7064-32-6Relevant articles and documents
Cracking under internal pressure: Photodynamic behavior of vinyl azide crystals through N2release
Shields, Dylan J.,Karothu, Durga Prasad,Sambath, Karthik,Ranaweera, Ranaweera A. A. Upul,Schramm, Stefan,Duncan, Alexander,Duncan, Benjamin,Krause, Jeanette A.,Gudmundsdottir, Anna D.,Naumov, Pan?e
, p. 18565 - 18575 (2020/12/01)
When exposed to UV light, single crystals of the vinyl azides 3- azido-1-phenylpropenone (1a), 3-azido-1-(4-methoxyphenyl)propenone (1b), and 3-azido-1-(4-chlorophenyl)propenone (1c) exhibit dramatic mechanical effects by cracking or bending with the release of N2. Mechanistic studies using laser flash photolysis, supported by quantum mechanical calculations, show that each of the vinyl azides degrades through a vinylnitrene intermediate. However, despite having very similar crystal packing motifs, the three compounds exhibit distinct photomechanical responses in bulk crystals. While the crystals of 1a delaminate and release gaseous N2 indiscriminately under paraffin oil, the crystals of 1b and 1c visibly expand, bend, and fracture, mainly along specific crystallographic faces, before releasing N2. The photochemical analysis suggests that the observed expansion is due to internal pressure exerted by the gaseous product in the crystal lattices of these materials. Lattice energy calculations, supported by nanoindentation experiments, show significant differences in the respective lattice energies. The calculations identify critical features in the crystal structures of 1b and 1c where elastic energy accumulates during gas release, which correspond to the direction of the observed cracks. This study highlights the hitherto untapped potential of photochemical gas release to elicit a photomechanical response and motility of photoreactive molecular crystals.
Harnessing Stereospecific Z-Enamides through Silver-Free Cp?Rh(III) Catalysis by Using Isoxazoles as Masked Electrophiles
Debbarma, Suvankar,Bera, Sourav Sekhar,Maji, Modhu Sudan
supporting information, p. 835 - 839 (2019/01/26)
The stereospecific synthesis of Z-enamides is described in this paper. For the first time, isoxazoles have been employed as electrophiles in C-H functionalization to afford thermodynamically less stable Z-enamides utilizing salicylaldehydes in an atom- and step-economic fashion. The stereochemistry of enamides might originate from the relative disposition of atoms present in isoxazole and the intramolecular hydrogen bonding. The reaction showed excellent scope as several structurally and electronically diverse salicylaldehydes and isoxazoles reacted efficiently.
TEMPO-catalyzed synthesis of 5-substituted isoxazoles from propargylic ketones and TMSN3
He, Yan,Xie, Yu-Yang,Wang, Ying-Chun,Bin, Xiao-Min,Hu, Da-Chao,Wang, Heng-Shan,Pan, Ying-Ming
, p. 58988 - 58993 (2016/07/06)
A novel and efficient TEMPO-catalyzed synthesis of 5-substituted isoxazoles from propargylic ketones and TMSN3via a radical mechanism process is described. This methodology provides an easy access to a variety of useful 5-substituted isoxazoles