US3154467A

US3154467A - Chlorinated unsaturated hydrocarbonisothiocyanate synergistic nematocidal compositions and method

Info

Publication number: US3154467A
Application number: US218837A
Authority: US
Inventors: Katsaros Constantine; Clare B Kenaga
Original assignee: Morton Salt Co
Current assignee: Morton Salt Co
Priority date: 1962-08-23
Filing date: 1962-08-23
Publication date: 1964-10-27
Anticipated expiration: 1981-10-27

Description

United States Patent CHLORINATED UNSATURATED HYDROCARBON- TSOTHEOCYANATE SYNERGHSTTC NEMATOCI- DAL (IOMPOSITHONS AND METHOD Constantine Katsaros, Crystal Lake, llll., and Clare B. Kenaga, Lake Geneva, Wis, assignors to Morton Salt (Zompany, Chicago, Ill., a corporation of Delaware No Drawing. Filed Aug. 23, 1962, Ser. No. 218,837

7 Claims. (Cl. 167-22) This invention relates to nematocidal compositions and more particularly to synergistic nematocidal compositions containing 1,4-dichloro-2-butene, 1,3-dichloro-2-butene or 1,4-dichloro-2-butyne.

Certain isothiocyanates have been used in the control of nematodes with variable results. One such material is allyl isothiocyanate (also known as mustard oil) which has been shown to be an effective nematocide in contact tests or when applied to nematode infestations. HoW- ever, it has been found that allyl isothiocyanate loses its practical effectiveness as a nematocide particularly when applied to nematode infestations in an organic, loam, or muck soil to such an extent as to be considered substantially inactive.

It has been found, however, that the drawbacks inherent in tie use of allyl and other organic isothiocyanates can be largely eliminated or minimized by the incorporation therewith of an unsaturated chlorinated hydrocarbon from the group of 1,4-dichloro-2-butene, 1,3-dichloro-2-butene and 1,4-dichloro-2-butyne. It has also been found that the combination of isothiocyanate and dichlorobutene or dichlorobutyne results in a synergism, the resultant compositions having unexpectedly high activity as a nematocide and greater effectiveness than either compound when used alone.

Accordingly, in one broad form, the present invention comprises the provision of a synergistic nematocidal composition comprising an admixture of a compound selected from the group consisting of 1,4-dichloro-2-butene, 1,3- dichloro-Z-butene and 1,4-dichloro-2-butyne with a compound selected from the group consisting of alkyl, alkenyl, and cycloalkyl isothiocyanates.

A further aspect of the present invention is the provision of a process for controlling nematodes in soils which comprises applying to nematodes and their habitats a composition containing an admixture of 1,3-dichloro-2- butene, 1,4-dichloro-2-butene or 1,4-dichloro-2-butyne and an isothiocyanate selected from the group consisting of alkyl isothiocyanates, alkenyl isothiocyanates and cycloalkyl isothiocyanates.

The alkyl and the alkenyl isothiocyanates contemplated for use in the synergistic compositions of this invention are lower alkyl and alkenyl isothiocyanates'preferably wherein said alkyl or alkenyl substituents contain up to about '6 carbon atoms. Exemplary of such substituents are groups, such as methyl, ethyl, N-propyl, isopropyl, butyl, amyl, isoamyl, allyl, butenyl and the like. With respect to cycloalkyl derivatives, substituents containing up to 8 carbon atoms are contemplated, exemplified by cyclohexyl, cyclopentyl, methylcyclopentyl, methylcyclohexyl and dimethylcyclohexyl isothiocyanate.

The organic isothiocyanate and chlorinated unsaturated hydrocarbon may be present in varying proportions, preferably however, the organic isothiocyanate is present in amounts of from to 50 percent (by weight) and the chlorinated hydrocarbon in amounts of from 50 to 95 ercent. In the most preferred form the isothiocyanate constitutes from 10 to 30 percent and the chlorinated unsaturated hydrocarbon from 70 to 90 percent, said percentages being based on the relative proportions of the named components Alternatively, the perecntages may "ice be expressed as ratios of parts by weight of the components, i.e., containing from 5 to 50 parts isothiocyanate and from 50 to parts by weight of chlorinated hydrocarbon, and preferably containing from 10 to 30 parts isothiocyanate and from 70 to '90 parts chlorinated hydrocarbon.

Since the nematocidal compositions of this invention may be utilized in various forms including formulations containing diluents or carriers, the recited percentages have reference to the isothiocyanate and chlorinated unsaturated hydrocarbon components without reference to any ancillary diluents.

The following procedure Was utilized in evaluating the toxicity and effectiveness as a nematocide of the compositions of the present invention.

TEST PROCEDURE The product to be tested is dissolved in N,N-dimethylformamide in at least a 5% concentration. One end of a 5-inch glass tube, having a 1 inch I.D., is corked and the tube filled with about 57 grams of black loam soil, previously adjusted to a 20% moisture level and passed through a No. 12 sieve (US. Standard Sieve Series). The soil is gently and evenly compacted in the tube. When compacted, the soil column is 3% to 3 /2 inches long. A onefourth inch layer of dry sea sand is then added. Nematodes to be tested are removed from an oatmeal culture by means of the Baerman funnel technique using physiological saline, 0.85% sodium chloride. The concentration of nematodes should be between 12,000 to 15,000 nematodes per cc. with a volume of 35-50 ml. By means of a medicine dropper 4-6 drops of the nematode suspension (30005()O() nematodes) are distributed evenly over the surface of the sand. An additional /4 inch layer of dry sea sand is added to the tube and moistened with 1 ml. of physiological saline. A thin polyethylene film is placed over the open end of the tube and a cork pushed into the tube to the point of contact with the sand. The tube is then inverted and the first cork removed. A small depression is made in the soil with a glass rod. The solution to be tested is pipetted into the tube in the depression. The compound to be tested is added in the desired amount. After addition of the test compound the open end of the tube is covered with a thin film of polyethylene and recorked. All treatments are replicated three times. The tubes are left in the dark at 80 F. in an upright position (nematodes at the bottom of the tube) for 48 hours.

To determine the effectiveness of the compound, the sea sand containing the nematodes is removed from the tube and flushed with 10 ml. of physiological saline, and the saline solution decanted to a watch glass. The count on the check is carried out by noting the number of nematodes in the check required to give live nematodes. The figure obtained is used as a basis of count in the counting of the treated nematodes. The following results were obtained using Panagrellus redivivus as the test nematode.

The following tables illustrate the synergistic nematocidal effect obtained by the use of an admixture of an organic isothiocyanate with 1,4-dichloro-2-butene, 1,3-dichloro-Z-butene, or 1,4-dichloro-2-butyne. The test procedure was as described above. The dosage is given in micrograms g) per tube in each test. The degree of synergism is shown in terms of increase in percent kill over the theoretical.

Table A shows the results obtained by the use of methyl isothiocyanate alone, 1,4-dichloro-2-butene alone and by the use of a mixture of the compounds.

Table B shows the results obtained by the use of methyl isothiocyanate alone, 1,3-dichloro-2-butene alone, and by the use of a mixture of the compounds.

3 Table C shows the results obtained by the use of 1,41 dichloro-Z-butyne alone, methyl isothiocyanate alone and by the use of a mixture of the compounds.

Table A Nematocidal Composition, Conccn- Theoretitration in gJtube cal Percent Amount Actual Kill 01 Syner- Kill Based on gism 1,4di- Methyl- Additive chloroisothio- Efiects Z-butene cyanatc Table B N ematocidal Composition, Oonccn- Theoreti tration in gJtube cal Percent Amount Actual Kill of Syn- Kill Based on crgism 1,3-di- Methyl- Additive chloroisothio- Eflects 2-butene cyanate Table C Nematocidal Composition, Concen- Theoretitration in g/tube cal Percent Amount Actual Kill of Syn- Kill Based on ergism 1,4- di- Methyl- Additive chloroisothio- Effects 2-butyne cyanate While the foregoing compositions may readily be applied to loam soils in their undiluted form, it is also true that they may, if desired, be applied in conjunction with diluents or carriers which are inert or inactive to aid in the distribution of the active synergistic composition. For example, solvents, such as deodorized kerosene, ketones, esters, alcohols, chlorinated hydrocarbons and various low-boiling petroleum fractions, may be utilized in conjunction with the present synergistic compositions. In addition to organic solvent carriers of the type described above, the present nematocidal compositions may be applied in the form of emulsions, dispersions or the like. The amount of material varies of course with the type of infestation and the characterof the particular area to be treated, but application of the compositions at rates from about 2 to about 100 gallons per acre is satisfactory.

It is also contemplated that admixtures of one or more of the unsaturated chlorinated hydrocarbons may be employed with one or several of the organic isothiocyanates described in the foregoing.

While several embodiments of this invention are shown above, it will be understood that the invention is not limited thereto, since many modifications may be made, and it is contemplated, therefore, by the appended claims, to cover any such modifications as fall within the true spirit and scope of this invention.

We claim:

1. A synergistic nematocidal composition comprising an admixture containing on a relative proportion basis from about 50 to percent by weight of a chlorinated unsaturated hydrocarbon selected from the group consisting of 1,4-dichloro-2-butene, 1,3-dichloro-2-butene and 1,4-dichloro-2-butyne and from about 5 to about 50 percent by weight of methyl isothiocyanate.

2. The composition of claim 1 wherein the chlorinated unsaturated hydrocarbon is 1,4-dichloro-2-butene.

3. The composition of claim 1 wherein the chlorinated unsaturated hydrocarbon is 1,3-dichloro-2-butene.

4. The composition of claim 1 wherein the chlorinated unsaturated hydrocarbon is 1,4-dichloro-2-butyne.

5. A synergistic nematocidal composition comprising an admixture containing on a relative proportion basis from about 50 to 95 percent by weight of a chlorinated unsaturated hydrocarbon selected from the group consisting of 1,4-dichloro-2-butene, 1,3-dlchloro-2-butene and 1,4-dichloro-2-butyne and from about 5 to about 50 percent by weight of methyl isothiocyanate and a carrier therefor.

6. A process for controlling nematode infestations in soils which comprises applying to nematodes and their habitats an admixture containing on a relative proportion basis from about 50 to 95 percent by weight of a chlorinated unsaturated hydrocarbon selected from the group consisting of 1,4-dichloro-2-butene, 1,3-dichloro-2-butene and 1,4-dichloro-2-butyne and from about 5 to 50 percent by weight of methyl isothiocyanate.

7. The process of claim 6 wherein the admixture is applied in conjunction with a carrier.

References Cited in the file of this patent UNITED STATES PATENTS 2,057,044 Meisenburg et al Oct. 13, 1936 2,112,688 Bousquet Mar. 29, 1938 2,824,887 Klopping Feb. 25, 1958 2,849,366 Youngson et al. Aug. 26, 1958

Claims

1. A SYNERGISTIC NEMATOCIDAL COMPOSITION COMPRISING AN ADMIXTURE CONTAINING ON A RELATIVE PROPORTION BASIS FROM ABOUT 50 TO 95 PERCENT BY WEIGHT OF A CHLORIDATED UNSATURATED HYDROCARBON SELECTED FROM THE GROUP CONSSISTING OF 1,4-DICHLORO-2-BUTENE, 1,3-DICHLORO-2-BUTENE AND 1,4-DICHLORO-2-BUTYNE AND FROM ABOUT 5 TO ABOUT 50 PERCENT BY WEIGHT OF METHYL ISOTHIOCYANATE.