10486-08-5Relevant articles and documents
Nucleophilic Reactivities of Thiophenolates
Jüstel, Patrick M.,Pignot, Cedric D.,Ofial, Armin R.
supporting information, p. 5965 - 5972 (2021/05/04)
The nucleophilic reactivities of substituted thiophenolates were determined by following the kinetics of their reactions with a series of quinone methides (reference electrophiles) in DMSO at 20 °C. The experimentally determined second-order rate constants were analyzed according to the Mayr-Patz equation log k = sN(N + E) to derive the nucleophile-specific reactivity parameters N and sN for ten thiophenolate ions.
NOVEL HETEROCYCLIC COMPOUNDS USEFUL FOR THE TREATMENT OF INFLAMMATORY AND ALLERGIC DISORDERS: PROCESS FOR THEIR PREPARATION AND PHARMACEUTICAL COMPOSITIONS CONTAINING THEM
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Page/Page column 42, (2009/12/24)
The present invention relates to novel Phosphodiesterase type 4 (PDE4) inhibitors of the formula (1) and analogs, tautomers, enantiomers, a diasteromers, regioisomers, stereoisomers, polymorphs, pharmaceutically acceptable salts, appropriate N-oxides, pharmaceutically acceptable solvates thereof and the pharmaceutical compositions containing them which are useful in the treatment of allergic and inflammatory diseases including asthma, chronic bronchitis, atopic dermatitis, urticaria, allergic rhinitis, allergic conjunctivitis, vernal conjunctivitis, eosinophilic granuloma, psoriasis, rheumatoid arthritis, septic shock, ulcerative colitis, Crohn's disease, reperfusion injury of the myocardium and reperfusion injury of the brain, chronic glomerulonephritis, endotoxic shock and adult respiratory distress syndrome.
Nucleophilic Attacks on Carbon-Carbon Double Bonds. 34. Intramolecular Element Effect in Competitive Expulsion of Two Halide Nucleofuges as a Tool for Investigating the Rapid Step of Nucleophilic Vinylic Substitution
Avramovitch, Bianca,Weyerstahl, Peter,Rappoport, Zvi
, p. 6687 - 6697 (2007/10/02)
The substitution of 9-(bromochloromethylene)fluorene (8) and β,β-bis(p-nitrophenyl)-α-bromo-α-chloroethylene (9) by p-toluenethiolate and p-cresolate ions gives the monobromo, the monochloro, and the disubstitution products.The / substitution product ratios were determined in CD3CN, DMSO-d6, and DMSO-d6-CD3OD under conditions where the disubstitution was negligible.The ratios were 2.0-3.2, were slightly higher for 8 than for 9, and showed no discernible solvent dependence.The ratios did not change in the presence of radical traps although an ESR spectrum was observed with 8 and p-MeC6H4S-.The "intermolecular element effects" kBr/kCl derived from competitive substitution of 8 or 9 with their dibromo or dichloro analogues were 1.2-1.76.The results were interpreted in terms of a multistep nucleophilic vinylic substitution proceeding via an intermediate carbanion, which may be formed either directly or by an initial single-electron transfer followed by combination of the anion radical and the radical.The ratios of the products were hence identified as the ratios of the rate constants for expulsion of Br- and Cl- (kel(Br)/kel(Cl)-the "intramolecular element effect") from the carbanion.The low ratios and their relative insensitivity to the solvent and to the delocalizing ability of negative charge of the β-substituents were ascribed to an early transition state for the expulsion of halide ions from the carbanion.Generalizations concerning the expulsion of poor and good nucleofuges from carbanions substituted by poor and good electron-withdrawing groups are discussed.
