LT4112B - Fungicidal cyclic amides - Google Patents

Abstract

Cyclic amides, used as fungicides, with the general formula I, in which:A is O; S; N; NR5 or CR14;G is C or N;W is O or S;X is OR1, S(O)mR halogen;R1, R2, and R5, not dependent on each other, are partially, C1-C6 alkyl;Y may be -O-; -S(O)n; -CHR6O- or -CHR6O-N=C(R7)-;Z may be possibly modified cyclo-alkyl, phenyl, pyridinyl, pyrimidinyl or naphthyl; andR3, R4, R6, R7, R14, m and n are indicated in description.

Description

The present invention provides cyclic amides substituted at the α-position by various aryl groups, their agrochemically acceptable salts and compositions, and their use as general or selective fungicides.

European Patent EP-A-398 692 describes amides of formula (i) as crop protection fungicides. The compounds of formula (i) are:

to which

9th

R and R are each hydrogen, lower alkyl or lower cycloalkyl.

All of the compounds described in EP-A-398 692 have an aryl side linked to an acyclic alkoxyiminoacetamide group. It does not describe the cyclic amides of the present invention.

WO 93/07116 describes compounds of general formula (ii) as crop protection fungicides. Compounds of general formula (ii):

^(CH 2) u -C-ZR ² wherein:

W is

Me OOC ^^ CH or Me

OMe

OMe

OMe

The cyclic amides of the present invention are also not described in the claimed application.

J. Heterocyclic Chem., (1987), 24,465, J. Heterocyclic Chem., (1988), 25, 1307, and Australian J. Chem., (1977), 30 (8), 1815, respectively, describe 4nitrophenylisoxazoles (iii). ), phenylpyrazolones (iv) and arylthiazolones (v).

However, fungicidal uses and orthopedic compounds of the invention are not mentioned in the cited literature.

The compounds of the present invention represented by the general formula (I) include all geometric isomers and stereoisomers, their agrochemically acceptable salts, their agrotechnical compounds and their use as fungicides:

to which

A is O; S; N; NR ⁵ ; or CR ¹⁴ ;

G is C or N; with the proviso that when G is C, A is O, S or NR ⁵ and the fluctuating double bond is attached to G; and when G is N, A is N or CR ⁴ and the fluctuating double bond is attached to A;

W is O or S;

X is OR ¹ ; SįOjmR ^1; or halogen;

R ¹ , R ² and R ^{5 are} each independently H; C 8 -C 8 alkyl; C 1 -C 8 haloalkyl; C 1 -C 8 alkenyl; C 2 -C ₆ -haloalkenyl; C 2 -C 8 alkynyl; C2-C8-haloalkynyl; Cg-Cg-cycloalkynyl; C ₂ C ₄ alkylcarbonyl; C 1 -C 6 alkoxycarbonyl; or benzoyl, optionally substituted;

R ³ and R ^{4 are} each independently H; cyano; nitro; C ₁ -C ₆ alkyl; CpC8 -haloalkyl; C 2 -C 8 alkenyl; C 0 -C 8 haloalkenyl; C 1 -C 8 alkynyl; C 2 -C 8 haloalkynyl; C4-C5 alkoxy; C 1 -C 8 haloalkoxy; C 2 -C 8 alkenyloxy; or C 2 -C 8 alkynyloxy;

Y is -O-; -S (O) n -; -CHR ⁶ -CHR ⁶ -; - CR ⁶ = CR ⁶ -; -OC; -CHR ^fi O-;

OCHR ⁶ -; -CHR ⁰ S (O) n; -S (O) _n CHR ⁶ -; -CHR ⁶ ON = C (R ⁷ ) -; - (R ⁷ ) CY N-OCH (R ⁶ ) -; -C (R ⁷ ) = NO -; - ON = C (R ⁷ ) -; -CHR ⁶ OC (= O) N (R ¹⁵ ) -; or direct connection; and the direction of the Y bond is defined such that the portion to the left of the bond is joined to the phenyl ring and the portion to the right of the bond is joined to Z;

R ⁶ is independently H or C 1 -C 3 alkyl;

R ⁷ is H; C 1 -C 8 -alkyl; CpC8 -haloalkyl; C 1 -C 8 -C 8 alkoxy; C 1 -C 8 haloalkoxy; C2-C8-alkenyl; C2-C8-haloalkenyl; C2-C8-alkynyl; C2-C8-haloalkynyl; C3-C8-cycloalkyl; C2-C4-alkylcarbonyl; C 2 -C ₄ alkoxycarbonyl; cyano; or morpholine;

Z is C 1 -C 8 alkyl, C 2 -C 10 alkenyl, or C 8 -C 10 alkynyl, each o

optionally substituted with R; or Z is C 1 -C 8 -cycloalkyl or phenyl, each optionally substituted with one of R ⁹ , R ¹⁰ , or both of R ⁹ and R ¹⁰ ; or Z is a 3 to 14 membered non-aromatic heterocyclic ring system selected from the monocyclic ring system, fused bicyclic ring and fused tricyclic ring, or Z is a 5 to 14 membered aromatic ring system selected from the monocyclic ring, fused bicyclic ring ii · A system of a fused tricyclic ring, each non-aromatic or aromatic ring system having from 1 to 6 heteroatoms independently selected from 1-4 nitrogen atoms, 1-2 oxygen atoms and 1-2 sulfur atoms, each non-aromatic or aromatic ring system being optionally substituted by one R ⁹ , R ^10, or both R ⁹ and R ¹⁰ ; or

R ⁷ and Z together are taken from CH 2 CH 2 OH 2, CH 2 CH 2 CH 2 CH 2,

CH2CH2OCH2CH2, each CH2 group optionally substituted with 1-2 halogen atoms; or

Y and Z together form R ³ ;

R ⁶

I - (CH) ·

; or

Y and Z together with the phenyl ring form a naphthalene ring substituted in any ring at a non-volatile group with R, provided that when R, Y and Z taken together with the phenyl ring form a naphthalene ring substituted with R ⁴ and A is S, W is O, X is SCH 3 and R ² is CH 3, then R ⁴ is not H;

J is -CH ₂ -; -CH ₂ CH ₂ -; -OCH _? -; -CH ₂ O-; -SCH ₂ -; -CH ₂ S-; -N (R ¹⁶ ) CH 2 -; or -CH 2 N (R ¹⁶ ) -; each CH2 group, possibly substituted with 1 to 2 ch ₃ .

R 1 is 1-6 halogen atoms; C 1 -C 8 alkoxy; C 1 -C 8 haloalkoxy; C 1 -C 8 alkyl; C 1 -C 8 haloalkylthio; C 1 -C 8 alkylsulfinyl; C 1 -C 8 alkylsulfonyl-C 1 -C 8 cycloalkyl; C 1 -C 8 alkenyloxy; CO ₂ (C ₁ -C 6 alkyl); NH 1 Cl (C 8 -alk)); N (C _r Cg alkflas) _2; cyano or nitro; or o

R is phenyl, phenoxy, pyridinyl, pyridinyloxy, thienyl, furanyl, pyrimidinyl, or pyrimidinyloxy, each optionally substituted with one of R ¹¹ , R ¹² , or both of R ¹¹ and R ¹² ;

R ⁹ is 1-2 halogen atoms; C ₃ -C 8 alkyl; C 1 -C 8 haloalkyl; C ₃ -C ₈ alkoxyCpC 8 -haloalkoxy C ₂ -C 8 alkenyl; C ₂ -C 8 -haloalkenyl;

C ₂ -C 8 alkynyl; C 1 -C 8 alkylthio; C 1 -C 8 haloalkylthio; C 1 -C 8 alkylsulfinyl; C 1 -C 8 alkylsulfonyl; G 1 -C 8 -cycloalkyl; C 1 -C 8 alkenoxy; CO ₂ (C 1 -C 8 alkyl); NH (C _R alkflas Cg) N (C _r Cg alkflas) _2;

Q 17 o

-C (R) = NOR; cyano or nitro; or R is phenyl, benzyl, benzoyl, phenoxy, pyridinyl, pyridinyloxy, thienyl, thienyloxy, furanyl, pyrimidinyl, or pyrimidinyloxy, each optionally substituted with one of R ¹¹ , R ¹² , or both R ¹¹ and R ¹² ;

R ¹⁰ is halogen; C 1 to C ₄ alkyl; C 1 -C 6 haloalkyl; C 1 -C 6 alkoxy; nitro; or cyano; or

R ⁹ and R ¹⁰ , when attached to a neighboring atom, are taken together as -OCH ₂ O or -OCH ₂ CH ₂ O-; each CH ₂ group is optionally substituted with 1-2 halogen atoms;

R and R are each independently halogen; C 1 -C 4 alkyl; C ₁ -C ₄ haloalkyl; C 1 -C 6 alkoxy; C 1 -C 6 haloalkoxy; nitro; or cyano;

R is halogen; C ₃ -C ₃ alkyl; C-To-G ₃ -haloalkyl; CPC ₃ alkoxy; C--C G G halhaloalkoxy; nitro; or cyano;

R ¹⁴ is H; halogen; C 1 -C 4 alkyl; C 1-4 haloalkyl; C 2 -C 8 alkenyl;

C 1 -C 8 haloalkenyl; C 1 -C 6 -alkynyl; C2-C5-haloalkynyl; or

C8-C8 cycloalkinyl;

1S 1A 17 i o

R, R, R and R are each independently H; (-C 1 -C 6 -alkyl; or phenyl optionally substituted with halogen, C 1 -C ₄ -alkyl; C ₁ -C ₄ -haloalkyl; C ₁ -C ₄ -alkyl; C ₁ -C ₄ -alkyl; nitro or cyano;

m, n and q are each independently 0.1 or 2; and p and r are each independently 0 or 1.

The term alkyl as used herein, alone or in combination with words such as haloalkyl, means a linear or branched alkyl, i.e., methyl, ethyl, npropyl, i-propyl or different butyl, phenyl or bexyl isomers. Alkenyl refers to linear or branched alkenes, such as 1-propenyl, 2-propenyl, and the different isomers of butenyl, pentyryl and hexenyl. Alkenyl also means polyene such as 1,3-hexadiene. Alkynyl means linear or branched alkynes such as ethynyl, 1-propynyl. 3-propynyl and hexinyl isomers. Alkynyl may also refer to moieties consisting of multiple triple bonds, such as 2,4-hexadecane. Alkoxy means, for example, the different butoxy, pentoxy and hexyloxy isomers of methoxy, ethoxy, n-propyloxy, isopropyloxy. Alkenyloxy refers to linear or branched alkenyloxy moieties. Examples of alkenyloxy include H2C-CHCH2O, (Cb ^^ C = CHCH? O. Alkyloxy means linear or branched alkynyloxy moieties. Examples include HCs CCH2O, CPACACCH '^ OTHER ·) · The term halogen alone or in a compound of words such as haloalkoxy means fluorine such as chlorine, bromine or iodine. Further, when a phrase such as haloalkyl is used, this alkyl may be partially or completely substituted by halogen atoms, which may be the same or different. Examples of haloalkyl include F3C, C1CH ?, CF3CH? * ^r CF3CCI7. The term eicloalkyl includes cyclopropyl, cyclopentyl and cyclohexyl moieties. The term non-aromatic heteracyclic ring system includes fully saturated heterocycles and partially aromatic heterocycles. The total number of carbon atoms in the substituent group is denoted C 1 -C 6, wherein the indices i and j are numbers from 1 to 10. For example, C 3 -C 3 alkyl denotes methyl to propyl; C 1-4 alkoxy denotes CH 3 Cl 12; and C 1 -C 6 alkoxy denotes, for example, CH 3 CH 2 O or (CH-CH 2 O). As above when a compound of the general formula 1. is composed of one or more aromatic nitrogen-containing rings (i.e., pyridinyl and pyrimidinyl), all of these heterocycles the bonds are formed through the carbon atom (s) of said moieties.

The proposed compounds, compositions containing them and methods of use for their enhanced activity and / or simpler synthesis are:

offer. Compounds of formula I above wherein:

W is O;

R ¹ is alkyl or haloalkyl;

R ² is H; C 1 -C 8 alkyl; C-C 1 -C 8 -haloalkyl; or C 1 -C 8 cycloalkyl; R ³ and R ^{4 are} each independently H; halogen; cyano; nitro;

C 1 -C 8 alkyl; CpC8-haloalkyl; C 1 -C 8 alkoxy; or C 1 -C 8 haloalkoxy;

Y is -O-; -CH = CH-; -CH ₂ O-; -OCH ₂ -; -CH _? S (O) _n -; -CH ₂ ON = C (R ⁷ ) -; -C (R ⁷ ) = NO-; -CH ₂ OC (O) NH-; or direct communication;

R ⁷ is H; C 1 -C 8 alkyl; C 1 -C 8 haloalkyl; C ₂ -C 8 alkenyl; C 1 -C 8 alkynyl; or cyano;

O

Z is C-C 1 -C 8 alkyl optionally substituted with R; or C 1 -C 8 -cycloalkyl or phenyl, each optionally substituted with one of R ⁹ , R ¹ ® or both of R ⁹ and R ¹⁰ ; or Z is present

Z-3 i

Z u

Z-2

Z-5

Z-IO Z-ll Z-12 N - N <7 Λ-N 77 «-N 7> 2> 13 Z-14 2-15

2.35

S '' 's or

In Z-49, each group is optionally substituted with one of R ⁹ , R ^10, or both of R ⁹ and R ¹⁹ ; or a

R, Y and Z taken together with the phenyl ring form a naphthalene ring substituted with R ⁴ fluctuating in any one of the two rings; or

Y and Z are taken together to form

R

R is 1-6 halogen atoms; C 1 -C 8 alkoxy; C 1 -C 6 -haloalkoxy or R is phenyl, phenoxy, pyridinyl, pi'idinyloxy, pi'-imidinyl, or ii 19 pyrimidinyloxy, each optionally substituted with one of R ¹ , R ¹ or both R ¹ and R ^{1 '} ;

R ⁹ is 1-2 halogen atoms; C 1 -C 8 alkoxy; C 1 -C 8 haloalkyl; Cp-C8-alkoxy Cp-C8-haloalkoxy, C-C6-C8-alkylthio; cyano; CO (C 1 -C 8 alkyl); NH (C 1 -C 8 alkyl); or N-C 1 -C 8 -alkyl ^; or R ⁹ is C3Cg -cycloalkyl, phenyl, phenoxy, pyridinyl, pyridinyloxy, pyrimidinyl, or pyrimidinyloxy each optionally substituted with one of R ^11, R ^ ¹ or both R ⁹ and R ¹ ®; and

R ¹⁹ is H; CpC8 alkyl; C 1 -C 8 haloalkyl; or phenyl optionally substituted with halogen, C 1 -C ₄ alkyl, C 1 -C ₄ haloalkyl, C 1 -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, nitro or cyano.

offer. Offer compounds 1, in which:

Z is phenyl or Z 1 to Z-21, each optionally substituted with one of R ⁹ , R ^10, or both of R ⁹ and R ¹⁰ ; or

Y and Z are taken together to form

or

J is -GH ₂ - or -CH ₂ CH ₂ -; p is O; and r is 1.

offer. Proposition 2 compounds in which:

A is O; N; NR ⁵ ; or CR ¹⁴ ;

X is OR ¹ ;

R ¹ is C ¹ -C 3 alkyl;

R ⁷ is H or CpC0-alkyl;

R ³ and R ^{4 are} each H;

Y is -O-; -CH = CH-; -CH ₂ O-; -OCH ₂ -; -CH ₂ ON = C (R ⁷ ) -;

or -CH ₂ OC (= O) NH-;

1

R 'is H; G 1 -C 1 alkyl; or R 8 is -G 1 -haloalkyl; and Z is phenyl, pyridinyl, pyrimidinyl, or thienyl, each optionally substituted with one of R ⁹ , or both of R ⁹ h R ¹⁰ .

offer. Proposition 3 compounds in which:

A is O or NR ⁵ ;

G is C;

Y is -O-; -CH ₂ O-; -OCH ₂ -; or -CH ₂ ON = C (R ⁷ ) -; and R ⁷ is H; C 1 -C 2 alkyl; or R ¹ C ¹ -C 2 -haloalkyl.

offer. Proposition 3 compounds in which:

A is N or CR ¹⁴ ;

G is N;

Y is -O-; -CH ₂ O-; -OCH ₂ -; or -CH ₂ ON = C (R ⁷ ) -; and R ⁷ is H; C 1 -C 2 alkyl; or R ^{1 is} C ¹ -C ₂ -haloalkyl.

offer. Proposition 4 compounds in which:

R ¹ is methyl;

η

R is methyl; and

Z is phenyl, optionally substituted with one of R ⁹ , R ¹⁰ , or both of R ⁹ and R ¹⁰ .

offer. Offer compounds 6, where:

R ¹ is methyl;

R ¹ is methyl, and

Z is phenyl, optionally substituted with one of R ^, R ^, or both of R ^ and R ^.

It is recognized that some of the reagents and reaction conditions described below may be incompatible in the preparation of compounds of formula I with some of the functions defined by R, R, R ', R, A, G, W, X, Y and Z. introduction of protective / deprotecting sequences into the synthesis may be necessary to obtain the desired products. The cases in which protecting groups are needed and which protecting groups to use will be apparent to those skilled in the art of chemical synthesis.

The following is the preparation of compounds of formula I, the compounds of formula Ia to formula Ik being exclusively different subgroups of compounds of formula I. All substituents of the compounds of formulas Ia to Ik and 1-39 are as defined above for formula I, except where otherwise indicated.

These compounds of the invention may exist as one or more stereoisomers. The various stereoisomers include enantiomers, diastereomers and geometric isomers. One skilled in the art will appreciate that one stereoisomer may be more active than the other and how to distinguish between these stereoisomers. Therefore, the present invention includes compositions, individual stereoisomers, and optically active mixtures of compounds of formula Ia, as well as their agriculturally suitable salts.

One skilled in the art will appreciate that some compounds of formula Ia may exist in one or more tautomeric forms. For example, a compound of Formula I wherein R ² is H may exist as a tautomer of Formula Ia or Ib, or tautomer of both Formulas Ia and Ib. The present invention includes all tautomeric forms of Formula I.

Compounds of Formula I may be prepared as described below in Operations 1) to 5). Operations 1) to 4) describe syntheses involving the construction of an ainide ring after the aryl moiety is formed. 5) The operation describes the synthesis of the aryl moiety with the already formed amide ring.

1) Alkylation

Compounds of Formula I are prepared by treating compounds of Formula I with an appropriate alkyl-carrying reagent in an inert solvent, with or without additional acid or base reagents, or other reagents (Scheme 1). Suitable solvents are selected from the group consisting of polar aprotic solvents such as acetonitrile, dimethylformamide or dimethylsulfoxide; ethers such as tetrahydrofuran, dimethoxyethane or diethyl ether; ketones such as acetone or 2-butanone;

and perhalogen hydrocarbons, hydrocarbons such as toluene or benzene; such as dichloromethane or trichloromethane.

scheme

- 4 Ways

i

X = OH or SH

X = OR ¹ or SR ¹ way: Q-CH = N ₂ (Q = H or (CF ^ Si)

NH mode: II: Lewis acid a ₃ c ^z ^ or ¹

Method J: ( ^{r1 +} BF ₄ 'Method: (R ^ SO ^ j. R ¹ OSO ₂ Q; or R ^ -hal;

optional base (hal - F, Cl, Br, or I) (Q - C ₃ - C ₈ alkyl, C ₁ - C ₈ haloalkyl)

For example, compounds of Formula I may be prepared by reacting diazoalkane reagents of Formula 2, such as diazomethane (O-H) or trimethylsilyldiazomethane (Q = (CfTj ^ Si) with dicarbonyl compounds of Formula 1). methanol Examples of such operations are Client Pharm. Bull. (1984) 32, 3759.

As shown in Method 2, the compounds of Formula I may also be prepared by contacting the carbonyl compounds of Formula 1 with alkyltrichloroacetimidates of Formula 3 and a Tunisian (Levvis) acid catalyst. Suitable Lewis acids include triethylsilyl tritylate and tetrafluoroboric acid. Alkyl trichloroacetimidates can be prepared from the appropriate alcohol and trichloroacetonitrile as described in the literature (J. Danklmaicr and H. Honig, Synth. Commun. (1990), 20, 203).

The compounds of Formula I may also be prepared by treating the compounds of Formula I with a trialkyloxam tetrafluoroborate of Formula 4 (Method 3) (i.e., Meervvein salt). The use of trialkyloxamate salts as effective alkylating agents is well known (see U. Schollkopf, U. Groth, C. Deng. Angew. Chem., Int. Ed. Engi, (1981), 20, 798).

Other alkylating agents that can convert compounds of formula 1 into compounds of formula I include dialkyl sulfates such as dimethosulfate, haloalkyl sulfonates such as methyl trifluoromethanesulfonate, and alkyl halides such as iodomethane and propalgyl bromide (method 4). These alkylations may be carried out with or without an additional base. Suitable bases include alkali metal alkoxides. such as potassium tert-butoxide, inorganic bases such as sodium hydride and potassium carbonate, or tertiary amines such as triethylamine, pyridine, 1,8-diazabicyclo [4.5.0] undec-7-one (DBU) and triethylenediamine. For alkylation examples, this type of material is used, see R. E. Benson, T. L. Cairns, J. Am. Chem. Soc., (1948), 70, 2115.

Compounds of formula Ia (compounds of formula 1 wherein G = C, W = O and X = OH) may be prepared by condensation of malonates of formula 5 or malonate derivatives with suitable nucleophilic reagents of formula 6 (Scheme 2). The nucleophilic reagents of Formula 6 are N-substituted hydroxylamines (HO-NHR ^) and substituted hydrazines (HN (R ⁵ ) NHR). Examples of such nucleophilic reagents are N-methylhydroxyamine and methylhydrazine. Formate 5 malonate esters may be prepared by the methods described below. The esters of Formula 5 may also be activated by first hydrolyzing the ester to form the corresponding acid and then converting the acid to the acid chloro anhydride (T = Cl) using thionyl chloride or oxalic saline chloride or to acylimidazolyl (T = 1-imidazolyl), by treatment with Ι, Γ-carbonyldiimidazole.

scheme

T = O (C 8 -C 8 -alkyl), Cl, 1-imidazolyl

Esters of Formula 5a may be prepared by reaction of the copper (I) malonate esters of Formula 7 with the appropriate iodobenzenes of Formula 8 according to the methods described by A. Osuka, T. Kobayashi and H. Suzuki, Synthesis (1983) 67 and depicted in Scheme 3.

scheme r ²⁰ o ₂ c ^ _/ co ₂ r ²⁰

Z

--------->

Cul, base

R ²⁰ = C 1 -C ₄ alkyl

In addition, the malonate esters of Formula 5a may be prepared by treating the phenylacetic acid esters of Formula 9 with a dialkyl carbonate in the presence of a suitable base such as, but not limited to, metal sodium and sodium hydride (Scheme 4). For example, watch /. Am Chem. Soc., (1928), 50, 2758.

scheme

O

II

C

R ^{? C} 'c / Y) R ²⁰ or

5a

O

II

base

R ²⁰ = C _r C ₄ alkyl

Esters of Formula 9 may be prepared by reaction of the alcohol / acetonitrile alcohol of Formula 10 with a catalyzed acid or by esterification of the phenylacetic acid of Formula 11 as shown in Scheme 5 (see Org. Synth., 1941, 270).

OR ²⁰

R f 2 ° oh

Y acid

I

OH

R ²⁰ = C ₁ -C ₄ alkyl

The phenylacetic acid esters of Formula 9 may also be prepared by the copper (I) catalyzed reaction of the phenyl / halide condensation of Formula 12 with the compounds of Formula 13 as described in FP-A-307103 and shown in Scheme 6 below.

scheme

HY - Z

9a

R ²⁰ = C _r C _r alkfl

Y ^ O, S, OCHR ⁶ , SCHR ⁶ , ON = C (R ⁷ )

Some esters of Formula 9 (Formula 9b) may also be prepared by forming a Y bridge using a conventional nucleophilic substitution reaction (Scheme 7). Substitution of the corresponding leaving group (Lg) in Formula 15 or 16 for an electrophile with a nucleophilic ester of Formula 14 affords compounds of Formula 9b. A base, such as sodium hydride, is used to prepare the compound of formula 14, respectively alkoxide or thioalkoxide.

scheme

Lg — Z or

Lg-CHR ⁶ -Z;

base

R ^ CpCą-alkiias

R ²¹ = OH, SH, chr ⁶ oh, chr ⁶ sh Y ^ O, S, OCHR ⁶ , SCHR ⁶ , CHR ⁶ O, CHR ⁶ S

Ig = Br, α, I, OSO ₂ CH ₃ , OSO ₂ (4-Me-Ph)

Some esters of Formula 9 (Formula 9e) may also be prepared by forming a Y bridge from the substituted formyl hydroxylamine of Formula 9d and the carbonyl compounds of Formula 14a. The hydroxylamine of formula 9a is in turn prepared from the esters of formula 9c. This method was described in EP-600 835 and depicted in Scheme 8 below.

OR ²⁰

9c B = CPIR ⁶ Br 9d B = CHR ⁶ ONH, HQ

OR ²⁰

R 1 C 1 -C 10 alkyl

Y ³ = CHR ⁶ ON = C (R ⁷ )

2) Exchange and join / back reactions

Compounds of formula I may also be prepared by reacting compounds of formula 17 with alkali metal alkoxides (R ¹ 'OM ⁴ ) or alkali metal thioalkoxides (R ¹ S'NF) in a suitable solvent (Scheme 9). The amide leaving group L1 of Formula 17 is any group suitable for this type of substitution reaction. Examples of suitable leaving groups include chlorine, bromine, and sulfinyl and sulfonate groups. Examples of suitable inert solvents are dimethylformamide and dimethylsulfoxide.

scheme

R ²

¹⁷ Lg ^{= 1} Q, Br, -SO ₂ Q or -OSO ₂ QiQ = C]-C4 alkyl, or (A-C ^ haloalkyl, M = K or Na

Compounds of formula 17a may be prepared by reacting compounds of formula 16 (compounds of formula 1 wherein X is OH) with halogenating agents such as thionochloride or phosphorus oxybromide to form the corresponding β-halogen-substituted derivatives (Scheme 10). In contrast, compounds of formula 1b may be treated with an alkylsulfonyl halide or a haloalkylsulfonyl anhydride such as methanesulfonyl chloride, p-toluenesulfonyl chloride and trifluoromethanesulfonyl anhydride to form the corresponding β-alkylsulfonate of formula 17a. The reaction with sulfonyl halides may be carried out in the presence of a suitable base (for example, tri-inine).

Scheme Ib: halogenating agent or QSO ₂ -hal _z or QSO ₂ -OO ₂ SQ

17a

Eg ² = 0, Br, or -OSO ₂ Q

Q = CpCg-alkyl or C 1 -C 8 -halogenoalkyl hal = Br, 0 or F

As shown in Scheme 11, the sulfonyl compounds of Formula 17b can be prepared by oxidation of the corresponding thio compounds of Formula 18 using well known sulfur oxidation techniques (see Schrenk, K., The Chemistry of Sulphones and Sulphoxides; Patai, S. et al., Eds .; Wiley: New York, 1988). Suitable oxidation reagents include meta-chloro-peroxybenzoic acid, hydrogen peroxide, and Oxone (KHSO5).

Q is C 1 -C 8 alkyl or Cp C 8 haloalkyl

In contrast, the halo compounds of formula 17a (compounds of formula 17a where A = N, G = N and W = O) can be prepared from the hydrazides of formula 19 as shown in Scheme 12. When R ² is -C (-S 1 -C 1 -C 1 -C 4 -alku), the diacyl compound of formula 19 is treated with an excess of thionyl halide, such as an excess of thionyl chloride. The first product to be formed is a closed-loop compound of formula 20, which may be isolated or recycled in situ to a compound of formula 17c; for a description of this process see P. Molina, A. Tarraga, A. Espinosa, Syntesis (1989), 923.

In contrast, when R 1 '- R as defined above, the hydrazide of formula 19 is cyclized with phosgene to form a cyclic urea of formula 17c where hal is 0. This process is described in detail in J. Org. Chem., 1989, 54, 1048.

scheme

N - N

I7c h ai = a Br, I

The hydrazides of Formula 19 may be prepared as shown in Scheme 13. Formulas

T. Kond Condensation of the isocyanate with the hydrazine of the formula H HN'NR ^ R '' · ' ⁴ ' in an inert solvent such as tetrahydrofuran yields the hydrazide.

scheme

R ²² = C (= S) SC _r C ₆ -alk) or R ²

3) Accession / cyclization reactions

In addition to the methods described above, compounds of formula I wherein X = SR ^J and G = C (formula I) may be prepared by treating the ketene dithioacetal of formula 22 with a suitable nucleophilic reagent of formula 6 (Scheme 14). The nucleofuric reagent of Formula 16 is described above.

scheme

The dithioacetals of the ketene of Formula 22a may be prepared by condensing the phenylacetic acid esters of Formula 9 with carbon disulfide in the presence of a suitable base, followed by reaction with two equivalents of R 4 halide such as iodomethane or propargyl bromide (Scheme 15).

scheme

Compounds of formula Ia (compounds of formula 1 where A = N, G-N) can be prepared by condensing the N-aminourea of formula 23 with a carbonylating agent of formula 24 (Scheme 16). Carbonylation agents of Formula 24 include carbonyl or thiocarbonyl transfer reagents such as phosgene, thiophosgene, diphosgene (C1C (= OjOCCl3), triphosgene (Cl3COC (= O) OCCl3), Ν, Ν'-carbonyldiimidazole, N, N'-thiocarbonyl, l-Carboxylic acid (1,2,4-triazole) Conversely, compounds of formula 24 may be alkynyl formates or dialkyl carbonates. Some of these carbonylation reactions may require additional bases to carry out the reaction. Suitable bases include alkali metal alkoxides such as potassium tert-butoxide, inorganic bases such as sodium hydride and potassium carbonate, or tertiary amines such as tretylamine, pyridine, 1,8-diazolicyclo [5.4.0] -undec-7-one (DBU.), or triethylenediamine. Suitable solvents include suppository aprotic solvents, such as acetonitrile, dimethylformamide, dimethylsulfoxide; ethers such as tetrahydrofuran, dimethoxyethane or diethyl ether; ketones such as acetone or 2-butanone; hydrocarbons such as toluene or benzene; or perhalogen hydrocarbons such as dichloromethane or trichloromethane. The reaction temperature may range from 0 ° C to 150 ° C and the reaction time may be from 1 to 72 hours depending on the base, solvent, temperature and substrate chosen.

scheme

R ⁴

1-imidazolyl, 1,2,4-triazolyl X = OH or S SH X ¹ = O or S

The N, N ¹ -aminourea of Formula 23 may be prepared as shown in Scheme 17.

z

Treatment of the aniline of formula 23 with phosgene, thiophosgene, N, N-carbonyldiimidazole or Ν, Ν'-thiocarbonyldiimidazole affords isocyanate or isothiocyanate of formula 26. A base may be added for the reaction with phosgene or thiophosgene. Further iso (thio) cyanate y

treatment with R-substituted hydrazine yields N-aminourea of formula 23.

scheme

R ⁴

NH ₂

CV / CI2. or w

R ⁴

R ³

2.

optional base

n

Compounds of formula 1b (compounds of formula 1 where A = CR ^A , G = N and N = O) may also be prepared in the manner shown in Scheme 18. The urea of Formula 27 is reacted with activated 2-halo-carboxylic acid derivatives such as 2-halo-carboxylic acid chloro anhydride, 2-halo-carboxylic acid esters or 2-halo-acylimidazoles. Initial acylation of the aniline nitrogen is followed by intramolecular 2-halo substitution and cyclization occurs. A base may be added to accelerate acylation and / or subsequent cyclization. Suitable bases include triethylamine and sodium hydride. Conversely, compounds of formula 1b may be prepared by reacting the isocyanates of formula 26 with the esters of formula 28a. As described above, a base may be added to accelerate the reaction h for subsequent cyclization of compounds of formula lb.

scheme

R ⁵ '

lb

The ureas of Formula 27 may be prepared by the routes depicted in Scheme 19. The anilines of Formula 25 may bind to the isocyanates or isothiocyanates of the formula R N = C = W as described above. Conversely, isocyanates of formula 26 or isothiocyanates can be condensed with amines of formula R-NH 2 to form urea. The anilines and iso (thio) cyanates of formulas 25 and 26, respectively, are commercially available or are prepared by methods well known in the art. For example, the isothiocyanate can be prepared in J. Herterocycl. Chem., (1990), 27, 407. Isocyanates may be prepared as described in March, J. Advanced Organic Chemistry; John Wiley: New York, (1985), pp 944, 1166.

4) Sulphidation

Compounds of formula Ie, compounds of formula I wherein W = S may be prepared by treating compounds of formula Id (formula I wherein W = O) with sulfidation reagents such as P2S5 or Lavesan's (Lawesson's) reagent [2,4-bis (4- methoxyphenoxy) -1, 3dithio-2,4-diphosphenolate-2,4-disulfide] as shown in Scheme 20 (see Bull. Soc. Chim. Belg. (1978) 87, 229; and Tetrahedron Lett. (1983) ), 24, 3815).

Id scheme

P2S5 or

Lavesan's reagent X = OR ^J or SR ¹

R2

Ie

5) Synthesis of the aryl moiety

Compounds of formula If (Formula I wherein Y is CHR ^b O, CHR ⁶ S or z; n

CHR O-N = CR) compounds may be prepared by coupling halides of formula 29 with various nucleophilic reagents (Scheme 21). A suitable alcohol or thiol is treated with a base such as sodium hydride to provide the corresponding alkoxide or thioalkoxide which acts as a nucleophilic reagent.

scheme

II

Y ⁴ = chr ⁶ o. chr ^ on ^ ⁷ , chr ^ s

The benzo / halides of Formula 29 may be prepared from the corresponding alkyl compound, m.p. in formula 29 H instead of halogen, by radical halogenation or by acidic decomposition of the corresponding methyl ether (i.e. in formula 29 OMe instead of halogen).

Compounds of Formula I wherein Y is CR 1 -CR * 'and CHR 1 - CHR 2 (Formula Ig and Formula Ih _; respectively) may be prepared as shown in Scheme 22. Treatment of the benzo / halides of formula 29 with triphenylphosphine or trialkyl phosphite yields the corresponding phosphonium salts (formula 30) or phosphonates (formula 31), respectively. Condensation of the phosphorus compound with a base and a C = O carbonyl compound of formula Z (R ^b ) yields an olefin of formula Ig.

scheme

halide 31: P ¹ = P {O (C 1 -C 6)

O = CTR ^) Z ->.

base

A-N

A —N

Ih

1) halogenation

2) dehalogenation

N

V

II

Formula Ig definitions may be processed into saturated compounds of Formula Ih by hydrogenation over a metal catalyst (such as palladium or carbon) as is well known in the art (Rylander, Catalytic Hydrogenation in Organic Synthesis; Academic: New York, 1979).

Alkines of Formula II may be prepared by halogenation / dehalogenation of Ig olefins of Formula I using procedures well known in the art (March, J. Advanced Organic Chemistry; 3rd ed., John Wiley: New York, (1985), p. 924). In addition, alkynes of formula II may be prepared by a well-known reaction of aromatic halides with alkyne derivatives in the presence of a catalyst such as nickel or palladium (see / Organomet. Chem., (1975), 93, 253-257).

Formula Ig olefin may also be prepared by changing the reactivity of the reactants by Vitig (Wittig) or Horner-Emmons condensation. For example, 2-alkylphenyl derivatives of Formula 31 may be converted to the corresponding dibromo compound of Formula 33 as shown in Scheme 23 (see Synthesis, (1988), 330). The dibromo compound can be hydrolyzed to the carbonyl compound of formula 34, which in turn can be condensed with the phosphorus-containing nucleophilic reagents of formula 35 or 36 to yield an olefin of formula Ig.

scheme

CH2 ^r6

W

I) Br _{2 or} NBS

2dcv., CCU

Sweat-.a

R ⁴

CR ⁶ J ^! . 2) raorfolinas machine. HCl, H ₂ O

NBS = N-Bromosuccinimide

33: J ¹ = Br ₂ 34: 1 ^ (= 0) (± H ₅ ) 3R = CXR <hz

M 'or f? , '{(CpOpO ^ P-OR ^

The oximes of Formula Ij (Formula 1 wherein Y is C (R) = N-O) may be prepared by condensation of carbonyl compounds of Formula 37 with hydroxylamine, followed by O-alkylation with electrophiles of Formula Z- (C1, Br, or I) (Scheme 24). In contrast, the O-substituted hydroxyamines can be condensed with the carbonyl compound of formula 37 to directly produce oximes of formula Ij.

scheme

The carbamates of Formula Ik can be prepared by reacting the benzoalcohols of Formula 38 with the isocyanates of Formula 39 (Scheme 25). A base such as triethylamine may be added to catalyze the reaction.

scheme

The following examples illustrate the preparation of novel cyclic amides of formula I. In the NMR spectrum shown below, the shifts are in m.d. from tetramethylsilane: s = singlet, d = doublet, t = triplet, dt = double triplet, td = triple doublet, m = multiplet.

EXAMPLE

Step A: Preparation of methyl 2- (3-methoxyphenoxy) phenyl acetate (2-chlorophenyl) acetic acid (60 g), 3-methoxyphenol (87 g), potassium carbonate (97.2 g), and copper (I) chloride (0) , 6 g) was combined ii 'mechanically mixed to give a thick brown suspension. The suspension was heated for 4.5 h, then cooled to 70 ° C and 10 mL of Ν, Ν-dimethylformamide was added. The mixture was poured into ice water and acidified with concentrated aqueous HCl. The mixture was extracted with diethyl ether and the combined extracts were washed with water (4 times) dried (MgSO ₄ ), filtered and concentrated under reduced pressure to give 122 g of oil. The crude material was dissolved in 73 mL of methanol and then 2.1 mL of concentrated sulfuric acid was added. The mixture was heated for 4 hours. in a reflux flask. The mixture was poured into ice water and extracted with diethyl ether. The combined organic phase was washed with 10% aqueous NaOH solution (2 times) followed by water (4 times) followed by brine. The organic phase was dried (MgSO ₄ ), filtered and concentrated under reduced pressure to yield 46.4 g (48%) of the title compound as a pink oil.

^! 1 H NMR (CDCl ₃ ): δ 6.45-7.4 (m, 8H), 3.78 (s, 3H), 3.69 (s, 2H), 3.62 (s, 3H).

Step B: Preparation of dimethylf2- (3-methoxyphenoxy) phenyl] propanedioate

Methyl 2- (3-methoxyphenoxy) phenylacetate (6.81 g) was dissolved in 11 mL of dimethyl carbonate and 600 mg of sodium was added. The mixture was heated in a reflux flask for 10 hours, then cooled. The reaction mixture was quenched with water, acidified with concentrated aqueous HCl and extracted with dichloromethane. The combined organic extracts were dried (MgSO ₄ ), filtered and concentrated under reduced pressure by the addition of oil. The desired material was isolated from the unreacted starting material by high-pressure flash chromatography (4: 1 hexane: ethyl acetate as eluent) to yield 3.54 g (43%) of the title compound.

NMR (CD ₃ ): δ 7.46 (dd, J = 1.5.7.5Hz, 1H), 7.29 (t, J = 8Hz, 1H), 7.2 (m, 2H),

6.92 (d, J = 8Hz, 1H), 6.65 (td, J = 1.5.7.5Hz, 1H), 6.5 (m, 2H), 5.14 (s, 1H), 3.77 (s, 3H), 3.73 ( s, 6H).

Step C: Preparation of 5-Hydroxy-4- [2-3-methoxyphenoxy) phenylb 2 -methyl-3 (2H) -isoxazolone

N-Methydroxylamine hydrochloride (2.79 g) was dissolved in 20 mL of methanol by heating in a reflux flask. The solution was cooled and treated with 3.76 g of sodium hydride in 15 ml of methanol. The potassium chloride precipitate was removed by filtration and 3.54 g of a solution of dimethyl [2- (3-methoxyphenoxy) phenfl] propaodioate in 25 ml of methanol was added dropwise. The mixture was stirred overnight at room temperature. The reaction mixture was condensed in vacuo to about 30 mL and acidified with concentrated HCl under cooling. The solvents were removed under reduced pressure and the residue partitioned between water and dichloromethane. The combined organic phases were dried (MgSO ₄ ), filtered, and concentrated under reduced pressure to yield 2.95 (88%) of the title compound.

NMR (CDCl ₃ ): δ 7.2-7.4 (m, 3H), 7.12 (dt, J = 7.5, 1H), 6.81 (d, J = 8.5Hz, 1H), 6.72 (d, J = 8Hz, 1H), 6.6 (m, 2H), 4.43 (s, 1H), 3.77 (s, 3H), 3.28 (s, 3H).

Step D: Delivery of 5-Methoxy-4- [2- (3-methoxyphenoxy) phenyl-2-methyl] -3 (2H ') -isoxazolone

5-Hydroxy-4- [2- (3-methoxyphenoxy) phenyl] -2-methyl-3 (2H) -isoxazolone (2.5 g) was dissolved in 3 mL of methanol and 15 mL of toluene and frozen in an ice bath. Trimethylsilyldiazomethane (5 mL of a 2.0 M solution in hexane) was added dropwise. Gas evolution was observed. The resulting yellow solution was stirred overnight at room temperature. The solvents were removed under reduced pressure and the residue was purified by flash chromatography (1: 1 hexane: ethyl acetate as eluent). Another flush component was selected to give 950 mg (36%) of the title compound of Step D.

¹ H NMR (CDCl ₃ ): δ 7.51 (dd, J = 1.7,7.5IIz, 1H), 7.27 (dt, J = 1.7,7.5Hz, 1H), 7.17 (m, 2H), 6.97 (dd, J = 1.8 Hz, 1H), 6.5 (m, 311), 3.92 (s, 3H), 3.74 (s, 3H), 3.33 (s, 3H).

EXAMPLE

Step A: Preparation of 1- (Bromomethoxy) -2-iodobenzene

To a solution of 2-iodobenzylethanol (50 g) in diethyl ether (500 mL) cooled in an ice bath was added dropwise phosphorus tribromide (28 mL). Reaction mixture 3.5 h. was cooled in a refrigerator, then cooled by the slow addition of methanol (50 mL). The mixture was washed with water then saturated with sodium bicarbonate followed by water (100 mL each). The organic phase was dried (MgSO ₄ ), filtered, and condensed under reduced pressure to a white crystalline solid which was triturated with hexane and collected by filtration to yield 58 g (91%) of the crystalline title compound, m.p. temp. 55-57 ° C.

Step B: Preparation of 1-iodo-2-r (2-methylphenoxy) methylbenzene

Sodium hydride (60% oil dispersion) (7.8 g) was added portionwise to a solution of? -Cresol (21.1 g) in tetrahydrofuran (500 mL) cooled in ice water. The mixture was stirred for 20 minutes and then 1- (bromomethyl) -2-iodobenzene (58 g) was added. The mixture was heated for 16 h. to 60 ° C. Additional potassium hydride (2 g) was added and the reaction mixture was heated for an additional 3 h. The reaction mixture was cooled and carefully treated with water and extracted with ethyl acetate (2 x 250 mL). The combined organic extracts were dried (MgSO 4), filtered, and condensed under reduced pressure to an oil which was quenched with cold hexane to give crystals collected by filtration to yield 59.1 g (94%) of the title compound as a white solid. crystals, m.p. temp. Mp 106-108 ° C.

Step C: Preparation of dimethylf2-f (2-methylphenoxy) methylphenyl propanedionate

A drop of dimethylmalonate ( 44 ml) solution in DMPU (150 ml). When the addition was complete, the mixture was stirred for 20 min. and then 1-iodo-2 - [(2-methylphenoxy) -ethyl] -benzene (62.5 g) and copper iodide (73.3 g) were added. The resulting mixture was stirred at 100 ° C for 5 hours, then stirred overnight at 25 ° C. The mixture was diluted with 1N HCl (approximately 150 mL) and extracted with diethyl ether (3x400 mL). The combined organic extracts were dried (MgSO _4), filtered, and condensed under reduced pressure to a semi-solid material that was purified by high pressure adsorption flash chromatography (Flesch chromatography) on silica gel (5: 2 hexane: ethyl acetate as eluent). The title compound was collected by filtration, yielding 56.9 g (79%) of the title compound as a white crystal, m.p. temp. 99-103 ° C.

Step D: 5-Hydroxy-4- [2- (f-2-methylphenoxy) methyl] phenyl] -3 (2H). preparation of isoxazolone

A solution of potassium hydroxide (46.6 g) in methanol (80 ml) was added dropwise to a solution of N-methylhydroxylamine chlorohydrate (34.7 g) in methanol (120 ml) cooled in an ice-water bath. When the addition was complete, the mixture was stirred for 10 minutes. The potassium chloride precipitate was removed by filtration and a solution of dimethyl [2 - [(2-methylenenoxy) methyl] phenyl] propanedioate (44 g) in 100 ml of methanol was added to a solution of N-methyl-hydroxylamine. The mixture was stirred for 3 days and then cooled in an ice-water bath. Concentrated HCl (15 mL) was added and the crystals were removed by filtration. The solution was separated in vacuo and the precipitate was diluted with ca.

100 mL water and then extracted with dichloromethane (3x150 mL) followed by acetate (3x100 mL). The combined organic extracts were dried (MgSO ₄ ), filtered, and condensed under reduced pressure to yield 31.3 g (75%) of the title compound of Step D.

^{: 1} H NMR (DMSO-d 6): δ 7.4 (m, 2H), 7.15 (m, 2H), 7.10 (m, 2H), 6.8 (m, 2H), 5.16 (s, 2H), 2.9 (s, 3H) ), 2.23 (s, 3H).

Step E: Preparation of 5-Methoxy-2-methyl-4- [2 - [(2-methylphenoxy) methyl) phenyl-3 (2H) -isoxazolone

5-Hydroxy-4- (2 - ((2-methylphenoxy) methyl] phenyl] -3 (2H) -isoxazolone (31.3 g) was dissolved in 330 mL of 10: 1 toluene: methanol and cooled in an ice water bath. a2M in hexane) (55 mL) was added dropwise A gas evolution was observed The yellow solution was stirred at 25 ° C for 2 h The solution was diluted with 100 mL water ii ^- extracted with ethyl acetate (4 x 100 mL) The combined organic extracts were dried (MgSO ₄ ). ), filtered and condensed under reduced pressure to give an oil which was purified by high pressure adsorbent flash chromatography (silica gel, 1: 1 hexane: ethyl acetate as eluent) The other washed component was collected to give 4.35 g (13%) of Step E). mp 90-92 ° C as a white solid.

¹ H NMR (CDCl ₃ ): δ 7.61 (d, 1H) 7.35 (m, 3H), 7.12 (m, 2H), 6.84 (m, 2H), 5.12 (s, 2H), 3.96 (s, 3H), 3.41 (s, 3H), 2.24 (s, 3H).

EXAMPLE

Step A: Preparation of 1-Methyl-N- (2-phenoxymethyl) hydrazinecarboxamide

2-Phenoxyaniline (5.57 g) and triethylamine (4.2 mL) were dissolved in 100 mL of 1,2-dichloroethane. Triphosgene (ChCOCCOjOCCb, 2.97 g) was added and a precipitate formed. The mixture was heated in a reflux flask and the solid was redissolved. After 5.5 or. the solution was cooled and 1.6 mL of methyl / hydrazine was added and a new precipitate formed. The mixture was stirred overnight at room temperature. The solvent was removed and the residue was partitioned between ethyl acetate and 1N aqueous HCl. The organic phases were dried (MgSO ₄ ), filtered and concentrated under reduced pressure. The precipitate was purified by high pressure adsorbent flash chromatography (1: 1 hexane: ethyl acetate as eluent). The second smallest polar component was collected, the eluent was removed under reduced pressure and the residue was triturated with hexane to yield 3.86 g (50%) of the title compound, m.p. temp. 117-119 ° C.

Step B: Preparation of 2-Methyl-4- (2-phenoxyphenyl) -5-thioxo-1,2,4-triazolin-3-one

A solution of 1.54 g of 1-Methyl-N- (2-phenoxyphenyl) hydrazinecarboxamide in 50 ml of tetrahydrofuran in a chilled ice bath was treated with 0.46 ml of thiophosgene followed by 1.68 ml of triethylamine. A precipitate formed and the mixture was stirred overnight at ambient temperature. The precipitate was removed by filtration and washed with tetrahydrofuran. The combined filtrate and washings were concentrated under reduced pressure to yield 1.8 g of amber glass oil. The crude material was used in other stages.

NMR (CDCl ₃ ): δ 6.8-7.4 (m, 9H), 3.57 (s, 3H).

Step C: Preparation of 2,4-dihydro-2-methyl-5- (methylthio) -4- (2-phenoxyphenyl) -3H-1,2,4-triazol-3-one

900 mg of a crude solution of 2-methyl-4- (2-phenoxymethyl) -5-thioxo-1,2,4-triazolidin-3-one in 50 ml of tetrahydrofuran were treated with 150 mg of sodium hydride (60% dispersion in oil). After 5 minutes 0.5 ml of iodomethane was added and the mixture was stirred overnight at room temperature. The solvent was removed by filtration and the filtrate was concentrated to an oil. The oil was partitioned between ether and IN hydrochloric acid solution. The organic phase was dried (MgSO 4), filtered and concentrated under reduced pressure. The residue was triturated with hexane / n-butyl chloride to yield 530 mg (56%) of the title compound, m.p. temp. 129-130 ° C.

EXAMPLE

Step A: Preparation of 2,2-dimethyl-N- (2-methylphenyl) hydrazine carboxamide o-Tolyl isocyanate (10.0 mg) was dissolved in 75 mL of toluene by passing N ?.

The solution was cooled to 5 ° and a solution of 1,1-dimethylhydrazine (5.7 mL) in toluene was carefully added. After the addition, the ice bath was removed and the reaction suspension was stirred for an additional 10 minutes. The solid was filtered by successive rinsing with hexane, a small amount of 20% diethyl ether / hexane, then again with hexane. Yield: 11.1 g (77%) of the title compound.

^! 1 H NMR (CDCl ₃ ): δ 8.1 (ps, 1H), 7.94 (d, 1H), 7.21-7.15 (m, 3H), 6.99 (t, 1H), 5.23 (ps, 1H), 2.63 (s, 6H) ), 2.27 (s, 3H).

Step B: Preparation of 5-chloro-2,4-dihydro-2-methyl-4- (2-methylphenyl) -3H-1,2,4-triazol-3-one

To a solution of 11.1 g of 2,2-dimethyl-N- (2-methylphenyl) hydrazine carboxamide in 600 ml of methylene chloride under N2 was added 17.1 g of triphosgene. The solution was heated in a refluxing flask overnight, cooled, then concentrated under reduced pressure. The resulting precipitate was dissolved in ethyl acetate and washed with water followed by saturated aqueous NaCl. The organic phase was dried (MgSO 4), filtered and concentrated under reduced pressure. The residue was purified by high pressure adsorbent flash chromatography (30-50% ethyl acetate / hexane as eluent) to yield 8.25 g (64%) of the title compound.

¹ H NMR (CDCl ₃ ): δ 7.42 - 7.30 (m, 3H), 7.17 (d, 1H), 3.54 (s, 3H), 2.22 (s, 3H).

Step C: Preparation of 2,4-dihydro-5-methoxy-2-methoxy-4- (2-methylphenyl) -3H-1,2,4-triazol-3-one

8.25 g of 5-chloro-2,4-dihydro-2-methyl-4- (2-methylsulfenyl) -3H-1,2,4-triazol-3-one were dissolved in 80 ml of 1: 1 dimethoxyethane / methanol , In the atmosphere of N2. 14.0 mL of sodium methoxide (30% solution in methanol) was added and the solution was heated in reflux for 3 hours. The mixture was allowed to cool, diluted with ethyl acetate, washed with water, then saturated with aqueous NaCl. The combined organic extracts were dried (MgSO ₄ ), filtered, and concentrated under reduced pressure. The residue was purified by high pressure adsorbent flash chromatography (50-70% ethyl acetate / hexane as eluent) and triturated with 50% diethyl ether / hexane to yield 6.7 g of the title compound (95% purity).

Td NMR (CDCl ₃ ): δ 7.35-7.27 (m, 3H), 7.18 (d, 1H), 3.94 (s, 3H), 3.46 (s, 3H), 2.22 (s, 3H).

Step D: Preparation of 4- {2- (Bromomethyl) phenyl-2,4-dihydro-5-methoxy-2-methyl-3H-1,2,4-triazol-3-one

6.7 g of a solution / suspension of 2,4-dihydro-5-methoxy-2-methyl-4- (2-methylphenyl) -3H-1,2,4-triazol-3-one was dissolved in 95 ml of tetrachloromethane under N2, Nbromo-succinimide was added. (6.53 g), hereafter catalytic amount of benzoyl peroxide. The solution was 2 hours. heat in a reflux flask. Another 1.63 g of Nbromo-succinimide was added and the catalytic amount of benzoyl peroxide was added and the solution was refluxed for one hour. After cooling, dichloromethane was added and the organic layer was washed sequentially with water followed by 0.1 N disodium thiosulfate solution followed by NaQ saturated aqueous solution. The combined organic extracts were dried (MgSO ₄ ), filtered, and concentrated under reduced pressure. The residue was purified by high pressure adsorbent flash chromatography (3-10% diethyl ether / dichloromethane as eluent) to yield 3.12 g of the title compound of Step D.

NMR (CDCl ₃ ): δ 7.5 (m, 1H), 7.44 (m, 2H), 7.22 (m, 1H), 4.60 (d, 1H), 4.36 (d, 1H), 3.96 (s, 3H), 3.47 (s, 3H).

Step E: Preparation of 2,4-dihydro-5-methoxy-2-methyl-4- [2- [fi (phenylmethylene) 'aminoloxymethylphenyl-3H-1,2,4-triazol-3-one

0.40 g of 4- [2- (bromomethyl) phenyl] -2,4-dihydro-5-methoxy-2-methyl-3H-1,2,4-triazol-3-one was dissolved in about 5 ml of Ν, Ν-dimethylformamide Np atmosphere, to which 0.20 g of acetophenone oxime was added, followed by 0.07 g of 60% sodium hydride. The solution was 4 hours. stirred at room temperature, then diluted with ethyl acetate, washed with water then saturated aqueous NaCl. The organic phase was dried (MgSO ₄ ), filtered and concentrated under reduced pressure. The precipitate was purified by high pressure adsorbent flash chromatography (60% ethyl acetate / hexane as eluent) to yield 0.38 g of the title compound of Step E.

NMR (CD ₃ ): δ 7.6 (m, 3H), 7.44 (m, 2H), 7.35 (m, 3H), 7.25 (m, 1H), 5.26 (d, 1H), 5.22 (d, 1H), 3.88 (s, 3H), 3.40 (s, 3H), 2.20 (s, 3H).

The compounds in Tables 1-26 can be obtained by the basic methods described herein or modifications thereof.

The following tables use abbreviations. All alkyl groups unless otherwise indicated are normal isomers.

n = normal i - Treasury

Me = methyl Et - ethyl

MeO- methoxy Pr = propu CN = cyano

MeS = methylthio Bu = butyl Ph = phenyl

NO ₂ = nitro

Compounds of Formula I wherein: G = C, W - O, R ³ = R ⁴ - H, Y = CH ₂ ON = C (CH ₃ ), Z - 3-CF ₃ -Ph, a double fluctuating bond attached to G, and

R ² = Me X A MeO O EtO O n-PrO O h ₂ o = chch ₂ o O hc = cch ₂ o O cf ₃ o O (c-propflas) O O

X A MeS O EtS O n-PrS O H ₂ OHCH ₂ S O hc = cch ₂ s O cf ₃ s O (c-propyl) S 0

LT 4112 B X A X A MeO S MeS S EtO S EtS S n-PrO s n-PrS S h ₂ ochch ₂ o s h ₂ c = chch ₂ s S hc = cch ₂ o s hc = cch ₂ s S cf ₃ o s cf ₃ s S (c-propflas) O s (c-propflas) S S R ² = Et X A X A MeO O MeS O EtO O EtS 0 n-PrO 0 n-PrS 0 H ₂ C = CHCH ₂ O 0 h ₂ c = hch ₂ s 0 hc = cch ₂ o O hc = cch ₂ s 0 CF ₃ O O cf ₃ s 0 (c-Propyl) O O (c-propyl) S 0 X A X A MeO S MeS S EtO S EtS s η-ΡιΌ S n-PrS S h ₂ cychch ₂ o S ei ₂ c = chch ₂ s s ho = cch ₂ o s hc = cch ₂ s s CF ₃ O s cf ₃ s s (c-Propyl) O s (e-Propyl) S s R ² = n-Pr X Oh X A MeO O MeS O EtO O EtS O n-PrO O n-PrS 0 H ₂ C = CHCH ₂ O O H ₂ C = HCH ₂ S 0 hc = cch ₂ o O ho = cch ₂ s 0 CE3O O cf ₃ s 0 (c-Propyl) O O (c-propyl) S 0

X A X Oh MeO S MeS S EtO S EtS S n-PrO S n-PrS S h ₂ c = chch ₂ o S H ₂ C = CHCH ₂ S S hc = cch ₂ o S hc = cch ₂ s S cf ₃ o S cf ₃ s S (c-propflas) O S (c-Prop.) S S r ² = h X A X Oh MeO O MeS O EtO O EtS 0 n-PrO O n-PrS 0 H ₂ C = CHCH ₂ O O H ₂ C = HCH ₂ S 0 hc = cch ₂ o O fic = cch ₂ s 0 CF ₃ O O cf ₃ s 0 (c-Propyl) O O (c-propyl) S 0 X Oh X A MeO S MeS S EtO S EtS S n-PrO S n-PrS S H ₂ C = CHCH ₂ O s H ₂ O = CHCH ₂ S S hc = cch ₂ o s hc = cch ₂ s S cf ₃ o s cf ₃ s S (c-Propyl) O s (c-propyl) S S R ² -Me X A X A MeO NH MeS NH EtO NH EtS NH n-PrO NH n-PrS NH H ₂ C = CHCH ₂ O NH H ₂ C = HCH ₂ S NH hc = cch ₂ o NH hc = cch ₂ s NH CF3O NH cf ₃ s NH (c-Propyl) O NH (c-propflas) S NH

X Oh X Oh MeO NMe MeS NMe EtO NMe EtS NMe n-PrO NMe n-PrS NMe h ₂ c = chch ₂ o NMe H ₂ C = CHCH ₂ S NMe hc = cch ₂ o NMe hc = cch ₂ s NMe CF3O NMe cf ₃ s NMe (c-Prop.) O NMe (c-propyl) S NMe r ² = h X A X A MeO NH MeS NH EtO NH EtS NH 11-Pro NH n-PrS NH H ₂ C = CHCH ₂ O NH h ₂ c = hch ₂ s NH hc = cch ₂ o NH hg = cch ₂ s NH CF3O NH cf ₃ s NH (c-Propyl) O NH (c-propyl) S NH X Oh X A MeO NMe MeS NMe EtO NMe EtS NMe n-PrO NMe n-PrS NMe H ₂ C = CHCH ₂ O NMe h ₂ c = chch ₂ s NMe hc = cch ₂ o NMe hc = cch ₂ s NMe cf ₃ o NMe cf ₃ s NMe (c-Propyl) O NMe (c-Prop.) S NMe

table

Compounds of Formula I wherein: G = C, W = O, R ³ - R ⁴ - H, Y = CH ₂ ON = C (CH ₃ ), Z = 3-CF ₃ -Ph, a double fluctuating bond attached to A, and R ² = Me

X Oh X MeO N MeS EtO N EtS n-PrO N n-PrS H ₂ C = CHCH ₂ O N h ₂ c = hch ₂ s HC = CeH ₂ O N hc = cch ₂ s cf ₃ o N cf ₃ s (c-Propyl) O N (c-propyl) S X Oh X MeO CH MeS EtO CH EtS n-PrO CH n-PrS h ₂ c = chch ₂ o CH H ₂ C = CHCH ₂ S HC = CCH ₂ O CH HC = CCH 0 S Ay CF ₃ O CH cf ₃ s (c-Propyl) O CH (c-propyl) S R ² = Et X Oh X MeO N MeS EtO N EtS n-PrO N n-PrS h ₂ ochch ₂ o N H ₂ OHCH ₂ S hocch ₂ o N hocch ₂ s cf ₃ o N cf ₃ s (c-Propyl) O N (c-propyl) S

A

N

N

N

N

N

N

N

X A X MeO CH MeS EtO CH EtS n-PrO CH n-PrS H ₂ CCCHCH ₂ O CH H ₂ O = CHCH ₂ S hg = cch ₂ o CH hocch ₂ s cf ₃ o CH cf ₃ s (c-Propyl) O CH (c-propyl) S

SSSSSSS ^ ASSSS9S '>

R ² = n-Pr X A X MeO N MeS EtO N EtS n-PrO N n-PrS h ₂ c = chch ₂ o N H ₂ C = HCH ₂ S hc = cch ₂ o N hc = cch ₂ s CF ₃ O N cf ₃ s (c-Propyl) O N (c-propflas) S X A X MeO CH MeS EtO CH EtS n-PrO CH n-PrS h ₂ c = chch ₂ o CH h ₂ c = chch ₂ s ho = cch ₂ o CH hc = cch ₂ s cf ₃ o CH cf ₃ s (c-Propyl) O CH (c-propyl) S R ² = H X A X MeO N MeS EtO N EtS n-PrO N n-PrS H ₂ C = CHCH ₂ O N h ₂ cmich ₂ s hc = cch ₂ o N hocch ₂ s cf ₃ o N cf ₃ s (c-Propyl) O N (c-propflas) S X A X MeO CH MeS EtO CH EtS n-PrO CH n-PrS H ₂ C = CHCH ₂ O CH h ₂ ochch ₂ s hocch ₂ o CH ho = cch ₂ s cf ₃ o CH cf ₃ s (c-Propyl) O CH (c-propyl) S

SSSSSSS ""Z2zzzzzi> SSSSQSg ^i:> zzzzzzzi>

R ² = Me

X Oh X A MeO CMe MeS CMe EtO CMe EtS CMe n-PrO CMe n-PrS CMe H ₂ C = CHCH ₂ O CMe H ₂ C = HCH ₂ S CMe hc = cch ₂ o CMe hg = cch ₂ s CMe CF ₃ O CMe cf ₃ s CMe (c-Prop.) O CMe (c-propflas) S CMe X A X Oh MeO CEt MeS CEt EtO CEt EtS CEt n-PrO CEt n-PrS CEt Η ₂ 0 = <ΞΉ <ΞΉ ₂ 0 CEt H ₂ C = CHCH ₂ S CEt hc = cch ₂ o CEt hc = cch ₂ s CEt CF ₃ O CEt cf ₃ s CEt (c-propflas) O CEt (c-propyl) S CEt

R ² = H

X A X A MeO CEt MeS CEt EtO CEt EtS CEt n-PrO CEt n-PrS CEt h ₂ c = chch ₂ o CEt H ₂ C = HCH ₂ S CEt HC = CCH ₂ O CEt hc = cch ₂ s CEt CF ₃ O CEt cf ₃ s CEt (c-Propyl) O CEt (c-propflas) S CEt X A X Oh MeO CMe MeS CMe EtO CMe EtS CMe n-PrO CMe n-PrS CMe H ₂ C = CHCH ₂ O CMe H ₂ C = CHCH ₂ S CMe hc = cch ₂ o CMe hcycch ₂ s CMe cf ₃ o CMe cf ₃ s CMe (c-Propyl) O CMe (c-propyl) S CMe

table

Compounds of Formula I wherein: G = C, W = O, R ³ = R ⁴ = H, Y = CH ₂ O, Z = 2-Me-Ph, a double fluctuating bond attached to G, and R ² = Me

X A X A MeO 0 MeS 0 EtO O EtS O n-PrO O n-PrS 0 H ₂ C = CHCH ₂ O o H ₂ G = HCH ₂ S 0 hc = cch ₂ o o hc = cch ₂ s O cf ₃ o o cf ₃ s 0 (c-Propyl) O o (c-Prop.) S 0

X A X A MeO S MeS S EtO S EtS S n-PrO S n-PrS s h ₂ ochch ₂ o S H ₂ C = CHCH ₂ S s hc = cch ₂ o S hc = cch ₂ s s cf ₃ o S cf ₃ s s (c-Propyl) O S (c-propyl) S s R ² = Et X A X A MeO O MeS 0 EtO O EtS o n-PrO O n-PrS o H ₂ C = CHCH ₂ O O H ₂ C ^ HCH ₂ S o HO = CCH ₂ O O hc = cch ₂ s o cf ₃ o o cf ₃ s 0 (c-Propyl) O o (c-propyl) S 0

X Oh X MeO S MeS EtO S EtS n-PrO S n-PrS h ₂ c = chch ₂ o S H ₂ O = CHCH ₂ S hocch ₂ o S ho = cch ₂ s cf ₃ o S cf ₃ s (c-propflas) O S (c-propflas) S R ² = n-Pr X Oh X MeO O MeS EtO 0 EtS n-PrO O n-PrS h ₂ ochch ₂ o O H ₂ O = HCH ₂ S hc = cch ₂ o 0 hc = cch ₂ s cf ₃ o O cf ₃ s (c-propflas) O O (c-propflas) S X Oh X MeO S MeS EtO S EtS n-PrO S n-PrS h ₂ ochch ₂ o S H ₂ C = CHCH ₂ S hc = cch ₂ o S ho = cch ₂ s cf ₃ o S cf ₃ s (c-Propyl) O S (c-propyl) S r ² = h X Oh X MeO 0 MeS EtO O EtS n-PrO O n-PrS H ₂ C = CHCH ₂ O O H ₂ CYHCH ₂ S hocch ₂ o O hocch ₂ s cf ₃ o 0 cf ₃ s (c-propflas) O O (c-propflas) S

Oh

S

S

S

S

S

S

S

O l> cn cn {Λ w {Λ 71 w |> OOOOOOOI>

o o

o o

o o

X Oh X Oh MeO S MeS S EtO S EtS S n-PrO S n-PrS S h ₂ c = chch ₂ o S H ₂ C = CHCH ₂ S S ho = cch ₂ o S hg = cch ₂ s S cf ₃ o S cf ₃ s S (c-propflas) O s (c-propflas) S S R ² = Me X Oh X Oh MeO NH MeS NH EtO NH EtS NH n-PrO NH n-PrS NH h ₂ c = chch ₂ o NH H ₂ O = HCH ₂ S NH hc = cch ₂ o NH hc = cch ₂ s NH cf ₃ o NH cf ₃ s NH (c-propflas) O NH (c-propflas) S NH X Oh X Oh MeO NMe MeS NMe EtO NMe EtS NMe n-PrO NMe n-PrS NMe H ₂ C = CHCH ₂ O NMe H ₂ CVCHCH ₂ S NMe hg = cch ₂ o NMe hc = cch ₂ s NMe cf ₃ o NMe cf ₃ s NMe (c-Propyl) O NMe (c-propflas) S NMe R ^{2 is} -H X Oh X Oh MeO NH MeS NH EtO NH EtS NH n-PrO NH n-PrS NH h ₂ c = chch ₂ o NH h ₂ c = hch ₂ s NH hc = cch ₂ o NH hcvcch ₂ s NH cf ₃ o NH cf ₃ s NH (c-Propyl) O NH (c-propflas) S NH

X A X A MeO NMe MeS NMe EtO NMe EtS NMe n-PrO NMe n-PrS NMe h ₂ c = chch ₂ o NMe h ₂ c = chch ₂ s NMe hc = cch ₂ o NMe hc = cch ₂ s NMe cf ₃ o NMe cf ₃ s NMe (c-Propyl) O NMe (c-propyl) S NMe

table

Compounds of Formula 1 wherein G = N, W = O, R ³ = R ⁴ - H, Y = CH ₂ O, Z - 2-Me-Ph, a double fluctuating bond attached to A, and

R ² = Me X A X A MeO N MeS N EtO N EtS N n-PrO N n-PrS N h ₂ c = chch ₂ o N h ₂ c = hch ₂ s N hc = cch ₂ o N hc = cch ₂ s N cf ₃ o N cf ₃ s N (c-Propyl) O N (c-propflas) S N

X A X A MeO CH MeS CH EtO CH EtS CH n-PrO CH n-PrS CH H ₂ C = CHCH ₂ O CH H ₂ C = CHCH ₂ S CH hc = cch ₂ o CH hcncch ₂ s CH cf ₃ o CH cf ₃ s CH (c-Propyl) O CH (c-propyl) S CH

R ² = Et

X A MeO N EtO N n-PrO N H ₂ C = CHCH ₂ O N ho = cch ₂ o N cf ₃ o N (c-Propyl) O N X A MeO CH EtO CH n-PrO CH H ₂ C = CHCH ₂ O CH hc = cch ₂ o CH cf ₃ o CH (c-Propyl) O CH R ² = n-Pr X A MeO N EtO N n-PrO N H ₂ C = CHCH ₂ O N hc = cch ₂ o N cf ₃ o N (c-Propyl) O N X A MeO CH EtO CH n-PrO CH h ₂ o = chch ₂ o CH hc = cch ₂ o CH cf ₃ o CH (c-Propyl) O CH

X A

MeS N

EtS N n-PrS N

H ₂ C = HCH ₂ SN

HC = CCH ₂ SN cf ₃ sn (c-propflas) SN

X

MeS

EtS n-PrS

H ₂ C = CHCH ₂ S hc = cch ₂ s cf ₃ s (c-prop) S

X

MeS

EtS n-PrS

H ₂ C = HCH ₂ S

HC = CCH ₂ S cf ₃ s (c-propyl) S

X

MeS

EtS n-PrS

H ₂ C = CHCH ₂ S ho = cch ₂ s cf ₃ s (c-prop) S r ² = h

X Oh X Oh MeO N MeS N EtO N EtS N n-PrO N n-PrS N H ₂ C = CHCH ₂ O N H ₂ C = HCH ₂ S N hc = cch ₂ o N HC = CCH ₂ S N CF ₃ O N cf ₃ s N (c-propflas) O N (c-propyl) S N X A X Oh MeO CH MeS CH EtO CH EtS CH n-PrO CH n-PrS CH HoOCHCHoO CH H ₂ C = CHCH ₂ S CH hc = cch ₂ o CH HC = CCH ₂ S CH CF3O CH cf ₃ s CH (c-propflas) O CH (c-propyl) S CH

R ² -Me

X A X A MeO CMe MeS CMe EtO CMe EtS CMe n-PrO CMe n-PrS CMe H ₂ G = CHCH ₂ O CMe h ₂ c = hch ₂ s CMe hc = cch ₂ o CMe hc = cch ₂ s CMe CF3O CMe CF ₃ S CMe (c-Propyl) O CMe (c-propyl) S CMe X Oh X Oh MeO CEt MeS CEt EtO CEt EtS CEt n-PrO CEt n-PrS CEt h ₂ c = chch ₂ o CEt H ₂ C = CHCH ₂ S CEt hocch ₂ o CEt hc = cch ₂ s CEt CF ₃ O CEt cf ₃ s CEt (c-Propyl) O CEt (c-propyl) S CEt

r ² = h

X Oh X A MeO CEt MeS CEt EtO CEt EtS CEt n-PrO CEt n-PrS CEt H ₂ C = CHCH ₂ O CEt H ₂ C = HCH ₂ S CEt hc = cch ₂ o CEt hc = cch ₂ s CEt CE3O CEt cf ₃ s CEt (c-Propyl) O CEt (c-propyl) S Cet X A X A MeO CMe MeS CMe EtO CMe EtS CMe n-PrO CMe n-PrS CMe H ₂ C = CHCH ₂ O CMe H ₂ C = CHCH ₂ S CMe hc = cch ₂ o CMe hocch ₂ s CMe CF3O CMe CF ₃ S CMe (c-Propyl) O CMe (c-propyl) S CMe

table

Compounds of Formula I wherein: G - C, W = S, R ³ = R ⁴ = H, Y = CH ₂ ON = Cl (CF)), Z = 3 - CF 3 - PI 1, a double fluctuating bond attached to G, and

R ² = Me X A X A MeO O MeS 0 EtO 0 EtS 0 n-PrO O n-PrS 0 H ₂ G = CHCH ₂ O O h ₂ c = hch ₂ s 0 HC = CCH ₂ O O hocch ₂ s 0 cf ₃ o 0 cf ₃ s 0 MeO NH MeO Ni

X Oh X Oh MeO S MeS S EtO S EtS S n-PrO S n-PrS S h ₂ c = chch ₂ o s h ₂ c = chch ₂ s S hc = cch ₂ o s hc = cch ₂ s S cf ₃ o s cf ₃ s S MeO NEt MeS NPr

table

Compounds of Formula I wherein: A = N, G = N, W = S, R ³ = R ⁴ = H, Y = CH ₂ ON C (Me), Z = 3-CF 3 -Cl 1, a double fluctuating bond attached to A , and

R ² = Me X X X X MeO EtO n-PrO h ₂ c = chch ₂ s hc = cch ₂ o CF3O OCF ₂ H OCH2CF3 (c-Propyl) O MeS EtS n-PrS H2OCHCH2O HC = CCH ₂ S CF ₃ S (c-propyl) S Table 7

Compounds of Formula I wherein: G = C, W = S, R ³ = R ⁴ = H, Y = CH ₂ O, Z = 2-Me-Ph, a double fluctuating bond attached to G, and R ² = Me X A X A MeO 0 MeS O EtO 0 EtS 0 n-PrO O n-PrS 0 h ₂ c = chch ₂ o 0 h ₂ c = hch ₂ s 0 hc = cch ₂ o 0 hc = cch ₂ s 0 cf ₃ o 0 cf ₃ s 0 MeO NH MeO NMe

X A X A MeO S MeS S EtO S EtS S n-PrO s n-PrS S h ₂ c = chch ₂ o s h ₂ ochch ₂ s s hc = cch ₂ o s hc = cch ₂ s s cf ₃ o s cf ₃ s s MeO NEt MeS NPr

table

Compounds of Formula I wherein A = N, G = N, W = S, R ³ = R ⁴ = H, Y = CH ₂ O, Z = 2

Me-Ph, a double fluctuating bond connected to A, and

R ² = Me X X X X MeO EtO n-PrO h ₂ c = chch ₂ s hc = cch ₂ o CF ₃ O OCF ₂ H och ₂ cf ₃ (c-Propyl) O MeS EtS n-PrS H ₂ C = CHCH ₂ O HG = CCH ₂ S CF ₃ S (c-propyl) S

table

Compounds of Formula I wherein: G = C, A = W = O, X = MeO, R ² = Me, Y = CH ₂ ON

C (Me), Z = 3-CF ₃ -Ph, double fluctuating bond attached to G, and R ⁴ Z R ³ R ⁴ R ³ R ⁴ Z R ³ Z 3-F H 5-NO ₂ H 3-F 5-F 5-F H 6-Me H 3-a 5-a 3-a H 3-Me H 4-Me 5-a 4-a H 4-MeO H 3-F 5-CF ₃ 5-Br H 5-CF ₃ O H 3-a 5-NO ₂ 4-CE ₃ H 5-allyl H 6-CF ₃ O H 5-CN H 4-propargyl H 5-Pr H

table

Compounds of Formula I in which: A = N, G = N, W = O, X = MeO, R ² = Me, YCH ₂ ON = C (Me), Z = 3-CF ₃ -Ph, double fluctuating bond attached to A, yes

R ³ R ⁴ R ³ R ⁴ R ³ R ⁴ 3-F H 5-NO ₂ H 3-F 5-F 5-F H 6-Me H 3-a 5-a 3-C1 H 3-Me H 4-Me 5-a 4-a H 4-MeO H 3-F 5-CF3 5-Br H 5-CF3O H 3-a 5-NO ₂ 4-CF ₃ H 5-allyl H 6-CF3O H 5-CN H 4-propargyl H 5-Pr H

table

O

Compounds of Formula I wherein: A - O, G = C, W = O, X = MeO, R = Me, a double fluctuating bond attached to G, and

table

Compounds of Formula I wherein: A - N, G = N, W - O, X = MeO, R ² = Me, a double fluctuating bond attached to G, and

table

Compounds of Formula I wherein: G = C, W = O, X - MeO, R ² = Me, R ³ = R ⁴ = H, Z = Ph, a double fluctuating bond attached to G, and

A = O

Y Y Y Y Y s CHoCHo to. L. CH (Me) O sch ₂ C (Me> N-O) CH = CH CH (Me) CH ₂ and ₂ SCH (Me) O-N = CH C (Me) = CH CH ₂ CH (Me) OCH (Me) CH ₂ ON = CH O-N = C (Me) CH = C (Me) CH (Me) CH (Me) CH ₂ S CH ₂ ON = C (Me) CH ₂ OC (= O) C (Me> C (Me) CH ₂ O CH (Me) S CH = N-0 CH (Me) OC (= O) direct connection CYC A = S · Y Y Y_ Y S ch ₂ ch ₂ CH (Me) O sch ₂ C (Me> N-O) CH = CH CH (Me) CH ₂ and ₂ SCH (Me) O-N = CH C (Me) = CH CH ₂ CH (Me) OCH (Me) CH ₂ ON = CH O-N = C (Me) CH = C (Me) CH (Me) CH (Me) CH ₂ S CH ₂ ON = C (Me) CH ₂ OC (= O) C (Me> C (Me) CH ₂ O CH (Me) S CH = N-0 CH (Me) OC (= O) direct connection C = C

A = NMe Y Y Y Y_ Y S CH ₂ CH ₂ CH (Me) O sch ₂ C (Me> N-O) CH - CH CH (Me) CH ₂ and ₂ SCH (Me) O-N = CH C (Me) = CH CH ₂ CH (Me) OCH (Me) CH ₂ ON = CH O-N = C (Me) CH = C (Me) CH (Me) CH (Me) CH ₂ S CH ₂ ON = C (Me) CH ₂ OC (= O) C (Me> C (Me) CH ₂ O CH (Me) S CH = N-0 CH (Me) 0C <> 0) direct connection C = C

table

Compounds of Formula I wherein: G = N, W = O, X = MeO, R ² = Me, R ³ = R ⁴ = H, Z = Ph, a double fluctuating bond attached to G, and

A = N Y Y Y Y Y S CH ₂ CH ₂ CH (Me) O sch ₂ C (Me> N-O) CH = CH CH (Me) CH ₂ and ₂ SCH (Me) O-N = CH C (Me> CH) CH ₂ CH (Me) OCH (Me) CH ₂ ON = CH O-N = C (Me) CH = C (Me) CH (Me) CH (Me) CThS CH ₂ ON = C (Me) CH ₂ OC (= O) C (Me> C (Me) CH ₂ O CH (Me) S CH = N-O CH (Me) OC (= O) direct connection C = C

A_ = S Y Y Y Y S CH ₂ CH ₂ CH (Me) O sch ₂ C (Me) = N-O CH = CH CH (Me) CH ₂ and ₂ SCH (Me) O-N = CH C (Me> CH) CH ₂ CH (Me) OCH (Me) CH ₂ ON = CH O-N = C (Me) CH = C (Me) CH (Me) CH (Me) CH ₂ S CH ₂ ON = C (Me) CH ₂ OC (= O) C (Me> C (Me) CH ₂ O CH (Me) S CH = N-0 CH (Me) OC (= O) direct connection c = c

A = NMe Y Y Y Y_ Y S ch ₂ ch ₂ CH (Me) O sch ₂ C (Me> N-O) CH = CH CH (Me) CH ₂ and ₂ SCH (Me) O-N = CH C (Me> CH) CH ₂ CH (Me) OCH (Me) ch ₂ on = ch O-N = C (Me) CH = C (Me) CH (Me) CH (Me) CH ₂ S CH ₂ ON = C (Me) CH ₂ OC (= O) C (Me> C (Me) CH ₂ O CH (Me) S CH = N-0 CH (Me) OC (= O) direct connection c = c

table

Compounds of Formula I wherein: G = C, W - O, X = MeO, R ² = Me, R ³ = R ⁴ = H, a double fluctuating bond attached to G, and

Y = O, A = O

Z Z Z Z hexyl 4-octenyl 3-Pentinyl 4-PhO-2-pyridinyl PhO (CH 2) 3 PhCH = CHCH ₂ Phc = cai ₂ (c-propyl) CH ₂ 2-Br-Ph 2-Me-Ph 2-Et-Ph 6- (2-CN-PhO) -4- pyrimidinyl 2-CN-Ph 2-F-Ph 2-Cl-Ph 6-PhO-4-pyrimidinyl 2,4-diCl-Ph 2-Me-4-Cl-Ph 2,4,6-Tria-Ph 4-Et Ο-2-pyrim idinfl as 2-CF ₃ -Ph 4-Ph-Ph 3-PhO-Ph 3- (4-pyrimidinyloxy) -Ph 2-I-Ph 3- (2-O-PhO) -Ph 3- (2-Et-Ph) -Ph 4- (2-thien) Ph c-hexyl 3,5-diCl-Ph 6-Ph-2-pyridinyl 3- (2-Pyridinoxy) Ph 4-NO ₂ -Ph 3,5-diCF ₃ -Ph 6-PhO-4-pyridinyl 3-pyridinyl PhCH ₂ CH ₂ 2-MeO-Ph 3-Thienyloxy-Ph 4- (3-d-2-pyridinyl oxy) -Ph (2-CN-Ph) CH ₂ 2,6-diMeO-Ph 3- (4-CF ₃ -PhO) -Ph 4- (PhO) -c-hexyl CF ₃ CH ₂ 3- (2CN-PhO) -Ph 3- (2-Me-PhO) -Ph 5 -PhO-2-pyrimidinyl 2-MeS-Ph 5-PhO-3 pyridinyl 5-PhO-2-pyridinyl 6- (2-NO ₂ -PhO) -4-pyrimidinyl i-Bu 6-Me-2-Plridinyl 6-PhO-2-pyridinyl 6- (2-a-PhO) -4- pyrimidinyl 2-CF ₃ O-Ph 3-CFO-Ph 6-CF-2-pyridinyl as 6- (2-CF ₃ -PhO) -4-pyrimidinyl 4-Me-Ph 4-Br-Ph 6-PhO-3-pyridinyl 4,6-diMeO-2- pyrimidine 4-Cl-Ph 3-Et-Ph 2-pyrimidinyl 4,6-diMe-2- pyrimidinyl 3-Me-Ph 4-Et-Ph 4-Pyrimidinyl 6-CF ₃ -4-Pyrimidinyl 3-CF ₃ -Ph 4-MeO-Ph 4-MeO-2-pyrimidinyl 4-CF ₃ -2-pyridinyl 3-Cl-2-MePh 4-t-Bu-Ph 4-Me-2-pyrimidinyl 4-CF ₃ -2-pyrimidinyl 3-t-Bu-Ph 4-CN-Ph 6-MeO-4-pyrimidinyl 2-pyridinyl 3-NO ₂ -Ph 4-NO ₂ -Ph 2-Ph-4-thiazolyl 6-CF ₃ -2-pyrazinyl 3-F-Ph 4-F-Ph 3-MeO-6-pyridazinyl 5-CF ₃ -3-pyridinyl 4-CF-Ph 3-Ph-Ph 5-Me-2-furanyl 3-MeO-2-pyridinyl 3,4-diCl-Ph 3,4-DiMe-Ph 2,5-diMe-3-thienyl 5-CN-2-pyridinyl 3,4-diCF-Ph 3,5-DiMe-Ph 3-OCF ₂ H-Ph 6-Me-2-pyridinyl 3-EtO-Ph 3-MeS-Ph 4-OCF ₂ H-PH

Y = CH, O. A = 0

Z Z Z Z hexyl 4-octenyl 3-Pentinyl 4-PhO-2-pyridine £ las PhO (CH 2) 3 PhCH = CHCH ₂ PhCsCCH ₂ (c-propyl) CH ₂ 2-Br-Ph 2-Me-Ph 2-Et-Ph 6- (2-CN-PhO) -4- pyrimidinyl 2-CN-Ph 2-F-Ph 2-Cl-Ph 6-PhO -4-pyr im idinflas 2,4-diCl-Ph 2-Me-4-Cl-Ph 2,4,6-triCl-Ph 4-EtO-2-pyrimidinyl 2-CF3-Ph 4-Ph-Ph 3-PhO-Ph 3- (4-pyrimidinyloxy) -Ph 2-I-Ph 3- (2-a-PhO) -Ph 3- (2-Et-Ph) -Ph 4- (2-thienyl) Ph c-hexyl 3,5-diCl-Ph 6-Ph-2-pyridinyl 3- (2-pyridine oxy) Ph 4-NO ₂ -Ph 3,5-diCF ₃ -Ph 6-PhO-4-pyridinyl 3-pyridinyl PhCH ₂ CH ₂ 2-MeO-Ph 3-Thienyloxy-Ph 4- (3-Cl-2-pyridinyloxy) -Ph (2-CN-Ph) CH ₂ 2,6-diMeO-Ph 3- (4-CF ₃ -PhO) -Ph 4- (PhO) ~ c -hexyl CF ₃ CH ₂ 3- (2CN-PhO) -Ph 3- (2-Me-PhO) -Ph 5 -PhO-2-pyrim idinfl 2-MeS-Ph 5-PhO-3 pyridinyl 5-PhO-2-pyridinyl 6- (2-NO ₂ -PhO) -4-pyrimidinyl i-Bu 6-Me-2-pyridinyl 6-PhO-2-pyridinyl 6- (2-Cl-PhO) -4- pyrimidinfl 2-CF ₃ O-Ph 3-CFO-Ph 6-CF-2-pyridinyl as 6- (2-CF ₃ -PhO) -4-pyrimidinyl 4-Me-Ph 4-Br-Ph 6-PhO-3-pyridinyl 4,6-diMeO-2- pyrimidinfl 4-a-Ph 3-Et-Ph 2-pyrimidinyl 4,6-diMe-2pirim idinflas 3-Me-Ph 4-Et-Ph 4-Pyrimidinyl 6-CF3-4-pyrim idinfl 3-CF ₃ -Ph 4-MeO-Ph 4-MeO-2-pyrimidinyl 4-CF ₃ -2-Pyridinyl 3-Cl-2-MePh 4-t-Bu-Ph 4-Me-2-pyrimidinyl 4-CF3-2-Pyrimidinyl 3-t-Bu-Ph 4-CN-Ph 6-MeO-4-pyrimidinyl 2-Pyridine yl 3-NO ₂ -Ph 4-NO ₂ -Ph 2-Ph-4-thiazolyl 6-CF3-2-pyrazinyl 3-F-Ph 4-F-Ph 3-MeO-6-pyridazinyl 5-CF ₃ -3-pyridinyl 4-CF-Ph 3-Ph-Ph 5-Me-2-furanyl 3-MeO-2-pyridinyl 3,4-diCl-Ph 3,4-DiMe-Ph 2,5-diMe-3-thienyl 5-CN-2-pyridine mustard 3,4-diCF-Ph 3,5-DiMe-Ph 3-OCF ₂ H-Ph 6-Me-2-pyridinyl 3-EtO-Ph 3-MeS-Ph 4-OCF ₂ H-PH

Y = O, A = NMe

Z Z Z Z hexyl 4-octenyl 3-Pentinyl 4-PhO-2-pyridine PhO (CH ₂ ) 3 PhCH = CHCH ₂ PhCsCCH ₂ (c-propyl) CH ₂ 2-Br-Ph 2-Me-Ph 2-Et-Ph 6- (2-CN-PhO) -4- pyrimidinfl 2-CN-Ph 2-F-Ph 2-Cl-Ph 6-PhO-4-pyrimidinyl 2,4-diCJ-Ph 2-Me-4-Cl-Ph 2,4,6-triCl-Ph 4-EtO-2-pyrimidinyl 2-CF ₃ -Ph 4-Ph-Ph 3-PhO-Ph 3- (4-pyrimidinyloxy) -Ph 2-I-Ph 3- (2-Cl-PhO) -Ph 3- (2-Et-Ph) -Ph 4- (2-thienyl) Ph c-hexyl 3,5-diCl-Ph 6-Ph-2-pyridinyl 3- (2-Pyridinyloxy) Ph 4-NO ₂ -Ph 3,5-diCF ₃ -Ph 6-Ph 0-4-Pyridinyl 3-pyridinyl PhCH ₂ CH ₂ 2-MeO-Ph 3-Thienyloxy-Ph 4- (3-Cl-2-pyridinoxy) -Ph (2-CN-Ph) CH ₂ 2,6-diMeO-Ph 3- (4-CF ₃ -PhO) -Ph 4- (PhO) -c-hexyl CF3CH2 3- (2CN-PhO) -Ph 3- (2-Me-PhO) -Ph 5-PhO-2-pyrimidinyl 2-MeS-Ph 5-PhO-3 pyridinyl 5-PhO-2-pyridinyl 6- (2-NO ₂ -PhO) -4-pyrimidinyl i-Bu 6-Me-2-pyridinyl 6-PhO-2-pyridinyl 6- (2-Cl-PhO) -4- pyrimidinfl 2-CF ₃ O-Ph 3-CFO-Ph 6-CF-2-pyridinyl 6- (2-CF ₃ -PhO) -4-pyrimidinyl 4-Me-Ph 4-Br-Ph 6-PhO-3-pyridinyl 4,6-diMeO-2- pyrimidinyl 4-Cl-Ph 3-Et-Ph 2-pyrimidinyl 4,6-diMe-2- pyrimidine 3-Me-Ph 4-Et-Ph 4-Pyrimidinyl 6-CF ₃ -4-pyrimidine 3-CF ₃ -Ph 4-MeO-Ph 4-MeO-2-pyrimidinyl 4-CF ₃ -2-pyridinyl 3-Cl-2-MePh 4-t-Bu-Ph 4-Me-2-pyrimidinyl 4-CF ₃ -2-pyrimidine 3-t-Bu-Ph 4-CN-Ph 6-MeO-4-pyrimidinyl 2-pyridine fll 3-NO ₂ -Ph 4-NO ₂ -Ph 2-Ph-4-thiazolyl 6-CF ₃ -2-pyrazinyl 3-F-Ph 4-F-Ph 3-MeO-6-pyridazinyl 5-CF ₃ -3-pyridinyl 4-CF-Ph 3-Ph-Ph 5-Me-2-furanyl 3-MeO-2-pyridinyl 3,4-diCl-Ph 3,4-DiMe-Ph 2,5-diMe-3-thienyl 5-CN-2-pyridinyl 3,4-diCF-Ph 3,5-DiMe-Ph 3-OCF ₂ H-Ph 6-Me-2-Pyridine 3-EtO-Ph 3-MeS-Ph 4-OCF ₂ H-PH

Y = CH ₇ O, A = NMe Z Z Z Z hexyl 4-octenyl 3-Pentinyl 4-PhO-2-pyridine PhO (CH ₂ ) 3 PhCH = CHCH ₂ PhC = CCH ₂ (c-propyl) CH ₂ 2-Br-Ph 2-Me-Ph 2-Et-Ph 6- (2-CN-PhO) -4- pyrimidine 2-CN-Ph 2-F-Ph 2-ci-Ph 6-PhO-4-pyrimidinyl 2,4-diCl-Ph 2-Me-4-Cl-Ph 2,4,6-triCl-Ph 4-EtO-2-pyrimidinyl 2-CF ₃ -Ph 4-Ph-Ph 3-PhO-Ph 3- (4-pyrimidinyloxy) -Ph 2-I-Ph 3- (2-Cl-PhO) -Ph 3- (2-Et-Ph) -Ph 4- (2-thienyl) Ph c-hexyl 3,5-diCl-Ph 6-Ph-2-pyridinyl 3- (2-Pyridinyloxy) Ph 4-NO ₂ -Ph 3,5-diCF 3 -Ph 6-PhO-4-pyridinyl 3-pyridinyl PhCH ₂ CH ₂ 2-MeO-Ph 3-Thienyloxy-Ph 4- (3-Cl-2-pyridinyloxy) -Ph (2-CN-Ph) CH ₂ 2,6-diMeO-Ph 3- (4-CF ₃ -PhO) -Ph 4- (PhO) -c-hexyl CF ₃ CH ₂ 3- (2CN-PhO) -Ph 3- (2-Me-PhO) -Ph 5-PhO-2-pyrimidinyl 2-MeS-Ph 5-PhO-3 pyridinyl 5-PhO-2-pyridinyl 6- (2-NO ₂ -PhO) -4-pyrimidinyl i-Bu 6-Me-2-pyridinyl 6-PhO-2-pyridinyl 6- (2-Q-PhO) -4- pyrimidinyl 2-CF ₃ O-Ph 3-CFO-Ph 6-CF-2-pyridine! 6- (2-CF ₃ -PhO) -4-pyrimidinyl 4-Me-Ph 4-Br-Ph 6-PhO-3-pyridinyl 4,6-diMeO-2-pyrimidinyl 4-Cl-Ph 3-Et-Ph 2-pyrimidinyl 4,6-diMe-2-pyrimidinyl 3-Me-Ph 4-Et-Ph 4-pyrimidyl 6-CE ₃ -4-Pyrimidinyl 3-CF ₃ -Ph 4-MeO-Ph 4-MeO-2-pyrimidinyl 4-CF ₃ -2-Pyridine 3-Cl-2-MePh 4-t-Bu-Ph 4-Me-2-pyrimidinyl 4-CF ₃ -2-pyrimidinyl 3-t-Bu-Ph 4-CN-Ph 6-MeO-4-pyrimidinyl 2-pyridinyl 3-NO ₂ -Ph 4-NO ₂ -Ph 2-Ph-4-thiazolyl 6-CF ₃ -2-pyrazinyl 3-F-Ph 4-F-Ph 3-MeO-6-pyridazinyl 5-CF ₃ -3-pyridinyl 4-CF-Ph 3-Ph-Ph 5-Me-2-furanyl 3-MeO-2-pyridine 3,4-diCl-Ph 3,4-DiMe-Ph 2,5-di Me-3-thienyl as 5-CN-2-pyridinyl 3,4-diCF-Ph 3,5-DiMe-Ph 3-OCF ₂ H-Ph 6-Me-2-Pyridine 3-EtO-Ph 3-MeS-Ph 4-OCF ₂ H-PH

table

Compounds of Formula I wherein: A = O, G = C, W = O, X = MeO, R ² = Me, R ³ = R ⁴ H, the double fluctuating bond is attached to G, and

Y = CFbON = C (CH ₃ ) Z z Z Z hexyl 4-octenyl 3-Pentinyl 4-PhO-2-pyridine PhO (CH ₂ ) 3 PhCH = CHCH ₂ PhCsCCH ₂ (c-propyl) CH ₂ 2-Br-Ph 2-Me-Ph 2-Et-Ph 6- (2-CN-PhO) -4- pyrimidinyl 2-CN-Ph 2-F-Ph 2-Cl-Ph 6-PhO-4-pyrimidinyl 2,4-diCl-Ph 2-Me-4-Cl-Ph 2,4,6-triCl-Ph 4-EtO-2-pyrimidinyl 2-CF ₃ -Ph 4-Ph-Ph 3-PhO-Ph 3- (4-pyrimidinyloxy) -Ph 2-I-Ph 3- (2-Cl-PhO) -Ph 3- (2-Et-Ph) -Ph 4- (2-thienyl) Ph c-hexyl 3,5-diCl-Ph 6-Ph-2-pyridinyl 3- (2-Pyridinyloxy) Ph 4-NO ₂ -Ph 3,5-diCF 3 -Ph 6-PhO-4-pyridinyl 3-pyridine fll PhCH ₂ CH ₂ 2-MeO-Ph 3-Thienyloxy-Ph 4- (3-Cl-2-pyridinyloxy) -Ph (2-CN-Ph) CH ₂ 2,6-diMeO-Ph 3- (4-OF ₃ -PhO) -Ph 4- (PhO) -c-hexyl CF3CH2 3- (2CN-PhO) -Ph 3- (2-Me-PhO) -Ph 5-PhO-2-pyrimidinyl 2-MeS-Ph 5-PhO-3 pyridinyl 5-PhO-2-pyridinyl 6- (2-NO ₂ -PhO) -4-pyrimidinyl i-Bu 6-Me-2-pyridinyl 6-PhO-2-pyridinyl 6- (2-Cl-PhO) -4- pyrimidinyl 2-CF ₃ O-Ph 3-CFO-Ph 6-CF-2-pyridinyl 6- (2-CF ₃ -PhO) -4-pyrimidinyl 4-Me-Ph 4-Br-Ph 6-PhO-3-pyridinyl 4,6-diMeO-2-pyrimidinyl 4-Cl-Ph 3-Et-Ph 2-pyrimidinyl 4,6-diMe-2-pyrimidine 3-Me-Ph 4-Et-Ph 4-Pyrimidinyl 6-CF ₃ -4-Pyrimidine 3-CF ₃ -Ph 4-MeO-Ph 4-MeO-2-pyrimidinyl 4-CF ₃ -2-pyridinyl 3-Cl-2-MePh 4-t-Bu-Ph 4-Me-2-pyrimidinyl 4-CF ₃ -2-pyrimidinyl 3-t-Bu-Ph 4-CN-Ph 6-MeO-4-pyrimidinyl 2-pyridinyl 3-NO ₂ -Ph 4-NO ₂ -Ph 2-Ph-4-thiazolyl 6-CF ₃ -2-pyrazine 3-F-Ph 4-F-Ph 3-MeO-6-pyridazinyl 5-CF ₃ -3-pyridinyl 4-CF-Ph 3-Ph-Ph 5-Me-2-furanyl 3-MeO-2-pyridinyl 3,4-diCl-Ph 3,4-DiMe-Ph 2,5-diMe-3-thienyl 5 -CN-2-pyridine 3,4-diCF-Ph 3,5-DiMe-Ph 3-OCF ₂ H-Ph 6-Me-2-pyridinyl 3-EtO-Ph 3-MeS-Ph 4-OCF ₂ H-PH Table 17

Compounds of Formula I wherein: A = NMe, G = C, W = O, X = MeO, R ² = Me, R ³ = H, the double fluctuating bond is attached to G, and

Y = CH? ON = C (CH ₃ F Z z Z Z hexyl 4-octenyl 3-Pentinyl 4-PhO-2-pyridine ii as PhO (CH ₂ ) 3 PhCH = CHCH ₂ PhC = CCH ₂ (c-propyl) CH ₂ 2-Br-Ph 2-Me-Ph 2-Et-Ph 6- (2-CN-PhO) -4- pyrimidinyl 2-CN-Ph 2-F-Ph 2-Cl-Ph 6-PhO-4-pyrimidinyl 2,4-diCl-Ph 2-Me-4-Cl-Ph 2,4,6-triCl-Ph 4-EtO-2-pyrimidine 2-CF ₃ -Ph 4-Ph-Ph 3-PhO-Ph 3- (4-pyrimidinyloxy) -Ph 2-I-Ph 3- (2-Cl-PhO) -Ph 3- (2-Et-Ph) -Ph 4- (2-thien) Ph c-hexyl 3,5-diCl-Ph 6-Ph-2-pyridinyl 3- (2-Pyridinyloxy) Ph 4-NO ₂ -Ph 3,5-diCF 3 -Ph 6-PhO-4-pyridinyl 3-pyridine PhCH ₂ CH ₂ 2-MeO-Ph 3-Thienyloxy-Ph 4- (3-Cl-2-pyridin-yloxy) -Ph (2-CN-Ph) CH ₂ 2,6-diMeO-Ph 3- (4-CF ₃ -PhO) -Ph 4- (PhO) -c-hexafl CF ₃ CH ₂ 3- (2CN-PhO) -Ph 3- (2-Me-PhO) -Ph 5-PhO-2-pyrimidinyl 2-MeS-Ph 5-PhO-3 pyridinyl as 5-PhO-2-pyridinyl 6- (2-NO ₂ -PhO) -4-pyrimidinyl i-Bu 6-Me-2-pyridinyl 6-PhO-2-pyridinyl 6- (2-Cl-PhO) -4- pyrimidine 2-CF ₃ O-Ph 3-CFO-Ph 6-CF-2-pyridinyl 6- (2-CF ₃ -PhO) -4-pyrimidinyl 4-Me-Ph 4-Br-Ph 6-PhO-3-pyridinyl 4,6-diMeO-2-pyrimidinyl 4-Cl-Ph 3-Et-Ph 2-pyrimidinyl 4,6-diMe-2-pyrimidinyl 3-Me-Ph 4-Et-Ph 4-Pyrimidinyl 6-CF ₃ -4-pyrimidinyl 3-CF ₃ -Ph 4-MeO-Ph 4-MeO-2-pyrimidinyl 4-CF ₃ -2-pyridinyl 3-Cl-2-MePh 4-t-Bu-Ph 4-Me-2-pyrimidinyl 4-CF ₃ -2-pyrimidinyl 3-t-Bu-Ph 4-CN-Ph 6-MeO-4-pyrimidinyl 2-pyridinyl 3-NO ₂ -Ph 4-NO ₂ -Ph 2-Ph-4-thiazolyl 6-CF ₃ -2-pyrazinyl 3-F-Ph 4-F-Ph 3-MeO-6-pyridazinyl 5-CF ₃ -3-pyridinyl 4-CF-Ph 3-Ph-Ph 5-Me-2-furanyl 3-MeO-2-pyridinyl 3,4-diCl-Ph 3,4-DiMe-Ph 2,5-DiMe-3-thienyl 5-CN-2-pyridine 3,4-diCF-Ph 3,5-DiMe-Ph 3-OCF ₂ H-Ph 6-Me-2-pyridinyl 3-EtO-Ph 3-MeS-Ph 4-OCF ₂ H-PH

table

Formulas in which: A = N, G - N, W = O, X = MeO, R ² = Me, R ³ = R ⁴ = H, double fluctuating bond connected to A,

Y = ch ₉ is = C (CH ₃ ) z Z Z Z hexyl 4-octenyl 3-Pentinyl 4-PhO-2-pyridinyl PhO (CH ₂ ) 3 PhCH = CHCH ₂ PhCsCCH ₂ (c-propyl) CH ₂ 2-Br-Ph 2-Me-Ph 2-Et-Ph 6- (2-CN-PhO) -4- pyrimidinyl 2-CN-Ph 2-F-Ph 2-Cl-Ph 6-PhO-4-pyrimidinyl 2,4-diCl-Ph 2-Me-4-Cl-Ph 2,4,6-triCl-Ph 4-EtO-2-pyrimidinyl 2-CF ₃ -Ph 4-Ph-Ph 3-PhO-Ph 3- (4-pyrimidinyloxy) -Ph 2-I-Ph 3- (2-Cl-PhO) -Ph 3- (2-Et-Ph) -Ph 4- (2-thienyl) Ph c-hexyl 3,5-diCl-Ph 6-Ph-2-pyridinyl 3- (2-Pyridinyloxy) Ph 4-NO ₂ -Ph 3,5-diCF ₃ -Ph 6-PhO-4-pyridinyl 3-pyridinyl PhCH ₂ CH ₂ 2-MeO-Ph 3-Thienyloxy-Ph 4- (3-Q-2-pyridinyloxy) -Ph (2-CN-Ph) CH ₂ 2,6-diMeO-Ph 3- (4-CF ₃ -PhO) -Ph 4- (PhO) -c-hexyl cf ₃ ch ₂ 3- (2CN-PhO) -Ph 3- (2-Me-PhO) -Ph 5 -PhO-2-pyrimidinyl 2-MeS-Ph 5-PhO-3 pyridinyl 5-PhO-2-pyridinyl 6- (2-NO ₂ -PhO) -4-pyrimidinyl i-Bu 6-Me-2-pyridinyl 6-PhO-2-pyridine 1 as 6- (2-a-PhO) -4- pyrimidinyl 2-CF ₃ O-Ph 3-CFO-Ph 6-CF-2-pyridinyl as 6- (2-CF ₃ -PhO) -4-pyrimidinyl 4-Me-Ph 4-Br-Ph 6-PhO-3-pyridinyl 4,6-diMeO-2- pyrimidinyl 4-Cl-Ph 3-Et-Ph 2-pyrimidinyl 4,6-diMe-2- pyrimidinyl 3-Me-Ph 4-Et-Ph 4-Pyrimidinyl 6-CF ₃ -4-pyrimidinyl 3-CF ₃ -Ph 4-MeO-Ph 4-MeO-2-pyrimidinyl 4-CF ₃ -2-pyridinyl 3-Cl-2-MePh 4-t-Bu-Ph 4-Me-2-Pyrimidinyl 4-CF ₃ -2-pyrimidinyl 3-t-Bu-Ph 4-CN-Ph 6-MeO-4 pyrimidinyl 2-pyridinyl 3-NO ₂ -Ph 4-NO ₂ -Ph 2-Ph-4-thiazolyl 6-CF ₃ -2-pyrazinyl 3-F-Ph 4-F-Ph 3-MeO-6-pyridazinyl 5-CF ₃ -3-pyridinyl 4-CF-Ph 3-Ph-Ph 5-Me-2-furanyl 3-MeO-2-pyridinyl 3,4-diCl-Ph 3,4-DiMe-Ph 2,5-diMe-3-thienyl 5-CN-2-pyridinyl 3,4-diCF-Ph 3,5-DiMe-Ph 3-OCF ₂ H-Ph 6-Me-2-pyridinyl 3-EtO-Ph 3-MeS-Ph 4-OCF ₂ H-PH

Y ^ CH _? S

Z Z Z Z hexyl 4-octenyl 3-Pentinyl 4-PhO-2-pyridinyl PhO (CH ₂ ) 3 PhCH = CHCH ₂ PhCsCCH ₂ (c-propyl) CH2 2-Br-Ph 2-Me-Ph 2-Et-Ph 6- (2-CN-PhO) -4- pyrimidinyl 2-CN-Ph 2-F-Ph 2-Cl-Ph 6-PhO-4-pyrimidinyl 2,4-diCl-Ph 2-Me-4-Cl-Ph 2,4,6-triCl-Ph 4-EtO-2-pyrimidinyl 2-CF ₃ -Ph 4-Ph-Ph 3-PhO-Ph 3- (4-pyrimidinyloxy) -Ph 2-I-Ph 3- (2-a-PhO) -Ph 3- (2-Et-Ph) -Ph 4- (2-thiol) Ph c-hexyl 3,5-diCl-Ph 6-Ph-2-pyridinyl 3- (2-Pyridinoxy) Ph 4-NO ₂ -Ph 3,5-diCF ₃ -Ph 6-PhO-4-pyridinyl 3-pyridinyl PhCH ₂ CH ₂ 2-MeO-Ph 3-Thienyloxy-Ph 4- (3-a-2-Pyridine-phloxy) -Ph (2-CN-Ph) CH ₂ 2,6-diMeO-Ph 3- (4-CF ₃ -PhO) -Ph 4- (PhO) -c-hexxlas CF ₃ CH ₂ 3- (2CN-PhO) -Ph 3- (2-Me-PhO) -Ph 5-PhO-2-pyrimidinyl 2-MeS-Ph 5-PhO-3 pyridinyl 5-PhO-2-pyridinyl 6- (2-NO ₂ -PhO) -4-pyrimidinyl i-Bu 6-Me-2-pyridinyl 6-PhO-2-pyridinyl as 6- (2-d-PhO) -4- pyridinidinyl 2-CF ₃ O-Ph 3-CFO-Ph 6-CF-2-pyridinyl 6- (2-CF ₃ -PhO) -4-pyrimidinyl 4-Me-Ph 4-Br-Ph 6-PhO-3-pyridinyl 4,6-diMeO-2- pyrimidinfl 4-a-Ph 3-Et-Ph 2-pyrimidinyl as 4,6-diMe-2- pyrimidinyl 3-Me-Ph 4-Et-Ph 4-Pyrimidinyl 6-CF ₃ -4-pyrimidinyl 3-CF ₃ -Ph 4-MeO-Ph 4-MeO-2-pyrimidinyl 4-CF ₃ -2-pyridinyl 3-Q-2-MePh 4-t-Bu-Ph 4-Me-2-pyrimidinyl 4-CF ₃ -2-pyrimidinyl 3-t-Bu-Ph 4-CN-Ph 6-MeO-4-pyrimidinyl 2-pyridine fll 3-NO ₂ -Ph 4-NO ₂ -Ph 2-Ph-4-thiazolyl 6-CF ₃ -2-pyrazinyl 3-F-Ph 4-F-Ph 3-MeO-6-pyridazine 5-CF ₃ -3-pyridinyl 4-CF-Ph 3-Ph-Ph 5-Me-2-furanyl 3-MeO-2-pyridinyl 3,4-diCl-Ph 3,4-DiMe-Ph 2,5-diMe-3-thienyl 5-CN-2-pyridinyl 3,4-diCF-Ph 3,5-DiMe-Ph 3-OCF ₂ H-Ph 6-Me-2-pyridinyl 3-EtO-Ph 3-MeS-Ph 4-OCF ₂ H-PH

Table 6i

Compounds of Formula I wherein: A = N, G = N, W = O, X = MeO, R ² = Me, R ³ = R ⁴ H, the double fluctuating bond is attached to A, and Y is CH ₂ ON = C ( H _? )

2-Me-Pb

4-Cl-Ph

3- Me-Pb 3-CF ₃ -Ph 3-Cl-Ph

Table of 4- CF ₃ -Ph 2,5-diMe-Pb 3,5-dia-Pb

Compounds of Formula I wherein: A = N, G = N, W = O, X = MeO, Z = 3-CF ₃ -Ph, R ² Me, R ³ = R ⁴ = H, a double fluctuating bond attached to A, L ·

Y = CH3ON = C (H _? )

R ⁷ R ⁷ R ⁷ R ⁷

CF ₃ OCH ₂ CF ₃ Et

C1 MeO EtO n-Pr

MeS Table

Compounds of Formula I wherein A = O, G = C, W = O, X = MeO, R ³ = R ⁴ - H, Y 7

CH ₂ ON = C (R), double fluctuating bond connected to G, and

R ² - Me

R ⁷ Z R ⁷ Z c-propyl 3,4- (OCH ₂ CH ₂ O) -Ph c-propyl 3,4- (OCHFCF ₂ O) -Ph c-propyl 3,4- (OCF ₂ O) -Ph c-propyl Ph c-propyl 4-CF ₃ -Ph c-propyl 3-CF ₃ -Ph c-propyl 4-Cl-Ph c-propyl 3-Cl-Ph c-propyl 2-Me-Ph c-propyl 3-OCF ₃ -Ph cf ₃ 3,4- (OCH ₂ CH ₂ O) -Ph cf ₃ 3,4- (OCHFCF ₂ O) -Ph cf ₃ 3,4- (OCF ₂ O) -Ph cf ₃ Ph cf ₃ 4-CF ₃ -Ph cf ₃ 3-CF ₃ -Ph cf ₃ 4-Cl-Ph cf ₃ 3-Cl-Ph cf ₃ 2-Me-Ph cf ₃ 3-OCF ₃ -Ph No. 3,4- (OCH ₂ CH ₂ O) -Ph No. 3,4- (OCHFCF ₂ O) -Ph No. 3,4- (OCF ₂ O) -Ph No. Ph No. 4-CF ₃ -Ph No. 3-CF ₃ -Ph No. 4-Cl-Ph No. 3-Cl-Ph No. 2-Me-Ph No. 3-OCF ₃ -Ph

table

Compounds of Formula I wherein: A = NMe, G = C, W = O, X = MeO, R ³ = R ⁴ = H, Y σ

CH ₂ ON = C (R), double fluctuating bond connected to G, and

R ² = Me

R ⁷ Z R ⁷ Z c-propyl 3,4- (OCH ₂ CH ₂ O) -Ph c-propyl 3,4- (OCHFCF ₂ O) -Ph c-propyl 3,4- (OCF ₂ O) -Ph c-propyl Ph c-propyl 4-CF ₃ -Ph c-propyl 3-CF ₃ -Ph c-propyl 4-Cl-Ph c-propyl 3-Cl-Ph c-propyl 2-Me-Ph c-propyl 3-OCF ₃ -Ph cf ₃ 3,4- (OCH ₂ CH ₂ O) -Ph cf ₃ 3,4- (OCHFCF ₂ O) -Ph cf ₃ 3,4- (OCF ₂ O) -Ph cf ₃ Ph cf ₃ 4-CF ₃ -Ph cf ₃ 3-CF ₃ -Ph cf ₃ 4-Cl-Ph cf ₃ 3-Cl-Ph cf ₃ 2-Me-Ph cf ₃ 3-OCF ₃ -Ph No. 3,4- (OCH ₂ CH ₂ O) -Ph No. 3,4- (OCHFCF ₂ O) -Ph No. 3,4- (OCF ₂ O) -Ph No. Ph No. 4-CF ₃ -Ph No. 3-CF ₃ -Ph No. 4-Cl-Ph No. 3-Cl-Ph No. 2-Me-Ph No. 3-OCF ₃ -Ph

table

Compounds of Formula I in which: A = N, G = N, W = O, X = MeO, R ³ = R ⁴ = H, Y = CH ₂ ON C (R ⁷ ), double fluctuating bond attached to A, ii63

R ² = Me

R ⁷ Z R ⁷ Z c-propyl 3,4- (OCH ₂ CH ₂ O) -Ph c-propyl 3,4- (OCHFCF ₂ O) -Ph c-propyl 3,4- (OCF ₂ O) -Ph c-propyl Ph c-propyl 4-CF ₃ -Ph c-propyl 3-CF ₃ -Ph c-propyl 4-a-Ph c-propyl 3-a-Ph c-propyl 2-Me-Ph c-propyl 3-OCF ₃ -Ph CF ₃ 3,4- (OCH ₂ CH ₂ O) -Ph cf ₃ 3,4- (OCHFCF ₂ O) -Ph cf ₃ 3,4- (OCF ₂ O) -Ph cf ₃ Ph cf ₃ 4-CF ₃ -Ph cf ₃ 3-CF ₃ -Ph cf ₃ 4-a-Ph cf ₃ 3-a-Ph cf ₃ 2-Me-Ph cf ₃ 3-OCF ₃ -Ph No. 3,4- (OCH ₂ CH ₂ O) -Ph No. 3,4- (OCHFCF ₂ O) -Ph No. 3,4- (OCF ₂ O) -Ph No. Ph No. 4-CF ₃ -Ph No. 3-CF ₃ -Ph No. 4-a-Ph No. 3-a-Ph No. 2-Me-Ph No. 3-OCF ₃ -Ph

table

Compounds of Formula I wherein A = O, G = C, W = O, X = MeO, R ^J -; R ⁴ = H, a double fluctuating bond attached to G, and R ² = Me

'Table 3

Q J

Compounds of Formula I wherein: A = NMe, G = C, W = O, X = MeO, R = R = H, a double fluctuating bond attached to G, and R ² = Me

table

Compounds of Formula I wherein A = N, G = N, W = O, X = MeO, R ³ = R ⁴ = H, a double fluctuating bond attached to A, and R ² = Me

p p F cf ₃ ^Z / a -ON = Z 2 -ON-p \ p p p F F

-ον-ΛΛ —Is ^ Q, —ON ^ /% p p p F CF3

Recipes / Uses

The compounds of the present invention will generally be used in formulations with agrotechniques. 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 1 (a) a surfactant, (b) an organic solvent, and (c) at least one solid or liquid solvent. Useful recipes can be prepared in an agreed manner. These include dusts, granules, peas, solutions, suspensions, emulsions, wetting powders, emulsion concentrates, dry flowing agents and the like. Spray formulations can be expanded to a suitable medium and applied in spray volumes from about one to several hundred liters per hectare. High capacity formulations are primarily used as intermediates for future formulations. The formulations contain an effective amount of the active ingredient, diluent, and surfactant in an amount of 100% by weight, with amounts selected from the ranges in the table.

Surfactant

Weight percentages

Active Thinner ingredient

Moisturizing powder 5-90 0-74 1-10 Oil suspensions, emulsions, solutions (these may include emulsifying concentrates) 5-50 40-95 0-15 Dust 1-25 70-99 0-5 Pellets, baits and peas 0.01-99 5-99.99 0-15 High-capacity 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, Calrhvell, 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., Ine., New York, (1964) provides a list of surfactants and identifies users. All formulations may contain minor amounts of additives that reduce foaming, sintering, corrosion, microbiological growth, and the like.

όό

Methods for making these compositions are well known in the art. Solutions made by simple mixing of ingredients. Particulate solid compositions are formed by mixing and, usually, grinding in a dry mill or by using the energy of a fluid. Water dispersible granules may be prepared by sintering fine powder formulations, see, e.g., Cross et al., Pesticide Formulations, Washington, D.C. (1988), pp. 251-259. Suspensions are prepared by wet crushing; see, for example, U.S. Pat. 3 060 084. Granules and pellets may be prepared by spraying the active substance on a granular carrier or sintering agent.

technique. See Browning, Agglomeration, Chemical Engineering, December 4, 1967, pp 147-148, Pen / s Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, (1963), pp 8-57 et seq., Also WO. 91/13546. Peas can be made in U.S. Pat. 4,172,714. The water-dispersible and water-soluble granules may be prepared as described in DE patent no. 3,246,493.

For more information on formula science see patents: US no. 3,235,361, column 6, line 16, to column 7, line 19, and 10 to 41 examples; US 3,309,192 from column 5, line 43 to column 7, line 62 and examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167, and 169-182; US 2,891,855 from Row 3, Row 66 to Row 5, Row 17 and Examples 1-4; also Klingman, Weed Control as a Science, John Wuey and Sons, Ine., 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 prepared by known methods. Compound 1 is shown in Table A of the indices below.

Example A

Moisturizing powder compound 65.0% dodecylphenolpolyethylene glycol ether 2.0% sodium lignin sulphonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%

Example B

Granule compound 10.0% atapulgite granules (low volatility,

0.71 / 0.30 mm; U.S. sieve

No. 25-50 eyes) 90.0%

Example C

Pressed powder

Compound 1 25.0% anhydrous sodium sulphate 10.0% crude calcium lignosulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium / magnesium bentonite 59.0% Example D Emulsion concentrate Compound 1 20.0% oil-soluble sulfonates and polyoxy- a mixture of ethylene ethers 10.0% isophorones 70.0%

The compounds of the present invention are useful as agents for protecting plants against disease. The present invention further encompasses methods of treating plant diseases caused by fungal plant pathogens comprising applying to the plant or a portion thereof or to a seed or seedling an effective amount of a compound of formula I or a fungicidal composition containing the compound. The compounds and compositions of the present invention provide for the control of diseases caused by a broad spectrum of fungal plant pathogens of the classes Basidioroycete, Ascomycete, Oomycete and Deuteromycete. They are effective against a wide range of plant diseases, particularly vegetable, field, cereal and crop leaf orn amen f necrotic diseases. Such pathogens include Plasmopara viticola, Phytophthora infestans, Peronospora tabacina, Pseudoperonospora cubensis, Pythium aphanidermatum. Aemaria brassicae, Septoria nodorum, Cercosporidium personatum, Cercospora arachidicola, Pseudocercosporella herpotricchoides, Cercospora beticola, Badytis cinerea, Monilima frucdcola, Pyriculatia otyzae, Podosphaera leucotricha, Venturia in. Puccinia recondita, Puccinia graminis, Hemileia vastatrbc, Puccinia striiformis, Puccinia arachidis. Rhizoctonia solani, Sphaerotheca Fuliginea, Fusarium oxysporum, Verticillium dahliae, Pythium aphanidermatum, Phytophthora megaspemia and other strains ύ species closely related to these pathogens.

The compounds of the present invention may also be admixed with one or more other insecticides, fungicides, nematocides, bacteriocides, acaricides, repellents, attractants, pheromones, nutritional stimulants, and other biologically active compounds to form a multi-component pesticide having the same broad spectrum of agrocult. Examples of other agricultural crop protection agents with which the compounds of the invention may be used include: insecticides such as acetate, avermectin B, azinphos-methyl, bifenthrin, biphenate, buprofezin, carbofuran, chlordimeform, chlorpyrifos, cyfluthrin, deltamethrin, diazinon, difzinon, , fenpropatrine, fenvalerate, fipronone, flucitrinate, flufenprox, fluvalinate, phonophos, isofenphos, malathion, metaldehyde, metamidophos, methidathion, methomyl, methoprene, methoxychlor, monocrotophos, oxampflon, parionmone, methyl, perion, ethyl, pirimicarb, profenofos, rotenone, sulprofos, terbufos, tetrachlorvinphos, thiodicarb, tralomethrin, trichlorfon, and triflumuron; fungicides such as benomyl, blasticidine S, bromuconazole, captafol, captan, carbendazim, chloroneb, chlorothalonil, copper oxychloride, copper salts, cymoxanyl, ciproconazole, dichlorane, diclobutazole, diclomezone, diphenoconazole, diphenoconazole, diphenoconazole, diphenoconazole, , fenpropidine, fenpropimorph, flucquinconazole, flusflazole, flutolanone, flutriafol, folpet, furalax, hexaconazole, ipconazole, iprobenfos, iprodione, isoprothiolol, kasugamycin, mancozeb, maneb, mepro, -Al, probenzol, prochloraz, propiconazole, pirifenox, pyroquilone, sulfur, tebuconazole, tetraconazole, thiabendazole, thiophanate-methyl, thiuram, triadirephone, triadimenol, tricyclazole, uniconzole, validamycin and vincozoline; nematocides such as aldoxycarb, fenamiphos and phosiethane; bactericides such as oxytetracycline, streptomycin and tribasic copper sulfate; acaricides such as amitraz, binapacryl, chlorobenzylate, cyhexatin, dicofol, dienochlor, fenbutatin, oxide, hexithiazox, oxythioquinox, propargite and tebufenpyrad; ή Biological agents such as Baculus thuringiensis and baculovirus.

Undoubtedly, combining with other fungicides with a similar spectrum of action but with a different mode of action in individual cases will be particularly useful for resistance management.

Plant disease surveillance is generally accomplished by utilizing an effective amount of a compound of the invention, either before or after infestation, on the part of the plant to be protected, such as roots, stems, fruit, seeds, tubers or bulbs, or medium (soil or sand) plants. The compounds may also be applied to the seed to protect the seed and seedling.

The rates of application of these compounds may depend on environmental factors and are determined by the conditions of use. Foliage is usually protected when the amount of active ingredient used for treatment is less than 1 g / ha to 5000 g / ha. Seed and seedlings may be normally protected when the seed is treated in an amount of between 0,1 g and 10 g per kilogram of seed.

The following TESTS demonstrate the efficacy of the compounds of the present invention against specific pathogens. Compounds provide disease protection v

pathogen control is unlimited for the species listed below. See Tables A to D of the Compound Types.

Test compounds were first dissolved in acetone at 3% final volume and then suspended in 200 ml. song concentrations in pure water containing 250 mill. song surfactants Trem® 014 (polyhydric alcohol ester). The resulting test suspension was used in the following tests.

A TEST

The test suspension was sprayed onto sprouted wheat. The next day, the seedlings were infected with Eiysiphe graminis f. m.p. tritici (powdery mildew of wheat powder) in spore dust and placed in a growth room at 20 ° C for 7 days, after which the disease state was evaluated.

TEST B

The test suspension was sprayed onto sprouted wheat sprouts. The next day, the seedlings were infected with a spore suspension of Puccinia recondita (wheat leaf brown inducing agent) and incubated in a saturated environment at 20 ° C for 24 hours, then the sample was transferred to a growth room at 20 ° C for 6 days and then disease status was evaluated.

C TEST

The test suspension was sprayed onto sprouted rice seedlings. The next day, the sprouts were inoculated with a spore suspension of Pyricularia oryzae (rice sprouting agent) and incubated in a saturated atmosphere at 27 ° C for 24 hours, then transferred to a growth room where kept at 30 ° C for 5 days, after which the disease state was evaluated.

TEST D

The test suspension was sprayed onto sprouted tomato sprouts. The next day, the seedlings were inoculated with Phytophthora infestans (potato and tomato late blight disease agent) spore suspension ii 'incubated in a saturated environment at 20 ° C for 24 hours, then transferred to a growth room where kept at 20 ° C for 5 days, followed by assessed disease status.

E TEST

The test suspension was sprayed onto seedlings of seedlings. The next day, the seedlings were inoculated with a spore suspension of Plasmopara viticola (Grapefruit Agent) and incubated in a saturated environment at 20 ° C for 24 hours, then transferred to a growth room where kept at 20 ° C for 6 hours, then transferred to a growth room, where they were stored at 20 ° C for 6 days, then placed in a saturated environment at 20 ° C for 24 hours, after which the disease state was evaluated.

F TEST

The test suspension was sprayed onto sprouted cucumber sprouts. The next day, the seedlings were inoculated with a spore suspension of Botrytis cinerea (gray mold causative agent) and incubated in a saturated environment at 20 ° C for 48 hours, then transferred to a growth room at 20 ° C for 5 days, after which the disease was evaluated. standing.

TABLE A OF INDICATORS

Compound_lyd, temp. (° C)

The compound Y z melt temp (° C) 2 O 2-Me-Ph oil * 3 O CH ₂ -Ph oil * 4 - Me oil * 5 ch ₂ o 2-Me-Ph oil *

INDICATOR TABLE C

ch ₃

The compound W X Y Z melt you (Ώ 6th O MeS O Ph 129-130 7th O MeO 0 Me 123-126 8th O MeO - Me 95-97 9th O MeS - Me 95-97 10th O a - Me 99-100 11th O MeO 0 Ph 88-91 12th O a o 2-Me-Ph 88-96 13th O MeO ch ₂ o 2-Me-Ph 110-113 14th O EtO ch ₂ o 2-Me-Ph oil * 15th O MeS ch ₂ o 2-Me-Ph 80-88 16th O OCH ₂ C = CH ch ₂ o 2-Me-Ph 122-130 17th O a CH ₂ ON = C (Me) 4-Me-Ph oil * 18th O MeO CH ₂ ON = C (Me) 4-Me-Ph 116-118 19th O MeS CH ₂ ON = C (Me) 4-Me-Ph oil * 20th O a oil

• N - O

S MeS O

O MeO

Ph oil *

126-136

Ph oil *

O MeS oil *

O a CH ₂ O 3- (OPhO-Ph oil * o MeO ch ₂ o 3- (OPhO-Ph for oil o MeO CH ₂ ON = C (H) Ph 101-104 o MeS ch ₂ o 3- (OPhO-Ph 95-100 o a CH ₂ s 2-Me-Ph 106-109 o MeO CH ₂ s 2-Me-Ph 115-118 o MeS CH ₂ s 2-Me-Ph 82-86 o a CH ₂ s 2-Benzothiazole 95-97 o MeOl c = c Ph 164-166 o MeO CH ₂ ON = C (Me) 4-Br-Ph 115-120 o a CH ₂ ON-C (Me) 4-Br-Ph resin* o a ch ₂ o 3- (benzoyl) -Ph oil * o MeS CH ₂ ON = C (Me) 4-Br-Ph 117-122 o MeO ch ₂ o 3- (benzoyl) -Ph oil * o a ch ₂ on = ch ₂ 4-Cl-Ph oil *

40 0 a CH ₂ ON = C (Me) 3-piperonyl oil 41 O MeO CH-NOCH ₂ 4-Cl-Ph oil 42 O MeO CH ₂ ON = C (Me) 3-piperonyl oil 43 O Cl 0 4- (6-Oph) -1,3 pyrimidine oil 44 O MeO CH ₂ s 2-Benzothiazole 95-97 45 0 MeO CH ₂ ON = C (Me) 2-Me-Ph oil 46th O MeO CH ₂ ON-C (Me) 4-CF ₃ -Ph 138-144 47 O MeO CH ₂ ON = C (Me) Ph oil 48 O MeO CH ₂ ON-C (Me) Ph oil 49 O MeO CH ₂ ON = C (Me) 3-Me-Ph oil 50 O MeO CPI ₂ ON = C (Me) 4-MeO-Ph oil 51 0 MeO CH ₂ ON = C (Me) 3-Cl-Ph oil 52 0 MeO CH ₂ ON = C (Me) Ph oil 53 0 MeO CH = NOCH ₂ 3-Me-Ph oil

* See MBR values in Table D of Indices.

TABLE D OF INDICATORS

Compound MBR Values (200MHz, CDC1 Solution ₃ )

Nos. Δ 7.51 (dd, 1H), 7.27 (dt, 1H), 7.17 (m, 2H), 6.97 (dd, lh), 6.6 (m, 3H), 3.92 ( _δ , 3Η), 3.74 (s, 3H) ₅ 3:33 _(s, 3H) δ 7:32 (m, 7H), 6.99 (m, 2H) 5.08 (s, 2H), 3.84 (s, 3H), 3:42 (s, 3H), 'δ 7.25 (m, 4H); , 3.98 (s, 3H), 3.45 (s, 3H), 2.30 (s, 3H) δ 7.61 (d, 1H), 7.35 (m, 3H), 7.11 (m, 2H), 6.84 (t, 2H), 5.12 (s, 2H), 3.96 (s, 3H), 3.415 (s, 3H), 2.24 (s, 3H) δ 7.65 (d, 1H), 7.45 (m, 2H), 7.23 (m, 1H), 7.10 (m, 2H),

6.82 (t, 1H), 6.78 (d, 1H), 5.08 (s, 2H), 4.29 (m, 2H), 3.41 (s, 3H), 2.24 (s, 3H), 1.31 (t, 3H) δ 7.6 -7.45 (m, 5H), 7.20 (m, 1H), 7.14 (d, 2H), 5.27 (d, 1H),

5.16 (d, 1H), 3.46 (s, 3H), 2.34 (s, 3H), 2.16 (s, 3H) δ 7.6 (d, 1H), 7.5 (m, 3H), 7.4 (t, 1H), 7.25 (m, 1H), 7.15 (d, 2H), 5.26 (d, 1H), 5.20 (d, 1H), 3.48 (s, 3H), 2.41 (s, 3H), 2.43 (s, 3H), 2.18 ( s, 3H) δ 7.62 (m, 2H), 7.5 (m, 2H), 7.35-7.2 (m, 4H), 5.25 (d, 1H), 5.15 (d, 1H), 3.48 (s, 3H), 3.02 (m, 2H), 2.85 (m, 2H) δ 7.42 (m, 2H), 7.10 (m, 1H), 7.06 (m, 3H), 6.99 (t, 1H), 6.68 (d, 2H), 3.37 ( s, 3H), 2.51 (s, 3H) δ 8.01 (s, 1H), 7.61 (d, 1H), 7.52 (m, 4H), 7.35 (m, 3H), 7.25 (d, 1H), 5.23 (d) , 1H), 5.15 (d, 1H), 3.49 (s, 3H) δ 7.6 (m, 2H), 7.5-7.4 (m, 3H), 7.3-7.2 (m, 3H), 5.24 (d, 1H), 5.20 (d, 1H), 3.48 (s, 3H), 2.40 (s, 3H) δ 7.6-7.4 (m, 4H), 7.35 (m, 2H), 7.2 (m, 2H), 7.0 (d, 2H) , 6.6 (m, 3H), 5.04 (d, 1H), 5.00 (d, 1H), 3.45 (s, 3H) δ 7.6 (d, 1H), 7.45 (m, 2H), 7.33 (t, 2H), 7.19 (m, 2H), 7.10 (t, 1H), 7.01 (d, 2H), 6.6 (m, 3H), 5.03 (m, 2H), 3.87 (s, 3H), 3.39 (s, 3H) δ 7.6 -7.4 (m, 7H), 7.23 (d, 1H), 5.28 (d, 1H), 5.17 (d, 1H), 3.46 (s, 3H), 2.14 (s, 3H) δ 7.80 (d, 2H), 7.65 -7.45 (m, 6H), 7.36 (d, 2H), 7.30 (m, 1H), 7.25 (m, 1H), 7.10 (t, 1H), 5.15 (d, 1H), 5.10 (d, 1H), 3.45 (s, 2H) δ 7.77 (d, 2H), 7.6 (m, 2H), 7.47 (m, 4H), 7.35 (m, 3H), 7.25 (m, 1H), 7.10 (m, 1H), 5.13 (d, 1H), 5.12 (d, 1H),

3.89 (s, 3H), 3.38 (s, 3H) δ 8.03 (s, 1H), 7.70 (d, 1H), 7.53 (m, 2H), 7.35-7.25 (m, 5H), 5.06 (s, 2H) , 3.46 (s, 3H) δ 7.6-7.5 (m, 3H), 7.24 (m, 1H), 7.13 (s, 1H), 7.02 (d, 1H), 6.78 (d, 1H), 5.96 (s, 2H) ), 5.26 (d, 1H), 5.14 (d, 1H), 3.48 (s, 3H), 2.13 (s, 3H), δ 8.04 (s, 1H), 7.8 (m, 1H), 7.45 (m, 2H) ), 7.35-7.25 (m, 5H), 5.10 (s, 2H), 3.86 (s, 3H), 3.41 (s, 3H) δ 7.58 (m, 1H), 7.43 (m, 2H), 7.25 ( m, 1H), 7.15 (m, 1H), 7.02 (d, 1H), 6.76 (d, 1H), 5.96 (s, 2H), 5.22 (d, 1H), 5.18 (d, 1H), 3.89 (s) , 3H), 3.42 (s, 3H), 2.15 (s, 3H) δ 8.04 (s, 1H), 7.6 (m, 1H), 7.5-7.4 (m, 5H), 7.3 (d, 1H), 7.18 ( m, 2H), 6.38 (s, 1H), 3.45 (s, 3H) δ 7.55 (d, 1H), 7.40 (m, 3H), 7.20 (m, 4H), 5.21 (d, 1H), 3.87 (s) , 3H), 3.42 (s, 3H), 2.24 (s, 3H) δ 7.6-7.2 (m, 9H), 5.4-5.2 (m, 2H), 3.87, 3.83 (s, 3H), 3.41, 3.40 (s) , 3H) δ 7.6 (m, 3H), 7.44 (m, 2H), 7.35 (m, 3H), 7.25 (m, 1H), 5.26 (d, 1H), 5.22 (d, 1H), 3.88 (s, 3H), 3.49 (s, 3H), 2.20 (s, 3H) δ 7.5 (d, 1H), 7.40 (m, 4H), 7.23 (m, 2H), 7.18 (d, 1H),

5.26 (d, 1H), 5.21 (d, 1H), 3.88 (s, 3H), 3.41 (s, 3H), 2.36 (s, 3H),

2.19 (s, 3H) δ 7.56 (m, 3H), 7.45 (m, 2H), 7.25 (m, 1H), 6.86 (d, 2H),

5.24 (d, 1H), 5.19 (d, 1H), 3.88 (s, 3H), 3.81 (s, 3H), 3.41 (s, 3H),

2.17 (s, 3H) δ 7.5 (m, 2H), 7.45 (m, 3H), 7.3 (m, 3H), 5.27 (d, 1H),

5.22 (d, 1H), 3.89 (s, 3H), δ 8.02, 8.01 (s, 1H), 7.8, 7.7 (m, 1H), 7.45 (m, 2H), 7.35 (m, 4H), 7.25 (m , 2H), 5.25 (m, 1H), 3.88, 3.74 (s, 3H), 3.45, 3.39 (s, 3H),

1.62-1.56 (m, 3H) δ 8.04 (s, 1H), 7.81 (m, 1H), 7.45 (m, 2H), 7.38-7.18 (m, 5H),

5.18 (s, 2H), 3.86 (s, 3H), 3.42 (s, 3H), 2.38 (s, 3H)

The results of the A-F tests are shown in Table 1. The rating in Table 100 shows 100

% disease detection and a score of 0 indicates no disease (corresponding to the amount tested). table Jungian Aban- B ban- C ban- D ban- E ban- F ban- nys no. diction diction diction diction diction diction 1 57 79 0 0 17th 68 O Z-r 86 93 0 0 100 0 3 57 79 0 61 100 68 4 0 0 0 0 100 0 5 99 100 0 46th 100 43 6th 98 100 36 85 100 42 7th 73 9th 0 33 5 3 8th 0 0 0 0 35 46th 9th 0 0 0 0 35 0 10th 35 3 0 43 78 0 11th 100 100 0 64 100 50 12th 95 97 0 47 92 71 13th 98 100 0 0 69 * 63 14th 78 81 0 0 0 0 15th 100 100 0 63 100 36 16th 92 57 0 0 0 0 17 * 78 91 0 0 36 44

18th 52 0 0 0 0 0 19th 0 0 0 0 0 62 20th 63 84 0 26th 99 65 21st - - 0 - - - 22nd 38 100 0 47 100 47 23rd 38 89 0 0 100 0 24th 0 98 97 47 100 70 25th 0 84 88 16th 100 0 26th 72 100 0 73 100 44 27th 72 93 0 16th 100 2 28th 83 97 19th 59 100 0 29th 16th 97 0 25th 8th 0 30th 95 96 0 47 100 47 31st 89 99 0 46th 100 0 32 60 53 0 0 100 47 33 95 98 0 77 100 0 34 90. 100 88 64 100 0 35 0 97 0 0 99 9th 36 63 93 62 46th 100 0 37 98 100 93 63 100 48 38 0 99 73 26th 100 0 39 32 85 73 0 45 0 40 59 97 93 0 76 49 41 97 100 0 0 100 0 42 92 100 62 64 100 68 43 97 99 50 ^26th 97 0 44 73 100 0 47 100 69 45 94 100 0 0 100 47 46th 100 100 100 93 100 0 47 96 100 0 0 100 0 48 100 100 0 47 100 0 49 100 100 88 86 100 47 50 92 100 97 77 - 45 51 Tried 100 40 m.d. 100 100 97 - 89

Claims (10)

DEFINITION OF INVENTION A compound of the general formula I and its agrochemically acceptable salts, wherein A is O; S; N; NR ⁵ ; or CR ¹⁴ ; G is C or N; with the proviso that when G is C, A is O, S or NR ⁵ and the double fluctuating bond is attached to G; and when G is N, A is N or NR ⁵ and the double fluctuating bond is attached to A; W is O or S; X is OR ¹ ; S (O) _m R 5 or halogen; R ¹ is C ¹ -C 8 alkyl; CpC8 -haloalkyl; C ₂ -C 8 alkenyl; C ₂ -C ₈ haloalkenyl; C ₂ -C 8 alkynyl; C ₂ -C 8 -haloalkynyl; C 1 -C 8 cycloalkynyl; C ₂ -C ₄ alkylcarbonyl; C ₂ -C ₄ alkoxycarbonyl; or benzoyl optionally substituted with R ¹³ ; R ² and R ^{3 are} each independently H; C 1 -C 8 alkyl; GpCghalogenalkilas C _2-C₈ alkenyl; C ₂ -C 8 -haloalkenyl; C ₂ - C ₈ alkynyl; C ₂ -C 8 -haloalkynyl: C ₈ -C 8 -cycloalkynyl; C ₂ -C ₄ alkylcarbonyl; C ₂ -C ₄ alkoxycarbonyl; or benzoyl optionally substituted with R; R ³ and R ^{4 are} each independently H; cyano; nitro; C 1 -C 8 alkyl; C 1 -C 8 haloalkyl; C ₂ -C 8 alkenyl; C ₂ -C 8 -haloalkenyl; C ₂ -C ₈ alkynyl; C ₂ -C 8 -haloalkynyl; C 1 -C 8 alkoxy; C 1 -C 8 haloalkoxy; C ₂ -C 8 alkenyloxy; or C ₂ -C 8 alkynyloxy; Y is -O-; -S (O) _n -; -CHR ⁶ -CHR ⁶ -; - CR ⁶ = CR ⁶ -; -OC; -CHR ⁶ O-; 'OCHR ⁶ -; -CHR ⁶ S (O) _n -; -S (O) _n CHR ⁶ -: -CHR ⁶ ON = C (R ⁷ ) -; '- (R ⁷ ) C = N-OCH (R ⁶ ) -: -C (R ⁷ > NO -; - ON = C (R ⁷⁾ -CHR ⁶ OC (= O) N (R ¹⁵ ) -; or direct connection; and the direction of the Y bond is defined such that the portion to the left of the bond is joined to the phenyl ring and the portion to the right of the bond is joined to Z; R ⁶ is independently H or C 1 -C 6 alkyl; R ⁷ is H; C _r C ₆ alkyl; C _r C ₆ -haloalkyl; C ₁ -C ₆ alkoxy; C ₁ -C ₆ haloalkoxy; C ₂ -C 8 alkenyl; C ₂ -C 8 -haloalkenyl; C ₂ -C ₅ -alkynyl; C 1 -C 8 haloalkynyl; C 1 -C 6 -cycloalkyl; C ₂ -C ₄ alkylcarbonyl; C ₂ -C ₄ -alkoxycarbonyl; cyano; or morpholine; Z is C ₁ -C ₈ alkyl, C ₂ -C ₁₀ alkenyl, or C ₂ -C ₁₀ alkynyl, and each optionally substituted R; or Z is C _{3-C₈-cycloalkyl} or phenyl, each optionally substituted with one of R ^9, R ^i0, or both R ⁹ and R ^10: or Z is a 3 to 14-membered non-aromatic heterocyclic ring system selected from a monocyclic ring system, , a fused bicyclic ring and a fused tricyclic ring, or Z is a 5 to 14 membered aromatic ring system selected from the group of a monocyclic ring, a fused bicyclic ring and a fused tricyclic ring, each non-aromatic or aromatic ring system having from 1 to 6 heteroatoms independently selected from 1-4 nitrogen atoms, 1-2 oxygen atoms, and 1-2 sulfur atoms, each non-aromatic or aromatic ring system being optionally substituted with one of R ⁹ , R ^10, or both of R ⁹ and R ¹⁰ ; or R ⁷ and Z taken together form CH ₂ CH ₂ CH ₂ , CH ₂ CH ₂ CH ₂ CH ₂ , CH ₂ CH ₂ OCH ₂ CH _2> , each CH ₂ group is optionally substituted with 1-2 halogen atoms; or Y and Z taken together form R, Y and Z taken together with the phenyl ring form a naphthalene ring substituted at any ring at a non-volatile group with R ⁴ , provided that when R ³ , Y and Z taken together with the phenyl ring form a naphthalene ring substituted with R ⁴ , and A is S, W is O, X is SCH 3 and R ² is CH 3, then R ⁴ is not H; J is -CH ₂ -; -CH ₂ CH ₂ -; -OCH ₂ -; -CH ₂ O-; -SCH ₂ -; -CH ₂ S-; -N (R ¹⁶ ) CH 2 -; or -CH 2 N (R ^1b ) -; each CH 2 group is optionally substituted with 1 to 2 CH ₃ ; R is 1-6 halogen atoms; C 1 -C 8 alkoxy; CpC8 -haloalkoxy; C 1 -C 8 alkylthio; C 1 -C 8 haloalkyl; CpC8-alkosulfinyl; C 1 -C 6 -alkylsulfonyl; Cy-C 1 -cycloalkyl; C 8 -C 8 alkenyloxy; CO ₂ (C ₁ -C ₆ alkyl); NH (C ₁ -C ₆ alkyl); N (C _r C -alkflas _{6) 2;} O cyano or nitro; or R is phenyl, phenoxy, pyridinyl, pyridinyloxy, thienyl, furanyl, pyrimidinyl, or 11 1? pyrimidinyloxy, each optionally substituted with one of R, R, or both of R ¹¹ and R ¹² ; R ⁹ is 1-2 halogen atoms; C 1 -C 8 alkyl; C 1 -C 8 haloalkyl; C 1 -C 8 alkoxy; C 1 -C 8 haloalkoxy; C 2 -C 8 alkenyl; C ₂ -C ₈ haloalkenyl; C ₂ -C 8 alkynyl; C 1 -C 8 alkylthio; C 1 -C 8 haloalkylthio; CpC8 alkylsulfinyl; C 1 -C 8 alkylsulfonyl; C 1 -C 8 cycloalkyl; C 1 -C 8 alkoxy; CO ₂ (C _r Cg alkyl), ·. NH (C _R Alkua Cg) N (C _r Cg alkflas) _2; -C (R) = NOR; cyano or nitro; or R 'is phenyl, benzyl, benzoyl, phenoxy, pyridinyl, pyridinyloxy, thienyl, thienyloxy, furanyl, pyrimidinyl, or pyrimidinyloxy, each optionally substituted with one of R ¹¹ , R ¹² , or both R ¹¹ and R ¹² ; R ^1U is halogen; C ₁ -C ₄ alkyl; C ₁ -C ₄ haloalkyl; C ₁ -C ₄ alkoxy; nitro; or cyano; or R ⁹ and R ^, when connecting adjacent atoms are taken together as-OCH ₂ CH ₂ Oarba -OCH ₂ O-; each CH ₂ group is optionally substituted with 1-2 halogen atoms; R and R are each independently halogen; C ₃ -C ₄ alkyl; C ₁ -C ₄ haloalkyl; C ₁ -C ₄ alkoxy; C 1 -C ₄ haloalkoxy; nitro; or cyano; R is halogen; C 1 -C 8 alkyl; C 8 -C 10 haloalkyl; C 1 -C 1 alkoxy; C 1 -C 7 haloalkoxy nitro; or cyano; R ¹⁴ is H; halogen; C-C 1 -C 8 alkyl; C 1 -C 8 -haloalkyl; C ₂ -C ₈ alkenyl; C ₂ -C 8 -haloalkenyl; C ₂ -C 8 -alkyl; C ₂ -C ₈ haloalkynyl; or C 8 -C 8 -cycloalkynyl; R ¹⁵ , R ¹⁶ , R ¹⁷ and R ^{18 are} each independently H; C 1-10 alkyl; or phenyl optionally substituted with halogen, CpG1-alkyl; C ₁ -C ₄ haloalkyl; C 1 -C ₄ alkoxy; C 1 -C ₄ haloalkoxy, nitro or cyano; m, n and q are each independently 0, 1 or 2; and p and r are each independently 0 or 1; with the proviso (a) when A is N, G is N, X is SiO ^ R ¹ and m is 0, then the combination of Ύ and Z is not alkyl, haloalkyl or alkoxy; and (b) when A is NR ⁵ , G is C, X is OR ¹ and R ¹ is alkylcarbonyl, alkoxycarbonyl or optionally substituted benzoyl, then the combination of Y and Z is non-alkyl or alkoxy. 2. A compound according to claim 1, wherein W is O; R ¹ is alkyl or haloalkyl; R 'is H; C 1 -C 6 -alkyl; C 1 -C 6 -haloalkyl; or O-C 1-6 -cycloalkyl; R ³ and R ^{4 are} each independently H; halogen; cyano; nitro; C ₁ -C ₆ alkyl; C-C 1 -C 8 -haloalkyl; C 1 -C 8 -C 8 alkoxy; or C 1 -C 8 haloalkoxy; Y is -O-; -CH = CH-; -CH ₂ O-; -OCH ₂ -; -CU ₂ S (O) _n -; - CH ₂ ON = C (R ⁷ ) -; C (R ⁷ ) = NO-; -CH ₂ OC (O) NH-; or direct communication; R ⁷ is H; C 1 -C 6 -alkyl; C 1 -C 8 haloalkyl; C ₂ -C 8 alkenyl; C ₃ -C ₈ alkynyl; or cyano; O Z is C 1 -C 8 alkyl optionally substituted with R; or C 1 -C 8 -cycloalkyl or phenyl, each optionally substituted with one of R ⁹ , R ¹⁰ or both of R ⁹ and R ¹⁰ ; or Z is _ G G G Z-l Z-2 Z-3 G G G Z-4 Z-5 Z-6 (J pi i R19 R19 Z-7 Z-8 Z-9 N— G V to ,, N ^- —N Z-10 R ^iy Zl 1 Z-12 Z-13 z-14 Z-16 Z-17 Z-18 Z-36 In Z-37, each group is optionally substituted with one of R ⁹ , R ^10, or both of R ⁹ and R ¹⁰ ; or O R, Y and Z are taken together with the phenyl ring to form a naphthalene ring substituted at any two rings by a group R ⁴ ; or Y and Z are taken together to form R ⁸ is 1-6 halogen atoms; C 1 -C 8 alkoxy; C 1 -C 8 haloalkoxy; or R ⁸ is phenyl, phenoxy, pyridinyl, pyridinoxy, pyrimidine, or 11 19 pyrimidinyloxy, each optionally substituted with one of R, R or both of R ¹¹ and R ¹² ; R ⁹ is 1-2 halogen atoms; C 1 -C 8 -alkyl; C 1 -C 8 haloalkyl; C 1 -C 8 alkoxy; C 1 -C 8 -haloalkoxy C 1 -C 8 -alkyl; cyano; CO-C 1 -C 8 alkyl); NH (C ₁ -C ₆ alkyl); or N 1 -C 8 -C 8 -alkyl ^; or R ⁹ is C 3 -C ⁸ -cycloalkyl, phenyl, phenoxy, pyridinyl, pyridinoxy, pyrimidine, or pyrimidine oxy, each optionally substituted with one of R ¹¹ , R ¹² or both of R ^{11 and} R ¹² ; and R ¹⁹ is H; C 1 -C 8 -alkyl; C 1 -C 6 -haloalkyl; or phenyl optionally substituted with halogen, CPC -alkūu ₄ C ₁ -C ₄ -halogenalkūu, Ci-C ₄ -alkoksūu C _r C ₄ -halogenalkoksūu, nitro or cyano. 3. The compound of claim 2, wherein Or Z is fenflas from Zl to Z-21, each optionally substituted with one of R ^9, R ¹⁰ or both R ⁹ and R ^10; or Y and Z are taken together to form J is -CH ₂ - or -CH ₂ CH ₂ -; p is O; and r is 1. ⁴ 4. A compound according to claim 3 wherein A is O; N; NR ⁵ ; or CR ¹⁴ ; X is OR ¹ ; R ¹ is CpC ¹ -alkyl; R ² is H or C ₁ -C ₂ -alkyl; R ³ and R ^{4 are} each H; Y is -O-; -CH = CH-; -CH ₂ O-; -OCH ₂ -; -CH ₂ ON = C (R ⁷ ) -; or -CH ₂ OC (= O) NH-; R ⁷ is H: C 1 -C 10 alkyl; or R ¹ C ^ -Cj haloalkyl; and Z is phenyl, pyridinyl, pyrimidinyl, or thienyl, each optionally substituted with one of R ⁹ , R 6, or both R ⁹ and R 6. The compound of claim 4, wherein A is O or NR ^{5 *} ; G is C; Y is -O-; -CH ₂ O-; -OCH ₂ -; or -CH ₂ ON = C (R ⁷ ) -; and R ⁷ is H; C 1 -C 2 alkyl; or R ^{3 is} C 1 -C 2 -haloalkyl. 6. A compound according to claim 4, wherein A is N or CR ¹⁴ ; G is N; Y is -O-; -CH ₂ O-; -OCH ₂ -; or -CH ₂ ON = C (R ⁷ ) -; R ⁷ is H; C 1 -C 12 alkyl; or R ^{1 is} C ¹ -C ₂ -haloalkyl. The compound of claim 5, wherein R ¹ is methyl; R ⁷ is methyl; and Z is phenyl, optionally substituted with one of R ⁹ , R ¹⁰ , or both of R ⁹ and R ¹⁰ . 8. The compound of claim 6, wherein R ¹ is methyl; η R is methyl; and Z is phenyl, optionally substituted with one of R ⁹ , R ¹⁰ , or both of R ⁹ and R ¹⁰ . A fungicidal composition comprising at least one of (a) a surfactant, (b) an organic solvent, and (c) at least one solid or liquid diluent, characterized in that it contains an effective amount of a compound according to claim 1. A method of protecting plants against diseases caused by fungal plant pathogens that damage plants, parts thereof or plant seeds or sprouts, wherein the plant parts or plant seeds or sprouts are treated with an effective amount of a compound according to claim 1.