109-92-2Relevant articles and documents
Pd(II)-CATALYZED 1,3-ALKYL MIGRATION OF 1-ALKENYL ETHYL ACETALS. PREPARATION OF α-ALKYLATED (E)-α,β-UNSATURATED CARBONYL COMPOUNDS.
Takahashi, Mitsuru,Ishii, Norio,Suzuki, Hiroharu,Moro-Oka, Yoshihiko,Ikawa, Tsuneo
, p. 1361 - 1362 (1981)
Palladium(II) complexes, such as (CH3CN)2PdCl2 and (diene)PdCl2, catalyze 1,3-alkyl migration of 1-alkenyl ethyl acetals and subsequent elimination of ethanol to give α-alkylated (E)-α,β-unsaturated carbonyl compounds in excellent yields.
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Lussi
, p. 1681,1683 (1966)
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Experimental and theoretical study of the 2-alkoxyethylidene rearrangement
Graves, Kimberly S.,Thamattoor, Dasan M.,Rablen, Paul R.
, p. 1584 - 1591 (2011)
The rearrangement of 2-ethoxyethylidene, generated photochemically from a nonnitrogenous precursor, leads to ethyl vinyl ether. Although this product could result, in principle, from a 1,2-hydrogen shift and/or a 1,2-ethoxy shift in the carbene, a deuterium labeling study indicates an essentially exclusive preference for hydrogen migration. The experimental results are in agreement with CCSD and W1BD calculations for the simpler 2-methoxyethylidene system that show a prohibitively large barrier for the methoxy shift and a negligible barrier for the hydride shift. 2011 American Chemical Society.
Generation and Trapping of α,α'-Dioxosulfines from 1,4-Oxathiine-S-Oxides
Capozzi, Giuseppe,Fratini, Paola,Menichetti, Stefano,Nativi, Cristina
, p. 5089 - 5092 (1995)
The 1,4-oxathiine-S-oxides 6 when heated at 60 deg C in CHCl3 undergo a retro Diels-Alder reaction with generation of α,α'-dioxosulfine 8.This reactive intermediate can be trapped by electron rich dienophiles as well as by dienes.In both cases the cycloaddition reactions show interesting stereoselective features.
Infrared Photochemistry of Oxetanes: Mechanism of Chemiluminescence
Farneth, William E.,Johnson, Douglas G.
, p. 773 - 780 (1986)
The infrared multiphoton (IRMP) induced photolysis of several oxetanes is examined at low pressures (ca. 100 mtorr) while experimental variables such as laser frequency, laser energy, bath gas, and bath gas pressure are altered.The products of the IRMP induced photolysis of 2-acyl-3 ethoxy-2-methyloxetane, Ox1, are primarily biacetyl and ethyl vinyl ether.When the photolysis is run with the collimated beam of a CO2 laser (1-3 J/cm2) luminescence is observed.The intensity of the luminescence varies with the efficiency of the unimolecular decomposition of the oxetane.On the basis of the spectral distribution and temporal behavior of the luminescence following irradiation of Ox1, the emitter is believed to be vibrationally hot electronically excited biacetyl.Similar experiments with 2,2-dimethyl-3-ethoxyoxetane give a weaker emission apparently due to excited-state acetone.Results are discussed in terms of the reverse of the Paterno-Buchi reaction - a diabatic retrophotocycloaddition.
Phosphine-Catalyzed Vinylation at Low Acetylene Pressure
Bienewald, Frank,Comba, Peter,Hashmi, A. Stephen K.,Menche, Maximilian,Rominger, Frank,Schafer, Ansgar,Schaub, Thomas,Sitte, Nikolai A.,Tuzina, Pavel
, p. 13041 - 13055 (2021/09/18)
The vinylation of various nucleophiles with acetylene at a maximum pressure of 1.5 bar is achieved by organocatalysis with easily accessible phosphines like tri-n-butylphosphine. A detailed mechanistic investigation by quantum-chemical and experimental methods supports a nucleophilic activation of acetylene by the phosphine catalyst. At 140 °C and typically 5 mol % catalyst loading, cyclic amides, oxazolidinones, ureas, unsaturated cyclic amines, and alcohols were successfully vinylated. Furthermore, the in situ generation of a vinyl phosphonium species can also be utilized in Wittig-type functionalization of aldehydes.
Decomposition of a Β-O-4 lignin model compound over solid Cs-substituted polyoxometalates in anhydrous ethanol: acidity or redox property dependence?
Wu, Xuezhong,Jiao, Wenqian,Li, Bing-Zheng,Li, Yanming,Zhang, Yahong,Wang, Quanrui,Tang, Yi
, p. 1216 - 1228 (2017/07/10)
Production of aromatics from lignin has attracted much attention. Because of the coexistence of C–O and C–C bonds and their complex combinations in the lignin macromolecular network, a plausible roadmap for developing a lignin catalytic decomposition process could be developed by exploring the transformation mechanisms of various model compounds. Herein, decomposition of a lignin model compound, 2-phenoxyacetophenone (2-PAP), was investigated over several cesium-exchanged polyoxometalate (Cs-POM) catalysts. Decomposition of 2-PAP can follow two different mechanisms: an active hydrogen transfer mechanism or an oxonium cation mechanism. The mechanism for most reactions depends on the competition between the acidity and redox properties of the catalysts. The catalysts of POMs perform the following functions: promoting active hydrogen liberated from ethanol and causing formation of and then temporarily stabilizing oxonium cations from 2-PAP. The use of Cs-PMo, which with strong redox ability, enhances hydrogen liberation and promotes liberated hydrogen transfer to the reaction intermediates. As a consequence, complete conversion of 2-PAP (>99%) with excellent selectivities to the desired products (98.6% for phenol and 91.1% for acetophenone) can be achieved.
