Abstract:
A method of controlling plant disease using thioxooxazolidinones, oxazolidinediones and related heterocycles, and agriculturally suitable compositions containing them.

Description:
BACKGROUND OF THE INVENTION 
     This invention pertains to a novel method-of-use of compounds of Structure I as fungicides for protecting plants from disease. 
     Processes for the preparation of the compounds described in this invention are disclosed in the following references: 
     Geffken, D.; Z. Naturforsch, 1983, 38b, 1008 
     Geffken, D.; Zinner, G.; Chem. Ber., 1973, 106, 2246 
     Geffken, D.; Arch. Pharm., 1982, 315. 802; 
     Geffken, D. Z. Naturforsch, 1987, 42b, 1202 
     Hanefield, W.; Jalili, M. A., Arch. Pharm., 1987, 320, 367 
     No particular utility for the compounds is described in the above references. 
     A new process for the preparation of these compounds is also disclosed in this application, and disclosed and claimed in copending application No. BA-8800. 
     Compounds related to I are broadly disclosed as medicines, agrochemicals and microbicides in Japanese Patent No. 61/200978-A, and as general biocides in EP No. 249328-A. However, these applications do not encompass compounds of the instant invention, nor do they suggest the use of the compounds of this invention as fungicides particularly effective for the protection of crops against disease. 
     SUMMARY OF THE INVENTION 
     This invention comprises the method of use of compounds of Formula I and their agriculturally suitable compositions as broad-spectrum crop protection chemicals, ##STR1## wherein; A is O or NR 4 , 
     Q is O or S, 
     W is O or S, 
     R 1  is H, C 1  to C 6  alkyl, C 1  to C 6  haloalkyl, C 3  to C 6  cycloalkyl, C 2  to C 6  alkenyl, C 2  to C 6  alkynyl, C 2  to C 6  alkoxyaIkyl, C 1  to C 3  phenyl or benzyl, wherein said phenyl or benzyl ring is substituted on the ring with R6, and the benzylic carbon is substituted with R7; 
     R 2  is phenyl substituted with R 5  and R 6 , naphthyl substituted with, 1 to 2 groups selected from R 6 , thienyl substituted with R 5  and R 6 , furyl substituted with R 6 , pyridyl substituted with one of the following: 
     R 6 , phenoxy substituted with R 6 , or phenylthio substituted with R 6  ; 
     C 1  to C 2  alkyl substituted with phenoxy or phenylthio, said phenoxy or phenylthio being substituted on the ring with R 6 , 
     C 1  to C 6  alkyl; or 
     R 1  and R 2  can be taken together, along with the carbon to which they are attached, to form a carbocyclic or heterocyclic ring (containing O, N--R 7 , or S) of 5 to 7 ring atoms. The heterocyclic ring can be fused with an R 5  -substituted benzene ring or an R 6  -substituted thiophene ring, the heteroatom not being attached to the spiro center, the carbocyclic ring can be fused with 1 or 2 R 5  -substituted benzene rings or with an R 6  -substituted thiophene ring; 
     R 3  is phenyl substituted with R 5  and R 6 , benzyl substituted on the benzylic carbon with a group selected from R 7  and substituted on the phenyl ring with R 6 , naphthyl substituted with R 6 , thienyl substituted with R 6 , furyl substituted with R 6 , pyridyl substituted with R 6 , pyrazyl 
     substituted with R 6 , pyrimidyl 
     substituted with R 6 , pyridazyl 
     substituted with R 6 , C 2  to C 10  alkyl, C 5   
     to C 7  cycloalkyl; 
     R 4  is hydrogen, formyl, C 2  to C 4  alkylcarbonyl, C 2  to C 4  haloalkylcarbonyl, C 2  to C 4  alkoxyalkylcarbonyl, C 2  to C 4  alkoxy carbonyl, C 2  to C 5  alkylaminocarbonyl, C 1  to C 4  alkylsulfonyl, C 1  to C 6  alkyl, C 4  to C 6  cycloalkyl, benzyl substituted with R 6  on the phenyl ring and substituted with R 7  on the benzylic carbon, phenylaminocarbonyl where said phenyl is substituted with R 6 , C 3  to C 4  alkenyl, C 3  to C 4  alkynyl; or 
     R 3  and R 4  can be taken together, along with the nitrogen atom to which they are attached, to form a pyrrolidino, piperidino or hexamethylenimino ring, which rings can be fused to an R 6  -substituted benzene ring; R 5  is hydrogen, halogen, C 1  to C 6  alkyl, C 1  to C 6  haloalkyl, C 1  to C 6  alkoxy, C 3  to C 4  alkenyloxy, C 1  to C 5  alkylthio, C 1  to C 4  haloalkylthio, C 1  to C 4  haloalkoxy, C 1  to C 4  alkylsulfonyl, C 1  to C 4  haloalkylsulfonyl, nitro, phenyl substituted with R 6 , phenoxy substituted with R 6 , phenylthio substituted with R 6 , cyano, C 3  to C 4  alkynyloxy, C 2  to C 6  alkoxyalkyl, C 2  to C 6  alkoxyalkyoxy, phenoxymethyl substituted On the phenyl ring with R 6 , benzyloxy substituted on the phenyl ring with R 6 , phenethyloxy substituted on the phenyl ring with R 6 , phenethyl substituted on the phenyl ring with R 6  or benzyl substituted on the phenyl ring with R 6 , phenoxy substituted with R 6 , C 2  to C 6  carboalkoxy, C 5  to C 6  cycloalkyl; 
     R 6  is hydrogen, 1 to 2 halogen, methyl, trifluoromethyl, C 1  to C 4  alkoxy, methylthio, nitro; 
     R 7  is hydrogen, C 1  to C 4  alkyl; provided that, (1) when A is oxygen, R 3  is phenyl substituted with R 5  and R 6 , 
     and (2) when R 1  is H, Q is not sulfur. 
     Preferred for reasons of their greater fungicidal activity and/or more favorable ease of synthesis are: 
     (1) Compounds of Formula I where A is NR 4   
     (2) Compounds of Preferred 1 where W is sulfur. 
     (3) Compounds of Preferred 2 where Q is oxygen. 
     (4) Compounds of Preferred 3 where: 
     R 1  is C 1  to C 4  alkyl, C 1  to C 4  haloalkyl, C 3  to C 4  cycloalkyl, C 2  to C 4  alkenyl, C 2  to C 4  alkynyl, C 2  to C 4  alkoxyalkyl; 
     R 2  is phenyl substituted with R 5  and R 6 , substituted with R 6 , thienyl substituted with R 5  and R 6 , furyl substituted with R 6 , pyridyl substituted with R 6;  or 
     R 1  and R 2  can be taken together, along with the carbon to which they are attached, to form a carbocyclic ring of 5 to 6 ring atoms. The carbocyclic ring can be fused with an R 5  -substituted benzene ring or with an R 6  -substituted thiophene ring; and 
     R 3  is phenyl substituted with R 5  and R 6 , thienyl substituted with R 6 , furyl substituted with R 6 , pyridyl substituted with R 6 . 
     (5) Compounds of Preferred 4 where: 
     R 1  is C 1  to C 4  alkyl, trifluoromethyl, C 2  to C 3  alkenyl, C 2  to C 3  alkynyl; 
     R 2  is phenyl substituted with R 5  and R 6 , thienyl substituted with R 5  and R 6  ; 
     R 3  is phenyl substituted with R 5  and R 6  ; 
     R 4  is hydrogen, C 1  to C 4  alkyl; 
     R 5  is hydrogen, halogen, C 1  to C 4  alkyl, C 1  to C 4  haloalkyl, C 1  to C 4  alkoxy, C 1  to C 4  alkylthio, C 1  to C 4  alkylsulfonyl, nitro, phenyl substituted with R 6 , phenoxy substituted with R 6  ; 
     R 6  is hydrogen, 1 to 2 halogen, methyl, trifluoromethyl, methoxy; and 
     R 7  is hydrogen. 
     (6) Compounds of Preferred 5 where: 
     R 5  is hydrogen, halogen, methyl, trifluoromethyl, methoxy, phenoxy substituted with hydrogen or 1 to 2 of the following: halogen, methyl, methoxy or trifluoromethyl, nitro; 
     R 6  is hydrogen, halogen, methyl, methoxy, or trifluoromethyl. 
     Specifically preferred for greatest fungicidal activity and/or ease of synthesis are: 
     (1) 5-methyl-5-phenyl-3-(phenylamino)-2-thioxo-4-oxazolidinone; ##STR2## 
     (2) 5-(4-fluorophenyl)-5-methyl-3-(phenylamino)-2-thioxo-4-oxazolidinone; ##STR3## 
     (3) 5-methyl-5-(4-phenoxyphenyl)-3-(phenylamino)-2-thioxo-4-oxazolidinone. ##STR4## 
     DETAILED DESCRIPTION OF THE INVENTION 
     Synthesis 
     The compounds of this invention may be prepared by the route outlined below to 5-methyl-5-phenyl-3-(phenylamino)-2-thioxo-4-oxazolidinone: ##STR5## 
     Additionally, a patent application, BA-8800, describing a novel, expeditious synthesis of these compounds is copending. 
     The compounds of Formula I can be prepared according to one or more of the methods described in Equations 1, 2, 9, 10, 11 and 14. 
     As shown in Equation 1, compounds of Formula I can be prepared by treating heterocycles of type II with an appropriate amine III. 
     Equation 1 ##STR6## 
     The reactions are conducted at 0° C. to 50° C. in an inert solvent such as methylene chloride, THF, or benzene. Detailed experimental procedures are disclosed in the references cited below. 
     Compounds described by Formula I wherein Q is O and W is S can be prepared by two methods. The first method is illustrated in Equation 2. 
     Equation 2 ##STR7## 
     Treatment of thioxodioxazinones IIa with hydroxylamines (A=O) or hydrazines (A=NR 4 ) in an inert solvent such as methylene chloride, benzene, or THF at temperatures ranging from -10° C. to 35° C. gives the thioxooxazolidinones Ia. [Geffken, D.; Z. Naturforsch, 1983, 38b, 1008] 
     The thioxodioxazinones IIa are prepared according to the method outlined in Equation 3. 
     Equation 3 ##STR8## 
     The hydroxamic acids IV are reacted with a thionoating agent V, such as thiophosgene (X=Cl) in the presence of a base or 1,1&#39;-thiocarbonyldiimidazole (X=imidazole), to afford the thioxodioxazinones IIa. The reactions are performed at -20° C. to 25° C. in an inert solvent. [Geffken, D., Z. Naturforsch, 1983, 38b, 1008] The products are generally unstable at ambient temperature and therefore are reacted with the desired amine III immediately upon isolation. 
     Preparation of the hydroxylamines [Castellino, A. J.; Rapoport, H.; J. Org. Chem., 1984, 49, 1348] (III, A=O) and hydrazines [J. Timberlake; J. Stowell; The Chemistry of the Hydrazo, Azo, and Azoxy Groups  (S. Patai, Ed.) John Wiley and Sons, Ltd., London (1975), p. 69; Demers, J. P.; Klaubert, D. J.; Tetrahedron Lett.. 1987, 4933] (III, A=NR 4 ) can be accomplished by literature methods by one skilled in the art. 
     The synthesis of the requisite hydroxamic acids IV can be accomplished by several known methods. As shown in Equation 4, the condensation of an α-hydroxycarboxylic acid VI (Z=H) with N-methylhydroxylamine hydrochloride affords the desired hydroxamic acids IV. [Geffken, D.; Kampf, H.; J. Chem. Ztg., 1979, 103, 19] Triethylamine is commonly used as an added base and 1,3-dicyclohexylcarbodiimide (DCC) is used as the dehydrating agent. 
     Equation 4 ##STR9## 
     Many α-hydroxyacids VI are available from commercial sources. Others can be obtained by hydrolysis of the cyanohydrin derived from the corresponding ketone or aldehyde. 
     Alternative methods for producing the same types of compounds are known in the literature. As illustrated in Equation 5, α-hydroxyhydroxamic acids IV can also be synthesized by treating α-ketohydroxamic acids VII with an excess of a Grignard reagent. [Geffken, D.; Burchardt, A.; Arch. Pharm., 1988, 321, 311] The reactions are conducted in refluxing ether for 2 to 6 hours. 
     Equation 5 ##STR10## 
     This procedure works best in cases where R 2  of the hydroxamic acids VII is a non-enolizable group, for example phenyl. 
     The α-ketohydroxamic acids VII can be prepared by condensing the glyoxylic acid chlorides VIII, derived from the corresponding carboxylic acids, [Geffken, D.; Burchardt, A.; Arch. Pharm., 1988, 321, 311] with O-trimethylsilyl-N-methylhydroxylamine [Geffken, D.; Burchardt, A.; Arch. Pharm., 1988, 321, 311] (Equation 6). 
     Equation 6 ##STR11## 
     These reactions are conducted in a mixture of pyridine and methylene chloride at 0° C. to 25° C. 
     The starting α-ketoacids VIII are either purchased from commercial sources or obtained by oxidation of the corresponding methyl ketone with selenium dioxide. [Hallmann, G.; Haegele, K.; Annalen, 1963, 662, 147] 
     A third method for producing α-hydroxyhydroxamic acids IV is specific to examples in which R 1  =R 2  (IVa). This method, illustrated in Equation 7, involves adding an excess of Grignard reagent, typically five equivalents, to a solution of the hydroxamic acids IX in ether. [Geffken, D., Arch. Pharm, 1987, 320, 382] The reactions are normally performed at reflux. 
     Equation 7 ##STR12## 
     The starting hydroxamic acids IX are prepared by treating ethyl oxalyl chloride X with N-methylhydroxylamine hydrochloride. Sodium carbonate is added as an acid scavenger (Equation 8). [Geffken, D., Arch. Pharm., 1987, 321, 382] 
     Equation 8 ##STR13## 
     A second and more expeditious route to compounds of Formula I in which Q is O, W is S, and A is NR 4  (Ib) is shown in Equation 9. This method involves sequential treatment of α-hydroxyesters VI (e.g. Z=methyl) with a base (e.g. potassium t-butoxide), carbon disulfide, an acylating agent (e.g. ethyl chloroformate), and finally a hydrazine. These reactions can be performed in inert solvents, for example THF, or neat at temperatures ranging from about 0° C. to 50° C. The intermediates need not be isolated and therefore the reaction can be conducted in one flask. A detailed discussion of this process is disclosed in copending application No. BA-8800. 
     Equation 9 ##STR14## 
     The preparation of α-hydroxycarboxylic acids VI (Z=H) used to prepare the corresponding esters VI (e.g. Z=alkyl) is discussed above. 
     Compounds of general Formula I wherein Q, W, and A are all O (Ic) are prepared by the methods shown in Equation 10. 
     Equation 10 ##STR15## 
     The addition of a carbonylating agent, e.g. phosgene (X=Cl), 1,1&#39;-thiocarbonyldiimidazole (X=imidazole), or oxalyl chloride, to hydroxamic acids of type XI produces dioxotetrahydrooxazoles Ic. The cyclizations can be conducted in an inert solvent, for example benzene or methylene chloride, at temperatures ranging from 0° C. to 80° C. Experimental details for reactions of this type have been reported as have the preparation of the starting hydroxamic acids XI. [Geffken, D.; Zinner, G.; Chem. Ber., 1973, 106, 2246] 
     Compounds of Formula I in which Q and W are O and A is NR 4  (Id) are synthesized by treating hydroxamic acids IIb with various hydrazines, as illustrated in Equation 11. Depending on the nature of the substituents on IIb and the reacting hydrazine, the intermediate N-aminocarbamates XII may or may not be isolated. For cases in which ring closure is not spontaneous under the reaction conditions, treatment of XII with triethylamine in an inert solvent (such as THF) at temperatures ranging from 25° C. to 80° C. induces cyclization to Id. [Geffken, D.; Arch. Pharm.. 1982, 315, 802; Geffken, D. Synthesis. 1981, 38] 
     Equation 11 ##STR16## 
     The dioxazinediones IIb are readily prepared from the corresponding α-hydroxyhydroxamic acid by treatment with 1,1&#39;-carbonyldiimidazole (Equation 12). The cyclization is performed in an inert solvent such as methylene chloride and is complete in less than one minute at 25° C. [Geffken, D.; Arch. Pharm.. 1982, 315, 802; Geffken, D., Synthesis, 1981, 38] 
     Equation 12 ##STR17## 
     The preparation of compounds of Formula I where A and W are O and Q is S (Ie) follows directly from the teachings of Geffken, D. Z. Naturforsch. 1987, 42b, 1202. As shown in Equation 13, reaction of 2-mercaptoamides XIII with ureas of type XIV afford the thiazolidinediones Ie. 
     Equation 13 ##STR18## 
     The starting acyl imidzoles XIII are readily synthesized by condensation of the corresponding carboxylic acids of 1,1&#39;-carbonyldiimidazole. [Geffken, D. Z. Naturforsch, 1987, 42b, 1202] Mercaptocarboxylic acids have been prepared by several methods [Biilmann, E., Ann. Chem., 1906, 348, 120; Bonner, W. A., J. Org. Chem., 1968, 33, 1831] The preparaton of the ureas of Formula XIV as also disclosed in Geffken, D. Z. Naturforsch, 1987, 42b, 1202. 
     Compounds of Formula I wherein Q is S and A is NR 4  (If) are synthesized by the method shown in Equation 14. 
     Equation 14 ##STR19## 
     Treatment of carboxylic acids XV with 1,3-dicyclohexylcarbodiimide in an inert solvent (e.g. toluene) at 25° C. to 80° C. affords the thiazolidinediones (W=O) [Hanefield, W.; Jalili, M. A., Arch. Pharm., 1987, 320, 367] and thioxothiazolidinones (W™S) If. 
     The preparation of the precyclization substrates XV for the case in which W is O is discussed in the same article disclosing the cyclization. [Hanefield, W.; Jalili, M. A., Arch. Pharm., 1987, 320, 367] The same procedure can also be applied to the preparation of the thioxothiazolidinones (W=S). As illustrated in Equation 15, the carboxylic acids Xv are obtained by treating α-bromocarboxylate salts XVI with XVII in water in the presence of a base, for example sodium carbonate. [Hanefield, W.; Jalili, M. A., Arch. Pharm., 1987, 320, 367] 
     Equation 15 ##STR20## 
     In the case of the thiazolidinediones (If, W=O), the preparation of the carbazoylthiolates XVII from carbonyl sulfide, triethylamine, and various hydrazines is discussed in the literature. [Hanefield, W.; Jalili, M. A., Arch. Pharm., 1987, 320, 367] The thioxothiazolidinones (If, W=S) can be prepared from the carbazoylthiolates XVIII (W=S) which are prepared in the same manner except carbon disulfide is used rather than carbonyl sulfide. 
     Tables I and II on the following pages show fungicidal compounds that can be advantageously prepared by the methods described above. 
     COMPOUND TABLES 
     
                                           TABLE 1__________________________________________________________________________ ##STR21##EX #    Q W R.sup.1       R.sup.2     R.sup.3        R.sup.4  mp__________________________________________________________________________                                                     (°C.)1   S S Me            Ph          Ph             H2   S O Me            Ph          Ph             H3   O S Me            Ph          Ph             H        1094   O O Me            Ph          Ph             H5   O S H             Ph          Ph             H        1426   O S Et            Ph          Ph             H         967   O S  -n-Hexyl     Ph          Ph             H8   O S CF.sub.3      Ph          Ph             H9   O S CF.sub.3 CH.sub.2 CH.sub.2 CH.sub.2                 Ph          Ph             H10  O S cyclopropyl   Ph          Ph             H         9811  O S cyclohexyl    Ph          Ph             H12  O S vinyl         Ph          Ph             H        10713  O S allyl         Ph          Ph             H        11314  O S acetylenyl    Ph          Ph             H15  O S propargyl     Ph          Ph             H16  O S methoxymethyl Ph          Ph             H17  O S cyclopropylmethyl                 Ph          Ph             H18  O S benzyl        Ph          Ph             H        11619  O S 4&#39;-methoxybenzyl                 Ph          Ph             H20  O S 4&#39;-nitrobenzyl                 Ph          Ph             H21  O S 4&#39;-trifluoromethylbenzyl                 Ph          Ph             H22  O S 4&#39;-methylbenzyl                 Ph          Ph             H23  O S 2&#39;,4&#39;-dichlorobenzyl                 Ph          Ph             H24  O S 4&#39;-fluorobenzyl                 Ph          Ph             H25  O S Ph            Ph          Ph             H26  O O Ph            Ph          Ph             H27  O S 3-methoxyphenyl                 3-methoxyphenyl                             Ph             H         9628  O O 3-methoxyphenyl                 3-methoxyphenyl                             Ph             H         9529  O S 4-chlorophenyl                 4-chlorophenyl                             Ph             H        15630  O O 4-chlorophenyl                 4-chlorophenyl                             Ph             H        18031  O S 4-fluorophenyl                 4-fluorophenyl                             phenyl         H        15232  O O 4-fluorophenyl                 4-fluorophenyl                             phenyl         H        11333  O S 3-chlorophenyl                 3-chlorophenyl                             3-chlorophenyl H34  O O 3-chlorophenyl                 3-chlorophenyl                             3-chlorophenyl H        13635  O S 3-chlorophenyl                 3-chlorophenyl                             4-methoxyphenyl                                            H         9936  O O 3-chlorophenyl                 3-chlorophenyl                             4-methoxyphenyl                                            H        10937  O S H             Me          Ph             H        11738  O S H              .sub.-t-Bu Ph             H         9839  O S H              .sub. -i-Pr                             Ph             H        10740  O S H             cyclohexyl  Ph             H         9041  O S H             benzyl      Ph             H        14142  O S Me            Me          Ph             H        13243  O S Me            benzyl      Ph             H         9944  O S Me            phenoxymethyl                             Ph             H         7745  O S Me             -n-Hexyl   Ph             H46  O S Me            4-chlorophenyl                             Ph             H        15647  O O Me            4-chlorophenyl                             Ph             H        11648  S S Me            4-chlorophenyl                             Ph             H49  S O Me            4-chlorophenyl                             Ph             H50  O S Me            4-chlorophenyl                             Ph             H51  O S Me            2-chlorophenyl                             Ph             H52  O S Me            4-fluorophenyl                             Ph             H        15053  O O Me            4-fluorophenyl                             Ph             H        10254  S S Me            4-fluorophenyl                             Ph             H55  S O Me            4-fluorophenyl                             Ph             H56  O S Me            3-fluorophenyl                             Ph             H        10857  O S Me            4-bromophenyl                             Ph             H58  O S Me            3,5-dichlorophenyl                             Ph             H59  O S Me            3,4-dichlorophenyl                             Ph             H        14360  O S Me            2,4-difluorophenyl                             Ph             H61  O S Me            2-methylphenyl                             Ph             H62  O S Me            2,5-dimethylphenyl                             Ph             H63  O S Me            4- .sub.-t-butylphenyl                             Ph             H64  O S Me            4-cyclohexylphenyl                             Ph             H        16065  O S Me            3-trifluoromethylphenyl                             Ph             H66  O S Me            3-nonafluorobutyl-                             Ph             H                 phenyl67  O S Me            4-methoxyphenyl                             Ph             H        15668  O O Me            4-methoxyphenyl                             Ph             H        10469  O S Me            4- -n-pentyloxyphenyl                             Ph             H70  O S Me            4-allyloxyphenyl                             Ph             H71  O S Me            3-methylthiophenyl                             Ph             H72  O S Me            4-trifluoro-                             Ph             H                 methylthiophenyl73  O S Me            4-trifluoro-                             Ph             H                 methoxyphenyl74  O S Me            4-cyanophenyl                             Ph             H75  O S Me            4-phenoxyphenyl                             Ph             H        11576  O O Me            4-phenoxyphenyl                             Ph             H77  S S Me            4-phenoxyphenyl                             Ph             H78  S O Me            4-phenoxyphenyl                             Ph             H79  O S Me            3-phenoxyphenyl                             Ph             H80  O O Me            3-phenoxyphenyl                             Ph             H81  S S Me            3-phenoxyphenyl                             Ph             H82  S O Me            3-phenoxyphenyl                             Ph             H83  O S H             3-(3,5-dichloro-                             Ph             H        130                 phenoxy)phenyl84  O S H             3-(3-trifluoro-                             Ph             H                 methylphenoxy)phenyl85  O S H             3-phenoxyphenyl                             Ph             H        13686  O S Me            4-(4-trifluoro-                             Ph             H                 methylphenoxy)phenyl87  O S Me            4-(4-methoxy-                             Ph             H                 phenoxy)phenyl88  O S Me            4-(2,4-dichloro-                             Ph             H                 phenoxy)phenyl89  O S Me            4-methanesul-                             Ph             H                 fonylphenyl90  O S Me            4-nitrophenyl                             Ph             H        17091  O O Me            4-nitrophenyl                             Ph             H        11692  O S Me            3-trifluoro-                             Ph             H        134                 methylphenyl93  O S Me            4-phenylthiophenyl                             Ph             H94  O S Me            4-phenylphenyl                             Ph             H        17295  O S Me            2-naphthyl  Ph             H        15296  O S Me            1-naphthyl  Ph             H97  O S Me            2-thienyl   Ph             H98  O O Me            2-thienyl   Ph             H99  S S Me            2-thienyl   Ph             H100 S O Me            2-thienyl   Ph             H101 O S Me            5-chloro-2-thienyl                             Ph             H102 O S Me            5-methyl-2-thienyl                             Ph             H103 O S Me            3-methoxy-2-thienyl                             Ph             H104 O S Me            3-thienyl   Ph             H        121105 O O Me            3-thienyl   Ph             H106 S S Me            3-thienyl   Ph             H107 S O Me            3-thienyl   Ph             H108 O S Me            2,5-dichloro-3-thienyl                             Ph             H109 O S Me            2,5-dimethyl-3-thienyl                             Ph             H110 O S Me            2-phenoxy-3-thienyl                             Ph             H111 O S Me            2-nitro-4-thienyl                             Ph             H112 O S Me            3-methoxy-4-thienyl                             Ph             H113 O S Me            2-furyl     Ph             H114 O S Me            3-furyl     Ph             H115 O S Me            2-pyridyl   Ph             H116 O S Me            3-pyridyl   Ph             H117 O S Me            4-pyridyl   Ph             H118 O S CH.sub.2 (CH.sub.2).sub.3 CH.sub.2                             Ph             H        oil119 O S CH.sub.2 (CH.sub.2).sub.3 CH.sub.2                             3,5-dichlorophenyl                                            H        184120 O S CH.sub.2 CH.sub.2 NMeCH.sub.2 CH.sub.2                             Ph             H121 O S CH.sub.2 CH.sub.2 SCH.sub.2 CH.sub.2                             Ph             H122##STR22##                    Ph             H        168123##STR23##                    Ph             H124##STR24##                    Ph             H125 O S Me            4-carbomethoxyphenyl                             Ph             H126 O S Me            4-benzylphenyl                             Ph             H127##STR25##                    Ph             H        189128 O S Me            Ph          3,5-di-chlorophenyl                                            H        142129 O S cyclopropyl   Ph          3,5-di-chlorophenyl                                            H        133130 O S Me            phenoxymethyl                             3,5-dichlorophenyl                                            H        146131 O S Me            Ph          2,6-dichlorophenyl                                            H        157132 O S Me            4-phenoxyphenyl                             2,6-dichlorophenyl                                            H        118133 O S Me            phenoxymethyl                             2,6-dichlorophenyl                                            H        122134 O S H              .sub.-t-Bu 2,6-dichlorophenyl                                            H         87135 O S Me            Ph          4-fluorophenyl H         72136 O O Me            Ph          4-fluorophenyl H137 S S Me            Ph          4-fluorophenyl H138 O S Me            4-fluorophenyl                             4-fluorophenyl H         91139 O S Me            4-cyclohexylphenyl                             4-fluorophenyl H        155140 O S Me            phenylthiomethyl                             4-fluorophenyl H141 O S Me            phenylthiomethyl                             4-fluorophenyl H         68142 O S Me            Ph          3-fluorophenyl H143 O S Me            Ph          4-chlorophenyl H144 O S Me            Ph          3-chlorophenyl H        132145 O O Me            Ph          3-chlorophenyl H         59146 O O Me            4-methoxyphenyl                             3-chlorophenyl H        152147 O S Me            Ph          2-fluorophenyl H148 O S Me            Ph          2,5-difluorophenyl                                            H        oil149 O S Me            Ph          4-methylphenyl H        142150 O S Me            4-fluorophenyl                             4-methylphenyl H151 O S Me            4-phenoxyphenyl                             4-methylphenyl H        146152 O O Me            4-phenoxyphenyl                             4-methylphenyl H153 O S Me            phenylthiomethyl                             4-methylphenyl H         89154 O S Me            phenoxymethyl                             4-methylphenyl H        155155 O S Me            Ph          2,6-dimethylphenyl                                            H        101156 O S Me            Ph          4- .sub.-t-butylphenyl                                            H        125157 O S Me            Ph          3-methylphenyl H158 O S Me            Ph          2-methylphenyl H159 O S Me            Ph          4-methoxyphenyl                                            H        135160 O O Me            Ph          4-methoxyphenyl                                            H        134161 O S Me            Ph          4- -n-pentyloxyphenyl                                            H        oil162 O S Me            Ph          4-allyloxyphenyl                                            H163 O S Me            Ph          4-trifluoromethylphenyl                                            H164 O S Me            Ph          3-trifluoromethylphenyl                                            H165 O S Me            Ph          4-methylthiophenyl                                            H166 O S Me            Ph          4-methanesulfonylphenyl                                            H167 O S Me            Ph          4-nitro        H168 O S Me            Ph          4-cyano        H169 O S Me            Ph          4-carbomethoxy H170 O S Me            Ph          benzyl         H171 O S Me            Ph          2-thienyl      H172 O S Me            Ph          3-furyl        H173 O S Me            Ph          2-pyridyl      H        147174 O S Me            Ph          5-trifluoromethyl-2-pyridyl                                            H        150175 O S Me            Ph          2-pyrimidyl    H        187176 O S Me            Ph          6-chloro-3-pyridazyl                                            H        184177 O S Me            Ph          ethyl          H178 O S Me            Ph          cyclohexyl     H179 O S Me            Ph           .sub.-t-Bu    H         48180 O S Me            Ph           -n-decyl      H181 O S Me            Ph          Ph             formyl182 O S Me            Ph          Ph             acetyl    96183 O S Me            Ph          Ph             trifluoro-                                                      62                                            acetyl184 O S Me            Ph          Ph             methoxyacetyl                                                     oil185 O S Me            Ph          Ph             methoxycarbonyl186 O S Me            Ph          Ph             methylamino-                                            carbonyl187 O S Me            Ph          Ph             methanesulfonyl188 O S Me            Ph          Ph             methyl189 O S Me            3-thienyl   Ph             methyl190 O S 4-flurorphenyl                 Ph          Ph             methyl191 O S 4-phenoxyphenyl                 Ph          Ph             methyl192 O S Me            Ph          Ph             methyl193 O O Me            Ph          Ph             methyl194 S S Me            Ph          Ph             methyl195 S O Me            Ph          Ph             methyl196 O S Me            Ph          Ph             phenylamino-                                            carbonyl197 O S Me            Ph          Ph             allyl198 O S Me            Ph          Ph             propargyl199 O S Me            Ph          Ph             cyclobutyl200 O S me            Ph          Ph             benzyl201 O S Me            Ph          CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2                             CH.sub.2 CH.sub.2        83202 O S Me            Ph                              ##STR26##__________________________________________________________________________ 
    
     
                                           TABLE 2__________________________________________________________________________ ##STR27##EX #    Q W R.sup.1 R.sup.2     R.sup.5  R.sup.6                                     mp (°C.)__________________________________________________________________________202 O S Me      Ph          H        H203 O O Me      Ph          H        H204 S S Me      Ph          H        H205 S O Me      Ph          H        H206 O S H       Ph          H        H207 O S trifluoromethyl           Ph          H        H208 O S Me      3-thienyl   H        H209 O S Me      4-fluorophenyl                       H        H210 O S Me      4-phenoxyphenyl                       H        H211 O S Me      3-trifluoromethylphenyl                       H        H212 O S Me      Ph          4-fluoro H213 O S Me      Ph          3-trifluoromethyl                                H214 O S Me      Ph          4-phenoxy                                H215 O S Me      Ph          2-chloro 4-chloro216 O S Me      Ph          2-Me     6-Me__________________________________________________________________________ 
    
     Formulation 
     The compounds of this invention will generally be used in formulation with a liquid or solid diluent or with an organic solvent. Useful formulations of the compounds of Formula I can be prepared in conventional ways. They include dusts, granules, pellets, solutions, 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 about one to several hundred liters per hectare. High strength compositions are primarily used as intermediates for further formulation. The formulations, broadly, contain about 1% to 99% by weight of active ingredient(s) and at least one of (a) about 0.1% to 35% surfactant(s) and (b) about 5% to 99% solid or liquid inert diluent(s). More specifically, they will contain these ingredients in the following approximate proportions: 
     
         ______________________________________       Active  Percent by Weight       Ingredient               Diluent(s)                         Surfactant(s)______________________________________Wettable Powders         20-90      0-74     1-10Oil Suspensions,          5-50     40-95     0-35Emulsions, Solutions,(including EmulsifiableConcentrates)Aqueous Suspensions         10-50     40-84     1-20Dusts          1-25     70-99     0-5Granules and Pellets          1-95      5-99     0-15High Strength 90-99      0-10     0-2Compositions______________________________________ 
    
     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.. &#34;Handbook of Insecticide Dust Diluents and Carriers&#34;, 2nd Ed., Dorland Books, Caldwell, N.J. The more absorptive diluents are preferred for the wettable powders and the denser ones for dusts. Typical liquid diluents and solvents are described in Marsden, &#34;Solvents Guide,&#34; 2nd Ed., Interscience, New York, 1950. Solubility under 0.1% is preferred for suspension concentrates; solution concentrates are preferably stable against phase separation at 0° C. &#34;McCutcheon&#39;s Detergents and Emulsifiers Annual&#34;, MC Publishing Corp., Ridgewood, N.J., as well as Sisely and Wood, &#34;Encyclopedia of Surface Active Agents&#34;, Chemical Publ. Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foam, caking, corrosion, microbiological growth, etc. Preferably, ingredients should be approved by the U.S. Environmental Protection Agency for the use intended. 
     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. Pat. No. 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, &#34;Agglomeration&#34;, Chemical Engineering, Dec. 4, 1967, pp. 147ff. and &#34;Perry&#39;s Chemical Engineer&#39;s Handbook&#34;, 4th Edn., McGraw-Hill, N.Y., 1963, pp. 8-59ff. 
     For further information regarding the art of formulation, see for example: 
     H. M. Loux, U.S. Pat. No. 3,235,361, Feb. 15, 1966, Col. 6, Line 16 through Col. 7, Line 19 and Examples 10 through 41. 
     R. W. Luckenbaugh, U.S. Pat. No. 3,309,192, Mar. 14, 1967, Col. 5, Line 43 through Col. 7, Line 2 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167, 169-182. 
     H. Gysin and E. Knusli, U.S. Pat. No. 2,891,855, June 23, 1959, Col. 3, Line 66 through Col. 5, Line 17 and Examples 1-4. 
     G. C. Klingman, &#34;Weed Control as a Science&#34;, John Wiley and Sons, Inc., New York, 1961, pp. 81-96. 
     J. D. Fryer and S. A. Evans, &#34;Weed Control Handbook&#34;, 5th Edn. Blackwell Scientific Publications, Oxford, 1968, pp. 101-103. 
     Examples of useful formulations of compounds of the present invention are as follows. 
    
    
     EXAMPLES 
     EXAMPLE 217 
     Wettable Powder 
     
         ______________________________________5-methyl-5-phenyl-3-(phenylamino)-2-                  80%thioxo-4-oxazolidinoneSodium Alkylnaphthalenesulfonate                  4%Sodium Ligninsulfonate 2%Synthetic Amorphous Silica                  1%Kaolinite              13%______________________________________ 
    
     The ingredients are blended, hammermilled, re-blended and packaged. 
     EXAMPLE 218 
     High Strength Concentrate 
     
         ______________________________________5-methyl-5-phenyl-3-(phenylamino)-2-                  98.5%thioxo-4-oxazolidinoneSilica Aerogel         0.5%Synthetic Amorphous Silica                  1.0%______________________________________ 
    
     The ingredients are blended and ground in a hammermill to produce a high strength concentrate essentially all passing a U.S.S. No. 50 Sieve (0.3 mm openings). This material may then be formulated in a variety of ways. 
     EXAMPLE 219 
     Solution 
     
         ______________________________________5-methyl-5-phenyl-3-(phenylamino)-2-                  25%thioxo-4-oxazolidinoneN-methyl-2-pyrrolidone 75%______________________________________ 
    
     The ingredients are combined and stirred to produce a solution, which can be used for low volume applications. 
     EXAMPLE 220 
     Emulsifiable Concentrate 
     
         ______________________________________5-methyl-5-phenyl-3-(phenylamino)-2-                  15%thioxo-4-oxazolidinoneBlend of calcium sulfonates and                  6%non-ionic surfactantsAcetophenone           79%______________________________________ 
    
     The ingredients are combined and stirred until the active is dissolved. A fine screen filter is included in packaging operation to insure the absence of any extraneous undissolved material in the product. 
     Utility 
     The compounds of this invention are useful as plant disease control agents. They provide control of diseases caused by a broad spectrum of plant pathogens in the basidiomycete, and ascomycete classes and particularly against fungi in the oomycete class. They are effective in controlling a broad spectrum of plant diseases, particularly foliar pathogens of ornamental, vegetable, field, cereal and fruit crops, such as Plasmopara viticola, Phytophthora infestans, Peronospora tabacina, Pseudperonospora cubensis, Phytophthora megasperma, Botrytis cinerea, Venturia inaequalis, Puccinia recondita, Pythium aphanidermatum, Alternaria brassicola, Septoria nodorum, Cercosporidium personatum and species related to these 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 ethylenebisdithiocarbamate (maneb) 
     1,4-dichloro-2,5-dimethoxybenzene (chloroneb)methyl 1-(butylcarbamoyl)-2-benzimidazolecarbamate (benomyl) 
     2-cyano-N-ethylcarbamoyl-2-methoxyiminoacetamide (cymoxanil) 
     N-trichloromethylthiotetrahydrophthalamide (captan) 
     N-trichloromethylthiophthalimide (folpet) 
     dimethyl 4,4&#39;-(o-phenylene)bis(3-thioallophanate) (thiophanate-methyl) 
     2-(thiazol-4-yl)benzimidazole (thiabendazole) 
     aluminum tri(O-ethyl phosphonate)(phosethyl aluminum) 
     tetrachloroisophthalonitrile (chlorothalonil) 
     2,6-dichloro-4-nitroaniline (dichloran) 
     N-(2,6-dimethylphenyl)-N-(methoxyacetyl)alanine methyl ester (metalaxyl) 
     cis-N-[1,1,2,2-tetrachloroethyl)thio]cyclohex-4-ene1,2-dicarbioximide (captafol) 
     3-(3,5-dichlorophenyl)-N-(1-methylethyl)-2,4-dioxo-1imidazolidine carboxamide (iprodione) 
     3-(3,5-dichlorophenyl)-5-ethenyl-5-methyl-2,4-oxazolidinedione (vinclozolin) 
     kasugamycin 
     O-ethyl-S,S-diphenylphosphorodithioate (edifenphos) 
     4-(3-(4-(1,1-dimethyl-ethyl)phenyl)-2-methyl)propyl-2,6-dimethylmorpholine (Fenpropimorph) 
     4-(3-4(1,1-dimethyl-ethyl)phenyl)-2methyl)propylpiperidine (Fenpropidine) 
     Bayleton® 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H1,2,4- triazol-1-yl)butane 
     Systhane® 2-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1ylmethyl)hexanenitrile Folicur.RTM. (tebuconazol) 
     Score® 3-chloro-4-[4-methyl-2-(1H-1,2,4-triazol)-1- ylmethyl)-1,3-dioxolan-2-yl]phenyl-4-chlorophenyl ether 
     Topaz® 1-[2-(2,4-dichlorophenyl)pentyl]1H-1,2,4triazole 
     Impact® (±)-α-(2-fluorophenyl-α-(4-fluorophenyl)-1H1,2,4-triazole-1-ethanol 
     Nustar® 1-[[bis(4-fluorophenyl)methylsilyl]methyl]-1H-1,2,4-triazole 
     Sportak® 1-N-propyl-N-[2(2,4,6-trichlorophenoxy)ethyl]carbamoylimidazole 
     Tilt® 1-[[2-(2,4-dichlorophenyl)-4-propyl-1,3-di-oxolan-2-yl]methyl]-1H-1,2,4-triazole 
     Rubigan® α-(2-chlorophenyl-α-(4-chlorophenyl)-5pyridinemethanol 
     copper oxychloride furalaxyl methyl N-(2,6-dimethylphenyl)-N-(2-furanylcarbonyl)-DL-alaninate 
     Anvil® (hexaconazole) 
     Bactericides 
     tribasic copper sulfate 
     streptomycin sulfate 
     oxytetracycline 
     Acaricides 
     senecioic acid, ester with 2-sec-butyl-4,6-dinitrophenol (binapacryl) 
     6-methyl-1,3-dithiolo[2,3-B]quinonolin-2-one (oxythioquinox) 
     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-[diethoxyphosphinylimino]-1,3-diethietane (fosthietan) 
     S-methyl-1-(dimethylcarbamoyl)-N-(methylcarbamoyloxy)thioformimidate (oxamyl) 
     S-methyl-1-carbamoyl-N-(methylcarbamoyloxy)thioformimidate 
     N-isopropylphosphoramidic acid, O-ethyl-O&#39;-[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-α-(chloromethyl)benzyl]phosphoric acid, O&#39;,O&#39;-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 α-naphthol (carbaryl) methyl N-[[(methylamino)carbonyl]oxy]ethanimidothioate (methomyl) 
     N -(4-chloro-o-tolyl)-N,N-dimethylformamidine (chlorodimeform) 
     O,O-diethyl-O-(2-isopropyl-4-methyl-6-pyrimidyl)phosphorothioate (diazinon) 
     octachlorocamphene (toxaphene) 
     O-ethyl O-P-nitrophenyl phenylphosphonothioate (EPN) 
     cyano(3-phenoxyphenyl)-methyl 4-chloro-α-(1-methylethyl)benzeneacetate (fenvalerate) 
     (3-phenoxyphenyl)methyl (±)-cis,trans-3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarboxylate (permethrin) 
     dimethyl N,N&#39;-[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 (flucythrinate) 
     O,O-diethyl-O-(3,5,6-trichloro-2-pyridyl)phosphorothioate (chlorpyrifos) 
     O,O-dimethyl-S-[(4-oxo-1,2,3-benzotriazin-3-(4H)-yl)methyl]phosphorodithioate (azinphos-methyl) 
     5,6-dimethyl-2-dimethylamino-4-pyrimidinyl dimethyl carbamate (pirimicarb) 
     S-(N-formyl-N-methylcarbamoylmethyl)-O,O-dimethyl phosphorodithioate (formothion) 
     S-2-(ethylthioethyl)-O,O-dimethyl phosphiorothioate (demeton-S-methyl) 
     α-cyano-3-phenoxybenzyl cis-3(2,2-dibromovinyl)-2,2-dimethylcyclopropane carboxylate (deltamethrin) 
     cyano(3-phenoxyphenyl)methyl ester of N-(2-chloro-4-trifluoromethylphenyl)alanine (fluvalinate) 
     Application 
     Disease control is ordinarily accomplished by applying an effective amount of the compound either pre- or post-infection to the portion of the plant to be protected such as the roots, stems, foliage, fruit, seeds, tubers or bulbs. The compound may also be applied to the seed from which the plants to be protected are to be grown. 
     Rates of application for these compounds can be influenced by many factors of the environment and should be determined under actual use conditions. Foliage can normally be protected when treated at a rate of from less than 1 g/ha to 10,000 g/ha of active ingredient. Seed and seedlings can normally be protected when seed is treated at a rate of from 1 to 10 grams per kilogram of seed. 
     EXAMPLE A 
     The test compounds were dissolved in acetone in an amount equal to 3% of the final volume and then suspended at a concentration of 200 ppm in purified water containing 250 ppm of the surfactant Trem 014 (polyhydric alcohol esters). 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) and 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. 
     EXAMPLE B 
     The test compounds were dissolved in acetone in an amount equal to 3% of the final volume and then suspended at a concentration of 200 ppm in purified water containing 250 ppm of the surfactant Trem 014 (polyhydric alcohol esters). 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 Cercosporidium personatum (the causal agent of peanut late leafspot) and incubated in a saturated atmosphere at 22° C. for 24 hr, a high humidity atmosphere at 22 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. 
     EXAMPLE C 
     The test compounds were dissolved in acetone in an amount equal to 3% of the final volume and then suspended at a concentration of 200 ppm in purified water containing 250 ppm of the surfactant Trem 014 (polyhydric alcohol esters). This suspension was sprayed to the point of run-off on wheat seedlings. The following day the seedlings were inoculated with a spore suspension of Puccinia recondita (the causal agent of wheat leaf rust) and incubated in a saturated atmosphere at 20° C. for 24 hr, and then moved to a growth chamber at 20° C. for 6 days, after which disease ratings were made. 
     EXAMPLE D 
     The test compounds were dissolved in acetone in an amount equal to 3% of the final volume and then suspended at a concentration of 200 ppm in purified water containing 250 ppm of the surfactant Trem 014 (polyhydric alcohol esters). 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 Phytophthora infestans (the causal agent of potato and tomato late blight) and 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. 
     EXAMPLE E 
     The test compounds were dissolved in acetone in an amount equal to 3% of the final volume and then suspended at a concentration of 200 ppm in purified water containing 250 ppm of the surfactant Trem 014 (polyhydric alcohol esters). 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) and 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. 
     EXAMPLE F 
     The test compounds were dissolved in acetone in an amount equal to 3% of the final volume and then suspended at a concentration of 200 ppm in purified water containing 250 ppm of the surfactant Trem 014  (polyhydric alcohol esters). This suspension was sprayed to the point of run-off on cucumber seedlings. The following day the seedlings were inoculated with a spore suspension of Botrytis cinerea (the causal agent of gray mold on many crops) and incubated in a saturated atmosphere at 20° C. for 48 hr, and moved to a growth chamber at 20° C. for 5 days, after which disease ratings were made. 
     EXAMPLE G 
     The test compounds were dissolved in acetone in an amount equal to 3% of the final volume and then suspended at a concentration of 1000 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 tobacco seedlings. The following day the seedlings were inoculated with a spore suspension of Peronospora tabacina (the causal agent of tobacco blue mold) and incubated in a saturated atmosphere at 20° C. for 24 hr, moved to a growth chamber at 22° C. for 6 days, and then incubated in a saturated atmosphere at 20° C. for 24 hr, after which disease ratings were made. 
     EXAMPLE H 
     The test compounds were dissolved in acetone in an amount equal to 3% of the final volume and then suspended at a concentration of 200 ppm in purified water containing 250 ppm of the surfactant Trem 014 (polyhydric alcohol esters). This suspension was sprayed to the point of run-off on cucumber seedlings. The following day the seedlings were inoculated with a spore suspension of Pseudoperonospora cubensis (the causal agent of cucumber downy mildew) and incubated in a saturated atmosphere at 20° C. for 24 hr, moved to a growth chamber at 20° C. for 6 days, and the incubated in a saturated atmosphere at 20° C. for 24 hr, after which disease ratings were made. 
     Examples which further illustrate the invention can be found in the following tables (Tables 3 to 5). In the table, a rating of 100 indicates 100% disease control and a rating of 0 indicates no disease control (relative to the carrier sprayed controls). A &#34;-&#34; indicates that no test was performed at that concentration on that disease. 
     
                       TABLE 3______________________________________UNREPLICATED TEST DATA AT 200 PPMEX #     EX. A   EX. B       EX. D EX. F______________________________________135      64      71          64    0122      39      43          77    96179      50      0           0     0175      --      --          76    0174      --      --          0     03        59      91          99    --42       77      23          0     027       0       0           0     046       61      79          93    047       39      23          0     052       88      23          99    053       11      23          93    067       61      58          64    068       11      23          86    090       61      23          64    091       39      23          0     029       61      23          0     030       77      23          0     031       39      0           0     032       39      0           0     028       39      0           0     033       11      0           0     034       61      0           0     025       11      23          0     026       39      23          0     0144      39      23          86    0145      61      23          0     0159      11      23          0     0160      61      23          0     043       39      0           0     075       61      23          26    0146      61      0           0     035       61      0           0     036       61      23          0     04        39      23          47    0104      0       43          99    88118      6       0           47    35119      0       0           0     039       0       0           0     9638       64      0           0     885        39      0           47    9940       81      0           26    7941       81      0           0     35182      39      94          26    3518       39      0           0     63188      6       43          77    0128      39      43          0     06        81      0           0     010       6       43          0     0129      39      0           0     35______________________________________ 
    
     
                       TABLE 4______________________________________UNREPLICATED TEST DATA AT 200 PPMEX #     EX. A         EX. B   EX. C______________________________________ 3       --            92      10075       56            --      --______________________________________ 
    
     
                       TABLE 5______________________________________REPLICATED TEST DATA AT THE SPECIFIED RATEEX #  PPM        EX. D   EX. E   EX. G EX. H______________________________________135   200        97      100     --    --135   40         47      100     --    --3     200        100     100     --    --3     40         98      100     100   10042    200        25      --      --    --42    40         0       17      --    --27    200        0       --      --    --27    40         0       61      --    --46    200        88      --      --    --46    40         91      97      98    7947    200        76      --      --    --47    40         8       88      62    6752    200        100     --      --    --52    40         98      100     100   10053    200        92      --      --    --53    40         67      99      99    10067    200        88      --      --    --67    40         67      100     55    6268    200        15      --      --    --68    40         25      75      --    --90    200        82      --      --    --90    40         52      25      --    --91    200        17      --      --    --91    40         0       32      --    --29    200        15      --      --    --29    40         8       24      --    --30    200        17      --      --    --30    40         0       32      --    --31    200        8       --      --    --31    40         8       65      --    --32    200        0       --      --    --32    40         17      80      --    --28    200        0       --      --    --28    40         8       72      --    --33    200        0       --      --    --33    40         8       32      --    --34    200        15      --      --    --34    40         0       42      --    --25    200        0       --      --    --25    40         0       24      --    --26    200        0       --      --    --26    40         8       17      --    --144   200        94      --      --    --144   40         57      97      --    --145   200        62      --      --    --145   40         39      --      --    --159   200        0       --      --    --159   40         17      73      --    --160   200        8       --      --    --160   40         0       0       --    --43    200        0       --      --    --43    40         0       49      --    --75    200        91      100     --    --75    40         65      100     100   100146   200        0       --      --    --146   40         0       34      --    --35    200        0       --      --    --35    40         0       15      --    --36    200        0       --      --    --36    40         0       17      --    --4     200        88      --      --    --4     40         52      98      97    100104   200        100     100     --    --104   40         71      100     92    89118   200        84      100     --    --118   40         8       48       0     0119   200        0       78      --    --119   40         16      15       0     039    200        16      48      --    --39    40         0       23       0     038    200        0       86      --    --38    40         8       --       0    115     200        86      100     --    --5     40         8       97       0    2540    200        52      68      --    --40    40         0       15       0     641    200        8       71      --    --41    40         0       --       0     6182   200        23      96      --    --182   40         0       45      13    1118    200        21      93      --    --18    40         0       79       0    39188   200        65      100     --    --188   40         16      82      32    46128   200        15      100     --    --128   40         0       89       0    116     200        33      100     --    --6     40         0       --       0     010    200        0       100     --    --10    40         8       77       0     0129   200        0       100     --    --129   40         0       58       0     6______________________________________