127905-51-5Relevant articles and documents
Structure and mechanism of hydrolysis of diaryl(acylamino)(chloro)-λ4-sulfanes and diaryl(acylamino)sulfonium salts
Nagy, Peter,Csampai, Antal,Szabo, Denes,Varga, Jeno,Harmat, Veronika,Ruff, Ferenc,Kucsman, Arpad
, p. 339 - 349 (2007/10/03)
Aryl (methylaminocarbonylaryl) sulfides were converted by t-BuOCl to diaryl(acylamino)(chloro)-λ4-sulfanes or the corresponding diaryl(acylamino)sulfonium chlorides depending on the substituent of the S-aryl group. 1H NMR data showed that chloro-λ4-sulfanes exist only in CDCl3 and DMSO-d6 solvents, whereas in CD3OD complete ionic dissociation takes place, leading to sulfonium chlorides. Both the chemical shifts of 1H NMR signals and NOE data suggest that chloro-λ4-sulfanes and sulfonium salts having an o-MeO, o-Cl or o-Me substituent on the phenyl ring assume a skew conformation, whereas the aryl ring in compounds without an ortho-substituent can rotate practically free about the S-C(1') axis. In o-MeO-substituted derivatives there exists an equatorial 1,4 type S...O close contact. Sulfonium salts with axial 1,5 type S...O close contacts involving neighbouring COOMe, CONHMe, COMe or NO2 groups occur in butterfly conformation, like spiro-λ4-sulfanes. There is a correlation between the 15N chemical shift of the amide-nitrogen and the elongation of the S-N covalent bond, by which the interdepending S-N, S-Cl and S...O bonds can be characterized. Effective intermolecular S...O interaction was detected between the sulfonium centre and solvent molecules having a negatively polarized oxygen atom. The hydrolysis of sulfonium salts yielding sulfoxides was investigated by a kinetic method in 98:2 (v/v) dioxane-water mixture and in water. On the basis of medium, substituent (ρ + 1.03), steric, salt and kinetic isotope effects detailed mechanisms involving a hydroxy-λ4-sulfane intrmediate are proposed. The more reactive sulfonium salts with a five-membered hetero ring are hydrolyzed by water, whereas the sulfonium centre of the less reactive analogues with a six-membered ring is attacked only by OH- ions.
POTENTIAL ANTIDEPRESSANTS: 2-(METHOXY- AND HYDROXY-PHENYLTHIO)BENZYLAMINES AS SELECTIVE INHIBITORS OF 5-HYDROXYTRYPTAMINE RE-UPTAKE IN THE BRAIN
Jilek, Jiri,Sindelar, Karel,Pomykacek, Josef,Kmonicek, Vojtech,Sedivy, Zdenek,et al.
, p. 3294 - 3338 (2007/10/02)
2-, 3- and 4-Methoxythiophenol, and 2,4-, 2,5- and 3,4-dimethoxythiophenol were transformed in two steps to the corresponding 2-(methoxyphenylthio)benzoyl chlorides XIII which were reacted with ammonia, methylamine, dimethylamine, diethylamine, dipropylamine, and di(2-propyl)amine to give the amides XIV-XIX.These were reduced mostly with lithium aluminium hydride to the amines II-VII.These methoxylated amines were demethylated mostly either by heating with pyridine hydrochloride or by treatment with boron tribromide.Some of the 2-(methoxy- and hydroxy-phenylthio)benzylamines prepared, especially compounds II, III, XXI, and XXII, indicated properties of potential antidepressants being highly active and selective inhibitors of 5-hydroxytryptamine re-uptake in the brain structures and having the typical antireserpine activity.The most interesting compound of the series is XXIb (hydrogen maleate VUFB-15 468) which is undergoing preclinical studies.On the basis of its structure, some further compounds (XXVII-XXIX, XXXIX-XLI) were prepared by various methods.