WO1991019703A2 - Fungicidal iminooxazolidinones - Google Patents

Abstract

This invention pertains to certain novel compounds of formula (I), including geometric and stereoisomers, agricultural compositions containing them, and their use as fungicides.

Description

TITLE

FUNGICEDAL IMINOOXAZOLIDINONES CROSS-REFERENCE TO RELATED APPLICATION This is a continuation-in-part of application U.S.S.N. 07/535,644, filed June 11, 1990.

BACKGROUND OF THE INVENTION

This invention pertains to certain novel compounds, including geometric and stereoisomers, agricultural compositions containing them, and their use as fungicides.

New compounds effective for controlling the growth of undesired fungi are in constant demand. In the most common situation, such compounds are sought to selectively control the growth of fungi in useful crops such as cotton, rice, corn, wheat and soybeans, to name a few

Unchecked fungus growth in such crops can cause significant losses, reducing profit to the farmer and increasing costs to the consumer. There are many products commercially available for these purposes, but the need continues for products which are more effective, less costly and environmentally safe.

Punja (U.S. 3,843,669) discloses pesticidal compounds (insecticides, fungicides, algicides and herbicides) of the formula:

wherein:

Q is sulfur, sulfoxide, sulfone or oxygen;

X or Y is oxygen, sulfur, alkylimino, or

R¹ and R² are independently H or C₁-C₄ alkyl;

R³ is H, C₁-C₈ alkyl, allyl, benzyl, dimethylamino, methyl

thiomethyl, ethoxycarbonylmethyl or halo-substituted pyridyl; and

R⁴ and R⁵ are independently H, C₁-C₄ alkyl, phenyl, chloro substituted phenyl, acetyl, chloromethyl, methoxymethyl, ethoxymethyl or ethylthiomethyl. SUMMARY OF THE INVENTION

This invention pertains to compounds of the Formula I including all geometric, optical and stereoisomers, agricultural compositions containing them, and their use as fungicides.

wherein:

Q is O, NR¹¹ or a direct bond;

G is Rl2, C(=O)R¹³, C( =O)OR¹³, C(=O)SR¹³, C( =O)NR¹³R¹⁴, SO₂R¹³ or P(=WXOR¹⁵)₂;

W is O or S;

R¹ is H; C₁-C₄ alkyl; C₁-C₄ haloalkyl; C₃-C₆ cycloalkyl; C₂-C₄ alkenyl; hydroxycarbonyl; C₂-C₇ alkoxycarbonyl; or benzyl optionally substituted on the phenyl ring with R⁶ and on the benzylic carbon with R⁷ ;

R² is C₁-C₆ alkyl; C₅-C₇ cycloalkyl; phenyl optionally substituted with R⁵ and R⁶; 2-naphthyl; thienyl optionally substituted with R⁵ and R⁶; furyl optionally substituted with R⁶; or pyridyl optionally substituted with one substituent selected from the group consisting of R⁶, phenoxy optionally substituted with R¹⁶ and phenylthio optionally substituted with R⁶; further

R¹ and R² can be taken together to form structures selected from the group consisting of -CH₂(CH₂)₂CH₂-, -CH₂(CH₂)₃CH₂-, -CH₂(CH₂)₄CH₂-, -CH₂CH₂OCH₂CH₂-, -CH₂CH₂SCH₂CH₂-, -CH₂CH₂N(R⁷)CH₂CH₂-,

R³ is phenyl optionally substituted with R¹⁰; benzyl; pyridyl

optionally substituted with R¹⁰; pyrimidinyl optionally

substituted with R¹⁰; or pyridazyl optionally substituted with R¹⁰; provided that when R³ is pyridyl optionally substituted with R¹⁰. pyrimidinyl optionally substituted with R¹⁰ or pyridazyl optionally substituted with R¹⁰, these moieties are connected through a carbon atom;

R⁴ is H, methyl or acetyl;

R⁵ is halogen; C₁-C₆ alkyl; C₁-C₆ haloalkyl; C₁-C₆ alkoxy; C₃-C₆ alkenyl; C₃-C₆ haloalkenyl; C₃-C₆ alkenyloxy; C₃-C₆ alkynyl;

C₃-C₆ haloalkynyl; C₁-C₆ alkylthio; C₁-C₆ haloalkylthio;

C₁-C₆ haloalkoxy; C₁-C₆ alkylsiilfonyl; C₁-C₆

6aloalkylsulfonyl; nitro; phenyl optionally substituted with R⁶; phenozy optionally substituted with R¹⁶; phenylthio optionally substituted with R⁶; cyano; C₃-C₆ alkynyloxy; C₂-C₆

alkoxyalkyl; C₂-C₆ alkoxyalkoxy; phenoxymethyl optionally substituted on the phenyl ring with R⁶; benzyloxy optionally substituted on the phenyl ring with R⁶; phenethyl optionally substituted on the phenyl ring with R⁶; benzyl optionally substituted on the phenyl ring with R⁶; C₂-C₆ alkoxycarbonyl;

C₅-C₆ cycloalkyl; C₅-C₆ cycloalkyloxy; or NHR⁸;

R6 is 1-2 halogen; C₁-C₄ alkyl; C₁-C₄ alkoxy; trifluoromethyl; methylthio; or nitro;

R⁷ is H, C₁-C₄ alkyl;

R⁸ is C₁-C₄ alkyl; C₂-C₆ alkoxycarbonyl; (R⁹R¹⁴N)C=O; phenyl optionally substituted with R¹⁰; or phenoxycarbonyl optionally substituted with R¹⁷;

R⁹ is C₁-C₆ alkyl; or phenyl optionally substituted with R¹⁸;

RlO is 1-2 substituents selected from the group consisting of

trifluoromethyl, trifluoromethoxy, nitro, CO₂CH₃, halogen,

C₁-C₄ alkyl, C₁-C₄ alkoxy and cyano; provided that when the phenyl ring is disubstituted, one of the alkyl or alkoxy groups is no larger than C₁;

R¹¹ is H, C₁-C₄ alkyl, C₃-C₆ alkenyl or C₃-C₆ alkynyl; R¹² is H; C₁-C₈ alkyl optionally substituted with hydroxycarbonyl,

C₂-C₈ alkoxyalkyl, or C₂-C₇ alkoxycarbonyl; C₃-C₈ cycloalkyl; C₃-C₈ alkenyl; C₃-C₈ alkynyl; benzyl optionally substituted on the phenyl ring with R⁶ and on the benzylic carbon with R⁷; benzyloxycarbonyl optionally substituted on the phenyl ring with R⁶ and on the benzylic carbon with R⁷; phenyl optionally substituted with R⁵ and R⁶; or pyridyl, connected through a carbon atom, optionally substituted with R⁶; or

R¹¹ and R¹² can be taken together along with the nitrogen to which they are attached to form pyrrole, pyrazoline, 1,3,4-triazole, or 1,2,4-triazole rings, or structures selected from the group consisting of -CH₂(CH₂)₂CH₂-, -CH₂(CH₂)₃CH₂-,

-CH₂(CH₂)₄CH₂-, -CH₂CH₂OCH₂CH₂-, -CH₂CH₂SCH₂CH₂-,

-CH₂CH₂N(R⁷)CH₂CH₂- or -CH₂CH₂N(R⁷)CH₂CH₂CH₂-;

R¹³ is C₁-C₆ alkyl; C₃-C₆ cycloalkyl; C₁-C₄ haloalkyl; phenyl

optionally substituted with R⁵ and R⁶; or benzyl optionally substituted on the phenyl ring with R⁶ and on the benzylic carbon with R⁷;

R¹⁴ is H or C₁-C₄ alkyl;

R¹⁵ is C₁-C₄ alkyl; and

R¹⁶ is 1-2 halogen; nitro; cyano; C₁-C₆ alkyl; C₁-C₆ haloalkyl; C₁- C₆ alkoxy; C₁-C₆ haloalkoxy; C₁-C₄ alkylsulfonyl; C₂-C₆ alkoxyalkyl; C₁-C₄ alkylthio; C₅-C₆ cycloalkyl; C₅-C₆ cycloalkyloxy; C₂-C₆ alkenyl; C₂-C₆ haloalkenyl; C₂-C₆ alkynyl; hydroxycarbonyl; C₂-C₄ alkoxycarbonyl; phenoxy optionally substituted with R⁶;

R¹⁷ and R¹⁸ are independently 1-2 halogen; C₁-C₂ alkyl;

trifluoromethyl; or C₁-C₂ alkoxy.

In the above recitations, the term "alkyl", used either alone or in compound words such as "alkylthio" or "haloalkyl" denotes straight chain or branched alkyl such as methyl, ethyl, n-propyl, i-propyl, or the different butyl, pentyl or hexyl isomers. "Alkenyl" denotes straight chain or branched alkenes such as 1-propenyl, 2-propenyl, 3-propenyl and the different butenyl , pentenyl and hexenyl isomers. "Alkenyloxy" denotes straight chain or branched alkenyloxy moieties. Examples of alkenyloxy moieties include H₂C=CHCH₂O, (CH₃)2C=CHCH₂O,

(CH₃)CH=CHCH₂O, (CH₃)CH=C(CH₃)CH₂O and CH₂=CHCH₂CH₂O.

"Alkynyl" denotes straight chain or branched alkynes such as ethynyl,

1-propynyl, 3-propynyl and the different butynyl, pentynyl and hexynyl isomers. "Alkynyloxy" denotes straight or branched alkynyloxy moieties such as HC≡CCH₂O, CH₃C≡CCH₂0 and CH₃O≡CCH₂CH₂O.

"Alkylthio" denotes methylthio, ethylthio, and the different propylthio, butylthio, pentylthio and hexylthio isomers. "Alkylsulfonyl" includes, for example, CH₃SO₂, CH₃CH₂SO₂, CH₃CH₂CH₂SO₂, (CH₃)₂CHSO₂ and the different butylsulfonyl, pentylsulfonyl and hexylsulfonyl isomers. "Alkoxy" denotes methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers. "Cycloalkyl" denotes cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

The term "halogen", either alone or in compound words such as

"haloalkyl", denotes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as "haloalkyl", the alkyl may be partially or fully substituted with halogen atoms which may be the same or different. Examples of "haloalkyl" include, but are not limited to, F₃C,

CICH₂, CF₃CH₂ and CF₃CF₂. Examples of "haloalkenyl" include, but are not limited to, (Cl)₂C=CHCH₂ CF₃CH₂CH=CHCH₂ Examples of "haloalkynyl" include, but are noτ mnited to, HC≡CCHCl, CF₃C≡C,

CCI₃C≡C and FCH₂C≡CCH₂. Examples of "haloalkoxy" include, but are not limited to, CF₃O, CCI₃CH₂O, CF₂HCH₂CH₂O and CF₃CH₂O.

Examples of "haloalkylthio" include, but are not limited to, CCI₃S, CF₃S, CCI₃CH₂S and CH₂CICH₂CH₂S. Examples of "haloalkylsulfonyl" include, but are not limited to, CF₃SO₂, CCI₃SO₂, CF₃CH₂SO₂ and CF₃CF₂SO₂. The total number of carbon atoms in a substituent group is indicated by the "C_i-C_j" prefix where i and j are numbers from 1 to 8. For example, C₁-C₃ alkylsulfonyl designates methylsulfonyl through propylsulfonyl; C₂ alkoxyalkoxy designates CH₃OCH₂O; C₃

alkoxyalkoxy designates CH₃OCH₂CH₂O or CH₃CH₂OCH₂O; and C4 alkoxyalkoxy designates the various isomers of an alkoxy group

substituted with a second alkoxy group containing a total of 4 carbon atoms, examples including CH₃CH₂CH₂OCH₂O, and

CH₃CH₂OCH₂CH₂O. Examples of "alkoxyalkyl" include, but are not limited to, CH₃OCH₂, CH₃OCH₂CH₂, CH₃CH₂OCH₂,

CH₃CH₂CH₂CH₂OCH₂ and CH₃CH₂OCH₂CH₂. Examples of

"alkoxycarbonyl" include, but are not limited to, CH₃OC(=O),

CH₃CH₂OC(=O), CH₃CH₂CH₂OC(=O), (CH₃)₂CHOC(=O) and the different butoxy-, pentoxy- or hexyloxycarbonyl isomers.

Preferred for greatest fungicidal activity and/or ease of synthesis are the compounds of Group 1 that are the compounds of Formula I wherein:

R¹ is C₁-C₄ alkyl, C₁-C₃ haloalkyl or vinyl;

R² is C₅-C₇ cycloalkyl; phenyl optionally substituted with R⁵ and R⁶; thienyl optionally substituted with R⁶; or pyridyl optionally substituted with R⁶; and

R³ is phenyl optionally substituted with R¹⁰.

More preferred are the compounds of Group 2 that are the compounds of Group 1 wherein:

R¹ is C¹-C² alkyl or vinyl;

R² is phenyl optionally substituted with R⁵ and R⁶;

R⁴ is H or methyl;

R⁵ is halogen; C₁-C₄ alkyl; trifluoromethyl; C₁-C₆ alkoxy;

C₁-C₆ haloalkoxy; phenoxy optionally substituted with

R¹⁶; benzyloxy; provided that when R⁵ is not H or F, then R⁵ is para to the point of attachment to the ring; R⁶ is 1-2 halogen selected from the group consisting of F and

Cl; methyl; or xnethoxy; and

R¹⁰ is C₁-C₂ alkyl, xnethoxy or 1-2 halogen.

Even more preferred are the compounds of Group 3 that are the compounds of Group 2 wherein:

R¹ is methyl;

R⁴ is H;

R⁵ is F; Cl; methyl; C₁-C₆ alkoxy; or phenoxy optionally

substituted with R₁₆;

R⁶ js F;

R¹⁰ is methyl or F; and

R¹⁶ is 1-2 halogen selected from the group consisting of F and Cl; C₁-C₄ alkyl, C₁-C₄ haloalkyl; C₁-C₄ alkoxy; C₁-C₄ haloalkoxy; C₂-C₄ alkoxyalkyl; C₅-C₆ cycloalkyloxy; C₂-C₄ alkenyl; or phenoxy;

Especially preferred as the compounds of Group 4 that are the compounds of Group 3 wherein:

R ^{1 1} is H;

R¹³ is C₁-C₂ alkyl; or phenyl optionally substituted with R^; provided that when Q is NH, R¹² is H; C₁-C₈ alkyl; allyl; benzyl; or phenyl optionally substituted with R⁵ and R⁶.

Even more especially preferred is the compound of Group 5 that is a compound of Group 4 wherein:

G is R¹².

Specifically Preferred for greatest fungicidal activity and/or ease of synthesis are the compounds of Formula I that are:

5-(2,4-difluorophenyl)-5-metiιyl-3-(phenylamino)-2,4- oxazolidinedione, 2-(phenylhydrazone); and 5-methyl-5-(4-phenoxyphenyl)-3-(phenylamino)-2,4- oxazolidinedione, 2-oxime.

Having briefly summarized the invention, the invention will now be described in detail by reference to the following specification and nonlimiting examples. Unless otherwise specified, all percentages are by weight and all temperatures are in degrees Celsius.

DETAILED DESCRIPTION OF THE INVENTION

Synthesis

The compounds of this invention may be prepared by the route outlined in Equation 1 below to yield 5-methyl-5-phenyl-3-(phenylamino)- 2,4-oxazohdinedione, 2-oxime.

Equation I

Details of the above procedures and related variations are described in the following Equations.

One skilled in the art will recognize that when R¹ and R² are different, compounds of Formula I in Equation 2 below possess a chiral center.

This invention therefore pertains to racemic mixtures and to pure enantiomers. Although one enantiomer may have superior fungicidal activity for a given compound of Formula I, the other enantiomer is not devoid of activity nor does the other enantiomer interfere with the activity of the more potent enantiomer.

One skilled in the art will also notice that compounds of Formula I can exist as a mixture of E- and Z-imine isomers. This invention.

therefore also pertains to mixtures of geometric isomers as well as the individual isomers.

As shown in Equation 2 below, compounds of Formula I can be prepared by treating heterocycles of Formula II with an appropriate hydrazine of Formula III (where Q=NRH), hydroxylamine (where Q=O), or primary amine (where Q=direct bond).

Equation 2

As shown in Equation 2, the thioxooxazolidinone of Formula II is dissolved in an inert solvent such as methylene chloride, tetrahydrofuran (THF), ethanol or benzene and treated with the hydrazine (Q=NR^{1 1}), hydroxylamine (Q=O) or primary amine (Q=direct bond) sometimes used in excess, at temperatures from 0°C to 80°C. Acid salts of the hydrazzne, hydroxylamine or amine such as dhnethylhydrazine hydrochloride and hydroxylamine hydrochloride also may be used, and in these cases an equivalent of additional base is necessary. Triethylamine,

diisopropylethylamine and other tertiary amine bases are preferred.

The product (I) can be isolated by evaporation of the solvent and dissolving the residue in a water-immiscible solvent such as ether. This solution then may be washed with mineral acid, water, and brine, and dried. Evaporation of the solvent followed by crystallization or

chromatography affords the purified product.

The hydrazines of Formula III (Q=NRU) are commercially available or can be prepared by one skilled in the art according to methods known in the art. See, for example, Timberlake et al., The

Chemistry of the Hvdrazo. Azo. and Azoxv Groups (S. Patai, Ed.), John Wiley and Sons, Ltd., London (1975), p. 69. Demers et al., Tetrahedron LstL, 1987, 4933 and Somei et al., Chem. Pharm. Bull.. 1978, 2£, 2522. The preparation of the hydroxylamines also can be accomplished by methods known in the art. See Castellino et al., J. Org. Chem.. 1984, 4S, 1348.

Compounds described by Formula II can be prepared as illustrated in Equation 3.

Equation 3

Treatment of the thioxodioxazinones of Formula IV with

hydrazines V in an inert solvent such as methylene chloride, benzene, or THF at temperatures ranging from -10°C to 35°C gives the

thioxoόxazolidinones of Formula II. See Geffken, Z Naturforsch. 1983, 38b. 1008.

The thioxodioxazinones of Formula IV are prepared according to the method outlined in Equation 4.

Equation 4

The hydroxamic acids of Formula VI are reacted with a thionoating agent of Formula VEI such as thiophosgene (X=C1), in the presence of a base or l,l'-t&ocarbonyldiimidazole (X=imidazole) to afford the

thioxodioxazinones of Formula IV. The reactions are performed at -20°C to 25°C in an inert solvent. See Geffken, Z. Naturforsch. 1983, 38b, 1008. The products are generally unstable at ambient temperature and therefore are reacted with the desired hydrazine of Formula V

immediately upon isolation.

The synthesis of the requisite hydroxamic acids of Formula VI can be accomplished by several known methods. As shown in Equation 5, the condensation of an α-hydroxycarboxylic acid of Formula VHI (Z=H) with N-methylhydroxylamine hydrochloride affords the desired hydroxamic acids VI. See Geffken et al., Chem Ztg.. 1979, 103, 19. Triethylamine is commonly used as an added base and 1,3-dicyclohexyl-carbodiimide (DCC) is used as the dehydrating agent. Equation 5

2-Hydroxycarboxylic acids can be purchased from commercial sources, or generally prepared from ketones or aldehydes by formation of cyanohydrins, then hydrolysis, as is known in the art. For example, Org. Syn. Coll. Vol. IV, 58 (1968) teaches the preparation of atrolactic acid from acetophenone. The ketones and aldehydes also can be easily prepared by one skilled in the art according to known methods. For example, see Johnson, Org. React. 1949, 2., 114, Johnson et al., J. Am Chem Soc. 1949, 21, 1092, and Premasagar et al., J. Org. Chem. 1981, 46.2974 for the preparation of some of the starting ketones.

Esters can be prepared from the 2-hydroxycarboxylic acids by methods known in the art. Alternatively, aryl α-hydroxycarboxylic acid esters can be prepared by treating pyruvate esters with nucleophilic organometallic reagents such as phenylmagnesium bromide or

phenyllithium as described by Salomon et al., J. Org. Chem.. 1982, 4J7, 4692. Also, the "Dictionary of Organic Compounds", Vol. 3, 4th ed.

(1965), page 1791 (Oxford Univ. Press) lists atrolactic acid and esters.

In addition to the methods discussed above, some 2-aryl-2- hydroxyesters and acids can be prepared by acylation of aromatics with an activated carbonyl compound in the presence of a protic or Lewis acid. Aromatic substrates capable of undergoing this reaction are benzene, diphenyl ether, furan and other aromatic species known by one skilled in the art to be of sufficient reactivity and stability to undergo FriedelCrafts-type reactions. In the case of mono-substituted benzene derivatives, the acylation occurs preferentially, but not necessarily exclusively, para the point of attachment of the substituent.

Carbonyl compounds known to undergo this reaction include pyruvate esters and adds, glyoxylate esters and acids, and diesters of oxomalonates. For example, Salomon et al., J. Org. Chem.. 1982, 47, 4692, describe the acylation of substituted benzenes with diethyl oxomalonate and, in a separate case, glyoxylic arid.

The acid used in the acylation reaction can either be protic in nature, for example, a mixture of acetic and sulfuric acid, or be a Lewis acid such as aluminum chloride, tin tetrachloride, titanium tetrachloride, or other Lewis acid known to effect Friedel-Crafts-type reactions. The acid can be used either catalytically or in excess. In some cases, the acid may react destructively with the carbonyl substrate and excess carbonyl compound must be used.

The acylation can be conducted neat or in a solvent known by one skilled in the art to be suitable for Friedel-Crafts reactions, for example, methylene chloride, carbon disulfide, and nitrobenzene. The reaction may be conducted between -50° to 100°C. The specific choice of acid, solvent, temperature, and reaction time will depend on the carbonyl and aromatic substrates to be reacted.

Alternative methods for producing compounds of Formula VI are known in the literature. See Geffken et al., Arch. Pharm.. 1988, 321. 311. As illustrated in Equation 6, α-hydroxyhydroxamic acids VI also can be synthesized by treating α-ketohydroxamic acids of Formula IX with an excess of a Grignard reagent. The reactions are conducted in refluxing ether for 2 to 6 hours.

Equation 6

This procedure works best in cases where R² of the hydroxamic adds of Formula IX is a non-enolizable group, for example phenyl.

The α-ketohydroxamic adds of Formula IX can be prepared as described in Equation 7 by condensing the glyoxylic add chlorides of Formula X, derived from the corresponding carboxy lie adds, with

O-trimetliylsilyl-N- meth ylhydroxylamine. See Geffken et al., Arch.

Pham , 1988, 321, 311.

Equation 7

The reactions of Equation 7 are conducted in a mixture of pyridine and methylene chloride at 0°C to 25°C. The α-ketoadds from which the add chloride of Formula X are derived can be purchased from commerrial sources or obtained by oxidation of the corresponding methyl ketone with selenium dioxide. See Hallmann et al., Annalen, 1963, 662. 147.

A third method for producing the α-hydroxyhydroxamic adds of

Formula VI is spedfic to examples in which R¹=R² in Formula Via as described in Equation 8. The method illustrated in Equation 8 involves adding an excess of Grignard reagent, typically five equivalents, to a solution of the hydroxamic adds of Formula XI in ether. See Geffken, Arch. Pharm.. 1987, 320. 382. The reactions are normally performed at reflux.

Equation 8

The starting hydroxamic adds of Formula XI as set forth in Equation 9 are prepared by treating ethyl oxalyl chloride of Formula XII with N-methymydroxylamine hydrochloride. Sodium carbonate is added as an add scavenger. See Geffken, Arch. Pharm.. 1987, 320. 382.

Equation 9

Another process for preparing the thioxooxazolidinones of Formula

II expeditiously and in good yield is also described herein. The process comprises four sequential reactions:

(1) reaction of a 2-hydroxycarboxylic add ester with a base;

(2) reaction of the product of reaction (1) with carbon

disulfide;

(3) reaction of the product of reaction (2) with an acylating agent; and (4) reaction of the product of reaction (3) with a substituted hydrazine.

This sequence of reactions can be conveniently conducted in a single reaction vessel without isolation of chemical intermediates. This process is represented in Equation 10 for the specific case of preparation of 5-meth yl-5-phenyl-3-(phenylanniιo)-2-tnioxo-4-oxazolidinone, and in Equation 11 for the general case:

Equation 10

Equation 11

Preparation of the α-hydroxyesters of Formula VIII in Equation 11 is discussed above. The ester group can be alkyl (C₁-C₁₂), alkenyl (C₃-C₄), cycloalkyl (C₃-C₁₂), cycloalkylalkyl (C₆-C₇), alkoxyalkyl (C₂-C₄) or benzyl. Preferred for ease of synthesis, lower expense or greater utihty are esters in which Z is C₁-C₄ alkyl.

In each of the reaction steps of Equations 10 and 11, the optimum combination of reaction time, reaction temperature, stoichiometry, solvents), and the like will depend on the exact product being prepared. For example: The reaction time should be sufficient to effect the desired reaction; the reaction temperature should be suffident to effect the desired reaction in the desired time without undue

decomposition or side reactions; the stoichiometry of reactants should generally be the theoretical values, in the interest of economy, with variations as needed to compensate for evaporative or other losses; and solvent(s) can be selected, for example, so that reaction ingredients have a substantial solubility in order to obtain relatively fast reaction rates. In reaction (1) above, usable bases are those capable of

deprotonation of the hydroxy group without unacceptable side reactions. Included are the alkali metal tertiary alkoxides, hydrides, and

hydroxides. Preferred among these are the potassium tertiary alkoxides such as potassium tert.-butoxide and potassium tert.-amylate. Espedally preferred is potassium tert -butoxide.

Usable solvents in reaction (1) are 2-hydroxycarboxylic add ester, or non-hydroxylic solvents such as ethers, particularly diethyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, esters, particularly methyl and ethyl acetate, amides, particularly N,N-dimethylformamide, N,N-dimethylacetemide, 1-methyl-2-pyrrolidone, nitriles, particularly acetonitrile, and the like, as well as mixtures containing one or more of these solvents. Preferred among these solvents are those in which the reactants have substantial solubility.

The temperature can vary from -80°C to +100°C, with -20°C to +80°C preferred, and with -5°C to +50°C more preferred. A range of temperatures from 0°C to ambient temperature is convenient for conducting the reaction.

The needed reaction time is short with soluble reactants. No more than a few minutes are required at ice to ambient temperatures, such as 0.5 to 15 minutes. In reaction (2) above, carbon disulfide (CS2) is contacted with the product of reaction (1) at -20°C to +100°C, preferably -10°C to +50°C, for 5 seconds to 24 hrs., preferably for 5 to 30 min. The reaction is rapid for soluble reactants. Ice temperature to ambient temperature is a

convenient range at which to conduct the reaction.

In reaction (3), an acylating agent capable of forming a mixedanhydride with the product of reaction (2) is contacted with the product of reaction (2). Such acylating agents include chloroformates, such as methyl chloroformate, ethyl chloroformate, propyl chloroformate, butyl chloroformate, and benzyl chloroformate, as well as other acylating agents. Preferred acylating agents are methyl and ethyl chloroformate. Reaction (3) is rapid, and is complete in 5 seconds to an hour with soluble reactants. Most reactions are complete in 1 to 30 minutes. The

temperature can range from -20°C to +50°C. The preferred range is from -10°C to +25°C. Ice to ambient temperature is a convenient temperature range for conducting this reaction.

In reaction (4), the substituted hydrazine reactant is contacted with the product of reaction (3). The substituted hydrazine can be used as the free base or as a mixture of its add salt with an added add scavenger such as a tertiary amine base, particularly triethylamine and N,Ndϋsopropyl-N-ethylamine. Reaction (4) is rapid, requiring no more than a few minutes for completion with soluble reactants. Reaction times may be 10 seconds to 1 day, preferably 1 minute to 8 hrs. Reaction temperatures can range from -20°C to +100°C. Ice to ambient temperature is a convenient range at which to conduct the reaction.

The product of reaction (4) can be isolated by evaporation of the reaction solvent, and it can be purified if desired by dissolving in a water-immiscible solvent, particularly carbon tetrachloride, butyl chloride, or ether, washing with water, mineral add, and base, followed by drying and evaporation of solvent, in turn followed by crystallization or

chromatography as desired. In addition to the methods illustrated in Equation 2, compounds of

Formula la wherein G is C(=O)R¹³, C(=O)OR¹³, C(=O)SR¹³,

C(=O)NR¹³R¹⁴, SO₂R¹³, or P(=W)(OR¹³)₂ can be prepared by treating compounds of Formula lb with the appropriate acylating, sulfonylating, or phosphonating agent of Formula XIII as set forth in Equation 12 below. Equation 12

In Equation 12, the leaving group X in the compound of Formula XIII may be a halogen, acetate, or another moiety used by those skilled in the art for acylating, sulfonylating, or phosphonating. Chlorine is the most commonly used leaving group X. In those cases, the compound of Formula XIII can be an add chloride, chloroformate, chlorothioformate, sulfonyl chloride, chlorophosphate or carbamoyl chloride.

The iminooxazolidinone of Formula lb is dissolved in an inert solvent such as methylene chloride, tetrahydrofuran (THF), or benzene and treated with the compound of Formula XIII and a base at a

temperature ranging from 0°C to 100ºC. Triethylamine,

diisopropylethylamine, and other tertiary amine bases are preferred.

The product of Formula la can be isolated by evaporation of the solvent and dissolving the residue in a water-immiscible solvent such as ether. This solution may be washed with a dilute aqueous mineral acid, water, and brine, and dried. Evaporation of the solvent followed by crystallization or chromatography affords the purified product. In cases where G is C(=O)NR¹³R¹⁴ and R¹⁴ is H, the

iminooxazolidinone of Formula Ic can be prepared by treating the compound of Formula lb with an isocyanate as set forth in Equation 13.

Equation 13

The iminooxazolidinone of Formula lb is dissolved.in an inert solvent such as toluene, THF, acetonitrile,or dichloroethane and treated with the isocyanate at temperatures from 0°C to 50°C. The product of Formula Ic can be isolated by evaporation of the solvent, and dissolving the residue in a water-immiscible solvent such as methylene chloride. This solution may be washed with dilute aqueous mineral add, water, brine, and dried. Evaporation of the solvent followed by crystallization or chromatography affords the product of Formula Ic.

Specific compounds that can be made by this invention are described in the Examples and Tables which follow. These are intended to be only exemplary, and are not all-inclusive.

EXAMPLE 1

Preparation of Ethyl 2-(3-fluoropyrid-4-yl)lactate

A 27 mL portion of commercially-available 2.03 M lithium

d-usopropylamide-THF/heptane solution (Lithco) was diluted with 50 mL of dry THF, cooled to -60°C under nitrogen, and stirred while adding a solution of 4.3 mL (4.8 g, 50 mmol) of 3-fluoropyridine in 10 mL of. dry THF at a rate that held the mixture below -55°C. The resulting slurry was stirred at -60°C for another 30 minutes, and then with continued cooling and stirring a solution of 6.0 mL (6.4 g, 55 mmol) of ethyl pyruvate in 30 mL of dry THF was added as quickly as possible while maintaining an internal temperature of -60°C. The resulting thin slurry was allowed to come to -10°C, then diluted with 200 mL each of water and ether. The aqueous phase was adjusted to pH 7 by addition of IN aqueous HCl, the ether phase was separated, the aqueous phase was extracted with two 100 mL portions of ether, and the combined ether phases were washed with three 100 mL portions of water and 100 mL of brine, dried over magnesium sulfate, and evaporated to leave 5.8 g of a dark brown oil. Chromatography over silica gel, eluting with methylene chloridexnethanol 99:1, provided 3.7 g (35%) of the title compound as a pale yellow solid: mp 56-60°C; IR (Nujol) 2600-3400, 1755, 1730 cm^-1; NMR (CDCl₃,

200 MHz) 1.2 (3H, t, J=7), 1.8 (3H, s), 3.9 (1H, s), 4.3 (2H, q, J=7), 7.5 (1H, d of d, J=5,7), 8.4-8.5 (2H, m)

EXAMPLE 2

Preparation of Ethyl 2-(4-phenoxyphenyl)lactate

A 250-mL flask fitted with magnetic stirring, water condenser,

125 mL dropping funnel, thermometer, and nitrogen inlet was charged with 2.7 g (110 mmol) of magnesium metal and dried with a heat gun under strong nitrogen purge. After cooling, the funnel was charged with a solution of 17.5 mL (24.9 g, 100 mmol) of 4-bromodiphenyl. ether in 67 mL of dry THF, and 10 mL was run into the flask. With stirring, the Grignard initiated spontaneously, and the rest of the bromide solution was added over l5 minutes, maintaining an internal temperature of 67-68°C. When addition was complete, the temperature held at 68°C for 5 minutes, then began to drop, reaching 30°C after 45 minutes.

Meanwhile, a 250 mL flask, magnetic stirrer, and 125 mL dropping funnel that had been oven-dried were assembled hot under nitrogen and allowed to cool. A low-temperature thermometer was then added, the flask was charged with a solution of 11.5 mL (12.2 g, 105 mmol) of ethyl pyruvate in 66 mL of dry THF, and the solution of Grignard reagent was transferred to the dropping funnel by means of a syringe. The pyruvate solution was chilled to -10°C, and the Grignard solution was run in over 15 minutes with good stirring, cooling to maintain an internal

temperature of -5 to -10°C.

The resulting solution was stirred and treated with 50 mL of water followed by 50 mL of saturated aqueous ammonium chloride, giving two clear phases. These were separated, and the upper phase was subjected to rotary evaporation to remove most of the THF. Addition of 50-mL portions of water and methylene chloride gave two clear phases. These were separated, the aqueous phase was washed with another

25 mL of methylene chloride, and the combined organic phases were washed with water and brine, dried over magnesium sulfate, and evaporated to leave 23.8 g of yellow-orange oil. Kugelrohr distillation at

140ºC/0.1-0.2 mm for 60 minutes removed volatile impurities, leaving 17.1 g (60%) of the product as a dear orange oil: np26 l.5555; IR (neat)

3490, 1725 cm^-1; NMR (CDCI₃, 200 MHz) 1.3 (3H, t, J=7), 1.8 (3H, s), 3.8

(1H, broad s), 4.2 (2H, m), 6.9-7.0 (4H, m), 7.1 (1H, t, J=7), 7.3 (2H, t, J=7), 7.5 (2H, d, J=9). EXAMPLE 3

Preparation of 5-Methyl-5-phenyl-3- (phenylanιino)-2-thioxo-4-oxazolidinone

A solution of methyl atrolactate (7.64g, 0.0424mole) in

tetrahydrofuran (80mL) was stirred and cooled in an ice bath, and potassium tert.-butoxide (4.76g, 0.0424mole) was added. The ice bath was removed, and the mixture was stirred for lOminutes. This procedure provided a clear, yellow solution at 21°C.

Carbon disulfide (2.8mL, 0.046mole) was added, and caused the formation of an orange color and a temperature rise to 32°C. The solution was cooled in an ice bath for 10 minutes, causing the temperature to fall to 4°C.

Ethyl chloroformate (4.1mL, 0.043mole) was added to the ice-cooled solution, inducing the formation of a turbid yellow mixture and a temperature rise to 12°C. The mixture was stirred with ice-bath cooling for 5 minutes as the temperature fell to 5°C.

Phenylhydrazine (97%, 4.5mL, 0.044mole) was added. The temperature rose to 24°C while the cooling bath was applied. After the temperature fell to 20°C, the mixture was stirred for 10 minutes, then evaporated under reduced pressure to an oil.

The oil was mixed with 1-chlorobutane and water, and the layers were separated. The organic layer was washed with IN HCl, water, and saturated aq. sodium bicarbonate solution. The organic solution was dried (magnesium sulfate), filtered, and evaporated under reduced pressure to an oil. The oil was crystallized from carbon

tetrachloride/hexane (-40 mL/20 mL), providing the product (7.40g, 68.6% of theory) as a light-yellow solid, m.p. 104-105°C. The product was further purified by recrystallization from carbon tetrachloride/hexane with 93% recovery.

In another preparation of the same product, carbon tetrachloride was used instead of 1-chlorobutane during the workup. Crystallization from the carbon tetrachloride solution by dilution with hexane provided the product in 54% yield. Recrystallization from isopropanol/water provided the product as a white solid, m p. 108-109°C, with 92% recovery.

EXAMPLE 4

Preparation of

5-Phenyl-3-(phenylamino)-2-thioxo-4-oxazolidinone

A stirred solution of potassium tert.-butoxide (11.22 g, 0.1 mole) in tetrahydrofuran (100 mL), held at 0°C to -5°C, was treated portionwise with a solution of methyl mandelate (16.62 g, 0.1 mole) in

tetrahydrofuran (70 mL), providing an orange-red solution. After 4 minutes carbon disulfide (6.04mL, 0.1 mole) was added. After 5 minutes at 0°C to -5°C, the orange solution was cooled to -30°C and treated with ethyl chloroformate (9.5 mL, 0.1 mole). After 2 minutes the solution was warmed to -10°C. After 5 minutes at -10°C, the solution was cooled to -30°C and treated with 97% phenylhydrazine (10.1 mL, 0.1mole). The yellow solution was warmed to 25°C, and after 10 minutes the mixture was evaporated under reduced pressure to a turbid oil. The oil was mixed with water and 1-chlorobutane, the layers were separated, and the organic solution was washed with IN HCl, water (twice), and saturated sodium bicarbonate solution. The dried (magnesium sulfate) solution was evaporated under reduced pressure to a yellow-orange oil, and the oil was dissolved in chloroform. A silica-gel filtration ofthe chloroform solution followed by evaporation ofthe filtrate under reduced pressure provided a green oil which began to solidify. Further purification was accomplished by crystallization from 1-chlorobutane. This procedure provided the product as 9.9 g (35% of theoretical) of a white solid, m.p. 140-141°C. The infrared spectrum (Nujol mull) showed the characteristic absorption at 3295cm-l (N-H) and 1760 cm^-1 (imide C=O).

EXAMPLE 5

Preparation of 5-(3-Fluoropyrid-4-yl)-5-methyl- 3-(phenylammo)-2-t-hioxo-4-oxazolidinone

A solution of 3.2 g (16 mmol) of ethyl 2-(3-fluoropyrid-4-yl)lactate in 20 mL of THF was stirred and chilled in an ice-water bath while 1.6 g (15 mmol) of solid potassium tertiary-butoxide was added in portions. The cooling bath was then removed, 1.0 mL (1.2 g, 16.6 mmol) of carbon disulfide was added, the mixture was stirred for 10 minutes, cooling was resumed, 1.4 mL (1.6 g, 16 mmol) of ethyl chloroformate was added, the mixture was stirred for 10 minutes, 1.5 mL (15 mmol) of phenylhydrazine was added, the resulting slurry was stirred and allowed to come to room temperature, another 20 mL of THF was added, and the mixture was stirred another 15 minutes at room temperature. Most ofthe solvent was then removed by rotary evaporation, the residue was partitioned between 1-chlorobutane and water, and the organic phase was separated, washed with 0.1N aqueous HCl, water, saturated aqueous sodium bicarbonate, water, and brine, dried over magnesium sulfate, and evaporated to leave 3.7 g of a green gum. Chromatography over silica gel, eluting with methylene chloride:methanol 98:2, provided 1.7 g (36%) ofthe title compound as a semi solid. Crystallization from ethyl acetate-hexanes 1:1 gave pale yellow crystals: mp 165-169°C; IR (Nujol) 3200, 3130, 1780 cm^-1; NMR (CDCI₃, 200 MHz) 2.2 (3H, s), 6.4 (1H, s), 6.8 (2H, d, J=8), 7.0 (1H, t, J=8), 7.3 (2H, t, J=8), 7.5 (1H, t, J=6), 8.6 (2H, m).

Applying a similar procedure to ethyl 2-(2-fluoropyrid-3-yl)acetate gave 5-(2-fluoropyrid-3-yl)-5-methyl-3-(phenylamino)-2-thioxo-4-oxazolidinone, mp 130-135°C.

EXAMPLE 6

Preparation of (S)-5-Methyl-5-phenyl-3-(phenylamino)-2-thioxo-4-oxazolidinone

A solution of 1.0 g (6.0 mmol) of (S)-atrolactic add in 7 mL of methanol was cooled in an ice-water bath and stirred while 0.70 mL (1.15 g, 9,6 mmol) of thionyl chloride was added dropwise. The resulting mixture was stirred at room temperature for one hour, then concentrated under reduced pressure to give 1.1 g of methyl (S)-atrolactate, n 25p

1.5096.

This material was dissolved in 10 mL of THF, and the solution was stirred and chilled in an ice-water bath while 0.68 g (6.1 mmol) of solid potassium tertiary-butoxide was added in one portion. The resulting slurry was stirred at room temperature for 40 minutes, then 0.40 mL (0.51 g, 6.7 mmol) of carbon disulfide was added, giving a solution. Ice-water cooling was resumed, and after 10 minutes 0.58 mL (0.66 g, 6.1 mmol) of ethyl chloroformate was added, giving a slurry.

After another 5 minutes 0.60 mL (0.66 g, 6.1 mmol) of

phenylhydrazine was added, the cooling bath was removed, and the mixture was allowed to come to room temperature. Most of the THF was removed under reduced pressure, the residue was partitioned between water and 1-chlorobutane, and the organic phase was washed

sequentially with IN aqueous HCl, water, saturated aqueous sodium bicarbonate, and brine, dried over magnesium sulfate, and evaporated to leave 1.4 g of an oil. Chromatography over silica gel, eluting with methylene chloride-hexanes 70:30, provided 0.89 g (50%) of the title compound as an oil that slowly solidified on standing. Crystallization from 1-chlorobutane-hexanes 6:3 gave colorless needles: mp 81-85°C; [α]_D23 +70.1 (c=0.52, EtOH); IR (Nujol) 3250, 1775 cm^-1; NMR (CDCl₃,

200 MHz) 2.05 (3H, s), 6.37 (1H, s), 6.73 (2H, d, J=8), 7.02 (1H, t, J=8), 7.24 (2H, t, J=8), 7.4-7.5 (3H, m), 7.5-7.6 (2H, m).

Applying similar procedures to (R)-atrolactic add gives (R) 5- methyl-5-phenyl-3-(phenylamino)-2-thioxo-4-oxazohdinone: mp 81-85°C; [α]_D23 -70.5 (c=0.52, EtOH).

EXAMPLE 7

Preparation of 5-(2,4-Difluorophenyl)-5-methyl-3-(phenylamino)- 2,4-oxazolidinedione, 2-phenylhydrazone

A solution of 5-(2,4-difluorophenyl)-5-methyl-3-(phenylamino)-2- thioxo-4-oxazolidinone (600 mg, 2 mmol) in 10 mL of dichloromethane was treated with phenylhydrazine (650 mg, 6 mmol) at room temperature for

24 hours. The solvent was evaporated, and the resulting oil was dissolved in ether/petroleum ether (1:1, 100 mL) and washed wth cold 6N HCl (10 mL). The organic layer was separated and washed with water

(10 mL) and dried (MgSO₄). Filtration followed by evaporation and recrystallization from ether/petroleum ether (1:1) afforded pure product; m.p. 148°C. EXAMPLE 8

Preparation of 5-Methyl-5-phenyl- 3-(phenylamino)-2,4-oxazolidinedione, 2-oxime

A solution of 5-methyl-5-phenyl-3-(phenylamino)-2-thioxo-4-oxazolidinone (1.6 g, 6.4 mmol) in dichloromethane (20 mL) was treated with triethylamine (0.8 mL, 5.6 mmol) and hydroxylamine hydrochloride

(390 mg, 5.6 mmol). The reaction mixture was stirred overnight at room temperature, then at reflux for eight hours. The reaction was then poured into IN HCl (75 mL) and extracted with dichloromethane (2 × 75 mL).

The organic layers were washed with water (75 mL) and brine (75 mL) and dried (MgSO₄). Filtration followed by evaporation afforded an oily residue. Purification by flash chromatography (1:2 ethyl acetate:hexanes) on silica gel afforded pure product as a white solid; mp. 201-203°C

(decomposes).

EXAMPLE 9

Preparation of 5-Methyl-5-phenyl-3-(phenylamino)- 2-(benzylimino)-4-oxazolidinone

To a solution of 5-metnyl-5-phenyl-3-(phenylamino)-2-thioxo-4- oxazohdinone (1.0 g, 3.36 mmole) in tetrahydrofuran (10 mL) at room temperature, benzylamine (0.36 g, 3.36 mmole) was added. The reaction mixture was stirred at room temperature overnight. More benzylamine was added (0.36 g, 3.36 mmole). The reaction mixture was further stirred at room temperature for 1 h, poured into water, and extracted with diethylether. The diethylether extracts were combined, washed with water, dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure to a solid which was

recrystallized from 1-chlorobutane to give the product: m.p. 135-136°C; NMR (CDCI₃, 200 MHz) 1.96 (3H, s), 4.67 (2H, s), 6.17 (1H, s), 6.78 (2H, d, J=8Hz), 6.98 (1H, t, J=8Hz), 7.19-7.65 (15H, m).

Tables I and II on the following pages show fungiridal compounds that can be advantageously prepared by the methods described above.

These tables are illustrative ofthe invention only, and are not intended to be inclusive.

Formulations

Useful formulations ofthe compounds of Formula I can be prepared in conventional ways. They include dusts, granules, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates and the like. Many of these may be applied directly. Sprayable formulations can be extended in suitable media and used at spray volumes of from a few liters to several hundred liters per hectare. High strength

compositions are primarily used as intermediates for further formulation. The formulations, broadly, contain about 0.1% to 99% by weight of active ingredient(s) and at least one of (a) about 0.1% to 20% Burfactant(s) and (b) about 1% to 99.9% solid or liquid inert diluent(s). More specifically, they will contain these ingredients in the following approximate

proportions:

Weight Percent*

Ingredient Diluent(s) Surfactant(s)

Wettable Powders 20-90 0-74 1-10 Oil Suspensions, 3-50 40-95 0-15

Emulsions, Solutions,

(including Emulsifiable

Concentrates) Aqueous Suspension 10-50 40-84 1-20 Dusts 1-25 70-99 0-6

Granules and Pellets 0.1-95 5-99.9 0-15

High Strength 90-99 0-10 0-2

Compositions

^*Active ingredients plus at least one of a surfactant or a diluent equals 100 weight percent. Lower or higher levels of active ingredient can, of course, be present depending on the intended use and the physical properties of the compound. Higher ratios of surfactant to active ingredient are sometimes desirable, and are achieved by incorporation into the formulation or by tank mixing.

Typical solid diluents are described in Watkins et al., "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Dorland Books,

Caldwell, NewJersey, but other solids, either mined or manufactured, may be used. The more absorptive diluents are preferred for wettable powders and the denser ones for dusts. Typical liquid diluents and solvents are described in Marsden, "Solvents Guide", 2nd Ed.,

Interβcience, New York, 1950. Solubility under 0.1% is preferred for suspension concentrates; solution concentrates are preferably stable against phase separation at 0°C. "McCutcheon's Detergents and

Emulsifiers Annual", MC Publishing Corp., Ridgewood, NewJersey, as well as Sisely and Wood, "Encyclopedia of Surface Active Agents", Chemical Publishing Co., Inc., NewYork, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foaming, caking, corrosion, microbiological growth, etc.

The methods of making such compositions are well known.

Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer or fluid energy mill. Suspensions are prepared by wet milling (see, for example, Littler, U.S. Patent 3,060,084). Granules and pellets may be made by spraying the active material upon preformed granular carriers or by agglomeration techniques. See J.E.Browning,

"Agglomeration", Chemical Engineering. December 4, 1967, pp. 147ff and "Perry's Chemical Engineer's Handbook", 5th Ed., McGraw-Hill, New York, 1973, pp. 8-59ff. For further information regarding the art of formulation, see for example:

H. M. Loux, U.S. Patent 3,235,361, February 15, 1966, CoL 6, line 16 through Col. 7, line 19 and Examples 10 through 41;

R. W. Luckenbaugh, U.S. Patent 3,309,192, Marchl4, 1967, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12, l5, 39, 41, 62, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182;

H. Gysin and E. Knusli, U.S. Patent 2,891,855, June 23, 1959, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4;

G. C. Klingman, "Weed Control as a Science", John Wiley & Sons, Inc., New York, 1961, pp. 81-96; and

J. D. Fryer and S. A. Evans, "Weed Control Handbook", 5th Ed., Blackwell Scientific Publications, Oxford, 1968, pp. 101-103.

In the following examples, all parts are by weight unless otherwise indicated.

Example A

Wettable Powder

5-(2,4-difluorophenyl)-5-methyl-3-(phenylamino)-2,4-oxazolidinedione, 2-phenylhydrazone 80%

sodium alkylnaphthalenesulfonate 2% sodium liginsulfonate 2% synthetic amorphous silica 3% kaolinite 13% The ingredients are blended, hammer-milled until all the solid are essentially under 50 microns, reblended, and packaged.

Example B

Wettable powder

5-(2,4-difluorophenyl)-5-methyl-3-(phenylamino)-2,4-oxazolidinedione, 2-phenylhydrazone 50%

sodium alkylnaphthalenesulfonate 2% low viscosity methyl cellulose 2% diatomaceous earth 46%

The ingredients are blended, coarsely hammer-milled and then airmilled to produce particles essentially all below 10 microns in diameter. The product is reblended before packaging. Example C

Granule

Wettable Powder of Example A 5% attapulgite granules 95% (U.S.S. 20-40 mesh; 0.84-0.42 mm)

A slurry of wettable powder containing 25% solids is sprayed on the surface of attapulgite granules in a double-cone blender. The granules are dried and packaged. Example D

Exfruded Pellet

5-(2,4-difluorophenyl)-5- methyl-3-(phenylamino)-2,4-oxazolidinedione, 2-phenylhydrazone 25%

anhydrous sodium sulfate 10% crude calcium liginsulfonate 5% sodium alkylnaphthalenesulfonate 1% calcium/magnesium bentonite 59 %

The ingredients are blended, hammer-milled and then moistened with about 12%. water. The mixture is extruded as cylinders about 3 mm diameter which are cut to produce pellets about 3 mm long. These may be used directly after drying, or the dried pellets may be crushed to pass a U.S.S. No. 20 sieve (0.84 mm openings). The granules held on a U.S.S. No. 40 sieve (0.42 mm openings) may be packaged for use and the fines recycled. Oil Suspension

5-(2,4-difluorophenyl)-5-methyl-3-(phenylamino)-2,4-oxazolidinedione, 2-phenylhydrazone 25% polyoxyethylene sorbitol hexaoleate 5% highly aliphatic hydrocarbon oil 70%

The ingredients are ground together in a sand mill until the solid particles have been reduced to under about 5 microns. The resulting thick suspensions may be applied directly, but preferably after being extended with oils or emulsified in water,

Example F

Wettable Powder

5-(2,4-difluorophenyl)-5-methyl-3-(phenylamino)-2,4-oxazolidinedione, 2-phenylhydrazone 20% sodium alkylnaphthalenesulfonate 4% sodium liginsulfonate 4% low viscosity methyl cellulose 3% attapulgite 69%

The ingredients are thoroughly blended. After grmding in a hammer-mill to produce particles essentially all below 100 microns, the material is reblended and sifted through a U.S.S. No. 50 sieve (0.3 mm opening) and packaged.

Example G

Low Strength Granule

5-(2,4-difluorophenyl)-5-methyl-3-(phenylamino)-2,4-oxazolidinedione, 2-phenylhydrazone 1%

N,N-dimethylformamide 9% attapulgite granule 90% (U.S.S. 20-40 sieve) The active ingredient is dissolved in the solvent and the solution is sprayed upon dedusted granules in a double cone blender. After spraying ofthe solution has been completed, the blender is allowed to run for a short period and then the granules are packaged. Example H

Aqueous Suspension

5-(2,4-difluorophenyl)-5-methyl-3-(phenylamino)-2,4-oxazolidinedione, 2-phenylhydrazone 40%

polyacrylic acid thickener 0.3% dodecylphenol polyethylene glycol ether 0.5% disodium phosphate 1% monosodium phosphate 0.5% polyvinyl alcohol 1.0% water 56.7% The ingredients are blended and ground together in a sand mill to produce particles essentially all under 5 microns in size.

Example I

Low Strength Granule

5-(2,4-difluorophenyl)-5-methyl-3-(phenylamino)-2,4-oxazoIidinedione, 2-phenylhydrazone 0.1% attapulgite granules 99.9%

(U.S.S.20-40 mesh)

The active ingredient is dissolved in a solvent and the solution is sprayed upon dedusted granules in a double cone blender. After spraying ofthe solution has been completed, the material is warmed to evaporate the solvent. The material is allowed to cool and then packaged.

Example J

Granule

5-(2,4-difluorophenyl)-5-methyl-3-(phenylamino)-2,4-oxazolidinedione, 2-phenylhydrazone 80%

wetting agent 1% crude ligninsulfonate salt 10%

(containing 6-20% ofthe natural sugars)

attapulgite clay 9%

The ingredients are blended and milled to pass through a 100 mesh screen. This material is then added to a fluid bed granulator, the air flow is adjusted to gently fluidize the material, and a fine spray of water is sprayed onto the fluidized material. The fluidization and spraying are continued until granules ofthe desired size range are made. The spraying is stopped, but fluidization is continued, optionally with heat, until the water content is reduced to the desired level, generally less than 1%. The material is then discharged, screened to the desired size range, generally 14-100 mesh (1410-149 microns), and packaged for use.

Example K

High Streqgth Concentrate

5-(2,4-difluorophenyl)-5-methyl-3-(phenylamino)-2,4-oxazolidinedione, 2-phenylhydrazone 99%

silica aerogel 0.5% synthetic amorphous silica 0.5% The ingredients are blended and ground in a hammer-mill to produce a material essentially all passing a U.S.S. No. 50 screen (0.3 mm opening). The concentrate may be formulated further if necessary.

Example L

Wettable Powder

5-(2,4-difluorophenyl)-5-methyl-3-(phenylamino)-2,4-oxazoIidinedione, 2-phenylhydrazone 90% dioctyl sodium suKosucάnate 0.1% synthetic fine silica 9.9%

The ingredients are blended and ground in a hammer-mill to produce particles essentially all below 100 microns. The material is sifted through a U.S.S. No. 50 screen and then packaged. Example M

Wettable Powder

5-(2,4-difluorophenyl)-5-methyl-3-(phenylamino)-2,4-oxazoIidinedione, 2-phenylhydrazone 40% sodium Ugninsulfonate 20% montmorillonite clay 40%

The ingredients are thoroughly blended, coarsely hammer-milled and then air-milled to produce particles essentially all below 10 microns in size. The material is reblended and then packaged. Example N

Oil Suspension

5-(2,4-difiuorophenyl)-5-methyl-3-(phenylamino)-2,4-oxazohdinedione, 2-phenylhydrazone 35% blend of polyalcohol carboxylic 6% esters and oil soluble petroleum sulfonates

xylene 59%

The ingredients are combined and ground together in a sand mill to produce particles essentially all below 5 microns. The product can be used directly, extended with oils, or emulsified in water. Example O

Emulsifiable Concentrate

5-(2,4-difluorophenyl)-5-methyl-3-(phenylamino)-2,4-oxazoIidinedione, 2-phenylhydrazone 20%

chlorobenzene 74% sorbitan monostearate and polyoxy6% ethylene condensates thereof

The ingredients are combined and stirred to produce a solution which can be emulsified in water for application. Utility

The compounds of this invention are useful as plant disease control agents. They provide control of diseases caused by a broad spectrum of fungal plant pathogens in the Basidiomvcete. Ascomvcete. and Oomycete classes. They are effective in controlling a broad spectrum of plant diseases, particularly foliar pathogens of ornamental, vegetable, field, cereal, and fruit crops. These pathogens include Venturia inaequalis.

Cercosporidium personatum, Cercospora arachidicola, Cercospora beticola. Pseudocercosporella herpotrichoides. Ervsiphe graminis.

Septoria tritici. Uncinula necatur. Podosphaera leucotricha.

Phytophthora infestans. Plasmopara viticola. Peronospora tabacina.

Pseudpperonospora cubensis, Pythi um aphanidermatu m, and other species closely related to these pathogens. They also control seed pathogens.

The compounds of this invention can be mixed with fungicides, bactericides, acaricides, nematicides, insecticides or other biologically active compounds in order to achieve desired results with a minimum of expenditure of time, effort and material. Suitable agents of this type are well-known to those skilled in the art. Some are listed below. Fungicides methyl 2-benzimidazolecarbamate (carbendazim)

tetramethylthiuram disulfide (thiuram)

n-dodecylguanidine acetate (dodine)

manganese ethylenebiβdithiocarbamate (maneb)

1,4-dichloro-2,5-dimethoxybenzene (chloroneb)

methyl 1-(butylcarbamoyl)-2-benzim idazolecarbamate (benomyl)

2-cyano-N-ethylcarbamoyl-2-rnethoxyiminoacetamide (cymoxanil) N-trichloromethylthiotetrahydrophthalamide (captan)

N-trichloromethylthiophthalimide (folpet)

dimethyl 4,4'-(o-phenylene)-bis-(3-thioallophanate) (thiophanate-methyl) 2-(thiazol-4-yl)benzimidazole (thiabendazole)

aluminum tris(O-ethylphosphonate)(phosethyl aluminum)

tetrachloroisophthalonitrile (chlorothalonil)

2,6-dichloro-4-nitroaniline (dichloran)

N-(2,6-dimethylphenyl)-N-(methoxyacetyl)alanine methyl ester

(metalaxyl)

ds-N-[1,1,2,2-tetracMoroethyl)thio]cyclohex-4-ene-1,2-dicarbioximide

(captafol)

3-(3,5-dic hlorophenyl)-N-(1-methylethyl)-2,4-dioxo-1-imidazolidine carboxamide (iprodione)

3-(3,5-dichlorophenyl)-5-ethenyl-5-methyl-2,4-oxazoIidinedione

(vinclozolin)

kasugamycin

O-ethyl-S,S-diphenylphosphorodithioate (edifenphos)

4-(3-(4-(1,1-dimethylethyl)phenyl)-2-methyl)propyl-2,6-dimethylmorpholine (fenpropimorph)

4-(3-4(1,1-dimethylethyl)phenyl)-2-methyl)yplropylpiperidine

(fenpropidine)

1-(4-chlorophenoxy)-3,3-dimethyl-1-1H-1,2,4-triazol-1-yl)butanone

(triadimefon) 2-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-ylmethyl)hexanenitrile

(myclobutanil)

1-[2-(4-chlorophenyl)ethyl]-1-(1,1-dimethylethyl)-1-(1H-1,2,4-triazole1-yl)ethanol (tebuconazol)

3-chloro-4-[4-methyl-2-(1H-1,2,4-triazol)-1-ylmethyl)-1,3-dioxolan2-yl]phenyl-4-chlorophenyl ether (difenaconazole)

1-[2-(2,4-dichlorophenyl)pentyl]1H-1,2,4-triazole (penconazole)

2,4'-difluoro-1-(1H-1,2,4-triazole-1-ylmethyl)benzhydryl alcohol

(flutriafol)

1-[[[bis(4-fluorophenyl)3methylsilyl]methyl]-1H-1,2,4-triazole (flusilazole) N-propyl-N-[2-(2,4,6-trichlorophenoxy)ethyl]imidazole-1-carboxamide (prochloraz)

1-[2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2-ylmethyl]-1H- 1,2,4-triazole (propiconazole)

1-(2-chlorophenyl-1-(4-duorophenyl)-1-(5-pyrinndmyl)methanol

(fenarimol)

1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazole-1-yl)butan-2-ol (triadimenol)

1-(2,4-dichlorophenyl)-4,4-dimethyl-2-(1H-1,2,4-triazol-1-yl)pentan-3-ol (diclobutrazol)

copper oxychloride

methyl N-(2,6-dimethylphenyl)-N-(2-furanylcarbonyl)-DL-alaninate (furalaxyl)

4-[3-(4-chlorophenyl)-3-(3,4-dimethoxvphenyl)-1-oxo-2-propenyl]- morpholine

propyl [3-(dimethylamino)propyl]carbamate monohydrochloride

(propamocarb hydrochloride)

quazatine acetates

9-aza-1,17-diquanidinoheptadecane triacetate (iminoctadine) Bactericides tribasic copper sulfate

streptomycin sulfate

oxytetracycline

Acaricides senecioic acid, ester with 2-sec-butyl-4,6-dinitro-phenol (binapacryl) 6-methyl-1,3-dithiolo[2,3-B]quinonolin-2-one (oxythio-quinox)

2,2,2-trichloro-1,1-bis(4-chlorophenyl)ethanol (dicofol)

bis(pentachloro-2,4-cyclopentadien-1-yl)(dienochlor)

tricyclohexyltin hydroxide (cyhexatin)

hexakis(2-methyl-2-phenylpropyl)distannoxane (fenbutin oxide) Nematicides

2-[dietboxyphosphinylimino]-1,3-diethietane (fosthietan)

S-methyl-1-(dimethylcarbamoyl)-N-(methylcarbamoyloxy)- thioformimidate (oxamyl)

S-methyl-1-carbam oyl-N-(methylcarbamoyloxy)thioformimidate

N-isopropylphosphoramidic acid, O-ethyl-O'-[4-(methyl-thio)- m-tolyl]diester (fenamiphos)

Insecticides

3-hydroxy-N-methylcrotonamide(dimethylphosphate)ester

(monocrotophos)

methylcarbamic acid, ester with 2,3-dihydro-2,2-dimethyl-7-benzofuranol

(carbofuran)

O-[2,4,5-trichloro-a-(chloromethyl)benzyl]phosphoric acid, O',O'-dimethyl ester (tetrachlorvinphos) 2-mercaptosuccinic acid, diethyl ester, S-ester with thionophosphoric acid, dimethyl ester (malathion)

phosphorothioic acid, O,O-dimethyl, O-p-nitrophenyl ester (methyl parathion)

methylcarbamic acid, ester with a-naphthol (carbaryl)

methyl N-[[(methylammo)carbonyl]oxy]ethanimidothioate (methomyl) N-(4-chloro-o-tolyl)-N,N-dimethylformamidine (chlordimeform)

O,O-diethyl-O-(2-isopropyl-4-methyl -6-pyri midyl)phosphorothioate (diazinon)

octachlorocamphene (toxaphene)

O-ethyl O-p-nitrophenyl phenylphosphonothioate (EPN)

cyano(3-phenoxyphenyl)-methyl 4-chloro-α-(1-methyl-ethyl)benzeneacetate (fenvalerate)

(3-phenoxyphenyl)methyl 3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarboxylate (permethrin)

dimethyl N,N'-[thiobis(N-methylimmo)carbonyloxy]]-bis[ethanimidothioate] (thiodicarb)

phosphorothiolothionic acid, O-ethyl-O-[4-(methylthio)phenyl]-S-n-propyl ester (sulprofos)

α-cyano-3-phenoxybenzyl 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate (cypermethrin)

cyano(3-phenoxyphenyl)methyl 4-(difluoromethoxy)-α-(methylethyl)- benzeneacetate (fiucythrinate)

O,O-diethyl-O-(3,5,6-trichloro-2-pyridyl)phosphorothioate (chlorpyrifos)

O,O-dLimetiιyl-S-[(4-oxo-1,2,3-benzotτiazin-3-(4H)-yl)-methyl]phosphorodithioate (azinphos-methyl)

5,6-dimethyl-2-dimethylammo-4-pyrimidinyl dimethyl carbamate

(pirimicarb)

S-(N-fonnyl-N-methylcarbamoylmethyl)-O,O-dimethyl phosphorodithioate (formothion)

S-2-(ethylthioethyl)-O,O-dimethyl phosphiorothioate(demeton-S-methyl) (S)-α-cyano-3-phenoxybenzyl (1R,3R)-3-(2,2-dibromo vinyl)-2,2-dimethylcyclopropanecarboxylate (deltamethtrin)

cyano(3-phenoxyphenyl)methyl ester of N-(2-chloro-4-txifluoromethylphenyl)alanine (fluvalinate) In some instances, combinations with other fungicides having a similar spectrum of disease control but a different mode of action will be particularly advantageous for resistance management and/or improved properties such as curative activity for established infections. A

particularly effective combination in both regards is one involving a compound of Formula I and cymoxanil.

APPLICATION

Disease control is ordinarily accomplished by applying an effective amount ofthe compound either pre-infection or post-infection to the portion of the plant to be protected such as the roots, stems, foliage, fruit, seeds, tubers or bulbs, or to the media (soil or sand) in which the plants to be protected are growing. The compound may also be applied to the seed, to protect the seed and seedling.

Rates of application for these compounds can be influenced by many factors ofthe environment and should be determined under actual use conditions. Foliage can normally be protected when treated at a rate of from less than 1 g/ha to 10,000 g/ha of active ingredient. Plants growing in soil treated at a concentration from 0.1 to about 20 kg/ha can be protected from disease. Seed and seedlings can normally be protected when seed is treated at a rate of from 0.1 to 10 g per kilogram of seed.

The following tests show the fungicidal utility of compounds of Formula I. They are illustrative only, and are not intended to be allinclusive. Test A

The test compounds were dissolved in acetone in an amount equal to 3 % ofthe final volume and then suspended at a concentration of 200 ppm in purified water containing 260 ppm ofthe surfactant Trem 014 (polyhydric alcohol esters). This suspension was sprayed to the point of run-off on apple seedlings. The following day the seedlings were inoculated with a spore suspension of Venturia inaequalis (the causal agent of apple scab), incubated in a saturated atmosphere at 20°C for 24 hr, and then moved to a growth chamber at 22°C for 11 days, after which disease ratings were made.

Test B

The test compounds were dissolved in acetone in an amount equal to 3 % ofthe final volume and then suspended at a concentration of 200 ppm in purified water containing 260 ppm ofthe surfactant Trem 014 (polyhydric alcohol esters). This suspension was sprayed to the point of run-off on peanut seedlings. The following day the seedlings were inoculated with a spore suspension of Cercosrtoridium perspnatum (the causal agent of peanut late leafspot), incubated in a saturated

atmosphere at 22°C for 24 hr, followed by a high humidity atmosphere at 22°C to 30°C for 5 days, and then moved to a growth chamber at 29°C for 6 days, after which disease ratings were made.

Test C

The test compounds were dissolved in acetone in an amount equal to 3 % ofthe final volume and then suspended at a concentration of 200 ppm in purified water containing 260 ppm ofthe surfactant Trem 014 (polyhydric alcohol esters). This suspension was sprayed to the point of run-off on wheat seedlings. The following day the seedlings were inoculated with a spore dust of Ervsiphe graminis f. sp. tritici. (the causal agent of wheat powdery mildew) and incubated in a growth chamber at 20ºC for 7 days, after which disease ratings were made. Test D

The test compounds were dissolved in acetone in an amount equal to 3 % ofthe final volume and then suspended at a concentration of 200 ppm in purified water containing 250 ppm ofthe surfactant Trem 014 (polyhydric alcohol esters). This suspension was sprayed to the point of run-off on tomato seedlings. The following day the seedlings were inoculated with a spore suspension of Phvtophthora infestan s (the causal agent of potato and tomato late blight), incubated in a saturated atmosphere at 20°C for 24 hr, and then moved to a growth chamber at 20°C for 5 days, after which disease ratings were made.

Test E

The test compounds were dissolved in acetone in an. amount equal to 3 % ofthe final volume and then suspended at a concentration of 200 ppm in purified water containing 250 ppm of the surfactant Trem 014 (polyhydric alcohol esters). This suspension was sprayed to the point of run-off on grape seedlings. The following day the seedlings were inoculated with a spore suspension of Plasmopara viticola (the causal agent of grape downy mildew), incubated in a saturated atmosphere at 20°C for 24 hr, moved to a growth chamber at 20°C for 6 days,and then incubated in a saturated atmosphere at 20°C for 24 hr, after which disease ratings were made.

Results for certain compounds of Formula I in tests conducted according to Tests A to E are given in Table IV. In the table, a rating of 100 indicates 100% disease control and a rating of 0 indicates no disease control (relative to untreated control plants sprayed with carrier solution alone). NT indicates that no test was performed under conditions described in the Test.

)

TABLE IV

CMPD. TEST TEST TEST TEST TEST NO. A B C D E

1 67 0 0 0 7

2 46 21 0 94 99*

3 8 0 0 98 75*

4 57 0 0 100 99*

5 8 33 0 93 100*

6 0 0 0 0 59

7 28 0 0 25 100

8 0 0 0 0 39*

9 53 0 0 0 100

10 53 33 0 0 100

11 67 58 0 0 95*

12 0 0 0 0 41*

13 0 22 0 0 33*

14 26 0 0 0 100*

15 0 0 0 0 14**

16 0 22 0 0 21***

17 0 22 0 0 100*

18 0 22 0 0 81*

19 0 0 0 0 68*

20 53 0 0 0 47

21 67 22 0 0 0*

23 26 22 0 0 10*

24 53 33 0 98 97*

25 0 22 0 0 100*

26 0 22 0 0 13*

* = Data at 40 ppm, the highest rate tested.

** = Data at 20 ppm.

*** = Data at 10 ppm. CMPD. TEST TEST TEST TEST TEST

NO. A B C D E 27 0 0 0 0 62*

28 0 22 0 0 10*

29 0 0 0 0 79

30 28 33 0 0 69

31 0 100 0 99 NT

32 0 100 0 99 NT

33 44 100 0 76 NT

34 44 100 0 99 NT

35 44 86 0 97 NT

36 64 100 0 76 NT

37 0 100 0 99 NT

38 0 59 32 100 100*

39 64 71 0 99 NT

40 79 43 0 86 NT

41 64 71 0 86 NT

42 28 49 38 45 100*

43 17 27 0 25 98

44 18 71 0 23 NT

45 26 0 0 43 100*

46 26 78 0 92 100

47 NT NT 31 80 78*

48 NT NT 0 87 79*

49 NT NT NT 0 14*

50 NT NT NT 0 21*

51 NT NT 0 99 93*

52 NT NT NT 88 75* CMPD. TEST TEST TEST TEST TEST NO. A B C D E

53 NT NT 69 96 95*

54 NT NT NT 100 67*

55 NT NT NT 8 45

56 NT NT NT 63 52*

57 NT NT 0 6 84*

58 NT NT NT 0 NT

59 NT NT 0 71 57*

60 NT NT 0 17 83*

61 NT NT NT 95 100*

62 NT NT 0 100 100*

63 NT NT NT 15 69*

64 NT NT NT 0 14*

65 99 0 0 0 84*

Claims

CLAIMS What is claimed is: 1. Compounds of Formula I

wherein:

Q is O, HR¹¹ or a direct bond;

G is R¹², C(=O)R¹³, C(=O)OR¹³, C(=O)SR¹³,

C(=O)NR¹³R¹⁴, SO₂R¹³ or P( =WXOR¹⁵)2;

W is O or S;

R¹ is H; C₁-C₄ alkyl; C₁-C₄ haloalkyl; C₃-C₆ cycloalkyl;

C₂-C₄ alkenyl; hydroxycarbonyl; C₂-C₇ alkoxycarbonyl; or benzyl optionally substituted on the phenyl ring with R⁶ and on the benzylic carbon with R⁷;

R² is C₁-C₆ alkyl; C₅-C₇ cycloalkyl; phenyl optionally

substituted with R⁵ and R⁶; 2-naphthyl; thienyl optionally substituted with R⁵ and R⁶; furyl optionally substituted with R⁶; or pyridyl optionally substituted with one substituent selected from the group consisting of R⁶, phenoxy optionally substituted with R¹⁶ and phenylthio optionally substituted with R⁶; further

R¹ and R² can be taken together to form structures selected from the group consisting of -CH₂(CH₂)₂CH₂-, -CH₂(CH₂)₃CH₂-, -CH₂(CH₂)₄CH₂-,

-CH₂CH₂OCH₂CH₂-, -CH₂CH₂SCH₂CH₂-,

-CH₂CH₂N(R⁷)CH₂CH₂-,

R³ is phenyl optionally substituted with R¹⁰; benzyl; pyridyl optionally substituted with R¹⁰; pyrimidinyl optionally substituted with R¹⁰; or pyridazyl optionally substituted with R¹⁰; provided that when By is pyridyl optionally substituted with R¹⁰, pyrimidinyl optionally substituted with R¹⁰ or pyridazyl optionally substituted with R¹⁰, these moieties are connected through a carbon atom;

R⁴ is H, methyl or acetyl;

R⁵ is halogen; C₁-C₆ alkyl; C₁-C₆ haloalkyl; C₁-C₆ alkoxy;

C₃-C₆ alkenyl; C₃-C₆ haloalkenyl; C₃-C₆ alkenyloxy; C₃-C₆ alkynyl; C₃-C₆ haloalkynyl; C₁-C₆ alkylthio;

C₁-C₆ haloalkylthio; C₁-C₆ haloalkoxy; C₁-C₆

alkylsulfonyl; C₁-C₆ haloalkylsulfonyl; nitro; phenyl optionally substituted with Bβ; phenoxy optionally substituted with R¹⁶; phenylthio optionally substituted with R⁶; cyano; C₃-C₆ alkynyloxy; C₂-C₆ alkoxyalkyl; C₂-C₆ alkoxyalkoxy; phenoxymethyl optionally

substituted on the phenyl ring with R⁶; benzyloxy optionally substituted on the phenyl ring with R⁶;

phenethyl optionally substituted on the phenyl ring with R⁶; benzyl optionally substituted on the phenyl ring with R⁶; C₂-C₆ alkoxycarbonyl; C₅-C₆ cycloalkyl; C₅-C₆ cycloalkyloxy; or NHR⁸;

R⁶ is 1-2 halogen; C₁-C₄ alkyl; C₁-C₄ alkoxy;

trifluoromethyl; methylthio; or nitro;

R⁷ is H, C₁-C₄ alkyl;

R⁸ is C₁-C₄ alkyl; C₂-C₆ alkoxycarbonyl; (R⁹R¹⁴ N)C=O; phenyl optionally substituted with R¹⁰; or

phenoxycarbonyl optionally substituted with R¹⁷;

R⁶ is C₁-C₆ alkyl; or phenyl optionally substituted with R¹⁸;

R¹⁰ ig 1-2 substituents selected from the group consisting of trifluoromethyl, trifluoromethoxy, nitro, CO₂CH₃, halogen, C₁-C₄ alkyl, C₁-C₄ alkoxy and cyano; provided that when the phenyl ring is disubstituted, one of the alkyl or alkoxy groups is no larger than C₁;

R¹¹ is H, C₁-C₄ alkyl, C₃-C₆ alkenyl or C₃-C₆ alkynyl;

R^l2 is H; C₁-C₈ alkyl optionally substituted with

hydroxycarbonyl, C₂-C₈ alkoxyalkyl, or C₂-C₇

alkoxycarbonyl; C₃-C₆ cycloalkyl; C₃-C₈ alkenyl; C₃-C₈ alkynyl; benzyl optionally substituted on the phenyl ring with R⁶ and on the benzylic carbon with R⁷;

benzyloxycarbonyl optionally substituted on the phenyl ring with R⁶ and on the benzylic carbon with R⁷; phenyl optionally substituted with R⁵ and R⁶; or pyridyl, connected through a carbon atom, optionally substituted with R⁶; or

R¹¹ and R¹² can be taken together along with the nitrogen to which they are attached to form pyrrole, pyrazoline,

1,3,4-triazole, or 1,2,4-triazole rings, or structures selected from the group consisting of -CH₂(CH₂)₂CH₂-,

-CH₂(CH₂)₃CH₂-, -CH₂(CH₂)₄CH₂-,

-CH₂CH₂OCH₂CH₂-, -CH₂CH₂SCH₂CH₂-,

-CH₂CH₂N(R⁷)CH₂CH2- or

-CH₂CH₂N(R⁷)CH₂CH₂CH₂-;

R¹³ is C₁-C₆ alkyl; C₃-C₆ cycloalkyl; C₁-C₄ haloalkyl; phenyl optionally substituted with R⁵ and R⁶; or benzyl optionally substituted on the phenyl ring with R⁶ and on the benzyhc carbon with R⁷;

R¹⁴ is H or C₁-C₄ alkyl;

R¹⁵ is C₁-C₄ alkyl; and

R¹⁶ is 1-2 halogen; nitro; cyano; C₁-C₆ alkyl; C₁-C₆ haloalkyl;

C₁-C₆ alkoxy; C₁-C₆ haloalkoxy; C₁-C₄ alkylsulfonyl;

C₂-C₆ alkoxyalkyl; C₁-C₄ alkylthio; C₅-C₆ cycloalkyl;

C₅-C₆ cycloalkyloxy; C₂-C₆ alkenyl; C₂-C₆ haloalkenyl; C₂-C₆ alkynyl; hydroxycarbonyl; C₂-C₄ alkoxycarbonyl; phenoxy optionally substituted with R⁶;

R¹⁷ and R¹³ are independently 1-2 halogen; C₁-C₂ alkyl;

trifluoromethyl; or C₁-C₂ alkoxy. 2. Compounds of Claim 1 wherein:

R¹ is C₁-C₄ alkyl, C₁-C₃ haloalkyl or vinyl;

R² is C₅-C₇ cycloalkyl; phenyl optionally substituted with R⁵ and R⁶; thienyl optionally substituted with R⁶; or pyridyl optionally substituted with R⁶; and

R³ is phenyl optionally substituted with R¹⁰. 3. Compounds of Claim 2 wherein:

R¹ is C₁-C₂ alkyl or vinyl;

R² is phenyl optionally substituted with R⁵ and R⁶;

R⁴ is H or methyl

R⁵ is halogen; C₁-C₄ alkyl; trifluoromethyl; C₁-C₆ alkoxy;

C₃-C₆ haloalkoxy; phenoxy optionally substituted with

R¹⁶; benzyloxy; provided that when R⁵ is not H or F, then R⁵ is para to the point of attachment to the ring; R⁶ is 1-2 halogen selected from the group consisting of F and Cl; methyl; or methoxy; and

R¹⁰ is C₁-C₂ alkyl, methoxy or 1-2 halogen.

4. Compounds of Claim 3 wherein:

R¹ is methyl;

R⁴ is H;

R⁵ is F; Cl; methyl; C₃-C₆ alkoxy; or phenoxy optionally substituted with R¹⁶;

R⁶ is F;

R¹⁰ is methyl or F; and

R¹⁶ is 1-2 halogen selected from the group consisting of F and Cl; C₁-C₄ alkyl, C₁-C₄ haloalkyl; C₁-C₄ alkoxy;

C₁-C₄ haloalkoxy; C₂-C₄ alkoxyalkyl; C₃-C₆

cycloalkyloxy; C₂-C₄ alkenyl; or phenoxy.

5. Compounds of Claim 4 wherein:

R¹¹ is H; R¹² is C₁-C₂ alkyl; or phenyl optionally substituted with R⁵; provided that when Q is NH, R¹² is H; C₁-C₆ alkyl; allyl; benzyl; or phenyl optionally substituted with R⁵ and R⁶.

6. Compounds of Claim 5 wherein:

G is R¹².

Compounds of Claim 1 selected from the group 5-(2,4-difluorophenyl)-5-methyl-3-(phenylamino)-2,4- oxazolidinedione, 2-(phenylhydrazone); and

5-methyl-5-(4-phenoxyphenyl)-3-(phenylaminb)-2,4- oxazolidinedione, 2-oxime.

8. An agriculturally suitable composition comprising a fungicidally effective amount of a compound of any one of Claims 1 to 7 and at least one ofthe following: surfactant, solid diluent or liquid diluent.

9. A method for controlling fungus disease in plants which comprises applying to the locus to be protected an effective amount of a compound of any one of Claims 1 to 7.