WO1993023398A1

WO1993023398A1 - Substituted pyrido[1,2-a]pyrimidinone derivatives as fungicides

Info

Publication number: WO1993023398A1
Application number: PCT/US1993/004188
Authority: WO
Inventors: Thomas Paul Selby
Original assignee: EI Du Pont de Nemours and Co
Current assignee: EIDP Inc
Priority date: 1992-05-13
Filing date: 1993-05-10
Publication date: 1993-11-25
Anticipated expiration: 1994-11-13
Also published as: AU4231293A; EP0640083A1

Abstract

Substituted pyrido[1,2-a]pyrimidinone compounds of formula (I) wherein Q is O or S; W is O; S; S(O); S(O)2; NH; or NR9; X is CR3 or N; Y is CR4 or N; Z is CR?5=CR6; CR5¿=N; N=CR6; S; O; or NR?7; and R1, R2, R3, R4, R5, R6 and R7¿ are various groups; and agricultural compositions containing one or more such compounds useful as fungicides for control of diseases in plants are disclosed.

Description

TITLE

SUBSTITUTED PYRIDO ( 1 ,2-A) PYRIMIDINONE DERIVATIVES AS FUNGICIDES

This invention relates to certain substituted pyrido [1,2-a]pyrimidinone compounds useful as

fungicides, their agriculturally suitable salts and compositions, and methods of their use as general or selective fungicides, in particular for the control of wheat powdery mildew both preventive and curativeUrban et al., Helv. Chim . Acta, 1970, 53, 905, disclose pyrido [1,2-a]pyrimidinones of Formula i and their use as analgesics and antiinflammatory agents.

U.S. 3,755,582 issued August 28, 1973 and U.S. 3,867,384 issued February 18, 1975, each disclose 4 (3H)-quinazolinones of Formula ii and their use as agricultural fungicides.

wherein:

W is O; S or NH; and

Z is O or S. SUMMARY OF THE INVENTION

This invention comprises compounds of Formula I including all geometric and stereoisomers, N-oxides, agriculturally-suitable salts thereof, agricultural compositions containing them and method of use of said compounds, salts, or compositions as fungicides,

wherein:

Q is O or S;

W is O; S; S(O); S(O)₂; NH; or NR⁹;

X is CR³ or N;

Y is CR⁴ or N;

Z is CR⁵=CR⁶; CR⁵=N; N=CR⁶; S; O; or NR⁷; having the directionality of the CR⁵=CR⁶, CR⁵=N and N=CR⁶ linkages such that the moiety depicted on the left side of the double bond is bonded to Y and the moiety on the right side of the double bond is bonded to the ring junction;

R¹ is C₁-C₁₈ alkyl; C₃-C₇ cycloalkyl; C₂-C₁₈

alkenyl; C₂-C₁₈ alkynyl; C₁-C₁₈ haloalkyl; C₂-C₁₈ haloalkenyl; C₂-C₁₈ haloalkynyl; C₂-C₁₈ alkoxyalkyl; C₂-C₁₈ alkylthioalkyl; C₂-C₁₈ alkylsulfinylalkyl; C₂-C₁₈ alkylsulfonylalkyl;

C₄-C₁₈ cycloalkylalkyl; C₄-C₁₈ alkenyloxyalkyl; C₄-C₁₈ alkynyloxyalkyl; C₄-_C18 cycloalkyloxyalkyl; C₄-C₁₈ alkenylthioalkyl; C₄-C₁₈ alkynylthioalkyl; C₆-C₁₈ cycloalkylthioalkyl; C₂-C₁₈ haloalkoxyalkyl; C₃-C₁₈ haloalkenyloxyalkyl;

C₄-C₁₈ haloalkynyloxyalkyl; C₄-C₁₈ alkoxyalkenyl; C₄-C₁₈ alkoxyalkynyl; C₄-C₁₈ alkylthio alkenyl; C₄-C₁₈ alkylthioalkynyl; C₄-C₁₈ trialkylsilylalkyl; C₁-C₁₈ alkyl substituted with NR⁸R¹⁰, cyano, or nitro; C₁-C₈ alkyl substituted with CO₂R⁸; C₁-C₁₈ alkoxy; C₁-C₁₈ haloalkoxy; C₃-C₁₈ alkynyloxy; C₃-C₁₈ alkenyloxy; C₁-C₁₈ alkylthio; C₃-C₁₈ alkenylthio; or C₃-C₁₈ alkynylthio;

R² is C₁-C₁₈ alkyl; C₃-C₇ cycloalkyl; C₃-C₁₈

alkenyl; C₃-C₁₈ alkynyl; C₁-C₁₈ haloalkyl;

C₃-C₁₈ haloalkenyl; C₃-C₁₈ haloalkynyl; C₂-C₁₈ alkoxyalkyl; C₂-C₁₈ alkylthioalkyl; C₂-C₁₈ alkylsulfinylalkyl; C₂-C₁₈ alkylsulfonylalkyl; C₄-C₁₈ cycloalkylalkyl; C₄-C₁₈ alkenyloxyalkyl; C₄-C₁₈ alkynyloxyalkyl; C₄-C₁₈ cycloalkyloxyalkyl; C₄-C₁₈ alkenylthioalkyl; C₄-C₁₈ alkynylthioalkyl; C₆-C₁₈ cycloalkylthioalkyl; C₂-C₁₈ haloalkoxyalkyl; C₃-C₁₈ haloalkenyloxyalkyl; C₄-C₁₈ haloalkynyloxyalkyl; C₄-C₁₈ alkoxyalkenyl; C₄-C₁₈ alkoxyalkynyl; C₄-C₁₈ alkylthioalkenyl; C₄-C₁₈ alkylthioalkynyl; C₄-C₁₈ trialkylsilylalkyl; C₁-C₁₈ alkyl substituted with NR⁸R¹⁰; C₂-C₁₈ cyanoalkyl; C₂-C₁₈

nitroalkyl; C₁-C₈ alkyl substituted with CO₂R⁸; or phenyl, benzyl, or phenethyl each optionally substituted on the phenyl ring with R¹³; or

R¹ and R² can be taken together along with the

C=C-W fragment to which they are attached to form a 5-7 membered ring in which the R¹-R² bridge is a saturated, all-carbon chain

optionally substituted with C₁-C₁₂ alkyl;

R³ and R⁵ are each independently hydrogen; halogen;

C₁-C₄ alkyl; C₁-C₄ haloalkyl; C₁-C₄ alkoxy; or C₂-_C4 haloalkoxy;

R⁴ and R⁶ are each independently hydrogen; halogen;

C₁-C₈ alkyl; C₃-C₈ cycloalkyl; C₂-C₈ alkenyl;

C₂-C₈ alkynyl; C₁-C₈ haloalkyl; C₃-C₈ halo- alkenyl; C₃-C₈ haloalkynyl; C₁-C₈ alkoxy; C₁-C₈ haloalkoxy; C₃-C₈ alkenyloxy; C₃-C₈ alkynyloxy; C₁-C₈ alkylthio; C₃-C₈ alkenylthio; C₃-C₈ alkynylthio; C₁-C₈ alkylsulfinyl; C₁-C₈ alkylsulfonyl; C₂-C₈ alkoxyalkyl; C₂-C₈ alkylthioalkyl; C₂-C₈ alkylsulfinylalkyl; C₂-C₈ alkylsulfonylalkyl; C₄-C₈ cycloalkylalkyl; C₃-C₈ trialkylsilyl; cyano; nitro; carbomethoxy;

carboethoxy; or NR¹¹R¹²;

R⁷ is C₁-C₄ alkyl or C₁-C₄ haloalkyl;

R⁸ and R⁹ are each independently C₁-C₄ alkyl;

R¹⁰ and R¹¹ are each independently H or C₁-C₄ alkyl; R¹² is C₁-C₈ alkyl;

R^8' and R¹⁰, or the groups R¹¹ and R¹², can be taken together to form -CH₂CH₂CH₂CH₂-, -CH₂(CH₂)₃CH₂-,

-CH₂CH₂OCH₂CH₂-, -CH₂CH (Me) CH₂CH (Me)CH₂-, or -CH₂CH (Me) OCH (Me) CH₂-; and

R¹³ is halogen; C₁-C₄ alkyl, C₁-C₄ alkoxy, or C₁-C₄ haloalkyl;

provided that:

i) when Z is CR⁵=CR⁶, then at least one substituent selected from the group consisting of R³, R⁴, R⁵ and R⁶, is hydrogen; and

ii) the total number of carbons in R³, R⁴,

R⁵ and R⁶ is equal to or less than 16; iii) the total number of nitrogen atoms

incorporated into the bicyclic

framework is less than or equal to four;

iv) R³ and R⁴ are not both hydrogen; and v) X and Y are not both nitrogen.

Preferred for reasons of ease of synthesis or greater fungicidal activity are compounds of Formula I, denoted as Preferred 1, wherein: W is O; S; NH; or NR⁹;

X is CR³;

Y is CR⁴;

R¹ is C₁-C₈ alkyl; C₂-C₈ alkenyl; C₂-C₈

alkynyl; C₁-C₈ haloalkyl; C₂-C₈

haloalkenyl; C₂-C₈ alkoxyalkyl; C₂-C₈ alkylthioalkyl; C₄-C₈ cycloalkylalkyl; C₂-C₈ cyanoalkyl; C₁-C₈ alkoxy; C₁-C₁₈ haloalkoxy; C₃-C₈ alkenyloxy; C₃-C₈ alkenylthio; or C₄-C₈ alkenyloxyalkyl;

R² is C₁-C₈ alkyl; C₂-C₈ alkenyl; C₂-C₈

alkynyl; C₁-C₈ haloalkyl; C₂-C₈

haloalkenyl; C₂-C₈ alkoxyalkyl; C₂-C₈ alkylthioalkyl; C₄-C₈ cycloalkylalkyl; C₂-C₈ cyanoalkyl; C₄-C₈ alkenyloxyalkyl; or phenyl optionally substituted with R¹³; and

R⁴ and R⁶ are each independently hydrogen; halogen; C₁-C₈ alkyl; C₃-C₈ cycloalkyl; C₁-C₈ haloalkyl; C₁-C₈ alkoxy; C₁-C₈ haloalkoxy; C₁-C₈ alkylthio; C₁-C₈ alkylsulfonyl; C₂-C₈ alkoxyalkyl; C₂-C₈ alkylthioalkyl; C₄-C₈ cycloalkylalkyl; C₃-C₈ trialkylsilyl; or cyano.

More preferred are compounds denoted as Preferred 2, of the above Preferred 1, wherein:

Q is O;

W is O; S; NH; or NMe;

Z is CR⁵=CR⁶; CR⁵=N; S; or O;

R¹ is C₁-C₈ alkyl; C₂-C₈ alkenyl; C₂-C₈

alkynyl; C₁-C₈ haloalkyl; C₂-C₈ halo- alkenyl; C₁-C₈ alkoxy; C₂-C₈ alkoxyalkyl; or C₃-C₈ alkenyloxy;

R² is C₁-C₈ alkyl; C₂-C₈ alkenyl; C₂-C₈

alkynyl; C₁-C₈ haloalkyl; C₂-C₈ halo- alkenyl; C₂-C₈ alkoxyalkyl; or phenyl optionally substituted with R¹³; and R⁴ and R⁶ are each independently hydrogen; halogen; C₁-C₈ alkyl; C₁-C₈ haloalkyl; C₁-C₈ alkoxy; C₁-C₈ haloalkoxy; C₃-C₈ trialkylsilyl; or cyano.

Even more preferred are compounds denoted as

Preferred 3, of the above Preferred 2, wherein:

Z is CR⁵=CR⁶ or S;

R¹ is C₁-C₈ alkyl; C₂-C₈ alkenyl; C₂-C₈

alkynyl; C₁-C₈ haloalkyl; or C₂-C₈ haloalkenyl;

R² is C₁-C₈ alkyl; C₂-C₈ alkenyl; C₂-C₈

alkynyl; C₁-C₈ haloalkyl; C₂-C₈

haloalkenyl; or phenyl optionally

substituted with R¹³; and

R⁴ and R⁶ are each independently hydrogen; halogen; C₁-C₈ alkyl; C₁-C₈ haloalkyl; C₁-C₈ alkoxy; or C₁-C₈ haloalkoxy.

Specifically preferred are compounds of Preferred 3 wherein said compounds are:

7-bromo-3-(n-propyl)-2-(n-propyloxy)-4H- pyrido[1,2-a]pyrimidin-4-one;

7,9-dibromo-3-(n-propyl)-2-(n-propyloxy)-4H- pyrido[1,2-a]pyrimidin-4-one; or

7-iodo-3-(n-propyl)-2-(n-propyloxy)-4H- pyrido[1,2-a]pyrimidin-4-one.

DETAILED DESCRIPTION OF THE INVENTION

In the above recitations, the term "alkyl", used either alone or in compound words such as "alkylthio," "haloalkyl," or "alkylthioalkyl" denotes straight-chain or branched alkyl; e.g., methyl, ethyl, n-propyl, i-propyl, or the different butyl, pentyl, hexyl, etc. isomers.

"Cycloalkyl" denotes cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. The term "cycloalkyl oxyalkyl" denotes the cycloalkyl groups linked through an oxygen atom to an alkyl chain. Examples include cyclopentyloxymethyl and cyclohexyloxybutyl. The term "cycloalkylthioalkyl" are the cycloalkyl groups linked through a sulfur atom to an alkyl chain; e.g., cyclopropylthiopentyl. "Cycloalkylalkyl" denotes a

cycloalkyl ring attached to a branched or straight-chain alkyl; e.g. cyclopropylmethyl and cyclohexylbutyl.

"Alkenyl" denotes straight chain or branched alkenes; e.g., 1-propenyl, 2-propenyl, 3-propenyl and the different butenyl , pentenyl, hexenyl, etc.

isomers. Alkenyl also denotes polyenes such as

1,3-hexadiene and 2,4,6-heptatriene.

"Alkynyl" denotes straight chain or branched alkynes; e.g., ethynyl, 1-propynyl, 3-propynyl and the different butynyl, pentynyl, hexynyl, etc. isomers. "Alkynyl" can also denote moieties comprised of

multiple triple bonds; e.g., 2,7-octadiyne and

2, 5, 8-decatriyne.

"Alkoxy" denotes methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy, pentoxy,

hexyloxy, etc. isomers. "Alkoxyalkenyl" and "alkoxyalkynyl" denoted groups in which the alkoxy group is bonded throught the oxygen atom to an alkenyl or alkynyl group, respectively. Examples include

CH₃OCH₂CH=CH and (CH₃) ₂CHOCH₂C≡CCH₂. The corresponding sulfur derivatives are denoted "alkylthioalkenyl and "alkylthioalkynyl." Examples of the former include CH₃SCH₂CH=CH and CH₃CH₂SCH₂ (CH₃) CH=CHCH₂, and an example of the latter is CH₃CH₂CH₂CH₂SCH₂C≡C.

"Alkenyloxy" denotes straight chain or branched alkenyloxy moieties. Examples of alkenyloxy include H₂C=CHCH₂O, (CH₃)₂C=CHCH₂O, (CH₃) CH=CHCH₂O,

(CH₃)CH=C(CH₃)CH₂O and CH₂=CHCH₂CH₂O. "Alkenylthio" denotes the similar groups wherein the oxygen atom is replaced with a sulfur atom; e.g., H₂C=CHCH₂S and

(CH₃)CH=C(CH₃)CH₂S. The term "alkenyloxyalkyl" denotes groups in which the alkenyloxy moiety is attached to an alkyl group. Examples include H₂C=CHCH₂OCH₂CH₂,

H₂C=CHCH₂OCH(CH₃)CH₂, etc. "Alkenylthioalkyl" denotes the alkenylthio moieties bonded to an alkyl group.

Examples include H₂C=CHCH₂SCH(CH₃) CH(CH₃) and

(CH₃) CH=C (CH₃) CH₂SCH₂.

"Alkynyloxy" denotes straight or branched

alkynyloxy moieties. Examples include HC≡CCH₂O,

CH₃C≡CCH₂O and CH₃C≡CCH₂CH₂O . "Alkynyloxyalkyl" denotes alkynyloxy moieties bonded to alkyl groups; e.g.,

CH₃C≡CCH₂OCH₂CH₂ and HC≡CCH₂OCH (CH₃) CH₂.

"Alkynylthioalkyl" denotes alkynylthio moieties bonded to alkyl groups. Example include CH₃C≡CCH₂SCH₂CH₂ and CH₃C≡CCH₂CH₂SCH(CH₃)CH₂.

"Alkylthio" denotes methylthio, ethylthio, and the different propylthio, butylthio, pentylthio and

hexylthio isomers. "Alkylthioalkyl" denotes alkylthio groups attached to an alkyl chain; e.g.,

CH₃CH₂SCH₂CH(CH₃) and (CH₃) ₂CHSCH₂.

"Alkylsulfinyl" denotes both enantiomers of an alkylsulfinyl group. For example, CH₃S(O), CH₃CH₂S(O), CH₃CH₂CH₂S(O), (CH₃)₂CHS(O) and the different

butylsulfinyl, pentylsulfinyl and hexylsufinyl isomers. "Alkylsulfinylalkyl" denotes alkylsulfinyl groups attached to an alkyl chain; e.g., CH₃CH₂S(O)CH₂CH(CH₃) and (CH₃)₂CHS(O)CH₂.

Examples of "alkylsulfonyl" include CH₃S(O)₂,

CH₃CH₂S(O)₂, CH₃CH₂CH₂S(O)₂, (CH₃)₂CHS(O)₂ and the different butylsulfonyl, pentylsulfonyl and hexylsulfonyl isomers. "Alkylsulfonylalkyl" denotes alkylsulfonyl groups attached to an alkyl chain; e.g.,

CH₃CH₂S(O)₂CH₂CH(CH₃) and (CH₃)₂CHS(O)₂CH₂.

The term "halogen", either alone or in compound words such as "haloalkyl", denotes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as "haloalkyl", said alkyl may be partially or fully substituted with halogen atoms which may be the same or different. Examples of "haloalkyl" include F₃C, ClCH₂, CF₃CH₂ and CF₃CF₂. Examples of

"haloalkenyl" include (Cl)₂C=CHCH₂ and CF₃CH₂CH=CHCH₂. "Haloalkenyloxyalkyl" denotes haloalkenyl groups bonded to oxygen and in turn bonded to alkyl groups. Examples include CF₃CH₂CH=CHCH₂OCH2 and (Cl) ₂C=CHCH₂OCH₂CH₂.

Examples of "haloalkynyl" include HC≡CCHCl, CF₃C≡C,

CCl₃C≡C and FCH₂C≡CCH₂. "Haloalkynyloxyalkyl" denotes haloalkynyl groups bonded through an oxygen atom to an alkyl moiety. Examples include CF₃C≡CCH₂OCH₂CH₂,

ClCH₂C≡CCH₂CH₂OCH(CH₃), etc. Examples of "haloalkoxy" include CF₃O, CCl₃CH₂O, CF₂HCH₂CH₂O and CF₃CH₂O.

"Haloalkoxyalkyl" denotes haloalkoxy groups bonded to straight-chain or branched alkyl groups; e.g.,

CF₂HCH₂CH₂OCH₂CH₂, CCl₃CH₂OCH (CH₃) and CF₃OCH₂.

"Trialkylsilyl" designates a group with three alkyl groups bonded to silicon; e.g., (CH₃)₃Si and

t-Bu(CH₃)₂Si. "Trialkylsilylalkyl" denotes

trialkylsilyl groups bonded to another straight-chain or branched alkyl group. Examples include (CH₃)₃SiCH₂ and t-Bu(CH₃)₂SiCH₂CH(CH₃)CH₂.

The total number of carbon atoms in a substituent group is indicated by the "C_i-C_j" prefix where i and j are numbers from 1 to 20. For example, C₁-C₃ alkyl-sulfonyl designates methylsulfonyl through propyl-sulfonyl; C₂ alkoxyalkoxy designates CH₃OCH₂O; C₃ alkoxyalkoxy designates, for example, CH₃OCH₂CH₂O or

CH₃CH₂OCH₂O; and C₄ alkoxyalkoxy designates the various isomers of an alkoxy group substituted with a second alkoxy group containing a total of 4 carbon atoms, examples including CH₃CH₂CH₂OCH₂O, and CH₃CH₂OCH₂CH₂O. Examples of "alkoxyalkyl" include CH₃OCH₂, CH₃OCH₂CH₂, CH₃CH₂OCH₂, CH₃CH₂CH₂CH₂OCH₂ and CH₃CH₂OCH₂CH₂. Compounds of Formula I can be prepared using one or more of the reactions and techniques described in

Schemes 1-4 hereinafter, or by following the procedures given in Examples 1-6. The variables W, X, Y, and Z and substituents R¹-R¹³ in the compounds of Formulae

Ia-Ig and II-VII illustrated in Schemes 1-4 hereinafter are defined as for compounds of Formula I above.

The general method for preparing compounds of

Formula la is shown in Scheme 1. Based on a known synthetic method (A. E. Tschitschibabin, Chem. Ber. , 1924, 57, 168; G. R. Lappin, et. al., J. Org. Chem., 1950, 15, 377; A. R. Katritzky and A. J. Waring, J.

Chem. Soc. , 1962, 1544; J. Klosa, J. Prakt . Chem. , 1964, 26, 150; K. E. Schulte and J. Witt, Arch . Pharm., 1958, 252, 298), heating substituted aminoheterocycles of Formula II with substituted malonates of Formula III neat at 150-250°C or by heating in a high boiling solvent such as diethylbenzene (and allowing for the evaporation or distillation of ethanol formed in the reaction) gives zwitterionic intermediates of Formula IV. Substituted aminoheterocycles of Formula II and malonates of Formula III are known and in many cases are commercially available. Reaction of heterocycles of Formula IV with alkylating agents in the presence of base can give rise to alkylation on both oxygen and nitrogen (R. Urban, Helv. Chim. Acta, 1970, 53, 905). However, alkylation of heterocycles of Formula IV with reagents of Formula R²L wherein L is Cl, Br, I, OTs or OMs, in the presence of a mild base, such as potassium carbonate, in a polar aprotic solvent, such as

dimethylformamide, affords predominantly the desired O-alkylated product of Formula Ia with only a small amount of the more polar (by thin layer chromatography) N-alkylated mesoionic adduct of Formula V being

obtained. Products of Formulae Ia and V can be

separated by chromatography.

As illustrated in Scheme 2, heating intermediates of Formula IV in thionyl chloride or phosphorous oxychloride furnishes chloro-substituted heterocycles of Formula VI. Displacement of the chloro substituent, by reacting heterocycles of Formula VI with nucleophilic reagents of Formula R²GH (generally in the presence of base, e.g., sodium hydride or sodium methoxide, in a solvent such as tetrahydrofuran or dimethylformamide) gives products of Formula lb wherein G is O, S, NH, or NR⁹. Oxidation of compounds of

Formula lb wherein G is S with a suitable oxidizing agent such as meta-chloroperoxybenzoic acid furnishes products of Formula Ic.

Thiation of heterocycles of Formula Id with

phosphorous pentasulfide or Lawesson ' s reagent gives thiones of Formula Ie (Scheme 3) .

Compounds of Formula If can be made by the

procedure illustrated in Scheme 4. Intermediates of Formula Ig can be initially prepared by the methods shown in Schemes 1 and 2 whereby diethylmalonate is used as the malonate starting material (i.e., compounds of Formula III wherein R¹ = H) in Scheme 1.

Bromination of compounds of Formula Ig with bromine or N-bromosuccinimide (NBS) yields brominated adducts of Formula VII which can be coupled with stannanes of Formula R¹⁴Sn (C_H3) ₃ in the presence of a palladium catalyst such as tetrakis(triphenylphosphine)-palladium(O) or bis(triphenylphosphine)palladium (II) chloride to afford products of Formula If.

Bromoheterocycles of Formula VII can also be coupled with terminal alkynes using palladium catalysis in the presence of base (such as triethylamine) and cuprous iodide.

Salts of compounds of Formula I can be formed by treating the free base of Formula I with strong acids such as hydrochloric or sulfuric acid. N-oxides of compounds of Formula I can be made by oxidizing

compounds of Formula I with a strong oxidizing agent such as meta-chloroperoxybenzoic acid.

INTERMEDIATE 1

Preparation of 7-Chloro-2-hydroxy-4-oxo-3-(2-propenyl)- pyrido[1,2-a]pyrimidin-1-ium Hydroxide, Inner Salt A mixture of 10.0 g (77.8 mmol) of 2-amino-5-chloropyridine and 23.0 g (115 mmol) of diethyl allyl-malonate in 60 mL of diethylbenzene was heated at reflux for 1 h with stirring. Ethanol generated during heating was removed by distillation. A solution initially formed followed by gradual precipitation of a yellow solid. On cooling, n-butyl chloride was added to enhance precipitation of this solid which was filtered, washed with n-butyl chloride, and dried. A 13.5 g yield of the title compound (m.p. 284-287°C) was obtained and used in subsequent steps without further purification.

EXAMPLE 1

Preparation of 7-Chloro-2-methoxy-3-(2-propenyl)-4H- pyrido[1,2-a]pyrimidin-4-one

To 2.0 g (8.5 mmol) of 7-chloro-2-hydroxy-4-oxo-3- (2-propenyl)-pyrido[1,2-a]pyrimidin-1-ium hydroxide, inner salt and 3.5 g (25.4 mmol) of potassium carbonate stirring in 50 mL of N,N-dimethylformamide, 2.6 mL of iodomethane was added and the mixture was stirred at room temperature for 18 h. Excess water and 200 mL of ethyl acetate were added. The organic layer was separated, washed with water (3 times) and brine, and dried over magnesium sulfate. The solvent was

evaporated in vacuo to give a dark oil which was flash chromatographed on silica gel (1:1 hexane/ethyl

acetate) to afford 0.7 g of the title compound, m.p. 139-141°C; ¹H NMR (CDCl₃) : δ 9.05 (d, 1H), 7.65, 7.60 (dd, 1H), 7,45 (d, 1H), 6.05-5.85 (m, 1H), 5.15-4.95 (m, 2H), 4.03 (s, 3H), 3.40 (d, 2H).

EXAMPLE 2

Preparation of 7-Chloro-3-(2-propenyl)-2-(2- propenyloxy)-4H-pyrido[1 ,2-a]pyrimidin-4-one

To 1.0 g (4.2 mmol) of 7-chloro-2-hydroxy-4-oxo-3-(2-propenyl)-pyrido[1,2-a]pyrimidin-1-ium hydroxide, inner salt and 1.5 g (10.8 mmol) of potassium carbonate stirring in 35 mL of N,N-dimethylformamide, 0.9 mL of allyl bromide was added and the mixture stirred at room temperature for 15 h. Excess water was added and the aqueous mixture was extracted with 125 mL of ethyl acetate. The organic layer was then washed with water (3 times) and brine and dried over magnesium sulfate. Evaporating in vacuo gave a solid residue which was flash chromatographed on silica gel (3:1 followed by 1:1 hexane/ethyl acetate) to afford 0.55 g of the title compound, m.p. 104-105°C; ¹H NMR (CDCl₃) : δ 9.07 (d, 1H), 7.63 (broad d, 1H), 7.42 (d, 1H), 6.10-5.90 (m, 2H), 5.42 (broad d, 1H), 5.25, 5.23 (dd, 1H), 5.13 (d, 1H), 5.05-4.95 (m, 3H), 3.42 (d, 2H).

INTERMEDIATE 2

Preparation of 7-Chloro-2-hydroxy-4-oxo-3-propyl- pyrido[1,2-a]pyrimidin-1-ium Hydroxide, Inner Salt A mixture of 11.5 g (89.4 mmol) of 2-amino-5-chloropyridine and 49.0 g (242 mmol) of diethyl propylmalonate was heated neat at 175°C for 3.5 h. Ethanol formed during heating was allowed to evaporate. A solution formed initially followed by gradual

precipitation of a yellow solid. After cooling, 25 mL of hexane were added and the solid was filtered, washed with hexane, and dried to yield 8.0 g of the title compound. This solid (m.p. 298-305°C) was used without further purification in the subsequent steps.

EXAMPLE 3

Preparation of 7-Chloro-2-methoxy-3-propyl- 4H-pyrido[1,2-a]pyrimidin-4-one

To 5.0 g (21.0 mmol) of 7-chloro-2-hydroxy-4-oxo-3-propyl-pyrido[1,2-a]pyrimidin-1-ium hydroxide, inner salt and 4.3 g (31.2 mmol) of potassium carbonate stirring in 35 ml of N,N-dimethylformamide, 4.5 g

(31.7 mmol) of iodomethane was added and the mixture was stirred at room temperature for 3 h. The reaction mixture was partitioned between 250 mL of water and 250 mL of ethyl acetate and the organic layer was separated followed by washing with water (3 times) and brine. After drying over magnesium sulfate, the solvent was removed in vacuo to give a yellow solid residue which was flash chromatographed on silica gel (5:1 followed by 3:1 hexane/ethyl acetate) to afford 2.8 g of the title compound, m.p. 135-137°C; ¹H NMR (CDCl₃) : δ 9.07 (d, 1H), 7.65, 7.60 (dd, 1H), 7.45 (d, 1H), 4.02 (s, 3H), 2.63 (t, 2H), 1.70-1.50 (m, 2H) , 0.97 (t, 3H).

EXAMPLE 4

Preparation of 7-Chloro-3-propyl-2-propyloxy- 4H-pyrido[1,2-a]pyrimidin-4-one

To 7.0 g (29 mmol) of 7-chloro-2-hydroxy-4-oxo-3-propyl-pyrido[1,2-a]pyrimidin-1-ium hydroxide, inner salt and 5.7 g (41 mmol) of potassium carbonate

stirring in 35 mL of N, N-dimethylformamide, 6.5 g

(38 mmol) of n-propyl iodide was added and the mixture stirred at room temperature for 14 h. The reaction mixture was partitioned between 150 mL of water and 200 mL of ethyl acetate and the organic layer separated followed by washing with water (3 times) and brine.

After drying over magnesium sulfate, the solvent was evaporated in vacuo to give a yellow solid residue which was flash chromatographed on silica gel

(10:1-5:1-3:1 hexane/ethyl acetate) to afford 5.2 g of the title compound as a white solid, m.p. 105-107°C; ¹H NMR (CDCl₃) : δ 9.04 (d, 1H), 7.60 (dd, 1H), 7.42 (d, 1H), 4.37 (t, 2H), 2.63 (t, 2H), 1.80 (q, 2H), 1.60 (q, 2H), 1.10-0.90 (m, 6H).

INTERMEDIATE 3

Preparation of 2,7-Dichloro-3-propyl-4H- pyrido[1,2-a]pyrimidin-4-one

A mixture of 10.0 g (42 mmol) of 7-chloro-2-hydroxy-4-oxo-3-propyl-pyrido[1,2-a]pyrimidin-1-ium hydroxide, inner salt stirring in 80 mL of phosphorous oxychloride was heated at reflux for 88 h. The dark reaction mixture was poured onto a large excess of ice. After extracting the resulting aqueous mixture with

800 mL of ethyl acetate, the organic layer was washed with water (2 times), saturated sodium bicarbonate and brine and dried over magnesium sulfate. Evaporating in vacuo gave dark oily/solid residue which was flashed chromatographed on silica gel (10:1-5:1-3:1

hexane/ethyl acetate) to give 1.8 g of the title compound, m.p. 169-171°C; ¹H NMR (CDCl₃) : δ 8.99 (d, 1H), 7.67 (dd, 1H), 7.55 (d, 1H), 2.80 (t, 2H), 1.65 (q, 2H), 1.02 (t, 3H).

EXAMPLE 5

Preparation of 7-Chloro-3-propyl-2-propylthio- 4H-pyrido[1,2-a]pyrimidin-4-one

To 0.5 g (2.0 mmol) of 2,7-dichloro-3-propyl-4H-pyrido[1,2-a]pyrimidin-4-one and 0.43 g (3.1 mmol) of potassium carbonate stirring in 30 mL of N,N-dimethyl-formamide at room temperature, 0.21 mL (2.3 mmol) of 1-propanethiol was added and the reaction was stirred at room temperature for 5 h. Water (75 mL) and ethyl acetate (125 mL) were added and the organic layer was separated and washed with water (3 times) and brine followed by drying over magnesium sulfate. Evaporation of solvent in vacuo provided an oily solid residue which was flash chromatographed on silica gel

(15:1-10:1 hexane/ethyl acetate) to yield 0.27 g of the title compound, m.p. 91-93°C; ¹H NMR (CDCl₃) : δ 9.0 (d, 1H), 7.55 (dd, 1H), 7.44 (d, 1H), 3.22 (t, 2H), 2.68

(t, 2H), 1.75 (q, 2H), 1.65 (q, 2H), 0.99-1.07 (m, 6H).

EXAMPLE 6

Preparation of 7-Chloro-3-propyl-2-propyloxy- 4H-pyrido[1,.2-a]pyrimidin-4-thione A mixture of 1.0 g (3.6 mmol) of 7-chloro-3-propyl-2-propyloxy-4H-pyrido[1,2-a]pyrimidin-4-one and 4.7 g (11 mmol) of phosphorous pentasulfide was heated at reflux for 32 h. An additional 3.0 g (6.8 mmol) of phosphorous pentasulfide was added and the mixture was heated at reflux for an additional 16 h. After

partitioning the reaction mixture between 150 mL of ethyl acetate and 10% aqueous hydrogen chloride, the organic layer was separated and washed with 10% aqueous hydrogen chloride (3 times with 100 mL), saturated sodium bicarbonate, and brine. The organic layer was dried over magnesium sulfate and evaporated in vacuo to give a solid residue. Flash column chromatography on silica gel (n-butyl chloride) afforded 0.16 g of the title compound, m.p. 117-120°C; ¹H NMR (CDCl₃) : δ 10.63 (d, 1H), 7.75 (dd, 1H), 7.57 (d, 1H), 4.43 (t, 2H), 3.07 (t, 2H), 1.84 (q, 2H), 1.68 (q, 2H),

0.95-1.15 (m, 6H).

Using the procedures outlined in Schemes 1-4, the compounds of Tables 1-7 can be prepared.

The following abbreviations are used in the tables which follow. t - is tertiary OMe - is methoxy

s - is secondary SEt - is ethylthio

n - is normal CN - is cyano

i - is iso TMS - is trimethylsilyl

Me - is methyl S(O)Me - is methylsulfinyl Et - is ethyl S(O)₂Me - is methylsulfonyl Ph - is phenyl

TABLE 1

Compounds of Formula Ih

R³=R⁵=H; W=O

R⁴ R⁶ R¹ R²

Cl H Me Me

Cl H Et n-propyl

Cl H n-propyl Me

Cl H 2-propenyl Me

Cl H 2-propenyl 2-propenyl

Cl H 2-propenyl n-propyl

Cl H n-propyl 2-propenyl

Br H 2-propenyl n-propyl

Br H 2-propenyl 2-propenyl

Br H 2-propenyl n-butyl

Br H Et n-propyl

Br H Et Et

Cl H Et 2-propenyl R⁴ R⁶ R¹ R²

Cl H Me n-propyl

Cl H Me 2-propenyl

Cl H n-hexyl Me

Cl H n-butyl Et

Cl H i-propyl n-propyl

I H Me n-propyl

I H n-propyl i-propyl

I H 2-propenyl 2-propenyl

I H n-propyl Me

I H 2-propenyl n-propyl

I H Me n-heptyl

I H Et n-dodecyl

CF₃ H Me Et

CF₃ H n-propyl 2-propenyl

CF₃ H 2-propenyl 2-propenyl

CF₃ H 2-propenyl n-propyl

CF₃ H 2-butenyl 2-propenyl

Cl H s-butyl Me

Cl Me i-pentyl 2-propenyl

Cl Me n-dodecyl n-hexyl

Br Me 2-propenyl 2-propenyl

Br Me n-propyl 2-propenyl

Me Me 2-propenyl 2-propenyl

Me Cl n-propyl Et

Me Br 2-butenyl 2-propenyl

Me Br n-propyl (CH₂)₁₇Me

Cl Cl 2-propenyl 2-propenyl

Cl Cl 2-pentenyl n-propyl

Cl Cl 2-hexenyl 2-butenyl

Br Br 2-propenyl 2-propenyl

Br Br n-propyl Me

I Me n-octyl n-heptyl

I H Me (CH₂) ₁₁Me

Me Me n-propyl s-butyl R⁴ R⁶ R¹ R²

OCHF₂ H 2-propenyl n-heptyl

OCH₂CF₃ H 2-propenyl n-octyl

OCF₂CHF₂ H 3-pentenyl 3-butynyl

OCH₂CH₂Cl H 5-hexynyl CH₂OEt

OMe H 2-octenyl CH₂CH₂Cl

OEt Me CH₂CH₂F CH₂CH₂OMe

O-i-propyl H (CH₂)₃CF₃ CH₂CH₂CH₂F

O-s-pentyl H CHCl(CH₂)₁₄Me Me

O-n-octyl H CH₂SMe 2-pentenyl

OCH₂CH=CH₂ H (CH₂)₇CH₂F CH₂SEt

SCH₂C≡CH H CH₂CH₂CF₃ CH₂CH₂Cl

Cl n-propyl 2-propynyl 2-butenyl t-butyl H (CH₂)₃OMe Et

i-pentyl H s-butyl 2-propenyl n-propyl H 2-butynyl n-decyl cyclopropyl H 3-butynyl (CH₂)₄OMe cyclopropylmethyl H CH₂CH₂OEt CH₂CH₂Cl cyclohexylmethyl H CH=CHMe Et

OCH₂C(Me)₃ H 4-pentenyl Me

S(O)₂Et H (CH₂)₂CHMe₂ n-propyl

CH₂S (O) ₂Me H 1-butenyl Me

Me OMe 2-heptenyl CH₂CH=CH(CH₂)₈Me

Me OCHF₂ 2-dodecynyl C≡CCH₂OMe

Me OCHMe₂ C≡CCH₂CH₂OEt Me

Cl CH₂OMe 6-hexenyl CH₂CH₂NMe₂

Cl OCH₂CH=CH₂ CH₂CH₂NEt₂ CH₂CH=CMe₂

TMS H CH₂CH₂CN Et

NO₂ H n-propyl 2-propenyl

NMe₂ H 2-propenyl n-butyl

C≡CCF₃ H Et Et

CH=CHCF₃ H Me n-hexyl

SCH₂CH=CH₂ Me Me Et

CH₂C≡CEt H Et Me

Cl n-butyl Et CH₂CH₂TMS R⁴ R⁶ R¹ R²

Me F Me CH₂CH₂SEt

F F Me cyclohexylmethyl

Br Et Et cyclooctyl

I H Me phenethyl

Cl H Et CH₂CH₂CN

Cl H Me CH₂CH₂NO₂

Cl H 2-propenyl cyclopropylmethyl

Cl Cl Et benzyl

Br Me n-propyl phenyl

Cl H Et 4-chlorophenyl

Cl H n-propoxy n-butyl

CF₃ H ethoxy 2-propenyl

Br H methoxy (CH₂)₁₇Me

Cl H n-propyl CH₂CH=CHCl Cl H OCH₂CH₂Cl 2-butenyl

CF₃ H CH₂C(Cl)=CH₂ n-butyl

Br Me CH₂CH=CHCl CH₂CH=CMe₂ t-butyl H CH₂CH=CMe₂ OCH₂CF₃

CH=CHMe H Me cyclohexyl

C≡CMe H Me n-butyl

OCH₂C≡CH H Et 2-cyclohexenyl

S(O)Me H Et CH₂C≡CCF₃

CH₂S (O)Me H Me Et

CN H n-propyl 2-propenyl

CO₂Me H Et n-propyl

CO₂Et H Et 2-butenyl

Cl cyclohexyl Et Et

Cl CH=CHMe Et Et

Cl C≡CEt Me n-pentyl

Cl CH₂Br Me 2-butynyl

Me CF₃ 2-propenyl 2-propenyl

Cl CH=CHCF₃ n-butyl Me

Cl C≡CCF₃ n-propyl n-propyl

Br OCH₂C≡CH n-propyl CH₂CH₂Cl R⁴ R⁶ R¹ R²

Cl SMe Me Et

Cl SCH₂CH=CH₂ Et 2-propynyl

Cl SCH₂C≡CH Et 2-butynyl

Cl S(O)Me n-propyl Et

Cl S(O)₂Me Et 2-hexenyl

Cl CH₂SMe Et 2-propenyl

Cl CH₂S(O)Me Me n-butyl

Cl CH₂S(O)₂Me Et CH₂CH₂F

Cl cyclopropylmethyl Et Et

Cl SiMe₃ Me n-propyl

Me CN 2-propenyl Et

Me NO₂ Me n-propyl

Me CO₂Me Me Et

Me CO₂Et n-propyl Me

Cl NMe₂ Et Et

Cl H cyclopropyl 2-propenyl

Cl H C≡CCF₃ Me

Br H CH₂S(O)Me Et

Br H CH₂S(O)₂Me Me

Br H cyclopropylmethyl Me

Br H CH₂OCH₂C≡CH Me

Cl H CH₂O[-CH₂(CH₂)₃CH₂-] Me

Cl H CH₂SCH₂CH=CH₂ Me

Cl H CH₂SCH₂C≡CH Et

Cl H CH₂S[-CH₂(CH₂)₃CH₂-] Me

Cl H CH₂CH₂OCHF₂ n-propyl

Cl H CH₂OCH₂CF=CF₂ Me

Cl H CH₂OCH₂C≡CCF₃ Me

Cl H CH=CHCH₂OCHF₂ Et

Cl H CH₂SCH₂CH=CH₂ Me

Cl H CH=CHCH₂SMe Me

Cl H C≡CCH₂SEt Me

Cl H CH₂CH₂SiMe₃ Me

Cl H CH₂CH₂NMe₂ Et R⁴ R⁶ R¹ R²

Cl H CH₂CH₂NO₂ n-propyl

Cl H CH₂CH₂CO₂Me Et

Cl H O(CH₂)₃Me Me

Br H Et Et

Cl H SMe n-propyl

Cl H SCH₂CH=CH₂ Et

Cl H SCH₂C≡CH 2-propenyl

Cl H Me CH₂S(O)Me

Cl H Et CH₂S(O)₂Me

Cl H n-propyl CH₂OCH₂CH=CH₂

Cl H n-propyl CH₂OCH₂C≡CH

Cl H Et CH₂O[-CH₂(CH₂)₃CH₂-]

Cl H Me CH₂SCH₂CH=CH₂

Cl H 2-propenyl CH₂SCH₂C≡CH

Cl H 2-propenyl CH₂S[-CH₂(CH₂)₃CH₂-]

Cl H Me CH₂CH₂OCHF₂

Cl H Et CH₂OCH₂CF=CF₂

Cl H 2-butenyl CH₂OCH₂C≡CCF₃

Cl H Me CH₂CH=CHCH₂SMe

Cl H 2-propenyl CH₂C≡CCH₂SEt

Cl H n-propyl CH₂CH₂NEt₂

Cl H 2-propenyl CH₂CH₂CO₂Et

Cl H CH₂CH₂N[-CH₂(CH₂)₃CH₂-] Me

Cl H Me CH₂CH₂N[-CH₂(CH₂)₃CH₂-]

Cl H Me 4-methylphenyl

Br H Et 3-methoxyphenyl

Cl Me n-propyl 3-CF₃-Ph

Cl H 2-propenyl 4-bromophenyl

Cl H Me 4-bromophenethyl

I H Me 3-methylphenethyl

Cl H Et 2-chlorobenzyl R⁴ R⁶ R¹ R²

Cl H Et 4-methylbenzyl Cl H Et 4-CF₃-benzyl

Cl H Et 3-CF₃-phenethyl Cl H Et 4-methoxybenzyl Cl H Me 4-methoxyphenethyl

R³=R⁵=H; W=S

R⁴ R⁶ R¹ R²

CH₂OEt Me CH=CHCF₃ CH₂CH=CHCl

CH₂CH₂OMe Cl n-propyl Et

cyclohexyl H n-butyl Me

SCH₂CHMe₂ Br 2-dodecenyl CH₂CH₂OEt

Cl H Me n-propyl

Cl H 2-propenyl 2-propenyl

CF₃ H 2-propenyl n-propyl

Cl H Et 2-propenyl

Br H 2-butenyl n-propyl

Br Me n-propyl n-butyl

I H n-hexyl i-propyl

CF₃ H Et i-butyl

CF₃ H Me s-pentyl

CF₃ H 2-propenyl Me

CF₃ Me 2-hexenyl Et

Br Me 2-butynyl n-butyl

I H CH₂CH₂OMe 2-propenyl t-butyl H CH₂SCHMe₂ 2-pentenyl

Et Me 1-butenyl phenyl

Cl Me Me 4-chlorophenyl

R³=R⁵=H

R⁴ R ⁶ W R¹ R²

Cl H S (O) n-propyl n-propyl

Br H S (O) ₂ n-pentyl Et

CF₃ Me S (O) ₂ i-propyl n-propyl R⁴ R⁶ W R¹ R²

Cl H NH n-propyl n-butyl

Cl H NMe Et n-propyl

Cl H NH n-propyl phenyl

Br Me NMe n-butyl Me

I H n-butyl n-pentyl n-butyl

Br H NEt n-pentyl Et

Br H NH 2-propenyl phenyl

CF₃ H NH 2-propenyl phenyl

Cl Cl NH n-propyl phenyl

I H NH n-butyl 2-chlorophenyl

Cl H NH Me n-hexyl

Br H NMe n-butyl n-heptyl

Br H NMe n-propyl benzyl

CF₃ H NEt Et n-octyl

n-butyl H NH CH₂CH₂OMe phenyl

OCHF₂ H NH CH₂CH₂F 2-heptenyl

Cl OEt NH CH₂CH₂CF=CF₂ n-butyl TABLE 2

Compounds of Formula Ih

R³ R⁴ R⁵ R⁶ W R¹ R²

H Cl Me H O n-propyl Me

H Cl Et H O n-propyl 2-propenyl

Cl H H H S 2-propenyl n-propyl

Me Br H H O Et Et

H Br OMe H O 2-butenyl n-propyl CF₃ Br H H S n-butyl Et

H CF₃ Me H O 2-propenyl 2-butenyl

Br H H H O 2-butynyl 2-pentenyl

Me Cl H H S 2-propenyl 2-propenyl

H I Me H O n-propyl 2-propenyl

H Br Me Me O n-heptyl CH₂CH₂OMe

H H OCHF₂ Br S n-octyl CH₂CH₂OEt

Cl Me H Me O n-dodecyl CH₂CH₂Cl R³ R⁴ R⁵ R⁶ W R¹ R²

H Cl Me Et O 2-decenyl CH₂CH₂CF₃

H Cl Me OCHF₂ O CH₂OEt phenyl

Me OCHF₂ H H O CH₂CH₂CN cyclopropylmet

F Me H Cl O s-pentyl 2-butynyl

H t-butyl F H O i-propyl n-propyl

OMe n-hexyl H H O 3-butenyl CH₂CF₃

H OCH₂CF₃ Et H O 5-hexynyl 3-butynyl CF₃ NMe₂ H H O OCH₂CH=CH₂ phenethyl

H OCH₂CH₂Cl Cl H O CH₂CH₂SMe 4-pentynyl

H SEt Et H O Me benzyl

H OEt OEt Me O CH₂CH₂F CH₂CH₂NMe₂

OEt S(O)₂CHMe₂ H H O 2-hexyl CH₂CH₂NO₂

H CH₂OMe H H S CH₂CH=CHCl n-propyl

Me CF₃ H H S OCH₂CH₂Cl Me

H Cl Me Me O OCH₂CF₃ CH₂CH=CHCl

H Cl Cl H NH n-propyl phenyl

OEt OCH₂CHMe₂ H H NMe n-butyl Me

H Br Br H NH 2-propenyl phenyl

H H Cl H NH CH₂CH₂OMe 4-chlorophenyl

H H Et H NEt n-hexyl n-butyl

H Cl H H NH Et benzyl

Me Me H H O i-pentyl Et

Br H H H O CH₂OCH₂CH=CH₂ n-propyl

Cl H H F O CH₂SCH₂CH₂Me Et

CF₃ H H H S 2-butenyl Me

Me CF₃ H H S Me phenyl

H Cl Et H O CH₂C(Cl)=CH₂ n-propyl

OCHF₂ H H H O n-propyl 2-propenyl

H Me CF₃ H O 2-propenyl n-propyl TABLE 3

Compounds of Formula Ii

R³ R⁴ R⁵ Q W R¹ R²

H Cl H O O n-propyl Me

H Cl H O O n-propyl 2-propenyl

H Cl H O S 2-propenyl n-propyl

H Br H S O Et Et

H Br H O O 2-butenyl n-propyl

H Br H O S n-butyl Et

H CF₃ H O O 2-propenyl 2-butenyl

H I H O O 2-butynyl 2-pentenyl

Me Cl H O S 2-propenyl 2-propenyl

H Cl Me O O n-propyl 2-propenyl

H Br Me O O n-heptyl CH₂CH₂OMe

H Me H O S n-octyl CH₂CH₂OEt

H Me H O O n-dodecyl CH₂CH₂Cl

H Cl H O O 2-decenyl CH₂CH₂CF₃

H Cl H S O CH₂OEt phenyl

H OCHF₂ H O O CH₂CH₂CN cyclopropyi

F Me H O O s-pentyl 2-butynyl

H t-butyl H O O i-propyl n-propyl

H n-hexyl H O O 3-butenyl CH₂CF₃

H OCH₂CF₃ H O O 5-hexynyl 3-butynyl

H NMe₂ H O O OCH₂CH=CH₂ phenethyl

H OCH₂CH₂Cl H O O CH₂CH₂SMe 4-pentynyl

H SEt H O O Me benzyl

H OEt H O O CH₂CH₂F CH₂CH₂NMe₂

H S(O)₂CHMe₂ H O O 2-hexyl CH₂CH₂NO₂

H CH₂OMe H O S CH₂CH=CHCl n-propyl

H CF₃ H O S OCH₂CH₂Cl Me

H I H O O OCH₂CF₃ CH₂CH=CHCl

H Cl H O NH n-propyl phenyl

H OCH₂CHMe₂ H O NMe n-butyl Me

H Br H O NH 2-propenyl phenyl R³ R⁴ R⁵ Q W R¹ R²

H Br H O NH CH₂CH₂OMe 4-chlorophenyl

H Cl H S NEt n-hexyl n-butyl

H Cl H O NH Et benzyl

Me Me H O O i-pentyl Et

H I H O O CH₂OCH₂CH=CH₂ n-propyl

H Cl H S O CH₂SCH₂CH₂Me Et

H CF₃ H O S 2-butenyl Me

H CF₃ H O S Me phenyl

H Cl H O O CH₂C(Cl)=CH₂ n-propyl

H Me Cl O O n-propyl 2-pentenyl

TABLE 4

Compounds of Formula Ij

R³ R⁴ R⁶ Q W R¹ R²

H Cl H O O n-propyl Me

H Cl H O O n-propyl 2-propenyl

H Cl H O S 2-propenyl n-propyl

H Br H S O Et Et

H Br Me O O 2-butenyl n-propyl

H Br H O S n-butyl Et

H CF₃ H O O 2-propenyl 2-butenyl

H I H O O 2-butynyl 2-pentenyl

Me Cl H O S 2-propenyl 2-propenyl

H Cl Me O O n-propyl 2-propenyl

H Br Me O O n-heptyl CH₂CH₂OMe

H Me H O S n-octyl CH₂CH₂OEt

H Me Br O O n-dodecyl CH₂CH₂Cl

H Cl Cl O O 2-decenyl CH₂CH₂CF₃

H Cl H S O CH₂OEt phenyl

H OCHF₂ H O O CH₂CH₂CN cyclopropylmethyl

F Me H O O s-pentyl 2-butynyl

H t-butyl H O O i-propyl n-propyl

H n-hexyl H O O 3-butenyl CH₂CF₃ R³ R⁴ R⁶ Q W R¹ R²

H OCH₂CF₃ H O O 5-hexynyl 3-butynyl

H NMe₂ H O O OCH₂CH=CH₂ phenethyl

H OCH₂CH₂Cl H O O CH₂CH₂SMe 4-pentynyl

H SEt H O O Me benzyl

H OEt H O O CH₂CH₂F CH₂CH₂NMe₂

H S(O)₂CHMe₂ H O O 2-hexyl CH₂CH₂NO₂

H CH₂OMe H O S CH₂CH=CHCl n-propyl

H CF₃ H O S OCH₂CH₂Cl Me

H I H O O OCH₂CF₃ CH₂CH=CHCl

H Cl Me O NH n-propyl phenyl

H OCH₂CHMe₂ H O NMe n-butyl Me

H Br H O NH 2-propenyl phenyl

H Br H O NH CH₂CH₂OMe 4-chlorophenyl

H Cl H S NEt n-hexyl n-butyl

H Cl H O NH Et benzyl

Me Me H O O i-pentyl Et

H I H O O CH₂OCH₂CH=CH₂ n-propyl

H Cl H S O CH₂SCH₂CH₂Me Et

H CF₃ H O S 2-butenyl Me

H CF₃ H O S Me phenyl

H Cl H O O CH₂C(Cl)=CH₂ n-propyl

H Me Cl O O n-propyl 2-pentenyl TABLE 5

Compounds of Formula Ik

R⁴ R⁵ R⁶ Q W R¹ R²

Cl H H O O n-propyl Me

Cl H H O O n-propyl 2-propenyl

Cl H H O S 2-propenyl n-propyl

Br H H S O Et Et

Br H Me O O 2-butenyl n-propyl

Br H H O S n-butyl Et R⁴ R⁵ R⁶ Q W R¹ R²

CF₃ H H O O 2-propenyl 2-butenyl

I H H O O 2-butynyl 2-pentenyl

Cl Me H O A 2-propenyl 2-propenyl

Cl H Me O O n-propyl 2-propenyl

Br H Me O O n-heptyl CH₂CH₂OMe

Me Cl H O A n-octyl CH₂CH₂OEt

Me H Br O O n-dodecyl CH₂CH₂Cl

Cl H Cl O O 2-decenyl CH₂CH₂CF₃

Cl H H S O CH₂OEt phenyl

OCHF₂ H H O O CH₂CH₂CN cyclopropylmethyl

Me F H O O s-pentyl 2-butynyl t-butyl H H O O i-propyl n-propyl n-hexyl H H O O 3-butenyl CH₂CF₃

OCH₂CF₃ H H O O 5-hexynyl 3-butynyl

NMe₂ H H O O OCH₂CH=CH₂ phenethyl

OCH₂CH₂CH H H O O CH₂CH₂SMe 4-pentynyl

SEt H H O O Me benzyl

OEt H H O O CH₂CH₂F CH₂CH₂NMe₂

S (O) ₂CHMe₂ H H O O 2-hexyl CH₂CH₂NO₂

CH₂OMe H H O A CH₂CH=CHCl n-propyl

CF₃ H H O A OCH₂CH₂Cl Me

I H H O O OCH₂CF₃ CH₂CH=CHCl

Cl H Me O NH n-propyl phenyl

OCH₂CHMe₂ H H O NMe n-butyl Me

Br H H O NH 2-propenyl phenyl

Br H H O NH CH₂CH₂OMe 4-chlorophenyl

Cl H H A NEt n-hexyl n-butyl

Cl H H O NH Et benzyl

Me Me H O O i-pentyl Et

I H H O O CH₂OCH₂CH=CH₂ n-propyl

Cl H H A O CH₂SCH₂CH₂Me Et

CF₃ H H O S 2-butenyl Me

CFo H H O S Me phenyl R⁴ R⁵ R⁶ Q W R¹ R²

Cl H H O O CH₂C(Cl)=CH₂ n-propyl

Me H Cl O O n-propyl 2-pentenyl

TABLE 6

Compounds of Formula Il

R³ R⁶ R⁵ Q W R¹ R²

H Cl H O O n-propyl Me

H Cl H O O n-propyl 2-propenyl

H Cl H O S 2-propenyl n-propyl

H Br H S O Et Et

H Br Me O O 2-butenyl n-propyl

H Br H O S n-butyl Et

H CF₃ H O O 2-propenyl 2-butenyl

H I H O O 2-butynyl 2-pentenyl

Me Cl H O S 2-propenyl 2-propenyl

H Cl Me O O n-propyl 2-propenyl

H Br Me O O n-heptyl CH₂CH₂OMe

Cl Me H O S n-octyl CH₂CH₂OEt

H Me Br O O n-dodecyl CH₂CH₂Cl

H Cl Cl O O 2-decenyl CH₂CH₂CF₃

H Cl H S O CH₂OEt phenyl

H OCHF₂ H O O CH₂CH₂CN cyclopropylmethyl

F Me H O O s-pentyl 2-butynyl

H t-butyl H O O i-propyl n-propyl

H n-hexyl H O O 3-butenyl CH₂CF₃

H OCH₂CF₃ H O O 5-hexynyl 3-butynyl

H NMe₂ H O O OCH₂CH=CH₂ phenethyl

H OCH₂CH₂Cl H O O CH₂CH₂SMe 4-pentynyl

H SEt H O O Me benzyl

H OEt H O O CH₂CH₂F CH₂CH₂NMe₂

H S(O)₂CHMe₂ H O O 2-hexyl CH₂CH₂NO₂

H CH₂OMe H O S CH₂CH=CHCl n-propyl

H CF₃ H O S OCH₂CH₂Cl Me

H I H O O OCH₂CF₃ CH₂CH=CHCl R³ R⁶ R⁵ Q W R¹ R²

H Cl Me O NH n-propyl phenyl

H OCH₂CHMe₂ H O NMe n-butyl Me

H Br H O NH 2-propenyl phenyl

H Br H O NH CH₂CH₂OMe 4-chlorophenyl H Cl H S NEt n-hexyl n-butyl H Cl H O NH Et benzyl

Me Me H O O i-pentyl Et

H I H O O CH₂OCH₂CH=CH₂ n-propyl H Cl H S O CH₂SCH₂CH₂Me Et

H CF₃ H O S 2-butenyl Me

H CF₃ H O S Me phenyl

H Cl H O O CH₂C(Cl)=CH₂ n-propyl H Me Cl O O n-propyl 2-pentenyl

TABLE 7

compounds of Formula I

X Y Z Q R¹ R²

CH CCl S O O 2-propenyl n-propyl

CH CCl S O O 2-propenyl 2-propenyl

CH CCl S O O n-butyl n-hexyl

CH CCl S O O s-butyl 2-butenyl

CMe CCl S O O Et 2-pentenyl

CH CBr S O O n-propyl 2-propenyl

CH CCF₃ S O O 2-propenyl n-propyl

CH CCF₃ S O O 2-butenyl Et

CH CCF₃ S O O Me n-propyl

CCF₃ CH S O O CH₂CH₂OMe Et

CH CCF₃ S O O CH₂CH₂Cl 2-hexenyl

CH CBr S O O 2-propenyl 2-propenyl

CH CBr S O O 2-butenyl n-propyl

CH CBr S O O CH=CHMe n-heptyl

CH CBr S O S n-butyl Et

CH CCF₃ S S O 2-propenyl 2-butenyl

CMe CH S O O 2-butynyl 2-pentenyl X Y Z Q W R¹ R²

CCl CMe S O S 2-propenyl 2-propenyl

CH CCl O O O n-propyl 2-propenyl

CH CCl O O O 2-propenyl n-propyl

CH CCl O O O 2-butenyl 2-propenyl

CH CCF₃ O O O n-dodecyl Me

CH CBr O O O CH₂C=CHCH₂OMe n-butyl

CH CCF₃ O O O CH₂CH₂CH₂F Et

CMe CBr O O O n-heptyl CH₂CH₂OMe

CEt CCF₃ O O S n-octyl CH₂CH₂OEt

CH CCl O O O n-dodecyl CH₂CH₂Cl

CH CCl O O O 2-decenyl CH₂CH₂CF₃

CH CBr O O O CH₂OMe CH₂CF₃

CH CCl O S O CH₂OEt phenyl

CH CBr S O O CH₂CH₂CN cyclopropylmethyl

CH C-OCHF₂ S O O CH₂CH₂OEt Me

CH C-t-butyl S O O n-propoxy s-butyl

CF C-Me S O O s-pentyl 2-butynyl

CH C-i-butyl S O O s-butyl n-propyl

CH C-n-hexyl S O O 3-butenyl CH₂CF₃

CH C-OCH₂CF₃ S O S 5-hexynyl 3-butynyl

CH C-NMe₂ S O O OCH₂CH=CH₂ phenethyl

CH C-OCH₂CH₂Cl S O O CH₂CH₂SMe 4-pentynyl

CH C-SEt S O O Me benzyl

CH C-OEt S O O CH₂CH₂F CH₂CH₂NMe₂

CH C-S(O)₂CHMe₂ S O O 2-hexyl CH₂CH₂NO₂

CH CCH₂OMe S O S CH₂CH=CHCl n-propyl

CH CCF₃ S O S OCH₂CH₂Cl Me

CH CCl O O O OCH₂CF₃ CH₂CH=CHCl

CH CCl O O NH n-propyl phenyl

CH C-OCHMe₂ O O NMe n-butyl Me

CH CBr S O NH 2-propenyl phenyl

CH CBr S O NH CH₂CH₂OMe 4-chlorophenyl X Y Z Q W R¹ R²

CH CCl S S NEt n-hexyl n-butyl

CH CCl S O NH Et benzyl

CH CCl S O NH n-hexyl 4-chorophenyl

CH CBr S O NH 2-butenyl s-pentyl

CH CBr O O NEt CH₂CH=CMe₂ Et

CMe CMe S S O i-pentyl Et

CH CCl S S O CH₂OCH₂CH=CH₂ n-propyl

CH CCl S S O CH₂SCH₂CH₂Me Et

CH CCF₃ S O S(O)₂ 2-butenyl Me

CH CCF₃ S O S Me phenyl

CH CCl S O O CH₂C(Cl)=CH₂ n-propyl

CH CMe O S O n-propyl 2-pentenyl

CH CCF₃ S O O n-propyl phenyl

CH CCl S O S(O)₂ n-propyl n-propyl

CH CBr NMe O O n-butyl Et

CH CCl NMe O O Et Et

CH CCF₃ NMe S O 2-propenyl n-propyl

CH CCl NCHF₂ O O Me 2-butenyl

CH CCF₃ NEt O O CH₂SEt CH₂CH₂F

CCF₃ CH NCH₂CF₃ O O Me Et

CH CBr n-propyl O O Me benzyl

CH CCl NCHF₂ O O CH₂OCH₂CF₃ 2-hexenyl

CMe CMe S O O OCH₂CH=CH₂ CH₂CH=CHCl

CH CCH₂OMe S O O CH₂CH₂CN CH₂CH₂CH₂F

CH C-t-butyl S O O CH₂CF=CF₂ Et

CH CEt S O O n-dodecyl n-octyl

CH C-i-propyl S O O CH=CHEt CH₂CH₂CF₃

CH CBr O S O 1-butynyl CH₂CH=CMe₂

CH CCl O S O 3-butynyl CH₂SEt

CH CCH₂CF₃ O S O methoxy s-pentyl

CH CMe S S O CH₂OCH₂CHMe₂ 4-chlorobenzyl

CH CCl S O O CH₂C(Me)=CH₂ Et X Y Z Q W R¹ R²

CH CBr S O O Me 2-chlorophenyl

CH CBr S O O 1-hexynyl Et

CH CBr S O O n-propyl CH₂CH₂NMe₂

CH CCl S O O CH=CHCF₃ n-butyl

CH CBr S O O (CH₂) ₇CH₂F Et

CH CCl S O O OCH₂C≡CH n-propyl

CH CCF₃ O O O 2-dodecenyl Me

CH CCl S O O Et CH₂CH₂TMS

CH CCl S O O Me phenethyl

Formulation/Utility

Compounds of this invention will generally be used in an agriculturally suitable composition. The

compositions of this invention comprise an effective amount of a compound of Formula I as defined above and at least one of (a) a surfactant, (b) an organic solvent, and (c) at least one solid or liquid diluent, useful formulations include dusts, granules, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates, dry flowables and the like, consistent with the physical properties of the active ingredient, mode of application and environmental factors such as soil type, moisture and temperature. Sprayable formulations can be extended in suitable media and used at spray volumes from about one to several hundred liters per hectare. High strength compositions are primarily used as intermediates for further formulation. The formulations will typically contain effective amounts of active ingredient, diluent and surfactant within the following approximate ranges which add up 100 weight percent. Weight Percent

Active

Ingredient Diluent Surfactant

Wettable Powders 25-90 0-74 1-10

Oil Suspensions, Emulsions, 5-50 40-95 0-15 Solutions, (including

Emulsifiable Concentrates)

Dusts 1-25 70-99 0-5

Granules, Baits and Pellets 0.01-99 5-99.99 0-15

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

Typical solid diluents are described in Watkins, et al., Handbook of Insecticide Dust Diluents and

Carriers, 2nd Ed., Dorland Books, Caldwell, New Jersey. Typical liquid diluents and solvents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950. McCutcheon 's Detergents and Emulsifiers Annual, Allured Publ. Corp., Ridgewood, New Jersey, as well as Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foam, caking, corrosion, microbiological growth, etc.

Solutions are prepared by simply mixing the

ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer mill or fluid energy mill. Water-dispersible granules can be produced be agglomerating a fine powder composition; see for example, Cross et al., Pesticide Formulations, Washington, D.C., 1988, pp 251-259. Suspensions are prepared by wet-milling; see, for example, U.S.

3,060,084. Granules and pellets can be made by

spraying the active material upon preformed granular carriers or by agglomeration techniques. See Browning, "Agglomeration", Chemical Engineering, December 4,

1967, pp 147-148, Perry 's Chemical Engineer 's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pp 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 DE 3,246,493.

For further information regarding the art of formulation, see U.S. 3,235,361, Col. 6, line 16 through Col. 7, line 19 and Examples 10 through 41;

U.S. 3,309,192, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132,

138-140, 162-164, 166, 167 and 169-182; U.S.

2,891,855, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4; Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, pp 81-96; and Hance et al.. Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989.

In the following Examples, all percentages are by weight and all formulations are worked up in

conventional ways. Compound numbers refer to compounds in Index Tables A and B, hereinafter.

Example A

Wettable Powder

Compound 3 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%.

Example B

Granule

Compound 3 10.0% attapulgite granules (low volative

matter, 0.71/0.30 mm; U.S.S. No.

25-50 sieves) 90.0%.

Example C

Extruded Pellet

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

Example D

Emulsifiable Concentrate

Compound 3 20.0% blend of oil soluble sulfonates

and polyoxyethylene ethers 10.0% isophorone 70.0%. The compounds and compositions 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, to the media in which the plant to be protected is growing, or to the plant seed or seedling an effective amount of a compound of

Formula I, an N-oxide thereof, an agriculturally suitable salt thereof, or a fungicidal composition containing said compound, N-oxide, or salt. The compounds and 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, vegetable, field, cereal, and fruit crops. These pathogens include Plasmopara viticola, Phytophthora infestans, Peronospora tabacina, Pseudoperonospora cubensis, Pythium aphanidermatum, Alternaria brassicae, Septoria nodorum, Cercosporidium personatum, Cercospora arachidicola, Pseudocercosporella herpotrichoides, Cercospora beticola, Botrytis cinerea, Monilinia fructicola, Pyricularia oryzae, Podosphaera

leucotricha, Venturia inaequalis, Erysiphe graminis, Uncinula necatur, Puccinia recondita, Puccinia graminis, Hemileia vastatrix, Puccinia striiformis, Puccinia arachidis, Rhizoctonia solani, Sphaerotheca fuliginea, Fusarium oxysporum, Verticillium dahliae, Pythium aphanidermatum, Phytophthora megasperma and other generea and species closely related to these pathogens. They are particularly effective in the control of Erysiphe graminis, the causal agent of wheat powdery mildew, both preventive and curative.

Compounds of this invention can also be mixed with one or more other insecticides, fungicides,

nematocides, bactericides, acaricides, semiochemicals, repellants, attractants, pheromones, feeding stimulants or other biologically active compounds to form a multicomponent pesticide giving an even broader spectrum of agricultural protection. Examples of other

agricultural protectants with which compounds of this invention can be formulated are: insecticides such as monocrotophos, carbofuran, tetrachlorvinphos,

malathion, parathion-methyl, methomyl, chlordimeform, diazinon, deltamethrin, oxamyl, fenvalerate,

esfenvalerate, permethrin, profenofos, sulprofos, triflumuron, diflubenzuron, methoprene, buprofezin, thiodicarb, acephate, azinphosmethyl, chlorpyrifos, dimethoate, fipronil, flufenprox, fonophos, isofenphos, methidathion, methamidophos, phosmet, phosphamidon, phosalone, pirimicarb, phorate, terbufos, trichlorfon, methoxychlor, bifenthrin, biphenate, cyfluthrin, fenpropathrin, fluvalinate, flucythrinate,

tralomethrin, metaldehyde and rotenone; fungicides such as carbendazim, thiuram, dodine, maneb, chloroneb, benomyl, cymoxanil, fenpropidine, fenpropimorph, triadimefon, captan, thiophanate-methyl, thiabendazole, phosethyl-Al, chlorothalonil, dichloran, metalaxyl, captafol, iprodione, oxadixyl, vinclozolin,

kasugamycin, myclobutanil, tebuconazole, difenoconazole, diniconazole,- fluquinconazole, ipconazole, metconazole, penconazole, propiconazole, uniconzole, flutriafol, prochloraz, pyrifenox, fenarimol,

triadimenol, diclobutrazol, copper oxychloride, furalaxyl, folpet, flusilazol, blasticidin S,

diclomezine, edifenphos, isoprothiolane, iprobenfos, mepronil, neo-asozin, pencycuron, probenazole,

pyroquilon, tricyclazole, validamycin, and flutolanil; nematocides such as aldoxycarb, fenamiphos and

fosthietan; bactericides such as oxytetracyline, streptomycin and tribasic copper sulfate; acaricides such as binapacryl, oxythioquinox, chlorobenzilate, dicofol, dienochlor, cyhexatin, hexythiazox, amitraz, propargite, tebufenpyrad and fenbutatin oxide; and biological agents such as Bacillus thuringiensis and baculovirus.

In certain instances, combinations with other fungicides having a similiar spectrum of control but a different mode of action will be particularly

advantageous for resistance management.

Plant disease control is ordinarily accomplished by applying an effective amount of a compound of this invention either pre- or post-infection, to the plant or 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 the seed to protect the seed and seedling.

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 1 g/ha to 5,000 g/ha of active ingredient. Seed and seedlings can normally be

protected when seed is treated at a rate of from 0.1 to 10 g per kilogram of seed. 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 and B for compound

descriptions.

Test compounds were first dissolved in acetone in an amount equal to 3% of the final volume and then suspended at a concentration of 200 ppm in purified water containing 250 ppm of the surfactant Trem^® 014

(polyhydric alcohol esters). The resulting test suspensions were then used in the following tests.

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 7 days, after which 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 (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 6 days, after which disease ratings were made.

TEST C

The test suspension was sprayed to the point of run-off on rice seedlings. The following day the seedlings were inoculated with a spore suspension of Pyricularia oryzae (the causal agent of rice blast) and incubated in a saturated atmosphere at 27°C for 24 h, and then moved to a growth chamber at 30°C for 5 days, after which disease ratings were made. TEST D

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 potato and 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 5 days, after which disease ratings were made.

TEST E

The test suspension was sprayed to the point of run-off on grape seedlings. The following day the 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, moved to a growth chamber at 20°C for 6 days, and then incubated in a saturated atmosphere at 20°C for 24 h, after which disease ratings were made.

TEST F

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 Botrytis cinerea (the causal agent of gray mold on many crops) and incubated in a saturated atmosphere at 20°C for 48 h, and moved to a growth chamber at 20°C for 5 days, after which disease ratings were made.

Index Table A

Compounds of Formula Ih wherein:

Cpd m.p.

# R³ R⁴ R ⁵ R⁶ W R¹ R² °C

1 H Me H Br O allyl Me 149-150

2 H Cl H H O allyl Me 139-141

3 H Cl H H O allyl allyl 104-105

4 H Cl H H O allyl Et 111-113

5 H Cl H H O n-propyl Me 135-137 Cpd m.p.

# R³ R⁴ R⁵ R⁶ W R¹ R² ºC

6 H Cl H H O allyl i-propyl 105-107

7 H Cl H H O allyl n-propyl 107-109

8 H Cl H Cl O allyl Me 121-122

9 H Cl H H O allyl propargyl 125-126

10 H Cl H H O -CH₂CH₂CH₂- 222-224

11 H H Me H O allyl Me 90-92

12 H Cl H H O Et Me 131-133

13 H Cl H H O Me Me 165-167

14 H Cl H H O n-butyl Me 101-102

15 H Me H Br O allyl allyl 108-110

16 H Cl H H O allyl n-hexyl 94-95

17 H H H Me O allyl Me 106-107

18 H Cl H H O n-propyl n-propyl 105-107

19 H Cl H H O CH₂CH₂CN n-propyl 137-138 20 H Cl H H O n-propyl allyl 101-103

21 H Cl H H O 2-butenyl allyl 130-132 22 H Cl H H O 2-butenyl Me 155-157

23 H Cl H Cl O allyl allyl 101-103 24 H Cl H Cl O allyl n-propyl 79-81 25 H Cl H H O allyl CH₂C(C1)=CH₂ 130-131 26 H Cl H H O allyl 2-butenyl 105-107 27 H Br H H O allyl Me 143-144 28 H Cl H H O n-butyl allyl 115-117 29 H Cl H H O allyl CH₂CH=CHCl 120-125

30 H Br H H O allyl allyl 113-115 31 H Cl H H O Et allyl 112-114 32 H CF₃ H H O allyl Me 140-142

33 H Cl H H O n-propyl Ph 159-162 34 H Cl H H O allyl Me 91-93

35 H Br H Me O n-propyl n-propyl 142-144 36 H Br H H O n-propyl n-propyl 114-116 37 H Cl H H O n-butyl n-propyl 111-113 38 H Br H H O allyl n-propyl 124-125 Cpd m.p.

# R³ R⁴ R⁵ R⁶ W R¹ R² °C

39 H CF₃ H H O allyl n-propyl 89-92

40 H CF₃ H H O n-propyl n-propyl 80-81

41 H Cl H H O i-propyl Me 146-148

42 H Cl H H S n-propyl n-propyl 91-93

43 H Me H Br O n-propyl n-propyl 101-104

44 H Cl H H O i-propyl n-propyl 92-94

45 H Cl H H O n-propyl 2-butenyl 95-97

46 H Cl H H O n-propyl CH₂CH=CMe₂ 95-97

47 H Cl H H O n-propyl CH₂CF₃ 112-115

48 H Cl H H O n-propyl n-butyl 92-94

49 H Cl H H O n-propyl CHF₂ 103-105

50 H Cl H H O n-propyl phenethyl 96-98

51 H H H Me O n-propyl n-propyl 69-71

52 H Cl H H O n-propyl n-hexyl 92-94

53 H Cl H H O n-propyl i-butyl 122-124

54 H NO₂ H H O n-propyl n-propyl 100-102

55 H NO₂ H H O allyl allyl 94-96

56 H Me H H O n-propyl n-propyl 72-74 57 H Cl H H NH n-propyl n-propyl 101-103

58 H Cl H H O n-propyl n-heptyl 90-92 59 H Cl H H O n-propyl FCH₂CH₂CH₂ 109-110

60 H Cl H Cl O n-propyl n-propyl 97-99

61 H I H I O n-propyl n-propyl 192-194

62 H Br H H O n-hexyl n-propyl 88-90

63 H Cl H H O n-hexyl Me 103-109 64 H Cl H H O n-hexyl n-propyl 94-96 65 H Cl H H O n-propyl Et 110-112

66 H Br H Br O n-propyl n-propyl 131-133 67 H I H H O n-propyl n-propyl 121-124 68 H Cl H H O n-propyl CH₂CH₂OMe 95-96 69 H MeS H H S n-propyl Me 111-113 70 H Cl H H S n-propyl Me 125-127 Cpd m.p.

# R³ R⁴ R⁵ R⁶ W R¹ R² °C

71 H Cl H H NMe n-propyl Me 85-88

72 H Cl H H O OMe n-propyl 120-122

73 H Cl H H O OMe Me 168-170

74 Br H H H O n-propyl n-propyl 56-59

75 H Cl H Br O n-propyl n-propyl 110-112

76 H H H I O n-propyl n-propyl 82-85

Results for Tests A-F are given in Table C. In the table, a rating of 100 indicates 100% disease control and a rating of 0 indicates no disease control

(relative to the controls). NT = Not Tested.

TABLE C

Cmpd Test Test Test Test Test Test

No. A B C D E F

1 100 79 7 0 21* 40*

2 99 0 28* 0 0 0

3 100 17 0 0 18 38

4 98 0 0 16 18 0

5 100 0 0 0 0 38*

6 96 12 71 74 84 7

7 100 12 23 18* 13* 0

8 100 63 0 0 22* 0

9 97 0 0 25 0 0

10 34* 0 0 0 25 0

11 77 18 0 24 22 0

12 81 14 0 0 75 0

13 93 14 0 0 62 41

14 99 62 0 22 44 0

15 99 14 0 0 97 0

16 100 0 0 0 22 41

17 98 14 0 0 22 0

18 100 0 0 0 22 0

19 49 0 0 0 0 0

20 100 5 1 0 74 0

21 99 5 1 15 19 0

22 94 5 1 15 42 0

23 100 5 1 15 19 0

24 100 5* 1 40* 74 0

25 100* 16* 0* 0* 9* 0*

26 100 16* 0 22 56 0

27 100 0 0 22* 9 70*

28 100 0 0 0 71 0

29 100 0 0 22 9 0

30 100 62 0 0 35 47

31 100 16 0 22 100 0

32 74 16 0 22 9 0 Cmpd Test Test Test Test Test Test

No. A B C D E F

33 87 0 0 0 0 41

34 100 1 0 43 25* 0

35 100 1 0 0 25 10

36 100 1 0 0 25* 10

37 100 1 1 1 25 98*

38 100 1 0 0 46 0

39 100 1 0 0 0 0

40 100 1 0 0 0 0

41 97 1 0 0 0 0

42 98 1 0 20 25 0

43 100* 40* 0* 0* 13* 0*

44 99* 0* 0* 0* 13* 0*

45 100* 0* 0* 0* 38* 0*

46 100* 0* 0* 0* 13* 0*

47 98* 4* 0* 24* 14* 9*

48 100* 0* 0* 0* 13* 0*

49 16* 40* 0* 0* 38* 0*

50 0* 40 0 0 0 0

51 99* 40* 0* 0* 38* 0*

52 100* 40 0 0 0 0

53 99* 40 0 0 13 0

54 96 57 0* 18* 12* 0

55 69 3 0* 0* 0* 0*

56 98* 39* 0* 0* 12* 0*

57 97* 39* 0* 0* 12* 0*

58 89* 52* 0* 0* 43* 0*

59 100* 0* 0* 0* 43* 0*

60 100* 0* 0* 0* 43* 46*

61 100* 81* 0* 24* 0* 0*

62 84* 0* 0* 0* 17* 0*

63 84* 0* 0* 14* 17* 0*

64 57* 0* 0* 0* 18* 4*

65 NT 0* 0* 7* 0 4* Cmpd Test Test Test Test Test Test

No. A B C D E F

66 NT 0* 0* 0* 42* 4*

67 100* 0* 0* 0* 0* 4*

68 98* 0* 0* 20* 59* 0*

69 60* 0* 0* 0* 0* 0*

70 91* 0* 0* 0* 36* 0*

71 76* 0* 0* 0* 58* 31*

72 55* 19* 0* 61* 0* 0*

73 0* 64* 0* 0* 0* 0*

74 100* 41* 0* 0* 11* 81*

75 100* 0 0* 0* 13* 0*

*The compound was spray at a concentration of 40 ppm.

Claims

What is claimed is:

1. A compound of Formula I

wherein:

Q is O or S;

W is O; S; S (O) ; S(O)₂; NH; or NR⁹;

X is CR³ or N;

Y is CR⁴ or N;

R¹ is C₁-C₁₈ alkyl; C₃-C₇ cycloalkyl; C₂-C₁₈

alkenyl; C₂-C₁₈ alkynyl; C₁-C₁₈ haloalkyl;

C₂-C₁₈ haloalkenyl; C₂-C₁₈ haloalkynyl; C₂-C₁₈ alkoxyalkyl; C₂-C₁₈ alkylthioalkyl; C₂-C₁₈ alkylsulfinylalkyl; C₂-C₁₈ alkylsulfonylalkyl; C₄-C₁₈ cycloalkylalkyl; C₄-C₁₈ alkenyloxyalkyl; C₁-C₁₈ alkynyloxyalkyl; C₄-C₁₈ cycloalkyloxyalkyl; C₄-C₁₈ alkenylthioalkyl; C₄-C₁₈ alkynylthioalkyl; C₆-C₁₈ cycloalkylthioalkyl; C₂-C₁₈ haloalkoxyalkyl; C₃-C₁₈ haloalkenyloxyalkyl; C₄-C₁₈ haloalkynyloxyalkyl; C₄-C₁₈ alkoxyalkenyl; C₄-C₁₈ alkoxyalkynyl; C₄-C₁₈ alkylthioalkenyl; C₄-C₁₈ alkylthioalkynyl; C₄-C₁₈ trialkylsilylalkyl; C₁-C₁₈ alkyl substituted with NR⁸R¹⁰, cyano, or nitro; C₁-C₈ alkyl substituted with CO₂R⁸; C₁-C₁₈ alkoxy; C₁-C₁₈ haloalkoxy; C₃-C₁₈ alkynyloxy; C₃-C₁₈ alkenyloxy; C₁-C₁₈ alkylthio; C₃-C₁₈ alkenylthio; or C₃-C₁₈ alkynylthio;

R² is C₁-C₁₈ alkyl; C₃-C₇ cycloalkyl; C₃-C₁₈

alkenyl; C₃-C₁₈ alkynyl; C₁-C₁₈ haloalkyl;

C₃-C₁₈ haloalkenyl; C₃-C₁₈ haloalkynyl; C₂-C₁₈ alkoxyalkyl; C₂-C₁₈ alkylthioalkyl; C₂-C₁₈ alkylsulfinylalkyl; C₂-C₁₈ alkylsulfonylalkyl;

C₄-C₁₈ cycloalkylalkyl; C₄-C₁₈ alkenyloxyalkyl; C₄-C₁₈ alkynyloxyalkyl; C₄-C₁₈ cycloalkyloxyalkyl; C₄-C₁₈ alkenylthioalkyl; C₄-C₁₈ alkynylthioalkyl; C₆-C₁₈ cycloalkylthioalkyl; C₂-C₁₈ haloalkoxyalkyl; C₃-C₁₈ haloalkenyloxyalkyl;

C₄-C₁₈ haloalkynyloxyalkyl; C₄-C₁₈ alkoxyalkenyl; C₄-C₁₈ alkoxyalkynyl; C₄-C₁₈ alkylthioalkenyl; C₄-C₁₈ alkylthioalkynyl; C₄-C₁₈ trialkylsilylalkyl; C₁-C₁₈ alkyl substituted with NR⁸R¹⁰; C₂-C₁₈ cyanoalkyl; C₂-C₁₈

nitroalkyl; C₁-C₈ alkyl substituted with CO₂R⁸; or phenyl, benzyl, or phenethyl each optionally substituted on the phenyl ring with R¹³; or R¹ and R² can be taken together along with the

optionally substituted with C₁-C₁₂ alkyl;

R³ and R⁵ are each independently hydrogen; halogen;

C₁-C₄ alkyl; C₁-C₄ haloalkyl; C₁-C₄ alkoxy; or

C₁-C₄ haloalkoxy;

R⁴ and R⁶ are each independently hydrogen; halogen;

C₁-C₈ alkyl; C₃-C₈ cycloalkyl; C₂-C₈ alkenyl; C₂-C₈ alkynyl; C₁-C₈ haloalkyl; C₃-C₈

haloalkenyl; C₃-C₈ haloalkynyl; C₁-C₈ alkoxy;

C₁-C₈ haloalkoxy; C₃-C₈ alkenyloxy; C₃-C₈ alkynyloxy; C₁-C₈ alkylthio; C₃-C₈ alkenylthio; C₃-C₈ alkynylthio; C₁-C₈ alkylsulfinyl; C₁-C₈ alkylsulfonyl; C₂-C₈ alkoxyalkyl; C₂-C₈

alkylthioalkyl; C₂-C₈ alkylsulfinylalkyl; C₂-C₈ alkylsulfonylalkyl; C₄-C₈ cycloalkylalkyl;

C₃-C₈ trialkylsilyl; cyano; nitro; CO₂Me;

CO₂Et; or NR¹¹R¹²;

R⁷ is C₁-C₄ alkyl or C₁-C₄ haloalkyl;

R⁸ and R⁹ are each independently C₁-C₄ alkyl;

R⁸ and R¹⁰, or the groups R¹¹ and R¹², can be taken together to form -CH₂CH₂CH₂CH₂-, -CH₂(CH₂)₃CH₂-, -CH₂CH₂OCH₂CH₂-, -CH₂CH(Me)CH₂CH(Me)CH₂-, or -CH₂CH(Me)OCH(Me)CH₂-; and

R¹³ is halogen; C₁-C₄ alkyl, C₁-C₄ alkoxy, or C₁-C₄ haloalkyl;

provided that:

ii) the total number of carbons in R³, R⁴, R⁵ and R⁶ is equal to or less than 16; iϋ) the total number of nitrogen atoms

incorporated into the bicyclic

framework is less than or equal to four;

iv) R³ and R⁴ are not both hydrogen; and v) X and Y are not both nitrogen.

N-oxides and agriculturally suitable salts thereof.

2. A compound of Claim 1 wherein:

W is O; S; ΝH; or ΝR⁹;

X is CR³;

Y is CR⁴; R¹ is C₁-C₈ alkyl; C₂-C₈ alkenyl; C₂-C₈ alkynyl; C₁-C₈ haloalkyl; C₂-C₈ haloalkenyl; C₂-C₈ alkoxyalkyl; C₂-C₈ alkylthioalkyl; C₄-C₈ cycloalkylalkyl; C₂-C₈ cyanoalkyl; C₁-C₈ alkoxy; C₁-C₁₈ haloalkoxy; C₃-C₈ alkenyloxy; C₃-C₈ alkenylthio; or C₄-C₈ alkenyloxyalkyl; R² is C₁-C₈ alkyl; C₂-C₈ alkenyl; C₂-C₈

alkynyl; C₁-C₈ haloalkyl; C₂-C₈ haloalkenyl; C₂-C₈ alkoxyalkyl; C₂-C₈ alkylthioalkyl; C₄-C₈ cycloalkylalkyl; C₂-C₈ cyanoalkyl; C₄-C₈ alkenyloxyalkyl; or phenyl optionally substituted with R¹³; and

R⁴ and R⁶ are each independently hydrogen; halogen; C₁-C₈ alkyl; C₃-C₈ cycloalkyl; C₁-C₈ haloalkyl; C₁-C₈ alkoxy; C₁-C₈ haloalkoxy; C₁-C₈ alkylthio; C₁-C₈ alkylsulfonyl; C₂-C₈ alkoxyalkyl; C₂-C₈ alkylthioalkyl; C₄-C₈ cycloalkylalkyl;

C₃-C₈ trialkylsilyl; or cyano.

3. A compound of Claim 2 wherein:

Q is O;

W is O; S; NH; or NMe;

Z is CR⁵=CR⁶; CR⁵=N; S; or O;

R¹ is C₁-C₈ alkyl; C₂-C₈ alkenyl; C₂-C₈

alkynyl; C₁-C₈ haloalkyl; C₂-C₈ haloalkenyl; C₁-C₈ alkoxy; C₂-C₈ alkoxyalkyl; or C₃-C₈ alkenyloxy;

R² is C₁-C₈ alkyl; C₂-C₈ alkenyl; C₂-C₈

alkynyl; C₁-C₈ haloalkyl; C₂-C₈ haloalkenyl; C₂-C₈ alkoxyalkyl; or phenyl optionally substituted with R¹³; and R⁴ and R⁶ are each independently hydrogen; halogen; C₁-C₈ alkyl; C₁-C₈ haloalkyl; C₁-C₈ alkoxy; C₁-C₈ haloalkoxy; C₃-C₈ trialkylsilyl; or cyano.

4. A compound of Claim 3 wherein:

Z is CR⁵=CR⁶ or S;

R¹ is C₁-C₈ alkyl; C₂-C₈ alkenyl; C₂-C₈

alkynyl; C₁-C₈ haloalkyl; or C₂-C₈ haloalkenyl;

R² is C₁-C₈ alkyl; C₂-C₈ alkenyl; C₂-C₈

alkynyl; C₁-C₈ haloalkyl; C₂-C₈

haloalkenyl; or phenyl optionally

substituted with R¹³; and

5. A compound of Claim 4 which is

7-bromo-3-(n-propyl)-1-(n-propyloxy)-4H- pyrido[1,2-a]pyrimidin-4-one;

7,9-dibromo-3-(n-propyl)-2-(n-propyloxy)-4H- pyrido[1,2-a]pyrimidin-4-one; or

7-iodo-3-(n-propyl)-2-(n-propyloxy)-4H- pyrido[1,2-a]pyrimidin-4-one.

6. A fungicidal composition comprising an effective amount of a compound of Formula I

wherein:

Q is O or S;

W is O; S; S (O); S(O)₂; NH; or NR⁹;

X is CR³ or N;

Y is CR⁴ or N; Z is CR⁵=CR⁶; CR⁵=N; N=CR⁶; S; O; or NR⁷; having the directionality of the CR⁵=CR⁶, CR⁵=N and N=CR⁶ linkages such that the moiety depicted on the left side of the double bond is bonded to Y and the moiety on the right side of the double bond is bonded to the ring junction;

R¹ is C₁-C₁₈ alkyl; C₃-C₇ cycloalkyl; C₂-C₁₈

alkenyl; C₂-C₁₈ alkynyl; C₁-C₁₈ haloalkyl;

C₂-C₁₈ haloalkenyl; C₂-C₁₈ haloalkynyl; C₂-C₁₈ alkoxyalkyl; C₂-C₁₈ alkylthioalkyl; C₂-C₁₈ alkylsulfinylalkyl; C₂-C₁₈ alkylsulfonylalkyl; C₄-C₁₈ cycloalkylalkyl; C₄-C₁₈ alkenyloxyalkyl; C₄-C₁₈ alkynyloxyalkyl; C₄-C₁₈ cycloalkyloxyalkyl; C₄-C₁₈ alkenylthioalkyl; C₄-C₁₈

alkynylthioalkyl; C₆-C₁₈ cycloalkylthioalkyl;

C₂-C₁₈ haloalkoxyalkyl; C₃-C₁₈ haloalkenyloxyalkyl; C₄-C₁₈ haloalkynyloxyalkyl; C₄-C₁₈ alkoxyalkenyl; C₄-C₁₈ alkoxyalkynyl; C₄-C₁₈ alkylthioalkenyl; C₄-C₁₈ alkylthioalkynyl;

C₄-C₁₈ trialkylsilylalkyl; C₁-C₁₈ alkyl

substituted with NR⁸R¹⁰, cyano, or nitro; C₁-C₈ alkyl substituted with CO₂R⁸; C₁-C₁₈ alkoxy;

C₁-C₁₈ haloalkoxy; C₃-C₁₈ alkynyloxy; C₃-C₁₈ alkenyloxy; C₁-C₁₈ alkylthio; C₃-C₁₈ alkenylthio; or C₃-C₁₈ alkynylthio;

R² is C₁-C₁₈ alkyl; C₃-C₇ cycloalkyl; C₃-C₁₈

alkenyl; C₃-C₁₈ alkynyl; C₁-C₁₈ haloalkyl;

C₄-C₁₈ haloalkynyloxyalkyl; C₄-C₁₈ alkoxy alkenyl; C₄-C₁₈ alkoxyalkynyl; C₄-C₁₈ alkylthioalkenyl; C₄-C₁₈ alkylthioalkynyl; C₄-C₁₈ trialkylsilylalkyl; C₁-C₁₈ alkyl substituted with NR⁸R¹⁰; C₂-C₁₈ cyanoalkyl; C₂-C₁₈ nitro- alkyl; C₁-C₈ alkyl substituted with CO₂R⁸; or phenyl, benzyl, or phenethyl each optionally substituted on the phenyl ring with R¹³; or R¹ and R² can be taken together along with the

optionally substituted with C₁-C₁₂ alkyl;

R³ and R⁵ are each independently hydrogen; halogen;

C₁-C₄ alkyl; C₁-C₄ haloalkyl; C₁-C₄ alkoxy; or C₁-C₄ haloalkoxy;

R⁴ and R⁶ are each independently hydrogen; halogen;

C₁-C₈ alkyl; C₃-C₈ cycloalkyl; C₂-C₈ alkenyl; C₂-C₈ alkynyl; C₁-C₈ haloalkyl; C₃-C₈ haloalkenyl; C₃-C₈ haloalkynyl; C₁-C₈ alkoxy; C₁-C₈ haloalkoxy; C₃-C₈ alkenyloxy; C₃-C₈ alkynyloxy;

C₁-C₈ alkylthio; C₃-C₈ alkenylthio; C₃-C₈ alkynylthio; C₁-C₈ alkylsulfinyl; C₁-C₈ alkylsulfonyl; C₂-C₈ alkoxyalkyl; C₂-C₈ alkylthioalkyl; C₂-C₈ alkylsulfinylalkyl; C₂-C₈ alkylsulfonylalkyl; C₄-C₈ cycloalkylalkyl; C₃-C₈ trialkylsilyl; cyano; nitro; CO₂Me; CO₂Et; or NR¹¹R¹².

R⁷ is C₁-C₄ alkyl or C₁-C₄ haloalkyl;

R⁸ and R⁹ are each independently C₂-C₄ alkyl;

R⁸ and R¹⁰, or the groups R¹¹ and R¹², can be taken together to form -CH₂CH₂CH₂CH₂-, -CH₂(CH₂)₃CH₂-, -CH₂CH₂OCH₂CH₂-, -CH₂CH(Me)CH₂CH(Me)CH₂-, or -CH₂CH(Me)OCH(Me)CH₂-; and R¹³ is halogen; C₁-C₄ alkyl, C₁-C₄ alkoxy, or C₁-C₄ haloalkyl;

provided that :

incorporated into the bicyclic

framework is less than or equal to four;

iv) R³ and R⁴ are not both hydrogen; and v) X and Y are not both nitrogen; and at least one of (a) a surfactant, (b) an organic solvent, and (c) at least one solid or liquid diluent.

7. A method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof to be protected, to the media in which the plant to be protected is growing, or to the plant seed or seedling to be protected an effective amount of a compound of Formula I

wherein:

Q is O or S;

W is O; S; S (O); S(O)₂; NH; or NR⁹;

X is CR³ or N;

R¹ is C₁-C₁₈ alkyl; C₃-C₇ cycloalkyl; C₂-C₁₈

alkenyl; C₂-C₁₈ alkynyl; C₁-C₁₈ haloalkyl;

C₂-C₁₈ haloalkenyl; C₂-C₁₈ haloalkynyl; C₂-C₁₈ alkoxyalkyl; C₂-C₁₈ alkylthioalkyl; C₂-C₁₈ alkylsulfinylalkyl; C₂-C₁₈ alkylsulfonylalkyl; C₄-C₁₈ cycloalkylalkyl; C₄-C₁₈ alkenyloxyalkyl; C₄-C₁₈ alkynyloxyalkyl; C₄-C₁₈ cycloalkyloxyalkyl; C₄-C₁₈ alkenylthioalkyl; C₄-C₁₈ alkynylthioalkyl; C₆-C₁₈ cycloalkylthioalkyl; C₂-C₁₈ haloalkoxyalkyl; C₃-C₁₈ haloalkenyloxyalkyl; C₄-C₁₈ haloalkynyloxyalkyl; C₄-C₁₈ alkoxyalkenyl; C₄-C₁₈ alkoxyalkynyl; C₄-C₁₈ alkylthioalkenyl; C₄-C₁₈ alkylthioalkynyl; C₄-C₁₈

trialkylsilylalkyl; C₁-C₁₈ alkyl substituted with NR⁸R¹⁰, cyano, or nitro; C₁-C₈ alkyl substituted with CO₂R⁸; C₁-C₁₈ alkoxy; C₁-C₁₈ haloalkoxy; C₃-C₁₈ alkynyloxy; C₃-C₁₈ alkenyloxy; C₁-C₁₈ alkylthio; C₃-C₁₈ alkenylthio; or C₃-C₁₈ alkynylthio;

R² is C₁-C₁₈ alkyl; C₃-C₇ cycloalkyl; C₃-C₁₈

alkenyl; C₃-C₁₈ alkynyl; C₁-C₁₈ haloalkyl;

C₄-C₁₈ haloalkynyloxyalkyl; C₄-C₁₈ alkoxy alkenyl; C₄-C₁₈ alkoxyalkynyl; C₄-C₁₈ alkylthioalkenyl; C₄-C₁₈ alkylthioalkynyl; C₄-C₁₈ trialkylsilylalkyl; C₁-C₁₈ alkyl substituted with NR⁸R¹⁰; C₂-C₁₈ cyanoalkyl; C₂-C₁₈

optionally substituted with C₁-C₁₂ alkyl;

R³ and R⁵ are each independently hydrogen; halogen;

R⁴ and R⁶ are each independently hydrogen; halogen;

haloalkenyl; C₃-C₈ haloalkynyl; C₁-C₈ alkoxy; C₁-C₈ haloalkoxy; C₃-C₈ alkenyloxy; C₃-C₈ alkynyloxy; C₁-C₈ alkylthio; C₃-C₈ alkenylthio; C₃-C₈ alkynylthio; C₁-C₈ alkylsulfinyl; C₁-C₈ alkylsulfonyl; C₂-C₈ alkoxyalkyl; C₂-C₈

C₃-C₈ trialkylsilyl; cyano; nitro; CO₂Me;

CO₂Et; or NR¹¹R¹²;

R⁷ is C₁-C₄ alkyl or C₁-C₄ haloalkyl;

R⁸ and R⁹ are each independently C₁-C₄ alkyl;

provided that:

incorporated into the bicyclic

framework is less than or equal to four;

iv) R³ and R⁴ are not both hydrogen; and v) X and Y are not both nitrogen; or

N-oxides or agriculturally suitable salts thereof.

8. A method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof to be protected, to the media in which the plant to be protected is growing, or to the plant seed or seedling to be protected an effective amount of a composition of Claim 6.

9. A method for controlling wheat powdery mildew comprising applying to the plant or portion thereof to be protected, to the media in which the plant to be protected is growing, or to the plant seed or seedling to be protected an effective amount of a compound of Claim 1.

10. A method for controlling wheat powdery mildew comprising applying to the plant or portion thereof to be protected, to the media in which the plant to be protected is growing, or to the plant seed or seedling to be protected an effective amount of a composition of Claim 6.