AZOLE-SUBSTITUTED OXATHIOLANES AS PESTICIDES AND PLANT GROWTH REGULATORS

Abstract: This invention relates to novel imidazole and triazole substituted oxathiolane compounds and compositions con­ taining said compounds having fungicidal and plant growth regulant activity and methods for preparing same. The com­ pounds may be represented by the formula:- wherein R is C₂-C₄ alkylene unsubstituted or substituted with C₁-­ C₁₀ alkyl, alkenyl, alkynyl or alkoxyalkyl; R¹ is (a) C₅-C₈ bridged or non-bridged cycloalkyl or cyclo­ alkenyl; (b) phenyl, methylenedioxyphenyl, naphthyl, pyridyl, furanyl or thienyl; the (b) substituents being un­ substituted or substituted with: C₁-C₁₀ alkyl, OH, SH, cyclo­ hexyl, C₁-C₁₀ haloalkyl, C₁-C₁₀ alkenyl, cyano, nitro, XR³ or a single halogen wherein X is O, S, SO or SO₂ and R³ is C₁-C₁₀ alkyl, C₁-C₁₀ alkenyl, C₁-C₁₀ alkoxyalkyl, C₁-C₆ haloalkyl, C₁-C₆ haloalkenyl, C₅-C₆ cycloalkyl, C₇-C₉ aralkyl; C₁-C₄ alkylsulfonyloxy, phenylsul­ fonyloxy, wherein R⁴ is C₁-C₄ alkyl or phenyl; wherein R⁵ and R⁶ are individually H, C₁-C₄ alkyl or phenyl with the proviso that R⁵ and R⁶ are not both H; NR⁷R⁸ wherein R⁷ and R⁸ are individually H or C₁-C₄ alkyl, R⁷ is H, R⁸ is COR⁹, COOR⁹ or SO₂R⁹ wherein R⁹ is C₁-C₄ alkyl or phenyl or R⁷ and R⁸ together form C₄-C₆ alkylene, C₄-C₆ oxy­ dialkylene or phenylmethylene; R² is H or C₁-C₆ alkyl; Y is N or CH; and n is 0, 1 or 2, and the physiologically acceptable addition salts thereof.

Description: SUBSTITUTED OXATHIOLANES BACKGROUND OF THE INVENTION Field of the Invention This invention relates to novel imidazole and triazole substituted oxathiolane compounds having fungi cide and plant growth regulant activity and methods for preparing same. Description of the Prior Art As a result of the economic loss which accompanies fungicidal attack on plants, especially crops, there is a constant need for new broad spectrum fungicides. Moreover, the need for agricultural chemicals having significant effects on the growth and development of crop plant species is similarly well known. Thus, for many crops, it is highly desirable that certain plant growth regulatory effects be accomplished. In general, these growth regulatory effects include one or more of the following: dwarfing, cessation of terminal growth, inhibition or stimulation of axillary and intercalary growth, retardation or stimulation of internode elongation, inhibition or stimulation of flowering or reproductive development, and the like. Of particular interest is the growth retardancy of such important commercial crops as soy bean, cotton, bean and cereal grains, including barley. Among the any classes and types of compounds developed for antimicrobial use are the various classes of imidazole and triazole dithiolanes as exemplified in United States Patent (U.S.P.) 4,483,865, U.S.P. 4,359,475 and European Patent Publication (EPO) 0,061,789 and dioxolanes as taught in U.S.P.--4,160, U.S.P.4,160,838,3,575,999, 4,402,963, 4,079,062, Australian Patent A-86640/82 and J. Med. Chem. 12, 784 (1969). SUMMARY OF THE INVENTION The instant invention is directed to a new class of imidazole or triazole substituted compounds whose activity against a wide spectrum of fungi is greater than the imidazole or triazole substituted compounds of the prior art and which provides a new aid in plant growth regulant technology. In accordance with this invention, said compounds are set forth by the following general formula: EMI2.1 wherein R is C2-C4 alkylene unsubstituted or substituted with C1-C10 alkyl, alkenyl, alkynyl or alkoxyalkyl; R1 is (a) C5-C8 bridged or non-bridged cycloalkyl or cycloalkenyl; (b) phenyl, methylenedioxyphenyl, naph thyl, pyridyl, furanyl or thienyl; the (b) substituents being unsub stituted or substituted with: : C1-C10 alkyl, OH, SH, cyclohexyl, Cl-C10 haloalkyl, Cl-Cl0 alkenyl, cyano, nitro, XR3 or a single halogen wherein X is O, S, SO or S02 and R3 is Cl-Clo alkyl, C1-C10 alkenyl, C1-C10 alkoxyal kyl, C1-C6 haloalkyl, C1-C6 haloalkenyl, C5-C6 cycloal kyl, C7-C9 aralkyl; Cl-C4 alkylsulfonyloxy, phenylsulfonyloxy, EMI3.1 wherein R4 is C1-C4 alkyl or phenyl; EMI3.2 wherein R5 sd R6 are individually H, C1-C4 alkyl or phenyl with the proviso that R5 and R6 are not both H; ; NR7R8 wherein R7 and R8 are individually H or C1-C4 alkyl, R7 is H, R8 is COR9, COOR9 or S02R9 wherein R9 is C1-C4 alkyl or phenyl, or R8 R7 and R8 together form C4-C6 alkylene, C4-C6 oxydialkylene or phenylmethylene; R2 is H or C1-C6 alkyl; Y is N or CH; and n is 0, 1 or 2; and the physiologically acceptable addition salts thereof. The instant invention is furthermore directed to a process for controlling fungi by the application of a fungicidally effective amount of a compound within the above generic formula. The invention is still further characterized by a fungicidal composition which comprises a compound as recited above with a carrier therefor. Finally, the instant invention is di; ted to a plant growth regulant composition comprising a compound of the instant invention and a carrier therefor. Also, the instant invention is directed to a method for regulating plant growth by employing the plant growth composition of this invention. DETAILED DESCRIPTION OF THE INVENTION This invention relates to compounds of the following generic formula I: EMI5.1 wherein R is C2-C4 alkylene unsubstituted or substituted with C1-C10 alkyl, alkenyl, alkynyl or alkoxyalkyl; R1 is (a) C5-C8 bridged or non-bridged cycloalkyl or cycloalkenyl; (b) phenyl, methylenedioxyphenyl, naph thyl, pyridyl, furanyl or thienyl; the (b) substituents being unsub stituted or substituted with: : C1-C10 alkyl, OH, SH, cyclohexyl, Cl-Cl0 haloalkyl, C1-C10 alkenyl, cyano, nitro, XR3 or a single halogen where in X is O, S, SO or S02 and R3 is C1-C10 alkyl, C1 -C10 alkenyl, C1-C10 alkoxy kyl, C1-C6 haloalkyl, C1-C6 haloalkenyl, C5-C6 cycloal kyl, C7-C9 aralkyl; C1-C4 alkylsulfonyloxy, phenylsulfonyloxy, EMI6.1 wherein R4 is C1-C4 alkyl or phenyl; EMI6.2 wherein R5 and R6 are individully H, C1-C4 alkyl or phenyl with the proviso that R5 and R6 are not both H; ; NR7R8 wherein R7 and R8 are individually H or C1-C4 alkyl, R7 is H, R8 is COR9, COOR9 or SO2R9 wherein R9 is C1 -C4 alkyl or phenyl, or R7 and R8 together form C4-C6 alkylene, C4-C6 oxydialkylene or phenylmethylene; R2 is H or C1-C6 alkyl; Y is N or CH; and n is 0, 1 or 2; and the physiologically acceptable addition salts thereof. The compounds of formula I contain an asymmetric carbon atom at the 2-position of the oxathiolane ring which results in the existence of optical isomers. These isomers and their mixtures are within the scope of this invention. Preferred compounds of this invention are those according to formula I wherein R is C2 alkylene unsubstituted or substituted with C1-C3 alkyl; R is (a) C5-C6 cycloalkyl; (b) unsubstituted phenyl, naphthyl, thienyl; phenyl or thienyl substituted with F, C1, Br, C1-C7 alkyl, XR3 wherein X is O, S, SO or SO2 and R3 is C1-C7 alkyl, cyclohexyl; methylsulfonyloxy, phenylsulfonyloxy, diinethylaminocarbonyloxy or NR7R8 wherein R7 and R8 are individually H or C1-C2 alkyl R7 and R8 together are phenylinethylene and where R7 is H, R8 is methylsulfonyl, phenylsulfonyl or C1-C4 alkyoxycarbonyl; R2 is H; Y is N or CH; and n is 0, 1 or 2. More preferred compounds of this invention are those of formula I wherein R is C2 alkylene unsubstituted or substituted with C1-C3 alkyl; R1 is (a) cyclohexyl; (b) unsubstituted phenyl, naphthyl, thienyl; phenyl or thienyl substituted with F, C1, Br, C1-C7 alkyl or C2-C7 alkoxy; R2 is H; Y is N or CH; and n is 0, 1 or 2. Most preferred compound of this invention are those of formula I wherein R is C2 alkylene unsubstituted or substituted with C1-C3 alkyl; R1 is (a) cyclohexyl; (b) phenyl or thienyl substituted with F, C1, Br, C1-C7 alkyl or C2-C7 alkoxy; R2 is H; Y is N or CH; and n is 0, 1 or 2. The compounds of this invention have particular application as fungicides in the control of fungus growth on plants and vegetation. It is particularly noteworthv that the compounds of this invention are effective against phytopathogenic fungi which are systemic in the plant or deeply embedded in plant tissue. Among these classes of fungi which are effectively controlled by the compounds of this invention is powdery mildew disease in barley (Erysiphe graminis) and cucumber (Erysiphe cichoracearum) and rust diseases such as bean rust (Uromyces phaseoli). Certain compounds of this invention have also demonstrated effectiveness against other fungi which cause plant disease, including, for example, Alternaria solani, Cercospora arachidicola, Phytophthora infestans, Sclerotinia sclerotiorum, Sclerotium rolfsii, Fusarium oxysporum, Helminthosporium maydis and Piricularia oryzae. The compounds of this invention can be prepared by catalytic reaction of azole-substituted ketones with mercapto-alcohols and the subsequent cyclization of the intermediate so formed. Azole-substituted ketones may be prepared from haloketones by substitution of the halogen atom with an azole (imidazole or 1H-1,2,4-triazole) by methods disclosed in Canadian Patent No. 1,054,613 and French Patent No. 2,303,475. Conversion of azole-substituted ketones to compounds of this invention where n=0 is accomplished by reaction of the azoleketone with a mercaptoalcohol. At least one mole, and preferably an excess of mercaptoalcohol is required for the cyclization for which an acid catalyst is necessary, preferably p-toluenesulfonic acid. The cyclization is preferably carried out in a solvent mixture such as toluene and l-butanol and is accompanied by azeotropic removal of water. Sulfoxides and sulfones are obtained by oxidation of compounds where n=0 with hydrogen peroxides or organic hydroperoxides such as m-chloroperoxybenzoic acid in a chlorinated hydrocarbon solvent, preferably dichloroe- thane or chloroform. Sulfoxides may specifically be formed by reaction of oxathiolanes with one equivalent of m-chloroperoxybenzoic acid at between 0 C and ambient temperature. Conversion of oxathiolanes to sulfones may be carried out by reaction with at least two equivalents and preferably an ex,ess of m-chloroperoxybenzoic acid in a chlorinated hydrocarbon solvent at the reflux temperature of the solvent. Compounds of formula I where R is substituted ethylene (-CH2-CH(R*)-) may be separately synthesized as either of two isomeric compounds where substitution of the alkyl substituent R* is either at the 4-position or the 5-position of the oxathiolane ring. In order to effectively employ the compounds of this invention in their prime use, as fungicides, the compounds may be applied neat or in admixture with inert carriers and/or additives to form fungicidally effective compositions. In one such embodiment, the compound is combined with a solid inert carrier. Among the inert carriers within the contemplation of this invention, are the mineral silicates, e.g., mica, talc, pyrophylite and the clays. Other solid carriers, within the contemplation of this invention, include vermiculite, charcoal and corn cobs. Solid compositions made by combining the inert carriers recited above with the active compound are applied by well-known methods in the art such as broadcasting, side dressing, soil incorporation and seed treatment. In another preferred embodiment of this invention, a liquid composition comprising an active compound and a liquid inert carrier is employed. In this embodiment, the liquid carrier may be a solvent or a suspending agent for the active compound of this invention. It is emphasized that the carrier itself is inert in terms of providing fungicidal activity. Among the liquid carriers within the contemplation of this invention are water, alkanols and aromatic solvents such as substituted and unsubstituted phenol, benzene, kerosene, toluene and xylene. Another preferred embodiment of the liquid composition is an emulsion formed by dissolving an active compound of this invention in a suitable organic solvent and then adding the solvent to water. Of course, a suitable emulsifying agent, such as a surface active agent which may be anionic, non-ionic or cationic, is added in the formation of the emulsion. In yet another embodiment of the liquid composition, an active compound of this invention is combined with water to form a dispersion in the absence of an organic solvent. Again, surface-active dispersing agents are employed in the preparation of the suspension. The surface-active agents effective in the preparation of liquid compositions are known to the art. For example, U.S. Patent 2,547,734 provides detailed examples of such agents employed in emulsions and dispersions. In yet another liquid composition embodiment, solutions are prepared for aerosol application of a compound of this invention. These compositions are prepared by dissolving the active compound directly in an aerosol solvent which is a liquid at elevated pressures. The aerosol method involves releasing the aerosol solution in the atmosphere at a pressure at which the carrier is a gas. Alternatively, the aerosol solution may be prepared by first dissolving an active compound of this invEntion in a less volatile solvent and then admixing the thus formed solution with a highly volatile liquid aerosol carrier and proceeding as discussed above. In another embodiment, a two-phase composition is provided. In this application, an active compound of this invention is first absorbed on the surface of an inert solid carrier. As stated above, the various mineral silicates are particularly preferred in this application. These inert silicates are then dispersed, in the presence of a dispersing agent, in a suitable non-solvent medium, usually water. Illustrative, non-limiting examples of suitable solvents which may be used in the application of the microbiocides of this invention are acetone, methanol, isopropanol, t-butyl alcohol, cyclohexanol, cyclohexanone, n-butyl alcohol, toluene, xylene, dioxane, dimethyl formamide, dimethylsulfoxide, ethylene dichloride, diacetone alcohol, and n-methyl pyrrolidone. Water emulsions prepared from these solutions may also be applied to the locus under attack by microbes. The microbiocides of this invention can be applied foliarly to the plant to be protected or to the soil in which the plants to be protected are grown. If applied foliarly, the concentration of the active ingredient is applied at a rate of from about 0.125 to about 10.0 kilograms per hectare (kg/ha). More preferably, the rate of foliar application is in the range of between 0.125 and 5.0 kglha. Those skilled in the art will appreciate that the exact ccncentrarion depends greatly on the disease being controlled and the crop being protected. In the embodiment wherein protection is provided by application of the active ingredient to the soil, the dosage rate is from about 5 to 500 parts per million (ppm) of active ingredient. The particular dosage within this range again depends on the disease being controlled and the crop being protected. In the microbiocidal use of the active compounds of this invention, the application of the active may be applied prior to any infection or after a microbe attack has begun. In still another application of the microbiocidal use of the compound of this invention, the active is applied to seeds as a coating. This method accomplishes the same purpose as is provided by protecting the plant chemotherapeutically or systemically by absorbing the active into the plant. WEen the microbiocidal use is as a coating to seeds, the appropriate dosage is in the range of from about 5 to 75 grams of active per hundred kilograms of seed. In yet another aspect of this invention, a process is provided for regulating plant growth which includes the application of a compound of this invention as a plant growth regulant. In this process, the active ingredient is preferably applied foliarly. As in the case of the microbiocidal use of the active ingredient, the compound is applied as a liquid, either as an organic solution, or as a water emulsion. Most preferably, the plant growth regulant is , plied as a water emulsion, suspension or solution. In the use of a compound of this invention as a plant growth regulant, the dosage applied is in the range of from about 0.125 to about 10.0 kilograms of active ingredient per hectare (kg/ha). More preferably, the concentration of active as a plant growth regulant is in the range of from about 0.125 to about 5.0 kg/ha. It is preferred that the application as a plant growth regulant be as an atomized spray or as a soil treatment. The most suitable dosage and method of application of the active ingredient(s) for plant growth regulatory effects and the type and amount of adjuvant substances to be added to the spray solution will depend on a number of factors, including the plant species; the stage of plant development; the mode of application; the specific biological effect desired; the air and soil temperature; the quantity and intensity of rainfall before and after treatment; the soil type, pH, fertility and moisture and organic matter content; the physiological condition and vigor of the target plants; the relative humidity and wind velocity of the air around the crop; the extent and density of the foliar canopy of the target plant; the light quality, intensity and duration each day; the type and interval of previous and subsequent crop protectant chemical applications. All of these factors may have an influence on the efficacy of chemicals applied as plant growth regulators. However, one skilled in the art can, by routine experimentation, readily determine optimum conditions for the employment of any particular compound of this invention. The following examples are given to illustrate this invention and no express or implied limitation of the invention to these examples is intended. EXAMPLE 1 1-[(2-phenyl-1,3-oxathiolan-2-yl)methyl]-1H-1,2,4-tria- zole (Cpd. No. 1) To a solution of 5.6 g 1-phenyl-2-lH-1,2,4-triazo' l-yl)ethanone and 4.7 g 2-mercaptoethanol in 100 ml dry toluene and 50 ml l-butanol was added with stirring 7.6 g p-toluenesulfonic acid, which resulted in the formation of a slurry. The mixture was refluxed under a Dean-Stark trap for about 40 hours, until no more water collected. The solvent was evaporated, the residue taken up in dichloromethane and washed twice with 10% aqueous sodium hydroxide and once with water. The solution was dried, filtered and evaporated leaving a solid which was recrystallized from toluene/petroleum ether to give 4.6 g of product. EXAMPLE 2 1-[12-(4-methoxyphenyl)-l,3-oxathiolan-2-yllmethyl]-lH- 1,2,4-triazole (Cpd. No. 22) To a slurry of 32.5 g 1-(4-methoxyphenyl)-2-(lH1,2,4-triazole-l-yl) ethanone in 500 ml dry toluene and 250 ml 1-butanol was added 23.4 g 2-mercapt thanol and 38.0 g p-toluenesulfonic acid. The thickened slurry was refluxed under a Dean-Stark trap for about 40 hours, until no more water collected. The solvent was evaporated leaving a solid residue which was dissolved in dichloromethane and washed twice with 10Z aqueous sodium hydroxide and once with water. The organic layer was dried, filtered and evaporated to leave an oily residue which partially solidified on high vacuum pumping. Thf residue was triturated with hot toluene/cyclohexane, cooled and filtered to give 6.5 g of product. EXAMPLE 3 I-[I2-(4-chlorophenyl)-1,3-oxathiolan I-yl]metbyl]-1H- 1,2,4-triazole (Cpd. No. 6) To a slurry of 44.3 g l-(4-chlorophenyl)-2-(1H1,2,4-triazol-1-yl) ethanone in 800 ml dry toluene end 400 ml l-butanol was added 31.2 g 2-mercaptoethanol and 51.0 g p-toluenesulfonic acid. The mixture was refluxed under a Dean-Stark trap for 48 hours. On cooling, a white solid precipitated out, which was removed by filtration. The filtrate was evaporated, the residue dissolved in dichloromethane and washed twice with 10Z aqueous sodium hydroxide and once with water. The organic layer was dried, filtered and evaporated to leave an oil which was taken up in cyclohexane. The cyclohexane was evaporated to azeotrope off any remaining 1-butanol, leaving an oily solid which was triturated with petroleum ether to give 15.7 g of product. EXAMPLE 4 l-ll2-(4-bromophenyS 3-oxathiolan-2-yllmethyl]-lH 1,2,4-triazole (Cpd. No. 9) To a slurry of 27.8 g 1-(4-bromophenyl)-2-(lH-1,2,4- triazol-l-yl) ethanone in 350 ml dry toluene and 175 ml l-butanol were added 15.6 g 2-mercaptoethanol and 24.7 g p-toluenesulfonic acid. The mixture was refluxed under a Dean-Stark trap for 50 hours. After cooling, a white solid was removed by filtration and the filtrate evaporated. The residue was taken up in chloroform and washed twice with 10% aqueous sodium hydroxide and once with water. The organic layer was dried, filtered and evaporated to leave a liquid residue. The l-butanol in the residue was removed azeotropically three times with cyclohexane leaving a slurry. The solid was isolated by filtration to give 5.2 g of product. EXAMPLE 5 1[[2-(4-chlorophenyl)-1,3-oxathiolan-2-yl]methyl]-1H- 1,2,4-triazole S-oxide (Cpd. No. 7) To a solution of 6.7 g l-[[2-(4-chlorophenyl)-1,3- oxathiolan-2-yllmethyl]-1H-1,2,4-triazole in 60 ml dichloromethane was added dropwise 4.9 g of 80-85X m-chloroperoxybenzoic acid in 50 ml dichloromethane at O"C. After the addition was complete, the reaction mixture was allowed to warm to room temperature and was stirred overnight. The solution was washed twice with 52 aqueous sodium bicarbonate, once with water, dried and evaporated leaving a sticky yellow solid. The product was triturated with ether to leave as a white powder 3.8 g of product. EXAMPLE 6 l-[ (2-(4-chlorophenyl)-1 ,3-oxathiolan-2-yl]methyl]-1H- 1,2,4-triazole S,S-dioxide (Cpd. No. 8) To a solution of 5.6 g 1-[!2-(4-chlorophenyl)-1,3- oxathiolan-2-ylAmethyl]-lH-1,2,4-triazole in 90 ml dichloromethane was added dropwise 10.1 g m-chloroperoxybenzoic acid in 175 ml dichloromethane at room temperature. After the addition was complete, the reaction mixture was refluxed for 18 hours. The volume was then reduced by one-half and the resulting precipitate was removed by filtration. The filtrate was washed twice with 5Z aqueous sodium bicarbonate, once with water, dried and evaporated to leave a sticky solid. Recrystallization of this solid from toluene/petroleum ether gave 3.4 g of product. Additional compounds were prepared following procedures similar to those set forth in Examples 1 through 6. TABLE I EMI20.1 EMI20.2 <tb> Cpd. <SEP> No. <SEP> R1 <SEP> n <SEP> m.p.( C) <tb> <SEP> 1 <SEP> < <SEP> 0 <SEP> 100-102 <tb> <SEP> 2 <SEP> " <SEP> 1 <SEP> 100-112 <tb> <SEP> 3 <SEP> " <SEP> 2 <SEP> 121-125 <tb> <SEP> 4 <SEP> + <SEP> F <SEP> 0 <SEP> 117-118 <tb> <SEP> 5 <SEP> II <SEP> 2 <SEP> 173-175 <tb> <SEP> 6 <SEP> < <SEP> C1 <SEP> 0 <SEP> 110-112 <tb> <SEP> 7 <SEP> ·Cl <SEP> 1 <SEP> 125-130 <tb> <SEP> 8 <SEP> " <SEP> 2 <SEP> 155-160 <tb> <SEP> 9 <SEP> < <SEP> Br <SEP> 0 <SEP> 122-124 <tb> EMI21.1 <tb> Cpd. <SEP> No. <SEP> R1 <SEP> n <SEP> m.p.(0C) <tb> <SEP> 10 <SEP> 4 <SEP> Br <SEP> 2 <SEP> 144-148 <tb> <SEP> 11 <SEP> TICH3 <SEP> 0 <SEP> 114-117 <tb> <SEP> 12 <SEP> Il <SEP> 2 <SEP> 135-140 <tb> <SEP> 13 <SEP> < <SEP> CH2-CH2-CH3 <SEP> 0 <SEP> 40-42 <tb> <SEP> CH <tb> <SEP> 14 <SEP> < <SEP> 0 <SEP> 66-68 <tb> <SEP> CH3 <tb> <SEP> CH, <tb> <SEP> 15 <SEP> v <SEP> C1-CH3 <SEP> - <SEP> C3 <SEP> 0 <SEP> 105-106 <tb> <SEP> CH3 <tb> <SEP> 16 <SEP> 2 <SEP> 153-155 <tb> <SEP> 17 <SEP> < <SEP> 0 <SEP> 88-90 <tb> <SEP> 18 <SEP> " <SEP> 2 <SEP> 155-157 <tb> <SEP> 19 <SEP> NO <SEP> < <SEP> 0 <SEP> 186-188 <tb> <SEP> 20 <SEP> thou <SEP> 0 <SEP> 96-100 <tb> EMI22.1 <tb> Cpd. <SEP> No. <SEP> R1 <SEP> n <SEP> m.p.(µC) <tb> <SEP> 21 <SEP> > <SEP> OH <SEP> 2 <SEP> 185-187 <tb> <SEP> 22 <SEP> 7mOCH3 <SEP> 0 <SEP> 145-155 <tb> <SEP> 23 <SEP> " <SEP> 2 <SEP> 65-70 <tb> <SEP> CH3 <tb> <SEP> 24 <SEP> 4 <SEP> O--CH <SEP> 0 <SEP> 78-79 <tb> <SEP> CH3 <tb> <SEP> 25 <SEP> " <SEP> 1 <SEP> 134-135 <tb> <SEP> 26 <SEP> " <SEP> 2 <SEP> 138-139 <tb> <SEP> 27(1) <SEP> < <SEP> O-(CH2)4-CH3 <SEP> 0 <SEP> Oil <tb> <SEP> 28 <SEP> 1I <SEP> 2 <SEP> 128-129 <tb> <SEP> 29(1) <SEP> > <SEP> O-(CH2)4-CH3 <SEP> 0 <SEP> Oil <tb> <SEP> 30 <SEP> CH3-CH2-O <SEP> < <SEP> 0 <SEP> 73-75 <tb> <SEP> 31 <SEP> CH <SEP> CH73-CH-O <SEP> 0 <SEP> 97-99 <tb> <SEP> CH3 <tb> <SEP> 32 <SEP> CH3 <SEP> (CH2)4 <SEP> 0 <SEP> < <SEP> 68-70 <tb> EMI23.1 <tb> Cpd. <SEP> No. <SEP> R1 <SEP> n <SEP> m.p,(eC) <tb> <SEP> 33(1) <SEP> CH3-(CH2)4-O <SEP> 2 <SEP> Oil <tb> <SEP> 34(1) <SEP> CH3-(CH2)6- <SEP> < <SEP> 0 <SEP> Oil <tb> <SEP> 0 <tb> <SEP> II <tb> <SEP> 35 <SEP> CH3-S-O <SEP> < <SEP> 0 <SEP> 191-193 <tb> <SEP> 0 <tb> <SEP> 0 <tb> <SEP> II <tb> <SEP> 36 <SEP> CH3-NH-C-O <SEP> < <SEP> O <SEP> 140-142 <tb> <SEP> 37(1) <SEP> > <SEP> NH2 <SEP> O <SEP> Oil <tb> <SEP> /CH3 <tb> <SEP> 38(1) <SEP> > <SEP> N <SEP> O <SEP> Oil <tb> <SEP> CH3 <tb> <SEP> C <tb> <SEP> H2-CH3 <tb> <SEP> 39(1) <SEP> N <SEP> 0 <SEP> Oil <tb> <SEP> CH2-CH3 <tb> <SEP> 2 <SEP> 3 <tb> <SEP> 40 <SEP> + <SEP> NH2 <SEP> O <SEP> 105-108 <tb> <SEP> CH3 <tb> <SEP> 41 <SEP> + <SEP> N <SEP> O <SEP> 87-89 <tb> <SEP> 3 <tb> EMI24.1 <tb> Cpd. <SEP> No. <SEP> R1 <SEP> n <SEP> m.p.( C) <tb> <SEP> / <SEP> CH2-CH3 <tb> <SEP> 42(1) <SEP> N <SEP> O <SEP> Oil <tb> <SEP> CH2 <SEP> -CH3 <tb> <SEP> 43 <SEP> + <SEP> N-CH <SEP> < <SEP> 0 <SEP> 97-99 <tb> <SEP> 0 <tb> <SEP> 44 <SEP> + <SEP> NH-C <SEP> < <SEP> O <SEP> 119-123 <tb> <SEP> 45 <SEP> " <SEP> 1 <SEP> 162-165 <tb> <SEP> 0 <tb> <SEP> 46 <SEP> > <SEP> NH-C-O-(CH2)3-CH3 <SEP> 0 <SEP> 96-97 <tb> <SEP> 47 <SEP> " <SEP> 2 <SEP> 141-143 <tb> <SEP> 0 <tb> <SEP> 48(1) <SEP> > <SEP> NH-S <SEP> 0 <SEP> Oil <tb> <SEP> o <tb> <SEP> o <tb> <SEP> 49 <SEP> + <SEP> NH-S-CH3 <SEP> 0 <SEP> 188-190 <tb> <SEP> o <tb> <SEP> o <tb> <SEP> 50 <SEP> + <SEP> NH-C-O-CH2-CH3 <SEP> 0 <SEP> 126-128 <tb> EMI25.1 <tb> Cpd. <SEP> No. <SEP> R1 <SEP> n <SEP> m.p. <SEP> (C) <tb> <SEP> 0 <tb> <SEP> 51 <SEP> > <SEP> NH-C-O-(CH2)3-CH3 <SEP> O <SEP> 136-137 <tb> <SEP> 51 <SEP> 0 <SEP> 136-137 <tb> <SEP> 52 <SEP> " <SEP> 1 <SEP> 154-156 <tb> <SEP> 53 <SEP> " <SEP> 2 <SEP> 157-159 <tb> <SEP> 54 <SEP> X <SEP> 0 <SEP> 80-82 <tb> <SEP> 55 <SEP> " <SEP> 1 <SEP> 125-130 <tb> <SEP> 56 <SEP> " <SEP> 2 <SEP> 149-154 <tb> <SEP> 57 <SEP> e <SEP> 0 <SEP> 96-98 <tb> <SEP> 58 <SEP> " <SEP> 2 <SEP> 128-132 <tb> <SEP> 59 <SEP> See <SEP> Table <SEP> II <tb> <SEP> 60 <tb> <SEP> 61 <SEP> CH3-O <SEP> E <SEP> (Methiodide <SEP> 0 <SEP> 196-199 <tb> <SEP> Salt) <tb> <SEP> 62 <SEP> < <SEP> 0 <SEP> 61-63 <tb> <SEP> 63 <SEP> " <SEP> 2 <SEP> 116-120 <tb> EMI26.1 <tb> Cpd. <SEP> No. <SEP> R1 <SEP> ¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯ <SEP> m,p.("C) <tb> <SEP> S <SEP> B <SEP> Br <tb> <SEP> 64 <SEP> CBr <SEP> <SEP> 85-87 <tb> <SEP> 65 <SEP> " <SEP> 2 <SEP> 140-142 <tb> <SEP> 66 <SEP> ¸mC1 <SEP> 0 <SEP> 66-70 <tb> <SEP> 67 <SEP> " <SEP> 2 <SEP> 132-136 <tb> <SEP> 68 <SEP> ¸Th7 <SEP> CH3 <SEP> 0 <SEP> 88-90 <tb> <SEP> 69 <SEP> " <SEP> 2 <SEP> 120-124 <tb> 70-73 <SEP> See <SEP> Table <SEP> II <tb> <SEP> 74 <SEP> Th <SEP> Br <SEP> 0 <SEP> 75-80 <tb> <SEP> 75(1) <SEP> 2 <SEP> oil <tb> <SEP> 76 <SEP> v <SEP> CH2-CH2-CH3 <SEP> 1 <SEP> 104-106 <tb> <SEP> 77 <SEP> II <SEP> 2 <SEP> 90-92 <tb> <SEP> /CH3 <tb> <SEP> 78 <SEP> CH <SEP> 1 <SEP> 108-111 <tb> <SEP> CH3 <tb> EMI27.1 <tb> Cpd. <SEP> No. <SEP> R1 <SEP> n <SEP> m.p.(eC) <tb> <SEP> CH <tb> <SEP> 79 <SEP> + <SEP> CH <SEP> 2 <SEP> 112-118 <tb> <SEP> CH3 <tb> <SEP> 80 <SEP> + <SEP> (CH2)3 <SEP> CH3 <SEP> 0 <SEP> 45-46 <tb> <SEP> 81(1) <SEP> CH3-O <SEP> 0 <SEP> Oil <tb> <SEP> 82 <SEP> CH3-CH2-CH2-O <SEP> < <SEP> 0 <SEP> 73-75 <tb> <SEP> 83 <SEP> CH3-(CH2)3- <SEP> < <SEP> 0 <SEP> 60-62 <tb> <SEP> 0 <tb> <SEP> II <tb> <SEP> 84 <SEP> CH3-C-O <SEP> < <SEP> 0 <SEP> 133-135 <tb> <SEP> 0 <tb> <SEP> 85 <SEP> > <SEP> C1-O <SEP> < <SEP> 0 <SEP> 85-88 <tb> <SEP> 86 <SEP> ThCH <SEP> 0 <SEP> 45-47 <tb> <SEP> 3 <tb> <SEP> 87 <SEP> " <SEP> (p-toluenesulfonic <SEP> 0 <SEP> 131-133 <tb> <SEP> acid <SEP> saLt) <tb> EMI28.1 <tb> (d. <SEP> No. <SEP> R1 <SEP> ¯ <SEP> n <SEP> m.p.( C) <tb> <SEP> 0 <tb> <SEP> 1 <SEP> 1 <tb> <SEP> 88 <SEP> > <SEP> OSj <SEP> < <SEP> 0 <SEP> Oil <tb> <SEP> 0 <tb> <SEP> -0-- <SEP> 0 <SEP> Oil <tb> <SEP> 89(1) <SEP> > <SEP> I¯O <SEP> < <SEP> 0 <SEP> Oil <tb> <SEP> o <tb> <SEP> 90 <SEP> cLI, <SEP> CH2I:1) <SEP> 0 <SEP> 109-110 <tb> TABLE II LI EMI29.1 EMI29.2 <tb> Cpd. <SEP> No. <SEP> ¯¯¯¯¯¯¯¯¯¯¯ <SEP> R <SEP> y <SEP> R <SEP> Y <SEP> n <SEP> m.p. <SEP> (C) <tb> <SEP> 59 <SEP> + <SEP> C1 <SEP> -CH(CH3)-CH2- <SEP> N <SEP> 0 <SEP> 70-76 <tb> <SEP> 60 <SEP> " <SEP> " <SEP> " <SEP> 2 <SEP> 175-177 <tb> <SEP> 70(0) <SEP> -CH2-CH2- <SEP> CH <SEP> 0 <SEP> 67-70 <tb> <SEP> 71 <SEP> " <SEP> " <SEP> " <SEP> 1 <SEP> 125-129 <tb> <SEP> 72 <SEP> < <SEP> (1 <SEP> " <SEP> " <SEP> 0 <SEP> 88-90 <tb> <SEP> 73 <SEP> (( <SEP> o <SEP> " <SEP> 1 <SEP> 175-180 <tb> (1) Nuclear Magnetic Resonance (n.m.r.) data,: Cpd. No. 27 (deuterated chloroform, CDCl3): 8.0(1H,s) 7.8(1H,s), 7.3(2H,d), 6.8(2H,d), 4.7(2H,s), 4.1-4.5(2H,m), 3.9(2R,t), 2.8-3.1(2H,m), 0,7-2.1(9H,m). Cpd. No. 29 (dimethylsulfoxide, DMSO-d6): 8.2(1H,s), 7.8(1H,s), 6.7-7.4(4H,m), 4.8(2H,s), 4.0-4.5(2H,m), 3.9(2H,t), 2.8-3.2(2H,m), 0.7-2.0(9H,m). Cpd. No. 33 CDC13): 7.7(2H,bs), 6.7-7.4(4H,m), 5.4(1H,d), 4.8(1H,d), 3.7-4.7 (4H,m), 3.2(2H,t), 0.7-2.2(9H,m). Cpd. No. 34 (CDCl3): 7.9(1H,s), 7.7(1H,s), 6.7-7.4(4H,m), 4.8(2H,s), 3.8-4.6(2H,m), 2.5-2.9(2H,m), 0.7-2.1(13H,m). Cpd. No. 37 (CDC13): 8.0(1H,s), 7.8(1H,s), 6.4-7.4(4H,m), 4.6(2H,s), 3.8-4.5(2H,m), 3.7(2H,bs), 2.6-3.1(2H,m). Cpd. No. 38 (CDC13): 8.0(1H,s), 7.8(1H,s), 6.4-7.4(4H,m), 4.7(2H,s), 3.6-4.5(2H,m), 2.9(6H,s), 2.6-2.9(2H,m). Cpd. No. 39 (CDC13): 8.0(1H,s), 7.8(1H,s), 6.4-7.3(4H,m), 4.7(2H,s), 3.7-4.5(2H,m), 3.3(4H,q), 2.9(2H,m), 1.2(6H,t). Cpd. No. 42 (CDCl3): 8.0(1H,s), 7.9(1H,s), 7.2(2H,d), 6.6(2H,d), 4.6(2H,s), 3.7-4.5(2H,m), 3.3(4H,q), 2.8-3.1(2H,m), 1.1(6H,t). Cpd. No. 48 (CDC13): 8.6 (lH,6s), 6.9-8.0(11H,m), 4.7(2H,s), 3.7-4.5(2H,m), 2.7-3.1(2H,m). Cpd. No. 75 (CDC13) i.68-3.31(2H,m), 3.82-4.68(2H,m), 4.89(2H,s), 6.33(2H,m), 7.46(1H,m), 7.86(1H,s), 8.08(1H,s). Cpd. No. 81 (CDC13): 8.0(1H,s), 7.8(1H,s), 6.8-7.4(4H,m), 4.8(2H,s), 3.8-4.6(2H,m), 3.9(3H,s), 2.7-3.0(2H,m). Cpd. No. 88 (CDC13): 7.9(1H,s), 7.8(1H,s), 6.7-7.9(9H,m), 4.5(2H,s), 3.6-4.4(2H,m), 2.7-3.0(2H,m). Cpd. No. 89 (CDCl3): 7.9(1H,s), 7.7(1H,s), 7.0-8.3(9H,m), 4.7(2H,s), 3.7-4.6(2H,m), 2.6-2.9(2H,m). Typical of additional compounds considered to be within the scope of this invention are listed in Table III below. TABLE TABLE III EMI32.1 EMI32.2 <tb> Cpd. <SEP> No. <SEP> R <SEP> R1 <SEP> R2 <tb> <SEP> Cl <SEP> t <SEP> \ <tb> <SEP> 91 <SEP> -CH(CH3)-CH < CH3)- <SEP> N <SEP> &commat; <SEP> H <tb> <SEP> 92 <SEP> -CH(n-c4H9)-cH2- <SEP> CH3 <SEP> X <SEP> H <tb> <SEP> 93 <SEP> -CH(n-Cg <SEP> Hlg)CH2CH2- <SEP> CH3-(CH2)9 <SEP> 9 <tb> <SEP> 94 <SEP> -CH2-CH2- <SEP> CS > -T) <SEP> CH3 <tb> <SEP> 95 <SEP> 111 <SEP> SH <SEP> H <tb> <SEP> 96 <SEP> 1I <SEP> CY.3-(CH2)9-S <SEP> X <tb> <SEP> o <tb> <SEP> 97 <SEP> " <SEP> 9 <SEP> CH2-S <SEP> e <SEP> H <tb> <SEP> 98 <SEP> 1 <SEP> C(CH3)2 <SEP> <SEP> X <SEP> H <tb> EMI33.1 <tb> Cpd. <SEP> No. <SEP> R <SEP> R1 <SEP> - <SEP> R2 <tb> <SEP> 0 <tb> <SEP> I <SEP> H <tb> <SEP> 99 <SEP> -CH2-CH2- <SEP> a <tb> <SEP> CH3-(CH2)3 <SEP> 0 <tb> <SEP> 100 <SEP> " <SEP> / <SEP> -C-O <SEP> &commat; <SEP> H <tb> <SEP> CH3- <SEP> (CH2)3 <tb> <SEP> CH3-(CH2)3 <tb> <SEP> 101 <SEP> " <SEP> / <SEP> N <SEP> < <SEP> H <tb> <SEP> CH3-(CH2)3 <tb> <SEP> 102 <SEP> " <SEP> MN· <SEP> H <tb> <SEP> CH <tb> <SEP> CH-CH2 <tb> <SEP> 103 <SEP> 0 <SEP> N <SEP> N <SEP> < <SEP> H <tb> <SEP> CH-CH2 <tb> <SEP> CH3 <tb> <SEP> 104 <SEP> (( <SEP> Bicyclo(2.2.1)hept- <SEP> H <tb> <SEP> 5-en- <SEP> 2-yl <tb> EXAMPLE 7 POWDERY MILDEW SYSTEMIC CONTROL TEST The following procedure was used to evaluate the chemicals of this invention for effectiveness in preventing or controlling the Powdery Mildew disease of barley (Erysiphe graminis) and cucumber Powdery Mildew (Erysiphe cichoracearum) by systemic root uptake; BMS and CMS respectively. Barley and cucumber plants in pots measuring 4 x 4 x 3.5 inches and containing several plants each were grown to age 6 days and 10 days respectively, to bring them to a growth stage suitable for testing. The varieties used were "Herta" barley and "Marketmore 70" cucumber. Chemicals for drenching the potted plants were prepared by dissolving the technical chemical in 5 to 7 ml of acetone or other suitable solvent, adding 1-2 drops of an emulsifying agent such as Triton X-100 (trademark), and emulsifying the chemical in a quantity of water to give a concentration of 250 ppm of active ingredient. For each treatment, a 45 ml quantity of solution was added to the soil in which the plants were growing. This is an amount which will saturate the soil without losing significant amounts of the chemical solution through drainage into the saucers below. Twenty-for hours after treatment, both cucumber and barley plants were inoculated by brushing leaves from infected barley or cucumber plants on each of the treated plants and untreated controls. Six days after inocula tion, disease control was evaluated on a 0-6 rating scale, with 0 equal to no disease present and 6 being severe disease. Percent control is computed by comparing the treatment ratings with that of untreated control plants. The data are shown in Table IV. EXAMPLE 8 The following example illustrates the usefulness of the chemicals of this invention for controlling bean powdery mildew (E. polygoni) and barley powdery mildew (E. graminis) by foliar application; BEF and BAF respectively. The procedures are as follows: Bean Mildew Pinto bean plants, at the primary leaf stage of growth, were sprayed with the chemicals of the invention, at a dosage of 1000 ppm. Plants were then placed in the greenhouse at 70"F and inoculated with the Erysiphe polygoni spores by brushing the first and second trifoliate leaves with previously infected bean leaves covered with spores. The disease developed on untreated controls in 4 - 6 days. This test measures the ability of the chemical to be trans located systemically from the primary to the trifoliate leaves to provide disease control. Barley Mildew Seven day old barley plants were sprayed with the chemicals of the invention and were allowed to dry. The leaves of these plants were then inoculated with Erysiphe graminis mildew spores by brushing them with previously infected leaves which were covered with spores. The plants were then kept in the greenhouse at 70"F for 5 days to allow disease development. Control of disease was assessed by comparing treated plants with non-treated controls for percent of disease reduction or control. The results are shown in Table IV. ¯¯¯¯¯ EXAMPLE 9 This concerns laboratory tests for evaluating the fungitoxicity of chemicals to various Phytophthora infestans (PHY) and Botrytis cinerea (BOT). The candidate chemicals were solubilized in acetone at a concentration of 500 ppm. Antibiotic testing discs (11 millimeters) were dipped in the chemical test solutions, then were allowed to dry to remove the acetone solvent. The treated discs were then placed on agar plates, and the test organisms were added to the center of each paper disc in the form of a culture plug with the fungus mat in contact with the treated paper. The plates were incubated and then evaluated by measuring the diameter of the fungus colony on the treated discs vs. that on untreated discs. Percent inhibition of growth was calculated and data from such tests appears in Table IV below. TABLE IV (Z Control at (ppm)) Cpd PHY BOT BEF BAF BMS CMS No. (500) (500) (1000) (1000) (250) (250) 1 80 70 85 NT 100 100 2 0 10 NT 100 100 100 3 NT 45 100 NT 100 100 4 85 100 100 100 100 100 5 15 50 100 100 100 100 6 100 80 100 NT 100 100 7 0 10 0 100 100 100 8 10 50 100 100 100 100 9 100 100 100 100 100 100 10 45 50 100 100 100 100 11 95 100 100 100 100 100 12 30 0 100 100 100 100 13 90 100 90 100 100 100 14 90 100 90 100 100 100 15 40 0 0 85 0 0 16 40 100 0 60 25 0 17 45 100 0 NT 0 0 18 15 100 0 100 0 15 19 35 0 0 0 100 100 20 35 25 0 0 85 0 21 0 0 0 0 75 0 22 0 30 0 NT 100 100 23 5 0 o NT 35 0 24 100 100 100 100 100 100 25 60 0 100 100 100 100 26 0 70 0 NT 0* 35* 27 85 100 80 NT 100 100 28 25 0 0 85 0* 40* 29 95 65 40 100 75* 0* TABLE IV - Cont'd (Z Control at (ppm)) Cpd PHY BOT BEF BAF BMS CMS No. (500) (500) (1000) (1000) (250) t250) 30 31 32 100 100 100 100 100 100 33 0 65 100 100 100 100 34 100 100 100 100 0 80 35 10 0 95 85 100 100 36 55 0 0 25 100 100 37 10 0 0 NT O 5 38 100 0 0 NT O 5 39 0 0 0 NT 0 30 40 20 0 0 100 20 65 41 50 15 100 50 0 30 42 50 0 95 65 0 70 43 15 0 O NT 90 0 44 40 10 0 NT O 0 45 65 0 0 NT O 0 46 35 50 0 NT O 0 47 55 0 0 NT 0 75 48 0 0 0 0 0 25** 49 20 15 60 0 0 20 50 0 70 50 NT 100 100 51 35 100 NT 85 0 0 52 25 0 0 100 100 55 53 10 0 0 95 35 35 54 80 100 0 75 100 100 55 0 60 75 15 15 100 56 0 10 95 100 65 100 57 100 100 90 100 100 100 58 60 10 0 100 100 100 59 0 100 100 100 100 100 60 35 0 100 100 100 100 TABLE IV - Cont'd (Z Control at (ppm)) Cpd PHY BOT BEF BAF BMS CMS No. (500) (500) (1000) (1000) (250) (250) 61 62 40 75 50 50 100 100 63 0 25 0 0 15 50 64 100 100 90 100 100 100 65 35 0 0 100 90 100 66 100 100 100 100 100 100 67 0 0 95 20 100 100 68 55 20 75 70 80 100 69 15 0 0 0 30 30 70 100 85 95 100 85 100 71 0 0 100 60 0 70 72 100 95 50 90 100 100 73 50 50 100 85 90 100 Remarks: * Tested at 500 ppm ** Tested on Helminthosporium at 500 ppm The following are the preferred fungicidally active compounds of this invention: Cmpd 9s 1H-1,2,4-triazole, 1-[[2-(4-bromophenyl)-1,3- oxathiolan-2-yllmethyll ss lH-1,3-imidazole, 1-l[2-(4-bromophenyl)-1,3- oxathiolan-2-yl]methyl]; Cmpd 24: 1H-1,2,4-triazole, 1-[[2-[4-(1-methylethoxy)- phenyl]-1,3-oxathiolan-2-yl]methyl]; IH-1,3-imidazole, 1-[[2-[4-(1-methylethoxy)phe- nyl]-1,3-oxathiolan-2-yl]methyl]; Cmpd 32: 1H-1,2,4-triazole, 1-[[2-[2-(pentyloxy)phenyl]- 1,3-oxathiolan-2-yl]methyl]; 1H-1,3-imidazole, 1-[[2-[2-(pentyloxy)phenyl]- 1,3-oxathiolan-2-yl]methyl]; Cmpd 27: 1H-1,2,4-triazole, 1-[(2-[4-(pentyloxy)phenyl]- 1,3-oxathiolan-2-yl]methyl]; 1H-1,3-imidazole, 1-[[2-[4-(pentyloxy)phenyl]- 1,3-oxathiolan-2-yl]methyl]; Cmpd 72: 1H-1,3-imidazole, 1-112-(4-chlorophenyl)-1,3- oxathiolan-2-yl ]methyl; Cmpd 4: 1H-1,2,4-triazole, 1-[12-( 4-fluorophenyl)-1,3 - oxathiolan-2-yl ]methyl; 1H-1,3-imidazole, 1-[[2-(4-fluorophenyl)-1,3- oxathiolan-2-yl]methyl; Cmpd 59: 1H-1,2,4-triazole, 1-112-(4-chlorophenvl)-5- methyl-1,3-oxathiolan-2-yl]methyl; 1H-1,3-imidazole, 1-[[2-(4-chlorophenyi)-5- methyl-1,3-oxathiolan-2-yl]methyl; Cmpd 66: 1H-1,2,4-triazole, 1-[[2-(5-chloro-2-thienyl)- 1,3-oxathiolan-2-yl]methyl; 1H-1,3-imidazole, 1-[[2-(5-chloro-2-thienyl)- 1,3-oxathiolan-2-yl]methyl; Cmpd 64: 1H-1,2,4-triazole, 1-[[2-(5-bromo-2-thienyl)- 1,3-oxathiolan-2-yl]methyl; lH-1,3-imidazole, 1-I [2-(5-bromo-2-thienyl)- 1,3-oxathiolan-2-yl]methyl. The most preferred fungicidally active compounds are: Cmpd 9: lH-1,2,4-triazole, 1-lt2-(4-bromophenyl)-le3 oxathiolan-2-yl ]methyl; 1H-1,3-imidazole, 1-[[2-(4-bromophenyl)-1,3- oxathiolan-2-yl]methyl; Cmpd 32: 1H-1,2,4-triazole, 1-[[2-(2-pentyloxy)phenyll- 1,3-oxathiolan-2-yl]methyl; and lH-1,3-imidazole, 1-[[2-(2-pentyloxy)phenyl)- 1,3-oxathiolan-2-ylAmethyl. EXAMPLE 10 To illustrate the effectiveness of the described compounds as growth regulants, 600 mg of chemical were dissolved in a composition comprising 10 ml acetone to which 30 mg conventional emulsifying agent (e.g., ethoxylated sorbitan monolaurate, Tween 20 [trademark]) were added. This solution was diluted to 200 ml with distilled water, producing a 3000 ppm solution. A 1000 ppm spray solution was also made by appropriate dilution of the 3000 ppm stock solution. The spray solutions were atomized with a DeVilbiss [trademark] No. 152 sprayer, and the foliage of targeted plants was wetted to the drip point. The dosage applied to each plant species is indicated in Table V. The target plants included: soybean, Glycine max (L.) Merr. cv. Williams, 2 ¯ weeks old; cotton, Gossypium hirsutum L. cv. Stoneville 213, 3-4 weeks old; TABLE V Growth Retardation. X (at concentration) Cpd. Bean Cotton Soybean No. (1000 ppm) (3000 ppm) (3000 ppm) 1 25 0 2 0 20 75 3 60 95 80 4 50 30 0 5 50 100 90 6 30 60 0 7 30 20 100 8 95 80 90 9 60 20 80 10 90 100 100 11 50 40 100 12 50 50 100 13 50 0 90 14 50 50 50 15 20 0 0 16 0 0 80 18 0 30 0 19 90 0 0 24 20 0 0 25 10 20 20 26 0 20 0 27 0 0 0 30 90 75 90 31 80 0 0 32 60 .30 30 33 50 100 100 34 90 50 75 54 0 0 30 55 80 50 80 56 50 0 30 57 0 30 90 bean, PE,dseolus vulgaris L. cv. Pinto III, 2 weeks old; After 2-3 weeks in the greenhouse, the plants were scored for retardation of vegetative growth. TABLE Growth Retardation, X (at concentration) Cpd. Bean Cotton Soybean No. (1000 ppm) (3000 ppm) (3000 ppm) 58 0 90 90 59 80 95 100 60 80 75 100 61 62 50 90 50 64 80 30 80 65 0 30 0 66 80 95 100 67 50 50 80 68 0 0 50 72 30 0 0 73 50 0 0 74 25 20 60 76 0 1 20 50 77 0 60 30 78 0 30 80 79 0 10 20 80 0 0 30 81 **50 ***100 82 95 90 0 83 **60 ***50 ***10O 87 0. 90 90 89 80 0 0 90 20 0 20 REMARKS * Tested at 500 ppm ** Tested at 1333 ppm *** Tested at 4000 ppm The preferred plan growth regulating compounds of this invention are the following: Cmpd 8: 1-([2-(4-chlorophenyl)-1,3-oxathiclan-2 yl]methyl)-1H-1,2,4-triazole S,S-dioxide; Cmpd 5: 1-[[2-(4-fluorophenyl)-1,3-oxathiolan-2- yl]methyl)-1H-1,2,4-triazole S,S-dioxide; Cmpd 10: 1-[[2-(4-bromophenyl)-1,3-oxathiolan-2- yl]methyl] -111-,2, 4-triazole S,S-dioxide; Cmpd 30: 1-[[2-(2-ethoxyphenyl)-1,3-oxathiolan-2- yl]methyl)-1H-1,2,4-triazole; Cmpd 33: 1-[[2-(2-pentyloxyphenyl)-1,3-oxathiolan-2- yl]methyl]-lH-1,2,4-triazole S,S-dioxide; Cmpd 59: 1-[[2-(4-chlorophenyl)-5-methyl-1,3- oxathiolan-2-yl]methyl] -1H-1 2 ,4-triazole; Cmpd 60: 1-[[2-(4-chlorophenyl)-5-methyl-l,3- oxathiolan-2-yl]methyl]-1H-1,2,4-triazole S,S-dioxide; and Cmpd 66: 1-[[2-(5-chloro-2-thienyl)-1,3-oxathiolan- 2-yl]methyl]-lH-1,2,4-triazole. EXAMPLE 11 Compound No. 1 was evaluated as a fungicide in comparison to the chemical l-[(2-phenyl-1,3-dithiolan-2- yl)methyl]-lH-1,2,4-triazole (within the disclosure of EPO 61789) following essentially the procedures of Examples 7, 8 and 9, respectively. Whereas both chemicals exhibited essentially the same activity against certain fungi (Sclerotium rolfsii, Fusarium oxysporium, Cercospora arachidicola and phytophthora infestans) the compound of this invention far exceeded the fungicidal efficacy of the prior art chemical against the majority of fungi tested. For results, see Table VI. TABLE VI Fungicidal Control, X, Comparison Prior Art Test Fungus at ppm Cpd. 1 (dithiolane) ALT (1) 500 35 0 BARBLST (2) 1000 10 ¯¯¯ 100 BMS (3) 62 100 66 31 NT 17 12 100 not BOT (4) 500 70 0 BRED (5) 100 50 80 CERC (6) 500 + + CMS (7) 250 100 0 12 100 NT FUS (8) 500 65 65 H-MAY (9) 500 35 65 PHYTOF (10) 20 33 41 PMPRO (11) 1000 85 0 SCLERM (12) 500 25 25 SCLERO (13) 500 35 0 Remarks: (1) Alternaria solani (2) Barley Blast (3) Barley Mildew, systemic (4) Botrytis cenerea (5) Bean rust eradicant (6) Cercospora (7) Cucumber mildew, systemic (8) Fusarium (9) Helminthosporium maydis (10) Phytophthora (11) Barley powdery mildew protectant (12) Sclerotium (13) Sclerotinia NT Not tested at that concentration EXAMPLE 12 Compound No. 6 was evaluated as a fungicide in comparison to the chemical l-[(2-(4-chlorophenyl)-1,3- dioxolan-2-yl)methyl]-lH-1 ,2,4-triazole (within the disclosure of United States Patent 4,160,838) following essentially the procedures of Examples 7, 8 and 9, respectively. Whereas both chemicals exhibited essentially the same activity against certain fungi (barley mildew1 bean rust eradicant, cucumber mildew and sclerotium) the compound of this invention far exceeded the fungicidal efficacy of the prior art chemical against the majority of fungi tested. For results, see Table VII. TABLE VII Fungicidal Control, Z, Comparison Prior Art Test Fungus at ppm Cpd. 6 (dioxolane) ALT 500 45 0 BARBLST 100 100 35 BMS 62 100 100 BOT 500 80 35 BRED 1000 100 100 CERC 500 + CMS 250 100 100 FUS 500 80 50 H-MAY 500 100 35 PHYTOF 20 100 65 PMPRO 1000 100 0 SCLERM 500 50 65 SCLERO 500 55 0 Although the invention has been illus. Ated by the preceding examples, it is not to be construed as being limited to those embodiments, but rather, the invention encompasses the generic area as hereinbefore disclosed. Various modifications and embodiments can be made without departing from the spirit and scope thereof.

Claims: CLAIMS: 1. A compounds characterized ih that it has the formula: EMI51.1 wherein R is C2-C4 alkylene unsubstituted or substituted with C1-C10 alkyl, alkenyl, alkynyl or alkoxyalkyl; R1 is (a) C5-C8 bridged or non-bridged cycloalkyl or cycloalkenyl; (b) phenyl, methylenedioxyphenyl, naph thyl, pyridyl, furanyl or thienyl; the (b) substituents being unsub stituted or substituted with: : C1-C10 alkyl, OH, SH, cyclohexyl, C1-Cl0 haloalkyl, C1-C10 alkenyl, cyano, nitro, XR3 or a single halogen wherein X is O, S, SO or S02 and R3 is Cl-Cl0 alkyl, C1-Cl0 alkenyl, C1-C10 alkoxyal kyl, C1-C6 haloalkyl, C1-C6 haloalkenyl, C5-C6 cycloal kyl, C7-Cg aralkyl; C1-C4 alkylsulfonyloxy, phenylsulfonyloxy, EMI52.1 wherein R4 is C1-C4 alkyl or phenyl; EMI52.2 wherein R5 and R6 are individually H, C1-C4 alkyl or phenyl with the proviso that R5 and R6 are not both H; ; NR7R8 wherein R7 and R8 are individually H or C1-C4 alkyl, This H, R8 is COR9, COOR9 or 9 SO2R wherein R9 is C1-C4 alkyl or phenyl, or R7 and R8 together form C4-C6 alkylene, C4-C6 oxydialkylene or phenylmethylene; R2 is H or C1-C6 alkyl; Y is N or CH; and a n is 0, 1 or 2; and the physiologically acceptable addition salts thereof. 2. A compound according to clai=Aharacterid in that: R is C2 alkylene unsubstituted or substituted with C1-C3 alkyl; R1 is (a) C5-C6 cycloalkyl; (b) unsubstituted phenyl, naphthyl, thienyl; phenyl or thienyl substituted with F, C1, Br, C1-C7 alkyl, XR3 wherein X is O, S, SO or S02 and R3 is 5 C1-C7 alkyl, cyclohexyl; methylsulfonyloxy, phenylsulfonyloxy, dimethylaminocarbonyloxy or NR7R8 wherein R7 and R8 are individually H or C1-C2 alkyl 7 R and R8 together are phenylmethylene and where R7 is H, R8 is methylsulfonyl, phenylsul fonyl or C1-C4 alkyoxycar bonyl; R2 is H; Y is N or CH; and n is Q, 1 or 2. 3. A compound according to claim 1 characterized in that: R is C2 alkylene unsubstituted or substituted with C1-C3 alkyl; R1 is (a) cyclohexyl; (b) unsubstituted phenyl, naphthyl, thienyl; phenyl or thienyl substituted with F, C1, Br, C 1-C7 alkyl or C2-C7 alkoxy; R2 is H; Y is N or CH; and n is 0, 1 or 2. 4. A compound according to claim 1 wherein: R is C2 alkylene unsubstituted or substituted with C1-C3 alkyl; R1 is (a) cyclohexyl; (b) phenyl or thienyl substituted with F, C1, Br, C1-C7 alkyl or C2-C7 alkoxy; R2 is H; Y is N or CH; and n is 0, 1 or 2. 5. A compound characterised in that it is lH-1,2,4-triazole, l-[[2-(4-bromophenyl)-1,3- oxathiolan-2-yl]methyll; lH-1,3-imidazole, 1-[[2-(4bromophenyl)-l,3-oxathiolan-2-yl]methyl); lH-1,2,4triazole, 1-[[2-[4-(l-methylethoxy)phenyl]-l,3- oxathiolan-2-yl]methyl]; lH-1,3-imidazole, 1-[[2-[4 (1-methylethoxy)phenyl]-1,3-oxathiolan-2-yl]methyl]; lH-1,2,4-triazole, 1-[[2-[2-(pentyloxy)phenyl]-1,3- oxathiolan-2-yl]methyl]; lH-1,3-imidazole, 1-[[2-[2- (pentyloxy)phenyl]-1,3-oxathiolan-2-yl]methyl]; lH-1,2,4triazole, 1-[[2-[4-(pentyloxy)phenyl]-1,3-oxathiolan-2- yl)methyl]; lH-1,3-imidazole, 1-[[2-[4-(pentyloxy)phe- nyl]-1,3-oxathiolan-2-yl]methyl]; lH-1,3-imidazole, 1-[[2-(4-chlorophenyl)-1,3-oxathiolan-2-yl]methyl; lH-1,2,4-triazole, 1-[[2-(4-fluorophenyl)-1,3-oxathiolan- 2-yl)inethyl; lH-i,3-iinidazole, 1-[[2-(4-fluorophenyl)- 1,3-oxathiolan-2-yl]methyl; lH-1,2,4-triazole, 1-[[2-(4- chlorophenyl)-5-methyl-1,3-oxathiolan-2-ylZmethyl; lH-1,3-imidazole, 1-[[2-(4-chlorophenyl)-5-methyl-1,3- oxathiolan-2-yl]methyl; lH-1,2,4-triazole, 1-[[2-(5- chloro-2-thienyl)-1,3-oxathiolan-2-yl]methyl; lH-1,3- imidazole, l-[[2-(5-chloro-2-thienyl)-1,3-oxathiolan-2- yl]methyl; lH-1,2,4-triazole, 1-[[2-(5-bromo-2-thienyl)- l,3-oxathiolan-2-yl)methyl; lH-1,3-imidazole, 1-[[2-(5- bromo-2-thienyl)-1,3-4xathiolan-2-yl]methyl. 5. A fungicidal composition characterized in that it comprises an inert carrier and, as an active ingredient, a fungicidally effective amount of a compound as claimed in any of the preceding claims. 6. A growth regulating composition characterized in that it comprises an inert carrier and, as an active ingredient, a growth retardingly effective amount of a triazole as claimed in any of claims 1 to 4. 7. A growth regulating composition characterized in that it comprises an inert carrier and, as the active ingredient, a growth regulatingly effective amount of a compound selected from 1-Z22-(4-chlorophenyl)-1,3- oxathiolan-2-yl]methyl)-lH-l,2,4-triazole S,S-dioxide; 1-[[2-(4-fluorophenyl)-1,3-oxathiolan-2-yl]methyl]-1H-1, 2,4-triazole S,S-dioxide; l-[[2-(4-bromophenyl)-l,3- oxathiolan-2-yl]methyl]-1H-1,2,4-triazole S,S-dioxide; 1-[[2-(2-ethoxyphenyl)-1,3-oxathiolan-2-yl]methyl]-1H- 1,2,4-triazole; 1-112-(2-pentyloxyphenyl)-1,3-oxathi- olan-2-yl]methyl)-lH-1,2,4-triazole S,S-dioxide; 1-[[2 (4-chlorophenyl)-5-methyl-1,3-oxathiolan-2-yl)methyl)-lH- 1,2,4-triazole; 1-[[2-C4-chlorophenyl)-5-methyl-1,3- oxathiolan-2-yl]methyl]-lH-l,2,4-triazole S,S-dioxide; and i-[ [2-(5-chloro-2-thienyl)-l,3-oxathiolan-2- yl]methyl]-1H-1,2,4-triazole. 8. A method of protecting crops from fungicidal attack characterized in that the method comprises treating said crops with an effective amount of a compound as claimed in any of claims 1 to 4. 9. A method for regulating the growth of crops characterized in that the method comprises treating said crops with an effective amount of a triazole as claimed in any of claims 1 to 4. 10. A process for the preparation of a compound as claimed in claim 1 characterized in that the process comprises reacting an azole-ketone of the formula II: EMI56.1 with a mercapto-alcohol of the formula III: HO - R - SH III wherein R, R1, R2 and Y are as set forth in claim 1, cyclizing in the presence of an acid catalyst.

Inventors: BLEM, ALLEN R., DAVIS, ROBERT A., FRIEDLANDER, BARRY T., WALKER, DAVID L.
Applicants: UNIROYAL CHEMICAL COMPANY, INC., UNIROYAL LIMITED
Application year: 1986
Main classification: C07D411
IPC codes: A01N47, C07D327, C07D333, C07D521, A01N43, C07D411, A01P3