16053-58-0

Upstream product

• 66-27-3 Methyl methanesulfonate 
• 13133-62-5 thiophenolate 
• 45797-13-5 4-nitrophenylthiolate 
• 18143-34-5 methanesulfonyl trimethylsilyl chloride 
• 62586-48-5 p-Tolylsulfonylmethyl-methansulfonate 
• 130155-90-7 bicyclo<2.1.1>hex-2-yl mesylate 
• 130155-95-2 1-methylbicyclo<2.1.1>hex-2-yl mesylate 
• 130155-94-1 2-cyanobicyclo<2.1.1>hex-2-yl mesylate 
• 109704-41-8 methyl 2-mesyloxybicyclo<2.1.1>hexane-2-carboxylate 
• 109704-42-9 methyl 2-mesyloxybicyclo<2.1.1>hexane-1-carboxylate 
• 80653-57-2 N,O-Dimesyl-N-methylhydroxylamin 
• 51323-71-8 dodecyl mesylate 
• 110-68-9 N-n-butyl-N-methylamine 
• 105551-42-6 (mesyloxyhydroxyiodo)benzene 

Downstream Products

• 50-00-0 formaldehyd 

Relevant academic research and scientific papers

The reduced flavin-dependent monooxygenase SfnG converts dimethylsulfone to methanesulfinate

The biochemical pathway through which sulfur may be assimilated from dimethylsulfide (DMS) is proposed to proceed via oxidation of DMS to dimethylsulfoxide (DMSO) and subsequent conversion of DMSO to dimethylsulfone (DMSO2). Analogous chemical oxidation processes involving biogenic DMS in the atmosphere result in the deposition of DMSO2 into the terrestrial environment. Elucidating the enzymatic pathways that involve DMSO2 contribute to our understanding of the global sulfur cycle. Dimethylsulfone monooxygenase SfnG and flavin mononucleotide (FMN) reductase MsuE from the genome of the aerobic soil bacterium Pseudomonas fluorescens Pf0-1 were produced in Escherichia coli, purified, and biochemically characterized. The enzyme MsuE functions as a reduced nicotinamide adenine dinucleotide (NADH)-dependent FMN reductase with apparent steady state kinetic parameters of Km = 69 μM and kcat/Km = 9 min?1 μM ?1 using NADH as the variable substrate, and Km = 8 μM and kcat/Km = 105 min?1 μM ?1 using FMN as the variable substrate. The enzyme SfnG functions as a flavoprotein monooxygenase and converts DMSO2 to methanesulfinate in the presence of FMN, NADH, and MsuE, as evidenced by 1H and 13C nuclear magnetic resonance (NMR) spectroscopy. The results suggest that methanesulfinate is a biochemical intermediate in sulfur assimilation.

Methanesulfonyl Iodide

Methanesulfonyl iodide is produced in aqueous solutions from the reaction of triiodide with methanesulfinate. Dichroic crystals of (CH3SO2I)4·KI3·2I2 are formed from KI/I2 solutions with high concentrations of CH3SO2-, while dichroic crystals of (CH3SO2I)2·RbI3 are formed from RbI/I2 solutions. X-ray crystallography of these two compounds shows that the CH3SO2I molecules coordinate through their oxygen atoms to the metal cations and that the S-I bond length is 2.44 ?. At low concentrations of CH3SO2-, the solutions remain homogeneous and the sulfonyl iodide is formed in a rapid equilibrium: CH3SO2- + I3- ? CH3SO2I + 2I-, KMSI = 1.07 ± 0.01 M at 25 °C (μ = 0.1 M, NaClO4). The sulfonyl iodide solutions display an absorbance maximum at 309 nm with a molar absorptivity of 667 M-1 cm-1. Stopped-flow studies reveal that the equilibrium is established within the dead time of the instrument (～2 ms). Solutions of CH3SO2I decompose slowly to form the sulfonate: CH3SO2I + H2O → CH3SO3- + I- + 2H+, khyd. In dilute phosphate buffer, this decomposition occurs with khyd = 2.0 × 10-4 s-1 the decomposition rate shows an inverse-squared dependence on [I-] because of the KMSI equilibrium.

Scaled-up electrochemical reactor with a fixed bed three-dimensional cathode for electro-Fenton process: Application to the treatment of bisphenol A

In this study, we report on the development of an open undivided electrochemical reactor with a compact fixed bed of glassy carbon pellets as three-dimensional cathode for the application of electro-Fenton process. Bisphenol A (BPA) was chosen as model molecule in order to improve its efficiency to the treatment of persistent pollutants. The study of the BPA removal efficiency in function of the applied current intensity was investigated in order to determine the limiting current of O2 reduction (optimal conditions of H2O2 production at flow rate of 0.36?m3.h?1) which was 0.8?A (0.5?A/100?g of glassy carbon pellets). Many parameters have been carried out using this electro-Fenton reactor namely degradation kinetics, influence of anodic reactions on DSA, effect of initial pollutant concentration. In the optimal current condition, the global production rate of H2O2 and [rad]OH was investigated. The yield of electro-Fenton reaction (conversion of H2O2 to [rad]OH) was very high (>?90%). The absolute rate of BPA degradation was determined as 4.3?×?109?M?1?s?1. COD, TOC and BOD5 measurements indicated that only few minutes of treatment by electro-Fenton process were needed to eliminate BPA for dilute solutions (10 and 25?mg.L?1). In this case, the biodegradability of the treated solutions occurred rapidly. For higher concentration levels, an efficient removal of BPA appeared for treatment time higher than 1?hour and more than 90?minutes were necessary to obtain the biodegradability of BPA solutions. In optimum conditions, the scale-up of the electrochemical reactor applied to electro-Fenton process was suggested and depended on the concentration level of the pollutant. The operating parameters of the scaled-up reactor might be deduced from the new section of each fixed bed exposed to the flow, from values of liquid flow velocity and from the corresponding limiting current density obtained with the reactor at laboratory scale. The compact fixed bed cathode in an open undivided electrochemical reactor appears as an appropriate solution as pre-treatment electro-Fenton process followed by the biological treatment of persistent pollutant.

Chloride triggered reversible switching from a metallosupramolecular [Pd2L4]4+ cage to a [Pd2L2Cl4] metallo-macrocycle with release of endo- and exo-hedrally bound guests

A metallosupramolecular [Pd2L4]4+ cage can be cleanly converted into a [Pd2L2Cl4] metallo-macrocycle upon addition of chloride ions. The process is reversible, treatment of the [Pd2L2Cl4] macrocycle with silver(i) ions regenerates the [Pd2L4]4+ cage. Additionally, it is shown that guest molecules could be released on chloride triggered cage dis-assembly and taken up anew on re-assembly. This journal is

Photochemical cleavage reactions of 8-quinolinyl sulfonates in aqueous solution

Photochemical cleavage reactions of 8-quinolinyl benzenesulfonate derivatives and related sulfonates in aqueous solutions are reported. The 8-quinolinyl benzenesulfonates undergo photolysis upon photoirradiation at 300-330 nm to give the corresponding 8-quinolinols and benzenesulfonic acids with the production of only negligible amounts of byproducts. The effects of substituent groups of the 8-quinolinyl moiety and the benzene ring on the photolysis reactions were examined. Based on steady-state mechanistic studies using a triplet sensitizer, a triplet quencher, and electron donors, it was suggested that the photolysis proceeds mainly via the homolytic cleavage of S-O bonds in the excited triplet state.

Kinetics of radical heterolysis reactions forming alkene radical cations

Rate constants for heterolytic fragmentation of β-(ester)alkyl radicals were determined by a combination of direct laser flash photolysis studies and indirect kinetic studies. The 1,1-dimethyl-2-mesyloxyhexyl radical (4a) fragments in acetonitrile at ambient temperature with a rate constant of khet > 5 × 109 s-1 to give the radical cation from 2-methyl-2-heptene (6), which reacts with acetonitrile with a pseudo-first-order rate constant of k = 1 × 106 s-1 and is trapped by methanol in acetonitrile in a reversible reaction. The 1,1-dimethyl-2-(diphenylphosphatoxy)hexyl radical (4b) heterolyzes in acetonitrile to give radical cation 6 in an ion pair with a rate constant of khet = 4 × 106 s-1, and the ion pair collapses with a rate constant of k ≤ 1 ± 109 s -1. Rate constants for heterolysis of the 1,1-dimethyl-2-(2,2- diphenylcyclopropyl)-2-(diphenylphosphatoxy)ethyl radical (5a) and the 1,1-dimethyl-2-(2,2-diphenylcyclopropyl)-2-(trifluoroacetoxy)ethyl radical (5b) were measured in various solvents, and an Arrhenius function for reaction of 5a in THF was determined (log k = 11.16-5.39/2.3RT in kcal/mol). The cyclopropyl reporter group imparts a 35-fold acceleration in the rate of heterolysis of 5a in comparison to 4b. The combined results were used to generate a predictive scale for heterolysis reactions of alkyl radicals containing β-mesyloxy, β-diphenylphosphatoxy, and β-trifluoroacetoxy groups as a function of solvent polarity as determined on the ET(30) solvent polarity scale.

Characterization of species present in aqueous solutions of [hydroxy(mesyloxy)iodo]benzene and [hydroxy(tosyloxy)iodo]benzene

Upon solution in water, both [hydroxy(mesyloxy)iodo]benzene and [hydroxy(tosyloxy)iodo]benzene undergo complete ionization to give the hydroxy(phenyl)iodonium ion (PhI+OH) and the corresponding sulfonate ion (RSO2O-) as fully solvated species, i.e., 'free' ions. The phenyliodonium solution species do not form ion pairs with the organosulfonate ions. The hydroxy(phenyl)iodonium ion is presumed to be ligated with at least one water molecule at an apical site of the iodine(m) atom originally occupied by the sulfonate ion. In view of the relative basicities of HO- and H2O, the hydroxy ligand of the [hydroxy(aquo)iodo]benzene ion (PhI+(OH2)OH) is expected to be strongly bound and the water ligand is expected to be weakly bound to the iodine(m) center. This species has a pK(A) at (4.30 ± 0.05). PhI+(OH2)OH and its conjugate base are present in equilibrium with the [hydroxy(auqo)]-μ-oxodiphenyldiiodine cation (Ph(HO)I-O-I+(OH2)Ph). This μ-oxo dimer is present at significant levels even in relatively dilute solutions as the combination equilibrium constant is (540 ± 50). This dimer can be protonated, and the pK(A) of the conjugate acid is ~2.5. The equilibrium constant for dimerization of [oxo(aquo)iodo]benzene (PhI+(OH2)O-), the most important monomer in acidic solutions, is ~8.6.

Relative Reactivities in Aminolysis Reactions of Alkyl Alkenesulfonates

It is found that N-methylbutylamine is ten times more selective than N-methylaniline for the reaction at a methyl group than at a higher alkyl group, and that the greater reactivity of N-methylbutylamine than N-methylaniline is due to differences in entropy of activation rather than differences in activation energy.

Mechanisms of Hydrolysis of (Trimethylsilyl)methanesulfonyl Chloride. Sulfene-Enamine Reactions in Water

Kinetic, product analysis, and deuteration experiments are consistent with the following mechanisms of hydrolysis of (trimethylsilyl)methanesulfonyl chloride (1) (in 0.01 M KCl at 1 deg C): (a) pH /= 10.0, attack of hydroxide anion (i) at silicon to yield sulfene (5) and (ii) at an α-hydrogen to form (trimethylsilyl)sulfene (4), in each case followed by trapping of the sulfene to give either methanesulfonate (3) or (trimethylsilyl)methanesulfonate (6) salts.Aqueous potassium fluoride catalyzes the hydrolysis of 1 with formation of the methanesulfonate 3, evidently by way of silicophilic attack of fluoride anion on 1 with formation of sulfene (5).Reaction of 1 with an enamine 7 in water (at pH 8 or 9), with or without fluoride, gives two characteristic sulfene-enamine products, (i) the four-membered cycloadduct 8 and (ii) the methylsulfonyl aldehyde 9.The same or related products are also obtained from methanesulfonyl, 2-propanesulfonyl, and phenylmethanesulfonyl chlorides and enamines in water (at pH 9).Hydrolysis of 1 is also catalyzed by aniline or triethylamine evidently giving 5.

Rearrangement of Substituted Bicyclohex-2-yl Mesylates Under Solvolytic Conditions

When heated in formic acid, methyl 2-mesyloxybicyclohexane-2-carboxylate (3) ionizes significantly faster than expected and yields the rearranged isomer (6) essentially quantitatively.The latter, on the other hand, solvolyses at a much reduced rate.These data are interpreted as evidnce for the presence in the ester of a favourable mesomeric interaction which largely offsets an otherwise destabillizing inductive effect when the ester is attached to a carbocationic centre.The corresponding cyano mesylates (8) and (29) were found to behave in an analogous manner when exposed to the solvolytic conditions.Heating the related acid mesylate (25) in an aqueous medium leads to the 1,2 hydroxy acid (24), whereas its sodium salt (26) is considerably more reactive and gives the 2,2-hydroxy acid (11).These observations are rationalized on the basis of the greatly enhanced ability of the COO- group relative to a COOH to stabilize an adjacent positively charged centre.The methyl substituent is also found to exert a profound effect on the nature of the solvolysis products, in hot formic acid, for example, 1-methylbicyclohex-2-yl mesylate (31) produces the formate (32) in which the substitution pattern is retained.Under milder conditions, however, the ester (31) solvolyses with rearrangement to give the 2,2-formate (33).