70401-56-8Relevant articles and documents
Radical Hydrodehalogenation of Aryl Bromides and Chlorides with Sodium Hydride and 1,4-Dioxane
Hokamp, Tobias,Dewanji, Abhishek,Lübbesmeyer, Maximilian,Mück-Lichtenfeld, Christian,Würthwein, Ernst-Ulrich,Studer, Armido
supporting information, p. 13275 - 13278 (2017/10/09)
A practical method for radical chain reduction of various aryl bromides and chlorides is introduced. The thermal process uses NaH and 1,4-dioxane as reagents and 1,10-phenanthroline as an initiator. Hydrodehalogenation can be combined with typical cyclization reactions, proving the nature of the radical mechanism. These chain reactions proceed by electron catalysis. DFT calculations and mechanistic studies support the suggested mechanism.
Photoelectron transfer induced decarboxylation of substituted carboxylic acids across a liquid/liquid interface
Rajesh,Thanulingam,Das, Suresh
, p. 16817 - 16834 (2007/10/03)
Methylene blue photocatalyzed electron transfer reactions of some phenoxyacetic acid derivatives and N-phenylglycine across a liquid/liquid interface led to their efficient decarboxylation. Nanosecond laser flash photolysis studies of this process, in a reverse micellar system of Aerosol- OT (AOT)-benzene-water indicated that the liquid/liquid interface acts as a barrier in controlling the energy wasting back electron transfer. Intramolecular C-C bond forming reactions of these radicals were utilized for the synthesis of various chroman derivatives.
Thermal Decomposition of 2,3-Dihydro-1,4-benzodioxin and 1,2-Dimethoxybenzene
Schraa, Gerrit-Jan,Arends, Isabel W. C. E.,Mulder, Peter
, p. 189 - 198 (2007/10/02)
Rates and mechanisms of decomposition of 2,3-dihydro-1,4-benzodioxin (1) and 1,2-dimethoxybenzene (27) have been investigated in the gas phase near atmospheric pressure between 750 and 900 K in a tubular flow reactor in a large excess of radical trapping agents.The following rate expressions for decomposition have been determined: log kt/s-1 (1) = 15.7 - (271 kJ mol-1/2.303 RT); log kt/s-1 (27) = 15.7 - (251 kJ mol-1/2.303 RT).The main decomposition routes for 1 are the formation of o-benzoquinone (2) and 2-methyl-1,3-benzodioxole (7) through a biradical intermediate.The measured activation energy is 20 kJ mol-1 above the required C-O bond dissociation energy.Compound 2 rapidly loses CO to form cyclopenta-2,4-dien-1-one (6) which after dimerisation decomposes mainly into 3-phenylprop-2-enal (12) and indenols (14).The main product of the thermolysis of 27 is o-hydroxybenzaldehyde (33).The O-methyl bond is weakened by 16 kJ mol-1 compared to methoxybenzene as a result of the o-methoxy-substitution.