2,841,485 United States Patent Office Patented July 1, 1958 2 1,4,5,6,7,7-hexachloro - 2 - methylbicyclo[2.2.11 - 5 2,841,485 heptene-2,3-diol cyclic carbonate, HEXAHALOBICYCLOESEPTENEDOLS AND 1,4,5,6,7,7-hexachioro 2 "ethylbicyclo[2.2.11 - 5 DERVATIVES THEREOF heptene-2,3-diol cyclic carbonate, 1,4,5,6,7,7 - hexachloro - 2 - phenylbicyclo[2.2.1 - 5 William K. Johnson, Dayton, Ohio, and Tad Le Marre heptene-2,3-diol cyclic carbonate, Patton, Houston, Tex., assignors to Monsanto Chemi 1,4,5,6,7,7-hexachloro - 2,3-dimethylbicyclo[2.2.1 - 5 cal Company, St. Louis, Mo., a corporatio of Dela heptene-2,3-diol cyclic carbonate, ware 1,4,5,6,7,7-hexachloro - 2 - methyl - 3 - phenylbi No Drawing. Application May 20, 1955 0. cyclo2.2.1]-5-heptene-2,3-diol cyclic carbonate, Serial No. 510,053 1,4,5,6,7,7-hexabromobicyclo[2.2.1] - 5 - heptene - 2,3- diol cyclic carbonate, 26 Claims. (C. 71-23) 1,4,5,6 - tetrachloro - 7,7 - difluorobicyclo[2.2.1 - 5 heptene-2,3-diol cyclic carbonate, etc. This invention relates to hexahalobicycloheptenediols and derivatives thereof, to methods of making the same, The preparation of 1,4,5,6,7,7 - hexachlorobicyclo and to the use of these compounds as biological (2.2.1]-5-heptene-2,3-diol carbonate, for example, may toxicants. - be carried out as follows: The present invention provides new and useful com Example 1 pounds of the general formula. 20 A mixture of 8.6 g. (0.1 mole) of vinylene carbonate with 28.5 g. (approximately 0.1 mole) of hexachloro x1 cyclopentadiene in 50 ml. of o-dichlorobenzene was re fluxed for four hours. Removal of the solvent by - X b OT vacuum distillation left 39 g. of solid, which was re S-1N crystallized from hexane, giving 35 g. (94.5 percent yield) where X is a halogen having an atomic weight of below of 1,4,5,6,7,7-hexachlorobicyclo[2.2.11 - 5 - heptene 100, R is selected from the class consisting of hydrogen 2,3-diol cyclic carbonate, white needles, melting at 232 and hydrocarbon radicals of from 1 to 6 carbon atoms, 233 C. T and T taken separately are selected from the class : 1,4,5,6,7,7-hexachloro - 2 - methylbicyclo[2.2.11 - 5 consisting of hydrogen, hydrocarboncarbonyl radicals, hepteine-2,3-diol cyclic carbonate is prepared similarly, and hydrocarboncarbamyl radicals wherein the hydro by reaction of 1-propene-1,2-diol cyclic carbonate with carbon portion of the said hydrocarbon-substituted radi hexachlorocyclopentadiene. cals is a hydrocarbon radical containing from 1 to 18 The aforementioned carbonates are relatively stable carbon atoms and from 0 to 2 carbocyclic rings con compounds; for example, on refluxing the product of taining up to 6 carbon atoms per ring, and i and T Example 1 with a chlorophenoxyacetic acid in toluene taken together represent the bivalent di-substituted car for four hours, the starting materials were recovered bon atom-containing radical substantially unchanged. However, we have found that Q the carbonates can be cleaved to the reactive diols by 40 treatment with acidic hydrolysis catalysts. The hydrolysis Dog of the cyclic carbonates to the present diols may be Q' represented as follows: where Q taken separately is a hydrocarbon radical free X R u R of aliphatic unsaturation and containing up to 6 carbon X 4-ox Hso OE atoms, Q’ taken separately is selected from the class X CircO --> CX -- CO consisting of hydrogen and Q, and Q and Q' taken X s-o/ X k OH together represent a chain of up to 5 carbon atoms, the X R R terminal carbon atoms of which are singly bonded to the carbon atom to which Q and Q are attached wherein where X is a halogen having an atomic weight of below the carbon atoms of the said chain of carbon atoms are 50 100, and R is hydrogen or a hydrocarbon radical of from attached to substituents selected from the class consisting 1 to 6 carbon atoms. of hydrogen, chlorine and lower alkyl radicals. in hydrolyzing the carbonate to the diol, the carbonate The compounds provided by this invention are the is simply contacted with a small amount of an acidic 1,4,5,6,7,7-hexahalobicyclo[2.2.11 - 5 - heptene - 2,3- hydrolysis catalyst, preferably in an ionizing solvent diols, the carboxylic and carbamic acid esters of these 5 Inedium. The hydrolysis catalyst may be present in an diols, and the acetals of these diols. The preparation amount of from 0.1 to 20 percent, preferably 1 to 5 of the present compounds is hereinafter described. The percent by weight of the carbonate. As examples of new compounds provided by this invention are useful hydrolysis catalysts may be mentioned, for example, for a variety of purposes, and are particularly effective mineral acids such as hydrochloric, sulfuric or phos as biological toxicants. phoric acids, etc. The solvent medium for the reaction The diols of the present invention are prepared from may be any ionizing solvent, such as water, ethyl alcohol, 1,4,5,6,7,7-hexahalobicyclo[2.2.1] - 5 - heptene - 2,3- or mixtures thereof, dioxane, etc. If the hydrolysis re diol cyclic carbonates, which latter may be synthesized action is carried out in solution in a lower alkyl alcohol, by the reaction of hexahalocyclopentadienes and vinylene such as ethanol, the products of the reaction will in carbonates, as disclosed in our copending application 85 clude, in addition to the halobicycloheptenediol, the filed of even date here with as Serial Number 510,052, dialkyl carbonate corresponding to the alkyl alcohol now Patent No. 2,799,567, which application is assigned employed as solvent; the dialkyl carbonate may then be to the same assignee as the present case. As examples recovered at the end of the reaction, e.g., by distilla tion. The temperature of the reaction mixture may vary of suitable cyclic carbonates may be mentioned, e. g. from ambient room temperature up to the reflux tem 1,4,5,6,7,7-hexachlorobicyclo[2.2.11 - 5 - heptene - 2,3- perature of the mixture; while atmospheric pressures are diol cyclic carbonate, - useful, Sub- or super-atmospheric pressures may be ap 3,841,485 9 4. plied to the reaction if desired. The cyclic carbonate tracted twice with 200 ml, portions of ether, and the is simply contacted with the acidic catalyst, e. g., by ether extracts were combined with the oil. After the stirring, refluxing, etc., until the hydrolysis is complete; combined oil and ether solutions had been dried, the the reaction may require, for example, from 0.5 to 30 ether was removed and the resulting Solid dissolved in a hours. On completion of the reaction, if water is used t minimum of benzene. On addition of hexane to the as a solvent, any residual acid in the aqueous Solution benzene, 80 g. of crystals, melting at 236-237 C., sep may be neutralized with a weakly basic compound, Such arated. Concentration of the filtrate yielded another as sodium carbonate, sodium acetate, etc. The product 61 g. of crystals, which were combined with the first crop, diol is isolated by distilling off the solvent and decanting, treated with charcoal and recrystallized from benzene extracting, etc., as illustrated below. (, hexane, giving 10 g., melting at 239-240 C., of the diol. Examples of the diois provided by the above procedure The hexahalobicycloheptenediols are stable, well a. defined crystalline compounds which are useful for a variety of agricultural and industrial purposes. They 1,4,5,6,7,7 - hexachloro - 2 - methylbicyclo[2.2.1) - 5 may be used, for example, in the preparation of con heptene-2,3-diol, densation polymers, either the alkyd type, in which the 1,4,5,6,7,7 - hexachloro - 2 - ethylbicyclo[2.2.1 - 5 alcohol groups are reacted with polycarboxylic acids, or heptene-2,3-diol, the polyurethan type, in which the hydroxy groups are 1,4,5,6,7,7-hexachloro - 2 - phenylbicyclo[2.2.1 - 5 reacted with polyisocyanates; when used in Such resins, heptene-2,3-diol, the diols may impart, for example, excellent flame-proof 14,5,6,7,7 - hexachloro - 2,3 - dimethylbicyclo[2.2.1- 20 ing properties to the polymer. The diols of the invention 5-heptene-2,3-diol, are reactive compounds which are of great utility in 1,4,5,6,7,7-hexachloro - 2 - methyl - 3 - phenylbicyclo organic synthesis, e.g., in the preparation of compounds I2.2.1]-5-heptene-2,3-dio, further described below. The hexahalobicycloheptene 1,4,5,6,7,7-hexachlorobicyclo[2.2.1 - 5 - heptene - 2,3- diols and their derivatives, furthermore, are active bio diol, 2 5 logical toxicants, possessing a wide spectrum of biological 1,4,5,6,7,7-hexabronobicyclo2.2.1 - 5 - heptene - 2,3- activity; they are active, for example, as herbicides, diol, fungicides, bactericides, and nematocides, etc. 1,4,5,6 - tetrachloro - 7,7 - difluorobicyclo2.2.1]. - 5 By esterification of the diols described above, new and heptene-2,3-diol, useful esters are provided. The new bicyclic carboxylic 1,4,5,6 - tetrachloro - 7.7 - difluoro - 2 - methylbicyclo 3: acid esters provided by the present invention may be 2.2.13-5-heptene-2,3-diol, illustrated by the following formula 1,4,5,6 - tetrachloro - 7,7 - difluoro - 2 - phenylbicyclo 2.2.11-5-heptene-2,3-diol, 1,4,5,6 - tetrachloro - 7,7 - difluoro - 2,3 - dimethyl X s 46--R bicyclo?2.2.11-5-heptene-2,3-diol, etc.