The reaction of trihalogenomethyl anions with carbonyl compounds: competitive reactivity comparisons and applications to the synthesis of α-trihalogenomethyl alcohols

Abstract

Trihalogenomethyl anions, generated by decarboxylation of trichloro- and tribromo-acetic acid in dimethyl sulphoxide solution, react with added aldehydes. In the presence of 1,3,5-trinitrobenzene, the reaction with aldehydes competes with the formation of the coloured Meisenheimer adduct. The reduction in absorbance from the value in the absence of aldehyde has been used to measure the reactivity of trihalogenomethyl anions towards a series of aldehydes relative to their reactivity towards trinitrobenzene. For 4-substituted benzaldehydes, the reactivities obey a linear ρσ– relationship. The most reactive aldehyde used is only two times less reactive towards CCl3– or CBr3– than hydrogen ions, and it is concluded that, in dimethyl sulphoxide solutions, the reaction between trichloromethyl anions and hydrogen ions is not encounter-controlled. The reactions with aldehydes have been used to prepare several new compounds of the formula RCH(OY)CX3 where R = aryl or pyridyl, X = Br or Cl, and Y = H or COCH3.