Trifluoromethylfluoroformate

Abstract

Trifluoromethylfluoroformate (CF30CFO) was produced as a secondary product in the mercuryphotosensitized oxidation of 2-C,Fs. It was identified by its mass, infrared, and fluorine n.m.r. spectra, as well as by vapor density and physical property determinations.Canadian Journal of Chemistry, 46. 332 (1968) The only published report of C F 3 0 C F 0 was by Aymonino (I), who produced it from the photolysis of a inixture of C F 3 0 F and CO, listed some of its physical properties, and reported its infrared spectrum. We wish to report the formatioil of C F 3 0 C F 0 as a secondary product in the mercury-sensitized oxidation of 2-C4Fs. In addition to the properties reported 'Present address: Department of Chemistry, Penn State University, University Park, Pennsylvania 16802.by Aymonino, we have also obtained the mass and fluorine nuclear magnetic resonance (n.m.r.) spectra.In the mercury-photosensitized oxidation of 2-C4Fs, it was observed (2) that the rate of formation of CF3CF0 decreased as the exposure time was lengthened. Simultaneously, a secondary product was formed. Thus, it appeared that C F 3 C F 0 decomposed (presumably by mercury sensitization) to ultimately yield the secondary product. To check this hypothesis, Can. J. Chem. Downloaded from www.nrcresearchpress.com by 34.216.127.252 on 05/10/18For personal use only. NOTES 333we examined the mercury-sensitized oxidation of C3F6 for lengthy exposures, where CF3CF0 is also produced, and observed the same results.The secondary product was isolated by gas chromatography, utilizing a 20 ft column composed of 20% fluorolube FS-5 on firebrick at 0 "C. The retention time of the secondary product was identical with that for perfluoropropyleneoxide, another product in the C3F6 system. Since with 2-C4Fs, pe~uoropropylene-oxide is not produced, a clean separation could be effected in this system. Gas density measurements of the secondary product gave a molecular weight of 131 compared with the expected value of 132 for CF30CF0. The mass spectrum of the product is summarized in Fig. 1. In order to co~npensate for any material bleeding from the column, a sample was collected at the appropriate retention time from an unexposed mixture of 2-C4Fs and 02. This background mass spectrum indicated small anlounts of fluorocarbons containing no oxygen. The sample from the photolyzed mixture gave intense peaks at m/e 28(CO+), 44(C02+), 47(FCO+), 66(CF20+), 69(CF3+), and 85(CF30+). The peak of highest m/e is at 132 and must correspond to the parent molecule ion. The low intensity of the parent ion is a common feature of fluorocarbon mass spectra. Significantly, there are no peaks suggesting a carbon-carbon bond. The mass spectrum clearly indicates that the molecule is C F 3 0 C F 0 .The infrared spectrum, shown in Fig. 2, supports the identification as C F 3 0 C F 0 . The spectrum is simple with bands at 5. 28, 7.70, 7.93, 8.50, 9.80, 11.20, 13.05, and 15.0 p. The prominent band at 5.28 p, characteristic of the -CFO group, is slightly shifted from the value of 5.25 p reported b...

A novel synthesis of trifluoromethyl fluoroformate from trifluoromethyl hypofluorite and carbon monoxide in the presence of fluorine gas

“…The overall isolated yield of CF 3 OC( O)F was 18.4%. The characteristic properties and spectral values of CF 3 OC( O)F agreed with the literature [1,8]. 19 F NMR (CDCl 3 ): d = À60.5 ppm (d, 3F, 3 J F-F = 9.9 Hz, CF 3 ), d = À13.5 ppm (q, 1F, CF).…”

“…A later patent described the preparation of 1 as the dimer of carbonyl fluoride, COF 2 (2), using a variety of catalysts [2]. It was also isolated as a minor product or the rearranged product in a variety of other reactions [3][4][5][6][7][8][9]. The efficient preparation of 1 is of considerable interest currently as the key intermediate to a vinyl ether, CF 3 OCF 2 OCF CF 2 , whose copolymers have been used to formulate novel fluoroelastomers with very low glass transition temperatures [10][11][12][13][14][15][16][17].…”

Synthesis of trifluoromethyl fluoroformate from trifluoromethyl hypofluorite and carbon monoxide: Thermal and catalyzed reaction

“…The overall yield of 4 was 86.5%. The characteristic properties and spectral values of 4 match with those described in the earlier reports [1,8].…”

“…Its formation by other reactions as a minor or a side product was also reported later [3][4][5][6][7][8][9]. Another two homologs in this series, CF 3 CF 2 OC(O)F and (CF 3 ) 2 CFOC(O)F, were prepared in low yield through an oxidation of CF 3 CF5 5CFCF 3 in presence of CF 3 OF [10] and a reaction between (CF 3 ) 2 CFO À Cs + and COF 2 [11,12].…”

Atmospheric chemistry of CF3CFHOCF3: Reaction with OH radicals, atmospheric lifetime, and global warming potential

“…CH 3 ONO was prepared by the dropwise addition of concentrated H 2 SO 4 to a saturated solution of NaNO 2 in methanol and was devoid of any detectable impurities using FTIR analysis. The reference spectrum of FC(O)OCF 3 was taken from the reference library at Ford [ Johnston et al , 1968; Mashino et al , 2000]. Unless otherwise stated all uncertainties quoted in the present manuscript are 2 standard deviations from regression analyses.…”