75562-69-5

Upstream product

• 109-77-3 malononitrile 
• 611-70-1 phenyl isopropyl ketone 
• 21863-81-0 2-(2-methyl-1-phenylpropylidene)propanedinitrile 

Downstream Products

• 75562-75-3 3,3-dimethyl-2-phenyl-1,1-cyclopropanedicarbonitrile 

Relevant academic research and scientific papers

Regiochemistry in alkylation, acylation and methoxycarbonylation of alkali salts from 2-substituted alkenylpropanedinitriles

Alkali salts (4-) of several 2-substituted alkenylpropanedinitriles are prepared, isolated and characterised by 1H and 13C NMR spectroscopy. By treating the salt 4a- with 4a a dimer, 2-dicyanomethylene-6-methyl-4,6-diphenyl-1,2,5,6-tetrahydronicotinonitrile 6, is formed, for which a single-crystal X-ray structure is presented. Alkylation of the ambident salts 4- with MeX (X = I, Tf, or Br) leads to regioisomers, 1-and 3-alkylation, and comparison with O vs. C-alkylation of ketones is made. Double alkylation is also observed, 3-alkylation followed by 1-alkylation. Thus from 4a- a mixture of (E)-and (Z)-2-methyl-2-(1-phenylprop-1-enyl)propanedinitrile 9b is formed, and the X-ray structure of the former is presented. Acylation of 4a- with benzoyl chloride gives only the 3-regioisomer; using equimolar amounts of reactants gives a ring-closure product, 2-oxo-4,6-diphenyl-2H-pyran-3-carbonitrile 12, while excess of benzoyl chloride gives the double-acylation product, (Z)-4,4-dicyano-1,3-diphenylbuta-1,3-dienyl benzoate (Z)-13, for which the X-ray structure is presented. Acylation of 4a- with acetyl chloride gives both regioisomers; the 1-acylated product evaded isolation, and the 3-acylation product reacted further to give the (E)- and (Z)-form of 4,4-dicyano-1-methyl-3-phenylbuta-1,3-dienyl acetate 15. The X-ray structure of the latter isomer, (Z)-15, is presented. Methoxycarbonylation of salts 4- with methyl chloroformate gives both regioisomers, while use of methyl cyanoformate gives only the 3-regioisomer, in addition to a Michael adduct from reaction of the CN- group with protonated salt 4-.

Formation of Cyclopropanes from 2-Bromo-1-phenylalkylidenemalononitriles and Nucleophiles

The reaction of the title compounds with selected nucleophiles was studied.With cyanide and hydride (from sodium borohydride) ions, substituted cyclopropanes were obtained in good yields.With alkoxide ions, cyclopropanes were formed only when the bromide