Trifluoroacetyl nitrate

Reactions of nitronium sulfates: Hunting for dinitro sulfate

“…The Raman spectrum of the solid reaction mixture (Figure ) showed no intense lines of the starting compound 2 (1,097 and 1,400 cm −1, Figure S1). Apart from the lines of solid [NO 2 ] + [NO 3 ] − (1,045 and 1,395 cm −1 , Figure S2), we observed new lines at 1,403 and 1,081 cm −1 . So far as all solid symmetric dinitronium polysulfates ( 2 – 4 ) in the Raman spectra have a characteristic wave number at 1,400 ± 1 cm −1 , this fact points to the formation of new nitronium sulfate in the mixture, and wave numbers observed were assigned to ν s NO2 and ν s SO2 of sulfate 1 , respectively.…”

“…Sulfate 6 reacted with a stoichiometric amount of HNO 3 to yield disulfate 2 , N 2 O 5 , and CF 3 COOH (Scheme , Paths G and B ). The intense line of the starting compound 6 at 1,056 cm −1 was not observed in the Raman spectrum of the mixture obtained, whereas the presence of CF 3 COOH can be easily detected from the characteristic band at about 810 cm −1 (Figure S6). We consider that transformation of compound 6 into salt 2 occurred via unstable dinitrosulfate 1 (Scheme , Path G ), then dimerization of sulfate 1 gave disulfate 2 and gaseous N 2 O 5 (Scheme , Path B ).…”

“…In this case, a new band in the range of ~1,320 cm −1 in the Raman spectrum of the N 2 O 5 ·(NO 2 ) 2 SO 4 mixture (Figure ) may correspond to the nitro ester moiety. This band is not observed in the spectra of the parent compounds, ionic (NO 2 ) 2 S 2 O 7 ( 2 ), and [NO 2 + ][NO 3 − ] (Figures S1 and S2). This wave number value is close to ν s NO2 of covalent compounds containing electron‐withdrawing groups, for example, O 2 NONO 2 and C n Hal m C(O)ONO 2 (1,332–1,340 cm −1 ).…”

“…Our attempt to synthesize solid monosulfate 1 by the reaction of NO 2 HSO 4 ( 5 ) with CF 3 COONO 2 (Scheme , Path E1 ) obtained from HNO 3 –(CF 3 CO) 2 O mixture led to the trifluoroacetyl compound 6 in quantitative yield (Scheme , Paths E1 and E2 ). Dissolution of monosulfate 5 in CF 3 COONO 2 –CF 3 COOH mixture was followed by rapid crystallization from the whole bulk of the solution to give a monolith unsuitable for filtration.…”

“…This assumption is also supported by the fact that an increase in the molar content of SO 3 leads to polysulfates (NO 2 ) 2 S n O 3 n + 1 3 ( n = 3) or 4 ( n = 4; Scheme .1) . Recently, the first nitronium monosulfates, NO 2 HSO 4 ( 5 ) and (NO 2 )(CF 3 CO)SO 4 ( 6 ), were obtained by a new method from H 2 SO 4 and CF 3 COONO 2, but related nitronium monosulfate 1 before our study was still a hypothetical compound.…”