UNITED STATES PATENT of FICE
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Patented Dec. 27, 1949 2,492,266 UNITED STATES PATENT of FICE 2,492,266 TETRAHYDRODICYCLOPENTADENE ETHER COMPOUNDS AND INSECTC DES THERE OF George Allen Buntin, Wilmington, Del, assignor to Hercules Powder Company, Wilmington, Del, a corporation of Delaware No Drawing. Application October 15, 1947, Serial No. 780,102 11. Claims. (C. 16-30) 2 This invention relates to new polychloro ethers g-chloroethoxytetrahydrodicyclopentadienes were and, more particularly, to chlorinated ethers of tested for their insecticidal activity against house hydroxydihydrodicyclopentadiene and to insecti flies. In this and the following examples, the test cidal compositions containing these new products for insecticidal activity against houseflies was as the toxic ingredient. made in the following manner and is referred to It is known that ethers of hydroxydihydrodicy in this Specification as the bell jar method. clopentadiene may be obtained by the addition of Approximately 100 five-day old flies (Musca an alcohol to one of the double bonds of dicyclo domestica) were placed in a bell jar and a prede pentadiene in the presence of an acidic catalyst. termined quantity of the insecticide to be tested The remaining double bond of the dicyclopenta 10 was atomized into the bell jar. The quantity of diene ring will undergo further addition reactions, insecticide used was equal to the amount of the as with halogen, etc. These dihalo ethers, such Official Test Insecticide which was necessary to as the dichloro ether, have many valuable prop give a 30%-55% kill and must be within the lim erties but lack any insecticidal activity. its of 0.4–0.6 ml. After spraying the insecticide Now in accordance with this invention it has into the chamber, the flies were placed in an ob been discovered that alkyl ethers of hydroxydihy Servation cage containing a wad of cotton wet drodicyclopentadiene may be chlorinated to pre with a dilute sugar solution. At the end of 24 pare polychloro alkoxytetrahydrodicyclopentadi hours, the number of dead and moribund flies enes containing from about 50% to about 75% of Were counted. All tests were carried out at 80° chlorine and that compositions containing these 20 90°F. and 50%-70% relative humidity. polychloro ethers have a high degree of insecti The results of the analysis for chlorine content cidal activity. and of tests made on solutions in deodorized kero The following examples illustrate the prepara Sene of the above three polychloro ethers are tion of the new polychloro ethers in accordance given in the following table. The data are an with this invention and the insecticidal activity 25 average of tests made on each solution. of compositions containing then as the toxic ingredient. All parts and percentages are by 5%. Solution 2%% Solution 1% Solution d --- -- Weight unless otherwise indicated. eit O. T., O.T. O. T. Chlorine 24-Er. Differ. 24-Er. Differ- 24-Hr. DifferS." Eacample 30 Kill ence Kill ence Kill ece B-chloroethoxydihydrodicyclopentadiene was prepared by heating a mixture of 500 parts of eth 6.4 97 --46 89 h;88 ------------------ yene chlorohydrin, 750 parts of dicyclopentadi 66. 00 -49 98 --47 67 --16 ene, and 5.5 parts of concentrated sulfuric acid 67.1 99 --48 100 - 49 68 --17 to a temperature of 10° C. for four hours, the mixture being agitated during the heating period. Eacgample 2 The reaction mixture was then dissolved in petro Isopropoxydihydrodicyclopentadiene was pre leum ether, washed with water until neutral, and pared by heating a mixture of 500 parts of isopro dried over Sodium sulfate. The petroleum ether pyl alcohol, 930 parts of dicyclopentadiene and 18 Was removed by distillation under reduced pres 40 parts of concentrated sulfuric acid to reflux tem Sure and, on continuing the distillation, 488 parts perature for 8 hours. The reaction mixture was of the product were collected at 95°-105 C. at then poured into water and the organic layer was 0.3 mm. pressure. On analysis it was found to diluted with petroleum ether and washed with contain 15.7% chlorine. Sodium bicarbonate until neutral. The petroleu Two hundred parts of the above ether were 45 ether solution was dried over anhydrous sodium dissolved in 600 parts of carbon tetrachloride. Sulfate and Subjected to fractional distillation. Chlorine was then passed into the agitated solu The fraction boiling at 120°-123° C. at 20 mm. tion in the presence of ultraViolet light, the ten pressure was collected and identified as isopro perature being kept below 30° C. during the chlo poxydihydrodicyclopentadiene. rination. Samples were removed after 7%, 16A, 50 Eighty-four parts of the above isopropoxydihy. and 25A2 hours of chlorination. The carbon tet rachloride was removed from each of these sam drodicyclopentadiene were dissolved in 700 parts ples by distillation under reduced pressure using of carbon tetrachloride. Chlorine was passed into a nitrogen sparge. The product in each case was the agitated solution in the presence of ultra a viscous, yellow liquid. The three polychloro 55 violet light, the temperature rising to about 66 2,492,266 3 4. C. during the chlorination. Samples were re polychloro derivatives are prepared in accord moved after 7% and 18% hours of chlorination. ance with this invention may be any aliphatic, The carbon tetrachloride was removed from each cycloaliphatic, chloroaliphatic, or chlorocycloali of these samples by distillation under reduced phatic ether of hydroxydihydrodicyclopentadiene. pressure using a nitrogen sparge. The product in 5 Such ethers are readily prepared by the addi each case was a viscous red liquid. These poly tion of an alcohol to dicyclopentadiene in the chloro isopropoxytetrahydrodicyclopentadienes presence of an acidic catalyst. The alcohols were tested for their insecticidal activity against which may be added to dicyclopentadiene to form house flies by the bell jar method. The results the intermediates used to prepare the polychloro of the analysis for chlorine content and of the O ethers may be any alkanol, such as methyl, ethyl, tests made on 10% solutions of the above two isopropyl, butyl, amyl, hexyl, etc., alcohols or any polychloro ethers in a 2:1 mixture of deodorized chloroalkanol, such as ethylene chlorohydrin, etc. kerosene and acetone are given in the following The cycloaliphatic ethers, such as the terpene table: ethers, are readily formed by the addition of the unsaturated terpene to hydroxydihydrodicyclo Percent 24-Hr. o. T.I. pentadiene. Any terpene may be used in prepar Chorina Kill Difference ing these cycloaliphatic ethers as, for example, camphene, piene, dipentene, terpinene, etc. 58. 5 s --58 88. 2 80 --38 The reaction between the alcohol and the di 20 cyclopentadiene is readily carried out in the pres ence of an acidic condensing agent, such as sul Eacamaple 3 furic acid, alkyl or aryl sulfonic acids, boron tri Isobornyloxydihydrodicyclopentadiene was pre fluoride, or its molecular complexes, etc. The pared by heating a mixture of 88 parts of hy temperature at which the reaction is carried out droxydihydrodicyclopentadiene, 95 parts of cam may vary from a temperature as low at 0° C. to phene, and 5 parts of an activated clay catalyst a temperature of 125° C. or higher, the actual to 110° C. for 8 hours. The reaction mixture was temperature used usually being determined by cooled and filtered to remove the clay catalyst and the catalyst, Solvent for the reaction if one is then was distilled under reduced pressure. The used, etc. fraction boiling at 150-160° C. at 0.5 mm. pres When alcohol is added to dicyclopentadiene in sure was a viscous light yellow liquid which was the presence of an acid catalyst, it is believed identified as isobornyloxydihydrodicyclopenta that the alcohol adds to the endomethylene cy diene. cle; i. e., the double bond in the six-membered Eighty-five parts of the above isobornyl ether ring, with Saturation of the double bond. Simul were dissolved in 790 parts of carbon tetrachlo taneously, a rearrangement is believed to occur, ride. Chlorine was passed into the agitated solu the molecule changing from an endo configura tion in the presence of ultraviolet light, the tem tion to an exo configuration. While it is believed perature rising to about 70° C. during the chlo to be quite well established that the ether so pre rination. Samples were removed after 1% and pared has an exo configuration, the configuration 3 hours of chlorination. The carbon tetrachloride 40 of the cyclic structure is not believed to be ma was removed from each of these samples by dis terial to the present invention. In the chlorina tillation under reduced pressure using a nitrogen tion of the ether, the configuration, whether it sparge. The product in each case was a viscous be endo or exo, is not believed to be disturbed. red liquid which upon cooling became a brittle The insecticidal activity of the polychloroethers resin. These polychloro isobornyloxytetrahydro 4. 5 of this invention is not believed to be dependent dicyclopentadienes were tested for their insecti upon the endo-exo configuration but is, instead, cidal activity against house flies by the bell jar believed to be dependent upon the combination of method. The results of the analysis for chlorine percent of chlorine in the molecule together with content and of tests made on solutions in de the dicyclopentadiene structure (endo or exo) odorized kerosene are given in the following and the ether linkage. As used in this applica table: tion and the claims appended, the term “poly chloro alkoxytetrahydrodicyclopentadiene' is meant to include both the endo and exo forms. 5%. Solution 2-1-2%. Solution The chlorination of the alkyl ethers of hy Per Cent droxydihydrodicyclopentadiene may be carried Chlorine 24-H. O. T.I. 24-Er. O.