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.
Isomerization and Decomposition of 2,3-Dimethyloxirane. Studies with a Single-Pulse Shock Tube
Lifshitz, Assa,Tamburu, Carmen
, p. 10251 - 10260 (1995)
The isomerizations and decompositions of cis- and trans-2,3-dimethyloxirane were studied behind reflected shocks in a pressurized driver single-pulse shock tube over the temperature range 900-1150 K and overall densities of ca. 3*1E-5 mol/cm3.In addition to a cis trans structural isomerization, four isomerization products, methyl ethyl ketone, isobutyraldehyde, ethyl vinyl ether, and 2-butene-3-ol, were obtained under shock heating.A large number of decomposition products were also obtained.The major ones in decreasing order of abundance were CO, C2H4, C2H6, and CH4.In a similar manner to the decomposition of oxirane and methyloxirane, the free-radical reactions in the present system are initiated by a direct decomposition of a thermally excited methyl ethyl ketone which is produced in the course of the isomerization.A reaction scheme composed of 41 species and 65 elementary reactions accounts for the product distribution over the entire temperature range of this investigation provided decomposition channels of thermally excited isomers are included in the scheme.The rate constants obtained for the isomerization reactions are in good agreement with the values extrapolated from low temperatures.First-order Arrhenius rate parameters for the formation of the various reaction products are given and a sensitivity analysis for their production is summarized.
Ruthenium-Catalyzed Olefin Cross-Metathesis with Tetrafluoroethylene and Analogous Fluoroolefins
Takahira, Yusuke,Morizawa, Yoshitomi
, p. 7031 - 7034 (2015)
This Communication describes a successful olefin cross-metathesis with tetrafluoroethylene and its analogues. A key to the efficient catalytic cycle is interconversion between two thermodynamically stable, generally considered sluggish, Fischer carbenes. This newly demonstrated catalytic transformation enables easy and short-step synthesis of a new class of partially fluorinated olefins bearing plural fluorine atoms, which are particularly important and valuable compounds in organic synthesis and medicinal chemistry as well as the materials and polymer industries.
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.
Iridium Pincer-Catalyzed Dehydrogenation of Ethers Featuring Ethylene as the Hydrogen Acceptor
Lyons, Thomas W.,Bzier, David,Brookhart, Maurice
, p. 4058 - 4062 (2015)
We describe efficient methods to dehydrogenate ethers by using iridium pincer complexes (iPr4Anthraphos)-Ir(H)(Cl), 4, iPr4PC(sp3)P-Ir(H)(Cl), 5, and (iPr4PCP)-Ir(H)(Cl), 6. At 120°C, cyclic ethers were dehydrogenated with tert-butylethylene as the hydrogen acceptor with high turnover numbers (over 400 in many cases). Acyclic ethers such as diethyl ether can also be dehydrogenated catalytically with TONs up to 90. The efficient dehydrogenation of cyclic and acyclic ethers using ethylene as a more practical hydrogen acceptor has been demonstrated for the first time. (Figure Presented)
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.
Microwave spectrum, structure, and dipole moment of the trans-cis isomer of ethyl vinyl ether
Hayashi,Inada
, p. 195 - 204 (1994)
Microwave spectra of the trans-cis isomer of ethyl vinyl ether and its nine deuterated species were measured. A plausible molecular structure was obtained from the observed moments of inertia by an application of a diagnostic least-squares technique. The dipole moment and its direction were determined by the Stark effect measurements of several low J transitions for the normal and two deuterated species.
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.
Photosonoelectrochemical analysis of Lawsonia inermis (henna) and artificial dye used in tattoo and dye industry
Chandrakalavathi,Sudha,Sindhuja,Harinipriya,Jeyalakshmi
, p. 44 - 57 (2018/04/30)
Photosonoelectrochemical (PSEC) analysis of Lawsonia inermis, lawsone and ?-Phenylenediamine were investigated in ethanol to understand the degradation mechanism and harmful byproducts. To simulate the operating conditions of the tattoo ink, dye solutions
