Allyl Methyl Ether Research Articles

Ion–molecule reactions of fragment ions derived from protonated allyl methyl ether

AbstractUnusual behaviour has been noted for allyl methyl ether (1) chemically ionized in a high‐pressure ion source. Tandem mass spectrometry indicates the formation of methylcyclopentadienyl and methoxy‐1‐propenylcarbenium ions (d, m/z 81 and e, m/z 85). The origin of these unexpected ions has been elucidated using conventional and Fourier transform ion cyclotron resonance experiments: primary fragment ions derived from protonated 1 (allyl ions a and methoxymethyl cations b) generate collision complexes with neutral 1, giving rise to the ions d and e, respectively, after methanol elimination.

Diastereoselective [2,3] Wittig rearrangement of tertiary α-lithio ethers

Tertiary allylic methyl(tri-n-butylstannyl) ethers undergo transmetallation and subsequent diastereoselectve [2,3] Wittig rearrangement, wherein chirality transfer and olefin selectivity for the [2,3] sigmatropic event is mediated by a stereogenic center external to the sigmatropic framework.

Facile catalytic methods for intermolecular generation of allylic oxonium ylides and their stereoselective [2,3]- sigmatropic rearrangement

Allylic oxonium ylides, generated by rhodium(II) acetate-catalyzed decomposition of diazo carbonyl compounds in the presence of allyl methyl ethers, undergo the [2,3]-sigmatropic rearrangement with a high degree of diastereoselectivity.

ChemInform Abstract: An Effective Activation of Allyl Methyl Ethers by a Catalytic Amount of Trityl Perchlorate in the Allylation of Silyl Enol Ethers.

AbstractThe methoxy allyl derivatives (I) react with the silylenol ethers (II) in the presence of trityl perchlorate to yield the isomeric adducts (III) and (IV).

AN EFFECTIVE ACTIVATION OF ALLYL METHYL ETHERS BY A CATALYTIC AMOUNT OF TRITYL PERCHLORATE IN THE ALLYLATION OF SILYL ENOL ETHERS

Abstract In the presence of a catalytic amount of trityl perchlorate, secondary and tertiary allyl methyl ethers smoothly react with silyl enol ethers to afford the corresponding γ,δ-unsaturated carbonyl compounds in good yields. By the combination of this reaction with the trityl perchlorate catalyzed allylation of acetals γ,δ-unsaturated ketones are synthesized from α,β-unsaturated acetals by a one-pot procedure.

Stereoselective coordination of the vinylic ligand in cis-dichloro( p-toluidine) (olefin)platinum(II) complexes

Variable temperature 1H NMR studies on cis-dichloro( p-toluidine) (olefin)platinum(II) complexes have shown that the coordination of the olefin ligand is completely stereoselective, only one stereoisomer being present in solution. Steric repulsive interactions determine the conformational arrangement of the ligands in the complexes containing simple α-olefins, namely 1-butene and 4,4′-dimethyl-1-pentene. Attractive interactions involving the formation of an intramolecular hydrogen bond predominate over the repulsive steric interactions in the case of the complexes containing unsaturated ethers, viz. t-butyl vinyl ether, ( Z)-1-ethoxy-1-propene and methyl allyl ether.

Cumulene photochemistry: photoaddition of neutral methanol to phenylallenes

Ultraviolet irradiation of tetra-, tri-, or diphenylallene in methanol leads to allylic methyl ethers. A mechanism is proposed with intermediacy of a strongly polarized planar allene excited state, initially protonated at C 2.

Iron catalysis of grignard reductions. Mechanism of 1, 3-reductive eliminations from γ-propyl halides

The iron-catalyzed reduction of various 3-substituted propyl bromides by Grignard reagents affords propylene and cyclopropane. The reduction to propylene is particularly noteworthy since it formally represents a 1, 2-hydrogen shift. Two key intermediates have been identified in propylene formation, in which 3-methoxypropyl bromide is first catalytically reduced to the magnesium derivative by Grignard reagent. The iron-catalyzed β-elimination of the 3-methoxypropylmagnesium intermediate affords allyl methyl ether, which is then reduction cleaved to propylene. Extensive studies of deuterium labeling in the reactants, as well as in both intermediates, allow the course of the hydrogen shift to be followed unequivocally. The mechanism of iron catalysis is proposed in Scheme 2 and 3, representing the first and second stages of the reduction to propylene.

Reaction of allylic and benzylic methyl ethers with sodium and trimethylchlorosilane. Evidence for the intermediacy of allylic radicals and anions

Reaction of allylic and benzylic methyl ethers with sodium and trimethylchlorosilane. Evidence for the intermediacy of allylic radicals and anions

Reactions of alkynes with [Os3(CO)11(NCCH3)]: the crystal structures of [Os3(CO)9(C3H2OH)H] and [Os3(CO)9(C3H2OCH3)H

The reaction of [Os3(CO)11(NCCH3)] with hydrous C2H2, CH3CCH, or PhCCH yields, as the major product, [Os3(CO)9(RC3H2O)H](R = H, CH3, or C6H5). The backbone of the organic ligand, an allyl alcohol, is formed from an alkyne molecule and a CO ligand from the cluster. It bonds to a face of the triangular cluster through two σ bonds and one π-allyl bond. The complexes exist in two isomeric forms which have not been separated. The complex [Os3(CO)9(C3H2OH)H] crystallizes in space group Pbca with a= 16.291(5), b= 16.861(5), c= 12.234(3)Å, and Z= 8. Its structure has been solved by a combination of direct methods and Fourier-difference techniques, and refined by full-matrix least squares to an R of 0.060 for 1 327 diffractometer data. Both isomers co-crystallize in this complex, and the structure shows that the organic ligand is disordered, preventing an assessment of the nature of the isomers. Conversion of the allyl alcohol ligand into an allyl methyl ether has allowed the determination of one of the isomers. Thus [Os3(CO)9(C3H2OCH3)H] crystallizes in space group P21/n with a= 6.975(3), b= 30.960(6), c= 8.695(4)Å, β= 107.62(2)°, and Z= 4. Its structure has been solved by a combination of direct methods and Fourier-difference techniques, and refined by full-matrix least squares to an R of 0.053 for 1 671 diffractometer data. The two isomers in the [Os3(CO)9(RC3H2O)H] molecules are thought to be due to restricted rotation about the C–O bond of the alcohol, giving rise to two possible orientations for the O–H proton. Only one of these orientations is accessible to the allyl methyl ether derivative.

ChemInform Abstract: A NOVEL METHOXYLATION OF ALLYLIC ALCOHOLS VIA ALLYLIC REARRANGEMENT USING DICHLOROBIS(TRIPHENYLPHOSPHINE)PLATINUM(II)‐TIN(II)CHLORIDE DIHYDRATE COMPLEX CATALYST

Several allylic steroidal alcohols give rearranged allyl methyl ethers by dichlorobis(triphenylphosphine)platinum(II)–tin(II)chloride dihydrate complex catalyst in methanol.

A NOVEL METHOXYLATION OF ALLYLIC ALCOHOLS VIA ALLYLIC REARRANGEMENT USING DICHLOROBIS(TRIPHENYLPHOSPHINE)PLATINUM(II)-TIN(II)CHLORIDE DIHYDRATE COMPLEX CATALYST

Abstract Several allylic steroidal alcohols give rearranged allyl methyl ethers by dichlorobis(triphenylphosphine)platinum(II)–tin(II)chloride dihydrate complex catalyst in methanol.

ChemInform Abstract: A Convenient Method for the Preparation of Olefins by Reductive Demethoxylation of Allyl Methyl Ethers Using TiCl4‐LiAlH4.

AbstractMit dem aus Titantetrachlorid durch Lithiumaluminiumhydrid‐Reduktion hergestellten Titan‐Reagens werden die Allylmethyl‐äther (I) in die Olefine (II) umgewandelt.

Unimolecular decomposition of chemically activated methylallylether

AbstractThe unimolecular decomposition of chemically activated methylallylether (MAE) formed by the cross combination of methoxymethyl and vinyl radicals was studied in the gas phase. The experimentally determined rate constant was found to be 1.11 × 108 sec−1 at 9.6°C for the decomposition of MAE into propene and formaldehyde. The decomposition of MAE via the six‐center retro‐“ene” type transition state is analyzed by using the RRKM unimolecular reaction theory. For the molecular parameter assignments of energized MAE, a model which contains one internal rotational mode is supported, and MAE decomposition is characterized by a tight complex model. The best agreement between experimental and theoretical results was found when a critical energy of 40.1 kcal/mol was used.

Ätherspaltungen mit magnesium : III. Kriterien für die spaltbarkeit von thioäthern

Only 7 out of 25 thioethers investigated were attacked by magnesium in boiling tetrahydrofuran. It seems that the presence of a thiophenyI group in combination with an sp 2 carbon atom in the β-position on the other side of the sulfur atom is necessary for cleavability. Allyl methyl sulfide, in contrast to allyl methyl ether, is not cleaved. The cleavable thioethers, on the other hand, react faster than the corresponding oxygen ethers. In order to explain the selective cleavability of the thioethers under investigation it is assumed that the sulfur atom while partially positive by resonance with the phenyl ring attracts electrons interacting with the α,β- or β,γ-π electron systems, respectively. The rate-determining step of the reaction is the electron transfer from the magnesium to the thioether followed by detachment of the unsaturated group from the sulfur, presumably as a radical. The stability of the finally by another electron transfer formed organomagnesium compound therefore has no influence on the cleavability of the thioethers.

A CONVENIENT METHOD FOR THE PREPARATION OF OLEFINS BY REDUCTIVE DEMETHOXYLATION OF ALLYL METHYL ETHERS USING TiCl4–LiAlH4

Abstract The reductive demethoxylation of allyl methyl ethers using TiCl4–LiAlH4 afforded various olefins in good yields accompanied with double bond migration.

Halomethyl metal compounds. XXXIX. Reactions of phenyl(trihalomethyl)mercury-derived dihalocarbenes with cyclic allylic alcohols, acetates, and methyl ethers

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTHalomethyl metal compounds. XXXIX. Reactions of phenyl(trihalomethyl)mercury-derived dihalocarbenes with cyclic allylic alcohols, acetates, and methyl ethersDietmar Seyferth and Virginia A. MaiCite this: J. Am. Chem. Soc. 1970, 92, 25, 7412–7424Publication Date (Print):December 1, 1970Publication History Published online1 May 2002Published inissue 1 December 1970https://doi.org/10.1021/ja00728a027RIGHTS & PERMISSIONSArticle Views546Altmetric-Citations20LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (1 MB) Get e-Alerts Get e-Alerts