3288-39-9

Upstream product

• 104-92-7 1-bromo-4-methoxy-benzene 
• 1116-98-9 cyanoacetic acid tert-butyl ester 
• 201230-82-2 carbon monoxide 
• 98-88-4 benzoyl chloride 

Downstream Products

• 3672-47-7 3-oxo-3-(4'-methoxyphenyl)propanenitrile 
• 614-16-4 Benzoylacetonitrile 

Relevant academic research and scientific papers

Palladium-Catalyzed Carbonylative α-Arylation of tert -Butyl Cyanoacetate with (Hetero)aryl Bromides

A three-component coupling protocol has been developed for the generation of 3-oxo-3-(hetero)arylpropanenitriles via a carbonylative palladium-catalyzed α-arylation of tert-butyl 2-cyanoacetates with (hetero)aryl bromides followed by an acid-mediated decarboxylation step. Through the combination of only a stoichiometric loading of carbon monoxide and mild basic reaction conditions such as MgCl2 and dicyclohexylmethylamine for the deprotonation step, an excellent functional group tolerance was ensured for the methodology. Through the use of 13C-labeled carbon monoxide generated from 13COgen, the corresponding 13C-isotopically labeled β-ketonitriles were obtained, and these products could subsequently be converted into cyanoalkynes and 3-cyanobenzofurans with site specific 13C-isotope labeling. (Chemical Equation Presented).

Steric and electronic control in the addition of hydrazine and phenylhydrazine to α-[(dimethylamino)methylene]-β-oxoarylpropanenitriles

Reaction of hydrazine with α-[(dimethylamino)methylene]-β-oxoarylpropanenitriles 2 gives a mixture of the 4-aroyl-5-aminopyrazoles 3 and the 5-aryl-4-cyanopyrazoles 4. Similarly reaction of 2 with phenylhydrazine gives rise to the 5-amino-4-aroyl-1-phenylpyrazoles 5 and 5-aryl-4-cyano-1-phenylpyrazoles 6. The regioselectivity of addition has been investigated with respect to the electronic nature and steric requirements of the aromatic substitution. The ratio of products was found to be independent of the electronic nature of the substituent. The outcome of the reaction was however very sensitive to steric factors. Substituents in the para- and meta-positions favoured formation of the pyrazole-nitrile products 4 and 6, whereas sterically demanding ortho-substituents favoured the pyrazole-amino ketones 3 and 5.