367967-56-4

Upstream product

• 54557-00-5 methyl 3-phenyl-3-oxo-2-(triphenylphosphoranylidene)propionate 
• 1076-59-1 3-phenyl-4H-isoxazol-5-one 
• 3356-89-6 3-phenyl-5-chloroisoxazole 
• 18803-02-6 5-methoxy-3-phenylisoxazole 
• 99073-85-5 4-bromo-5-methoxy-3-phenylisoxazole 

Downstream Products

• 179092-78-5 R*R* 2-methoxycarbonyl-3-phenylaziridine 
• 18709-45-0 methyl 3-phenyl-2H-azirine-2-carboxylate 
• 1403871-49-7 ethyl 2-[(E)-2-bromo-3-methoxy-3-oxo-1-phenylprop-1-enylimino]-3-oxobutanoate 
• 1403871-53-3 methyl (2E)-2-bromo-3-(1-methoxy-1,3-dioxo-3-phenylpropan-2-ylideneamino)-3-phenylacrylate 

Relevant academic research and scientific papers

Easy Access to 2-Fluoro- And 2-Iodo-2 H -azirines via the Halex Reaction

A simple gram-scale method for the preparation of esters and dialkylamides of 2-(fluoro/iodo)-2 H -azirine-2-carboxylic acids via the halogen exchange (Halex) reaction of 2-bromo-substituted analogues is reported. The method operates with inexpensive and safe reagents, Bu 4 NF and potassium iodide, providing high product yields. Alternatively, 2-fluoro-2 H -azirine-2-carboxylates can be prepared from 2-iodo- and 2-chloro-analogues. The latter compounds can be obtained in practically quantitative yield by treating the 2-iodo- and 2-bromo-2 H -azirine-2-carboxylic esters with Bu 4 NCl.

Metal-Catalyzed Isomerization of 5-Heteroatom-Substituted Isoxazoles as a New Route to 2-Halo-2 H -azirines

A convenient gram-scale method for the preparation of 2-halo-2 H -azirine-2-carboxylic acid esters, thioesters and amides via metal-catalyzed isomerization of 5-heteroatom-substituted 4-haloisoxazoles is developed. The formation of the esters and amides is efficiently catalyzed by Rh 2 (Piv) 4, while FeCl 2 ·4H 2 O is the catalyst of choice for the synthesis of the thioesters. In addition, rhodium catalysis is successfully applied in the synthesis of azirine-2-carboxylates from non-halogenated 5-alkoxyisoxazoles.

Synthesis of 2-halo-2H-azirines

α-Oxophosphonium ylides react with N-chlorosuccinimide, N-bromosuccinimide and N-iodosuccinimide in the presence of azidotrimethylsilane giving the corresponding haloazidoalkenes which were completely converted to the 2-halo-2H-azirines on heating in heptane.