Catalysis by hydrogen chloride in the gas‐phase elimination kinetics of 2‐phenyl‐2‐propanol and 3‐methyl‐1‐buten‐3‐ol

A homogeneous, molecular, gas‐phase elimination kinetics of 2‐phenyl‐2‐propanol and 3‐methyl‐1‐ buten‐3‐ol catalyzed by hydrogen chloride in the temperature range 325–386 °C and pressure range 34–149 torr are described. The rate coefficients are given by the following Arrhenius equations: for 2‐phenyl‐2‐propanol log k₁ (s^?1) = (11.01 ± 0.31) ? (109.5 ± 2.8) kJ mol^?1 (2.303 RT)^?1 and for 3‐methyl‐1‐buten‐3‐ol log k₁ (s^?1) = (11.50 ± 0.18) ? (116.5 ± 1.4) kJ mol^?1 (2.303 RT)^?1. Electron delocalization of the CH₂?CH and C₆H₅ appears to be an important effect in the rate enhancement of acid catalyzed tertiary alcohols in the gas phase. A concerted six‐member cyclic transition state type of mechanism appears to be, as described before, a rational interpretation for the dehydration process of these substrates. Copyright © 2007 John Wiley & Sons, Ltd.     

Joint theoretical and experimental study of the gas‐phase elimination kinetics of tert‐butyl ester of carbamic,N, N‐dimethylcarbamic,N‐hydroxycarbamic acids and 1‐(tert‐butoxycarbonyl)‐imidazole

The gas‐phase elimination kinetics of the title compounds were carried out in a static reaction system and seasoned with allyl bromide. The working temperature and pressure ranges were 200–280 °C and 22–201.5 Torr, respectively. The reactions are homogeneous, unimolecular, and follow a first‐order rate law. These substrates produce isobutene and corresponding carbamic acid in the rate‐determining step. The unstable carbamic acid intermediate rapidly decarboxylates through a four‐membered cyclic transition state (TS) to give the corresponding organic nitrogen compound. The temperature dependence of the rate coefficients is expressed by the following Arrhenius equations: for tert‐butyl carbamate logk₁ (s^?1) = (13.02 ± 0.46) – (161.6 ± 4.7) kJ/mol(2.303 RT)^?1, for tert‐butyl N‐hydroxycarbamate logk₁ (s^?1) = (12.52 ± 0.11) – (147.8 ± 1.1) kJ/mol(2.303 RT)^?1, and for 1‐(tert‐butoxycarbonyl)‐imidazole logk₁ (s^?1) = (11.63 ± 0.21)–(134.9 ± 2.0) kJ/mol(2.303 RT)^?1. Theoretical studies of these elimination were performed at Møller–Plesset MP2/6‐31G and DFT B3LYP/6‐31G(d), B3LYP/6‐31G(d,p) levels of theory. The calculated bond orders, NBO charges, and synchronicity (Sy) indicate that these reactions are concerted, slightly asynchronous, and proceed through a six‐membered cyclic TS type. Results for estimated kinetic and thermodynamic parameters are discussed in terms of the proposed reaction mechanism and TS structure. Copyright © 2007 John Wiley & Sons, Ltd.     

The kinetics and mechanism of the homogeneous,unimolecular gas‐phase elimination of 2‐(4‐substituted‐phenoxy)tetrahydro‐2H‐pyranes

The gas‐phase elimination kinetics of tetrahydropyranyl phenoxy ethers: 2‐phenoxytetrahydro‐2H‐pyran, 2‐(4‐methoxyphenoxy)tetrahydro‐2H‐pyran, and 2‐(4‐tert‐butylphenoxy)tetrahydro‐2H‐pyran were determined in a static system, with the vessels deactivated with allyl bromide, and in the presence of the free radical inhibitor toluene. The working temperature and pressure were 330 to 390°C and 25 to 89 Torr, respectively. The reactions yielded DHP and the corresponding 4‐substituted phenol. The eliminations are homogeneous, unimolecular, and satisfy a first‐order rate law. The Arrhenius equations for decompositions were found as follows:

• 2‐phenoxytetrahydro‐2H‐pyran
• log k₁ (s^?1) = (14.18 ± 0.21) ? (211.6 ± 0.4) kJ mol^?1 (2.303 RT)^?1
• 2‐(4‐methoxyphenoxy)tetrahydro‐2H‐pyran
• log k₁ (s^?1) = (14.11 ± 0.18) ? (203.6 ± 0.3) kJ mol^?1 (2.303 RT)^?1
• 2‐(4‐tert‐butylphenoxy)tetrahydro‐2H‐pyran
• log k₁ (s^?1) = (14.08 ± 0.08) ? (205.9 ± 1.0) kJ mol^?1 (2.303 RT)^?1

The analysis of kinetic and thermodynamic parameters for thermal elimination of 2‐(4‐substituted‐phenoxy)tetrahydro‐2H‐pyranes suggests that the reaction proceeds via 4‐member cyclic transition state. The results obtained confirm a slight increase of rate constant with increasing electron donating ability groups in the phenoxy ring. The pyran hydrogen abstraction by the oxygen of the phenoxy group appears to be the determinant factor in the reaction rate.     

Kinetics of the gas‐phase homogeneous unimolecular elimination of selected ethyl esters of 2‐oxo‐carboxylic acids

The gas‐phase elimination kinetics of selected ethyl esters of 2‐oxo‐carboxylic acid have been studied over the temperature range of 270–415 °C and pressures of 37–114 Torr. The reactions are homogeneous, unimolecular, and follow a first‐order rate law in a seasoned static reaction vessel, with an added free radical suppressor toluene. The observed overall and partial rate coefficients are expressed by the following Arrhenius equations:

• Ethyl oxalyl chloride
• log k_overall (s^?1) = (13.22 ± 0.45) ? (179.4 ± 4.9) kJ mol^?1 (2.303 RT)^?1
• Ethyl piperidineglyoxylate
• log k_(CO2) (s^?1) = (12.00 ± 0.30) ? (191.2 ± 3.9) kJ mol^?1 (2.303 RT)^?1
• log k_(CO) (s^?1) = (12.60 ± 0.09) ? (210.7 ± 1.2) kJ mol^?1 (2.303 RT)^?1
• log k_t(overall) (s^?1) = (12.22 ± 0.26) ? (193.4 ± 3.4) kJ mol^?1 (2.303 RT)^?1
• Ethyl benzoyl formate
• log k_(CO2) (s^?1) = (12.89 ± 0.72) ? (203.8 ± 9.0) kJ mol^?1 (2.303 RT)^?1
• log k_(CO) (s^?1) = (13.39 ± 0.31) ? (213.3 ± 3.9) kJ mol^?1 (2.303 RT)^?1
• log k_t(overall) (s^?1) = (13.24 ± 0.60) ? (205.8 ± 7.6) kJ mol^?1 (2.303 RT)^?1

The kinetic and thermodynamic parameters of these reactions, together with those reported in the literature, lead to consider three different mechanistic pathways of elimination. Copyright © 2010 John Wiley & Sons, Ltd.     

Kinetics and mechanism for acid‐catalyzed disproportionation of 2,2,6,6‐tetramethylpiperidine‐1‐oxyl

Disproportionation of cyclic nitroxyl radicals (NRs) in acid solutions is of key importance for the chemistry of these compounds. Meanwhile, the data reported on the mechanism of this reaction in dilute acids are inconsistent with those on the stability of NRs in concentrated acids. Here we have examined the kinetics and stoichiometry for the disproportionation of 2,2,6,6‐tetramethylpiperidine‐1‐oxyl ( 1 ) in aqueous H₂SO₄ (1.0–99.3 wt%) and found that (1) the disproportionation of 1 proceeds by the same mechanism over the entire range of acid concentrations, (2) the effective rate constant of the process exhibits a bell‐shaped dependence on the excess acidity function X peaked at X = ?pK _1H+ = 5.8 ± 0.3, (3) a key step of the process involves the oxidation of 1 with its protonated counterpart 1H ⁺ yielding oxopiperidinium cation 2 and hydroxypiperidine 3 at a rate constant of (1.4 ± 0.8) × 10⁵ M^?1 · s^?1, and (4) the reaction is reversible and, upon neutralization of acid, disproportionation products 2 and 3H ⁺ comproportionate to starting 1 . In highly acidic media, the protonated form 1H ⁺ is relatively stable due to a low disproportionation rate. Based on the known and newly obtained values of equilibrium constants, both the standard redox potential for the 1H ⁺ / 3 pair (955 ± 15 mV) and the pH‐dependences have been calculated for the reduction potentials of 1 and 2 to hydroxylamine 3 that is in equilibrium with its protonated 3H ⁺ and deprotonated 3 ^? forms. The data obtained provide a deeper insight into the mechanism of nitroxyl‐involving reactions in chemical and biological systems. Copyright © 2008 John Wiley & Sons, Ltd.     

Combined experimental and theoretical studies of the elimination kinetic of 2‐methoxytetrahydropyran in the gas phase

The products formed in 2‐methoxytetrahydropyran elimination reaction in the gas phase are 3, 4‐dihydro‐2H‐pyran and methanol. The kinetic study was carried out in a static system, with the vessels deactivated with allyl bromide, and the presence of the free radical suppressor toluene. Temperature and pressure ranges were 400–450 °C and 25–83 Torr, respectively. The process is homogeneous, unimolecular, and follows a first‐order rate law. The observed rate coefficient is represented by the following equation: log k (s^?1) = (13.95 ± 0.15) ? (223.1 ± 2.1) (kJ mol^?1) (2.303RT)^?1. The reactant exists mainly in two low energy chair‐like conformations, with the 2‐methoxy group in axial or equatorial position. However, the transition state (TS) for the elimination of the two conformers is the same. Theoretical calculations of this reaction were carried for two possible mechanisms from these conformations by using DFT functionals B3LYP, MPW1PW91, and PBE with the basis set 6‐31G(d,p) and 6‐31G++(d,p). The calculation results demonstrate that 2‐methoxytetrahydropyran exists mainly in two conformations, with the 2‐methoy group in axial or equatorial position, that are thermal in equilibrium. The average thermodynamic and kinetic parameters, taking into account the populations of the conformers in the equilibrium, are in good agreement with experimental values at B3LYP/6‐31++(d,p) level of theory. Copyright © 2010 John Wiley & Sons, Ltd.     

The mechanism of the homogeneous,unimolecular gas‐phase elimination kinetic of 1,1‐dimethoxycyclohexane: experimental and theoretical studies

The gas‐phase elimination of 1,1‐dimethoxycyclohexane yielded 1‐methoxy‐1‐cyclohexene and methanol. The kinetics were determined in a static system, with the vessels deactivated with allyl bromide, and in the presence of the free radical inhibitor cyclohexene. The working temperature was 310–360 °C and the pressure was 25–85 Torr. The reaction was found to be homogeneous, unimolecular, and follows a first‐order rate law. The temperature dependence of the rate coefficients is given by the following Arrhenius equation: log k(s^?1) = [(13.82 ± 0.07) – (193.9 ± 1.0)(kJ mol^?1)](2.303RT)^?1; r = 0.9995. Theoretical calculations were carried out using density functional theory (DFT) functionals B3LYP, MPW1PW91, and PBE with the basis set 6‐31G(d,p) and 6‐31G++(d,p). The calculated values for the energy of activation and enthalpy of activation are in reasonably good agreement with the experimental values using the PBE/6‐31G (d,p) level of theory. Both experimental results and theoretical calculations suggest a molecular mechanism involving a concerted polar four‐membered cyclic transition state. The transition state structure of methanol elimination from 1,1‐dimethoxycyclohexane is characterized by a significantly elongated C? O bond, while the C_β? H bond is stretched to a smaller extent, as compared to the reactant. The process can be described as moderately asynchronic with some charge separation in the TS. Copyright © 2010 John Wiley & Sons, Ltd.     

Gas‐phase oxidation of CH2 = C(CH3)CH2Cl initiated by OH radicals and Cl atoms: kinetics and fate of the alcoxy radical formed

Relative kinetics of the reactions of OH radicals and Cl atoms with 3‐chloro‐2‐methyl‐1‐propene has been studied for the first time at 298 K and 1 atm by GC‐FID. Rate coefficients are found to be (in cm³ molecule^?1 s^?1): k₁ (OH + CH₂ = C(CH₃)CH₂Cl) = (3.23 ± 0.35) × 10^?11, k₂ (Cl + CH₂ = C(CH₃)CH₂Cl) = (2.10 ± 0.78) × 10^?10 with uncertainties representing ± 2σ. Product identification under atmospheric conditions was performed by solid phase microextraction/GC‐MS for OH reaction. Chloropropanone was identified as the main degradation product in accordance with the decomposition of the 1,2‐hydroxy alcoxy radical formed. Additionally, reactivity trends and atmospheric implications are discussed. Copyright © 2015 John Wiley & Sons, Ltd.     

Homogeneous and unimolecular gas‐phase thermal decomposition kinetics of methyl benzoylformate: experimental and theoretical study

The kinetics of the gas‐phase thermal decomposition of the α‐ketoester methyl benzoylformate was carried out in a static system with reaction vessel deactivated with allyl bromide, and in the presence of the free radical inhibitor propene. The rate coefficients were determined over the temperature range of 440–481 °C and pressures from 32 to 80 Torr. The reaction was found to be homogenous, unimolecular and obey a first‐order rate law. The products are methyl benzoate and CO. The temperature dependence of the rate coefficient gives the following Arrhenius parameters: log₁₀ k (s^?1) = 13.56 ± 0.31 and E_a (kJ mol^?1) = 232.6 ± 4.4. Theoretical calculations of the kinetic and thermodynamic parameters are in good agreement with the experimental values using PBE1PBE/6‐311++g(d,p). A theoretical Arrhenius plot was constructed at this level of theory, and the good agreement with the experimental Arrhenius plot suggests that this model of transition state may describe reasonably the elimination process. These results suggest a concerted non‐synchronous semi‐polar three‐membered cyclic transition state type of mechanism. The most advanced coordinate is the bond breaking C^δ+‐‐‐^δ‐OCH₃ with an evolution of 66.7%, implying this as the limiting factor of the elimination process. Copyright © 2014 John Wiley & Sons, Ltd.     

Theoretical investigations on 4,4′,5,5′‐tetranitro‐2,2′‐1H,1′H‐2,2′‐biimidazole derivatives as potential nitrogen‐rich high energy materials

The ―NH₂, ―NO₂, ―NHNO₂, ―C(NO₂)₃ and ―CF(NO₂)₂ substitution derivatives of 4,4′,5,5′‐tetranitro‐2,2′‐1H,1′H‐2,2′‐biimidazole were studied at B3LYP/aug‐cc‐pVDZ level of density functional theory. The crystal structures were obtained by molecular mechanics (MM) methods. Detonation properties were evaluated using Kamlet–Jacobs equations based on the calculated density and heat of formation. The thermal stability of the title compounds was investigated via the energy gaps (?E_{LUMO ? HOMO}) predicted. Results show that molecules T5 (D = 10.85 km·s^?1, P = 57.94 GPa) and T6 (D = 9.22 km·s^?1, P = 39.21 GPa) with zero or positive oxygen balance are excellent candidates for high energy density oxidizers (HEDOs). All of them appear to be potential explosives compared with the famous ones, octahydro‐1,3,5,7‐tetranitro‐1,3,5,7‐tetraazocane (HMX, D = 8.96 km·s^?1, P = 35.96 GPa) and hexanitrohexaazaisowurtzitane (CL‐20, D = 9.38 km·s^?1, P = 42.00 GPa). In addition, bond dissociation energy calculation indicates that T5 and T6 are also the most thermally stable ones among the title compounds. Copyright © 2014 John Wiley & Sons, Ltd.     

Homo‐Diels–Alder reaction of a very inactive diene,bicyclo[2,2,1]hepta‐2,5‐diene,with the most active dienophile, 4‐phenyl‐1,2,4‐triazolin‐3,5‐dione. Solvent,temperature, and high pressure influence on the reaction rate

Solvent, temperature, and high pressure influence on the rate constant of homo‐Diels–Alder cycloaddition reactions of the very active hetero‐dienophile, 4‐phenyl‐1,2,4‐triazolin‐3,5‐dione (1), with the very inactive unconjugated diene, bicyclo[2,2,1]hepta‐2,5‐diene (2), and of 1 with some substituted anthracenes have been studied. The rate constants change amounts to about seven orders of magnitude: from 3.95^.10^?3 for reaction (1+2) to 12200 L mol^?1 s^?1 for reaction of 1 with 9,10‐dimethylanthracene (4e) in toluene solution at 298 K. A comparison of the reactivity (ln k₂) and the heat of reactions (?_r‐nH) of maleic anhydride, tetracyanoethylene and of 1 with several dienes has been performed. The heat of reaction (1+2) is ?218 ± 2 kJ mol^?1, of 1 with 9,10‐dimethylanthracene ?117.8 ± 0.7 kJ mol^?1, and of 1 with 9,10‐dimethoxyanthracene ?91.6 ±0.2 kJ mol^?1. From these data, it follows that the exothermicity of reaction (1+2) is higher than that with 1,3‐butadiene. However, the heat of reaction of 9,10‐dimethylanthracene with 1 (?117.8 kJ mol^?1) is nearly the same as that found for the reaction with the structural C=C counterpart, N‐phenylmaleimide (?117.0 kJ mol^?1). Since the energy of the N=N bond is considerably lower (418 kJ/bond) than that of the C=C bond (611 kJ/bond), it was proposed that this difference in the bond energy can generate a lower barrier of activation in the Diels–Alder cycloaddition reaction with 1. Linear correlation (R = 0.94) of the solvent effect on the rate constants of reaction (1+2) and on the heat of solution of 1 has been observed. The ratio of the volume of activation (?V^≠) and the volume of reaction (?V_r‐n) of the homo‐Diels–Alder reaction (1+2) is considered as “normal”: ?V^≠/?V_r‐n = ?25.1/?30.95 = 0.81. Copyright © 2012 John Wiley & Sons, Ltd.     

Theoretical studies on structure and performance of [1,2,5]‐oxadiazolo‐[3,4‐d]‐pyridazine‐based derivatives

Based on energetic compound [1,2,5]‐oxadiazolo‐[3,4‐d]‐pyridazine, a series of functionalized derivatives were designed and first reported. Afterwards, the relationship between their structure and performance was systematically explored by density functional theory at B3LYP/6‐311 g (d, p) level. Results show that the bond dissociation energies of the weakest bond (N–O bond) vary from 157.530 to 189.411 kJ · mol^?1. The bond dissociation energies of these compounds are superior to that of HMX (N–NO_2, 154.905 kJ · mol^?1). In addition, H1, H2, H4, I2, I3, C1, C2, and D1 possess high density (1.818–1.997 g · cm^?3) and good detonation performance (detonation velocities, 8.29–9.46 km · s^?1; detonation pressures, 30.87–42.12 GPa), which may be potential explosives compared with RDX (8.81 km · s^?1, 34.47 GPa ) and HMX (9.19 km · s^?1, 38.45 GPa). Finally, allowing for the explosive performance and molecular stability, three compounds may be suggested as good potential candidates for high‐energy density materials. Copyright © 2016 John Wiley & Sons, Ltd.     

Experimental and theoretical study of the mechanism for the kinetic of elimination of methyl carbazate in the gas phase

The elimination kinetic of methyl carbazate in the gas phase was determined in a static system over the temperature range of 340–390 °C and pressure range of 47–118 Torr. The reaction is homogeneous, unimolecular, and obeys a first order rate law. The decomposition products are methyl amine, nitrous acid, and CO gas. The variation of the rate coefficients with temperatures is given by the Arrhenius expression: log k₁ (s^?1) = (11.56 ± 0.34) ? (180.7 ± 4.1) kJ mol^?1(2.303 RT)^?1. The estimated kinetics and thermodynamics parameters are in good agreement to the experimental values using B3LYP/6‐31G (d,p), and MP2/6‐31G (d,p) levels of theory. These calculations imply a molecular mechanism involving a concerted non‐synchronous quasi three‐membered ring cyclic transition state to give an unstable intermediate, 1,2‐oxaziridin‐3‐one. Bond order analysis and natural charges implies that polarization of O (alkyl)? C (alkyl) bond of the ester is rate determining in this reaction. Copyright © 2008 John Wiley & Sons, Ltd.     

1,5‐electrocyclization versus 1,5‐proton shift in imidazolium allylides and 2‐phospha‐allylides: a DFT investigation

The competitive 1,5‐electrocyclization versus intramolecular 1,5‐proton shift in imidazolium allylides and imidazolium 2‐phosphaallylides has been investigated theoretically at the DFT (B3LYP/6‐311 + +G**//B3LYP/6‐31G**) level. 1,5‐Electrocyclization follows pericyclic mechanism and its activation barrier is lower than that for the pseudopericyclic mechanism by ～5–6 kcal mol^?1. The activation barriers for 1,5‐electrocyclization of imidazolium 2‐phosphaallylides are found to be smaller than those for their nonphosphorus analogues by ～3–5 kcal mol^?1. There appears to be a good correlation between the activation barrier for intramolecular 1,5‐proton shift and the density of the negative charge at C8, except for the ylides having fluorine substituent at this position ( 7b and 8b ). The presence of fluorine atom reduces the density of the negative charge at C8 (in 7b it becomes positively charged) and thus raises the activation barrier. The ylides 7f and 8f having CF₃ group at C8, in preference to the 1,5‐proton shift, follow an alternative route leading to different carbenes which is accompanied by the loss of HF. The carbenes Pr _{7 , 8b – e} resulting from intramolecular 1,5‐proton shift have a strong tendency to undergo intramolecular S_N2 type reaction, the activation barrier being 7–28 kcal mol^?1. Copyright © 2011 John Wiley & Sons, Ltd.     

Room‐temperature scavengers for macromolecular crystallography: increased lifetimes and modified dose dependence of the intensity decay

The advent of highly intense wiggler and undulator beamlines has reintroduced the problem of X‐ray radiation damage in protein crystals even at cryogenic temperatures (100 K). Although cryocrystallography can be utilized for the majority of protein crystals, certain macromolecular crystals (e.g. of viruses) suffer large increases in mosaicity upon flash cooling and data are still collected at room temperature (293 K). An alternative mechanism to cryocooling for prolonging crystal lifetime is the use of radioprotectants. These compounds are able to scavenge the free radical species formed upon X‐ray irradiation which are thought to be responsible for part of the observed damage. Three putative radioprotectants, ascorbate, 1,4‐benzoquinone and 2,2,6,6‐tetramethyl‐4‐piperidone (TEMP), were tested for their ability to prolong lysozyme crystal lifetimes at 293 K. Plots of relative summed intensity against dose were used as a metric to assess radioprotectant ability: ascorbate and 1,4‐benzoquinone appear to be effective, whereas studies on TEMP were inconclusive. Ascorbate, which scavenges OH radicals (k_OH = 8 × 10⁹ M^?1 s^?1) and electrons with a lower rate constant (k_e‐(aq) = 3.0 × 10⁸ M^?1 s^?1), doubled the crystal dose tolerance, whereas 1,4‐benzoquinone, which also scavenges both OH radicals (k_OH = 1.2 × 10⁹ M^?1 s^?1) and electrons (k_e‐(aq) = 1.2 × 10¹⁰ M^?1 s^?1), offered a ninefold increase in dose tolerance at the dose rates used. Pivotally, these preliminary results on a limited number of samples show that the two scavengers also induced a striking change in the dose dependence of the intensity decay from a first‐order to a zeroth‐order process.     

A computational study of the thermolysis of β‐hydroxy ketones in gas phase and in m‐xylene solution

Theoretical calculations at the M05‐2X/6‐31+G(d) level of theory have been carried out in order to explore the nature of the mechanism of the thermal decomposition reactions of the β‐hydroxy ketones, 4‐hydroxy‐2‐butanone, 4‐hydroxy‐2‐pentanone, and 4‐hydroxy‐2‐methyl‐2‐pentanone in gas phase and in m‐xylene solution. The mechanism proposed is a one‐step process proceeding through a six‐membered cyclic transition state. A reasonable agreement between experimental and calculated activation parameters and rate constants has been obtained, the tertiary : secondary : primary alcohol rate constant ratio being calculated, at T = 503.15 K, as 5.9:4.7:1.0 in m‐xylene solution and 44.1:5.0:1.0 in the gas phase, compared with the experimental values, 3.7:1.3:1.0 and 13.5:3.2:1.0, respectively. The progress of the thermal decomposition reactions of β‐hydroxy ketones has been followed by means of the Wiberg bond indices. The lengthening of the O₁–C₂ bond with the initial migration of the H₆ atom from O₅ to O₁ can be seen as the driving force for the studied reactions. Calculated synchronicity values indicate that the mechanisms correspond to concerted and highly synchronous processes. The transition states are “advanced”, nearer to the products than to the reactants. Copyright © 2012 John Wiley & Sons, Ltd.     

Measurement of the third‐order nonlinear optical susceptibility χ(3) for the 1002‐cm–1 mode of benzenethiol using coherent anti‐Stokes Raman scattering with continuous‐wave diode lasers

The components of the third‐order nonlinear optical susceptibility χ⁽³⁾ for the 1002‐cm^–1 mode of neat benzenethiol have been measured using coherent anti‐Stokes Raman scattering with continuous‐wave diode pump and Stokes lasers at 785.0 and 852.0 nm, respectively. Values of 2.8 ± 0.3 × 10^–12, 2.0 ± 0.2 × 10^–12, and 0.8 ± 0.1 × 10^–12 cm·g^–1·s² were measured for the xxxx, xxyy, and xyyx components of |3χ⁽³⁾|, respectively. We have calculated these quantities using a microscopic model, reproducing the same qualitative trend. The Raman cross‐section σ_RS for the 1002‐cm^–1 mode of neat benzenethiol has been determined to be 3.1 ± 0.6 × 10^–29 cm² per molecule. The polarization of the anti‐Stokes Raman scattering was found to be parallel to that of the pump laser, which implies negligible depolarization. The Raman linewidth (full‐width at half‐maximum) Γ was determined to be 2.4 ± 0.3 cm^–1 using normal Stokes Raman scattering. The measured values of σ_RS and Γ yield a value of 2.1 ± 0.4 × 10^–12 cm·g^–1·s² for the resonant component of 3χ⁽³⁾. A value of 1.9 ± 0.9 × 10^–12 cm·g^–1·s² has been deduced for the nonresonant component of 3χ⁽³⁾. Copyright © 2011 John Wiley & Sons, Ltd.     

Thermolysis and photolysis of 2‐ethyl‐4‐nitro‐1(2H)‐isoquinolinium hydroperoxide

The thermal and light‐induced O ? O bond breaking of 2‐ethyl‐4‐nitro‐1(2H)‐isoquinolinium hydroperoxide (IQOOH) were studied using ¹H NMR, steady‐state UV/vis spectroscopy, femtosecond UV/vis transient absorption (fs TA) and time‐dependent density functional theory (TD DFT) calculations. Thermal O ? O bond breaking occurs at room temperature to generate water and the corresponding amide. The rate of this reaction, k = 5.4 · 10^?6 s^?1, is higher than the analogous rates of simple alkyl and aryl hydroperoxides; however, the rate significantly decreases in the presence of small amounts of methanol. The calculated structure of the transition state suggests that the thermolysis is facilitated by a 1,2 proton shift. The photochemical process yields the same products, as confirmed using NMR and UV/vis spectroscopy. However, the quantum yield for the photolysis is low (Φ = 0.7%). Fs TA studies provide additional detail of the photochemical process and suggest that the S₁ state of IQOOH undergoes fast internal conversion to the ground state, and this process competes with the excited‐state O ? O bond breaking. This result was supported by the fact that the model compound IQOH exhibits similar excited‐state decay lifetimes as IQOOH, which is assigned to the S₁ → S₀ internal conversion. Copyright © 2013 John Wiley & Sons, Ltd.     

Gas‐phase reactions of Cl atoms with hydrochloroethers: relative rate constants and their correlation with substituents' electronegativities

Rate constants for the reactions of Cl atoms with CH₃OCHCl₂ and CH₃OCH₂CH₂Cl were determined at (296 ± 2) K and atmospheric pressure using synthetic air as bath gas. Decay rates of these organic compounds were measured relative to the following reference compounds: CH₂ClCH₂Cl and n‐C₅H₁₂. Using rate constants of 1.33 × 10^?12 and 2.52 × 10^?10 cm³ molecule^?1 sec^?1 for the reaction of Cl atoms with CH₂ClCH₂Cl and n‐C₅H₁₂, respectively, the following rate coefficients were derived: k(Cl + CH₃OCHCl₂) = (1.05 ± 0.11) × 10^?12 and k(Cl + CH₃OCH₂CH₂Cl) = (1.14 ± 0.10) × 10^?10, in units of cm³ molecule^?1 s^?1. The rate constants obtained were compared with previous literature data and a correlation was found between the rate coefficients of some CH₃OCHR¹R² + Cl reactions and ΔElectronegativity of ? CHR¹R². Copyright © 2008 John Wiley & Sons, Ltd.     

Pulse radiolysis studies of 2‐ and 3‐hydroxybenzyl alcohols: inhibition of dehydration of ·OH‐(hydroxybenzyl alcohols) adducts by H2PO4− ions

Reactions of ·OH/O ^.? radicals and H‐atoms as well as specific oxidants such as Cl₂^.? and N₃· radicals have been studied with 2‐ and 3‐hydroxybenzyl alcohols (2‐ and 3‐HBA) at various pH using pulse radiolysis technique. At pH 6.8, ·OH radicals were found to react quite fast with both the HBAs (k = 7.8 × 10⁹ dm³ mol^?1 s^?1 with 2‐HBA and 2 × 10⁹ dm³ mol^?1 s^?1 with 3‐HBA) mainly by adduct formation and to a minor extent by H‐abstraction from ? CH₂OH groups. ·OH‐(HBA) adduct were found to undergo decay to give phenoxyl type radicals in a pH dependent way and it was also very much dependent on buffer‐ion concentrations. It was seen that ·OH‐(2‐HBA) and ·OH‐(3‐HBA) adducts react with HPO₄^2? ions (k = 2.1 × 10⁷ and 2.8 × 10⁷ dm³ mol^?1 s^?1 at pH 6.8, respectively) giving the phenoxyl type radicals of HBAs. At the same time, this reaction is very much hindered in the presence of H₂PO ions indicating the role of phosphate ion concentration in determining the reaction pathway of ·OH adduct decay to final stable product. In the acidic region adducts were found to react with H⁺ ions. At pH 1, reaction of ·OH radicals with HBAs gave exclusively phenoxyl type radicals. Proportion of the reducing radicals formed by H‐abstraction pathway in ·OH/O ^.? reactions with HBAs was determined following electron transfer to methyl viologen. H‐atom abstraction is the major pathway in O ^.? reaction with HBAs compared to ·OH radical reaction. H‐atom reaction with 2‐ and 3‐HBA gave transient species which were found to transfer electron to methyl viologen quantitatively. Copyright © 2010 John Wiley & Sons, Ltd.