Patented July 16, 1957 United States Patent Office 1. 2 be isolated from a solution in petroleum ether by frac tional crystallization. 2,799,685 The homologues, i. e. for example the pentachloro and tetrachloro-derivatives and the corresponding ana UNSATURATEDPROCESS FOR POLYCYCLIC THEIR MANUFACTURE SULFITES AND A logues of methyl and ethyl can be obtained in a corre einz Frensch, Helmut Goebel, Wilhelm Staudermann, sponding manner. : and Walter Finkenbrink, Frankfurt am Main, Ger. As Diels-Alder-components suitable for the manufac many, assignors to Farbwerke Hoechst Aktiengesell ture of Sulfites of the kind described above, there come schaft yormals Meister Lucius & Brining, Frankfurt also into consideration the halogenated alkyl derivatives, am Main, Germany; a corporation of the Federal Re O for example, dimethylcyclopentadiene. public of Germany The polycyclic halogenated sulfites are readily crystal lizing colorless compounds. No Drawing. Application April 8, 1955, The products of this invention may be used for pro Serial No. 500,264 tecting wood, paper, textiles and leather and as inter Claims priority, application Germany April 17, 1954 5 mediates for the manufacture of drugs. In the pure state, they are practically, odourless and are, therefore, 9 Claims. (CI. 260-327) especially suitable for the mentioned purposes. They The present invention provides new unsaturated poly have a curative and prophylactic effect and are prefer cyclic sulfites corresponding to the following general ably used, if desired in admixture with other insecticides, 20 ovicides, fungicides, herbicides or fertilizers, for combat formula: ing animal and fungoid pests. Y - In addition to their excellent action as pesticides the substances hereinbefore described are distinguished by 4R/V their chemical stability. SO 25 The products of this invention have a lethal action on. 2 insects of the various classes and kinds in every state of development, for example, on imagines, larvae and eggs Y of, for example, beetles, butterflies, flies, grasshoppers, and their derivatives containing two hydrogen atoms in cockroaches, bugs and lice of plants and animals. The 5.6-position, in which X represents hydrogen, halogen or 30 most important fields of application of the products of alkyl and Y represents hydrogen or alkyl. this invention are plant protection, stock protection and the so-called hygienic pest-control. The new compounds can be obtained by reacting diols A.-spraying preparation composed of 20 percent of of the general formula: hexachlorobicyclo - 2:2:11 - heptene'. (2)-bis-hydroxy ... Y. 35 methylene- (5:6)-sulfite, 70 percent of dipentene and 10 X - percent of oxyethylated alkyl phenol can successfully be N-o-o: used for combating fungoid pests, especially genuine mil dew... A preparation of 0.5 percent strength timely ck sprayed on the plants completely avoids the attack of the 40 mildew on plants. The lethal action or a preparation of the above con or their derivatives containing two hydrogen atoms in stitution on diphterene larvae can be demonstrated in the 56-position, in which X and Y have the meanings given following manner: . above, with thionylchloride, if desired in the presence of Hexachlorobicyclo - 2:2:12-heptene-(2)-bis-hydroxy an indifferent solvent. Chlorine derivatives of the un 45 methylene-(5:6)-sulfite. is intimately mixed with cottage saturated diols are preferably used for this purpose. cheese and young larvae of domestic flies (Musca As indifferent solvents there are suitably used, for ex domestica) are then placed on the poisoned food. A ample, CH2Cl2, CHCl3 or CCl4, benzene, toluene, xylene toxicity of, for example, 0.0125 percent suffices already and petroleum ether. The reaction may be performed to kill all the larvae within 1 to 3 days. while cooling or at a raised temperature with or without 50 Common bed-bugs (Cimex lectularius) are killed with the addition of an agent capable of binding hydrochloric in a few hours when sprayed with an aqueous emulsion acid. of 0.01 percent strength of a preparation composed of The diols required for the reaction can be obtained 15 percent of hexachloro-bicyclo-I2:2:11-heptene-(2)- by reacting an ester of an unsaturated dialcohol with a bis-hydroxymethylene-(5:6)-sulfite, 75 percent of diox halogenated diene of the cyclopentadiene type, preferably 55 ane and 10 percent of oxyethylated alkyl phenol as emuil hexachlorocyclopentadiene, at a raised temperature and, sifier. if desired, with application of pressure; the addition prod An emulsion of 0.05 percent strength of a spraying uct so obtained is then transformed into the correspond preparation composed of 15 percent of hexachlorobicyclo ing free alcohol, for example, by re-esterification in an 2:2:1) - heptene - (2)-bis - hydroxymethylene - (5:6) - alcoholic solution in the presence of a substance serving 60 sulfite, 75 percent of cyclohexanone and 10 percent of as a catalyst, for example, a mineral acid. The Diels oxyethylated alkyl phenol when sprayed or dusted has a Aldersynthesis may be performed by using a solvent, for rapid action on caterpillars, for example, of the brown example, benzene and its homologues or the correspond tail moth (Euproctis chrysorrhoea). They are rapidly seriously injured and die after 1-2 days. - ing chlorine- and nitro-derivatives of chlorinated hydro 65 An emulsifiable spraying preparation composed of 15 carbons, for example, methylene chloride, chloroform or percent of hexachlorobicyclo-E2:2:11-heptene-(2)-bis-hy carbon tetrachloride, or alcohol, ether or ketones. droxymethylene-(5:6)-sulfite, 75 percent of dioxane and Thus, for example, hexachlorobicyclo-I2:2:11-heptene 10 percent of oxyethylated alkyl phenol when applied in (2)-bis-hydroxymethylene-(5:6) can be treated with a concentration of 0.015 percent, brings about the com thionylbicyclo-(2:2:11-heptene-(2)-bis-hydroxymethylene-(5:6) chloride to obtain the sulfite of hexachloro 70 plete destruction of aphids (Aphidae), for example, on in the form of a mixture of isomers from which the pure Cinerariae or Chrysanthemums. - - - isomers melting at 108-110° C. and 208-210 C. can An emulsifiable spraying preparation composed of 15 2,799,685 A- - -...-a, -n- 3 4 ... - percent of hexachlorobicyclo-I2:2:17-heptene-(2)-bis substantially contains 2 isomers boiling at 108-110.C. hydroxymethylene-(5:6)-sulfite, 75 percent of dioxane and and 208-210° C. The isomers may be separated from 10 percent of oxyethylated alkyl phenol is useful for the one another by fractional crystallization from a solution destruction of caterpillars, for example, Liinantria dispar. in petroleum ether. When this spraying preparation is applied in the form Analysis.--Calculated for C9H6O3Cl6S: C: 26.56; H: of an aqueous emulsion of 0.1 percent strength, the insects 1.48; O: 11.80; Cl: 52.28; S: 7.88; molecular weight: that come in contact with the sprayed emulsion are rapid 406.92. Found: C: 26.36; H: 1.28; O: 11.74; Cl: 52.46; ly paralyzed and die within a few hours. S: 7.84. Migratory locusts are killed when sprayed with an The analytical values found correspond in both cases emulsion of 0.1 percent strength of a preparation com 10 posed of 15 percent of hexachlorobicyclo-2:2: 1-hep to the theoretical values; the molecular weight determi tene-(2)-bis-hydroxymethylene-(5:6)-sulfite, 75 percent nation likewise shows no differences. of dioxane and 10 percent of a wetting agent as emulsi EXAMPLE 3 fier. Hexachlorobicyclo - 2:2:II - heptene - (2) - bis - The substances may be used in the form of a dust or a 5 hydroxyethylene - (5:6) - sulfite spray and may be used in admixture with a substance, for example, a diluent or a solvent, a wetting, emulsifying or 71.6 grams of finely powdered hexachlorobicyclo adhering agent. 2:2:1 J-heptene-(2)-bis-hydroxymethylene-(5:6) are sus A wettable powder composed of 25 percent of hexa pended in 300 grams of carbon tetrachloride and the cal chlorobicyclo - 2:2:1 - heptadiene - (2:5) - bis - hy 20 culated amount of thionyl chloride is added at room droxyethylene - (5:6) - sulfite, 10 percent of cell pitch, temperature, while stirring. To accelerate the reaction, 0.25 percent of oxyethylated alkyl phenol and 64.75 per the reaction mixture is gradually heated to the boiling cent of chalk, when sprayed on apple trees in a concentra temperature of the solvent. When the evolution of hydro tion of 0.1 percent has a prophylactic action against the chloric acid is complete, the solution is cooled, stirred caterpillars of the brown tail moth (Euproctis chrysor 25 with water and subsequently treated with an aqueous solu rhoea) and other kinds of caterpillars leaving the window tion of sodium bicarbonate until the reaction solution is nest by killing them before considerable devouring dam neutral. age on the trees occurs. After drying and distillation of the solvent, the reac A dusting preparation composed of 1 percent of hexa tion product is obtained in the form of a fused mass chlorobicyclo - 2:2:1) - heptadiene - (2:5) - bis - hy 30 which soon solidifies. It is then worked up as described droxyethylene - (5:6) - sulfite and 99 percent of talc, in Example 2. when applied to corn in a proportion of 1 kilogram to EXAMPLE 4 1000 kilograms of corn, is very useful for combating Pentachlorobicyclo-2.2.1]-heptene-(2)-bis-hydroxy grain weevils and other stock pests. methylene-(5:6)-sulfite An emulsifying product containing 15 percent of hex 35 achlorobicyclo-I2:2:11 - heptadiene - (2:5) - bis - hy According to the process described in Example 2, the droxyethylene - (5:6) - sulfite, when sprayed on cin calculated amount of pentachlorobicyclo- 2:2:1) - hep erariae in a concentration of 0.1 to 0.05 percent, has a tene-(2)-bis-hydroxymethylene-(5:6) (obtained from pen rapid and lethal action on sucking pests, for example, tachlorobicyclo- 2:2:1 - heptence-(2)-bis-acetoxymethyl green aphids.