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3,084,094 1C6 Patented Apr. 2, 1963 2 sentative compounds comprising this group of haloalkyl 3,0s4n94 Samuel I. Ger-tier, Washington, D.C., dedicated to the public No Drawing. Filed ca. 4, 1955, Ser. No. 538,537 esters. NEMATOCHDAL HALOALKYL ACID ESTER TABLE I. NEMATOCIDAL ACTION OF HALOALKYL ESTERS AGAINST Heterodera Rostochiensis 8 Claims. ((11.167-22) (Granted under Title 35, US. Code (1952), sec. 266) Concentra Name of Toxic Compound A non-exclusive, irrevocable, royalty-free license in the invention described, for all governmental purposes, 10 throughout the world, with the power to grant sublicenses for such purposes, is hereby granted to the Government of the United States of America. The patent rights for the United States in any inven tion in the patent to be granted on this application are dedicated to the public. This invention relates to nematocides, their prepara tion and their method of application. 1 tion, per cent by No. of weeks be fore ex- ' amining cysts Percent Mortality of Nema todes 100 100 100 Butyl chloroaeetate _____________ __ Do _____________ .. H. 100 100 2-Ch1oro1sopropy1 Z-chloropro pionate _______________________ __ p-Methylcyclohexyl 2-chlor0pro oco0:0 100 8800SOH pionate _______________________ __ 2-ChIl)or0ethyl 3-chloropropionate Nematodes belong to a class of unsegmented worms of the phylum Nemathelminthes. Certain species of this class of worm, members of the subfamily Pratylenchinae p are known to effect a number ‘of subtropical ‘and tropical u c _____________________ __ 2-Octyl 3-chl0roprop1onate ______ _ _ plants. They have been found in the roots of citrus Z-Ethylhexyl 3-chloropropionate. _ 2-Butyloety1 3-chloropropionate- _ and a wide rvariety of other plants including many orna mentals. These root inhibiting nematodes are believed Bengl 3-chloropropionate ...... _ o _________________ __ to be responsible for “spreading decline” in citrus and cause millions of dollars of annual damage in the United D0 4-Isopropylcyclohexyl 2-Phenoxyethyl B-chloropro States. It has ‘been found that esters of haloalkyl acids are pionate _______________________ __ effective agents for treating the roots of plants for the 30 pionate _______________________ _ control of harmful nematodes contained therein. These esters can be represented by the general formula EXAMPLE II R-(?J-O R1 0 35 Nematocide Tests Using Pratylenchus sp. For these tests the nematocidal emulsions were pre wherein R is selected from a group consisting of pared as in Example I using concentrations of from GHi-—-, CH;—(|JH—- and urn-Cirr 0.1 percent to 1.0 percent by 'volume. ‘Ornamental plants such as azalea, philodendron, hibiscus, Chinese evergreen, 40 midget palm and the like, the roots of which were infested and wherein R1 is selected from a group comprising an with meadow nematode (Pratylenchus sp.) were used alkyl group, a halogen-substituted alkyl group, a cyclo as a host. The roots of these plants were washed free aliphatic group, an alkyl-substituted cycloaliphatic group, of adherent soil and the excess Water removed prior to an aralkyl group and an aroxyalkyl group. ' ' The compounds were prepared by the esteri?cation 45 treatment. The plants were then arranged in the treat ing vessels so that only the roots were immersed in the of the halogenated acid with the required alcohol by nematocidal medium for one hour. Splashing is avoided methods known in the art, using a suitable catalyst, such on the rest of the plant to prevent any possibility of as sulphuric acid or toluene-sulfonic acid. The following examples illustrate the effectiveness of injury to foliage. The plants are then removed, replanted times as much of a Wetting agent, such as Triton X-lOO 55 TERS AGAINST PRATYLENCHUS SP. the compositions made according to this invention. 50 in sterile soil and examined at daily intervals. The roots were chopped in a Waring Blendor, the nematodes col Nematocide test compositions according to this invention ‘looted by sieving and the e?ectiveness of the control thus contain from a minimum of 0.001 percent to 1.0 percent determined. of eliective compound on a volume-volume basis in an TABLE II.——NEMATOCIDAL ACTION OF EALOALKYL ES aqueous medium having dissolved therein from 2 to 10 or Tergitol 4, by volume as the toxicant. Speci?c test organisms were the golden nematode (Heterodera rostochiensis) and the meadow nematode (Pratylenchus Name of Toxic Compound EXAMPLE 1 tlon, per- percent cent by control volume sp.). Nematocide Tests Using Heterodera Rostochiensis Nematocidal emulsion compositions were prepared by Concentra- Minimum, 60 Butyl chloroacetate _________________________ __ 0.01 98 2-Isopropylcyolohexyl chloroacetate _ _ _ 1. 0 90-95 2-seo-Butylcyclohcxyl chloroaCetate. _ _ 1. 0 90-95 Z-Chlorois opropyl 2-chlor0propionate. - 1. 0 90-95 p-Methylcyelohexyl 2-chloroproplonat 1. 0 90-95 Z-Chloroethyl ii-chloropropionate ____ _ _ 0. 01 98 treating an aqueous mixture containing from 0.001 to 2-Methylpentyl 3-ch1oropropionote__ 1. 0 90-95 1.0 percent by volume of the nematocide with 0.005 Z-Ootyl 3-chloropropionate _____ .1. 0 90-95 65 2-Ethylhexyl 3-chloropropionate._ 1. 0 90-95 to 5.0 percent of Triton X-lOO. 1A cyst mixture con 2-Buty1octyl 3-chloropropionate.. 1. 0 90-95 taining 100-300 nematode cysts per test was dipped into Benzyl 3-chloropropionate ______ __ ____ 1. 0 90-95 Cyclohexyl 3~eh1oropropionate ______________ _ _ 1. 0 90-95 the haloalkyl ester composition ‘for periods from 1 to 4-Isopropylcyclohexyl 3-chlor0pr0pionate ____ _ _ 1. 0 90-95 30 minutes. After removing from the toxicant the cysts Z-Phenoxyethyl 3~chloropropionate .......... _. 0. 1 98 were set aside and examined after a period of weeks and 70 the percentage of nonviable nematodes determined. The These nematocidal compositions may be applied to following table shows the results on a number of repre growing plants in the ?eld ‘by treating the soil around 3,084,094. 3 4 todes which comprises applying to nematode-infested roots of the plants a haloalkyl ester of the formula the roots. For this purpose the composition is applied in a suitable manner at the rate of 10 to 50 pounds of active ingredient per acre. The compositions may also be used in greenhouses. I claim: 1. A method of preventing damage to plants by-nema todespwhich comprises contacting the nematodes with a where R is a radical selected from the group consisting of ClCH2—, GHQ-011 haloalkyl ester of the formula 10 and ClCHT-CH2-— and where R1 is a radical selected from the group consisting of alkyl, halogen-substituted where R is a radical selected from the group consisting alkyl, cyclohexyl, alkyl-substituted cyclohexyl, benzyl, and of ClCH2—, phenoxyethyl, the ‘hydrocarbon moiety of the radical R1 containing from 2 to 12 carbon atoms. CHiCH <51 15 References Cited in the ?le of this patent UNITED STATES PATENTS and ClCH2—CH2—— and where R1 is a radical selected from the group consisting of alkyl, halogenisubstituted alkyl, cyclohexyl, alkyl-substituted cycloheXyl, benzyl, and phenoxyethyl, the hydrocarbon moiety of the radical 20 R1 containing from 2 to 12 carbon atoms. 2. The method of claim 1 wherein the haloalkyl ester is butyl chloroacetate. 3. The method of claim 1 wherein-the haloalkyl ester is 2-chloroethyl 3-chloropropionate. 4. The method of claim 1 wherein the haloalkyl ester is 2-phenoxyethyl 3-chlor0propionate. 5. The method of claim lewherein the haloalkyl ester is 2-isopropylcyclohexyl chloroacetate. 6. The method of claim lvwherein the haloalkyl ester 30 is benzyl 3-chloropropionate. 7. A method of preventing damage to plants by nema todes which comprises applying to nematode-infested soil a haloalkyl ester of the-formula 35 where R is a radical selected from the group consisting of C1CHr-3 1,851,040 1,982,909 ~Fikentscher et al _______ __ Mar. 29, 1932 Flint _________________ __ Dec. 4, 1934 ‘2,217,905 Hoffman ____' _________ __ Oct. 15, 1940 2,282,732 2,377,446 2,415,251 2,422,728 2,430,326 Lean ________________ __ May 12, Payne ________________ _._ June 5, Leavitt ________________ __ Feb. 4, Gresham et a1 _________ __ June 24, Cheney _______________ __ Nov. 4, 2,448,265 Kagy ________________ __ Aug. 31, 1948 2,502,244 2,543,580 2,726,485 2,730,547 2,770,638 2,779,680 2,794,727 Carter _______________ _- Mar. 28, Kay _________________ __ Feb. .27, Thomas ______________ __ Dec. 13, Dye _________________ _._ Jan. 10, Giolito ______________ __ Nov. 13, Wolf _________________ __ Jan. 29, Barrons _______________ __ June 4, 1950 1951 1955 1956 1956 1957 1957 2,802,021 2,802,818 2,802,831 2,809,983 Heininger _____________ __ Aug. 6, Wheeler ______________ _.. Aug. 13, Wheeler ______________ __ Aug. 13, Heining‘er _____________ _- Oct. 15, 1957 1957 1957 1957 1942 1945 1947 1947 1947 and ClCH2—-‘CH2-- and where R1 is a radical selected OTHER REFERENCES Hiemenz et al.: J. Am. Chem. Soc. 71 (1949), pp. 1137-8. Roark et al.: 1nd. Eng. Chem. 20 (1928), pp. 512-3. from the group ‘consisting of alkyl, halogen-substituted Webster’s ‘New International Dictionary of the English omen c1 alkyl, c'yclohexyl, ‘alkyl-substituted cyclohexyl, benzyl, 40 45 Language, 2nd Ed., 1940, G. & C. Merriman & Co., p. and phenoxyethyl, the hydrocarbon moiety of the radical 818. R1 containing from 2 to 12 carbon atoms. 8. A method of preventing damage to plants by nema King: US. Dept. Agr. Handbook No. 69, May 1954, pp. 29, 292.