7314-84-3Relevant articles and documents
The Hydrogen-Bond Basicity pKHB Scale of Peroxides and Ethers
Berthelot, Michel,Besseau, Francois,Laurence, Christian
, p. 925 - 931 (1998)
Using 4-fluorophenol as a reference hydrogen-bond donor, equilibrium constants, Kf, for the formation of 1:1 hydrogen-bonded complexes have been obtained by FTIR spectrometry for 39 ethers of widely different structure (cyclic and acyclic ethers, crown ethers, glymes, acetals, orthoesters, and disiloxane) and 3 peroxides, in CCl4 at 298 K. The pkHB scale of monoethers extends from 1.44 for 2,3-diadamant-2-yloxirane to -0.53 for hexamethyldisiloxane. The main effects explaining the variation of the hydrogen-bond basicity of sp3 oxygen atoms are (i) the electron-withdrawing field-inductive effect [e.g. in (CF3)2CHOMe], (ii) the electron-withdrawing resonance effect (e.g. in EtOCH=CH2) (iii) the steric effect (e.g. in tBu2O), (iv) the lone-pair-lone-pair repulsion (e.g. in cyclic peroxides), and (v) the cyclization giving the basicity order: oxetane > tetrahydrofuran > tetrahydropyran > oxirane. A spectroscopic scale of hydrogen-bond basicity is constructed from, the infrared frequency shift Δv(OH) of methanol hydrogen-bonded to peroxides and ethers. The thermodynamic pKHB scale does not correlate with the Δv(OH) scale because of (i) statistical effects in polyethers and peroxides (ii) secondary hydrogen-bond acceptor sites (e.g. in benzyl ether), (iii) variations of the s character of oxygen lone pairs either by conjugation or cyclization, (iv) steric effects, (v) lone-pair-lone-pair repulsions, and (vi) anomeric effects. The v(OH...O) band shape reveals two stereoisomeric complexes, the most stable being tetrahedral at the ether oxygen atom.
Geluk
, p. 652 (1970)
Semipinacol and protoadamantane-adamantane rearrangements of 5,6-dibromoadamantan-2-one and -2-ol
Wang, Xiaofang,Dong, Yuxiang,Ezell, Edward L.,Garrison, Jered C.,Wood, James K.,Hagen, James P.,Vennerstrom, Jonathan L.
, p. 2972 - 2976 (2017/04/26)
A number of new polybrominated adamantanes were formed by rearrangements and bromination of 2,2,6,6-tetrabromoadamantane under Friedel-Crafts conditions. Protoadamantane-4,10-dione, 10-acetoxyprotoadamantan-4-one, 1,2,6-triacetoxyadamantane and 5,6-diacetoxyadamantan-2-one were formed by successive semipinacol and protoadamantane-adamantane rearrangements of 5,6-dibromoadamantan-2-one and 5,6-dibromoadamantan-2-ol. This work may open up new pathways for the synthesis of 1,2,6-trisubstituted adamantanes.