¹H and ¹³C NMR study of substituent effects in 2‐ and 3‐substituted diphenyl sulphides and sulphones and 4‐substituted 2′,6′‐dimethyldiphenyl sulphides

Abstract

The proton and carbon NMR spectra of nine 2-substituted diphenyl sulphides (SZX), seven 3-substituted diphenyl sulphides (S-3-X), nine 2-substituted diphenyl sulphones (S02-2-X), nine hubstituted diphenyl sulphones (SO2-% X) and nine 4-substituted-2',6'-dimethyldiphenyl sulphides (Me2-S-4-X) were obtained. Correlations of the 'H and I3C chemical shifts were made with benzene substituent-induced chemical shifts (Lynch plots) and Hammett and dual-substituent parameters and the results were compared with those of 4-substituted diphenyl sulphides (S4-X) and sulphones (S02-4-X). The main conclusions are as follows: (i) the transmission of the substituent effects in substituted diphenyl sulphides decreases in the order S-4-X x S-2-X > Me,SQX > S-3-X; (ii) the inductive effects are transmitted to a larger extent than the resonance effects to the unsubstituted ring in Isubstituted diphenyl sulphides, while the reverse trend is observed in other substituted diphenyl sulphides; (iii) in 2-methoxy-, khloro-, 2-bromo-and 2-nitrodiphenyl sulphides, an increase in the size of the substituent causes an upfield shift for H d ascribable to the repulsion between the lone pairs of electrons on the sulphur and the substituent and its influence on the conformation; (iv) the diminished transmission of substituent effects to the remote rings in 4-substituted 2',6'-dimethyldiphenyl sulphides is probably due to the orthogonal orientation of the rings; and (v) the signal due to the H-6 of 2-substituted diphenyl sulphones suffers a downfield shift with an increase in the size of the substituent, this being ascribable to the increasing steric interaction between the 2-substituent and the sulphonyl oxygen and consequent changes in the conformation.

1‐D‐Tin(II) Phenylchalcogenolato Complexes ∞1[Sn(EPh)2] (E = S, Se, Te) – Synthesis, Structures, Quantum Chemical Studies and Thermal Behaviour

“…The cleavage products of the thermolysis of 1 under N 2 atmosphere could by careful condensation be almost completely separated in a yellow crystalline powder and a pale yellow liquid. However apart from the identification of the liquid main product SPh 2 by NMR37,38 it was not possible to clearly identify the other compounds (see experimental section). In contrast, for the thermolysis of 1 under vacuum conditions only the formation of a light yellow solid precipitate on the walls of the glass tube outside the furnace is observed which is identified by powder XRD to consist mainly of 1 (Figure 8).…”

Influence of the Morphology of Lithiated Copper(I) Sulfides with the Formal Composition “Li2Cu4S3” on Their Stability in Electrochemical Cycling

“…The 1 H and 13 C NMR spectroscopic data of the volatile cleavage products, which were collected in a cool trap, reveal the almost clean cleavage of either dme or diglyme along with the formation of SPh 2 under vacuum conditions, [18,19] which confirms in principle the decomposition reaction in Scheme 2 (see Experimental Section). The formation of SR 2 and metal sulfides is a well-established decomposition pathway for group 12 metal thiolates M(SR) 2 (M = Zn, Cd).…”

Magnetically Separable Copper Ferrite Nanoparticles‐Catalyzed Synthesis of Diaryl, Alkyl/Aryl Sulfones from Arylsulfinic Acid Salts and Organohalides/Boronic Acids

“…2‐(Phenylsulfonyl)benzaldehyde (3g): [ 45b] White solid; yield: 202 mg (82%); mp 90–92 °C (Lit 45b. 92.0–93.5 °C).…”