22093-99-8Relevant academic research and scientific papers
Regiospecific Synthesis of Allylic Dimethylmethoxysilanes
Tzeng, Dongjaw,Weber, William P.
, p. 693 - 696 (1981)
Photochemically generated dimethylsilylene reacts regiospecifically with allylic methyl ethers to yield allylic dimethylmethoxysilanes.Reaction of allylic methyl ethers with dimethyldichlorosilane and sodium metal likewise gives allylic dimethylmethoxysilanes in preparatively useful yields.Regiospecificity, however, is not always observed in this latter reaction.Such allylic dimethylmethoxysilanes can be converted to allylic trimethylsilanes easily by reaction with methyllithium.
Kinetics and Mechanism of the Gold-Catalyzed Intermolecular Hydroalkoxylation of Allenes with Alcohols
Harris, Robert J.,Carden, Robert G.,Duncan, Alethea N.,Widenhoefer, Ross A.
, p. 8941 - 8952 (2018/09/06)
The mechanism of the hydroalkoxylation of 3-methyl-1,2-butadiene (1) with 1-phenylpropan-1-ol (2) catalyzed by (IPr)AuOTf in toluene has been evaluated through a combination of kinetic analysis, deuterium labeling studies, and in situ spectral analysis of catalytically active mixtures. These data are consistent with a mechanism involving endergonic conversion of (IPr)AuOTf and 1 to the cationic gold π-allene complex (IPr)Au[n2-H2C=C=CMe2][OTf] (5·OTf), which undergoes outer-sphere addition of 2 followed by rapid protodemetalation to form 1-(3-methyl-2-butenyloxy)propyl)benzene (3a) as the kinetic product. The microscopic rate constants associated with the formation and consumption of 5·OTf are of similar magnitude, such that the kinetic behavior of catalytic hydroalkoxylation changes as a function of the relative and absolute concentrations of allene and alcohol.
Reaction of orthoesters with alcohols in the presence of acidic catalysts: A study
Sampath Kumar,Joyasawal, Sipak,Reddy,Pawan Chakravarthy,Krishna,Yadav
, p. 1686 - 1692 (2007/10/03)
Allylic and benzylic alcohols are converted into corresponding unsymmetrical ethers when reacted with various orthoesters in the presence of montmorillonite KSF at ambient temperature. A detailed study has been undertaken to examine the mechanism and generality of these reactions with regard to various acidic catalysts, which reveal interesting competitive reactions mainly O-acetylation, together with trace amount of dimerized product. The type of the side product and their relative quantity depends upon the nature of the catalyst employed. Furthermore, the low yields of the Claisen rearrangement product obtained from allylic alcohols under heating is rationalized due to the formation of some of these products.
Intramolecular rearrangements of but-3-enoic esters
Tsaconas, Michael,Prager, Rolf H.,Millan, David S.
, p. 435 - 437 (2007/10/03)
Support for the proposal by Khalafy and Prager1 of a cheletropic rearrangement of a 6-methylidenecyclohexa-2,4-diene-1-carboxylate under flash vacuum pyrolysis (f.v.p.) conditions has been obtained by a study of the f.v.p. products obtained from methyl 1-methyl-6-methylidenecyclohexa-2,4-diene-1-carboxylate and methyl 2,2-dimethylbut-3-enoate. A significant product in each case arises from a reaction involving decarbonylation and transfer of a methoxy group to C4 (but-3-enoate numbering). CSIRO 2000.
Clay catalyzed highly selective O-alkylation of primary alcohols with orthoesters
Kumar, H. M. Sampath,Reddy, B. V. Subba,Mohanty, Pradyumna K.,Yadav
, p. 3619 - 3622 (2007/10/03)
Montmorillonite KSF catalyzes the selective O-alkylation of various primary allylic and benzylic alcohols when reacted with different orthoesters at room temperature to afford ethers in moderate to high yields.
Synthesis of functionalized 3,3,9,9-tetramethyl-4,8-diazaundecane-2,10-dione dioximes (propylene amine oximes, PnAOs)
Ramalingam,Zeng,Nanjappan,Nowotnik
, p. 743 - 752 (2007/10/02)
The syntheses of several new derivatives of PnAO and their chloronitroso precursors are described. The PnAOs were prepared by an improvement of the reported general procedure. An unexpected product, an isooxalone, was formed while attempting to prepare 1-
PHOTOELECTRON SPECTRA AND MO CALCULATIONS OF ELECTRONIC AND STERIC STRUCTURE OF ALKYL 3-METHYL-2-BUTENYL OXIDES AND SULFIDES
Plemenkov, V. V.,Zverev, V. V.,Balakireva, E. G.,Appolonova, S. A.
, p. 1485 - 1488 (2007/10/03)
He(I) photoelectron spectra of alkyl 3-methyl-2-butenyl oxides and sulfides were measured, and their molecules were calculated by the MNDO method.On the basis of the PE spectra and MO calculations, ionization potentials IP1 and IP2 of the oxides were assigned to ? and n transitions respectively, while for the sulfides the reverse order of the two lowest levels was found.The preferable conformations of all compounds are gauche and trans.Reactivity of 3-methyl-2-butenyl oxides and sulfides toward carbenes is discussed in connection with their electronic structure.
CATALYTIC ACID DEHYDROCHLORINATION OF TERTIARY AND BENZYLIC CHLORIDES
Arakelyan, A. S.,Dvoryanchikov, A. I.,Gevorkyan, A. A.
, p. 1193 - 1196 (2007/10/02)
For the case of a series of tertiary and bezylic chlorides it was shown that elimination by the acid-catalyzed generation of cationoid intermediates is no less effective for the production of olefins than the widely employed alkaline dehydrochlorination.
Detection of C-Nitroso Dimer Formation by Field Desorption Mass Spectrometry
Johnson, R. L.,Lever, O. W.,Brent, D. A.
, p. 36 - 41 (2007/10/02)
Field desorption mass spectrometry is shown to be a useful technique for observing dimer formation in C-nitroso compounds.Mixed dimer formation (RN2O2R') is shown to be readily observed by field desorption mass spectrometry.
