FLUORINATION OF ORTHOCARBONATES AND POLYALKOXYPROPANES

Abstract: Perfluoroalkylorthocarbonates and perfluoropolyalkoxypropanes are disclosed. The perfluoro compounds are synthesized by direct fluorination procedures. The perfluoro compounds are useful lubricants, heat exchangers, vapor phase soldering fluids, solvents, and oxygen carriers.

Description: -1- FLUORINATION OF ORTHOCARBONATES AND POLYALKOXYPROPANES Background The difficulty with the synthesis of perfluoro 5 esters lies in instability of the ester linkage toward hydrogen fluoride and the facile dissociation of perfluoro esters by nucleophilic attack. The electrolytic fluorination of esters is precluded because they are spontaneously decomposed in the 10 acidic solution. The direct fluorination of ethyl acetate (See Adcock, J.L. et al. , J. Org. Chem. 40, 3271 (1975)) represents the first successful fluorination of an ester, giving CF 3 COOCF 2 CF 3 and CF_COOCHFCF_ in 5% and 20% yield respectively. 15 Extension of this direct fluorination technigue has, previously led to the conversion of hydrocarbon polyesters to highly fluorinated polyesters, which are important precursors to perfluoropolyethers. Persico, D.F. et al., J. Am. Chem. Soc. 107, 1197 20 (1985) . There were few reports of the preparation of perfluoroesters by indirect methods. The first reported reactions were the di erization and tri- merization of COF 2 to yield FC0 2 CF 3 and (CF 3 0) 2 C0 25 respectively. Photolysis reaction of CF-OF and CF-OOCF- in the presence of CO resulted in the same products as above reactions. Aymonino, P.J., Chem. Commun. 241 (1965) ; Varetti, E.L. and Aymonino, P.J., Chem. Commun. 91 (1971). A more general 3I synthesis is the low temperature reaction of per- fluoroacyl fluorides with perfluoro alkoxide salts. ith the execption of the reaction of fluoro- esters R f C00CH 3 with dimethyl sulfone to yield ortho esters R f C(OCH 3 ) 3 (Holm, T., U.S. Patent No. 2,611,787 (1952)) and the isolation of CHFClC(OC 2 H 5 ) 3 by Tarrant and Brown (Tarrant, P. and Brown, H.A., J. Am. Chem. Soc. 73, 1781 (1951)) little synthetic information on fluorinated ortho esters has appeared in the literature. Summary of the Invention This invention pertains to perfluoroalkyl orthocarbonates and perfluoropolyalkoxypropanes and to methods of producing these perfluorinated com¬ pounds. The perfluoroalkyoorthocarbonates are repre- sented by the formula: R fl 0 R f4 ' ° " ? " ° " R f2 0 I R f3 wherein fl , R f? ' R fτ and R f4 are the saιne or different short, straight or branched chain per¬ fluoroalkyl radicals. In preferred embodiments, R f , R , R f3 and R f4 are the same or different and are selected from -CF 3 , -CF 2 CF 3 , -CF 2 CF 2 CF 3 , -CF(CF 3 ) 2 , -CF 2 CF 2 CF 2 CF 3 , -CF(CF 3 )CF 2 CF 3 , -CF 2 CF(CF 3 ) 2 , and -C(CF 3 ) 3 . The perfluoroalkoxypropanes are represented by the formula: R fl R f3 0 0 1 I CF - CF - CF I I 0 0 1 I R f2 ' R f4 wherein R fl , R f2 , R f3 and R f4 are short, straight or branched chain perfluoroalkyl radicals. In pre¬ ferred embodiments, R fχ , f2 , R and R f4 are the same or different and are selected from -CF 3' -CF 2 CF 3 , -C 2 CF 2 C 3 , -CF(CF 3 ) 2 , -CF 2 CF 2 CF 2 CF 3 , -CF(CF 3 )CF 2 CF 3 , -CF 2 CF(CF 3 ) 2 , and -C(CF 3 ) 3 . The- perfluoroalkylorthocarbonates and per- fluoroalkoxypropanes of this invention are produced by direct fluorination with elemental fluorine. The perfluoro compounds are more volatile than per- fluoropolyethers of the same molecular weight. They are unaffected by concentrated sulfuriσ acid and nitric acid, but decompose in hydrogen fluoride solution and concentrated hydrochloric acid. They are stable at 150°C and above. The perfluoro compounds of this invention are useful as lubri¬ cants, heat exchangers, solvents, vapor phase soldering fluids and oxygen carriers. Brief Description of the Figures Figure 1 shows the reactions of elemental fluorine in the production of perfluoroalkylortho- ■ carbonates and perfluoroalkyoxypropanes. Detailed Description of the Invention The perfluoroalkylorthocarboήate of this invention are represented by the formula: wherein Rf_x. , -2_, R~3, and R„4. are the same or different and are selected from short, straight or branched chain perfluoroalkyl radicals. In pre¬ ferre d embo d iments, R fl , R f2 ' R 3 and R f4 are selected from -CF 3 , -C 2 CF 3 , -CF 2 CF 2 CF 3 , -CF(CF 3 ) 2 , -CF 2 CF 2 CF 2 C 3 , -CF(CF 3 )CF 2 CF 3 , -CF 2 CF(CF 3 ) 2 , and -C(CF 3 ) 3 . Especially preferred perfluoroalkylortho¬ carbonates are represented by the formula: C'(OR f ) 4 wherein R f is selected from -CF 3 , -CF 2 CF 3 , CF CF CF 3 and CF(CF 3 ) 2 . The perfluoroalkyoxypropanes of this invention are represented by the formula: wherein R fl R f 2' R f 3 and R f4 are short r straight or branched chain perfluoroalkyl radicals. In prefer¬ red embodiments, R fχ , R f2 , R f3 and R f are selected from -CF 3 , -CF 2 CF 3 , -CF 2 CF 2 CF 3 , -CF(CF 3 ) 2 , and -CF 2 CF 2 CF 2 C 3 , -CF(CF 3 )CF 2 CF 3 , -CF 2 CF(CF 3 ) , -C(CF 3 ) 3 . Especially preferred perfluoroalkyoxy¬ propanes are represented by the formula: (R f O) 2 CFCF 2 CF(OR f ) 2 wherein R f is selected from -CF 3 , -CF CF 3 , CF,CF 2 CF 3 and -CF(CF 3 ) 2 .In addition, the fluorination pro¬ cedures for production of perfluoroalkoxy propanes can yield novel compounds of the formula: (R f O) 2 CFCF 2 CF 2 OR f wherein R_ is as defined above. The perfluoro compounds of this invention are produced by the direct fluorination technique of agow and Margrave, Prog, of Org. Chem. 26, 161: (1979) . Appropriate orthocarbonate or polyalkoxy- propane starting materials are selected. For example, orthocarbonates can be selected from compounds of the formula: 0 I R.O - C - OR_ ? R 3 wherein R-, R 2 , 3 and R 4 can be the same or dif¬ ferent and are selected from -CH_, -CH_CH 3 , -CH 2 CH 2 CH 3 , -CH(CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -CH(CH 3 )CH 2 CH 3 , -CH 2 CH(CH 3 ) 2 , and -C(CH 3 ) 3 . Polyalkoxypropanes can be selected from compounds of the formula: are selected from -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH(CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -CH(CH 3 )CH 2 CH 3 , -CH 2 CH(CH 3 ) 2 , and -C(CH 3 ) 3 . The starting material is placed in a fluorine reactor such as the reactor described by Lagow and Margrave , supra. The reactor is cooled and flushed with an inert gas such as helium or nitrogen after which the fluorine is initiated under controlled conditions. Typically, low fluorine concentrations between about one and about ten percent are used initially. The dilute fluorine is passed over the material to be fluorinated. As the fluorination reaction proceeds the fluorine concentration and flow rate of the gas are gradually increased until pure fluorine conditions are achieved and the material is perfluorinated. The best results are obtained when the fluorination is performed in the presence of a hydrogen fluoride scavenger such as sodium fluoride as described in United States Patent Application Serial Number 924,198, entitled "Perfluorination of Ethers in the Presence of Hydrogen Fluoride Scaven¬ gers", filed October 27, 1986, the teachings of which are incorporated herein. The presence of a hydrogen fluoride scavenger allows the use of more severe fluorination conditions in this direct fluorination procedure, that is, higher fluorine concentrations and faster rates of fluorine delivery can be used in the presence of a hydrogen fluoride scavenger than can be used in the absence of a scavenger. For example, initial fluorine levels of over 15% and up to 25% and fluorine flow rates of over 8cc/min/gram of starting material can be used. In addition, the yield and quality of the perfluoropolyether product is improved when fluorina¬ tion is conducted in the presence of a hydrogen fluoride scavenger. The scavenger is believed to prevent the formation of ether-HF acid base com¬ plexes during the fluorination reaction. Fluorination in the presence of a hydrogen fluoride scavenger can be performed in several ways. In the preferred mode, the hydrogen fluoride scavenger (in powdered or pellet form) is mixed with the orthocarbonate or polyalkoxypropane. The blend is placed in a suitable fluorination reactor and fluorinated by exposure to gradually increasing concentrations of fluorine gas. Alternatively, the orthocarbonate or polyalkoxypropane may be coated onto the scavenger and fluorinated in this form. The perfluoroalkyorthocarbonates and perfluoro- alkoxypropanes of this invention are useful as lubricants, heat exchangers, vapor phase soldering fluids, solvents and oxygen carriers. For example, the oils are useful as vacuum pump oils and oils for diffusion pumps. The more volatile orthocarbonates and alkoxypropanes are used to cool electronic devices such as computers. The perfluoro compounds are also useful as perfluorocarbon solvents, as oxygen carriers in biomedical applications and as oxygen carriers for organic oxidation reactions. This invention is illustrated further by the following examples. EXAMPLES Tetramethyl orthocarbonate, tetraethyl ortho- carbonate, tetra-i-propyl- orthocarbonate, 1,1,3,3- tetramethoxypropane, and 1,1,3,3-tetraethoxypropane were used as received from Aldrich Chemicals. Fluorine was research grade and obtained from air Products and Chemicals, Inc. Elemental analyses were performed by E+R Mecroanalytical Laboratory, Inc. , Corona, New York. 19F n r spectra were recorded on a Varian EM 390 spectrometer operating at 84.67 MHz. Chemical shifts were reported rela¬ tive to CFC1 3 . Negative shifts refer o high field of the reference. Mass spectra were measured in a gas phase on a Bell & Howell Model 21-490 mass spectrometer. A Bendix 2300-gas chromatograph equipped with a cryogenic controller and a thermal- conductivity detector was used for separation. Infrared spectra were recorded on a Beckman Acculab 8 spectrometer utilizing a gas cell with KBr win¬ dows. In a typical reaction, a mixture of measured amounts of starting material with approximately 10 grams of powdered NaF was packed in a 5 in. x 1 in. copper tube, which was then placed in the first zone of the four-zone cryogenic reactor described pre¬ viously. Lagow, R. . and Margrave, J.L. , Prog. Org. Chem. 26, 161 (1979) . The last three zones were packed with fluorinated copper turnings. After all zones were cooled to - 100 "C for two hours the system was flushed with helium for ten hours. The fluorination was then initiated under controlled conditions. As reactions was completed, the products were fractionated into -78, -131, and -196 * C on a vacuum line. Final purification was done by gas chromatography using a fluorosilicone column. -10- lnfrrtnnfion of 1.1 . .3-fetrπm gfh oyvnroπnne A 1.49 g of 1,1,3,3-tetramethoxypropane was fluorinated using the conditions as shown in Table 1. The crude product weighing 2.53 g was obtained in the -78 °C trap. Gas chromatographic separation of this portion (0 °C for 10 min., 5 °C/min.- to 10 °C for 15 min., 10 °C/min. to 90 °C for 10 mϊn.) gave perfluoro 1,1,3,3-tetramethoxy propane (1.92 g, 46.8%), and perfluoro 1,1,3-trimethoxy propane (0.48 g, 13.7%). Perfluoro 1,1,3,3-tetramethoxypropane, bp. 93 °C. Anal. Calcd. for C7F16O4: C, 18.60; F, 69.24. Found: C, 18.50; F, 66.97. MS, m/e(fragment iff ion): 433 (C7F15O4, P-F), 367 (C6Fι 3 0 3! P-OCF3), 279 (C5F9O3), 213 (C4F7O2), 201 (C3F7O2), 191 (C4F5O3), 185 (C3F7O), 163 (C3F5O2), 135 (C 2 F 5 0), ' " 125 CC3F3O2), 97 (C2F3O), 78 (C2F2O), 69 (CF3, base peak), 50 (CF 2 ), 47 (CFO). IR: 1300 (vs, br), 1240 (vs, br), 1130 (vs, br), 1020 (w), 892 (m), 865 (m), 795 (m), 725 (m) cm *1 . The FNMR data were reported in Table 5. 15 Perfluoro 1,1,3-trimethoxypropane, bp. 75 °C. Anal. Calcd. for C 6 Fi4θ 2 : C, 18.67; F, 68.90. Found: C, 18.21; F,68.29. MS, m/e(fragment ion): 367 (C 6 Fi3θ 2 , P-F), 301 . (C5F11O2, P-OCF3), 213 (C4F7O2, base peak), 201 (C3F7O2), 185 (C3F7O), 163 (C3F5O2), 147 (C3F5O), 135 (C2F5O), 125 (C3F3O), 119 (C2F5), 113 (C2F3O2), 100 (C2F4), 97 (C 2 F 3 0), 78 (C 2 F 2 0), 69 za (CF3), 50 (CF2), 47 (CFO). IR: 1320 (vs), 1250 (vs, br), 1150 (vs, br), 1020 Cm, sh), 1004 (m, sh), 918 (w), .822 (m), 800 (m), 720 (m) cm-l. The FNMR data were reported in Table 5. Flπorinntioπ of 1 .1 .3.3-fefrn ethoxy prnpππ e A 1.82 g of 1,1,3,3-tetraethoxypropane was fluorinated using the 25 same conditions as those for 1 , 1,3 ,3-tetramethoxypropane. After fractionation 2.72 grams of crude products were collected. From GC separation at 25 °C were isolated perfluoro 1 ,1,3,3-tetraethoxypropane (a), perfluoro-l ,l,3-triethoxypropane (b), perfIuoro-l ,3-diethoxypropane (c), and perfluoro-l ,l-diethoxypropane (d). The yields were 13.0%, 23.4%, 20.0%, and 9.3% respectively, based on the starting 1, 1,3,3-tetraethoxy ^propane. GC retention time increased in the order: d < c < b < a. Perfluoro-l,l,3,3-tetraethoxypropane, bp. 143 °C. Anal. Calcd. for C11F24O4: C, 20.26; F, 69.92. Found: C, 20.04; F, 69.63. MS, m/e(fragment ion): 517 (C9F19O3, P-OC 2 F 5 ), 301 (C5F11O2), 263 (C5F9O2), 235 (C4F9O), 119. CC2F5, base peak), 100 (C 2 F 4 ), 97 (C2F3O), 69 (CF 3 ), 50 (CF 2 ). IR: 1284 (s), 1230 (vs, br), 1150 (vs, br), 1090 (vs), 974 (m, sh), 835 (m), 746 (s, sh), 728 (s, sh), 704 (s, sh) cπr . The FNMR data were reported in Table 5. Perfluoro-l , l ,3-triethoxypropane, bp. 115 °C. Anal. Calcd. for C9F20O3: C, 20.17; F, 70.88. Found: C, 19.86; F, 70.55. MS, m/e(fragment ion): 401 (C7F15O2, P-OC 2 F 5 ), 301 (C5F11O2), 263 (C5F9O2), 235 (C4F9O), 185 (C3F7O), 147 (C3F5O), 119 (C2F5, base peak), 100 (C 2 F 4 ), 97 (C2F3O), 69 (CF3), 50 (CF 2 ), 47. (CFO). . IR:.. -1300 (s), .1220 (vs, sh), 1135 (vs, br), 1090 (vs), 980 (m, sh), 724 (s, sh), 705 (s, sh) cm-1. The FNMR data were reproted in Table 5. Perfluoro-l,3-diethoxypropane, bp. 77 °C. Anal. Calcd. for C7F16O2: C, 20.02; F, 72.37. Found: C, 19.65; F, 72.17. MS, m/e(fragment ion): 401 (C7F15O2, P-F), 285 (C5F11O), 263 (C5F9O2), 235 (C4F9O), 185 (C3F7O), 169 (C3F7), 147 (C3F5O), 119 (C2F5, base peak), 100 (C 2 F 4 ), 97 (C 2 F 3 0), 69 (CF3), 50 (CF 2 ), 47 (CFO). IR: 1330 (s, sh), 1230 (vs, sh), 1150 (vs, br), 1100 (vs, sh), 994 (s, sh), 730 (s, sh), 718 (s, sh) cm" 1 . The FNMR data were reported in Table 5. Perfluoro-l,l-diethoxyethane, bp. 53 °C Anal. Calcd. for C6F14O 2: C, 19.48; F, 71.88. Found: C, 19.20; F, 71.44. MS, m/e(fragment ion): 301 (C5F11O2, P-CF3), 235 (C4F9O), 185 (C3F7O), 169 (C3F7), 131 (C3F5), 119 (C 2 F 5 , base* peak), 100 (C 2 F 4 ), 97 (C2F3O), 69 (CF3), 50 (CF 2 ), 47 (CFO). IR: 1230 (vs) * 1195 (vs), 1158 (vs), 1100 (vs, br), 746 (s, sh), 720 (s, sh), 694 (s, sh) cm ~r . The FNMR data were reported in Table 5. FTπorinntoπ of feframethyl orthocarbonate Tetramethyl orthocarbonate was introduced into the reactor in different manner. Inside the cryogenic reactor the first two zones were packed with a mixture of NaF and copper turnings, and the last two zones were- packed with fluorinated copper turnings. Tetramethyl i orthocarbonate (2.04 g) was slowly injected into the evaporator and condensed in the first zone by the passage of 60 cc/min of helium flow, while zones 2, 3, 4 were cooled to -100 °C. The reactor was then cooled to -120 °C and the fluorinaton was started using the conditions listed in Table 2- The majority of products stopped in the -78 °C trap on the vacuum-line j T separation. Final purification on a fluorosilicone column at 0 °C produced 2.63 . g of perfluoro tetramethyl .orthocar.bonate,.. corresponding, to . a 49.5% yield. Perfluoro tetramethyl orthocarbonate, bp. 20.8 °C. The FNMR spectrum gave a singlet peak at -59.0 ppm upfield from CFCI3. MS, za m/e(fragment ion : 267 (C(OCF3)3), 201 (CF(OCF3) 2 , base peak), 113 (OCOCF3), 85 (OCF3), 47 (OCF). IR: 1170 (vs, br), 1050 (vs, br), 1010 (vs, br), 750 (m), 710 (m) cm-l. F ioriπnfion of tetrπethyl orthocnrbonafe Tetraethyl orthocarbonate (1.6 g) was handled in an usual way and 25 fluorinated from -100 °C to room temperature (see Table 3). A 2.6 g of perfluoro tetraethyl orthocarbonate was isolated from 2.86 g of crude praducts. The ' yield was 56.5% based on the starting tetraethyl orthocarbonate. Perfluoro tetraethyl orthocarbonate, bp. 80 °C. Anal. Calcd. for C9F20O4: C, 19.58; F, 68.33. Found: C, 19.33; F, 69.05. MS, m/e(fragment 5 ion):...301 (CF(OC 2 F 5 ) 2 ), .163 (OCOC2F5), 119 (C 2 F 5 , base peak), 100 (C 2 F 4 ), 97 (OC2F3), 69 (CF3), 50 (CF2). IR: 1240 (vs, br), 1100 (vs, br), 850 (m), 750 (s, sh), 725 (s), 675 (m) cm" 1 . The FNMR spectrum consisted of two peaks at -88.3 ppm (-CF3) and -91.0 ppm (-CF2-). The relative ratio was 2 : 1. Fluorination of tetrn-i-propyl orthocnrbonnte roc Tetra-i-propyl orthocarbonate (1.4 g) was fluorinated using the similar conditions as those for tetraethyl orthocarbonate, except the reaction was initiated at -120 °C (see Table 4). Large amounts of low- •boiling products- passed to -131 -°C on a vacuum-line- separation. The GC assay indicated the presence of a number of components, which were T5_ inseparable. The -78 °C fraction contained the desired products, from .which a mixture . of perfluoro . .tetra-n.-prop.yl ..orthocarbonate and perfluoro tetra-i-propyl orthocarbonate was isolated in an amount of 0.55 grams. The total yield was 12.8%. Perfluoro tetra-n-propyl orthocarbonate and Perfluoro tetra-i-propyl 0 orthocarbonate were inseparable under the experminental GC conditions. Both compounds were thus characterized in a mixture state. The boiling point is around 130 oC. Anal. Calcd. for 3F28O4: C, 20.76; F, 70.73. Found: C, 20.97; F, 70.80. MS, m/e(fragment ion): 567 (C(OC 3 F 7 )3), 401 (CF(OC 3 F 7 )2, base peak), 213 (OCOC3F7), 169 (C3F7), 147 (OC3F5), 119 (C 2 F 5 ), 100 (C2F4), 69 (CF3), 47 (CFO): • The nmr chemical shifts for C(OCF(CF 3 )2)4 are -80.6 ppm (-CF3) and -146.5 ppm (-OCF=). The assignments for C(OCF 2 CF 2 CF 3 )4 are -81.8 ppm (-CF3), -85.3 ppm (-OCF 2 -) and -130.3 ppm (-CF2-). The relative intensities were consistent with the theoretical value. - - TABLE 1 Fluorination conditions for 1,1,3,3-tetramethoxypropan and 1,1,3,3-tetraethoxypropane 10 15 TABLE 2 Fluorination conditions for Tetramethyl Orthocarbonate TABLE 3 Fluorination conditions for Tetraethyl Orthocarbonate TABLE 4 Fluorination conditions for tetra-i-propyl orthocarbonate TABLE 5 19 F nmr spectra of new perfluorinated polyalkoxy compounds Compound d a F e c b CF3O-C-CF2CF2-OCF3 OCF3 a b b a F c a C2F5O-C-CF2- - C2F5 OC2F5 OC2F5 a a. d a F e b c a C2F5O-C-CF2CF2OGF2CF3 - OC2F5- a b c d c b a CF 3 CF2C3 CF 2 CF2θCF2CF3 c a a F a a CF3CF2O-C-OCF2CF3 CF3 b Equivalents Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many ' equivalents to the specific embodiments of the invention described herein. Such equivalents are intended to be encompassed by the following claims.

Claims: CLAIMS 1. Perfluorotetra alkylorthocarbontes of the formula: R fl 0 Rf4 0 - έ - o - R f2 0 I R f3 wherein R fl , R f2 ' R 3 and R f4 re P resent tne same of different, short, straight or branched chain perfluoroalkyl groups. 2. A perfluorotetraalkylorthocarbonate of Claim 1, wherein ___£„. , R- , R f and R f . are the same or different and are selected from the group consisting of -CF 3 , -CF 2 CF , -CF 2 CF 2 CF 3 , -CF(CF 3 ) 2 , -CF 2 ' CF 2 CF 2 CF 3 , -CF(CF 3 )CF 2 CF 3 , -CF 2 CF(CF 3 ) 2 , and -C(CF 3 ) 3 . 3. Perfluorotetraalkylorthocarbonates of the formula: C(OR f ) 4 wherein f is selected from the group con¬ sisting of -CF 3 , -CF 2 CF 3 , -CF 2 CF 2 CF 3 , and -CF(CF 3 ) 2 . C(OCF 3 ) 4 5. C(OCF 2 CF 3 ) 4 . 6. C(OC 2 CF 2 CF 3 ) 4 . 7. C(OCF(CF 3 ) 2 ) 4 . 8. Perfluoroalkyoxypropanes of the formula: R fl R f3 0 0 1 I CF - CF- CF I 2 I 0 0 1 I R f2 R f4 wherein ^- > , R f2 , -- and R~. are the same or different, short, straight or branched chain perfluoroalkyl groups. 9. A perfluoroalkyoxypropane of Claim 9, wherein R- , f2 R f3 and R f4 are the same or different and are selected from the group consisting of -CF 3 , -CF 2 CF 3 , -CF 2 C 2 CF 3 , -C (CF 3 ) 2 , -CF 2 CF 2 CF 2 CF 3 , -CF(CF 3 )CF 2 CF 3 , -CF 2 CF(CF 3 ) 2 , and -C(CF 3 ) 3 . 10. A compound of the formula: (R f O) 2 CFCF 2 CF(OR f ) 2 wherein R- is selected from the group con¬ sisting of -CF 3 , -CF 2 CF 3 , and -CF 2 CF 2 CF 3 - 11. A compound of the formula: (R f 0) 2 CFCF 2 C 2 OR f wherein R f is selected from the group con¬ sisting of -CF 3 , -CF CF. and CF 2 CF 2 CF 3 . 12. Perfluoro-1,1,3,5,-tetraalkyoxypropane. 13. Perfluoro 1,1,3,3,-tetramethoxypropan . 14. A method of fluorinating an alkyl ortho¬ carbonate, comprising the steps of: a. placing the alkyl orthocarbonate and a hydrogen fluoride scavenger into a fluorine reactor, the amount of hydrogen fluoride scavenger in relation to the amount of orthocarbonate being sufficient to react with the hydrogen fluoride formed during fluorination; and b. fluorinating the orthocarbonate by: (i) establishing a flow of gas mixture of fluorine gas and an inert gas into the reactor under conditions which allow fluorination of the orthocar¬ bonate, the fluorine concentration of the gas mixture being, for example, about 0.5% to about 25%; (ii) maintaining or gradually increasing the concentration of fluorine gas in the gas mixture to fluorinate the orthocarbonate; and c. after the fluorination reaction is com¬ pleted to desired degree, removing the fluorinated orthocarbonate and the hydro¬ gen fluoride scavenger from the reactor. 15. A method of Claim 14, wherein the alkyl ortho¬ carbonate has the formula: R 4° wherein R1. , R2-, R3_ and R4. are the same or different and are selected from the group consisting of -CH 3 , -CH 2 CH 3 , - CH 2 CH 2 CH 3 , -CH(CH 3 ) 3 , -CH 2 CH 2 CH 2 CH 3 , -CH(CH 3 )CH 2 CH 3 , -CH 2 CH(CH 3 ) 2 , and -C(CH 3 ) 3 . 16. The method of Claim 14, wherein the ortho¬ carbonate is perfluorinated. 17. The method of Claim 14, wherein the hydrogen fluoride scavenger is in the form of a powder or pellet. 18. The method of Claim 14, wherein the hydrogen fluoride scavenger is sodium fluoride or potassium fluoride. Ϊ 19. A method of fluorinating a polyalkoxypropane, comprising the steps of: a. placing the polyalkoxypropane and a hydrogen fluoride scavenger into a fluorine reactor, the amount of hydrogen fluoride scavenger in relation to the amount of polyalkoxypropane being suf¬ ficient to react with the hydrogen fluoride formed during fluorination; and b. fluorinating the polyalkoxypropane by: (i) establishing a flow of gas mixture of fluorine gas and an inert gas into the reactor under conditions which allow fluorination of the polyal¬ koxypropane, the fluorine concen¬ tration of the gas mixture being, for example, about 0.5% to about 25%; (ii) maintaining or gradually increasing the concentration of fluorine gas in the gas mixture to fluorinate the polyalkoxypropane; and c. after the fluorination reaction is com¬ pleted to desired degree, removing the fluorinated polyalkoxypropane and the hydrogen fluoride scavenger from the reactor. 20. The method of Claim 19, wherein the poly¬ alkoxypropane has the formula: wherein R1. , 2_, R3, and R4. are the same or different and are selected from the group consisting of -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH(CH 3 ) 2 , -CH 2 CH 2 CH 2 CH 3 , -CH(CH 3 )CH 2 CH 3 , -CH 2 CH(CH 3 ) 2 , and -C(CH 3 ) 3 . 21. The method of Claim 19, wherein the poly¬ alkoxypropane is perfluorinated. 22. The method of Claim 19, wherein the hydrogen fluoride scavenger is in the form of a powder or pellet. 23. The method of Claim 19, wherein the hydrogen fluoride scavenger is sodium fluoride or potassium fluoride.

Inventors: LAGOW RICHARD J, LAGOW, RICHARD, J.
Applicants: EXFLUOR RES CORP, EXFLUOR RESEARCH CORPORATION
Application year: 1988
Main classification: C07C43
IPC codes: C07C41, C07C43