15031-77-3Relevant articles and documents
Proton NMR and IR study of self-association in pyridylalkanols: Open or cyclic dimers? Higher polymers?
Lomas, John S.,Adenier, Alain,Cordier, Christine
, p. 295 - 307 (2006)
1H NMR measurements indicate that (X-pyridyl)alkanols of the general formula (C5H4N)(CH2)nOH, where n = 1, 2 or 3, self-associate as open dimers, cyclic dimers, trimers and tetramers, with considerable variations depending on the position of the alkyl chain and its length. (X-Pyridyl)propan-2-ols behave like the corresponding pyridylmethanols with, however, somewhat lower association constants. The IR spectra of 3-(X-pyridyl)-2,2,4,4-tetramethylpentan-3-ols (X = 3 or 4) in carbon tetrachloride suggest weak association, while the 2-pyridyl derivative occurs mainly as the intramolecularly hydrogen-bonded rotamer. The OH NMR shifts for the 3- and 4-pyridyl derivatives in benzene are concentration-dependent, but neither the equilibrium constants nor the degree of association can be evaluated. Benzyl alcohol in benzene associates as an open dimer and a cyclic tetramer, as does 2phenylpropan-2-ol, only more weakly. Rotation barriers for 3-(X-pyridyl)-2,2,4,4-tetramethylpentan-3-ols (X = 2, 3 or 4) in DMSO or nitrobenzene are 20-21 kcal mol-1. Copyright
Access to "friedel-Crafts-Restricted" tert -alkyl aromatics by activation/methylation of tertiary benzylic alcohols
Hartsel, Joshua A.,Craft, Derek T.,Chen, Qiao-Hong,Ma, Ming,Carlier, Paul R.
experimental part, p. 3127 - 3133 (2012/05/20)
Herein we describe a two-step protocol to prepare m-tert-alkylbenzenes. The appropriate tertiary benzylic alcohols are activated with SOCl2 or concentrated HCl and then treated with trimethylaluminum, affording the desired products in 68-97% yields (22 examples). This reaction sequence is successful in the presence of a variety of functional groups, including acid-sensitive and Lewis-basic groups. In addition to t-Bu groups, 1,1-dimethylpropyl and 1-ethyl-1-methylpropyl groups can also be installed using this method.
Tert-butyldiphenylsilylmethyl triflate: Preparation and dipolar cycloaddition reactions of 1-(tert-butyldiphenylsilylmethyl)-6-cyano-4-methyl-1,2,5,6-tetrah ydropyridine
Hart, David J.,Huang, Ying
, p. 3203 - 3213 (2007/10/03)
Alkylation of substituted pyridines with tert-butyldiphenylsilylmethyl triflate provides N-[tert-butyldiphenylsilylmethyl]pyridinium triflates in excellent yields. Reductive cyanation of the pyridinium triflates provides 1-(tert-butyldiphenylsilylmethyl)-6-cyano-1,2,5,6-tetrahydropyrid ines, azomethine ylid precursors, in modest yields. An unexpected dipolar cycloaddition reaction of an ylid derived from the title 6-cyanopiperidine is described.
