Thermolysis of 3-methyl-3-(o-aryl)-1,2-dioxetanes: Activation parameters and chemiexcitation yields

3-Methyl-3-(o-tolyl)-1,2-dioxetane 1 and 3-methyl-4-(o-bromophenyl)-1,2-dioxetane 2 were synthesized in low yield by the β-bromo hydroperoxide method. The activation parameters were determined by the chemilumin-escence method (for 1 ΔG^? = 24.7 ± 0.3 kcal/mol, ΔH^? = 25.4, ΔS^? = + 1.9 e.u., k₆₀ = 3.4 × 10^?4s^?1; for 2 ΔG^? = 24.7 ± 0.4 kcal/mol, ΔH^? = 24.7, ΔS^? = 0.0 e.u., k₆₀ = 4.1 × 10^?4s^?1). Thermolysis of 1–2 directly produced high yields of excited triplets as expected for this type of dioxetane [triplet chemiexcitation yields (?⁷) for 1 0.03; for 2 0.02; the ?^T/?^S ratios were estimated to be approximately 200 for both compounds]. The effect of ortho-aryl substituents was inconsistent with electronic effects. The ortho substitution in 1–2 resulted in a marked increase in stability of the dioxetanes. The results are discussed in relation to a diradical-like mechanism.     

Thermolysis of disubstituted 1,2-dioxetanes: Activation parameters and chemiexcitation yields

trans-3-Methyl-4-(p-anisyl)-1,2-dioxetane 1, trans-3-methyl-4-(o-anisyl)-1,2-dioxetane 2 , 3-methyl-3-benzyl-1,2-dioxetane 3 , and 3-methyl-3-p-methoxybenzyl-1,2-dioxetane 4 were synthesized in low yield by the β-bromo hydroperoxide method. The activation parameters were determined by the chemiluminescence method (for 1 ΔG≠ = 22.8 ± 0.3 kcal/mol, Δ≠ = 22.2, ΔS≠ = −1.7 e.u., k₆₀ = 7.6 × 10⁻³s⁻¹; for 2 ΔG≠ + 23.6 ± 0.3 kcal/mol, ΔH≠ = 22.8, ΔS≠ = −2.2 e.u., k₆₀ = 2.5 × 10⁻³S⁻¹; for 3 ΔG≠ = 24.0 ± 0.4 kcal/mol, ΔH≠ = 23.1, ΔS≠ = −2.7 e.u., k₆₀ = 1.2 × 10⁻³S⁻¹; for 4 ΔG≠ = 24.0 ± 0.2 kcal/mol, ΔH≠, = 23.2, ΔS≠, = −2.4 e.u., k₆₀ = 1.2 × 10⁻³s⁻¹). Thermolysis of 1–4 produced excited carbonyl fragments (direct production of high yields of triplets relative to excited singlets) [chemiexcitation yields ϕ^T, ϕ^S, respectively: for 1 0.02, 0.0001; for 2 0.02, 0.0001; for 3 0.03, 0.0002; for 4 0.02, 0.0001]. The effect of paramethoxyaryl substitution was consistent with electronic effects. The ortho substitution in 2 resulted in an increase in stability of the dioxetane, opposite that observed for an electronic effect. The results are discussed in relation to a diradical-like mechanism.     

Thermolysis of 3‐alkyl‐3‐methyl‐1,2‐dioxetanes: activation parameters and chemiexcitation yields

3‐Methyl‐3‐(3‐pentyl)‐1,2‐dioxetane 1 and 3‐methyl‐3‐(2,2‐dimethyl‐1‐propyl)‐1,2‐dioxetane 2 were synthesized in low yield by the α‐bromohydroperoxide method. The activation parameters were determined by the chemiluminescence method (for 1 ΔH‡ = 25.0 ± 0.3 kcal/mol, ΔS‡ = −1.0 entropy unit (e.u.), ΔG‡ = 25.3 kcal/mol, k₁ (60°C) = 4.6 × 10⁻⁴s⁻¹; for 2 ΔH‡ = 24.2 ± 0.2 kcal/mol, ΔS‡ = −2.0 e.u., ΔG‡ = 24.9 kcal/mol, k₁ (60°C) = 9.2 × 10⁻⁴s⁻¹. Thermolysis of 1–2 produced excited carbonyl fragments (direct production of high yields of triplets relative to excited singlets) (chemiexcitation yields for 1: ϕ^T = 0.02, ϕ^S ≤ 0.0005; for 2: ϕ^T = 0.02, ϕ^S ≤ 0.0004). The results are discussed in relation to a diradical‐like mechanism. © 2001 John Wiley & Sons, Inc. Heteroatom Chem 12:176–179, 2001     

Dynamics of a conformational change in aqueous 18-crown-6 by an ultrasonic absorption method

A temperature dependence study of the ultrasonic amplitudes, velocities, and relaxation times for a presumed conformational transition of noncomplexed aqueous 18-crown-6 (1,4,7,10,13,16-hexaoxacyclooctadecane) is discussed. At all temperatures a single relaxation was observed within a 15–255-MHz frequency range. The equilibrium constant for the presumed conformational transition \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm CR}_1 \mathop \rightleftarrows\limits^{K_{12} } {\rm CR}_2 $\end{document} was determined to be K₂₁ = (2 ± 2) × 10^?2. The activation parameters are ΔH₂₁^≠ = 10.2 ± 1.0 kcal/mol, ΔS₂₁^≠ = 7.7 ± 0.2 cal/(mol·deg), ΔH₁₂^≠ = 7.4 ± 1.0 kcal/mol, and ΔS₁₂^≠ = 7.7 ± 0.2 cal/(mol·deg), while the thermodynamic enthalpy and entropy were found to be ?2.6 ± 1.0 kcal/mol and 0 ± 0.2 cal/(mol·deg), respectively. The rate constants at 25.0°C for the presumed conformational transition are k₂₁ = (1.0 ± 0.3) × 10⁷ sec^?1 and k₁₂ = (6.2 ± 0.2) × 10⁸ sec^?1.     

Novel Membrane Potentiometric Thiocyanate Sensor Based on Tribenzyltin(IV) Dithiocarbamate

A novel PVC membrane ion‐selective electrode based on tribenzyltin(IV) dithiocarbamate [Sn(IV)–TBDTB] as neutral carrier was developed for thiocyanate (SCN^?) determination. The electrode exhibits a near‐Nernstian response for SCN^? with a slope of 62.8±2.0 mV per decade over a wide concentration range 1.0×10^?1–2.0×10^?6 mol L^?1 and a detection limit of 1.0×10^?6 mol L^?1 in MES–NaOH buffer, pH 6.0, at 25 °C. The electrode prepared with 1.5 wt.% Sn(IV)–TBDTB, 32.5 wt.% PVC and 66.0 wt.% 2‐nitrophenyloctyl ether (o‐NPOE) shows optimal response characteristics. Anti‐Hofmeister selectivity sequence for a series of anions shown by the electrode was as follows: SCN^?>Sal^?>I^?>ClO >phCOO^?>CH₃COO^?>Br^?>Cl^?>NO >NO >Citrate>SO₄^2?. The useful pH range for the electrode was found to be 3–7 with a response time 30–40 s. The electrode has been used for direct determination of thiocyanate in wastewater with satisfactory results.     

Substitution and Isomerization of Nitrite Ion at a Cobalt(III) Centre Having a Coordinated Pentadentate Ligand with Two Nitrogen and Three Sulfur Donor Atoms

The influence of placing thioether linkages trans to a site of nitrito substitution and spontaneous nitrito-tonitro isomerization is reported for the [CoQS(H₂O)]³⁺ cation where QS is 1,11-diamino-3,6,9-trithiaundecane. Preparation and characterization is described for the aqua and nitrito complexes. Rate data for the substitution process is presented at 17.7, 25.0 and 35.0°C. It is consistent with the mechanism first proposed by Basolo and Pearson in which N₂O₃ is the nitrosation agent. [CoQS(H₂O)]³⁺ is three hundred times more reactive than [Co(NH₃)₅H₂O]³⁺ under identical conditions. Isomerization is dramatically slower than the conversion of [CoQS(H₂O)³⁺ to [CoQS(ONO)]²⁺. The isomerization process was studied at 5 wavelengths, 3 temperatures and various conditions of acid and nitrite ion at an ionic strength of 0.11–0.60 M. Studies at 25°C give k_isom = 1.21 ± 0.12 × 10^?4 sec ^?1. Similar determinations at 17.7 and 35.0°C give k_isom = 3.84 ± 0.65 × 10^?5 sec^?1 and 3.59 ± 0.13 × 10^?4 sec^?1 respectively. The thermodynamic activation parameters ΔH^≠, ΔG^≠, and ΔS^≠ obtained from an Eyring plot gives ΔH^≠ = 111.3 kJ/mol, ΔS^≠ = + 53 J/molK and ΔG^≠ = 95.4 kJ/mol. These results are discussed in the context of present knowledge and experience with other cobalt(III) ligand systems.     

Homogeneous decomposition of vinyl ethers. The heat of formation of ethanal-2-yl

The thermal unimolecular decomposition of three vinylethers has been studied in a VLPP apparatus. The high-pressure rate constant for the retro-ene reaction of ethylvinylether was fit by log k (sec^?1) = (11.47 + 0.25) - (43.4 ± 1.0)/2.303 RT at <T> = 900 K and that of t - butylvinylether by log k (sec^?1) = (12.00 ± 0.27) - (38.4 ± 1.0)/2.303 RT at <T> = 800 K. No evidence for the competition of the higher energy homolytic bond-fission process could be obtained from the experimental data. The rate constant compatible with the C? O bond scission reaction in the case of benzylvinylether was log k (sec^?1) = (16.63 ± 0.30) - (53.74 ± 1.0)/2.303 RT at <T> = 750 K. Together with ΔH_f,300⁰(benzyl·) = 47.0 kcal/mol, the activation energy for this reaction results in ΔH_f,300⁰(CH₂CHO) = +3.0 ± 2.0 kcal/mol and a corresponding resonance stabilization energy of 3.2 ± 2.0 kcal/mol for 2-ethanalyl radical.     

Ion-pair formation in the outer-sphere electron transfer reactions between tris-(1, 10) phenanthroline iron(II) and the halopentacyanocobaltate(III) complexes in aqueous acidic solutions

The kinetics of the reactions between Fe(phen) ₃ ²⁺ [phen = tris–(1,10) phenanthroline] and Co(CN)₅X³⁻ (X = Cl, Br or I) have been investigated in aqueous acidic solutions at I = 0.1 mol dm⁻³ (NaCl/HCl). The reactions were carried out at a fixed acid concentration ([H⁺] = 0.01 mol dm⁻³) and the second-order rate constants for the reactions at 25 °C were within the range of (0.151–1.117) dm³ mol⁻¹ s⁻¹. Ion-pair constants K _ip for these reactions, taking into consideration the protonation of the cobalt complexes, were 5.19 × 10⁴, 3.00 × 10² and 4.02 × 10⁴ mol⁻¹ dm⁻³ for X = Cl, Br and I, respectively. Activation parameters measured for these systems were as follows: ΔH* (kJ K⁻¹ mol⁻¹) = 94.3 ± 0.6, 97.3 ± 1.0 and 109.1 ± 0.4; ΔS* (J K⁻¹) = 69.1 ± 1.9, 74.9 ± 3.2 and 112.3 ± 1.3; ΔG* (kJ) = 73.7 ± 0.6, 75.0 ± 1.0 and 75.7 ± 0.4; E _a (kJ) = 96.9 ± 0.3, 99.8 ± 0.4, and 122.9 ± 0.3; A (dm³ mol⁻¹ s⁻¹) = (7.079 ± 0.035) × 10¹⁶, (1.413 ± 0.011) × 10¹⁷, and (9.772 ± 0.027) × 10²⁰ for X = Cl, Br, and I respectively. An outer – sphere mechanism is proposed for all the reactions.     

Solution-Structure and Aggregation Behavior of Two Dilithiostyrene Derivatives

The solution structure and the aggregation behavior of (E)-2-lithio-1-(2-lithiophenyl)-1-phenylpent-1-ene ( 1 ) and (Z)-2-lithio-1-(2-lithiophenyl)ethene ( 2 ) were investigated by one- and two-dimensional ¹H-, ¹³C-, and ⁶Li-NMR spectroscopy. In Et₂O, both systems form dimers which show homonuclear scalar ⁶Li,⁶Li spin-spin coupling. In the case of 2 , extensive ⁶Li,¹H coupling is observed. In tetrahdrofuran and in the presence of 2 mol of N,N,N′,N′-tetramethylethylylenediamine (tmeda), the dimeric structure of 1 coexists with a monomer. The activation parameters for intra-aggregate exchange in the dimers of 1 and 2 ( 1 (Et₂O): ΔH≠ = 62.6 ± 13.9 kJ/mol, ΔS≠ = 5.8 ± 14.0 J/mol K, ΔG≠(263) = 61.1 kJ/mol; 2 (dimethoxyethane): ΔH≠ = 36.9 ± 6.5 kJ/mol, ΔS≠ = ?61 ± 25 J/mol K, ΔG≠(263) = 54.0 kJ/mol) and the thermodynamic parameters for the dimer-monomer equilibrium for 1 (ΔH°; = 26.7 ± 5.5 kJ/mol, ΔS° = 63 ± 27 J/mol K), where the monomer is favored at low temperature, were determined by dynamic NMR studies.     

Thermolysis of 3‐alkyl‐3‐methyl‐1,2‐dioxetanes: Activation parameters and chemiexcitation yields

3‐Methyl‐3‐(3‐pentyl)‐1,2‐dioxetane 1 and 3‐methyl‐3‐(2,2‐dimethyl‐1‐propyl)‐1,2‐dioxetane 2 were synthesized in low yield by the α‐bromohydroperoxide method. The activation parameters were determined by the chemiluminescence method (for 1 ΔH‡ = 25.0 ± 0.3 kcal/mol, ΔS‡ = −1.0 entropy unit (e.u.), ΔG‡ = 25.3 kcal/mol, k₁ (60°C) = 4.6 × 10⁻⁴s⁻¹; for 2 ΔH‡ = 24.2 ± 0.2 kcal/mol, ΔS‡ = −2.0 e.u., ΔG‡ = 24.9 kcal/mol, k₁ (60°C) = 9.2 × 10⁻⁴s⁻¹. Thermolysis of 1–2 produced excited carbonyl fragments (direct production of high yields of triplets relative to excited singlets) (chemiexcitation yields for 1: ϕ^T = 0.02, ϕ ≤ 0.0005; for 2: ϕ^T = 0.02, ϕ^S ≤ 0.0004). The results are discussed in relation to a diradical‐like mechanism. © 2001 John Wiley & Sons, Inc. Heteroatom Chem 12:459–462, 2001     

Synthesis and Diels-Alder Reactivity of 2,3,5,6-Tetramethylidenenorbornane

Pd-catalyzed double carbomethoxylation of the Diels-Alder adduct of cyclo-pentadiene and maleic anhydride yielded the methyl norbornane-2,3-endo-5, 6-exo-tetracarboxylate ( 4 ) which was transformed in three steps into 2,3,5,6-tetramethyl-idenenorbornane ( 1 ). The cycloaddition of tetracyanoethylene (TCNE) to 1 giving the corresponding monoadduct 7 was 364 times faster (toluene, 25°) than the addition of TCNE to 7 yielding the bis-adduct 9 . Similar reactivity trends were observed for the additions of TCNE to the less reactive 2,3,5,6-tetramethylidene-7-oxanorbornane ( 2 ). The following second order rate constants (toluene, 25°) and activation parameters were obtained for: 1 + TCNE → 7 : k₁ = (255 + 5) 10^?4 mol^?1 · s^?1, ΔH≠ = (12.2 ± 0.5) kcal/mol, ΔS≠ = (?24.8 ± 1.6) eu.; 7 + TCNE → 9 , k₂ = (0.7 ± 0.02) 10^?4 mol^?1 · s^?1, ΔH≠ = (14.1 ± 1.0) kcal/mol, ΔS≠ = ( ?30 ± 3.5) eu.; 2 + TCNE → 8 : k₁ = (1.5 ± 0.03) 10^?4 mol^?1 · s^?1, ΔH≠ = (14.8 ± 0.7) kcal/mol, ΔS≠ = (?26.4 ± 2.3) eu.; 8 + TCNE → 10 ; k₂ = (0.004 ± 0.0002) 10^?4 mol^?1 · s^?1, ΔH≠ = (17 ± 1.5) kcal/mol, ΔS≠ = (?30 ± 4) eu. The possible origins of the relatively large rate ratios k₁/k₂ are discussed briefly.     

INO thermodynamic properties and ultraviolet spectrum

The equilibrium I₂(g) + 2NO(g) = 2INO(g) has been studied at room temperature by ultraviolet absorption spectroscopy. The equilibrium constant has been measured as K_p = (2.7 ± 0.3) × 10^?6 atm^?1 at 298 K. Third-law calculations lead to ΔH°_f,298 (INO) = 120.0 ± 0.3 kJ/mol. The relative absorption spectrum of INO has been measured between 225 and 300 nm. Quantitative measurements gave ?(λ_max = 238 nm) = (1.79 ± 0.5) × 10⁴ L/mol·cm and ?(410 nm) = 234.7 ± 21 L/mol·cm.     

Thermolysis of hexasubstituted‐4,5‐dihydro‐3H‐pyrazoles: Kinetics and activation parameters

A kinetics study of the thermolysis of a series of hexasubstituted‐4,5‐dihydro‐3H‐pyrazoles (pyrazolines 1a: 3,3,4,4‐tetramethyl‐5‐phenyl‐5‐acetoxy; 1b: cis‐3,5‐diphenyl‐3,3,4‐trimethyl‐5‐acetoxy; 1c: cis‐3,5‐diphenyl‐3,4,4‐trimethyl‐5‐methoxy; 1d: 3,3,5‐triphenyl‐4,4‐dimethyl‐5‐acetoxy), which produced the corresponding hexasubstituted cyclopropanes 2a–d in quantitative yields was carried out. The first order rate constants (k₁) for thermal decomposition and activation parameters were determined. The relative reactivity series was found to be 1d >> 1b ∼ 1c > 1a. The activation parameters for thermolysis were found to be: for 1a ΔH‡ = 39.8 kcal/mol, ΔS‡ = 14 eu, k_150° = 6.8 × 10⁻⁵ s⁻¹; for 1b ΔH‡ = 33.5 kcal/mol, ΔS ‡ = 0.2 eu, k_150° = 1.7 × 10⁻⁴s⁻¹; for 1c ΔH‡ = 32.7 kcal/mol, ΔS‡ = −1.8 eu, k_150° = 1.2 × 10⁻⁴s⁻¹; for 1d ΔH‡ = 30.1 kcal/mol, ΔS‡ = −1.6 eu, k_150° = 8.8 × 10⁻³s⁻¹. The effect of variation of C3 substituents on the activation parameters for thermolysis paralleled the trend reported for acyclic analogs. The results are consistent with the formation of a (singlet) 1,3‐diradical intermediate with subsequent closure to yield the cyclopropanes. The mechanism of diradical formation appears to involve N₂‐C₃ bond cleavage as the rate determining step rather than simultaneous two bond scission. © 2000 John Wiley & Sons, Inc. Heteroatom Chem 11:299–302, 2000     

Sterically crowded cyclohexanes - 81). Synthesis,crystal structure,conformation and dynamics of pentaspiro[2.0.2.0.2.0.2.0.2.1]hexadecane,pentaspiro[3.0.2.0.3.0.2.0.3.1]- nonadecane and pentaspiro[3.0.3.0.3.0.3.0.3.1] heneicosane

The synthesis, crystal structure (7,8), conformation and dynamics of pentaspiro[2.0.2.0.2.0.2.0.2.1] hexadecane 6, pentaspiro [3.0.2.0.3.0.2.0.3.1] nonadecane 7 and pentaspiro [3.0.3.0.3.0.3.0.3.1] heneicosane 8 are described. Chair conformations have been found in the solid state (7,8) and in solution (6,7,8). The activation parameters of the chair-to-chair interconversion have been determined from bandshape analyses of exchange broadened ¹H-NMR (6,7) and¹³ C-NMR spectra (8), respectively. The results were as follows: 6: ΔH³ = 48.9 ± 0.8 kJ/mol, ΔS³ = -20.7 ± 2.8 J/mol, grd, ΔG³₂₉₈ = 55.0 ± 0.1 kJ/mol; 7: ΔH³=51.2±0.7 kJ/mol, ΔS³ = -12.0±2.4 J/mol, grd, ΔG³₂₉₈ = 54.8±0.1 kJ/mol; 8: ΔH³ - 74.2±0.6 kJ/mol, ΔS³ =-21.9 ± 1.5 J/mol, grd, ΔG³₂₉₈ = 80.7 ± 0.2 kJ/mol. On the basis of these values the barrier of inversion of the still unknown hexaspirane 5 is predicted to exceed 160 kJ/mol.     

Mutual combination of ClO radicals

The mutual combination reaction is proposed as the rate-limiting step in the removal of ClO radicals at moderate pressures. The third--order rate constants measured at room temperature were k₁(Ar) = 3.51 ± 0.14 × 10⁹ l²/mol²·ec; k₁(He) ≈ 2.8 × 10⁹ l²/mol²·sec, and k₁(O₂) ≈ 7.9 × 10⁹ l²/mol²·sec. There is also an independent second-order reaction for which k₃ ≈ 8 × 10⁶ l/mol·sec. A new absorption spectrum has been observed in the ultraviolet and attributed to Cl₂O₂. The extinction coefficient for Cl₂O₂ has been measured at six wavelengths, and, between 292 and 232 nm, it increases from 0.4 × 10³ to 2.9 × 10³ l/mol·cm. In the presence of the chlorine atom scavengers OClO or Cl₂O, Cl₂O₂ exists in equilibrium with ClO. The equilibrium constant Ke₁ = 3.1 ± 0.1 × 10⁶ l/mol at 298 K, and, with ΔS₁⁰ estimated to be ?133 ± 11 J/K·mol, ΔH₁⁰ = ?69 ± 3 kJ/mol and ΔH_f⁰(Cl₂O₂) = 136 ± 3 kJ/mol.     

Nucleophilic and electrophilic promotion of ligand substitution reactions in oxo‐bridged,dinuclear chromium(III) complexes

Base hydrolysis reactions of [Cr(tmpa)(NCSe)]₂O²⁺, [Cr(tmpa)(N₃)]₂O²⁺, [Cr₂(tmpa)₂(μ−O)(μ−PhPO₄)]⁴⁺ and [Cr₂(tmpa)₂(μ−O)(μ−CO₃)]²⁺ follow the pseudo‐first‐order relationship (excess OH⁻): k_obsd=k_o+k_bQ_p[OH⁻]/(1+Q_p[OH⁻]). For the CO₃²⁻ complex, k_b(60°C)=(1.50±0.03)×10⁻² s⁻¹; ΔH‡=61±2 kJ/mol, ΔS‡=−99±7 J/mol K; Q_p(60°C)=(3.8±0.3)×10¹ M⁻¹; ΔH°=67±2 kJ/mol, ΔS°=230±7 J/mol K (I=1.0 M). An isokinetic relationship among k_OH(=k_bQ_p) activation parameters for five (tmpa)CrOCr(tmpa) complexes shows that all follow essentially the same pathway. Activated complex formation is thought to require nucleophilic attack of coordinated OH⁻ at the chromium‐leaving group bond in the k_b step, accompanied by reattachment of a tmpa pyridyl arm displaced by OH⁻ in the Q_p preequilibrium. Abstraction of both thiocyanate ligands was observed upon mixing [Cr(tmpa)(NCS)]₂O²⁺ with [Pd(CH₃CN)₄]²⁺ in CH₃CN solution. The proposed mechanism requires rapid complexation of both reactant thiocyanate ligands by Pd(II) (K_p(25°C)=(4.5±0.2)×10⁸ M⁻²; ΔH°=−32±6 kJ/mol, ΔS°=59±19 J/mol K) prior to rate‐limiting Cr NCS bond‐breaking (k₂(25°C)=(1.17±0.02)×10⁻³ s⁻¹; ΔH‡=98±2 kJ/mol, ΔS‡=27±5 J/mol K). Pd(II)‐assisted NCS⁻ abstraction is not driven by weakening of the Cr( )NCS⁻ bond through ligation of the sulfur atom to palladium, but rather by a favorable ΔS‡ resulting from the release of Pd(NCS)⁺ fragments and weak solvation of the activated complex in CH₃CN solution. © 1999 John Wiley & Sons, Inc. Int J Chem Kinet 31: 351–356, 1999     

Molecularly imprinted polymers as artificial steroid receptors

The polymers selective to six different steroids (testosterone, Δ⁴-androstene-3,17-dione, 1,4-androstadiene-3,17-dione, β-estradiol, progesterone, testosterone propionate) have been synthesized using molecular imprinting based on noncovalent interactions. Analysis of the influence of structural features of the steroids under study has shown that molecules with a relatively rigid structure and the OH group at C-17 position are the most efficient templates for methacrylic acid-containing imprinted polymers. The chromatographic study of the polymers synthesized has demonstrated a strong dependence of the selectivity and intensity of interaction with analytes on the composition of solvents used both as porogen and chromatographic mobile phase. To obtain polymers with highly selective recognition sites and to create the optimal conditions for molecular recognition, all possible interactions (between template and functional monomer, template and solvent, solvent and functional monomer) should be taken into account. <?TF="palat-i"> The batch rebinding study of testosterone by the imprinted polymer in acetonitrile has revealed some heterogeneity of recognition sites, and permitted determination of K_ass = 1.05 × 10⁴ M ⁻¹, ΔG° = −5.4 kcal/mol and N = 1.2 μmol/g for high-affinity sites and K_ass = 0.33 × 10⁴ M ⁻¹, ΔG° = −4.8 kcal/mol and N = 2.2 μmol/g for low-affinity sites. <?TF="palat-i"> The results obtained show how it is possible to regulate in different modes the molecular recognition by imprinted polymers as well as to fabricate polymers possessing the necessary properties depending on their practical application.© 1998 John Wiley & Sons, Ltd.     

Kinetics and mechanism of the thermal decomposition reaction of acetone cyclic diperoxide in methyl tert‐butyl ether solution

The thermal decomposition reaction of acetone cyclic diperoxide (3,3,6,6‐tetramethyl‐1,2,4,5‐tetroxane, ACDP), in the temperature range of 130.0–166.0°C and initial concentrations range of 0.4–3.1 × 10^?2 mol kg^?1 has been studied in methyl t‐butyl ether solution. The thermolysis follows first‐order kinetic laws up to at least ca 60% ACDP conversion. Under the experimental conditions, the activation parameters of the initial step of the reaction (ΔH^# = 33.6 ± 1.1 kcal mol^?1; ΔS^# = ?4.1 ± 0.7 cal mol^?1 K^?1; ΔG^# = 35.0 ± 1.1 kcal mol^?1) and acetone, as the only organic product, support a stepwise reaction mechanism with the homolytic rupture of one of its peroxidic bond. Also, participation of solvent molecules in the reaction is postulated given an intermediate diradical, which further decomposes by C? O bond ruptures, yielding a stoichiometric amount of acetone (2 mol per mole of ACDP decomposed). The results are compared with those obtained for the above diperoxide thermolysis in other solvents. © 2004 Wiley Periodicals, Inc. Int J Chem Kinet 36: 302–307, 2004     

A quantitative study of alkyl radical reactions by kinetic spectroscopy. IV. The flash photolysis of azopropanes

The flash photolysis of azo?n?propane and of azoisopropane has been studied by kinetic spectroscopy. Transient absorption spectra in theregion of 220–260 nm have been assigned to the n-propyl and isopropyl radicals. For the n-propyl radical, ?_max = 744 ± 39 l/mol cm at 245 nm and the rate constants for the mutual reactions were measured to be k_c = (1.0 ± 0.1) × 10¹⁰ l/mol sec (combination) and k_d = (1.9 ± 0.2) × 10⁹ l/mol sec (disproportionation). For the isopropyl radical, ?_max = 1280 ± 110 l/mol cm at 238 nm, with k_c = (7.7 ± 1.6) × 10⁹ l/mol sec and k_d = (5.0 ± 1.2) × 10⁹ l/mol sec The rate constant for the dissociation of the vibrationally excited triplet state of the azopropanes into radicals was measured from the variation in the quantum yield of radicals with pressure. For azo-n-propane k = (6.6 ± 1.3) × 10⁷ sec^?1, and for azoisopropane k = (1.6 ± 0.4) × 10⁸ sec^?1. Collisional deactivation of the vibrationally excited singlet and triplet states was found to occur on every collision for n-pentane; but nitrogen and argon were inefficient with a rate constant of 1.1 × 10¹⁰ l/mol sec. Spectra observed in the region of 220–260 and 370–400 nm areattributed to the cis isomers of the parent trans-azopropanes. These are formed, as permanent products, in increasing amounts as the pressure is increased.     

A question concerning the pk range within which an organic free radical exhibits normal radical behaviour. The case of galvinoxyl

Galvinoxyl (G^*) reacts with a series of substituted acetic acids and forms hydrogalvinoxyl (GH) as the sole product. The kinetic data conform with a Bronsted type analysis. Hydrogalvinoxyl may dissociate to the relevant cation G⁺, in a process which appears to be a thermal hydride ejection. In addition GH exhibits thermochromism with the following parameters: ΔH = -17.0 ±0.8 kcal mol^-1 and at 298 K, K_e = 1.16 (±0.28) × 10^-5 M^-1, ΔS = -79.0±8.0 cal Kcal mol^-1. The behaviour of G^* at various acidities is described.