isomers, (such as (li?,25)-l,l'-bicyclopropyl-2-yl and (1R,2R)-1,1'- bicyclopropyl-2-yl). The term "cycloalkoxy" denotes cycloalkyl attached to and linked through an oxygen atom such as cyclopentyloxy and cyclohexyloxy. "Cycloalkylalkoxy" denotes cycloalkyl substitution on an alkoxy group. Examples of "cycloalkylalkoxy" include cyclopropylmethoxy, cyclopentylethoxy, and other cycloalkyl moieties bonded to straight-chain or branched alkoxy groups. "Cycloalkylcarbonyl" denotes cycloalkyl bonded to a C(=0) group including, for example, cyclopropylcarbonyl and cyclopentylcarbonyl. The term "cycloalkoxycarbonyl" means cycloalkoxy bonded to a C(=0) group, for example, cyclopropyloxycarbonyl and cyclopentyloxycarbonyl. The term "cycloalkylene" denotes a cycloalkanediyl ring. Examples of "cycloalkylene" include cyclopropylene, cyclobutylene, cyclopentylene and cyclohexylene. The term "cycloalkenylene" denotes a cycloalkenediyl ring containing one olefmic bond. Examples of "cycloalkenylene" include cyclopropenylene and cyclopentenylene.

"Cyanoalkyl" denotes an alkyl group substituted with one cyano group. Examples of

"cyanoalkyl" include NCCH₂, NCCH₂CH₂ and CH₃CH(CN)CH₂. "Hydroxyalkyl" denotes an alkyl group substituted with one hydroxy group. Examples of "hydroxyalkyl" include HOCH₂, HOCH₂CH₂ and CH₃CH₂(OH)CH. "Nitroalkyl" denotes an alkyl group substituted with one nitro group. Examples of "nitroalkyl" include N0₂CH₂ and N0₂CH₂CH₂.

"Alkylcarbonyl" denotes a straight-chain or branched alkyl group bonded to a C(=0) moiety. Examples of "alkylcarbonyl" include CH₃C(=0), CH₃CH₂CH₂C(=0) and (CH₃)₂CHC(=0). Examples of "alkoxycarbonyl" include CH₃OC(=0), CH₃CH₂OC(=0), CH₃CH₂CH₂OC(=0), (CH₃)₂CHOC(=0) and the different pentoxy- or hexoxycarbonyl isomers. The term "alkylcarbonyloxy" denotes straight-chain or branched alkyl bonded to a C(=0)0 moiety. Examples of "alkylcarbonyloxy" include CH₃CH₂C(=0)0 and (CH₃)₂CHC(=0)0. "(Alkylthio)carbonyl" denotes a straight-chain or branched alkylthio group bonded to a C(=0) moiety. Examples of "(alkylthio)carbonyl" include CH₃SC(=0), CH₃CH₂CH₂SC(=0) and (CH₃)₂CHSC(=0). "Alkoxy(thiocarbonyl)" denotes a straight-chain or branched alkoxy group bonded to a C(=S) moiety. Examples of "alkoxy(thiocarbonyl)" include CH₃OC(=S), CH₃CH₂CH₂OC(=S) and (CH₃)₂CHOC(=S). The term "alkylcarbonylamino" denotes alkyl bonded to a C(=0)NH moiety. Examples of "alkylcarbonylamino" include CH₃C(=0)NH and CH₃CH₂C(=0)NH.

"Trialkylsilyl" includes 3 branched and/or straight-chain alkyl radicals attached to and linked through a silicon atom, such as trimethylsilyl, triethylsilyl and tert-butyldimethylsilyl.

The term "halogen", either alone or in compound words such as "halomethyl", "haloalkyl", includes fluorine, chlorine, bromine or iodine. 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, CICH2, CF3CH2 and CF₃CC1₂. The terms "haloalkenyl", "haloalkoxy", "haloalkylthio", "haloalkylsulfinyl" "haloalkylsulfonyl", "halocycloalkyl" and the like are defined analogously to the term "haloalkyl". Examples of "haloalkenyl" include Cl2C=CHCH2 and CF₃CH₂=CH. Examples of "haloalkoxy" include CF₃0, CC1₃CH₂0, F₂CHCH₂CH₂0 and CF₃CH₂0. Examples of "haloalkylthio" include CC1₃S, CF₃S, CC1₃CH₂S and C1CH₂CH₂CH₂S. Examples of "haloalkylsulfinyl" include CF₃S(=0), CC1₃S(=0), CF₃CH₂S(=0) and CF₃CF₂S(=0). Examples of "haloalkylsulfonyl" include CF₃S(=0)₂, CC1₃S(=0)₂, CF₃CH₂S(=0)₂ and CF₃CF₂S(=0)₂. Examples of "halocycloalkyl" include chlorocyclopropyl, fluorocyclobutyl and chlorocyclohexyl.

The total number of carbon atoms in a substituent group is indicated by the "C -Cj" prefix where i and j are numbers from 1 to 12. For example, C 1 -C3 alkylsulfonyl designates methylsulfonyl through propylsulfonyl; C2 alkoxyalkyl designates CH₃OCH₂; C₃ alkoxyalkyl designates, for example, CH₃OCH2CH2 or CH₃CH20CH2; 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 CH₃CH2CH20CH2 and CH₃CH₂OCH₂CH₂.

The term "unsubstituted" in connection with a group such as a ring means the group does not have any substituents other than its one or more attachments to the remainder of Formula 1. The term "optionally substituted" means that the number of substituents can be zero. Unless otherwise indicated, optionally substituted groups may be substituted with as many optional substituents as can be accommodated by replacing a hydrogen atom with a non-hydrogen substituent on any available carbon or nitrogen atom. Commonly, the number of optional substituents (when present) range from 1 to 3. As used herein, the term "optionally substituted" is used interchangeably with the phrase "substituted or unsubstituted" or with the term "(un)substituted."

The number of optional substituents may be restricted by an expressed limitation. For example, the phrase "optionally substituted with up to 3 substituents independently selected from R^3a on carbon atom ring members" means that 0, 1, 2 or 3 substituents can be present (if the number of potential connection points allows). Similarly, the phrase "optionally substituted with up to 5 substituents independently selected from R^3a" means that 0, 1, 2, 3, 4 or 5 substituents can be present if the number of available connection points allows.

When a compound is substituted with a substituent bearing a subscript that indicates the number of said substituents can vary (e.g., (R ^a)_p in Table 1 wherein p is 0 to 5), then said substituents are independently selected from the group of defined substituents, unless otherwise indicated. When a variable group is shown to be optionally attached to a position, for example (R^3a)_p in Table 1 wherein p may be 0, then hydrogen may be at the position even if not recited in the definition of the variable group. Unless otherwise indicated, a "ring" or "ring system" as a component of Formula 1 (e.g., Q¹ or Q²) is carbocyclic (e.g., phenyl or naphthalenyl) or heterocyclic (e.g., pyridinyl). The term "ring member" refers to an atom (e.g., C, O, N or S) forming the backbone of a ring. The term "ring system" denotes two or more fused rings (e.g., quinazolinyl).

The term "nonaromatic" includes rings that are fully saturated as well as partially or fully unsaturated, provided that none of the rings are aromatic. The term "aromatic" indicates that each of the ring atoms of a fully unsaturated ring are essentially in the same plane and have a /^-orbital perpendicular to the ring plane, and that (4n + 2) π electrons, where n is a positive integer, are associated with the ring to comply with Huckel's rule.

The terms "carbocyclic ring" or "carbocycle" denote a ring wherein the atoms forming the ring backbone are selected only from carbon. When a fully unsaturated carbocyclic ring satisfies Huckel's rule, then said ring is also called an "aromatic carbocyclic ring". The term "saturated carbocyclic ring" refers to a ring having a backbone consisting of carbon atoms linked to one another by single bonds; unless otherwise specified, the remaining carbon valences are occupied by hydrogen atoms.

The terms "heterocyclic ring", "heterocycle" or "heteroaromatic ring system" denote a ring or ring system in which at least one atom forming the ring backbone is not carbon (e.g., N, O or S). Typically a heterocyclic ring contains no more than 3 N atoms, no more than 2 O atoms and no more than 2 S atoms. Unless otherwise indicated, a heterocyclic ring can be a saturated, partially unsaturated or fully unsaturated ring. When a fully unsaturated heterocyclic ring satisfies Huckel's rule, then said ring is also called a "heteroaromatic ring" or "aromatic heterocyclic ring". Unless otherwise indicated, heterocyclic rings can be attached through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen.

In the context of the present invention when an instance of Q¹ and Q² comprises a phenyl or 6-membered heterocyclic ring (e.g., pyridinyl), the ortho, meta and para positions of each ring are relative to the connection of the ring to the remainder of Formula 1.

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. The compounds of the invention may be present as a mixture of stereoisomers, individual stereoisomers or as an optically active form.

One skilled in the art recognizes that because in the environment and under physiological conditions salts of chemical compounds are in equilibrium with their corresponding nonsalt forms, salts share the biological utility of the nonsalt forms. Thus a wide variety of salts of the compounds of Formula 1 are useful for control of plant diseases caused by fungal plant pathogens (i.e. are agriculturally suitable). The salts of the compounds of Formula 1 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.

Compounds selected from Formula 1, stereoisomers, N-oxides, and salts thereof, typically exist in more than one form, therefore Formula 1 includes all crystalline and noncrystalline forms of the compounds that Formula 1 represents. Non-crystalline forms include embodiments which are solids such as waxes and gums as well as embodiments which are liquids such as solutions and melts. Crystalline forms include embodiments which represent essentially a single crystal type and embodiments which represent a mixture of polymorphs (i.e. different crystalline types). The term "polymorph" refers to a particular crystalline form of a chemical compound that can crystallize in different crystalline forms, these forms having different arrangements and/or conformations of the molecules in the crystal lattice. Although polymorphs can have the same chemical composition, they can also differ in composition due to the presence or absence of co-crystallized water or other molecules, which can be weakly or strongly bound in the lattice. Polymorphs can differ in such chemical, physical and biological properties as crystal shape, density, hardness, color, chemical stability, melting point, hygroscopicity, suspensibility, dissolution rate and biological availability. One skilled in the art will appreciate that a polymorph of a compound represented by Formula 1 can exhibit beneficial effects (e.g., suitability for preparation of useful formulations, improved biological performance) relative to another polymorph or a mixture of polymorphs of the same compound represented by Formula 1. Preparation and isolation of a particular polymorph of a compound represented by Formula 1 can be achieved by methods known to those skilled in the art including, for example, crystallization using selected solvents and temperatures.

Embodiments of the present invention as described in the Summary of the Invention include those described below. In the following Embodiments, Formula 1 includes stereoisomers, N-oxides and salts thereof, and reference to "a compound of Formula 1" includes the definitions of substituents specified in the Summary of the Invention unless further defined in the Embodiments.

Embodiment 1. A compound of Formula 1 wherein Q¹ is a phenyl, pyridinyl,

pyrimidinyl, pyrazinyl or pyridazinyl ring, each ring optionally substituted with up to 3 substituents independently selected from R^3a and R ^b.

Embodiment 2. A compound of Embodiment 1 wherein Q¹ is a phenyl ring optionally substituted with up to 3 substituents independently selected from R^3a and R ^b. Embodiment 3. A compound of Formula 1 or any one of Embodiments 1 through 2 wherein Q¹ is a phenyl ring optionally substituted with up to 2 substituents independently selected from R^3a and substituted with 1 to 2 substituents independently selected from R³^.

Embodiment 4. A compound of Embodiment 3 wherein Q¹ is a phenyl ring optionally substituted with up to 2 substituents independently selected from R^3a and substituted with 1 substituent selected from R ^b.

Embodiment 5. A compound of Embodiment 4 wherein Q¹ is a phenyl ring optionally substituted with up to 1 substituent selected from R ^a and substituted with 1 substituent selected from R ^b.

Embodiment 6. A compound of Formula 1 or any one of Embodiments 1 through 5 wherein Q¹ is a phenyl ring substituted with 1 to 3 substituents independently selected from R^3a and R³^.

Embodiment 7. A compound of Embodiment 6 wherein Q¹ is a phenyl ring substituted with 1 to 2 substituents independently selected from R ^a and 1 substituent selected from R³^.

Embodiment 8. A compound of Embodiment 7 wherein Q¹ is a phenyl ring substituted with 2 substituents independently selected from R ^a and 1 substituent selected from R^3b.

Embodiment 9. A compound of Embodiment 6 wherein Q¹ is a phenyl ring substituted with 1 substituent selected from R ^a and 1 to 2 substituents independently selected from R^3b.

Embodiment 10. A compound of Embodiment 9 wherein Q¹ is a phenyl ring substituted with 1 substituent selected from R ^a and 1 substituent selected from R ^b.

Embodiment 11. A compound of Formula 1 or any one of Embodiments 1 through 10 wherein Q¹ is a phenyl ring substituted with at least 1 substituent selected from R^3a attached at the 2-position (relative to the connection of the Q¹ ring to the remainder of Formula 1).

Embodiment 12. A compound of Formula 1 or any one of Embodiments 1 through 11 wherein Q¹ is a phenyl ring substituted with at least 1 substituent selected from R³^ attached at the 4-position (relative to the connection of the Q¹ ring to the remainder of Formula 1).

Embodiment 13. A compound of Formula 1 or any one of Embodiments 1 through 12 wherein Q¹ is a phenyl ring substituted with at least 1 substituent selected from R³^ attached at the 3-position (relative to the connection of the Q¹ ring to the remainder of Formula 1).

Embodiment 14. A compound of Formula 1 or any one of Embodiments 1 through 13 wherein Q¹ is a phenyl ring substituted at the 2-position with a substituent selected from R^3a and at the 4-position with a substitutent selected from R^3b (relative to the connection of the Q¹ ring to the remainder of Formula 1). Embodiment 15. A compound of Formula 1 or any one of Embodiments 1 through 13 wherein Q¹ is a phenyl ring substituted at the 2- and 6-positions with substituents independently selected from R^3a and at the 4-position with a substitutent selected from R^3b (relative to the connection of the Q¹ ring to the remainder of Formula 1).

Embodiment 16. A compound of Formula 1 or any one of Embodiments 1 through 13 wherein Q¹ is a phenyl ring substituted at the 2-position with a substituent selected from R^3a and at the 4-position with a substituent selected from R^3b; or a phenyl ring substituted at the 2- and 6-positions with substituents independently selected from R^3a and at the 4-position with a substituent selected from R^3b.

Embodiment 17. A compound of Formula 1 or any one of Embodiments 1 through 13 wherein Q¹ is a phenyl ring substituted at the 2- and 6-positions with substituents independently selected from R ^a; or a phenyl ring substituted at the 2-, 4- and 6-positions with substituents independently selected from R ^a.

Embodiment 18. A compound of Formula 1 or any one of Embodiments 1 through 17 wherein Q² is a phenyl, pyridinyl, pyrimidinyl, pyrazinyl or pyridazinyl ring, each ring optionally substituted with up to 3 substituents independently selected from R^3a and R^3b.

Embodiment 19. A compound of Embodiment 18 wherein Q² is a phenyl ring

optionally substituted with up to 3 substituents independently selected from R ^a and R^3b.

Embodiment 20. A compound of Embodiment 19 wherein Q² is a phenyl ring

optionally substituted with up to 2 substituents independently selected from R ^a and R^3b.

Embodiment 21. A compound of Formula 1 or any one of Embodiments 1 through 20 wherein Q² is a phenyl ring substituted with 1 to 3 substituents independently selected from R^3a and R^3b.

Embodiment 22. A compound of Embodiment 21 wherein Q² is a phenyl ring

substituted with 1 to 3 substituents independently selected from R ^a.

Embodiment 23. A compound of Embodiment 22 wherein Q² is a phenyl ring

substituted with 3 substituents independently selected from R ^a.

Embodiment 24. A compound of Embodiment 22 wherein Q² is a phenyl ring

substituted with 2 substituents independently selected from R ^a.

Embodiment 25. A compound of Embodiment 21 wherein Q² is a phenyl ring

substituted with 2 substituents independently selected from R ^a and 1 substituent selected from R^3b. Embodiment 26. A compound of Embodiment 25 wherein Q² is a phenyl ring substituted with 1 substituent selected from R^3a and 1 substituent selected from R3 .

Embodiment 27. A compound of Embodiment 21 wherein Q² is a phenyl ring

substituted with 1 substituent selected from R^3a and 1 to 2 substituents independently selected from R³^.

Embodiment 28. A compound of Formula 1 or any one of Embodiments 1 through 27 wherein Q² is a phenyl ring substituted with at least 1 substituent selected from R^3a attached at the 2-position (relative to the connection of the Q² ring to the remainder of Formula 1).

Embodiment 29. A compound of Formula 1 or any one of Embodiments 1 through 28 wherein Q² is a phenyl ring substituted with at least 1 substituent selected from R³^ attached at the 4-position (relative to the connection of the Q² ring to the remainder of Formula 1).

Embodiment 30. A compound of Formula 1 or any one of Embodiments 1 through 29 wherein Q² is a phenyl ring substituted with at least 1 substituent selected from R³^ attached at the 3-position (relative to the connection of the Q² ring to the remainder of Formula 1).

Embodiment 31. A compound of Formula 1 or any one of Embodiments 1 through 30 wherein Q² is a phenyl ring substituted with at least 2 substituents independently selected from R^3a attached at the 2- and 6-positions (relative to the connection of the Q² ring to the remainder of Formula 1).

Embodiment 32. A compound of Formula 1 or any one of Embodiments 1 through 31 wherein Q² is a phenyl ring substituted at the 2- and 6-positions with substituents independently selected from R^3a (relative to the connection of the Q² ring to the remainder of Formula 1).

Embodiment 33. A compound of Formula 1 or any one of Embodiments 1 through 31 wherein Q² is a phenyl ring substituted at the 2-, 4- and 6-postions with substituents independently selected from R^3a (relative to the connection of the Q² ring to the remainder of Formula 1).

Embodiment 34. A compound of Formula 1 or any one of Embodiments 1 through 32 wherein Q² is a phenyl ring substituted at the 2- and 6-positions with substituents independently selected from R ^a; or a phenyl ring substituted at the 2-, 4- and 6-positions with substituents independently selected from R ^a.

Embodiment 35. A compound of Formula 1 or any one of Embodiments 1 through 31 wherein Q² is a phenyl ring substituted at the 2-position with a substituent selected from R^3a and at the 4-position with a substituent selected from R³^; or a phenyl ring substituted at the 2- and 6-positions with substituents independently selected from R^3a and at the 4-position with a substituent selected from R³b.r Embodiment 36. A compound of Formula 1 or any one of Embodiments 1 through 35 wherein when each Q¹ and Q² is a phenyl ring, then Q¹ is substituted with 1 to 2 substituents independently selected from R^3a and 1 substituent selected from R ^b and Q² is substituted with 2 to 3 substituents independently selected from R ^a. Embodiment 37. A compound of Formula 1 or any one of Embodiments 1 through 36 wherein X is O, S, NR⁴ or CR^5aOR^5b.

Embodiment 38. A compound of Embodiment 37 wherein X is O, NR⁴ or CHOR⁵^. Embodiment 39. A compound of Embodiment 38 wherein X is NR⁴ or CHOR⁵^.

Embodiment 40. A compound of Embodiment 39 wherein X is CHOR⁵^.

Embodiment 41. A compound of Embodiment 39 wherein X is NR⁴.

Embodiment 42. A compound of Formula 1 or any one of Embodiments 1 through 41 wherein when R¹ is taken alone (i.e. not taken together with R^la), then R¹ is H, cyano, halogen, C1-C3 alkyl, C1-C3 haloalkyl, C2-C4 alkenyl, C2-C4 alkynyl, cyclopropyl, C2-C4 alkoxyalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C(=0)OR⁶ or

C(=0)NR⁷R⁸.

Embodiment 43. A compound of Embodiment 42 wherein R¹ is H, cyano, halogen, C1-C3 alkyl, C1-C3 haloalkyl, C2-C4 alkoxyalkyl, C1-C3 alkoxy or C1-C3 haloalkoxy.

Embodiment 44. A compound of Embodiment 43 wherein R¹ is H, cyano, halogen, Ci -C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy or C1-C3 haloalkoxy.

Embodiment 45. A compound of Embodiment 44 wherein R¹ is H, halogen or C1-C3 alkyl.

Embodiment 46. A compound of Embodiment 45 wherein R¹ is H or methyl.

Embodiment 47. A compound of Embodiment 46 wherein R¹ is H.

Embodiment 48. A compound of Formula 1 or any one of Embodiments 1 through 47 wherein R¹ is taken alone.

Embodiment 49. A compound of Formula 1 or any one of Embodiments 1 through 48 wherein R^la is H.

Embodiment 50. A compound of Formula 1 or any one of Embodiments 1 through 49 wherein R^la is taken alone.

Embodiment 51. A compound of Formula 1 or any one of Embodiments 1 through 49 wherein when R^la and R¹ are taken together with the carbon atom to which they are attached to form a ring, then said ring is cyclopropyl (i.e. unsubstituted).

Embodiment 52. A compound of Formula 1 or any one of Embodiments 1 through 47 wherein R^la and R¹ are taken together. Embodiment 53. A compound of Formula 1 or any one of Embodiments 1 through 52 wherein R² is cyano, halogen, Ci -C2 alkyl, halomethyl, cyanomethyl, hydroxymethyl, methoxy or methylthio; or cyclopropyl optionally substituted with up to 2 substituents independently selected from halogen and methyl.

Embodiment 54. A compound of Embodiment 53 wherein R² is Br, CI, I or C 1 -C2 alkyl.

Embodiment 55. A compound of Embodiment 54 wherein R² is Br, CI or methyl.

Embodiment 56. A compound of Embodiment 55 wherein R² is methyl.

Embodiment 57. A compound of Formula 1 or any one of Embodiments 1 through 56 wherein each R^3a is independently cyano, halogen, Ci -C4 alkyl, Ci -C4 haloalkyl, C2-C4 alkenyl, C3-C4 cycloalkyl, C4-C6 cycloalkylalkyl, C4-C6 alkylcycloalkyl, C1-C3 alkylthio, C1-C3 alkylsulfmyl, C1-C3 alkylsulfonyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C3-C7 cycloalkoxy, C1 -C2 alkylsulfonyloxy, C2-C3 alkylcarbonyloxy, C2-C3 alkylcarbonyl, amino, methylamino, C2-C4 dialkylamino, C₂-C₃ alkylcarbonylamino, -CH(=0), -NHCH(=0), -SF₅, -SC≡N,

-C(=S)NR^9aR^9b or -U-V-T.

Embodiment 58. A compound of Embodiment 57 wherein each R^3a is independently cyano, halogen, methyl, halomethyl, cyclopropyl, methylthio, methoxy, methylsulfonyloxy, methylcarbonyloxy, methylcarbonyl, -C(=S)NR^9aR^9b or -U-V-T.

Embodiment 59. A compound of Embodiment 58 wherein each R^3a is independently cyano, halogen, methyl, halomethyl or methoxy.

Embodiment 60. A compound of Embodiment 59 wherein each R^3a is independently cyano, halogen or methoxy.

Embodiment 61. A compound of Embodiment 60 wherein each R^3a is independently cyano, Br, CI, F or methoxy.

Embodiment 62. A compound of Embodiment 61 wherein each R^3a is independently Br, CI or F.

Embodiment 63. A compound of Embodiment 62 wherein each R^3a is F.

Embodiment 64. A compound of Formula 1 or any one of Embodiments 1 through 63 wherein each R^3b is independently C2-C4 haloalkenyl, C5-C8 cycloalkylalkenyl, C5-C8 cycloalkylalkynyl, C4-C6 alkoxy, C2-C6 alkenyloxy, C2-C6

haloalkenyloxy, C3-C6 alkynyloxy, C3-C6 haloalkynyloxy, C4-C8

cycloalkylalkoxy, C3-C6 alkylsulfonyloxy, C3-C6 haloalkylsulfonyloxy, C3-C9 trialkylsilyl, C4-C9 trialkylsilylalkyl, C4-C9 trialkylsilylalkoxy,

-C(=NR^9a)NR^9aOR^9a, -CR^10a=NOR^10b, -CR^10c= NR^9aR^9b or

-ON=CR^{l la}R^{l lb}; or -A(CR^12aR^12b)_nW. Embodiment 65. A compound of Embodiment 64 wherein each R^3b is independently C2-C4 haloalkenyl, C5-C8 cycloalkylalkenyl, C4-C6 alkoxy, C2-Cg alkenyloxy, C2-C6 haloalkenyloxy, C3-C6 alkynyloxy, C3-C6 haloalkynyloxy, C4-C8 cycloalkylalkoxy, C3-C6 alkylsulfonyloxy, C3-C6 haloalkylsulfonyloxy, C3-C9 trialkylsilyl, C4-C9 trialkylsilylalkyl, C4-C9 trialkylsilylalkoxy, -CR¹ O^NOR^{1 ob} or -ON=CR^{l la}R^{l lb}; or -A(CR^12aR^12b)_nW.

Embodiment 66. A compound of Embodiment 65 wherein each R^3b is independently C4-C6 alkoxy, C2-C6 alkenyloxy, C2-C6 haloalkenyloxy, C3-C6 alkynyloxy, C3-C6 haloalkynyloxy, C4-C8 cycloalkylalkoxy, C3-C6 alkylsulfonyloxy, C3-C6 haloalkylsulfonyloxy, C3-C9 trialkylsilyl, C4-C9 trialkylsilylalkyl, C4-C9 trialkylsilylalkoxy, -CR^10a=NOR^10b or -ON=CR^{l la}R^{l lb}; or -A(CR^12aR^12b)_nW.

Embodiment 67. A compound of Embodiment 66 wherein each R^3b is independently C2-C6 alkenyloxy, C2-Cg haloalkenyloxy, C3-C6 alkynyloxy, C3-C6

haloalkynyloxy, C4-C8 cycloalkylalkoxy, C3-C9 trialkylsilyl, C4-C9

trialkylsilylalkyl, C4-C9 trialkylsilylalkoxy, -CR¹ O^NOR^{1 ob} or

-ON=CR^{l la}R^{l lb}; or -A(CR^12aR^12b)_nW.

Embodiment 68. A compound of Embodiment 64 wherein each R^3b is independently C4-C6 alkoxy, C3-C6 alkenyloxy, C3-C6 haloalkenyloxy, C3-C6 alkynyloxy, C3-C6 haloalkynyloxy, C3-C6 alkylsulfonyloxy, C3-C6 haloalkylsulfonyloxy, C₄-C₇ trialkylsilylalkoxy, -CR^10a=NOR⁹ or -ON=CR! ^laR! ^lb; or

-A(CR^12aR^12b)_nW.

Embodiment 69. A compound of Embodiment 68 wherein each R^3b is independently C4-C5 alkoxy, C3-C5 alkenyloxy, C3-C5 haloalkenyloxy, C3-C6 alkynyloxy, C3-C5 alkylsulfonyloxy, C3-C5 haloalkylsulfonyloxy, C4-C5 trialkylsilylalkoxy, -CR^10a=NOR⁹ or -ON=CR! ^laR! ^lb; or -A(CR^12aR^12b)_nW.

Embodiment 70. A compound of Embodiment 64 wherein each R^3b is independently C2-C4 haloalkenyl, C5-C8 cycloalkylalkenyl, C5-C8 cycloalkylalkynyl, C4-C6 alkoxy, C2-C6 alkenyloxy, C2-C6 haloalkenyloxy, C3-C6 alkynyloxy, C3-C6 haloalkynyloxy, C₄-C₈ cycloalkylalkoxy, -C(=NR^9a)NR^9aOR^9a,

-CR^10a=NOR^10b, -CR^10c= NR^9aR^9b or -ON=CR^{l la}R^{l lb}; or

-A(CR^12aR^12b)_nW.

Embodiment 71. A compound of Embodiment 70 wherein each R^3b is independently C2-C6 alkenyloxy, C2-C6 haloalkenyloxy, C3-C6 alkynyloxy, C3-C6

haloalkynyloxy, C₄-C₈ cycloalkylalkoxy, -C(=NR^9a)NR^9aOR^9a,

-CR^10a=NOR^10b or -CR^10c= NR^9aR^9b; or -A(CR^12aR^12b)_nW.

Embodiment 72. A compound of Embodiment 71 wherein each R^3b is independently C2-C4 alkenyloxy, C2-C4 haloalkenyloxy, C3-C5 alkynyloxy, C3-C5 haloalkynyloxy, C₄-C₈ cycloalkylalkoxy, -CR^10a=NOR^10b or -CR^10c=NNR^9aR^9b; or -A(CR^12aR^12b)_nW.

Embodiment 73. A compound of Formula 1 or any one of Embodiments 1 through 72 wherein each R^3b is -A(CR^12aR^12b)_nW.

Embodiment 74. A compound of Formula 1 or any one of Embodiments 1 through 73 wherein each A is O.

Embodiment 75. A compound of Formula 1 or any one of Embodiments 1 through 73 wherein each A is a direct bond.

Embodiment 76. A compound of Formula 1 or any one of Embodiments 1 through 75 wherein each W is independently a 3- to 7-membered heterocyclic ring containing ring members selected from carbon atoms and 1 to 3 heteroatoms independently selected from up to 2 O, up to 2 S and up to 3 N atoms, wherein up to 1 carbon atom ring member is C(=0), the ring optionally substituted with up to 3 substituents independently selected from R¹³ on carbon atom ring members and R¹⁴ on nitrogen atom ring members.

Embodiment 77. A compound of Embodiment 76 wherein each W is independently a 3- to 7-membered heterocyclic ring containing ring members selected from carbon atoms and 1 to 2 heteroatoms independently selected from up to 2 O, up to 2 S and up to 2 N atoms, wherein up to 1 carbon atom ring member is C(=0), the ring optionally substituted with up to 3 substituents independently selected from

R¹³ on carbon atom ring members and R¹⁴ on nitrogen atom ring members. Embodiment 78. A compound of Embodiment 76 wherein each W is independently a 3- to 6-membered heterocyclic ring containing ring members selected from carbon atoms and 1 to 3 heteroatoms independently selected from up to 2 O, up to 2 S and up to 3 N atoms, the ring optionally substituted with up to 3 substituents independently selected from R¹³ on carbon atom ring members and R¹ on nitrogen atom ring members.

Embodiment 79. A compound of Embodiment 78 wherein each W is independently a 3- to 5-membered heterocyclic ring containing ring members selected from carbon atoms and 1 to 2 heteroatoms independently selected from up to 2 O and up to 2

N atoms, the ring optionally substituted with up to 2 substituents independently selected from R¹³ on carbon atom ring members and R¹ on nitrogen atom ring members.

Embodiment 80. A compound of Embodiment 79 wherein each W is independently a 3- to 5-membered heterocyclic ring containing ring members selected from carbon atoms and 1 to 2 heteroatoms independently selected from up to 2 O and up to 2 N atoms. Embodiment 81. A compound of Formula 1 or any one of Embodiments 1 through 80 wherein each W is independently selected from W-1 through W-52 depicted in Exhibit 1;

Exhibit 1

W-1 W-2 -3 -4

W-5 W-6 W-7 W-8

-9 -10 -l l W-12

W-13 W-14 W-15 W-16

W-17 W-18 W-19 W-20

W-21 W-22 W-23 W-24

W-49 W-50 W-51 W-52 wherein the bond shown projecting to the left is bonded to the remainder of the

Formula 1; R^{1 a} is selected from H and R¹⁴; and each x is independently 0, 1 or 2.

Embodiment 82. A compound of Embodiment 81 wherein each W is independently selected from W-l through W-5, W-8, W-9 and W-12 through W-23.

Embodiment 83. A compound of Embodiment 82 wherein each W is independently selected from W-l, W-2, W-3, W-4, W-5, W-8, W-9, W-12, W-13, W-16, W-17,

W-l 9 and W-20.

Embodiment 84. A compound of Embodiment 83 wherein each W is independently selected from W-l, W-2, W-3, W-5, W-12, W-13 and W-20.

Embodiment 85. A compound of any one of Embodiments 81 through 84 wherein each x is independently 0 or 1.

Embodiment 86. A compound of Embodiment 85 wherein each x is 0.

Embodiment 87. A compound of Formula 1 or any one of Embodiments 1 through 86 wherein R⁴ is H, amino, C2-C3 alkenyl, C3-C4 alkynyl, cyclopropyl, -CH(=0),

-S(=0)₂OM, -S(=0)_mR¹⁵, -(C=Z)R¹⁶ or OR¹⁷; or C_rC₃ alkyl or C_rC₃ haloalkyl, each optionally substituted with up to 2 substituents independently selected from R¹⁸.

Embodiment 88. A compound of Embodiment 87 wherein R⁴ is H, cyclopropyl,

-CH(=0), -S(=0)₂OM, -S(=0)_mR¹⁵, -(C=Z)R¹⁶, OR¹⁷, C_rC₃ alkyl or C_rC₃ haloalkyl.

Embodiment 89. A compound of Embodiment 88 wherein R⁴ is H, -CH(=0),

-S(=0)_mR¹⁵, -(C=Z)R¹⁶, OR¹⁷, C_rC₃ alkyl or C_rC₃ haloalkyl.

Embodiment 90. A compound of Embodiment 89 wherein R⁴ is H, -CH(=0), OR¹⁷, C_rC₃ alkyl or C_rC₃ haloalkyl.

Embodiment 91. A compound of Embodiment 90 wherein R⁴ is H, -CH(=0) or

methoxy.

Embodiment 92. A compound of Embodiment 91 wherein R⁴ is H.

Embodiment 93. A compound of Formula 1 or any one of Embodiments 1 through 92 wherein R^5a is H or methyl.

Embodiment 94. A compound of Embodiment 90 wherein R^5a is H.

Embodiment 95. A compound of Formula 1 or any one of Embodiments 1 through 94 wherein R^5b is H, -CH(=0), C_rC₃ alkyl, C_rC₂ haloalkyl, C₂-C₃ alkoxyalkyl,

C₂-C4 cyanoalkyl, C₂-C4 alkylcarbonyl, C₂-C4 alkoxycarbonyl, C₂-C4

(alkylthio)carbonyl or C₂-C4 alkoxy(thiocarbonyl).

Embodiment 96. A compound of Embodiment 95 wherein R^5b is H, -CH(=0), C^-C₃ alkyl, C_j-C₂ haloalkyl, C₂-C₃ alkoxyalkyl, C₂-C4 cyanoalkyl, C₂-C4

alkylcarbonyl or C₂-C4 alkoxycarbonyl. Embodiment 97. A compound of Embodiment 96 wherein R⁵^ is H, -CH(=0), methyl, halomethyl, cyanomethyl, methylcarbonyl or methoxycarbonyl.

Embodiment 98. A compound of Embodiment 97 wherein R⁵^ is H.

Embodiment 99. A compound of Formula 1 or any one of Embodiments 1 through 98 wherein R⁶ is H or C^-C^ alkyl.

Embodiment 100. A compound of Embodiment 99 wherein R⁶ is H or Ci -C2 alkyl.

Embodiment 101. A compound of Embodiment 100 wherein R⁶ is H or methyl.

Embodiment 102. A compound of Embodiment 101 wherein R⁶ is H.

Embodiment 103. A compound of Formula 1 or any one of Embodiments 1 through 102 wherein when R⁷ is taken alone (i.e. not taken together with R⁸ to form a ring), then R⁷ is H or C_rC₆ alkyl.

Embodiment 104. A compound of Embodiment 103 wherein R⁷ is H.

Embodiment 105. A compound of Formula 1 or any one of Embodiments 1 through 104 wherein R⁷ is taken alone.

Embodiment 106. A compound of Formula 1 or any one of Embodiments 1 through 105 wherein when R⁸ is taken alone (i.e. not taken together with R⁷ to form a ring), then R⁸ is H, C^-C^ alkyl, C^-C^ haloalkyl or Cz Cg alkylcycloalkyl.

Embodiment 107. A compound of Embodiment 106 wherein R⁸ is H or C^-C^ alkyl.

Embodiment 108. A compound of Embodiment 107 wherein R⁸ is H.

Embodiment 109. A compound of Formula 1 or any one of Embodiments 1 through 108 wherein R⁸ is taken alone.

Embodiment 110. A compound of Formula 1 or any one Embodiments 1 through 109 wherein when R⁷ and R⁸ are taken together with the nitrogen atom to which they are attached to form a 4- to 7-membered nonaromatic heterocyclic ring, then said ring contains ring members, in addition to the connecting nitrogen atom, selected from carbon atoms and up to 1 ring member selected from O and NR¹⁹.

Embodiment 111. A compound of Embodiment 110 wherein R⁷ and R⁸ are taken

together with the nitrogen atom to which they are attached to form a 6-membered nonaromatic heterocyclic, containing ring members, in addition to the connecting nitrogen atom, selected from carbon atoms and up to 1 ring member selected from O and NR¹⁹.

Embodiment 112. A compound of Embodiment 111 wherein R⁷ and R⁸ are taken

together with the nitrogen atom to which they are connected to form a piperidinyl, piperazinyl or morpholinyl ring.

Embodiment 113. A compound of Formula 1 or any one of Embodiments 1 through 112 wherein each R^10a is independently H, methyl or halomethyl.

Embodiment 113a. A compound of Formula 1 or any one of Embodiments 1 through

112 wherein each R^10a is independently H or methyl. Embodiment 114. A compound of Embodiment 113a wherein each R^10a is H.

Embodiment 115. A compound of Formula 1 or any one of Embodiments 1 through 114 wherein each R¹⁰^ and R^10c is independently H, C1-C₃ alkyl, C1-C₃ haloalkyl,

C₃-C4 cycloalkyl or C₃-C4 halocycloalkyl.

Embodiment 116. A compound of Embodiment 115 wherein each R¹⁰^ and R^10c is independently H, methyl, halomethyl or cyclopropyl.

Embodiment 116a. A compound of Embodiment 116 wherein each R¹⁰^ and R^10c is independently H or methyl.

Embodiment 117. A compound of Formula 1 or any one of Embodiments 1 through 116a wherein each R^12a is independently H, cyano or methyl.

Embodiment 118. A compound of Embodiment 117 wherein each R^12a is

independently H or methyl.

Embodiment 119. A compound of Embodiment 118 wherein each R^12a is H.

Embodiment 120. A compound of Formula 1 or any one of Embodiments 1 through 119 wherein each R¹²^ is independently H or methyl.

Embodiment 121. A compound of Embodiment 120 wherein each R¹²^ is H.

Embodiment 122. A compound of Formula 1 or any one of Embodiments 1 through 121 wherein each R¹³ is independently halogen, cyano, methyl, halomethyl, methoxy or halomethoxy.

Embodiment 123. A compound of Embodiment 122 wherein each R¹³ is independently halogen, methyl, halomethyl or methoxy.

Embodiment 123a. A compound of Embodiment 123 wherein each R¹³ is methyl. Embodiment 124. A compound of Formula 1 or any one of Embodiments 1 through 123a wherein each R¹⁴ is independently methyl or methoxy.

Embodiment 124a. A compound of Embodiment 124a wherein each R¹⁴ is methyl.

Embodiment 125. A compound of Formula 1 or any one of Embodiments 1 through

124a wherein R¹⁵ is methyl or halomethyl.

Embodiment 126. A compound of Formula 1 or any one of Embodiments 1 through 125 wherein R¹⁶ is C^-C^ alkyl, C^-C^ alkoxy or C^-C^ alkylthio.

Embodiment 127. A compound of Embodiment 126 wherein R¹⁶ is methyl, ethyl, methoxy, ethoxy, methylthio or ethylthio.

Embodiment 128. A compound of Embodiment 127 wherein R¹⁶ is methyl, methoxy or methylthio.

Embodiment 129. A compound of Formula 1 or any one of Embodiments 1 through 128 wherein R¹⁷ is H, -CH(=0), cyclopropyl, -S(=0)₂OM or -(C=Z)R²⁰; or C_rC₃ alkyl or C1-C₃ haloalkyl, each optionally substituted with up to 2 substituents independently selected from R²¹. Embodiment 130. A compound of Formula 1 or any one of Embodiments 1 through 129 wherein each R¹⁸ and R²¹ is independently cyano, C₃-C6 cycloalkyl or C1-C₃ alkoxy.

Embodiment 131. A compound of Embodiment 130 wherein each R¹⁸ and R²¹ is

independently cyano, cyclopropyl or methoxy.

Embodiment 132. A compound of Embodiment 131 wherein each R¹⁸ and R²¹ is

independently cyclopropyl or methoxy.

Embodiment 133. A compound of Formula 1 or any one of Embodiments 1 through 132 wherein R¹⁹ is H or CH₃.

Embodiment 134. A compound of Embodiment 133 wherein R¹⁹ is CH₃.

Embodiment 135. A compound of Formula 1 or any one of Embodiments 1 through 134 wherein R²⁰ is C^-C^ alkyl, C^-C^ alkoxy or C^-C^ alkylthio.

Embodiment 136. A compound of Embodiment 135 wherein R²⁰ is methyl, ethyl, methoxy, ethoxy, methylthio or ethylthio.

Embodiment 137. A compound of Embodiment 136 wherein R²⁰ is methyl, methoxy or methylthio.

Embodiment 138. A compound of Formula 1 or any one of Embodiments 1 through 137 wherein each U is independently O or NR²².

Embodiment 139. A compound of Embodiment 138 wherein each U is independently O or NH.

Embodiment 140. A compound of Formula 1 or any one of Embodiments 1 through 139 wherein each V is C2-C4 alkylene.

Embodiment 141. A compound of Formula 1 or any one of Embodiments 1 through 140 wherein each T is independently NR^23aR²³^ or OR²⁴.

Embodiment 142. A compound of Formula 1 or any one of Embodiments 1 through 141 wherein each R^23a and R²³^ is independently H, C^-C^ alkyl or C^-C^ haloalkyl. Embodiment 143. A compound of Embodiment 142 wherein each R^23a and R²³^ is independently H, methyl or halomethyl.

Embodiment 144. A compound of Formula 1 or any one of Embodiments 1 through 143 wherein each R²⁴ is independently H, C^-C^ alkyl or C^-C^ haloalkyl.

Embodiment 145. A compound of Embodiment 144 wherein each R²⁴ is methyl.

Embodiment 146. A compound of Formula 1 or any one of Embodiments 1 through 145 wherein Z is O.

Embodiment 147. A compound of Formula 1 or any one of Embodiments 1 through 146 wherein M is K or Na.

Embodiment 148. A compound of Formula 1 or any one of Embodiments 1 through 147 wherein m is 0. Embodiment 149. A compound of Formula 1 or any one of Embodiments 1 through 148 wherein each n is independently 1, 2 or 3.

Embodiment 150. A compound of Formula 1 or any one of Embodiments 1 through 148 wherein each n is independently 0, 1 or 2.

Embodiment 151. A compound of Embodiment 150 wherein each n is independently 0 or 1.

Embodiment 152. A compound of Embodiment 150 wherein each n is independently 1 or 2.

Embodiment 153. A compound of Embodiment 152 wherein each n is 1.

Embodiments of this invention, including Embodiments 1-153 above as well as any other embodiments described herein, can be combined in any manner, and the descriptions of variables in the embodiments pertain not only to the compounds of Formula 1 but also to the starting compounds and intermediate compounds useful for preparing the compounds of Formula 1 unless further defined in the Embodiments. In addition, embodiments of this invention, including Embodiments 1-153 above as well as any other embodiments described herein, and any combination thereof, pertain to the compositions and methods of the present invention. Combinations of Embodiments 1-153 are illustrated by:

Embodiment A. A compound of Formula 1 wherein

Q¹ is a phenyl, pyridinyl, pyrimidinyl, pyrazinyl or pyridazinyl ring, each ring optionally substituted with up to 3 substituents independently selected from R^3a and R^3b;

Q² is a phenyl, pyridinyl, pyrimidinyl, pyrazinyl or pyridazinyl ring, each ring optionally substituted with up to 3 substituents independently selected from R^3a and R^3b;

X is O, S, NR⁴ or CR^5aOR^5b;

R¹ is H, cyano, halogen, C1-C3 alkyl, C1-C3 haloalkyl, C2-C4 alkenyl, C2-C4 alkynyl, cyclopropyl, C2-C4 alkoxyalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C(=0)OR⁶ or C(=0)NR⁷R⁸;

R^la is H;

R² is Br, Cl, I or C_rC₂ alkyl;

each R ^a is independently cyano, halogen, -C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl, C3-C4 cycloalkyl, C4-C6 cycloalkylalkyl, C4-C6 alkylcycloalkyl, C1-C3 alkylthio, C1-C3 alkylsulfinyl, C1-C3

alkylsulfonyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C3-C7 cycloalkoxy, C1-C2 alkylsulfonyloxy, C2-C3 alkylcarbonyloxy, C2-C3 alkylcarbonyl, amino, methylamino, C2-C4 dialkylamino, C2-C4 alkylcarbonylamino, -CH(=0), -NHCH(=0), -SF₅, -SC≡N, -C(=S)NR^9aR^9b or -U-V-T; each R^3b is independently C2-C4 haloalkenyl, C5-C8 cycloalkylalkenyl, C5-C8 cycloalkylalkynyl, C4-C6 alkoxy, C2-C6 alkenyloxy, C2-C6 haloalkenyloxy, C3-C6 alkynyloxy, C3-C6 haloalkynyloxy, C4-C8 cycloalkylalkoxy, C3-C6 alkylsulfonyloxy, C3-C6 haloalkylsulfonyloxy, C3-C9 trialkylsilyl, C4-C9 trialkylsilylalkyl, C4-C9 trialkylsilylalkoxy, -C(=NR^9a)NR^9aOR^9a, -CR^10a=NOR^10b, -CR^10c=NNR^9aR^9b or -ON=CR^{l la}R^{l lb}; or -A(CR^12aR^12b)_nW;

each W is independently a 3- to 6-membered heterocyclic ring containing ring members selected from carbon atoms and 1 to 3 heteroatoms independently selected from up to 2 O, up to 2 S and up to 3 N atoms, the ring optionally substituted with up to 3 substituents independently selected from R¹³ on carbon atom ring members and R¹⁴ on nitrogen atom ring members;

R⁴ is H, cyclopropyl, -CH(=0), -S(=0)₂OM, -S(=0)_mR¹⁵, -(C=Z)R¹⁶, OR¹⁷, C1-C3 alkyl or C1-C3 haloalkyl;

R^5a is H or methyl;

R^5b is H, -CH(=0), C_rC₃ alkyl, C_rC₂ haloalkyl, C₂-C₃ alkoxyalkyl, C₂-C₄ cyanoalkyl, C2-C4 alkylcarbonyl or C2-C4 alkoxycarbonyl;

R⁶ is H or methyl;

R⁷ is H or C_rC₆ alkyl;

R⁸ is H, -Q alkyl, -Cg haloalkyl or C₄-C₈ alkylcycloalkyl;

each R^10a is independently H, methyl or halomethyl;

each R^10b and R^10c is independently H, C_rC₃ alkyl, C_rC₃ haloalkyl, C3-C4 cycloalkyl or C3-C4 halocycloalkyl;

each R^12a is independently H, cyano or methyl;

each R^12b is independently H or methyl;

each R¹³ is independently halogen, methyl, halomethyl or methoxy;

each R¹⁴ is independently methyl or methoxy;

R¹⁵ is methyl or halomethyl;

R¹⁶ is methyl, ethyl, methoxy, ethoxy, methylthio or ethylthio;

R¹⁷ is H, -CH(=0), cyclopropyl, -S(=0)₂OM or -(C=Z)R²⁰; or C_rC₃ alkyl or

C1-C3 haloalkyl, each optionally substituted with up to 2 substituents independently selected from R²¹;

R²⁰ is methyl, methoxy or methylthio;

each U is independently O or NR²²;

each V is independently C2-C4 alkylene;

each T is independently NR^23aR^23b or OR²⁴;

each R^23a and R^23b is independently H, C^-C^ alkyl or C^-C^ haloalkyl; each R²⁴ is independently H, C^-C^ alkyl or C^-C^ haloalkyl; and

Z is O.

Embodiment B. A compound of Embodiment A wherein

Q¹ is a phenyl ring optionally substituted with up to 3 substituents independently selected from R^3a and from R^3b;

Q² is a phenyl ring optionally substituted with up to 3 substituents independently selected from R^3a and R^3b;

X is O, NR⁴ or CHOR^5b;

R¹ is H, cyano, halogen, C1-C3 alkyl, C1-C3 haloalkyl, C2-C4 alkoxyalkyl, Ci -C3 alkoxy or C1-C3 haloalkoxy;

each R ^a is independently cyano, halogen, methyl, halomethyl, cyclopropyl, methylthio, methoxy, methylsulfonyloxy, methylcarbonyloxy, methylcarbonyl, -C(=S)NR^9aR^9b or -U-V-T;

each R^3b is independently C2-C4 haloalkenyl, C5-C8 cycloalkylalkenyl, C5-C8 cycloalkylalkynyl, C4-C6 alkoxy, C2-C6 alkenyloxy, C2-C6 haloalkenyloxy, C3-C6 alkynyloxy, C3-C6 haloalkynyloxy, C4-C8 cycloalkylalkoxy, -C(=NR^9a)NR^9aOR^9a, -CR^10a=NOR^10b,

-CR^10c=NNR^9aR^9b or -ON=CR^{l la}R^{l lb}; or -A(CR^12aR^12b)_nW each W is independently selected from W-l through E-52 (as depicted in Exhibit 1) wherein the bond shown projecting to the left is bonded to the remainder of the Formula 1; R^{1 a} is selected from H and R¹⁴; and each x is independently 0, 1 or 2;

R⁴ is H, -CH(=0) or methoxy;

R^5b is H, -CH(=0), methyl, halomethyl, cyanomethyl, methylcarbonyl or methoxycarbonyl;

each R^12a is independently H or methyl; and

each U is independently O or NH.

Embodiment C. A compound of Embodiment B wherein

X is NR⁴ or CHOR^5b;

R¹ is H, halogen or C1-C3 alkyl;

R² is Br, CI or methyl;

each R^3a is independently cyano, halogen or methoxy;

each R ^b is independently C2-Cg alkenyloxy, C2-Cg haloalkenyloxy, C3-C6 alkynyloxy, C3-C6 haloalkynyloxy, C4-C8 cycloalkylalkoxy,

-C(=NR^9a)NR^9aOR^9a, -CR^10a=NOR^10b or -CR^10c= NR^9aR^9b; or -A(CR^12aR^12b)_nW

R⁴ is H;

R^5a is H; R^5b is H;

each R^10a is H;

each R^10b and R^10c is independently H, methyl, halomethyl or cyclopropyl; each R^12a is H; and

each R^12b is H.

Embodiment D. A compound of Embodiment C wherein

Q¹ is a phenyl ring optionally substituted with up to 2 substituents independently selected from R^3a and substituted with 1 substituent selected from R ^b;

Q² is a phenyl ring substituted with 1 to 3 substituents independently selected from R^3a;

R¹ is H;

R² is methyl; and

each R^3a is independently cyano, Br, CI, F or methoxy.

Embodiment E. A compound of Embodiment D wherein

Q¹ is a phenyl ring substituted with at least 1 substituent selected from R ^a attached at the 2-position;

Q² is a phenyl ring substituted with at least 1 substituent selected from R ^a attached at the 2-position; and

each R^3a is independently Br, CI or F.

Embodiments of the present invention also include:

Embodiment Al . A compound of Formula 1 wherein

Q¹ is a phenyl ring substituted at the 2-position with a substituent selected from R^3a and at the 4-position with a substituent selected from R^3b; or a phenyl ring substituted at the 2- and 6-positions with substituents independently selected from R^3a and at the 4-position with a substituent selected from R ^b;

Q² is a phenyl ring substituted at the 2- and 6-positions with substituents independently selected from R ^a; or a phenyl ring substituted at the 2-, 4- and 6-positions with substituents independently selected from R ^a;

X is NR⁴;

R¹ is H;

R^la is H;

R² is methyl;

each R ^a is independently cyano, Br, CI or F;

each R^3b is independently C2-C4 haloalkenyl, C5-C8 cycloalkylalkenyl, C5-C8 cycloalkylalkynyl, C4-C6 alkoxy, C2-C6 alkenyloxy, C2-C6 haloalkenyloxy, C3-C6 alkynyloxy, C3-C6 haloalkynyloxy, Cz Cg cycloalkylalkoxy, -C(=NR^9a)NR^9aOR^9a, -CR^10a=NOR^10b,

-CR^10c=NNR^9aR^9b or -ON=CR^{l la}R^{l lb}; or -A(CR^12aR^12b)_nW;

each A is independently O or a direct bond;

each W is independently selected from W-1 through E-52 (as depicted in Exhibit 1) wherein the bond shown projecting to the left is bonded to the remainder of the Formula 1; R^{1 a} is selected from H and R¹⁴; and each x is independently 0, 1 or 2;

R⁴ is H;

each R^9a and R^9b is independently H or Ci -C4 alkyl;

each R^10a is independently H, methyl or halomethyl;

each R^{l la} and R^{l lb} is independently H, -C3 alkyl or C1-C3 haloalkyl; each R^12a is independently H, cyano or methyl;

each R^12b is independently H or methyl;

each R¹³ is independently halogen, methyl, halomethyl or methoxy; each R¹⁴ is independently methyl or methoxy; and

n is 0, 1, 2 or 3.

Embodiment B 1. A compound of Embodiment Al wherein

each R^3b is independently C2-Cg alkenyloxy, C2-Cg haloalkenyloxy, C3-C6 alkynyloxy, C3-C6 haloalkynyloxy, C4-C8 cycloalkylalkoxy,

__CR10a_=NORl0b _or -CR¹⁰c=NNR^9aR^9b; or -A(CR^12aR^12b)_nW;

each W is independently selected from W-1 through W-5, W-8, W-9 and W-12 through W-23;

each R^9a and R^9b is independently H or methyl

each R^10a is independently H or methyl;

each R^10b and R^10c is independently H or methyl;

each R^{1 la} and R^{1 lb} is independently H or methyl;

each R^12a is independently H;

each R^12b is independently H;

each R¹³ is independently halogen, methyl or halomethyl; and

each R¹ is methyl.

Embodiment CI . A compound of Formula 1 wherein

Q¹ is a phenyl ring substituted at the 2- and 6-positions with substituents independently selected from R^3a; or a phenyl ring substituted at the 2-,

4- and 6-positions with substituents independently selected from R^3a; Q² is a phenyl ring substituted at the 2-position with a substituent selected from R^3a and at the 4-position with a substituent selected from R^3b; or a phenyl ring substituted at the 2- and 6-positions with substituents independently selected from R^3a and at the 4-position with a substituent selected from R ^b;

X is NR⁴;

R¹ is H;

R^la is H;

R² is methyl;

each R^3a is independently cyano, Br, CI or F;

-CR^10c=NNR^9aR^9b or -ON=CR^{l la}R^{l lb}; or -A(CR^12aR^12b)_nW;

each A is independently O or a direct bond;

R⁴ is H;

each R^9a and R^9b is independently H or Ci -C4 alkyl;

each R^10a is independently H, methyl or halomethyl;

each R^{l la} and R^{l lb} is independently H, C1-C3 alkyl or C1-C3 haloalkyl; each R^12a is independently H, cyano or methyl;

each R^12b is independently H or methyl;

n is 0, 1, 2 or 3.

Embodiment D 1. A compound of Embodiment C 1 wherein

__CR10a_=NORl0b _or -CR¹⁰c=NNR^9aR^9b; or -A(CR^12aR^12b)_nW;

each R^9a and R^9b is independently H or methyl

each R^10a is independently H or methyl;

each R^10b and R^10c is independently H or methyl; each R^{1 la} and R¹ ^ is independently H or methyl;

each R^12a is independently H;

each R¹²^ is independently H;

each R¹³ is independently halogen, methyl or halomethyl; and

each R¹ is methyl.

Embodiments of the present invention additionally include:

Embodiment A2. A compound of Formula 1 wherein

Q¹ is a phenyl ring or a naphthalenyl ring system, each ring or ring system optionally substituted with up to 5 substituents independently selected from R^3a and R³^; or a 5- to 6-membered fully unsaturated heterocyclic ring or an 8- to 10-membered heteroaromatic bicyclic ring system, each ring or ring system containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, wherein up to 3 carbon ring members are independently selected from C(=0) and C(=S), and the sulfur atom ring members are independently selected from S(=0)_u(=NR²⁷)_v, each ring or ring system optionally substituted with up to 5 substituents independently selected from R^3a and R³^ on carbon atom ring members and selected from cyano, C1-C3 alkyl, C2-C3 alkenyl, C2-C3 alkynyl, C3-C6 cycloalkyl, C2-C3 alkoxyalkyl, C1-C3 alkoxy, C2-C3

alkylcarbonyl, C2-C3 alkoxycarbonyl, C2-C3 alkylaminoalkyl and

C3-C4 dialkylaminoalkyl on nitrogen atom ring members;

Q² is a phenyl ring or a naphthalenyl ring system, each ring or ring system optionally substituted with up to 5 substituents independently selected from R^3a and R³^; or a 5- to 6-membered fully unsaturated heterocyclic ring or an 8- to 10-membered heteroaromatic bicyclic ring system, each ring or ring system containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, wherein up to 3 carbon ring members are independently selected from C(=0) and C(=S), and the sulfur atom ring members are independently selected from S(=0)_u(=NR²⁷)_v, each ring or ring system optionally substituted with up to 5 substituents independently selected from R^3a and R³^ on carbon atom ring members and selected from cyano, C1-C3 alkyl, C2-C3 alkenyl, C2-C3 alkynyl, C3-C6 cycloalkyl, C2-C3 alkoxyalkyl, C1-C3 alkoxy, C2-C3

alkylcarbonyl, C2-C3 alkoxycarbonyl, C2-C3 alkylaminoalkyl and

C3-C4 dialkylaminoalkyl on nitrogen atom ring members;

X is O, S(=0)_m, NR⁴ or CR^5aOR^5b; R¹ is H, cyano, halogen, C^-Cg alkyl, C^-Cg haloalkyl, C2-Cg alkenyl, C2-Cg alkynyl, C3-C6 cycloalkyl, C2-C6 alkoxyalkyl, C^-C^ alkoxy, C^-C^ haloalkoxy, C(=0)OR⁶ or C(=0)NR⁷R⁸;

R^la is H; or

R^{l a} and R¹ are taken together with the carbon atom to which they are attached to form a cyclopropyl ring optionally substituted with up to 2

substituents independently selected from halogen and methyl;

R² is H, cyano, halogen, C1-C3 alkyl, C2-C3 alkenyl, C2-C3 alkynyl, C1-C3 haloalkyl, C2-C3 haloalkenyl, C2-C3 cyanoalkyl, C1-C3 hydroxyalkyl, C1-C3 alkoxy or C1-C3 alkylthio; or cyclopropyl optionally substituted with up to 2 substituents independently selected from halogen and methyl;

each R^3a is independently cyano, halogen, hydroxy, nitro, Ci -C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1 -C4 haloalkyl, C3-C4 cycloalkyl, C3-C7 halocycloalkyl, C4-C6 cycloalkylalkyl, C4-C6 alkylcycloalkyl, C1-C3 alkylthio, C 1 -C3 haloalkylthio, C1 -C3 alkylsulfinyl, C1 -C3

haloalkylsulfinyl, C 1 -C3 alkylsulfonyl, C1 -C3 haloalkylsulfonyl, C 1 -C3 alkoxy, C 1 -C3 haloalkoxy, C3-C7 cycloalkoxy, C1 -C2 alkylsulfonyloxy, C 1 -C2 haloalkylsulfonyloxy, C2-C3 alkylcarbonyloxy, C2-C3 alkylcarbonyl, amino, methylamino, C2-C4 dialkylamino, C2-C3 alkylcarbonylamino, -CH(=0), -NHCH(=0), -SF₅, -SC≡N,

-C(=S)NR^9aR^9b or -U-V-T;

each R^3b is independently C5-C8 alkyl, C5-C8 haloalkyl, C5-C8 alkenyl,

C5-C8 alkynyl, C2-Cg haloalkenyl, C2-Cg haloalkynyl, Ci -Cg nitroalkyl, C2-Cg nitroalkenyl, C5-Cg cycloalkyl, C₇-Cg alkylcycloalkyl, C₇-Cg cycloalkylalkyl, C5-C12 cycloalkylalkenyl, C5-C12 cycloalkylalkynyl, C6^_Ci2 cycloalkylcycloalkyl, C4-Cg alkylthio, C4-Cg haloalkythio, C4-Cg alkylsulfinyl, C4-Cg haloalkylsulfinyl, C4-Cg alkylsulfonyl, C4-Cg haloalkylsulfonyl, C4-Cg alkoxy, C5-Cg haloalkoxy, C2-Cg alkenyloxy, C2-Cg haloalkenyloxy, C3-Cg alkynyloxy, C3-Cg haloalkynyloxy, Cg-C^ cycloalkoxy, C3-C12 halocycloalkoxy, C4-C12 cycloalkylalkoxy, C5-C12 cycloalkylalkenyloxy, C5-C12

cycloalkylalkynyloxy, C3-Cg alkylsulfonyloxy, C3-Cg

haloalkylsulfonyloxy, C4-Cg alkylcarbonyloxy, C4-Cg alkylcarbonyl, C2-Cg alkylamino, C4-Cg alkylcarbonylamino, C3-C12 trialkylsilyl, C₄-C₁₂ trialkylsilylalkyl, C₄-C₁₂ trialkylsilylalkoxy, -CR^10a=NOR^10b, -CR^10c= NR^9aR^9b, -NR^9aN=CR^{l l a}R^{l lb} or -ON=CR^{l l a}R^{l lb}; or each R^3b is independently -A(CR^12aR^12b)_nW; each A is independently O or a direct bond;

each W is independently a 3- to 7-membered heterocyclic ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, wherein up to 3 carbon atom ring members are independently selected from C(=0) and C(=S), the ring optionally substituted with up to 3 substituents independently selected from R¹³ on carbon atom ring members and R¹⁴ on nitrogen atom ring members;

R⁴ is H, amino, C₂-Cg alkenyl, C3-C6 alkynyl, C3-C6 cycloalkyl, -CH(=0), -S(=0)₂OM, -S(=0)_mR¹⁵, -(C=Z)R¹⁶ or OR¹⁷; or C_rC₆ alkyl or C_rC₆ haloalkyl, each optionally substituted with up to 2 substituents independently selected from R¹⁸;

R^5a is H or C_rC₆ alkyl;

R^5b is H, -CH(=0), C_rC₆ alkyl, C₂-C₆ alkenyl, C₃-C₆ alkynyl, C_rC₆

haloalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C₂-Cg alkoxyalkyl,

C2-C6 cyanoalkyl, C₂-Cg alkylcarbonyl, C₂-Cg alkoxycarbonyl, C₂-Cg

(alkylthio)carbonyl, C4-C8 cycloalkylcarbonyl, Cz Cg

cycloalkoxycarbonyl, C4-C8 (cycloalkylthio)carbonyl, C₂-Cg alkoxy(thiocarbonyl) or C4-C8 cycloalkoxy(thiocarbonyl);

R⁶ is H, C ! -C₆ alkyl or C _l -C₆ haloalkyl;

R⁷ and R⁸ are each independently H, C^-Cg alkyl, C^-Cg haloalkyl, C3-C6 cycloalkyl, C4-C8 cycloalkylalkyl or C4-C8 alkylcycloalkyl; or

R⁷ and R⁸ are taken together with the nitrogen atom to which they are

attached to form a 4- to 7-membered nonaromatic heterocyclic ring containing ring members, in addition to the connecting nitrogen atom, selected from carbon atoms and up to 1 ring member selected from O,

S(=0)_m and NR¹⁹;

each R^9a and R^9b is independently H or C1-C4 alkyl;

each R^10a is independently H, C1-C3 alkyl or C1-C3 haloalkyl;

each R^10b and R^10c is independently H, C_rC₃ alkyl, C₂-C₄ alkenyl, C₂-C₄ alkynyl, C1-C3 haloalkyl, C₂-C4 haloalkenyl, C3-C4 cycloalkyl, C4-C8 cycloalkylalkyl or C3-C4 halocycloalkyl;

each R^{l la} and R^{l lb} is independently H, C1-C3 alkyl or C1-C3 haloalkyl; each R^12a is independently H, halogen, cyano or C1-C4 alkyl;

each R^12b is independently H or C1-C4 alkyl;

each R¹³ is independently halogen, cyano, C_j-C₂ alkyl, Ci-C₂ haloalkyl,

C}-C₂ alkoxy or C^-C₂ haloalkoxy;

each R¹⁴ is independently cyano, C_j-C₂ alkyl or Ci-C₂ alkoxy; R¹⁵ is C_rC₆ alkyl or C_rC₆ haloalkyl;

R¹⁶ is C^-Cg alkyl, C2-Cg alkoxyalkyl, C2-C6 alkylaminoalkyl, C3-C6

dialkylaminoalkyl, C^-C^ alkoxy, C^-C^ alkylthio or C2-C6

alkylthioalkyl;

R¹⁷ is H, -CH(=0), C₃-C₆ cycloalkyl, -S(=0)₂OM or -(C=Z)R²⁰; or C_rC₆ alkyl or C^-C^ haloalkyl, each optionally substituted with up to 2 substituents independently selected from R²¹;

each R¹⁸ and R²¹ is independently cyano, C3-C6 cycloalkyl, C^-Cg alkoxy,

C_j-Cg haloalkoxy, C^-Cg alkylthio, C^-Cg alkylsulfinyl or C^-Cg alkylsulfonyl;

R¹⁹ is H, C_rC₃ alkyl or C₂-C₃ haloalkyl;

R²⁰ is C^-Cg alkyl, C2-C6 alkoxyalkyl, C2-C6 alkylaminoalkyl, C3-C6

dialkylaminoalkyl, C^-C^ alkoxy, C^-C^ alkylthio or C2-C6

alkylthioalkyl;

each U is independently O, S(=0)_m, NR²² or a direct bond;

each V is independently C^-Cg alkylene, C2-Cg alkenylene, C3-C6

alkynylene, C3-C6 cycloalkylene or C3-C6 cycloalkenylene, wherein up to 3 carbon atoms are C(=0), each optionally substituted with up to 5 substituents independently selected from halogen, cyano, nitro, hydroxy, C^-Cg alkyl, C^-Cg haloalkyl, C^-Cg alkoxy and C^-Cg haloalkoxy;

each T is independently cyano, NR^23aR^23b, OR²⁴ or S(=0)_mR²⁵;

each R²² is independently H, C^-Cg alkyl, C^-Cg haloalkyl, C2-Cg

alkylcarbonyl, C2-Cg alkoxycarbonyl, C2-Cg (alkylthio)carbonyl, C2-Cg alkoxy(thiocarbonyl), C4-C8 cycloalkylcarbonyl, C4-C8

cycloalkoxycarbonyl, C4-C8 (cycloalkylthio)carbonyl or C4-C8 cycloalkoxy(thiocarbonyl);

each R^23a and R^23b is independently H, C_rC₆ alkyl, C_rC₆ haloalkyl, C₂-C₆ alkenyl, C3-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C2-Cg alkylcarbonyl, C2-Cg alkoxycarbonyl, C2-Cg (alkylthio)carbonyl, C2-Cg alkoxy(thiocarbonyl), C4-C8 cycloalkylcarbonyl, C4-C8

cycloalkoxycarbonyl, C4-C8 (cycloalkylthio)carbonyl or C4-C8 cycloalkoxy(thiocarbonyl); or

a pair of R^23a and R^23b attached to the same nitrogen atom are taken together with the nitrogen atom to form a 3- to 6-membered heterocyclic ring, the ring optionally substituted with up to 5 substituents independently selected from R²⁶; each R²⁴ and R²⁵ is independently H, C^-Cg alkyl, C^-Cg haloalkyl, C2-Cg alkenyl, C3-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C2-Cg alkylcarbonyl, C2-Cg alkoxycarbonyl, C2-Cg (alkylthio)carbonyl, C4-C8 cycloalkylcarbonyl, C4-C8 cycloalkoxycarbonyl, C4-C8 (cycloalkylthio)carbonyl, C2-C6 alkoxy(thiocarbonyl) or C4-C8 cycloalkoxy(thiocarbonyl);

each R²⁶ is independently halogen, C^-Cg alkyl, C^-Cg haloalkyl or C^-Cg alkoxy;

each R²⁷ is independently H, cyano, Ci -C3 alkyl or C1-C3 haloalkyl;

Z is O or S;

M is K, Na or Li;

each m is independently 0, 1 or 2;

each n is independently 1, 2 or 3; and

each u and v are independently 0, 1 or 2 in each instance of S(=0)_u(=NR²⁷)_v; provided that:

(a) the sum of u and v is 0, 1 or 2;

(b) when Q¹ and Q² are each an optionally substituted phenyl ring, an optionally substituted naphthalenyl ring system, an optionally substituted 5- to 6-membered fully unsaturated heterocyclic ring or an optionally substituted 8- to 10-membered heteroaromatic bicyclic ring system, then at least one of Q¹ or Q² is substituted with at least one R^3b substituent; and

(c) W is linked through a carbon atom to the remainder of Formula 1. Embodiment B2. A compound of Embodiment A2 wherein

X is O, S, NR⁴ or CR^5aOR^5b;

R^la is H;

R² is Br, Cl, I or C_rC₂ alkyl;

each R ^a is independently cyano, halogen, Ci -C4 alkyl, Ci -C4 haloalkyl, C2-C4 alkenyl, C3-C4 cycloalkyl, C4-C6 cycloalkylalkyl, C4-C6 alkylcycloalkyl, C1-C3 alkylthio, C1-C3 alkylsulfmyl, C1-C3 alkylsulfonyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C3-C7 cycloalkoxy, C 1 -C2 alkylsulfonyloxy, C2-C3 alkylcarbonyloxy, C2-C3 alkylcarbonyl, amino, methylamino, C2-C4 dialkylamino, C2-C4 alkylcarbonylamino, -CH(=0), -NHCH(=0), -SF₅, -SC≡N, -C(=S)NR^9aR^9b or -U-V-T; each R^3b is independently C2-C4 haloalkenyl, C5-C8 cycloalkylalkenyl,

C4-C6 alkoxy, C2-C6 alkenyloxy, C2-C6 haloalkenyloxy, C3-C6 alkynyloxy, C3-C6 haloalkynyloxy, C4-C8 cycloalkylalkoxy, C3-C6 alkylsulfonyloxy, C3-C6 haloalkylsulfonyloxy, C3-C9 trialkylsilyl, C4-C9 trialkylsilylalkyl, C4-C9 trialkylsilylalkoxy, -CR^10a=NOR^10b or -ON=CR^{l l a}R^{l lb}; or -A(CR^12aR^12b)_nW;

each W is independently a 3- to 7-membered heterocyclic ring containing ring members selected from carbon atoms and 1 to 2 heteroatoms independently selected from up to 2 O, up to 2 S and up to 2 N atoms, wherein up to 1 carbon atom ring member is C(=0), the ring optionally substituted with up to 3 substituents independently selected from R¹³ on carbon atom ring members and R¹⁴ on nitrogen atom ring members;

R⁴ is H, cyclopropyl, -CH(=0), -S(=0)₂OM, -S(=0)mR¹⁵, -(C=Z)R¹⁶, OR¹⁷, C1-C3 alkyl or C1-C3 haloalkyl;

R^5a is H or methyl;

R⁶ is H or methyl;

R⁷ is H or C_rC₆ alkyl;

R⁸ is H, -Q alkyl, -Cg haloalkyl or C₄-C₈ alkylcycloalkyl;

each R^10a is independently H, methyl or halomethyl;

each R^12a is independently H, cyano or methyl;

each R^12b is independently H or methyl;

each R¹³ is independently halogen, methyl, halomethyl or methoxy;

each R¹⁴ is independently methyl or methoxy;

R¹⁵ is methyl or halomethyl;

R¹⁶ is methyl, ethyl, methoxy, ethoxy, methylthio or ethylthio;

R²⁰ is methyl, methoxy or methylthio; each U is independently O or NR²²;

each V is independently C2-C4 alkylene;

each T is independently NR^23aR^23b or OR²⁴;

each R^23a and R^23b is independently H, C^-C^ alkyl or C^-C^ haloalkyl; each R²⁴ is independently H, C^-Cg alkyl or C^-Cg haloalkyl;

Z is O; and

n is 1.

Embodiment C2. A compound of Embodiment B2 wherein

X is O, NR⁴ or CHOR^5b;

each R ^a is independently cyano, halogen, methyl, halomethyl, cyclopropyl, methoxy, methylthio, methylsulfonyloxy, methylcarbonyloxy, methylcarbonyl, -C(=S)NR^9aR^9b or -U-V-T;

each R ^b is independently C4-C6 alkoxy, C2-Cg alkenyloxy, C2-Cg haloalkenyloxy, C3-C6 alkynyloxy, C3-C6 haloalkynyloxy, C4-C8 cycloalkylalkoxy, C3-C6 alkylsulfonyloxy, C3-C6 haloalkylsulfonyloxy, C3-C9 trialkylsilyl, C4-C9 trialkylsilylalkyl, C4-C9 trialkylsilylalkoxy, ._CR10a_=NORl0b _or -ON=CR^{l la}R^{l lb}; or -A(CR^12aR^12b)_nW;

each W is independently a 3- to 5-membered heterocyclic ring containing ring members selected from carbon atoms and 1 to 2 heteroatoms

independently selected from up to 2 O and up to 2 N atoms, the ring optionally substituted with up to 2 substituents independently selected from R¹³ on carbon atom ring members and R¹ on nitrogen atom ring members;

R⁴ is H, -CH(=0) or methoxy;

each R^12a is independently H or methyl;

each R^12b is independently H or methyl; and

each U is independently O or NH.

Embodiment D2. A compound of Embodiment C2 wherein

X is NR⁴ or CHOR^5b;

R¹ is H, halogen or C1-C3 alkyl; R² is Br, CI or methyl;

each R^3a is independently cyano, halogen or methoxy;

each R ^b is independently C3-C5 alkenyloxy, C3-C5 haloalkenyloxy, C3-C6 alkynyloxy, C₄-C₅ trialkylsilylalkoxy, -CR^10a=NOR⁹ or

-ON=CR^{l la}R^{l lb};

R⁴ is H;

R^5b is H;

each R^10a is H;

each R^12b is H.

Embodiment E2. A compound of Embodiment D2 wherein

Q¹ is a phenyl ring optionally substituted with up to 2 substituents

independently selected from R^3a and substituted with 1 substituent selected from R ^b;

Q² is a phenyl ring substituted with up to 3 substituents independently

selected from R ^a;

R¹ is H;

R² is methyl; and

each R^3a is independently cyano, Br, CI, F or methoxy.

Embodiment F2. A compound of Embodiment E2 wherein

Q¹ is a phenyl ring substituted with at least 1 substituent selected from R ^a attached at an ortho position;

Q2 is a phenyl ring substituted with at least 1 substituent selected from R ^a attached at an ortho position; and

each R^3a is independently Br, CI or F.

Specific embodiments include compounds of Formula 1 selected from the group consisting of:

4-[2,6-difluoro-4-(2-propyn- 1 -yloxy)phenyl]- 1 ,3-dimethyl-N-(2,4,6-trifluorophenyl)- lH-pyrazol-5-amine (Compound 2),

4-[2,6-difluoro-4-(2-propen-l-yloxy)phenyl]-l,3-dimethyl-N-(2,4,6-trifluorophenyl)- lH-pyrazol-5-amine (Compound 3),

4-[4-[[3-chloro-2-propen-l-yl]oxy]-2,6-difluorophenyl]-l,3-dimethyl-N-(2,4,6- trifluorophenyl)-lH-prazol-5-amine (Compound 7),

4-[2,6-difluoro-4-(2-oxiranylmethoxy)phenyl]-l,3-dimethyl-N-(2,4,6- trifluorophenyl)-lH-pyrazol-5-amine (Compound 8), 4-[2,6-difluoro-4-[(3-methyl-3-oxetanyl)methoxy]phenyl]-l,3-dimethyl-N-(2,4,6- trifluorophenyl)-lH-pyrazol-5-amine (Compound 9),

4-[4-(l,3-dioxolan-2-ylmethoxy)-2,6-difluorophenyl]-l,3-dimethyl-N-(2,4,6- trifluorophenyl)-lH-pyrazol-5-amine (Compound 10),

4-[2,6-difluoro-4-[(tetrahydro-2-furanyl)methoxy]phenyl]-l,3-dimethyl-N-(2,4,6- trifluorophenyl)-lH-pyrazol-5-amine (Compound 11),

4-[2,6-difluoro-4-[3-(2-methyl-l,3-dioxolan-2-yl)propoxy]phenyl]-l,3-dimethyl-N- (2,4,6-trifluorophenyl)-lH-pyrazol-5-amine (Compound 12),

4-[l,3-dimethyl-5-[(2,4,6-trifluorophenyl)amino]-lH-pyrazol-4-yl]-3,5- difluorobenzaldehyde 2,2-dimethylhydrazone (Compound 18),

4-[2,6-difluoro-4-(lH- 1 ,2,4-triazol- 1 -yl)phenyl]- 1 ,3-dimethyl-N-(2,4,6- trifluorophenyl)-lH-pyrazol-5-amine (Compound 24), and

4-[2,6-difluoro-4-(lH-pyrazol-yl)phenyl]- 1 ,3-dimethyl-N-(2,4,6-trifluorophenyl)- 1H- pyrazol-5 -amine (Compound 25).

One or more of the following methods and variations as described in Schemes 1-18 can be used to prepare the compounds of Formula 1. The definitions of Q¹, Q², X, R¹, R^la R² and R⁴ in the compounds of Formulae 1-25 below are as defined above in the Summary of the Invention unless otherwise noted. Formulae la, lb, lc, Id, le, If and lg are various subsets of Formula 1. Substituents for each subset formula are as defined for its parent formula unless otherwise noted

As shown in Scheme 1, Compounds of Formula 1 can be prepared by reaction of a compound of Formula 2 (e.g., 5-aminopyrazoles for X being NR⁴, 5-hydroxypyrazoles for X being O or 5-mercaptopyrazoles for X being S) with a compound of Formula 3 wherein L¹ is a leaving group such as halogen (e.g., CI, Br or I) or (halo)alkylsulfonate (e.g., p- toluenesulfonate, methanesulfonate or trifluoromethanesulfonate) optionally in the presence of a metal catalyst, and generally in the presence of a base and a polar aprotic solvent such as N,N-dimethylformamide or dimethyl sulfoxide. For compounds of Formula 3 wherein Q² is attached through a sp -hybridized carbon atom, L¹ is typically CI, Br, I or a sulfonate (e.g., methanesulfonate). For Compounds of Formula 3 wherein Q² is an aromactic ring lacking an electron-withdrawing substituent(s), or in general, to improve reaction rate, yield or product purity, the use of a metal catalyst (e.g., metal or metal salt) in amounts ranging from catalytic up to superstoichiometric can facilitate the desired reaction. Typically for these conditions, L¹ is Br or I or a sulfonate such as methyl trifluoromethanesulfonate or -OS(0)2(CF2)3CF3. For example, the reaction can be run in the presence of a metal catalyst such as copper salt complexes (e.g., Cul with N,A/"-dimethylethylenediamine, proline or bipyridyl), palladium complexes (e.g., tris(dibenzylideneacetone)dipalladium(0)) or palladium salts (e.g., palladium acetate) with ligands such as 4,5-bis(diphenylphosphino)- 9,9-dimethylxanthene, 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl or 2,2'-bis- (diphenylphosphino)l,l'-binaphthalene, with a base such as potassium carbonate, cesium carbonate, potassium phosphate, sodium phenoxide or sodium tert-butoxide and a solvent such as N,N-dimethylformamide, 1 ,2-dimethoxy ethane, dimethyl sulfoxide, 1,4-dioxane or toluene, optionally containing an alcohol such as ethanol. For relevant references, see PCT Patent Publication WO 2010/020363, and Archives of Pharmacal Research 2002, 25(6), 781-785.

One skilled in the art will appreciate that the leaving group L¹ attached to compounds of Formula 3 should be selected in view of the relative reactivity of other functional groups present on Formula 3 (i.e. substituents attached to Q²), so that the group L¹ is displaced and not the functional group to give the final desired compounds of Formula 1.

General methods useful for preparing starting compounds of Formula 2 are well- known in the art; see, for example, J. Heterocyclic Chem. 1982, 19, 1173-1177, and Organic & Biomolecular Chemistry 2011, 9(10), 3714-3725 for conditions for preparing 5-aminopyrazoles of Formula 2; and Chemical & Pharmaceutical Bulletin 1994, 42(8), 1617-1630 for conditions for preparing 5-hydroxypyrazoles of Formula 2. To prepare 5-thiopyrazoles of Formula 2 the corresponding 5-hydroxypyrazoles can be treated with phosphorus pentasulfide or 2,4-bis(4-methoxyphenyl)-l,3-dithia-2,4-diphosphetane-2,4- disulfide (Lawesson's reagent) in solvents such as toluene, xylene or tetrahydrofuran. For references see, for example, PCT Patent Publication WO 2005/118575, and Justus Liebigs Annalen der Chemie 1908, 361, 251.

Scheme 1

As illustrated in Scheme 2, compounds of Formula 1 can also be prepared by reacting a compound of Formula 4 wherein L¹ is a leaving group such as halogen (e.g., CI, Br or I) or (halo)alkylsulfonate (e.g., /?-toluenesulfonate, methanesulfonate or trifluoromethane- sulfonate) with a compound of Formula 5 under conditions analogous to those described for Scheme 1. For references illustrating the method of Scheme 2 see, for example, Archive for Organic Chemistry 2009, 126-142, Journal of Agricultural and Food Chemistry 2008, 56, 10160-10167, and Biooganic & Medicinal Chemistry Letters 2007, 17, 1189-1192. Scheme 2

4 1

As shown in Scheme 3, intermediates of Formula 4 wherein L¹ is Br or I can be prepared by reaction of compounds of Formula 2 wherein X is NH under diazotization conditions optionally in the presence of copper salts containing bromide or iodide. For example, addition of tert-butyl nitrite to a solution of a 5-aminopyrazole of Formula 2 in the presence of CuBr₂ in a solvent such as acetonitrile provides the corresponding 5- bromopyrazole of Formula 4. Likewise, a 5-aminopyrazole of Formula 2 can be converted to a diazonium salt and then to a corresponding 5-bromo or 5-iodopyrazole of Formula 4 by treatment with sodium nitrite in solvents such as water, acetic acid or trifluoroacetic acid, in the presence of a mineral acid typically containing the same halide atom as L¹ (e.g., aqueous HI solution for L¹ being I), followed by treatment with the corresponding copper(I) or copper(II) salt according to general procedures well-known to those skilled in the art. For a related reference, see J. Comb. Chem. 2003, 5, 118-124.

Scheme 3

2 4 wherein X is NH wherein L¹ is Br or I.

As shown in Scheme 4, compounds of Formula 4 wherein L¹ is Br can also be prepared by reacting pyrazolones of Formula 6 with phosphorus tribromide using the method described in Tetrahedron Lett. 2000, 47(24), 4713-4716. Pyrazolones of Formula 6 can be prepared by condensation of ketoesters of Formula 7 with alkylhydrazines using the method described in J. Heterocyclic Chem. 1987, 24, 149-153. Scheme 4

7

wherein L is Br

As shown in Scheme 5, compounds of Formula 4 wherein L¹ is fluoroalkylsulfonyl can be prepared from compounds of Formula 2 wherein X is O using the method described in Synlett 2004, (5), 795-798.

heme 5

such as CF₃ or CF₃(CF₂)₃ wherein X is O wherein L is RfS0₂0-

In an alternative method, as shown in Scheme 6, compounds of Formula 1 are prepared by reacting a compound of Formula 8 with an alkylating agent of formula Li-CHRiR¹^¹ wherein L¹ is a leaving group such as halogen (e.g., CI, Br or I) or (halo)alkylsulfonate (e.g., /?-toluenesulfonate, methanesulfonate or trifluoromethanesulfonate), preferably in the presence of a base such as l ,8-diazabicyclo[5.4.0]undec-7-ene, potassium carbonate or potassium hydroxide, and in a solvent such as N,N-dimethylformamide, tetrahydrofuran, toluene or water. General procedures for alkylations of this type are well-known in the art and can be readily adapted to prepare compounds of the present invention. Particularly useful alkylating agents for preparing compounds of Formula 1 wherein R¹ and R^{l a} are H are diazomethane or iodomethane using general procedures known in the art, such as those described in Canada Journal of Chemistry 1986, 64, 221 1-2219, and Heterocycles 2000, 55(12), 2775-2780. Compounds of Formula 1 wherein R¹ and R^{l a} form an optionally substituted cyclopropyl ring can likewise be prepared by reaction of a compound of Formula 8 with an organometallic reagent, such as tricyclopropylbismuth, in the presence of a catalyst, such as copper acetate, under conditions known in the art such as those described in J. Am. Chem. Soc. 2007, 129(1), 44-45. Scheme 6

Compounds of Formula 8 are known and can be prepared by a variety of methods disclosed in the chemical literature. For example, as shown in Scheme 7, compounds of Formula 8 wherein R² is halogen or alkyl can be prepared from the corresponding compounds of Formula 9 wherein R² is H by halogenation or alkylation. Typically halogenation can be achieved using a variety of halogenating agents known in the art such as elemental halogen (e.g., Cl₂, Br₂, ½), sulfuryl chloride, iodine monochloride or a N-halosuccinimide (e.g., NBS, NCS, NIS) in an appropriate solvent such as N,N-dimethylformamide, carbon tetrachloride, acetonitrile, dichloromethane or acetic acid. Alkylation is achieved by reacting a compound of Formula 9 with a metalating agent, followed by an alkylating agent of formula R²-L! (wherein L¹ is a leaving group such as CI, Br, I or a sulfonate, for example, /?-toluenesulfonate, methanesulfonate or trifluoromethanesulfonate). Suitable metalating agents include, for example, /? -butyl lithium (ft-BuLi), lithium diisopropylamide (LDA) or sodium hydride (NaH). As used herein, the terms "alkylation" and "alkylating agent" are not limited to R² being an alkyl group, and include in addition to alkyl such groups as alkylthio, haloalkyl, alkenyl, haloalkenyl, alkynyl, and the like. For reaction conditions see, Journal of Medicinal Chemistry 2003, 46(16), 3463-3475, Heterocycles 1997, 44, 67-70, Synthetic Communications 2008, 55(5), 674-683, and PCT Patent Publication WO 2009/137651, Example 39, Step D.

Also shown in Scheme 7, intermediate compounds of Formula 9 can be prepared by reacting a compound of Formula 10 with hydrazine hydrochloride. The reaction can be run in a variety of solvents, but optimal yields are typically obtained when the reaction is run in ethanol at a temperature between about room temperature and the reflux temperature of the solvent. General procedures for this type of reaction are well documented in the chemical literature; see, for example, Bioorganic & Medicinal Chemistry 2005, 13(6), 2097-2107, Journal of Heterocyclic Chemistry 1989, 26(4), 1147-1158, and PCT Patent Publication WO 2009/137651, Example 39, Step C. Scheme 7

10

L is a leaving group such as ₂

wherein R is halogen or alkyl halogen or (halo)alkylsulfonate

As shown in Scheme 8, compounds of Formula 10 can be prepared from ketones of Formula 11 and N,N-dimethylformamide dimethyl acetal using the method described by Maya et al, Bioorganic & Medicinal Chemistry 2005, 13(6), 2097-2107. The reaction is typically conducted in a solvent such as benzene, toluene or xylenes at a temperature between about room temperature and the reflux temperature of the solvent.

Scheme 8

Ketones of Formula 11 can be prepared by reaction of acid chlorides of Formula 12 with a compound of formula Q²X-H under Friedel-Crafts condensation reaction conditions. Friedel-Crafts reactions are documented in a variety of published references; see, for example, J. March, Advanced Organic Chemistry, McGraw-Hill, New York, p. 490 and references cited therein, and PCT Patent Publications WO 2005/037758 and WO 2009/137651 (Example 39, Step A).

Scheme 9

Compounds of Formula 1 can also be prepared as shown in Scheme 10. In this method a compound of Formula 13 is first treated with an organometallic agent of Formula 14 such an alkyl lithium base (e.g., n-butyllithium, s-butyllithium or lithium diisopropylamide) or a Grignard reagent in a solvent such as toluene, ethyl ether, tetrahydrofuran or dimethoxymethane at temperatures ranging from about -78 °C to ambient temperature. Anions of Formula 13a are then contacted with an electrophile of Formulae 15 or 16. The use and choice of an appropriate electrophile of Formulae 15 or 16 will depend on the desired compound of Formula 1 and will be apparent to one skilled in chemical synthesis. For example, aldehydes of the formula Q²CHO provide compounds Formula 1 wherein X is CH(OH) and chlorosulfides of formula QiSCl or disulfies formula of QiS-S-Q¹ provide compounds Formula 1 wherein X is S. There are a wide-variety of general methods described in the synthetic literature for metallation/alkylation reactions which can be readily adapted to prepare compounds of the present invention; see, for example, J. Org. Chem. 2010, 75, 984-987.

Scheme 10

Electrophiles of Formulae 15 and 16 are commercially available and can be prepared by methods known in the art. Compounds of Formula 13 are known and can be prepared by methods analogous to those disclosed in Schemes 3 and 4 and by a variety of methods disclosed in the chemical literature.

As shown in Scheme 11, keto compounds of Formula 17 can be treated with alkylmagnesium halides to provide compounds of Formula la (i.e Formula 1 wherein X is CR^5aOR^5b, R^5a is alkyl and R^5b is H). Typically the reaction is run in the presence of zinc chloride and in a solvent such as diethyl ether or tetrahydrofuran at temperatures from about 0 to 100 °C (for references see, for exmple, Organic Lett. 2009, 11, 1659-1662, and J. Am. Chem. Soc. 2006, 128, 9998-9999). Scheme 11

17 la

As shown in Scheme 12, compounds of Formula 17 can be prepared by contacting a compound of Formula 18 with an acid chloride of Formula 19 in the presence of a Lewis acid (e.g., aluminum chloride, boron trifluoride diethyl etherate or tin tetrachloride) in a solvent such as dichloromethane, tetrachloroethane, or nitrobenzene, at temperatures ranging between about 0 to 200 °C.

Scheme 12

18 17

As shown in Scheme 13, compounds of Formula lb (i.e. Formula 1 wherein X is NR⁴ and R⁴ is H) can be prepared by reacting a compound of Formula 20 with an alkylhydrazine of Formula 21 in a solvent such as ethanol or methanol and optionally in the presence of an acid or base catalyst such as acetic acid, piperidine or sodium methoxide, according to general procedures known in the art.

heme 13

lb

wherein R^ is H or lower alkyl (e.g.,

CH₃, CH₂CH₃ or (CH₂)₂CH₃)

As shown in Scheme 14, compounds of Formula 20 can be prepared by reaction of corresponding ketene dithioacetal compounds of Formula 22 with compounds of formula Q²-NH₂ optionally in the presence of a base, such as sodium hydride or ethylmagnesium chloride, in solvents such as toluene, tetrahydrofuran or dimethoxymethane, at temperatures ranging from -10 °C to the boiling point of the solvent. Methods useful for preparing compounds of Formula 20 are known in the art; see, for example, J. Heterocycl. Chem. 1975, 12(1), 139.

Scheme 14

22

wherein is H or lower alkyl (e

CH₃, CH₂CH₃ or (CH₂)₂CH₃)

As shown in Scheme 15, compounds of Formula lb (i.e. Formula 1 wherein X is NR⁴ and R⁴ is H) can also be prepared by condensing a compound of Formula 23 with an alkylhydrazine of Formula 21 in a solvent such as tetrahyrofuran, ethanol or methanol and optionally in the presence of an acid or base catalyst such as acetic acid, piperidine or sodium methoxide, according to general procedures known in the art (see Chemistry of Heterocyclic Compounds 2011, 47(8), 970-976). Compounds of Formula 23 can readily be prepared by reacting enolates of Formula 24 with isothiocyantes followed by methylsulfanylation using the method described by Tong et al, Bioorganic & Medicinal Chemistry Letters 2008, 18, 5206-5208. Compounds of Formula 24 can be prepared from commercially available amines according to procedures described in the art (see Synthetic Communications 2007, 37, 985-991). The method of Scheme 15 is also illustrated by Example 1, Steps A-B.

Scheme 15

Compounds of Formula 1 can be subjected to various nucleophilic and metallation reactions to add substituents or modify existing substituents, and thus provide other functionalized compounds of Formula 1. For example, as shown in Scheme 16, compounds of Formula lc (i.e. Formula 1 wherein X in NR⁴ and R⁴ is other than H) can be prepared by reacting corresponding compounds of Formula lb (i.e. Formula 1 wherein X is NR⁴ and R⁴ is H) with an electrophile comprising R⁴ (i.e. Formula 25) typically in the presence of a base such as NaH and a polar solvent such as N,N-dimethylformamide. In this context the expression "electrophile comprising R⁴" means a chemical compound capable of transferring an R⁴ moiety to a nucleophile (such as the nitrogen atom attached to Q² in Formula lb). Often electrophiles comprising R⁴ have the formula R L² wherein L² is a nucleofuge (i.e. leaving group in nucleophilic reactions). Typical nucleofuges include halogens (e.g., CI, Br, I) and sulfonates (e.g., OS(0)₂CH₃, OS(0)₂CF₃, OS(0)2-(4-CH₃-Ph)). However, some electrophiles comprising R⁴ do not comprise a nucleofuge; an example is sulfur trioxide (S0₃), which after deprotonation (such as by a base of the formulae M⁺H^~ wherein M⁺ is a cation) of the nitrogen atom attached to Q² in Formula lb, can bond to the nitrogen atom as a -SO3M substituent.

Scheme 16

R is other than H

As shown in Scheme 17, a fluoro can be introduce at the 3-position of the pyrazole ring by treating compounds Formula Id (i.e. Formula 1 wherein R² is chlorine) with potassium fluoride or cesium fluoride in presence of a solvent such as dimethyl sulfoxide or A ,N-dimethylformamide at 0-25 °C for time periods of 30 minutes to 4 h, using procedures such as described in Zhurnal Organicheskoi Khimii 1983, 19, 2164-2173.

Scheme 17

As shown in Scheme 18, sulfoxides and sulfones of Formula lg (i.e. Formula 1 wherein X is S(=0)_m and m is 1 or 2) can be prepared by oxidation of compounds of Formula If (i.e. Formula 1 wherein X is S). Typically an oxidizing agent in an amount from about 1 to 4 equivalents, depending on the oxidation state of the desired product, is added to a mixture of a compound of Formula If and a solvent. Useful oxidizing agents include Oxone® (potassium peroxymonosulfate), potassium permanganate, hydrogen peroxide, sodium periodate, peracetic acid and 3-chloroperbenzoic acid. The solvent is selected with regard to the oxidizing agent employed. Aqueous ethanol or aqueous acetone is preferably used with potassium peroxymonosulfate, and dichloromethane is generally preferable with 3-chloroperbenzoic acid. Useful reaction temperatures typically range from about -78 to 90 °C. Oxidation reactions of this type are described by Brand et al, J. Agric. Food Chem. 1984, 32, 221-226 and Ouyang, et al, J. Agric. Food Chem. 2008, 56, 10160-10167.

Scheme 18

m is 1 or 2

It is recognized by one skilled in the art that various functional groups can be converted into others to provide different compounds of Formula 1. For example, compounds of Formula 1 in which R² is methyl, ethyl, cyclopropyl, and the like, can be modified by free-radical halogenation to form compounds of Formula 1 wherein R² is halomethyl, haloethyl, halocyclopropyl, and the like. Compounds of Formula 1 wherein R² is halomethyl can be used to prepare compounds of Formula 1 wherein R² is hydroxymethyl or cyanomethyl. Compounds of Formula 1, or intermediates for their preparation, may contain aromatic nitro groups, which can be reduced to amino groups, and then converted via reactions well-known in the art (e.g., Sandmeyer reaction) to various halides. By similar known reactions, aromatic amines (anilines) can be converted via diazonium salts to phenols, which can then be alkylated to prepare compounds of Formula 1 with alkoxy substituents. Likewise, aromatic halides such as bromides or iodides prepared via the Sandmeyer reaction can react with alcohols under copper-catalyzed conditions, such as the Ullmann reaction or known modifications thereof, to provide compounds of Formula 1 that contain alkoxy substituents. Additionally, some halogen groups, such as fluorine or chlorine, can be displaced with alcohols under basic conditions to provide compounds of Formula 1 containing the corresponding alkoxy substituents. The resultant alkoxy compounds can themselves be used in further reactions to prepare compounds of Formula 1 wherein R^3a is - U-V-T (see, for example, PCT Patent Publication WO 2007/149448). Compounds of Formula 1 or precursors thereof in which R² is halide, preferably bromide or iodide, are particularly useful intermediates for transition metal-catalyzed cross-coupling reactions to prepare compounds of Formula 1. These types of reactions are well documented in the literature; see, for example, Tsuji in Transition Metal Reagents and Catalysts: Innovations in Organic Synthesis, John Wiley and Sons, Chichester, 2002; Tsuji in Palladium in Organic Synthesis, Springer, 2005; and Miyaura and Buchwald in Cross Coupling Reactions: A Practical Guide, 2002; and references cited therein.

It is recognized that some reagents and reaction conditions described above for preparing compounds of Formula 1 may not be compatible with certain functionalities present in the intermediates. In these instances, the incorporation of protection/deprotection sequences or functional group interconversions into the synthesis will aid in obtaining the desired products. The use and choice of the protecting groups will be apparent to one skilled in chemical synthesis (see, for example, Greene, T. W.; Wuts, P. G. M. Protective Groups in Organic Synthesis, 2nd ed.; Wiley: New York, 1991). One skilled in the art will recognize that, in some cases, after the introduction of a given reagent as it is depicted in any individual scheme above, it may be necessary to perform additional routine synthetic steps not described in detail to complete the synthesis of compounds of Formula 1. One skilled in the art will also recognize that it may be necessary to perform a combination of the steps illustrated in the above schemes in an order other than that implied by the particular sequence presented to prepare the compounds of Formula 1. One skilled in the art will also recognize that compounds of Formula 1 and the intermediates described herein can be subjected to various electrophilic, nucleophilic, radical, organometallic, oxidation, and reduction reactions to add substituents or modify existing substituents.

Without further elaboration, it is believed that one skilled in the art using the preceding description can utilize the present invention to its fullest extent. The following Examples are, therefore, to be construed as merely illustrative, and not limiting of the disclosure in any way whatsoever. Steps in the following Examples illustrate a procedure for each step in an overall synthetic transformation, and the starting material for each step may not have necessarily been prepared by a particular preparative run whose procedure is described in other Examples or Steps. Percentages are by weight except for chromatographic solvent mixtures or where otherwise indicated. Parts and percentages for chromatographic solvent mixtures are by volume unless otherwise indicated. ¾ NMR spectra are reported in ppm downfield from tetramethylsilane in CDCI3 unless otherwise noted; "s" means singlet, "d" means doublet, "t" means triplet, "m" means multiplet, and "br s" means broad singlet.

EXAMPLE 1

Preparation of 4-[2,6-difluoro-4-(2-propyn-l-yloxy)phenyl]-l,3-dimethyl-N-(2,4,6- trifluorophenyl)-lH-pyrazol-5-amine (Compound 2)

Step A: Preparation of l-(2,6-difluoro-4-methoxyphenyl)-2-propanone

To a mixture of concentrated sulfuric acid (15.6 g, 159 mmol) in water (75 mL) at 0 °C was added 2,6-difluoro-4-methoxybenzenamine (12.4 g, 78.0 mmol), followed by sodium nitrite (6.65 g, 81.7 mmol) in water (30 mL) while maintaining the reaction temperature below 10 °C. After 45 minutes, isopropenyl acetate (16.4 g, 164 mmol) was added to the reaction mixture followed by copper(II) sulfate pentahydrate (0.982 g, 3.90 mmol). After an additional 30 minutes, a solution of sodium sulfite (4.91 g, 38.9 mmol) in water (60 mL) was added to the reaction mixture while maintaining the temperature below 10 °C. The reaction mixture was allowed to warm to room temperature, stirred for 3 h and then sodium sulfite (0.5 g, 3.97 mmol) was added in three portions. The resulting mixture was extracted with hexanes (2 x 300 mL) and the combinded organic layers were washed with sodium hydroxide (0.5 N) (5 x 100 mL) and water (100 mL). The organic layer was dried over magnesium sulfate, filtered and concentrated under reduced pressure to provide the title compound (6.19 g) .

Step B: Preparation of 4-(2,6-difluoro-4-methoxyphenyl)-l,3-dimethyl-N-(2,4,6- trifluorophenyl)-lH-pyrazol-5-amine

To a mixture of l-(2,6-difluoro-4-methoxyphenyl)-2-propanone (i.e. the product of Step A) (2.38 g, 11.9 mmol) in tetrahydrofuran (30 mL) at 0 °C was added potassium tert- butoxide (1.51 g, 13.1 mmol). After 1 h, the reaction mixture was cooled to -10 °C and l,3,5-trifluoro-2-isothiocyanatobenzene (2.25 g, 11.9 mmol) was added. After an additional 1 h, iodomethane (2.11 g, 14.9 mmol) was added to the reaction mixture and the mixture was allowed to warm to room temperature. Glacial acetic acid (2.15 g, 35.7 mmol), water (1.3 g, 72.2 mmol) and methyl hydrazine (2.74 g. 59.54 mmol) were sequentially added to the reaction mixture, and the mixture was then heated at reflux for about 16 h. The reaction mixture was concentrated under reduced pressure and the resulting material was purified by medium pressure liquid chromatography (0 to 50% gradient of ethyl acetate in hexanes as eluant) to provide the title compound (1.9 g).

in NMR (CDCI3): δ 6.49 (m, 2H), 6.37 (m, 2H), 7.10 (m, 2H), 5.05 (br s, 1H), 3.79 (s, 3H), 3.75 (s, 3H), 2.12 (s, 3H).

Step C: Preparation of 4-[l,3-dimethyl-5-[(2,4,6-trifluorophenyl)amino]-lH-pyrazol-

4-yl]-3,5-difluorophenol

To a mixture of 4-(2,6-difluoro-4-methoxyphenyl)-l,3-dimethyl-N-(2,4,6- trifluorophenyl)-lH-pyrazol-5-amine (i.e. the product of Step B) (1.9 g, 5.0 mmol) in dichloromethane (30 mL) at 0 °C was added boron tribromide (1 M in dichloromethane) (5.0 g, 20 mmol). The reaction mixture was warmed to room temperature, stirred for about 16 h, and then water was added to the mixture. The resulting precipitate was collected by filtration, dissolved in a solution of tetrahydrofuran and sodium hydroxide (I N) (2: 1, 90 mL) and the pH was brought to 7 by the addition of concentrated hydrochloric acid. The resulting mixture was extracted with dichloromethane, dried over magnesium sulfate, filtered and concentrated under reduced pressure to provide the title compound (1.2 g).

!H NMR (CDCI3): δ 6.49 (m, 2H), 6.33 (m, 2H), 5.03 (br s, 1H), 3.80 (s, 3H), 2.12 (s, 3H). Step D: Preparation of 4-[2,6-difluoro-4-(2-propyn-l-yloxy)phenyl]-l,3-dimethyl-N-

(2,4,6-trifluorophenyl)- lH-pyrazol-5 -amine

A mixture of 4-[l,3-dimethyl-5-[(2,4,6-trifluorophenyl)amino]-lH-pyrazol-4-yl]-3,5- difluorophenol (i.e. the product of Step C) (0.30 g, 0.80 mmol), propargyl bromide (0.10 g, 0.90 mmol) and potassium carbonate (0.17g, 1.2 mmol, 325 mesh) in acetonitrile (5 mL) was heated at 50 °C for about 16 h. The reaction mixture was concentrated under reduced pressure and the resulting material was purified by medium pressure liquid chromatography (0 to 50% gradient of ethyl acetate in hexanes as eluant) to provide the title compound (1.9 g), a compound of the present invention.

lH NMR (CDCI3): δ 6.48 (m, 4H), 5.04 (br s, 1H), 4.63 (d, 2H), 3.79 (s, 3H), 2.56 (t, 1H), 2.13 (s, 3H).

EXAMPLE 2

Preparation of 4-[2,6-difluoro-4-(lH-l,2,4-triazol-l-yl)phenyl]-l,3-dimethyl-N-(2,4,6- trifluorophenyl)-lH-pyrazol-5-amine (Compound 24)

A mixture of 4-(4-bromo-2,6-difluorophenyl)-l,3-dimethyl-N-(2,4,6-trifluorophenyl)- lH-pyrazol-5-amine (prepared in an analogous manner to Example 1, Step B) (0.4 g, 0.93 mmol), 1,2,4-triazole (0.097 g, 1.4 mmol), copper iodide (0.017 g, 0.090 mmol), trans- N,N-dimethyl-l,2-cyclohexanediamine (0.065 g, 0.9 mmol) and potassium carbonate (0.38 g, 0.28 mmol) in dioxane (10 mL) was heated to 100° C for three days in a sealed tube. The reaction mixture was then diluted with ethyl acetate and washed with water (2 x 20 mL). The combined organic layers were dried, filtered and concentrated under reduced pressure. The resulting material was purified by preparative thin layer chromatography to provide the title compound (0.18 g), a compound of the present invention, as a solid,

in NMR (CDCI3): δ 8.52 (s, 1H), 8.10 (s, 1H), 7.25 (d, 2H), 6.52 (t, 2H), 5.11 (br s, 1H), 3.81 (s, 3H), 2.16 (s, 3H).

EXAMPLE 3

Preparation of 4-[4-(2-cyclopropylethynyl)-2,6-difluorophenyl]- 1 ,3-dimethyl-N-(2,4,6- trifluorophenyl)-lH-pyrazol-5-amine (Compound 13)

To a mixture of 4-(4-bromo-2,6-difluorophenyl)-l,3-dimethyl-N-(2,4,6- trifluorophenyl)-lH-pyrazol-5-amine (prepared in an analogous manner to Example 1, Step B) (0.3 g, 0.69 mmol) in cyclopyropylacetylene (5 mL) was added triethylamine (0.48 g, 4.8 mmol), copper iodide (0.013 g, 0.068 mmol) and dichlorobis(triphenylphosphine)palladium (0.024 g, 0.034 mmol). The reaction mixture was heated in a sealed tube at 100° C for 4 h, and then concentrated under reduced pressure. The resulting material was purified by silica gel column chromatography (30% ethyl acetate in hexanes as eluent) to provide the title compound (0.16 g), a compound of the present invention, as a solid. in NMR (CDCI3): δ 6.82 (m, 2H), 6.51 (m, 2H), 5.07 (m, 1H), 3.79 (s, 3H), 2.12 (s, 3H), 1.42 (m, 1H), 0.90 (m, 2H), 0.79 (m, 2H).

By the procedures described herein together with methods known in the art, the compounds disclosed in the Tables that follow can be prepared. The following abbreviations are used in the Tables which follow: i means iso, c means cyclo, n means normal, s means secondary, Me means methyl, Bu means butyl, Pr means propyl, MeO means methoxy, CN means cyano, and Ph means phenyl.

Q² is 2,4,6-tri-F-Ph, (R^: ^3a)p is 2,6-di-F.

_R3b _R3b _R3b _R3b

4-(HC≡CCH₂0)- 4-(MeC≡CCH₂0)- 4-(HC≡CCH₂CH₂0)- 4-(MeC≡CCH₂CH₂0)-

4-(H₂C=CHCH₂0)- 4-(MeHC=CHCH₂0)- 4-(ClHC=CHCH₂0)- 4-(Cl₂C=CHCH₂0)-

4-(HC≡C(Me)CHO)- 4-(H₂C=CH(Me)CHO)- 4-(H₂C=CHCH(Me)0)- 4-(MeHC=CHCH(Me)0)-

4-«-butoxy 4-z^'-butoxy 4-5-butoxy 4-«-pentoxy

4-z-pentoxy 4-5-pentoxy 4-(c-Pr-HC=CHCH₂0)- 4-(c-Pr-C≡CCH₂0)-

4-(c-Pr-HC=CH)- 4-(c-Pr-C≡C)- 4-(c-Pr-CH₂0)- 4-(c-Bu-CH₂0)-

4-(c-pentyl-CH₂0)- 4-(HO-N=CH)- 4-(MeO-N=CH)- 4-(HO-N=C(Me))-

4-(MeO-N=C(Me))- 4-(MeHC=N-0)- 4-(Me₂C=N-0)- 4-(H₂C=N-0)-

4-(H₂N-N=CH)- 4-(MeNH-N=CH)- 4-(Me₂N-N=CH)- 4-(H₂N-N=C(Me))-

4-(MeNH-N=C(Me))- 4-(Me₂N-N=C(Me))- 4-(MeHC=N-NH)- 4-(Me₂C=N-NH)-

4-(H₂C=N-NH)- 4-(MeHC=N-N(Me))- 4-(Me₂C=N-N(Me))- 4-(H₂C=N-N(Me))-

3-(HC≡CCH₂0)- 3-(MeC≡CCH₂0)- 3-(HC≡CCH₂CH₂0)- 3-(MeC≡CCH₂CH₂0)-

3-(H₂C=CHCH₂0)- 3-(MeHC=CHCH₂0)- 3-(ClHC=CHCH₂0)- 3-(Cl₂C=CHCH₂0)-

3-(HC≡C(Me)CHO)- 3-(H₂C=CH(Me)CHO)- 3-(H₂C=CHCH(Me)0)- 3 -(MeHC=CHCH(Me)0)-

3-«-butoxy 3-z^'-butoxy 3-5-butoxy 3-«-pentoxy

3-z-pentoxy 3-5-pentoxy 3-(c-Pr-HC=CHCH₂0)- 3-(c-Pr-C≡CCH₂0)-

3-(c-Pr-HC=CH)- 3-(c-Pr-C≡C)- 3-(c-Pr-CH₂0)- 3-(c-Bu-CH₂0)-

3-(c-pentyl-CH₂0)- 3-(HO-N=CH)- 3-(MeO-N=CH)- 3-(HO-N=C(Me))-

3-(MeO-N=C(Me))- 3-(MeHC=N-0)- 3-(Me₂C=N-0)- 3-(H₂C=N-0)-

3-(H₂N-N=CH)- 3-(MeNH-N=CH)- 3-(Me₂N-N=CH)- 3-(H₂N-N=C(Me))- Q² is 2,4,6-tri-F-Ph, (R^3a)_p is 2,6-di-F.

_R3b _R3b _R3b R3

3-(MeNH-N=C(Me))- 3-(Me₂N-N=C(Me))- 3-(MeHC=N-NH)- 3-(Me₂C=N-NH)- 3-(H₂C=N-NH)- 3- MeHC=N-N(Me))- 3- Me₂C=N-N(Me)> -(H₂C=N-N(Me))-

The present disclosure also includes Tables 1A through 215A, each of which is constructed the same as Table 1 above, except that the row heading in Table 1 (i.e. "Q² is 2,4,6-tri-F-Ph, (R ^a)_p is 2,6-di-F") is replaced with the respective row headings shown below. For Example, in Table 1A the row heading is "Q² is 2,4,6-tri-F-Ph, (R^3a)_p is 2-F", and R³^ is as defined in Table 1 above. Thus, the first entry in Table 1A specifically discloses 1 ,3-dimethyl-N-(2,4,6-trifluorophenyl)-4-[2-fluoro-4-(-propyn- 1 -yloxy)phenyl]- lH-pyrazol-5-amine. Tables 2A through 215A are constructed similarly.

Table Row Heading Table Row Heading

1A Q² is 2,4,6-tri-F-Ph, (R^3a)_p is 2-F. 108A Q² is 2-Br-4-MeO-6-F-Ph, (R^3a)_p is 2-Me.

2A Q² is 2,4,6-tri-F-Ph, (R^3a)_p is 2-Cl. 109A Q² is 2-Br-4-MeO-6-F-Ph, (R^3a)_p is 2-Cl, 6-F.

3A Q² is 2,4,6-tri-F-Ph, (R^3a)_p is 2-Br. 110A Q² is 2-Br-4-MeO-6-F-Ph, (R^3a)_p is 2-Cl, 6-Br.

4A Q² is 2,4,6-tri-F-Ph, (R^3a)_p is 2-Me. 111A Q² is 2-Br-4-MeO-6-F-Ph, (R^3a)_p is 2,6-di-Cl.

5A Q² is 2,4,6-tri-F-Ph, (R^3a)_p is 2-Cl, 6-F. 112A Q² is 2,6-di-Cl-4-Me-Ph, (R^3a)_p is 2,6-di-F.

6A Q² is 2,4,6-tri-F-Ph, (R^3a)_p is 2-Cl, 6-Br. 113A Q² is 2,6-di-Cl-4-Me-Ph, (R^3a)_p is 2-F.

7A Q² is 2,4,6-tri-F-Ph, (R^3a)_p is 2,6-di-Cl. 114A Q² is 2,6-di-Cl-4-Me-Ph, (R^3a)_p is 2-Cl.

8A Q² is 2,6-di-F-Ph, (R^3a)_p is 2,6-di-F. 115A Q² is 2,6-di-Cl-4-Me-Ph, (R^3a)_p is 2-Br.

9A Q² is 2,6-di-F-Ph, (R^3a)_p is 2-F. 116A Q² is 2,6-di-Cl-4-Me-Ph, (R^3a)_p is 2-Me.

10A Q² is 2,6-di-F-Ph, (R^3a)_p is 2-Cl. 117A Q² is 2,6-di-Cl-4-Me-Ph, (R^3a)_p is 2-Cl, 6-F.

11A Q² is 2,6-di-F-Ph, (R^3a)_p is 2-Br. 118A Q² is 2,6-di-Cl-4-Me-Ph, (R^3a)_p is 2-Cl, 6-Br.

12A Q² is 2,6-di-F-Ph, (R^3a)_p is 2-Me. 119A Q² is 2,6-di-Cl-4-Me-Ph, (R^3a)_p is 2,6-di-Cl.

13A Q² is 2,6-di-F-Ph, (R^3a)_p is 2-Cl, 6-F. 120A Q² is 2,6-di-Br-4-Me-Ph, (R^3a)_p is 2,6-di-F.

14A Q² is 2,6-di-F-Ph, (R^3a)_p is 2-Cl, 6-Br. 121A Q² is 2,6-di-Br-4-Me-Ph, (R^3a)_p is 2-F.

15A Q² is 2,6-di-F-Ph, (R^3a)_p is 2,6-di-Cl. 122 A Q² is 2,6-di-Br-4-Me-Ph, (R^3a)_p is 2-Cl.

16A Q² is 2,6-di-F-4-MeO-Ph, (R^3a)_p is 2,6-di-F. 123A Q² is 2,6-di-Br-4-Me-Ph, (R^3a)_p is 2-Br.

17A Q² is 2,6-di-F-4-MeO-Ph, (R^3a)_p is 2-F. 124 A Q² is 2,6-di-Br-4-Me-Ph, (R^3a)_p is 2-Me.

18A Q² is 2,6-di-F-4-MeO-Ph, (R^3a)_p is 2-Cl. 125A Q² is 2,6-di-Br-4-Me-Ph, (R^3a)_p is 2-Cl, 6-F.

19A Q² is 2,6-di-F-4-MeO-Ph, (R^3a)_p is 2-Br. 126A Q² is 2,6-di-Br-4-Me-Ph, (R^3a)_p is 2-Cl, 6-Br. Table Row Heading Table Row Heading

20A Q² is 2,6-di F -4-MeO-Ph, (R^3a)_p is 2-Me. 127A Q² is 2,6-di-Br-4-Me-Ph, (R^3a)_p is 2,6-di-Cl.

21A Q² is 2,6-di F -4-MeO-Ph, (R^3a)_p is 2-Cl, 6-F. 128A Q² is 2,4,6-tri-Cl-Ph, (R^3a)_p is 2,6-di-F.

22A Q² is 2,6-di F -4-MeO-Ph, (R^3a)_p is 2-Cl, 6-Br. 129 A Q² is 2,4,6-tri-Cl-Ph, (R^3a)_p is 2-F.

23A Q² is 2,6-di F -4-MeO-Ph, (R^3a)_p is 2,6-di-Cl. 130A Q² is 2,4,6-tri-Cl-Ph, (R^3a)_p is 2-Cl.

24A Q² is 2,6-di F -4-Me-Ph, (R^3a)_p is 2,6-di-F. 131A Q² is 2,4,6-tri-Cl-Ph, (R^3a)_p is 2-Br.

25A Q² is 2,6-di F -4-Me-Ph, (R^3a)_p is 2-F. 132A Q² is 2,4,6-tri-Cl-Ph, (R^3a)_p is 2-Me.

26A Q² is 2,6-di F -4-Me-Ph, (R^3a)_p is 2-Cl. 133A Q² is 2,4,6-tri-Cl-Ph, (R^3a)_p is 2-Cl, 6-F.

27A Q² is 2,6-di F -4-Me-Ph, (R^3a)_p is 2-Br. 134A Q² is 2,4,6-tri-Cl-Ph, (R^3a)_p is 2-Cl, 6-Br.

28A Q² is 2,6-di F -4-Me-Ph, (R^3a)_p is 2-Me. 135A Q² is 2,4,6-tri-Cl-Ph, (R^3a)_p is 2,6-di-Cl.

29A Q² is 2,6-di F -4-Me-Ph, (R^3a)_p is 2-Cl, 6-F. 136A Q² is 2-C1-4-F, (R^3a)_p is 2,6-di-F.

3 OA Q² is 2,6-di F -4-Me-Ph, (R^3a)_p is 2-Cl, 6-Br. 137A Q² is 2-C1-4-F, (R^3a)_p is 2-F.

31A Q² is 2,6-di F -4-Me-Ph, (R^3a)_p is 2,6-di-Cl. 138A Q² is 2-C1-4-F, (R^3a)_p is 2-Cl.

32A Q² is 2,6-di F -4-CN-Ph, (R^3a)_p is 2,6-di-F. 139A Q² is 2-C1-4-F, (R^3a)_p is 2-Br.

33A Q² is 2,6-di F -4-CN-Ph, (R^3a)_p is 2-F. 140A Q² is 2-C1-4-F, (R^3a)_p is 2-Me.

34A Q² is 2,6-di F -4-CN-Ph, (R^3a)_p is 2-Cl. 141A Q² is 2-C1-4-F, (R^3a)_p is 2-Cl, 6-F.

35A Q² is 2,6-di F -4-CN-Ph, (R^3a)_p is 2-Br. 142 A Q² is 2-C1-4-F, (R^3a)_p is 2-Cl, 6-Br.

36A Q² is 2,6-di F -4-CN-Ph, (R^3a)_p is 2-Me. 143A Q² is 2-C1-4-F, (R^3a)_p is 2,6-di-Cl.

37A Q² is 2,6-di F -4-CN-Ph, (R^3a)_p is 2-Cl, 6-F. 144 A Q² is 2-Cl-4-Me, (R^3a)_p is 2,6-di-F.

38A Q² is 2,6-di F -4-CN-Ph, (R^3a)_p is 2-Cl, 6-Br. 145A Q² is 2-Cl-4-Me, (R^3a)_p is 2-F.

39A Q² is 2,6-di F -4-CN-Ph, (R^3a)_p is 2,6-di-Cl. 146A Q² is 2-Cl-4-Me, (R^3a)_p is 2-Cl.

40A Q² is 2,6-di F -4-Cl-Ph, (R^3a)_p is 2,6-di-F. 147A Q² is 2-Cl-4-Me, (R^3a)_p is 2-Br.

41A Q² is 2,6-di F -4-Cl-Ph, (R^3a)_p is 2-F. 148A Q² is 2-Cl-4-Me, (R^3a)_p is 2-Me.

42A Q² is 2,6-di F -4-Cl-Ph, (R^3a)_p is 2-Cl. 149 A Q² is 2-Cl-4-Me, (R^3a)_p is 2-Cl, 6-F.

43A Q² is 2,6-di F -4-Cl-Ph, (R^3a)_p is 2-Br. 150A Q² is 2-Cl-4-Me, (R^3a)_p is 2-Cl, 6-Br.

44A Q² is 2,6-di F -4-Cl-Ph, (R^3a)_p is 2-Me. 151A Q² is 2-Cl-4-Me, (R^3a)_p is 2,6-di-Cl.

45A Q² is 2,6-di F -4-Cl-Ph, (R^3a)_p is 2-Cl, 6-F. 152A Q² is 2-Cl-4-MeO, (R^3a)_p is 2,6-di-F.

46A Q² is 2,6-di F -4-Cl-Ph, (R^3a)_p is 2-Cl, 6-Br. 153A Q² is 2-Cl-4-MeO, (R^3a)_p is 2-F.

47A Q² is 2,6-di F -4-Cl-Ph, (R^3a)_p is 2,6-di-Cl. 154A Q² is 2-Cl-4-MeO, (R^3a)_p is 2-Cl.

48A Q² is 2,6-di F -4-Br-Ph, (R^3a)_p is 2,6-di-F. 155A Q² is 2-Cl-4-MeO, (R^3a)_p is 2-Br.

49A Q² is 2,6-di F -4-Br-Ph, (R^3a)_p is 2-F. 156A Q² is 2-Cl-4-MeO, (R^3a)_p is 2-Me.

50A Q² is 2,6-di F -4-Br-Ph, (R^3a)_p is 2-Cl. 157A Q² is 2-Cl-4-MeO, (R^3a)_p is 2-Cl, 6-F.

51A Q² is 2,6-di F -4-Br-Ph, (R^3a)_p is 2-Br. 158A Q² is 2-Cl-4-MeO, (R^3a)_p is 2-Cl, 6-Br.

52A Q² is 2,6-di F -4-Br-Ph, (R^3a)_p is 2-Me. 159A Q² is 2-Cl-4-MeO, (R^3a)_p is 2,6-di-Cl.

53A Q² is 2,6-di F -4-Br-Ph, (R^3a)_p is 2-Cl, 6-F. 160A Q² is 2-Br-4-F, (R^3a)_p is 2,6-di-F.

54A Q² is 2,6-di F -4-Br-Ph, (R^3a)_p is 2-Cl, 6-Br. 161A Q² is 2-Br-4-F, (R^3a)_p is 2-F.

55A Q² is 2,6-di F -4-Br-Ph, (R^3a)_p is 2,6-di-Cl. 162A Q² is 2-Br-4-F, (R^3a)_p is 2-Cl.

56A Q² is 2,4-di F -Ph, (R^3a)_p is 2,6-di-F. 163A Q² is 2-Br-4-F, (R^3a)_p is 2-Br. Table Row Heading Table Row Heading

57A Q² is 2,4-di-F-Ph, (R^3a)_p is 2-F. 164A Q² is 2-Br-4-F, (R^3a)_p is 2-Me.

58A Q² is 2,4-di-F-Ph, (R^3a)_p is 2-Cl. 165 A Q² is 2-Br-4-F, (R^3a)_p is 2-Cl, 6-F.

59A Q² is 2,4-di-F-Ph, (R^3a)_p is 2-Br. 166A Q² is 2-Br-4-F, (R^3a)_p is 2-Cl, 6-Br.

60A Q² is 2,4-di-F-Ph, (R^3a)_p is 2-Me 167A Q² is 2-Br-4-F, (R^3a)_p is 2,6-di-Cl.

61A Q² is 2,4-di-F-Ph, (R^3a)_p is 2-Cl, 6-F. 168A Q² is 2-Br-4-Me, (R^3a)_p is 2,6-di-F.

62A Q² is 2,4-di-F-Ph, (R^3a)_p is 2-Cl, 6-Br. 169A Q² is 2-Br-4-Me, (R^3a)_p is 2-F.

63A Q² is 2,4-di-F-Ph, (R^3a)_p is 2,6-di-Cl. 170A Q² is 2-Br-4-Me, (R^3a)_p is 2-Cl.

64A Q² is 2,4-di-F-6-Cl-Ph, (R^3a)_p is 2,6-di-F. 171A Q² is 2-Br-4-Me, (R^3a)_p is 2-Br.

65A Q² is 2,4-di-F-6-Cl-Ph, (R^3a)_p is 2-F. 172A Q² is 2-Br-4-Me, (R^3a)_p is 2-Me.

66A Q² is 2,4-di-F-6-Cl-Ph, (R^3a)_p is 2-Cl. 173A Q² is 2-Br-4-Me, (R^3a)_p is 2-Cl, 6-F.

67A Q² is 2,4-di-F-6-Cl-Ph, (R^3a)_p is 2-Br. 174A Q² is 2-Br-4-Me, (R^3a)_p is 2-Cl, 6-Br.

68A Q² is 2,4-di-F-6-Cl-Ph, (R^3a)_p is 2-Me. 175 A Q² is 2-Br-4-Me, (R^3a)_p is 2,6-di-Cl.

69A Q² is 2,4-di-F-6-Cl-Ph, (R^3a)_p is 2-Cl, 6-F. 176A Q² is 2-Br-4-MeO, (R^3a)_p is 2,6-di-F.

70A Q² is 2,4-di-F-6-Cl-Ph, (R^3a)_p is 2-Cl, 6-Br. 177A Q² is 2-Br-4-MeO, (R^3a)_p is 2-F.

71A Q² is 2,4-di-F-6-Cl-Ph, (R^3a)_p is 2,6-di-Cl. 178A Q² is 2-Br-4-MeO, (R^3a)_p is 2-Cl.

72A Q² is 2,4-di-F-6-Br-Ph, (R^3a)_p is 2,6-di-F. 179A Q² is 2-Br-4-MeO, (R^3a)_p is 2-Br.

73A Q² is 2,4-di-F-6-Br-Ph, (R^3a)_p is 2-F. 180A Q² is 2-Br-4-MeO, (R^3a)_p is 2-Me.

74A Q² is 2,4-di-F-6-Br-Ph, (R^3a)_p is 2-Cl. 181A Q² is 2-Br-4-MeO, (R^3a)_p is 2-Cl, 6-F.

75A Q² is 2,4-di-F-6-Br-Ph, (R^3a)_p is 2-Br. 182A Q² is 2-Br-4-MeO, (R^3a)_p is 2-Cl, 6-Br.

76A Q² is 2,4-di-F-6-Br-Ph, (R^3a)_p is 2-Me. 183 A Q² is 2-Br-4-MeO, (R^3a)_p is 2,6-di-Cl.

77A Q² is 2,4-di-F-6-Br-Ph, (R^3a)_p is 2-Cl, 6-F. 184A Q² is 2,4-di-Cl, (R^3a)_p is 2,6-di-F.

78A Q² is 2,4-di-F-6-Br-Ph, (R^3a)_p is 2-Cl, 6-Br. 185A Q² is 2,4-di-Cl, (R^3a)_p is 2-F.

79A Q² is 2,4-di-F-6-Br-Ph, (R^3a)_p is 2,6-di-Cl. 186A Q² is 2,4-di-Cl, (R^3a)_p is 2-Cl.

80A Q² is 2-Cl-4-Me-6-F-Ph, (R^3a)_p is 2,6-di-F. 187A Q² is 2,4-di-Cl, (R^3a)_p is 2-Br.

81A Q² is 2-Cl-4-Me-6-F-Ph, (R^3a)_p is 2-F. 188A Q² is 2,4-di-Cl, (R^3a)_p is 2-Me.

82A Q² is 2-Cl-4-Me-6-F-Ph, (R^3a)_p is 2-Cl. 189A Q² is 2,4-di-Cl, (R^3a)_p is 2-Cl, 6-F.

83A Q² is 2-Cl-4-Me-6-F-Ph, (R^3a)_p is 2-Br. 190A Q² is 2,4-di-Cl, (R^3a)_p is 2-Cl, 6-Br.

84A Q² is 2-Cl-4-Me-6-F-Ph, (R^3a)_p is 2-Me. 191A Q² is 2,4-di-Cl, (R^3a)_p is 2,6-di-Cl.

85A Q² is 2-Cl-4-Me-6-F-Ph, (R^3a)_p is 2-Cl, 6-F. 192 A Q² is 2,6-di-Cl, (R^3a)_p is 2,6-di-F.

86A Q² is 2-Cl-4-Me-6-F-Ph, (R^3a)_p is 2-Cl, 6-Br. 193A Q² is 2,6-di-Cl, (R^3a)_p is 2-F.

87A Q² is 2-Cl-4-Me-6-F-Ph, (R^3a)_p is 2,6-di-Cl. 194 A Q² is 2,6-di-Cl, (R^3a)_p is 2-Cl.

88A Q² is 2-Cl-4-MeO-6-F-Ph, (R^3a)_p is 2,6-di-F. 195A Q² is 2,6-di-Cl, (R^3a)_p is 2-Br.

89A Q² is 2-Cl-4-MeO-6-F-Ph, (R^3a)_p is 2-F. 196A Q² is 2,6-di-Cl, (R^3a)_p is 2-Me.

90A Q² is 2-Cl-4-MeO-6-F-Ph, (R^3a)_p is 2-Cl. 197A Q² is 2,6-di-Cl, (R^3a)_p is 2-Cl, 6-F.

91A Q² is 2-Cl-4-MeO-6-F-Ph, (R^3a)_p is 2-Br. 198A Q² is 2,6-di-Cl, (R^3a)_p is 2-Cl, 6-Br.

92A Q² is 2-Cl-4-MeO-6-F-Ph, (R^3a)_p is 2-Me. 199 A Q² is 2,6-di-Cl, (R^3a)_p is 2,6-di-Cl.

93A Q² is 2-Cl-4-MeO-6-F-Ph, (R^3a)_p is 2-Cl, 6-F. 200A Q² is 2,4-di-Me, (R^3a)_p is 2,6-di-F. Table Row Heading Table Row Heading

94A Q² is 2-Cl-4-MeO-6-F-Ph, (R^3a)_p is 2-Cl, 6-Br. 201A Q² is 2,4 -di-Me, (R^3a)_p is 2-F.

95A Q² is 2-Cl-4-MeO-6-F-Ph, (R^3a)_p is 2,6-di-Cl. 202A Q² is 2,4 -di-Me, (R^3a)_p is 2-Cl.

96A Q² is 2-Br-4-Me-6-F-Ph, (R^3a)_p is 2,6-di-F. 203A Q² is 2,4 -di-Me, (R^3a)_p is 2-Br.

97A Q² is 2-Br-4-Me-6-F-Ph, (R^3a)_p is 2-F. 204A Q² is 2,4 -di-Me, (R^3a)_p is 2-Me.

98A Q² is 2-Br-4-Me-6-F-Ph, (R^3a)_p is 2-Cl. 205A Q² is 2,4 -di-Me, (R^3a)_p is 2-Cl, 6-F.

99A Q² is 2-Br-4-Me-6-F-Ph, (R^3a)_p is 2-Br. 206A Q² is 2,4 -di-Me, (R^3a)_p is 2-Cl, 6-Br.

100A Q² is 2-Br-4-Me-6-F-Ph, (R^3a)_p is 2-Me. 207A Q² is 2,4 -di-Me, (R^3a)_p is 2,6-di-Cl.

101A Q² is 2-Br-4-Me-6-F-Ph, (R^3a)_p is 2-Cl, 6-F. 208A Q² is 2,6 -di-Me, (R^3a)_p is 2,6-di-F.

102 A Q² is 2-Br-4-Me-6-F-Ph, (R^3a)_p is 2-Cl, 6-Br. 209A Q² is 2,6 -di-Me, (R^3a)_p is 2-F.

103 A Q² is 2-Br-4-Me-6-F-Ph, (R^3a)_p is 2,6-di-Cl. 210A Q² is 2,6 -di-Me, (R^3a)_p is 2-Cl.

104 A Q² is 2-Br-4-MeO-6-F-Ph, (R^3a)_p is 2,6-di-F. 211A Q² is 2,6 -di-Me, (R^3a)_p is 2-Br.

105 A Q² is 2-Br-4-MeO-6-F-Ph, (R^3a)_p is 2-F. 212A Q² is 2,6 -di-Me, (R^3a)_p is 2-Me.

106A Q² is 2-Br-4-MeO-6-F-Ph, (R^3a)_p is 2-Cl. 213A Q² is 2,6 -di-Me, (R^3a)_p is 2-Cl, 6-F.

107A Q² is 2-Br-4-MeO-6-F-Ph, (R^3a)_p is 2-Br. 214A Q² is 2,6 -di-Me, (R^3a)_p is 2-Cl, 6-Br.

215A Q² is 2,6 -di-Me, (R^3a)_p is 2,6-di-Cl.

Formulation/Utility

A compound of this invention will generally be used as a fungicidal active ingredient in a composition, i.e. formulation, with at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, which serve as a carrier. The formulation or composition ingredients are selected to be consistent with the physical properties of the active ingredient, mode of application and environmental factors such as soil type, moisture and temperature.

Useful formulations include both liquid and solid compositions. Liquid compositions include solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions and/or suspoemulsions) and the like, which optionally can be thickened into gels. The general types of aqueous liquid compositions are soluble concentrate, suspension concentrate, capsule suspension, concentrated emulsion, microemulsion and suspo-emulsion. The general types of nonaqueous liquid compositions are emulsifiable concentrate, microemulsifiable concentrate, dispersible concentrate and oil dispersion.

The general types of solid compositions are dusts, powders, granules, pellets, prills, pastilles, tablets, filled films (including seed coatings) and the like, which can be water-dispersible ("wettable") or water-soluble. Films and coatings formed from film- forming solutions or flowable suspensions are particularly useful for seed treatment. Active ingredient can be (micro)encapsulated and further formed into a suspension or solid formulation; alternatively the entire formulation of active ingredient can be encapsulated (or "overcoated"). Encapsulation can control or delay release of the active ingredient. An emulsifiable granule combines the advantages of both an emulsifiable concentrate formulation and a dry granular formulation. High-strength compositions are primarily used as intermediates for further formulation.

Sprayable formulations are typically extended in a suitable medium before spraying. Such liquid and solid formulations are formulated to be readily diluted in the spray medium, usually water. Spray volumes can range from about one to several thousand liters per hectare, but more typically are in the range from about ten to several hundred liters per hectare. Sprayable formulations can be tank mixed with water or another suitable medium for foliar treatment by aerial or ground application, or for application to the growing medium of the plant. Liquid and dry formulations can be metered directly into drip irrigation systems or metered into the furrow during planting. Liquid and solid formulations can be applied onto seeds of crops and other desirable vegetation as seed treatments before planting to protect developing roots and other subterranean plant parts and/or foliage through systemic uptake.

The formulations will typically contain effective amounts of active ingredient, diluent and surfactant within the following approximate ranges which add up to 100 percent by weight.

Weight Percent

Active

Ingredient Diluent Surfactant

Water-Dispersible and Water- 0.001-90 0-99.999 0-15 soluble Granules, Tablets and

Powders

Oil Dispersions, Suspensions, 1-50 40-99 0-50 Emulsions, Solutions (including

Emulsifiable Concentrates)

Dusts 1-25 70-99 0-5

Granules and Pellets 0.001-95 5-99.999 0-15

High Strength Compositions 90-99 0-10 0-2

Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, gypsum, cellulose, titanium dioxide, zinc oxide, starch, dextrin, sugars (e.g., lactose, sucrose), silica, talc, mica, diatomaceous earth, urea, calcium carbonate, sodium carbonate and bicarbonate, and sodium sulfate. Typical solid diluents are described in Watkins et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, New Jersey.

Liquid diluents include, for example, water, N,N-dimethylalkanamides (e.g., N,N-dimethylformamide), limonene, dimethyl sulfoxide, N-alkylpyrrolidones (e.g., N-methylpyrrolidinone), ethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, propylene carbonate, butylene carbonate, paraffins (e.g., white mineral oils, normal paraffins, isoparaffins), alkylbenzenes, alkylnaphthalenes, glycerine, glycerol triacetate, sorbitol, aromatic hydrocarbons, dearomatized aliphatics, alkylbenzenes, alkylnaphthalenes, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy- 4-methyl-2-pentanone, acetates such as isoamyl acetate, hexyl acetate, heptyl acetate, octyl acetate, nonyl acetate, tridecyl acetate and isobornyl acetate, other esters such as alkylated lactate esters, dibasic esters and γ-butyrolactone, and alcohols, which can be linear, branched, saturated or unsaturated, such as methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, n-hexanol, 2-ethylhexanol, n-octanol, decanol, isodecyl alcohol, isooctadecanol, cetyl alcohol, lauryl alcohol, tridecyl alcohol, oleyl alcohol, cyclohexanol, tetrahydrofurfuryl alcohol, diacetone alcohol and benzyl alcohol. Liquid diluents also include glycerol esters of saturated and unsaturated fatty acids (typically C6-C22), such as plant seed and fruit oils (e.g., oils of olive, castor, linseed, sesame, corn (maize), peanut, sunflower, grapeseed, safflower, cottonseed, soybean, rapeseed, coconut and palm kernel), animal-sourced fats (e.g., beef tallow, pork tallow, lard, cod liver oil, fish oil), and mixtures thereof. Liquid diluents also include alkylated fatty acids (e.g., methylated, ethylated, butylated) wherein the fatty acids may be obtained by hydrolysis of glycerol esters from plant and animal sources, and can be purified by distillation. Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950.

The solid and liquid compositions of the present invention often include one or more surfactants. When added to a liquid, surfactants (also known as "surface-active agents") generally modify, most often reduce, the surface tension of the liquid. Depending on the nature of the hydrophilic and lipophilic groups in a surfactant molecule, surfactants can be useful as wetting agents, dispersants, emulsifiers or defoaming agents.

Surfactants can be classified as nonionic, anionic or cationic. Nonionic surfactants useful for the present compositions include, but are not limited to: alcohol alkoxylates such as alcohol alkoxylates based on natural and synthetic alcohols (which may be branched or linear) and prepared from the alcohols and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof; amine ethoxylates, alkanolamides and ethoxylated alkanolamides; alkoxylated triglycerides such as ethoxylated soybean, castor and rapeseed oils; alkylphenol alkoxylates such as octylphenol ethoxylates, nonylphenol ethoxylates, dinonyl phenol ethoxylates and dodecyl phenol ethoxylates (prepared from the phenols and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); block polymers prepared from ethylene oxide or propylene oxide and reverse block polymers where the terminal blocks are prepared from propylene oxide; ethoxylated fatty acids; ethoxylated fatty esters and oils; ethoxylated methyl esters; ethoxylated tristyrylphenol (including those prepared from ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); fatty acid esters, glycerol esters, lanolin-based derivatives, polyethoxylate esters such as polyethoxylated sorbitan fatty acid esters, polyethoxylated sorbitol fatty acid esters and polyethoxylated glycerol fatty acid esters; other sorbitan derivatives such as sorbitan esters; polymeric surfactants such as random copolymers, block copolymers, alkyd peg (polyethylene glycol) resins, graft or comb polymers and star polymers; polyethylene glycols (pegs); polyethylene glycol fatty acid esters; silicone-based surfactants; and sugar-derivatives such as sucrose esters, alkyl polyglycosides and alkyl polysaccharides.

Useful anionic surfactants include, but are not limited to: alkylaryl sulfonic acids and their salts; carboxylated alcohol or alkylphenol ethoxylates; diphenyl sulfonate derivatives; lignin and lignin derivatives such as lignosulfonates; maleic or succinic acids or their anhydrides; olefin sulfonates; phosphate esters such as phosphate esters of alcohol alkoxylates, phosphate esters of alkylphenol alkoxylates and phosphate esters of styryl phenol ethoxylates; protein-based surfactants; sarcosine derivatives; styryl phenol ether sulfate; sulfates and sulfonates of oils and fatty acids; sulfates and sulfonates of ethoxylated alkylphenols; sulfates of alcohols; sulfates of ethoxylated alcohols; sulfonates of amines and amides such as N,N-alkyltaurates; sulfonates of benzene, cumene, toluene, xylene, and dodecyl and tridecylbenzenes; sulfonates of condensed naphthalenes; sulfonates of naphthalene and alkyl naphthalene; sulfonates of fractionated petroleum; sulfosuccinamates; and sulfosuccinates and their derivatives such as dialkyl sulfosuccinate salts.

Useful cationic surfactants include, but are not limited to: amides and ethoxylated amides; amines such as N-alkyl propanediamines, tripropylenetriamines and dipropylenetetramines, and ethoxylated amines, ethoxylated diamines and propoxylated amines (prepared from the amines and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); amine salts such as amine acetates and diamine salts; quaternary ammonium salts such as quaternary salts, ethoxylated quaternary salts and diquaternary salts; and amine oxides such as alkyldimethylamine oxides and bis-(2-hydroxyethyl)-alkylamine oxides.

Also useful for the present compositions are mixtures of nonionic and anionic surfactants or mixtures of nonionic and cationic surfactants. Nonionic, anionic and cationic surfactants and their recommended uses are disclosed in a variety of published references including McCutcheon 's Emulsifiers and Detergents, annual American and International Editions published by McCutcheon's Division, The Manufacturing Confectioner Publishing Co.; Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964; and A. S. Davidson and B. Milwidsky, Synthetic Detergents, Seventh Edition, John Wiley and Sons, New York, 1987.

Compositions of this invention may also contain formulation auxiliaries and additives, known to those skilled in the art as formulation aids (some of which may be considered to also function as solid diluents, liquid diluents or surfactants). Such formulation auxiliaries and additives may control: pH (buffers), foaming during processing (antifoams such polyorganosiloxanes), sedimentation of active ingredients (suspending agents), viscosity (thixotropic thickeners), in-container microbial growth (antimicrobials), product freezing (antifreezes), color (dyes/pigment dispersions), wash-off (film formers or stickers), evaporation (evaporation retardants), and other formulation attributes. Film formers include, for example, polyvinyl acetates, polyvinyl acetate copolymers, polyvinylpyrrolidone-vinyl acetate copolymer, polyvinyl alcohols, polyvinyl alcohol copolymers and waxes. Examples of formulation auxiliaries and additives include those listed in McCutcheon 's Volume 2: Functional Materials, annual International and North American editions published by McCutcheon's Division, The Manufacturing Confectioner Publishing Co.; and PCT Publication WO 03/024222.

The compound of Formula 1 or Formula 1A and any other active ingredients are typically incorporated into the present compositions by dissolving the active ingredient in a solvent or by grinding in a liquid or dry diluent. Solutions, including emulsifiable concentrates, can be prepared by simply mixing the ingredients. If the solvent of a liquid composition intended for use as an emulsifiable concentrate is water-immiscible, an emulsifier is typically added to emulsify the active-containing solvent upon dilution with water. Active ingredient slurries, with particle diameters of up to 2,000 μιη can be wet milled using media mills to obtain particles with average diameters below 3 μιη. Aqueous slurries can be made into finished suspension concentrates (see, for example, U.S. 3,060,084) or further processed by spray drying to form water-dispersible granules. Dry formulations usually require dry milling processes, which produce average particle diameters in the 2 to 10 μιη range. Dusts and powders can be prepared by blending and usually grinding (such as with a hammer mill or fluid-energy mill). Granules and pellets can be prepared by spraying the active material upon preformed granular carriers or by agglomeration techniques. See Browning, "Agglomeration", Chemical Engineering, December 4, 1967, pp 147-48, Perry 's Chemical Engineer 's Handbook, 4th Ed., McGraw- Hill, New York, 1963, pages 8-57 and following, and WO 91/13546. Pellets can be prepared as described in U.S. 4,172,714. Water-dispersible and water-soluble granules can be prepared as taught in U.S. 4,144,050, U.S. 3,920,442 and DE 3,246,493. Tablets can be prepared as taught in U.S. 5,180,587, U.S. 5,232,701 and U.S. 5,208,030. Films can be prepared as taught in GB 2,095,558 and U.S. 3,299,566.

For further information regarding the art of formulation, see T. S. Woods, "The Formulator's Toolbox - Product Forms for Modern Agriculture" in Pesticide Chemistry and Bioscience, The Food-Environment Challenge, T. Brooks and T. R. Roberts, Eds., Proceedings of the 9th International Congress on Pesticide Chemistry, The Royal Society of Chemistry, Cambridge, 1999, pp. 120-133. See also U.S. 3,235,361, Col. 6, line 16 through Col. 7, line 19 and Examples 10-41; U.S. 3,309,192, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182; U.S. 2,891,855, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4; Klmgman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, pp 81-96; Hance et al, Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989; and Developments in formulation technology, PJB Publications, Richmond, UK, 2000.

In the following Examples, all percentages are by weight and all formulations are prepared in conventional ways. Compound numbers refer to compounds in Index Table A. Without further elaboration, it is believed that one skilled in the art using the preceding description can utilize the present invention to its fullest extent. The following Examples are, therefore, to be constructed as merely illustrative, and not limiting of the disclosure in any way whatsoever. Percentages are by weight except where otherwise indicated.

Example A

High Strength Concentrate

Compound 9 98.5% silica aerogel 0.5% synthetic amorphous fine silica 1.0%

Example B

Wettable Powder

Compound 10 65.0% dodecylphenol polyethylene glycol ether 2.0%> sodium ligninsulfonate 4.0%> sodium silicoaluminate 6.0%> montmorillonite (calcined) 23.0%

Example C

Granule

Compound 2 10.0% attapulgite granules (low volatile matter, 0.71/0.30 mm; 90.0% U.S.S. No. 25-50 sieves)

Example D

Extruded Pellet

Compound 3 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0%> sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%

Example E

Emulsifiable Concentrate

Compound 24 10.0% polyoxyethylene sorbitol hexoleate 20.0%

C^-Cio fatty acid methyl ester 70.0%

Example F

Microemulsion

Compound 27 5.0% polyvinylpyrrolidone -vinyl acetate copolymer 30.0% alkylpolyglycoside 30.0%> glyceryl monooleate 15.0% water 20.0%

Example G

Seed Treatment

Compound 2 20.00% polyvinylpyrrolidone -vinyl acetate copolymer 5.00% montan acid wax 5.00% calcium ligninsulfonate 1.00% polyoxyethylene/polyoxypropylene block copolymers 1.00% stearyl alcohol (POE 20) 2.00% polyorganosilane 0.20%> colorant red dye 0.05%> water 65.75%

Water-soluble and water-dispersible formulations are typically diluted with water to form aqueous compositions before application. Aqueous compositions for direct applications to the plant or portion thereof (e.g., spray tank compositions) typically at least about 1 ppm or more (e.g., from 1 ppm to 100 ppm) of the compound(s) of this invention.

The compounds of this invention are useful as plant disease control agents. The present invention therefore further comprises a method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof to be protected, or to the plant seed to be protected, an effective amount of a compound of the invention or a fungicidal composition containing said compound. The compounds and/or compositions of this invention provide control of diseases caused by a broad spectrum of fungal plant pathogens in the Basidiomycete, Ascomycete, Oomycete and Deuteromycete classes. They are effective in controlling a broad spectrum of plant diseases, particularly foliar pathogens of ornamental, turf, vegetable, field, cereal, and fruit crops. These pathogens include: Oomycetes, including Phytophthora diseases such as Phytophthora infestans, Phytophthora megasperma, Phytophthora parasitica, Phytophthora cinnamomi and Phytophthora capsici, Pythium diseases such as Pythium aphanidermatum, and diseases in the Peronosporaceae family such as Plasmopara viticola, Peronospora spp. (including Peronospora tabacina and Peronospora parasitica), Pseudoperonospora spp. (including Pseudoperonospora cubensis) and Bremia lactucae; Ascomycetes, including Alternaria diseases such as Alternaria solani and Alternaria brassicae, Guignardia diseases such as Guignardia bidwell, Venturia diseases such as Venturia inaequalis, Septoria diseases such as Septoria nodorum and Septoria tritici, powdery mildew diseases such as Erysiphe spp. (including Erysiphe graminis and Erysiphe polygoni), Uncinula necatur, Sphaerotheca fuliginea, Podosphaera leucotricha and Pseudocercosporella herpotrichoides, Botrytis diseases such as Botrytis cinerea, Monilinia fructicola, Sclerotinia diseases such as Sclerotinia sclerotiorum, Sclerotinia minor, Magnaporthe grisea, and Phomopsis viticola, Helminthosporium diseases such as Helminthosporium tritici repentis and Pyrenophora teres, anthracnose diseases such as Glomerella or Colletotrichum spp. (such as Colletotrichum graminicola and Colletotrichum orbiculare), and Gaeumannomyces graminis; Basidiomycetes, including rust diseases caused by Puccinia spp. (such as Puccinia recondita, Puccinia striiformis, Puccinia hordei, Puccinia graminis and Puccinia arachidis), Hemileia vastatrix and Phakopsora pachyrhizi; other pathogens including Rutstroemia floccosum (also known as Sclerotinia homoeocarpa); Rhizoctonia spp. (such as Rhizoctonia solani); Fusarium diseases such as Fusarium roseum, Fusarium graminearum and Fusarium oxysporumVerticillium dahliae; Sclerotium rolfsii; Rynchosporium secalis; Cercosporidium personatum, Cercospora arachidicola and Cercospora beticola; Rhizopus spp. (such as Rhizopus stolonifer); Aspergillus spp. (such as Aspergillus flavus and Aspergillus parasiticus); and other genera and species closely related to these pathogens. In addition to their fungicidal activity, the compositions or combinations also have activity against bacteria such as Erwinia amylovora, Xanthomonas campestris, Pseudomonas syringae, and other related species. Furthermore, the compounds of this invention are useful in treating postharvest diseases of fruits and vegetables caused by fungi and bacteria. These infections can occur before, during and after harvest. For example, infections can occur before harvest and then remain dormant until some point during ripening (e.g., host begins tissue changes in such a way that infection can progress); also infections can arise from surface wounds created by mechanical or insect injury. In this respect, the compounds of this invention can reduce losses (i.e. losses resulting from quantity and quality) due to postharvest diseases which may occur at any time from harvest to consumption. Treatment of postharvest diseases with compounds of the invention can increase the period of time during which perishable edible plant parts (e.g, fruits, seeds, foliage, stems, bulbs, tubers) can be stored refrigerated or un-refrigerated after harvest, and remain edible and free from noticeable or harmful degradation or contamination by fungi or other microorganisms. Treatment of edible plant parts before or after harvest with compounds of the invention can also decrease the formation of toxic metabolites of fungi or other microorganisms, for example, mycotoxins such as aflatoxins. Plant disease control is ordinarily accomplished by applying an effective amount of a compound of this invention either pre- or post-infection, to the portion of the plant to be protected such as the roots, stems, foliage, fruits, seeds, tubers or bulbs, or to the media (soil or sand) in which the plants to be protected are growing. The compounds can also be applied to seeds to protect the seeds and seedlings developing from the seeds. The compounds can also be applied through irrigation water to treat plants. Control of postharvest pathogens which infect the produce before harvest is typically accomplished by field application of a compound of this invention, and in cases where infection occurs after harvest the compounds can be applied to the harvested crop as dips, sprays, fumigants, treated wraps and box liners.

Rates of application for these compounds (i.e. a fungicidally effective amount) can be influenced by factors such as the plant diseases to be controlled, the plant species to be protected, ambient moisture and temperature and should be determined under actual use conditions. One skilled in the art can easily determine through simple experimentation the fungicidally effective amount necessary for the desired level of plant disease control. Foliage can normally be protected when treated at a rate of from less than about 1 g/ha to about 5,000 g/ha of active ingredient. Seed and seedlings can normally be protected when seed is treated at a rate of from about 0.1 to about 10 g per kilogram of seed.

Compounds of this invention can also be mixed with one or more other biologically active compounds or agents including fungicides, insecticides, nematocides, bactericides, acaricides, herbicides, herbicide safeners, growth regulators such as insect molting inhibitors and rooting stimulants, chemosterilants, semiochemicals, repellents, attractants, pheromones, feeding stimulants, plant nutrients, other biologically active compounds or entomopathogenic bacteria, virus or fungi to form a multi-component pesticide giving an even broader spectrum of agricultural protection. Thus the present invention also pertains to a composition comprising a compound of Formula 1 (in a fungicidally effective amount) and at least one additional biologically active compound or agent (in a biologically effective amount) and can further comprise at least one of a surfactant, a solid diluent or a liquid diluent. The other biologically active compounds or agents can be formulated in compositions comprising at least one of a surfactant, solid or liquid diluent. For mixtures of the present invention, one or more other biologically active compounds or agents can be formulated together with a compound of Formula 1, to form a premix, or one or more other biologically active compounds or agents can be formulated separately from the compound of Formula 1, and the formulations combined together before application (e.g., in a spray tank) or, alternatively, applied in succession.

Of note is a composition which in addition to the compound of Formula 1 include at least one fungicidal compound selected from the group consisting of the classes (1) methyl benzimidazole carbamate (MBC) fungicides; (2) dicarboximide fungicides; (3) demethylation inhibitor (DMI) fungicides; (4) phenylamide fungicides; (5) amine/morpholine fungicides; (6) phospholipid biosynthesis inhibitor fungicides; (7) carboxamide fungicides; (8) hydroxy(2-amino-)pyrimidine fungicides; (9) anilinopyrimidine fungicides; (10) N-phenyl carbamate fungicides; (11) quinone outside inhibitor (Qol) fungicides; (12) phenylpyrrole fungicides; (13) quinoline fungicides; (14) lipid peroxidation inhibitor fungicides; (15) melanin biosynthesis inhibitors-reductase (MBI-R) fungicides; (16) melanin biosynthesis inhibitors-dehydratase (MBI-D) fungicides; (17) hydroxyanilide fungicides; (18) squalene-epoxidase inhibitor fungicides; (19) polyoxin fungicides; (20) phenylurea fungicides; (21) quinone inside inhibitor (Qil) fungicides; (22) benzamide fungicides; (23) enopyranuronic acid antibiotic fungicides; (24) hexopyranosyl antibiotic fungicides; (25) glucopyranosyl antibiotic: protein synthesis fungicides; (26) glucopyranosyl antibiotic: trehalase and inositol biosynthesis fungicides; (27) cyanoacetamideoxime fungicides; (28) carbamate fungicides; (29) oxidative phosphorylation uncoupling fungicides; (30) organo tin fungicides; (31) carboxylic acid fungicides; (32) heteroaromatic fungicides; (33) phosphonate fungicides; (34) phthalamic acid fungicides; (35) benzotriazine fungicides; (36) benzene-sulfonamide fungicides; (37) pyridazinone fungicides; (38) thiophene-carboxamide fungicides; (39) pyrimidinamide fungicides; (40) carboxylic acid amide (CAA) fungicides; (41) tetracycline antibiotic fungicides; (42) thiocarbamate fungicides; (43) benzamide fungicides; (44) host plant defense induction fungicides; (45) multi-site contact activity fungicides; (46) fungicides other than classes (1) through (45); and salts of compounds of classes (1) through (46).

Further descriptions of these classes of fungicidal compounds are provided below. (1) "Methyl benzimidazole carbamate (MBC) fungicides" (Fungicide Resistance Action Committee (FRAC) code 1) inhibit mitosis by binding to β-tubulin during microtubule assembly. Inhibition of microtubule assembly can disrupt cell division, transport within the cell and cell structure. Methyl benzimidazole carbamate fungicides include benzimidazoles and thiophanates. The benzimidazoles include benomyl, carbendazim, fuberidazole and thiabendazole. The thiophanates include thiophanate and thiophanate-methy 1.

(2) "Dicarboximide fungicides" (Fungicide Resistance Action Committee (FRAC) code 2) are proposed to inhibit a lipid peroxidation in fungi through interference with NADH cytochrome c reductase. Examples include chlozolinate, iprodione, procymidone and vinclozolin.

(3) "Demethylation inhibitor (DMI) fungicides" (Fungicide Resistance Action Committee (FRAC) code 3) inhibit C14-demethylase, which plays a role in sterol production. Sterols, such as ergosterol, are needed for membrane structure and function, making them essential for the development of functional cell walls. Therefore, exposure to these fungicides results in abnormal growth and eventually death of sensitive fungi. Demethylation fungicides include piperazines, pyridines, pyrimidines, imidazoles and triazoles. The piperazines include triforine. The pyridines include buthiobate and pyrifenox. The pyrimidines include fenarimol, nuarimol and triarimol. The imidazoles include clotrimazole, imazalil, oxpoconazole, prochloraz, pefurazoate and triflumizole. The triazoles include azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole (including diniconazole-M), epoxiconazole, etaconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, quinconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole, 1 -[[(25',3i?)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxiranyl]methyl]- 1H- 1,2,4-triazole, 2-[[(25',3i?)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxiranyl]methyl]- l,2-dihydro-3H-l,2,4-triazole-3-thione and l-[[(2S,3R)-3-(2-chlorophenyl)-2-(2,4- difluorophenyl)-2-oxiranyl]methyl]-5-(2-propen-l-ylthio)-lH-l,2,4-triazole. The imidazoles include clotrimazole, imazalil, oxpoconazole, prochloraz, pefurazoate and triflumizole. Biochemical investigations have shown that all of the above mentioned fungicides are DMI fungicides as described by K. Η. Kuck et al. in Modern Selective Fungicides - Properties, Applications and Mechanisms of Action, Η. Lyr (Ed.), Gustav Fischer Verlag: New York, 1995, 205-258.

(4) "Phenylamide fungicides" (Fungicide Resistance Action Committee (FRAC) code 4) are specific inhibitors of RNA polymerase in Oomycete fungi. Sensitive fungi exposed to these fungicides show a reduced capacity to incorporate uridine into rRNA. Growth and development in sensitive fungi is prevented by exposure to this class of fungicide. Phenylamide fungicides include acylalanines, oxazolidinones and butyrolactones. The acylalanines include benalaxyl, benalaxyl-M, furalaxyl, metalaxyl and metalaxyl- M/mefenoxam. The oxazolidinones include oxadixyl. The butyrolactones include ofurace.

(5) "Amine/morpholine fungicides" (Fungicide Resistance Action Committee (FRAC) code 5) inhibit two target sites within the sterol biosynthetic pathway, Δ⁸→ Δ⁷ isomerase and Δ¹⁴ reductase. Sterols, such as ergosterol, are needed for membrane structure and function, making them essential for the development of functional cell walls. Therefore, exposure to these fungicides results in abnormal growth and eventually death of sensitive fungi. Amine/morpholine fungicides (also known as non-DMI sterol biosynthesis inhibitors) include morpholines, piperidines and spiroketal-amines. The morpholines include aldimorph, dodemorph, fenpropimorph, tridemorph and trimorphamide. The piperidines include fenpropidin and piperalin. The spiroketal-amines include spiroxamine.

(6) "Phospholipid biosynthesis inhibitor fungicides" (Fungicide Resistance Action

Committee (FRAC) code 6) inhibit growth of fungi by affecting phospholipid biosynthesis. Phospholipid biosynthesis fungicides include phophorothiolates and dithiolanes. The phosphorothiolates include edifenphos, iprobenfos and pyrazophos. The dithiolanes include isoprothiolane.

(7) "Carboxamide fungicides" (Fungicide Resistance Action Committee (FRAC) code 7) inhibit Complex II (succinate dehydrogenase) fungal respiration by disrupting a key enzyme in the Krebs Cycle (TCA cycle) named succinate dehydrogenase. Inhibiting respiration prevents the fungus from making ATP, and thus inhibits growth and reproduction. Carboxamide fungicides include phenyl benzamides, pyridinyl ethyl benzamides, furan carboxamides, oxathiin carboxamides, thiazole carboxamides, pyrazole carboxamides and pyridine carboxamides. The phenyl benzamides include benodanil, flutolanil and mepronil. The pyridinyl ethyl benzamides include fluopyram. The furan carboxamides include fenfuram. The oxathiin carboxamides include carboxin and oxycarboxin. The thiazole carboxamides include thifluzamide. The pyrazole carboxamides include furametpyr, penthiopyrad, bixafen, isopyrazam, benzovindiflupyr, N-[2-(lS,2R)- [1,1 '-bicyclopropyl]-2-ylphenyl]-3-(difluoromethyl)- 1 -methyl- lH-pyrazole-4-carboxamide, penflufen, (N-[2-(l ,3-dimethylbutyl)phenyl]-5-fluoro- 1 ,3-dimethyl- lH-pyrazole-4- carboxamide), N-[2-(2,4-dichlorophenyl)-2-methoxy-l-methylethyl]-3-(difluoromethyl)-l- methyl- lH-pyrazole-4-carboxamide and N-cyclopropyl-3 -(difluoromethyl)-5 -fluoro- 1 - methyl-N-[[2-(l-methylethyl)phenyl]methyl]-lH-pyrazole-4-carboxamide. The pyridine carboxamides include boscalid.

(8) "Hydroxy(2-amino-)pyrimidine fungicides" (Fungicide Resistance Action

Committee (FRAC) code 8) inhibit nucleic acid synthesis by interfering with adenosine deaminase. Examples include bupirimate, dimethirimol and ethirimol.

(9) "Anilinopyrimidine fungicides" (Fungicide Resistance Action Committee (FRAC) code 9) are proposed to inhibit biosynthesis of the amino acid methionine and to disrupt the secretion of hydrolytic enzymes that lyse plant cells during infection. Examples include cyprodinil, mepanipyrim and pyrimethanil.

(10) "N-Phenyl carbamate fungicides" (Fungicide Resistance Action Committee (FRAC) code 10) inhibit mitosis by binding to β-tubulin and disrupting microtubule assembly. Inhibition of microtubule assembly can disrupt cell division, transport within the cell and cell structure. Examples include diethofencarb.

(11) "Quinone outside inhibitor (Qol) fungicides" (Fungicide Resistance Action Committee (FRAC) code 11) inhibit Complex III mitochondrial respiration in fungi by affecting ubiquinol oxidase. Oxidation of ubiquinol is blocked at the "quinone outside" (Q₀) site of the cytochrome bc\ complex, which is located in the inner mitochondrial membrane of fungi. Inhibiting mitochondrial respiration prevents normal fungal growth and development. Quinone outside inhibitor fungicides (also known as strobilurin fungicides) include methoxyacrylates, methoxycarbamates, oximinoacetates, oximinoacetamides, oxazolidinediones, dihydrodioxazines, imidazolinones and benzylcarbamates. The methoxyacrylates include azoxystrobin, coumoxystrobin, enestroburin, flufenoxystrobin, picoxystrobin and pyraoxystrobin. The methoxycarbamates include pyraclostrobin, pyrametostrobin and triclopyricarb. The oximinoacetates include kresoxim-methyl and trifloxystrobin. The oximinoacetamides include dimoxystrobin, metominostrobin, orysastrobin, a-[methoxyimino]-N-methyl-2-[[[ 1 -[3-(trifluoromethyl)phenyl]ethoxy]imino]- methyljbenzeneacetamide and 2-[[[3-(2,6-dichlorophenyl)- 1 -methyl-2-propen- 1 -ylidene]- amino]oxy]methyl]-a-(methoxyimino)-N-methylbenzeneacetamide. The oxazolidinediones include famoxadone. The dihydrodioxazines include fluoxastrobin. The imidazolinones include fenamidone. The benzylcarbamates include pyribencarb. Class (11) also includes 2- [(2,5-dimethylphenoxy)methyl]-a-methoxy-N-benzeneacetamide.

(12) "Phenylpyrrole fungicides" (Fungicide Resistance Action Committee (FRAC) code 12) inhibit a MAP protein kinase associated with osmotic signal transduction in fungi. Fenpiclonil and fludioxonil are examples of this fungicide class.

(13) "Azanaphthalene fungicides" (Fungicide Resistance Action Committee (FRAC) code 13) are proposed to inhibit signal transduction by affecting G-proteins in early cell signaling. They have been shown to interfere with germination and/or appressorium formation in fungi that cause powder mildew diseases. Azanaphthalene fungicides include aryloxyquinolines and quinazolinone. The aryloxyquinolines include quinoxyfen and tebufloquin. The quinazolinones include proquinazid.

(14) "Lipid peroxidation inhibitor fungicides" (Fungicide Resistance Action

Committee (FRAC) code 14) are proposed to inhibit lipid peroxidation which affects membrane synthesis in fungi. Members of this class, such as etridiazole, may also affect other biological processes such as respiration and melanin biosynthesis. Lipid peroxidation fungicides include aromatic carbons and 1,2,4-thiadiazoles. The aromatic carbon fungicides include biphenyl, chloroneb, dicloran, quintozene, tecnazene and tolclofos-methyl. The 1,2,4-thiadiazole fungicides include etridiazole.

(15) "Melanin biosynthesis inhibitors-reductase (MBI-R) fungicides" (Fungicide Resistance Action Committee (FRAC) code 16.1) inhibit the naphthal reduction step in melanin biosynthesis. Melanin is required for host plant infection by some fungi. Melanin biosynthesis inhibitors-reductase fungicides include isobenzofuranones, pyrroloquinolinones and triazolobenzothiazoles. The isobenzofuranones include fthalide. The pyrroloquinolinones include pyroquilon. The triazolobenzothiazoles include tricyclazole.

(16) "Melanin biosynthesis inhibitors-dehydratase (MBI-D) fungicides" (Fungicide Resistance Action Committee (FRAC) code 16.2) inhibit scytalone dehydratase in melanin biosynthesis. Melanin in required for host plant infection by some fungi. Melanin biosynthesis inhibitors-dehydratase fungicides include cyclopropanecarboxamides, carboxamides and propionamides. The cyclopropanecarboxamides include carpropamid. The carboxamides include diclocymet. The propionamides include fenoxanil. (17) "Hydroxy anilide fungicides (Fungicide Resistance Action Committee (FRAC) code 17) inhibit C4-demethylase which plays a role in sterol production. Examples include fenhexamid.

(18) "Squalene-epoxidase inhibitor fungicides" (Fungicide Resistance Action Committee (FRAC) code 18) inhibit squalene-epoxidase in ergosterol biosynthesis pathway.

Sterols such as ergosterol are needed for membrane structure and function, making them essential for the development of functional cell walls. Therefore exposure to these fungicides results in abnormal growth and eventually death of sensitive fungi. Squalene- epoxidase inhibitor fungicides include thiocarbamates and allylaminess. The thiocarbamates include pyributicarb. The allylamines include naftifine and terbinafme.

(19) "Polyoxin fungicides" (Fungicide Resistance Action Committee (FRAC) code 19) inhibit chitin synthase. Examples include polyoxin.

(20) "Phenylurea fungicides" (Fungicide Resistance Action Committee (FRAC) code 20) are proposed to affect cell division. Examples include pencycuron.

(21) "Quinone inside inhibitor (Qil) fungicides" (Fungicide Resistance Action

Committee (FRAC) code 21) inhibit Complex III mitochondrial respiration in fungi by affecting ubiquinol reductase. Reduction of ubiquinol is blocked at the "quinone inside" (Qi) site of the cytochrome bc\ complex, which is located in the inner mitochondrial membrane of fungi. Inhibiting mitochondrial respiration prevents normal fungal growth and development. Quinone inside inhibitor fungicides include cyanoimidazoles and sulfamoyltriazoles. The cyanoimidazoles include cyazofamid. The sulfamoyltriazoles include amisulbrom.

(22) "Benzamide fungicides" (Fungicide Resistance Action Committee (FRAC) code 22) inhibit mitosis by binding to β-tubulin and disrupting microtubule assembly. Inhibition of microtubule assembly can disrupt cell division, transport within the cell and cell structure. Examples include zoxamide.

(23) "Enopyranuronic acid antibiotic fungicides" (Fungicide Resistance Action Committee (FRAC) code 23) inhibit growth of fungi by affecting protein biosynthesis. Examples include blasticidin-S.

(24) "Hexopyranosyl antibiotic fungicides" (Fungicide Resistance Action Committee

(FRAC) code 24) inhibit growth of fungi by affecting protein biosynthesis. Examples include kasugamycin.

(25) "Glucopyranosyl antibiotic: protein synthesis fungicides" (Fungicide Resistance Action Committee (FRAC) code 25) inhibit growth of fungi by affecting protein biosynthesis. Examples include streptomycin.

(26) "Glucopyranosyl antibiotic: trehalase and inositol biosynthesis fungicides" (Fungicide Resistance Action Committee (FRAC) code 26) inhibit trehalase in inositol biosynthesis pathway. Examples include validamycin. (27) "Cyanoacetamideoxime fungicides (Fungicide Resistance Action Committee (FRAC) code 27) include cymoxanil.

(28) "Carbamate fungicides" (Fungicide Resistance Action Committee (FRAC) code 28) are considered multi-site inhibitors of fungal growth. They are proposed to interfere with the synthesis of fatty acids in cell membranes, which then disrupts cell membrane permeability. Propamacarb, propamacarb-hydrochloride, iodocarb, and prothiocarb are examples of this fungicide class.

(29) "Oxidative phosphorylation uncoupling fungicides" (Fungicide Resistance Action Committee (FRAC) code 29) inhibit fungal respiration by uncoupling oxidative phosphorylation. Inhibiting respiration prevents normal fungal growth and development. This class includes 2,6-dinitroanilines such as fluazinam, pyrimidonehydrazones such as ferimzone and dinitrophenyl crotonates such as dinocap, meptyldinocap and binapacryl.

(30) "Organo tin fungicides" (Fungicide Resistance Action Committee (FRAC) code 30) inhibit adenosine triphosphate (ATP) synthase in oxidative phosphorylation pathway. Examples include fentin acetate, fentin chloride and fentin hydroxide.

(31) "Carboxylic acid fungicides" (Fungicide Resistance Action Committee (FRAC) code 31) inhibit growth of fungi by affecting deoxyribonucleic acid (DNA) topoisomerase type II (gyrase). Examples include oxolinic acid.

(32) "Heteroaromatic fungicides" (Fungicide Resistance Action Committee (FRAC) code 32) are proposed to affect DNA/ribonucleic acid (RNA) synthesis. Heteroaromatic fungicides include isoxazoles and isothiazolones. The isoxazoles include hymexazole and the isothiazolones include octhilinone.

(33) "Phosphonate fungicides" (Fungicide Resistance Action Committee (FRAC) code 33) include phosphorous acid and its various salts, including fosetyl-aluminum.

(34) "Phthalamic acid fungicides" (Fungicide Resistance Action Committee (FRAC) code 34) include teclofthalam.

(35) "Benzotriazine fungicides" (Fungicide Resistance Action Committee (FRAC) code 35) include triazoxide.

(36) "Benzene-sulfonamide fungicides" (Fungicide Resistance Action Committee (FRAC) code 36) include flusulfamide.

(37) "Pyridazinone fungicides" (Fungicide Resistance Action Committee (FRAC) code 37) include diclomezine.

(38) "Thiophene-carboxamide fungicides" (Fungicide Resistance Action Committee (FRAC) code 38) are proposed to affect ATP production. Examples include silthiofam.

(39) "Pyrimidinamide fungicides" (Fungicide Resistance Action Committee (FRAC) code 39) inhibit growth of fungi by affecting phospholipid biosynthesis and include diflumetorim. (40) "Carboxylic acid amide (CAA) fungicides" (Fungicide Resistance Action Committee (FRAC) code 40) are proposed to inhibit phospholipid biosynthesis and cell wall deposition. Inhibition of these processes prevents growth and leads to death of the target fungus. Carboxylic acid amide fungicides include cinnamic acid amides, valinamide carbamates, carbamates and mandelic acid amides. The cinnamic acid amides include dimethomorph and flumorph. The valinamide carbamates include benthiavalicarb, benthiavalicarb-isopropyl, iprovalicarb, valifenalate and valiphenal. The carbamates include tolprocarb. The mandelic acid amides include mandipropamid, N-[2-[4-[[3-(4- chlorophenyl)-2-propyn-l-yl]oxy]-3-methoxyphenyl]ethyl]-3-methyl-2-[(methylsulfonyl)- amino Jbutanamide and N-[2-[4-[[3-(4-chlorophenyl)-2-propyn-l-yl]oxy]-3-methoxyphenyl]- ethyl] -3 -methyl-2- [(ethylsulfonyl)amino]butanamide.

(41) "Tetracycline antibiotic fungicides" (Fungicide Resistance Action Committee (FRAC) code 41) inhibit growth of fungi by affecting complex 1 nicotinamide adenine dinucleotide (NADH) oxidoreductase. Examples include oxytetracycline.

(42) "Thiocarbamate fungicides" (Fungicide Resistance Action Committee (FRAC) code 42) include methasulfocarb.

(43) "Benzamide fungicides" (Fungicide Resistance Action Committee (FRAC) code 43) inhibit growth of fungi by derealization of spectrin-like proteins. Examples include acylpicolide fungicides such as fluopicolide.

(44) "Host plant defense induction fungicides" (Fungicide Resistance Action

Committee (FRAC) code P) induce host plant defense mechanisms. Host plant defense induction fungicides include benzothiadiazoles, benzisothiazoles and thiadiazolecarboxamides. The benzothiadiazoles include acibenzolar-S-methyl. The benzisothiazoles include probenazole. The thiadiazolecarboxamides include tiadinil and isotianil.

(45) "Multi-site contact fungicides" inhibit fungal growth through multiple sites of action and have contact/preventive activity. This class of fungicides includes: (45.1) "copper fungicides" (Fungicide Resistance Action Committee (FRAC) code Ml)", (45.2) "sulfur fungicides" (Fungicide Resistance Action Committee (FRAC) code M2), (45.3) "dithiocarbamate fungicides" (Fungicide Resistance Action Committee (FRAC) code M3), (45.4) "phthalimide fungicides" (Fungicide Resistance Action Committee (FRAC) code M4), (45.5) "chloronitrile fungicides" (Fungicide Resistance Action Committee (FRAC) code M5), (45.6) "sulfamide fungicides" (Fungicide Resistance Action Committee (FRAC) code M6), (45.7) "guanidine fungicides" (Fungicide Resistance Action Committee (FRAC) code M7), (45.8) "triazine fungicides" (Fungicide Resistance Action Committee (FRAC) code M8) and (45.9) "quinone fungicides" (Fungicide Resistance Action Committee (FRAC) code M9). "Copper fungicides" are inorganic compounds containing copper, typically in the copper(II) oxidation state; examples include copper oxychloride, copper sulfate and copper hydroxide, including compositions such as Bordeaux mixture (tribasic copper sulfate). "Sulfur fungicides" are inorganic chemicals containing rings or chains of sulfur atoms; examples include elemental sulfur. "Dithiocarbamate fungicides" contain a dithiocarbamate molecular moiety; examples include mancozeb, metiram, propineb, ferbam, maneb, thiram, zineb and ziram. "Phthalimide fungicides" contain a phthalimide molecular moiety; examples include folpet, captan and captafol. "Chloronitrile fungicides" contain an aromatic ring substituted with chloro and cyano; examples include chlorothalonil. "Sulfamide fungicides" include dichlofluanid and tolyfluanid. "Guanidine fungicides" include dodine, guazatine, iminoctadine albesilate and iminoctadine triacetate. "Triazine fungicides" include anilazine. "Quinone fungicides" include dithianon.

(46) "Fungicides other than fungicides of classes (1) through (45)" include certain fungicides whose mode of action may be unknown. These include: (46.1) "thiazole carboxamide fungicides" (Fungicide Resistance Action Committee (FRAC) code U5), (46.2) "phenylacetamide fungicides" (Fungicide Resistance Action Committee (FRAC) code U6), (46.3) "arylphenylketone fungicides" (Fungicide Resistance Action Committee (FRAC) code U8) and (46.4) "triazolopyrimidine fungicides". The thiazole carboxamides include ethaboxam. The phenylacetamides include cyflufenamid and N-[[(cyclopropylmethoxy)- amino][6-(difluoromethoxy)-2,3-difluorophenyl]-methylene]benzeneacetamide. The arylphenylketones include benzophenones such as metrafenone and benzoylpyridines such as pyriofenone. The triazolopyrimidines include ametoctradin. Class (46) (i.e. "Fungicides other than classes (1) through (45)") also includes bethoxazin, fluxapyroxad, neo-asozin (ferric methanearsonate), pyrrolnitrin, quinomethionate, tebufloquin, isofetamid, N-[2-[4-[[3- (4-chlorophenyl)-2-propyn- 1 -yl]oxy] -3 -methoxyphenyl] ethyl] -3 -methyl-2- [(methylsulfonyl)amino]butanamide, N-[2-[4-[[3-(4-chlorophenyl)-2-propyn-l-yl]oxy]-3- methoxyphenyl] ethyl]-3 -methyl-2- [(ethylsulfonyl)amino]butanamide, 2- [ [2-fluoro-5 -

(trifluoromethyl)phenyl]thio]-2-[3-(2-methoxyphenyl)-2-thiazolidinylidene]acetonitrile, 3- [5-(4-chlorophenyl)-2,3-dimethyl-3-isoxazolidinyl]pyridine, 4-fluorophenyl N-[ 1 -[[[1 -(4- cyanophenyl)ethyl]sulfonyl]methyl]propyl] carbamate, 5-chloro-6-(2,4,6-trifluorophenyl)-7- (4-methylpiperidin- 1 -yl)[ 1 ,2,4]triazolo[ 1 ,5-a]pyrimidine, N-(4-chloro-2-nitrophenyl)-N- ethyl-4-methylbenzenesulfonamide, N-[[(cyclopropylmethoxy)amino] [6-(difluoromethoxy)- 2,3-difluorophenyl]methylene]benzeneacetamide, N'-[4-[4-chloro-3-(trifluoromethyl)- phenoxy]-2,5-dimethylphenyl]-N-ethyl-N-methylmethanimidamide, l-[(2-propenylthio)- carbonyl]-2-(l-methylethyl)-4-(2-methylphenyl)-5-amino-lH-pyrazol-3-one, N"-[4-[[3-[(4- chlorophenyl)methyl]-l,2,4-thiadiazol-5-yl]oxy]-2,5-dimethylphenyl]-N-ethyl-N-methyl- methanimidamide, 1,1-dimethylethyl N-[6-[[[[(l-methyl-lH-tetrazol-5-yl)phenylmethylene]- amino]oxy]methyl]-2-pyridinyl]carbamate, 3-butyn- 1 -yl N-[6-[[[[(l -methyl- lH-tetrazol-5- yl)phenylmethylene]amino]oxy]methyl]-2-pyridinyl]carbamate, 2,6-dimethyl-lH,5H- [l,4]dithiino[2,3-c:5,6-c']dipyrrole-l,3,5,7(2H,6H)-tetrone, 5-fluoro-2-[(4-methylphenyl)- methoxy]-4-pyrimidinamine, 5-fluoro-2-[(4-fluorophenyl)methoxy]-4-pyrimidinamine, a-[3- (4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)isoxazol-4-yl]pyrid-3-ylmethanol, (a5)-[3- (4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)isoxazol-4-yl]pyrid-3-ylmethanol and (ai?)- [3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)isoxazol-4-yl]pyrid-3-ylmethanol.

Therefore of note is a mixture (i.e. composition) comprising a compound of Formula 1 and at least one fungicidal compound selected from the group consisting of the aforedescribed classes (1) through (46). Also of note is a composition comprising said mixture (in fungicidally effective amount) and further comprising at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents. Of particular note is a mixture (i.e. composition) comprising a compound of Formula 1 and at least one fungicidal compound selected from the group of specific compounds listed above in connection with classes (1) through (46). Also of particular note is a composition comprising said mixture (in fungicidally effective amount) and further comprising at least one additional surfactant selected from the group consisting of surfactants, solid diluents and liquid diluents.

Examples of other biologically active compounds or agents with which compounds of this invention can be formulated are: insecticides such as abamectin, acephate, acetamiprid, acrinathrin, amidoflumet (S-1955), avermectin, azadirachtin, azinphos-methyl, bifenthrin, bifenazate, buprofezin, carbofuran, cartap, chlorantraniliprole, chlorfenapyr, chlorfluazuron, chlorpyrifos, chlorpyrifos-methyl, chromafenozide, clothianidin, cyantraniliprole (3-bromo- l-(3-chloro-2-pyridinyl)-N-[4-cyano-2-methyl-6-[(methylamino)carbonyl]phenyl]-lH- pyrazole-5-carboxamide), cyflumetofen, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda- cyhalothrin, cypermethrin, cyromazine, deltamethrin, diafenthiuron, diazinon, dieldrin, diflubenzuron, dimefluthrin, dimethoate, dinotefuran, diofenolan, emamectin, endosulfan, esfenvalerate, ethiprole, fenothiocarb, fenoxycarb, fenpropathrin, fenvalerate, fipronil, flonicamid, flubendiamide, flucythrinate, tau-fluvalinate, flufenerim (UR-50701), flufenoxuron, fonophos, halofenozide, hexaflumuron, hydramethylnon, imidacloprid, indoxacarb, isofenphos, lufenuron, malathion, meperfluthrin, metaflumizone, metaldehyde, methamidophos, methidathion, methomyl, methoprene, methoxychlor, methoxyfenozide, metofluthrin, milbemycin oxime, monocrotophos, nicotine, nitenpyram, nithiazine, novaluron, noviflumuron (XDE-007), oxamyl, parathion, parathion-methyl, permethrin, phorate, phosalone, phosmet, phosphamidon, pirimicarb, profenofos, profluthrin, pymetrozine, pyrafluprole, pyrethrin, pyridalyl, pyrifluquinazon, pyriprole, pyriproxyfen, rotenone, ryanodine, spinetoram, spinosad, spirodiclofen, spiromesifen (BSN 2060), spirotetramat, sulfoxaflor, sulprofos, tebufenozide, teflubenzuron, tefluthrin, terbufos, tetrachlorvinphos, tetramethylfluthrin, thiacloprid, thiamethoxam, thiodicarb, thiosultap- sodium, tolfenpyrad, tralomethrin, triazamate, trichlorfon and triflumuron; and biological agents including entomopathogenic bacteria, such as Bacillus thuringiensis subsp. aizawai, Bacillus thuringiensis subsp. kurstaki, and the encapsulated delta-endotoxins of Bacillus thuringiensis (e.g., Cellcap, MPV, MPVII); entomopathogenic fungi, such as green muscardine fungus; and entomopathogenic virus including baculovirus, nucleopolyhedro virus (NPV) such as HzNPV, AfNPV; and granulosis virus (GV) such as CpGV.

Compounds of this invention and compositions thereof can be applied to plants genetically transformed to express proteins toxic to invertebrate pests (such as Bacillus thuringiensis delta-endotoxins). The effect of the exogenously applied fungicidal compounds of this invention may be synergistic with the expressed toxin proteins.

General references for agricultural protectants (i.e. insecticides, fungicides, nematocides, acaricides, herbicides and biological agents) include The Pesticide Manual, 13th Edition, C. D. S. Tomlin, Ed., British Crop Protection Council, Farnham, Surrey, U.K., 2003 and The BioPesticide Manual, 2nd Edition, L. G. Copping, Ed., British Crop Protection Council, Farnham, Surrey, U.K., 2001.

For embodiments where one or more of these various mixing partners are used, the weight ratio of these various mixing partners (in total) to the compound of Formula 1 is typically between about 1 :3000 and about 3000: 1. Of note are weight ratios between about 1 :300 and about 300: 1 (for example ratios between about 1 :30 and about 30: 1). One skilled in the art can easily determine through simple experimentation the biologically effective amounts of active ingredients necessary for the desired spectrum of biological activity. It will be evident that including these additional components may expand the spectrum of diseases controlled beyond the spectrum controlled by the compound of Formula 1 alone.

In certain instances, combinations of a compound of this invention with other biologically active (particularly fungicidal) compounds or agents (i.e. active ingredients) can result in a greater-than-additive (i.e. synergistic) effect. Reducing the quantity of active ingredients released in the environment while ensuring effective pest control is always desirable. When synergism of fungicidal active ingredients occurs at application rates giving agronomically satisfactory levels of fungal control, such combinations can be advantageous for reducing crop production cost and decreasing environmental load.

Of note is a combination of a compound of Formula 1 with at least one other fungicidal active ingredient. Of particular note is such a combination where the other fungicidal active ingredient has different site of action from the compound of Formula 1. In certain instances, a combination with at least one other fungicidal active ingredient having a similar spectrum of control but a different site of action will be particularly advantageous for resistance management. Thus, a composition of the present invention can further comprise a biologically effective amount of at least one additional fungicidal active ingredient having a similar spectrum of control but a different site of action.

Of particular note are compositions which in addition to a compound of Formula 1 include at least one compound selected from the group consisting of (1) alkylenebis(dithiocarbamate) fungicides; (2) cymoxanil; (3) phenylamide fungicides; (4) proquinazid (6-iodo-3-propyl-2-propyloxy-4(3H)-quinazolinone); (5) chlorothalonil; (6) carboxamides acting at complex II of the fungal mitochondrial respiratory electron transfer site; (7) quinoxyfen; (8) metrafenone; (9) cyflufenamid; (10) cyprodinil; (11) copper compounds; (12) phthalimide fungicides; (13) fosetyl-aluminum; (14) benzimidazole fungicides; (15) cyazofamid; (16) fluazinam; (17) iprovalicarb; (18) propamocarb; (19) validomycin; (20) dichlorophenyl dicarboximide fungicides; (21) zoxamide; (22) fluopicolide; (23) mandipropamid; (24) carboxylic acid amides acting on phospholipid biosynthesis and cell wall deposition; (25) dimethomorph; (26) non-DMI sterol biosynthesis inhibitors; (27) inhibitors of demethylase in sterol biosynthesis; (28) bc\ complex fungicides; and salts of compounds of (1) through (28).

Further descriptions of classes of fungicidal compounds are provided below.

Sterol biosynthesis inhibitors (group (27)) control fungi by inhibiting enzymes in the sterol biosynthesis pathway. Demethylase-inhibiting fungicides have a common site of action within the fungal sterol biosynthesis pathway, involving inhibition of demethylation at position 14 of lanosterol or 24-methylene dihydrolanosterol, which are precursors to sterols in fungi. Compounds acting at this site are often referred to as demethylase inhibitors, DMI fungicides, or DMIs. The demethylase enzyme is sometimes referred to by other names in the biochemical literature, including cytochrome P-450 (14DM). The demethylase enzyme is described in, for example, J. Biol. Chem. 1992, 267, 13175-79 and references cited therein. DMI fungicides are divided between several chemical classes: azoles (including triazoles and imidazoles), pyrimidines, piperazines and pyridines. The triazoles include azaconazole, bromuconazole, cyproconazole, difenoconazole, diniconazole (including diniconazole-M), epoxiconazole, etaconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, quinconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole and uniconazole. The imidazoles include clotrimazole, econazole, imazalil, isoconazole, miconazole, oxpoconazole, prochloraz and triflumizole. The pyrimidines include fenarimol, nuarimol and triarimol. The piperazines include triforine. The pyridines include buthiobate and pyrifenox. Biochemical investigations have shown that all of the above mentioned fungicides are DMI fungicides as described by K. Η. Kuck et al. in Modern Selective Fungicides - Properties, Applications and Mechanisms of Action, Η. Lyr (Ed.), Gustav Fischer Verlag: New York, 1995, 205-258.

bc\ Complex Fungicides (group 28) have a fungicidal mode of action which inhibits the be i complex in the mitochondrial respiration chain. The bc\ complex is sometimes referred to by other names in the biochemical literature, including complex III of the electron transfer chain, and ubihydroquinone: cytochrome c oxidoreductase. This complex is uniquely identified by Enzyme Commission number EC 1.10.2.2. The bc\ complex is described in, for example, J. Biol. Chem. 1989, 264, 14543-48; Methods Enzymol. 1986, 126, 253-71; and references cited therein. Strobilurin fungicides such as azoxystrobin, dimoxystrobin, enestroburin (SYP-Z071), fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin and trifloxystrobin are known to have this mode of action (H. Sauter et al., Angew. Chem. Int. Ed. 1999, 38, 1328-1349). Other fungicidal compounds that inhibit the bc\ complex in the mitochondrial respiration chain include famoxadone and fenamidone.

Alkylenebis(dithiocarbamate)s (group (1)) include compounds such as mancozeb, maneb, propineb and zineb. Phenylamides (group (3)) include compounds such as metalaxyl, benalaxyl, furalaxyl and oxadixyl. Carboxamides (group (6)) include compounds such as boscalid, carboxin, fenfuram, flutolanil, furametpyr, mepronil, oxycarboxin, thifluzamide, penthiopyrad and N-[2-(l,3-dimethylbutyl)phenyl]-5-fluoro-l,3-dimethyl-lH- pyrazole-4-carboxamide (PCT Patent Publication WO 2003/010149), and are known to inhibit mitochondrial function by disrupting complex II (succinate dehydrogenase) in the respiratory electron transport chain. Copper compounds (group (11)) include compounds such as copper oxychloride, copper sulfate and copper hydroxide, including compositions such as Bordeaux mixture (tribasic copper sulfate). Phthalimides (group (12)) include compounds such as folpet and captan. Benzimidazole fungicides (group (14)) include benomyl and carbendazim. Dichlorophenyl dicarboximide fungicides (group (20)) include chlozolinate, dichlozoline, iprodione, isovaledione, myclozolin, procymidone and vinclozolin.

Non-DMI sterol biosynthesis inhibitors (group (26)) include morpholine and piperidine fungicides. The morpho lines and piperidines are sterol biosynthesis inhibitors that have been shown to inhibit steps in the sterol biosynthesis pathway at a point later than the inhibitions achieved by the DMI sterol biosynthesis (group (27)). The morpho lines include aldimorph, dodemorph, fenpropimorph, tridemorph and trimorphamide. The piperidines include fenpropidin.

The control efficacy of compounds of this invention on specific pathogens is demonstrated in TABLE A below. The pathogen control protection afforded by the compounds is not limited, however, to the species described in Tests A-E below. Descriptions of the compounds are provided in Index Table A below. The following abbreviations are used in the index table: Me is methyl, NO2 is nitro and Ph is phenyl, "Cmpd. No." means compound number, and "Ex." stands for "Example" and is followed by a number indicating in which example the compound is prepared. In Index Table A the numerical value reported in the column "AP⁺ (M+l)", is the molecular weight of the observed molecular ion formed by addition of H⁺ (molecular weight of 1) to the molecule having the greatest isotopic abundance (i.e. M). The presence of molecular ions containing one or higher atomic weight isotopes of lower abundance (e.g., ⁷C1, ⁸¹Br) is not reported. The reported M+1 peaks were observed by mass spectrometry using atmospheric pressure chemical ionization (AP⁺).

AP+ (M+l)

Cmpd. No. Q¹ m.p. (°C) AP+ (M+l)

35 2,6-di-Cl-4-Me-Ph 185-189

36 2,6-di-Cl-4-Me-Ph 170-175

* See synthesis example for ⁱH NMR.

BIOLOGICAL EXAMPLES OF THE INVENTION

General protocol for preparing test suspensions for Tests A-E: the test compounds were first dissolved in acetone in an amount equal to 3% of the final volume and then suspended at the desired concentration (in ppm) in acetone and purified water (50/50 mix by volume) containing 250 ppm of the surfactant Trem® 014 (polyhydric alcohol esters). The resulting test suspensions were then used in Tests A-E. Spraying a 200 ppm test suspension to the point of run-off on the test plants was the equivalent of a rate of 800 g/ha.

TEST A

The test suspension was sprayed to the point of run-off on wheat seedlings. The following day the seedlings were inoculated with a spore suspension of Puccinia recondita f. sp. tritici (the causal agent of wheat leaf rust) and incubated in a saturated atmosphere at 20 °C for 24 h, and then moved to a growth chamber at 20 °C for 7 days, after which time visual disease ratings were made.

TEST B

The test suspension was sprayed to the point of run-off on wheat seedlings. The following day the seedlings were inoculated with a spore suspension of Septoria tritici (the causal agent of wheat leaf blotch) and incubated in a saturated atmosphere at 24 °C for 48 h, and then moved to a growth chamber at 20 °C for 19 days, after which time visual disease ratings were made.

TEST C

The test suspension was sprayed to the point of run-off on tomato seedlings. The following day the seedlings were inoculated with a spore suspension of Botrytis cinerea (the causal agent of tomato Botrytis) and incubated in a saturated atmosphere at 20 °C for 48 h, and then moved to a growth chamber at 24 °C for 3 days, after which time visual disease ratings were made.

TEST D

The test suspension was sprayed to the point of run-off on wheat seedlings. The following day the seedlings were inoculated with a spore dust of Blumeria graminis f. sp. tritici, (also known as Erysiphe graminis f. sp. tritici, the causal agent of wheat powdery mildew) and incubated in a growth chamber at 20 °C for 8 days, after which time visual disease ratings were made.

TEST E

The test suspension was sprayed to the point of run-off on wheat seedlings. The following day the seedlings were inoculated with a spore suspension of Septoria nodorum (the causal agent of Septoria glume blotch) and incubated in a saturated atmosphere at 24 °C for 48 h, and then moved to a growth chamber at 20 °C for 9 days, after which time visual disease ratings were made.

Results for Tests A-E are given in Table A. In the Table, a rating of 100 indicates 100% disease control and a rating of 0 indicates no disease control (relative to the controls). A dash (-) indicates no test results. An asterisk "*" next to the rating value indicates a 40 ppm test suspension was used.

Table A

Cmpd. No Test A Test B Test C Test D Test E

1 28 100 44 89 0

2 100 97 100 100 100

3 99 99 100 100 98

4 19 96 91 100 0 Cmpd. No Test A Test B Test C Test D Test E

5 0 98 0 96 0

6 23 0 0 0 0

7 99 100 100 98 78

8 99 100 100 94 97

9 99 100 100 94 100

10 99 100 100 96 99

11 99 100 100 98 98

12 94 100 100 98 100

13 22 96 0 0 0

14 92 96 48 99 0

15 55 91 40 0 0

16 100 69 0 79 100

17 55 - 30 0 0

18 89 - 42 96 94

19 98 94 98 99 89

20 32 - 52 86 0

21 99 - 95 99 73

22 0 - 0 0 0

23 0* 88* 99* 96* 0*

24 100 99 100 97 99

25 99 100 100 21 0

26 22 16 0 0 0

27 99 98 50 99 64

28 - - - - -

29 - - - - -

30 - - - - -

31 - - - - -

32 - - - - -

33 - - - - -

34 - - - - -

35 - - - - -

36 - - - - -

37 - - - - -

38

Claims

CLAIMS What is claimed is:

1. A compound selected from Formula 1 N-oxides and salts thereof,

1

wherein

Q¹ is a phenyl ring or a naphthalenyl ring system, each ring or ring system optionally substituted with up to 5 substituents independently selected from R^3a and R^3b; or a 5- to 6-membered fully unsaturated heterocyclic ring or an 8- to 10-membered heteroaromatic bicyclic ring system, each ring or ring system containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, wherein up to 3 carbon ring members are independently selected from C(=0) and C(=S), and the sulfur atom ring members are independently selected from S(=0)_u(=NR²⁷)_v, each ring or ring system optionally substituted with up to 5 substituents independently selected from R^3a and R³^ on carbon atom ring members and selected from cyano, Ci-C₃ alkyl, C₂-C₃ alkenyl, C₂-C₃ alkynyl, C₃-C₆ cycloalkyl, C₂-C₃ alkoxyalkyl, C^-C₃ alkoxy, C₂-C₃ alkylcarbonyl, C₂-C₃ alkoxycarbonyl, C₂-C₃ alkylaminoalkyl and C₃-C4 dialkylaminoalkyl on nitrogen atom ring members; Q² is a phenyl ring or a naphthalenyl ring system, each ring or ring system optionally substituted with up to 5 substituents independently selected from R^3a and R^3b; or a 5- to 6-membered fully unsaturated heterocyclic ring or an 8- to 10-membered heteroaromatic bicyclic ring system, each ring or ring system containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, wherein up to 3 carbon ring members are independently selected from C(=0) and C(=S), and the sulfur atom ring members are independently selected from S(=0)_u(=NR²⁷)_v, each ring or ring system optionally substituted with up to 5 substituents independently selected from R^3a and R³^ on carbon atom ring members and selected from cyano, C₁-C₃ alkyl, C₂-C₃ alkenyl, C₂-C₃ alkynyl, C₃-C₆ cycloalkyl, C₂-C₃ alkoxyalkyl, C^-C₃ alkoxy, C₂-C₃ alkylcarbonyl, C₂-C₃ alkoxycarbonyl, C₂-C₃ alkylaminoalkyl and C₃-C4 dialkylaminoalkyl on nitrogen atom ring members; X is O, S(=0)_m, NR⁴ or CR^5aOR^5b; R¹ is H, cyano, halogen, C^-Cg alkyl, C^-Cg haloalkyl, C2-Cg alkenyl, C2-Cg alkynyl, C3-C6 cycloalkyl, C2-C6 alkoxyalkyl, C^-C^ alkoxy, C^-C^ haloalkoxy, C(=0)OR⁶ or C(=0)NR⁷R⁸;

R^{l a} is H; or

R^{l a} and R¹ are taken together with the carbon atom to which they are attached to form a cyclopropyl ring optionally substituted with up to 2 substituents independently selected from halogen and methyl;

each R^3a is independently cyano, halogen, hydroxy, nitro, Ci -C4 alkyl, Ci -C4

haloalkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-C4 cycloalkyl, C3-C7

halocycloalkyl, C4-C6 cycloalkylalkyl, C4-C6 alkylcycloalkyl, C1-C3 alkylthio, C1-C3 haloalkylthio, C1-C3 alkylsulfinyl, C1-C3 haloalkylsulfinyl, C1-C3 alkylsulfonyl, C1-C3 haloalkylsulfonyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C3-C7 cycloalkoxy, C 1 -C2 alkylsulfonyloxy, C1 -C2 haloalkylsulfonyloxy, C2-C3 alkylcarbonyloxy, C2-C3 alkylcarbonyl, amino, methylamino, C2-C4

dialkylamino, C₂-C₃ alkylcarbonylamino, -CH(=0), -NHCH(=0), -SF₅, -SC≡N, -C(=S)NR^9aR^9b or -U-V-T;

each R^3b is independently C5-C8 alkyl, C5-C8 haloalkyl, C5-C8 alkenyl, C5-C8

alkynyl, C2-Cg haloalkenyl, C2-Cg haloalkynyl, Ci -Cg nitroalkyl, C2-Cg nitroalkenyl, C5-Cg cycloalkyl, C₇-Cg alkylcycloalkyl, C₇-Cg cycloalkylalkyl, C5-C12 cycloalkylalkenyl, C5-C12 cycloalkylalkynyl, Cg-C^

cycloalkylcycloalkyl, C4-Cg alkylthio, C4-Cg haloalkythio, C4-Cg alkylsulfinyl, C4-Cg haloalkylsulfinyl, C4-Cg alkylsulfonyl, C4-Cg haloalkylsulfonyl, C4-Cg alkoxy, C5-Cg haloalkoxy, C2-Cg alkenyloxy, C2-Cg haloalkenyloxy, C3-Cg alkynyloxy, C3-Cg haloalkynyloxy, C2-Cg cyanoalkoxy, Cg-C^ cycloalkoxy, C3-C12 halocycloalkoxy, C4-C12 cycloalkylalkoxy, C5-C12

cycloalkylalkenyloxy, C5-C12 cycloalkylalkynyloxy, C3-Cg alkylsulfonyloxy, C3-Cg haloalkylsulfonyloxy, C4-Cg alkylcarbonyloxy, C4-Cg alkylcarbonyl, C2-Cg alkylamino, C4-Cg alkylcarbonylamino, C3-C12 trialkylsilyl, C4-C12 trialkylsilylalkyl, C₄-C₁₂ trialkylsilylalkoxy, -C(=NR^9a)NR^9aOR^9a,

-CR^10a=NOR^10b, -CR^10c= NR^9aR^9b, -NR^9aN=CR^{l l a}R^{l lb} or -ON=CR^{l l a}R^{l lb}; or

each R^3b is independently -A(CR^12aR^12b)_nW;

each A is independently O or a direct bond; each W is independently a 3- to 7-membered heterocyclic ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, wherein up to 3 carbon atom ring members are independently selected from C(=0) and C(=S), the ring optionally substituted with up to 3 substituents independently selected from R¹³ on carbon atom ring members and R¹⁴ on nitrogen atom ring members;

R⁴ is H, amino, C2-Cg alkenyl, C3-C6 alkynyl, C3-C6 cycloalkyl, -CH(=0),

R^5a is H or C_rC₆ alkyl;

C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C2-Cg alkoxyalkyl, C₂-C6 cyanoalkyl, C₂-C6 alkylcarbonyl, C₂-C6 alkoxycarbonyl, C₂-C£ (alkylthio)carbonyl, C4-C8 cycloalkylcarbonyl, Cz Cg cycloalkoxycarbonyl, C4-C8

(cycloalkylthio)carbonyl, C₂-C6 alkoxy(thiocarbonyl) or C4-C8

cycloalkoxy(thiocarbonyl);

R⁶ is H, C_rC₆ alkyl or C_rC₆ haloalkyl;

R⁷ and R⁸ are taken together with the nitrogen atom to which they are attached to form a 4- to 7-membered nonaromatic heterocyclic ring containing ring members, in addition to the connecting nitrogen atom, selected from carbon atoms and up to 1 ring member selected from O, S(=0)_m and NR¹⁹;

each R^9a and R^9b is independently H or C _γ - C₄ alkyl;

each R^10a is independently H, -C3 alkyl or C1-C3 haloalkyl;

each R^{l la} and R^{l lb} is independently H, C_rC₃ alkyl or C_rC₃ haloalkyl;

each R^12a is independently H, halogen, cyano or Ci -C₄ alkyl;

each R^12b is independently H or Ci -C₄ alkyl;

each R¹⁴ is independently cyano, Ci -C2 alkyl or Ci -C2 alkoxy;

R¹⁵ is C_rC₆ alkyl or C_rC₆ haloalkyl;

R¹⁶ is Ci -Cg alkyl, C2-C6 alkoxyalkyl, C2-C6 alkylaminoalkyl, C3-C6

dialkylaminoalkyl, Ci -Cg alkoxy, Ci -Cg alkylthio or C2-Cg alkylthioalkyl; R¹⁷ is H, -CH(=0), C₃-C₆ cycloalkyl, -S(=0)₂OM or -(C=Z)R²⁰; or C_rC₆ alkyl or Cj-Cg haloalkyl, each optionally substituted with up to 2 substituents independently selected from R²¹;

each R¹⁸ and R²¹ is independently cyano, C3-C6 cycloalkyl, C^-Cg alkoxy, C^-Cg haloalkoxy, C^-Cg alkylthio, C^-Cg alkylsulfinyl or C^-Cg alkylsulfonyl;

R¹⁹ is H, C_rC₃ alkyl or C₂-C₃ haloalkyl;

R²⁰ is C^-Cg alkyl, C2-C6 alkoxyalkyl, C2-C6 alkylaminoalkyl, C3-C6

dialkylaminoalkyl, C^-C^ alkoxy, C^-C^ alkylthio or C2-C6 alkylthioalkyl; each U is independently O, S(=0)_m, NR²² or a direct bond;

each V is independently C^-Cg alkylene, C2-Cg alkenylene, C3-C6 alkynylene, C3-C6 cycloalkylene or C3-C6 cycloalkenylene, wherein up to 3 carbon atoms are C(=0), each optionally substituted with up to 5 substituents independently selected from halogen, cyano, nitro, hydroxy, C^-Cg alkyl, C^-Cg haloalkyl, C^-Cg alkoxy and C^-C^ haloalkoxy;

each T is independently cyano, NR^23aR^23b, OR²⁴ or S(=0)_mR²⁵;

each R²² is independently H, C^-Cg alkyl, C^-Cg haloalkyl, C2-Cg alkylcarbonyl,

C2-C6 alkoxycarbonyl, C2-Cg (alkylthio)carbonyl, C2-Cg alkoxy(thiocarbonyl), C4-C8 cycloalkylcarbonyl, C4-C8 cycloalkoxycarbonyl, C4-C8

(cycloalkylthio)carbonyl or C4-C8 cycloalkoxy(thiocarbonyl);

each R^23a and R^23b is independently H, C_rC₆ alkyl, C_rC₆ haloalkyl, C₂-C₆ alkenyl,

C3-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C2-Cg alkylcarbonyl, C2-C6 alkoxycarbonyl, C2-Cg (alkylthio)carbonyl, C2-Cg alkoxy(thiocarbonyl), C4-C8 cycloalkylcarbonyl, C4-C8 cycloalkoxycarbonyl, C4-C8

(cycloalkylthio)carbonyl or C4-C8 cycloalkoxy(thiocarbonyl); or

a pair of R^23a and R^23b attached to the same nitrogen atom are taken together with the nitrogen atom to form a 3- to 6-membered heterocyclic ring, the ring optionally substituted with up to 5 substituents independently selected from R²⁶;

each R²⁴ and R²⁵ is independently H, C^-Cg alkyl, C^-Cg haloalkyl, C2-Cg alkenyl, C3-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C2-Cg alkylcarbonyl, C2-C6 alkoxycarbonyl, C2-Cg (alkylthio)carbonyl, C4-C8 cycloalkylcarbonyl,

C4-C8 cycloalkoxycarbonyl, C4-C8 (cycloalkylthio)carbonyl, C2-Cg

alkoxy(thiocarbonyl) or C4-C8 cycloalkoxy(thiocarbonyl);

each R²⁶ is independently halogen, C^-Cg alkyl, C^-Cg haloalkyl or C^-Cg alkoxy; each R²⁷ is independently H, cyano, C1-C3 alkyl or C1-C3 haloalkyl;

Z is O or S;

M is K, Na or Li;

each m is independently 0, 1 or 2;

each n is independently 0, 1, 2 or 3; and each u and v are independently 0, 1 or 2 in each instance of S(=0)_u(=NR²⁷)_v;

provided that:

(a) the sum of u and v is 0, 1 or 2;

substituted naphthalenyl ring system, an optionally substituted 5- to 6-membered fully unsaturated heterocyclic ring or an optionally substituted 8- to 10-membered heteroaromatic bicyclic ring system, then at least one of Q¹ or Q² is substituted with at least one R ^b substituent; and

Formula 1.

2. A compound of Claim 1 wherein:

Q¹ is a phenyl, pyridinyl, pyrimidinyl, pyrazinyl or pyridazinyl ring, each ring

optionally substituted with up to 3 substituents independently selected from R^3a and R^3b;

Q² is a phenyl, pyridinyl, pyrimidinyl, pyrazinyl or pyridazinyl ring, each ring

X is O, S, NR⁴ or CR^5aOR^5b;

R^la is H;

R² is Br, Cl, I or C_rC₂ alkyl;

each R ^a is independently cyano, halogen, -C4 alkyl, C1-C4 haloalkyl, C2-C4

alkenyl, C3-C4 cycloalkyl, C4-C6 cycloalkylalkyl, C4-C6 alkylcycloalkyl, C1-C3 alkylthio, C1-C3 alkylsulfinyl, C1-C3 alkylsulfonyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C3-C7 cycloalkoxy, C1-C2 alkylsulfonyloxy, C2-C3

alkylcarbonyloxy, C2-C3 alkylcarbonyl, amino, methylamino, C2-C4 dialkylamino, C₂-C₄ alkylcarbonylamino, -CH(=0), -NHCH(=0), -SF₅, -SC≡N, -C(=S)NR^9aR^9b or -U-V-T;

each R ^b is independently C2-C4 haloalkenyl, C5-C8 cycloalkylalkenyl, C5-C8

cycloalkylalkynyl, C4-C6 alkoxy, C2-Cg alkenyloxy, C2-Cg haloalkenyloxy, C3-C6 alkynyloxy, C3-C6 haloalkynyloxy, C4-C8 cycloalkylalkoxy, C3-C6 alkylsulfonyloxy, C3-C6 haloalkylsulfonyloxy, C3-C9 trialkylsilyl, C4-C9 trialkylsilylalkyl, C4-C9 trialkylsilylalkoxy, -C(=NR^9a)NR^9aOR^9a, -CR^10a=NOR^10b, -CR^10c= NR^9aR^9b or -ON=CR^{l la}R^{l lb}; or

-A(CR^12aR^12b)_nW; each W is independently a 3- to 6-membered heterocyclic ring containing ring members selected from carbon atoms and 1 to 3 heteroatoms independently selected from up to 2 O, up to 2 S and up to 3 N atoms, the ring optionally substituted with up to 3 substituents independently selected from R¹³ on carbon atom ring members and R¹ on nitrogen atom ring members;

R⁴ is H, cyclopropyl, -CH(=0), -S(=0)₂OM, -S(=0)_mR¹⁵, -(C=Z)R¹⁶, OR¹⁷, C_rC₃ alkyl or C_}-C₃ haloalkyl;

R^5a is H or methyl;

R^5b is H, -CH(=0), C_rC₃ alkyl, C_rC₂ haloalkyl, C₂-C₃ alkoxyalkyl, C₂-C₄

cyanoalkyl, C₂-C4 alkylcarbonyl or C₂-C4 alkoxycarbonyl;

R⁶ is H or methyl;

R⁷ is H or C_rC₆ alkyl;

R⁸ is H, -Q alkyl, C_rC₆ haloalkyl or C₄-C₈ alkylcycloalkyl;

each R^10a is independently H, methyl or halomethyl;

each R^10b and R^10c is independently H, C_rC₃ alkyl, C_rC₃ haloalkyl, C₃-C₄

cycloalkyl or C₃-C4 halocycloalkyl;

each R^12a is independently H, cyano or methyl;

each R^12b is independently H or methyl;

each R¹³ is independently halogen, methyl, halomethyl or methoxy;

each R¹⁴ is independently methyl or methoxy;

R¹⁵ is methyl or halomethyl;

R¹⁶ is methyl, ethyl, methoxy, ethoxy, methylthio or ethylthio;

R¹⁷ is H, -CH(=0), cyclopropyl, -S(=0)₂OM or -(C=Z)R²⁰; or C_rC₃ alkyl or C_rC₃ haloalkyl, each optionally substituted with up to 2 substituents independently selected from R²¹;

R²⁰ is methyl, methoxy or methylthio;

each U is independently O or NR²²;

each V is independently C₂-C4 alkylene;

each T is independently NR^23aR^23b or OR²⁴;

each R^23a and R^23b is independently H, C^-Cg alkyl or C^-Cg haloalkyl;

each R²⁴ is independently H, C^-C^ alkyl or C^-C^ haloalkyl; and

Z is O.

3. A compound of Claim 2 wherein

X is O, NR⁴ or CHOR^5b; R¹ is H, cyano, halogen, C1-C3 alkyl, C1-C3 haloalkyl, C2-C4 alkoxyalkyl, C1-C3 alkoxy or C1-C3 haloalkoxy;

each R^3a is independently cyano, halogen, methyl, halomethyl, cyclopropyl,

methylthio, methoxy, methylsulfonyloxy, methylcarbonyloxy, methylcarbonyl, -C(=S)NR^9aR^9b or -U-V-T;

each R ^b is independently C2-C4 haloalkenyl, C5-C8 cycloalkylalkenyl, C5-C8

cycloalkylalkynyl, C4-C6 alkoxy, C2-Cg alkenyloxy, C2-Cg haloalkenyloxy, C3-C6 alkynyloxy, C3-C6 haloalkynyloxy, C4-C8 cycloalkylalkoxy,

-C(=NR^9a)NR^9aOR^9a, -CR^10a=NOR^10b, -CR^10c= NR^9aR^9b or

-ON=CR^{l la}R^{l lb}; or -A(CR^12aR^12b)_nW

each W is independently selected from W-1 through E-52 wherein the bond shown projecting to the left is bonded to the remainder of the Formula 1; R^{1 a} is selected from H and R¹⁴; and each x is independently 0, 1 or 2;

R⁴ is H, -CH(=0) or methoxy;

R^5b is H, -CH(=0), methyl, halomethyl, cyanomethyl, methylcarbonyl or

methoxycarbonyl;

each R^12a is independently H or methyl; and

each U is independently O or NH.

4. A compound of Claim 3 wherein

X is NR⁴ or CHOR^5b;

R¹ is H, halogen or C1-C3 alkyl;

R² is Br, CI or methyl;

each R^3a is independently cyano, halogen or methoxy;

each R^3b is independently C2-Cg alkenyloxy, C2-Cg haloalkenyloxy, C3-C6

alkynyloxy, C3-C6 haloalkynyloxy, C4-C8 cycloalkylalkoxy,

-C(=NR^9a)NR^9aOR^9a, -CR^10a=NOR^10b or -CR^10c= NR^9aR^9b; or

-A(CR^12aR^12b)_nW

R⁴ is H;

R^5a is H;

R^5b is H;

each R^10a is H;

each R^10b and R^10c is independently H, methyl, halomethyl or cyclopropyl;

each R^12a is H; and

each R^12b is H.

5. A compound of Claim 4 wherein

Q¹ is a phenyl ring optionally substituted with up to 2 substituents independently selected from R ^a and substituted with 1 substituent selected from R ^b; Q² is a phenyl ring substituted with 1 to 3 substituents independently selected from

R^3a;

R¹ is H;

R² is methyl; and

each R^3a is independently cyano, Br, CI, F or methoxy.

6. A compound of Claim 4 wherein

Q¹ is a phenyl ring substituted with at least 1 substituent selected from R^3a attached at the 2-position;

Q² is a phenyl ring substituted with at least 1 substituent selected from R^3a attached at the 2-position; and

each R^3a is independently Br, CI or F.

7. A compound of Claim 1 which is selected from the group:

4-[2,6-difluoro-4-(2-propyn- 1 -yloxy)phenyl]- 1 ,3-dimethyl-N-(2,4,6-trifluorophenyl)- lH-pyrazol-5-amine,

4-[2,6-difluoro-4-(2-propen- 1 -yloxy)phenyl]- 1 ,3-dimethyl-N-(2,4,6-trifluorophenyl)- lH-pyrazol-5-amine,

4-[4-[[3-chloro-2-propen-l-yl]oxy]-2,6-difluorophenyl]-l,3-dimethyl-N-(2,4,6- trifluorophenyl)-lH-prazol-5-amine,

4-[2,6-difluoro-4-(2-oxiranylmethoxy)phenyl]-l,3-dimethyl-N-(2,4,6-trifluorophenyl)- lH-pyrazol-5-amine,

4-[2,6-difluoro-4-[(3-methyl-3-oxetanyl)methoxy]phenyl]-l,3-dimethyl-N-(2,4,6- trifluorophenyl)-lH-pyrazol-5-amine,

4-[4-(l,3-dioxolan-2-ylmethoxy)-2,6-difluorophenyl]-l,3-dimethyl-N-(2,4,6- trifluorophenyl)-lH-pyrazol-5-amine,

4-[2,6-difluoro-4-[(tetrahydro-2-furanyl)methoxy]phenyl]-l,3-dimethyl-N-(2,4,6- trifluorophenyl)-lH-pyrazol-5-amine,

4-[2,6-difluoro-4-[3-(2 -methyl- 1 ,3-dioxolan-2-yl)propoxy]phenyl]- 1 ,3-dimethyl-N-

(2,4,6-trifluorophenyl)-lH-pyrazol-5-amine,

4-[l,3-dimethyl-5-[(2,4,6-trifluorophenyl)amino]-lH-pyrazol-4-yl]-3,5- difluorobenzaldehyde 2,2-dimethylhydrazone,

4-[2,6-difiuoro-4-(lH-l ,2,4-triazol-l -yl)phenyl]-l ,3-dimethyl-N-(2,4,6- trifluorophenyl)-lH-pyrazol-5-amine, and

4-[2,6-difiuoro-4-(lH-pyrazol-yl)phenyl]-l,3-dimethyl-N-(2,4,6-trifluorophenyl)-lH- pyrazol-5-amine.

8. A compound of Claim 1 wherein

Q¹ is a phenyl ring substituted at the 2-position with a substituent selected from R ^a and at the 4-position with a substituent selected from R³^; or a phenyl ring substituted at the 2- and 6-positions with substituents independently selected from R^3a and at the 4-position with a substituent selected from R^3b;

Q² is a phenyl ring substituted at the 2- and 6-positions with substituents

independently selected from R^3a; or a phenyl ring substituted at the 2-, 4- and 6-positions with substituents independently selected from R ^a;

X is NR⁴;

R¹ is H;

R^la is H;

R² is methyl;

each R ^a is independently cyano, Br, CI or F;

each R ^b is independently C2-C4 haloalkenyl, C5-C8 cycloalkylalkenyl, C5-C8

-C(=NR^9a)NR^9aOR^9a, -CR^10a=NOR^10b, -CR^10c=NNR^9aR^9b or

-ON=CR! ^laR! ^lb; or -A(CR^12aR^12b)_nW;

R⁴ is H;

each R^10a is independently H, methyl or halomethyl;

each R^10b and R^10c is independently H, C_rC₃ alkyl, C_rC₃ haloalkyl, C3-C4

cycloalkyl or C3-C4 halocycloalkyl;

each R^12a is independently H, cyano or methyl;

each R^12b is independently H or methyl;

each R¹³ is independently halogen, methyl, halomethyl or methoxy; and

each R¹⁴ is independently methyl or methoxy.

9. A compound of Claim 8 wherein

each R ^b is independently C2-Cg alkenyloxy, C2-Cg haloalkenyloxy, C3-C6

alkynyloxy, C₃-C₆ haloalkynyloxy, C₄-C₈ cycloalkylalkoxy, -CR^10a=NOR^10b or -CR^10c=NNR^9aR^9b; or -A(CR^12aR^12b)_nW;

each W is independently selected from W-1 through W-5, W-8, W-9 and W-12

through W-23;

each R^9a and R^9b is independently H or methyl

each R^10a is independently H or methyl;

each R^10b and R^10c is independently H or methyl;

each R^{1 la} and R^{1 lb} is independently H or methyl;

each R^12a is independently H;

each R^12b is independently H; each R¹³ is independently halogen, methyl or halomethyl; and

each R¹⁴ is methyl.

10. A compound of Claim 1 wherein

Q¹ is a phenyl ring substituted at the 2- and 6-positions with substituents

independently selected from R^3a; or a phenyl ring substituted at the 2-, 4- and

6-positions with substituents independently selected from R^3a;

Q² is a phenyl ring substituted at the 2-position with a substituent selected from R^3a and at the 4-position with a substituent selected from R^3b; or a phenyl ring substituted at the 2- and 6-positions with substituents independently selected from R^3a and at the 4-position with a substituent selected from R^3b;

X is NR⁴;

R¹ is H;

R^la is H;

R² is methyl;

each R^3a is independently cyano, Br, CI or F;

each R^3b is independently C2-C4 haloalkenyl, C5-C8 cycloalkylalkenyl, C5-C8

cycloalkylalkynyl, Cz Cg alkoxy, C2-Cg alkenyloxy, C2-Cg haloalkenyloxy, C3-C6 alkynyloxy, C3-C6 haloalkynyloxy, Cz Cg cycloalkylalkoxy,

-C(=NR^9a)NR^9aOR^9a, -CR^10a=NOR^10b, -CR^10c=NNR^9aR^9b or

-ON=CR! ^laR! ^lb; or -A(CR^12aR^12b)_nW;

R⁴ is H;

each R^10a is independently H, methyl or halomethyl;

cycloalkyl or C3-C4 halocycloalkyl;

each R^12a is independently H, cyano or methyl;

each R^12b is independently H or methyl;

each R¹³ is independently halogen, methyl, halomethyl or methoxy; and

each R¹⁴ is independently methyl or methoxy.

11. A compound of Claim 10 wherein

each R^3b is independently C2-Cg alkenyloxy, C2-Cg haloalkenyloxy, C3-C6

each W is independently selected from W-1 through W-5, W-8, W-9 and W-12

through W-23; each R^9a and R⁹^ is independently H or methyl

each R^10a is independently H or methyl;

each R¹⁰b and R^10c is independently H or methyl;

each R^{1 la} and R¹ ^ is independently H or methyl;

each R^12a is independently H;

each R¹²^ is independently H;

each R¹³ is independently halogen, methyl or halomethyl; and

each R¹⁴ is methyl.

12. A fungicidal composition comprising (a) a compound of Claim 1; and (b) at least one other fungicide.

13. A fungicidal composition comprising (a) a compound of Claim 1; and (b) at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents.

14. A method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof, or to the plant seed, a fungicidally effective amount of a compound of Claim 1.