[93-61-8] · C8H9NO · N-Methylformanilide · (MW 135.18)
Alternate Name: N-methyl-N-phenylformamide.
Physical Data: mp 8-13 °C; bp 243-244 °C; d 1.095 g cm-3.
Form Supplied in: colorless liquid; widely available.
Analysis of Reagent Purity: IR, NMR.
Handling, Storage, and Precautions: irritant, toxic.
N-Methylformanilide (1) has been used for formylating organolithium and Grignard reagents (eq 1).1
Alternatively, formylation can be achieved under Vilsmeier-Haack reaction conditions.2 In this manner, aromatic compounds such as (2) can be formylated by treatment with the chloromethylene ammonium salt generated from reagent (1) (eq 2).
1,3-Cyclohexanediones and vinyl acetates undergo some interesting transformations on reaction with (1) in the presence of Phosphorus Oxychloride (eqs 3 and 4).3 A wide variety of vinyl compounds other than vinyl acetate have been successfully utilized in this reaction (eq 4).3b
1,3,5-Triazines (3) can be obtained by condensing cyanoamidines with (1) and phosphorus oxychloride (eq 5).4 Enaminals can be afforded by the reaction of (1) with a vinyl ether and Oxalyl Chloride.5
A convenient synthesis of both symmetrical and unsymmetrical 1,5-diketones (4) has been achieved (eq 6).6
N-Acylamino-2-azaallene salts are the products of reaction of (1) with nitrilium salts.7 Enamines can be easily made by reacting metal carbene complexes with (1).8 Reduction of (1) to N,N-dimethylaniline can be effected using bis(2-bromoethylselenium dibromide) and sodium borohydride.9
Daniel L. Comins & Sajan P. Joseph
North Carolina State University, Raleigh, NC, USA