18886-64-1

Upstream product

• 16717-64-9 1-azidostyrene 
• 1517-00-6 3-azido-1-phenyl-2-propen-1-one 
• 16722-99-9 β-azidostyrene 

Downstream Products

• 36879-72-8 4,5-diphenyl-3-oxazoline 

Relevant academic research and scientific papers

Catalytic asymmetric synthesis of 3,2′-pyrrolinyl spirooxindoles: Via conjugate addition/Schmidt-type rearrangement of vinyl azides and (E)-alkenyloxindoles

A catalytic asymmetric conjugate addition/Schmidt-type rearrangement of vinyl azides and (E)-alkenyloxindoles was realized. It afforded a variety of optically active 3,2′-pyrrolinyl spirooxindoles with high yields (up to 98%), and excellent diastereo- and enantioselectivities (up to 98% ee, >19 : 1 dr), even at the gram-scale in the presence of a chiral N,N′-dioxide-nickel(ii) complex. In addition, a possible catalytic cycle and transition state model were proposed to rationalize the stereoselectivity. This journal is

Cracking under internal pressure: Photodynamic behavior of vinyl azide crystals through N2release

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.

Ring Enlargement of Three-Membered Heterocycles by Treatment with In Situ Formed Tricyanomethane

Although the chemistry of elusive tricyanomethane (cyanoform) has been studied during a period of more than 150 years, this compound has very rarely been utilized in the synthesis or modification of heterocycles. Three-membered heterocycles, such as epoxides, thiirane, aziridines, or 2H-azirines, are now treated with tricyanomethane, which is generated in situ by heating azidomethylidene-malonodinitrile in tetrahydrofuran at 45 °C or by adding sulfuric acid to potassium tricyanomethanide. This leads to ring expansion with formation of 2-(dicyanomethylidene)oxazolidine derivatives or creation of the corresponding thiazolidine, imidazolidine, or imidazoline compounds and opens up a new access to these push–pull-substituted olefinic products. The regio- and stereochemistry of the ring-enlargement processes are discussed, and the proposed reaction mechanisms were confirmed by using 15N-labeled substrates. It turns out that different mechanisms are operating; however, tricyanomethanide is always acting as a nitrogen-centered nucleophile, which is quite unusual if compared to other reactions of this species.