Interaction of carboxylic acids with phosphorus trichloride, or butyl phosphorodichloridite, or the chloridite in the absence, and in the presence of pyridine

A practical chlorination of tert-butyl esters with PCl3 generating acid chlorides

“…Based on the above results and previous literature reports, 19,27,28 we speculated that there are two paths for the reaction. As shown in Scheme 2, one pathway involves the protonation of 1 by HCl generated from the reaction of PCl 3 with H 2 O present in air or solvent (path a).…”

“…was used instead of PCl 3 in the reaction and an 89% yield of PhCOOH was generated (equation 1). According to the literature, 27,28 an acid can react with PCl 3 to give the corresponding chloride. To confirm the critical role of HCl in the reaction, 2.0 equiv.…”

Synthesis of 1-hydroxy-1,1-bisphosphonates

“…An explanation put forward by Cade and Gerrard [25] is that the reaction proceeds by the stepwise hydroxylation of phosphorus trichloride, producing the intermediates HPOCl 2 and HPO(OH)Cl, which may react with other molecules of carboxylic acid or degrade to hydrogen chloride and condensed phosphorus acids. The yield is very dependent on the conditions of the reaction.…”

Atom-efficient chlorination of benzoic acids with PCl3 generating acyl chlorides

“…Literature searches revealed the chlorination of carboxylic acids with phosphorus trichloride (PCl 3 ), a cheap and readily available industrial chemical (5 equiv.). [13][14][15] We were fascinated by the remarkable potential that one molecule of PCl 3 may possibly produce three molecules of the RCOCl (100% Cl utilization), without producing toxic by-products! Furthermore, since the HP(O)(OH) 2 by-product is sparingly soluble in an organic solvent, the isolation of the acyl chloride product becomes very easy.…”

“…Furthermore, since the HP(O)(OH) 2 by-product is sparingly soluble in an organic solvent, the isolation of the acyl chloride product becomes very easy. Although a few examples of the use of PCl 3 could be found in the literature, 13,[16][17][18][19][20][21][22][23][24] a detailed study on the scope, limitations, and mechanism of the chlorination of carboxylic acids with PCl 3 are clearly desirable.…”