WO1993022311A1

WO1993022311A1 - Fungicidal 1,3,4-oxadiazines and 1,3,4-thiadiazines

Info

Publication number: WO1993022311A1
Application number: PCT/US1993/003583
Authority: WO
Inventors: Deborah Ann Frasier; Gerard Michael Koether; Zen-Yu Chang
Original assignee: E.I. Du Pont De Nemours And Company
Priority date: 1992-04-27
Filing date: 1993-04-22
Publication date: 1993-11-11
Also published as: CN1078722A; AU4288293A

Abstract

Fungicidal 1,3,4-oxadiazines and 1,3,4-thiadiazines of general formula (I) are disclosed, wherein G?1 is -CR1R7¿-, -(CHR1CHR2)-, -(CHR?1CHR2CHR3¿)-, or -(CHR?1CHR2CHR3CHR4)-; G2¿ is -O-, -S-, -S(O)-, -S(O)¿2?-, or -NR?27-; G3 is -CR4R8¿-, -(CHR5CHR6)-, or -(CHR?3CHR5CHR6¿)- or a direct bond; X is N or CR13; Y is N or CR13; and E, R?9, and R10¿ are various groups.

Description

TITLE

FUNGICIDAL 1 ,3 ,4-OXADIAZINES AND 1 ,3 ,4-THIADIAZINES

This invention relates to heterocyclic thiadiazines arid related heterocycles useful as agricultural

fungicides and compositions containing them.

BACKGROUND OF THE INVENTION

U . S . S . R. patent 461 , 929 generically discloses oxadiazines of Formula i and ii

wherein:

R¹, R³, R⁴, R⁵, and R⁶ are hydrogen, alkyls,

carboxyalkyls, aminoalkyls, phenyl, substituted phenyls, pyridyls, quinolyls, furyls, or thienyls, and

R² is alkyl, substituted alkyl, phenyl, substituted phenyl, or heteroaryl.

U.S.S.R. 461,929 does not specifically name any of the compounds of the instant invention, nor is any utility for the compounds disclosed, in this patent.

SUMMARY OF THE INVENTION

This invention pertains to compounds of Formulae I, II, III and IV including all geometric and stereo-ispmers, agriculturally-suitable salts thereof,

agriculturally-suitable metal complexes thereof, compositions containing them and their use as

fungicides.

wherein:

-G¹-G²-G³- taken together with the attached atoms form a 5-8 membered ring, wherein

-G¹- is -CR¹R⁷-; -(CHR¹CHR²)-; - (CHR¹CHR²CHR³)-; or - (CHR¹CHR²CHR³CHR⁴) -;

-G²- is -O-; -S-; -S(O)-; -S(O)₂- or -NR²⁷-;

-G³- is -CR⁴R⁸; (CHR⁵CHR⁶) -; - (CHR³CHR⁵CHR⁶) - or a direct bond;

For example, -G¹-G²-G³- can be

-CHR¹CHR²-S-CR⁴R⁸-, wherein -G¹- is

-(CHR¹CHR²)-, -G²- is -S-, and -G³- is -CR⁴R⁸-.

The directionality of the -G¹-G²-G³- linkage is defined as -G¹-G²-G³- in compounds of Formulae I and III and -G³-G²-G¹- in compounds of Formulae II and IV. Therefore, for example, when -G¹- is -(CHR¹CHR²)- in a compound of

Formula I or III, then the carbon of the CHR² unit of -G¹- is bonded to -G²-. In a compound of Formula II or IV, when -G¹- is - (CHR¹CHR²) , the carbon of the CHR¹ unit is bonded to -G²-. X is N or CR¹³;

Y is N or CR¹⁴;

E is H; C₁-C₆ alkyl; C₃-C₇ cycloalkyl optionally substituted with 1-2 methyl; C₁-C₆ haloalkyl; C₁-C₆ alkylthio; C₁-C₆ alkoxy; C₁-C₆ haloalkoxy; or phenyl, phenoxy, phenylthio, phenylamino, phenylmethyl, indanyl, tetrahydronaphthalenyl, 1-naphthalenyl, 2-naphthalenyl, thienyl, furanyl or pyridyl each optionally substituted with R¹¹, R¹² and R²⁸;

R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ are each

independently H; C₁-C₄ alkyl; C₁-C₄ haloalkyl, halogen, CO₂CH₃, CO₂CH₂CH₃, cyano or phenyl optionally substituted with R²⁵;

provided that

(i) when -G¹- = -CR¹R⁷- and -G³- = -CR⁴R⁸-, then at least one of R¹, R⁴, R⁷ and R⁸ is hydrogen; in other words the maximum number of carbon atoms in -G¹-G²-G³- with geminal disubstitution is one;

(ii) the maximum number of optionally

substituted phenyl substituents on

-G¹-G²-G³- is one;

(iii) -G³- is other than a direct bond in

compounds of Formulae III and IV; and (iv) -G²-G³- is other than -NR²⁷- in compounds of Formulae I and II;

R⁹, R¹⁰ and R¹³ are each independently H; halogen; cyano; hydroxy; C₁-C₆ alkyl; C₁-C₄ haloalkyl; C₁-C₄ alkylthio; C₁-C₄ alkylsulfinyl; C₁-C₄ alkylsulfonyl; C₃-C₆ cycloalkyl optionally substituted with 1-2 methyl groups; C₁-C₄ alkoxy; C₁-C₄ haloalkoxy; C₂-C₄ alkoxyalkyl;

C₂-C₄ alkenyl; C₂-C₄ haloalkenyl; C₂-C₄ alkenyloxy; C₂-C₄ alkynyl; C₂-C₄ alkynyloxy; NR²⁹R³⁰; or phenyl or phenoxy optionally substituted with R³¹; or

R⁹ and R¹³, or R¹⁰ and R¹³, or R⁹ and R¹⁴ can be

taken together to form - (CH₂)₃-, -(CH₂)₄- or a fused benzene ring optionally substituted with R³¹;

R¹¹, R¹², R²¹, R²⁴, R²⁶ and R³¹ are each

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

R¹⁴ is H; halogen; C₁-C₂ alkyl; or C₁-C₂ alkoxy; R¹⁵, R¹⁶, R¹⁷, R¹⁸, R²⁹ and R³⁰ are each

independently H or C₁-C₂ alkyl; or

R¹⁵ and R¹⁶, or R¹⁷ and R¹⁸, or R²⁹ and R³⁰ can be taken together along with the nitrogen atom to which they are attached to form a

4-morpholinyl, pyrrolidinyl or piperidinyl ring;

R²⁰ and R²⁷ are each independently H; C₁-C₄ alkyl;

C₁-C₄ haloalkyl; C₂-C₅ alkylcarbonyl; phenylcarbonyl optionally substituted with R²¹; C₃-C₄ alkenyl; C₃-C₄ alkynyl; phenylmethyl optionally substituted with R²¹ on the phenyl ring; C₁-C₄ alkylsulfinyl; C₁-C₄ alkylsulfonyl; phenylsulfinyl, phenylsulfonyl or phenoxycarbonyl each optionally substituted with R²¹; C₂-C₄ alkoxycarbonyl; C(=O)NR²²R²³; C(=S)NHR²³;

P (=S) (C₁-C₄ alkoxy)₂; P (=O) (C₁-C₄ alkoxy)₂; or S(=O)₂NR²²R²³;

R²² is H or C₁-C₃ alkyl;

R²³ is C₁-C₄ alkyl; or phenyl optionally

substituted with R²⁴; or

R²² and R²³ can be taken together along with the nitrogen atom to which they are attached to form a 4-morpholinyl, pyrrolidinyl, piperidinyl or imidazolyl ring; R²⁵ is 1-2 halogen; C₁-C₄ alkyl; C₁-C₄ haloalkyl; C₁-C₄ alkoxy; C₁-C₄ haloalkoxy; nitro; cyano or C₁-C₄ alkylthio;

R²⁸ is halogen; cyano; nitro; hydroxy;

hydroxycarbonyl; C₁-C₆ alkyl; C₃-C₆ cycloalkyl; C₁-C₆ haloalkyl; C₁-C₄ alkylthio; C₁-C₄ alkylsulfinyl; C₁-C₄ alkylsulfonyl; (C₁-C₄ alkyl) 3- silyl; C₂-C₅ alkylcarbonyl; C₂-C₄ alkenyl; C₃-C₄ alkenyloxy; C₂-C₄ alkynyl; C₃-C₄ alkynyloxy; C₁-C₄ alkoxy; C₁-C₄ haloalkoxy; C₂-C₄ alkoxyalkyl; C₂-C₅ alkoxycarbonyl; C₂-C₄ alkoxyalkoxy; NR¹⁵R¹⁶; C(=O)NR¹⁷R¹⁸; or phenyl, phenoxy or phenylthio each optionally

substituted with R²⁶;

provided that

when E is, C₁-C₆ alkylthio, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy, phenoxy, phenylthio or phenylamino, then E may only substitute compounds of Formula I.

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

"Alkenyl" denotes straight-chain or branched alkenes; e.g., 1-propenyl, 2-propenyl, 3-propenyl and the different butenyl, pentenyl and hexenyl isomers. "Alkenyl" also denotes polyenes such as 1,3-hexadiene and 2,4,6-heptatriene.

"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.

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

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

2,5, 8-decatriyne.

"Alkynyloxy" denotes straight-chain or branched alkynyloxy moieties. Examples include HC≡CCH₂O,

CH₃C≡CCH₂O and CH₃C≡CCH₂CH₂O.

"Alkylthio" denotes branched or straight-chain alkylthio moieties; e.g. methylthio, ethylthio, and the different propylthio, butylthio, pentylthio and

hexylthio isomers.

Examples of "alkylsulfonyl" include CH₃SO₂,

CH₃CH₂SO₂, CH₃CH₂CH₂SO₂, (CH₃)₂CHSO₂ and the different butylsulfonyl, pentylsulfonyl and hexylsulfonyl

isomers.

"Alkylsulfinyl" denotes both enantiomers of an alkylsulfinyl group. For example, CH₃SO, CH₃CH₂SO, CH₃CH₂CH₂SO, (CH₃)₂CHSO and the different butylsulfinyl, pentylsulfinyl and hexylsulfinyl isomers.

"Alkoxy" denotes, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers.

"Cycloalkyl" denotes, for example, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

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.

Examples of "haloalkynyl" include HC≡CCHCl, CF₃C≡C, CCl₃C≡C and FCH₂C≡CCH₂. Examples of "haloalkoxy" include CF₃O, CCl₃CH₂O, CF₂HCH₂CH₂O and CF₃CH₂O.

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 8. For example, C₁-C₃ alkylsulfonyl 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. Examples of "alkoxycarbonyl" include CH₃OC(=O), CH₃CH₂OC (=O) ,

CH₃CH₂CH₂OC(=O), (CH₃)₂CHOC(=O) and the different butoxy-, pentoxy- or hexyloxycarbonyl isomers.

Preferred for reasons of greatest fungicidal activity and/or ease of synthesis are

1. Compounds of Formula I wherein:

Y is N;

E is phenyl, indanyl, tetrahydronaphthalenyl,

1-naphthalenyl, thienyl, or pyridyl each optionally substituted with R¹¹, R¹² and

_R28.

R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ are each

independently H or methyl;

R¹¹ and R¹² are each independently F, Cl,

methyl, trifluoromethyl, methoxy or trifluoromethoxy;

R¹³ is H;

R⁹ and R¹⁰ are each independently halogen;

C₁-C₄ alkyl; cyclopropyl; C₁-C₄ haloalkyl; allyl; or C₂-C₃ alkynyl; or

R⁹ and R¹³ can be taken together to form a

fused benzene ring optionally substituted with R³¹;

R²⁸ is halogen; cyano; C₁-C₄ alkyl; C₁-C₄

haloalkyl; allyl; propargyl; C₁-C₄ alkoxy; C₁-C₄ haloalkoxy; or phenyl or phenoxy each optionally substituted with R²⁶;

R³¹ is halogen; C₁-C₄ alkyl or C₁-C₄ haloalkyl;

and agriculturally-suitable metal complexes thereof.

2. Compounds of Formula III wherein:

Y is N

E is phenyl, indanyl, tetrahydronaphthalenyl, 1-naphthalenyl, thienyl, or pyridyl each optionally substituted with R¹¹, R¹² and R28.

R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ are each

independently H or methyl;

R⁹ and R¹⁰ are each independently halogen;

R⁹ and R¹³ can be taken together to form a fused benzene ring optionally substituted with R³¹;

R¹¹ and R¹² are each independently F, Cl,

methyl, trifluoromethyl, methoxy or trifluoromethoxy;

R¹³ is H;

R²⁰ is H;

R²⁷ is H; C₁-C₄ alkyl; C₂-C₅ alkoxycarbonyl;

C₃-C₄ alkenyl or C₃-C₄ alkynyl;

R²⁸ is halogen; cyano; C₁-C₄ alkyl; C₁-C₄

R³¹ is halogen; C₁-C₄ alkyl or C₂-C.₄ haloalkyl;

and agriculturally-suitable metal complexes thereof. 3. Compounds of Preferred 1 wherein:

G² is O; S or NR²⁷;

E is phenyl optionally substituted with R¹¹, R¹² and R²⁸; indanyl or tetrahydronaphthalenyl; and agriculturally-suitable metal complexes thereof.

4. Compounds of Preferred 3 wherein:

G² is O; S; NH or N(C₁-C₄ alkyl);

E is phenyl optionally substituted with R¹¹, R¹² and R²⁸; and agriculturally-suitable metal complexes thereof.

Specifically preferred for greatest fungicidal activity and/or ease of synthesis are:

3-(4,6-dimethyl-2-pyrimidinyl)-3,6-dihydro-5- phenyl-2H-1,3,4-oxadiazine

3-(4,6-dimethyl-2-pyrimidinyl)-5-(4-ethylphenyl)- 3,6-dihydro-2H-1,3,4-oxadiazine 2-(2-chlorophenyl)-4-(4,6-dimethyl-2- pyrimidinyl)-5,6-dihydro-4H-l,3,4-thiadiazine

4-(4,6-dimethyl-2-pyrimidinyl)-2-(4-ethylphenyl)- 5,6-dihydro-4H-1,3,4-thiadiazine

DETAILED DESCRIPTION OF THE INVENTION

Compounds of Formula I wherein E is as described in the Summary of the Invention except that E is not phenoxy, phenylthio, phenylamino, C₁-C₆ alkoxy, C₁-C₆ alkylthio and C₁-C₆ haloalkoxy can be prepared by one or more of the methods described in Equations 1-6 and 13.

Compounds of Formula 2 in Equation 1 can be

prepared by reacting hydrazine 1 with an acid chloride and a base such as pyridine or triethylamine at 0°C in a solvent such as dichloromethane, THF, or pyridine (Equation 1). The hydrazines 1 are known in the literature (J. Pest . Sci . , 1990, 15, 13) and can be prepared by one skilled in the art as taught in EP 293,743-A and by Naito et al. in Chem . Pharm. Bull. , 1969, 17, 1467.

Equation 1

Compounds of Formula 4 can be prepared by treatment of hydrazides of Formula 2 with P₂S₅ in pyridine at reflux for 1-2 h to form thiohydrazides of Formula 3, followed by reaction with an appropriate alkylating agent, wherein L can be Cl, Br, I or tosylate, in the presence of two equivalents of base, such as triethylamine (Equation 2). In some cases, additional base such as sodium hydride is necessary to induce

cyclization. The cyclization reaction is typically performed at 25° to 100°C in an inert aprotic solvent such as THF or acetonitrile.

Equation 2

Compounds of Formula 5 can be prepared similarly by treatment of hydrazides of Formula 2 with an alkylating agent and two equivalents of base using the cyclization procedure previously described for the preparation of compounds of Formula 4 (Equation 3).

Equation 3

Compounds of Formula 7 can be prepared by the reaction of hydrazines of Formula 1 with ketones of Formula 6 in a solvent such as acetonitrile, dichloromethane or acetic acid. The desired heterocycles of Formula 8 can be formed by treatment of the resulting product with a ketone or aldehyde in the presence of a catalytic amount of acid such as butanesulfόnic acid (Equation 4). This reaction is typically conducted at 25° to 100°C in an anhydrous organic solvent such as THF or acetonitrile for 12 to 24 h.

Equation 4

Compounds of Formula 6 wherein m=l and Q=O can be prepared by α-hydroxylation of a methyl ketone with iodosobenzene as described by Moriarty et al. in

Tetrahedron Lett . , 1981, 22, 1283.

Thiols of Formula 7b and amines of Formula 7c can be prepared as outlined in Equation 5. Alcohols of Formula 7a (Q=O) can be converted to the corresponding mesylate by methods known in the art. The mesylates can be treated with sodium sulfide to form the thiols 7b, or they can be reacted with potassium phthalimide and then hydrazine to form amines of Formula 7c. Equation 5

Formation of heterocycles of Formula 9 can be accomplished by treatment of hydrazones of Formula 7 with the appropriate alkylating agent as previously described for the preparation of heterocycles of Formula 4 (Equation 6).

Equation 6

Compounds of Formula I wherein E is phenoxy, phenylthio, phenylamino, C₁-C₆ alkoxy, C₁-C₆ alkylthio or C₁-C₆ haloalkoxy can be prepared by one or more of the methods described in Equations 7-13.

Heterocycles of Formula 11 can be prepared by treating methylthio-substituted compounds of Formula 10 with various nucleophiles in the presence of a base. Suitable nucleophiles can be optionally substituted phenols, thiophenols, or anilines, C₁-C₆ alkylthiols, C₁-C₆ alcohols and C₁-C₆ halo-substituted alcohols (Equation 7).

Equation 7

Nu = optionally substituted phenol, thiophenol, or aniline; C₁-C₆ alkylthiol; C₁-C₆ alcohol, C₁-C₆ halo-substituted alcohol

n = 0,1,2,3

Q = O,S,N-R²⁷

R,R^a,R^b = R¹,R²,R³,R⁴,R⁷

The methythio-substituted heterocycles of Formula 10 can be synthesized by reaction of carbazates of Formula 12 with an alkylating agent in the presence of two equivalents of base, such as triethylamine

(Equation 8). This type of cyclization was described previously for the preparation of compounds of Formula 4 (Equation 2). Compounds of Formula 12 are known in the literature and can be prepared by one skilled in the art (e.g., see G. W. Stacy, "Heterocyclic

Compounds," R. C. Elderfield, ed., Wiley, NY, 1961, vol. 7, p 835).

Equation 8

Alternatively, compounds of Formula 10a can be prepared by sequential treatment of carbazates of

Formula 13 with P₂S₅ and iodomethane in pyridine

(Equation 9). Carbazates of Formula 13 are known in the literature (e.g., see Dox, J. Am . Chem. Soc. , 1926, 48, 1951).

Equation 9

Methylthio-substituted heterocycles of Formula 15 can be prepared by treating hydrazides of Formula 14 with P₂S₅ in pyridine at reflux and then alkylating the resulting thio derivative with iodomethane in the presence of a base such as triethylamine (Equation 10). Reaction of compounds of Formula 15 with nucleophiles and base, as previously described for the preparation of compounds of Formula 11 in Equation 7 , yields products of Formula 16. The seven-membered ring analogs , compounds of Formula 17, can be prepared from hydrazides of Formula 14a by the same procedure

(Equation 10) .

Equation 10

Treatment of hydrazides of Formula 19 with an aldehyde or ketone in the presence of. a catalytic amount of acid, such as butanesulfonic acid, yields heterocycles of Formula 14 (Equation 11 ) . The

cyclization is typically performed at 25 ° to 100°C in an anhydrous organic solvent such as THF or

acetonitrile.

Equation 11

Compounds of Formula 19a (Q=O) can be synthesized by condensing hydrazine 1 with hydroxyacids of Formula 18 in the presence of a dehydrating agent such as dicyclohexylcarbodiimide in an inert aprotic solvent such as THF or dichloromethane. Hydroxyacids of

Formula 18 are well-known to one skilled in the art. Thiols of Formula 19b (Q=S) and amines of Formula 19c (Q=NR²⁷) can be prepared by forming the mesylate of alcohols of Formula 19a followed by displacement with nucleophiles in a manner similar to that previously described for the preparation of compounds of Formulae 7b and 7c (Equation 5).

Compounds of 14a can be prepared by treatment of hydrazides of Formula 19d (m=l) with the appropriate alkylating agent, as illustrated in Equation 12, according to procedures described above (see Equations 2 and 3). Equation 12

Compounds of Formula lb wherein G² is S(O) or S(O)₂ can be prepared from the corresponding thio analogue la by well-known methods for oxidation of sulfur (Equation 13). Typical reagents for this type of oxidation include m-chloroperoxybenzoic acid, hydrogen peroxide, sodium metaperiodate, and OXONE^® (potassium peroxymono-. sulfate).

Equation 13

Compounds of Formula II can be prepared by one or more of the following methods described in Equations 14-19.

Hydrazides of Formula 22 can be synthesized by the reaction of hydrazine 21 with an acid chloride of Formula 20 in the presence of a base such as triethylamine or pyridine (Equation 14). Typical solvents for this reaction are dichloromethane and THF.

Equation 14

The acid chloride of Formula 20 can be prepared by treatment of the corresponding carboxylic acid with thionyl chloride. Methods for preparing acid chlorides from carboxylic acids are well-known in the literature.

Procedures for preparing pyrimidine carboxylic acids are described by Sakamoto, T., and Yamanaka, H. in Heterocycles, 1981, 15,, 583.

Heterocycles of Formula 24 can be prepared by treating hydrazides of Formula 22 with P₂S₅ in pyridine at reflux to form the thiohydrazides of Formula 23, followed by reaction of 23 with an alkylating agent in the presence of two equivalents of base such as

triethylamine (Equation 15). Typically, these

reactions are conducted at 25° to 100°C in an inert aprotic solvent such as THF or acetonitrile.

Equation 15

Compounds of Formula 25 can be prepared similarly by treatment of hydrazides of Formula 22 with an alkylating agent and two equivalents of base according to the previously described cyclization procedure (Equation 16).

Equation 16

Compounds of Formula 28 can be synthesized by the reaction of hydrazines of Formula 21 with ketones of Formula 26 in a solvent such as dichloromethane or acetonitrile to form hydrazones of Formula 27 (Equation 17). The hydrazone can then be treated with a ketone or aldehyde in the presence of a catalytic amount of acid, such as butanesulfonic acid, to form cycloadducts of Formula 28. This reaction is typically carried out at 25° to 100°C in an anhydrous organic solvent such as THF or acetonitrile.

Equation 17

Hydroxyketones of Formula 26a (Q=O, m=l) can be prepared by α-hydroxylation of the corresponding methyl ketone 29 with iodosobenzene as described by Moriarty et al. in Tetrahedron Lett. , 1981, 22, 1283, and illustrated in Equation 18. Methods to prepare

heteroaryl ketones of Formula 29 are well-known in the art. The corresponding thiols of Formula 26b (Q=S) and amines of Formula 26c (Q=NR²⁷) can be prepared by methods previously described for thiols and amines of Formulae 7b and 7c, respectively (Equation 5). Equation 18

Compounds of Formula IIb can be synthesized from the corresponding thio analogue of Formula IIa by oxidation (Equation 19). Typical reagents for this type of oxidation include m-chloroperoxy benzoic acid, hydrogen peroxide, sodium metaperiodate, and OXONE^® (potassium peroxymonosulfate).

Equation 19

Compounds of Formulae IIIa and IVa can be prepared by reduction of compounds of Formulae I and II,

respectively, with sodium borohydride/titanium (IV) chloride according to the procedure taught by Kano et al. in Synthesis, 1980, 695, and set forth in Equation 20. In cases where substituents in compounds of

Formulae I and II are not compatible with the reduction conditions, protection and deprotection techniques, which are well-known in the art may be employed. Equation 20

Compounds of Formulae IIIa and IVa can be capped on nitrogen with various substituents (R²⁰) by treating with the appropriate alkylating, acylating,

sulfonylating or phosphonylating agent of Formula 30 as shown in Equation 21. The leaving group (Lg) in compounds of Formula 30 may be Cl, Br, I, acetate or other moeity known to act as a leaving group.

Typically, these reactions are run in inert solvents such as THF, benzene or dichloromethane in the presence of a tertiary amine base, such as triethylamine, at a temperature ranging from 0° to 100°C.

Equation 21

i

Compounds of Formula IIIb and XVb wherein R²⁰ is C(=O)NR²²R²³ or C(=S)NHR²³ can be prepared by treating compounds of Formulae IIIa or IVa with an isocyanate or isothiocyanate by methods well-known in the art (Equation 22). Typical solvents for this type of reaction are THF, acetonitrile and dichloromethane.

Equation 22

Compounds of Formula 3, as illustrated in Equation 2 , can also be prepared by reacting hydrazine 1 with the appropriate carboxymethyl dithioate 31 in aqueous sodium hydroxide at 25 °C (Equation 23 ) . Carboxymethyl dithioates are known in the literature and can be prepared by one skilled in the art (see Jensen, K. A. and Pedersen, C . , Acta Chemica Scandinavica, 1961 , 15 , 1087 ) .

Equation 23

Likewise, thiohydrazides of Formula 23, as

illustrated in Equation 15, can be synthesized by reaction of a hydrazine of Formula 21 with a carboxymethyl dithioate of Formula 32 in aqueous sodium hydroxide (Equation 24).

Equation 24

Compounds of Formula 11, wherein E is phenoxy or phenylthio, can also be synthesized by treating a hydrazine of Formula 1 with phenyl-chlorothionoformate or phenyl-chlorodithioformate of Formula 33 to form a thiocarbazate hydrochloride of Formula 34 (Equation 25). This type of reaction is typically run in a solvent such a methylene chloride from about -10°C to 0°C. The cyclization is performed by treating 39 with the appropriate alkylating agent in a solvent mixture of aqueous sodium hydroxide and THF at 25°C.

Equation 25

The metal complexes of compounds of Formulae I-IV of the instant invention include complexes with copper, zinc, iron, magnesium, or manganese. These complexes can be formed by combining the compound of Formulae I-IV with the metal salt in either aprotic solvents, such as ether or THF, or protic solvents, such as methanol. EP-A-459,662 discloses metal complexes of other nitrogen containing compounds as agricultural fungicides.

EXAMPLE 1

Preparation of 1-(4-ethylphenyl)-2-hydroxyethanone(4 , 6- dimethyl-2-pyrimidinyl)hydrazone To a solution of 3.57 g (21.7 mmol) of p-ethyl-2-hydroxyacetophenone in 100 mL of acetonitrile was added 3.00 g (21.7 mmol) of 4,6-dimethyl-2-hydrazinopyrimi dine, 3A molecular sieves, and a catalytic amount of butanesulfonic acid. The reaction mixture was stirred overnight at room temperature and then diluted with dichloromethane and chloroform. The organic phase was washed successively with saturated sodium bicarbonate and brine, dried over sodium sulfate, filtered and concentrated. The crude product was passed through a plug of silica gel and triturated with hexanes to yield 3.45 g of product. ¹R NMR (CDCl₃) δ 10.65 (bs, 1H), 7.61 (d, 2H), 7.15 (d, 2H), 6.47 (s, 1H), 6.10 (bs,

1H), 4.86 (S, 2H), 2.64 (q, 2H), 2.38 (s, 6H), 1.22 (t, 3H).

EXAMPLE 2

Preparation of 3-(4,6-dimethyl-2-pyrimidinyl)-5- 4- ethylphenyl)-3,6-dihydro-2H-1,3,4-oxadiazine

A solution of 1.00 g (3.52 mmol) of 1-(4-ethylphenyl)-2-hydroxyethanone(4,6-dimethyl-2-pyrimidinyl)-hydrazone, 0.21 g (7.04 mmol) of paraformaldehyde, and a catalytic amount of butanesulfonic acid was heated at reflux for 3 h in 20 mL of acetonitrile. After

cooling, the reaction mixture was diluted with

dichloromethane and chloroform. The organic phase was washed successively with saturated sodium bicarbonate and brine, dried over sodium sulfate, filtered and concentrated. Chromatography on silica gel gave 70 mg of desired product as a gum. ¹H NMR (CDCl₃) δ 7.66 (d, 2H), 7.21 (d, 2H), 6.56 (s, 1H), 5.54 (s, 2H), 4.81 (S, 2H), 2.67 (q, 2H), 2.42 (s, 6H), 1.24 (t, 3H).

EXAMPLE 3

Preparation of 4-ethylbenzoic acid 2-(4,6-dimethyl-2- pyrimidinyl)hydrazide

4,6-Dimethyl-2-hydrazinopyrimidine (3.72 g,

26.95 mmol) was suspended in 80 mL of pyridine and the reaction mixture was cooled to 10°C. After slowly adding p-ethylbenzoyl chloride (5.00 g, 29.66 mmol), the reaction mixture was allowed to warm to room temperature over 1 h. Addition of ice and water precipitated the product which was filtered and washed with hexanes to yield 6.85 g of a white solid, mp 118-119°C. ¹H NMR (CDCl₃) δ 9.15 (bs, 1H), 7.8 (d, 2H), 7.35 (bs, 1H), 7.2 (d, 2H), 6.52 (s, 1H), 2.7 (q, 2H), 2.33 (s, 6H), 1.23 (t, 3H).

EXAMPLE 4

Preparation of 4-(4,6-dimethyl-2-pyrimidinyl)-2-(4- ethylphenyl)-5,6-dihydro-4H-1,3,4-thiadiazine

A solution of 5.30 g (18.52 mmol) of 4-ethylbenzoic acid 2-(4,6-dimethyl-2-pyrimidinyl)hydrazide and 6.18 g (13.89 mmol) of P₂S₅ in 60 mL of pyridine was heated at reflux for 1.5 h. After cooling, water was added and the reaction mixture was heated briefly at reflux to quench the reaction. The mixture was then cooled with an ice bath to precipitate the product. The solid was filtered and washed with water to give 6.57 g

(21.73 mmol) of thiohydrazide which was then dissolved in 100 mL of THF with 7.5 mL (54.33 mmol) of triethylamine and 2.1 mL (23.91 mmol) of 1,2-dibromoethane. The reaction mixture was heated at reflux overnight. After cooling, water and ether were added and the organic phase was separated and washed with brine. The organic extracts were dried over magnesium sulfate, filtered and concentrated. The crude product was passed through a plug of silica gel to give 200 mg of product as an oil. ¹H NMR (CDCl₃), 7.8 (d_r 2H), 7.2 (d, 2H), 6.53 (s, 1H), 4.45 (m, 2H), 3.35 (m, 2H), 2.67 (q, 2H), 2.41 (s, 6H), 1.22 (t, 3H).

EXAMPLE 5

Preparation of 4-(4,6-dimethyl-2-pyrimidinyl)-5,6- dihydro-2-(3-methylphenyl)-4H-1,3,4-oxadiazine

A solution of 1.00 g (3.89 mmol) of 3-methylbenzoic acid 2-(4,6-dimethyl-2-pyrimidinyl)hydrazide, 0.37 mL (4.28 mmol) of 1,2-dibromoethane, and 1.33 mL

(8.95 mmol) of DBU in 20 mL of dry THF was heated at reflux overnight. After cooling, 2.3 equivalents

(8.95 mmol) of sodium hydride and 0.37 mL (4.28 mmol) of 1,2-dibromoethane were added, and the reaction mixture was heated at reflux overnight. The mixture was allowed to cool to room temperature and saturated aqueous ammonium chloride was added. The product was extracted with dichloromethane and chloroform and the organic phase was washed with brine. The organic extracts were dried over sodium_. sulfate, filtered, concentrated, and passed through a plug of silica gel to give 100 mg of desired product as a gum. ¹H NMR (CDCl₃) δ 7.82 (m, 1H), 7.75 (m, 1H), 7.25 (m, 1H), 7.19 (m, 1H), 6.49 (s, 1H), 4.54 (m, 2H), 4.28 (m, 2H), 2.42 (s, 6H), 2.38 (s, 3H).

EXAMPLE 6

Preparation of 4-methoxybenzenecarbothioic acid

O-[2-(4,6-dimethyl-2-pyrimidinyl)hydrazide 4,6-Dimethyl-2-hydrazinopyrimidine (p-methoxythiobenzoylthio) acetic acid (2.00 g), 14.49 mmol) and p-methoxyphenylcarboxymethyldithioate (3.48 g,

14.4 mmol) were dissolved in 20 mL of 1N aqueous sodium hydroxide and 10 mL of water. The reaction mixture was stirred at 25°C for 16 h and then acidified with 1N HCl. The resultant precipitate was filtered, washed with water, and dried under vacuum to give 3.22 g

(11.2 mmol, 78%) of the title hydrazide as a white solid, m.p. 212-215°C ¹H NMR (CDCl₃) δ 9.5 (bs, 1H), 7.85 (d, 2H), 6.95 (d, 2H), 6.57 (s, 1H), 3.87 (s, 3H), 2.39 (s, 6H).

EXAMPLE 7

Preparation of 4-(4,6-dimethyl-2-pyrimidinyl)- 5,6-dihydro-2-phenyl-4H-1,3,4-thiadiazine Benzenecarbothioic acid O-[2-(4,6-dimethyl-2-pyrimidinyl)]hydrazide (0.500 g, 1.94 mmol),

triethylamine (4.85 mmol, 0.67 mL) and

1,2-dibromoethane (0.44 g, 2.33 mmol) were dissolved in 10 mL of THF and heated at reflux for 5 h. After cooling, water was added and the mixture was extracted with ethyl acetate. The organic layer was washed with brine, dried over sodium sulfate, filtered and

concentrated. The product was purified by flash chromatography on silica gel to yield 0.490 g

(1.73 mmol) of a solid in 89% yield, m.p. 138-142°C. ¹H NMR (CDCl₃) δ 7.88 (m, 2H), 7.37 (m, 3H), 6.55 (s, 1H), 4.47 (m, 2H), 3.36 (m, 2H), 2.42 (s, 6H).

EXAMPLE 8

Preparation of 4-(4,6-dimethyl-2-pyrimidinyl)-2-(4- ethylphenyl)-5,6-dihydro-4H-1,3,4-thiadiazine 1-oxide

4-(4,6-Dimethyl-2-pyrimidinyl)-2-(4-ethylphenyl)-5,6-dihydro-4H-1,3,4-thiadiazine (0.800 g, 2.56 mmol) was dissolved in 10 mL of methanol and 2.5 mL of water. Sodium metaperiodate (0.600 g, 2.82 mmol.) was added and the reaction mixture was heated at reflux for 1 h.

Ethanol (2.5 mL) was added and iieating was continued for 1 h more. The reaction mixture was then stirred at 25°C for 16 h. An additional 200 mg of sodium metaperiodate was added and the mixture was heated at reflux for 1 h. The reaction mixture was washed with water and extracted with methylene chloride. The organic layers were washed with brine, dried over sodium sulfate, and concentrated. The crude product was passed through a plug of silica gel to give 760 mg (91% yield) of a white solid, m.p. 149-164°C. ¹H NMR (CDCI₃) δ 7.95 (d, 2H), 7.28 (d, 2H), 6.7 (s, 1H), 5.45 (m, 1H), 3.9 (m, 1H), 3.4 (m, 1H), 2.85 (m, 1H), 2.7 (q, 2H), 2.49 (s, 6H), 1.26 (t, 3H).

EXAMPLE 9

Preparation of 4-(4, 6-dimethyl-2-pyrimidinyl)- 2-(4-ethylphenyl)-5,6-dihydro-4H-1,3,4-thiadiazine

1,1-dioxide

4-(4,6-Dimethyl-2-pyrimidinyl)-2-(4-ethylphenyl)-5,6-dihydro-4H-1,3,4-thiadiazine 1-oxide (0.350 g, 1.06 mmol) was dissolved in 5 mL of methanol and 2.5 mL of water. The mixture was cooled to 0°C and Oxone^® (potassium peroxymonosulfate) (0.490 g, 0.80 mmol) was added. The reaction was warmed to room temperature, stirred for 1 h, then heated at reflux for 10 min.

After stirring at 25°C for 16 h, water was added and the reaction mixture was extracted twice with methylene chloride. The combined organic layers were washed with brine, dried over sodium sulfate, and concentrated. The crude product was passed through a plug of silica gel to yield 350 mg (96%) of a white solid, m.p.

139-141°C. ¹H NMR (CDCl₃) δ 7.90 (d, 2H), 7.27 (d, 2H), 6.72 (s, 1H), 5.05 (m, 2H), 3.55 (m, 2H), 2.67 (q, 2H), 2.47 (s, 6H), 1.24 (t, 3H).

EXAMPLE 10

Preparation of 4-(4,6-dimethyl-2-pyrimidinyl)- 5,6-dihydro-2-phenoxy-4H-1,3,4-thiadiazine O-Phenyl 2-(4,6-dimethyl-2-pyrimidinyl)hydrazine-carbothioate hydrochloride (4.00 g, 12.74 mmol) was dissolved in 38.5 mL of 1N aqueous sodium. hydroxide, 40 mL of THF, and 1.31 mL (15.29 mmol) of

1,2-dibromoethane. The reaction mixture was stirred at 25°C for 4 days. Methylene chloride was added and the reaction was washed successively with water and brine. After drying over sodium sulfate and concentrating, the crude product was passed through a plug of silica gel to give 2.48 g (8.27 mmol, 65%) of a solid, m.p.

75-85°C. ¹H NMR (CDCl₃) δ 7.31 (m, 4H), 7.18 (m, 1H),

6.47 (s, 1H), 4.39 (m, 2H), 3.29 (m, 2H), 2.36 (s, 6H).

. The compounds illustrated below are referred to in the tables which follow. G¹, G², G³, X, Y, E and R¹-R²⁸ are as defined for compounds of Formulae I-IV in the

Summary of the Invention. In addition:

n = 0-2, as in the disclosure (e.g., Equation 2); n¹ = 1-3; n² = 0-1;

MCl_x = the metal chloride salts of copper, zinc, iron, magnesium, or manganese; and

x = 1-2.

The following abbreviations are used in the tables which follow. All alkyl groups are the normal isomers unless indicated otherwise. t - is tertiary t-Bu - is tertiary-butyl s - is secondary c-Pr - is cyclopropyl

n - is normal c-Hex - is cyclohexyl

i - is iso s-Bu - is secondary-butyl c - is cyclo OMe - is methoxy

Me - is methyl i-PrO - is isopropoxy

Et - is ethyl SEt - is ethylthio

Pr - is normal-propyl CN - is cyano

Bu - is normal-butyl TBS - is t-butyldimethylsilyl

Hex - is normal-hexyl Ac - is acetyl

Ph - is phenyl S(O)Me - is methylsulfinyl

Bzl - is benzyl S(O)2Me - is methylsulfonyl i-Pr - is isopropyl

TABLE 1

Compounds of Formula Id

G²=S, R⁹=Me, Y=N, OCH₂CH=CH₂ i-Pr

X=CH CH₂CH₂OMe C-Pr

R¹⁰ OCHF₂ c-Hex

H C≡CH 2-Me-c-Pr

Cl C≡CCH₂CH₃ CF₃

Br OCH₂C≡CH (CH₂)₃CF₃

F NH₂ SMe

CN NMe₂ SBu

OH NHEt S(O)Me

Me 4-morpholinyl S(O)Bu

Hex pyrrolidinyl S(O)₂Me

Et piperidinyl S(O)₂Bu i-Pr Ph OMe

C-Pr PhO OBu

c-Hex 4-Me-Ph OCH₂CF₃

2-Me-c-Pr 3-CF₃-Ph O(CH₂)₃CF₃

CF₃ 4-i-Pr-PhO CH₂OMe

(CH₂)₃CF₃ 4-F₂HCO-Ph (CH₂)₃OMe

SMe 3-Et-PhO CH=CHMe

SBu 4-MeO-PhO CH=CHCH₂CH₃

S (O)Me 4-MeO-Ph CH=CHCH₂CF₃

S (O) Bu CH=CCl₂

S (O) ₂Me G²=O, R⁹=Me, Y=N, OCH₂CH=CH₂

S (O) ₂Bu X=CH CH₂CH₂OMe

OMe R¹⁰ OCHF₂

OBu H C≡CH

OCH₂CF₃ Cl C≡CCH₂CH₃

O(CH₂)₃CF₃ Br OCH₂C≡CH

CH₂OMe F NH₂

(CH₂)₃OMe CN NMe₂

CH=CHMe OH NHEt

CH=CHCH₂CH₃ Me 4-morpholinyl

CH=CHCH₂CF₃ Hex pyrrolidinyl

CH=CCl₂ Et piperidinyl Ph OBu Cl

PhO OCH₂CF₃ Br

4-Me-Ph O(CH₂)₃CF₃ F

3-CF₃-Ph CH₂OMe CN

4-i-Pr-PhO (CH₂)₃OMe OH

4-F₂HCO-Ph CH=CHMe Me

3-Et-PhO CH=CHCH₂CH₃ Hex

4-MeO-PhO CH=CHCH₂CF₃ Et

4-MeO-Ph CH=CCl₂ i-Pr

OCH₂CH=CH₂ C-Pr

G²=S, Y=N, X=CH, CH₂CH₂OMe C-Hex

Rl°-H OCHF₂ 2-Me-c-Pr

R⁹ C≡CH CF₃

H C≡CCH₂CH₃ (CH₂ ) ₃CF₃

Cl OCH₂CsCH SMe

Br NH₂ SBu

F NMe₂ S (O) Me

CN NHEt S (O) Bu

OH 4-morpholinyl S (O) ₂Me

Me pyrrolidinyl S (O) ₂Bu

Hex piperidinyl OMe

Et Ph OBu i-Pr PhO OCH₂CF₃ c-Pr 4-Me-Ph O (CH₂ ) ₃CF₃ c-Hex 3-CF₃-Ph CH₂OMe

2-Me-c-Pr 4-i-Pr-PhO (CH₂ ) ₃OMe

CF₃ 4-F₂HCO-Ph CH=CHMe

(CH₂)₃CF₃ 3-Et-PhO CH=CHCH₂CH₃

SMe 4-MeO-PhO CH=CHCH₂CF₃

SBu 4-MeO-Ph CH=CCl₂

S(O)Me OCH₂CH=CH₂

S(O)Bu G²=S, R⁹=R¹⁰=Me, CH₂CH₂OMe

S(O)₂Me X=CR¹³, Y=N OCHF₂

S(O)₂Bu R¹³ C≡CH

OMe H C≡CCH₂CH₃ OCH₂C≡CH F NMe₂

NH₂ CN NHEt

NMe₂ OH 4-morpholinyl

NHEt Me pyrrolidinyl

4-morpholinyl Hex piperidinyl pyrrolidinyl Et Ph

piperidinyl i-Pr PhO

Ph c-Pr 4-Me-Ph

PhO c-Hex 3-CF₃-Ph

4-Me-Ph 2-Me-c-Pr 4-i-Pr-PhO

3-CF₃-Ph CF₃ 4-F₂HCO-Ph

4-i-Pr-PhO (CH₂)₃CF₃ 3-Et-PhO

4-F₂HCO-Ph SMe 4-MeO-PhO

3-Et-PhO SBu 4-MeO-Ph

4-MeO-PhO S(O)Me

4-MeO-Ph S(O)Bu G²=O, R⁹=R¹⁰=Me,

S(O)₂Me X=CR¹³, Y=N

G²=S, R⁹=R¹⁰=Me, S(O)₂Bu R¹³

X=CH, Y=CR¹⁴ OMe H

R¹⁴ OBu Cl

Cl OCH₂CF₃ Br

Br O(CH₂)₃CF₃ F

F CH₂OMe CN

Me (CH₂)₃OMe OH

Et CH=CHMe Me

OMe CH=CHCH₂CH₃ Hex

OEt CH=CHCH₂CF₃ Et

H CH=CCl₂ i-Pr

OCH₂CH=CH₂ c-Pr

G²=O, Y=N, X=CH, CH₂CH₂OMe c-Hex

R¹⁰=H OCHF₂ 2-Me-c-Pr

R⁹ C≡CH CF₃

H C≡CCH₂CH₃ (CH₂)₃CF₃

Cl OCH₂C≡≡H SMe

Br NH₂ SBu S(O)Me Ph

S(O)Bu G²=O, R⁹=R¹⁰=Me, PhO

S(O)₂Me X=CH, Y=CR¹⁴ 4-Me-Ph

S(O)₂Bu E¹⁴ 4-MeO-Ph

OMe Cl H

OBu Br

OCH₂CF₃ F G²=S, R⁹=Me, Y=CH,

O(CH₂)₃CF₃ Me X=N

CH₂OMe Et R¹⁰

(CH₂)₃OMe OMe Cl

CH=CHMe OEt Br

CH=CHCH₂CH₃ H F

CH=CHCH₂CF₃ CN

CH=CCl₂ G²=S, R⁹=Me, X=Y=N OH

OCH₂CH=CH₂ R¹⁰ Me

CH₂CH₂OMe Cl Et

OCHF₂ Br i-Pr

C≡CH F c-Pr

C≡CCH₂CH₃ CN CF₃

OCH₂C≡CH OH SMe

NH₂ Me S(O)Me

NMe₂ Et S(O)₂Me

NHEt i-Pr OMe

4-morpholinyl c-Pr OEt

pyrrolidinyl CF₃ OCH₂OMe

piperidinyl SMe OCH₂CF₃

Ph S(O)Me C=CHMe

PhO S (O)₂Me C≡CMe

4-Me-Ph OMe NMe₂

3-CF₃-Ph OEt Ph

4-i-Pr-PhO OCH₂OMe PhO

4-F₂HCO-Ph OCH₂CF₃ 4-Me-Ph

3-Et-PhO C=CHMe 4-MeO-Ph

4-MeO-PhO C≡CMe H

4-MeO-Ph NMe₂ G²=O, R⁹=Me, X=Y=N C=CHMe i-Pr

R¹⁰ C≡CMe c-Pr

Cl NMe₂ CF₃

Br Ph SMe

F PhO S (O) Me

CN 4-Me-Ph S (O) ₂Me

OH 4-MeO-Ph OMe

Me H OEt

Et OCH₂OMe i-Pr G²=O, R⁹=Me, Y=CH, OCH₂CF₃ c-Pr X=N C=CHMe

CF₃ R¹⁰ C≡CMe

SMe Cl NMe₂

S (O)Me Br Ph

S (O) ₂Me F PhO

OMe CN 4-Me-Ph

OEt OH 4-MeO-Ph

OCH₂OMe Me H

OCH₂CF₃ Et

G²=S

X Y R¹⁴ R⁹ R¹³ R¹⁰

N CR¹⁴ -(CH₂)₃- - - Me

CH CR¹⁴ -(CH₂)₃- - - Me

N CR¹⁴ -(CH₂)₄- - - Me

CH CR¹⁴ -(CH₂)₄- - - Me

CR¹³ N - - -(CH₂)₃- Me

CR¹³ CH - - -(CH₂)₃- Me

CR¹³ N - - -(CH₂)₄- Me

CR¹³ CH - - -(CH₂)₄- Me

CR¹³ CH - - Me -(CH₂)₃-

CR¹³ CH - - Me - (CH₂)₄- G²=O

X Y R¹⁴ R⁹ R¹³ R¹⁰

N CR¹⁴ -(CH₂)₃- - - Me

CH CR¹⁴ -(CH₂)₃- - - Me

N CR¹⁴ -(CH₂)₄- - - Me

CH CR¹⁴ -(CH₂)₄- - - Me

CR¹³ N - - -(CH₂)₃- Me

CR¹³ CH - - -(CH₂)₃- Me

CR¹³ N - - -(CH₂)₄- Me

CR¹³ CH - - -(CH₂)₄- Me

CR¹³ CH - - Me -(CH₂)₃-

CR¹³ CH - - Me -(CH₂)₄-

TABLE 2

Compounds of Formula Ie

G²=S, X=Y=N, R¹¹=R¹²=R²⁸=H

R¹⁰ c-Pr C=CHMe

Cl CF₃ C≡CMe

Br SMe NMe₂

F S(O)Me Ph

CN S (O) ₂Me PhO

OH OMe 4-Me-Ph

Me OEt 4-MeO-Ph

Et OCH₂OMe H

i-Pr OCH₂CF₃

G²=S

X Y R¹⁰ R¹¹ R¹² R²⁸ R³¹

CH N Me H H H H

N CH Me H H H H

N N Me H 3-Me 4-Me H

N N Me H 3-Me 4-Me 6-Me

N N Me Me H H 7-Me N N Me H H 4-i-Pr 6-OMe N N Me H 3-Me H 7-CF₃ N N Me H H 4-Et 7-Et N N Me H H 4-i-Pr 6-OCHF₂ N N Me H H H 8-Bu N N Me H H 4- c-Pr 6-OEt

G²=O, X=Y=N, R¹¹ =R¹²=R²⁸=H

R¹⁰ c-Pr C=CHMe

Cl CF₃ C≡CMe

Br SMe NMe₂

F S (O)Me Ph

CN S (O) ₂Me PhO

OH OMe 4-Me-Ph

Me OEt 4-MeO-Ph

Et OCH₂OMe H

i-Pr OCH₂CF₃

G²=O

X Y R¹⁰ R¹¹ R¹² R²⁸ R³¹

CH N Me H H H H

N CH Me H H H H

N N Me H 3-Me 4-Me H

N N Me H 3-Me 4-Me 6-Me

N N Me Me H H 7-Me

N N Me H H 4-i-Pr 6-OMe

N N Me H 3-Me H 7-CF₃

N N Me H H 4-Et 7-Et

N N Me H H 4-i-Pr 6-OCHF;

N N Me H H H 8-Bu

N N Me H H 4-c-Pr 6-OEt TABLE 3

Compounds of Formula If

G²=S, R¹²=H, R²⁸=H G²=S, R¹¹=R¹²=H 4-C≡CH

R¹¹ R²⁸ 4-C≡C -Et

H 4-Me 4-OCH₂C≡CH

Me 4-CN 4-NMe₂

Et 4-NO₂ 4-C(= O)NMe₂ i-Pr 4-OH 4-Ph

s-Bu 4-CO₂H 4-OPh

F 4-CO₂Et 4-SPh

Cl 4-Et 4-(3- Me-Ph)

Br 4-i-Pr

CF₃ 4-n-Hex G²=S

OMe 4-c-Pr R¹¹ R¹² R²⁸

OEt 4-CF₃ Cl H 6-Cl

OCHF₂ 4-SMe H 3-Me 4-Me

OBu 4-SBu H 3-Me 4-Et

O(CH₂)₃CF₃ 4-c-Hex H 3-OMe 4-OMe

(CH₂)₃CF₃ 4-Cl Me H 5-Me

G²=S, R¹¹=H, R²⁸=H 4-Br Me H 4-Me

R¹² 4-F Me 4-Me 5-Me

3-Me 4-(CH₂)₃CF₃ H 3-Cl 5-Cl

3-Et 4-S(O)Me Cl H 4-Cl

3-i-Pr 4-S(O)Bu

3-s-Bu 4-S (O) ₂Me G²=O, R¹²=H, R²⁸=H

3-F 4-S(O)₂Bu R¹¹

3-Cl 4-OMe H

3-Br 4-OBu Me

3-CF₃ 4-OCH₂CF₃ Et

3-OMe 4-OCH₂OMe i-Pr

3-OEt 4-CH₂OMe s-Bu

3-OCHF₂ 4-CH=CH-Me F

3-OBu 4-CH=CHCH₂Me Cl

3-O(CH₂)₃CF₃ 4-TBS Br

3-(CH₂)₃CF₃ 4-SiMe₃ CF₃ OMe 4-c-Pr H 3-Me 4-Me

OEt 4-CF₃ H 3-Me 4-Et

OCHF₂ 4-SMe H 3-OMe 4-OMe

OBu 4-SBu Me H 5-Me

O(CH₂)₃CF₃ 4-c-Hex Me H 4-Me

(CH₂)₃CF₃ 4-Cl Me 4-Me 5-Me

4-Br H 3-Cl 5-Cl

G²=O, R¹³=H, R²⁸=H 4-F Cl H 4-Cl

R¹² 4-(CH₂)₃CF₃

3-Me 4-S(O)Me G²=S(O), R¹²=H,

3-Et 4-S(O)Bu R²⁸=H

3-i-Pr 4-S(O)₂Me R¹¹

3-s-Bu 4-S(O)₂Bu H

3-F 4-OMe Me

3-Cl 4-OBu Et

3-Br 4-OCH₂CF₃ i-Pr

3-CF₃ 4-OCH₂OMe s-Bu

3-OMe 4-CH₂OMe F

3-OEt 4-CH=CH-Me Cl

3-OCHF₂ 4-CH=CHCH₂Me Br

3-OBu 4-TBS CF₃

3-O(CH₂)₃CF₃ 4-SiMe₃ OMe

3-(CH₂)₃CF₃ 4-C≡CH OEt

4-C≡C-Et OCHF₂

G²=O, R¹¹=R¹²=H 4-OCH₂C≡CH OBu

R²⁸ 4-NMe₂ O(CH₂)₃CF₃

4-Me 4-C(=O)NMe₂ (CH₂)₃CF₃

4-CN 4-Ph

4-NO₂ 4-OPh G²=S(O), R¹¹ =H,

4-OH 4-SPh R²⁸=H

4-CO₂H 4-(3-Me-Ph) R¹²

4-CO₂Et 3-Me

4-Et G²=O 3-Et

4-i-Pr R¹¹ R¹² R²⁸ 3-i-Pr

4-n-Hex Cl H 6-Cl 3-s-Bu 3-F 4-OMe Me

3-Cl 4-OBu Et

3-Br 4-OCH₂CF₃ i-Pr

3-CF₃ 4-OCH₂OMe S-Bu

3-OMe 4-CH₂OMe F

3-OEt 4-CH=CH-Me Cl

3-OCHF₂ 4-CH=CHCH₂Me Br

3-OBu 4-TBS CF₃

3-O(CH₂)₃CF₃ 4-SiMe₃ OMe

3-(CH₂)₃CF₃ 4-C≡CH OEt

4-G≡C-Et OCHF₂

G²=S(O), R¹¹=R¹²=H 4-OCH₂C≡CH OBu

R²⁸ 4-NMe₂ O(CH₂)₃CF₃

4-Me 4-C(=O)NMe₂ (CH₂)₃CF₃

4-CN 4-Ph

4-NO₂ 4-OPh G²=S(O)₂, R¹¹=H,

4-OH 4-SPh R²⁸=H

4-CO₂H 4-(3-Me-Ph) R¹²

4-CO₂Et 3-Me

4-Et G²=S (O) 3-Et

4-i-Pr R¹¹ R¹² R ²⁸ 3-i-Pr

4-n-Hex Cl H 6-Cl 3-s-Bu

4-c-Pr H 3-Me 4-Me 3-F

4-CF₃ H 3-Me 4-Et 3-Cl

4-SMe H 3-OMe 4-OMe 3-Br

4-SBu Me H 5-Me 3-CF₃

4 -c-Hex Me H 4-Me 3-OMe

4-Cl Me 4-Me 5-Me 3-OEt

4-Br H 3-Cl 5-Cl 3-OCHF₂

4-F Cl H 4-Cl 3-OBu

4-(CH₂)₃CF₃ 3-O(CH₂)₃CF₃

4-S(O)Me G²=S(O)₂, R¹²= H, 3-(CH₂)₃CF₃

4-S(O)Bu R²⁸=H

4-S(O)₂Me R¹¹

4-S(O)₂Bu G²=S (O)₂, 4-CH=CH-Me

R¹¹=R¹² _=H 4-CH=CHCH₂Me

R²⁸ 4-TBS

4-Me 4-SiMe₃

4-CN 4-C≡CH

4-NO₂ 4-C≡C-Et

4-OH 4-OCH₂CECH

4-CO₂H 4-NMe₂

4-CO₂Et 4-C(=O)NMe₂

4-Et 4-Ph

4-i-Pr 4-OPh

4-n-Hex 4-SPh

4-c-Pr 4-(3-Me-Ph)

4-CF₃

4-SMe G²=S(O)₂

4-SBu R¹¹ R¹² R²⁸

4-c-Hex Cl H 6-Cl

4-Cl H 3-Me 4-Me

4-Br H 3-Me 4-Et

4-F H 3-OMe 4-OMe

4-(CH₂)₃CF₃ Me H 5-Me

4-S(O)Me Me H 4-Me

4-S(O)Bu Me 4-Me 5-Me

4-S(O)₂Me H 3-Cl 5-Cl

4-S(O)₂Bu Cl H 4-Cl

4-OMe

4-OBu

4-OCH₂CF₃

4-OCH₂OMe

4-CH₂OMe TABLE 4

Compounds of Formula Ig n¹=1 Et

R²⁷ Bu

H i-Pr

Et CHF₂

Bu (CH₂)₃CF₃ i-Pr CO₂Et

CHF₂ C(=O)Me

(CH₂)₃CF₃ C(=O) (CH₂)₃Me

CO₂Et C(=O)Ph

C(=O)Me (3-Me-Ph)C(=O)

C(=O) (CH₂)₃Me (4-OMe-Ph)C(=O)

C(=O)Ph CH₂C=CH₂

(3-Me-Ph)C(=O) CH₂C≡CH

(4-OMe-Ph)C(=O) PhCH₂

CH₂C=CH₂ 4-Me-PhCH₂

CH₂C≡CH S(O)₂Me

PhCH₂ C(=O)NMe₂

4-Me-PhCH₂ C(=S)NHMe

S(=O)₂Me S(O)Me

C(=O)NMe₂ S(O)₂Ph

C(=S)NHMe (4-Me-Ph)S(O)₂

S(O)Me C (=O) NHPh

S (O)₂Ph C(=S)NHPh

(4-Me-Ph)S(O)₂ P(=S)(OEt)₂

C(=O)NHPh P(=O)(OEt)₂

C(=S)NHPh S(O)₂N(Et)₂

P(=S)(OEt)₂

P(=O)(OEt)₂ n¹=3

S(O)₂N(Et)₂ R²⁷

n¹=2 H

Et

R ²⁷ Bu

i-Pr CHF₂ 1 1 S(O)

(CH₂)₃CF₃ 1 2 S(O) CO₂Et 2 1 S(O) C (=O)Me 0 3 S(O) C(=O) (CH₂)₃Me 1 1 S(O)₂ C(=O)Ph 1 2 S(O)₂

(3-Me-Ph)C(=O) 2 1 S(O)₂

(4-OMe-Ph)C(=O) 0 3 S(O)₂ CH₂C=CH₂ 1 1 N-Me CH₂C--CH 1 2 N-Me PhCH₂ 2 1 N-Me 4-Me-PhCH₂

S(O)₂Me TABLE 6

C(=O)NMe₂ Compounds of Formula Ii C(=S)NHMe G²=S

S(O)Me n² R¹ R⁷ R⁴ R⁸ S(O)₂Ph 1 Me H H H

(4-Me-Ph)S(O)₂ 1 Bu H H H C(=O)NHPh 1 Me Me H H C(=S)NHPh 1 H H Me H P(=S) (OEt)₂ 1 H H Bu H P(=O) (OEt)₂ 1 Ph H H H S(O)₂N(Et)₂ 1 4-Me-Ph H H H

1 4-OMe-Ph H H H

0 Me H - - - -

Compounds of Formula Ih 0 Bu H - - - - n n1 G² 0 Me Me - - - -

1 1 S 0 Ph H - - - - 1 2 S 0 4-Me-Ph H - - - - 2 1 S

0 3 S G²=O

1 1 O n² R¹ R⁷ R⁴ R⁸ 1 2 O 1 Me H H H 2 1 O 1 Bu H H H

O 3 O 1 Me Me H H 1 H H Me H 1 4-Me-Ph H H

1 H H Bu H 1 H Ph H

1 Ph H H H 1 H 4-Me-Ph H

1 4-Me- Ph H H H 1 H H Ph

1 4-OMe -Ph H H H 1 H H 4-Me-Ph

0 Me H - - - -

0 Bu H - - - - G²=O

0 Me Me - - - - n² R¹ R² R³

0 Ph H - - - - 0 Me H - -

0 4-Me- Ph H - - - - 0 Bu H - -

0 H Me - - TABLE 7 0 H Bu - -

Compounds of Formula Ij 0 Ph H - -

G²=S 0 4-Me-Ph H - - n² R¹ R² R³ 0 H 4-OMe-Ph - -

0 Me H - - 1 Me H H

0 Bu H - - 1 Bu H H

0 H Me - - n² R¹ R² R³

0 H Bu - - 1 H Me H

0 Ph H - - 1 H Bu H

0 4- Me-Ph H - - 1 H H Me

0 H 4- OMe- Ph - - 1 H H Bu

1 Me H H 1 Ph H H

1 Bu H H n² R¹ R² R³

1 H Me H 1 4-Me-Ph H H

1 H Bu H 1 H Ph H

1 H H Me 1 H 4-Me-Ph H

1 H H Bu 1 H H Ph

1 Ph H H 1 H H 4-Me-Ph

TABLE 8

Compounds of Formula Ik

G²=S H H Ph H

R¹ R⁷ R⁵ R⁶ H H H MeH H Me H H H H Ph Me H H H Ph H H H

Me Me H H H Ph H H

Ph H H H H H Bu H

H Ph H H H H 4-Me-Ph H

H H Bu H H H H Bu

H H 4-Me-Ph H H H H 4-OMe-Ph

H H H Bu BU H H H

H H H 4-OMe-Ph 3-Me-Ph H H H

Bu H H H 4-OMe-Ph H H H

3-Me- Ph H H H

4-OMe -Ph H H H

G²=O

R¹ R⁷ R⁵ R⁶

H H Me H

H H Ph H

H H H Me

H H H Ph

Me H H H

Me Me H H

TABLE 9

Compounds of Formula Il

G²=S 3-thienyl

E 2,5-diMe-3-furanyl

H 2,5-diMe-3-thienyl

Me 4-Me-PhO

n-Hex 2-Cl-PhO

c-Hex 2,6-diMe-PhO

PhCH₂ 4-Me-PhNH

CH₂CH₂CF₃ 3-Me-PhS

OBu s-BuS

O (CH₂) ₅Cl 1-indanyl

1-naphthalenyl 5-Me-2-thienyl

2-naphthalenyl 5-Me-2-pyridyl

2-furanyl 4-Me-3-furanyl 2-Me-3-pyridyl c-Hex

PhCH₂

G²=O CH₂CH₂CF₃

E OBu

H O(CH₂)₅Cl

Me 1-naphthalenyl n-Hex 2-naphthalenyl c-Hex 2-furanyl

PhCH₂ 3-thienyl

CH₂CH₂CF₃ 2,5-diMe-3-furanyl

OBu 2,5-diMe-3-thienyl

O(CH₂)₅Cl 4-Me-PhO

1-naphthalenyl 2-Cl-PhO

2-naphthalenyl 2,6-diMe-PhO

2-furanyl 4-Me-PhNH

3-thienyl 3-Me-PhS

2, 5-diMe-3-furanyl s-BuS

2, 5-diMe-3-thienyl 1-indanyl

4-Me-PhO 5-Me-2-thienyl

2-Cl-PhO 5-Me-2-pyridyl

2, 6-diMe-PhO 4-Me-3-furanyl

4-Me-PhNH 2-Me-3-pyridyl

3-Me-PhS

s-BuS G²=S(O)₂

1-indanyl E

5-Me-2-thienyl H

5-Me-2-pyridyl Me

4-Me-3-furanyl n-Hex

2-Me-3-pyridyl c-Hex

PhCH₂

G²=S (O) CH₂CH₂CF₃

E OBu

H O(CH₂)₅Cl

Me 1-naphthalenyl n-Hex 2-naphthalenyl 2-furanyl 3-Me-PhS

3-thienyl s-BuS

2,5-diMe-3-furanyl 1-indanyl

2,5-diMe-3-thienyl 5-Me-2 -thienyl

4-Me-PhO 5-Me-2 -pyridyl

2-Cl-PhO 4-Me-3 -furanyl

2,6-diMe-PhO 2-Me-3 -pyridyl

4-Me-PhNH

TABLE 10

Compounds of Formula IIIc

G² n n¹ S(O) 1 1

S 0 1 S(O) 1 2

S 0 2 S(O) 2 1

S 0 3 S(O)₂ 0 1

S 1 1 S(O)₂ 0 2

S 1 2 S(O)₂ 0 3

S 2 1 S(O)₂ 1 1

O 0 1 S(O)₂ 1 2

O 0 2 S(O)₂ 2 1

O 0 3 NMe 0 1

O 1 1 NMe 0 2

O 1 2 NMe 0 3

O 2 1 NMe 1 1

S(O) 0 1 NMe 1 2

S(O) 0 2 NMe 2 1

S(O) 0 3

TABLE 11

Compounds of Formula IIc

G²=S, R⁹=Me , Y=N, Br Hex

X=CH F Et

R¹⁰ CN i-Pr H OH c-Pr

Cl Me c-Hex 2-Me-c-Pr 4-i-Pr-PhO (CH₂)₃OMe CF₃ 4-F₂HCO-Ph CH=CHMe

(CH₂)₃CF₃ 3-Et-PhO CH=CHCH₂CH₃ SMe 4-MeO-PhO CH=CHCH₂CF₃ SBu 4-MeO-Ph CH=CCl₂

S(O)Me OCH₂CH=CH₂ S(O)Bu G²=O, R⁹=Me, Y=N, CH₂CH₂OMe S(O)₂Me X=CH OCHF₂

S(O)₂Bu R¹⁰ C≡CH

OMe H C≡CCH₂CH₃ OBu Cl OCH₂C≡CH

OCH₂CF₃ Br NH₂

O(CH₂)₃CF₃ F NMe₂

CH₂OMe CN NHEt

(CH₂)₃OMe OH 4-morpholinyl CH=CHMe Me pyrrolidinyl CH=CHCH₂CH₃ Hex piperidinyl CH=CHCH₂CF₃ Et Ph

CH=CCl₂ i-Pr PhO

OCH₂CH=CH₂ c-Pr 4-Me-Ph

CH₂CH₂OMe c-Hex 3-CF₃-Ph

OCHF₂ 2-Me-c-Pr 4-i-Pr-PhO C≡CH CF₃ 4-F₂HCO-Ph C≡CCH₂CH₃ (CH₂)₃CF₃ 3-Et-PhO

OCH₂C≡CH SMe 4-MeO-PhO

NH₂ SBu 4-MeO-Ph

NMe₂ S(O)Me

NHEt S(O)Bu G²=S, Y=N, X=CH,

4-morpholinyl S(O)₂Me R¹⁰=H

pyrrolidinyl S(O)₂Bu R⁹

piperidinyl OMe H

Ph OBu Cl

PhO OCH₂CF₃ Br

4-Me-Ph O(CH₂)₃CF₃ F

3-CF₃-Ph CH₂OMe CN OH 4-morpholinyl S(O)₂Me

Me pyrrolidinyl S(O)₂Bu

Hex piperidinyl OMe

Et Ph OBu

i-Pr PhO OCH₂CF₃ c-Pr 4-Me-Ph O(CH₂)₃CF₃ c-Hex 3-CF₃-Ph CH₂OMe

2-Me-c-Pr 4-i-Pr-PhO (CH₂)₃OMe

CF₃ 4-F₂HCO-Ph CH=CHMe

(CH₂)₃CF₃ 3-Et-PhO CH-CHCH₂CH₃

SMe 4-MeO-PhO CH=CHCH₂CF₃

SBu 4-MeO-Ph CH=CCl₂

S(O)Me OCH₂CH=CH₂

S(O)Bu G²=S, R⁹=R¹⁰=Me, CH₂CH₂OMe

S(O)₂Me X=CR¹³, Y=N OCHF₂

S(O)₂Bu R¹³ C≡CH

OMe H C≡CCH₂CH₃

OBu Cl OCH₂C≡CH

OCH₂CF₃ Br NH₂

O(CH₂)₃CF₃ F NMe₂

CH₂OMe CN NHEt

(CH₂)₃OMe OH 4-morpholinyl

CH=CHMe Me pyrrolidinyl

CH=CHCH₂CH₃ Hex piperidinyl

CH=CHCH₂CF₃ Et Ph

CH=CCl₂ i-Pr PhO

OCH₂CH=CH₂ c-Pr 4-Me-Ph

CH₂CH₂OMe c-Hex 3-CF₃-Ph

OCHF₂ 2-Me-c-Pr 4-i-Pr-PhO C≡CH CF₃ 4-F₂HCO-Ph

C≡CCH₂CH₃ (CH₂) ₃CF₃ 3-Et-PhO

OCH₂C≡CH SMe 4-MeO-PhO

NH₂ SBu 4-MeO-Ph

NMe₂ S(O)Me

NHEt S(O)Bu G²=S, R⁹=R¹⁰=Me, S(O)₂Bu R¹³

X=CH, Y=CR¹⁴ OMe H

R¹⁴ OBu Cl

Cl OCH₂CF₃ Br

Br O(CH₂)₃CF₃ F

F CH₂OMe CN

Me (CH₂)₃OMe OH

Et CH=CHMe Me

OMe CH=CHCH₂CH₃ Hex

OEt CH=CHCH₂CF₃ Et

H CH=CCl₂ i-Pr

OCH₂CH=CH₂ C-Pr

G²=O, Y=N, X=CH, CH₂CH₂OMe c-Hex

R¹⁰=H OCHF₂ 2-Me-c-Pr

R⁹ C≡CH CF₃

H C≡CCH₂CH₃ (CH₂)₃CF₃

Cl OCH₂C≡CH SMe

Br NH₂ SBu

F NMe₂ S(O)Me

CN NHEt S(O)Bu

OH 4-morpholinyl S(O)₂Me

Me pyrrolidinyl S(O)₂Bu

Hex piperidinyl OMe

Et Ph OBu i-Pr PhO OCH₂CF₃ c-Pr 4-Me-Ph O(CH₂)₃CF₃ c-Hex 3-CF₃-Ph CH₂OMe

2-Me-c-Pr 4-i-Pr-PhO (CH₂)₃OMe

CF₃ 4-F₂HCO-Ph CH=CHMe

(CH₂)₃CF₃ 3-Et-PhO CH=CHCH₂CH₃

SMe 4-MeO-PhO CH=CHCH₂CF₃

SBu 4-MeO-Ph CH=CCl₂

S(O)Me OCH₂CH=CH₂

S(O)Bu G²=O, R⁹=R¹⁰=Me, CH₂CH₂OMe

S(O)₂Me X=CR¹³, Y=N OCHF₂ C≡CH F c-Pr

C≡CCH₂CH₃ CN CF₃

OCH₂C--CH OH SMe

NH₂ Me S (O)Me

NMe₂ Et S (O) ₂Me

NHEt i-Pr OMe

4-morpholinyl c-Pr OEt

pyrrolidinyl CF₃ OCH₂OMe

piperidinyl SMe OCH₂CF₃

Ph S(O)Me C=CHMe

PhO S(O)₂Me C≡CMe

4-Me-Ph OMe NMe₂

3-CF₃-Ph OEt Ph

4-i-Pr-PhO OCH₂OMe PhO

4-F₂HCO-Ph OCH₂CF₃ 4-Me-Ph

3-Et-PhO C=CHMe 4-MeO-Ph

4-MeO-PhO C≡CMe H

4-MeO-Ph NMe₂

Ph G²=O, R³=Me, X=Y=N

G²=O, R⁹=R¹⁰=Me, PhO R¹⁰

X=CH, Y=CR¹⁴ 4-Me-Ph Cl

R¹⁴ 4-MeO-Ph Br

Cl H F

Br CN

F G²=S, R⁹=Me, Y=CH, OH

Me X=N Me

Et R¹⁰ Et

OMe Cl i-Pr

OEt Br c-Pr

H F CF₃

CN SMe

G²=S, R⁹=Me, X=Y=N OH S (O) Me

R¹⁰ Me S (O) ₂Me

Cl Et OMe

Br i-Pr OEt OCH₂OMe Cl OEt

OCH₂CF₃ Br OCH₂OMe

C=CHMe F OCH₂CF₃

C≡CMe CN C=CHMe

NMe₂ OH C≡CMe

Ph Me NMe₂

PhO Et Ph

4-Me-Ph i-Pr PhO

4-MeO-Ph c-Pr 4-Me-Ph

H CF₃ 4-MeO-Ph

SMe H

G²=O, R⁹=Me, Y=CH, S(O)Me

X=N S(O)₂Me

R¹⁰ OMe

G²=S

X R ¹⁴ R⁹ R ¹³ R ¹⁰

N CR ¹⁴ -(CH₂)₃- - - Me

CH CR ¹⁴ -(CH₂)₃- - - Me

N CR¹⁴ -(CH₂)₄- - - Me

CH CR¹⁴ -(CH₂)₄- - - Me

CR¹³ N - - -(CH₂)₃- Me

CR¹³ CH - - -(CH₂)₃- Me

CR¹³ N - - -(CH₂)₄- Me

CR¹³ CH - - -(CH₂)₄- Me

CR¹³ CH - - Me -(CH₂)₃-

CR¹³ CH - - Me -(CH₂)₄-

G²=O

X Y R ¹⁴ R⁹ R¹³ R ¹⁰ N CR¹⁴ -(CH₂)₃- - - Me CH CR ¹⁴ -(CH₂)₃- - - Me N CR ¹⁴ -(CH₂)₄- - - Me CH CR ¹⁴ -(CH₂)₄- - - Me

CR¹³ N - - -(CH₂)₃- Me CR¹³ CH - - -(CH₂)₃- Me

CR¹³ N - - "(CH₂)₄- Me

CR¹³ CH - - -(CH₂)₄- Me

CR¹³ CH - - Me -(CH₂)₃-

CR¹³ CH - - Me -(CH₂)₄-

TABLE 12

Compounds of Formula IId

G²=S, X=Y=N, R¹¹=R¹²=R²⁸=H

R ¹⁰ C-Pr C=CHMe

Cl CF₃ C≡CMe

Br SMe NMe₂

F S(O)Me Ph

CN S(O)₂Me PhO

OH OMe 4-Me-Ph

Me OEt 4-MeO-Ph

Et OCH₂OMe H

i-Pr OCH₂CF₃

G²=S, R¹⁰=Me

X Y R¹¹ R¹² R²⁸ R³¹

CH N H H H H

N CH H H H H

N N H 3-Me 4-Me H

N N H 3-Me 4-Me 6-Me

N N Me H H 7-Me

N N H H 4-i-Pr 6-OMe

N N H 3-Me H 7-CF₃

N N H H 4-Et 7-Et

N N H H 4-i-Pr 6-OCHF₂

N N H H H 8-Bu

N N H H 4-c-Pr 6-OEt G²=O, X=Y=N, R¹¹=R¹²=R²⁸=H

R¹⁰ c-Pr OCH₂CF₃

Cl CF₃ C=CHMe

Br SMe C≡CMe

F S(O)Me NMe₂

CN S(O)₂Me Ph

OH OMe PhO

Me OEt 4-Me-Ph

Et OCH₂OMe 4-MeO-Ph

i-Pr H

G²=O, R¹⁰=Me

X Y R¹¹ R¹² R²⁸ R³¹

CH N H H H H

N CH H H H H

N N H 3-Me 4-Me H

N N H 3-Me 4-Me 6-Me

N N Me H H 7-Me

N N H H 4-i-Pr 6-OMe

N N H 3-Me H 7-CF₃

N N H H 4-Et 7-Et

N N H H 4-i-Pr 6-OCHF₂

N N H H H 8-Bu

N N H H 4-c-Pr 6-OEt TABLE 13

Compounds of Formula IIe

G²=S, R¹²=H, R²⁸=H Br G²=S, R¹¹=H, R²⁸=H

R¹¹ CF₃ R¹²

H OMe 3-Me

Me OEt 3-Et

Et OCHF₂ 3-i-Pr

i-Pr OBu 3-s-Bu

S-Bu O(CH₂)₃CF₃ 3-F

F (CH₂)₃CF₃ 3-Cl

Cl 3-Br 3-CF₃ 4-OCH₂OMe F

3-OMe 4-CH₂OMe Cl

3-OEt 4-CH= CH-Me Br

3-OCHF₂ 4-CH= CHCH₂Me CF₃

3-OBu 4-TBS OMe

3-O (CH₂) ₃CF₃ 4-SiMe₃ OEt

3- (CH₂) ₃CF₃ 4-CECH OCHF₂

4-C≡C -Et OBu

G²=S, R¹¹ =R¹²=H 4-OCH₂C≡CH O(CH₂)₃CF₃

R²⁸ 4-NMe₂ (CH₂)₃CF₃

4-Me 4-C(=O)NMe₂

4-CN 4-Ph G²=O, R¹¹=H, R²⁸=H

4-NO₂ 4-OPh R¹²

4-OH 4-SPh 3-Me

4-CO₂H 4-(3-1Me-Ph) 3-Et

4-CO₂Et 3-i-Pr

4-Et G²=S 3-s-Bu

4-i-Pr R¹¹ R¹² R²⁸ 3-F

4-n-Hex Cl H 6-Cl 3-Cl

4-c-Pr H 3-Me 4-Me 3-Br

4-CF₃ H 3-Me 4-Et 3-CF₃

4-SMe H 3-OMe 4-OMe 3-OMe

4-SBu Me H 5-Me 3-OEt

4-c-Hex Me H 4-Me 3-OCHF₂

4-Cl Me 4-Me 5-Me 3-OBu

4-Br H 3-Cl 5-Cl 3-O(CH₂)₃CF₃

4-F Cl H 4-Cl 3-(CH₂)₃CF₃

4- (CH₂) ₃CF₃ 4-Me

4-S (O)Me G²=O, R¹²=H, R²⁸=H

4-S (O) Bu R¹¹ G²=O, R¹¹=R¹²=H

4-S (O) ₂Me H R²⁸

4-S (O) ₂Bu Me 4-CN

4-OMe Et 4-NO₂

4-OBu i-Pr 4-OH

4-OCH₂CF₃ s-Bu 4-CO₂H 4-CO₂Et G²=S(O), R¹¹=H,4-Et G²=O R²⁸=H

4-i-Pr R¹¹ R¹² R²⁸ R¹²

4-n-Hex Cl H 6-Cl 3-Me

4-c-Pr H 3-Me 4-Me 3-Et

4-CF₃ H 3-Me 4-Et 3-i-Pr

4-SMe H 3-OMe 4-OMe 3-s-Bu

4-SBu Me H 5-Me 3-F

4 -c-Hex Me H 4-Me 3-Cl

4-Cl Me 4-Me 5-Me 3-Br

4-Br H 3-Cl 5-Cl 3-CF₃

4-F Cl H 4-Cl 3-OMe

4- (CH₂ ) ₃CF₃ 3-OEt

4-S (O)Me G²=S(O), R¹² =H, 3-OCHF₂

4-S (O) Bu R²⁸=H 3-OBu

4-S (O) ₂Me R¹¹ 3-O(CH₂)₃CF₃4-S (O) ₂Bu H 3-(CH₂)₃CF₃4-OMe Me

4-OBu Et G²=S(O), R¹¹=R¹²=H4-OCH₂CF₃ i-Pr R²⁸

4-OCH₂OMe s-Bu 4-Me

4-CH₂OMe F 4-CN

4-CH=CH-Me Cl 4-NO₂

4-CH=CHCH₂Me Br 4-OH

4 -TBS CF₃ 4-CO₂H

4-SiMe₃ OMe 4-CO₂Et

4-C≡CH OEt 4-Et

4-C≡C-Et OCHF₂ 4-i-Pr

4-OCH₂C-≡CH OBu 4-n-Hex

4-NMe₂ O(CH₂)₃CF₃ 4-c-Pr

4-C (=O) NMe₂ (CH₂)₃CF₃ 4-CF₃

4-Ph 4-SMe

4 -OPh 4-SBu

4-SPh 4-c-Hex

4- (3-Me-Ph) 4-Cl 4-Br H 3-Cl 5-Cl 3-OCHF₂

4-F Cl H 4-Cl 3-OBu

4-(CH₂)₃CF₃ 3-O(CH₂)₃CF₃

4-S(O)Me G²=S(O)₂, R¹²=H, 3-(CH₂)₃CF₃

4-S(O)Bu R²⁸=H

4-S(O)₂Me R¹¹ G²=S(O)₂,

4-S(O)₂Bu H R¹¹=R¹²=H

4-OMe Me R²⁸

4-OBu Et 4-Me

4-OCH₂CF₃ i-Pr 4-CN

4-OCH₂OMe s-Bu 4-NO₂

4-CH₂OMe F 4-OH

4-CH=CH-Me Cl 4-CO₂H

4-CH=CHCH₂Me Br 4-CO₂Et

4-TBS CF₃ 4-Et

4-SiMe₃ OMe 4-i-Pr

4-C≡CH OEt 4-n-Hex

4-C≡C-Et OCHF₂ 4-c-Pr

4-OCH₂C≡CH OBu 4-CF₃

4-NMe₂ O(CH₂)₃CF₃ 4-SMe

4-C(=O)NMe₂ (CH₂)₃CF₃ 4-SBu

4-Ph 4-c-Hex

4-OPh G²=S(O)₂, R¹¹=H, 4-Cl

4-SPh R²⁸=H 4-Br

4-(3-Me-Ph) R¹² 4-F

3-Me 4-(CH₂)₃CF₃

G²=S(O) 3-Et 4-S(O)Me

R¹¹ R¹² R²⁸ 3-i-Pr 4-S(O)Bu

Cl H 6-Cl 3-s-Bu 4-S(O)₂Me

H 3-Me 4-Me 3-F 4-S(O)₂Bu

H 3-Me 4-Et 3-Cl 4-OMe

H 3-OMe 4-OMe 3-Br 4-OBu

Me H 5-Me 3-CF₃ 4-OCH₂CF₃

Me H 4-Me 3-OMe 4-OCH₂OMe

Me 4-Me 5-Me 3-OEt 4-CH₂OMe 4-CH=CH-Me CHF₂ C (=O)Ph

4-CH= CHCH₂Me (CH₂)₃CF₃ (3-Me-Ph)C(=O)

4-TBS CO₂Et (4-OMe-Ph)C(=O)

4-SiMe₃ C(=O)Me CH₂C=CH₂

4-C≡CH C(=O) (CH₂)₃Me CH₂C≡CH

4-C≡C -Et C (=O) Ph PhCH₂

4-OCH₂C≡CH (3-Me-Ph)C(=O) 4-Me-PhCH₂

4-NMe₂ (4-OMe-Ph)C(=O) S(O)₂Me

4-C(= O)NMe₂ CH₂C=CH₂ C(=O)NMe₂

4-Ph CH₂C=CH C(=S)NHMe

4-OPh PhCH₂ S(O)Me

4-SPh 4-Me-PhCH₂ S(O)₂Ph

4-(3- Me-Ph) S(O)₂Me (4-Me-Ph)S(O)₂

C(=O)NMe₂ C(=O)NHPh

G²=S(O)₂ C(=S)NHMe C(=S)NHPh

R¹¹ R¹² R²⁸ S(O)Me P(=S) ((Et)₂

Cl H 6-Cl S(O)₂Ph P(=O) (OEt)₂

H 3-Me 4-Me (4-Me-Ph)S(O)₂ S(O)₂N(Et)₂

H 3-Me 4-Et C(=O)NHPh

H 3-OMe 4-OMe C(=S)NHPh n¹=3

Me H 5-Me P(=S) (OEt)₂ R²⁷

Me H 4-Me P(=O) (OEt)₂ H

Me 4-Me 5-Me S(O)₂N(Et)₂ Et

H 3-Cl 5-Cl Bu

Cl H 4-Cl n¹=2 i-Pr

R²⁷ CHF₂

TABLE 14 H (CH₂)₃CF₃

Compounds of Et CO₂Et

Formula IIf Bu C(=O)Me n¹=1 i-Pr C(=O) (CH₂)₃Me

R²⁷ CHF₂ C (=O) Ph

H (CH₂)₃CF₃ (3-Me-Ph)C(=O)

Et CO₂Et (3-Me-Ph)C(=O)

Bu C(=O)Me CH₂C=CH₂ i-Pr C(=O) (CH₂)₃Me CH₂C≡CH PhCH₂ 1 1 S(O)

4-Me-PhCH₂ TABLE 15 1 2 S(O)

S(O)₂Me Compounds of 2 1 S(O)

C(=O)NMe₂ Formula IIg 0 3 S(O)

C(=S)NHMe n n¹ G² 1 1 S(O)₂

S(O)Me 1 1 S 1 2 S(O)₂

S(O)₂Ph 1 2 S 2 1 S(O)₂

(4-Me-Ph)S(O)₂ 2 1 S 0 3 S(O)₂

C(=O)NHPh 0 3 S 1 1 N-Me

C(=S)NHPh 1 1 O 1 2 N-Me

P(=S)(OEt)₂ 1 2 O 2 1 N-Me

P (=O)(OEt)2 2 1 O

S(O)₂N(Et)₂ 0 3 O

TABLE 16 1 Me Me H H

Compounds of Formula IIh 1 H H Me H

G²=S 1 H H Bu H

R¹ R⁷ R⁴ R⁸ 1 Ph H H H

1 Me H H H 1 4-Me-Ph H H H 1 Bu H H H 1 4-OMe-Ph H H H 1 Me Me H H 0 Me H - - - - 1 H H Me H 0 Bu H - - - - 1 H H Bu H 0 Me Me - - - - 1 Ph H H H 0 Ph H - - - - 1 4-Me-Ph H H H 0 4-Me-Ph H - - - - 1 4-OMe-Ph H H H

0 Me H - - - - TABLE 17

0 Bu H - - - - Compounds of Formula IIi 0 Me Me - - - - G²=S

0 Ph H - - - - n² R¹ R² R³ 0 4-Me-Ph H - - - - 0 Me H - -

0 Bu H - -

G²=O 0 H Me - - n² R¹ R⁷ R⁴ R⁸ 0 H Bu - -

1 Me H H H 0 Ph H - - 1 Bu H H H 0 4-Me-Ph H - - 0 H 4-OMe-Ph - - 0 H Me - - n R¹ R² R³ 0 H Be - -

1 Me H H 0 Ph H - -

1 Bu H H 0 4-Me-Ph H - -

1 H Me H 0 H 4-OMe-Ph

1 H Bu H 1 Me H H 1 H H Me 1 Bu H H 1 H H Bu 1 H Me H 1 Ph H H 1 H Bu H 1 4-Me-Ph H H 1 H H Me 1 H Ph H 1 H H Bu 1 H 4-Me-Ph H 1 Ph H H 1 H H Ph 1 4-Me-Ph H H 1 H H 4-Me-Ph 1 H Ph H

1 H 4-Me-Ph H

G²=O 1 H H Ph n² R¹ R² R³ 1 H H 4-Me-Ph

0 Me H - -

0 Bu H - -

TABLE 18

Compounds of Formula IIj

G²=S H H H 4-OMe-Ph

R¹ R⁷ R⁵ R⁶ Bu H H H

H H Me H 3-Me- Ph H H H

H H Ph H 4-OMe -Ph H H H

H H H Me G²=O

H H H Ph R¹ R⁷ R⁵ R⁶

Me H H H H H Me H

Me Me H H H H Ph H

Ph H H H H H H Me

H Ph H H H H H Ph

H H Bu H Me H H H

H H 4-Me-Ph H Me Me H H

H H H Bu Ph H H H H Ph H H H i-Pr H

H H Bu H 2-Cl H H

H H 4-Me -Ph H 3-Cl H H

H H H Bu H Cl H

H H H 4-OMe-Ph 3-Me Me H

Bu H H H 2-Me H 5-Me

3-MeH Ph H H H 2-Cl H 6-Cl

4-OMe -Ph H H H

G₂=O, MCl_x=ZnCl₂

TABLE 19 R¹¹ R¹² R²⁸

Compounds of Formula IVc H Me H

G² n n¹ H Et H

S 1 1 H OMe H

S 1 2 H i-Pr H

S 2 1 2-Cl H H

O 1 1 3-Cl H H

O 1 2 H Cl H

O 2 1 3-Me Me H

S(O) 1 1 2-Me H 5-Me

S(O) 1 2 2-Cl H 6-Cl

S(O) 2 1

S(O)₂ 1 1 G₂=S, MCl_x=FeCl₃

S(O)₂ 1 2 R¹¹ R¹² R²⁸

S(O)₂ 2 1 H Me H

NMe 1 1 H Et H

NMe 1 2 H OMe H

NMe 2 1 H i-Pr H

2-Cl H H

TABLE 20 3-Cl H H

Compounds of Formula Im H Cl H

G₂=S, MCl_x=znCl₂ 3-Me Me H

R¹¹ R¹² R²⁸ 2-Me H 5-Me

H Me H 2-Cl H 6-Cl

H Et H

H OMe H G₂=O, MCl_x=FeCl₃ 3-Me Me H

R¹¹ R¹² R²⁸ 2-Me H 5-Me

H Me H 2-Cl H 6-Cl

H Et H

H OMe H G₂=S, MCl_x=MnCl₂

H i-Pr H R¹¹ R¹² R²⁸

2-Cl H H H Me H

3-Cl H H H Et H

H Cl H H OMe H

3-Me Me H H i-Pr H

2-Me H 5-Me 2-Cl H H

2-Cl H 6-Cl 3-Cl H H

H Cl H

G₂=S, MCl_x=CuCl₂ 3-Me Me H

R¹¹ R¹² R²⁸ 2-Me H 5-Me

H Me H 2-Cl H 6-Cl

H Et H

H OMe H G₂=O, MCl_x=MnCl₂

H i-Pr H R¹¹ R¹² R²⁸

2-Cl H H H Me H

3-Cl H H H Et H

H Cl H H OMe H

3-Me Me H H i-Pr H

2-Me H 5-Me 2-Cl H H

2-Cl H 6-Cl 3-Cl H H

H Cl H

G₂=O, MCl_x=CuCl₂ 3-Me Me H

R¹¹ R¹² R²⁸ 2-Me H 5-Me

H Me H 2-Cl H 6-Cl

H Et H

H OMe H G₂=S, MCl_x=MgCl₂

H i-Pr H R¹¹ R¹² R²⁸

2-Cl H H H Me H

3-Cl H H H Et H

H Cl H H OMe H H i-Pr H H Et H

2-Cl H H H OMe H

3-Cl H H H i-Pr H

H Cl H 2-Cl H H

3-Me Me H 3-Cl H H

2-Me H 5-Me H Cl H

2-Cl H 6-Cl 3-Me Me H

2-Me H 5-Me

G₂=O, MCl_x=MgCl₂ 2-Cl H 6-Cl

R¹¹ R¹² R²⁸

H Me H Formulation/Utility

Compounds of this invention will generally be used in formulation with an agriculturally suitable

composition. The fungicidal compositions of the present invention comprise an effective amount of at least one 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 can be prepared in conventional ways.

They include dusts, granules, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates, dry flowables and the like. 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, 5-50 40-95 0-15 Emulsions, Solutions,

(including Emulsifiable

Concentrates)

Dusts 1-25 70-99 0-5

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

Pellets

High Strength 90-99 0-10 0-2

Compositions

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.

Methods for formulating such compositions are well known. 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 Index Table A hereinafter.

Example A

Wettable Powder

Compound 11 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%.

Example B

Granule

Compound 11 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 11 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 11 20.0% blend of oil soluble sulfonates

and polyoxyethylene ethers 10.0% isophorone 70.0%.

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 or seedling to be protected, an effective amount of a compound of Formula I or a fungicidal composition containing said compound. 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.

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 multi-component 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, baculovirus and avermectin B.

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 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 Table A 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 Trent^® 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 1

Compounds of Formula I

R⁹=R¹⁰=Me; X=CH; Y=N

Cmpd. No. G¹-G²-G³ E mp (°C)

1 CH₂OCH₂ Ph a

2 CH₂CH₂S 4-Cl-Ph a 3 CH₂OCH₂ 4-Et-Ph a

4 CH₂CH₂O 3-Me-Ph a

5 CH₂CH₂S 3-Me-Ph a

6 CH₂CH₂O 2,6-diCl-Ph a

7 CH₂CH₂S 4-Me-Ph a

8 CH₂CH₂S 2-Cl-Ph 146-148

9 CH₂CH₂S 3-Cl-Ph a

10 CH₂CH₂O 4-Et-Ph 99-106

11 CH₂CH₂S 4-Et-Ph 84-87

12 CH₂CH₂SO 2-Cl-Ph 168-170

13 CH₂CH₂S Ph 142-145

14 CH₂CH₂S 3-CF₃-Ph 105-110

15 CH₂CH₂S 4-OMe-Ph 111-115

16 CH₂CH₂SO 4-Et-Ph 149-164

17 CH₂CH₂SO₂ 4-Et-Ph 139-141

18 CH₂CH₂S 4-t-Bu 114-121

19 CH₂ CH₂CH₂S 4-OMe-Ph 119-123

20 CH₂CH₂S OPh 75-85

21 CH₂CH₂CH₂S 4-Et-Ph 97-100

22 CH(CH₃)CH₂S 4-Et-Ph a

23 CH₂CH₂S 2-Me-Ph 86-91

24 CH₂CH₂S OBzl 81-93

25 CH₂CH₂S SPh a

26 CH₂CH₂S Bzl a

27 CH₂ CH₂CH₂S Ph 158-160

28 CH(CH₃)CH₂S Ph a

29 CH₂C (CHo)₂CH₂S Ph 116-121

30 CH₂CH (Ph)S Ph 196-208

31 CH₂CH₂S Et a

32 CH₂CH(CO₂Et)S Ph 124-133

33 CH₂CH (Ph) SO₂ Ph 201-206

34 CH(CF₃)CH₂S Ph 174-181

35 CH(CH₂CH₃)CH₂S Ph a

36 CH₂CH(CN)S Ph 208-212

37 CH(CN)CH₂S Ph 168-174 38 CH₂CH₂S 3,4-diCl-Ph 149-152

39 CH₂CH₂S 4-Ph-Ph 151-155

40 CH₂CH₂S 3,4-diOMe-Ph 172-174 a Oil or gum; ¹H NMR data in Index Table 2.

X=CR¹³; R⁹ and R¹³ are taken together to form a fused benzene ring; Y=N; R¹⁰=Me

Cmpd. No. G¹-G²-G³ E mp (°C)

38 CH₂CH₂S Ph 102-108

R⁹=R¹⁰=ethyl; X=CH; Y=N

Cmpd. No. G¹-G²-G³ E mp (°C)

39 CH₂CH₂S Ph oil; ¹H

NMR data in Index Table 2.

Index Table 2

Cmpd. No. ¹H NMR Data^a

1 7.75 (m, 2H), 7.37 (m, 3H), 6.57 (s, 1H),

5.54 (s, 2H), 4.83 (s, 2H), 2.42 (s, 6H).

2 7.83 (d, 2H), 7.35 (d, 2H), 6.56 (s, 1H),

4.47 (t, 2H), 3.36 (t, 2H), 2.43 (s, 6H).

3 7.66 (d, 2H), 7.21 (d, 2H), 6.56 (s, 1H),

5.54 (s, 2H), 4.81 (s, 2H), 2.67 (q, 2H), 2.42 (s, 6H), 1.24 (t, 3H).

4 7.82 (m, 1H), 7.75 (m, 1H), 7.25 (m, 1H),

7.19 (m, 1H), 6.49 (s, 1H), 4.54 (m, 2H), 4.28 (m, 2H), 2.42 (s, 6H), 2.38 (s, 3H).

5 7.7 (m, 2H), 7.2 (m, 2H), 6.54 (s, 1H),

4.45 (m, 2H), 3.35 (m, 2H), 2.42 (s, 6H), 2.39 (s, 3H).

6 7.31 (m, 2H), 7.25 (m, 1H), 6.5 (s, 1H),

4.55 (m, 2H), 4.35 (m, 2H), 2.38 (s, 6H). 7 7.77 (d, 2H), 7.18 (d, 2H), 6.53 (s, 1H),

4.46 (m, 2H), 3.35 (m, 2H), 2.42 (s, 6H),

2.37 (s, 3H) .

9 7.90 (m, 1H), 7.75 (m, 1H), 7.3 (m, 2H),

6.57 (s, 1H), 4.47 (m, 2H), 3.36 (m, 2H), 2.43 (s, 6H) .

22 7.82 (d, 2H), 7.22 (d, 2H)

5.7 (m, 1H), 3.45 (d, 1H),

2.7 (q, 2H), 2.42 (s, 6H),

1.24 (t, 3H) .

25 7.65 (m, 2H), 7.34 (m, 3H), 6.55 (s, 1H)

4.40 (m, 2H), 3.25 (m, 2H), 2.41 (s, 6H)

26 7.37 (d, 2H), 7.32 (t, 2H), 7.25 (d, 1H)

6.51 (s, 1H), 4.32 (m, 2H), 3.89 (s, 2H) 3.19 (m, 2H), 2.41 (s, 6H) .

28 7.93 (d, 2H), 7.37 (m, 3H), 6.54 (s, 1H)

5.7 (m, 1H), 3.45 (d, 1H), 3.02 (m, 1H), 2.42 (s, 6H), 1.40 (d, 3H) .

31 6.48 (s, 1H), 4.33 (t, 2H) 3.25 (t, 2H)

2.58 (q, 2H), 2.39 (s, 6H) 1.26 (t, 3H)

35 7.85 (d, 2H), 7.37 (m, 3H) 6.52 (s, 1H)

5.50 (m, 1H), 3.38 (d, 1H) 3.20 (d, 1H)

2.41 (s, 6H), 1.80 (m. 2H) 0.99 (t, 3H)

39 7.85 (d, 2H), 7.37 (m, 3H) 6.56 (s, 1H)

4.45 (m, 2H), 3.35 (m, 2H) 2.72 (q, 4H) 1.31 (t, 6H) .

a¹H NMR data are in ppm downfield from tetramethylsilane. Coupling are designated (s)-singlet,

(d)-doublet, (t)-triplet, (q)-quartet, (m)-multiplet. Samples were dissolved in CDCl₃.

Results for Tests A-F 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). NT = Not Tested. Table A

Cmpd Test Test Test Test Test Test

No. A B C D E F

1 98 100 65 23 75 65

2 76 93 99 11 91 2

3 86* 84* 72* 59* 44 77

4 73* 64* 73* 36* 0* 32*

5 24* 64* 73* 10* 0* 32*

6 0* 0* 29* 0* 86* 46*

8 0 80 85 3 100 98

9 98 100 99 82 92 98

10 94 100 99 52 85 82

11 99 100 97 52 92 98

12 56 0 0 60 92 0

13 98 96 91 91 100 77

14 98 82 100 73 100 47

15 96 98 97 0 100 98

16 82 0 0 0 13 0

17 61 14 0 NT 14 018 82 0 86 0 73 8319 29 21 57 18 96 9920 90 98 99 85 99 9921 98 98 94 0 100 6922 0 55 91 58 100 023 74 100 94 73 100 8024 83 91 32 63 84 025 90 100 91 63 100 7026 92 98 85 70 100 4627 55 23 91 14 74 9828 56* 96 91 0 100 9429 52 80 74 22* 92 9430 0 55 0 22 99 6631 89 55 0 44 0 6632 0 0 0 0 99 8233 0* 54* 0* 0* 9* 34*34 0* 54* 0* 0* 0* 0* 38 29 93 97 23 96 0

39 98 83 91 0 100 90

*=Applications of the compound was made at a rate of 40 ppm.

Claims

What is claimed is:

1. The compounds of Formulae I, II, III and IV,

wherein:

-G¹- is -CR¹-R⁷-; -(CHR¹CHR²)-; - (CHR¹CHR²CHR³)-; or

-(CHR¹CHR²CHR³CHR⁴) -;

-G²-is -O-; -S-; -S(O)-; -S(O)₂- or -NR²⁷-;

-G³-is -CR⁴R⁸-; - (CHR⁵CHR⁶)-; -(CHR³CHR⁵CHR⁶)- or a direct bond;

X is N or CR¹³;

Y is N or CR¹⁴;

R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ are each

provided that

(i) the maximum number of carbon atoms in

-G¹-G²-G³- with geminal disubstitution is one;

(ii) the maximum number of optionally

substituted phenyl substituents on -G¹-G²-G3- is one;

(iii) -G³- is other than a direct bond in compounds of Formulae III and IV; and (iv) -G²-G³- is other than -NR²⁷- in compounds of Formulae I and II;

C₂-C₄ alkenyl; C₂-C₄ haloalkenyl; C₂-C₄

alkenyloxy; C₂-C₄ alkynyl; C₂-C₄ alkynyloxy; NR²⁹R³⁰; or phenyl or phenoxy optionally substituted with R³¹; or

R⁹ and R¹³, or R¹⁰ and R¹³, or R⁹ and R¹⁴ can be

taken together to form -(CH₂)₃-, -(CH₂)₄- or a fused benzene ring optionally substituted with R³¹; R¹¹, R¹², R²¹, R²⁴, R²⁶ and R³¹ are each

independently H or C₁-C₂ alkyl; or

4-morpholinyl, pyrrolidinyl or piperidinyl ring;

R²⁰ and R²⁷ are each independently H; C₁-C₄ alkyl;

C₁-C₄ haloalkyl; C₂-C₅ alkylcarbonyl; phenylcarbony.1 optionally substituted with R²¹; C₃-C₄ alkenyl; C₃-C₄ alkynyl; phenylmethyl optionally substituted with R²¹ on the phenyl ring; C₁-C₄ alkylsulfinyl; C₂-C₄ alkylsulfonyl; phenylsulfinyl, phenylsulfonyl or phenoxycarbonyl each optionally substituted with R²¹; C₂-C₄ alkoxycarbonyl; C(=O)NR²²R²³; C(=S)NHR²³;

P(=S)(C₁-C₄ alkoxy) ₂; P (=O) (C₁-C₄ alkoxy)₂; or S(=O)₂NR²²R²³;

R²² is H or C₁-C₃ alkyl;

R²³ is C₁-C₄ alkyl; or phenyl optionally

substituted with R²⁴; or

R²² and R²³ can be taken together along with the nitrogen atom to which they are attached to form a 4-morpholinyl, pyrrolidinyl, piperidinyl or imidazolyl ring;

R²⁵ is 1-2 halogen; C₂-C₄ alkyl; C₁-C₄ haloalkyl;

C₁-C₄ alkoxy; C₁-C₄ haloalkoxy; nitro; cyano or C₂-C₄ alkylthio; and

R²⁸ is halogen; cyano; nitro; hydroxy; hydroxycarbonyl; C₁-C₆ alkyl; C₃-C₆ cycloalkyl; C₁-C₆ haloalkyl; C₁-C₄ alkylthio; C₁-C₄ alkyl sulfinyl; C₁-C₄ alkylsulfonyl; (C₁-C₄

alkyl)₃silyl3 C₂-C₅ alkylcarbonyl; C₂-C₄ alkenyl; C₃-C₄ alkenyloxy; C₂-C₄ alkynyl; C₃-C₄ alkynyloxy; C₁-C₄ alkoxy; C₁-C₄ haloalkoxy;

C₂-C₄ alkoxyalkyl; C₂-C₅ alkoxycarbonyl; C₂-C₄ alkoxyalkoxy; NR¹⁵R¹⁶; C(=O)NR¹⁷R¹⁸; or phenyl, phenoxy or phenylthio each optionally

substituted with R²⁶;

provided that

and agriculturally suitable salts and metal complexes thereof.

2. The compounds of Claim 1, Formula I, wherein:

Y is N;

E is phenyl, indanyl, tetrahydronaphthalenyl, 1-naphthalenyl, thienyl, or pyridyl each optionally substituted with R¹¹, R¹² and R²⁸;

R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ are each independently H or methyl;

R¹¹ and R¹² are each independently F, Cl, methyl, trifluoromethyl, methoxy or trifluoromethoxy;

R¹³ is H;

R⁹ and R¹⁰ are each independently halogen; C₁-C₄ alkyl; cyclopropyl; C₁-C₄ haloalkyl; allyl; or C₂-C₃ alkynyl; or

R²⁸ is halogen; cyano; C₁-C₄ alkyl; C₁-C₄ haloalkyl; allyl; propargyl; C₁-C₄ alkoxy; C₁-C₄ haloalkoxy; or phenyl or phenoxy each optionally substituted with R²⁶; and

R³¹ is halogen; C₁-C₄ alkyl or C₁-C₄ haloalkyl.

3. The compounds of Claim 2, wherein:

G² is O; S or NR²⁷; and

E is phenyl optionally substituted with R¹¹, R¹² and R²⁸; indanyl or tetrahydronaphthalenyl.

4. The compounds of Claim 3, wherein:

G² is O; S; NH or N(C₁-C₄ alkyl); and

E is phenyl optionally substituted with R¹¹, R¹² and R²⁸.

5. The compound of Claim 1, which is

3-(4,6-dimethyl-2-pyrimidinyl)-3,6-dihydro-5- phenyl-2H-1,3,4-oxadiazine.

6. The compound of Claim 1, which is

3-(4,6-dimethyl-2-pyrimidinyl)-5-(4-ethylphenyl)-3,6-dihydro-2H-1,3,4-oxadiazine.

7. The compound of Claim 1, which is

2-(2-chlorophenyl)-4-(4,6-dimethyl-2- pyrimidinyl)-5,6-dihydro-4H-1,3,4-thiadiazine.

8. The compound of Claim 1, which is

4-(4,6-dimethyl-2-pyrimidinyl)-2-(4-ethylphenyl)-5,6-dihydro-4H-1,3,4-thiadiazine.

9. A method of controlling fungus disease in plants which comprises treating the locus to be protected with an effective amount of at least one of the compounds of Formulae I, II, III or IV, agriculturally suitable salts thereof, agriculturally suitable metal complexes thereof, or agricultural compositions containing them;

wherein:

-G¹-is -CR²R⁷-; -(CHR¹CHR²)-; -(CHR¹CHR²CHR³)-; or - (CHR¹CHR²CHR³CHR⁴)-;

-G²- is -O-; -S-; -S(O)-; -S(O)₂- or -NR²⁷-;

-G³- is -CR⁴R⁸; (CHR⁵CHR⁶)-; -(CHR³CHR⁵CHR⁶)- or a direct bond;

X is N or CR¹³;

Y is N or CR¹⁴;

E is H; C₁-C₆ alkyl; C₃-C₇ cycloalkyl optionally substituted with 1-2 methyl; C₁-C₆ haloalkyl; C₁-C₆ alkylthio; C₁-C₆ alkoxy; C₁-C₆ haloalkoxy; or phenyl, phenoxy, phenylthio, phenylamino, phenylmethyl, indanyl, tetrahydronaphthalenyl, 1-naphthalenyl, 2-naphthalenyl, thienyl, furanyl or pyridyl each optionally substituted with R¹¹, R¹² and R²⁸; R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ are each

independently H; C₁-C₄ alkyl; C₁-C₄ haloalkyl, halogen, CO₂CH₃, CO₂CH₂CH₃, cyano, or phenyl optionally substituted with R²⁵;

provided that

(i) the maximum number of carbon atoms in -G¹-G²-G³- with geminal disubstitution is one;

(ii) the maximum number of optionally substituted phenyl substituents on

-G¹-G²-G³- is one;

(iii) -G³- is other than a direct bond in

R⁹, R¹⁰ and R¹³ are each independently H; halogen; cyano; hydroxy; C₁-C₆ alkyl; C₁-C₄ haloalkyl; C₁-C₄ alkylthio; C₁-C₄ alkylsulfinyl; C₁-C₄ alkylsulfonyl; C₃-C₆ cycloalkyl optionally substituted with 1-2 methyl groups; C₁-C₄ alkoxy; C₁-C₄ haloalkoxy; C₂-C₄ alkoxyalkyl; C₂-C₄ alkenyl; C₂-C₄ haloalkenyl; C₂-C₄

alkenyloxy; C₂_C₄ alkynyl; C₂-C₄ alkynyloxy;

NR²⁹R³⁰; or phenyl or phenoxy optionally

substituted with R³¹; or

R⁹ and R¹³, or R¹⁰ and R¹³, or R⁹ and R¹⁴ can be

taken together to form -(CH₂)₃-, -(CH₂)₄- or a fused benzene ring optionally substituted with R³¹;

R¹¹, R¹², R²¹, R²⁴, R²⁶ and R³¹ are each

independently halogen; C₁-C₄ alkyl; C₁-C₄ haloalkyl; C₁-C₄ alkoxy; or C₁-C₄ haloalkoxy; R¹⁴ is H; halogen; C₁-C₂ alkyl; or C₁-C₂ alkoxy;

R¹⁵, R¹⁶, R¹⁷, R¹⁸, R²⁹ and R³⁰ are each

independently H or C₁-C₂ alkyl; or R¹⁵ and R¹⁶, or R¹⁷ and R¹⁸, or R²⁹ and R³⁰ can be taken together along with the nitrogen atom to which they are attached to form a 4-morpholinyl, pyrrolidinyl or piperidinyl ring;

R²⁰ and R²⁷ are each independently H; C₁-C₄ alkyl;

P(=S)(C₁-C₄ alkoxy)₂; P (=O) (C₁-C₄ alkoxy)₂; or S(=O)₂NR²²R²³;

R²² is H or C₁-C₃ alkyl;

R²³ is C₁-C₄ alkyl; or phenyl optionally

substituted with R²⁴; or

R²⁵ is 1-2 halogen; C₁-C₄ alkyl; C₁-C₄ haloalkyl;

C₁-C₄ alkoxy; C₁-C₄ haloalkoxy; nitro; cyano or C₁-C₄ alkylthio; and

R²⁸ is halogen; cyano; nitro; hydroxy; hydroxycarbonyl; C₁-C₆ alkyl; C₃-C₆ cycloalkyl; C₁-C₆ haloalkyl; C₁-C₄ alkylthio; C₁-C₄ alkylsulfinyl; C₁-C₄ alkylsulfonyl; (C₁-C₄

alkyl) ₃silyl; C₂-C₅ alkylcarbonyl; C₂-C₄ alkenyl; C₃-C₄ alkenyloxy; C₂-C₄ alkynyl; C₃-C₄ alkynyloxy; C₁-C₄ alkoxy; C₁-C₄ haloalkoxy;

substituted with R²⁶.

provided that

10. A fungicidal composition comprising a

fungicidally effective amount of a compound of

Formula I, II, III or IV

wherein:

-G¹- is -CR¹-R⁷-; - (CHR¹CHR²)-; -(CHR¹CHR²CHR³)-; or -CHR¹CHR²CHR³CHR⁴)-;

-G²-is -O-; -S-; -S(O)-; -S(O)₂- or -NR²⁷-; -G³-is -CR⁴R⁸-; -(CHR⁵CHR⁶)-; -(CHR³CHR⁵CHR⁶)- or a direct bond;

X is N or CR¹³;

Y is N or CR¹⁴;

R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ are each

provided that

(ii) the maximum number of optionally

substituted phenyl substituents on -G¹-G²-G³- is one;

(iii) -G³- is other than a direct bond in compounds of Formulae III and IV; and

(iv) -G²-G³- is other than -NR²⁷- in compounds of Formulae I and II;

alkenyloxy; C₂-C₄ alkynyl; C₂-C₄ alkynyloxy; NR^29R30; or phenyl or phenoxy optionally substituted with R³¹; or

R⁹ and R¹³, or R¹⁰ and R¹³, or R⁹ and R¹⁴ can be

taken together to form -(CH₂)₃-, -(CH₂)₄- or a fused benzene ring optionally substituted with

R³¹;

R¹¹, R¹², R²¹, R²⁴, R²⁶ and R³¹ are each

independently halogen; C₁-C₄ alkyl; C₁-C₄ haloalkyl; C₁-C₄ alkoxy; or C₁-C₄ haloalkoxy; R¹⁴ is H; halogen; C₁-C₂ alkyl; or C₁-C₂ alkoxy; R¹⁵, R¹⁶, R¹⁷, R¹⁸, R²⁹ and R³⁰ are each

independently H or C₁-C₂ alkyl; or

4-morpholinyl, pyrrolidinyl or piperidinyl ring;

R²⁰ and R²⁷ are each independently H; C₁-C₄ alkyl;

R²² is H or C₁-C₃ alkyl;

R²³ is C₁-C₄ alkyl; or phenyl optionally

substituted with R²⁴; or

R²² and R²³ can be taken together along with the nitrogen atom to which they are attached to form a 4-morpholinyl, pyrrolidinyl, piperidinyl or imidazolyl ring; R²⁵ is 1-2 halogen; C₁-C₄ alkyl; C₁-C₄ haloalkyl;

C₁-C₄ alkoxy; C₁-C₄ haloalkoxy; nitro; cyano or

C₁-C₄ alkylthio; and

alkyl)₃silyl; C₂-C₅ alkylcarbonyl; C₂-C₄ alkenyl; C₃-C₄ alkenyloxy; C₂-C₄ alkynyl; C₃-C₄ alkynyloxy; C₁-C₄ alkoxy; C₁-C₄ haloalkoxy;

substituted with R²⁶;

provided that

when E is, C₁-C₆ alkylthio, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy, phenoxy, phenylthio or phenylamino, then E may only substitute compounds of Formula

I;

and agriculturally suitable salts and metal complexes thereof and at least one of (a) a surfactant, (b) an organic solvent and (c) at least one solid or liquid diluent.