12169-67-4

Upstream product

• 3141-58-0 tert-butoxy radical 
• 1165952-92-0 cyclohexa-1,4-diene 
• 55394-12-2 Bicyclo<3.1.0>hex-2-ene radical 
• 1165952-91-9 cyclohexa-1,3-diene 
• 536-74-3 phenylacetylene 
• 71-43-2 benzene 
• 171980-25-9 (1-oxido-pyridin-2-yl)sulfanyl radical 
• 147506-92-1 2,2-diphenyl-1-(2,4,6-trinitrophenyl)hydrazyl 
• 2025-56-1 ethyl radical 
• 4630-45-9 isobutyl radical 
• 2348-55-2 sec-Butyl-Radikal 
• 2348-46-1 ethanol radical 
• 2669-89-8 vinyl radical 
• 2597-43-5 hydroxymethyl radical 

Downstream Products

• 1605-73-8 t-Butyl radical 
• 71-43-2 benzene 
• 2025-56-1 ethyl radical 
• 2348-55-2 sec-Butyl-Radikal 
• 2025-55-0 isopropyl radical 
• 51314-23-9 methyl diphenylmethyl radical 
• 2348-51-8 1-phenylethyl radical 
• 57701-98-1 C₆H₇O₂ 
• 150648-13-8 C₆H₇O₂ 

Relevant academic research and scientific papers

Laser flash photolysis of 2,2′-dithiobis(pyridine N-oxide): Reactivity of N-oxypyridyl-2-thio radical

Reaction kinetics of radicals produced by the nanosecond laser flash photolysis of 2,2′-dithiobis(pyridine N-oxide) and related compounds have been studied. The transient absorption band at 360 nm was attributed to the radical in which the unpaired electron mainly localizes on the S atom (N-oxypyridyl-2-thio radical). The reactivities of the radical for conjugated dienes are lower than those of the pyridyl-2-thio radical, suggesting that a considerable unpaired electron density on the S atom delocalizes onto the N-oxypyridine moiety. The addition reaction rate of the radical to the conjugating diene was accelerated with hydrogen-bonding solvents and with addition of the cation, which may stabilize the N+-O- canonical structure, increasing the unpaired electron density on the S atom. By the photolysis of N-hydroxypyridine-2-thione, the N-O bond was predominantly dissociated producing a pyridy1-2-thio radical. By the photolysis of its anion, photoejection took place followed by the N-O bond fission, yielding pyridine-2-thione.

Rate Constants for Termination and TEMPO Trapping of Some Resonance Stabilized Hydroaromatic Radicals in the Liquid Phase

The rate constants for the termination reaction (2k1) of some resonance stabilized carbon centered radicals (SR.) derived from hydroaromatics (Sr. + SR. -> P) have been determined at 294 +/- 2 K by laser flash photolysis with UV-vis detection.The radicals were generated by hydrogen atom abstraction by t-BuO-radicals from the corresponding hydrocarbon (SRH + t-BuO. -> SR. + t-BuOH. k4).The extinction coefficients (e) of the SR., essential to calculate 2k1, were obtained using a relative kinetic technique.The change in 2k1 for the radicals derived from 1,4-cyclohexadiene, fluorine, 9,10-dihydroanthracene, diphenylmethane, tetralin, indan, indene, and phenol appeared to be modest; a range of 2k1 = 2-10 x 1E9 M-1 s-1 in mixtures of benzene and di-tert-butyl peroxide was observed.Most of the rate constants are near the diffusion controlled limit.In contrast, quenching the radicals with a persistent radical, 2,2,5,5-tetramethylpiperidin-1-oxyl (TEMPO), resulted in a larger variation of -1 s-1.The strength of the N-O bond formed in the latter process may have an important contribution to the observed rate constant.

Hydrogen atom abstraction by radical cations. The reactions of 9-substituted acridine radical cations with cyclohexa-1,4-diene

9-Substituted acridine radical cations undergo facile hydrogen atom abstraction reactions with cyclohexa-1,4-diene in dichloromethane-Bu4NPF6 (0.2 M). The kinetics of the reaction were studied by derivative cyclic voltammetry and obs

Diffusion controlled hydrogen atom abstraction from tertiary amines by the benzyloxyl radical. the importance of C-H/N hydrogen bonding

The rate constants for H-atom abstraction (kH) from 1,4-cyclohexadiene (CHD), triethylamine (TEA), triisobutylamine (TIBA), and DABCO by the cumyloxyl (CumO?) and benzyloxyl (BnO ?) radicals were measured. Comparable ksub

Radical-Type Reactivity of the Methylenedimethylsulfonium Ion, (CH3)2S(+)-CH2(.)

Ab initio molecular orbital calculations at the MP2/6-31G*//6-31G* + ZPVE level of theory suggest that the ion (CH3)2S(+)-CH2(.) is 75 kJ mol-1 higher in energy than ionized ethyl methyl sulfide.However, this distonic ion is stable toward isome

Energetics of the allyl group

(Figure Presented) Aiming to improve our understanding of the stability of radicals containing the allylic moiety, carbon-hydrogen bond dissociation enthalpies (BDEs) in propene, isobutene, 1-butene, (E)-2-butene, 3-metylbut-1-ene, (E)-2-pentene, (E)-1,3-pentadiene, 1,4-pentadiene, cyclohexene, 1,3-cyclohexadiene, and 1,4-cyclohexadiene have been determined by quantum chemistry calculations. The BDEs in cyclohexene, 1,3-cyclohexadiene, and 1,4-cyclohexadiene have also been obtained by time-resolved photoacoustic calorimetry. The theoretical study involved a DFT method as well as ab initio complete basis-set approaches, including the composite CBS-Q and CBS-QB3 procedures, and basis-set extrapolated coupled-cluster calculations (CCSD(T)). By taking the C(sp3)-H BDE in propene as a reference, we have concluded that one methyl group bonded to C3 in propene (i.e., 1-butene) leads to a decrease of 12 kJ mol-1 and that a second methyl group bonded to C3 (3-methylbut-1-ene) further decreases the BDE by 8 kJ mol-1. When the methyl group is bonded to C2 in propene (isobutene), an increase of 7 kJ mol-1 is observed. Finally, a methyl group bonded to C1 in propene (2-butene) has essentially no effect (-1 kJ mol-1). While this trend can be rationalized in terms of stabilization of the corresponding radical (through hyperconjugation and π-delocalization), the BDE values observed for the dienes can only be understood by considering the thermodynamic stabilities of the parent compounds.

Laser flash photolysis study of the photochemistry of 4,5-diaza-9-fluorenone

The triplet excited state of 4,5-diaza-9-fluorenone (1) shows absorption maxima at 410 and 470 nm and a lifetime of 3 μs, in acetonitrile. Its intersystem crossing quantum yield was determined using 9-fluorenone as a secondary standard and a value of 0.41 ± 0.01 was obtained. The reactivity of the triplet excited state of 1 towards several quenchers, in acetonitrile, was investigated employing the laser flash photolysis technique quenching rate constants ranging from 7.9 × 104 M-1 s-1 (2-propanol) to 1.0 × 1010 M-1 s-1 (triethylamine) were obtained. From the quenching rate constants obtained one can conclude that 4,5-diaza-9-fluorenone has a ππ? triplet excited state. A Hammett plot for the quenching rate constants of triplet 1 by phenols containing polar substituents against σ + gave a reaction constant ρ of -1.54 ± 0.10, which demonstrates the electrophilic character of the 4,5-diaza-9-fluorenone triplet excited state.

Accurate O-H bond dissociation energy differences of hydroxylamines determined by EPR spectroscopy: Computational insight into stereoelectronic effects on BDEs and EPR spectral parameters

Differences in O-H bond dissociation enthalpies (δBDEs) between the hydroxylamine of 15N-labeled TEMPONE and 10 N,N-di-tert-alkyl hydroxylamines were determined by EPR. These δBDEs, together with the g and aN values of the derived nitroxide radicals, are discussed in relation to various geometric, intramolecular dipole/dipole, and steric effects and in relation to the results from DFT calculations. We find that dipole/dipole interactions are the dominant factors in dictating aN values and O-H BDEs in all of these structurally similar nitroxides and hydroxylamines, respectively. The importance of including the Boltzmann distribution of conformations for each nitroxide in the aN calculations is emphasized.

Electronic transitions of protonated benzene and fulvene, and of C 6H7 isomers in neon matrices

Electronic transitions of protonated benzene (A 1B 2X 1A1, origin at 325 nm) and ±-protonated fulvene (A 1A′X 1A′, at 335 nm) trapped in 6 K neon matrices have been detected. The cations were produced from several different precursors, mass-selected, and co-deposited with neon. After neutralization of the cations, the electronic transitions of cyclohexadienyl (onsets at 549 and 310 nm) and ±-hydrogenated fulvene (532 and 326 nm) radicals were identified. Upon excitation of cyclohexadienyl to the B 2B1 state, photoisomerization to an open-chain structure and ±-hydrogenated fulvene was observed.

Gas-phase reaction of the OH-benzene adduct with O2: Reversibility and secondary formation of HO2

The reaction of OH radicals with benzene and consecutive reactions of benzene-OH adducts with O2 were studied in the gas phase in N2-O2 mixtures at atmospheric pressure and room temperature. OH was produced by pulsed 248 n