Chemiluminescence in the thermal decomposition of di(tert-butyl) trioxide

Intense chemiluminescence (CL) in the visible and IR regions arising during the thermal decomposition of di(tert-butyl) trioxide has been observed. The decomposition rate constants have been determined. The emitter of CL in the IR region is singlet oxygen, that of CL in the visible region is triplet excited acetone. Kinetic and spectral data and thermochemical and MNDO calculations point to a homolytic mechanism of decomposition. The formation of the CL emitters occurs in the reactions of radicals that arise upon the decay of di(tert-butyl) trioxide.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2056–2059, December, 1993.     

Effect of medium on the rate constant of decomposition of di(tert-butyl)trioxide

It was found that the medium affects the rate constant of the thermal decomposition of di(tert-butyl)trioxide. In all solvents studied, the decomposition occurred according to the first-order law. The effect of the solvent on the rate constant was analyzed within the framework of the Koppel-Palm equation.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1167–1168, June, 1995.The authors are grateful to O. N. Makarova for help in this work.This study was financially supported by the Russian Foundation for Basic Research (Grant No. 93-03-5231).     

Free-radical chain decomposition of ozone initiated by di(tert-butyl) trioxide

Di(tert-butyl) trioxide in a solution of CFCl₃ (Freon-11) at –23 °C exists in equilibrium with the tert-butoxyl and tert-butylperoxyl radicals virtually without irreversible decomposition. The above radicals decompose ozone to dioxygen with a high effective rate constant, which is proprotional to the square root of the Bu^tOOOBu^t concentration. The kinetic scheme describing the found relationships was proposed.     

Kinetics of radical decomposition of di(tert-butyl) trioxide

The kinetics of radical decomposition of di(tert-butyl) trioxide was studied by spectrophotometry from the consumption of an acceptor of free radicals, 2,6-di(tert-butyl)-4-methylphenol, in CFCl₃ and CH₂Cl₂ (in the latter case, in the presence of 0.1M Bu^tOOH). The activation parameters of the reaction (log(A/s ⁻¹)=14.8±1.2 and 14.1±1.6,E _a=21.6±1.4 and 20.1±1.9 kcal mol⁻¹ in CFCl₃ and CH₂Cl₂, respectively) and the probability of radical escape to the bulk (e=0.9±0.1) were determined. The known experimental and calculated values of the O−OO bond strength in trioxides were analyzed. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 61–65, January, 1999.     

Composition of products and mechanism of the reaction of ozone with 2,6-di(tert-butyl)-4-methylphenol

It was shown that two series of products with opening and with preservation of the aromatic nucleus are formed in the reaction of ozone with ionol, and a mechanism was proposed for the reaction.N. N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, 117334 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 5, pp. 1203–1207, May, 1992.     

Alkylation of acetylene by tert-butyl alcohol

A reaction of acetylene with tert-butyl alcohol in the presence of sulfuric acid leads to tert-butylacetylene.     

ESR study of the thermal decomposition of di-tert-butoxy-tert-butyl alumotrioxide formed in the reaction of tri-tert-butoxyaluminum with tert-butyl hydroperoxide

Tri-tert-butoxyaluminum reacts with tert-butyl hydroperoxide to produce di-tert-butoxy-tert-butyl alumotrioxide, which decomposes heterolytically to form singlet dioxygen and homolytically with the O—O bond cleavage. The Bu^tOO^·, (Bu^tO)₂AlOO^·, Bu^tO^·, and (Bu^tO)₂AlO^· radicals were identified by ESR using spin traps. These findings confirm the formation of aluminum-containing trioxide. The above radicals initiate alkylarene oxidation by the tri-tert-butoxyaluminum—tert-butyl hydroperoxide system. The carbon-centered and alkylperoxy radicals originated from the oxidized substrates were identified.     

Trisubstituted 1,3,5-Triazines. 5. Reaction of 2,4,6-Tris[di(tert-butoxycarbonyl)nitromethyl]-1,3,5-triazine with Nucleophiles

The reaction of 2,4,6-tris[di(tert-butoxycarbonyl)nitromethyl]-1,3,5-triazine with ammonia, amines, and hydrazine has been studied. It was possible to substitute one of the di(tert-butoxycarbonyl)nitromethyl groups in this compound in the presence of ammonia, primary aliphatic amines, dimethylamine, and morpholine. The reaction with hydrazine leads to both mono- and disubstituted products. A double dealkoxylation occurs in the presence of diethylamine to give the bis(dimethylammonium) salt of 2,4-bis(tert-butoxycarbonylnitromethyl)-6-[di(tert-butoxycarbonyl)nitromethyl]-1,3,5-triazine.     

Phosphorus-containing derivatives of 2,6-di(tert-butyl)phenol: The antioxidant activity and properties of the corresponding phenoxyl radicals

The properties of phenoxyl radicals generated by the oxidation of mono-, di-, and triphosphorus derivatives of 2,6-di(tert-butyl)-4-methylphenol (ionol) were studied by ESR. These compounds exist as conformers that are interconvertible with a temperature-dependent rate. Numerical processing of the ESR spectra gave the thermodynamic and activation parameters that characterize the interconversion of the conformers. The antioxidant activities of the compounds were studied in a model oxidation of oleic acid and with biological objects. These phenols efficiently inhibited radical oxidation reactions. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 744–750, April, 2007.     

Reaction of 4,6-bis(tert-butyl)-2,2,2-trichlorobenzo[d]-1,3,2-dioxaphosphole with phenylacetylene. ipso-Substitution of the tert-butyl group

The reaction of 4,6-bis(tert-butyl)-2,2,2-trichlorobenzo[d]-1,3,2-dioxaphosphole with phenylacetylene follows the mechanism of ipso-substitution of the tert-butyl group that is in para-position relative to the endocyclic O atom of the heterocycle, predominantly yielding 8-(tert-butyl)-2,6-dichloro-2-oxo-4-phenylbenzo[e]-1,2-oxaphosphorinine (NMR data). The structure of its hydrolysis product, 8-(tert-butyl)-6-chloro-2-hydroxy-2-oxo-4-phenylbenzo[e]-1,2-oxaphosphorinine, was proved by X-ray diffraction analysis.     

两个具有Sn4O8簇结构的二丁基锡芳氧乙酸酯配合物的合成、晶体结构及除草活性

以二丁基氧化锡分别与苯氧乙酸(L1)、邻氯苯氧乙酸(L2)反应,合成了2个四核二丁基锡芳氧乙酸酯配合物[(o-R—C₆H₄—OCH₂COOSn(n-Bu)₂)₂O]₂(R=H (C1)、Cl (C2))。经元素分析、IR、¹H和¹³C NMR以及X射线单晶衍射表征其结构。在配合物C1、C2的独立分子中,分别存在1个以Sn2O2平面四元环为中心的Sn₄O₄梯形结构,梯的两侧分别由羧基的2个O原子与梯边的Sn—O—Sn链桥联成六元环,形成一个含Sn₄O₈的锡氧簇结构。配合物在220℃(C1)、250℃(C2)的空气气氛下具有较好的热稳定性。除草活性结果表明,配合物C1对决明具有较好的生长调节作用,配合物C2在50 mg·L^-1浓度下可高效、选择性地抑制刺苋的茎和根的生长。     

两个具有Sn4O8簇结构的二丁基锡芳氧乙酸酯配合物的合成、晶体结构及除草活性

以二丁基氧化锡分别与苯氧乙酸(L1)、邻氯苯氧乙酸(L2)反应,合成了2个四核二丁基锡芳氧乙酸酯配合物[(o-R—C₆H₄—OCH₂COOSn(n-Bu)₂)₂O]₂(R=H (C1)、Cl (C2))。经元素分析、IR、¹H和¹³C NMR以及X射线单晶衍射表征其结构。在配合物C1、C2的独立分子中,分别存在1个以Sn₂O₂平面四元环为中心的Sn₄O₄梯形结构,梯的两侧分别由羧基的2个O原子与梯边的Sn—O—Sn链桥联成六元环,形成一个含Sn₄O₈的锡氧簇结构。配合物在220℃(C1)、250℃(C2)的空气气氛下具有较好的热稳定性。除草活性结果表明,配合物C1对决明具有较好的生长调节作用,配合物C2在50 mg·L^-1浓度下可高效、选择性地抑制刺苋的茎和根的生长。     

Kinetics of the Vapor-Phase Decomposition of Mtbe (Methyl Tert-Butyl Ether) over h3pw12o40/sio2

A kinetic study on the vapor-phase MTBE decomposition over H₃PW₁₂O₄₀/SiO₂ was carried out. Possible kinetic mechanisms are proposed and discussed. Rate expressions were ultimately developed after several verification processes.     

Reactions of 3,5-di(tert-butyl)-1,2-benzoquinone with terminal acetylenes in the presence of phosphorus trichloride. ipso-Substitution of the tert-butyl group

The reactions of 3,5-di(tert-butyl)-1,2-benzoquinone with aryl-and alkylacetylenes in the presence of phosphorus trichloride afford 4-aryl(alkyl)-8-tert-butyl-2,6-dichloro-2-oxo-2H-benzo[e][1,2]oxaphosphinines as the major ipso-substitution products of the tert-butyl group by the chlorine atom. 4-Aryl(alkyl)-6,8-di(tert-butyl)-2,5-dichloro-2-oxo-and 4-aryl(alkyl)-6-tert-butyl-2,8-dichloro-2-oxo-2H-benzo[e][1,2]oxaphosphinines were obtained as the minor products. The structures of the stable representatives of this series were confirmed by X-ray diffraction. Dedicated to Academician G. A. Abakumov on the occasion of his 70th birthday. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1836–1845, September, 2007.     

Electron-excited dioxygen generated by the tri-tert-butoxyaluminum—tert-butyl hydroperoxide system as an efficient oxidant of aniline and some N-substituted anilines

The tri-tert-butoxyaluminum—tert-butyl hydroperoxide system generates molecular oxygen in the electron-excited singlet state (¹O₂), which oxidizes diphenylamine, N-ethylaniline, aniline, and 2,6-diisopropylaniline to form nitroxyl radicals. The latters were identified by ESR at 240—293 K. Oxidation proceeds via the intermediate formation of nitrogen-containing N-peroxide compounds.     

Sterically hindered aliphatic amines in the controlled synthesis of polystyrene

The kinetic features of radical polymerization of styrene in the presence of primary and secondary aliphatic amines combined with benzoyl peroxide and the molecular-mass characteristics of the resulting polymers were studied. In the presence of peroxide initiators, aliphatic amines, as potential sources of stable aminoxyl radicals, provide the synthesis of polystyrene with a controlled molecular mass without gel effect at a relatively high rate. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 159–164, January, 2007.     

The Reactions of 6-(tert-Butyl)-3-hydrazino-1,2,4-triazin-5(2H)-one with Carbonyl Compounds

The reaction of 6-(tert-butyl)-3-hydrazino-1,2,4-triazin-5(2H)-one with acetone and benzaldehyde yields the corresponding hydrazones. In the presence of thionyl chloride the benzaldehyde hydrazone is converted to 3-(tert-butyl)-6-phenyl-1,2,4-triazolo[4,3-b]-1,2,4-triazin-2(1H)-one and this can also be formed via the acylation of the starting hydrazinotriazinone using benzoyl chloride.     

过氧化苯甲酸叔丁酯的热分解动力学研究及SADT推算

研究了过氧化苯甲酸叔丁酯的热分解动力学及不同包装规格下的自加速分解温度(SADT),利用C600微量热仪测试了过氧化苯甲酸叔丁酯的热分解特征,得到升温速率分别为0.1 K/min、0.2 K/min、0.5 K/min、1 K/min下热流随时间的变化曲线,并使用Friedman等转化率法对所得的实验数据进行分析处理,得到了过氧化苯甲酸叔丁酯的分解反应活化能、指前因子等热动力学参数,推算了不同包装规格的过氧化苯甲酸叔丁酯的SADT。结果表明TBPB分解活化能及指前因子随转化率变化而变化,活化能范围为42-135.5 kJ/mol,指前因子范围为0.25-33.5,在25L聚乙烯桶包装下的SADT为59℃,50L下为52℃,200L下为46℃。     

二(o-氟苄基)锡双(四氢吡咯二硫代氨基甲酸酯)和二(p-氯苄基)锡双(二甲基二硫代氨基甲酸酯)的合成、表征及晶体结构

Di(o-fluorbenzyl)tin bis(dithiotetrahydropyrrolcarbamate) (1) and di(p-chlorbenzyl)tin bis(dithiomethylcarbamate) (2) were synthesized. Their structure were characterized by elementary analysis, IR and ¹H NMR and the crystal structure were determined by X-ray single crystal diffraction. The crystal of complex 1 belongs to orthorhombic with space group Pccn, a=2.096 1(12) nm, b=1.018 5(6) nm, c=1.205 9(7) nm, Z=4, V=2.574(2) nm³, D_c=1.624 g·cm^-3, μ(MoKα)=1.348 mm^-1, F(000)=1 272，R₁=0.038 7, wR₂=0.088 5. The crystal of complex 2 belongs to monoclinic with space group C2/c, a=1.531 3(16), b=1.868 4(19), c=0.951 8(10) nm, β=112.602(14)°, Z=4, V=2.514(5) nm³, D_c=1.612 g·cm^-3, μ(MoKα)=1.572 mm^-1, R₁=0.025 4, wR₂=0.070 4. In the complexes 1 and 2, the structures consist of discrete molecules containing six-coordinate tin atom in a distorted octahedron configuration. In crystal of complex 1, molecules are packed in the unit cell in one-dimensional chain structure through a S…S interaction between adjacent molecule. CCDC: 225420, 1; 225421, 2.