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 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 , 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, , octanol, , and octa where X represents hydrogen or halogen, Y rep decanol; polyhydric aliphatic alcohols, such as resents hydrogen, halogen, or an alkyl radical,“ , , 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 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. C., largely as the result of autogeneous heat. The 70 Example VI butyne was compeltely absorbed. The reaction mixture was then cooled, neutralized with acetic ' 28 parts of alkali cellulose crumbs (made from acid, and an excess of water was added. An oil wood pulp steeped two hours in 17.8% NaOH ‘solu layer separated. It was washed with water and tion at 18° C. and pressed to a factor of 3) were dried over anhydrous sodium sulfate. The oil 75 placed in a stainless steel bomb. 36 parts of 2,522,566 5 hexa?uorobutyne-Z were added in the absence of groups which are reactive with hexa?uoro air. After 16 hours at room temperature and 24 butyne-Z, to the triple bond of hexafluorobutyne-Z hours at 50° the bomb was cooled, the excess which comprises heating the alcohol and butyne, butyne removed by evaporation and the resultant in the presence of an alkaline catalyst, at at product poured into water where it was neutral mospheric pressure, until the addition has been ized with dilute acetic acid, washed again with effected. water and dried. Quantitative ?uorine analysis 2. A process for the production of an addi showed that 16.9% of ?uorine was present. This tion product of hexa?uorobutyne-Z and ethanol corresponds to 0.24 m0le of hexa?uorobutyne per which comprises heating ethanol and the butyne, mole of glucose. in the presence of an alkaline catalyst, at at Example VII mospheric pressure, until the addition has been eifected. 25.8 parts of an alkali cellulose (made from wood 3. A process for the production of an addition pulp steeped 2 hours in 2% NaOH soln., pressed product of heXa?uorobutyne-2 and ethylene to a factor of 1.7) were sealed in a stainless 15 glycol which comprises heating ethylene glycol steel bomb with 40 parts of hexa?uorobutyne-Z. and the butyne, in the presence of an alkaline After 72 hours at 50° and 24 hours at 100° the ex catalyst, at atmospheric pressure, until the addi~ cess butyne was allowed to escape. The product tion has been effected. on treating as described in Example 2 was found 4. A process for the production of an addition to contain 1.4% of ?uorine. 20 product of hexa?uorobutyne-Z and trimethylene The new ethers are, in general, colorless liquids, glycol which comprises heating trimethylene all of which are substantially insoluble in Water. glycol and the butyne, in the presence of an‘ The ethers obtained by addition of the aliphatic alkaline catalyst, at atmospheric pressure, until and cycloaliphatic alcohols are variously soluble the addition has been effected. in the common organic solvents, whereas those 25 5. A process for the production of an addition derived from cellulose are insoluble in such sol product of hexa?uorobutyne-z and alkali cel vents, as well as in alkali and cuprammonium lulose which comprises heating alkali cellulose solution. The ethers are useful for many diverse and the butyne, in the presence of an alkaline purposes, such as insecticidal toxicants, wetting catalyst, at atmospheric pressure, until the addi agents, as solvents or diluents for use with plastic 30 tion has been e?ected. coating compositions, and as intermediates in 6. The addition product of hexa?uorobutyne-2 various chemical processes. and an alcohol selected from the group con Although the reaction is speci?c for butynes sisting of aliphatic and cycloaliphatic alcohols having two ?uorine atoms attached to a single in which each oxygen singly bonded to a carbon carbon, it is general for all butynes of that par 35 is further bonded to hydrogen and which con ticular type. Other ethers which may be pre tain no groups other than hydroxyl groups which pared are the ethers of such ?uorine-containing are reactive with heXa?uorobutyne-2, and pro butynes as penta?uoro-chloro-butyne-2, tetra duced by the process of claim 1. ?uoro-dichloro-butyne-Z, tetra?uoro - dibromo 7. The addition product of hexe?uorobutyne-Z butyne-2, penta?uoro-alkyl-substituted butyne-Z, 40 and ethanol, and produced by the process of tetra?uoro-chloro-alkyl substituted butyne-Z, etc. claim 2. Catalysts suitable for use in practicing the in 8. The addition product of hexa?uorobutyne-2 vention are basic, and preferably, are soluble in and ethylene glycol, and produced by the process the reaction mixture or yield compounds which of claim 3. are soluble therein. Typical basic catalysts which 45 9. The addition product of hexa?uorobutyne-Z are suitable are the alkali metals, i. e., sodium, and trimethylene glycol, and produced by the lithium, and potassium, the alkali metal alkoxides, process of claim 4. e. g., sodium ethylate, sodium methylate, sodium 10. The addition product of hexa?uoro hydroxide, potassium hydroxide, and salts of butyne-2 and alkali cellulose, and produced by alkali metals such as sodium and potassium car 50 the process of claim 5. bonates and acetates. DAVID W. CHANEY. Modi?cations and variations may be made in the procedure speci?cally disclosed in the ex REFERENCES CITED amples, which are given by way of illustration The following references are of record in the and not of limitation, without departing from 55 ?le of this patent: the spirit and scope of the invention as de?ned in the appended claims. UNITED STATES PATENTS I claim: Number Name Date 1. A process for the production of ethers by 1,959,927 Reppe ______May 22, 1934 the addition of an alcohol selected from the 60 2,067,385 Evans et a1 ______Jan. 12, 1937 group consisting of aliphatic and cycloaliphatic 2,140,713 Nieuwland et a1. ____ Dec. 20, 1933 alcohols in which each oxygen singly bonded to 2,409,274 Hanford ______Oct. 15, 1946 a carbon is further bonded to hydrogen and 2,433,844 I-Ianford ______Jan. 6, 1948 which contain no groups other than hydroxyl