With oxalyl fluoride

Ogden condensed azine 46 with oxalyl fluoride in the presence of cesium fluoride to isolate tetrakis(trifluoromethyl)tetrazocine271 [71JCS(C)2920]. Gol din and Tsiomo reacted dihydrazine 272 with biacetyl to make polyhy-... 

Interestingly, when large excesses of both trimethyl(trifluoromethyl)silane and potassium fluoride are reacted with oxalyl fluoride (3 or 4 1). a new oligomer (CF3)3C0[C(CF3)20] -C(0)Cp3 (n = 2-4) is obtained these symmetrical branched-chain polyethers are difficult to... 

Fluorinated ether-containing dicarboxyhc acids have been prepared by direct fluorination of the corresponding hydrocarbon (17), photooxidation of tetrafluoroethylene, or by fluoride ion-cataly2ed reaction of a diacid fluoride such as oxalyl or tetrafluorosuccinyl fluorides with hexafluoropropylene oxide (46,47). Equation 8 shows the reaction of oxalyl fluoride with HEPO. A difunctional ether-containing acid fluoride derived from HEPO contains regular repeat units of perfluoroisopropoxy group and is terminated by two alpha-branched carboxylates. 

Fluoroformyl peroxide [692-74-0] (20, R = R = F), has been prepared by the reaction of carbon monoxide, fluorine, and oxygen or by the photolytic reaction of oxalyl fluoride with oxygen (187). 

Oxalic acid, formation, 43 421-422 Oxalyl fluoride, reaction with hexafluoroace-tone, 30 271... 

Acyl chlorides can be converted to acyl fluorides in good yields with sodium fluoride. Oxalyl fluoride (23) is prepared in 95% yield by adding oxalyl chloride (22) to powdered sodium fluoride (size 15-100 m) in tetramethylene sulfone at 30°C over 4 hours and then stirring for 1 hour.21... 

Dioxolanones are accessible from the reactions of oxalyl fluoride (7/) and a-hydroxy acids (2S5) with HFA. 

Fluorination and chlorination cause a large decrease in the nonradiative decay rates. The intersystem crossing rate constant drops from 4 x 10 s for acetone to 1.5 x 10 s- - for hexafluoroacetone. For the cyclobutanone/perfluorocyclobutanone pair, the rates are 4.2 x 10 s- - and 1 x 10 s l, respectively. A similar decrease is likely for the glyoxal/oxalyl fluoride pair, where zero-pressure tp values of 2.4 ps and 24 ps, respectively, have been measured (19,25,26). The fluorescence yields of these compounds must be measured before the true extent of this effect is known. Mixed chlorofluoroacetones exhibit nonradiative rates of intermediate value, with k jR increasing at low energy excitation with increasing chlorination from 2.7 x 10 s l for chloropentafluoroacetone to 3.9 x 10 s l and 8.0 x 10 s l for dichlorotetrafluoroacetone and trichloro-trifluoroacetone, respectively (94). 

In all reactions of O2CIF3 with hydrogen-containing substances, HF is the most likely reaction product. Carbonyl fluoride, COF2, and other intermediate oxyfluorides—for example, oxalyl fluoride, C202F2—may be formed. In view of the violent explosion which took place, it is also likely that some C-H-containing compounds were present. 

It was reported (94IC415) that the reactions of 2,2,3,3 tetrafluorobutyleneglycol triethylsilyl ether with 1,4-dibromotetrafluorobenzene, tetrabromoethane, and oxalyl fluoride form oxygen-containing heterocycles (Scheme 143). Adamson et al. (92JFC(58)300) showed that 1,2,3,4-tetrafluoroacridines 154 are formed in quantitative yields in reactions of pentafluorobenzaldehyde with substituted anilines at room temperature (Scheme 144). 2,3-Diphenyl-4,5,6,7-tetrafluorobenzofuran is formed in a reaction of hexafluorobenzene with phenyl benzyl ketone in the presence of sodium hydride (79BCJ2657) (Scheme 145). The reaction involves intramolecular nucleophilic cyclization of the generated O-nucleophile due to tautomerization of the intermediate ketone. 

Titanium tetrachloride is an efficient reagent for the conversion of trialkyl phosphites and dialkyl hydrogen phosphonates into dialkyl phosphorochloridates. Imidazolides and dialkyl or diaryl phosphoric acids react with acyl fluorides - benzoyl fluoride and oxalyl difluoride being the reagents of choice - to give quantitative yields of the phosphoryl fluorides. The procedure is adaptable to the preparation of fluorides of carbohydrate phosphates in this field, the reaction between the ceu bohydrate and tris-l//-imidazolylphosphine oxide or sulphide with the replacement of one imidazole... 

CFaiN RfCOF + hvRr + COF Rr + CFjiN- -> RpN CFj. Extension of this to the bis-acyl fluorides FOC (CF2)3-COF and FOC-(CF2>4-COF, however, gives low yields of perfluoro-(Af-methylpyirolid-2-one) (15 %) and perfluoro-(A -methylplperidin-2-one) ca. 10%), respectively, instead of the imines CFg N-(CF2) N CF2 (a = 3 or 4), presumably via the sequence of events shown in Scheme 39. Fluoride-initiated (CsF) reactions between the formaldazine and these, and other, acyl fluorides leads to novel heterocyclic carbonyl compounds which suffer decarbonylation when irradiated with u.v. light (see Scheme 40). Carbonyl fluoride and oxalyl fluoride react with the formaldazine in the presence of caesium fluoride to yield the acylic and cyclic product (57) (70%) and (58) (ca. 55%), respectively the latter fragments to trifluoromethyl isocyanate when exposed to u.v. light. 

IR and Raman spectra gave quite detailed assignments for [HC(ox)(OMe)], where X = H or D ox = oxalato. TR data were reported for the carbonate radical anion, COs" - the data were consistent with C2V symmetryThe IR spectrum of matrix-isolated (COF)2 (oxalyl fluoride). This showed that a cis/trans mixture was present, (6). Detailed assignments were given with the aid of low-temperature Raman spectra. " ... 

Preparation of Arylcarboxylic Acids and Derivatives. The general Friedel-Crafts acylation principle can be successfully appHed to the preparation of aromatic carboxyUc acids. Carbonyl haUdes (phosgene, carbonyl chloride fluoride, or carbonyl fluoride) [353-50-4] are diacyl haUdes of carbonic acid. Phosgene [75-44-5] or oxalyl chloride [79-37-8] react with aromatic hydrocarbons to give aroyl chlorides that yield acids on hydrolysis (133) ... 

Ethane-1,2-dioyl dichloride oxalyl chloride (COCOj) reacts with antimony(V) fluoride above -35 "C to form COCIF (identified by in situ infrared analysis) and SbFj. The reaction was accompanied by the generation of a small quantity of CO, and possibly COFj. Examination of the infrared spectrum during the progress of the reaction when cooled to -50 C revealed the formation of an intermediate oxocarbonium salt. The reaction was interpreted in the following terms [7] ... 

Oxalyl-CPG is obtained by reacting oxalyl chloride and 1,2,4-triazole with a 3 -hydroxyl nucleoside and LCAA-CPG. Cleavage of the oxalyl linker can be effected by a variety of mild reagents including triethylamine, propylamine-DCM, 5% ammonium hydroxide in methanol, or 0.5 M cesium fluoride in methanol for 15 min. Alternatively, 0.5 M DBU in either pyridine, dichloromethane, or dioxane was shown to effect full cleavage of the oxalyl linkage in less than 30 min at room temperature [111]. 

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