2,2,2-trifluoroethyl formate: A versatile and selective reagent for the formylation of alcohols, amines, and N-hydroxylamines

Organic Letters

Volumn 4, Issue 1, 2002, Pages 111-113

  Hill, David R ^a   Hsiao, Chi Nung ^a   Kurukulasuriya, Ravi ^a   Wittenberger, Steven J ^a  

^a ABBOTT LABORATORIES   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

2,2,2 TRIFLUOROETHYL FORMATE; 2,2,2-TRIFLUOROETHYL FORMATE; ALCOHOL DERIVATIVE; AMINE; DYES, REAGENTS, INDICATORS, MARKERS AND BUFFERS; FORMIC ACID DERIVATIVE; HYDROXYLAMINE; METALLOPROTEINASE; PROTEINASE INHIBITOR;

ARTICLE; CHEMISTRY; DRUG ANTAGONISM; SYNTHESIS;

ALCOHOLS; AMINES; FORMATES; HYDROXYLAMINES; INDICATORS AND REAGENTS; METALLOENDOPEPTIDASES; PROTEASE INHIBITORS;

EID: 0037050427     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol016976d     Document Type: Article

References (19)

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17. Preparation of Trifluoroethyl Formate (TFEF). In a 3-L jacketed flask fitted with reflux condenser and temperature probe, 2.2,2-trifluoroethanol (500 g, 5.0 mol, 1.0 equiv) was combined with 95% formic acid (1000 g, 21.7 mol, 4.3 equiv). The mixture was then heated at an internal temperature of 80°C for 18 h. NMR analysis of a sample taken after 18 h showed a 1.4:1 ratio of trifluoroethanol to trifluoroethyl formate. The mixture was then subjected to fractional distillation though a 10-in. vacuum jacketed fractionating column packed with Aldrich "Pro-pak" packing. The fraction boiling at <70°C was collected; 448 g of distillate was obtained (70% yield adjusted for purity). The purity was assessed by NMR. Typically some 2,2,2-trifluoroethanol and formic acid codistill with the product if the distillation temperature is allowed to rise above 70°C.
18. 6-DMSO) δ 9.95 (br s, 0.5H), 9.80 (br s, 0.5H), 8.41 (br s, 0.5H). 8.37 (br s, 0.5H), 8.35 (s, 0.5H), 7.95 (s, 0.5H), 7.76 (d, 2H, J = 8.9 Hz), 7.65 (d, 2H, J = 8.5 Hz), 7.43 (d, 2H, J = 8.5 Hz), 7.04 (d, 2H, J = 8.9 Hz), 4.92-4.80 (m, 0.5H), 4.50-4.38 (m, 0.5H), 4.28-4.06 (m, 2H), 3.82-3.68 (m, 1H), 3.66-3.54 (m, 1H), 3.88 (s, 3H), 3.84 (s, 3H).
19. Katritzky, A. R.; Chang, H.-X.; Yang, B. Synthesis 1995, 503.