38537-30-3Relevant academic research and scientific papers
Synthesis and characterization of norbornanediol isomers and their fluorinated analogues
Grayson, Scott M.,Long, Brian K.,Kusomoto, Shiro,Osborn, Brian P.,Callahan, Ryan P.,Chambers, Charles R.,Willson, C. Grant
, p. 341 - 344 (2007/10/03)
Fluorinated norbornene monomers exhibit the requisite properties for inclusion in 157 nm photoresists, but traditional addition and radical polymerizations with these monomers have failed. Norbornanediols provide an alternate route to these materials via condensation polymerization, and methods have been developed for the efficient synthesis of the exo-2-syn-T- and endo-2-exo-3-dihydroxynorbornanes. Synthesis of the fluorinated analogues is complicated by steric and electronic effects; however, a high-yielding synthesis of endo-2-exo-3-dihydroxynorbornane bearing a 5-endo-[2,2-bis(trifluoromethyl) hydroxyethyl] substituent is reported.
Stereochemistry of acid-catalyzed cleavage of 3-chloro- and 3-bromonortricyclene in deuterated medium. Evidence for edge protonation of nortricyclenes
Werstiuk, Nick Henry,Timmins, George,Cappelli, Frank Peter
, p. 1709 - 1724 (2007/10/02)
Cleavage of 3-chloronortricyclene (4c) and 3-bromonortricyclene (4d) occurs faster than solvolysis in D2SO4-DOAc at 70-75 deg C and yields syn-7-, anti-7-, exo-5-, and endo-5-halo-exo-2-norbornyl acetates as products.That the 7-chloroacetates comprise 70percent of the reaction mixture, that 30percent of the 5-chloro-exo-2-norbornyl acetates which comprised 28percent of the reaction mixture are derived via rearrangement of the syn-7- and anti-7-chloronorbornyl cations, and that the deuterium at C-6 is at least 90percent stereochemically pure endo is evidence that cleavage of the bond farthest removed from the electron withdrawing halogen is preferred 5:1 over the other bonds of the three-membered ring.The stereochemistry of the ring-opening is rationalized on the basis of cleavage via edge-deuteronation with formation of classical halocations as intermediates.The location of deuterium in the 5-halo-exo-norbornyl acetates is used to define the pathways whereby the 5-haloacetates are formed.This study also establishes that C-6 endo deuterated 7-chloro- and 7-bromo-exo-2-norbornyl brosylates can be synthesized from the corresponding 3-halonortricyclenes.
