1007-70-1Relevant academic research and scientific papers
Manganese-Catalyzed Electrochemical Deconstructive Chlorination of Cycloalkanols via Alkoxy Radicals
Allen, Benjamin D. W.,Hareram, Mishra Deepak,Seastram, Alex C.,McBride, Tom,Wirth, Thomas,Browne, Duncan L.,Morrill, Louis C.
supporting information, p. 9241 - 9246 (2019/11/19)
A manganese-catalyzed electrochemical deconstructive chlorination of cycloalkanols has been developed. This electrochemical method provides access to alkoxy radicals from alcohols and exhibits a broad substrate scope, with various cyclopropanols and cyclobutanols converted into synthetically useful β- and γ-chlorinated ketones (40 examples). Furthermore, the combination of recirculating flow electrochemistry and continuous inline purification was employed to access products on a gram scale.
Hydrogenolysis of 1-alkoxybenzocyclobutenes with site-selective cleavage of the sterically hindered C(sp2)-C(sp3) bond
Sawano, Shota,Ishida, Naoki,Murakami, Masahiro
supporting information, p. 1521 - 1523 (2015/11/24)
1-Alkoxybenzocyclobutenes undergo ring-opening hydrogenolysis with site-selective cleavage of the sterically hindered C(sp2)-C(sp3) bond on Pd/C.
Cyclobutene photochemistry. Substituent effects on the photochemistry of 1-phenylcyclobutene
Leigh, William J.,Postigo, J. Alberto
, p. 191 - 203 (2007/10/02)
The photochemistry and photophysic of 1-phenylcyclobutene and five aryl-substituted derivatives have been studied in various solvents at room temperature.All six compounds fluoresce with quantum yields in the 0.2-0.3 range in cyclohexane and acetonitrile solution. 1-Phenylcyclobutene undergoes -cycloreversion (γ = 0.09) to yield phenylacetylene upon photolysis in either hydrocarbon or acetonitrile solution, and undergoes (Markovnikov) solvent addition upon irradiation in methanol solution (γ = 0.08) in addition to cycloreversion.Triplet sensitization and quenching experiments indicate that cycloreversion and methanol addition are both excited singlet state processes.None of the six compounds studied undergo ring opening to the corresponding 2-aryl-1,3-butadiene in detectable yield.Quantum yields for cycloreversion in cyclohexane, acetonitrile, and methanol solution and methanol addition have been determined for the six compounds, along with excited singlet state lifetimes.The quantum yields and rate constants for cycloreversion and methanol addition are both enhanced by substitution with electron-donating groups.The variation in the rate constant for cycloreversion with substituent indicates that there is substantial dipolar character developed in the cyclobutenyl ?-bond framework during the reaction, in almost exact correspondence with that developed in the ? system during photoprotonation.No deuterium scrambling is observed in 1-phenylcyclobutene-2,4,4-d3 after photolysis in pentane solution to ca. 80percent conversion, indicating that sleletal rearrangements leading to cyclopropyl carbenes do not occur in the direct photolysis of arylcyclobutene derivatives.A pericyclic mechanism for the photocycloreversion reaction is suggested.Triplet-triplet absorption spectra and triplet lifetimes of 1-phenyl-, 1-(para-methylphenyl)-, and 1-(para-trifluoromethylphenyl)cyclobutene in hydrocarbon solution are also reported. Key words: photochemistry, cyclobutene, fluorescence, -cycloreversion, substituent effects, nanosecond laser flash photolysis, lifetime, triplet state, styrene, photoaddition
Thermolabile Hydrocarbons, XXV. Relationships between Thermal Stability, Strain, and Structure of 1,1'-Diphenyl-1,1'-bicycloalkyls
Bernloehr, Werner,Beckhaus, Hans-Dieter,Lindner, Hans-Joerg,Ruechardt, Christoph
, p. 3303 - 3319 (2007/10/02)
The products and activation parameters of the thermolysis reaction of the title hydrocarbons 1a (n = 4-8) and 1b (n = 12) were determined.Strain enthalpies and structural data of the compounds 1a and of the radicals 2a, which are generated on thermolysis, were obtained from force field calculations.For 1a (n = 8) a crystal structure analysis was carried out. - The importance of i-strain action is estimated from the relationship between ΔG% of the thermolysis reaction and the strain enthalpy of 1 from which the ring strain of the corresponding cycloalkane was substracted as a correction factor.In addition, a linear correlation between ΔG% and the change in strain enthalpy (MM2 results) in the course of the dissociation process was found.The large variation in ΔS% can be rationalized by consideration of the change in internal mobility (MM2 results) during the dissociation process.
