Hydrogen fluoride chain

The standard synthesis method features side-chain chlorination of a methylpyridine (picoline), followed by exchange-fluoriaation with hydrogen fluoride or antimony fluorides (432,433). The fluoriaation of pyridinecarboxyHc acids by sulfur tetrafluoride (434) or molybdenum hexafluoride (435) is of limited value for high volume production operations due to high cost of fluorinating agent. 

Side chain fluonnaied aryl isocyanates are an important group of substances used in the manufacture of biologically active compounds The synthetic routes to the meta- and para trifluoromethylphenyl isocyanates permit the chlorine-fluonne exchange with hydrogen fluoride to proceed under moderate conditions and in a virtually quantitative manner (equation 22)... 

Diphenylperfluoropentan-l, 5-dione, m contrast to its shorter chain homo-logue, which gives the normal fluonnation product, on treatment with sulfur tetrafluoride and hydrogen fluoride torms a cyclic ether as the only product [178] (equation 90)... 

The crystal structure of many compounds is dominated by the effect of H bonds, and numerous examples will emerge in ensuing chapters. Ice (p. 624) is perhaps the classic example, but the layer lattice structure of B(OH)3 (p. 203) and the striking difference between the a- and 6-forms of oxalic and other dicarboxylic acids is notable (Fig. 3.9). The more subtle distortions that lead to ferroelectric phenomena in KH2PO4 and other crystals have already been noted (p. 57). Hydrogen bonds between fluorine atoms result in the formation of infinite zigzag chains in crystalline hydrogen fluoride... 

More recent work in the corticosteroid senes has involved modification of the dihydrox-yacetone side chain at the 17 position Activity is retained, for example, when the hydroxyl group at the 17 position is omitted Thus, addition of the elements of hypobromous acid to tnene 36 [8], gives the bromohydnn 37, treatment with base leads to internal elimination to form the p-epoxide 38, opening of the oxir.ine with hydrogen fluoride gives desoximetasone, 39, [9]... 

Sodium LAS synthesized via aluminum chloride catalysis dissolves better than sodium LAS from the hydrogen fluoride route. The main difference is the tetralin content. Dialkyltetralinsulfonates (DATs) function as hydrotropes and this influence can be larger than that of the 2-phenylalkane content. For a homolog (equal alkyl side chains), the higher the DAT content, the lower the... 

Due to its strong hydrogen bonds, in the vapor state hydrogen fluoride is found as short chains and rings. Draw the Lewis structure of an (HF)3 chain and indicate the approximate bond angles. 

Thus, the best compromises for Boc and Fmoc chemistries seem to be cyclohexyl and 2,4-dimethylpent-3-yl (Dmpn), which is of intermediate stability, and the removal of which by trifluoromethanesulfonic acid with the aid of thioanisole (see Section 6.22) leads to minimal imide formation (see Section 6.13). Points to note are that acidolysis of esters by hydrogen fluoride can lead to fission at the oxy-car-bonyl bond instead of the alkyl-oxy bond, thus generating acylium ions that can react with nucleophiles (see Sections 6.16 and 6.22), and that benzyl esters may undergo transesterification if left in methanol. The side reactions of cyclization (see Section 6.16) and acylation of anisole (see Section 6.22) caused by acylium ion formation do not occur at the side chain of aspartic acid.47-51... 

Lenard, J., and G. P. Hess An approach to the specific cleavage of peptide bonds. II. Specific cleavage of peptide chains based on the hydrogen fluoride induced nitrogen to oxygen. shift. Journ. Biol. Chem. 239, 3275 -3281 (1964). 

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