Patented Sept. 19, 1950 2,522,566 UNITED STATES PATENT OFFICE, 2,522,566 ETHERS DERIVED FROM HEXAFLUORO BUTYNE-Z David W. Chaney, Nether Providence Township, Delaware County, Pa., assignor to American Viscose Corporation, Wilmington, Del., a cor poration of Delaware No Drawing. Application December 27, 1946, Serial No. 718,887 1 10 Claims, (01.260-231) This invention relates to a new class of ethers r - 2 , . obtained by direct addition of an organic com Hexafluorobutyne-2 may be prepared by the pound containing at least one hydroxyl group to dechlorination of the compound CF3CC1=CC1CF3 as described in the literature. (JACS, vol. '71, p. the triple bond of a ?uorinated butyne of formula 298, 1949; JACS, vol. 69, p. 1820, 1947.) In general, the new ethers are obtained by mixing the ?uorinated butynes and aliphatic alcohol or alcohol containing other functional groups, together with an alkaline catalyst for the where X represents hydrogen or halogen, and Y reaction, in a suitable reactor, under atmospheric represents hydrogen, halogen, or an alkyl radical. pressure. The reactor may be externally heated I have found that organic compounds contain to about 50-75° C., at which temperature absorp~ ing at least one hydroxyl group add to the triple tion of the ?uorinated butyne usually » begins. bond of the ?uorinated butynes, inv the presence Higher or lower temperatures may be employed, of an alkaline catalyst, and under moderate heat dependent upon the particular reactants under ing to initiate the reaction, in all cases where at 15 consideration.’ 1 1 least one of the carbons of the butyne has two After the reaction has been initiated, external fluorine atoms attached to it, to produce ?uoro heat may be reduced or eliminated, since the re butyl ethers, ?uoro butylene ethers, or mixtures action is exothermic and proceeds to completion of the saturated and unsaturated ethers from under autogeneous heat. When the reaction is which the individual ethers may be separated by completed, generally a matter of a few hours, the fractional distillation. crude reaction mixture is Worked up for recovery The preferred hydroxyl-containing organic of the pure ethers. compounds for use in this invention are aliphatic The precise nature of the reaction product def alcohols which term includes the cycloaliphatic pends upon the particular aliphatic alcohol or alcohols, as well as such alcohols containing other 25 alcohol-like compound employed in the reaction. functional groups. Examples of the aliphatic For example,_when compounds containing a sin and cycloaliphatic alcohols are methanol, etha gle hydroxyl group are employed, the reaction nol, propanol, isopropanol, n-butanol, iso-buta product may be an unsaturated ether of formula: nol, terbutanol, and the straight and branched chain pentanols; higher alcohols, i. e., those con 30 CFzXC (OR) =CHC (X2) Y taining six or more carbon atoms, such as hexa nol, cyclohexanol, octanol, dodecanol, and octa where X represents hydrogen or halogen, Y rep decanol; polyhydric aliphatic alcohols, such as resents hydrogen, halogen, or an alkyl radical,“ ethylene glycol, glycerol, propylene glycol, 1,3 and (OR) represents the monovalent residue of butylene glycol, hexamethylene glycol, deca~ the hydroxyl-containing organic compound; a methylene glycol, and 1,12-octodecandiol, pen saturated ether of formula I taglvcol, diethylene glycol, and polyglycols gen erally including polyethylene glycols containing CFzXC (OR) 2CH2C(X2) Y as high as 20 or more ethylene oxide units. Ex X, Y, and (OR) having the same signi?cance as amples of aliphatic alcohols containing other 40 functional groups include the halo-hydrins, such above; or the reaction product may and usually as ethylene chlorhydrin, ethylene bromhydrin, does, comprise a mixture of the saturated and glycolic acid and its esters, the monomethyl, unsaturated ethers. monoethyl, and monobutyl ethers of ethylene Organic compounds containing more than one glycol, diethylene glycol and higher polyethylene hydroxyl group, such as, the polyhydric aliphatic glycols; unsaturated alcohols, such as allyl alco alcohols, may also yield unsaturated and/or satu hol, methallyl alcohol, and crotyl alcohol; cellu rated ethers, and the saturated ethers may be lose and celluose derivatives which may contain cyclic if the conditions are such as to favor the ether and ester linkages, starch and partially formation of a 5- or 6-membered ring. The formation of cyclic unsaturated ethers un methylated starch, and mono- and polysaccha 50 rides and their derivatives which contain ether der the conditions described herein appears to be and ester linkages. The alcohols containing other influenced by the‘ number of carbons in a straight functional groups in addition to the reactive chain‘ present in the hydroxy compound. Thus, when the lower members of the glycol series, that hydroxyl group are preferably used in amounts is, ethylene or propylene glycol, are reacted With in excess of the theoretical. ' 55 the ?uorinated butyne, under the conditions dee 2,522,566 '4 l 3 was fractionally distilled to yield two fractions scribed, the addition product usually comprises an ether of formula: as follows: . (1) 25 parts, B. P. 44-4s°/50 mm., N25°=1.3318 I CFrXG=CH-—C(X:)Y <2) 5 parts, B. P. same/20 mm., N25°==1.3450 owner-011 Both fractions were shown to have the same rela which may exist in either cis- or trans-form, n tive compositions of carbon, hydrogen, and ?uo being 2 or more and an ether of formula rine and molecular weights which corresponded in each case to a l to l combination of oFiXo-oHroXnr 10 CFaCECCFc and HOCH2CH2OH. Since the pres ence of a hydroxyl group in Fraction 2 was dem (CH1)1\ CH2 onstrated (by reaction with sodium), but not in Fraction 1, the fractions were assigned the fol X and Y in both formulae having the same signif lowing probable formulae: icance as above, and n in II being 1 or 2; the cyclic ether being present in varying amounts. When the hydroxyl-containing organic com pound contains a higher number of carbons in a straight chain, ring formation appears to be in- , hibited. Thus, the reaction product obtained by reacting the fluorinated butyne with glycols con 20 taining four or more CH2 groups, usually com prises a substantially pure unsaturated ether hav dHzoHioH ing a structural formula similar to I above, it Example III being 4 or more. Hexa?uorobutyne-Z was passed into a vessel Regardless of the particular type of ether containing trimethylene glycol under the same formed, whether saturated or unsaturated, or conditions as described in Example II. The addi mixtures of the two, in all instances the product tion product comprised traces of a cyclic satur obtained by reacting aliphatic including cyclo ated ether, and a preponderant quantity of an aliphatic alcohols, or aliphatic alcohols contain unsaturated ether of B. P. 83—84°/30 mm., and ing other functional groups, under the conditions 30 formula described herein is an ether resulting from the direct addition of the hydroxyl-containing com pound to the acetylenic linkage of the butyne. The following examples, in which the-parts are dmomonion given by weight, are illustrative of the invention: 35 Example IV Example I Hexafiuorobutyne-Z was added to tetramethe ylene glycol under the conditions described in Ex The apparatus used was a three neck vessel ?t ample II. The addition product comprised a sub ted with stirrer, gas inlet, and adapter bearing a 40 stantially pure ’ unsaturated ether of B. P_. thermometer and condenser. Five parts of sodium metal were dissolved in 125 75-80°/ 10 mm, and formula parts of ethanol in the ?ask. Fifty-four parts of hexa?uorobutyne-2 (CF3CECCF3) were passed into the solution at a temperature between 50-“ C. and 75° C. with rapid stirring, the temperature élHaCHaCHnCHzOH being maintained by autogeneous heat. The re Example V action mixture was then poured into 700 parts of 180 parts'of fresh alkali cellulose crumbs (made water. ' An oil separated and was drawn off, from wood pulp steeped two hours in 17.8% Washed with water and dried over calcium chlo NaOH solution at 18° C. and pressed to a factor ride. The oil was fractionated. Two fractions r of 3) were placed in an Erlenmeyer ?ask attached were obtained (1) a product having the‘formula to a monometer, a vacuum pump and a cylinder CF3C(OC2H5) :CHCFs, B. P. '72—73° C., containing hexafluorobutyne-Z. The ?ask was evacuated and the line to the pump was then ND25":1.3138 closed off. Hexa?uorobutyne was allowed to ?ll Anal.--Fluorine: calc. 54.8%, found 54.6% (on the flask to a pressure of approximately 1 at oxidation with potassium permanganate, Fraction mosphere and the valve closed off. The ab’ 1 yields CF3COOH;) and (2) a product having the sorption of hexa?uorobutyne could be followed by the drop in pressure and this rate increased with formula CF3C(OC2H5)2CH2CF3, B. P. 132-135“ C., increasing temperature. At 50-55° the rate of ab; ND25°=1.3394. Anal.—Fluorine: calc. 414.9%, sorption increased to 4 parts/hour, the pressure found 44.8%. ' being maintained at approximately 1 atmosphere Example II by addition of the butyne. After 8 hours the re= action was discontinued. The product was 2.3 parts of sodium metal were reacted with 31 washed with dilute acetic acid, then with water parts of ethylene glycol in a vessel equippedewith and then dried. Quantitative analysis for ?uo a stirrer, thermometer,-and condenser. 65 parts rine showed that 9.88% was present which corre-" of hexafluorobutyne-Z gas were then passed in, sponds to 0.14 mole of CFsECCFs per ‘mole of the temperature being maintained at about (SO-70° glucose.