ChemInform Abstract: ZUM MECHANISMUS DER RK. DES DIAETHYLCHLORPHOSPHITS MIT ACRYLSAEURE

Abstract

Setzt man Diäthylchlorphosphit (I) in Äther mit Acrylsäure (II) bei 20°C um und arbeitet das Reaktionsgemisch entweder mit Alkohol/Triäthylamin oder mit Triäthylphosphit (VI) auf, dann erhält man im ersten Fall die Verbindung (V), im anderen Fall die Verbindung (VII).

Reactions of halophosphines with conjugated heterodienes

“…Moreover, compounds 56 and 57 do add to each other to give the final product 55, which has been proved in a model reaction. 77,82 Scheme 3 is also consistent with increase in the reaction rate with the increase in the electron-donor ability of the substituents at the phosphorus atom. Finally, which is also proved by kinetic studies, 78 hydrogen chloride, which is always present in the reaction mixture, plays an important role in these reactions.…”

“…It is believed 82 that this scheme involves a preliminary stage of P-protonation of HP by the unsaturated acid 54.…”

“…It is most likely that in this case the reaction follows the same sequence of stages as that discussed for the preceding scheme. 82 54…”

“…Obviously, if acid chlorides 57 contain substituents indicated in the scheme, the addition of ethyl(dichloro)phosphine to compounds 57 occurs very slowly due to both spatial shielding of the b-carbon atom and delocalisation of the electron density on the b-substituent and only these compounds can be isolated from the reaction mixtures. 82 The reaction of dibutyl phosphorochloridite with acrylic acid at a reduced pressure gave only acryoyl chloride. 77 The acids 54 react with methyl phosphorodichloridite to give unsaturated carboxylic acid chlorides 57 and oligomers 60.…”