145995-55-7

Upstream product

• 719-80-2 Ethyl diphenylphosphinite 
• 948-43-6 N-methylacridinium iodide 
• 13360-94-6 (n-butyloxy)di(phenyl)phosphine 
• 27350-46-5 isopropyl diphenylphosphinite 
• 151484-28-5 1,1-dimethylethyl diphenylphosphinite 
• 67-56-1 methanol 
• 145995-56-8 C₂₉H₂₉NOP⁽¹⁺⁾*I^(1-) 
• 4020-99-9 diphenylphosphinous acid methyl ester 

Downstream Products

• 719-54-0 10-methyl-9, 10-dihydro-9-acridinone 

Relevant academic research and scientific papers

Reacivity of Phosphorus-Centered Radicals Generated during the Photoreaction of Diphenylphosphinous Acid with 10-Methylacridinium Salt

Diphenylphosphinous acid (1) reacts with 10-methylacridinium iodide (2a) in aqueous acetonitrile during irradiation by visible light under an argon atmosphere at 20 deg C to afford diphenylphosphinic acid (3) and 10-methylacridan (4).The effects of the solvent and atmosphere and the effect of added iodide ion (I(1-)) or iodine (I2) on the product distribution show that the mechanism involves initial single-electron transfer (SET) from 1 to 2a in the photoexcited state, by which cation radical 1(1+.) and dihydroacridinyl radical 2(.), are generated.Cation radical 1(1+.) undergoes electrophylic reaction with water in the solvent, and the resulting phosphoranyl radical decomposes through SET to iodine atom (I(.)) rather than unergoing β-scission, eventually giving 3.Protonation to 2(.) followed by reduction by I(1-) affords 4.These reaction sequences make up the catalytic I(.)/I(1-) couple.The results are interpreted on the basis of reported redox potentials.

The thermal- and photo-reactions of a diphenylphosphinite ester with 10-methylacridinium iodide. Discrimination between polar and single electron transfer processes

The thermal-reaction of isopropyl diphenylphosphinite with 10-methylacridinuim iodide results in the formation of a phosphonium ion through a polar process, whereas the reaction under the irradation of light affords 10-methylacridan as well as isopropyl diphenylphosphinate through single electron transfer (SET) from the former to the latter.

THE THERMAL AND PHOTO-REACTIONS OF DIPHENYLPHOSPHINITE ESTER WITH N-METHYLACRIDINIUM ION

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.

The Arbuzov Reaction of Alkyl Diphenylphosphinites with 10-Methylacridinium Ion. Kinetic Study on the Formation and the Decomposition of Phosphonium Intermediates

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.