US3224930A - Fungicidal compositions - Google Patents
Fungicidal compositions Download PDFInfo
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- US3224930A US3224930A US161384A US16138461A US3224930A US 3224930 A US3224930 A US 3224930A US 161384 A US161384 A US 161384A US 16138461 A US16138461 A US 16138461A US 3224930 A US3224930 A US 3224930A
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- 239000000203 mixture Substances 0.000 title claims description 66
- 230000000855 fungicidal effect Effects 0.000 title claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 56
- 239000004480 active ingredient Substances 0.000 claims description 29
- 238000009472 formulation Methods 0.000 description 46
- 239000011651 chromium Substances 0.000 description 26
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 25
- 229910052804 chromium Inorganic materials 0.000 description 25
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- -1 alkyl radicals Chemical class 0.000 description 10
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- SZFRZEBLZFTODC-UHFFFAOYSA-N 2,3,4-trimethylpent-2-ene Chemical group CC(C)C(C)=C(C)C SZFRZEBLZFTODC-UHFFFAOYSA-N 0.000 description 1
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- FCSKOFQQCWLGMV-UHFFFAOYSA-N 5-{5-[2-chloro-4-(4,5-dihydro-1,3-oxazol-2-yl)phenoxy]pentyl}-3-methylisoxazole Chemical compound O1N=C(C)C=C1CCCCCOC1=CC=C(C=2OCCN=2)C=C1Cl FCSKOFQQCWLGMV-UHFFFAOYSA-N 0.000 description 1
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- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 208000002474 Tinea Diseases 0.000 description 1
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- NWGKJDSIEKMTRX-MGMRWDBRSA-N [(2R)-2-[(2R,3R,4R)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] (Z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@@H](O)[C@H]1O NWGKJDSIEKMTRX-MGMRWDBRSA-N 0.000 description 1
- FMUCODQZBSTNBS-UHFFFAOYSA-N [Cr].C1C=CC=CC=C1 Chemical compound [Cr].C1C=CC=CC=C1 FMUCODQZBSTNBS-UHFFFAOYSA-N 0.000 description 1
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- MRNZSTMRDWRNNR-UHFFFAOYSA-N bis(hexamethylene)triamine Chemical compound NCCCCCCNCCCCCCN MRNZSTMRDWRNNR-UHFFFAOYSA-N 0.000 description 1
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- 125000002091 cationic group Chemical group 0.000 description 1
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- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 description 1
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- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 1
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- WMIYKQLTONQJES-UHFFFAOYSA-N hexafluoroethane Chemical class FC(F)(F)C(F)(F)F WMIYKQLTONQJES-UHFFFAOYSA-N 0.000 description 1
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- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
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- GKQPCPXONLDCMU-CCEZHUSRSA-N lacidipine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C1=CC=CC=C1\C=C\C(=O)OC(C)(C)C GKQPCPXONLDCMU-CCEZHUSRSA-N 0.000 description 1
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- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
- A01N55/02—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur containing metal atoms
Definitions
- rat tii are 1 3,224,930 FUNGKIHDAL COMfOSlTIGNS William E. Burt, Royal Gait, Mich, assignor to Ethyl Corporation, New York, N.Y., a corporation of Virginia No Drawing. Filed Dec. 22, 1961, Ser. No. 161,384 4 Claims. (Cl. 167-22)
- This invention relates to fungicidal compositions, and more particularly, to fungicidally potent organochromium compounds and their use in combating fungi.
- An object of this invention is to provide new fungicidal compositions. Still another object is to provide a new means for combating fungi. A further object is to provide new fungicidal compositions comprising conditioning agents and certain organochromium compounds as described herein.
- M is a metal of Group VIB of the Periodic Table according to Mendeleev;
- R R R R and R are selected from the class consisting of hydrogen and alkyl radicals having one to about 6 carbon atoms. and n and n are integers having the value one to six.
- Compounds of this type can be prepared by reacting the corresponding triamine with either Cr(CO) or cycloheptatriene chromium hexacarbonyl according to the general method of Abel et al., J. Chem. Soc. (1959), 2323.
- the most preferred metal is chromium.
- the fungicidally active compounds of this invention are represented by diethylene triamine chromium tricarbonyl and dihexylene triamine chromium tricarbonyl.
- other compounds wherein the nitrogen atoms in the amine portion of the molecule are substituted with hydrocarbon radicals are also applicable.
- the preferred compounds either have no substituents on the nitrogen atoms or all the nitrogen atoms are substituted with identical radicals.
- diethylene triamine chromium tricarbonyl pentaethylpropylene triamine chromium tricarhonyl, dipropylene triamine chromium tricarbonyl, dibutylene triamine chromium tricarbonyl, and the like.
- nitrogen atoms are substituted by hydrocarbon radicals can be arbitrarily divided into three subclasses.
- Symmetrical derivatives are illustrated by the compounds sym-trimethyl ethylene triamine chromium tricarbonyl, sym-dimethyl ethylene triamine chromium tricarbonyl and the like.
- Unsymmetrical nitrogen substituted fungicidally active compounds are unsym-N-methyl, N-ethyl, propylene tri- 3,224,939 Patented Dec. 21, 1965 amine chromium tricarbonyl, unsym-dimethylethylene triamme chromium tricarbonyl and the like.
- the most preferred compound is diethylene triamine.
- ch r qrpitup-trjgarbonyl Such compounds as described above are useful in comhating fungi when they are applied to the locus of the fungi. Such treatment, therefore, constitutes one aspect of the invention. It has been found that the above materials are useful in controlling and eliminating fungi which infest vegetables, animals and man.
- a facet of this invention is a novel method of combating and controlling fungi. Accordingly, one embodimnet of this invention is the method of combating fungi which comprises contacting the fungus with a fungitoxic amount of a compound having the formula given above. Another aspect of this invention is the provision of a method for controlling fungi which comprises treating matter suscepible to fungal infestation with the compound of the above formula.
- the active ingredient of the present invention is admixed in fungicidally effective amount with a conditioning agent of the type commonly referred to as a pest controlled adjuvant or modifier.
- a conditioning agent of the type commonly referred to as a pest controlled adjuvant or modifier.
- adjuvants have been referred to by names such as conditioning agent, dispersing agent, surface active agent, and surface active dispersing agent.
- Their purpose is to extend the active ingredient to assure its efficacious penetration of, or application to, the locus being treated and to adapt the active ingredients for ready and efiicient application by using conventional equipment.
- Formulations of the fungicidally active ingredient with a suitable conditioning agent comprise both liquid and solid types as well as the aerosol type of formulation.
- the liquid type of formulation can have water, an organic solvent, or an oil-Water emulsion and the like as the conditioning agent.
- conditioning agent include solid carriers such as talc, attaclay, kieselguhr, chalk, diatomaceous earth, and the like, and various mineral powders, such as calcium carbonate, which act as a dispersant, as a carrier, and in some instances, perform the function of a surface active agent.
- the conditioning agent may also be an industrial commodity such as paint, raw polymer, finished plastic and the like. Such industrial materials act as a diluent, dispersant, wetting agent, and extender for the active ingredient, thus, enhancing its fungicidal action.
- the fomulations of this invention therefore, comprise the above defined fungicidally active ingredient in a suitable material as a dispersant or conditioning agent. It is not intended that this invention be limited to any specific proportions of active ingredient and conditioning agent.
- the important feature of the invention is to provide a formulation of such concentration that is appropriate for the desired application.
- the conditioning agent will be present to provide the proper type of contact with the material being protected.
- fungicidally active ingredient in the presence of only a compound or product or material known as a conditioning agent. It has been found that other additives are useful in the preparation of the fungicidal preparations. Other materials found useful are classified as adhesives. Spreading agents tend to increase the area found to be most advantageous.
- QID covered by a spray liquid Many chemicals act as both wetting and spreading agents.
- Dried blood blood albumin
- sulfite lye both in the liquid and dehydrated forms, and petroleum emulsions belong to this group.
- Adhesives increase the adherence of the active agent to the treated surface to augment resistance to wear and mechanical action. Bentonite and other clays, gelatin and glue, are examples of adhesives.
- the fungicidal preparations are in the form of either liquid or dry or aerosol formulations.
- Liquid compositions either solutions or dispersions, frequently also contain a surface active dispersing agent in amounts suflicient to render the composition readily useful in aqueous spray application.
- the surface active dispersing agents referred to herein are sometimes known as wetting, dispersing or penetrating agents. They are agents which cause the formulations to be easily dispersed in water.
- They can be of the anionic, cationic, or nonionic type and include salts of long chain fatty acids, sulfonated oils, both vegetable and animal, petroleum oils, sulfates of long chain alcohols, phosphates of long chain alcohols, various polyethylene oxides, condensation products of ethylene oxide with alcohol and phenols, quaternary ammonium salts, and the like.
- the surface active agent wil l usually be present to the extent of 0.1 to percent of the formulation. Typical of the liquid formulations is the water solution or dispersion of the active ingredients.
- Example I below is an example for the preparation of an aqueous suspension of a typical active ingredient described in this invention.
- the active ingredients can also be dispersed or sus pended in various organic solvents such as alcohols, ketones, hydrocarbons, and petroleum fractions such as kerosene, dimethylformamide, and the like.
- organic solvents such as alcohols, ketones, hydrocarbons, and petroleum fractions such as kerosene, dimethylformamide, and the like.
- a surface active dispersing agent is usually present to provide ready dispersability with water.
- the solubility of the active ingredients of this invention in organic solvents is such that they can be applied advantageously in the form of a solution in this type of solvent.
- this type of vehicle is preferred, for example, in treating cloth, leather, or other fibrous articles.
- a solution may be the most practical vehicle for applying the protective film. Brushing, spraying, or dipping may be the application method of choice.
- fungicidal ingredients is an oil in water emulsion (see Example III).
- these are prepared by dissolving the fungicidally active ingredient in an organic solvent, usually a petroleum fraction like kerosene, and then dispersing this solution with vigorous agitation in a large volume of water containing a minor amount of a surface active agent.
- an adherent or sticking agent such as vegetable oils, naturally occurring gums, and other adhesives
- humectants can be employed in the formulations.
- the formulations can be employed in admixture with other pesticidal materials or other biocides such as insecticides, larvacides, bactericides, germicides, miticides or with other materials which it is desired to apply along with the fungicides.
- two or more of the active ingredients may be formulated together in a single composition, thus achieving control of a broader spectrum of fungi.
- Fungicides can be applied in dry media as well as in liquid suspensions or solutions.
- early practice in the art used dust formulations almost exclusively. It was only the advent of the introduction of spray machinery that caused dust formulations to be considered with disfavor. However, it was soon realized that spraying was often not as convenient as dusting, particularly when large, comparatively inaccessible cultivated fields are to be treated or when the area of interest necessarily requires that it be treated with a dry agent.
- Dust formulations of my active compounds have a ready place in the art and indeed the use of these dry formulations should grow with time, since they are utilizable when treating large areas for fungicidal infestation by airplane dusting. Dusting is also extensively employed in treating man and animals for fungicidal infestations.
- a dust formulation which is prepared generally by milling the active ingredient in ball mill within the presence of a dry material, for example, fullers earth. After milling, the mixture is screened and the fraction passing through a very fine sieve is collected. Thereafter, a further dilution is made by repeating the above procedure with an additional very large amount of a compound such as fullers earth.
- Example IV exemplifies a dust formulation.
- a preferred formulation of the compounds comprises a wettable powder.
- a wettable powder In preparing wettable powders, several formulation procedures are possible (see Example V for one type of procedure). It is one intention of this invention to provide compositions comprising the active ingredient defined herein in combination with a minor amount of surface active agent.
- Such surface active agents can be chosen for example from those previously mentioned in connection with aqueous dispersion. Still other surface active agents can be employed, the above merely showing a representative list of the more common material.
- Such formulations can be readily admixed with a solid carrier. Formulations thus formed then comprise the active ingredient of this invention, an inert carrier, and a surface active agent.
- inert carriers which can be employed in preparing wettable powders are soya bean flour, tobacco flour, walnut shell flour, gypsum, mica, talc, apatite, pumice and the like.
- in preparing concentrated wettable powders it is preferred to employ between 0.01 and 5 percent of the surface active agent, based upon the amount of active ingredient, and up to percent of the inert carrier based upon the total amount of the formulation.
- Such concentrated formulations provide the advantage of permitting economical storage and transportation of the fungicide and permit further dilution by simple admixture with water at the time of application.
- a colloidal formulation is prepared by passing a mixture of the active ingredient, a hydrocarbon solvent and a large amount of water through a colloid mill until homogenation of the oil and water is achieved.
- Example VI gives an example of the preparation of a colloidal formulation.
- the compounds also find effective use when formulated in aerosol formulations, i.e., when mixed with a liquid of low boiling point that changes to a gas when released from a confined space.
- diluent used in these formulations are fluorinated hydrocarbons such as tetrafluoromethane, and hexafluoroethane.
- fluorinated hydrocarbons such as tetrafluoromethane, and hexafluoroethane.
- Mixed halogenated compounds containing fluorine and chlorine such as difiuorodichloromethane and pentafluorochloroethane and the like can also be used as the l quid having the necessary low boiling point.
- Other materials such as carbon dioxide, sulfur dioxide, hydrogen sulfide and ammonia can be used, and of these, carbon dioxide generally is preferred.
- One method of preparing such aerosol formulations comprises introducing my new compounds into a pressure cylinder and later introducing the liquifying diluent under pressure followed by mixing the cylinder to obtain uniform solution. If desired, smaller containers can then be filled from the cylinder in which the formulation is prepared. In many cases it is desirable to add a second solvent to the low boiling material of the type described above so as to more readily dissolve my compounds. Examples of such co-solvents are benzene, acetone, carbon tetrachloride and the like.
- Example VII is an example of the preparation of an aerosol type formulation of my active ingredient.
- My compounds are also elfective when formulated in an ointment for topical application to the epidermis of animals and man.
- a typical ointment formulation is given in Example VIII below.
- concentration range desired in my invention is that range necessary to accomplish the desired end.
- a preferred range for agricultural application is between 0.1 and 2,000 parts per million.
- Formulations containing as high as 30 percent active ingredient are used in treating animals and man. Typical formulations of this invention are described in the following examples in which all parts are by weight.
- Diethylene triamine chromium tricarbonyl II Sym.-N,N-dimethyl ethylene triamine chromium tricarbonyl III. N,N,N,N,N-pentamethyl diethylene triamine chromium tricarbonyl IV. Unsym.-N,N,N-trimethyl diethylene triamine chrmium tricarbonyl V.
- N-ethyl diethylene triamine chromium tricarbonyl EXAMPLE I (WATER SUSPENSION) A formulation of Compound I is prepared by adding, with vigorous agitation, 10 parts of this material to 1,000 parts of water containing 1 part of Tween-80. This concentrated dispersion is further diluted 1,000 times by the addition of Water to obtain a formulation of suitable concentration for application. Thus, the resulting dispersion contains 10 parts per million of my fungicide in the water dispersion.
- EXAMPLE II (ORGANIC SOLUTION) A solution consisting of 5 parts of Compound H in 250 parts of cyclohexanone is prepared by stirring the two constituents for a period of two minutes at a temperature of about 25 C. This concentrated solution suitable for storage or transportation is further diluted with 99,750 parts of kerosene to form a final dilution of 50 p.p.m. suitable for application.
- EXAMPLE III (OIL IN WATER EMULSION) An oil and water emulsion is prepared by dissolving parts of Compound III in 1,000 parts of kerosene. This solution is dispersed with vigorous agitation in 99,000 parts of water containing one part of Triton X- 100 to provide a dispersion containing 100 ppm. of active 1ngredient.
- EXAMPLE IV (DUST FORMULATION) A dust formulation of the fungicide is prepared by adding one part of Compound IV to parts of fullers earth in a ball mill. The mixture is milled for a period of one hour, screened to collect a fraction passing a 100 mesh sieve. This one percent formulation can be applied directly or further diluted. Further dilution is made by repeating the above procedure with an additional 9,900 parts of fullers earth.
- EXAMPLE V WETTABLE POWDER
- a mixture of 100 parts of Compound V, 1,000 parts of attaclay and 0.01 part of Nacconol is intimately mixed in an L-shaped blender.
- the 10 percent wettable powder thus prepared produces a satisfactory water suspension when 11 parts are stirred into 10,000 parts of water, producing a suspension containing 100 ppm. active ingredient.
- EXAMPLE VI (COLLOIDAL FORMULATION) A colloidal formulation is prepared by passing a mix ture of 10 parts of Compound VI, 100 parts of kerosene, 1000 parts of water and 1 part of mannitan monooleate through the colloid mill until hom-ogenation of the oil in water is achieved.
- EXAMPLE VII (AEROSOL FORMULATION) Into a cylinder rated at 100 p.s.i. working pressure, is introduced 10 parts of Compound VII. The cylinder is then made pressure tight except for one opening through which is introduced a mixture of 10 parts acetone and 50 parts of dichloro difluoromethane from a container at 2000 p.s.i. The cylinder into which the ingredients are introduced is then sealed off and inverted to give a uniform aerosol solution of my active materials in the mixture of co-solvents.
- EXAMPLE VIII 2000 parts of Compound VIII is ground in a ball mill Agar-Plate Technique The compounds were screened for anti-fungal activity by the Agar-Plate Technique against five fungi repre: senting groups of economic importance. The test fungl and their occurrences are as follows:
- the method was the Agar-Plate Technic i f, e medium employed was Sabouraud Dextrose Agar. This medium is used for carrying the stock cultures as well as for the test itself. The agar is put into solutlon and then cooled to 42-45 C. To this is added a saline spore suspension of the test organism.
- the inoculated agar is then poured into sterile Petri dishes and allowed to harden.
- a suitable amount of the compound tested was placed on a one square centimenter area in the center of the agar. If the compound was solid, the compound was sprinkled upon this area of the plate.
- the compound was a liquid, a depression was cut out in the center of the agar by means of a cork borer having a diameter of 1.5 mm. Four drops of the liquid compound were placed in this depression.
- the agar plates were incubated for days at 25 C. If the compound is inhibitory, a zone of clear agar will be noted around the area of inoculation. The size of this zone is measured, and is an indication of the inhibitory value of the compound tested.
- the diffusibility of the compound will affect the area of inhibition. If the compound tested has no antifungicidal activity, there will be no area of inhibition, and in some cases, growth will appear under the compound tested.
- the sample was tested for activity against the same five fungi utilized in the Agar Plate Technique.
- the fungi for all tests were grown in a Bacto Sabouraud Liquid Medium, pH of 5.7.
- the sample was dissolved in a minimal quantity of ethanol and diluted with sterile water thereafter to give an original concentration of 512 p.p.m.
- the test cultures were grown upon the Bacto Sabouraud Dextrose Agar for days.
- a heavy spore suspension was prepared in buffered distilled water.
- the inoculum for each tube was one drop of the heavy spore suspension.
- the test cultures were incubated at 30 C. for 10 days.
- An effective concentration of 250 parts per million (p.p.m.) is generally accepted as the maximum concentration at which a chemical can be considered for use as an agricultural fungicide.
- test fungi used in this case were T richophyton interdigitale, T richophyton rubrum, T ryclzophyton schoenleinii, Microsporum audouini, Epidermophyton floccosum, Microsporum gypseum. These fungi were grown in Difcos Sabourauds liquid medium, pH 4.7. Sample preparation consisted of dissolving aliquots of each compound in 10 mls. of ethanol and diluting to 512 p.p.m. concentrations with distilled water. These stock solutions were serially diluted through 10 tubes of culture medium. The inoculum consisted of 1 drop per tube of a heavy spore suspension of the test fungi. The tests were incubated at 35 C. for one week.
- F oliar fungicide screening Ceral leaf rust wheat is grown in soil in paper pots with 20-30 plants per pot. When the plants are 68 inches tall, they are sprayed with the test solutions (300 p.p.m. and 75 p.p.m. concentration) with three pots used for each treatment applied. After the spray treatments have dried thoroughly, the plants are sprayed with a suspension of spores of wheat leaf rust disease, Paccinia rubz'govera, reared on live wheat leaf culture. After one week to ten days, disease symptoms are observed and percent control obtained by comparison of the sample With inoculated controls and manzate-treated positive controls.
- Tomato late blight-Susceptible species tomato plants are treated from seed and transplanted into soil in individual paper pots. When they are 6 to 8 inches high, they are sprayed with the test solutions (300 p.p.m. and 75 p.p.m. concentration) with three plants used for each treatment applied. After the spray treatments have dried .thorou hly, the plants are sprayed with a suspension of spores of the tomato late blight fungus, Phytophthora infestans, which is reared on lima bean agar culture. After a few days to one week disease symptoms are observed and percent control obtained by comparison of the sample with inoculated controls and manzate-treated positive controls.
- Powdery mildew of cucumbers-Susceptible species oncumbers are grown in soil in paper pots with 2-3 plants per pot. When the first leaf has reached a size of about 3 inches in diameter, they are sprayed with the test solutions (300 p.p.m. and 75 p.p.m. concentration) with 3 pots used for each treatment applied. After the spray treatments have dried thoroughly, the plants are dusted with spores of powdery mildew fungus Erysiphe cichoracearum, reared on live cucumber leaf culture. After one week to ten days, disease symptoms are observed and percent control obtained by comparison of the sample with inoculated controls and Karathane-treated positive controls.
- a fungicidal composition consisting of '(a) as a principal active ingredient a compound having the formula N-orn-onz-N-orn-orn-N one on wherein R and R are independently selected from the class consisting of hydrogen and alkyl radicals having from one to six carbon atoms,
- composition consisting essentially of a solid carrier selected from the class consisting of talc, attaclay, kieselguhr, chalk, diatoma- 'ceous earth, soybean fluor, tobacco fluor, walnut shell fluor, gypsum, mica, apatite, pumice and fullers earth.
- a solid carrier selected from the class consisting of talc, attaclay, kieselguhr, chalk, diatoma- 'ceous earth, soybean fluor, tobacco fluor, walnut shell fluor, gypsum, mica, apatite, pumice and fullers earth.
- Method of combating fungi comprising treating the locus of the fungi with a fungitoxic amount of a compound having the formula wherein R and R are independently selected from the class consisting of hydrogen and alkyl radicals having one to six carbon atoms.
- Method of combating fungi comprising treating the locus of the fungi with a fungitoxic amount of a diethylene triamine chromium tricarbonyl.
- 260-429 2,916,503 -'l2/ 1959 Kozikowski 260-429 (Other references on following page) 9 UNITED STATES PATENTS De Witt et a1. 260-429 Brown et a1. 260-429 Gash 260-242 Shapiro et a1. 260-429 De Witt et a1 260-429 Weinmayer 260-439 Graham 260-439 Closson at al 260-429 Sandel 23-14 Thomas 260-438" 1 0 3,032,570 5/1962 Haslam 260-4295 3,035,074 5/1962 Haven 260-439 OTHER REFERENCES 10 LEWIS GOTTS, Primary Examiner. MORRIS O. WOLK, Examiner.
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Description
hit.
rat tii are 1 3,224,930 FUNGKIHDAL COMfOSlTIGNS William E. Burt, Royal Gait, Mich, assignor to Ethyl Corporation, New York, N.Y., a corporation of Virginia No Drawing. Filed Dec. 22, 1961, Ser. No. 161,384 4 Claims. (Cl. 167-22) This invention relates to fungicidal compositions, and more particularly, to fungicidally potent organochromium compounds and their use in combating fungi.
An object of this invention is to provide new fungicidal compositions. Still another object is to provide a new means for combating fungi. A further object is to provide new fungicidal compositions comprising conditioning agents and certain organochromium compounds as described herein.
The above and other objects are accomplished by the present invention which resides in providing fungicidal compositions comprising a conditioning agent and as a principal active ingredient, a compound having the formula:
wherein M is a metal of Group VIB of the Periodic Table according to Mendeleev; R R R R and R are selected from the class consisting of hydrogen and alkyl radicals having one to about 6 carbon atoms. and n and n are integers having the value one to six. Compounds of this type can be prepared by reacting the corresponding triamine with either Cr(CO) or cycloheptatriene chromium hexacarbonyl according to the general method of Abel et al., J. Chem. Soc. (1959), 2323.
The most preferred metal is chromium. The fungicidally active compounds of this invention are represented by diethylene triamine chromium tricarbonyl and dihexylene triamine chromium tricarbonyl. However, other compounds wherein the nitrogen atoms in the amine portion of the molecule are substituted with hydrocarbon radicals are also applicable. The preferred compounds either have no substituents on the nitrogen atoms or all the nitrogen atoms are substituted with identical radicals. These preferred compounds are illustrated by the compounds diethylene triamine chromium tricarbonyl, pentaethylpropylene triamine chromium tricarhonyl, dipropylene triamine chromium tricarbonyl, dibutylene triamine chromium tricarbonyl, and the like. Further compounds wherein the nitrogen atoms are substituted by hydrocarbon radicals can be arbitrarily divided into three subclasses. They are, as mentioned above, compounds wherein the nitrogen atoms are fully substituted; symmetrical derivatives wherein R is identical with R in the above formula, or where R and R are equal to R and R and the third class of nitrogen substituted compounds of this invention are the unsymmetrical compounds wherein R is different from R and R and R are either alike or different but not identical with either R or R which again can be either alike or different.
Fully substituted nitrogen derivatives have been illustrated above by the compound pentaethyl ethylene triamine chromium tricarbonyl. Other compounds of this class are pentamethyl propylene triamine chromium tricarbonyl, and pentabutyl butylene triamine chromium tricarbonyl. The most preferred compound is pentaethyl ethylene triamine chromium tricarbonyl.
Symmetrical derivatives are illustrated by the compounds sym-trimethyl ethylene triamine chromium tricarbonyl, sym-dimethyl ethylene triamine chromium tricarbonyl and the like.
Unsymmetrical nitrogen substituted fungicidally active compounds are unsym-N-methyl, N-ethyl, propylene tri- 3,224,939 Patented Dec. 21, 1965 amine chromium tricarbonyl, unsym-dimethylethylene triamme chromium tricarbonyl and the like.
Because of its greater stability, the most preferred compound is diethylene triamine. ch r qrpitup-trjgarbonyl Such compounds as described above are useful in comhating fungi when they are applied to the locus of the fungi. Such treatment, therefore, constitutes one aspect of the invention. It has been found that the above materials are useful in controlling and eliminating fungi which infest vegetables, animals and man. A facet of this invention is a novel method of combating and controlling fungi. Accordingly, one embodimnet of this invention is the method of combating fungi which comprises contacting the fungus with a fungitoxic amount of a compound having the formula given above. Another aspect of this invention is the provision of a method for controlling fungi which comprises treating matter suscepible to fungal infestation with the compound of the above formula.
For maximum effectiveness, the active ingredient of the present invention is admixed in fungicidally effective amount with a conditioning agent of the type commonly referred to as a pest controlled adjuvant or modifier. Such adjuvants have been referred to by names such as conditioning agent, dispersing agent, surface active agent, and surface active dispersing agent. Their purpose is to extend the active ingredient to assure its efficacious penetration of, or application to, the locus being treated and to adapt the active ingredients for ready and efiicient application by using conventional equipment.
An advantage of using these conditioning agents is that the fungicidally active compounds may be too effective or too potent when used alone to be of practical utility. Another advantage derived from the use of these adjuvants is to permit field application by methods readily employed and still obtain elfectively complete coverage of the material being protected.
Formulations of the fungicidally active ingredient with a suitable conditioning agent comprise both liquid and solid types as well as the aerosol type of formulation. y
The liquid type of formulation can have water, an organic solvent, or an oil-Water emulsion and the like as the conditioning agent.
It is also intended that the term conditioning agent include solid carriers such as talc, attaclay, kieselguhr, chalk, diatomaceous earth, and the like, and various mineral powders, such as calcium carbonate, which act as a dispersant, as a carrier, and in some instances, perform the function of a surface active agent.
The conditioning agent may also be an industrial commodity such as paint, raw polymer, finished plastic and the like. Such industrial materials act as a diluent, dispersant, wetting agent, and extender for the active ingredient, thus, enhancing its fungicidal action.
The fomulations of this invention, therefore, comprise the above defined fungicidally active ingredient in a suitable material as a dispersant or conditioning agent. It is not intended that this invention be limited to any specific proportions of active ingredient and conditioning agent. The important feature of the invention is to provide a formulation of such concentration that is appropriate for the desired application. The conditioning agent will be present to provide the proper type of contact with the material being protected.
Nor is it intended that the invention be limited to the use of a fungicidally active ingredient in the presence of only a compound or product or material known as a conditioning agent. It has been found that other additives are useful in the preparation of the fungicidal preparations. Other materials found useful are classified as adhesives. Spreading agents tend to increase the area found to be most advantageous.
ingredient formulations.
QID covered by a spray liquid. Many chemicals act as both wetting and spreading agents. Dried blood (blood albumin), sulfite lye, both in the liquid and dehydrated forms, and petroleum emulsions belong to this group. Adhesives increase the adherence of the active agent to the treated surface to augment resistance to wear and mechanical action. Bentonite and other clays, gelatin and glue, are examples of adhesives.
As mentioned previously, the fungicidal preparations are in the form of either liquid or dry or aerosol formulations. Liquid compositions, either solutions or dispersions, frequently also contain a surface active dispersing agent in amounts suflicient to render the composition readily useful in aqueous spray application. The surface active dispersing agents referred to herein are sometimes known as wetting, dispersing or penetrating agents. They are agents which cause the formulations to be easily dispersed in water. They can be of the anionic, cationic, or nonionic type and include salts of long chain fatty acids, sulfonated oils, both vegetable and animal, petroleum oils, sulfates of long chain alcohols, phosphates of long chain alcohols, various polyethylene oxides, condensation products of ethylene oxide with alcohol and phenols, quaternary ammonium salts, and the like. The surface active agent wil lusually be present to the extent of 0.1 to percent of the formulation. Typical of the liquid formulations is the water solution or dispersion of the active ingredients. Example I below, is an example for the preparation of an aqueous suspension of a typical active ingredient described in this invention.
The active ingredients can also be dispersed or sus pended in various organic solvents such as alcohols, ketones, hydrocarbons, and petroleum fractions such as kerosene, dimethylformamide, and the like. In these cases a surface active dispersing agent is usually present to provide ready dispersability with water.
The solubility of the active ingredients of this invention in organic solvents, furthermore, is such that they can be applied advantageously in the form of a solution in this type of solvent. In certain uses, this type of vehicle is preferred, for example, in treating cloth, leather, or other fibrous articles. In these applications, it is preferred to apply the pesticides dissolved in a volatile solvent. After application, the volatile solvent evaporates leaving the fungicide impregnated throughout the surface of the article and in the dispersed form which has been Likewise, in applying the fungicides to smooth surfaces, as for example in treating wood, a solution may be the most practical vehicle for applying the protective film. Brushing, spraying, or dipping may be the application method of choice. The choice of an appropriate solvent is determined largely by the solubility of the active ingredients which it is desired to employ, by the volatility required in the solvent, by the spreading or flow characteristics thereof, and by the nature of the material being treated. Typical formulation of this type is described in Example II below.
Another typical formulation of the fungicidal ingredients is an oil in water emulsion (see Example III). Generally these are prepared by dissolving the fungicidally active ingredient in an organic solvent, usually a petroleum fraction like kerosene, and then dispersing this solution with vigorous agitation in a large volume of water containing a minor amount of a surface active agent.
In addition to the adjuvants and other ingredients described above, it has been found that one can incorporate an adherent or sticking agent such as vegetable oils, naturally occurring gums, and other adhesives in the active Likewise, humectants can be employed in the formulations. Furthermore, the formulations can be employed in admixture with other pesticidal materials or other biocides such as insecticides, larvacides, bactericides, germicides, miticides or with other materials which it is desired to apply along with the fungicides. In like manner, two or more of the active ingredients may be formulated together in a single composition, thus achieving control of a broader spectrum of fungi.
Fungicides can be applied in dry media as well as in liquid suspensions or solutions. In fact, early practice in the art used dust formulations almost exclusively. It was only the advent of the introduction of spray machinery that caused dust formulations to be considered with disfavor. However, it was soon realized that spraying was often not as convenient as dusting, particularly when large, comparatively inaccessible cultivated fields are to be treated or when the area of interest necessarily requires that it be treated with a dry agent. Dust formulations of my active compounds have a ready place in the art and indeed the use of these dry formulations should grow with time, since they are utilizable when treating large areas for fungicidal infestation by airplane dusting. Dusting is also extensively employed in treating man and animals for fungicidal infestations.
A measure of the utility of the dust formulation is the impressive amount of research which has been performed in this area. The particles shape, the size, density and hardness, and the nature of the dry diluent have been shown to be factors which are important as well as the absorption and absorption characteristics thereof. Therefore, another desired and efficacious formulation of the fungicidally active ingredient is a dust formulation which is prepared generally by milling the active ingredient in ball mill within the presence of a dry material, for example, fullers earth. After milling, the mixture is screened and the fraction passing through a very fine sieve is collected. Thereafter, a further dilution is made by repeating the above procedure with an additional very large amount of a compound such as fullers earth. Example IV exemplifies a dust formulation. A preferred formulation of the compounds comprises a wettable powder. In preparing wettable powders, several formulation procedures are possible (see Example V for one type of procedure). It is one intention of this invention to provide compositions comprising the active ingredient defined herein in combination with a minor amount of surface active agent. Such surface active agents can be chosen for example from those previously mentioned in connection with aqueous dispersion. Still other surface active agents can be employed, the above merely showing a representative list of the more common material. Such formulations can be readily admixed with a solid carrier. Formulations thus formed then comprise the active ingredient of this invention, an inert carrier, and a surface active agent. Among the inert carriers which can be employed in preparing wettable powders are soya bean flour, tobacco flour, walnut shell flour, gypsum, mica, talc, apatite, pumice and the like. In preparing concentrated wettable powders it is preferred to employ between 0.01 and 5 percent of the surface active agent, based upon the amount of active ingredient, and up to percent of the inert carrier based upon the total amount of the formulation. Such concentrated formulations provide the advantage of permitting economical storage and transportation of the fungicide and permit further dilution by simple admixture with water at the time of application.
The compounds described above are also active in colloidal formulations. A colloidal formulation is prepared by passing a mixture of the active ingredient, a hydrocarbon solvent and a large amount of water through a colloid mill until homogenation of the oil and water is achieved. Example VI gives an example of the preparation of a colloidal formulation.
The compounds also find effective use when formulated in aerosol formulations, i.e., when mixed with a liquid of low boiling point that changes to a gas when released from a confined space. Examples of diluent used in these formulations are fluorinated hydrocarbons such as tetrafluoromethane, and hexafluoroethane. Mixed halogenated compounds containing fluorine and chlorine such as difiuorodichloromethane and pentafluorochloroethane and the like can also be used as the l quid having the necessary low boiling point. Other materials such as carbon dioxide, sulfur dioxide, hydrogen sulfide and ammonia can be used, and of these, carbon dioxide generally is preferred. One method of preparing such aerosol formulations comprises introducing my new compounds into a pressure cylinder and later introducing the liquifying diluent under pressure followed by mixing the cylinder to obtain uniform solution. If desired, smaller containers can then be filled from the cylinder in which the formulation is prepared. In many cases it is desirable to add a second solvent to the low boiling material of the type described above so as to more readily dissolve my compounds. Examples of such co-solvents are benzene, acetone, carbon tetrachloride and the like. Example VII is an example of the preparation of an aerosol type formulation of my active ingredient.
My compounds are also elfective when formulated in an ointment for topical application to the epidermis of animals and man. A typical ointment formulation is given in Example VIII below.
It i not intended that the finished formulations of my fungicidally active compounds be limited to any particular concentration range. The concentration range desired in my invention is that range necessary to accomplish the desired end. A preferred range for agricultural application is between 0.1 and 2,000 parts per million. Formulations containing as high as 30 percent active ingredient are used in treating animals and man. Typical formulations of this invention are described in the following examples in which all parts are by weight.
The compounds in the following examples will have the designations given below:
I. Diethylene triamine chromium tricarbonyl II. Sym.-N,N-dimethyl ethylene triamine chromium tricarbonyl III. N,N,N,N,N-pentamethyl diethylene triamine chromium tricarbonyl IV. Unsym.-N,N,N-trimethyl diethylene triamine chrmium tricarbonyl V. Diethylene triamine chromium tricarbonyl VI. N-hexyl diethylene triamine chromium tricarbonyl VII. Sym.-N,N-dipentyl diethylene triamine chromium tricarbonyl VIII. N-ethyl diethylene triamine chromium tricarbonyl EXAMPLE I (WATER SUSPENSION) A formulation of Compound I is prepared by adding, with vigorous agitation, 10 parts of this material to 1,000 parts of water containing 1 part of Tween-80. This concentrated dispersion is further diluted 1,000 times by the addition of Water to obtain a formulation of suitable concentration for application. Thus, the resulting dispersion contains 10 parts per million of my fungicide in the water dispersion.
EXAMPLE II (ORGANIC SOLUTION) A solution consisting of 5 parts of Compound H in 250 parts of cyclohexanone is prepared by stirring the two constituents for a period of two minutes at a temperature of about 25 C. This concentrated solution suitable for storage or transportation is further diluted with 99,750 parts of kerosene to form a final dilution of 50 p.p.m. suitable for application.
EXAMPLE III (OIL IN WATER EMULSION) An oil and water emulsion is prepared by dissolving parts of Compound III in 1,000 parts of kerosene. This solution is dispersed with vigorous agitation in 99,000 parts of water containing one part of Triton X- 100 to provide a dispersion containing 100 ppm. of active 1ngredient.
' USDA Circular No. 198, pages 12 and 14, 1931.
6 EXAMPLE IV (DUST FORMULATION) A dust formulation of the fungicide is prepared by adding one part of Compound IV to parts of fullers earth in a ball mill. The mixture is milled for a period of one hour, screened to collect a fraction passing a 100 mesh sieve. This one percent formulation can be applied directly or further diluted. Further dilution is made by repeating the above procedure with an additional 9,900 parts of fullers earth.
EXAMPLE V (WETTABLE POWDER) A mixture of 100 parts of Compound V, 1,000 parts of attaclay and 0.01 part of Nacconol is intimately mixed in an L-shaped blender. The 10 percent wettable powder thus prepared produces a satisfactory water suspension when 11 parts are stirred into 10,000 parts of water, producing a suspension containing 100 ppm. active ingredient.
EXAMPLE VI (COLLOIDAL FORMULATION) A colloidal formulation is prepared by passing a mix ture of 10 parts of Compound VI, 100 parts of kerosene, 1000 parts of water and 1 part of mannitan monooleate through the colloid mill until hom-ogenation of the oil in water is achieved.
EXAMPLE VII (AEROSOL FORMULATION) Into a cylinder rated at 100 p.s.i. working pressure, is introduced 10 parts of Compound VII. The cylinder is then made pressure tight except for one opening through which is introduced a mixture of 10 parts acetone and 50 parts of dichloro difluoromethane from a container at 2000 p.s.i. The cylinder into which the ingredients are introduced is then sealed off and inverted to give a uniform aerosol solution of my active materials in the mixture of co-solvents.
EXAMPLE VIII (OINTMENT) 2000 parts of Compound VIII is ground in a ball mill Agar-Plate Technique The compounds were screened for anti-fungal activity by the Agar-Plate Technique against five fungi repre: senting groups of economic importance. The test fungl and their occurrences are as follows:
Aspelgillus nigerMildew of fabrics and leather, molding of fruit, bakery good and stored grain. Penicillium expansumMolding of stored grain, hay and fruit. Alternaria solani-Early blight of potato and tomato. Glomerella cingulataBitter rot of apples. Trychophyton interdigitale-Pathogenic for man and animals. Specifically, the method was the Agar-Plate Technic i f, e medium employed was Sabouraud Dextrose Agar. This medium is used for carrying the stock cultures as well as for the test itself. The agar is put into solutlon and then cooled to 42-45 C. To this is added a saline spore suspension of the test organism. The inoculated agar is then poured into sterile Petri dishes and allowed to harden. A suitable amount of the compound tested was placed on a one square centimenter area in the center of the agar. If the compound was solid, the compound was sprinkled upon this area of the plate. When the compound was a liquid, a depression was cut out in the center of the agar by means of a cork borer having a diameter of 1.5 mm. Four drops of the liquid compound were placed in this depression. The agar plates were incubated for days at 25 C. If the compound is inhibitory, a zone of clear agar will be noted around the area of inoculation. The size of this zone is measured, and is an indication of the inhibitory value of the compound tested. The diffusibility of the compound will affect the area of inhibition. If the compound tested has no antifungicidal activity, there will be no area of inhibition, and in some cases, growth will appear under the compound tested.
Serial dilution tests The sample was tested for activity against the same five fungi utilized in the Agar Plate Technique. The fungi for all tests were grown in a Bacto Sabouraud Liquid Medium, pH of 5.7. The sample was dissolved in a minimal quantity of ethanol and diluted with sterile water thereafter to give an original concentration of 512 p.p.m. The test cultures were grown upon the Bacto Sabouraud Dextrose Agar for days. A heavy spore suspension was prepared in buffered distilled water. The inoculum for each tube was one drop of the heavy spore suspension. The test cultures were incubated at 30 C. for 10 days. An effective concentration of 250 parts per million (p.p.m.) is generally accepted as the maximum concentration at which a chemical can be considered for use as an agricultural fungicide.
Further screening of representative types of these compounds was carried out by the serial dilution test according to Burlingame and Reddish, J. Lab. Clin. Med. 24, page 765, 1939. The test fungi used in this case were T richophyton interdigitale, T richophyton rubrum, T ryclzophyton schoenleinii, Microsporum audouini, Epidermophyton floccosum, Microsporum gypseum. These fungi were grown in Difcos Sabourauds liquid medium, pH 4.7. Sample preparation consisted of dissolving aliquots of each compound in 10 mls. of ethanol and diluting to 512 p.p.m. concentrations with distilled water. These stock solutions were serially diluted through 10 tubes of culture medium. The inoculum consisted of 1 drop per tube of a heavy spore suspension of the test fungi. The tests were incubated at 35 C. for one week.
Particular effectiveness of the samples in this series of tests indicates possible therapeutic use in the treatment of athletes foot, ringworm of the nails and scalp and external fungal infection of animals. Some presently commercial fungicides, utilized in this field of therapy, contain an active ingredient in concentrations as high as 30 percent by weight (300,000 parts per 1,000,000).
F oliar fungicide screening Ceral leaf rust wheat is grown in soil in paper pots with 20-30 plants per pot. When the plants are 68 inches tall, they are sprayed with the test solutions (300 p.p.m. and 75 p.p.m. concentration) with three pots used for each treatment applied. After the spray treatments have dried thoroughly, the plants are sprayed with a suspension of spores of wheat leaf rust disease, Paccinia rubz'govera, reared on live wheat leaf culture. After one week to ten days, disease symptoms are observed and percent control obtained by comparison of the sample With inoculated controls and manzate-treated positive controls.
Tomato late blight-Susceptible species tomato plants are treated from seed and transplanted into soil in individual paper pots. When they are 6 to 8 inches high, they are sprayed with the test solutions (300 p.p.m. and 75 p.p.m. concentration) with three plants used for each treatment applied. After the spray treatments have dried .thorou hly, the plants are sprayed with a suspension of spores of the tomato late blight fungus, Phytophthora infestans, which is reared on lima bean agar culture. After a few days to one week disease symptoms are observed and percent control obtained by comparison of the sample with inoculated controls and manzate-treated positive controls.
Powdery mildew of cucumbers-Susceptible species oncumbers are grown in soil in paper pots with 2-3 plants per pot. When the first leaf has reached a size of about 3 inches in diameter, they are sprayed with the test solutions (300 p.p.m. and 75 p.p.m. concentration) with 3 pots used for each treatment applied. After the spray treatments have dried thoroughly, the plants are dusted with spores of powdery mildew fungus Erysiphe cichoracearum, reared on live cucumber leaf culture. After one week to ten days, disease symptoms are observed and percent control obtained by comparison of the sample with inoculated controls and Karathane-treated positive controls.
Agar plate Zone of inhibition in millimeters An Po As Ge Ti Diethylene triamine chromium tricarbonyL. 5 5 3 3 2 No'rE.-An=Aspergillus niger. Pe=Pcnicillum ezpansum. As=
lltetniaria solani. Ge: Glomeralla cingulata. Ti=Trychophyton inter- I claim: 1. A fungicidal composition consisting of '(a) as a principal active ingredient a compound having the formula N-orn-onz-N-orn-orn-N one on wherein R and R are independently selected from the class consisting of hydrogen and alkyl radicals having from one to six carbon atoms,
(b) from 0.1 to 5 weight percent of a surface active dispersing agent as a dispersant therefor, and
(c) the remainder of said composition consisting essentially of a solid carrier selected from the class consisting of talc, attaclay, kieselguhr, chalk, diatoma- 'ceous earth, soybean fluor, tobacco fluor, walnut shell fluor, gypsum, mica, apatite, pumice and fullers earth.
2. A fungicidal composition of claim 1 wherein said principal active ingredient is diethylene triamine chromium tricarbonyl.
-3. Method of combating fungi comprising treating the locus of the fungi with a fungitoxic amount of a compound having the formula wherein R and R are independently selected from the class consisting of hydrogen and alkyl radicals having one to six carbon atoms.
Method of combating fungi comprising treating the locus of the fungi with a fungitoxic amount of a diethylene triamine chromium tricarbonyl.
References Cited by the Examiner UNITED STATES PATENTS 2,178,099 10/1939 Gornitz et al. 260-431 2,208,253 7/ 1940 Flenner et al 167-22 2,278,965 4/ 1942 Van Peski et a1 260-429 2,818,416 12/1957 Brown et al. 260-429 2,818,417 12/1957 Brown et al. 260-429 2,839,552 6/1958 Shapiro et al 260-429 2,864,843 12/1958 De Witt et al 26O--429.9 2,898,354 8/ 1959 Shapiro et al. 260-429 2,916,503 -'l2/ 1959 Kozikowski 260-429 (Other references on following page) 9 UNITED STATES PATENTS De Witt et a1. 260-429 Brown et a1. 260-429 Gash 260-242 Shapiro et a1. 260-429 De Witt et a1 260-429 Weinmayer 260-439 Graham 260-439 Closson at al 260-429 Sandel 23-14 Thomas 260-438" 1 0 3,032,570 5/1962 Haslam 260-4295 3,035,074 5/1962 Haven 260-439 OTHER REFERENCES 10 LEWIS GOTTS, Primary Examiner. MORRIS O. WOLK, Examiner.
Claims (1)
1. A FUNGICIDAL COMPOSITION CONSISTING OF (A) AS A PRINCIPAL ACTIVE INGREDIENT A COMPOUND HAVING THE FORMULA
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