US3345258A - Fungicidal compositions and methods - Google Patents

Description

United States Patent 3,345,258 FUNGICIDAL COMPOSITIONS AND METHODS Harry A. Sidles, Wheaton, Ill., assignor to Velsicol Chemical Corporation, Chicago, Ill., a corporation of Illinois No Drawing. Filed Aug. 9, 1965, Ser. No. 478,431 15 Claims. (Cl. 167-39) This invention relates to new fumigant compositions having high residual activity. In particular this invention relates to compositions containing methyl bromide and insecticidally and fungicidally active materials and a method of applying them to the soil. Methyl bromide has been known for many years to be an extremely effective fumigant. It is extremely effective against a variety of insects, nematodes, weeds and fungi. It is used to fumigate warehouses, plants, mills and other buildings. It is particularly used to fumigate bulk grain. In addition it can be used as a soil fumigant. 7

While methyl bromide is extremely eifective as a fumigant and it gives relatively instantaneous results because it is a gas at normal room temperatures and pressures, it does not have appreciable residual activity. Thus, while it does give an excellent short-term protection against insects, weeds, fungi, it is relatively poor for protecting areas for long periods of time.

It is, therefore, an object of the present invention to provide an effective fumigant having improved residual eifect.

It is a further object of the present invention to provide short-term and residual protection against pests and undesirable plant life in a single application.

It is still another object of the present invention to provide compositions that will provide this short and long-term protection without the need for extensive amounts of inert carrier material.

It is still another object of the present invention to provide compositions which will give the desired protection on a uniform basis.

It is still another object of the present invention to devise a method for protecting plants from infestation and infection for a substantial time interval by a single application.

Other objects of the present invention will become apparent from the ensuing description.

It has now been found that compositions containing a major amount of methyl bromide and in addition containing a residual insecticide and a residual fungicide can be easily prepared. These compositions comprising the present invention containas their active components methyl bromide in combination with residual fungicides and residual insecticides. .Since methyl bromide is an odorless and somewhat hazardous material, it is normal to include in compositions containing it a warning agent. One of the most widely used warning agents is chloropicrin. This warning agent is normally present in amounts of about 1 or 2% by weight of the methyl bromide. Other warning agents can be used.

The ratio of the three active ingredients present in the compositions will vary with their identity and with the application for which the composition is being prepared. The reason for this is that various insecticides and fungicides will have different effectiveness and accordingly will require varied amounts to provide adequate protection.

Among the insecticides which can be used in these compositions are the chlorinated hydrocarbons including chlordane, heptachlor, aldrin, and dieldrin. Other insecti cides are also useful for specific purposes.

A variety of fungicidally active materials can be used in these compositions. As in the case with the insecticides, their selection will depend upon the material being protected. Among the fungicidally active materials useful are the mercurial fungicides such as mercuric chloride, mercurous chloride, N-methylmercuri-l,2,3,6-tetrahydro- 3,6 endomethano 3,4,5,6-,7,7 hexachlorophthalimide, N ethylmercuri 1,2,3,6-tetrahydro-3,6-endomethano-3, 4,5,6,7,7 hexachlorophthalimide, N phenylmercuri-1,2, 3,6 tetrahydro 3,6 endomethano 3,4,5,6,7,7-hexachlorophthalimide, N (ethylmercuri)-p-toluenesulfonan ilide, methylmercuric dicyandiamide, phenylmercury urea, phenylmercuric acetate and hydroxymercurichlorophenol; pentachloronitrobenzene; dithiocarbamate fungicides such as diammonium ethylenebisdithiocarbamate, ferric dimethyl dithiocarbamate, manganous ethylenebisdithiocarbamate, disodium ethylenebisdithiocarbamate, sodium N methyldithiocarbamate, zinc ethylenebisdithiocarbamate and zinc dimethyldithiocarbamate; organic copper fungicides such as: copper 8-hydroxyquinolinate, and copper naphthenate; and N-trichloromethylmercapto-4-cyclohexene-LZ-dicarboximide.

In selecting the insecticidal and fungicidal components of the present compositions it is important that they possess appreciable residual activity. This is true of most commercial insecticides and fungicides particularly those indicated above.

The amounts of the specific components of the present compositions as indicated above will vary appreciably depending upon the ultimate use of the composition. It must be kept in mind that in the present compositions different amounts of the methyl bromide, insecticide and fungicide are required for a given application and since all are being applied in a single application, the ratios of the components must be selected in accordance with the amounts of materials required to be applied to the area. For most applications the composition can contain fungicide in an amount by weight of from about 0.05 to 10% of the methyl bromide content. The insecticidal component can also be present in an amount by weight from about 0.05 to 10% by weight of the methyl bromide. For most applications the content of the insecticidal and fungicidal component can be from about 0.1 to 5% by weight of the methyl bromide. The organic mercurial fungicides need be present in many applications in relatively low concentrations. Normally it is sufficient that it be present in an amount from about 0.1 to 1% by weight of the methyl bromide.

Since methyl bromide is a gas at normal temperatures, it is applied from pressure containers. Procedures used for preparing methyl bromide containers can be used in preparing the present formulations. This can be readily accomplished by lowering the methyl bromide tov a temperature whereat it is a liquid. Temperatures of from about 10 to 20 C. are adequate.

Once the methyl bromide is in the liquid form the other components of the compositions can be readily dispersed in it. These components would of course include the insecticidally active material, the fungicidally active material and the warning agent such as chloropicrin. This solution is then placed in a suitable container from which it can be discharged as a vapor. It can be seen from this that by using the present compositions there is no need for inert diluent. The methyl bromide in fact acts as a diluent and dispersant for the other components. This eliminates the use of inactive components and maximizes the use of the available container space.

In certain instances it is advantageous to utilize a solvent for the residual fungicide and/or the residual insecticide. The use of this solvent can be of value in improving the uniiorm application of materials having low solubility in methyl bromide. It is not required by the present invention that these solvents be employed and it is a preferred feature of this invention that they not be present. When an auxiliary solvent is used it preferably will constitute a small percentage of the total composition, although larger amounts can be used.

The selection of the solvent will vary with the identity of the fungicide and insecticide. Compounds known to be useful solvents for these materials can be employed for this purpose. Exemplary of these solvents are the higher boiling alcohols, such as diacetone alcohol and carbitol; mineral spirits; and aromatic solvents, such as benzene, toluene, etc. which are particularly useful for the organic mercurial fungicides, the aromatic solvents also being useful in preparing solutions of pentachloro- 'nitrobenzene, the organic copper fungicides and the chlorinated hydrocarbon insecticides.

It has also been found that unusually uniform application of the components is obtained from these formulations. The release of the methyl bromide from the container disperses with it the other components in uniform lamounts over the protected area. This uniformity is not easily obtained by other means, particularly by a single application.

Applications of these formulations possess residual activity not possessed by methyl bromide alone. Accordingly, areas treated with this formulation have superior plant growth over a substantial period of time. It has alsso been found that these formulations remain in the upper layers of the soil where they are best able to protect the area from infestation. Soils treated with the present combination showed larger plants, more plants and a greener color plant than areas treated with methyl bromide alone.

Many formulations can be used by the foregoing procedure and as are illustrated by the following examples:

Example 1 Chlordane (4.5 g.), N-methylmercuri-1,2,3,6-tetrahydro 3,6-endomethano-3,4,5,6,7,7-hexachlorophthalirnide .[1.1 g. in diacetone alcohol (6.6 g.)] and chloropicrin procedure of Example 1.

Example 2 Components: Parts by wt.

N methylmercuri-1,2,3 ,6-tetrahydro-3 ,6-endomethano 3,4,5,6,7,7 hexachlorophthalimide 0.25 Heptachlor 0.50 Chloropicrin 1.00 Methyl bromide 98.25

Example 3 Components:

N methylmercuri-l,2,3,6-tetrahydro-3,6-endomethano 3,4,5,6,7,7 hexachlorophthalimide 0.25 Aldrin 0.50 Chloropicrin 1.00 Methyl bromide 98.25

Example 4 Components:

N methylmercuri-1,2,3,6-tetrahydro-3,6-endomethano 3,4,5,6,7,7 hexachlorophthalimide 0.25

Dieldrin 0.50 Chloropicrin 1.00 Methyl bromide 98.25

4 Example 5 Components: Parts by wt. Pentachloronitrobenzene 2.00 Chlordane 1.00 Chloropicrin 1.00 Methyl bromide 96.00

Example 6 Components:

Pentachloronitrobenzene 2.00 Heptachlor 0.50 Chloropicrin 1.00 Methyl bromide 96.50

Example 7 Components:

Pentachloronitrobenzene 2.00 Aldrin 0.50 Chloropicrin 1.00 Methyl bromide 96.50

Example 8 Components:

Pentachloronitrobenzene 2.00 Dieldrin 0.50 Chloropicrin 1.00 Methyl bromide 96.50

Example 9 Components:

N-trichloromethylmercapto-4-cyclohexene-1,2-

dicarboximide 1.00 Chlordane 1.00 Chloropicrin 1.00 Methyl bromide 97.00

Example 10 Components:

Zinc ethylenebisdithiocarbamate 1.00 Heptachlor 0.50 Chloropicrin 1.00 Methyl bromide 97.50

Example 11 Components:

N methylmercuri-l,2,3,6-tetrahydro-3,6-end0- methano 3,4,5,6,7,7 hexachlorophthalimide 0.05 Chlordane 1.50 Chloropicrin 1.00 Methyl bromide 97.45

Example 12 Components:

N ethylmercuri 1,2,3,6-tetrahydro-3,6-endomethano 3,4,5,6,7,7 hexachlorophthalimide 0.50 Chlordane 0.05 Chloropicrin 1.5 0 Methyl bromide 97.95

Example 13 Components:

Manganous ethylenebisdithiocarbamate 0.10 Aldrin 1.20 Chloropicrin 1.60 Methyl bromide 97.10

Example 14 Components:

Ferric dimethyl dithiocarbarnate 0.05 Heptachlor 9.00 Chloropicrin 1.00

Methyl bromide 89.95

Example I 5 Components: Parts by wt. Disodium ethylenebisdithiocarbamate 8.00 Aldrin 2.50 Chloropicrin 1.50 Methyl bromide 88.00

It can be seen from this that a variety of compositions of varied amounts of components can be prepared in accordance with the present invention.

While the present compositions are useful in protecting a variety of areas, one of its more important uses is in the protection of tobacco seed beds. Tobacco seed beds are areas where tobacco seedlings are grown for transplanting into tobacco fields. These seedlings are quite open to attack by a variety of pests. It has been found that the present compositions are particularly advantageous in providing this protection. Protection of other seedlings for transplanting can also be accomplished by use of these compositions.

I claim:

1. A composition which consists substantially of methyl bromide, residual fungicide in a content of about 0.05 to by weight of methyl bromide and a residual chlorinated hydrocarbon insecticide selected from the group consisting of chlordane, heptachlor, aldrin and dieldrin in a content of about 0.05 to 10% by weight of methyl bromide.

2. A composition which consists substantially of methyl bromide, residual mercurial fungicide in a content of about 0.05 to 10% by weight of methyl bromide and a residual chlorinated hydrocarbon insecticide selected from the group consisting of chlordane, heptachlor, aldrin and dieldrin in a content of about 0.05 to 10% by weight of methyl bromide.

3. A composition which consists substantially of methyl bromide, residual dithiocarbamate fungicide in a content of about 0.05 to 10% by weight of methyl bromide and a residual chlorinated hydrocarbon insecticide selected from the group consisting of chlordane, heptachlor, aldrin and dieldrin in a content of about 0.05 to 10% by weight of methyl bromide.

4. A new composition which consists substantially of methyl bromide, N-methylmercuri-l,2,3,6-tetrahydro-3,6- endomethano-3,4,5,6,7,7-hexachlorophthalimide in a content of about 0.05 to 10% by weight of methyl bromide and chlordane in a content of about 0.05 to 10% by weight of methyl bromide.

5. A new composition which consists substantially of methyl bromide, N ethyhnercuri 1,2,3,6-tetrahydro-3,6- endomethano-3,4,5,6,7,7-hexachlorophthalimide in a content of about 0.05 to 10% by weight of methyl bromide and chlordane in a content of about 0.05 to 10% by weight of methyl bromide.

6. A composition which consists substantially of methyl bromide, pentachloronitrobenzene in a content of about 0.05 to 10% by weight of methyl bromide and a residual chlorinated insecticide selected from the group consisting of chlordane, heptachlor, aldrin and dieldrin in a content of about 0.05 to 10% by weight of methyl bromide.

7. A method for the protection of plants against infestation and infection which comprises applying to the soil of the plants an effective amount of the composition of claim 6.

8. A composition which consists substantially of methyl bromide, N-methylmercuri-1,2,3,6-tetrahydro-3,6-endomethano-3,4,5,6,7,7-hexachlorophthalimide in a content of about 0.05 to 10% by weight of methyl bromide and a residual chlorinated hydrocarbon insecticide selected from the group consisting of chlordane, heptachlor, aldrin and dieldrin in a content of about 0.05 to 10% by weight of methyl bromide.

9. A composition which consists substantially of methyl bromide, residual organic copper fungicide in a con- 6 tent of about 0.05 to 10% by weight of methyl bromide and a residual chlorinated hydrocarbon insecticide selected from the group consisting of chlordane, heptachlor, aldrin and dieldrin in a content of about 0.05 to 10% by weight of methyl bromide.

10. A composition which consists substantially of methyl bromide, N-trichloromethylmercapto-4-cycl-ohexene- 1,2-dicarboximidein a content of about 0.05 to 10% by weight of methyl bromide and a residual chlorinated hydrocarbon insecticide selected from the group consisting of chlordane, heptachlor, aldrin and dieldrin in a content of about 0.05 to 10% by weight of methyl bromide.

11. A method for the protection of plants against infestation and infection which comprises applying to the soil of the plants an effective amount of a composition comprising methyl bromide, residual fungicide in a content of about 0.05 to 10% by weight of methyl bromide and a residual chlorinated hydrocarbon insecticide selected from the group consisting of chlordane, heptachlor, aldrin and dieldrin in a content of about 0.05 to 10% by weight of methyl bromide.

12. A method for the protection of plants against infestation and infection which comprises applying to the soil of the plants an effective amount of a composition comprising methyl bromide, residual mercurial fungicide in a content of about 0.05 to 10% by weight of methyl bromide and a residual chlorinated hydrocarbon insecticide selected from the group consisting of chlordane, heptachlor, aldrin and dieldrin in a content of about 0.05 to 10% by weight of methyl bromide.

13. A method for the protection of plants against infestation and infection which comprises applying to the soil of the plants an effective amount of a composition comprising methyl bromide, N-methylmercuri-l,2,3,6-tetrahydro-3,6-endomethano-3,4,5,6,7,7 hexachlorophthalimide in a content of about 0.05 to 10% by weight of methyl bromide and a residual chlorinated hydrocarbon insecticide selected from the group consisting of chlordane, heptachlor, aldrin and dieldrin in a content of about 0.05 to 10% by weight of methyl bromide.

14. A method for the protection of plants against infestation and infection which comprises applying to the soil of the plants an effective amount of a composition comprising methyl bromide, residual dithiocarbamate fungicide in a content of about 0.05 to 10% by weight of methyl bromide and residual chlorinated hydrocarbon insecticide selected from the group consisting of chlordane, heptachlor, aldrin and dieldrin in a content of about 0.0 to 10% by weight of methyl bromide.

15. A method for the protection of plants against infestation and infection which comprises applying to the soil of the plants an effective amount of a composition comprising methyl bromide, residual organic copper fungicide in a content of about 0.05 to 10% by weight of methyl bromide and a residual chlorinated hydrocarbon insecticide selected from the group consisting of chlordane, heptachlor, aldrin and dieldrin in a content of about 0.05 to 10% by weight of methyl bromide.

References Cited UNITED STATES PATENTS 2,598,562 5/1962 Kleiman 260-326 OTHER REFERENCES Frear: Pesticide Index (1963), College Science Publishers, PO. Box 798, State College, Pa., pp. 16, 47, 51, 123,156 and 181.

Thorn: The Dithiocarbamates and Related Compounds (1962), Elsevier Publishing Co., New York, pp. 3 and 4.

Frear: Pesticide Index (1961), p. 132.

ALBERT T. MEYERS, Primary Examiner. JULIAN S. LEV-ITT, Examiner. STANLEY J. FRIEDMAN, Assistant Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,345,258 October 3, 1967 Harry A. Sidles It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 3, line 25, for "alsso" read also column 6, line 48 for "0 0" read 0 .05

Signed and sealed this 15th day of October 1968.

(SEAL) Attest:

EDWARD J. BRENNER Edward M. Fletcher, Jr.

Commissioner of Patents Attcsting Officer

Claims (1)

1. A COMPOSITION WHICH CONSISTS SUBSTANTIALLY OF METHYL BROMIDE, RESIDUAL FUNGICIDE IN A CONTENT OF ABOUT 0.05 TO 10% BY WEIGHT OF METHYL BROMIDE AND A RESIDUAL CHLORINATED HYDROCARBON INSECTICIDE SELECTED FROM THE GROUP CONSISTING OF CHLORDANE, HEPTACHLOR, ALDRIN AND DIELDRIN IN A CONTENT OF ABOUT 0.05 TO 10% BY WEIGHT OF METHYL BROMIDE.