617-92-5Relevant articles and documents
An efficient synthesis of tertiary amines from nitriles in aprotic solvents
Shares, Jonathan,Yehl, Jenna,Kowalsick, Amanda,Byers, Philip,Haaf, Michael P.
scheme or table, p. 4426 - 4428 (2012/09/25)
Tertiary amines are utilized extensively as non-nucleophilic proton scavengers for a number of organic transformations. Herein we report the efficient syntheses of tertiary alkyl amines from their corresponding alkyl nitriles in the presence of a heterogeneous palladium catalyst and a source of dihydrogen in aprotic solvents. The reaction is atom economic, the conditions are mild, and the isolated yields are virtually quantitative. The degree of amine alkylation shows some solvent dependency; in polar protic solvents such as ethanol or methanol, the reaction affords a mixture of products with the secondary alkyl amine as the major product.
Influence of the reaction temperature on the regioselectivity in the rhodium-catalyzed hydroformylation of vinylpyrroles
Caiazzo, Aldo,Settambolo, Roberta,Uccello-Barretta, Gloria,Lazzaroni, Raffaello
, p. 279 - 284 (2007/10/03)
The influence of the temperature on the regioselectivity in the hydroformylation of the vinylpyrrole isomers and of the corresponding N-tosylated substrates has been investigated in the range 20-100°C, in the presence of Rh4(CO)12. At all the temperatures the branched aldehyde was prevailing with respect to the linear isomer for all the substrates ( α-regioselectivity). With increasing temperature, an increase of the linear aldehyde was observed to a different extent in dependence on the substrate nature. 2H NMR investigation of the crude reaction mixture recovered from deuterioformylation of 3-vinylpyrrole at partial substrate conversion points out that the observed depression of the α-regioselectivity with increasing temperature must be connected to a β-hydride elimination process occurring for the branched alkyl-rhodium intermediates but not for the linear ones.
Homolysis in the Reaction of Grignard Reagents. II. The Reaction of Pyridazine
Holm, Torkil
, p. 279 - 283 (2007/10/02)
Pyridazine reacts with Grignard reagents by a homolytic mechanism as seen the presence of N-alkylated dimers, dialkyl- and trialkyl-pyrroles as well as other 'radical-type' compounds in the reaction product.The non-alkylated product 1,4-dihydropyridazine was also found.The kinetics of the reaction indicate high reactivity of tertiary and secondary reagents and low reactivity of methylmagnesium bromide as expected for a homolytic reaction.