Imine salts from Grignard reagents

Aromatic Grignard reagents react smoothly with ethoxymethyleneaniline to give imines which are easily hydrolyzed to aldehydes. The reaction is easy to cary out, is adaptable to large-scale preparations, and gives high yields (65-82%). Its use is limited by the availability of the ethoxymethyleneaniline, which may be prepared in a pure condition from the dry silver salt of formanilide and ethyl iodide. 

Discussed in this chapter, for the most part, are documented cases where complexes derived from (one or more equivalents of) a Grignard or organolithium reagent, in combination with a copperfl) salt, have been used to add to an aldehyde, ketone, imine, amide or nitrile moiety. In the majority of examples, the key issue is one of stereocontrol. Hence, where available, data within the organocopper manifold versus those for other organometallic reagents are provided for comparison. 

---