The mechanism of the isomerisation of dimethyl sulphite to methyl methanesulphonate

Abstract

The isomerisation of dimethyl sulphite to methyl methanesulphonate is catalysed by the methanesulphonate ion. The reaction appears to proceed in two stages. First, dimethyl sulphite alkylates the methanesulphonate ion to form methyl methanesulphonate and methyl sulphite ion. The isomerisation is then completed by the alkylation of the methyl sulphite ion a t the sulphur atom by methyl methanesulphonate.Other anions, which can accept a methyl group to give a strong alkylating agent, also catalyse the reaction.

Reactions of Dimethyl Sulfite with Diorganotin Oxides. One-Pot Synthesis of Methoxydiorganotin Methanesulfonates through the Arbuzov Rearrangement, Spectroscopic Characterization of These Compounds and Their Derivatives, and X-ray Crystal Structures of n-Bu2Sn(X)OS(O)2Me (X = acac, bzbz, OH)

“…This speculation is not favorable, as an isolated reaction between preformed C and dimethyl sulfite under identical conditions (125 °C, 40 h) does not yield compound 2 . Alternatively, the nucleophilic assistance of A and/or B in the transformation of dimethyl sulfite to methyl methanesulfonate at the initial step can be invoked similarly to the rearrangement of dimethyl sulfite by tertiary nitrogen bases, methyl iodide, , etc. The reaction may proceed via an ionic mechanism (Scheme ).…”

“…Dimethyl sulfite also undergoes isomerization (Arbuzov rearrangement) to methyl methanesulfonate in the presence of organic tertiary amines, methyl iodide, etc. Mechanistic studies of such catalyzed processes have also been reported. ,, …”

Synthesis and Structural Studies of Three‐Dimensional Supramolecular Motifs Derived from Neutral and Cationic Zinc Alkanesulfonates

“…[32] An illustrative example highlighting the role of π···π stacking is Cu 2 (bipy) 2 -(O 3 SCH 2 CH 2 SO 3 )·3H 2 O (bipy = 4,4′-bipyridine), the structure of which is composed of linear chains formed by the coordination of metal ions and bipy ligands, whereas the disulfonate anions are bonded electrostatically to the cationic layers. [33] In the past, we have pursued the coordination chemistry of native alkanesulfonates, [RSO 3 ] -(R = Me, Et, nPr), and developed a facile synthetic protocol for the in situ generation of such ligands through the sulfur-centered Arbuzov-type rearrangement of dialkyl sulfites, (RO) 2 SO, following the early work of Brook et al [34][35][36][37] Recently, the method was extended successfully to the synthesis of the new homoleptic zincate salt [Et 4 N] 2 [Zn(OSO 2 Me) 4 ] through the reaction of anhydrous zinc acetate with dimethyl sulfite in the presence of tetraethylammonium iodide. [38] As part of our ongoing studies, we report Scheme (1); R = nPr, R 1 = nBu (2)] are useful precursors for the synthesis of neutral and cationic complexes (3-7; Scheme 1).…”

“…In the past, we have pursued the coordination chemistry of native alkanesulfonates, [RSO 3 ] – (R = Me, Et, n Pr), and developed a facile synthetic protocol for the in situ generation of such ligands through the sulfur‐centered Arbuzov‐type rearrangement of dialkyl sulfites, (RO) 2 SO, following the early work of Brook et al Recently, the method was extended successfully to the synthesis of the new homoleptic zincate salt [Et 4 N] 2 [Zn(OSO 2 Me) 4 ] through the reaction of anhydrous zinc acetate with dimethyl sulfite in the presence of tetraethylammonium iodide . As part of our ongoing studies, we report herein that the analogous zincate salts [R 1 4 N] 2 [Zn(OSO 2 R) 4 ] [R, R 1 = Et ( 1 ); R = n Pr, R 1 = n Bu ( 2 )] are useful precursors for the synthesis of neutral and cationic complexes ( 3 – 7 ; Scheme ).…”

Expanding the Scope of Sulfur-Centered Arbuzov Rearrangement in Diethyl/Di-n-propyl Sulfite for the Synthesis of Mixed-Ligand Di-n-butyltin Alkanesulfonates

“…Nevertheless, the role of alkyl iodide in the present reactions is indeed intriguing and is not completely understood yet. Brook et al have reported that quaternary ammonium iodide also catalyzes Arbuzov rearrangement in dimethyl sulfite to afford methyl methanesulfonate . By analogy, it is thus speculated that the formation of 1 − 4 may follow a mechanism in which the formation of the ion pair similar to that of I is initiated by iodide-ion-promoted C−O bond cleavage in diethyl/di- n -propyl sulfite.…”