A METHOD FOR THE PREPARATION OF VINYL COMPOUNDS

Abstract: Fluorovinyl compounds having the formula TLCF=CF₂ are prepared by reacting compounds having the formula TLZ for a time and at a temperature sufficient to from the vinyl compound: where X = Cl, I, or Br; Z = F, Cl, Br, OH, NRR′, OA, or SA; R and R′ are independently selected from the group consisting of hydrogen, an alkyl having one or more than one carbon atom, and aryl; A = Alkali metal, alkali earth metal, quaternary nitrogen, or R; L = oxygen or sulfur; and T = an alkyl or aryl radical which does not interfere with the reaction.

Description: A METHOD FOR THE PREPARATION OF VINYL COMPOUNDS The present invention relates to a method of producing vinyl compounds. U.S. 3,282,875 teaches pyrolyzing compounds having the general formulas EMI1.1 and EMI1.2 to form compounds represented by the general formula EMI1.3 where Rf is F or a perfluoroalkyl radical having from 1-10 carbon atoms; Y is F or a trifluoromethyl radical; n is an integer of 1-3, inclusive; M is F, hydroxyl radical, amino radical or OMe; Me is an alkali metal or quaternary nitrogen radical; and X is alkali metal. Yields in the decarboxylation reaction of about 80 percent were obtained at high temperatures (about 3000C) while yields of 20-30 percent were obtained at lower temperatures (about 2000C3. Also taught is the homo and copolymerization of the vinylether monomers to form useful polymers. Fearn et al., Journal of Polymer Science, Volume 4, pp. 131-140, "Polymers and Terpolymers of Perfluoro-l,4-pentadiene11 discloses that in the pyrolysis of sodium salts of carboxylic acids which contain fluorine and chlorine in the ss position, sodium chloride is preferentially, but not exclusively eliminated. For example EMI2.1 <tb> <SEP> 0 <tb> P <SEP> heac <tb> ClCF2CFClCF2CFClCF2C <SEP> 350 <SEP> r <tb> <SEP> 'ONa <tb> ClCF2CFClCF2CF=CF2 + CiCF2CFClCF2CCl = CF2 German patent 1,238,458 teaches that useful polymers are made from compounds of the general structure EMI3.1 where n = 1-8, p = 0-5 and m = 0-5. Crosslinked halogenated olefin copolymers are produced making use of the iodine group as a reactive site. U.S. Patent 3,450,684 to Darby teaches reacting a fluorocarbon ether with hexafluoropropylene epoxide, followed by decarboxylation; as shown by the following illustrated reactions: EMI3.2 EMI3.3 <tb> heat <tb> XCF2CF2O <SEP> (CFXCF2O)nCF(CF3)COF <SEP> activator <tb> XCF2CF2 0 (CFXCF2O)nCF=CF2 where X is F, C1, H, CF2H, CF2C1 or CF3; n is at least 1. U.S. Patent 3,560,568 teaches the following reaction: EMI3.4 where X = F or CF3. R. D. Chambers, in his book Fluorine in Organic Chemistry, published by John Wiley & Sons, 1973, pages 2l1-212, teaches that carboxylic acid derivatives may be converted to olefins. The conversion involves the loss of carbon dioxide and formation of an intermediate carbon ion. The intermediate then loses NaF to form the resulting olefin. According to the present invention fluorovinyl compounds having the formula TLCF=CF2 are prepared by reacting compounds having the formula EMI4.1 for a time and at a temperature sufficient to form the vinyl compound: where X = Cl, I, or Br; Z = F, Cl, Br, OH, NRR', OA, or SA; R and R are independently selected from the group consisting of hydrogen, an alkyl having one or more than one carbon atom, and aryl; A = Alkali metal, alkali earth metal, quaternary nitrogen, or R; L = oxygen or sulfur; and T = an alkyl or aryl radical which does not interfere with the reaction. The present reaction method is a decarboxylation reaction conducted according to known methods, such as those taught by Chambers. The decarboxylation temperatures may be from about -500C to about 6000C. The decarboxylation reaction may be conducted in the presence of an activator to initiate and speed the reaction. The activator may be a base such as sodium carbonate or ZnO, silica or other known activators. It is particularly convenient to use Na2 CO3 as the activator for the present decarboxylation reactions particularly where Z = F. Optionally, a dispersant may be used to enhance the decarboxylation reactions. Suitable dispersants should be unreactive with the reactants and the products and may include such things as tetraglyme, diglyme or glyme. The unexpected results obtained by the present invention and the mechanism by which the reactions occur are not fully understood. However, it is thought that the results are caused by X being Cl, I, or Br, instead of F as is taught in the prior art. The method of preparation of the invention is relatively independent from T. In other words, if the terminal group EMI5.1 is present, the method of preparation still operates effectively. Examples of complete molecules will now be described. It should be understood, however, that the specific description is not to be construed to limit the type of compounds which may be reacted or prepared. Thus, T may be any alkyl or aryl radical which does not interfere with the reaction. T may be branched or linear, substituted or unsubstituted alkyl having one or more carbon atoms or an aryl. T may contain oxygen in its structure. Preferably, T contains from 1 to about 20 carbon atoms. In the present invention, L preferably is oxygen. T, taken together with L, represents a nucleophile. The general chemistry employed for preparing the intermediates or starting materials for the present invention is well known. Fluorocarbon epoxides are known to react with nucleophiles to form acid fluoride intermediates. The starting materials employed to prepare the fluorovinyl compounds of the present invention are conveniently prepared by reaction of 3-chloro or bromopentafluoropropylene oxide with a nucleophile: EMI6.1 where X = Cl, I, or Br, Nuc = a nucleophile. These acid fluoride intermediates may then be converted to other acid derivatives by well known reactions of acid fluorides with bases, water, alcohols, thiols, ammonia or amines, if desired, before decar boxylation. The acids themselves (Z = OH) are easily converted to acid chlorides or bromides by reaction with halogenating agents such as PCIs or PBr5. The chemistry is discussed in Chambers (pp. 230-232) and more extensively in P. Tarrant et al., Fluorine Chem. Revs., 5, pp. 85-93 (1971). In general, the chemistry taught for reactions of hexafluoropropylene oxide (X = F above) has been found to apply equally well to halogen (Cl or Br) substituted fluoropropylene oxides used to prepare the intermediates used in the present invention. Nucleophiles such as alcohols, thiols, alkoxides, thioalkoxides, phenols or phenoxides react readily with the center carbon of the epoxide to form an intermediate fluoroalkoxide which can then either lose fluoride to form an acid fluoride or react with additional epoxides which are subsequently term. nated by loss of fluoride EMI7.1 Decarboxylation reactions performed directly on the acid fluoride terminal group or derivatives have been shown to be relatively independent of the rest of the molecule and to offer an improvement over the common method of preparing fluorocarbon olefins by reacting nucleophiles with hexafluoropropylene oxide and then decarboxylating. Conversion yields of greater than 99% are obtained with temperatures as low as 65-700C. However, excellent yields may be obtained using temperatures from -50 C to 2000C. The following examples illustrate the invention but should not be construed to limit the scope of the invention to the particular compounds shown in the examples. Example 1 300 ml of dry tetraglyme and 62.2 grams anhydrous Na CO were added to a 1000 ml 3-neck flask equipped with a magnetic stirrer, thermometer, reflux condenser and an inlet port. Two cold traps maintained at a temperature of -780C were located in series downstream of the reflux condenser. 154 gm of product containing 92.1 percent EMI8.1 as identified by gas chromatographic-mass spectrophotometry (GCMS) and VPC (Vapor Phase Chromatography) analyses were added dropwise. There was a slight temperature rise from 220C to about 350C over the period during the addition. The temperature of the reactor was increased to 820C. At this temperature there was obtained considerable reflux. The reflux condenser was removed and the product collected in the cold traps. The temperature was raised to 1500C with the system under vacuum. 80.5 gm of the product were collected in the first cold trap and 1 gm in the second. The product was analyzed by VPC (vapor phase chromatography) and IR (infra red). Essentially, all of the starting material had reacted. The yield was 70.6 percent as a product and analyzed as 95 percent FSO2CF2CF2OCF=CF2 by (V2C3 vapor phase chromatography. IR (Infra Red) analysis showed wave numbers as follows: Vinyl Ether - 1830 wave no. -SO2F - 1460 " -SO 2F - 1240 " 'I -SF - 810 " Boiling Point - 750-760C. A direct titration of the unsaturation in the above product with Br2 in CC14 was done to further confirm the structure. Twenty ml of CCl4 solution containing 2 gm of Br2 were made up as titrant. Two gm of the monomer were dissolved into 5 ml CC14 and titrated at ambient temperature to the point of color persistence. The titration required 10.9 ml of the bromine solution of 0.0068 moles of bromine. The apparent molecular weight of the monomer is then 29 mole = 293.6 or a difference from the proposed structure of 293.6-280 x 280 100 = 5.4%. This value is in excellent agreement with the purity indicated by VPC analysis. Comparative Example 1 100 ml of tetraglyme and 9.84 gm anhydrous Na2CO3 were added to a 500 ml 3-neck flask equipped with a magnetic stirrer, thermometer, (-780C) reflux condenser, and a dropping funnel. Two (-780) cold traps were located in series downstream of the reflux condenser. 29.35 gm of a product which was analyzed by VPC to contain 84.4 percent of EMI10.1 were added dropwise over a 3-hour period with evolution of CO2. The reflux condenser was removed. The reactor was heated to a temperature of 780C-800C while maintaining a slight N2 sweep through the reactor to remove the product. 15.69 gm were recovered in the first cold trap and 0.6 gm in the second. The product was analyzed by VPC and IR. Conversion of the EMI10.2 was essentially complete giving a yield of 77 percent to a product which was not a fluorosulfonylperfluoro vinyl ether. Following is the IR analysis: Wave No. 0 1360 - S 0 0 1150 - S 0 Boiling Point 800C. The product was believed to be the sulfone; EMI11.1 Described in U.S. Patent 3,560,568. Example 2 17 Grams of a mixture containing 68 percent EMI11.2 and higher homologs as analyzed by GCMS were added dropwise to a 3-neck reaction vessel containing 50 ml dried tetraglyme and 7.1 grams dried Na2CO3 under stirring and fitted with a thermometer, heating mantle, and a stillhead with vacuum takeoff and a pair of dry ice acetone traps under inert purge. Gas evolution was observed and a temperature rise from 250C up to 330C was observed during addition. After continued stirring for 1 hour, a 5 mm vacuum was applied and the temperature was raised slowly up to 1000C in the vessel. Seven grams of material were collected in the primary collection receiver and identified as 97.1% ClCF2CF2CF2OCF=CF2. Raising the temperature under vacuum, up to 450C, resulted in the collection of an additional 2 gm of material which was analyzed by GC-mass spectroscopy and I.R. as 22.35% ClCF2CF2CF2OCF=CF2 representing an 81% yield of ClCF2CF2CF2OCF=cF2. VPC analysis of the solvent in the reaction vessel showed a residual amount of ClCF2CF2CF2OCF=CF2 remaining along with higher homologs. Comparative Example 2 A mixture of 35 gm containing 31.7 percent of EMI12.1 plus higher homologs was added to a mixture of 15.5 gms Na2CO3 in 50 ml of tetraglyme at room temperature. After several hours and cessation of CO2 evolution, the mixture was raised to a temperature of 1200C whereupon there were indications of some slow CO2 evolution. After several hours at this condition, pulling a vacuum on the system to remove product resulted in little or no evidence, by VPC and I.RI, of vinyl ether formation. The temperature of the reactor was then raised to 160-170 C under atmospheric pressure. Under these conditions, boiling of the mixture resulted. The product collected (8 gms) showed a VPC peak at 0.74 min. retention time and absorption in the I.R. at 1840 cm 1 indicating formation of the vinyl ether. Example 3 15 ml of tetraglyme and 1.0 gm of anhydrous Na2CO3 were added to a 3-neck flask equipped with a thermometer, stirrer and reflux condenser. Cold traps (-78oc) were downstream of the condenser and a slight back pressure of N2 was maintained by means of a bubbler. 3 gm of FSO2CF2CF2OCF(CF3)CF2OCF(CF2Cl)CFO were added and after a brief evolution of CO2, the temperature was raised to 800C and held there for several hours until CO2 evolution ceased. A vacuum was pulled on the reactor and the temperature was slowly increased to 1360C while collecting 1.5 gms of product in the cold trap. The majority of the product was collected before the temperature reached 900 C. VPC analysis showed additional product remaining in the tetraglyme solvent. The product was confirmed as EMI13.1 by mass spectroscopy, I.R. and F19 NMR (Nuclear Magnetic Resonance). Example 4 To a 100 ml 3-neck flask were added 50 ml of dry tetraglyme and 9.75 gms of anhydrous Na2CO3. The flask was equipped with a stirring bar, reflux condenser, thermometer, and inlet port. Two -780C cold traps in series were located downstream of the reflux condenser. A slight back pressure was maintained on the system with a dry N2 bubbler. 15.95 gm of EMI13.2 were added slowly at room temperature. There was a small temperature rise to about 350C, and an evolution of CO2, upon addition of the acid fluoride. The temperature was increased to 670-680C and held there for 2.5 hours. The product was then distilled from the reactor. i2.59 gm of product were collected which analyzed at 97.37 percent of ClCF2CF2CF2OCF=CF2. This represents a 99.3 percent yield of the vinyl ether.

Claims: 1. A method of preparing vinyl compounds comprising the step of reacting one or more compounds having the general formula EMI14.1 for a time and at a temperature sufficient to form the vinyl compound: TLCF=CF2 where X = C1, I, or Br; Z = F, C1, Br, OH, NRR', OA, or SA; R and R' are independently selected from the group consisting of hydrogen, an alkyl having one or more than one carbon atom, and aryl; A = alkali metal, alkali earth metal, quaternary nitrogen, or R; L = oxygen, or sulfur; and T = an alkyl or aryl radical which does not interfere with the reaction. 2. The method of Claim 1 carried out in the presence of an activator. 3. The method of Claim 2 where the activator is a base. 4. The method of Claim 1 where the temperature is from -500C to 200 C. 5. The method of Claim 1 where L is oxygen. 6. The method of Claim 1 where Tis an alkyl having from 1 to 20 carbon atoms. 7. The method of Claim 6 where T is a perhalogenated radical. 8. The method of Claim 6 where T contains oxygen in its structure.

Inventors: CARL, WILLIAM PAUL, EZZELL, BOBBY RAY, MOD, WILLIAM AUGUST
Applicants: THE DOW CHEMICAL COMPANY
Application year: 1981
Main classification: C07C41
IPC codes: C07C301, C07C67, C07C313, C07C43, C07C323, C07C309, C07F9, C07C303, C07D327, C07C41, C08F14