Hydrogen fluoride, application

Anhydrous hydrogen fluoride, application of for the structural analysis of polysaccharides, 47, 167-202 Anomeric and exo-anomeric effects in carbohydrate chemistry, 47, 45-123 Anomeric-oxygen activation for glycoside synthesis, trichloroacetimidate method, 50,21-123... 

With very electrophilic olefins, an alternative hydrogen fluoride addition process is often preferred This process, involving reaction of the olefin with fluoride ion in the presence of a proton donor, is applicable to certain perhalogen ated alkenes [/] and substrates with other electron attracting groups attached to the double bond [i5, 36] (equations 4 and 5)... 

In order to achieve high yields, the reaction usually is conducted by application of high pressure. For laboratory use, the need for high-pressure equipment, together with the toxicity of carbon monoxide, makes that reaction less practicable. The scope of that reaction is limited to benzene, alkyl substituted and certain other electron-rich aromatic compounds. With mono-substituted benzenes, thepara-for-mylated product is formed preferentially. Super-acidic catalysts have been developed, for example generated from trifluoromethanesulfonic acid, hydrogen fluoride and boron trifluoride the application of elevated pressure is then not necessary. 

Hence, water, ammonia, hydrogen fluoride and carbon dioxide separate from the mixture into the gaseous phase. However, despite the possibility of a solid-state interaction, the application of ammonium acetate solutions for washing of... 

Polyphosphoric acid is a commonly used catalyst for this reaction however, in some cases a mixture of hydrogen bromide/acetic acid gives better results. Acylation of the S-phenyl-, V-(4-tolyl)- or S-(l-naphthyl)-substituted thiobenzenepyruvic acids 3a-c affords the corresponding dibenzo[A,/]thiepins in satisfactory yields, while reaction of the S-(4-methoxyphenyl) or S-(2-naphthyl) derivatives fails to provide any thiepin.60 The intramolecular Friedel-Crafts acylation of 2-(arylsulfanyl)benzeneacetic acids also yields the corrresponding dibenzothiepins in this case the use of hydrogen fluoride sometimes results in purer products.38 The applicability of this method is restricted to the synthesis of stable bisannulated thiepins. 

Hirata and Iwata, 1998, extended these studies to linear oligomers and an infinite linear hydrogen fluoride polymer. Also this study substantiates the applicability of the BLYP and B3LYP functionals, for which reasonable agreement with experiment has been found with respect to structure, binding energies and vibrational frequencies of the species explored. 

Rhone-Poulenc Chemicals). Preparation of Fluoro Compounds by Treatment of the Corresponding Amines with Hydrogen Fluoride and a Nitrosat-ing Agent Under Ultrasound or Micro-wave Irradiation. PCT International Application WO 41,083, 1997 (GB Application 96/9, 154, 1 May 1996) Chem. 

Hydrogen fluoride also is used as a catalyst in alkylation of aromatic compounds and for dimerization of isobutene. Other catalytic applications are in isomerization, polymerization, and dehydration reactions. Other uses are in... 

Hydrofluoric acid in contact with water behaves anomalous when compared to the heavier halogens. The hydrogen-fluoride bond is relatively strong and ion pairs of the type H3 0+F exist rather than free hydronium ions [10]. Anhydrous HF is an electrically conducting liquid (3HF = H2F+ + HF2 occurs) with a normal boiling point of 19.5 °C. Scheme (1) summarizes the most important forms, the standard potentials in acidic aqueous media, and typical applications of fluorine. 

Thus, although the CAVE process has definite value in its ability to fluorinate smoothly certain organic compounds which are not particularly amenable to other methods of fluorination, for example, by the ECF Simons process, its general application is obviously severely limited by the combined requirements that substrates be only slightly soluble in hydrogen fluoride and sufficiently volatile at the temperature of the cell ( 100 °C) to permit diffusion though the porous carbon matrix of the anode. 

---