54815-45-1Relevant articles and documents
Synthesis of Sulfinamidines and Sulfinimidate Esters by Transfer of Nitrogen to Sulfenamides
Andresini, Michael,Spennacchio, Mauro,Romanazzi, Giuseppe,Ciriaco, Fulvio,Clarkson, Guy,Degennaro, Leonardo,Luisi, Renzo
, p. 7129 - 7134 (2020/10/02)
In this work we report a new synthetic tactic for the straightforward preparation of hardly accessible sulfinamidines and sulfinamide esters, by using a simple metal-free protocol. The process is robust and uses readily available sulfenamides as the S-don
Hammett Correlations in the Photosensitized Oxidation of 4-Substituted Thioanisoles
Bonesi, Sergio M.,Fagnoni, Maurizio,Albini, Angelo
, p. 928 - 935 (2007/10/03)
Singlet oxygen is quenched by a series of 4-substituted thioanisoles (methoxy to nitro), with rate constant kt = 7 × 104 to 7 × 106 M-1 s-1, close to the value observed for the myoglobin-catalyzed sulfoxidation of the same sulfides. Correlations with σ (ρ = -1.97) and with Eox (slope -3.9 V-1) are evidence for an electrophilic mechanism. In methanol sulfoxides are formed (85%) via an intermediate quenched by diphenyl sulfoxide; competing minor paths lead to arylthiols, arylsulfenic acid, and aryl sulfoxides. In aprotic solvents, the sulfoxidation is quite sluggish, but carboxylic acids (mostly ≤0.1 M) enhance the rate by a factor of > 100. The protonated persulfoxide is formed in this case and acts as an electrophile with sulfides, again with a rate constant correlating with σ (ρ = -1.78).
Experimental Tests of the Stereoelectronic Effect at Phosphorus: Nucleophilic Reactivity of Phosphite Esters
Taira, Kazunari,Mock, William L.,Gorenstein, David G.
, p. 7831 - 7835 (2007/10/02)
Triethyl phosphite rapidly reacts with ethyl benzenesulfenate or diethyl peroxide to yield pentaethoxyphosphorane.In contrast, 1-methyl-4-phospha-3,5,8-trioxabicyclooctane (1) fails to react with either electrophile to yield the expected bicyclic phosphorane 5.The poor reactivity of the bicyclic phosphite 1 is due to a kinetic rather than a thermodynamic barrier because 5 is formed smoothly from an equimolar mixture of P(OEt)5 and the triol 1,1,1-tris(hydroxymethyl)ethane.This result is interpreted in terms of the stereoelectronic effect.The order of nucleophilic reactivity of trialkyl phosphites with 3-benzylidene-2,4-pentanedione is also shown to be consistent with the stereoelectronic effect.The bicyclic phosphite 1 reacted 750 times slower than the pseudoequatorial 2-methoxy ester of hexahydrobenzo-1,3,2-dioxaphosphorinane in a Michael addition reaction with 3-benzylidene-2,4-pentanedione.
