TITLE FUNGICIDAL TRICYCUC 1,2,4-TRIAZOLES

FIELD OF THE INVENTION

This invention relates to certain 1,2,4-triazoles, 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.

One area of need is for compounds that are useful for controlling plant diseases caused by Ascomycete fungal plant pathogens, such as powdery mildew diseases of cereal, broadleaf and fruit crops.

World Patent Application WO 1997/02262 discloses certain pyrimidinones of Formula i as fungicides.

wherein, inter alia, each R ¹ and R ² is independently CJ-CJO alkyl; W is O, S or NH; each R ³ and R ⁴ is independently hydrogen, halogen or C _j -C ₄ alkyl; and Q is O, S or NH.

SUMMARY OF THE INVENTION

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

wherein

W is O, S(O) _n , NR ⁵ or a direct bond; n is 0, 1 or 2; Q is O, S or NR ⁶ ;

G together with the two carbon atoms to which it is attached forms a 5- or 6- membered ring; R ¹ is C ₁ -C ₁₀ alkyl, C ₃ -C ₇ cycloalkyl, C ₃ -C ₁₀ alkenyl, C ₃ -C ₁₀ alkynyl, C ₂ -C ₁₀ alkoxyalkyl, C ₂ -C ₁₀ alkylthioalkyl, C ₄ -C ₁₀ cycloalkylalkyl, C ₄ -C ₁₀ alkylcycloalkyl, C5-C ₁₀ alkylcycloalkylalkyl, Cg-C ₁₂ cycloalkylcycloalkyl,

C ₂ -C ₁₀ alkylsulfonylalkyl, C ₄ -C ₁₀ alkenyloxyalkyl, C ₄ -C ₁₀ alkynyloxyalkyl, C ₄ -C ₁₀ alkenylthioalkyl, C ₄ -C ₁₀ alkynylthioalkyl, C ₄ -C ₁₀ alkoxyalkenyl, C ₄ -C ₁₀ alkylthioalkenyl, C ₄ -C ₁₀ trialkylsilylalkyl or C ₁ -C ₁₀ alkoxy, each optionally substituted with one or more substituents independently selected from halogen; or

R ¹ is NR ⁷ R ⁸ ; or

R ¹ is a phenyl, pyridinyl, furanyl or thienyl ring, or a naphthalenyl, benzofuranyl, benzothienyl or quinolinyl ring system, each ring or ring system optionally substituted with up to 3 substituents independently selected from R ⁹ ; or R ¹ is C ₁ -C ₁₀ alkyl substituted with NR ¹⁰ R ¹¹ , nitro, cyano, C(=O)OR ¹² , a phenyl ring or a 3-, 4-, 5- or 6-membered heterocyclic ring containing up to 4 heteroatoms independently selected from the group consisting of nitrogen, oxygen and sulfur, provided that each heterocyclic ring contains no more than 4 nitrogens, no more than 2 oxygens and no more than 2 sulfurs, each phenyl or heterocyclic ring optionally substituted with up to 3 substituents independently selected from R ⁹ ;

R ² is C ₁ -C ₁₀ alkyl, C ₃ -C ₇ cycloalkyl, C ₃ -C ₁₀ alkenyl, C ₃ -C ₁₀ alkynyl, C ₂ -C ₁₀ alkoxyalkyl, C ₂ -C ₁₀ alkylthioalkyl, C ₂ -C ₁₀ alkylsulfonylalkyl, C ₄ -C ₁₀ alkylcycloalkyl, C ₄ -C ₁₀ cycloalkylalkyl, C5-C ₁₀ alkylcycloalkylalkyl, C ₄ -C ₁₀ alkenyloxyalkyl, C ₄ -C ₁₀ alkynyloxyalkyl, C ₄ -C ₁₀ alkenylthioalkyl, C ₄ -C ₁₀ alkynylthioalkyl, C ₄ -C ₁₀ alkoxyalkenyl, C ₄ -C ₁₀ alkylthioalkenyl or C ₄ -C ₁₀

trialkylsilylalkyl, each optionally substituted with one or more substituents independently selected from halogen; or R ² is a phenyl or pyrrolyl ring, each ring optionally substituted with up to 3 substituents independently selected from R ⁹ ; or R ² is C ₁ -C ₁₀ alkyl substituted with NR ¹³ R ¹⁴ , nitro, cyano, C(=O)OR ¹⁵ , a phenyl ring or a 3-, 4-, 5- or 6-membered heterocyclic ring containing up to 4 heteroatoms independently selected from the group consisting of nitrogen, oxygen and sulfur, provided that each heterocyclic ring contains no more than 4 nitrogens, no more than 2 oxygens and no more than 2 sulfurs, each phenyl or heterocyclic ring optionally substituted with up to 3 substituents independently selected from R ⁹ ; or when W is NR ⁵ , R ² can also be OR ¹⁶ , C(=O)R ¹⁷ , N=CR ¹⁸ R ¹⁹ or NR ²⁰ R ²¹ ; or when W is O, R ² can also be N=CR ²² R ²³ or NR ²⁴ R ²⁵ ;

R ³ is hydrogen, halogen, nitro, cyano or NR ²⁶ R ²⁷ ; or C ₁ -Cg alkyl, C2-Cg alkenyl, C ₂ -C ₈ alkynyl, C ₃ -C ₈ cycloalkyl, C ₁ -C ₈ alkoxy, C ₃ -C ₈ alkenyloxy, C ₃ -C ₈ alkynyloxy, C ₁ -C ₈ alkylthio, C ₁ -C ₈ alkylsulfonyl or C ₂ -C ₈ alkoxyalkyl, each optionally substituted with one or more substituents independently selected from halogen; or a phenyl ring optionally substituted with one or more substituents independently selected from R ²⁸ ; R ⁴ is hydrogen, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy or C ₁ -C ₄ haloalkoxy;

R ⁵ is hydrogen, C ₁ -C ₄ alkyl or C(=O)R ¹⁷ ; R ⁶ is hydrogen; or C ₁ -C _1Q alkyl, C ₃ -C ₁₀ alkenyl, C ₃ -C ₁₀ alkynyl, C ₃ -C ₇ cycloalkyl,

C ₄ -C ₁₀ cycloalkylalkyl, C ₂ -C ₁₀ alkoxyalkyl, C ₂ -C ₁₀ alkylthioalkyl, C ₂ -C ₁₀ alkylsulfonylalkyl or C5-C ₁₀ alkylcycloalkylalkyl, each optionally substituted with one or more substituents independently selected from halogen; each R ⁹ is independently C ₂ -C ₄ alkoxycarbonyl, C ₂ -C ₄ dialkylamino, halogen,

C(=O)CH ₃ , cyano, nitro, trifluoromethyl or C(=O)NR ²⁹ R ³⁰ ; or C ₁ -C ₆ alkyl, C ₂ -C ₈ alkenyl, C ₂ -C ₈ alkynyl, C ₁ -C ₆ alkoxy or C ₁ -C ₆ alkylthio, each optionally substituted with one or more substituents independently selected from halogen; each R ⁷ , R ¹⁰ , Rl2, RB ₁ R15 _{; R} l8 _{? R} 20 _J R22 _{> R} 24, _R 26 _{and R} 29 _is independently hydrogen or C ₁ -C ₄ alkyl; each R8, Rl l, R ¹⁴ , Rl6, _R l9, _R 2l _; R23, _R 25 _{5 R} 27 _{and R} 30 _is independently hydrogen, C ₁ -C ₈ alkyl or C ₁ -C ₄ haloalkyl; or each R ⁷ and R ⁸ , R ¹⁰ and R ¹¹ , R ¹³ and R ¹⁴ , R ¹⁸ and R ¹⁹ , R ²⁰ and R ²¹ , R ²² and R ²³ , R ²⁴ and R ²⁵ , R ²⁶ and R ²⁷ , and R ²⁹ and R ³⁰ are independently taken together as -CH ₂ CH ₂ CH ₂ CH ₂ -, -CH ₂ (CH ₂ ) ₃ CH ₂ -, -CH ₂ CH ₂ OCH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )CH ₂ CH(CH ₃ )CH ₂ - or -CH ₂ CH(CH ₃ )OCH(CH ₃ )CH ₂ -;

R ¹⁷ is hydrogen, C ₁ -C ₄ alkyl or C ₁ -C4 alkoxy; and each R ²⁸ is independently halogen, Cj-C ₄ alkyl, C ₁ -C ₄ alkoxy, CpC ₄ haloalkyl, nitro or cyano; provided that: (i) when G is a fused phenyl ring, and R ¹ is CH ₂ -Ph, then at least one of R ³ and R ⁴ is other than hydrogen; (ii) when G is G-16, W is S, R ³ is hydrogen and R ⁴ is hydrogen, then R ² is other than methyl;

(iii) when G is G-36 or G-39, R ¹ is CH ₂ -Ph or CH ₃ , and W is S, then R ² is other than methyl;

(iv) when G is G-9, G-14 or G-15 then W is other than a direct bond; and

(v) when G is G-I, R ¹ is methyl, R ² is methyl and W is a direct bond, then R ³ and R ⁴ are other than methyl.

More particularly, this invention pertains to a compound of Formula 1 including all geometric and stereoisomers, an iV-oxide or a salt thereof.

This invention also relates to a fungicidal composition comprising a fungicidally effective amount of a compound of Formula 1 and 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 mixture of a compound of Formula 1 and 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).

DETAILS OF THE INVENTION

As used herein, the terms "comprises," "comprising," "includes," "including," "has,"

"having", "contains" or "containing" or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a composition, 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, process, method, article, or apparatus. 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 "broadleaf ' 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" 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 R ¹ and R ² .

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 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 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.

"Alkoxy" includes, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers. "Alkoxyalkyl" denotes alkoxy substitution on straight-chain or branched alkyl moieties. Examples of "alkoxyalkyl" include CH ₃ OCH ₂ , CH ₃ OCH ₂ CH ₂ , CH ₃ CH ₂ OCH ₂ , CH ₃ CH ₂ CH ₂ CH ₂ OCH ₂ and CH ₃ CH ₂ OCH ₂ CH ₂ . "Alkoxyalkenyl" denotes alkoxy substitution on straight-chain or branched alkenyl moieties. Examples of "alkoxyalkenyl" include CH ₃ OCH=CHCH ₂ , CH ₃ OCH=CHCH ₂ CH ₂ and CH ₃ CH ₂ OCH=CHCH ₂ . "Alkylthioalkenyl" denotes alkylthio substitution on straight-chain or branched alkenyl moieties. Examples of "alkylthioalkenyl" include

CH ₃ SCH=CHCH(CH ₃ ), CH ₃ SCH=CHCH ₂ CH ₂ and CH ₃ CH ₂ SCH=CHCH ₂ . "Alkenyloxy" includes straight-chain or branched alkenyloxy moieties. Examples of "alkenyloxy" include

H ₂ C=CHCH ₂ O, (CH ₃ ) ₂ C=CHCH ₂ O, (CH ₃ )CH=CHCH ₂ O, (CH ₃ )CH=C(CH ₃ )CH ₂ O and CH ₂ =CHCH^CH ₂ O. "Alkynyloxy" includes straight-chain or branched alkynyloxy moieties. Examples of "alkynyloxy" include HC≡CCH ₂ 0, CH ₃ C≡CCH ₂ O and CH ₃ C≡CCH ₂ CH ₂ O. "Alkylthio" includes branched or straight-chain alkylthio moieties such as methylthio, ethylthio, and the different propylthio, butylthio, pentylthio and hexylthio isomers. Alkylsulfinyl includes both enantiomers of an alkylsulfinyl group. Examples of "alkylsulfinyl" include CH ₃ S(O)-, CH ₃ CH ₂ S(O)-, CH ₃ CH ₂ CH ₂ S(O)-, (CH ₃ ) ₂ CHS(O)- and the different butylsulfinyl, pentylsulfϊnyl and hexylsulfinyl isomers. Examples of "alkylsulfonyl" include CH ₃ S(O) ₂ -, CH ₃ CH ₂ S(O) ₂ -, CH ₃ CH ₂ CH ₂ S(O) ₂ -, (CH ₃ ) ₂ CHS(O) ₂ -, and the different butylsulfonyl, pentylsulfonyl and hexylsulfonyl isomers. "Alkylsulfonylalkyl" denotes alkylsulfonyl substitution on alkyl. Examples of "alkylsulfonylalkyl" include CH ₃ S(=O) ₂ CH ₂ , CH ₃ S(=O) ₂ CH ₂ CH ₂ , CH ₃ CH ₂ S (=O) ₂ CH ₂ and CH ₃ CH ₂ S(=O) ₂ CH ₂ CH ₂ . "Alkylthioalkyl" denotes alkylthio substitution on alkyl. Examples of "alkylthioalkyl" include CH ₃ SCH ₂ , CH ₃ SCH ₂ CH ₂ , CH ₃ CH ₂ SCH ₂ , CH ₃ CH ₂ CH ₂ CH ₂ SCH ₂ and CH ₃ CH ₂ SCH ₂ CH ₂ . "Dialkylamino" denotes an amino group substituted with two alkyl groups. Examples of "dialkylamino" include (CH ₃ ) ₂ N. and (CH ₃ CH ₂ ) ₂ N. "Alkenyloxyalkyl", "alkynyloxyalkyl", "alkenylthioalkyl",

"alkynylthioalkyl" and the like are defined analogously to the above examples. "Trialkylsilylalkyl" denotes a branched or straight-chain alkyl substituted with a trialkylsilyl group. 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. Examples of "trialkylsilylalkyl" include (CH ₃ ) ₃ SiCH ₂ ,

(CH ₃ CH ₂ ) ₃ SiCH ₂ , (CH ₃ ) ₂ (rert-Bu)SiCH ₂ and (CH ₃ CH ₂ ) ₃ SiCH ₂ CH ₂ . "Cycloalkyl" includes, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. The term "alkylcycloalkyl" denotes alkyl substitution on a cycloalkyl moiety and includes, for example, ethylcyclopropyl, /-propylcyclobutyl, 3-methylcyclopentyl and 4-methylcyclohexyl. The term "cycloalkylalkyl" denotes cycloalkyl substitution on an alkyl moiety. Examples of "cycloalkylalkyl" include cyclopropylmethyl, cyclopentylethyl, and other cycloalkyl moieties bonded to straight-chain or branched alkyl groups. The term "alkylcycloalkylalkyl" denotes alkylcycloalkyl substitution on an alkyl moiety. Examples of alkylcycloalkylalkyl include ethylcyclopropylmethyl, i-propylcyclobutylethyl, and 3- methylcyclopentylpropyl .

The term "cycloalkylcycloalkyl" denotes cycloalkyl substitution on another cycloalkyl ring, wherein each cycloalkyl ring independently has from 3 to 6 carbon ring members. Examples of cycloalkylcycloalkyl radicals include cyclopropylcyclopropyl (such as 1,1'- bicyclopropyl-1-yl, l,l'-bicyclopropyl-2-yl), cyclohexylcyclopentyl (such as 4- cyclopentylcyclohexyl) and cyclohexylcyclohexyl (such as l,l'-bicyclohexyl-l-yl), and the

different cis- or trans-cycloalkylcycloalkyl isomers, (such as (l/?,25)-l,l'-bicyclopropyl-2-yl and ( IR,2R)- 1 , 1 '-bicyclopropyl-2-yl).

Alkylcarbonyl denotes a straight-chain or branched alkyl moieties bonded to a C(=O) moiety. Examples of alkylcarbonyl include CH ₃ C(=O)-, CH ₃ CH ₂ CH ₂ CC=O)- and (CH ₃ ) ₂ CHC(=O)-. Examples of "alkoxycarbonyl" include CH ₃ OC(=O)-, CH ₃ CH ₂ OC(=O)-,

CH ₃ CH ₂ CH ₂ OCC=O)-, (CH ₃ ) ₂ CHOC(=O)- and the different butoxy- or pentoxycarbonyl isomers.

The term "halogen", either alone or in compound words such as "haloalkyl", or when used in descriptions of groups optionally substituted with one or more substituents independently selected from halogen, includes: fluorine, chlorine, bromine or iodine. Further, when used in compound words such as "haloalkyl", or when used in descriptions of groups optionally substituted with one or more substituents independently selected from halogen, said groups may be partially or fully substituted with halogen atoms which may be the same or different. Examples of haloalkyl or alkyl optionally substituted with one or more substituents independently selected from halogen include F ₃ C-, ClCH ₂ -, CF ₃ CH ₂ - and CF ₃ CCl ₂ -. The term "haloalkoxy", and the like, are defined analogously to the term "haloalkyl". Examples of "haloalkoxy" include CF ₃ O-, CCl ₃ CH ₂ O-, HCF ₂ CH ₂ CH ₂ O- and CF ₃ CH ₂ O-.

Unless otherwise indicated, a "ring" or "ring system" as a component of Formula 1 (e.g., substituent R ¹ ) is carbocyclic or heterocyclic. The term "ring system" denotes two or more fused rings. The terms tricyclic and fused tricyclic when used in connection with a ring system denote a ring system consisting of three fused rings, in which either ring can be saturated, partially unsaturated, or fully unsaturated, unless otherwise indicated. The term "ring member" refers to an atom or other moiety (e.g., C(=O), C(=S), S(O) or S(O) ₂ ) forming the backbone of a ring or ring system.

The terms "carbocyclic ring", carbocycle or carbocyclic ring system denote a ring or ring system wherein the atoms forming the ring backbone are selected only from carbon. Unless otherwise indicated, a carbocyclic ring can be a saturated, partially unsaturated, or fully unsaturated ring. When a fully unsaturated carbocyclic ring satisfies Huckel's rule, then said ring is also called an "aromatic ring". "Saturated carbocyclic" 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 heterocyclic ring system denote a ring or ring system in which at least one atom forming the ring backbone is not carbon, e.g., nitrogen, oxygen or sulfur. Typically a heterocyclic ring contains no more than 4 nitrogens, no more than 2 oxygens and no more than 2 sulfurs. Unless otherwise indicated, a heterocyclic ring can be a saturated, partially unsaturated, or fully unsaturated ring. When a fully unsaturated heterocyclic ring satisfies Hiickel's rule, then said ring is also called a

"heteroaromatic ring" or aromatic heterocyclic ring. Unless otherwise indicated, heterocyclic rings and ring systems can be attached through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen.

"Aromatic" indicates that each of the ring atoms is essentially in the same plane and has a p-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 Hϋckel's rule. The term "aromatic ring system" denotes a carbocyclic or heterocyclic ring system in which at least one ring of the ring system is aromatic. The term "aromatic carbocyclic ring system" denotes a carbocyclic ring system in which at least one ring of the ring system is aromatic. The term "aromatic heterocyclic ring system" denotes a heterocyclic ring system in which at least one ring of the ring system is aromatic. The term "nonaromatic ring system" denotes a carbocyclic or heterocyclic ring system that may be fully saturated, as well as partially or fully unsaturated, provided that none of the rings in the ring system are aromatic. The term "nonaromatic carbocyclic ring system" in which no ring in the ring system is aromatic. The term "nonaromatic heterocyclic ring system" denotes a heterocyclic ring system in which no ring in the ring system is aromatic.

The total number of carbon atoms in a substituent group is indicated by the "Cj-C _j " prefix where i and j are numbers from 1 to 10. For example, C ₁ -C4 alkylsulfonyl designates methylsulfonyl through butylsulfonyl; C ₂ alkoxyalkyl designates CH3OCH2; C3 alkoxyalkyl designates, for example, CH ₃ CH(OCH ₃ ), CH ₃ OCH ₂ CH ₂ or CH ₃ CH ₂ OCH ₂ ; and C ₄ alkoxyalkyl designates the various isomers of an alkyl group substituted with an alkoxy group containing a total of four carbon atoms, examples including CH ₃ CH ₂ CH ₂ OCH ₂ and CH ₃ CH ₂ OCH ₂ CH ₂ .

When a compound is substituted with a substituent bearing a subscript that indicates the number of said substituents can exceed 1, said substituents (when they exceed 1) are independently selected from the group of defined substituents (e.g., (R ⁹ ) _r wherein r is 1, 2, or 3). Further, when the subscript indicates a range, e.g. (R) _j _ _j , then the number of substituents may be selected from the integers between i and j inclusive. When a group contains a substituent which can be hydrogen, for example R ³ or R ⁴ then when this substituent is taken as hydrogen, it is recognized that this is equivalent to said group being unsubstituted. When a variable group is shown to be optionally attached to a position, for example (R ⁹ ) _r wherein r may be 0, then hydrogen may be at the position even if not recited in the variable group definition. When one or more positions on a group are said to be "unsubstituted", then hydrogen atoms are attached to take up any free valency. The term "optionally substituted" in connection with the R ¹ , R ² , R ³ , R ⁶ and R ⁹ refers to groups which are unsubstituted or have at least one non-hydrogen substituent that does not extinguish the biological activity possessed by the unsubstituted analog. As used herein, the following definitions shall apply unless otherwise indicated. The term "optionally

substituted" is used interchangeably with the phrase "substituted or unsubstituted" or with the term "(un)substituted." Unless otherwise indicated, an optionally substituted group may have a substituent at each substitutable position of the group, and each substitution is independent of the other. Commonly, the number of optional substituents (when present) ranges from 1 to 5. When a range specified for the number of substituents (e.g., r being an integer from 0 to 3 in Exhibit 1) exceeds the number of positions available for substituents on a ring (e.g., 2 positions available for (R ⁹ ) _r on Y-16 through Y-18 in Exhibit 1), the actual higher end of the range is recognized to be the number of available positions. The term "optionally substituted" means that the number of substituents can be zero. For example, the phrase "optionally substituted with one or more substituents independently selected from halogen" means that all potential connection points can be substituted with halogen.

As noted above, each R ¹ and R ² can independently be (among others) C _J -C _1Q alkyl substituted with a 3-, 4-, 5- or 6-membered heterocyclic ring optionally substituted with up to 3 substituents independently selected from R ⁹ . Examples of optionally substituted 3-, 4-, 5- or 6-membered heterocyclic rings include the rings Y-I through Y-74 illustrated in Exhibit 1 wherein R ⁹ is any substituent as defined in the Summary of the Invention and r is an integer from 0 to 3.

Although R ⁹ groups are shown in the structures Y-I through Y-74, it is noted that they do not need to be present since they are optional substituents. When the attachment point between (R ⁹ ) _r and the Y group is illustrated as floating, (R ⁹ ) _r can be attached to any available carbon or nitrogen atom of the Y group. The nitrogen atoms that require a substitutent to fill their valence are substituted with either H or R ⁹ . Note that some Y groups can only be substituted with less than three R ⁹ groups (e.g., Y-16 through Y-18, Y-20 through Y-24, Y-52, Y-53, and Y-65 through Y-67). Exhibit 1

Y-6 Y-7 Y-8 Y-9 Y-IO

Y-I l Y-12 Y-13 Y-14 Y-15

Y-26 Y-27 Y-28 Y-29 Y-30

Y-41 Y-42 Y-43 Y-44 Y-45

Y-46 Y-47 Y-48 Y-49 Y-50

Y-51 Y-52 Y-53 Y-54 Y-55

As noted above, G together with the two carbon atoms to which it is attached forms a 5- or 6-membered ring substituted with R ³ and R ⁴ wherein each R ³ and R ⁴ is any substituent as defined in the Summary of the Invention. When G is a heterocyclic ring examples of said ring, hereafter identified as a G ring, include the rings illustrated as G-I to G-39 in Exhibit 2. When the attachment point between the G ring and R ³ and R ⁴ is illustrated as floating, R ³ and R ⁴ can be attached to any available carbon or nitrogen atom of the G ring. The nitrogen atoms that require a substitutent to fill their valence are substituted with either R ³ or R ⁴ . Note that some G rings can only be substituted with one R ³ or R ⁴ group; in those cases the G ring is substituted with R ³ (e.g., G-10 through G-13, G-26 and G-27 are substituted only with R ³ ). As illustrated below, in the exemplified G rings, the G ring encompasses the portion of the molecule enclosed in the brackets, and the wavy line indicates that the G ring is attached to the remainder of Formula 1.

G-6 G-7 G-8 G-9 G-IO

G-I l G-12 G-13 G-14 G-15

G-16 G-17 G-18 G-19 G-20

G-21 G-22 G-23 G-24 G-25

G-26 G-27 G-28 G-29 G-30

G-36 G-37 G-38 G-39

A wide variety of synthetic methods are known in the art to enable preparation of aromatic and nonaromatic heterocyclic rings and ring systems; for extensive reviews see the eight volume set of Comprehensive Heterocyclic Chemistry, A. R. Katritzky and C. W. Rees editors-in-chief, Pergamon Press, Oxford, 1984 and the twelve volume set of Comprehensive Heterocyclic Chemistry II, A. R. Katritzky, C. W. Rees and E. F. V. Scriven editors-in-chief, Pergamon Press, Oxford, 1996.

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 will appreciate that not all nitrogen containing heterocycles can form N-oxides since the nitrogen requires an available lone pair for oxidation to the oxide; one skilled in the art will recognize those nitrogen containing heterocycles which can form N-oxides. One skilled in the art will also recognize that tertiary amines can form N-oxides. Synthetic methods for the preparation of λf-oxides of heterocycles and tertiary amines are very well known by one skilled in the art including the oxidation of heterocycles and tertiary amines with peroxy acids such as peracetic and m-chloroperbenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as r-butyl hydroperoxide, sodium perborate,

and dioxiranes such as dimethyldioxirane. These methods for the preparation of N-oxides have been extensively described and reviewed in the literature, see for example: T. L. Gilchrist in Comprehensive Organic Synthesis, vol. 7, pp 748-750, S. V. Ley, Ed., Pergamon Press; M. Tisler and B. Stanovnik in Comprehensive Heterocyclic Chemistry, vol. 3, pp 18-20, A. J. Boulton and A. McKillop, Eds., Pergamon Press; M. R. Grimmett and B. R. T. Keene in Advances in Heterocyclic Chemistry, vol. 43, pp 149-161, A. R. Katritzky, Ed., Academic Press; M. Tisler and B. Stanovnik in Advances in Heterocyclic Chemistry, vol. 9, pp 285-291, A. R. Katritzky and A. J. Boulton, Eds., Academic Press; and G. W. H. Cheeseman and E. S. G. Werstiuk in Advances in Heterocyclic Chemistry, vol. 22, pp 390-392, A. R. Katritzky and A. J. Boulton, Eds., Academic Press.

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. When a compound of Formula 1 contains an acidic moiety such as a carboxylic acid, salts also include those formed with organic or inorganic bases such as pyridine, triethylamine or ammonia, or amides, hydrides, hydroxides or carbonates of sodium, potassium, lithium, calcium, magnesium or barium. Accordingly, the present invention comprises compounds selected from Formula 1, iV-oxides and agriculturally suitable salts thereof.

One skilled in the art also recognizes that intermediates of compounds of Formula 1 (e.g., Formula 2, 10, shown below) can exist in equilibrium with one or more of its respective tautomeric counterparts. Unless otherwise indicated, reference to a compound by one tautomer description is to be considered to include all tautomers.

Embodiments of the present invention as described in the Summary of the Invention include (where Formula 1 as used in the following Embodiments includes TV-oxides and salts thereof):

Embodiment 1. A compound of Formula 1 wherein W is O or S(O) _n . Embodiment 2. A compound of Embodiment 1 wherein W is O or S. Embodiment 3. A compound of Embodiment 2 wherein W is O. Embodiment 4. A compound of Formula 1 wherein W is NR ⁵ . Embodiment 5. A compound of Formula 1 wherein R ⁵ is hydrogen.

Embodiment 6. A compound of Formula 1 wherein W is a direct bond. Embodiment 7. A compound of Formula 1 wherein Q is O or S. Embodiment 8. A compound of Embodiment 7 wherein Q is O.

Embodiment 9. A compound of Formula 1 wherein G together with the two carbon atoms to which it is attached forms a phenyl, thiophene, pyridine, thiazole, oxazole or pyrimidine ring.

Embodiment 10. A compound of Embodiment 9 wherein G together with the two carbon atoms to which it is attached forms a phenyl, thiophene or pyridine ring.

Embodiment 11. A compound of Embodiment 10 wherein G together with the two carbon atoms to which it is attached forms a phenyl ring. Embodiment 12. A compound of Formula 1 wherein R ¹ is C ₁ -Cg alkyl, C ₃ -C ₅ cycloalkyl, C ₃ -Cg alkenyl, C ₃ -Cg alkynyl, C2-Cg alkoxyalkyl, C2-Cg alkylthioalkyl, C ₄ -C ₈ cycloalkylalkyl, C ₄ -C ₈ alkylcycloalkyl, C ₅ -C ₁₀ alkylcycloalkylalkyl, Cg-C ₁₀ cycloalkylcycloalkyl, C ₄ -C ₈ alkenyloxyalkyl or C ₁ -C ₈ alkoxy, each optionally substituted with one or more substituents independently selected from halogen.

Embodiment 12A. A compound of Embodiment 12 wherein R ¹ is C ₁ -C ₈ alkyl, C ₃ -C ₅ cycloalkyl, C ₃ -C ₈ alkenyl, C ₃ -C ₈ alkynyl, C ₂ -C ₈ alkoxyalkyl, C ₂ -C ₈ alkylthioalkyl, C ₄ -C ₈ cycloalkylalkyl, C ₅ -C ₁₀ alkylcycloalkylalkyl, C ₄ -C ₈ alkenyloxyalkyl or C ₁ -C ₈ alkoxy, each optionally substituted with one or more substituents independently selected from halogen. Embodiment 13. A compound of Embodiment 12 wherein R ¹ is C ₁ -C ₈ alkyl, C ₃ -C ₈ alkenyl, C ₃ -C ₈ alkynyl, C ₃ -C ₈ alkoxyalkyl, C ₄ -C ₈ cycloalkylalkyl,

C ₄ -C ₈ alkylcycloalkyl, C ₅ -C ₁₀ alkylcycloalkylalkyl or Cg cycloalkylcycloalkyl each optionally substituted with one or more substituents independently selected from halogen.

Embodiment 13A. A compound of Embodiment 13 wherein R ¹ is C ₁ -C ₈ alkyl, C ₃ -C ₈ alkenyl, C ₃ -C ₈ alkynyl, C ₃ -C ₈ alkoxyalkyl, C ₄ -Cg cycloalkylalkyl or

C ₅ -C ₁₀ alkylcycloalkylalkyl, each optionally substituted with one or more substituents independently selected from halogen. Embodiment 14. A compound of Embodiment 13 wherein R ¹ is C ₁ -C ₈ alkyl, C ₃ -C ₈ alkenyl, C ₃ -C ₈ alkynyl, C ₄ -C ₈ cycloalkylalkyl or C ₆ cycloalkylcycloalkyl, each optionally substituted with one or more substituents independently selected from halogen.

Embodiment 14A. A compound of Embodiment 14 wherein R ¹ is C ₁ -C ₈ alkyl, C ₃ -C ₈ alkenyl, C ₃ -C ₈ alkynyl or C ₄ -C ₈ cycloalkylalkyl, each optionally substituted with one or more substituents independently selected from halogen.

Embodiment 14B. A compound of Embodiment 14A wherein R ¹ is C ₁ -C ₈ alkyl, C ₃ -C ₈ alkenyl or C ₄ -C ₈ cycloalkylalkyl, each optionally substituted with one or more substituents independently selected from halogen.

Embodiment 14C. A compound of Embodiment 14B wherein R ¹ is CpCg alkyl optionally substituted with one or more substituents independently selected from halogen.

Embodiment 15. A compound of Formula 1 wherein R ¹ is NR ⁷ R ⁸ . Embodiment 16. A compound of Formula 1 wherein each R ⁷ , R ¹⁰ , R ¹² , R ¹³ , R ¹⁵ , R ¹⁸ ,

R ²⁰ , R ²² , R ²⁴ , R ²⁶ and R ²⁹ is hydrogen.

Embodiment 17. A compound of Formula 1 wherein each R ⁸ , R ⁿ , R ¹⁴ , R ¹⁶ , R ¹⁹ , R ²¹ , R ²³ , R ² S, R ²⁷ and R ³⁰ is C ₁ -C ₈ alkyl.

Embodiment 18. A compound of Formula 1 wherein R ¹ is a phenyl, pyridinyl, furanyl or thienyl ring, each ring optionally substituted up to 3 substituents independently selected from R ⁹ .

Embodiment 19. A compound of Embodiment 18 wherein R ¹ is a phenyl ring optionally substituted with up to 3 substituents independently selected from R ⁹ .

Embodiment 20. A compound of Formula 1 wherein R ⁹ is C ₂ -C ₄ alkoxycarbonyl, C ₂ -C ₄ dialkylamino, halogen, C(=O)CH ₃ , cyano, nitro or trifluoromethyl; or

C ₁ -C ₆ alkyl, C ₂ -C ₈ alkenyl, C ₂ -C ₈ alkynyl, C ₁ -C ₆ alkyloxy or C ₁ -C ₆ alkylthio, each optionally substituted with one or more substituents independently selected from halogen.

Embodiment 21. A compound of Embodiment 20 wherein R ⁹ is CH ₃ OC(=O)-, C2-C4 dialkylamino, halogen, C(=O)CH ₃ , cyano, nitro, trifluoromethyl, methyl, ethyl, ethynyl, 2-propynyl, methoxy, ethoxy, methylthio, ethylthio, C ₁ -C ₂ haloalkyl or C ₁ -C ₂ haloalkoxy.

Embodiment 22. A compound of Embodiment 21 wherein R ⁹ is C ₂ -C ₄ dialkylamino, halogen, trifluoromethyl, methyl, ethyl, methoxy or methylthio. Embodiment 23. A compound of Formula 1 wherein R ¹ is C ₁ -C _1Q alkyl substituted with cyano, or a 5- or 6-membered heterocyclic ring containing 1 to 4 heteroatoms independently selected from the group consisting of nitrogen, oxygen and sulfur, provided that each heterocyclic ring contains no more than 4 nitrogens, no more than 2 oxygens and no more than 2 sulfurs, each heterocyclic ring optionally substituted with up to 3 substituents independently selected from R ⁹ .

Embodiment 24. A compound of Embodiment 23 wherein R ¹ is C ₁ -C ₈ alkyl substituted with cyano.

Embodiment 25. A compound of Embodiment 23 wherein R ¹ is C ₁ -C ₁₀ alkyl substituted with a 5- or 6-membered heterocyclic ring selected from the group consisting of thiophene, furan, thiazole, oxazole, isothiazole, isoxazole, pyrrole, pyrazole, imidazole, tetrahydrofuran, 1,3-dioxolane, dihydrooxazole, dihydroimidazole, dihydropyrazole, dihydroisoxazole,

pyridine, dihydrooxazine, tetrahydropyran or morpholine, each heterocyclic ring optionally substituted up to 3 substituents independently selected from R ⁹ .

Embodiment 26. A compound of Formula 1 wherein W is NR ⁵ and R ² is selected from OR ¹⁶ , C(=O)R ¹⁷ , N=CR ¹ ^R ¹⁹ and NR20R21.

Embodiment 27. A compound of Embodiment 26 wherein R ² is C(=O)R ¹⁷ .

Embodiment 28. A compound of Formula 1 wherein R ² is CpC ₈ alkyl, C ₃ -Cg alkenyl, C ₃ -C ₈ alkynyl, C ₂ -C ₈ alkoxyalkyl, C ₂ -C ₈ alkylthioalkyl, C ₄ -C ₈ alkylcycloalkyl, C ₄ -C ₈ cycloalkylalkyl, C5-C ₁ 0 alkylcycloalkylalkyl or C ₄ -C ₈ alkenyloxyalkyl, each optionally substituted with one or more substituents independently selected from halogen.

Embodiment 28A. A compound of Embodiment 28 wherein R ² is C ₁ -C ₈ alkyl, C ₃ -C ₈ alkenyl, C ₃ -C ₈ alkynyl, C ₂ -C ₈ alkoxyalkyl, C ₂ -C ₈ alkylthioalkyl, C ₄ -C ₈ cycloalkylalkyl, C ₅ -C ₁₀ alkylcycloalkylalkyl or C ₄ -C ₈ alkenyloxyalkyl, each optionally substituted with one or more substituents independently selected from halogen.

Embodiment 29. A compound of Embodiment 28 wherein R ² is C ₁ -C ₈ alkyl, C ₃ -C ₈ alkenyl, C ₃ -C ₈ alkynyl, C ₃ -C ₈ alkoxyalkyl, C ₄ -C ₈ alkylcycloalkyl, C ₄ -C ₈ cycloalkylalkyl or C ₅ -C ₁₀ alkylcycloalkylalkyl, each optionally substituted with one or more substituents independently selected from halogen.

Embodiment 29 A. A compound of Embodiment 29 wherein R ² is C ₁ -C ₈ alkyl, C ₃ -C ₈ alkenyl, C ₃ -C ₈ alkynyl, C ₃ -C ₈ alkoxyalkyl, C ₄ -C ₈ cycloalkylalkyl or C ₅ -C ₁₀ alkylcycloalkylalkyl, each optionally substituted with one or more substituents independently selected from halogen.

Embodiment 30. A compound of Embodiment 29 wherein R ² is C ₁ -C ₈ alkyl, C ₃ -C ₈ alkenyl, C ₃ -C ₈ alkynyl, C ₄ -C ₈ alkylcycloalkyl or C ₄ -C ₈ cycloalkylalkyl, each optionally substituted with one or more substituents independently selected from halogen. Embodiment 30A. A compound of Embodiment 30 wherein R ² is C ₁ -C ₈ alkyl, C ₃ -C ₈ alkenyl, C ₃ -C ₈ alkynyl or C ₄ -C ₈ cycloalkylalkyl, each optionally substituted with one or more substituents independently selected from halogen.

Embodiment 30B. A compound of Embodiment 30A wherein R ² is C ₁ -C ₈ alkyl, C ₃ -C ₈ alkenyl or C ₄ -C ₈ cycloalkylalkyl, each optionally substituted with one or more substituents independently selected from halogen

Embodiment 3OC. A compound of Embodiment 30B wherein R ² is Cj-Cg alkyl optionally substituted with one or more substituents independently selected from halogen.

Embodiment 31. A compound of Formula 1 wherein R ² is phenyl optionally substituted with up to 3 substituents independently selected from R ⁹ .

Embodiment 32. A compound of Formula 1 wherein R ² is C ₁ -C ₁ Q alkyl substituted with cyano or a 5- or 6-membered heterocyclic ring containing 1 to 4 heteroatoms independently selected from the group consisting of nitrogen, oxygen and sulfur, provided that each heterocyclic ring contains no more than 4 nitrogens, no more than 2 oxygens and no more than 2 sulfurs, each heterocyclic ring optionally substituted with up to 3 substituents independently selected from R ⁹ . Embodiment 33. A compound of Embodiment 32 wherein R ² is C ₁ -Cg alkyl substituted with cyano. Embodiment 34. A compound of Embodiment 32 wherein R ² is C ₁ -C _1Q alkyl substituted with a 5- or 6-membered heterocyclic ring selected from the group consisting of thiophene, furan, thiazole, oxazole, isothiazole, isoxazole, pyrrole, pyrazole, imidazole, tetrahydrofuran, 1,3-dioxolane, dihydrooxazole, dihydroimidazole, dihydropyrazole, dihydroisoxazole, pyridine, dihydrooxazine, tetrahydropyran or morpholine, each heterocyclic ring optionally substituted with up to 3 substituents independently selected from R ⁹ . Embodiment 35. A compound of Formula 1 wherein R ³ is hydrogen, halogen or cyano;

Or C ₁ -C ₈ alkyl, C ₃ -C ₈ cycloalkyl, C ₂ -C ₈ alkynyl, C ₁ -C ₈ alkoxy, C ₁ -C ₈ alkylthio, C ₁ -C ₈ alkylsulfonyl or C ₂ -C ₈ alkoxyalkyl, each optionally substituted with one or more substituents independently selected from halogen. Embodiment 36. A compound of Embodiment 35 wherein R ³ is hydrogen, halogen or cyano; or C ₁ -C ₄ alkyl, ethynyl or C ₁ -C ₄ alkoxy each optionally substituted with one or more substituents independently selected from halogen. Embodiment 37. A compound of Embodiment 36 wherein R ³ is hydrogen, halogen, cyano, C ₁ -C ₄ alkyl, ethynyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkyl or C ₁ -C ₄ haloalkoxy. Embodiment 38. A compound of Embodiment 37 wherein R ³ is hydrogen or halogen.

Embodiment 39. A compound of Embodiment 38 wherein R ³ is halogen. Embodiment 40. A compound of Embodiment 39 wherein R ⁴ is hydrogen or halogen.

Embodiment 41. A compound of Formula 1 wherein G together with the two carbon atoms to which it is attached forms a phenyl ring substituted at the 7- position with R ³ and R ³ is other than hydrogen.

Embodiment 42. A compound of Embodiment 41 wherein R ³ is halogen or cyano; or C ₁ -C ₈ alkyl, C ₃ -C ₈ cycloalkyl, C ₂ -C ₈ alkynyl, C ₁ -C ₈ alkoxy, C ₁ -C ₈ alkylthio, C ₁ -C ₈ alkylsulfonyl or C ₂ -C ₈ alkoxyalkyl, each optionally substituted with one or more substituents independently selected from halogen.

Embodiment 43. A compound of Embodiment 42 wherein R ³ is halogen or cyano; or C ₁ -C ₄ alkyl, ethynyl or C ₁ -C ₄ alkoxy each optionally substituted with one or more substituents independently selected from halogen. Embodiment 44. A compound of Embodiment 43 wherein R ³ is halogen or cyano. Embodiment 45. A compound of Embodiment 44 wherein R ³ is halogen. Embodiment 46. A compound of Formula 1 wherein G together with the two carbon atoms to which it is attached forms a phenyl ring substituted at the 7- position with R ³ and at the 9-position with R ⁴ , and R ³ and R ⁴ are other than hydrogen. Embodiment 47. A compound of Embodiment 46 wherein R ³ and R ⁴ are independently halogen or cyano. Embodiment 48. A compound of Embodiment 47 wherein R ³ and R ⁴ are independently halogen. Embodiment 49. A compound of Formula 1 wherein R ³ and R ⁴ are other than hydrogen.

Embodiments of this invention, including Embodiments 1-49 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. In addition, embodiments of this invention, including Embodiments 1-49 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—49 are illustrated by:

Embodiment A. A compound of Formula 1, N-oxides and salts thereof, wherein

G together with the two carbon atoms to which it is attached forms a phenyl, thiophene, pyridine, thiazole, oxazole or pyrimidine ring; R ¹ is C ₁ -C ₈ alkyl, C ₃ -C ₅ cycloalkyl, C ₃ -C ₈ alkenyl, C ₃ -C ₈ alkynyl, C ₂ -C ₈ alkoxyalkyl, C ₂ -C ₈ alkylthioalkyl, C ₄ -C ₈ cycloalkylalkyl, C ₄ -C ₈ alkylcycloalkyl, C ₅ -C _1Q alkylcycloalkylalkyl, Cg-C ₁ Q cycloalkylcycloalkyl, C ₄ -C ₈ alkenyloxyalkyl or C ₁ -C ₈ alkoxy, each

optionally substituted with one or more substituents independently selected from halogen; or R ¹ is a phenyl, pyridinyl, furanyl or thienyl ring, each ring optionally substituted with up to 3 substituents independently selected from R ⁹ ; R ² is C ₁ -C ₈ alkyl, C ₃ -C ₈ alkenyl, C ₃ -C ₈ alkynyl, C ₂ -C ₈ alkoxyalkyl, C ₂ -C ₈ alkylthioalkyl, C ₄ -C ₈ alkylcycloalkyl, C ₄ -C ₈ cycloalkylalkyl, C ₅ -C ₁₀ alkylcycloalkylalkyl or C ₄ -C ₈ alkenyloxyalkyl, each optionally substituted with one or more substituents independently selected from halogen; or R ² is a phenyl ring optionally substituted with up to 3 substituents independently selected from R ⁹ ; or when W is NR ⁵ , then R ² can also be selected from OR ¹⁶ , C(=O)R ¹⁷ ,

N=CR ¹⁸ R ¹⁹ and NR ² OR ²¹ ;

R ³ is hydrogen, halogen or cyano; or C ₁ -C ₈ alkyl, C ₃ -C ₈ cycloalkyl, C ₂ -C ₈ alkynyl, C ₁ -C ₈ alkoxy, C ₁ -C ₈ alkylthio, C ₁ -C ₈ alkylsulfonyl or C ₂ -C ₈ alkoxyalkyl, each optionally substituted with one or more substituents independently selected from halogen; and each R ⁹ is independently CH ₃ OC(=O)-, C ₂ -C ₄ dialkylamino, halogen, C(=O)CH ₃ , cyano, nitro, trifluoromethyl, methyl, ethyl, ethynyl, 2-propynyl, methoxy, ethoxy, methylthio, ethylthio, C ₁ -C ₂ haloalkyl or

C ₁ -C ₂ haloalkoxy. Embodiment B. A compound of Embodiment A wherein

G together with the two carbon atoms to which it is attached forms a phenyl, thiophene or pyridine ring; R ¹ is C ₁ -C ₈ alkyl, C ₃ -C ₈ alkenyl, C ₃ -C ₈ alkynyl, C ₃ -C ₈ alkoxyalkyl, C ₄ -C ₈ cycloalkylalkyl, C ₄ -C ₈ alkylcycloalkyl, C ₅ -C ₁₀ alkylcycloalkylalkyl or C ₆ cycloalkylcycloalkyl each optionally substituted with one or more substituents independently selected from halogen; or R ¹ is phenyl optionally substituted with up to 3 substituents independently selected from R ⁹ ;

R ² is C ₁ -C ₈ alkyl, C ₃ -C ₈ alkenyl, C ₃ -C ₈ alkynyl, C ₃ -C ₈ alkoxyalkyl, C ₄ -C ₈ alkylcycloalkyl, C ₄ -C ₈ cycloalkylalkyl or C ₅ -C ₁₀ alkylcycloalkylalkyl, each optionally substituted with one or more substituents independently selected from halogen; or R ² is phenyl optionally substituted with up to 3 substituents independently selected from R ⁹ ;

R ³ is hydrogen, halogen, cyano, C ₁ -C ₄ alkyl, ethynyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkyl or C ₁ -C ₄ haloalkoxy; and

each R9 is independently C ₂ -C ₄ dialkylamino, halogen, trifluoromethyl, methyl, ethyl, methoxy or methylthio. Embodiment C. A compound of Embodiment B wherein

W is O or S; R ¹ is C ₁ -C ₈ alkyl, C ₃ -C ₈ alkenyl, C ₃ -C ₈ alkynyl, C ₄ -C ₈ cycloalkylalkyl or

Cg cycloalkylcycloalkyl, each optionally substituted with one or more substituents independently selected from halogen; R ² is C ₁ -C ₈ alkyl, C ₃ -C ₈ alkenyl, C ₃ -C ₈ alkynyl, C ₄ -C ₈ alkylcycloalkyl or

C ₄ -Cg cycloalkylalkyl, each optionally substituted with one or more substituents independently selected from halogen;

R ³ is hydrogen or halogen; and R ⁴ is hydrogen or halogen. Embodiment D. A compound of Embodiment C wherein

Q is O or S; G together with the two carbon atoms to which it is attached forms a phenyl ring;

R ¹ is C ₁ -C ₈ alkyl, C ₃ -C ₈ alkenyl or C ₄ -C ₈ cycloalkylalkyl, each optionally substituted with one or more substituents independently selected from halogen; R ² is C ₁ -C ₈ alkyl, C ₃ -C ₈ alkenyl or C ₄ -C ₈ cycloalkylalkyl, each optionally substituted with one or more substituents independently selected from halogen. Embodiment E. A compound of Embodiment D wherein

R ¹ is C ₁ -C ₈ alkyl optionally substituted with one or more substituents independently selected from halogen;

R ² is C ₁ -C ₈ alkyl optionally substituted with one or more substituents independently selected from halogen. Embodiment F. A compound of Embodiment E wherein

W is O; Q is O.

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

7-iodo-2-propoxy-4-propyl[l,2,4]triazolo[l,5-α]quinazolin-5 (4H)-one; and 4-(cyclopropylmethyl)-7-iodo-2-propoxy[l,2,4]triazolo[l,5-α ]quinazolin-5(4H)-one. Of note are compounds of Formula 1, iV-oxides and salts thereof, (including but not limited to Embodiments A and D above) wherein when Q is O, W is O, R ² is C ₁ ^ alkyl, G together with the two carbons atoms to which it is attached forms a phenyl ring, R ⁴ is η and

R ³ is other than H. Of further note are compounds of Formula 1, iV-oxides and salts thereof, other than compounds 1 through 5 listed in INDEX TABLE A below.

Of particular note are compounds of Formula 1, N-oxides and salts thereof, including Embodiments 1 through 49 and Embodiments A through F other than compounds wherein R ¹ is C ₄ -Ci ₀ alkylcycloalkyl or C ₆ -C ₁₂ cycloalkylcycloalkyl, or R ² is C ₄ -C ₁₀ alkylcycloalkyl, where applicable.

Also of note are compounds of Formula 1, N-oxides and salts thereof, (above) wherein when Q is O, W is O, R ² is C ₁ -C ₂ alkyl, G together with the two carbons atoms to which it is attached forms a phenyl ring, R ⁴ is H and R ³ is other than H. This invention provides a fungicidal composition comprising a compound of Formula

1 (including all geometric and stereoisomers, yV-oxides, and salts thereof), and at least one other fungicide. Of note as embodiments of such compositions are compositions comprising a compound corresponding to any of the compound embodiments described above.

This invention provides a fungicidal composition comprising a fungicidally effective amount of a compound of Formula 1 (including all geometric and stereoisomers, N-oxides, and salts thereof), and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents. Of note as embodiments of such compositions are compositions comprising a compound corresponding to any of the compound embodiments described above. This invention provides 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 Formula 1 (including all geometric and stereoisomers, N-oxides, and salts thereof). Of note as embodiments of such methods are methods comprising applying a fungicidally effective amount of a compound corresponding to any of the compound embodiments describe above. Of particular note are embodiments where the compounds are applied as compositions of this invention.

One or more of the following methods and variations as described in Schemes 1-14 can be used to prepare compounds of Formula 1. The definitions of R ¹ , R ² , R ³ , R ⁴ , Q, W, n and G in the compounds of Formulae 1-18 below are as defined above in the Summary of the Invention unless otherwise noted. Compounds of Formulae Ia-Ih are subsets of

Formula 1.

As outlined in Scheme 1, compounds of the Formula Ia (Formula 1 wherein Q is O) can be prepared by N-alkylation of compounds of Formula 2. In this method, compounds of Formula 2 are first contacted with a base, followed by an alkylating agent of Formula 3 wherein X ¹ is a nucleophic reaction leaving group such as halide (e.g., Cl, Br, I).

Although the preferred order of combination typically comprises contacting Formula 2 with a base and then a compound of Formula 3, it is not critical for the successful outcome of the reaction. In some cases, a compound of Formula 2, a base, and a compound of Formula 3

can be combined simultaneously. The reaction is typically run in an inert solvent (e.g., N,N- dimethylformamide) at temperatures between about -20 and 60 ⁰ C. Suitable bases comprise, for example, alkali metal (such as lithium, sodium, or potassium) hydrides, hydroxides or carbonates (e.g., NaOH, KOH, Na ₂ CO ₃ , K ₂ CO ₃ ). The method of Scheme 1 is illustrated in Step D of Example 1, Step B of Example 2, Step C of Example 3, Step B of Example 4, Step D of Example 6 and Step B of Example 9.

Scheme 1

wherein Q is O

As shown in Scheme 2, compounds of Formula 2 can be prepared by reacting hydrazino carboxylic acids or esters of Formula 4 with substituted λf-cyanocarbonimidates of

Formula 5. The reaction is typically conducted in a solvent such as an alcohol (e.g., methanol, ethanol or propanol) or iV,N-dimethylformamide, at temperatures between about

-20 °C and the normal boiling point of the solvent, and in the presence of a suitable base.

Suitable bases comprise, for example, triethylamine, l,8-diazabicyclo(5.4.0)undec-7-ene, potassium carbonate or sodium carbonate. The method of Scheme 2 is illustrated in Step C of Example 1, Step A of Example 2, Step B of Example 3 and Step A of Example 4. This type of transformation is also document in the chemical literature see, for example,

Heckendorn, et al., Helvetica Chimica Acta 1980, 63(1), 1-9.

Scheme 2

Hydrazino carboxylic acids or esters of Formula 4 can be prepared from the corresponding amino carboxylic acids or esters by methods well document in the art. For leading references, see PCT Patent Publication WO 2002/102359, and Stephenson, Emily F.

M., Organic Syntheses 1949, Collective Volume 3, 54-8. An example of the method described in WO 2002/102359 is illustrated in Step B of Example 1.

Substituted N-cyanocarbonimidates of Formula 5 are commercially available and can be prepared by methods described in the literature. For example, compounds of Formula 5 wherein WR ² is OCgH ₅ , OCH3 or SCH ₃ can be commercially obtained and can also be prepared by reacting dialkyl imidocarbonates with cyanogen halides (e.g., Br) as described in U.S. patent 5,237,084, or by reacting dialkyl imidocarbonates with cyanamide according to the general method of Han, Bo et. al., Organic Letters 2004, 6(21), 3691-3694. An example of the method described in Organic Letters 2004, 6(21), 3691-3694 is illustrated in Step A of Example 1, and an example of the method described U.S. 5,237,084 is illustrated in Step A of Example 3.

As depicted in Scheme 3, compounds of Formula 2 can also be synthesized from triazole carboxamides of Formula 6 via a cyclization reaction. The method is typically conducted in the presence of a base (e.g., potassium carbonate) and a catalyst (e.g., potassium iodide is particularly useful when X ² is Br or Cl). The method of Scheme 3 is illustrated in Step C of Example 6.

Scheme 3

₂ wherein X is Br, I or Cl

As shown in Scheme 4, triazole carboxamides of Formula 6 can be prepared by reacting carboxylic acids or acid chlorides of Formula 7 with aminotriazoles of Formula 8. Using N-^-dimethylaminopropyO-AT-ethylcarbodiimide hydrochlori de-mediated coupling conditions (typically at room temperature), kinetic reaction control prevails and this method provides the less stable amides of Formula 9. Treatment of compounds of Formula 9 with a base (e.g., potassium carbonate) in the presence of a solvent (e.g., N,N-dimethylformamide) and heating at temperatures between about 80 and 100 °C provides the thermodynamically stable triazole carboxamides of Formula 6. The method of Scheme 4 is illustrated in Step A and Step B of Example 6.

Scheme 4

Many substituted aminotriazoles of Formula 8 are commercially available, for example compounds of Formula 8 wherein WR2 is SMe, CH3, CF3, or cyclopropyl can be commercial obtained. Also, compounds of Formula 8 can be prepared by one of several methods, for example, by reacting an aminoguanidine sulfate with an acid according to the general method of Lipinski, Christopher et al., Journal of Medicinal Chemistry 1985, 25(11), 1628-36.

As illustrated in Scheme 5, under alternate conditions carboxylic acids or acid chlorides of Formula 7 can be converted to compounds of Formula 2 by reacting with aminotriazoles of Formula 8. This reaction works particularly well when X ² is adjacent to the heteroatom of a heterocycle, for example when G forms a pyridine ring. The reaction is typically run in a solvent (e.g., λf,N-dimethylformamide), and in the presence of a base (e.g., potassium carbonate), metal catalyst (e.g., copper powder), and an iodide catalyst (e.g., potassium iodide) according to the general method described in German patent application

DE 3825041. The method of Scheme 5 is illustrated in Step A of Example 9.

Scheme 5

2 wherein X is Br, I or Cl

Alternative methods exist for preparing compounds of Formula 1 wherein Q is O and W is O or S. For example, compounds of Formula Ib (Formula 1 wherein Q and W are O) can be obtained from compounds of Formula Ic (Formula 1 wherein Q is O and W is S(O) _n ) via alkoxide displacement of a sulfur moiety as shown in Scheme 6.

Scheme 6

wherein Q is O and W is S(O) _n wherein Q and W are O

In this method, compounds of Formula Ic are treated with metal alkoxides (e.g., NaOMe, NaOEt or NaOPr) in a solvent, such as the corresponding alcohols (e.g., methanol, ethanol or propanol), tetrahydrofuran, iV,iV-dimethylfbrmamide or dimethylsulfoxide at temperatures between about O and 150 °C. The metal alkoxides are commercially available and can be prepared by reacting the desired alcohol with a base, such as alkali metal (e.g., lithium, sodium or potassium) hydrides or sodium. In some cases compounds of Formula Ib may be obtained in higher yields when the metal alkoxide is freshly prepared just prior to use. Examples of reactions analogous to the reaction shown in Scheme 6 are found in U.S. patent 3,755,582. Also, the method of Scheme 6 is illustrated in Step A of Example 8 and Step A of Example 10.

Sulfoxides and sulfones of Formula Ic (wherein n is 1 or 2) can be prepared by treatment of the corresponding sulfides of Formula Id with an oxidizing reagent, for example, m-chloroperoxybenzoic acid. Oxidation reactions of this type are well documented; see, for example, March, J. Advanced Organic Chemistry; 3 ^rd ed., John Wiley: New York, (1985), 1089 and references cited within. The method of Scheme 7 for the preparation of a sulfone is illustrated in Step A of Example 7 and Step C of Example 9.

Scheme 7

wherein n is 1 or 2

Compounds of Formula Id can be obtained from thiols of Formula 10 as shown in Scheme 8. In the method of Scheme 8 the thiol of Formula 10 is first selectively alkylated

by reacting with an alkylating agent of Formula 11 wherein X ³ is a nucleophic reaction leaving group such as halide (e.g., Cl, Br, I) or sulfonate (e.g., mesylate, triflate, p- toluenesulfonate), and a base such as, for example, triethylamine, potassium carbonate, sodium hydroxide or sodium hydride. The reaction is typically run in an inert solvent (e.g., iV,N-dimethylformamide) at temperatures ranging between about -20 ⁰ C and the normal boiling point of the solvent. For conditions and variations of this reaction, see the following references: Heras, M. et al., Helvetica Chimica Acta 2003, 86(9), 3204-3214 and Chen, W. et al., Heteroatom Chemistry 2003, 14(1), 607-611.

N-alkylation of compounds of Formula 12 can be achieved using methods analogous to those already described for Scheme 1.

Scheme 8

Compounds of Formula 10 can be prepared by condensation of hydrazino carboxylic acids or esters of Formula 4 with iV-cyanothioiminocarbonates of Formula 13 as depicted in Scheme 9. Conditions for the method of Scheme 9 are analogous to those already described for the method of Scheme 2.

Scheme 9

N-cyanothioiminocarbonates of Formula 13 can be prepared from cyanamide, carbon disulfide and potassium hydroxide according to the general method described in PCT Patent Publication WO 1994/26724.

Compounds of Formula Ie (Formula 1 wherein Q is O and W is NR ⁵ ) can be prepared from compounds of Formula 14 by nucleophilic displacement of Z (wherein Z is methyl sulfoxide, methyl sulfone, methyl sulfide, chloride or bromide) by treatment with an amine of Formula 15 as illustrated in Scheme 10.

Scheme 10

wherein Z is S(O) _n Me, Cl or Br, wherein Q is O and W is NR ⁵ and n is 0, 1 or 2

In this reaction, one or more equivalents of Formula 15 amine can be used relative to Formula 14. Alternatively, one equivalent of an amine of Formula 15 and an acid scavenger (e.g., triethylamine) can be used. The reaction can be run with or without solvent, including using Formula 15 amine as the solvent, at temperatures ranging between about room temperature and the normal boiling point of the solvent. It is understood by one skilled in the art, that when an amine of Formula 15 is used as a solvent it will be in large stoichiometric excess relative to Formula 14. In cases where the boiling point of the amine at atmospheric pressure is low, the reaction can be maintained above atmospheric pressure to facilitate running the reaction at temperatures higher then the normal boiling point of the amine. The preferred reaction conditions will depend on the Z group. For general methods, see U.S. patent 3,867,384.

Amines of Formula 15 are commercially available or can be prepared by well known methods, see, for example, March, J. Advanced Organic Chemistry; 3 ^rd ed., John Wiley: New York, (1985), 1153-1154 and references cited within.

Compounds of Formula 14 wherein Z is S(O) _n Me can be prepared by the methods already described for Schemes 7, 8 and 9. Compounds of Formula 14 wherein Z is Cl or Br can be synthesized from compounds of Formula 16 as outlined in Scheme 11 using Sandmeyer reaction conditions. In this method the diazonium salt of the compound of Formula 16 is generated and then reacted with a copper salt (e.g., CuCl) in the presence of an acid. The diazonium salt of Formula 16 is generated under standard conditions, for example, strong acid and sodium nitrite or using non-aqueous conditions. For a review of the Sandmeyer reaction see Hodgson, Herbert H., Chemical Review 1947, 40(2), 251-277. Also, copper chloride, ført-butyl nitrite and acetonitrile can be used according to the general method disclosed by South, Michael, Journal of Heterocyclic Chemistry 1991, 28, 1003- 1011. The method of Scheme 11 is illustrated in Step C of Example 5.

Scheme 11

1. NaNCVAcid

2. copper salt wherein Z is Cl or Br

As shown in Scheme 12, amines of Formula 16 can be prepared by a modification of the methods already described for Schemes 1 and 2. In this method, the hydrazino carboxylic acids or esters of Formula 4 are reacted with sodium dicyanamide to provide the amines of Formula 17, which are then alkylated to give compounds of Formula 16. Step A of Example 5 illustrates the preparation of a compound of Formula 17, and Step B of Example 5 illustrates the preparation of a compound of the Formula 16 according to the method of Scheme 12. Scheme 12

alkyl)

As shown in Scheme 13, iV-acylation of compounds of Ig (wherein W is NHR ⁵ ) with an appropriate reagent of Formula 18, where L is a suitable leaving group such as halogen

(e.g., Cl, Br; or C(=O)H or C(=O)C _r C ₄ alky) provides compounds of Formula If (Formula 1 wherein W is NR^ _an d R2 j _s C(=O)R ¹⁷ ). Acylation reactions of this type are well known; see, for example, March, J. Advanced Organic Chemistry; 3 ^r ed., John Wiley: New York, (1985), 370 and references cited within.

Scheme 13

wherein W is NHR 5 wherein W is NR ⁵ and R ² is Q=O)R ¹⁷

As illustrated in Scheme 14, compounds of Formula Ih (Formula 1 wherein Q is S) can be prepared by treatment of compounds of Formula Ia with phosphorus pentasulfide or Lawesson's reagent in an inert solvent such as dioxane at temperatures ranging from between about 0 °C and the normal boiling point of the solvent. For a review of Lawesson's reagent chemistry applicable to the synthesis of compounds of Formula Ih, see Jesberger, Martin et al., Synthesis 2003, 13, 1929-1958.

Scheme 14

Lawesson s reagen

Ia Ih wherein Q is S Although the substituents R ³ and R ⁴ are shown in Schemes 1 through 14, one skilled in the art will recognize that for some compounds of Formula 1 each R ³ or R ⁴ substituent may be more conveniently introduced after the formation of the fused tricyclic ring system. For example, compounds of Formula 1 in which G forms a fused thiophene ring, can be halogenated on the thiophene ring to give the corresponding mono or dihalo substituted

compounds of Formula 1 (R ³ is halogen, or R ³ and R ⁴ are both halogen). Other R ³ and R ⁴ substituents can be introduced by displacement of a leaving group such as halogen. For example, compounds of Formula 1 in which G forms a fused thiophene ring and R ³ is bromine, the bromine can be displaced with the appropriate nucleophile to give the corresponding compounds of Formula 1 wherein R ³ is alkoxy, alkylthio or NR ²⁶ R ²⁷ .

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, 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. ¹ H NMR spectra are reported in ppm downfield from tetramethylsilane; "s" means singlet, "d" means doublet, "t" means triplet, "q" means quartet "m" means multiplet, "dd" means doublet of doublets and "br s" means broad singlet.

EXAMPLE l

Preparation of 4-(cyclopropylmethyl)-7-iodo-2-methoxy[l,2,4]triazolo[l,5-α ]quinazolin-

5(4H)-one

Step A: Preparation of dimethyl cyanocarbonimidate A stirred solution cyanamide (7.75 g, 0.18 mol) and tetramethyl orthocarbonate (25 g,

0.18 mol) was heated at reflux for 1 h. After 1 h, methanol (9.8 mL) was removed by distillation at atmospheric pressure. Cooled to room temperature and triturated the resulting residue with diethyl ether. The solid was collected filtration and dried to give the title compound as a white solid (10.67 g) melting at 53-57 °C. ¹ H NMR (DMSO-J ₆ ): 6 3.94 (s, 6H).

Step B: Preparation of 2-hydrazino-5-iodobenzoic acid monohydrochloride

To a stirred solution of 2-amino-5-iodobenzoic acid (4.75 g, 18.06 mmol) and concentrated hydrochloric acid (20 mL) at -10 °C, was added dropwise a solution of sodium nitrite (1.25 g, 18.05 mmol) in water (1O mL) while maintaining the temperature below -5 °C. The reaction mixture was stirred for 30 minutes at -5 °C, and then a solution of tin chloride dihydrate (14.7 g, 0.65 mmol) in concentrated hydrochloric acid (20 mL) was added dropwise while maintaining the temperature at -5 °C. After the addition was complete, the reaction mixture was allowed to warm to room temperature. After 1 h, the resulting solid precipitate was collected by filtration. The solid was washed with water (2 x 20 mL), diethyl ether (3 x 30 mL), and dichloromethane (3 x 30 mL) and dried overnight in a vacuum oven at 50 °C to provide the title compound as a cream colored solid (5.27 g). ¹ H NMR (CDCl ₃ ): δ 10.58 (br s, 2H), 9.05 (br s, IH), 8.13 (d, IH), 7.90 (dd, IH), 6.98 (d, IH). Step C: Preparation of 7-iodo-2-methoxy[l,2,4]triazolo[l,5-α]quinazolin-5(lH)-one To a stirred solution of dimethyl cyanocarbonimidate (i.e. the product of Step A)

(0.42 g, 3.66 mmol) and 1-propanol (20 mL) at 0 °C, was added triethylamine (0.97 g, 9.55 mmol) and 2-hydrazino-5-iodobenzoic acid monohydrochloride (i.e. the product of Step B) (I g, 3.18 mmol) alternately over 20 minutes. After the addition was complete the reaction mixture was allowed to warm to room temperature and stirred overnight. The reaction mixture was cooled to 0 ⁰ C, the pη adjusted to 3 by adding concentrated sulfuric acid, and then the mixture was heated at reflux for 3 h. After cooling, the resulting precipitate was collected by filtration, washed with water (3 x 10 mL) and dried overnight in a vacuum oven at 50 °C to provide the title compound as a dark tan solid (0.46 g) melting at > 220 ⁰ C. ¹ H NMR (DMSO-J ₆ ): 6 13.10 (s, IH), 8.37 (d, IH), 8.18 (dd, IH), 7.61 (d, IH), 3.98 (s, 3H).

Step D: Preparation of 4-(cyclopropylmethyl)-7-iodo-2-methoxy[ 1 ,2,4]triazolo[ 1,5- α]quinazolin-5(4H)-one

A mixture of 7-iodo-2-methoxy[l,2,4]triazolo[l,5-α]quinazolin-5(lH)-one (i.e. the product of Step C) (0.11 g, 0.31 mmol), (bromomethyl)cyclopropane (0.05 g, 0.37 mmol), potassium carbonate (0.09 g, 0.61 mmol) and anhydrous MN-dimethylformamide (4 mL) was heated at 60 °C overnight. After cooling, the reaction mixture was diluted with water (10 mL) and extracted with ethyl acetate (2 x 15 mL). The combined organic extracts were washed with water (3 x 30 mL), dried (MgSC^), filtered, and concentrated under reduced pressure to provide an oil. The oil was purified by flash column chromatography using a Supelco (division of Sigma-Aldrich Co., 595 North Harrison Road, Bellefonte, PA 16823, U.S.A.) tube prepacked with 10 g of silica gel (50 μm particle diameter, 70 A pore size) and as eluant ethyl acetate-hexanes (starting with 1:9 and ending with 1:1). The fractions were concentrated under reduced pressure and the residue triturated with hexanes to provide the title compound, a compound of the present invention, as a white solid (17 mg) melting at 132-134 °C.

¹ H NMR (DMSO-J ₆ ): 6 8.42 (d, IH), 8.20 (dd, IH), 7.65 (d, IH), 4.01 (s, 3H), 3.98 (d, 2H), 1.40-1.25 (m, IH), 0.60-0.40 (m, 4H).

EXAMPLE 2

Preparation of 4-(cyclopropylmethyl)-2-ethoxy[l,2,4]triazolo[l,5-α]quinazo lin-5(4H)-one Step A: Preparation of 2-ethoxy[l,2,4]triazolo[l,5-α]quinazolin-5(lH)-one

To a stirred solution of dimethyl cyanocarbonimidate (1.6 g, 11 mmol) in ethanol (20 mL) was simultaneously added triethylamine (3.0 g, 30 mmol) and 2-hydrazinobenzoic acid (1.5 g, 10 mmol) portionwise at 0 °C. After the addition was complete, the reaction mixture was stirred for 12 h at room temperature. The reaction mixture was acidified by adding concentrated hydrochloric acid and then heated at 80 °C for 3 h. After cooling, the solvent was evaporated under reduced pressure, and the residue was treated with ice-cooled water to give a precipitate. The precipitate was collected by filtration and recrystallized from ethyl acetate to provide the title compound.

¹ H NMR (DMSO-J ₆ ): 6 12.39 (s, IH), 8.15 (d, IH), 7.92-7.81 (m, 2H), 7.49 (t, IH), 4.34 (q, 2H), 1.37 (t, 3H).

Step B: Preparation of 4-(cyclopropylmethyl)-2-ethoxy[l,2,4]triazolo[l,5- α]quinazolin-5(4H)-one

To a vigorously stirred solution of 2-ethoxy[l,2,4]triazolo[l,5-α]quinazolin-5(4H)- one (i.e. the product of Step A) in N,N-dimethylformamide (5 mL) was added potassium carbonate (0.17 g, 1.2 mmol) portionwise over 20 minutes. After a further 20 minutes,

(bromomethyl)cyclopropane (0.41 g, 3 mmol) was added, and stirring was continued for

18 h. The reaction mixture was poured into ice-water, and the resulting precipitate was

collected by filtration, washed with water and dried. The crude solid was recrystallized from ethyl acetate to provide the title compound, a compound of the present invention, as a solid melting at 116 °C.

¹ H NMR (DMSO-J ₆ ): δ 8.38 (d, IH), 8.11-8.00 (m, 2H), 7.68 (t, IH), 4.47 (s, 2H), 4.17 (q, 2H), 1.56 (t, 3H), 0.69-0.63 (m, 5H).

EXAMPLE 3

Preparation of 7-iodo-2-propoxy-4-propyl[l,2,4]triazolo[l,5-α]quinzolin-5( 4H)-one Step A: Preparation of dipropyl cyanocarboimididate

A solution of cyanogen bromide (5.4 g, 50.9 mmol) in rerf-butyl methyl ether (5 mL) was added dropwise over 1.5 h to a stirred mixture of sodium hydroxide (4 g, 100 mmol), 1-propanol (7.5 mL, 6 g, 100 mmol) and re/t-butyl methyl ether (5 mL) at 0 °C. After stirring for 1 h at 0 °C, the reaction mixture was filtered and the collected solid washed with tørt-butyl methyl ether (5 mL).

A solution of cyanogen bromide in ferϊ-butyl methyl ether (5 mL) was added dropwise over 0.5 h at 0 °C to a mixture of the filtrate (from above), sodium carbonate (5.8 g, 54.7 mmol) and trimethylamine (2.3 g, 39 mmol). The reaction mixture was allowed to warm to room temperature, filtered and the solid collected was washed with tert-buty\ methyl ether (5 mL). The combined filtrates were concentrated to provide the crude product as a yellow liquid (5.76 g), which was used without further purification. Step B: Preparation of 7-iodo-2-propoxy[l,2,4]triazolo[l,5-α]quinazolin-5(lH)-one

To a stirred solution of dipropyl cyanocarboimididate (i.e. the product of Step A) (1.9O g, 11.2 mmol) in 1-propanol (4O mL) at 0 °C, was added triethylamine (2.07 g, 20.5 mmol) and 2-hydrazino-5-iodobenzoic acid monohydrochloride (i.e. the product of Example 1, Step B) (2.93 g, 9.33 mmol) alternately over 20 minutes. After the addition was complete the reaction mixture was allowed to warm to room temperature and stirred overnight. The reaction mixture was cooled to 0 °C, the pη was adjusted to 3 by adding concentrated sulfuric acid and the mixture was heated at 60 °C for 4 h. After cooling, the resulting precipitate was collected by filtration, washed with methylene chloride (3 x 10 mL), water (2 x 10 mL) and dried to provide the crude product as a gray solid (1.1 g). The combined filtrates were concentrated and extracted with ethyl acetate (3 x 15 mL). The combined organic extracts were washed with water, brine, dried (MgSC^), filtered and concentrated to provide the title product as a tan solid (92 mg).

Purification of the crude product described above (i.e. gray solid, 0.6 g) was done by flash column chromatography using a Supelco (division of Sigma-Aldrich Co., 595 North Harrison Road, Bellefonte, PA 16823, U.S.A.) tube prepacked with 10 g of silica gel (50 μm particle diameter, 70 A pore size) and as eluant ethyl acetate-hexanes (starting with 2:8 and ending with 1:1) to provide the title compound as a white solid (50 mg).

IH NMR (DMSO-Cf ₆ ): 6 13.10 (br s, IH), 8.37 (d, IH), 8.18 (dd, IH), 7.60 (d, IH), 4.25

(t, 2H), 1.80-1.70 (m, 2H), 0.98 (t, 3H).

Step C: Preparation of 7-iodo-2-propoxy-4-propyl[l,2,4]triazolo[l,5-α]quinazolin- 5(4H)-one A mixture of 7-iodo-2-propoxy[l,2,4]triazolo[l,5-α]quinazolin-5(lH)-one (i.e. the product of Step B) (50 mg, 0.14 mmol), potassium carbonate (37 mg, 0.27 mmol), 1-iodopropane (16 μL, 27.6 mg, lόmmol) and anhydrous N^V-dimethylformamide (0.5 mL) was stirred at room temperature for 3 h. The reaction mixture was diluted with water (5 mL) and filtered through a Chem Elut cartridge packed with diatomaceous earth (manufactured by Varian) using ethyl acetate as eluant. The solvent was evaporated under reduced pressure to provide the title compound, a compound of the present invention, as a white solid (37 mg) melting at 122-125 °C.

¹ H NMR (CDCl ₃ ): δ 8.67 (d, IH), 8.05 (dd, IH), 7.67 (d, IH), 4.33 (t, 2H), 4.19 (t, 2H), 1.95-1.80 (m, 4H), 1.07 (t, 3H), 1.00 (t, 3H). EXAMPLE 4

Preparation of 7-iodo-2-(methylthio)-4-propyl[l,2,4]triazolol[l,5-α]quinaz olin-5(4H)-one Step A: Preparation of 7-iodo-2-(methylthio)[l,2,4]triazolo[l,5-α]quinazolin-5(lH) - one A stirred mixture of 2-hydrazino-5-iodobenzoic acid monohydrochloride (i.e. the product of Example 1, Step B) (2.O g, 64 mmol), dimethyl cyanocarbonimidodithioate (0.93 g. 64 mmol), triethylamine (2.65 mL, 1.9 g, 19 mmol) and 2-propanol (4O mL) was heated at reflux overnight. After cooling, the solvent was removed under reduced pressure, ice-water (50 mL) was added to the resulting residue, and the pη was adjusted to 2 by adding hydrochloric acid (1 N). The resulting precipitate was collected by filtration and dried in a vacuum oven at 50 °C to provide the title compound as a tan solid (1.94 g) melting at >250 °C.

¹ H NMR (DMSO-J ₆ ): 6 13.14 (br s, IH), 8.38 (d, IH), 8.20 (dd, IH), 7.71 (d, IH), 2.62 (s, 3H). Step B: Preparation of 7-iodo-2-(methylthio)-4-propyl[l,2,4]triazolol[l,5- α]quinazolin-5(4H)-one

A mixture of 7-iodo-2-(methylthio)[l,2,4]triazolo[l,5-α]quinazolin-5(lH) -one (i.e. the product of Step A) (300 mg, 0.84 mmol), 1-iodopropane (163 μL, 285 mg, 1.7 mmol), potassium carbonate (347 mg, 2.5 mmol) and anhydrous ivyV-dimethylformamide (5 mL) was stirred at room temperature overnight. The reaction mixture was diluted with water and the resulting solid collected by filtration, rinsed with water (2 x 10 mL) and dried in a vacuum oven at 50 °C overnight to provide the title compound, a compound of the present invention, as a tan solid (174 mg) melting at 135-136 ⁰ C.

¹ H NMR (DMSO-^ ₆ ): δ 8.43 (d, IH), 8.22 (dd, IH), 7.73 (d, IH), 4.08 (t, 2H), 2.64 (s, 3H), 1.80-1.65 (m, 2H), 0.92 (t, 3H).

EXAMPLE 5

Preparation of 2-chloro-7-iodo-4-propyl[l,2,4]triazolo[l,5-α]quinazolin-5( 4H)-one Step A: Preparation of 2-amino-7-iodo[l,2,4]triazolo[l,5-α]quinazolin-5(lH)-one

A stirred mixture of 2-hydrazino-5-iodobenzoic acid monohydrochloride (i.e. the product of Example 1, Step B) (0.20 g, 0.64 mmol), cyanocyanamide sodium salt (0.14 g, 1.56 mmol) and anhydrous N//-dimethylformamide (2 mL) was heated at 40 ⁰ C for 3.5 h. The resulting precipitate was filtered and dried to provide the title compound as a green solid (0.155 g) melting at > 250 °C.

¹ H NMR (DMSO-^ ₆ ): δ 12.83 (br s, IH), 8.32 (d, IH), 8.13 (dd, IH), 7.48 (d, IH), 6.02 (br s, 2H).

Step B: Preparation of 2-amino-7-iodo-4-propyl[l,2,4]triazolo[l,5-α]quinazolin- 5(4H)-one A mixture of 2-amino-7-iodo[l,2,4]triazolo[l,5-α]quinazolin-5(lH)-one (i.e. the product of Step A) (0.10 g, 0.31 mmol), potassium carbonate (47 mg, 0.34 mmol), 1-iodopropane (3O uL, 52 mg, 0.31 mmol) and anhydrous iVyV-dimethylformamide (2 mL) was stirred at room temperature for 3 h. The reaction mixture was diluted with water, the resulting precipitate collected by filtration and dried to provide the title compound as a tan solid (72 mg) melting at 222-223 °C.

¹ H NMR (DMSO-^ ₆ ): δ 8.37 (d, IH), 8.15 (dd, IH), 7.50 (d, IH), 6.17 (br s, 2H), 4.03 (t, 2H), 1.79-1.69 (m, 2H), 0.91 (t, 3H).

Step C: Preparation of 2-chloro-7-iodo-4-propyl[l,2,4]triazolo[l,5-α]quinazolin- 5(4H)-one Tert-butyl nitrite (144 mg, 1.36 mmol) was added dropwise at 0 °C to a dark mixture of the 2-amino-7-iodo-4-propyl[l,2,4]triazolo[l,5-α]quinazolin-5(4 H)-one (i.e. the product of Step B) (500 mg, 1.36 mmol) and trifluoroacetic acid (10 mL). After 30 minutes at 0 °C, the reaction mixture was added to a solution of copper(I) chloride (50 mg, 0.51 mmol) and concentrated hydrochloric acid (3 mL) at 0 °C. The reaction mixture was allowed to warm to room temperature. After 3 h, the reaction mixture was poured into ice water and the pη was adjusted to 8 by adding sodium carbonate. The aqueous mixture was extracted with ethyl acetate (3 x 135 mL), the combined organic extracts washed with brine, dried (MgSC^), filtered and concentrated under reduced pressure to give a green solid. The solid was purified by flash column chromatography using a Supelco (division of Sigma-Aldrich Co., 595 North Harrison Road, Bellefonte, PA 16823, U.S.A.) tube prepacked with 10 g of silica gel (50 μm particle diameter, 70 A pore size) and as eluant 1: 1 ethyl acetate-hexanes to provide the title compound as light tan solid (114 mg) melting at 161-164 °C.

¹ H NMR (DMSO-^ ₆ ): 6 8.48 (d, IH), 8.26 (dd, IH), 7.76 (d, IH), 4.07 (t, 2H), 1.81-1.68 (m, 2H), 0.93 (t, 3H).

EXAMPLE 6

Preparation of 7-chloro-2-(methylthio)-4-propylthieno[3,2-e] [ 1 ,2,4]triazolo[ 1 ,5-α]pyrimidin- 5(4H)-one

Step A: Preparation of l-[(2,5-dichloro-3-thienyl)carbonyl]-3-(methylthio)-lH-l,2,4 - triazol-5-amine

A mixture of 2,5-dichloro-3-thiophenecarboxylic acid (10 g, 50 mmol), 5-(methylthio)-lH-l,2,4-triazol-3-amine (6 g, 46 mmol), N-(3-dimethylaminόpropyl)-λr- ethylcarbodiimide hydrochloride (10.7 g, 56 mmol) and dichloromethane (200 mL) was stirred at room temperature overnight. One third of the volume of solvent was evaporation under reduced pressure and water (250 mL) was added, resulting in a solid precipitate. The solid was collected by filtration, washed with water (100 mL) and dried in a vacuum oven at 50 °C overnight to provide the title compound as a white solid (13.15 g) melting at 149-150 °C.

¹ H NMR (DMSO-^ ₆ ): 6 7.88 (br s, 2H), 7.60 (s, IH), 2.45 (s, 3H).

Step B: Preparation of 2,5-dichloro-N-[5-(methylthio)-lH-l,2,4-triazol-3-yl]-3- thiophenecarboxamide A stirred mixture of l-[(2,5-dichloro-3-thienyl)carbonyl]-3-(methylthio)-lH-l,2,4 - triazol-5-amine (i.e. the product of Step A) (13.15 g, 43 mmol), potassium carbonate (11.8 g, 85 mmol) and TvVV-dimethylformamide (100 mL) was heated at 90-100 °C for 5 h, cooled to room temperature and diluted with ice water (100 mL). The mixture was slowly added to a stirred solution of hydrochloric (150 mL, 1 ν). The resulting solid precipitate was collected by filtration, washed with water (2 x 100 mL) and dried in a vacuum oven at 50 °C to provide the title compound as a white solid (13.14 g).

¹ H NMR (DMSO-^ ₆ ): δ 13.65 (br s, IH), 11.95 (br s, IH), 7.63 (s, IH), 2.51 (under DMSO, 3H).

Step C: Preparation of 7-chloro-2-(methylthio)thieno[3,2-e][l,2,4]triazolo[l,5- α]pyrimidin-5(lH)-one A mixture of the 2,5-dichloro-N-[5-(methylthio)-lH-l,2,4-triazol-3-yl]-3- thiophenecarboxamide (i.e. the product of Step B, and 1.38 g prepared by the method of Step B) (14.52 g, 46.3 mmol), potassium carbonate (12.79 g, 92.7 mmol), potassium iodide (1.43 g, 8.6 mmol) and N^-dimethylformamide (150 mL) was heated at 130 °C. After 24 h, the reaction mixture was slowly added to a stirred solution of hydrochloric acid (IN) and the pη was adjusted to 2. The resulting solid precipitate was collected by filtration, washed with water and dried in a vacuum oven at 50 °C to provide the title compound as a white solid (10.41 g) melting at > 220 °C.

¹ H NMR (DMSO-^ ₆ ): 5 13.23 (br s, IH), 7.53 (s, IH), 2.59 (s, 3H). Step D: Preparation of 7-chloro-2-(methylthio)-4-propylthieno[3,2- e] [ 1 ,2,4]triazolo[ 1 ,5-α]pyrimidin-5(4H)-one

A mixture of 7-chloro-2-(methylthio)thieno[3,2-e][l,2,4]triazolo[l,5-α]p yrimidin- 5(lH)-one (i.e. the product of Step C) (5 g, 18.4 mmol), potassium carbonate (3.05 g,

22.1 mmol), 1-iodopropane (1.97 mL, 20.2 mmol) and anhydrous N,iV-dimethylformamide

(100 mL) was stirred at room temperature overnight. The reaction mixture was diluted with water and the resulting solid precipitate collected by filtration, washed with water (5x) and dried in a vacuum oven at 50 °C to provide the title compound, a compound of the present invention, as a white solid (5.19 g) melting at 159-160 °C.

¹ H NMR (DMSO-d ₆ ): 5 7.59 (s, IH), 4.05 (t, 2H), 2.61 (s, 3H), 1.80-1.65 (m, 2H), 0.91 (t, 3H).

EXAMPLE 7

Preparation of 7-chloro-2-(methylsulfonyl)-4-propylthieno[3,2-e][l,2,4]tria zolo[l,5- α]pyrimidin-5(4H)-one

A solution of 7-chloro-2-(methlthio)-4-pyropylthieno[3,2-e][l,2,4]triazolo [l,5- α]pyrimidin-5(4H)-one (i.e. the product of Example 6, Step D) (5 g, 15.9 mmol), m-chloroperoxybenzoic acid (77%, 7.85 g, 35.0 mmol) in ethyl acetate (200 mL) was stirred overnight. More m-chloroperoxybenzoic acid (3.57 mg, 15.9 mmol) was added to the reaction mixture. After stirring overnight at room temperature, the mixture was diluted with sodium sulfite solution (10%, 300 mL), and the resulting solid precipitate was collected by filtration, washed with saturated aqueous sodium bicarbonate (2 x 200 mL), water (100 mL) and dried in a vacuum oven at 50 °C to provide the title compound, a compound of the present invention, as a white solid (4.06 g) melting at 203-204 °C. ¹ H NMR (DMSO-^ ₆ ): 57.70 (s, IH), 4.11 (t, 2H), 3.46 (s, 3H), 1.81-1.70 (m, 2H), 0.94 (t, 3H).

EXAMPLE 8

Preparation of 7-chloro-2-propoxy-4-propylthieno[3,2-e][l,2,4]triazolo[l,5- α]pyrimidin- 5(4H)-one A mixture of sodium hydride (60% in oil, 28 mg, 0.7 mmol) and 1-propanol (5 mL) was stirred at room temperature for 30 minutes, and then cooled to -78 ⁰ C. To the sodium hydride/ 1-propanol mixture, added 7-chloro-2-(methylsulfonyl)-4-propylthieno[3,2- e][l,2,4]triazolo[l,5-α]pyrimidin-5(4H)-one (i.e. the product of Example 7, Step A) (243 mg, 0.7 mmol), stirred at room temperature for 18 h, and then heated at reflux for 30 minutes. The reaction mixture was diluted with of water (5 mL) and the pη was adjusted to 2 by the addition of HCl (1 N). The solid precipitate was collected by filtration, washed

with water (3 x 20 mL) and dried in a vacuum oven at 50 ⁰ C. Purification of the solid by flash column chromatography using a Supelco (division of Sigma-Aldrich Co., 595 North Harrison Road, Bellefonte, PA 16823, U.S. A) tube prepacked with 10 g of silica gel (50 μm particle diameter, 70 A pore size) and as eluant ethyl acetate-hexanes (2:8) provided the title compound, a compound of the present invention, as a white solid (32 mg) melting at 147- 149 °C.

¹ H NMR (CDCl ₃ ): δ 7.33 (s, IH), 4.31 (t, 2H), 4.18 (t, 2H), 1.91-1.79 (m, 4H), 1.06 (t, 3H), 1.00 (t, 3H).

EXAMPLE 9 Preparation of 2-(methylsulfonyl)-4-propylpyrido[3,2-e][l,2,4]triazolo[l,5- α]pyrirnidin-

5(4H)-one Step A: Preparation of 2-(methylthio)pyrido[3,2-e][l,2,4]triazolo[l,5-α]pyrimidin- 5- (lH)-one

A stirred mixture of 2-chloro-3-pyridinecarboxylic acid (0.81 g, 5.1 mmol), 5-(methylthio)-lH-l,2,4-triazol-3-amine (0.67 g, 5.1 mmol), potassium carbonate (1.3 g, 9.4 mmol), copper powder (0.04 g, 0.63 mmol), potassium iodide (0.02 g, 0.12 mmol) and of anhydrous N,iV-dimethylformamide (5 mL) was heated at 150 °C. At 150 °C the reaction became very thick. More λf,λf-dimethylformamide (2 mL) was added, the temperature was reduced to 130 °C and the reaction mixture was held at this temperature for 5 h. The reaction mixture was cooled, diluted with water (50 mL) and the pη was adjusted to 2 by the addition of hydrochloric acid (1 N). The resulting orange solid was collected by filtration to provide the title compound (958 mg) melting at >250 °C.

¹ H NMR (DMSO-J ₆ ): δ 13.20 (br s, IH), (br s, IH), 8.55 (d, IH), 7.60 (dd, IH), 2.62 (s, 3H). Step B: Preparation of 2-(methylthio)-4-propylpyrido[3,2-e][l,2,4]triazolo[l,5- α]pyrimidin-5(4H)-one

A mixture of 2-(methylthio)pyrido[3,2-e][l,2,4]triazolo[l,5-α]pvrimidin- 5(lH)-one (i.e. the product of Step A) (900 mg, 3.9 mmol), potassium carbonate (641 mg, 4.6 mmol), 1-iodopropane (414 μL, 722 mg, 4.3 mmol) and anhydrous N,N-dimethylformamide (5 mL) was stirred at room temperature overnight. The reaction mixture was diluted with water (5 mL), the resulting solid precipitate was collected by filtration, washed with water (3 x) and dried to provide the title compound as a tan solid (720 mg) melting at 160-161 °C. ¹ H NMR (CDCl ₃ ): δ 8.87 (d, IH), 8.60 (dd, IH), 7.62 (dd, IH), 4.09 (t, 2H), 2.65 (s, 3H), 1.83-1.70 (m, 2H), 0.93 (t, 3H).

Preparation of 2-(methylsulfonyl)-4-propylpyrido[3,2-e] [ 1 ,2,4]triazolo[ 1 ,5-α]pyrimidin-

5(4H)-one

Step C: Preparation of 2-(methylsulfonyl)-4-propylpyrido[3,2-e][l,2,4]triazolo[l,5- α]pyrimidin-5(4H)-one A solution of 2-(methylthio)-4-propylpyrido[3,2-e][l,2,4]triazolo[l,5-α]p yrirnidin-

5(4H)-one (i.e. the product of Step B) (200 mg, 0.73 mmol) and /n-chloroperoxybenzoic acid (77%, 356 mg, 1.6 mmol) in ethyl acetate (5 mL) was stirred for 1 h. More m-chloroperoxybenzoic acid (162 mg, 0.72 mmol) was added to the reaction mixture. After stirring overnight at room temperature, the mixture was diluted with aqueous sodium sulfite solution (40 mL, 10%), and the resulting solid precipitate was collected by filtration, washed with saturated aqueous sodium bicarbonate (3 x 20 mL) and dried in a vacuum oven at 50 °C to provide the title compound, a compound of the present invention, as a off-white solid (111 mg) melting at 205-207 ⁰ C. ¹ H NMR (CDCl ₃ ): δ 8.96 (dd, IH), 8.68 (dd, IH), 7.77 (dd, IH), 4.14 (t, 2H), 3.49 (s, 3H), 1.83-1.70 (m, 2H), 0.96 (t, 3H).

EXAMPLE 10

Preparation of 2-propoxy-4-propylpyrido[3,2-e][l,2,4]triazolo[l,5-α]pyrimi din-5(4H)-one

A mixture of sodium hydride (60% in oil, 13 mg, 0.33 mmol) and 1-propanol (3 mL) was stirred at room temperature for 30 minutes, and then cooled to -78 °C. To the sodium hydride/1-propanol mixture was added 2-(methylsulfonyl)-4-propylpyrido[3,2- e][l,2,4]triazolo[l,5-α]pyrimidin-5(4H)-one (i.e. the product of Example 9, Step C) (96 mg,

0.31 mmol), the reaction mixture was stirred at room temperature for 18 h, and then heated at reflux for 30 minutes. The reaction mixture was diluted with water (5 mL) and the pη was adjusted to 2 by the addition of HCl (1 N). The solid precipitate was collected by filtration, washed with water (3 x 20 mL) and dried in a vacuum oven at 50 °C to provide the title compound, a compound of the present invention, as a white solid (23 mg) melting at

158-160 °C.

¹ H NMR (CDCl ₃ ): δ 8.85 (dd, IH), 8.58 (dd, IH), 7.58 (dd, IH), 4.29 (t, 2H), 4.07 (t, 2H),

1.83-1.70 (m, 4H), 1.00 (t, 3H), 0.93 (t, 3H). EXAMPLE I l

Preparation of 7-iodo-4-propyl-2-(lH-pyrrol-l-yl)[l,2,4]triazole[l,5-α]qui nazolin-5(4H)-one

A mixture of 2-amino-7-iodo[l,2,4]triazolo[l,5-α]quinazolin-5(lH)-one (i.e. the product of Example 5, Step B) (0.20 g, 0.54 mmol), 2,5-dimethyoxythtetrahydrofuran

(0.07 mL, 0.54 mmol), acetic acid (2 mL) and anhydrous 7v\N-dimethylformamide (2 mL) was heated at reflux for 1 h. The reaction mixture was concentrated under reduced pressure and the resulting residue was triturated with n-butyl chloride-hexanes to provide the title

compound, a compound of the present invention, as a white solid (23 mg) melting at 204- 206 ⁰ C.

¹ H NMR (DMSO-^ ₆ ): 6 8.68 (d, IH), 8.10 (dd, IH), 7.78 (d, IH), 7.52 (t, 2H), 6.35 (t, 2H), 4.29 (t, 2H), 1.94-1.85 (m, 2H), 1.04 (t, 3H). By the procedures described herein together with methods known in the art, the following compounds of Tables 1 to 9 can be prepared. The following abbreviations are used in the Tables: CN means cyano, NO2 means nitro, Ph means phenyl, Me means methyl, Et means ethyl, /-Pr means isopropyl, n means normal, c means cyclo, OMe means methoxy, CF ₃ means trifluoromethyl, SMe means methylthio. As defined above in the Summary of the Invention, G together with the two carbon atoms to which it is attached forms a 5- or 6-membered ring substituted with R ³ and R ⁴ wherein each R ³ and R ⁴ is any substituent as defined in the Summary of the Invention. Examples of said rings, hereafter identified as a G ring, include the rings illustrated as G-I to G-39 in Exhibit 2 in the Details of the Invention above. In Tables 1-9 below, when G is a fused 5- or 6-membered heterocyclic ring the G-number given in the Tables corresponds to the G ring illustrated in Exhibit 2 in the Details of the Invention above. For example, in Table 4 when G is G-I, R ³ is 6-Br and R ⁴ is H, then the structure would be as follows:

The numbering system for the G rings is as indicated in Exhibit 2 in the Details of the Invention.

In the Summary of the Invention, the definitions of R ¹ and R ² include CpC _j o alkyl substituted with a 3-, 4-, 5- or 6-membered heterocyclic ring containing 1 to 4 heteroatoms independently selected from the group consisting of nitrogen, oxygen and sulfur, provided that each heterocyclic ring contains no more than 4 nitrogens, no more than 2 oxygens and no more than 2 sulfurs, each heterocyclic ring optionally substituted with up to 3 substituents independently selected from R ⁹ . In Tables 1-9 below, when R ¹ or R ² is CJ-CI _Q alkyl substituted with a 3-, 4-, 5- or 6-membered heterocyclic ring, then the heterocyclic ring is indicated by a Y-number and said Y-number corresponds to the Y groups illustrated in Exhibit 1 in the Details of the Invention above. For example, in Table 8 when R ¹ is CH ₂ CH ₂ CH(CH ₃ )CH ₂ CH ₂ (Y-I) and Y-I is substituted with R ⁹ wherein R ⁹ is 2,3-di- CH ₃ , then R ¹ would be represents as illustrated below:

The wavy line indicates that the R ¹ is attached to the remainder of Formula 1. The numbering system for the ring portion of R ¹ is indicated in Exhibit 1 in the Details of the Invention.

Table 1

Q is O, W is O, R ² is n-Pr, R ³ is 7-Br and R ⁴ is H. Rl Rl

CH ₃ (CH ₂ ) ₄ CH ₃

CF ₃ c-propyl c-butyl CH ₂ CH=CH ₂

CH ₂ CH ₂ CH=CH ₂ CH ₂ CH ₂ C≡CH

CH ₂ C≡CC1 CH ₂ OCF ₃

CH ₂ OCH ₂ CH ₂ Cl CH ₂ CH ₂ SCH ₃

(CH ₂ ) ₃ S(O) ₂ CH ₃ CH ₂ (2-CH ₃ -c-propyl)

CH ₂ CH ₂ OCH ₂ CH=CH ₂ CH ₂ CH ₂ SCH ₂ C=CH

CH ₂ CH=CHCH ₂ OCH ₃ OCH ₂ CH ₂ CH ₃

NHCH ₂ CH ₂ CH ₃ 3-MeO-Ph

4-F-Ph 3-NO ₂ -Ph

4-MeS-Ph 2-pyridinyl

2-furanyl 1 -benzo[6]thiophen-3-yl

3-quinolinyl CH ₂ CH ₂ NO ₂

(CH ₂ ) ₃ CN CH ₂ (tetrahydro-2-furanyl)

Q is O, W is O, R ² is n-Pr, R ³ is 7-1 and R ⁴ is H

Rl Rl Rl R 1

(CH ₂ ) ₃ CH ₃ (CH ₂ ) ₄ CH ₃

CH ₂ CH(CH ₃ ) ₂ CH(CH ₃ )CH ₂ CH ₃

(CH ₂ ) ₃ Br c-propyl c-hexyl CH ₂ CH=CH ₂

Q is O, W is O, R ² is n-Pr, 1 * ³ is 7-1 and R ⁴ is 9-1.

Rl Rl Rl Rl

CH ₃ CH ₂ CH ₃ (CH ₂ ) ₃ CH ₃ (CH ₂ ) ₄ CH ₃

(CH ₂ ) ₅ CH ₃ i-Pr CH ₂ CH(CH ₃ ) ₂ CH(CH ₃ )CH ₂ CH ₃

CF ₃ CH ₂ CH ₂ Cl CH ₂ CH ₂ CH ₂ Br c-propyl c-butyl c-pentyl c-hexyl CH ₂ CH=CH ₂

CH ₂ CH ₂ CH=CH ₂ CH ₂ CH=CHCl CH ₂ C≡CH CH ₂ CH ₂ C≡CH

CH ₂ C≡CC1 CH ₂ OCH ₃ CH ₂ OCH ₂ CH ₃ CH ₂ OCF ₃

CH ₂ OCH ₂ CH ₂ Cl CH ₂ SCH ₃ CH ₂ SCH ₂ CH ₃ CH ₂ CH ₂ SCH ₃

(CH ₂ ) ₃ S(O) ₂ CH ₃ CH ₂ (c-propyl) CH ₂ (c-pentyl) CH ₂ (2-CH ₃ -c-propyl)

CH ₂ CH ₂ OCH ₂ CH=CH ₂ CH ₂ CH ₂ OCH ₂ C≡CH CH ₂ CH ₂ SCH ₂ CH=CH ₂ CH ₂ CH ₂ SCH ₂ C≡CH

CH ₂ CH=CHCH ₂ OCH ₃ CH ₂ CH=CHCH ₂ SCH ₃ CH ₂ CH ₂ Si(CH ₃ ) ₃ OCH ₂ CH ₂ CH ₃

NHCH ₂ CH ₂ CH ₃ N(CH ₃ )CH ₂ CH ₃ Ph 3-MeO-Ph

4-F-Ph 3-CF ₃ O-Ph 4-Cl-Ph 3-NO ₂ -Ph

4-MeS-Ph 2-F-4-Me-Ph _2- F-4-Cl-Ph 2-pyridinyl

2-furanyl 2-thienyl 5-benzofuranyl 1 -benzo[ft]thiophen-3-yI

3-quinolinyl (CH ₂ ) ₃ NHCH ₃ CH ₂ CH ₂ N(CH ₃ ) ₂ CH ₂ CH ₂ NO ₂

(CH ₂ ) ₃ CN CH ₂ CH ₂ CO ₂ CH ₃ CH ₂ Ph CH ₂ (tetrahydro-2-furanyl)

Q is O, W is S, R ² is n-Pr, R ³ is 7-1 and R ⁴ is H.

Rl Rl Rl R ¹

CH ₃ CH ₂ CH ₃ (CH ₂ )CH ₃ (CH ₂ ) ₄ CH ₃ (CH ₂ ) ₅ CH ₃ i-Pr CH ₂ CH(CH ₃ ) ₂ CH(CH ₃ )CH ₂ CH ₃

Q is O, W is NR ⁵ , R ⁵ is H, R ² is n-Pr, R ³ is 7-1 and R' * is H.

Rl Rl Rl Rl

CH ₃ CH ₂ CH ₃ (CH ₂ ) ₃ CH ₃ (CH ₂ ) ₄ CH ₃

(CH ₂ ) ₅ CH ₃ /-Pr CH ₂ CH(CH ₃ ) ₂ CH(CH ₃ )CH ₂ CH ₃

CF ₃ CH ₂ CH ₂ Cl (CH ₂ ) ₃ Br c-propyl c-butyl c-pentyl c-hexyl CH ₂ CH=CH ₂

CH ₂ CH ₂ CH=CH ₂ CH ₂ CH=CHCl CH ₂ C=CH CH ₂ CH ₂ C≡CH

CH ₂ C=CCl CH ₂ OCH ₃ CH ₂ OCH ₂ CH ₃ CH ₂ OCF ₃

CH ₂ OCH ₂ CH ₂ Cl CH ₂ SCH ₃ CH ₂ SCH ₂ CH ₃ CH ₂ CH ₂ SCH ₃

(CH ₂ ) ₃ S(O) ₂ CH ₃ CH ₂ (c-propyl) CH ₂ (c-pentyl) CH ₂ (2-CH ₃ -c-propyl)

CH ₂ CH ₂ OCH ₂ CH=CH ₂ CH ₂ CH ₂ OCH ₂ C=CH CH ₂ CH ₂ SCH ₂ CH=CH ₂ CH ₂ CH ₂ SCH ₂ C=CH

CH ₂ CH=CHCH ₂ OCH ₃ CH ₂ CH=CHCH ₂ SCH ₃ CH ₂ CH ₂ Si(CH ₃ ) ₃ OCH ₂ CH ₂ CH ₃

NHCH ₂ CH ₂ CH ₃ N(Me)CH ₂ CH ₃ Ph 3-MeO-Ph

4-F-Ph 3-CF ₃ O-Ph 4-Cl-Ph 3-NO ₂ -Ph

4-MeS-Ph 2-F-4-Me-Ph 2-F-4-Cl-Ph 2-pyridinyl

2-furanyl 2-thienyl 5-benzofuranyl l-benzo[Z>]thiophen-3-yl

3-quinolinyl (CH ₂ ) ₃ NHCH ₃ CH ₂ CH ₂ N(CH ₃ ) ₂ CH ₂ CH ₂ NO ₂

(CH ₂ ) ₃ CN CH ₂ CH ₂ CO ₂ CH ₃ CH ₂ Ph CH ₂ (tetrahydro-2-furanyl)

Q is O, W is a direct bond, R ¹ is n-Pr, R ³ is 7-Br and R ⁴ is H.

R2

(CH ₂ ) ₃ CH ₃

(CH ₂ ) ₅ CH ₃ c-propyl

Q is O, W is O, R ¹ is n-Pr, R ³ is 7-1 and R ⁴ is H.

R2 R2 R2 R2

CH ₂ CH ₃ CH ₂ CH ₂ CH ₃ J-Pr (CH ₂ ) ₃ CH ₃ CH ₂ CH(CH ₃ ) ₂ CH(Me)CH ₂ CH ₃ (CH ₂ ) ₄ CH ₃ (CH ₂ ) ₅ CH ₃

R2 R2 R2

/i-decyl CF ₃ CH ₂ CF ₃ CH ₂ CH ₂ Cl c-propyl c-hexyl CH ₂ (2-CH ₃ -c-propyl) 2-propenyl

CH ₂ CH=CHCH ₃ CH ₂ CH ₂ CH=CH ₂ 5-decenyl CH ₂ CH=CHCl

CH ₂ C≡CH CH ₂ C≡CCH ₃ CH ₂ CH ₂ C=CH CH ₂ C≡CBr

CH ₂ OCH ₃ CH ₂ OCH ₂ CH ₃ CH ₂ CH ₂ OCH ₃ CH ₂ OCH ₂ CH ₂ Cl

CH ₂ CH ₂ OCF ₃ CH ₂ SCH ₃ CH ₂ CH ₂ SCH ₃ (CH ₂ ) ₃ S(O) ₂ CH ₃

CH ₂ (c-propyl) CH ₂ (c-pentyl) CH ₂ CH ₂ OCH ₂ CH=CH ₂ CH ₂ CH ₂ OCH ₂ C≡CH

CH ₂ CH ₂ SCH ₂ CH=CH ₂ CH ₂ CH ₂ SCH ₂ C=CH CH ₂ CH ₂ Si(CH ₃ ) ₃ Ph

2-CN-Ph 2,4-di-Cl-Ph 2,4,6-tri-F-Ph 4-CF ₃ -Ph

4-CH ₃ O-Ph 4-Cl-Ph _2- F-4-Me-Ph (CH ₂ ) ₃ NHCH ₃

(CH ₂ ) ₃ N(CH ₃ ) ₂ CH ₂ CH ₂ NO ₂ CH ₂ CN CH ₂ CH ₂ CH ₂ CN

CH ₂ CH ₂ CO ₂ Et CH ₂ Ph (CH ₂ ) ₃ Ph CH ₂ CH ₂ (4-F-Ph)

CH ₂ (tetrahydro-2-furanyl) N=C(CH ₃ ) ₂ N(CH ₃ ) ₂ NHCH ₂ CH ₂ CH ₃

Q is O, W is a direct bond, Rl is n-Pr, R ³ is 7-1 and R ⁴ s H.

R2 R2 R2 R2

CH ₂ CH ₃ CH ₂ CH ₂ CH ₃ /-Pr (CH ₂ ) ₃ CH ₃

CH ₂ CH(CH ₃ ) ₂ CH(CH ₃ )CH ₂ CH ₃ (CH ₂ ) ₄ CH ₃ (CH ₂ ) ₅ CH ₃

CF ₃ CH ₂ CF ₃ CH ₂ CH ₂ Cl c-propyl c-hexyl 2-Cl-c-propyl CH ₂ (2-CH ₃ -c-propyl)

R2

(CH ₂ ) ₃ CH ₃ (CH ₂ J ₅ CH ₃ CH ₂ CH ₂ Cl 2-propenyl CH ₂ CH=CHCl

CH ₂ C≡CBr

CH ₂ OCH ₂ CH ₂ Cl

(CH ₂ ) ₃ S(O) ₂ CH ₃

CH ₂ CH ₂ OCH ₂ C≡CH

Ph

4-CF ₃ -Ph

(CH ₂ ) ₃ NHCH ₃

CH ₂ CH ₂ CH ₂ CN

R2 R2 R2 R2

CH ₂ CH ₂ CO ₂ Et CH ₂ Ph (CH ₂ ) ₃ Ph CH ₂ CH ₂ (4-F-Ph) CH ₂ (tetrahydro-2-furanyl) N=C(CH ₃ ) ₂ N(CH ₃ ) ₂ NHCH ₂ CH ₂ CH ₃

Q is O, W is a direct bond, R ¹ is n-Pr, R ³ is 7-1 and R ⁴ is 9-1.

R2 R2 R2 R2

CH ₂ CH ₃ CH ₂ CH ₂ CH ₃ i-Pr (CH ₂ ) ₃ CH ₃ CH ₂ CH(CH ₃ ) ₂ CH(CH ₃ )CH ₂ CH ₃ (CH ₂ ) ₃ CH ₃ (CH ₂ ) ₅ CH ₃

CF ₃ CH ₂ CF ₃ CH ₂ CH ₂ Cl c-propyl c-hexyl 2-Cl-c-propyl CH ₂ (2-CH ₃ -c-propyl)

Q is O, W is S, R ¹ is n-Pr, R ³ is 7-1 and R ⁴ is H. R2 R2 R2 R2

CH ₂ CH ₃ CH ₂ CH ₂ CH ₃ i-Pr (CH ₂ ) ₃ CH ₃

CH ₂ CH(CH ₃ ) ₂ CH(CH ₃ )CH ₂ CH ₃ (CH ₂ ) ₄ CH ₃ (CH ₂ ) ₅ CH ₃ n-decyl CF ₃ CH ₂ CF ₃ CH ₂ CH ₂ Cl c-propyl c-hexyl CH ₂ (2-CH ₃ -c-propyl) 2-propenyl

CH ₂ CH=CHCH ₃ CH ₂ CH ₂ CH=CH ₂ 5-decenyl CH ₂ CH=CHCl

CH ₂ C≡CH CH ₂ C≡CCH ₃ CH ₂ CH ₂ C≡CH CH ₂ C≡CBr

CH ₂ OCH ₃ CH ₂ OCH ₂ CH ₃ CH ₂ CH ₂ OCH ₃ CH ₂ OCH ₂ CH ₂ Cl

CH ₂ CH ₂ OCF ₃ CH ₂ SCH ₃ CH ₂ CH ₂ SCH ₃ (CH ₂ ) ₃ S(O) ₂ CH ₃

CH ₂ (c-propyl) CH ₂ (c-pentyl) CH ₂ CH ₂ OCH ₂ CH=CH ₂ CH ₂ CH ₂ OCH ₂ C≡CH

CH ₂ CH ₂ SCH ₂ CH=CH ₂ CH ₂ CH ₂ SCH ₂ C≡CH CH ₂ CH ₂ Si(CH ₃ ) ₃ Ph

2-CN-Ph 2,4-di-Cl-Ph 2,4,6-tri-F-Ph 4-CF ₃ -Ph

4-MeO-Ph 4-Cl-Ph 2-F-4-Me-Ph (CH ₂ ) ₃ NHCH ₃

CH ₂ CH ₂ CH ₂ N(CH ₃ ) ₂ CH ₂ CH ₂ NO ₂ CH ₂ CN CH ₂ CH ₂ CH ₂ CN

CH ₂ CH ₂ CO ₂ Et CH ₂ Ph (CH ₂ ) ₃ Ph CH ₂ CH ₂ (4-F-Ph) CH ₂ (tetrahydro-2-furanyl)

Q is O, W is NR ⁵ , R ⁵ is H, R ¹ is n-Pr, R ³ is 7-1 and R ⁴ is H. R2 R2

CH ₂ CH ₃ (CH ₂ ) ₃ CH ₃

CH ₂ CH(CH ₃ ) ₂ (CH ₂ ) ₅ CH ₃ n-decyl CH ₂ CH ₂ Cl c-propyl 2-propenyl

CH ₂ CH=CHCH ₃ CH ₂ CH=CHCl CH ₂ C≡CH CH ₂ C≡CBr

Q is O, W is O, R ¹ is CH ₂ (tetrahyrdro-2-furanyl), R ³ is 7-1 and R ⁴ is H.

R2 R2 R2 R2

CH ₂ CH ₃ CH ₂ CH ₂ CH ₃ /-Pr (CH ₂ ) ₃ CH ₃

CH ₂ CH(CH ₃ ) ₂ CH(CH ₃ )CH ₂ CH ₃ (CH ₂ ) ₄ CH ₃ (CH ₂ ) ₅ CH ₃

λz-decyl CF ₃ CH ₂ CF ₃ CH ₂ CH ₂ Cl c-propyl c-hexyl CH ₂ (2-CH ₃ -c-propyl) 2-propenyl

CH ₂ CH=CHCH ₃ CH ₂ CH ₂ CH=CH ₂ 5-decenyl CH ₂ CH=CHCl

CH ₂ C≡CH CH ₂ C≡CCH ₃ CH ₂ CH ₂ C≡CH CH ₂ C≡CBr

CH ₂ OCH ₃ CH ₂ OCH ₂ CH ₃ CH ₂ CH ₂ OCH ₃ CH ₂ OCH ₂ CH ₂ Cl

CH ₂ CH ₂ OCF ₃ CH ₂ SCH ₃ CH ₂ CH ₂ SCH ₃ (CH ₂ ) ₃ S(O) ₂ CH ₃

CH ₂ (c-propyl) CH ₂ (c-pentyl) CH ₂ CH ₂ OCH ₂ CH=CH ₂ CH ₂ CH ₂ OCH ₂ C≡CH

CH ₂ CH ₂ SCH ₂ CH=CH ₂ CH ₂ CH ₂ SCH ₂ C≡CH CH ₂ CH ₂ Si(CH ₃ ) ₃ Ph

2-CN-Ph 2,4-di-Cl-Ph 2,4,6-tri-F-Ph 4-CF ₃ -Ph

4-CH ₃ O-Ph 4-Cl-Ph 2-F-4-CH ₃ -Ph (CH ₂ ) ₃ NHCH ₃

(CH ₂ ) ₃ N(CH ₃ ) ₂ CH ₂ CH ₂ NO ₂ CH ₂ CN (CH ₂ ) ₃ CN

CH ₂ CH ₂ CO ₂ Et CH ₂ Ph CH ₂ CH ₂ CH ₂ Ph CH ₂ CH ₂ (4-F-Ph)

CH ₂ (tetrahydro-2-furanyl) N=C(CH ₃ ) ₂ N(CH ₃ ) ₂ NHCH ₂ CH ₂ CH ₃

Q is O, W is S, R ¹ is CH ₂ (tetrahyrdro-2-furanyl), R ³ is 7-1 and R ⁴ is H. R2

CH ₂ CH ₃

CH ₂ CH(CH ₃ ) ₂ n-decyl c-propyl

CH ₂ CH=CHCH ₃

Q is O, W is a direct bond, R ¹ is CH (tetrahyrdro-2-furanyl), R ³ is 7-1 and R ⁴ is H. R2

CH ₂ CH ₃

CH ₂ CH(CH ₃ ) ₂

CF ₃ c-hexyl

Q is O, W is O, R ¹ is CH (tetrahyrdro-2-furanyl), R ³ is 7-1 and R ⁴ is 9-1.

Q is O, W is S, R ¹ is CH ₂ (tetrahyrdro-2-furanyl), R ³ is 7-1 and R ⁴ is 9-1.

R2 R2 R2 R2

CH ₂ CH ₃ CH ₂ CH ₂ CH ₃ j-Pr (CH ₂ ) ₃ CH ₃

CH ₂ CH(CH ₃ ) ₂ CH(CH ₃ )CH ₂ CH ₃ (CH ₂ ) ₄ CH ₃ (CH ₂ ) ₅ CH ₃ rt-decyl CF ₃ CH ₂ CF ₃ CH ₂ CH ₂ CI c-propyl c-hexyl CH ₂ (2-CH ₃ -c-propyl) 2-propenyl

CH ₂ CH=CHCH ₃ CH ₂ CH ₂ CH=CH ₂ 5-decenyl CH ₂ CH=CHCl

CH ₂ C≡CH CH ₂ C≡CCH ₃ CH ₂ CH ₂ C≡CH CH ₂ C≡CBr

CH ₂ OCH ₃ CH ₂ OCH ₂ CH ₃ CH ₂ CH ₂ OCH ₃ CH ₂ OCH ₂ CH ₂ Cl

CH ₂ CH ₂ OCF ₃ CH ₂ SCH ₃ CH ₂ CH ₂ SCH ₃ (CH ₂ ) ₃ S(O) ₂ CH ₃

CH ₂ (c-propyl) CH ₂ (c-pentyl) CH ₂ CH ₂ OCH ₂ CH=CH ₂ CH ₂ CH ₂ OCH ₂ C≡CH

CH ₂ CH ₂ SCH ₂ CH=CH ₂ CH ₂ CH ₂ SCH ₂ C=CH CH ₂ CH ₂ Si(CH ₃ ) ₃ Ph

2-CN-Ph 2,4-di-Cl-Ph 2,4,6-tri-F-Ph 4-CF ₃ -Ph

4-CH ₃ O-Ph 4-Cl-Ph 2-F-4-Me-Ph (CH ₂ ) ₃ NHCH ₃

(CH ₂ ) ₃ N(CH ₃ ) ₂ CH ₂ CH ₂ NO ₂ CH ₂ CN CH ₂ CH ₂ CH ₂ CN

CH ₂ CH ₂ CO ₂ Et CH ₂ Ph (CH ₂ ) ₃ Ph CH ₂ CH ₂ (4-F-Ph)

CH ₂ (tetrahydro-2-furanyl)

Q is O, W is a direct bond, R ¹ is CH ₂ (tetrahyrdro-2-furanyl), R ³ is 7-1 and R ⁴ is 9-1. R2 R2

CH ₂ CH ₃ (CH ₂ ) ₃ CH ₃ CH ₂ CH(CH ₃ ) ₂ (CH ₂ ) ₅ CH ₃

CF ₃ c-propyl c-hexyl

Table 4

Q is O, W is O, R ¹ is n -propyl and R^ is π-propyl.

G R3 R4 R3 R4 G R3 R4

G-I 6-Br H G-I 6-C≡CH H G-I 6-CH=CH ₂ H

G-I 6-Cl H G-I 7-1 H G-I 7-CH=CH ₂ H

G-I 6-1 H G-I 6-CF ₃ H G-I 7-C≡CH 6-Br

G-I 6-1 7-1 G-I 6-c-propyl H G-I 7-Br 6-CH ₃

G-I 6-Br 7-Br G-I 7-C≡CH H G-I 6-1 7-CH ₂ CH ₃

G-I 7-Br H G-2 7-1 H G-2 8-CH=CH ₂ H

G-2 8-Br H G-2 8-C≡CH H G-2 7-CH=CH ₂ H

G-2 8-Cl H G-2 8-c-propyl H G-2 7-C≡CH 8-Br

G-2 8-1 H G-2 8-CF ₃ H G-2 7-Br 8-CH ₃

G-2 8-1 7-1 G-2 7-C≡CH H G-2 7-1 8-CH ₂ CH ₃

G-2 8-Br 7-Br G-2 8-CH ₂ Br H G-4 6-CH=CH ₂ H

G-2 7-Br H G-4 6-C≡CH H G-4 7-CH=CH ₂ H

G-4 6-Br H G-4 7-1 H G-4 7-C≡CH 6-Br

G-4 6-Cl H G-4 H H G-4 7-Br 6-CH ₃

G-4 6-1 H G-4 6-CF ₃ H G-4 6-1 7-CH ₂ CH ₃

G-4 6-1 7-1 G-4 7-C≡CH H G-5 8-CH=CH ₂ H

G-4 6-Br 7-Br G-5 7-1 H G-5 7-CH=CH ₂ H

G-4 7-Br H G-5 8-C≡CH H G-5 7-C≡CH 8-Br

G-5 8-Br H G-5 8-c-propyl H G-5 7-Br 8-CH ₃

G-5 8-Cl H G-5 8-CF ₃ H G-5 7-r 8-CH ₂ CH ₃

G-5 8-1 H G-5 7-C≡CH H G-16 7-CH ₂ F H

G-5 8-1 7-1 G-5 8-CH ₂ Br H G-16 7-CH=CH ₂ H

G-5 8-Br 7-Br G-16 6-Br 7-Br G-16 7-Br 8-CH ₃

G-5 7-Br H G-16 7-C≡CH H G-16 6-Br H

G-16 7-Br H G-16 7-c-propyl H G-16 6-Br 8-Br

G-16 7-Cl H G-16 7-CF ₃ H G-19 7-CH ₂ F H

G-16 7-1 H G-16 7-1 8-CH ₃ G-19 7-CH=CH ₂ H

G-16 7-1 8-1 G-19 7-Br 9-Br G-19 7-Br 9-CH ₃

R3 R4 G R3 R4 R3 R4

G-16 7-Br 8-Br G-19 7-C≡CH H G-19 9-Br H

G-16 7-1 6-1 G-19 7-c-propyl H G-19 9-1 H

G-19 7-Br H G-19 7-CF ₃ H G-19 7-Br 9-Br

G-19 7-Cl H G-19 7-1 9-CH ₃ G-19 7-1 9-1

G-19 7-1 H G-19 7-Cl 9-Cl G-7 H H

G-8 H H G-9 H H G-7 7-F 8-CH ₃

G-8 8-F 6-CH ₃ G-9 6-F 8-CH ₃ G-7 7-Cl 8-CH ₃

G-8 8-Cl 6-CH ₃ G-9 6-Cl 8-CH ₃ G-7 7-Br H

G-8 8-Br H G-9 6-Br H G-7 7-1 H

G-8 8-1 6-CH ₃ G-9 6-1 H G-7 7-OCH ₃ H

G-8 8-OCH ₃ H G-9 6-OCH ₃ H G-7 7-CF ₃ H

G-8 8-CF ₃ H G-9 6-CF ₃ H G-7 7-CH ₃ 8-CH ₃

G-8 8-CH ₃ 6-CH ₃ G-9 6-CH ₃ 8-CH ₃ G-14 H H

G-15 H H G-17 H H G-14 7-F 8-CH ₃

G-15 7-F 6-CH ₃ G-17 7-Cl H G-14 7-Cl 8-CH ₃

G-15 7-Cl 6-CH ₃ G-17 7-Br H G-14 7-Br H

G-15 7-Br H G-17 7-C≡CH H G-14 7-1 H

G-15 7-1 6-CH ₃ G-17 7-1 H G-14 7-OCH ₃ H

G-15 7-OCH ₃ H G-17 7-Br 9-Br G-14 7-CF ₃ H

G-15 7-CF ₃ H G-17 7-1 9-1 G-14 7-CH ₃ 8-CH ₃

G-15 7-CH ₃ 6-CH ₃ G-17 7-CH=CH ₂ H G-18 H H

G-20 H H G-21 H H G-18 8-Cl H

G-20 7-Cl H G-21 6-Cl H G-18 8-Br H

G-20 7-Br H G-21 6-Br H G-18 8-C≡CH H

G-20 7-C≡CH H G-21 6-C≡CH H G-18 8-1 H

G-20 7-1 H G-21 6-1 H G-18 8-Br 6-Br

G-20 7-Br 8-Br G-21 6-Br 8-Br G-18 8-1 6-1

G-20 7-1 8-1 G-21 6-1 8-1 G-18 8-CH=CH ₂ H

G-20 7-CH=CH ₂ H G-21 6-CH=CH ₂ H G-22 H H

G-23 H H G-24 H H G-22 7-Cl H

G-23 6-Cl H G-24 9-F H G-22 7-Br H

G-23 7-Br H G-24 6-Cl H G-22 7-C≡CH H

G-23 7-C≡CH H G-24 6-Br H G-22 7-1 H

G-23 7-1 H G-24 9-1 H G-22 7-Br 9-Br

G-23 6-Br 6-Br G-24 6-OCH ₃ H G-22 7-1 9-1

G-23 6-1 6-1 G-24 9-CF ₃ H G-22 7-CH=CH ₂ H

G-23 7-CH=CH ₂ H G-24 6-CH ₃ H G-25 H H

R3 R4 R3 R ⁴ R3 R4

G-31 H H G-33 H H G-25 9-F H G-31 9-CH ₃ H G-33 7-CH ₃ H G-25 8-Cl H G-31 9-CH ₃ 9-CH ₃ G-33 7-CH ₃ 8-CH ₃ G-25 9-Br H G-32 H H G-34 H H G-25 8-1 H G-32 6-Ph H G-34 7-CH ₃ H G-25 8-CH ₃ H G-32 9-CH ₃ H G-34 7-CH ₃ 9-CH ₃ G-35 H H G-36 H H G-37 H H G-35 9-CH ₃ H G-36 9-CH ₃ H G-37 8-CH ₃ 6-CH ₃ G-35 9-CH ₃ 9-CH ₃ G-36 9-CH ₃ 9-CH ₃ G-37 8-Cl H G-38 H H G-38 8-CH ₃ 8-CH ₃ G-38 6-CH ₃ 6-CH ₃ G-39 H H G-39 6-CH ₃ 8-CH ₃ G-39 8-Cl H

Table 5

Q is O, W is O, RI is n-propyl and R^ is n-propyl.

R3 R3 R3 R3 R3 R3

G-I l Br G-I l H G-IO Br G-IO H G-12 Br G-12 H G-I l Cl G-I l CF ₃ G-IO Cl G-IO CF ₃ G-12 Cl G-12 CF ₃ G-I l I G-I l CH ₂ Br G-IO I G-IO CH ₂ Br G-12 I G-12 CH ₂ Br G-I l CH ₃ G-I l CH=CH ₂ G-IO CH ₃ G-IO CH=CH ₂ G-12 CH ₃ G-12 CH=CH ₂ G-I l CH ₂ CH ₃ G-I l F G-IO CH ₂ CH ₃ G-IO F G-12 CH ₂ CH ₃ G-12 F G-I l C≡CH G-I l OCH ₃ G-IO C≡CH G-12 C≡CH G-12 OCH ₃ G-13 H G-13 I G-26 H G-26 I G-27 H G-27 I G-13 F G-13 CH ₃ G-26 F G-26 CH ₃ G-27 F G-27 CH ₃ G-13 Br G-13 CF ₃ G-26 Br G-26 CF ₃ G-27 Br G-27 CF ₃ G-13 Cl G-13 OCH ₃ G-26 Cl G-26 OCH ₃ G-27 Cl G-27 OCH ₃

Table 6

G is G-2, Q is O, W is O, R ² is n-propyl, R ³ is 7-Br and R ⁴ is H.

Rl Rl Rl Rl

CH ₃ CH ₂ CH ₃ (CH ₂ ) ₃ CH ₃ (CH ₂ ) ₄ CH ₃

(CH ₂ ) ₅ CH ₃ /-Pr CH ₂ CH(CH ₃ ) ₂ CH(CH ₃ )CH ₂ CH ₃

CF ₃ CH ₂ CH ₂ Cl (CH ₂ ) ₃ Br c-propyl c-butyl c-pentyl c-hexyl CH ₂ CH=CH ₂

CH ₂ CH ₂ CH=CH ₂ CH ₂ CH=CHCl CH ₂ C≡CH CH ₂ CH ₂ C≡CH

CH ₂ C≡CC1 CH ₂ OCH ₃ CH ₂ OCH ₂ CH ₃ CH ₂ OCF ₃

CH ₂ OCH ₂ CH ₂ Cl CH ₂ SCH ₃ CH ₂ SCH ₂ CH ₃ CH ₂ CH ₂ SCH ₃

(CH ₂ ) ₃ S(O) ₂ CH ₃ CH ₂ (c-propyl) CH ₂ (c-pentyl) CH ₂ (2-CH ₃ -c-propyl)

(CH ₂ ) ₂ OCH ₂ CH=CH ₂ CH ₂ CH ₂ OCH ₂ C≡CH CH ₂ CH ₂ SCH ₂ CH=CH ₂ CH ₂ CH ₂ SCH ₂ C=CH

CH ₂ CH=CHCH ₂ OCH ₃ CH ₂ CH=CHCH ₂ SCH ₃ CH ₂ CH ₂ Si(CH ₃ ) ₃ OCH ₂ CH ₂ CH ₃

NHCH ₂ CH ₂ CH ₃ N(CH ₃ )CH ₂ CH ₃ Ph 3-MeO-Ph

4-F-Ph 3-CF ₃ O-Ph 4-Cl-Ph 3-NO ₂ -Ph

4-MeS-Ph 2-F-4-Me-Ph 2-F-4-Cl-Ph 2-pyridinyl

2-furanyl 2-thienyl 5-benzofuranyl 1 -benzo[fc]thiophen-3-yl

3-quinolinyl (CH ₂ ) ₃ NHCH ₃ CH ₂ CH ₂ N(CH ₃ ) ₂ CH ₂ CH ₂ NO ₂

(CH ₂ ) ₃ CN CH ₂ CH ₂ CO ₂ CH ₃ CH ₂ Ph CH ₂ (tetrahydro-2-furanyl)

G is G-2, Q is O, W is NH, R ² is n-propyl, R ³ is 7-Br and R ⁴ is H.

G is G-2, Q is O, W is S, R ² is π-propyl, R ³ is 7-Br and R ⁴ is H. Rl

CH ₃ (CH ₂ ) ₅ CH ₃

CF ₃ c-butyl

CH ₂ CH ₂ CH=CH ₂

CH ₂ C≡CC1

CH ₂ OCH ₂ CH ₂ Cl

(CH ₂ ) ₃ S(O) ₂ CH ₃

(CH ₂ ) ₂ OCH ₂ CH=CH ₂

CH ₂ CH=CHCH ₂ OCH ₃

NHCH ₂ CH ₂ CH ₃

4-F-Ph 4-CH ₃ S-Ph

2-furanyl 3-quinolinyl (CH ₂ ) ₃ CN G is G-16, Q is O, W is O, R ² is n-propyl, R ³ is 7-1 and R ⁴ is H.

Rl Rl Rl Rl

CH ₂ CH=CHCH ₂ OCH ₃ CH ₂ CH=CHCH ₂ SCH ₃ CH ₂ CH ₂ Si(CH ₃ ) ₃ OCH ₂ CH ₂ CH ₃ NHCH ₂ CH ₂ CH ₃ N(CH ₃ )CH ₂ CH ₃ Ph 3-MeO-Ph

4-F-Ph 3-CF ₃ O-Ph 4-Cl-Ph 3-NO ₂ -Ph

4-CH ₃ S-Ph 2-F-4-CH ₃ -Ph _2- F-4-Cl-Ph 2-pyridinyl

2-furanyl 2-thienyl 5-benzofuranyl l-benzo[fc]thiophen-3-yl

3-quinoliny] (CH ₂ ) ₃ NHCH ₃ CH ₂ CH ₂ N(CH ₃ ) ₂ CH ₂ CH ₂ NO ₂

(CH ₂ ) ₃ CN CH ₂ CH ₂ CO ₂ CH ₃ CH ₂ Ph CH ₂ (tetrahydro-2-furanyl)

G is G-16, Q is O, W is S, R ² is n-propyl, R ³ is 7-1 and R ⁴ is H. Rl Rl Rl Rl

CH ₃ CH ₂ CH ₃ (CH ₂ ) ₃ CH ₃ (CH ₂ ) ₄ CH ₃ (CH ₂ ) ₅ CH ₃ j-Pr CH ₂ CH(CH ₃ ) ₂ CH(CH ₃ )CH ₂ CH ₃

CF ₃ CH ₂ CH ₂ Cl CH ₂ CH ₂ CH ₂ Br c-propyl c-butyl c-pentyl c-hexyl CH ₂ CH=CH ₂

CH ₂ CH ₂ CH=CH ₂ CH ₂ CH=CHCl CH ₂ C≡CH CH ₂ CH ₂ C≡CH

CH ₂ C≡CC1 CH ₂ OCH ₃ CH ₂ OCH ₂ CH ₃ CH ₂ OCF ₃

CH ₂ OCH ₂ CH ₂ Cl CH ₂ SCH ₃ CH ₂ SCH ₂ CH ₃ CH ₂ CH ₂ SCH ₃

(CH ₂ ) ₃ S(O) ₂ CH ₃ CH ₂ (c-propyl) CH ₂ (c-pentyl) CH ₂ (2-CH ₃ -c-propyl)

CH ₂ CH ₂ OCH ₂ CH=CH ₂ CH ₂ CH ₂ OCH ₂ C≡CH CH ₂ CH ₂ SCH ₂ CH=CH ₂ CH ₂ CH ₂ SCH ₂ C≡CH

CH ₂ CH=CHCH ₂ OCH ₃ CH ₂ CH=CHCH ₂ SCH ₃ CH ₂ CH ₂ Si(CH ₃ ) ₃ OCH ₂ CH ₂ CH ₃

NHCH ₂ CH ₂ CH ₃ N(Me)CH ₂ CH ₃ Ph 3-MeO-Ph

4-F-Ph 3-CF ₃ O-Ph 4-Cl-Ph 3-NO ₂ -Ph 4-CH ₃ S-Ph _2- F-4-Me-Ph _2- F-4-Cl-Ph 2-pyridinyl

2-furanyl 2-thienyl 5-benzofuranyl l-benzo[b]thiophen-3-yl 3-quinolinyl (CH ₂ ) ₃ NHCH ₃ CH ₂ CH ₂ N(CH ₃ ) ₂ CH ₂ CH ₂ NO ₂ (CH ₂ ) ₃ CN CH ₂ CH ₂ CO ₂ CH ₃ CH ₂ Ph CH ₂ (tetrahydro-2-furanyl)

Table 7

G is G- 1 , Q is O, W is NH ₁ R ² is n-propyl, R ³ is 7-Br and R ⁴ is H.

R2 R2 R2 R2

(CH ₂ J ₂ SCH ₂ CH=CH ₂ CH ₂ CH ₂ SCH ₂ C≡CH CH ₂ CH ₂ Si(CH ₃ ) ₃ Ph

2-CN-Ph 2,4-di-Cl-Ph 2,4,6-tri-F-Ph 4-CF ₃ -Ph

4-CH ₃ O-Ph 4-Cl-Ph 2-F-4-Me-Ph (CH ₂ ) ₃ NHCH ₃

(CH ₂ ) ₃ N(CH ₃ ) ₂ CH ₂ CH ₂ NO ₂ CH ₂ CN CH ₂ CH ₂ CH ₂ CN

CH ₂ CH ₂ CO ₂ Et CH ₂ Ph (CH ₂ ) ₃ Ph CH ₂ CH ₂ (4-F-Ph)

CH ₂ (tetrahydro-2-furanyl) N=C(CH ₃ ) ₂ N(CH ₃ ) ₂ NHCH ₂ CH ₂ CH ₃

OCH ₃ C(=O)CH ₃ CO ₂ CH ₃ N=CHCH ₂ CH ₂ CH ₃

G is G-I, Q is 0, W is a direct bond, R ¹ is n-propyl, R ³ is 7-1 and R ⁴ is H.

R2 R2 R2 R2

CH ₂ CH ₃ CH ₂ CH ₂ CH ₃ /-Pr (CH ₂ ) ₃ CH ₃ CH ₂ CH(CH ₃ ) ₂ CH(CH ₃ )CH ₂ CH ₃ (CH ₂ ) ₄ CH ₃ (CH ₂ ) ₅ CH ₃

CF ₃ CH ₂ CF ₃ CH ₂ CH ₂ Cl c-propyl c-hexyl 2-Cl-c-propyl CH ₂ (2-CH ₃ -c-propyl)

G is G- 16, Q is O, W is O, R ¹ is n-propyl, R ³ is 7-1 and R ⁴ is H.

R2 R2 R2 R2

CH ₂ CH ₃ CH ₂ CH ₂ CH ₃ j-Pr (CH ₂ ) ₃ CH ₃

CH ₂ CH(CH ₃ ) ₂ CH(CH ₃ )CH ₂ CH ₃ (CH ₂ ) ₄ CH ₃ (CH ₂ ) ₅ CH ₃ π-decyl CF ₃ CH ₂ CF ₃ CH ₂ CH ₂ Cl c-propyl c-hexyl CH ₂ (2-CH ₃ -c-propyl) 2-propenyl

CH ₂ CH=CHCH ₃ CH ₂ CH ₂ CH=CH ₂ 5-decenyl CH ₂ CH=CHCl

CH ₂ C≡CH CH ₂ C≡CCH ₃ CH ₂ CH ₂ C=CH CH ₂ C≡CBr

CH ₂ OCH ₃ CH ₂ OCH ₂ CH ₃ CH ₂ CH ₂ OCH ₃ CH ₂ OCH ₂ CH ₂ Cl

CH ₂ CH ₂ OCF ₃ CH ₂ SCH ₃ CH ₂ CH ₂ SCH ₃ (CH ₂ ) ₃ S(O) ₂ CH ₃

CH ₂ (c-propyl) CH ₂ (c-pentyl) CH ₂ CH ₂ OCH ₂ CH=CH ₂ CH ₂ CH ₂ OCH ₂ C≡CH

CH ₂ CH ₂ SCH ₂ CH=CH ₂ CH ₂ CH ₂ SCH ₂ C≡CH CH ₂ CH ₂ Si(CH ₃ ) ₃ Ph

2-CN-Ph 2,4-di-Cl-Ph 2,4,6-tri-F-Ph 4-CF ₃ -Ph

4-CH ₃ O-Ph 4-Cl-Ph 2-F-4-CH ₃ -Ph (CH ₂ ) ₃ NHCH ₃

(CH ₂ ) ₄ N(CH ₃ ) ₂ CH ₂ CH ₂ NO ₂ CH ₂ CN CH ₂ CH ₂ CH ₂ CN

CH ₂ CH ₂ CO ₂ Et CH ₂ Ph (CH ₂ ) ₃ Ph CH ₂ CH ₂ (4-F-Ph)

CH ₂ (tetrahydro-2-furanyl) N(CH ₃ ) ₂ NHCH ₂ CH ₂ CH ₃ N=CHCH ₂ CH ₂ CH ₃

N=C(CH ₃ ) ₂

R2 R2 R2 R2

CH ₂ CH(CH ₃ ) ₂ CH(CH ₃ )CH ₂ CH ₃ (CH ₂ ) ₄ CH ₃ (CH ₂ ) ₅ CH ₃

CF ₃ CH ₂ CF ₃ CH ₂ CH ₂ Cl c-propyl c-hexyl 2-Cl-c-propyl CH ₂ (2-CH ₃ -c-propyl)

G is G- 16, Q is O, W is NH, R ¹ is /i-propyl, R ³ is 7-1 and R ⁴ is H.

R2 R2

N=CHCH ₂ CH ₂ CH ₃ N=C(CH ₃ ) ₂

Q is O, R2 is n-propyl, R ³ is 7-1, R ⁴ is H, each R" listed in the table below is substituted on the Y-ring listed in the table below under the column Rl, and when R ⁹ is a dash ("-") then the Y-ring is unsubstituted. W R ¹ R ⁹

O CH ₂ (Y-I) -

O CH ₂ CH ₂ CH(CH ₃ )CH ₂ CH ₂ (Y- 1 ) 2,3-di-CH ₃

O (CH ₂ ) ₁₀ (Y-l) 3-(CH ₂ ) ₅ CH ₃ -3-CH ₃

O CH ₂ (Y-2) 3-CH ₂ CH ₃

O CH ₂ (Y-3) -

O CH ₂ (Y-4) 2-OCH ₃

O CH ₂ (Y-5) 2-OCH ₃

O CH ₂ (Y-6) -

O CH ₂ (Y-O) 5-Cl

O (CH ₂ ) ₅ (Y-7) 2,4,5-tri-Br

O CH ₂ (Y-8) -

O CH ₂ (Y-8) 3-OCF ₃

O CH ₂ (Y-8) 3-O(CF ₂ ) ₅ CF ₃ -4-CH ₃

O CH ₂ (Y-9) -

O CH ₂ (Y-9) 4-C≡C(CH ₂ ) ₅ CH ₃ -5-I

O CH ₂ (Y-9) 5-NO ₂

O (CH ₂ )J ₀ (Y-IO) 4-SCH ₃ -5-Cl

W Rl R9

O CH ₂ (Y- 12) -

O (CH ₂ ) ₅ (Y-12) 3-O(CH ₂ ) ₅ CH ₃

O CH ₂ CH ₂ CH(CH3)(CH2)2( Y- 12) 4-CN

O CH ₂ (Y- 12) 4-(CF ₂ ) ₅ CF ₃ -5,5-di-F

O CH ₂ (Y- 12) 3-Cl-4-CF ₃

O (CH ₂ ) ₁₀ (Y-13) 3-CF ₃

O CH ₂ (Y-13) 2-C≡CH-4-SCH ₃

O CH ₂ (Y- 19) 3-CH ₃

O CH ₂ (Y-23) 3-O(CH ₂ ) ₂ CH ₃ -5-CH ₂ CH ₃

O CH ₂ (Y-24) 3-Br

O CH ₂ (Y-24) 3-CO ₂ CH ₂ CH ₃

O CH ₂ (Y-24) 3-C(O)N(CH ₃ ) ₂

O CH ₂ (Y-24) 3-C(O)N(CH ₂ CH ₃ ) ₂

O CH ₂ (Y-24) 3-O(CH ₂ ) ₂ CH ₃ -4-CH ₂ CH ₃

O CH ₂ (Y-25) 3-Br

O CH ₂ (Y-25) 3-CO ₂ CH ₂ CH ₃

O CH ₂ (Y-25) 3-C(O)N(CH ₃ ) ₂

O CH ₂ (Y-25) 3-C(O)N(CH ₂ CH ₃ ) ₂

O CH ₂ (Y-25) 3-SCH ₂ CH ₂ CH ₃

O (CH ₂ ) ₁₀ (Y-25) 3-N(CH ₃ ) ₂

O (CH ₂ ) ₅ (Y-26) 3-N(CH ₂ CH ₃ ) ₂ -5-CH ₃

O (CH ₂ ) ₈ (Y-34) l-Cl-4-CO ₂ CH ₃

O CH ₂ (Y-38) 5-CO ₂ CH ₃

O CH ₂ (Y-38) 3-Cl

O CH ₂ (Y-40) 2,2-di-CH ₃

O CH ₂ (Y-40) 2-CH ₃

O (CH ₂ ) ₄ (Y-47) 3-CF ₂ CF ₂ CF ₃

O CH ₂ (Y-53) l-CH ₃ -3-N(CH ₃ ) ₂

O CH ₂ (Y-54) 1-CF ₃

O CH ₂ (Y-55) -

O CH ₂ (Y-56) -

O (CH ₂ ) ₇ (Y-56) 6-SCCl ₃ -5-Cl

O CH ₂ (Y-57) 2-S(CF ₂ ) ₅ CF ₃ -6-CF ₃

O CH ₂ (Y-62) -

O (CH ₂ ) ₉ (Y-63) 3,5,6-tri-F

O CH ₂ (Y-64) 4-(C(O)CH ₃ )-6-I

O CH ₂ (Y-70) 3-C(CH ₃ ) ₃

W Rl R9

O CH ₂ (Y-70) 3-CO ₂ CH ₃

O CH ₂ (Y-70) 3-CF ₂ CF ₂ CF ₃

O CH ₂ (Y-74) 4,5-di-CF ₃

O CH ₂ (Y-73) -

O CH ₂ (Y-71) -

NH CH ₂ (Y-I) -

NH CH ₂ CH ₂ CH(CH ₃ )(CH ₂ ) ₂ ( Y- 1 ) 2,3-di-CH ₃

NH (CH ₂ )I ₀ (Y-I) 3-(CH ₂ ) ₅ CH ₃ -3-CH ₃

NH CH ₂ (Y-2) 3-CH ₂ CH ₃

NH CH ₂ (Y-3) -

NH CH ₂ (Y-4) 2-OCH ₃

NH CH ₂ (Y-5) 2-OCH ₃

NH CH ₂ (Y-O) -

NH CH ₂ (Y-O) 5-Cl

NH (CH ₂ ) ₅ (Y-7) 2,4,5-tri-Br

NH CH ₂ (Y-8) -

NH CH ₂ (Y-8) 3-OCF ₃

NH CH ₂ (Y-8) 3-O(CF ₂ ) ₅ CF ₃ - 4-CH ₃

NH CH ₂ (Y-9) -

NH CH ₂ (Y-9) 4-C≡C(CH ₂ ) ₅ CH ₃ -5-I

NH CH ₂ (Y-9) 5-NO ₂

NH (CH ₂ ) ₁₀ (Y-10) 4-SCH ₃ -5-Cl

NH CH ₂ (Y- 12) -

NH (CH ₂ ) ₅ (Y-12) 3-O(CH ₂ ) ₅ CH ₃

NH CH ₂ CH ₂ CH(CH ₃ )(CH ₂ ) ₂ (Y-12) 4-CN

NH CH ₂ (Y- 12) 4-(CF ₂ ) ₅ CF ₃ -5,5-di-F

NH CH ₂ (Y- 12) 3-Cl-4-CF ₃

NH (CH ₂ ) ₁₀ (Y-13) 3-CF ₃

NH CH ₂ (Y-O) 2-C≡CH-4-SCH ₃

NH CH ₂ (Y- 19) 3-CH ₃

NH CH ₂ (Y-23) 3-O(CH ₂ ) ₂ CH ₃ -5-CH ₂ CH ₃

NH CH ₂ (Y-24) 3-Br

NH CH ₂ (Y-24) 3-CO ₂ CH ₂ CH ₃

NH CH ₂ (Y-24) 3-C(O)N(CH ₃ ) ₂

NH CH ₂ (Y-24) 3-C(O)N(CH ₂ CH ₃ ) ₂

NH CH ₂ (Y-24) 3-O(CH ₂ ) ₂ CH ₃ -4-CH ₂ CH ₃

NH CH ₂ (Y-25) 3-Br

W Rl R9

NH CH ₂ (Y-25) 3-CO ₂ CH ₂ CH ₃

NH CH ₂ (Y-25) 3-C(O)N(CH ₃ ) ₂

NH CH ₂ (Y-25) 3-C(O)N(CH ₂ CH ₃ ) ₂

NH CH ₂ (Y-25) 3-S(CH ₂ ) ₂ CH ₃

NH (CH ₂ ) ₁₀ (Y-25) 3-N(CH ₃ ) ₂

NH (CH ₂ ) ₅ (Y-26) 3-N(CH ₂ CH ₃ ) ₂ -5-CH ₃

NH (CH ₂ ) ₈ (Y-34) l-Cl-4-CO ₂ CH ₃

NH CH ₂ (Y-38) 5-CO ₂ CH ₃

NH CH ₂ (Y-38) 3-Cl

NH CH ₂ (Y-40) 2,2-di-CH ₃

NH CH ₂ (Y-40) 2-CH ₃

NH (CH ₂ ) ₄ (Y-47) 3-CF ₂ CF ₂ CF ₃

NH CH ₂ (Y-53) l-CH ₃ -3-N(CH ₃ ) ₂

NH CH ₂ (Y-54) 1-CF ₃

NH CH ₂ (Y-55) -

NH CH ₂ (Y-56) -

NH (CH ₂ ) ₇ (Y-56) 6-SCCl ₃ -5-Cl

NH CH ₂ (Y-57) 2-S(CF ₂ ) ₅ CF ₃ , 6-CF ₃

NH CH ₂ (Y-62) -

NH (CH ₂ ) ₉ (Y-63) 3,5,6-tri-F

NH CH ₂ (Y-64) 4-(C(O)CH ₃ )-6-I

NH CH ₂ (Y-70) 3-C(CH ₃ ) ₃

NH CH ₂ (Y-70) 3-CO ₂ CH ₃

NH CH ₂ (Y-70) 3-CF ₃ (CF ₂ ) ₃

NH CH ₂ (Y-74) 4,5-di-CF ₃

NH CH ₂ (Y-73) -

NH CH ₂ (Y-71) -

S CH ₂ (Y-I) -

S CH ₂ CH ₂ CH(CH ₃ )(CH ₂ ) ₂ ( Y- 1 ) 2,3-di-CH ₃

S (CH ₂ )J ₀ (Y-I) 3-(CH ₂ ) ₅ CH ₃ -3-CH ₃

S CH ₂ (Y-2) 3-CH ₂ CH ₃

S CH ₂ (Y-3) -

S CH ₂ (Y-4) 2-OCH ₃

S CH ₂ (Y-5) 2-OCH ₃

S CH ₂ (Y-O) -

S CH ₂ (Y-O) 5-Cl

S (CH ₂ ) ₅ (Y-7) 2,4,5-tri-Br

W Rl R9

S CH ₂ (Y-8) -

S CH ₂ (Y-8) 3-OCF ₃

S CH ₂ (Y-8) 3-O(CF ₂ ) ₅ CF ₃ -4-CH ₃

S CH ₂ (Y-9) -

S CH ₂ (Y-S ⁾ ) 4-C≡C(CH ₂ ) ₅ CH ₃ -5-I

S CH ₂ (Y-24) 3-O(CH ₂ ) ₂ CH ₃ -4-CH ₂ CH ₃

S CH ₂ (Y-25) 3-Br

S CH ₂ (Y-25) 3-CO ₂ CH ₂ CH ₃

S CH ₂ (Y-25) 3-C(O)N(CH ₃ ) ₂

S CH ₂ (Y-25) 3-C(O)N(CH ₂ CH ₃ ) ₂

S CH ₂ (Y-25) 3-SCH ₂ CH ₂ CH ₃

S (CH ₂ ) ₁₀ (Y-25) 3-N(CH ₃ ) ₂

S (CH ₂ ) ₅ (Y-26) 3-N(CH ₂ CH ₃ ) ₂ -5-CH ₃

S (CH ₂ ) ₈ (Y-34) 1-C1-4 CO ₂ CH ₃

S CH ₂ (Y-38) 5-CO ₂ CH ₃

S CH ₂ (Y-38) 3-Cl

S CH ₂ (Y-40) 2,2-di-CH ₃

S CH ₂ (Y-40) 2-CH ₃

S (CH ₂ ) ₄ (Y-47) 3-CF ₂ CF ₂ CF ₃

S CH ₂ (Y-53) l-CH ₃ -3-N(CH ₃ ) ₂

S CH ₂ (Y-54) 1-CF ₃

S CH ₂ (Y-55) -

S CH ₂ (Y-56) -

S (CH ₂ ) ₇ (Y-56) 6-SCCl ₃ -5-Cl

S CH ₂ (Y-57) 2-S(CF ₂ ) ₅ CF ₃ -6-CF ₃

S CH ₂ (Y-62) -

S (CH ₂ ) ₉ (Y-63) 3,5,6-tri-F

S CH ₂ (Y-64) 4-(C(O)CH ₃ )-6-I

S CH ₂ (Y-70) 3-C(CH ₃ ) ₃

S CH ₂ (Y-70) 3-CO ₂ CH ₃

S CH ₂ (Y-70) 3- (CF ₂ ) ₃ CF ₃

S CH ₂ (Y-74) 4,5-di-CF ₃

S CH ₂ (Y-73) — S CH ₂ (Y-71)

Q is O, R ¹ is π-propyl, R ³ is 7-1, R ⁴ is H and Y is substituted 1 to 3 substituents selected from the group R ⁹ , when R ⁹ is a dash ("-") then Y is unsubstituted (i.e. a ring bearing only hydrogens).

W R^ R9

O CH ₂ (Y-I) -

O (CH ₂ ) ₂ CH(CH3)(CH2)2(Y-1) 2,3-di-CH ₃

O (CH ₂ ) ₁₀ (Y-l) 3-(CH ₂ ) ₅ CH ₃ -3-CH ₃

O CH ₂ (Y-2) 3-CH ₂ CH ₃

O CH ₂ (Y-3) -

O CH ₂ (Y-4) 2-OCH ₃

O CH ₂ (Y-5) 2-OCH ₃

O CH ₂ (Y-O) -

O CH ₂ (Y-6) 5-Cl

O (CH ₂ ) ₅ (Y-7) 2,4,5-tri-Br

O CH ₂ (Y-8) -

O CH ₂ (Y-8) 3-OCF ₃

O CH ₂ (Y-8) 3-O(CF ₂ ) ₅ CF ₃ -4-CH ₃

O CH ₂ (Y-9) -

O CH ₂ (Y-9) 4-C≡C(CH ₂ ) ₅ CH ₃ -5-I

O CH ₂ (Y-9) 5-NO ₂

O (CH ₂ ) ₁₀ (Y-10) 4-SCH ₃ -5-Cl

O CH ₂ (Y- 12) -

O (CH ₂ ) ₅ (Y-12) 3-O(CH ₂ ) ₅ CH ₃

O (CH ₂ ) ₂ CH(CH ₃ )(CH ₂ ) ₂ (Y-12) 4-CN

O CH ₂ (Y- 12) 4-(CF ₂ )5CF ₃ -5,5-di-F

O CH ₂ (Y- 12) 3-Cl-4-CF ₃

O (CH ₂ ) ₁₀ (Y-13) 3-CF ₃

O CH ₂ (Y-B) 2-CsCH-4-SCH ₃

O CH ₂ (Y- 19) 3-CH ₃

O CH ₂ (Y-23) 3-OCH ₂ CH ₂ CH ₃ -5-CH ₂ CH ₃

O CH ₂ (Y-24) 3-Br

W R2 R9

O CH ₂ (Y-24) 3-CO ₂ CH ₂ CH ₃

O CH ₂ (Y-24) 3-C(O)N(CH ₃ ) ₂

O CH ₂ (Y-24) 3-C(O)N(CH ₂ CH ₃ ) ₂

O CH ₂ (Y-24) 3-OCH ₂ CH ₂ CH ₃ ^-CH ₂ CH ₃

O CH ₂ (Y-25) 3-Br

O CH ₂ (Y-25) 3-CO ₂ CH ₂ CH ₃

O CH ₂ (Y-25) 3-C(O)N(CH ₃ ) ₂

O CH ₂ (Y-25) 3-C(O)N(CH ₂ CH ₃ ) ₂

O CH ₂ (Y-25) 3-SCH ₂ CH ₂ CH ₃

O (CH ₂ ) ₁₀ (Y-25) 3-N(CH ₃ ) ₂

O (CH ₂ ) ₅ (Y-26) 3-N(CH ₂ CH ₃ ) ₂ -5-CH ₃

O (CH ₂ ) ₈ (Y-34) 2-Cl-4-CO ₂ CH ₃

O CH ₂ (Y-38) 5-CO ₂ CH ₃

O CH ₂ (Y-38) 3-Cl

O CH ₂ (Y-40) 2,2-di-CH ₃

O CH ₂ (Y-40) 2-CH ₃

O (CH ₂ ) ₄ (Y-47) 3-CF ₂ CF ₂ CF ₃

O CH ₂ (Y-53) l-CH ₃ -3-N(CH ₃ ) ₂

O CH ₂ (Y-54) 1-CF ₃

O CH ₂ (Y-55) -

O CH ₂ (Y-56) -

O (CH ₂ ) ₇ (Y-56) 6-SCCl ₃ -5-Cl

O CH ₂ (Y-57) 2-S(CF ₂ ) ₅ CF ₃ -6-CF ₃

O CH ₂ (Y-62) -

O (CH ₂ ) ₉ (Y-63) 3,5,6-tri-F

O CH ₂ (Y-64) 4-(C(O)CH ₃ )-6-I

O CH ₂ (Y-70) 3-C(CH ₃ ) ₃

O CH ₂ (Y-70) 3-CO ₂ CH ₃

O CH ₂ (Y-70) 3-(CF ₂ ) ₃ CF ₃

O CH ₂ (Y-74) 4,5-(Ji-CF ₃

O CH ₂ (Y-73) -

O CH ₂ (Y-71) -

Formulation/Utilitv

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 serves 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 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 0.001-99 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^V-dimethylalkanamides (e.g., iV^V-dimethylformamide), limonene, dimethyl sulfoxide, N-alkylpyrrolidones (e.g., iV-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, triacetin, 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-C ₂₂ X such as plant seed and fruit oils (e.g., oils of olive, castor, linseed, sesame, corn (maize), peanut, sunflower, grape seed, 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, emulsifϊers 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 λ^V-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 diquatemary 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 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 μm can be wet milled using media mills to obtain particles with average diameters below 3 μm. 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 μm 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 147^8, 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 Modem 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 \-^\ Klingman, 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 Tables A- D. 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 16 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 9 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 10 10.0% polyoxyethylene sorbitol hexoleate 20.0%

C ₆ -C ₁ Q f ^att y ^ac *d methyl ester 70.0%

Example F

Microemulsion

Compound 16 5.0% polyvinylpyrrolidone-vinyl acetate copolymer 30.0% alkylpolyglycoside 30.0% glyceryl monooleate 15.0% water 20.0%

Example G Seed Treatment

Compound 9 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%

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 fuligena and Podosphaera leucotricha, Pseudocercosporella herpotrichoides, Botrytis diseases such as Botrytis cinerea, Monilinia fructicola, Sclerotinia diseases such as Sclerotinia sclerotiorum, Magnaporthe grisea, Phomopsis viticola, Helminthosporium diseases such as Helminthosporium tritici repentis, 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 Rhizoctonia spp. (such as Rhizoctonia solani); Fusarium diseases such as Fusarium roseum, Fusarium graminearum and Fusarium oxysporum; Verticillium dahliae; Sclerotium rolfsiϊ, Rynchospoήum secalis; Cercospoήdium personatum, Cercospora arachidicola and Cercospora beticola; 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.

The compounds and/or compositions of this invention are particularly advantageous for controling diseases caused by Ascomycete fungal plant pathogens. They are effective in controlling a broad spectrum of plant diseases, particularly foliar pathogens of ornamental, vegetable, field, cereal, and fruit crops. These pathogens include: Ascomycetes, including powdery mildew diseases such as Erysiphe spp. (including Erysiphe graminis and Erysiphe polygoni), Uncinula necatur, Sphaerotheca fuligena and Podosphaera leucotricha, and other related species.

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

Rates of application for these compounds can be influenced by many factors of the environment and should be determined under actual use conditions. Foliage can normally be protected when treated at a rate of from less than about 1 g/ha to about 5,000 g/ha of active ingredient. Seed and seedlings can normally be protected when seed is treated at a rate of from about 0.1 to about 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 fungicidally effective amount of a compound of Formula 1 and a biologically effective amount of at least one additional biologically active compound or agent 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 (QoI) 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 (QiI) 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 benzimidazole and thiophanate fungicides. The benzimidazoles include benomyl, carbendazim, fuberidazole and thiabendazole. The thiophanates include thiophanate and thiophanate-methyl.

(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 (DMT) 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. DMI fungicides are divided between several chemical classes: azoles (including triazoles and imidazoles), pyrimidines, piperazines and pyridines. The triazoles include azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole (including diniconazole-M), epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole and uniconazole. The imidazoles include clotrimazole, imazalil, oxpoconazole, prochloraz, pefurazoate and triflumizole. The pyrimidines include fenarimol and nuarimol. The piperazines include triforine. The pyridines include pyrifenox. Biochemical investigations have shown that all of the above mentioned fungicides are DMI fungicides as described by K. H. Kuck et al. in Modern Selective Fungicides - Properties, Applications and Mechanisms of Action, H. 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 acylalanine, oxazolidinone and butyrolactone fungicides. 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, δ ⁸ → δ ⁷ isomerase and δ ¹⁴ 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 morpholine, piperidine and spiroketal-amine fungicides. 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 phophorothiolate and dithiolane fungicides. 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 benzamides, furan carboxamides, oxathiin carboxamides, thiazole carboxamides, pyrazole carboxamides and pyridine carboxamides. The benzamides include benodanil, flutolanil and mepronil. The furan carboxamides include fenfuram. The oxathiin carboxamides include carboxin and oxycarboxin. The thiazole carboxamides include thifluzamide. The pyrazole carboxamides include furametpyr, penthiopyrad, bixafen, N-[2-(15,2/?)-[l,r-bicyclopropyl]-2-ylphenyl]-3-(difluoromet hyl)- 1 -methyl- lH-pyrazole-4-carboxamide and λf-[2-(l,3-dimethylbutyl)phenyl]-5-fluoro-l,3- dimethyl-lH-pyrazole-4-carboxamide. The pyridine carboxamides include boscalid.

(8) "ηydroxy(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) 'W-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 (QoI) fungicides" (Fungicide Resistance Action Committee (FRAC) code 11) inhibit Complex HI mitochondrial respiration in fungi by affecting ubiquinol oxidase. Oxidation of ubiquinol is blocked at the "quinone outside" (Q ₀ ) site of the cytochrome bcγ 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 methoxyacrylate, methoxycarbamate, oximinoacetate, oximinoacetamide, oxazolidinedione, dihydrodioxazine, imidazolinone and benzylcarbamate fungicides. The methoxyacrylates include azoxystrobin, enestroburin (SYP-Z071) and picoxystrobin. The methoxycarbamates include pyraclostrobin. The oximinoacetates include kresoxim-methyl

and trifloxystrobin. The oximinoacetamides include dimoxystrobin, metominostrobin, orysastrobin, α-[methoxyimino]-N-methyl-2-[[[l-[3-(trifluoromethyl)phenyl ]ethoxy]imino]- methyl]benzeneacetamide and 2-[[[3-(2,6-dichlorophenyl)-l-methyl-2-propen- 1-ylidene]- amino]oxy]methyl]-a-(methoxyimino)-iV-methylbenzeneacetamide . The oxazolidinediones include famoxadone. The dihydrodioxazines include fluoxastrobin. The imidazolinones include fenamidone. The benzylcarbamates include pyribencarb.

(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) "Quinoline 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. Quinoxyfen is an example of this class of fungicide.

(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 carbon and 1,2,4-thiadiazole fungicides. 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 isobenzofuranone, pyrroloquinolinone and triazolobenzothiazole fungicides. 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 cyclopropanecarboxamide, carboxamide and propionamide fungicides. The cyclopropanecarboxamides include carpropamid. The carboxamides include diclocymet. The propionamides include fenoxanil.

(17) "Hydroxyanilide 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 thiocarbamate and allylamine fungicides. 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 (QiI) fungicides" (Fungicide Resistance Action Committee (FRAC) code 21) inhibit Complex IE mitochondrial respiration in fungi by affecting ubiquinol reductase. Reduction of ubiquinol is blocked at the "quinone inside" (Qi) site of the cytochrome bcγ 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 cyanoimidazole and sulfamoyltriazole fungicides. 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-dinitroani lines 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 π (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 isoxazole and isothiazolone fungicides. 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 amide, valinamide carbamate and mandelic acid amide fungicides. The cinnamic acid amides include dimethomorph and flumorph. The valinamide carbamates include benthiavalicarb,

benthiavalicarb-isopropyl, iprovalicarb and valiphenal. The mandelic acid amides include mandipropamid, N-[2-[4-[[3-(4-chlorophenyl)-2-propyn-l-yl]oxy]-3-methoxyphe nyl]ethyl]- 3-methyl-2-[(methylsulfonyl)amino]butanamide 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 (b42)" (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 and fluopyram.

(44) "Host plant defense induction fungicides" (Fungicide Resistance Action Committee (FRAC) code P) induce host plant defense mechanisms. Host plant defense induction fungicides include benzo-thiadiazole, benzisothiazole and thiadiazole-carboxamide fungicides. The benzo-thiadiazoles include acibenzolar-S-methyl. The benzisothiazoles include probenazole. The thiadiazole-carboxamides 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) "phenyl-acetamide fungicides" (Fungicide Resistance Action Committee (FRAC) code U6), (46.3) "quinazolinone fungicides" (Fungicide Resistance Action Committee (FRAC) code U7) and (46.4) "benzophenone fungicides" (Fungicide Resistance Action Committee (FRAC) code U8). The thiazole carboxamides include ethaboxam. The phenyl-acetamides include cyflufenamid and N-[[(cyclopropylmethoxy)amino][6-(difluoromethoxy)-2,3- difluorophenyl]-methylene]benzeneacetamide. The quinazolinones include proquinazid and 2-butoxy-6-iodo-3-propyl-4H-l-benzopyran-4-one. The benzophenones include metrafenone. The (b46) class also includes bethoxazin, neo-asozin (ferric methanearsonate), pyrrolnitrin, quinomethionate, N-[2-[4-[[3-(4-chlorophenyl)-2-propyn-l-yl]oxy]-3-methoxy- phenyl]ethyl]-3-methyl-2-[(methylsulfonyl)amino]butanamide, N-[2-[4-[[3-(4-chloro- phenyl)-2-propyn-l-yl]oxy]-3-methoxyphenyl]ethyl]-3-methyl-2 -[(ethylsulfonyl)amino]- butanamide, 2-[[2-fluoro-5-(trifluoromethyl)phenyl]thio]-2-[3-(2-methoxy phenyl)-2-thiazo- lidinylidene]acetonitrile, 3-[5-(4-chlorophenyl)-2,3-dimethyl-3-isoxazolidinyl]pyridine ,

4-fluorophenyl N-[l-[[[l-(4-cyanophenyl)ethyl]sulfonyl]methyl]propyl]carbam ate, 5-chloro- 6-(2,4,6-trifluorophenyl)-7-(4-methylpiperidin-l-yl)[l,2,4]t riazolo[l,5-α]pyrimidine, N-(4- chloro-2-nitrophenyl)-N-ethyl-4-methylbenzenesulfonamide, /V-[[(cyclopropylmethoxy)- amino][6-(difluoromethoxy)-2,3-difluorophenyl]methylene]benz eneacetamide, λ^-[4-[4- chloro-3-(trifluoromethyl)phenoxy]-2,5-dimethylphenyl]-N-eth yl-N-methylmethanimid- amide and l-[(2-propenylthio)carbonyl]-2-(l-methylethyl)-4-(2-methylph enyl)-5-amino-lH- pyrazol-3-one.

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 such biologically active compounds or agents with which compounds of this invention can be formulated are: insecticides such as abamectin, acephate, acetamiprid,

amidoflumet (S-1955), avermectin, azadirachtin, azinphos-methyl, bifenthrin, bifenazate, buprofezin, carbofuran, cartap, chlorantraniliprole (DPX-E2Y45), chlorfenapyr, chlorfluazuron, chloφyrifos, chloφyrifos-methyl, chromafenozide, clothianidin, cyflumetofen, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, cypermethrin, cyromazine, deltamethrin, diafenthiuron, diazinon, dieldrin, diflubenzuron, dimefluthrin, dimethoate, dinotefuran, diofenolan, emamectin, endosulfan, esfenvalerate, ethiprole, fenothiocarb, fenoxycarb, fenpropathrin, fenvalerate, fipronil, flonicamid, flubendiamide, flucythrinate, tau-fluvalinate, flufenerim (UR-50701), flufenoxuron, fonophos, halofenozide, hexaflumuron, hydramethylnon, imidacloprid, indoxacarb, isofenphos, lufenuron, malathion, metaflumizone, metaldehyde, methamidophos, methidathion, methomyl, methoprene, methoxychlor, metofluthrin, monocrotophos, methoxyfenozide, nitenpyram, nithiazine, novaluron, noviflumuron (XDE-007), oxamyl, parathion, parathion-methyl, permethrin, phorate, phosalone, phosmet, phosphamidon, pirimicarb, profenofos, profluthrin, pymetrozine, pyrafluprole, pyrethrin, pyridalyl, pyrifluquinazon, pyriprole, pyriproxyfen, rotenone, ryanodine, spinetoram, spinosad, spirodiclofen, spiromesifen (BSN 2060), spirotetramat, sulprofos, tebufenozide, teflubenzuron, tefluthrin, terbufos, tetrachlorvinphos, thiacloprid, thiamethoxam, thiodicarb, thiosultap-sodium, tralomethrin, triazamate, trichlorfon and triflumuron; fungicides such as acibenzolar, aldimorph, amisulbrom, azaconazole, azoxystrobin, benalaxyl, benomyl, benthiavalicarb, benthiavalicarb-isopropyl, binomial, biphenyl, bitertanol, blasticidin-S, Bordeaux mixture (tribasic copper sulfate), boscalid/nicobifen, bromuconazole, bupirimate, buthiobate, carboxin, carpropamid, captafol, captan, carbendazim, chloroneb, chlorothalonil, chlozolinate, clotrimazole, copper oxychloride, copper salts such as copper sulfate and copper hydroxide, cyazofamid, cyflunamid, cymoxanil, cyproconazole, cyprodinil, dichlofluanid, diclocymet, diclomezine, dicloran, diethofencarb, difenoconazole, dimethomorph, dimoxystrobin, diniconazole, diniconazole-M, dinocap, discostrobin, dithianon, dodemorph, dodine, econazole, enestroburin (SYP-Z071), etaconazole, edifenphos, epoxiconazole, ethaboxam, ethirimol, ethridiazole, famoxadone, fenamidone, fenarimol, fenbuconazole, fencaramid, fenfuram, fenhexamide, fenoxanil, fenpiclonil, fenpropidin, fenpropimoφh, fentin acetate, fentin hydroxide, ferbam, ferfurazoate, ferimzone, fluazinam, fludioxonil, flumetover, fluopicolide, fluoxastrobin, fluquinconazole, fluquinconazole, flusilazole, flusulfamide, flutolanil, flutriafol, folpet, fosetyl-aluminum, fuberidazole, furalaxyl, furametapyr, hexaconazole, hymexazole, guazatine, imazalil, imibenconazole, iminoctadine, iodicarb, ipconazole, iprobenfos, iprodione, iprovalicarb, isoconazole, isoprothiolane, kasugamycin, kresoxim- methyl, mancozeb, mandipropamid, maneb, mapanipyrin, mefenoxam, mepronil, metalaxyl, metconazole, methasulfocarb, metiram, metominostrobin/fenominostrobin, mepanipyrim, metrafenone, miconazole, myclobutanil, neo-asozin (ferric methanearsonate), nuarimol, octhilinone, ofurace, orysastrobin, oxadixyl, oxolinic acid, oxpoconazole, oxycarboxin,

paclobutrazol, penconazole, pencycuron, penthiopyrad, perfurazoate, phosphonic acid, phthalide, picobenzamid, picoxystrobin, polyoxin, probenazole, prochloraz, procymidone, propamocarb, propamocarb-hydrochloride, propiconazole, propineb, proquinazid, prothioconazole, pyraclostrobin, pryazophos, pyribencarb, pyrifenox, pyrimethanil, pyrifenox, pyrolnitrine, pyroquilon, quinconazole, quinoxyfen, quintozene, silthiofam, simeconazole, spiroxamine, streptomycin, sulfur, tebuconazole, techrazene, tecloftalam, tecnazene, tetraconazole, thiabendazole, thifluzamide, thiophanate, thiophanate-methyl, thiram, tiadinil, tolclofos-methyl, tolyfluanid, triadimefon, triadimenol, triarimol, triazoxide, tridemoφh, trimoprhamide tricyclazole, trifloxystrobin, triforine, triticonazole, uniconazole, validamycin, vinclozolin, zineb, ziram, and zoxamide; nematocides such as aldicarb, imicyafos, oxamyl and fenamiphos; bactericides such as streptomycin; acaricides such as amitraz, chinomethionat, chlorobenzilate, cyhexatin, dicofol, dienochlor, etoxazole, fenazaquin, fenbutatin oxide, fenpropathrin, fenpyroximate, hexythiazox, propargite, pyridaben and tebufenpyrad; 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 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) pyrimidinone fungicides; (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. Pyrimidinone fungicides (group (4)) include compounds of Formula Al

Al wherein M forms a fused phenyl, thiophene or pyridine ring; R ^{1 1} is C _j -C ₆ alkyl; R ¹² is C ₁ -C ₆ alkyl or C ₁ -C ₆ alkoxy; R ¹³ is halogen; and R ¹⁴ is hydrogen or halogen.

Pyrimidinone fungicides are described in PCT Patent Application Publication WO 94/26722 and U.S. Patents 6,066,638, 6,245,770, 6,262,058 and 6,277,858. Of note are pyrimidinone fungicides selected from the group: 6-bromo-3-propyl-2-propyloxy-

4(3H)-quinazolinone, 6,8-diiodo-3-propyl-2-propyloxy-4(3H)-quinazolinone, 6-iodo- 3-propyl-2-propyloxy-4(3H)-quinazolinone (proquinazid), 6-chloro-2-propoxy-3-propyl- thieno[2,3-cπpyrimidin-4(3H)-one, 6-bromo-2-propoxy-3-propylthieno[2,3-rf]pyrimidin- 4(3H)-one, 7-bromo-2-propoxy-3-propylthieno[3,2-cT|pyrimidin-4(3H)-one, 6-bromo- 2-propoxy-3-propylpyrido[2,3-rf]pyrimidin-4(3H)-one, 6,7-dibromo-2-propoxy-3-propyl- thieno[3,2-d]pyrimidin-4(3H)-one, and 3-(cyclopropylmethyl)-6-iodo-2-(propylthio)pyrido- [2,3--i]pyrimidin-4(3H)-one.

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. bcγ Complex Fungicides (group 28) have a fungicidal mode of action which inhibits the bcγ complex in the mitochondrial respiration chain. The bc _\ complex is sometimes referred to by other names in the biochemical literature, including complex IQ of the electron transfer chain, and ubihydroquinone:cytochrome c oxidoreductase. This complex is uniquely identified by Enzyme Commission number ECl.10.2.2. The bcγ 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 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 bcγ complex in the mitochondrial respiration chain include famoxadone and fenamidone.

Alkylenebis(dithiocarbamate)s (group (I)) 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 λf-[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 (H)) 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 morpholines 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 morpholines include aldimorph, dodemorph, fenpropimorph, tridemorph and trimorphamide. The piperidines include fenpropidin

Of further note are combinations of compounds of Formula 1 with azoxystrobin, kresoxim-methyl, trifloxystrobin, pyraclostrobin, picoxystrobin, dimoxystrobin, metominostrobin/fenominostrobin, carbendazim, chlorothalonil, quinoxyfen, metrafenone, cyflufenamid, fenpropidine, fenpropimorph, bromuconazole, cyproconazole, difenoconazole, epoxiconazole, fenbuconazole, flusilazole, hexaconazole, ipconazole, metconazole, penconazole, propiconazole, proquinazid, prothioconazole, tebuconazole, triticonazole, famoxadone, prochloraz, penthiopyrad and boscalid (nicobifen).

Preferred for better control of plant diseases caused by fungal plant pathogens (e.g., lower use rate or broader spectrum of plant pathogens controlled) or resistance management are mixtures of a compound of this invention with a fungicide selected from the group: azoxystrobin, kresoxim-methyl, trifloxystrobin, pyraclostrobin, picoxystrobin, dimoxystrobin, metominostrobin/fenominostrobin, quinoxyfen, metrafenone, cyflufenamid, fenpropidine, fenpropimorph, cyproconazole, epoxiconazole, flusilazole, metconazole, propiconazole, proquinazid, prothioconazole, tebuconazole, triticonazole, famoxadone and penthiopyrad.

Specifically preferred mixtures (compound numbers refer to compounds in Index Tables A-B) are selected from the group: combinations of Compound 7, Compound 8, Compound 9, Compound 10, Compound 11 or Compound 16 with azoxystrobin, combinations of Compound 7, Compound 8, Compound 9, Compound 10, Compound 11 or Compound 16 with kresoxim-methyl, combinations of Compound 7, Compound 8, Compound 9, Compound 10, Compound 11 or Compound 16 with trifloxystrobin, combinations of Compound 7, Compound 8, Compound 9, Compound 10, Compound 11 or Compound 16 with pyraclostrobin, combinations of Compound 7, Compound 8, Compound

9, Compound 10, Compound 11 or Compound 16 with picoxystrobin, combinations of Compound 7, Compound 8, Compound 9, Compound 10, Compound 11 or Compound 16 with dimoxystrobin, combinations of Compound 7, Compound 8, Compound 9, Compound

10, Compound 11 or Compound 16 with metominostrobin/fenominostrobin, combinations of Compound 7, Compound 8, Compound 9, Compound 10, Compound 11 or Compound 16 with quinoxyfen, combinations of Compound 7, Compound 8, Compound 9, Compound 10, Compound 11 or Compound 16 with metrafenone, combinations of Compound 7, Compound 8, Compound 9, Compound 10, Compound 11 or Compound 16 with cyflufenamid, combinations of Compound 7, Compound 8, Compound 9, Compound 10, Compound 11 or Compound 16 with fenpropidine, combinations of Compound 7, Compound 8, Compound 9, Compound 10, Compound 11 or Compound 16 with fenpropimorph, combinations of Compound 7, Compound 8, Compound 9, Compound 10, Compound 11 or Compound 16 with cyproconazole, combinations of Compound 7, Compound 8, Compound 9, Compound 10, Compound 11 or Compound 16 with epoxiconazole, combinations of Compound 7, Compound 8, Compound 9, Compound 10, Compound 11 or Compound 16 with flusilazole, combinations of Compound 7, Compound 8, Compound 9, Compound 10, Compound 11 or Compound 16 with metconazole, combinations of Compound 7, Compound 8, Compound 9, Compound 10, Compound 11 or Compound 16 with propiconazole, combinations of Compound 7, Compound 8, Compound

9, Compound 10, Compound 11 or Compound 16 with proquinazid, combinations of Compound 7, Compound 8, Compound 9, Compound 10, Compound 11 or Compound 16 with prothioconazole, combinations of Compound 7, Compound 8, Compound 9, Compound

10, Compound 11 or Compound 16 with tebuconazole, combinations of Compound 7, Compound 8, Compound 9, Compound 10, Compound 11 or Compound 16 with triticonazole, combinations of Compound 7, Compound 8, Compound 9, Compound 10, Compound 11 or Compound 16 with famoxadone, and combinations of Compound 7, Compound 8, Compound 9, Compound 10, Compound 11 or Compound 16 with penthiopyrad.

The following TESTS demonstrate the control efficacy of compounds of this invention on specific pathogens. The pathogen control protection afforded by the compounds is not

limited, however, to these species. See Index Tables A-D for compound descriptions. The following abbreviations are used in the Index Tables: Me means methyl, Et means ethyl, n-Pr means normal propyl, c means cyclo, Ph means phenyl. The abbreviation "Ex." stands for "Example" and is followed by a number indicating in which example the compound is prepared.

INDEX TABLE A

A dash ("-") indicates a direct bond.

Compound Rl R2 W R3 m.p. ( ⁰ C)

1 CH ₂ C≡CH Et O H *

2 (Ex. 2) CH ₂ (c-propyl) Et O H **

3 CH ₂ CH ₂ Ph Me O H *

4 CH ₂ -4-Br-Ph Et O H *

5 Et Et O H *

7 n-Pr Me O I 129-130

8 (Ex. 1) CH ₂ (c-propyl) Me O I **

9 (Ex.3) rt-Pr n-Pr O I **

10 CH ₂ (c-propyl) n-Pr O I 143-145

11 /z-Pr Ph O I 129-131

12 (Ex. 4) n-Pr Me S I **

13 n-Pr Me SO ₂ I 235-236

35 (Ex. 11) n-Pr lH-pyrrol-1-yl — I 204-206

* See Index Table E for ¹ H NMR data.

** See synthesis example for ^H NMR data.

Compound R ¹ R ² W R ³ m.p. ( ⁰ C)

14 (Ex. 6) n-Pr Me S Cl

15 (Ex. 7) n-Pr Me SO ₂ Cl

16 (Ex. 8) n-Pr n-Pr O Cl

See synthesis example for ^H NMR data. INDEX TABLE C

A dash ("-") indicates a direct bond. Compound R ¹ R ² W R ³ R ⁴ m.p. ( ⁰ C)

17 (Ex. 9) n-Pr Me SO ₂ H H **

18 (Ex. 10) n-Pr n-Pr O H H **

19 n-Pr Me S 8-CH ₂ CH(CH ₃ ) ₂ H 164-166

20 n-Pr Me SO ₂ 8-CH ₂ CH(CH ₃ ) ₂ H 131-132

21 n-Pr n-Pr O 8-CH ₂ CH(CH ₃ ) ₂ H 116-117

22 n-Pr CF ₃ - H H 154-155

23 CH2(c-propyl) CF ₃ - H H 125-126

24 n-Pr Me S 7-Br H 175-177

25 n-Pr n-Pr O 7-Br H 160-161

26 n-Pr Me S 8-N(CH ₃ ) ₂ H 169-170

33 n-Pr c-Pr - 7-Br H 194-195

34 CH ₂ (C-Pr) c-Pr — 7-Br H 201-203

¹ See synthesis example for ^H NMR data.

INDEX TABLE D

Compound Rl R2 W U X Y Z R3 R4 m.p. ( ⁰ C)

27 n-Pr Me S N C C N H H 234-236

28 w-Pr Me SO ₂ N C C N H H *

29 n-Pτ Me S C N C N H CF ₃ 176-177

30 n-Pr Me SO ₂ C N C N H CF ₃ 202-203

31 «-Pr n-Pr O C N C N H CF ₃ 100-103

32 π-Pr Me S N C N C SCH ₃ H 172-175

* See Index Table E for ¹ H NMR data.

INDEX TABLE E

Compound _{1 R NMR Data (CDC} , _{3 so} i _{ution unless} indicated otherwise) ³

1 (DMSO-^ ₆ ) δ 8.16 (d,lH), 7.93-7.89 (m, IH), 7.84 (d, IH), 7.81-7.77 (m, 6H), 4.64 (q, 2H),

4.63 (s, 2H), 3.58 (s, IH), 1.64 (t, 3H).

3 (DMSO-^ ₆ ) δ 8.16 (d, IH), 7.93-7.89 (m, IH), 8.19 (d, IH), 7.94-7.90 (m, IH), 7.52 (m, IH),

7.32-7.20 (m, 5H), 4.30 (t, 2H), 4.02 (s, 3H), 3.03 (t, 2H).

4 (DMSO-^ ₆ ) δ 8.30 (dd, IH), 8.05-8.00 (m, IH), 7.64-7.61 (m, 3H), 7.49 (d, 2H), 5.53 (q, 2H),

4.46 (d, 2H), 1.48 (t, 3H).

5 (DMSO-^ ₆ ) δ 8.47 (m, IH), 8.21-8.09 (m, 2H), 7.78 (t, IH), 4.61 (q, 2H), 4.37 (d, 2H), 1.63 (t,

3H), 1.53 (t, 3H).

28 (DMSO-^ ₆ ) δ 9.05 (d, IH), 9.03 (d, IH), 4.17 (t, 2H), 3.51 (s, 3H), 1.86-1.75, (m, 2H), 0.98

(t, 3H). ^a ^H NMR data are in ppm downfield from tetramethylsilane. Couplings are designated by (s)-singlet, (d)-doublet, (t)-triplet, (m)-multiplet and (dd)-doublet of doublets.

BIOLOGICAL EXAMPLES OF THE INVENTION

General protocol for preparing test suspensions for Tests A-K 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-K. Spraying a 200 ppm test suspension to the point of run-off on the test plants was the equivalent of a rate of 500 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 dust of 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 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 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 8 days, after time which disease ratings were made.

TEST C 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 Fusarium graminearum (the causal agent of wheat head scab) and incubated in a saturated atmosphere at 24 °C for 72 h, and then moved to a growth chamber at 20 °C for 5 days, after which time 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 suspension of Septoria nodorum

(the causal agent of wheat glume blotch) and incubated in a saturated atmosphere at 20 °C for 48 h, and then moved to a growth chamber at 20 °C for 7 days, after which time disease ratings were made.

TEST E

The test suspension was sprayed to the point of run-off on cucumber seedlings. The following day the seedlings were inoculated with a spore suspension of Colletotrichum orbiculare (the causal agent of cucumber Colletotrichum anthracnose) and incubated in saturated atmosphere at 20 °C for 24 h, and moved to a growth chamber at 24 °C for 5 additional days, after time which disease ratings were made.

TEST F

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 Alternaria solani (the causal agent of tomato early blight) and incubated in a saturated atmosphere at 27 °C for

48 h, and then moved to a growth chamber at 20 °C for 5 days, after which time disease ratings were made.

TEST G

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 saturated atmosphere at 20 °C for 48 h, and then moved to a growth chamber at 24 °C for 3 additional days, after which time disease ratings were made.

TEST H

The test suspension was sprayed to the point of run-off on creeping bent grass seedlings. The following day the seedlings were inoculated with a spore suspension of

Rhizoctonia oryzae (the causal agent of turf brown patch) and incubated in a saturated atmosphere at 27 ⁰ C for 48 h, and then moved to a growth chamber at 27 °C for 3 days, after which time disease ratings were made.

TEST I

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 Phytophthora infestans (the causal agent of tomato late blight) and incubated in a saturated atmosphere at

20 °C for 24 h, and then moved to a growth chamber at 20 °C for 4 days, after which time disease ratings were made.

TEST J

Grape seedlings were inoculated with a spore suspension of Plasmopara viticola (the causal agent of grape downy mildew) and incubated in a saturated atmosphere at 20 °C for 24 h. After a short drying period, the test suspension was sprayed to the point of run-off on the grape seedlings, which were then moved to a growth chamber at 20 °C for 6 days, after time which the test units were placed back into a saturated atmosphere at 20 °C for 24 h. Upon removal, disease ratings were made. TEST K

The test suspension was sprayed to the point of run-off on bluegrass seedlings. The following day the seedlings were inoculated with a spore suspension of Pythium aphanidermatum (the causal agent of bluegrass pythium blight) and incubated in a covered saturated atmosphere at 27 °C for 48 h, and then the covers were removed and the plants left at 27 °C for 3 additional days, after which time disease ratings were made.

Results for Tests A-K 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. All results are for 200 ppm except where followed by an

"**" which indicates 50 ppm, an "*" which indicates 40 ppm, "#" which indicates 20 ppm, or an "&" which indicates 10 ppm.