14314-91-1

Usage

Synthesis

Anthracene was reduced to 9,10-dihydroanthracene in good yield with triethylsilane and boron trifluoride hydrate.

Upstream product

• 613-31-0 9,10-dihydroanthracene 
• 2154-56-5 benzyl radical 
• 90-47-1 xanth-9-one 
• 120-12-7 anthracene radical anion 
• 98-83-9 isopropenylbenzene 
• 86-73-7 9H-fluorene 
• 120-12-7 anthracene 
• 2564-83-2 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical 
• 611-63-2 9,10-dihydroanthracen-9-ol 

Downstream Products

• 86-73-7 9H-fluorene 
• 120-12-7 anthracene 
• 613-31-0 9,10-dihydroanthracene 
• 41115-74-6 2-Methoxyphenoxyl radical 
• 85809-29-6 9-<2-(benzoylamino)-1,1-dimethylethyl>-9,10-dihydroanthracene 
• 10349-31-2 9,9',10,10'-tetrahydro-9,9'-bianthryl 
• 119-64-2 tetralin 

Relevant academic research and scientific papers

Unifying the Solution Thermochemistry of Molecules, Radicals, and Ions

A general cycle was developed that defines the thermodynamics for all of the homolytic and heterolytic cleavage reactions of a hydrocarbon, R-R', in solution.Only seven experimental parameters were needed in order to define the energetics for all 11 of the possible cleavage reactions of R-R'.These parameters were the oxidation and reduction potentials of R-R', R(.), and R'(.) and the homolytic, R-R', bond energy.The utility of this approach was demonstrated for the case where R was an arylmethyl group and R' was hydrogen.The oxidation and reduction potentials of thearylmethyl radicals were measured by modulation voltammetry in acetonitrile, and the homolytic C-H bond energies of the corresponding hydrocarbons were measured by photoacoustic calorimetry.The cycle was also extended to a case where R-R' was a radical rather than a closed-shell molecule.

Magnetic Field Effect on the Hydrogen Abstraction Reaction of Xanthone in Sodium Dodecyl Sulfate Micellar Solution

The magnetic field effect on the hydrogen abstraction of xanthone from xanthene, 9,10-dihydroanthracene, and sodium dodecyl sulfate (SDS) surfactant has been studied in SDS micellar solution by steady-state (/= 260 mT) and laser flash photolysis (/= 80 mT).In the steady-state photolysis, the relative quantum yield of the disappearance of xanthone decreases in the magnetic field.Transient absorption intensities of 9-xanthenyl and 9,10-dihydroanthracene-9-yl radicals in the laser flash photolysis show remarkable magnetic field dependence, when xanthene and 9,10-dihydroanthracene are used as the respective hydrogen donors.All the results are interpreted in terms of the radical-pair model.

Generation of Arenium Ions by a Self-Protonation Reaction in an Aprotic Molten Salt Medium

We have examined the reaction behavior of a group of polycyclic aromatic hydrocarbons in the aprotic liquid SbCl3-10 mol percent AlCl3 from 100 to 130 deg C by 1H NMR and by quench and separation techniques.For anthracene, pyrene, 9,10-dimethylanthracene, 9,10-diphenylanthracene, and naphthacene, we have observed a novel arene self-protonation reaction for which the proton source is the condensation-dehydrogenation of a portion of the arene combined with arene oxidation by SbCl3.Naphthalene and phenanthrene, however, do not undergo this reaction.Evidence is presented which indicates that the self-protonation reaction proceeds through the oxidation of the arene to its radical cation by SbCl3, and that the function of AlCl3 is to enhance the oxidizing power of the Sb3+/Sb0 couple.

C-H activation by a mononuclear manganese(III) hydroxide complex: Synthesis and characterization of a manganese-lipoxygenase mimic?

Lipoxygenases are mononuclear non-heme metalloenzymes that regio- and stereospecifically convert 1,4-pentadiene subunit-containing fatty acids into alkyl peroxides. The rate-determining step is generally accepted to be hydrogen atom abstraction from the p

OPTICAL STUDIES OF HYDRONAPHTHYL RADICALS EMBEDDED IN DIHYDRONAPHTHALENE CRYSTAL.

Radiation-induced radicals in dihydronaphthalene were investigated at 4. 2 K by absorption, fluorescence and fluorescence excitation studies. It was shown that the radicals in dihydronaphthalene are hydronaphtyl radicals. The advantges of using the dihydro compounds in the identification of cyclohexadienyl type radicals is discussed.

Predicting organic hydrogen atom transfer rate constants using the Marcus cross relation

Chemical reactions that involve net hydrogen atom transfer (HAT) are ubiquitous in chemistry and biology, from the action of antioxidants to industrial and metalloenzyme catalysis. This report develops and validates a procedure to predict rate constants for HAT reactions of oxyl radicals (RO ?) in various media. Our procedure uses the Marcus cross relation (CR) and includes adjustments for solvent hydrogen-bonding effects on both the kinetics and thermodynamics of the reactions. Kinetic solvent effects (KSEs) are included by using Ingold's model, and thermodynamic solvent effects are accounted for by using an empirical model developed by Abraham. These adjustments areshown to be critical to the success of our combined model, referred to as the CR/KSE model. As an initial test of the CR/KSE model we measured self-exchange and cross rate constants in different solvents for reactions of the 2,4,6-tri-tert-butylphenoxyl radical and the hydroxylamine 2,2′-6,6′-tetramethylpiperidin-1-ol. Excellent agreement is observed between the calculated and directly determined cross rate constants. We then extend the model to over 30 known HAT reactions of oxyl radicals with OH or CH bonds, including biologically relevant reactions of ascorbate, peroxyl radicals, and α-tocopherol. The CR/KSE model shows remarkable predictive power, predicting rate constants to within a factor of 5 for almost all of the surveyed HAT reactions.

Direct Comparison of the reactivity of model complexes for compounds 0, I, and II in oxygenation, hydrogen-abstraction, and hydride-transfer processes

The iron(III) meso-tetramesitylporphyrin complex is a good biomimetic to study the catalytic reactions of cytochrome P450. All of the three most discussed reactive intermediates concerning P450 catalysis (namely, Cpd 0, Cpd I, and Cpd II) can be selective

Generation of diarylcarbenium ion poolsviaelectrochemical C-H bond dissociation

The "cation pools" of diarylcarbenium ions have been generated by the low-temperature electrochemical oxidation of diphenylmethane derivatives. In addition to diphenylmethanes having various substituents, 9,10-dihydroanthracene, dibenzosuberane, and xanth

Hydrocarbon oxidation by bis-μ-oxo manganese dimers: Electron transfer, hydride transfer, and hydrogen atom transfer mechanisms

Described here are oxidations of alkylaromatic compounds by dimanganese μ-xo and μ-hydroxo dimers [(phen)2MnIV (μ-O)2MnIV(phen)2]4+ ([Mn2(O)2]4+), [(phen)2MnIV (μ-O)2MnIII(phen)2]3+ ([Mn2(O)2]3+), and [(phen)2MnIII (μ-O)(μ-OH)MnIII(phen)2]3+ ([Mn2(O)(OH)]3+). Dihydroanthracene, xanthene, and fluorene are oxidized by [Mn2(O)2]3+ to give anthracene, bixanthenyl, and bifluorenyl, respectively. The manganese product is the bis(hydroxide) dimer, [(phen)2MnIII (μ-OH)2Mn(phen)2]3+ ([Mn2(OH)2]3+). Global analysis of the UV/vis spectral kinetic data shows a consecutive reaction with buildup and decay of [Mn2(O)(OH)]3+ as an intermediate. The kinetics and products indicate a mechanism of hydrogen atom transfers from the substrates to oxo groups of [Mn2(O)2]3+ and [Mn2(O)(OH)]3+. [Mn2(O)2]4+ is a much stronger oxidant, converting toluene to tolyl-phenylmethanes and naphthalene to binaphthyl. Kinetic and mechanistic data indicate a mechanism of initial preequilibrium electron transfer for p-methoxytoluene and naphthalenes because, for instance, the reactions are inhibited by addition of [Mn2(O)2]3+. The oxidation of toluene by [Mn2(O)2]4+, however, is not inhibited by [Mn2(O)2]3+. Oxidation of a mixture of C6H5CH3 and C6H5CD3 shows a kinetic isotope effect of 4.3 ± 0.8, consistent with C-H bond cleavage in the rate-determining step. The data indicate a mechanism of initial hydride transfer from toluene to [Mn2(O)2]4+. Thus, oxidations by manganese oxo dimers occur by three different mechanisms: hydrogen atom transfer, electron transfer, and hydride transfer. The thermodynamics of e-, H?, and H- transfers have been determined from redox potential and pKa measurements. For a particular oxidant and a particular substrate, the choice of mechanism is influenced both by the thermochemistry and by the intrinsic barriers. Rate constants for hydrogen atom abstraction by [Mn2(O)2]3+ and [Mn2(O)(OH)]3+ are consistent with their 79 and 75 kcal mol-1 affinities for H?. In the oxidation of p-methoxytoluene by [Mn2(O)2]4+, hydride transfer is thermochemically 24 kcal mol-1 more facile than electron transfer; yet the latter mechanism is preferred. Thus, electron transfer has a substantially smaller intrinsic barrier than does hydride transfer in this system.

Comparison of pKR values of fluorenyl and anthracenyl cations

A value of pKR = -5.1 for the anthracenonium ion in 50:50 (v/v) aqueous trifluorethanol is reported based on a ratio of measured rate constants kH for acid-catalysed dehydration of the 9,10-hydrate of anthracene and kH2O for the reverse hydrolysis of the carbocation (KR = kH2O/kH. Comparison with pKR = -15.9 for the fluorenyl cation indicates that the latter ion is less stable by more than 10 log units (15 kcal mol-1). This difference is (a) considerably larger than that between the benzhydryl (pKR = -11.7) and fluorenyl cations (ΔpK = 4.2), which has been considered too small to indicate antiaromatic character for the fluorenyl cation, and (b) comparable to that between pKas for the ionization (in DMSO) of fluorene (22.6) and diphenylmethane (32.2), which has been interpreted as implying aromatic character for the fluorenyl anion. It is shown that a difference in stability of anthracene hydrate and 9-hydroxyfluorene makes only a minor contribution to the difference in pKR values and that the fluorenyl cation is destabilized by ca 10 kcal mol-1. A smaller difference in pKas for protonation of fluorenimine (5.85) and benzhydrylimine (7.0) is consistent with the expected moderating effect of an electron-donating substituent on relative carbocation stabilities. Evidence from calculations relating to the antiaromaticity of the fluorenyl cation is reviewed in the light of these measurements. An additional comparison between equilibrium constants for the ionization of aralkylazides (Kaz) and alcohols (KR) reveals the influence of differences in geminal σ-bond interactions for the hydroxy and azido groups in their respective reactants. Copyright