N,N'-二(二乙氧基硫代磷酰基)-1,4-苯二胺的合成、晶体结构及热性能研究

通过二乙氧基硫代磷酰氯与对苯二胺反应生成了标题化合物N,N'-二(二乙氧基硫代磷酰基)-1,4-苯二胺，并应用元素分析, FTIR及¹H NMR对标题化合物进行了表征. 利用X射线单晶衍射测定了其晶体结构, 同时应用TG分析法对其热性能进行了分析. 标题化合物的相对分子质量M_r＝412.42, 为正交晶系, Pbca空间群, 晶胞参数为a＝0.86936(16) nm, b＝1.2787(2) nm, c＝1.8897(3) nm, β＝90°, V＝2.1006(7) nm³, Z＝8, D_c＝1.304 g/cm³, μ(Mo Kα)＝0.425 mm^－1, F(000)＝872, S＝1.052. 最终偏离因子R＝0.0628, wR＝0.1860, 可观测衍射点1852个[I＞2σ(I)]. 该晶体通过对苯二胺连接并以中心对称分布, 并形成层状结构, 且存在弱的分子内氢键N—H…S. TG分析表明该化合物有很好的热稳定性及成炭性, 通过其阻燃聚丙烯腈表明, 该物质是一种高效能的膨胀型阻燃剂.     

4-Hydroxy-2-quinolones 131. Bromination of 3-allyl-4-hydroxy-2-oxo-1,2-dihydroquinoline

The bromination of 3-allyl-4-hydroxy-2-oxo-1,2-dihydroquinoline by molecular bromine is accompanied by the closure of a five membered furan ring and gives the corresponding 2-bromomethyl-3,9-dihydro-2H-furo[2,3-b]quinolin-4-one. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1677–1686, November, 2007.     

2A12-T6铝合金表面双-(γ-三乙氧基硅丙基)四硫化物薄膜的特性

采用傅立叶变换红外光谱分析了2A12-T6铝合金表面自组装双-(!-三乙氧基硅丙基)四硫化物硅烷偶联剂(SCA)薄膜结构特征,并采用电化学极化曲线评价了薄膜的耐蚀性能.结果表明,铝材表面自然晾干,SCA薄膜分子之间主要通过氢键连接,腐蚀电流密度减小1个数量级以上.120℃的加热处理促进铝板表面通过SiOSi链接而形成SCA网状薄膜结构,并通过在界面上形成SiOAl界面相结构而与铝板表面牢固连接,腐蚀电流密度降低2个数量级以上.SCA乙醇溶液浸泡处理10min比浸泡2s～1min的铝板表面SCA薄膜内氢键缔合羟基要多.     

取代1,1'-联-2-萘酚在铜胺络合物催化作用下的氧化反应

用CuCl2?2H2O与小分子的有机胺形成络合物,模拟氧化还原酶对多米诺式反应(Dominoreaction)进行催化反应,在氧气存在条件下,取代1,1'-联-2-萘酚化合物被氧化为二苯并呫吨类化合物,产物的结构经核磁共振、红外光谱及质谱进行确证.     

Thermodynamic Data for the Complex Formation of Alkylamines and Their Hydrochlorides with α-Cyclodextrin in Aqueous Solution

The formation of complexes between α-cyclodextrin and n-alkylamines and their hydrochlorides has been studied in aqueous solution using calorimetric titrations. All alkylamines form stronger complexes than the corresponding hydrochlorides. The values of the reaction enthalpies are smaller for the alkylamine hydrochlorides compared with the alkylamines. By increasing the number of methylene groups, these differences become smaller. In addition, the reaction enthalpies for protonation of the alkylamines and their complexes with α-cyclodextrin have been measured. The heat of protonation of these complexes is always smaller compared with the alkylamines. Due to the protonation and the formation of a strong solvation shell around the ammonium group the interactions with α-cyclodextrins are weakened. From a thermodynamic cycle using all measured reactions, it can be concluded that the aggregation of the alkylamines with long alkyl chains (heptyl-, octyl-, and nonylamine) has an influence on the values of the reaction enthalpies and entropies for the protonated form only.This revised version was published online in July 2005 with a corrected issue number.     

Xyloccensin L, a novel limonoid from Xylocarpus granatum

The isolation and structure elucidation of xyloccensin L from the stem bark of Xylocarpus granatum is described. Xyloccensin L is a highly oxidized heptacyclic A, B, D-seco limonoid with an α-8, 30-epoxy ring and a rare 1, 29 oxygen bridge.     

Synthesis ofO-methyloximes and nitrones of a series of substituted 4-[2-hydroxy-2-(1H-1,2,4-triazol-1-ylmethyl)cyclohexylidenemethyl]-benzaldehydes and their fungicidal activity

O-Methyloximes and nitrones of a series of substituted 4-[2-hydroxy-2-(1H-1,2,4-triazol-1-ylmethyl)cyclohexylidenemethyl]benzaldehydes have been synthesized, and their fungicidal activity has been assayed. All of them exhibit low fungicidal activity in thein vitro assays and high activity in thein vivo assays; theO-methyl oximes are more active than the corresponding nitrones.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2082–2087, December, 1993.     

Electron depleted bis(methylene)cyclobutenes: sulfinyl and sulfonyl substitution

Double [2,3] sigmatropic rearrangements of bis(propargyl sulfenates) to bis(allenic sulfoxides) and of bis(propargyl sulfinates) to bis(allenic sulfones) are shown to be a convenient and effective method for the preparation of conjugated diallene systems bearing two electron withdrawing trihalomethyl sulfoxide or sulfone substituents either on C-1 and C-6, or on C-3 and C-4. Such substituents are further shown to facilitate cyclization to bis(methylene)cyclobutenes, and to stabilize the latter. The electron withdrawing group substitution on the exocyclic methylene extremities proved more effective than similar substitution on the endocyclic double bond.     

Synthetic receptors based on calix[4]arene functionalized at the lower rim in molecular recognition of dicarboxylic, α-hydroxycarboxylic,and α-amino acids

New calix[4]arenes, di- and tetrasubstituted at the lower rim, with different functional groups were synthesized. They were studied as carriers of a series of dicarboxylic and -hydroxycarboxylic acids through a liquid impregnated membrane. The calix[4]arenes under study are capable of molecular recognition of oxalic acid in the series of structurally similar dicarboxylic and -hydroxycarboxylic acids. The regularities found make it possible to change purposefully the receptor ability of 1,3-disubstituted calix[4]arenes by variation of the nature of substituents.     

A High Sensitivity Fluorescent Chemo-sensory System Based on β-Cyclodextrin Dimer Modified with Dansyl Moieties

-Cyclodextrin dimer linked with ethylenediamine at the upper rim of the cyclodextrin has been synthesized and then modified with two dansyl moieties inthe presence of N,N'-dicyclohexylcarbodiimide. The sensing ability and bindingproperty of the title compound were investigated for steroids and terpenoids. Thefluorescence intensity of this dimer was decreased when a host–guest complex was formed. The value I/I⁰, where I⁰ and I are fluorescence intensitiesin the absence and presence of a guest and I is I⁰- I, was used as a parameter of sensitivity. This host exhibited a much higher sensitivity and selective molecular recognition ability for bile acids such as ursodeoxycholic acid andchenodeoxycholic acid and terpenoids such as (-)-borneol than the dansyl-modifiedcyclodextrins reported previously including -cyclodextrin dimer. The behaviors of the appended moieties of the host during the formation of host–guest complexes were studied using induced circular dichroism (ICD) and fluorescence spectra. The ICD intensityof this dimer was decreased on accommodation of a guest and this spectral pattern of the title dimer was opposite to that of bis dansyl-modified -cyclodextrin monomer. Theguest-induced variations in the fluorescence and ICD intensities suggest that this dimer formed a 1 : 1 host–guest complex and the appended moieties act as a hydrophobic cap.