Reaction Of Methyl Iodide Research Articles

A Facile Synthesis of Aldehyde and Ketone via Senochemical Barbier Reaction and Oxidation

AbstractMethyl ketone is prepared by a sonochemical Barbier reaction of methyl iodide, magnesium powder and aldehyde in Benzene/THF (9/1) solvent in a commercial ultrasonic cleaning bath (39 kHz), followed by the addition of N‐chlorosuccinimide (NCS) as an oxidizing agent.

Metal Basicity of Dirhodium and Diiridium Complexes Induced by Isocyanide Ligands. Model for the Oxidative-Addition Reaction of Methyl Iodide with Dinuclear Complexes

Reactions of [{Rh(μ-Pz)(CNBut)2}2] (1) and the new compounds [{M(μ-L)(CNBut)2}2] (M = Rh, L = SBut; M = Ir, L = pyrazolate (Pz)) with MeI give [{Rh(μ-Pz)(Me)(CNBut)2}2(μ-I)]I (2), [{Rh(μ-SBut)(Me)(CNBut)2}2(μ-I)]I, and [{Ir(μ-Pz)(Me)(CNBut)2}2(μ-I)]I, respectively. The oxidative-addition reactions that occur at each metal center are stereoselective. No differences in reactivity associated with the nature of the metals are observed due to the strong metal basicity induced by the isocyanide ligands. However, the influence of the nature of the metals is evident in the reactions of the mixed-ligand complexes [(cod)M(μ-Pz)2M(CNBut)2] (M = Rh, Ir; cod = 1,5-cyclooctadiene) with MeI to give the mixed-valence Rh(I)−Rh(III) complex [(cod)Rh(μ-Pz)2Rh(Me)(I)(CNBut)2] and the Ir(III) complex [(cod)(Me)Ir(μ-Pz)2(μ-I)Ir(Me)(CNBut)2]I, respectively. The former exists as a mixture of two conformers interconverting through a boat−boat inversion of the six-membered “Rh(Pz)2Rh” ring. The related Rh(I)−Rh(III) isocyanide complex [(CNBut)2Rh(μ-Pz)2Rh(Me)(I)(CNBut)2], which could not be isolated because it rearranges to complexes 1 and 2, reacts with MeI instantaneously and quantitatively to give 2. The nucleophilic character of the metals in 1 is shown by the reaction with MeCF3SO3 to give [{Rh(μ-Pz)(Me)(CNBut)2}2(μ-CF3SO3)]CF3SO3 with stereochemistry identical to that of 2. The structures of the complexes [{Rh(μ-Pz)(Me)(CNBut)2}2(μ-X)]CF3SO3 (X = I, CF3SO3), have been determined by X-ray diffraction and show discrete dimethyl dinuclear cationic complexes triply bridged by two pyrazolate groups and an iodo or monodentate triflate ligand.

Spectroscopic Evidence for Methyl Spillover on Silica-Supported Copper Catalysts

Fourier transform infrared spectroscopy has been used to investigate the bonding and chemistry of methyl groups, from the dissociative adsorption of methyl iodide, adsorbed on silica-supported copper catalysts. After reaction of methyl iodide on Cu/SiO 2 at room temperature, the infrared data show the presence of at least two different types of adsorbed methyl groups that differ in their thermal stability. The data suggest that methyl iodide initially dissociates on the Cu surface to form methyl groups and iodine atoms. Some of the methyl groups remain adsorbed on the copper particles whereas others migrate, or spillover, on to the nearby support where they react with SiOH to form SiOCH 3 . This is the first study to provide spectroscopic evidence for alkyl group spillover on an oxide-supported metal catalyst. Spillover of alkyl fragments has important implications for hydrocarbon catalysis.

The reactions of some sulfur compounds in water supplies in Perth, Australia

Some residents of Perth, Australia, receiving treated groundwater have complained of intermittent swampy, cooked vegetable odours in their drinking water. The compound primarily responsible is dimethyl trisulfide (CH3SSSCH3) which can be formed in the laboratory from the reaction of methyl iodide with thiosulfate (in the presence of iodine or sulfide) or with polysulfide (Sn2−). Addition of chlorine or sulfide to pre-formed S-methylthiosulfate (produced from the reaction of methyl iodide with sodium thiosulfate) at concentrations possibly expected in water supplies did not produce the swampy odour or only formed it slowly. Dimethyl trisulfide was formed upon the addition of methyl iodide to samples from each water supply system examined, even from those not prone to the formation of swampy odour, suggesting each contained polysulfide. Polysulfides and the reducing agents sodium oxalate, sodium borohydride and sodium thiosulfate reacted with dimethyl trisulfide in solution, removing 50-100% of that originally present.

The reactions of some sulfur compounds in water supplies in Perth, Australia

Some residents of Perth, Australia, receiving treated groundwater have complained of intermittent swampy, cooked vegetable odours in their drinking water. The compound primarily responsible is dimethyl trisulfide (CH3SSSCH3) which can be formed in the laboratory from the reaction of methyl iodide with thiosulfate (in the presence of iodine or sulfide) or with polysulfde (Sn2−). Addition of chlorine or sulfide to pre-formed Smethylthiosulfate (produced from the reaction of methyl iodide with sodium thiosulfate) at concentrations possibly expected in water supplies did not produce the swampy odour or only formed it slowly. Dimethyl trisulfide was formed upon the addition of methyl iodide to samples from each water supply system examined, even from those not prone to the formation of swampy odour, suggesting each contained polysulfide. Polysulfides and the reducing agents sodium oxalate, sodium borohydride and sodium thiosulfate reacted with dimethyl trisulfide in solution, removing 50-100% of that originally present.

Synthesis, Structure of Nitrogen‐ContainingPhosphinogold(I) Ferrocenes. In vitro Activity against Bladder andColon Carcinoma Cell Lines

The gold salt [(tht)AuCl] was reacted with [1-N,N-dimethylaminométhyl-2-diphenylphosphino]ferrocene (1) forming the bimetallic derivative 4. The reaction of methyl iodide and tetramethylammonium bromide on the chloride 4 produced the ammonium salt 5 and the bromide 6 respectively. New aminophosphines 2 and 3, which represent two of the rare phosphorylated metallocenes containing P(III)-N bond have also been coordinated to gold(I) to form 7 and 8. The presence of the ethoxy group in 7 provides evidence for the lability of one nitrogen-phosphorus bond. The X-ray structure of compounds 4 and 7 have been established. Both crystallize in space group P21/c, monoclinic, with a = 11.095(2) Å, b = 12.030(3) Å, c = 17.763(4) Å, β= 94.02(2)∘, Z = 4 for 4 and a = 14.863(3) Å, b = 8.036(5)Å, c = 18.062(5)Å, β =101.64(1)°, Z = 4 for 7. 197Au Mössbauer data are in good agreement with those for other linear P-Au-Cl containing complexes. The compounds were evaluated for in vitro anti-tumour activity against two human tumours. Differential cytotoxicity was observed with activity comparable to cisplatin, with the exception of one compound which was significantly more cytotoxic.

A Study of the Thermal Reactions of Methyl Iodide Coadsorbed with Hydrogen on Ni(111) Surfaces: Hydrogenation of Methyl Species to Methane

Chemistry on solid surfaces is central to many areas of practical interest such as heterogeneous catalysis, tribology, electrochemistry, and materials processing. With the development of many surface-sensitive analytical techniques in the past decades, great advances have been possible in our understanding of such surface chemistry at the molecular level. Earlier studies with model systems, single crystals in particular, have provided rich information about the adsorption and reaction kinetics of simple inorganic molecules. More recently, the same approach has been expanded to the study of the surface chemistry of relatively complex organic molecules, in large measure in connection with the selective synthesis of fine chemicals and pharmaceuticals. In this report, the chemical reactions of organic molecules and fragments on solid surfaces, mainly on single crystals of metals but also on crystals of metal oxides, carbides, nitrides, phosphides, sulfides and semiconductors as well as on more complex models such as bimetallics, alloys, and supported particles, are reviewed. A scheme borrowed from the organometallic and organic chemistry literature is followed in which key examples of representative reactions are cited first, and general reactivity trends in terms of both the reactants and the nature of the surface are then identified to highlight important mechanistic details. An attempt has been made to emphasize recent advances, but key earlier examples are cited as needed. Finally, correlations between surface and organometallic and organic chemistry, the relevance of surface reactions to applied catalysis and materials functionalization, and some promising future directions in this area are briefly discussed.

SYNTHESIS OF N-(HYDROGEN METHYLPHOSPHONOTHIONYL), N-(O-METHYL METHYLPHOSPHONOTHIONYL) AMINO ACID METHYL ESTERS AND THEIR ANTIMICROBIAL ACTIVITIES

Abstract The synthesis of some N-(hydrogen methylphosphonothionyl) amino acid methyl esters (II-VII) and N-(O-methyl methylphosphonothionyl) amino acid methyl esters (VIII-XIII) is described. Reaction of methyl iodide with compounds (II-XIII) afforded the corresponding methyl iodide quaternary salt derivatives (XIV-XXV). All the synthesized compounds were found to possess high and moderate antimicrobial activities towards a number of microorganisms.

Catalytic Effect of Silver-Impregnated Silica-Gel (AgS) on Reaction of Methyl Iodide with Nitrogen Dioxide.

(1994). Catalytic Effect of Silver-Impregnated Silica-Gel (AgS) on Reaction of Methyl Iodide with Nitrogen Dioxide. Journal of Nuclear Science and Technology: Vol. 31, No. 1, pp. 86-87.

Catalytic Effect of Silver-Impregnated Silica-Gel (AgS) on Reaction of Methyl Iodide with Nitrogen Dioxide

Catalytic Effect of Silver-Impregnated Silica-Gel (AgS) on Reaction of Methyl Iodide with Nitrogen Dioxide

Ion chromatographic analysis of the purity and synthesis of sulfonium and selenonium ions

The use of single-column ion chromatography with conductometric detection was shown to be useful for the analysis of sulfonium and selenonium ions. A Hamilton PRP X-200 cation column was eluted with either solvent A (5 m M nitric acid in 30% methanol) or solvent B (4 m M nitric acid). With solvent B, trimethylsulfonium ion was separated from trimethylselenonium ion. With solvent A, amounts of trimethylsulfonium ion from 2 to 250 nmol were detected with a linear response. The retention times and response factors for a series of sulfonium ions with various organic groups were determined. In general the ions with more hydrophobic groups eluted later, but all had similar response factors. The method was shown to be useful for optimizing conditions for the synthesis of methylsulfonium ions, specifically the reaction of methyl iodide with diallyl sulfide.

A Detailed Procedure for the Preparation of 1,3-Pentadiyne

Abstract 1,3-Pentadiyne, HC≡CC≡C-CH3, has been prepared with yields up to 78% by reaction of methyl iodide with sodium diacetylide, prepared in situ from 1,4-dichloro-2-butyne and three equivalents of sodamide in liquid ammonia.

Selectivity in reductive elimination from dialkyl(aryl)palladium(IV) complexes, and the observation of benzyl halide transfer from palladium(IV) to palladium(II). The X‐ray structure of methyl(phenyl)(2,2′‐bipyridyl)palladium(II)

AbstractThe first arylpalladium(IV) complexes, [PdXMePhR(bpy)] (bpy = 2,2′‐bipyridyl), have been isolated upon oxidative addition of methyl iodide or benzyl bromide to [PdMePh(bpy)]. These dialkyl(aryl)palladium(IV) complexes undergo reductive elimination in solution at ca. 0 °C: [PdBrMePh(CH2Ph)(bpy)] decomposes quantitatively into [PdBr(CH2Ph)(bpy)] and toluene whereas [PdIMe2Ph(bpy)] gives ethane and toluene in 4: 1 ratio together with the corresponding complexes [PdIR(bpy)] (R = Me or Ph). The reaction of methyl iodide with [PdMePh(tmeda)] at 0 °C yields ethane and [PdIPh(tmeda)] without detection of a palladium(IV) intermediate. No reaction of [PdMePh(tmeda)] with benzyl bromide was observed. The first demonstration that organic groups can be transferred from palladium(IV) to palladium(II) is reported. The molecular structure of [PdMePh(bpy)] in the solid state has been determined.

Reaction of methanol with hydriodic acid as a step of the CIS process

The reaction of methanol with hydriodic acid to produce methyl iodide was studied as a step of the CIS Process. The yield of methyl iodide increased with increasing iodine concentration. Following methyl iodide formation and activity decrease of hydriodic acid, dimethyl ether was formed by the reaction of methyl iodide and methanol. The dimethyl ether formation was accelerated by iodine. The co-existence of iodine and sulfuric acid caused no other side reactions. The separation of methyl iodide from the reaction mixture by distillation was discussed briefly.

Significance test of refractive index of solvent in evaluation of effect of medium on rates of quaternization reactions of methyl iodide with amines

The rate constants have been measured of the reactions of methyl iodide with triethylamine (I) and tributylamine (III) at 293 K in twelve aprotic solvents, methyl iodide with tripropylamine (II) at 293, 313, 323, and 333 K in fifteen solvents differing greatly in their dipole moments, relative permittivities, and refractive indexes, and diiodomethane with tripropylamine in diiodomethane at 293 K (k1 = 2.1 10-5 s-1). The aprotic solvents predominantly affect the activation entropy which for the reaction of II varies from -200 J mol-1 s-1 (in cyclohexane) to -108 J mol-1 s-1 (in diiodomethane). The activation enthalpy of the reaction of methyl iodide with tripropylamine (II) is only little affected by aprotic solvents, a significant increase in activation enthalpy has been observed in the case of amphiprotic solvents. The evaluation of effect of medium on the rate constants of the above-mentioned reactions by means of the Kirkwood functions of relative permittivity and refractive index has shown a significant contribution of the refractive index of solvent which is comparable with the effect of relative permittivity.

ChemInform Abstract: The Organic Chemistry of Platinum(IV)

Publisher Summary This discusses the salient discoveries made recently in the organic chemistry of platinum(IV). Investigations on monoorganoplatinum(IV) compounds are scanty, probably because of the absence of straightforward preparative methods and also because of their poor solubilities in organic solvents. Bromination of platinum(II) complexes having amine, tertiary phosphine, or arsine ligands containing at least one olefinic group often yields metallated platinum(IV) complexes. The first diorganoplatinum(IV) compound, [PtMe 2 I 2 ] n , was isolated by treating [PtCl 6 ] 2– with methylmagnesium iodide in diethyl ether. The isomers containing a water molecule trans to a methyl group are labile and crystallize from the solution as [PtMe 2 (X)(gly)] 2 (X = Br) species. The reaction of alkyl iodides with cis-[Pt(tol) 2 ,(py) 2 ] is accompanied by the displacement of a tolyl group and the formation of diorganoplatinum(IV) complexes. The reaction of methyl iodide with mercapto-bridged dinuclear platinum(II) complexes, [Pt(μ-SMe)R(PMe 2 Ph)] 2 (R=Me, Ph), involves dinuclear platinum(IV) intermediates, which ultimately yield mononuclear platinum(II) or (IV) complexes, depending on the nature of R. Nitrous oxide was the only gaseous product formed during the reaction. Pyrolysis of dimethylplatinum(IV) compounds yields methyl halide or ethane, depending on the configuration of the complex. Halides, pseudohalides, and related compounds are among the best known organoplatinum(IV) derivatives. Trimethylplatinum halides and pseudohalides are tetrameric in the solid state as well as in solution. Oxidative addition of chlorine to platinum(II) carbene complexes affords the corresponding platinum(IV) compounds when the carbene ligand contains only alkyl groups.

Preparation and physico-chemical properties of bis(salicylaldehyde hydrazonato)-iron(III), manganese(III) and chromium(III) iodides

Bis(salicytaldehyde hydrazonato)iron(llI) iodide has been prepared by reduction of tris(salicylaldehyde hydrazonato)iron(III) with hydrazine in dimethylformamide solution followed by reaction with methyl iodide. This reaction has been shown to involve an iron(I) chelate intermediate. Reaction of bis(salicylaldehyde hydrazonato)iron(II) with iodine in dimethylformamide solution also leads to formation of bis(salicylaldehyde hydrazonato)iron(III) iodide. The reaction of methyl iodide with a dimethylformamide solution of bis(salicylaldehyde hydrazonato)manganese(II) and hydrazine leads to the formation of bis(salicylaldehyde hydrazonato)- manganese(III) iodide which can also be obtained by reaction of the manganese(II) chelate with iodine. The reduction pathway has been shown to involve the formation of a manganese(O) hydrazine chelate while the use of hydroxylamine, sodium borohydride and sodium dithionite for the reduction of the manganese(II) chelate lead to the formation of a manganese(i) intermediate. Bis(salicylaldehyde hydrazonato)chromium(III) nitrate forms as a result of the reaction of hydrated chromium(III) nitrate with salicylaldehyde hydrazone in dimethylformamide and has been used to prepare the corresponding iodide, chloride, bromide, thiocyanate and cyanide by anion exchange reactions in dimethylformamide. Each product has been characterized by the observation of well resolved ESR spectra.

Preparation and properties of acetyliodotricarbonylcobaltate; a novel product from the reaction of methyl iodide with tetracarbonylcobaltate

The reaction of PPN[Co(CO) 4] with an excess of methyl iodide in THF at 0°C gives almost quantitatively PPN[Co(CO) 3{C(O)CH 3})I], which has been shown by X-ray crystallography and spectroscopic measurements to adopt a trigonal bipyramidal structure with three carbonyls in the equatorial plane; it reacts with hydrogen or with sulfuric acid to give acetaldehyde, and with methanol/pyridine to give methyl acetate. The new anion is of interest as a potential intermediate in the cobalt/iodine catalyzed carbonylation or hydrocarbonylation of methanol.

Orientational opacity function for CH3I+Rb reactive backscattering: The steric cone of nonreaction

An improved orientational opacity function is obtained for the reaction of methyl iodide with Rb. This opacity function (i.e., the reaction probability as a function of the ‘‘angle of attack’’ γ) results from an improved deconvolution (for the precessional effect) of the reactive backscattering data of Parker et al. (1981) at a collision energy of 13 kJ mol−1. From this opacity function, the cut-off angle of the steric cone blocked out by the methyl group in the course of a reactive encounter is found to be 53±2°. This is larger than the best previous estimate, and quite comparable with that predicted from a simple steric model. The shape of the orientational opacity function is well represented by the nonspherical rigid-body approximation formula of Evans et al. (1985), with a value of the colliding-pair anisotropy parameter of λ=0.41±0.01 and a cut-off angle of 50±2°.

1,2-Methyl shift between platinum and the coordinated aryl group in the reaction of methyl iodide with 2,6-bis[(dimethylamino)methyl]phenyl-N,N',C complexes of platinum(II). X-ray crystal structure of the arenonium-platinum compound [Pt(o-tolyl)(MeC6H3(CH2NMe2)2-o,o')

1,2-Methyl shift between platinum and the coordinated aryl group in the reaction of methyl iodide with 2,6-bis[(dimethylamino)methyl]phenyl-N,N',C complexes of platinum(II). X-ray crystal structure of the arenonium-platinum compound [Pt(o-tolyl)(MeC6H3(CH2NMe2)2-o,o')