Patented Feb. 12, 1946 2,394,583 UNITED STATES PATENT OFFICE

TBIOCYANO ALPEIATIC ACID ESTERS OF ENDOETY ENE TANON DANE HYDRoxYCYCLoPEN - Herman A. Bruson, Philadelphia, Pa., assignor to the Resinous Products & Chemical Como pany, Philadelphia, Pa., a corporation of Dela ware No Drawing. Application September 12, 1944, Serial No. 553,799 5 Clains. (C. 260-454) This invention relates to esters of thiocyano ethyl alcohol, propyl or isopropyl alcohol, ace aliphatic carboxylic acids and 3,5-endoethylene tone, or similar volatile organic solvents. The hydroxycyclopentanoindane. These esters are halogen salt which forms is readily separated new compounds having the formula, and the solution of thiocyano ester purified by conventional methods, such as decolorizing with C14H13-OCO-A-SCN charcoal, solvent extraction, or distillation. wherein A is an alkylene group and C14H15 is the As an acidic condensing agent in the above endoethylene cyclopentanoindane group as here reaction between 1,4-endomethylene tetrahydro in defined. A2-fluorene and a halo aliphatic carboxylic acid This application is a continuation-in-part of 0 there may eubsed boron trifluoride and its co copending application Serial No. 531,763, filed ordination complexes with oxygenated compounds April 19, 1944, and reference is made thereto as such as ethers, esters, carboxylic acids, ketones, to details of the raethod of preparation of the aldehydes, water, etc., sulfuric acid, acid esters new thiocyano esters which are specifically of sulfuric acid, such as ethyl acid sulfate, Sul claimed in the present specification. i fonic acids, such as toluene Sulfonic acid, or The new compounds are advantageously pre butyl sulfonic acid, other strong acids, and the pared by reacting a halogenated aliphatic car usual amphoteric metal halides with are effec boxylic acid preferably in the presence of an tive as acidic catalysts such as aluminum chlo acidic condensing agent, with 14-endomethylene ride. The amount of such catalyst used need be tetrahydro-A3-fluorene to form an ester of endo 39 only a small per cent of the weight of the start ethylene hydroxycyclopentanoindane by an addi ing hydrocarbon but may be as much as or more tion-rearrangement reaction and replacing the than a molar equivalent. halogen aton with a thiocyano radical. Alter The reaction may be performed with or without natively, the new compounds of this invention an organic solvent such as ethylene dichloride are prepared by esterifying the new compound, or dioxane. It may be performed at a temper 3,5 - endoethylene hydroxycyclopentano -4,5-in ature from room temperature up to 150 C. or dane, with a halo aliphatic carboxylic acid and more, although the range of about 50° C. to replacing the halogen with a thiocyano radicai. about 40° C. is preferred. Thus, in accordance with the first method mera According to the second method, 14-endo tioned above, 1,4-endomethylene tetrahydro-A- 30 methylene tetrahydro-A-fluorene is hydrated in fiorene reacts with a halo aliphatic carboxylic the presence of a strongly acidic catalyst, such acid, KACOOH, where 2, represents bromine or as sulfuric acid, addition and rearrangement also chlorine, as follows: occurring in this reaction. The reaction, full de C tails of which are given in application Serial No. 33 517,204, filed January 6, 1944, may be represented as follows: 1NI &H - XACOOH - ls.frt, This alcohol is then esterified with a halo ali E.I. (s phatic carboxylic acid by conventional methods Six. and the resulting ester treated with a metal thio wherein Z is the benzylene group attached to the cyanate as described above. 4 and 5 carbon atoms of the endoethylene cyclo As suitable halo aliphatic acids there may be pentano group. The halogen atom may now be used bromoacetic acid, chloroacetic acid, S-bro replaced with a thiocyano radical by metathesis 50 mopropionic acid, oz-chloro-propionic acid, or with a metal salt of thiocyanic acid, such as sodi chlorobutyric acid, a-bromobutyric acid, S-chlo um thiocyanate, potassium thiocyanate, ammoni robutyric acid, B-bromobutyric acid, a-bromoso um thiocyanate, lead thiocyanate, silver thiocyan butyric acid, a-chloro-isobutyric acid, and other ate, calcium thiocyanate, or the like, preferably chloro- and bromo-substituted fatty acids, par in a solvent medium such as methyl alcohol, ticularly those of two to eight carbon atoms, al

2 2,894,588 though halogen-substituted higher fatty acids tached to a water separator until water ceased may also be used. coming over. This required about three hours. The thiocyano esters of this invention are uses The product was cooled, washed with water, and ful as solvents and softeners, particularly for res dried in vacuo to yield the B-chloropropionate of inous materials and as toxicants in insecticidal endoethylene hydroxycyclopentanoindane as a compositions. They are also useful as additives pale amberecolored oil. in lubricating compositions. One mol of this ester in an equal volume of al The following examples describe the prepara cohol was boiled for eight hours with 1.1 mol tion of typical thiocyano esters of this invention equivalents of potassium thiocyanate. The prods end present typical properties thereof: uct was then washed with water and dried in vacuo to yield the B-thiocyanopropionic acid ester Eacample 1 of endoethylene hydroxycyclopentanoindane as a A mixture of 290 grams of chloroacetic acid, thick amber-colored oil. 550 grams of 1,4-endomethylene tetrahydro-A- It has powerful insecticidal action against flies, fluorene, and 20 grams of 40% sulfuric acid was 5 mosquitoes and other pests and is free from ob stirred and heated at 95 C. for six hours. The jectionable odor or irritation to the user. reaction mixture was cooled, washed with water, dried, and distilled in vacuo. The chloroacetate Eacample 3 of endoethylene hydroxy-cyclopentanoindane Instead of the B-chloropropionic acid in Exam distilled over at 165-170° C./1 mm. as a colorless 20 ple 2, an equivalent molecular quantity of a-chlo oil. V roisobutyric acid may be used. The oz-chloroisor A mixture of 195 grams of the above ester, 65 butyrate of endoethylene hydroxycyclopentano grams of sodium thiocyanate and 200 grams of indane is obtained as a pale yellow oil. When ethanol was stirred and boiled under reflux for heated in isopropanol solution with an equivalent eight hours. The resulting mixture was cooled 25 amount of Sodium thiocyanate it yields the corre and washed thoroughly with water. The prod sponding og-thiocyanoisobutyrate of endoethylene uct thus obtained was dried in vacuo at 95 C., hydroxy-cyclopentanoindane as a pale yellow oil, yielding an amber-colored oil, weighing 203 useful as a toxicant for the preparation of in grams and consisting of Over 98% pure thiocya secticides. noacetate of endoethylene hydroxycyclopentano 30 The phenyl group which is present in the mole indane. A 5% solution of this compound in de cule of the addition-rearrangement product per odorized kerosene gave a 100% kill when tested mits the introduction of a great variety of sub by the Peet-Grady method as an insecticide stituents in that part of the molecule. One or against flies, and was free of objectionable odor more such substituents may be introduced into or irritation. 35 the phenyl ring. Typical groups which may be . . Eacample 2 introduced include alkyl groups, such as methyl, A mixture of 75 grams of 1,4-endomethylene ethyl, isopropyl, butyl, tert.-butyl, octyl, isooctyl, tetrahydro-A-fluorene and 100 grams of aqueous ozozyy-tetramethyl butyl, nonyl, etc., keto, such 40% sulfuric acid was rapidly Stirred and boiled as the acetyl group, nitro, sulfonate, halogen, etc. under reflux at 120-125° C. for four and One-half 40 I claim: hours. The mixture was cooled and the resulting 1. As a new compound, an ester of a thiocyano dark, viscous oil separated, and taken up in ben saturated aliphatic carboxylic acid and 3,5-endo zene. The benzene solution was washed thor ethylene hydroxycyclopentanoindane. oughly with water and dilute sodium hydroxide 2. As a new compound, an ester of a Saturated Solution. The benzene was then stripped off and 45 thiocyano aliphatic carboxylic acid of two to the residual oil distilled in vacuo. eight carbon atoms and 3,5-endoethylene hydrox The endoethylene hydroxycyclopentanoindane ycyclopentanoindane. thus prepared distilled over at 165-175 C./5 mm. 3. As a new compound, the thiocyanoacetate of as a viscous pale yellow oil which crystallizes on . 3,5-endoethylene hydroxycyclopentanoindane. standing. After recrystallization from nitro 50 4. As a new compound, the 8-thiocyanopropi methane it formed colorless crystals melting at onate of 3,5-endoethylene hydroxycyclopentano 107-108° C. indane. One molecular equivalent of the above alcohol 5. As a new compound, the a-thiopyanoisobuty and 1.1 molls of beta-chloropropionic acid togeth rate of 3,5-endoethylene hydroxycyclopentano er with 1 gram of 40% sulfuric acid was boiled in 55 indane, benzene solution under a reflux condenser at HERMAN A. BRUSON.

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