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 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--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 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 , 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 . 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. CX X The procedure of preparing these diols is further illus Yulo-T,X R trated, but not limited, by the following examples: where X is a halogen having an atomic weight of below Example 2 100, R is hydrogen or a hydrocarbon radical of from To a medium consisting of 100 ml, water and 125 m. 40 1 to 6 carbon atoms, R' is a hydrocarbon radical contain ethanol, 17.9 g, of the product of Example 1 and one ml. ing from 1 to 18 carbon atoms and from 0 to 2 carbo of concentrated hydrochloric acid (1.18 sp. gr.) were cyclic rings containing up to 6 carbon atoms per ring and added, and the mixture was refluxed for 16.5 hours. At T is hydrogen or a hydrocarboncarbonyl the end of this time, the reaction mixture was neutralized O with sodium acetate and subjected to vacuum distillation " | to remove the ethanol, whereupon an oily layer separated -C-ER from the aqueous solution. The oil was decanted and radical, where R' is as defined above. Esters of the above mixed with two 100 ml. portions of ether with which the formula are readily prepared by contacting the present aqueous layer had been extracted; this mixture was de diols with a carboxylic acid of the formula colorized with active charcoal and dried. Evaporation of the ether left a residue which was again treated with 2e active charcoal and recrystallized from hexane, giving Ric, 10 g. of small white needles, melting at 240° C. The OE identity of this product with the desired 1,4,5,6,7,7-hexa or with a reactive carboxylic acid derivative, such as chlorobicyclo2.2.1]-5-heptene-2,3-diol was indicated by a carboxylic acid halide of the formula the characteristics of its infrared spectrum, and corrobo O | rated by the following analysis: RC-X

Found Calculated for where X is halogen, or a carboxylic acid anhydride of CHCl60 the formula

Percent C------25.36 25.27 Percent H------1.80 1, 13 Percent Cl------647 63.92 where R' in the above formulae is as defined above. Ex GS amples of suitable carboxylic acids which may be used in A further 5 grams of material, melting at 239 C., preparing the present esters are, e.g., acrylic acid, butyric were recovered by concentration of the filtrate, making acid, vinylacetic acid, 2-ethylhexanoic acid, benzoic acid, the total hydrolysis yield 15 grams, or 90 percent of cyclohexanecarboxylic acid, etc. Examples of suitable theoretical. acid halides for preparing these bicyclic esters are: pro Example 3 70 pionyl chloride, hexanoyl bromide, p-soluyi chloride, etc. In 1000 ml. of a 2:3 water-ethanol mixture, 147.6 g. Examples of acid anhydrides which are useful in the of the product of Example 1 was refluxed for 6 hours Synthesis of the present esters are acetic anhydride, with 10 ml. of concentrated (28 percent) hydrochloric butyric anhydride, benzoic anhydride, etc. acid. On removal of the ethanol by distillation, an oil Depending on the reaction conditions and the relative separated; this was removed, the aqueous layer was ex ratios of diol and acid or acid derivative used, there are 2,841,485 6 prepared monoesters of the present diols, of the above 1,4,5,6- tetrachloro-7,7-difluorobicyclo[2.2.1]-5-heptene formula where T is hydrogen, or diesters of the above 2,3-diol dibenzoate, etc., and with araliphatic and formula, where T is a hydrocarboncarbonyl radical. cycloaliphatic acids, to provide esters such as: Examples of monoesters of the present diols prepared in 1,4,5,6,7,7-hexachlorobicyclo[2.2.1]- 5 -heptene-2,3-diol accordance with this invention are, e.g., 5 mono (phenylacetate), 1,4,5,6,7,7-hexachlorobicyclo[2.2.1]- 5 - heptene-2,3-diol 1,4,5,6,7,7-hexachlorobicyclo[2.2.1 5-heptene-2,3-diol monoacetate, Inono (naphthylacetate), 1,4,5,6,7,7-hexachlorobicyclo[2.2.1] - 5 - heptene-2,3-diol 1,4,5,6,7,7-hexachlorobicyclo[2.2.1 - 5-heptene-2,3-diol monopropionate, - di(3-phenylpropionate), 1,4,5,6,7,7-hexachlorobicyclo[2.2.1]- 5 - heptene-2,3-diol () 1,4,5,6,7,7 - hexachloro - 2 - methylbicyclo[2.2.11 - 5 monoacrylate, heptene-2,3-diol mono (p-tolylacetate), 1,4,5,6,7,7-hexachlorobicyclo[2.2.11 - 5 - heptene-2,3-diol 1,4,5,6,7,7 - hexachloro - 2 - methylbicyclo[2.2.11 - 5 mono-2-ethylhexanoate, heptene-2,3-diol di(cyclohexylcarboxylate), 1,4,5,6,7,7-hexachlorobicyclo[2.2.1 - 5 - heptene-2,3-diol 1,4,5,6,7,7-hexabromobicyclo[2.2.1]- 5 - heptene-2,3-diol monododecanoate, 5 di-(4-naphthylbutyrate), 1,4,5,6 - tetrachloro-7,7-difluorobicyclo[2.2.1]-5-heptene 1,4,5,6 - tetrachloro-7,7-difluorobicyclo[2.2.11-5-heptene 2,3-diol monoacetate, 2,3-diol moio (phenyiacetate), 1,4,5,6 - tetrachloro-7,7-difluorobicyclo[2.2.1]-5-heptene 1,4,5,6 - tetrachloro-7,7-difloro-2-methylbicyclo[2.2.1]- 2,3-diol monopentanoate, 5-heptene-2,3-diol di(o-tolylaceiate), etc. 1,4,5,6 - tetrachloro-7,7-difluorobicyclo(2.2.11-5-heptene 20 To prepare the present esters, the diol is contacted with 2,3-diol mono-(vinylacetate), the acid or acid derivative, preferably in the presence of 1,4,5,6,7,7-hexachloro - 2 - methylbicyclo[2.2.1 - 5 a condensation catalyst. The free acid may be employed, heptene-2,3-diol monoacetate, - if desired, but it is preferred to use an acid derivative 1,4,5,6,7,7-hexachloro - 2 - methylbicyclo[2.2.11 - 5 such as the acid halide or anhydride. Suitable acid halides heptene-2,3-diol monononanoate, are, e. g., acetyl chloride, propionyl chloride, etc. Par 1,4,5,6,7,7-hexachloro - 2 - phenylbicyclo[2.2.1]- 5 ticularly suitable for the present process are the acid heptene-2,3-diol monoacetate, anhydrides, such as acetic, propionic, butyric, pentanoic, 1,4,5,6,7,7-hexachloro - 2 - phenylbicyclo[2.2.1]- 5 and benzoic acid anhydrides, for example. The condensa heptene-2,3-diol monoacrylate, etc. tion to form the ester is preferably carried out in the Diesters of alkanoic monocarboxylic acids provided by presence of a dehydrating condensation catalyst. Suit the present invention are, e.g.: able catalysts are, for example, mineral acids Such as sulfuric - or hydrochloric acids, or gaseous hydrogen 1,4,5,6,7,7-hexachlorobicyclo[2.2.1 - 5-heptene-2,3-diol chioride, or a salt of a weak acid, Such as sodium acetate. diacetate, The reaction mixture may be heated, if desired, but 1,4,5,6,7,7-hexachlorobicyclo[2.2.1]-.5-heptene-2,3-diol generally heating is not necessary, since the reaction is dipropionate, usually exothermic. A possible procedure is to cool the 1,4,5,6,7,7-hexachlorobicyclo[2.2.11 - 5-heptene-2,3-dic reaction when the reactants are first mixed, and later to diacrylate, heat it to drive the reaction towards completion. Depend 1,4,5,6,7,7-hexachlorobicyclo[2.2.1 - 5-heptene-2,3-diol ing on the reactants, solvents or diluents may or may dibutyrate, 40 not be used, i. e., a solvent will be necessary if both re 1,4,5,6,7,7-hexachlorobicyclo[2.2.11 - 5-heptene-2,3-diol actants are solid at reaction temperature. Sub- or Super dihexanoate, atmospheric pressures may be applied if desired. The 1,4,5,6,7,7-hexachlorobicyclo[2.2.1 - 5-heptene-2,3-diol proportions of the reactants will be determined by whether di(2-ethylhexanoate), a mono- or di-ester is desired. in reacting a monocar 1,4,5,6,7,7-hexachlorobicyclo[2.2.1]- 5-heptene-2,3-diol 5 boxylic anhydride, such as acetic anhydride, with one of dinonanoate, the diols of the present invention, there may be used, for 1,4,5,6,7,7-hexachloro - 2 - methylbicyclo[2.2.1 - 5 exampie, one mole of anhydride, or a slight excess above heptene-2,3-diol diacetate, this, to cine mole of diol, to produce a diester. A mono 1,4,5,6,7,7 - hexachloro - 2 - methylbicyclo[2.2.4 - 5 carboxylic acid halide will require two moles per mole heptene-2-3-diol di(2-ethylhexanoate), of dioi, by the stoichiometry of the reaction to produce a 1,4,5,6,7,7-hexachloro-2-phenylbicyclo[2.2.1]-5-heptene diester, or one mole per mole of diol, to make the mono 2,3-diol diacetate, ester. An excess of either the acid derivative or the diol 1,4,5,6,7,7-hexachloro-2-phenylbicyclo[2.2.11-5-hepteine may be employed, if desired, for example, to drive the 2,3-diol dipropionate, reaction towards completion in the desired direction, i.e., 1,4,5,6,7,7-hexachloro-2-phenylbicyclo[2.2.1-5-hepterie to give the mono- or the di-ester; unreacted acid or diol 2,3-diol di C2-ethylhexanoate), is then removed at the end of the reaction. The con 1,4,5,6 - tetrachloro - 7,7-difluoro-2-methylbicyclo[2.2.1- densation promoter, i. e., sulfuric or hydrochloric acid, 5-heptene-2,3-diol diacetate, etc., need be present only in catalytic amounts. 1,4,5,6 - tetrachloro - 7,7-difluoro-2-methylbicyclo[2.2.1]- The esters prepared by the present process are liquid 5-heptene-2,3-dic diacrylate, () to crystalline solid stable materials which have a variety 1,4,5,6 - tetrachloro - 7,7-difluoro-2-methylbicyclic 2.2.1]- of uses. For example, the esters with long-chain acids 5-heptene-2,3-diol didodecancate, etc. such as 2-ethylhexanoic acid may be useful as plasticizers. In addition to esters of the present diols with alkanoic, The esters with unsaturated acids such as acrylic acid alkenoic and haloalkanoic acids as shown above, the diois are potential monomers for preparation of addition poly of the invention may be condensed with aromatic acids, (35 mers, to which they may impart flexibility and flame to provide esters such as: resistance. The esters of the diols are particularly use 1,4,5,6,7,7-hexachlorobicyclo[2.2.11 - 5-heptene-2,3-diol ful as biological toxicants, i.e., as fungicides and nemato monobenzoate, cides. The preparation of the present carboxylic acid 1,4,5,6,7,7-hexachlorobicyclo (2.2.11 - 5-heptene-2,3-diol esters is further illustrated, but not limited, by the fol di-p-toluate, lowing examples: - 1,4,5,6,7,7-hexachloro - 2 - methylbicyclo[2.2.1 - 5 Example 4 heptene-2,3-diol mono-2-naphthoate, A mixture of 6.9 g, of the product of Example 2, 50 1,4,5,6,7,7-hexachloro - 2 - methylbicyclo[2.2.1 - 5 ml. of acetic anhydride and 0.5 g. of anhydrous sodium heptene-2,3-diol dibenzoate, - 75 acetate was refluxed for one hour, then cooled and poured --- 2,84i,485 Fy 8 into 250 ml. of a mixture of ice and water. A brownish Monocarbamates which may be prepared by reaction of solid crystallized and was separated by filtration and the present diols and isocyanates include, e.g., dried, giving 9 g. of brownish crystals, which were re 1,4,5,6,7,7-hexachlorobicyclo2.2.1-5 - heptene - 2,3-diol crystallized twice from hexane, giving 7 grams of very mono(methylcarbamate), large crystals which meited at 110-111 C. The prod i,4,5,6,7,7-hexachlorobicyclo[2.2.1-5 - heptene - 2,3-diol uct, 1,4,5,6,7,7-hexachlorobicycic2.2.1 - 5 - heptene-2,3- mono (ethylcarbamate), diol diacetate, analyzed as follows: 1,4,5,6,7,7-hexachlorobicyclo[2.2.1-5 - heptene - 2,3-diol mono (octadecylcarbamate), Found Calculated for 1,4,5,6-tetrachloro-7,7-difluorobicyclo[2.2.1-5 - heptene CHSCCs 2,3-diol menocarbanilate, -- 1,4,5,6-tetrachloro-7,7-difluorobicyclo[2.2.1-5 - heptene Percent C.------32. Ot 369 2,3-diol mono(methylcarbamate), m Percent H------2. 44 .94 1,4,5,6-tetrachloro-7,7 - difluorobicyclo[2.2.1-5 - heptene 2,3-diol mono (octadecylcarbamate), Example 5 1,4,5,6,7,7-hexachloro-2-methylbicyclo[2.2.1-5 - heptene The procedure of the above example was varied as 2,3-diol monocarbanilate, follows: A mixture of 13.8 g. of the dio of Example 2 1,4,5,6,7,7-hexachloro-2-phenylbicyclo[2.2.1-5 - heptene with 100 ml. of 95 percent acetic anhydride and two drops 2,3-diol monocarbanilate, etc. of concentrated sulfuric acid was allowed to stand for EDicarbamate esters which may be prepared by reaction one hour (exothermic reaction). After addition of ice ice and water to decompgse the excess acetic anhydride, a of the present diols with isocyanates include, e.g., white precipitate settled, was filtered off and dried. After 4,5,6,7,7-hexachloro-2-methylbicyclo[2.2.13 - 5 - hep recrystallization from hexane, there were obtained 17 g. tene-2,3-diol di(methylcarbamate), (98 percent yield) of the diacetate, melting at 11° C. ,4,5,6,7,7-hexachloro-2-phenylbicyclo[2.2.11 - 5 - hep in addition to the carboxylic acid esters of hexahalo tene-2,3-diol di(methylcarbamate), bicycloheptenediols, the present invention also includes 1,4,5,6,7,7-hexachloro-2,3-dimethylbicyclo[2.2.11-5 - hep the carbarnate esters of these diois. tene-2,3-dio di(methylcarbamate), Carbamic acid esters are preferabiy prepared from iso 1,4,5,6,7,7-hexachloro-2-methylbicyclo[2.2.11 - 5 - hep cyanates, when the N-incineSubstituted derivative is de tene-2,3-diol di(ethylcarbamate), sired, and from carbamyl halides, when the N-disubsti 30 1,4,5,6,7,7-hexachloro-2-phenylbicyclo[2.2.1 - 5 - hep tuted derivatives are required. With the present diols, tene-2,3-diol di(ethylcarbamate), either monocarbamate esters, i. e., those in which one 14,5,6,7,7-hexachloro - 2,3 - dimethylbicyclo[2.2.1 - 5 hydroxy group of the diol is esterified, of N-mono- and hepiene-2,3-diol di(ethylcarbamate), N-di-substituted carbamic acids, or dicarbamate esters ,4,5,6,7,7-hexachloro-2-methylbicyclo[2.2.1] - 5 - hep in which both hydroxy groups of the diol are esterified, 35 teine-2,3-dici di (octadecylcarbamate), of N-mono- and N-disubstituted carbamic acids can be 1,4,5,6,7,7-hexachloro-2 - propylbicyclo2.2.1 - 5 - hep prepared. These esters may be represented by the general tene-2,3-diol di(octadecylcarbamate), formula 1,4,5,6,7,7-hexachloro-2-phenylbicyclo[2.2.1 - 5 - hep tene-2,3-diol di(hexadecylcarbamate), i,4,5,6,7,7-hexachloro-2-phenylbicyclo 2.2.11 - 5 - hep tene-2,3-diol dicarbanilate, 1,4,5,6-tetrachloro - 7,7-difluorobicyclo2.2.1 - 5 - hep tene-2,3-diol di(methylcarbamate), 1,4,5,6-tetrachloro - 7,7-difluorobicyclo[2.2.1 - 5 - hep where X is a halogen having an atomic weight of below tene-2,3-diol di(ethylcarbamate), 100 and R is hydrogen or a hydrocarbon radical of from 1,4,5,6-tetrachloro - 7,7-difluorobicyclo[2.2.1 - 5 - hep 1 to 6 carbon atoms, R’ is a hydrocarbon radical con tene-2,3-diol di(octadecylcarbamate), taining from 1 to 18 carbon atoms and from 0 to 2 car 1,4,5,6-tetrachloro - 7.7 - difluorobicyclo[2.2.1 - 5 - hep bocyclic rings containing up to 6 carbon atoms per ring, tene-2,3-diol dicarbanilate, etc. R’ is selected from the class censisting of hydrogen and it will be readily evident to those skilled in the art R, and T is selected from the class consisting of hy that reaction of the present diols with diisocyanates under drogen and hydrocarboncarbamyl radicals of the formula polymerizing conditions will give valuable polyurethan R resins of the type Yst 5 5 / s . R -C-NE-R-NH-C-O O R- R where R' and R'' are as defined above. While the carbamic acid esters of the present diols could be pre Kox. X pared by alcoholysis, we prefer to prepare the carbamates (i) X X of the invention by reaction of the halobicycloheptenediols where X, R, and R' are as hereinbefore defined. How with isocyanates or with carbamyl halides. ever, this invention also contemplates the reaction of the To prepare the present N-monoSabstituted carbamates, present diois with diisocyanates in which the isocyano there may be used an alkyl, cycloalkyl, aralkyl or ary groS are of different reactivities, so that monomeric monoisocyanate. The isocyanates are readily available, 83 carbarnate esters are obtained, e.g., of the type commercial materials; they may be prepared, e. g., by reaction of a primary amine with phosgene. Examples R. X. of monoisocyanates Sitable for use in the present process O=C=N-g SatD)-( )-N-g-o- - six are: alkyl isocyanates Stich as methyl isocyanate, ethyl Series/ E () isocyanate, propy isocyanate, hexyl isocyanate, octadecyl O O is-- isocyanate, hexadecyl isocyanate, octadecenyl isocyanate, R. X. etc.; cycloalkyl isocyanates Such as cyclohexyl isocyanate; in addition to the above-listed N-monosubstituted car aryl isocyanates, e.g., phenyl isocyanate, tolyl isocyanate, bamate esters of the present diols, the N-disubstituted 2-naphthyl isocyanate, etc., and aralkyl isocyanates, such Carbariate esters of the present diols are also included in as phenethyl isocyanate, etc. 5 the invention. The present N-disubstituted carbamate 2,841,485 O esters may be prepared as mentioned above, by reaction carbons such as benzene or toluene, aliphatic solvents of one of the dicls of this invention with an N-disubsti such as cyclohexane or hexane, halogenated solvents Such tuted carbamyl halide, as illustrated by the following as dichloride, oxygenated solvents such as equation showing the reaction of 1,4,5,6-tetrachloro-7,7- dioxane, isobutyl acetate, etc. Catalysts for the reaction, difluoro-2-methylbicyclo (2.2.1]-5-heptene-2,3-diol with such as aluminum chloride, may be used if desired, but dimethylcarbamyl chloride to produce 1,4,5,6-tetrachloro are not generally necessary. The proportions of diol and 7,7-difluoro-2-methylbicyclo[2.2.1]-5-heptene - 2,3 - diol isocyanate or carbamyl halide used will depend, e.g., on bis(dimethylcarbamate) whether the mono- or di-ester is desired. Equimolecular C CH3 . . . proportions of diol and isocyanate, for example, may be c-TSZoH cF. 0. used, to form the monocarbamate, while two or more CF2 -- NC-C) m3 moles of isocyanate per mole of diol may be used for Cl OH of making the dicarbamate. If desired, an excess of one of C the reactants may be used, e.g., to facilitate the prepara Cl CH3 CH, tion of a particular desired product, i. e., the mono- or 5 the di-ester; the unreacted excess material may be readily Cl f O-C-N-CH removed at the end of the reaction. The reaction is gen F. erally complete within 2 to 30 hours, depending on the diol and isocyanate used; on removal of the solvent, the C ul-g-NCH, product readily separates. 20 The present carbamates are stable, high-melting crystal As in the case of the reaction of the present diols with line compounds which are useful for a variety of industrial isocyanates, the conditions of reaction may be controlled and agricultural applications, e.g., as dielectrics, for the to produce either the monoester or the diester of the diol. preparation of Surface-active quaternary compounds, as Examples of N-disubstituted carbamyl halides useful in biological toxicants, etc. preparing the present esters are dialkylcarbamyl halides 2 5 The preparation of the carbamates of the invention is such as dimethylcarbamyl chloride, dipropylcarbamyl further illustrated by the following examples: bromide, etc., di(aralkyl)carbamyl halides such as di benzycarbamyl chloride, diarylcarbamyl halides such as Example 6 dipherylcarbamyl chloride, di-o-tolylcarbamyl chloride, A mixture of 16.7 grams (0.05 mole) of 1,4,5,6,7,7- etc. The N-disubstituted carbamyl chlorides are pre hexachlorobicyclo[2.2.1]-5-heptene-2,3-diol with 11.9 pared, e. g., by reaction of a disubstituted amine with grams (0.1 mole) of phenyi isocyanate in 100 ml. of dry phosgene. The products which may be produced by the toluene was refluxed for 20 hours. After removal of the present method include monoesters such as: Solvent and recrystallization of the residual solid from 1,4,5,6,7,7-hexachlorobicyclo[2.2.il-5-heptene - 2,3 - diol carbon tetrachloride, 10 g. of the dicarbanilate of the mono (dimethylcarbamate), 35 diol was obtained. This material melted at 174-176 C. 1,4,5,6,7,7-hexachlorobicycloL2.2.11-5-heptene-2,3-diol and analyzed as follows: mono (diphenylcarbamate), 1,4,5,6,7,7-hexachlorobicyclo[2.2.1]-5-heptene - 2,3 - diol mono (dibenzylcarbamate), Found Calculated for 1,4,5,6,7,7-hexachloro-2-methylbicyclo[2.2.1] - 5 - hep 40 C2H14Cl6N2O4 Percent C------43.54 44.17 tene-2,3-diol mono (dimethylcarbamate), Percent H. - 2.92 2.47 1,4,5,6-tetrachloro-7,7-difluorobicyclo[2.2.11-5 - heptene Percent Cl 38.5 37.24 2,3-diol mono (dimethylcarbamate), Percent N-- 5.04 4.91 1,4,5,6-tetrachloro-7,7-difluorobicyclo[2.2.11-5 - heptene 2,3-diol mono (diisopropylcarbamate), 1,4,5,6,7,7-hexachloro-2-phenylbicyclo[2.2.1]- 5 - hep Example 7 tene-2,3-diol monoditolylcarbamate), etc., and di On refluxing a mixture of 16.7 g. of the diol of Ex esters such as: ample 2 with 11.9 g, of phenyl isocyanate in 100 ml. of 1,4,5,6,7,7-hexachlorobicyclo[2.2.1]-5-heptene-2,3-diol benzene for 8 hours, removal of the solvent and solidifica bis(dimethylcarbamate), () tion of the residue by treatment with hexane, followed by 1,4,5,6,7,7-hexachlorobicyclo[2.2.1]-5-heptene - 2,3 - diol recrystallization from a toluene-hexane mixture, there bis(dibutylcarbamate), resulted a white microcrystalline solid, weighing 14.g., 1,4,5,6,7,7-hexachlorobicyclo?2.2.11-5-heptene - 2,3-diol bis(dinaphthylcarbamate), and melting at 168-169 C. Recrystallization from car 1,4,5,6,7,7-hexabromobicyclo 2.2.1]-5-heptene-2,3-diol bon tetrachloride again gave 14 g. melting at 168-169 C. bis(dimethylcarbamate), This compound analyzed as follows: 1,4,5,6-tetrachloro-7,7-difluorobicyclo[2.2.11-5 - heptene 2,3-diol bis(diethylcarbamate), Found Calculated for C14H9CNO; 1,4,5,6,7,7-hexachloro-2-ethylbicyclot2.2.1 - 5 - heptene 60 2,3-diol bis(dinonylcarbamate), etc. Percent C------37.68 37.21 Percent B - 2.46 2.0. The carbamate esters of the diols of the present inven Percent Cl------46.38 47.0 tica are prepared by simply contacting the diol with the Percent N------3.30 3.0 isocyanate or the carbamyl halide. We have found that the extent of esterification appears to depend on the dura 65 tion of contact and the reaction temperatures; thus, the The product of this reaction was thus the 1,4,5,6,7,7- monocarbamate of the diol is first formed, and on con hexachlorobicyclo[2.2.11 - 5 - heptene - 2,3-diol mono tinued heating, the dicarbamate is obtained. The tem carbanilate. perature at which the condensation of the diol with the Example 8 isocyanate or carbamyl halide takes place may vary from 70 By reaction of two moles of dimethylcarbamyl chloride 50 to 200° C., preferably 80-120° C. Sub- or super-at with one mole of the diol of Example 2 in benzene solu mospheric pressures may be used, if desired. The reac tion, 1,4,5,6,7,7-hexachlorobicyclo[2.2.1 - 5 - heptene tion may take place without a solvent medium i.e., if the 2,3-diol bis(dimethylcarbamate) is prepared. isocyanate is a liquid; or a solvent or diluent may be used. A further embodiment of the present invention is the Suitable media for the reaction are, e.g., aromatic hydro- 75 reaction of the diols described hereinabove with alde 2,841,485

as as 2 hydes and ketones to produce acetals. The general re The above and similar acetals are readily prepared by action is: simply contacting the diols of the present invention with a ketone or aldehyde in the presence of an acidic catalyst. As examples of catalysts for acetal formation Inay be 5 isted salts such as calcium, zinc or ferric chlorides; boro; trifluoride, ammonium chloride and dry hydrogen chie ride, as well as organic acids such as benzene-Sulfonic acid, p-toluenesulfonic acid, etc. The reaction may be where X is a halogen having an atomic weight cf below carried out in the absence or presence of a scivent or 100, R is hydrogen or a hydrocarbon radical of diluent. As solvents may be used inert liquids such as from 1 to 6 carbon atoms, Q taken Separately is a hydro benzene, toluene, Xylene, ethylene dichloride, hexane, carbon radical free of aliphatic unsaturation and con cyclohexane, etc. The diol and ketone of aldehyde can taining up to 6 carbon atoms, Q’ taken separately is se be present in equimolecular quantities, as required by the lected from Q and hydrogen, and Q and Q' taken together stoichiometry of the reaction as shown above, or a slight represent a chain of up to 5 carbon atoms, th2 termia excess of the more readily available component may be carbon atoms of which are singly bonded to the carb{il used. Ordinary atmospheric, or sub- or superatmospheric atom to which Q and Q are attached, wherein the car pressures may be employed, as desired. The temper bon atoms of the said chain of carbon atoms are attached atures of the reaction depends on the reactants, aid may to Substituents selected from the class consisting of hy vary from ambient room temperature to 200 C., pref drogen, chlorine and lower alkyl radicals. The products 20 erably 40-130° C. The reaction is complete within froit when Q and Q are taken separately are tricyclic di a few mintues to 20 hours; the reaction mixture is then oxanes, e.g., the product of the reaction of acetone and neutralized and the acetal isolated, e. g., by extraction, hexachlorobicyclo[2.2.1 - 5 - heptene - 2,3 - diol has the distillation, etc. formula The present acetals are high-melting, stable solids, use ful in the chemical and allied industries, e. g., as inter C 3 mediates, plasticizers (particularly the acetals of long chain aldehydes or ketones), etc., and also of utility in o, oC biological and agricultural applications. They are active, ol--C. E.O M \ch, for example, as toxicants, e. g., as fungicides, themato cides, etc. Their preparation is illustrated by the follow which may be named 1,7,8,9,10,10-hexachloro-4,4-di ing examples: methyl-3,5-dioxatricyclo[5.2.1.036J-8-, i. e., the Example 9 acetone acetal of 1,4,5,6,7,7-hexachlorobicyclo[2.2.1]-5- hepteine-2,3-dici; and when Q and Q' taken together are Anhydrous gaseous was passed into a bivalent carbon chain, the products are tetracyclic, e. g. 3 5 50 ml. of anhydrous acetone until two grams had been absorbed. Then 6.9 grams of the diol of Example 2 were ul- Cl Cl added to the acetone and the mixture was refluxed for C1 four hours. After cooling, the reaction mixture was 1). "X poured into 250 ml. of water containing sodium carbonate CN-N / Y is c) 40 in an amount in excess of that required to neutralize the C E O hydrogen chloride. The mixture was immediately ex which may be named 1,2,3,4,4,5,6,7,8,9,10,10'-dodeca tracted with ether. After evaporation of the ether, there chloroSpirol. 2,5 – cyclohexadiene - 1,4'-3',5' - dioxatri was obtained a solid, very soluble in hexane, which was cyclo5.2.1.02',6'-3'-decene, or, the hexachloro-2,5- recrystallized twice from 30 percent aqueous ethanai, cyclohexadien-1-one acetal of 1,4,5,6,7,7-hexachlorobi 5 leaving 5.0 grams of the acetone acetal of hexachloro cyclo[2.2.1]-5-heptene-2,3-diol. bicyclo[2.2.1]-5-heptene-2,3-diol, melting at 77-78° C., Thus, there inay be prepared the acetone acetal of with the characteristic odor of acetals, analyzing as fol 1,4,5,6,7,7-hexachlorobicyclo 2.2.1 - 5 - heptene - 2,3- lows: diol, the 2-butanone acetal of 1,4,5,6,7,7-hexachloro bicyclo[2.2.1]-5-heptene-2,3-diol, the 2-pentanone acetal : of 1,4,5,6,7,7-hexachlorobicyclo 2.2.1 - 5 - heptene Found Calculated for 2,3-diol, the 3-pentanone acetal of 1,4,5,6,7,7-hexachloro C10H8O2Cl6 bicyclo[2.2.1]-5-heptene-2,3-diol, the 2-hexanone acetal Percent C------32.33 3. 2.2 of 1,4,5,6,7,7-hexachlorobicyclol.2.2.1]- 5 - heptene-2,3- Percent H------2.6 diol, the acetophenone acetal of 1,4,5,6,7,7-hexachlorobi 5 5 55.93 57.04 cyclo2.2.1]-5-heptene-2,3-diol, the isophorone acetal of 1,4,5,6,7,7-hexachlorobicyclo[2.2.1 - 5 - heptene - 2,3- Example 10 diol, the acetaldehyde acetal of 1,4,5,6,7,7-hexachloro bicycloI2.2.1-5. heptene-2,3-diol, the heptaldehyde acetal Treatment of 6.7 grams (0.02 mole) of the diol of of 1,4,5,6,7,7-hexachlorobicyclo(2.2.11 - 5 - heptene-2,3- Example 2 and 6.0 grams (0.02 mole) of hexachloro diol, the benzaldehyde acetal of 1,4,5,6,7,7-hexachloro 2,5-cyclohexadien-1-one with 1.0 gram of p-toluenesul bicyclo[2.2.1]-5-heptene-2,3-diol, the furfural acetal of fonic acid monohydrate in 100 mi. of toileine by reflux 1,4,5,6,7,7-hexachlorobicyclo[2.2.1 - 5 - heptene - 2,3- ing for four hours (0.2 ml. of water collected), neu diol, the hexachloro-2,5-cyclohexadien-1-one acetal of tralization and drying gives the hexachloro-2,5-cyclohexa 1,4,5,6,7,7-hexachlorobicyclo2.2.1]. - 5 - heptene - 2,3- dien-1-one acetal of 1,4,5,6,7,7-hexachlorobicyclo[2.2.1]-. digi, the 2-butanone acetal of 1,4,5,6-tetrachloro-7,7-di 5-heptene-2,3-diol. fluorobicyclo[2.2.1]-5-heptene-2,3-diol, the 2-hexanole It will be readily apparent to those skilled in the art acetal of 1,4,5,6-tetrachloro-7,7-difiuorobicyclo[2.2.1]-5- that the present diols, their carboxylic and carbamic acid heptene-2,3-diol, the acetophenone acetal of 1,4,5,6- esters, and their acetals may exist in a variety of stereo tetrachloro - 7.7 - difluorobicyclo[2.2.1] - 5 - heptene chemical configurations. The bicyclic compounds may 2,3-diol, the benzophenone acetal of 1,4,5,6-tetrachloro be trans, endo-cis or exo-cis. The tricyclic structures 7,7-difluorobicyclo[2.2.11-5-heptene-2,3-diol, the acetone may have an endo or an exo orientation. Further pcs acetal of 1,4,5,6,7,7-hexachloro-2-methylbicyclo2.2.11-5- sibilities with respect to enantiomorphs and diasterio heptene-2,3-diol, the isophorone acetal of 1,4,5,6,7,7-hexa isomers, etc., will be apparent to skilled stereochemists. chloro-2-phenylbicyclo[2.2.1-5-heptene-2,3-diol, etc. 75 It is intended that the present invention include all of 2,841,485 13 14. the possible stereoisomers of the present compounds, as The carbanilate was then evaluated against Stem represented by the planar formulae given herein. phylium solani, the incitant of tomato gray leaf-spot, as The present compounds possess outstanding biological follows: activity, as will be illustrated below. The herbicidal effect Example 13 of the diol of Example 2, e.g., was evaluated as follows: 5 A Bonny Best variety of tomatoes having four true Example II leaves was sprayed with an atomizer until run-off with an emulsion of the carbanilate prepared by mixing a An 0.5 percent by weight solution of 1,4,5,6,7,7-hexa solution of the chemical in acetone, water sufficient to chlorobicyclo2.2.1-5-heptene-2,3-diol in acetone was make a concentration of 1250 p. p. m., and as an emulsi prepared, and sprayed by means of an atomizer onto two 0. fying agent, 0.1 ml. of "Tween 20,' a surface-active week old seedlings of corn and of broad-leaf plants, e.g., agent reputed to be a sorbitan monolaurate polyoxyalkyl clover, cotton and radish. The pan containing the seed ene derivative. The plant was then sprayed with a spore lings was then placed on a wet sand bench in a greenhouse suspension of Stemphylium solani, held in an incubator for ten days. At the end of this time, the plants were at 70 F. for three days, and then removed to a green observed: whereas the broad-leaf plants were substan house and held for two days there. At the end of this tially unaffected by the treatment, the corn, a narrow time, whereas a control tomato plant which had been leaf plant species, was severely damaged. treated similarly with the exception of the application of This experiment demonstrates the activity of the present the carbanilate emulsion spray was severely diseased, diols as selective herbicides. Application of these com the plant sprayed with the carbanilate exhibited only pounds as herbicides is usually most conveniently effected 20 moderate to slight infection with leaf spot, in admixture with any of the conventional adjuvants and A similar test of the carbanilate by spraying an emul carriers; for example, a solution of the diol may be pre sion of this material on tomato plants which were then pared, and the resulting herbicidal composition applied exposed to tomato wilt disease, by immersion of their as a spray from an atomizer. Another form in which roots in a culture of Fusarium lycopersici, showed that the present diols may be applied to plants is as a dust, in substantial suppression of this disease was also obtained, admixture with a solid powdered carrier, such as clay, whereas unsprayed plants under the same conditions were talc, pumice or bentonite. The compounds may also be severely damaged. applied to plants in admixture with other agricultural In application of the present compounds as fungicides, pesticides, e.g., insecticides or fungicides. Particularly concentrations of from 10 to 5000 parts per million may effective as a means for the application of herbicides to 30 be used, for example. The present compounds may be living plants are emulsions of the herbicidally toxic com applied to the foliage of infected plants as an emulsion pounds. Emulsions of the present diols may be prepared spray, formulated as described above, e. g. by dissolving the compound in an organic solvent, such Parts as hexane, adding a wetting agent, and then treating the Petroleum oil------9 organic solution with water to form an oil-in-water 35 Water ------989 emulsion. (The word "oil" is here used to designate Wetting agent------1. any liquid insoluble in water.) Wetting agents which Toxicant ------may be used to prepare such emulsions include, e. g., alkylbenzenesulfonates, polyalkylene glycols, salts of sul In addition to application to plants for the prevention fated long-chain , sorbitan fatty acid esters, etc. 40 or control of disease, the present compounds may also Rates of application of the present diols to produce de be applied, for example, to fabric, wood, and other sired herbicidal effects may be particularly low where materials susceptible to fungicidal attack. these compounds are applied as emulsions, i.e., rates of An additional field of biological toxicity in which the 3-5 lbs. per acre, or even as low as 1 lb. per acre or less, effectiveness of the present compounds has been demon may be effective in selective eradication of weeds from de 45 strated is nematocidal activity. The effect of a nemato sired crops. cide can be estimated by counting the rate at which the Testing of the present compounds demonstrating their nematodes flex their bodies when suspended in water. The motility of nematodes was reduced 50 percent as effectiveness as fungicides is illustrated below: compared to a control, for example, by an 0.1 percent Example 12 50 concentration of the acetone acetal of 1,4,5,6,7,7-hexa chlorobicyclo[2.2.1]-5-heptene-2,3-diol, in 24 hours ex Samples of 0.3 gram, respectively, of 1,4,5,6,7,7-hexa posure. In a similar test, the 1,4,5,6,7,7-hexachlorobi chlorobicyclo[2.2.11-5-heptene-2,3-diol (I) and 1,4,5,6, cyclo[2.2.1]-5-heptene-2,3-diol diacetate of Example 4 7,7-hexachlorobicyclo[2.2.1]-5-heptene-2,3-diol mono reduced the motility of the nematodes 75 percent in 24 carbanilate (II), prepared as described in Examples 2 5 5. hours at an 0.1 percent concentration. and 7, were dissolved in acetone to make one percent The above examples indicate the widespread biological solutions. Portions of each of these solutions were then toxicity spectrum of the present compounds. The activi diluted with water to make 0.1 percent solutions, and ties of the different compounds vary in different applica." two 0.2 ml. aliquots of the solution of I and two 0.2 tions, naturally, and they will be applied in concentrations ml. aliquots of the solution of II were pipetted into slide 60 and applications suitably according to their activities. . wells and evaporated to dryness. Next, to one of the While the invention has been described herein with wells containing I, and to one of the wells containing particular reference to various preferred embodiments II were added suspensions of 5000 spores of Stemphylium thereof, and examples have been given of suitable pro sarcinaeforme in 0.1 ml. of water. The other two wells portions and conditions, it will be appreciated that varia were treated similarly with a suspension of Monilinia tions from the details given herein can be made without fructicola spores. departing from the invention. After incubation of these slides in Petri dishes contain What is claimed is: ing water for 16 to 24 hours, the percentage of spore 1. A compound of the formula germination was determined. It was found that both X R the diol (I) and the carbanilate (II) gave a 100 percent suppression of germination of the spores of Monilinia x1SZoT and the carbanilate (II) also gave a 100 percent Sup X SunOT pression of germination of Stemphylium spores, while the N diol (I) had killed better than 50 percent of the Stem where X is a halogen having an atomic weight of below phylium spores. 75 100, R is selected from the class consisting of hydrogen 2,841,485 5 16 and hydrocarbon radicals of from 1 to 6 carbon atoms, 5. An acetal of the formula T and T taken separately are selected from the class consisting of hydrogen, hydrocarboncarbonyl radicals X O wherein the hydrocarbon portions of the said hydrocar is 2 bon-substituted radicals are hydrocarbon radicals con r). taining from 1 to 18 carbon atoms and from 0 to 2 carbo x N-roX R Q cyclic rings containing up to 6 carbon atoms per ring, where X is a halogen having an atomic weight of below and hydrocarboncarbamyl radicals, and T and T taken 100, R is selected from the class consisting of hydrogen together represent the bivalent disubstituted carbon and hydrocarbon radicals of from 1 to 6 carbon atoms, atom-containing radical O Q taken separately is a hydrocarbon radical free of ali phatic unsaturation and containing up to 6 carbon atoms, Q' taken separately is selected from the class consisting of hydrogen and Q, and Q and Q’ taken together repre sent a chain of up to 5 carbon atoms, the terminal car where Q taken separately is a hydrocarbon radical free of 5 bon atoms of which are singly bonded to the carbon aliphatic unsaturation and containing up to 6 carbon atom to which Q and Q are attached, wherein the carbon atoms, Q’ taken separately is selected from the class con atoms of the said chain of carbon atoms are attached to sisting of hydrogen and Q, and Q and O' taken together Substituents selected from the class consisting of hydro represent a chain of up to 5 carbon atoms, the terminal gen, chlorine and lower alkyl radicals. carbon atoms of which are singly bonded to the carbon 20 6. 1,4,5,6,7,7-hexachlorobicyclo[2.2.1 - 5 - heptene atom to which Q and Q are attached, wherein the carbon 2,3-diol. atoms of the said chain of carbon atoms are attached to 7. 1,4,5,6,7,7-hexachlorobicyclo[2.2.1] - 5 - heptene substituents selected from the class consisting of hydro 2,3-diol diacetate. gen, chlorine and lower alkyl radicals. 8. 1,4,5,6,7,7-hexachlorobicyclo[2.2.11 - 5 - heptene 2. A diol of the formula 25 2,3-diol dicarbanilate. X R 9. 1,4,5,6,7,7-hexachlorobicyclo[2.2.1] - 5 - heptene 2,3-diol monocarbanilate. CXR OB 10. The acetone acetal of 1,4,5,6,7,7-hexachlorobi 30 cyclo[2.2.1]-5-heptene-2,3-diol. xU-ROHX R 11. The method which comprises contacting a cyclic where X is a halogen having an atomic weight of below carbonate of the formula 100 and R is selected from the class consisting of hydro R gen and hydrocarbon radicals of from 1 to 6 carbon X O atOnS. 35 3. A carboxylic acid ester of the formula X EIO- O X R where X is a halogen having an atomic weight of below X N O-C-R. 100 and R is selected from the class consisting of hydro 40 gen and hydrocarbon radicals of from 1 to 6 carbon X f 1NOT atoms with an acidic hydrolysis catalyst, isolating where X is a halogen having an atomic weight of below from the reaction product a 1,4,5,6,7,7-hexahalobicy 100, R is selected from the class consisting of hydrogen clo[2.2.1]-5-heptene-2,3-diol, contacting said diol with and hydrocarbon radicals of from 1 to 6 carbon atoms, a carbonylic compound selected from the class consist R’ is a hydrocarbon radical containing from 1 to 18 car ing of carboxylic acid anhydrides, carboxylic acid hal bon atoms and from 0 to 2 carbocyclic rings containing ides, isocyanates, carbamyl halides, aldehydes, and ke up to 6 carbon atoms per ring and T2 is selected from the tones, and isolating from the reaction product a com class consisting of hydrogen and hydrocarboncarbonyl pound of the formula radicals of the formula 50 ZoT O CX RC xU OT where R' is as defined hereinabove. X R 4. A carbamic acid ester of the formula where X and R are as hereinbefore defined, T taken separately is selected from the class consisting of hydro X R gen and T4, Ta taken separately is selected from the class X N O-C-N-R consisting of hydrocarboncarbonyl and hydrocarbon CX y carbamyl radicals wherein the hydrocarbon portions of xUul OTs 8) the said hydrocarboncarbonyl and hydrocarboncarbamyl X R radicals are hydrocarbon radicals containing from 1 to where X is a halogen having an atomic weight of below 18 carbon atoms and from 0 to 2 carbocyclic rings con 100, R is selected from the class consisting of hydrogen taining up to 6 carbon atoms per ring, and T and T and hydrocarbon radicals of from 1 to 6 carbon atoms, taken together represent a bivalent disubstituted carbon R is a hydrocarbon radical containing from 1 to 18 car atom-containing radical bon atoms and from 0 to 2 carbocyclic rings containing up to 6 carbon atoms per ring, R' is selected from the class consisting of hydrogen and R', and T is selected from the class consisting of hydrogen and hydrocarbon carbamyl radicals of the formula m where Q taken separately is a hydrocarbon radical free R. O. of aliphatic unsaturation and containing up to 6 carbon Yli atoms, Q’ taken separately is selected from the class con sisting of hydrogen and Q, and Q and Q' taken together r? represent a chain of up to 5 carbon atoms, the terminal where R' and R' are as defined hereinabove. carbon atoms of which are singly bonded to the carbon 2,841,485 17 18 atom to which Q and Q are attached, wherein the carbon consisting of aldehydes and ketones, and isolating from atoms of the said chain of carbon atoms are attached to substituents selected from the class consisting of hydro the reaction product an acetal of the formula gen, chlorine and lower alkyl radicals. X R Q 12. The method which comprises contacting a cyclic X r OY^ carbonate of the formula xU o/ Yo, X R X R X O where X is a halogen having an atomic weight of below r Yo-o 100, R is selected from the class consisting of hydrogen x- o/ 10 and hydrocarbon radicals of from 1 to 6 carbon atoms, X R Q taken separately is a hydrocarbon radical free of ali phatic unsaturation and containing up to 6 carbon atoms, where X is a halogen having an atomic weight of below Q' taken separately is selected from the class consisting 100 and R is selected from the class consisting of hydro of hydrogen and Q, and Q and Q taken together repre gen and hydrocarbon radicals of from 1 to 6 carbon 15 sent a chain of up to 5 carbon atoms, the terminal car atoms, with an acidic hydrolysis catalyst, and isolating bonatoms of which are singly bonded to the carbon atom from the reaction product a 1,4,5,6,7,7-hexahalobicy to which Q and Q are attached, wherein the carbon atoms clo[2.2.1]-5-heptene-2,3-diol. of the chain of carbon atoms are attached to substit 13. The method which comprises contacting a 1,4,5,6, uents selected from the class consisting of hydrogen, 7,7-hexahalobicyclo[2.2.1]-5-heptene-2,3-diol with a car 20 chlorine and lower alkyl radicals. bonylic compound selected from the class consisting of 16. The method which comprises contacting 1,4,5,6,7,7- carboxylic acid anhydrides and carboxylic acid halides hexachlorobicyclo[2.2.11 - 5 - heptene - 2,3 - diol cyclic and isolating from the reaction product a carboxylic acid carbonate with aqueous hydrochloric acid, isolating from ester of the formula the reaction product 1,4,5,6,7,7-hexachlorobicyclo 25 (2.2.1]-5-heptene-2,3-diol, contacting the said diol with X R phenyl isocyanate, and isolating from the reaction prod X r. O-C-R uct 1,4,5,6,7,7-hexachlorobicyclo[2.2.11 - 5 - heptene X 2,3-diol monocarbanilate. X OT 17. The method which comprises contacting 1,4,5,6,7,7- X R 30 hexachlorobicyclo[2.2.1]-5-heptene - 2,3-diol cyclic car where X is a halogen having an atomic weight of below bonate with aqueous hydrochloric acid and isolating 100, R is selected from the class consisting of hydrogen 1,4,5,6,7,7-hexachlorobicyclo[2.2.1]-5-heptene-2,3-diol. and hydrocarbon radicals of from 1 to 6 carbon atoms, 18. The method which comprises heating 1,4,5,6,7,7- R’ is a hydrocarbon radical containing from 1 to 18 35 hexachlorobicyclo[2.2.11 - 5 - heptene - 2,3 ... diol with carbon atoms and from 0 to 2 carbocyclic rings contain acetic anhydride and isolating from the reaction product ing up to 6 carbon atoms per ring and Ta is selected from 1,4,5,6,7,7-hexachlorobicyclo - 2.2.1 - 5 - heptene the class consisting of hydrogen and hydrocarboncar 2,3-diol diacetate. bonyl radicals of the formula 19. The method which comprises contacting 1,4,5,6,7,7- 40 hexachlorobicyclo[2.2.1 - 5 - heptene - 2,3 - diol with O phenyl isocyanate and isolating from the reaction product Ré a compound selected from the group consisting of 1,4,5,6,7,7 - hexachlorobicyclo[2.2.1 - 5 - heptene wherein R' is as defined hereinabove. 2,3-diol dicarbanilate and 1,4,5,6,7,7-hexachlorobicyclo 14. The method which comprises contacting a 45 (2.2.1]-5-heptene-2,3-diol monocarbanilate. 1,4,5,6,7,7-hexahalobicyclo[2.2.11 - 5 - heptene - 2,3- 20. The method which comprises heating 1,4,5,6,7,7- diol with a carbonylic compound selected from the class hexachlorobicyclo[2.2.1]-5-heptene-2,3-diol with acetone consisting of hydrocarbon isocyanates and dihydrocar and isolating from the reaction product the acetone acetal boncarbamyl halides and isolating from the reaction prod of 1,4,5,6,7,7-hexachlorobicyclo[2.2.1 - 5 - heptene uct a carbamic acid ester of the formula 50 2,3-diol. 21. A biological toxicant comprising an inert carrier, X R and, as the essential effective ingredient a compound of x1 6--N-R the formula CX2 y X. R X OTs 55 x1 OT X R CX X. OT where X is a halogen having an atomic weight of below X R 100, R is selected from the class consisting of hydrogen where X is a halogen having an atomic weight of below and hydrocarbon radicals of from 1 to 6 carbon atoms, 60 100, R is selected from the class consisting of hydrogen R’ is a hydrocarbon radical containing from 1 to 18 car and hydrocarbon radicals of from 1 to 6 carbon atoms, bon atoms and from 0 to 2 carbocyclic rings containing T and T taken separately are selected from the class con up to 6 carbon atoms per ring, R' is selected from the sisting of hydrogen, hydrocarbon carbonyl radicals where class consisting of hydrogen and R', and T8 is selected in the hydrocarbon portions of the said hydrocarboncar from the class consisting of hydrogen and hydrocarbon 65 bonyl and hydrocarboncarbamyl radicals contain from 1 carbamyl radicals of the formula to 18 carbon atoms and from 0 to 2 carbocyclic rings con taining up to 6 carbon atoms per ring, and hydrocarbon R carbamyl radicals, and T and T taken together represent NC the bivalent disubstituted carbon atom-containing radical O Q where R' and R' are as defined hereinabove. Nc1 15. The method which comprises contacting a / NQ 14,5,6,7,7-hexahalobicyclo[2.2.1 - 5 - heptene - 2,3- where Q taken separately is a hydrocarbon radical free diol with a carbonylic compound selected from the class 75 of aliphatic unsaturation and containing up to 6 carbon 2,841,485 19 20 atoms, Q’ taken separately i: selected from the class con as the essential effective ingredient, 1,4,5,6,7,7-hexachlo sisting of hydrogen and Q, and Q and Q' taken together robicyclo[2.2.1]-5-heptene-2,3-diol. represent a chain of up to 5 carbon atoms, the terminal 25. A fungicidal composition comprising an inert car carbon atoms of which are singly bonded to the carbon rier and, as the essential effective ingredient, 1,4,5,6,7,7- atom to which Q and Q are attached, wherein the carbon hexachlorobicyclo[2.2.1 - 5 - heptene - 2,3-diol mono atoms of the said chain of carbon atoms are attached to carbanilate. ... . substituents selected from the class consisting of hydro 26. The method of killing fungi which comprises ex gen, chlorine and lower alkyl radicals. . . posing said fungi to a toxic quantity of 1,4,5,6,7,7-hexa 22. A herbicidal composition comprising an inert car chlorobicyclo[2.2.1 - 5 - heptene - 2,3 - diol monocar rier and, as the essential effective ingredient, a diol of 10 banilate. the formula X R . References Cited in the file of this patent X OE, UNITED STATES PATENTS X 2,351,311 Alder ------June 13, 1944 X O 15 2,528,654 Herzfeld et al. ------Nov. 7, 1950 X R 2,552,567 McBee ------May 15, 1951 where X is a halogen having an atomic weight of below 2,606,910 Herzfeld ------Aug. 12, 1952 100 and R is selected from the group consisting of hydro 2,635,979 Lidov ------Apr. 21, 1953 gen and hydrocarbon radicals of from 1 to 6 carbon 20 2,697,103 Ordas ------Dec. 14, 1954 atomS. 2,717,851 Lidov ------Sept. 13, 1955 23. A herbicidal composition comprising an oil-in 2,736,730 Kleiman ------Feb. 28, 1956 water emulsion of 1,4,5,6,7,7 - hexachlorobicyclo 2.2.11-5-heptene-2,3-diol. OTHER REFERENCES 24. The method of destroying vegetation which com Palomaa et al.: Ber. Deut. Chem, vol. 72 (1939), page prises applying to living plants a phytotoxic amount of a 25 313 (1 page). herbicidal composition comprising an inert carrier and, UNITED STATES PATENT OFFICE Certificate of Correction Patent No. 2,841,485 July 1, 1958 William K. Johnson et al. It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below. '', , . " 3. Column (, line 21, before the word “and” strike out “ice? ; column 11, lines 36 to 40 inclusive, the formula should appear as shown below instead of as in the patent: Cl H. O. C o \ Cl Cl C C chN/ XX el ( Cl Signed and sealed this 23rd day of September 1958.

SEAL

Attest: KARL. H. AXLINE, ROBERT C. WATSON, Attesting Officer. Commissioner of Patents.