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United States Patent Office Patented Mar 2,827,471 United States Patent Office Patented Mar. 18, 1958 2 CONH, or CHNH. The preferred embodiments are 2,827,471 the straight-chain compounds, wherein n is an integer from 6 to 16 and Y is carboxylic illustrated by specific PROCESS FOR PREPARING LONG-CHAN substances such as omega-trifluoroctanoic, omega-tri TRFLUOROALKANOIC ACDS fluoronomanoic, omega-triflucrodecanoic, omega-trifluo Gilbert Gavlin and Richard G. Maguire, Chicago, Ill., rododecanoic, omega-trifluorocctadecanoic or omega-tri assignors, by mesne assignments, to the United States fluorostearic acid and the like. The corresponding amides of America as represented by the Secretary of the Navy and amines constitute specific examples of the type of No Drawing. omega-trifluoroalkyl amides and amines respectively conn Application February 28, 1955 10 ing within the scope of the present invention. Serial No. 491236 The starting material for the synthesis of the higher 6 Claims. (C. 260-408) members of the series of omega-trifluoroalkanoic acids, omega-trifluoroalkyl amides and amines as previously indicated is omega-trifluorobutyric acid which may be This invention relates to new organofluorine com 5 prepared from such widely available materials as ethylene pounds. More particularly, this invention relates to and carbon tetrachloride. For best results, the procedure new omega-trifluoroalkanoic acids and the correspond of Joyce et al. described in the J. Am. Chem. Soc., 70, theiring a preparation. nines and amides thereof and also to methods for 2529 (1948), preferably modified by the use of slightly lower reaction temperatures (70 to 80 C.) may be used. Aliphatic fluorine compounds having eight or more 20 The conversion of the reaction product, 1,1,1,3-tetra carbon atoms in the chain and further characterized by chloropropane, separated from the reaction mixture, to the presence of a -CF3 group at one end of the molecule 1,1,1-trifluoro-3-chloropropane is carried out by the use and an adsorbable polar group at the other extremity of a fluorinating agent preferably consisting of a pre thereof are highly desirable surface-active agents hav heated mixture of antimony trifluoride and antimony ing b)th hydrophobic and organophobic properties. For 25 pentachloride and maintaining a reaction temperature be example, when a long chain omega-trifluoroalkanoic acid tween 0 and 45° C. Formation of omega-trifluorobutyric is applied to the polished surface of a solid, such as acid from 1,1,1-trifluoro-3-chloropropane is preferably platinum, glass, copper, etc., it has been found that an accomplished via the Grignard reaction essentially as de extremely high degree of nonwettability is imparted there scribed by McBee and Truchan in the J. Am. Chem. to as determined by contact angle measurements using 30 Soc., 70, 2911 (1948). various liquids. The chain-lengthening reactions applied to omega Although such compounds are valuable as surface wifluorobutyric acid for producing the long-chain homo active agents and for other technical applications as logues thereof without adversely affecting the omega boundary lubricants as well as synthesis intermediates trifluoromethyl configuration include the following Suc for the preparation of more complex compounds having cessive steps: (1) reduction of the acid to the corre the omega-trifluoro configuration, the long-chain members sponding alcohol, (2) formation of the omega-trifluoro of the omega-trifluoroalkanoic acid series and the corre alkyl halide therefrom, (3) preparation of the cadmium sponding amides and amines have not been made avail organometallic compound, (4) reacting the di-(omega able heretofore despite the fact that lower members of trifluoroalkyl) cadmium with an ester acid halide, and the series as, for example, omega-trifluorobutyric acid, 40 (5) reducing the keto-ester to convert the keto group are known. An essential part of the present invention to methylene and hydrolizing the ester to restore the con prises the providing of a method for utilizing the carboxylic group. The same sequence of steps may be latter substance as a starting material in preparing the repeated if desired to further increase the chain length members of the series containing at least 8 carbon atoms depending upon the ester acid halide used in the reac in the chain without deterioration of the -CF3 group 45 tion and the number of methylene groups required. A the rein. This is accomplished through a sequence of single carbon atom may be introduced into the molecule steps involving a number of reactions for lengthening by the well-known Grignard reaction using carbon di the chain carried out under the mildest conditions con oxide, and this method used in conjunction with the sistent with a reasonable reaction rate to preclude forma aforesaid reactions is often suitable for obtaining the tion of pyrolysis or degradation products and also, to 50 long-chain members of the series containing an odd num eliminate rearrangement or other conditions which could ber of carbon atoms. In each case, the amide may be lead to a breakdown of the essential omega-CF3 group prepared from the omega-trifluoroalkanoic acid by react within the molecule. ing the same with thionyl chloride and ammonia. Reduc It is accordingly an object of the invention to provide tion of the carbonyl group to methylene provides the new omega-trifluoroalkanoic acids and their correspond 55 ing amides and amines. corresponding amino compound. Purification steps in A further object of the invention is to provide a method clude conventional crystallization and fractionation pro for preparing long-chain omega-trifluoroalkanoic acids cedures except where otherwise indicated below. and related amides and amines from omega-trifluoro For maintaining the omega-CF3 group intact during butyric acid without destroying the omega-CF3 configura 60 the series of reactions aimed at preparing the necessary tion of the molecule. intermediates for increasing the chain length and also Another object is to provide new omega-trifluoro for the purpose of enhancing the yields at the various methyl compounds containing an adsorbable polar group stages in the synthesis, several important modifications on the opposite end of the molecule which compounds have been found to be essential to the production of the are excellent surface-active reagents having nonwettable aforesaid long-chain compounds insofar as conventional characteristics and other useful properties. 65 methods of synthesis are concerned. One procedural Other objects and advantages will become apparent as modification consists of the preparation of the omega the specification proceeds. trifluoroalkyl bromide by adding the alcohol to phos The new compositions of the present invention may be phorus tribromide thereby reversing the conventional designated by the structural formula CF (CH)Y, where 70 practice of reagent addition. By this means, dehydra in n is a positive integer from 6 to 22 and Y is a mono tion and rearrangement of the alcohol by anhydrous valent radical forming a polar group as -COOH, phosphoric acid is virtually eliminated, and yields up 2,827,471 3 4. wards of 90% or better of the desired omega-trifluoro denser, calcium chloride drying tube, filling tube with alkyl bromide may be obtained consistently. pressure-equalizing connection and a stirrer. After the A second improvement leading to considerable yield flask and contents had been cooled to 0° C. in an ice increase comprises the use of solvent exchange by frac bath, 38.4 g. (0.3 mole) of omega-trifluoro-n-butyl al tional distillation under vacuum after preparation of the cohol was added dropwise over a one-hour period. The di-(omega-trifluoroalkyl) cadmium compound and prior reaction temperature was raised about 10 per hour to the reaction of the same with an ester acid halide. over a 10-hour period by heating with an oil bath after The exchange from ether to benzene is known to de which the reaction mixture was cooled and poured into crease markedly the extent of diester formation during 500 ml. of ice water. The organic layer was washed reaction of the organometallic compound with the ester O with three portions of concentrated sulfuric acid; then acid halide. By avoiding the stripping of the ether from by water until free of acid. The reaction mixtures the cadmium compound to dryness, however, and utiliz from two such runs were combined, dried over anhy ing reduced pressures in the solvent exchange step, pre drous calcium sulfate, and distilled over phosphorous viously obtained keto-ester yields ranging from 30 to pentoxide to yield 106 g. (90% yield) of omega-trifiu 64% have been upgraded to consistent yields of from 15 oro-n-butyl bromide, B. P. 104 C./755 mm. 69 to 77%. Preparation of 8,8,8-trifluoro-4-ketooctanoate.-The Reduction reactions used in the chain-lengthening Grignard reagent of omega-trifluoro-n-butyl bromide reactions consists of (1) the use of lithium aluminum 42.9 g. (0.224 mole) was prepared in accordance with hydride in converting the acid to the corresponding conventional practice excepting that a system capable of alcohol and (2) the Clemmensen procedure for re 20 being operated in vacuo was used. The reaction product ducing the carbonyl group of the keto-ester to methylene. was cooled to 0° C. by immersing the flask in an ice The latter technique is essential since the generally more bath after which 24.7 g (0.135 mole) anhydrous cadmi widely used method for similar purposes, namely, the um chloride was added with stirring over a period of Huang-Minion-Wolff-Kishner procedure, resulted in the 20 minutes, utilizing a powder flask connected to the 25 reaction vessel by means of wide rubber tubing. After equimolar elimination of hydrogen fluoride thereby in the addition was completed, the mixture was agitated dicating destruction of the -CF3 substituent in the for the same period of time at 0° C.
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