US3242040A - Method for controlling fungi with esters of dicarboxylic acids - Google Patents

Method for controlling fungi with esters of dicarboxylic acids Download PDF

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US3242040A
US3242040A US373079A US37307964A US3242040A US 3242040 A US3242040 A US 3242040A US 373079 A US373079 A US 373079A US 37307964 A US37307964 A US 37307964A US 3242040 A US3242040 A US 3242040A
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nitro
acid
weight
butyl
fungicidal
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David J Beaver
Paul J Stoffel
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Monsanto Co
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Monsanto Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/39—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by esterified hydroxy groups
    • C07C205/40—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by esterified hydroxy groups having nitro groups and esterified hydroxy groups bound to acyclic carbon atoms of the carbon skeleton

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  • This invention relates to novel esters of dicarboxylic acids and to the preparation of same. Additionally this invention relates to fungicidal methods and compositions employing at least one ester ofthis invention as an active ingredient.
  • esters of this invention can be represented by the formula wherein A and B are like or unlike nitro substituted alkyl radicals containing 2 to 6 carbon atoms, the nitro substituent of each radical being attached to a carbon atom atleast one carbon atom removedfrom the -O- group to which each is attached as indicated above, and wherein Zis the residue ofa dicarboxylic acid containing 2 to 14 carbon atoms upon removal'of the respective acidic hydroxy radicals (e.g.
  • a dicarboxylic acid containing 2 to 14' carbon atoms as employed herein and in the appended claims is meantto include the various aromatic dicarboxylic acids, the various saturated and unsaturated aliphatic dicarboxylic acids, the various saturated and un saturated cycloaliphatic dicarboxylic acids, etc., containing 2 to 14 carbon atoms and includes phthalic acid, isophthalic acid, terephthalic acid, the various homophthalic acids such as 1,2-homophthalic acid; the various phenylenediacetic acids such as p-phenylenediac'etic acid, 0- phenyleneacetic-b-propionic acid [or Z-(hydroxycarbonylmethyl) hydrocinnamic acid], S-methylisophthalic acid, S-ethylisophthalic acid, -isopropylisophthalic acid, 4- methylisophthalic acid, 4'-methylterephthalic acid, 2,5-dimethylterephthalic acid,
  • the nitro substituted alkyl radicals of the esters of this invention contain from 2 to 6 carbon atoms and as representative thereof are 2-nitroethyl, 2-nitropropyl, 3- nitropropyl, 2-nitro-n-butyl, 3-nitro-n-butyl, 4-nitro-nbutyl, 2-nitro-n-amyl, 3-nitro-n-amyl, Z-nitronhexyl, 6- nitro-n-hexyl, 2-nitro-2-methylpropyl, 2-nitro-2-methyl-n butyl, 1-nitro-2-n-butyl, 2-nitro-3-hexyl, etc., and the various isomers and homologues thereof containing 2 to 6 carbon atoms wherein the nitro substituent is attached to a carbon atom at least one carbon atom removed from the oxy group of the carbonyloxy group to which the nitroalkyl radicalis attached.
  • theZ-nitro substituted primary alkyl radicals of the formula wherein m is an integer from- 0 to 3 are
  • novel esters of this invention can be prepared by reacting the appropriate acid halide (bromide or and preferably chloride) with the appropriate nitroalkanol (i.e., AOH or B-OH or mixture thereof wherein A and B have the aforedescribed significance).
  • This reaction is exothermic and the by-product hydrogen halide evolves and is drawn off via a venting means. While a wide range of reaction temperatures can be employed in general it will be conducted in the range of 20 C. to 120 C. Where and when desired an inert organic solvent can be used, although such in general is not necessary.
  • the desired product is a bis-ester (i.e., A and B are alike) at least two mols of the nitroalkanol will be used per mol of the acid halide.
  • the desired product is a mixed ester (i.e., A and B are unlike) initially one mol of the acid halide will be reacted with one mol of the nitroalkanol (e.g., AOH) and the half ester so'obtained reacted with an equimolecular amount of another nitroalkanol (e.g., BOT-I).
  • Example 1 To a suitable reaction vessel equipped with a thermometer, agitator and off-gas tube is charged 2318 parts by weight (substantially 0.2 mol) of 2-nitro-n-butanol. At room temperature and while agitating is added dropwise 15.5 parts by Weight (substantial-1y 0.1 mol) of succinyl chloride. The temperature rises to about 50 C. during the addition and the evolving hydrogen chloride is vented off through the off-gas tube. The reaction mass is then heated to about 80 C. and held at that temperature for about 3 hours. The reaction product is then cooled to room temperature, taken up with about parts by weight of diethyl ether, and washed twice with water. The sowashed organic solution is then dried over anhydrous calcium chloride.
  • the so-dried organic solution is then evaporated under vacuum to remove the low-boiling volatiles and then fractionally distilled to about 175 C. at 1.3 mm. Hg.
  • the residue, 17.5 par-ts by Weight of a syrupy liquid, remaining in the still pot is di(2-nitro-nbutyl) succinate.
  • Example II Employing the procedure of Example I but replacing 2-nitro-n-butanol with an equimolecular amount of 2- nitroethanol there is obtained di(2-nitroethyl) succinate.
  • Example lIl Employing the procedure of Example I but replacing 2-r1itro-n-butanol with an equimolecular amount of 3- nitro-propanol there is obtained di(3-nitropropyl) succinate.
  • Example IV To a suitable reaction vessel equipped with a thermometer, agitator and off-gas tube is charged 23.8 parts by weight (substantially 0.2 mol) of 2-nitro-n-butanol. At room temperature and While agitating there is added dropwise 20.3 parts by weight (substantially 0.1 mol) of phthalyl chloride. The temperature rises to about 50 C. during the addition and the evolving hydrogen chloride is vented off through the oil-gas tube. The reaction mass is then heated to about 75 C. and held at that temperature for about 4 hours. The reaction product is then cooled to room temperature, taken up with about 75 parts by weight of diethyl ether, then washed twice with water. The so-washed organic solution is then dried over anhydrous calcium chloride.
  • the so-dried organic solution is then evaporated under vacuum to remove the low-boiling volatiles and then fractionally distilled to about 180 C. at 1.9 mm. Hg.
  • the residue, 20 parts by weight of a syrupy liquid, remaining in the still pot is di(2-nitro-n-butyl) phthalate.
  • Example VI To a suitable reaction vessel equipped with a thermometer, agitator and off-gas tube is charged 23.8 parts by weight (substantially 0.2 mol) of 2-nitro-n-butanol. At room temperature and while agitating is added dropwise 18.3 parts by Weight (substantially 0.1 mol) of adipyl chloride. The temperature rises to about 50 C. during the addition and the evolving hydrogen chloride is vented off through the oflY-gas tube. The reaction mass is then heated to about 7580 C. and held at that temperature for about 4 hours. The reaction product is then cooled to room temperature, taken up with about 75 parts by weight of diethyl ether, and Washed twice with water. The so-washed organic solution is then dried over anhydrous calcium chloride.
  • the so-dried organic solution is then evaporated under vacuum to remove the low boiling volatiles and then fractionally distilled up to 200 C. at 1.9 mm. Hg.
  • the residue, 21.5 parts by weight of a syrupy liquid, is di(2-nitro-n-butyl) adipate.
  • Example VII Employing the procedure of Example VI but replacing 2-nitro-n-'butanol with an equimolecular amount of 2 nitroethanol there is obtained di(2-nitroethyl) adipate.
  • Example VIII Employing the procedure of Example VI but replacing 2-nitro-n-buta11o1 with an equimolecular amount of 2- 4 nitro-n-pentanol there is obtained di(2-nitro-n-pentyl) adipate.
  • Example IX To a suitable reaction vessel equipped with a thermometer, agitator and off-gas tube is charged 35.7 parts by weight (substantially 0.3 mol) of 2-nitro-n-butanol. At 35-40 C. and while agitating is added dropwise 23.0 parts by weight (substantially 0.15 mol) of fumaryl chloride. Hydrogen chloride evolves freely during the addition and is vented off through the off-gas tube. The reaction mass is water-cooled throughout the addition. The mass upon completion of the chloride addition is heated to about 70 C. and held at that temperature for about 2 hours. The reaction mass is cooled to room temperature, taken up with about parts by weight of diethyl ether, and Washed twice with water.
  • the organic layer is separated and dried over anhydrous calcium chloride.
  • the so-dried organic solution is then evaporated in vacuum to remove the low boiling volatiles and then fractionally distilled to C. at 1.5 mm. Hg.
  • the residue, 25.4 parts by weight of an oil, is di(2nitro-nbutyl) ifumarate.
  • Example X Employing the procedure of Example IX but replacing fum'aryl chloride with an equimolecular amount of tetraethylsuccinyl chloride there is obtained di(2-nitro-n-butyl) tetraethylsuccinate.
  • Example XI To a suitable reaction vessel equipped with a thermometer, agitator and off-gas tube is charged 35.7 parts by weight (substantially 0.3 mol) of 2-nitro-n-but-anol. At 3540 C. and while agitating is added dropwise 19.0 parts by weight (substantially 0.15 mol) of oxalyl chloride. Hydrogen chloride evolves freely during the addition and is vented off through the off-gas tube. The reaction mass is water-cooled throughout the chloride addition. The reaction mass upon completion of the chloride addition is heated up to 75 C. and held at that temperature for 4 hours. The reaction mass is then cooled to room temperature, taken up with 110 parts by weight of diethyl ether, and Washed twice with water.
  • the S0 Washed organic solution is dried over anhydrous calcium chloride.
  • the so-dried organic solution is then evaporate under vacuum to remove the low boiling volatiles and then fractionally distilled to C. at 1.5 mm. Hg.
  • the residue is then recrystallized from methanol yielding 13 parts by Weight of white crystalline di(2-nitro-nbutyl) oxalate.
  • Example XII Employing the procedure of Example XI but replacing oxalyl chloride with an equimolecular amount of dodecane-1,12-dicarboxylic acid chloride there is obtained di(2- nitro-n-butyl) dodecane-1,12-dicarboxylate.
  • Example XIII To a suitable reaction vessel equipped with a thermometer, agitator and oil-gas tube is charged 23.8 parts by Weight (substantially 0.2 mol) of 2-nitro-n-butanol. At about 40 C. and with agitation is added dropwise 20.3 parts by Weight (substantially 0.1 mol) of terephthalyll chloride. The reaction mass is then heated up to 90 C. and held at that temperature for about 6 hours, the evolv-- ing hydrogen chloride being vented oil through the oil-gas. tube. The reaction mass is cooled to room temperature,, taken up with about 75 parts by weight of diethyl ether, and then Washed three times with water. The organic; solution is then dried over calcium chloride. The so-. dried solution is then evaporated under vacuum to remove, the low-boiling volatiles. The solid residue upon recrys 5 tallizing from methanol yields 32 parts by weight of di(2- nitro-n-butyl) terephthalate.
  • Example XIV Employing the procedure of Example XIII but replacing terephthalyl chloride with an equimolecular amount of cyclohexane-1,4-dicarboxylic acid chloride there is obtained di(2-nitro-n-butyl) cyclohexane-l,4-dicarboxylate.
  • Example XV To a suitable reaction vessel equipped with a thermometer, agitator and off-gas tube is charged 23.8 parts by weight (substantially 0.2 mol) of Z-nitro-n-butanol. At about 40 C. and with agitation is added dropwise 23.9 parts by weight (substantially 0.1 mol) of sebacyl chloride. Upon cessation of the hydrogen chloride evolution, the reaction mass is heated at 6070 C. for 2 hours. The reaction mass is cooled to room temperature, taken up with 75 parts by weight of diethyl ether, and washed twice with water. The so-washed organic solution is then dried over anhydrous calcium chloride.
  • the so-dried organic solution is then evaporated under vacuum to remove the low boiling volatiles and then fractionally distilled up to 150 .C. at 1.0 mm. Hg.
  • the residue, 29.8 parts by weight of an oil, is di(2-nitro-n-butyl) sebacate.
  • Example XVII Employing the procedure of Example XVI but replacing 2-nitro-n-butanol with an equimolecular amount of Z-nitroeth-anol there is obtained di(2-nitroethyl) sebacate.
  • Example XVIII Employing the procedure of Example XVI but replacing 2-n-itro-n-butanol with an equimolecular amount of Z-nitro-n-hexanol there is obtained di(Z-nitro-n-hexyl) sebacate.
  • esters of this invention are useful in .combatting a large variety of fungal organisms. They are particularly effective when applied directly to soil for controlling soil borne pathogenic fungi. To illustrate the fungicidal activity of the esters ofv this invention but not limitative thereof is the following.
  • the ester to be evaluated (itemized below) is dissolved in suflicient acetone to make a 1% by weight solution and then diluted with water to provide a formulation having a concentration of 0.1% by weight.
  • suflicient acetone to make a 1% by weight solution
  • water to provide a formulation having a concentration of 0.1% by weight.
  • a 2 B 3 C 2 D 3 E 4 G 2 In still another evaluation, 1000 grams of a top soilsand-cornmeal blend is prepared as immediately above. The blend is placed in a Hobart food mixer, and acetonewater-ester formulations are sprayed into the :blend as the latter is being mixed to provide a concentration of ester of 30 ppm. The treated blend is placed in plastic pots, seeded as immediately above, and kept in a greenhouse at 70 F. to await germination. Using the same rating code as in the immediately preceding evaluation, the results are:
  • novel fungicidal agents of this invention are useful per se in controlling a wide variety of fungal organisms, it is preferable that they be supplied to the organisms or to the environment of the organisms in a dispersed form in a suitable extending agent.
  • dispersed is used in its widest possible sense.
  • the particles of the fungicidal agents of this invention may be molecular in size and held in true solution in a suitable organic solvent. It means further, that the particles may be colloidal in size and distributed throughout a liquid phase in the form of suspensions or emulsions or in the form of particles held in suspension by wetting agents.
  • It also includes particles which are distributed in a semisolid viscous carrier such as petrolatum or soap or other ointment base in which they may be actually dissolved in the semi-solid or held in suspension in the semi-solid with the aid of suitable wetting or emulsifying agents.
  • a semisolid viscous carrier such as petrolatum or soap or other ointment base
  • the term dispersed also means that the particles may be mixed with and distributed throughout a solid carrier providing a mixture in particulate form, e.g. pellets, granules, powders, or dusts.
  • dispersed also includes mixtures which are suitable for use as aerosols including solutions, suspensions, or emulsion of the fungicidal agents of this invention in a carrier such as dichlorodifluoromethane and like fiuorochloroalkanes which boil below room temperature at atmospheric pressure.
  • a carrier such as dichlorodifluoromethane and like fiuorochloroalkanes which boil below room temperature at atmospheric pressure.
  • the expression extending agent includes any and all of those substances in which the fungicidal agents of this invention are dispersed. It includes, therefore, the solvents of a true solution, the liquid phase of suspensions, emulsions or aerosols, the semi-solid carrier of ointments and the solid phase of particulate solids, e.g., pellets, granules, dusts and powders.
  • concentration of the fungicidal agents of this invention employed in combatting or controlling fungal organisms can vary considerably provided the resuired dosage (i.e., toxic or lethal amount) thereof is supplied to the organisms or to the environment of the organisms.
  • the extending agent is a liquid or mixture of liquids (eg as in solutions, suspensions, emulsions, or aerosols) the concentration of the fungicidal agent employed to supply the desired dosage generally will be in the range of 0.001 to 50 percent by weight.
  • concentration of the fungicidal agent employed to supply the desired dosage generally will be in the range of 0.1 to 25 percent by weight.
  • the manufacturer must supply the agriculturist with a lowcost concentrate or spray base or particulate solid base in such form that, by merely mixing with water or solid extender (e.g., powdered clay or talc) or other low-cost material available to the agriculturist at the point of use,
  • water or solid extender e.g., powdered clay or talc
  • the fungicidal agent generally will be present in a concentration of 5 to 95 percent by weight, the residue being any one or more of the well-known fungicidal adjuvants, such as the various surface active agents (e.g., detergents, a soap or other emulsifying or wetting agent, surface-active clays), solvents, diluents, carrier media, adhesives, spreading agents, humectants, and the like.
  • the various surface active agents e.g., detergents, a soap or other emulsifying or wetting agent, surface-active clays
  • solvents e.g., diluents, carrier media, adhesives, spreading agents, humectants, and the like.
  • organic liquids which can be used for the preparation of solutions, suspensions, or emulsions of the fungicidal agents of this invention.
  • organic liquids for example, isopropyl ether, acetone, methyl ethyl ketone, dioxane, cyclohexanone, carbon tetrachloride, ethylene dichloride, tetrachloroethane, hexane, heptane and like higher liquid alkanes, hydrogenated naphthalenes, solvent naphtha, benzene, toluene, xylene, petroleum fractions (e.g., those boiling almost entirely under 400 F., at atmospheric pressure and having a flash point above about F., particularly kerosene), mineral oils having an unsulfonatable residue above about 80 percent and preferably above about percent.
  • organic liquid extending agent a portion of same can be replaced by such low molecular weight aliphatic hydrocarbons as dipentene, diisobutylene, propylene trimer, and the like or suitable polar organic liquids such as the aliphatic ethers and the aliphatic ketones containing not more than about 10 carbon atoms as exemplified by acetone, methyl ethyl ketone, diisobutyl ketone, dioxane, isopropyl ether, and the like.
  • suitable polar organic liquids such as the aliphatic ethers and the aliphatic ketones containing not more than about 10 carbon atoms as exemplified by acetone, methyl ethyl ketone, diisobutyl ketone, dioxane, isopropyl ether, and the like.
  • fungicidal agents of this invention When the fungicidal agents of this invention are to be supplied to the fungal organisms or to the environment of the organisms as aerosols, it is convenient to dissolve them in a suitable solvent and disperse the resulting solution in dichlorodifluoromethane or like chlorofiuoroalkane which boils below room temperature at atmospheric pressure.
  • the fungicidal agents of this invention are preferably supplied .to the fungal organisms or to the environment of the organisms in the form of emulsions or suspensions.
  • Emulsions or suspensions are prepared by dispersing one or more fungicidal agents of this invention either per se or in the form of an organic solution thereof in water with the aid of a water-soluble surfactant.
  • surfactant as employed here and in the appended claims is used as in volume II of Schwartz, Perry and Berchs Surface Active Agents and Detergents" (1958, Interscience Publishers, Inc., New York) in place of the expression emulsifying agent to connote generically the various emulsifying agents, dispersing agents, wetting agents and spreading agents that are adapted to be admixed with the fungicidal agents of this invention in order to secure better wetting and spreading of the active ingredients in the water vehicle or carrier in which they are insoluble throng-h lowering the surface tension of the water (see also Frear, Chemistry of Insecticides, Fungicides and Herbicides, second edition, page 280).
  • surfactants include the wellknown capillary-active substances which may be anionactive (or anionic), cation active (or cationic), or nonionizing (or non-ionic) which are described in detail in Volume I and II of Schwartz, Perry and Berchs Surface Active Agents and Detergents (1958, Interscience Publishers, Inc., New York), and also in the November 1947 issue of Chemical Industries (pages 811-824), in an article entitled, Synthetic Deter-gents by John W. McCutcheon and also in the July, August, September and October 1952 issues of Soap and Sanitary Chemicals under the title, Synthetic Detergents.
  • anionactive or anionic
  • cation active or cationic
  • nonionizing or non-ionic
  • surfactants i.e., the anion active, cation-active and non-ionizing capillary active substances
  • the preferred surfactants are the watersoluble anionic surface-active agents and the water soluble non-ionic surface-active agents set forth .in US. 2,846,398 (issued August 5, 1958). In general it is preferred that a mixture of water-soluble anionic and watersoluble non-ionic surfactants be employed.
  • the fungicidal agents of this invention can be dispersed by suitable methods (e.g., tumbling or grinding) in solid extending agents either of organic or inorganic nature and supplied to the fungal organisms environment in particulate form.
  • solid materials include for example, tricalcium phosphate, calcium carbonate, kaolin, bole, kieselguhr, talc, bentonite, fullers earth, pyrophillite diatomaceous earth, calcined magnesia, volcanic ash, sulfur and the like inorganic solid materials, and include, for example, such materials of organic nature as powdered cork, powdered wood, and powdered walnut shells.
  • the preferred solid carriers are the adsorbent clays, e.g., bentonite.
  • mixtures can be used for fungicidal purposes in the dry form, or, by addition of water-soluble surfactants or wetting agents the dry particulate solids can be rendered wettable by water so as to obtain stable aqueous dispersions or suspensions suitable for use as sprays.
  • the fungicidal agents of this invention can be dispersed in a semi-solid extending agent such as petrolatum or soap (e.g., sodium stearate or oleate or palmitate or mixtures thereof) with or without the aid of solubility promoters and/ or surfactants or dispersing agents.
  • a semi-solid extending agent such as petrolatum or soap (e.g., sodium stearate or oleate or palmitate or mixtures thereof) with or without the aid of solubility promoters and/ or surfactants or dispersing agents.
  • the dispersions can be provided ready for use in combatting fungal organisms or they can be provided in a concentrated form suitable for mixing with or dispersing in other extend-ing agents.
  • a particularly useful concentrate is an intimate mixture of one or more fungicidal agents of this invention with a water-soluble surfactant which lowers the surface tension of water in the weight proportions of 0.1 to 15 parts of surfactant with sufiic'ient of the fungicidal agent of this invention to make 100 parts by weight.
  • Such a concentrate is particularly adapted to be made into a spray for combatting various forms of fungal organisms by the addition of water thereto.
  • Such a concentrate is an intimate mixture of 95 parts by weight of di(2-nitro-nbutyl) sebacate and 5 parts by weight of a water-soluble non-ionic surfactant such as the polyoxyethylene derivative of sorbitan monolaurate.
  • Another useful concentrate adapted to be made into a spray for combatting fungal organisms is a solution (preferably as concentrated as possible) of one or more fungicidal agents of this invention in an organic solvent therefor.
  • the said liquid concentrate preferably contains dissolved therein a minor amount (e.g., 0.5 to 10 percent by weight of the weight of the new fungicidal agent) of a surfactant (or emulsifying agent), which surfactant is also water-soluble.
  • Such a concentrate is a solution of di(2-nitro-n-butyl) adipate in acetone which solution contains dissolved therein a water-soluble polyoxyethylene glycol non-ionic surfactant and a water-soluble alkylaryl sulfonate anionic surfactant.
  • a water-soluble polyoxyethylene glycol non-ionic surfactant a water-soluble polyoxyethylene glycol non-ionic surfactant and a water-soluble alkylaryl sulfonate anionic surfactant.
  • anionic and non-ionic surfactants are preferred.
  • the particularly preferred are the well-known watersoluble alkali metal alkylaryl sulfonates as exemplified by sodium decylbenzene sulfonate and sodium dodecylbenzene sulfonate.
  • the particularly preferred are the water-soluble polyoxyethylene derivatives of alkylphenols (particularly isooctylphenol) and the water-soluble polyoxyethylene derivatives of the mono-higher fatty acid esters of hexitol anhydrides such as mannitan or sorbitan.
  • the active ingredients can be one or more of the compounds of this invention.
  • the compounds of this invention can also be advantageously employed in combination with other pesticides, including, for example, insecticides, nematocides, bacterocides, and herbicides. In this manner it is possible to obtain mixtures which are effective against a wide variety of pests and other forms of noxious life.
  • the fungicidal agents of this invention either per se or compositions comprising same are supplied to the fungal or- 'ganisms or to their environment in a lethal or toxic amount. This can be done by dispersing the new fungicidal agent or fungicidal composition. comprising same in, on or over an infested environment or in, on or over an environment the fungal organisms frequent, e.g., agricultural soil or other growth media or other media infested with the fungal organisms or attractable to the organisms for habitational or sustenance or propagational purposes, in any conventional fashion which permits contact between the organisms and the fungicidal agents of this invention.
  • Such dispersing can be brought about by applying the fungicidal agent per se or sprays or particulate solid compositions containing same to a surface infested with the fungal organisms or attractable to the organisms, as for example, the surface of agricultural soil or other media such as the above ground surface of plants by any of the conventional methods, e.g., power dusters, boom and hand sprayers, and spray dusters.
  • such dispersing can be carried out by simply mixing the new fungicidal agent per se or fungicidal spray or particulate solid compositions comprising same with the infested environment or with the environment the fungal organisms frequent, or by employing a liquid carrier for the new fungicidal agent to accomplish subsurface penetration and impregnation therein.
  • the method which comprises applying to fungal organisms and their horticultural habitats at least one ester of the formula AOZO-B wherein A and B are nitro substituted alkyl radicals containing 2 to 6 carbon atoms, the nitro substituent of each radical being attached to a carbon atom at least one carbon atom removed from the -O group to which it is attached as indicated above, and wherein Z is the residue of a dicarboxylic acid upon removal of the respective acidic hydroxyl radicals, said dicarboxylic acid containing 2 to 14 carbon atoms.
  • a and B are nitro substituted alkyl radicals containing 2 to 6 carbon atoms, the nitro substituent of each radical being attached to a carbon atom at least one carbon atom removed from the -O group to which it is attached as indicated above, and wherein Z is the residue of a dicarboxylic acid upon removal of the respective acidic hydroxyl radicals, said dicarboxylic acid containing 2 to 14 carbon atoms.
  • the method which comprises applying to fungal organisms and their horticultural habitates at least one ester of the formula AO-ICIR(" ⁇ JO-IB o 0 wherein A and B are 2-nitro substituted primary alkyl radicals of the formula --OI-IzC
  • a and B are 2-nitro substituted primary alkyl radicals of the formula OI-Ia-(IJH(OHz)mH wherein m is an integer from 0 to 3, inclusive, and wherein R is a straight chain divalent aliphatic hydrocarbon radical of the empirical formula (CH wherein x is a whole number from 4 to 8, inclusive.

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Description

United States Pate 3,242,040 METHDDFQR CQNTRGLLING FUNGI WITH ESTERS F DHIARB'QXYLHG AtIlDS David J. Beaver, Richmond Heights, and Paul J..Stotfel, St. Louis, Mo., assignors to Monsanto Company, St. Louis, Mo., a corporation ofDelaware No Drawing.
No. 111,451. Divided and this application June 5, 1964, Ser. N0.373,079
4 Claims. (Cl. 167-22) This application is a divisioniof our Serial No. 111,451, filed May 22, 1961, now abandoned.
This invention relates to novel esters of dicarboxylic acids and to the preparation of same. Additionally this invention relates to fungicidal methods and compositions employing at least one ester ofthis invention as an active ingredient.
In accordance with this invention it has been found that uponapplication to fungal organisms and/or their horticultural habitats at least one ester ofthis invention effective control thereof is obtained. The esters of this invention can be represented by the formula wherein A and B are like or unlike nitro substituted alkyl radicals containing 2 to 6 carbon atoms, the nitro substituent of each radical being attached to a carbon atom atleast one carbon atom removedfrom the -O- group to which each is attached as indicated above, and wherein Zis the residue ofa dicarboxylic acid containing 2 to 14 carbon atoms upon removal'of the respective acidic hydroxy radicals (e.g.
is the residue of the dicarboxylic acid succinic acid).
By the expression a dicarboxylic acid containing 2 to 14' carbon atoms as employed herein and in the appended claims is meantto include the various aromatic dicarboxylic acids, the various saturated and unsaturated aliphatic dicarboxylic acids, the various saturated and un saturated cycloaliphatic dicarboxylic acids, etc., containing 2 to 14 carbon atoms and includes phthalic acid, isophthalic acid, terephthalic acid, the various homophthalic acids such as 1,2-homophthalic acid; the various phenylenediacetic acids such as p-phenylenediac'etic acid, 0- phenyleneacetic-b-propionic acid [or Z-(hydroxycarbonylmethyl) hydrocinnamic acid], S-methylisophthalic acid, S-ethylisophthalic acid, -isopropylisophthalic acid, 4- methylisophthalic acid, 4'-methylterephthalic acid, 2,5-dimethylterephthalic acid, the various phenylene-dipropionic acids such as p-phenylenedipropionic acid, the various phenylenediisobutyric acids such as p-phenylenediisobutyric acid, the various diaryl-dicarboxylic acids such as diphenic acid and 3,3'-dimethyl-diphenyl-4,4-dicarboxylic acid, the various cycloaliphatic dicarboxylic acids such-as cis and trans cyclopropanedicarboxylic acid and cis and trans cyclohexane-1,4-dicarboxy1ic acid, oxalic acid, malonic acid, methylmalonic acid,.dimethylmalonic acid, n-butylmalonic acid, succinic acid, methylsuccinic acid, sym-dirnethylsuccinic acid, isobutylsuccinic acid, phenylsuccinic acid, benzylsuccinic acid, tetramethylsuccinic acid, glutaric' acid, a-methylglutaric acid, adipic acid, a-ethyladipic acid, pirnelic acid, a-methylpimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, fumaric acid, maleic acid, citraconic acid, niesaconic acid, itaconic acid, glutaconic acid, muconic acid, glutinic acid, etc., and the various isomeric and homologous dicarboxyl substituted hydrocarbon forms thereof containing 2 to 14 carbon flriginal application May 22, 1961, Ser."
3,242,640 Patented Mar. 22, 1966 atoms. Ofthese dicarboxylic acids those which upon removal of the respective acidic hydroxyl radicalsthereof yield the residue C R C II II o 0 wherein R is a divalent aliphatic hydrocarbon radical (either branched or straight chain) having the empirical formula C H wherein n is a whole number from 2 to 10, inclusive, are a particularly effective class of substituents for purposes of this invention and of this class those residues wherein R is a straightchain divalent aliphatic hydrocarbon radical having the empirical formula (CH wherein x is a whole number from 4 to 8, inclusive, provide a particularly useful group of substituents for purposes of this invention.
The nitro substituted alkyl radicals of the esters of this invention contain from 2 to 6 carbon atoms and as representative thereof are 2-nitroethyl, 2-nitropropyl, 3- nitropropyl, 2-nitro-n-butyl, 3-nitro-n-butyl, 4-nitro-nbutyl, 2-nitro-n-amyl, 3-nitro-n-amyl, Z-nitronhexyl, 6- nitro-n-hexyl, 2-nitro-2-methylpropyl, 2-nitro-2-methyl-n butyl, 1-nitro-2-n-butyl, 2-nitro-3-hexyl, etc., and the various isomers and homologues thereof containing 2 to 6 carbon atoms wherein the nitro substituent is attached to a carbon atom at least one carbon atom removed from the oxy group of the carbonyloxy group to which the nitroalkyl radicalis attached. Of this class theZ-nitro substituted primary alkyl radicals of the formula wherein m is an integer from- 0 to 3 are a particularly economical group of substituents for purposes of this invention.
The novel esters of this invention can be prepared by reacting the appropriate acid halide (bromide or and preferably chloride) with the appropriate nitroalkanol (i.e., AOH or B-OH or mixture thereof wherein A and B have the aforedescribed significance). This reaction is exothermic and the by-product hydrogen halide evolves and is drawn off via a venting means. While a wide range of reaction temperatures can be employed in general it will be conducted in the range of 20 C. to 120 C. Where and when desired an inert organic solvent can be used, although such in general is not necessary. When the desired product is a bis-ester (i.e., A and B are alike) at least two mols of the nitroalkanol will be used per mol of the acid halide. When the desired product is a mixed ester (i.e., A and B are unlike) initially one mol of the acid halide will be reacted with one mol of the nitroalkanol (e.g., AOH) and the half ester so'obtained reacted with an equimolecular amount of another nitroalkanol (e.g., BOT-I).
As illustrative of the preparation of the novel esters. of this invention but not limitative thereof is the following:
Example 1 To a suitable reaction vessel equipped with a thermometer, agitator and off-gas tube is charged 2318 parts by weight (substantially 0.2 mol) of 2-nitro-n-butanol. At room temperature and while agitating is added dropwise 15.5 parts by Weight (substantial-1y 0.1 mol) of succinyl chloride. The temperature rises to about 50 C. during the addition and the evolving hydrogen chloride is vented off through the off-gas tube. The reaction mass is then heated to about 80 C. and held at that temperature for about 3 hours. The reaction product is then cooled to room temperature, taken up with about parts by weight of diethyl ether, and washed twice with water. The sowashed organic solution is then dried over anhydrous calcium chloride. The so-dried organic solution is then evaporated under vacuum to remove the low-boiling volatiles and then fractionally distilled to about 175 C. at 1.3 mm. Hg. The residue, 17.5 par-ts by Weight of a syrupy liquid, remaining in the still pot is di(2-nitro-nbutyl) succinate.
Analysis-Theory 8.75% N. Found 8.4% N.
Example II Employing the procedure of Example I but replacing 2-nitro-n-butanol with an equimolecular amount of 2- nitroethanol there is obtained di(2-nitroethyl) succinate.
Example lIl Employing the procedure of Example I but replacing 2-r1itro-n-butanol with an equimolecular amount of 3- nitro-propanol there is obtained di(3-nitropropyl) succinate.
Example IV To a suitable reaction vessel equipped with a thermometer, agitator and off-gas tube is charged 23.8 parts by weight (substantially 0.2 mol) of 2-nitro-n-butanol. At room temperature and While agitating there is added dropwise 20.3 parts by weight (substantially 0.1 mol) of phthalyl chloride. The temperature rises to about 50 C. during the addition and the evolving hydrogen chloride is vented off through the oil-gas tube. The reaction mass is then heated to about 75 C. and held at that temperature for about 4 hours. The reaction product is then cooled to room temperature, taken up with about 75 parts by weight of diethyl ether, then washed twice with water. The so-washed organic solution is then dried over anhydrous calcium chloride. The so-dried organic solution is then evaporated under vacuum to remove the low-boiling volatiles and then fractionally distilled to about 180 C. at 1.9 mm. Hg. The residue, 20 parts by weight of a syrupy liquid, remaining in the still pot is di(2-nitro-n-butyl) phthalate.
Analysis.Theory 7.62% N. Found 7.6% N.
Example V,
Employing the procedure of Example' -IV but replacing phthalyl chloride with an equimolecular amount of pphenylenediacetylchloride there is obtained di(2-nitro-nbutyl) p-phenylenedi'acetate.
Example VI To a suitable reaction vessel equipped with a thermometer, agitator and off-gas tube is charged 23.8 parts by weight (substantially 0.2 mol) of 2-nitro-n-butanol. At room temperature and while agitating is added dropwise 18.3 parts by Weight (substantially 0.1 mol) of adipyl chloride. The temperature rises to about 50 C. during the addition and the evolving hydrogen chloride is vented off through the oflY-gas tube. The reaction mass is then heated to about 7580 C. and held at that temperature for about 4 hours. The reaction product is then cooled to room temperature, taken up with about 75 parts by weight of diethyl ether, and Washed twice with water. The so-washed organic solution is then dried over anhydrous calcium chloride. The so-dried organic solution is then evaporated under vacuum to remove the low boiling volatiles and then fractionally distilled up to 200 C. at 1.9 mm. Hg. The residue, 21.5 parts by weight of a syrupy liquid, is di(2-nitro-n-butyl) adipate.
Analysis.Theory 8.05% N. Found 7.96% N.
Example VII Employing the procedure of Example VI but replacing 2-nitro-n-'butanol with an equimolecular amount of 2 nitroethanol there is obtained di(2-nitroethyl) adipate.
Example VIII Employing the procedure of Example VI but replacing 2-nitro-n-buta11o1 with an equimolecular amount of 2- 4 nitro-n-pentanol there is obtained di(2-nitro-n-pentyl) adipate.
Example IX To a suitable reaction vessel equipped with a thermometer, agitator and off-gas tube is charged 35.7 parts by weight (substantially 0.3 mol) of 2-nitro-n-butanol. At 35-40 C. and while agitating is added dropwise 23.0 parts by weight (substantially 0.15 mol) of fumaryl chloride. Hydrogen chloride evolves freely during the addition and is vented off through the off-gas tube. The reaction mass is water-cooled throughout the addition. The mass upon completion of the chloride addition is heated to about 70 C. and held at that temperature for about 2 hours. The reaction mass is cooled to room temperature, taken up with about parts by weight of diethyl ether, and Washed twice with water. The organic layer is separated and dried over anhydrous calcium chloride. The so-dried organic solution is then evaporated in vacuum to remove the low boiling volatiles and then fractionally distilled to C. at 1.5 mm. Hg. The residue, 25.4 parts by weight of an oil, is di(2nitro-nbutyl) ifumarate.
Analysis-Theory 8.8% N. Found 8.93% N.
Example X Employing the procedure of Example IX but replacing fum'aryl chloride with an equimolecular amount of tetraethylsuccinyl chloride there is obtained di(2-nitro-n-butyl) tetraethylsuccinate.
Example XI To a suitable reaction vessel equipped with a thermometer, agitator and off-gas tube is charged 35.7 parts by weight (substantially 0.3 mol) of 2-nitro-n-but-anol. At 3540 C. and while agitating is added dropwise 19.0 parts by weight (substantially 0.15 mol) of oxalyl chloride. Hydrogen chloride evolves freely during the addition and is vented off through the off-gas tube. The reaction mass is water-cooled throughout the chloride addition. The reaction mass upon completion of the chloride addition is heated up to 75 C. and held at that temperature for 4 hours. The reaction mass is then cooled to room temperature, taken up with 110 parts by weight of diethyl ether, and Washed twice with water. The S0 Washed organic solution is dried over anhydrous calcium chloride. The so-dried organic solution is then evaporate under vacuum to remove the low boiling volatiles and then fractionally distilled to C. at 1.5 mm. Hg. The residue is then recrystallized from methanol yielding 13 parts by Weight of white crystalline di(2-nitro-nbutyl) oxalate.
Analysis.'Iheory 9.6% N. Found 9.42% N.
Example XII Employing the procedure of Example XI but replacing oxalyl chloride with an equimolecular amount of dodecane-1,12-dicarboxylic acid chloride there is obtained di(2- nitro-n-butyl) dodecane-1,12-dicarboxylate.
Example XIII To a suitable reaction vessel equipped with a thermometer, agitator and oil-gas tube is charged 23.8 parts by Weight (substantially 0.2 mol) of 2-nitro-n-butanol. At about 40 C. and with agitation is added dropwise 20.3 parts by Weight (substantially 0.1 mol) of terephthalyll chloride. The reaction mass is then heated up to 90 C. and held at that temperature for about 6 hours, the evolv-- ing hydrogen chloride being vented oil through the oil-gas. tube. The reaction mass is cooled to room temperature,, taken up with about 75 parts by weight of diethyl ether, and then Washed three times with water. The organic; solution is then dried over calcium chloride. The so-. dried solution is then evaporated under vacuum to remove, the low-boiling volatiles. The solid residue upon recrys 5 tallizing from methanol yields 32 parts by weight of di(2- nitro-n-butyl) terephthalate.
Ana Iysis.--Theory 7.62% N. Found 7.48% N.
Example XIV Employing the procedure of Example XIII but replacing terephthalyl chloride with an equimolecular amount of cyclohexane-1,4-dicarboxylic acid chloride there is obtained di(2-nitro-n-butyl) cyclohexane-l,4-dicarboxylate.
Example XV To a suitable reaction vessel equipped with a thermometer, agitator and off-gas tube is charged 23.8 parts by weight (substantially 0.2 mol) of Z-nitro-n-butanol. At about 40 C. and with agitation is added dropwise 23.9 parts by weight (substantially 0.1 mol) of sebacyl chloride. Upon cessation of the hydrogen chloride evolution, the reaction mass is heated at 6070 C. for 2 hours. The reaction mass is cooled to room temperature, taken up with 75 parts by weight of diethyl ether, and washed twice with water. The so-washed organic solution is then dried over anhydrous calcium chloride. The so-dried organic solution is then evaporated under vacuum to remove the low boiling volatiles and then fractionally distilled up to 150 .C. at 1.0 mm. Hg. The residue, 29.8 parts by weight of an oil, is di(2-nitro-n-butyl) sebacate.
Ana lysis.Theory 6.95% N. Found 6.67% N.
Example XVII Employing the procedure of Example XVI but replacing 2-nitro-n-butanol with an equimolecular amount of Z-nitroeth-anol there is obtained di(2-nitroethyl) sebacate.
Example XVIII Employing the procedure of Example XVI but replacing 2-n-itro-n-butanol with an equimolecular amount of Z-nitro-n-hexanol there is obtained di(Z-nitro-n-hexyl) sebacate.
The esters of this invention are useful in .combatting a large variety of fungal organisms. They are particularly effective when applied directly to soil for controlling soil borne pathogenic fungi. To illustrate the fungicidal activity of the esters ofv this invention but not limitative thereof is the following.
An intimate mixture of 2 volumes of yellow corn meal and 3 volumes of White sand is infested with a particular pathogen .(below itemized) and incubated for two Weeks at 20 C. Then one volume of this infested mixture is blended uniformly with 3 volumes of a good grade of top soil which had been sterilized. To accomplish complete blending the composite of soil and infested mixture is passed through a No. 8 screen three times. A number of small cups are then tightly packed with 30 gram portions of the composite and the surface thereof leveled.
The ester to be evaluated (itemized below) is dissolved in suflicient acetone to make a 1% by weight solution and then diluted with water to provide a formulation having a concentration of 0.1% by weight. To provide the desired concentration in the aforedescribed composite the following further dilutions with water are made:
Cone. desired in Ml.:f 0.1% M]. of water soil in p.p.m. formulation added to formulation The 4 ml. pontions are drenched over the surface of the 6 soil in each cup, care being taken to insure even distribution. The cups are then placed in a 100% humidity chamber at F. for 44 hours. Upon removal from the chamber the amount of mycelial growth on the surface )f the soil is noted and rated as follows:
1:110 growth 2:growth from corn meal only 3=some growth in soil away from corn meal particles 4:surface covered but little aerial growth 5 growth equivalent to that on untreated soil.
The results obtained with several of the esters of this invention are set forth below for each of the two indicated fungal organisms:
Adi(2-nitro-n-butyl) succinate B-di(2-nitro-n-butyl) phthalate C--di(2-nitro-n-butyl) adipate D-di(2-nitro-n-butyl) fumarate E-di 2-nitro-n-butyl) oxalate Fdi(2-nitro-n-butyl) terephthalate Gdi(2-nitro-n-buty1) sebacate Pythium ultz'mum at- Rhizoctonia solam' at Ester p.p.m. 3O p.p.m. 100 p.p.m. 30 p.p.m.
In another procedure employed to evaluate the esters of this invention, 200 grams of a cornmeal-sand culture of a selected fungus is blended with 225 lbs. of a good grade of sterilized top soil in a ribbon blender. After a 48 hour incubation period at room temperature, a 200 gram portion of the blend is placed in each of a. number of plastic pots and packed with a template. In those pots where the fungus is Rhizoctonia so latni, 10 seeds of cotton are placed in the soil blend, and 50 additional grams thereof are placed over the seeds and lightly packed. When the fungus is Pythiwm ultimu m, 10 seeds of No. 3 American decorticated sugar beet are placed in the soil blend, and 50 additional grams thereof are placed over the seeds and lightly packed. Then eight ml. of an acetone-water-ester formulation is drenched over the soil of each pot providing a concentration of .ester of 30 p.p.m. The plastic pots are then placed in a greenhouse at 70 F. to await germination. The following rating code is employed based upon a total of twenty seeds (l0 cotton plus 10 sugar beet) at the indicated dilution of each ester in p.p.m.
1:17 to 20 healthy seedlings 2:13 to 16 healthy seedlings 3:8 to 12 healthy seedlings 4:4 to 7 heal-thy seedlings 5:0 to 3 healthy seedlings A-di Z-nitro-n-butyl) succinate B-di(2-nitro-n-butyl) phthalate Cdi(2-nitro-n-butyl) adipate Ddi(2-nitro-n-.butyl) fumarate 'E-di(2-nitro-n'butyl) oxalate F-di(2-nitro-n-butyl) terphthalate Gdi(2-nitro-n-butyl) sebacate Ester: .At 30 p.p.m. A 2 B 3 C 2 D 3 E 4 G 2 In still another evaluation, 1000 grams of a top soilsand-cornmeal blend is prepared as immediately above. The blend is placed in a Hobart food mixer, and acetonewater-ester formulations are sprayed into the :blend as the latter is being mixed to provide a concentration of ester of 30 ppm. The treated blend is placed in plastic pots, seeded as immediately above, and kept in a greenhouse at 70 F. to await germination. Using the same rating code as in the immediately preceding evaluation, the results are:
Adi(2-nitro-n-butyl) succinate Cdi(2-nitro-n-butyl) adipate G-di(2-nitro-n-butyl) sebacate Ester: At 30 ppm. A 3
Although the novel fungicidal agents of this invention are useful per se in controlling a wide variety of fungal organisms, it is preferable that they be supplied to the organisms or to the environment of the organisms in a dispersed form in a suitable extending agent.
In the instant specification and appended claims it is to be understood that the term dispersed is used in its widest possible sense. When it is said that the fungicidal agents of this invention are dispersed, it means that the particles of the fungicidal agents of this invention may be molecular in size and held in true solution in a suitable organic solvent. It means further, that the particles may be colloidal in size and distributed throughout a liquid phase in the form of suspensions or emulsions or in the form of particles held in suspension by wetting agents. It also includes particles which are distributed in a semisolid viscous carrier such as petrolatum or soap or other ointment base in which they may be actually dissolved in the semi-solid or held in suspension in the semi-solid with the aid of suitable wetting or emulsifying agents. The term dispersed also means that the particles may be mixed with and distributed throughout a solid carrier providing a mixture in particulate form, e.g. pellets, granules, powders, or dusts. The term dispersed also includes mixtures which are suitable for use as aerosols including solutions, suspensions, or emulsion of the fungicidal agents of this invention in a carrier such as dichlorodifluoromethane and like fiuorochloroalkanes which boil below room temperature at atmospheric pressure.
In the instant specification and appended claims it is to be understood that the expression extending agent includes any and all of those substances in which the fungicidal agents of this invention are dispersed. It includes, therefore, the solvents of a true solution, the liquid phase of suspensions, emulsions or aerosols, the semi-solid carrier of ointments and the solid phase of particulate solids, e.g., pellets, granules, dusts and powders.
The exact concentration of the fungicidal agents of this invention employed in combatting or controlling fungal organisms can vary considerably provided the resuired dosage (i.e., toxic or lethal amount) thereof is supplied to the organisms or to the environment of the organisms. When the extending agent is a liquid or mixture of liquids (eg as in solutions, suspensions, emulsions, or aerosols) the concentration of the fungicidal agent employed to supply the desired dosage generally will be in the range of 0.001 to 50 percent by weight. When the extending agent is a semi-solid or solid, the concentration of the fungicidal agent employed to supply the desired dosage generally will be in the range of 0.1 to 25 percent by weight. From a practical point of view, the manufacturer must supply the agriculturist with a lowcost concentrate or spray base or particulate solid base in such form that, by merely mixing with water or solid extender (e.g., powdered clay or talc) or other low-cost material available to the agriculturist at the point of use,
he will have an easily prepared fungicidal spray or particulate solid. In such a concentrate composition, the fungicidal agent generally will be present in a concentration of 5 to 95 percent by weight, the residue being any one or more of the well-known fungicidal adjuvants, such as the various surface active agents (e.g., detergents, a soap or other emulsifying or wetting agent, surface-active clays), solvents, diluents, carrier media, adhesives, spreading agents, humectants, and the like.
There are a large number of organic liquids which can be used for the preparation of solutions, suspensions, or emulsions of the fungicidal agents of this invention. For example, isopropyl ether, acetone, methyl ethyl ketone, dioxane, cyclohexanone, carbon tetrachloride, ethylene dichloride, tetrachloroethane, hexane, heptane and like higher liquid alkanes, hydrogenated naphthalenes, solvent naphtha, benzene, toluene, xylene, petroleum fractions (e.g., those boiling almost entirely under 400 F., at atmospheric pressure and having a flash point above about F., particularly kerosene), mineral oils having an unsulfonatable residue above about 80 percent and preferably above about percent. In those instances wherein there may be concern about the phytoxicity of the organic liquid extending agent a portion of same can be replaced by such low molecular weight aliphatic hydrocarbons as dipentene, diisobutylene, propylene trimer, and the like or suitable polar organic liquids such as the aliphatic ethers and the aliphatic ketones containing not more than about 10 carbon atoms as exemplified by acetone, methyl ethyl ketone, diisobutyl ketone, dioxane, isopropyl ether, and the like. In certain instances, it is advantageous to employ a mixture of organic liquids as the extending agent.
When the fungicidal agents of this invention are to be supplied to the fungal organisms or to the environment of the organisms as aerosols, it is convenient to dissolve them in a suitable solvent and disperse the resulting solution in dichlorodifluoromethane or like chlorofiuoroalkane which boils below room temperature at atmospheric pressure.
The fungicidal agents of this invention are preferably supplied .to the fungal organisms or to the environment of the organisms in the form of emulsions or suspensions. Emulsions or suspensions are prepared by dispersing one or more fungicidal agents of this invention either per se or in the form of an organic solution thereof in water with the aid of a water-soluble surfactant. The term surfactant as employed here and in the appended claims is used as in volume II of Schwartz, Perry and Berchs Surface Active Agents and Detergents" (1958, Interscience Publishers, Inc., New York) in place of the expression emulsifying agent to connote generically the various emulsifying agents, dispersing agents, wetting agents and spreading agents that are adapted to be admixed with the fungicidal agents of this invention in order to secure better wetting and spreading of the active ingredients in the water vehicle or carrier in which they are insoluble throng-h lowering the surface tension of the water (see also Frear, Chemistry of Insecticides, Fungicides and Herbicides, second edition, page 280). These surfactants include the wellknown capillary-active substances which may be anionactive (or anionic), cation active (or cationic), or nonionizing (or non-ionic) which are described in detail in Volume I and II of Schwartz, Perry and Berchs Surface Active Agents and Detergents (1958, Interscience Publishers, Inc., New York), and also in the November 1947 issue of Chemical Industries (pages 811-824), in an article entitled, Synthetic Deter-gents by John W. McCutcheon and also in the July, August, September and October 1952 issues of Soap and Sanitary Chemicals under the title, Synthetic Detergents. The disclosures of these articles with respect to surfactants, i.e., the anion active, cation-active and non-ionizing capillary active substances, are incorporated in this specification by reference in order to avoid unnecessary enlargement of this specification. The preferred surfactants are the watersoluble anionic surface-active agents and the water soluble non-ionic surface-active agents set forth .in US. 2,846,398 (issued August 5, 1958). In general it is preferred that a mixture of water-soluble anionic and watersoluble non-ionic surfactants be employed.
The fungicidal agents of this invention can be dispersed by suitable methods (e.g., tumbling or grinding) in solid extending agents either of organic or inorganic nature and supplied to the fungal organisms environment in particulate form. Such solid materials include for example, tricalcium phosphate, calcium carbonate, kaolin, bole, kieselguhr, talc, bentonite, fullers earth, pyrophillite diatomaceous earth, calcined magnesia, volcanic ash, sulfur and the like inorganic solid materials, and include, for example, such materials of organic nature as powdered cork, powdered wood, and powdered walnut shells. The preferred solid carriers are the adsorbent clays, e.g., bentonite. These mixtures can be used for fungicidal purposes in the dry form, or, by addition of water-soluble surfactants or wetting agents the dry particulate solids can be rendered wettable by water so as to obtain stable aqueous dispersions or suspensions suitable for use as sprays.
For special purposes the fungicidal agents of this invention can be dispersed in a semi-solid extending agent such as petrolatum or soap (e.g., sodium stearate or oleate or palmitate or mixtures thereof) with or without the aid of solubility promoters and/ or surfactants or dispersing agents.
In all of the forms described above the dispersions can be provided ready for use in combatting fungal organisms or they can be provided in a concentrated form suitable for mixing with or dispersing in other extend-ing agents. As illustrative of a particularly useful concentrate is an intimate mixture of one or more fungicidal agents of this invention with a water-soluble surfactant which lowers the surface tension of water in the weight proportions of 0.1 to 15 parts of surfactant with sufiic'ient of the fungicidal agent of this invention to make 100 parts by weight. Such a concentrate is particularly adapted to be made into a spray for combatting various forms of fungal organisms by the addition of water thereto. As illustrative of such a concentrate is an intimate mixture of 95 parts by weight of di(2-nitro-nbutyl) sebacate and 5 parts by weight of a water-soluble non-ionic surfactant such as the polyoxyethylene derivative of sorbitan monolaurate.
Another useful concentrate adapted to be made into a spray for combatting fungal organisms is a solution (preferably as concentrated as possible) of one or more fungicidal agents of this invention in an organic solvent therefor. The said liquid concentrate preferably contains dissolved therein a minor amount (e.g., 0.5 to 10 percent by weight of the weight of the new fungicidal agent) of a surfactant (or emulsifying agent), which surfactant is also water-soluble. As illustrative of such a concentrate is a solution of di(2-nitro-n-butyl) adipate in acetone which solution contains dissolved therein a water-soluble polyoxyethylene glycol non-ionic surfactant and a water-soluble alkylaryl sulfonate anionic surfactant. Of the surfactants aforementioned in preparing the various emusifiable, wettable or dispersible compositions or concentrates of this invention, the anionic and non-ionic surfactants are preferred. Of the anionic surfactants, the particularly preferred are the well-known watersoluble alkali metal alkylaryl sulfonates as exemplified by sodium decylbenzene sulfonate and sodium dodecylbenzene sulfonate. Of the non-ionic surfactants, the particularly preferred are the water-soluble polyoxyethylene derivatives of alkylphenols (particularly isooctylphenol) and the water-soluble polyoxyethylene derivatives of the mono-higher fatty acid esters of hexitol anhydrides such as mannitan or sorbitan.
In all of the various dispersions described hereinbefore for fungicidal purposes, the active ingredients can be one or more of the compounds of this invention. The compounds of this invention can also be advantageously employed in combination with other pesticides, including, for example, insecticides, nematocides, bacterocides, and herbicides. In this manner it is possible to obtain mixtures which are effective against a wide variety of pests and other forms of noxious life.
In controlling or combatting fungal organism-s the fungicidal agents of this invention either per se or compositions comprising same are supplied to the fungal or- 'ganisms or to their environment in a lethal or toxic amount. This can be done by dispersing the new fungicidal agent or fungicidal composition. comprising same in, on or over an infested environment or in, on or over an environment the fungal organisms frequent, e.g., agricultural soil or other growth media or other media infested with the fungal organisms or attractable to the organisms for habitational or sustenance or propagational purposes, in any conventional fashion which permits contact between the organisms and the fungicidal agents of this invention. Such dispersing can be brought about by applying the fungicidal agent per se or sprays or particulate solid compositions containing same to a surface infested with the fungal organisms or attractable to the organisms, as for example, the surface of agricultural soil or other media such as the above ground surface of plants by any of the conventional methods, e.g., power dusters, boom and hand sprayers, and spray dusters. Also for sub-surface application such dispersing can be carried out by simply mixing the new fungicidal agent per se or fungicidal spray or particulate solid compositions comprising same with the infested environment or with the environment the fungal organisms frequent, or by employing a liquid carrier for the new fungicidal agent to accomplish subsurface penetration and impregnation therein.
What is claimed is:
1. The method which comprises applying to fungal organisms and their horticultural habitats at least one ester of the formula AOZO-B wherein A and B are nitro substituted alkyl radicals containing 2 to 6 carbon atoms, the nitro substituent of each radical being attached to a carbon atom at least one carbon atom removed from the -O group to which it is attached as indicated above, and wherein Z is the residue of a dicarboxylic acid upon removal of the respective acidic hydroxyl radicals, said dicarboxylic acid containing 2 to 14 carbon atoms.
2. The method which comprises applying to fungal organisms and their horticultural habitates at least one ester of the formula AO-ICIR("\JO-IB o 0 wherein A and B are 2-nitro substituted primary alkyl radicals of the formula --OI-IzC|!H(CH2)mH wherein m is an integer from 0 to 3, inclusive, and wherein R is a straight chain divalent aliphatic hydrocarbon radical of the empirical formula (CH wherein x is a whole number from 4 to 8, inclusive.
3. The method which comprises applying to fungal organisms and their horticultural habitats di(2-nitro-nbutyl) sebacate.
4. The method of controlling soil borne fungi which comprises applying to soil at least one ester of the formula 11 wherein A and B are 2-nitro substituted primary alkyl radicals of the formula OI-Ia-(IJH(OHz)mH wherein m is an integer from 0 to 3, inclusive, and wherein R is a straight chain divalent aliphatic hydrocarbon radical of the empirical formula (CH wherein x is a whole number from 4 to 8, inclusive.
References Cited by the Examiner UNITED STATES PATENTS Lawrence 260--475 Hodge 16722 Stoffel et a1. 16722 Stoffel et a1. 16722 JULIAN S. LEVI'IT, Primary Examiner.

Claims (1)

1. THE METHOD WHICH COMPRISES APPLYING TO FUNGAL ORGANISMS AND THEIR HORTICULTURAL HABITATS AT LEAST ONE ESTER OF THE FORMULA
US373079A 1961-05-22 1964-06-05 Method for controlling fungi with esters of dicarboxylic acids Expired - Lifetime US3242040A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3996380A (en) * 1974-12-23 1976-12-07 Zoecon Corporation Alkynyl esters for controlling mites
US5122555A (en) * 1989-08-07 1992-06-16 Akzo Nv Uv-stabilization of polymers using nitro compounds
DE19829274A1 (en) * 1998-07-01 2000-01-05 Otb Oberflaechentechnik Berlin Process for the recovery of precious metals

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2368765A (en) * 1941-10-28 1945-02-06 Hercules Powder Co Ltd Composition of matter
US3098039A (en) * 1960-10-28 1963-07-16 Commercial Solvents Corp Process for the control of bacteria
US3149031A (en) * 1961-06-01 1964-09-15 Monsanto Co Nitroalkyl esters of hydrocarbyl-carboxylic acids as fungicides
US3160655A (en) * 1961-05-21 1964-12-08 Monsanto Co Nitro substituted alkyl oxo-loweralkyl-carboxylates

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2368765A (en) * 1941-10-28 1945-02-06 Hercules Powder Co Ltd Composition of matter
US3098039A (en) * 1960-10-28 1963-07-16 Commercial Solvents Corp Process for the control of bacteria
US3160655A (en) * 1961-05-21 1964-12-08 Monsanto Co Nitro substituted alkyl oxo-loweralkyl-carboxylates
US3149031A (en) * 1961-06-01 1964-09-15 Monsanto Co Nitroalkyl esters of hydrocarbyl-carboxylic acids as fungicides

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3996380A (en) * 1974-12-23 1976-12-07 Zoecon Corporation Alkynyl esters for controlling mites
US5122555A (en) * 1989-08-07 1992-06-16 Akzo Nv Uv-stabilization of polymers using nitro compounds
DE19829274A1 (en) * 1998-07-01 2000-01-05 Otb Oberflaechentechnik Berlin Process for the recovery of precious metals
DE19829274C2 (en) * 1998-07-01 2002-06-20 Otb Oberflaechentechnik Berlin Process for the recovery of precious metals

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