145995-56-8Relevant academic research and scientific papers
The Arbuzov Reaction of Alkyl Diphenylphosphinites with 10-Methylacridinium Ion. Kinetic Study on the Formation and the Decomposition of Phosphonium Intermediates
Yasui, Shinro,Shioji, Kosei,Yoshihara, Masakuni,Maeshima, Toshihisa,Ohno, Atsuyoshi
, p. 2077 - 2083 (1993)
Alkyl diphenylphosphinites (1) react rapidly with 10-methylacridinium iodide (2a) to afford the corresponding phosphonium ions (3), which gradually decompose to phosphine oxide, the expected Arbuzov product. Large difference in the rate of the first (phosphonium-forming) and the second (phosphonium-decomposing) steps enables us independent kinetic investigation for both steps, with which it has been found that the first step obeys second-order kinetics with first-order with respect to 1 and 2a, respectively. The second step proceeds according to either the SN2 mechanism when alkyl substituent in 1 is primary or secondary, in which iodide ion acts as a nucleophile, or the SN1 mechanism when the substituent is tertiary. Closer examination on the first step with activation parameters reveals that the transition state of this step becomes more reactant-like as the substituent in 1 becomes bulkier. For the second step, survey of the activation parameters shows that the breaking of the carbon-oxygen bond in 3 predominates over the formation of the oxygen-phosphorus double bond.
THE THERMAL AND PHOTO-REACTIONS OF DIPHENYLPHOSPHINITE ESTER WITH N-METHYLACRIDINIUM ION
Yasui, Shinro
, p. 197 - 200 (2007/10/02)
The thermal reaction of diphenylphosphinite esters (1b-f) with N-methylacridinium iodide (2) resulted in the formation of a phosphonium ion through a polar process.On the other hand, when isopropyl derivative (1f) was reacted with 2 under the irradiation with visible light, N-methylacridan, along with isopropyl diphenylphosphinate, was formed through single electron transfer (SET) from 1f to 2.
