678187-37-6Relevant articles and documents
High-Sensitivity Microcalorimetry and Gel Permeation Chromatography in Tandem Reveal the Complexity of the Synthesis of Poly-(2-isopropyl-2-oxazoline) Stars
Bullet, Jean-Richard,Korchagina, Evgeniya V.,Winnik, Fran?oise M.
, p. 6161 - 6170 (2021)
A series of star poly(2-isopropyl-2-oxazolines) (S-PIPOZ) was prepared by two different approaches: "coupling-onto (CO)"and "core-first (CF)". On the one hand, for "the core-first"approach, SCF-PIPOZ were prepared by direct cationic ring opening polymerization from a tetra tosylate-functionalized pentaerythrityl core. On the other hand, for the "coupling-onto"approach, SCO-PIPOZ were synthesized by coupling via copper alkyne-azide cycloaddition between L-PIPOZ-N3 and a tetrafunctionalized alkyne core. Taking advantage of the thermosensitive properties of PIPOZ, high-sensitivity microcalorimetry analyses (HS-DSC), in addition to commonly used 1H nuclear magnetic resonance (NMR), gel permeation chromatography (GPC), and spectrophotometry (UV analyses), proved to be powerful tools. On the one side, microcalorimetry analysis facilitates purification of the polymers by setting the appropriate temperature for centrifugal fractionation, and on the other side, it helps in the resolution of their microstructures. SCO-PIPOZ demonstrated good correlation between the 1H NMR, GPC, and UV results and showed sharp unimodal HS-DSC endotherms. Contrary to the SCO-PIPOZ data, SCF-PIPOZ results revealed a discrepancy between the molecular weights measured by 1H NMR and GPC. This issue was resolved with the help of HS-DSC, which allowed detection of different populations of polymers to analyze them before and after isolation by isothermal centrifugal fractionation. Cleavage of the arms of the isolated SCF-PIPOZ showed incomplete/not uniform synthesis of S-PIPOZ by the "core-first"approach. These results highlight the importance of HS-DSC coupled with the commonly used analytical techniques for both refinement and elucidation of the microstructure of architecturally complex thermosensitive polymers such as star polymers.
Cinchona alkaloid-based chiral catalysts act as highly efficient multifunctional organocatalysts for the asymmetric conjugate addition of malonates to nitroolefins
Ashokkumar, Veeramanoharan,Siva, Ayyanar
, p. 10216 - 10225 (2015/10/20)
New pentaerythritol tetrabromide-based chiral quaternary ammonium salts acting as organocatalysts (7a and 7b) have been prepared and used as organocatalysts for enantioselective Michael addition reactions between various nitroolefins and Michael donors (malonates) under mild reaction conditions, such as lower concentration of base and catalyst and room temperature, with very good chemical yields (up to 97%) and ee's (up to 99%).
The synthesis of spirophanes from a pentaerythrityl core
Rajakumar, Perumal,Sekar, Karuppannan,Srinivasan, Kannupal
, p. 1905 - 1907 (2007/10/03)
Various thia- and oxa-spirobicyclic cyclophanes were synthesized from a pentaerythrityl building block and appropriate dithiols/bisphenols.