无金属条件下通过与醚的自由基偶联反应实现N-氧化物的C-2烷基化反应（英文）

在无金属条件下通过自由基偶联反应,实现了醚类与N-氧化物的C-2烷基化反应,反应条件温和,只需加入氧化剂二叔丁基过氧化物(DTBP)就能够以中等至高产率获得各种所需产物.     

仲膦与直链单烯烃反应的原位^31P NMR研究（Ⅱ）

应用原位核磁波谱技术，在反应温度１４０－１４５℃，压力０．５ＭＰａ，氘代苯为溶剂，二叔丁基过氧化物为引发剂的条件下，考察了９膦双环壬烷与不同碳数直链单烯烃反应的原位＾３１Ｐ ＮＭＲ谱。实验结果表明，产产物均为烷基－９－膦环环壬烷Ｃ８ Ｈ１４ ＰＣｎＨ２ｎ＋１，但反应速度随烯烃碳数的增加而下降。     

叔丁基取代二苯并-18-冠-6的合成

以二甘醇和邻苯二酚为原料制得二苯并-18-冠-6;以多聚磷酸为催化剂和溶剂,将二苯并-18-冠-6与叔丁醇反应实现叔丁基化;利用正庚烷重结晶对叔丁基化反应产物进行纯化,得到4,4′-二叔丁基二苯并-18-冠-6和4,5′-二叔丁基二苯并-18-冠-6两种对称的二叔丁基二取代苯并冠醚产品.利用红外光谱和核磁共振谱表征了二叔丁基二取代苯并冠醚产物的结构。     

射流冷却下氧化二叔丁基瞬时热解反应的研究

采用射流冷却和高温瞬时热解技术研究了过氧化二叔丁基产物的质量分布和飞行时间谱。ＤＴＢＰ解离率与热解温度的关系表明，１３００Ｋ时ＤＴＢＰ全部解离。     

对二叔丁基苯合成的改进

本文报道用浓H2SO4作催化剂,代替传统的用无水AlCl3作催化剂合成对二叔丁基苯的方法。实验结果表明：当苯:叔丁基氯:浓硫酸摩尔比为：1.7:4.5:0.7,反应温度在5℃～10℃对二叔丁基苯的产率为77%,同传统方法相比,具有操作简便、反应时间短、粗产物纯化容易、产率高等优点。     

无金属参与的氧原子邻位C(sp~3)—S键的构筑

以二叔丁基过氧化物(DTBP)为氧化剂,苯硫酚为硫化试剂,在无金属参与的条件下,于120℃下采用一步法合成了硫代苄醚.这种构筑C(sp~3)—S键的方法具有高原子经济性和高选择性的优点,并以较高的收率获得了一系列目标化合物.     

无金属参与的氧原子邻位C(sp3)—S键的构筑

以二叔丁基过氧化物(DTBP)为氧化剂, 苯硫酚为硫化试剂, 在无金属参与的条件下, 于120 ℃下采用一步法合成了硫代苄醚. 这种构筑C(sp³)—S键的方法具有高原子经济性和高选择性的优点, 并以较高的收率获得了一系列目标化合物.     

烯醇硅醚经三氯甲基自由基加成串联消除反应合成β,β-二氯-α,β-不饱和酮

以二叔丁基过氧化物(DTBP)作氧化剂,氯仿或四氯化碳作三氯甲基自由基源及反应溶剂,由芳酮衍生的烯醇硅醚经自由基加成串联消除反应合成了β,β-二氯-α,β-不饱和酮,反应无需金属催化剂,条件温和,烯醇硅醚底物具有良好的普适性.     

衰减全反射傅里叶变换红外光谱法同时测定叔丁醇和二叔丁基过氧化物

分别应用914 cm-1和875 cm-1处的甲基特征峰作为叔丁醇和二叔丁基过氧化物的定量分析峰,使用峰面积作为吸光度的评估方法,得到的标准曲线的相关系数(R2)分别是0.9987和0.9952,叔丁醇的加标回收率在95％～110％之间,应用衰减全反射傅里叶变换红外光谱法测定3个样品,计算结果的F值、t值和p值,数据表明衰减全反射傅里叶变换红外光谱法与气相色谱法的测定结果一致.     

HY沸石上2，6—二叔丁工萘的择形合成

研究了脱铝HY沸石（n(Si)/n(Al)=3.8）上萘（naph）的选择性叔丁基化反应。结果表明，八面沸石对该反应过程有较好的择形催化作用，两种异构化产物（2，6－二叔丁基萘和2，7－二叔丁基萘)之间存在着热力学平衡，即两种异构化产物可在酸性中心上相互转化，在以叔丁醇为烷基化试剂，WHSV＝2h^-1，n(t-BuOH)/n(naph）＝3，反应温度为120℃的反应条件下，萘的转化率可达98．43％，β－位选择性可高达100％，二叔丁基萘收率可达74．34％，2，6－二叔丁基萘／2，7－二叔丁基萘/2,7-叔丁基萘质量比为6．24。     

Reactions of compounds containing SnLi and GeLi bonds with organic and organometallic peroxides

The reactions of tris(trimethylsilylmethyl)stannyllithium, tris(trimethylsilylmethyl)germyllithium and triethylgermyllithium with di-t-butyl peroxide, bis(trimethylsilyl)peroxide, trimethyl(t-butylperoxy)silane, triphenyl(t-butyl-peroxy)germane, bis(triphenylgermyl) peroxide, triphenyl(trimethylsilylperoxy)-germane, benzoyl peroxide and dicyclohexyl peroxydicarbonate were investigated. The reactions proceed under mild conditions with nucleophilic attack by the R₃M anion (R = Et, Me₃SiCH₂, M = Ge, Sn) on one of the peroxide oxygen atoms. In the case of unsymmetrical organometallic peroxides the character of nucleophilic cleavage is dependent on the nature of the starting nucleophile, steric effects of peroxide group substituents and other factors.     

Free radical addition of carboxylic esters to unsaturated epoxy compounds

Conclusion The addition of esters to unsaturated epoxy compounds, initiated by di-t-butyl peroxide, forms esters containing an epoxy group.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, pp. 2297–2300, October, 1969.     

PHOTOCHEMICAL AND FREE RADICAL INITIATED REACTIONS OF 1,3-DIMETHYLTHYMINE WITH ETHANOL

The photochemically induced reaction of 1,3-dimethylthymine (DMT) with ethanol gives four major alcohol adducts. These have been identified as l,3-dimethyl-6-(1-hydroxy-1-ethyl)thymine ( 1 ), 1,3-dimethyl-5-(2-hydroxy-l-pyl)uracil ( 2 ), and the cis and trans isomers of 5,6-dihydro-l,3-di-methyl-6-(l-hydroxy-l-ethyl) thymine ( 3 and 4 ). The compounds 3 and 4 have been shown to be identical to the adducts produced in y-ray irradiated ethanolic aqueous solutions of DMT. Cyclobutane dimers of DMT are also found in the photochemical reaction mixture. Reaction of 1-hydroxyethyl radicals with DMT, initiated by decomposition of di-t-butyl peroxide, leads to formation of the same alcohol adducts, as well as to DMT adducts containing two molecules of ethanol. The acetone sensitized reaction of DMT with ethanol gives 1,3, and 4, along with a variety of adducts incorporating the acetone sensitizer.     

The Decomposition of 2,2-Bis(tert-Butylperoxy)-butane under High Pressure

The thermal decomposition of the bifunctional peroxide 2,2-bis(tertbuty1 peroxy)butane was investigated in a flow reactor at temperatures of 135 to 212°C and pressures of up to 2000 bar. The concentration of the peroxide in isododecane was varied between 1 and 22% by weight. The rate of decomposition measured was used to determine the energy of activation (E_A = 151.1 ± 3 kJ/mol) and the activation volume (Δv” = 22.3 mL/mol). Up to a peroxide concentration of 5% by weight, the decomposition takes place according to a firat-order rate equation. Above this concentration, induced decomposition takes effect. Gas chromatographic analysis showed that the liquid decomposition products consisted mainly of acetone and tert-butyl alcohol apart from methyl ethyl ketone, propionic acid methyl ester, acetic acid ethyl ester, tert-butyl methyl ether, and oligomers of the solvent. The gaseous decomposition products consisted of methane and carbon dioxide as well as small quantities of ethane, propane, and ethylene. A theoretical explanation of the mechanism of decomposition is postulated which explains the spectrum of these components and its changes as a function of the peroxide concentration, the residence time, the temperature, and the pressure.     

Evaluation of Initiators and Fillers in Diallyl Phthalate Resins by Differential Scanning Calorimetry

Seven organic peroxide initiators for the polymerization of diallyl-o-phthalate prepolymers were studied using differential scanning calorimetry. Included were t-butyl perbenzoate, dicumyl peroxide, α,α′-bis(t-butyl peroxy) diisopropyl-benzene, 2,5-dimethyl-2,5-di(t-butyl peroxy) hexane, 2,5-dimethyl-2,5-di(t-butyl peroxy)hexyne-3, di-t-butyl peroxide, and t-butyl hydroperoxide. Heats of reaction and reaction rate constants are presented for each initiator at 1, 2, 3, and 4 phr of diallyl-o-phthalate prepolymers. The differences in reaction temperature and rate are discussed. Effects of four types of commonly used fillers (asbestos floats, ground quartz, calcium silicate, and clay) on the heats of reaction of diallyl-o-phthalate prepolymers using t-butyl perbenzoate and dicumyl peroxide initiators show the large inhibiting effect of untreated kaolinite clays on this polymerization.     

微量热法研究过氧化氢酶底物抑制动力学

过氧化氢酶是需氧生物体内抗氧化酶系的重要组分。过氧化氢酶催化过氧化氢分解是一个两底物酶促反应,依照Chance提出的机理,反应速率方程具有一级反应方程的形式。此反应在高浓度底物存在的情况下,表现出明显的不可逆底物抑制。本研究用热动力学方法研究了这一反应,提出了一种不可逆底物抑制机理,并应用该机理求出了相关动力学参数。在310.15K,pH=7.0时k0=9.6×10^5L·mol^-1^·s^-1,k1/k2=2.9×10^6。实验结果证明此机理正确有效。     

Isothermal decomposition of hydrogen peroxide dihydrate

We present a new method of growing pure solid hydrogen peroxide in an ultra high vacuum environment and apply it to determine thermal stability of the dihydrate compound that forms when water and hydrogen peroxide are mixed at low temperatures. Using infrared spectroscopy and thermogravimetric analysis, we quantified the isothermal decomposition of the metastable dihydrate at 151.6 K. This decomposition occurs by fractional distillation through the preferential sublimation of water, which leads to the formation of pure hydrogen peroxide. The results imply that in an astronomical environment where condensed mixtures of H(2)O(2) and H(2)O are shielded from radiolytic decomposition and warmed to temperatures where sublimation is significant, highly concentrated or even pure hydrogen peroxide may form.     

过氧化氢的热分解及其引发丙烯腈聚合反应的研究

本文研究了过氧化氢在二甲基甲酰胺中的热分解反应,测定了不同温度下的分解速率常数和表现活化能。同时研究了过氧化氢引发丙烯腈的聚合反应,确定了聚合动力学方程。     

Comparison of isothermal and non-isothermal chemiluminescence and differential scanning calorimetry experiments with benzoyl peroxide

Difference in the kinetics of chemiluminescence (CL) and differential scanning calorimetry records for decomposition of originally solid benzoyl peroxide continuing as a melt reaction was outlined. While the main portion of heat measured by DSC is released in the spontaneous decomposition of benzoyl peroxide starting as a homolytic scission of peroxidic bonds, the CL light emission in oxygen comes presumably from the subsequent disproportionation reaction of polyphenyl peroxyl radicals and monitors the induced decomposition of peroxide. Thermogravimetry revealed that oxygen remains partially bound to the products of benzoyl peroxide decomposition.     

脂族酰基过氧化物分解动力学的分研究 III: 过氧化3,5,5-三甲基己酰在萃中的解动力学和机理

The kinetics of decomposition of 3, 5, 5-trimethylhexanoyl peroxide (1) in benzene has been studied at 30, 40 and 50`C and the cage effect of decomposition has been determined by scavenging method. The relative amounts of the main products of decomposition of 1 at 50`C with change of initial concentration have been determined. The results showed that the decomposition of 1 followed first plus three halves order kinetics as reported for lauroyl peroxide (2), but had a larger cage effect of 0.6. The mechanism of decomposition of 1 is practically the same as what we have proposed for 2. The faster rate and larger cage effect but less induced decomposition of 1 than that of 2 are attributed to the branching of the molecule of 1, especially to the presence of β-methyl group, which causes a larger entropy increase in the transition state.