3740-04-3Relevant academic research and scientific papers
Electron-transfer nucleophilic substitution reactions on neopentyl- and phenyl-substituted alkyl chlorides. Effect of the bridge length on the intramolecular electron-transfer catalysis
Duca Jr., Jose S.,Gallego, Mariana H.,Pierini, Adriana B.,Rossi, Roberto A.
, p. 2626 - 2629 (1999)
The nucleophilic substitution reaction of the chlorides RMe2CCH2Cl (R = Me, 4; Ph, 5a; PhCH2, 5b) and their relative reactivities toward diphenyl phosphide ions were studied under irradiation in liquid ammonia. The relative reactivities determined were k5a/k4 ? 9 and k5b/k4 ? 0.85. These reactions are proposed to occur through the SRN1 mechanism. The higher reactivity of 5a is explained on the basis of its higher electron affinity due to the phenyl substitution and the efficient intramolecular electron transfer from this group to the C-Cl σ* bond (intra-ET catalysis). Although 5b also has a phenyl ring, its lower reactivity is ascribed to a decrease in the rate of the intra-ET by elongation of the bridge in one methylene unit. The relative reactivity of 5a versus 5b (k5a/k5b, ? 6.4) is proposed to indicate the ratio of the intra-ET rates of the radical anions of both compounds. AMI calculations performed on the system are in agreement with the experimental results.
Preparation method of alkyl phosphorylated substances
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Paragraph 0023, (2019/10/04)
The invention discloses a preparation method of alkyl phosphorylated substances. According to the invention, alkyl carboxylic acid is used as a starting material, and raw materials are easy to obtain and are various in types. Products prepared by the method disclosed by the invention are various in types and wide in application; and a part of the products can be prepared into important phosphorus ligands and drug key intermediates through simple reduction. In addition, use of high-toxicity phosphine reagents is avoided in the method, the reaction conditions are mild, operation is simple, the yield of the target product is high, pollution is small, and the reaction operation and post-treatment processes are simple, so that the method is suitable for industrial production.
Room temperature, palladium-mediated P-arylation of secondary phosphine oxides
Bloomfield, Aaron J.,Herzon, Seth B.
supporting information, p. 4370 - 4373 (2012/10/29)
We show that a broad range of aryl iodides are efficiently coupled with secondary phosphine oxides using 1 mol % of a catalyst formed in situ from tris(dibenzylideneacetone)dipalladium and Xantphos (1). Scalemic (S)-methylphenylphosphine oxide [(S)-2e] is shown to undergo arylation without detectable stereoerosion. The application of this method to the synthesis of novel P-chiral phosphines and PCP ligands is demonstrated.
Reactions of Neopentyl Bromide with Nucleophiles by the SRN1 Mechanism
Pierini, Adriana B.,Penenory, Alicia B.,Rossi, Roberto A.
, p. 2739 - 2742 (2007/10/02)
The photostimulated reaction of neopentyl bromide (1) with benzenethiolate ion gave neopentyl phenyl sulfide in high yields.The photostimulated reaction of 1 with benzeneselenate ion gave neopentyl phenyl selenide, dineopentyl selenide, and diphenyl selenide but in low overall yields.The photostimulated reaction of 1 with diphenylphosphide and diphenylarsenide ions gave good yields of the substitution products.These reactions are slow in the dark and the photostimulated reactions are inhibited by radical scavengers such as di-tert-butyl nitroxide.All these resultssuggest that 1 reacts with these nucleophiles by the SRN1 mechanism of nucleophilic substitution.
