Chemistry of Dioxacyclanes: X. Synthesis and Properties of Chlorinated 1,3-Dioxolanes Derived from 4-Cyclohexenecarbaldehydes

4-Cyclohexenecarbaldehyde, its 2-methyl-, 4-methyl-, 2'4-dimethyl derivatives werereacted with 1,2-diols [1,2-propanediol and 3-chloro-, 3-(2-chloroethoxy)-, and 3-(2-chloro-1-chloromethyl-ethoxy-1,2-propandiol] to synthesize the corresponding 2,4-disubstituted 1,3-dioxolanes. Epoxidation and bromination of the products were performed, as well as their condensation with hexachlorocyclopentadiene.     

Chemistry of Dioxacycloalkanes: VII. Synthesis and Properties of Substituted 1,3-Dioxolanes Derived from Carbocyclic Aldehydes

Reactions of 3-cyclohexenecarbaldehyde, 6-methyl-3-cyclohexenecarbaldehyde, bicyclo[2.2.1]-hept-5-ene-endo-2-carbaldehyde, benzaldehyde with 1,2-propanediol, 3-chloro-1,2-propanediol gavethe corresponding 2,4-substituted 1,3-dioxolanes. Their reactions with peroxyacetic acid, bromine, dichloro-carbene, and nucleophiles were studied. The effect of the substituents in the diol and aldehyde on their relative reactivity is discussed.     

Chemistry of Dioxacyclanes: VII. Synthesis of 1,3-Dioxolane Derivatives from 3-(2-Propenyloxy)propane-1,2-diol and Their Properties

2,4-Disubstituted 1,3-dioxolanes were synthesized by reactions of benzaldehyde, its para-chloro derivatives, as well as 3-cyclohexenecarboxaldehyde with 3-(2-propenyloxy)-1,2-propanediol. Theproducts were brought into bromination, dichlorocarbene addition, and epoxidation reactions. It is found that when both components of the heterogeneous reaction of dioxolane ring formation have a double bond, the acid catalyst in strongly deactivated.     

三苯基锗不饱和烃基膦酸衍生物的合成和性质

随着倍半锗氧类化合物的合成及应用研究的日益广泛,含Ge_O键的烃基锗衍生物的合成及应用也逐渐引起了人们的关注.1984年,Lukevics等[1]合成了具有抗癌活性的介吗川类化合物,1990年Kakimoto等[2]报道了具有杀菌活性的环状烃基羧酸的合成与应用.     

三苯基锗不饱和烃基酸衍生物的合成和性质

随着倍半锗氧类化合物的合成及应用研究的日益广泛 ,含 Ge_ O键的烃基锗衍生物的合成及应用也逐渐引起了人们的关注 .1 984年 ,L ukevics等 [1]合成了具有抗癌活性的介吗川类化合物 ,1 990年Kakimoto等 [2 ] 报道了具有杀菌活性的环状烃基羧酸的合成与应用 .但是三烃基锗的膦酸类衍生物的合成及生物活性研究均未见文献报道 .为了研究该类化合物的生理活性 [3～ 5] ,本文以三苯基氯化锗和炔基 (烯基 )膦酸钠为原料 ,在苯中反应 ,合成了一系列双 - O- (三苯基锗 )炔基 (烯基 )膦酸酯和单 - O-三苯基锗炔基 (烯基 )膦酸 ,部分化合物初步生理…     

Quantitative Structure-Property Relationship: XI. Properties of Methyl Benzene Derivatives

A general relationship taking into account multiparticle contributions was applied to benzene methyl derivatives as rigid molecules in which the relative arrangement of two substituents is independent of the presence of other substituents. It was found that this relationship allows estimation of various properties of organic compounds (boiling point, ionization potential, octanol-water partition factor, heat capacity at constant pressure, entropy, standard enthalpy and free energy of formation) with a very good accuracy: The rms deviations of the calculated values can be comparable with the experimental errors.     

Metallocenyl-containing and Unsaturated Fulleropyrrolidine Derivatives: Synthesis and Hydrogenation

Russian Journal of Coordination Chemistry - The possibility of Pd/C-catalyzed hydrogenation of ferrocenyl, cymantrenyl, and ruthenocenyl derivatives of N-methyl-2-(3-chlorovinyl)fulleropyrrolidine...     

Identification of 1,3-Dioxolanes in Coffee-Like Flavorings

This paper concerns a number of commercially available coffee-like flavoring preparations, identifying certain dioxolane structures of particular interest. The research was carried out by GC/MS, and spectral characterization was performed of the compounds in question, and especially of the acetals and ketals produced from compounds with carbonyl functions and 1,2-propylene glycol. Some determinations by means of chiral gas chromatography and by Isotope Ratio Mass Spectrometry (IRMS) have been useful in improving the analytical characterization of certain dioxolanes.     

1,3-二羟基丙酮衍生物的合成

以五氧化二磷为引发剂 ,二甲亚砜氧化 1,3 二芳氧基 (烷氧基 ) 2 丙醇化合物合成了一系列 1,3 二羟基丙酮衍生物 .通过IR和1HNMR对化合物进行了表征     

Synthesis and Chemistry of Phosphonic Derivatives

Abstract

The reaction of thionyl chloride with mixed diesters of the type RP(O)(OCH₂CH₂NR′₂)OR″ are discussed.     

Liquid-Crystalline Properties of Unsaturated Piperazine-2,5-dione Derivatives

The synthesis, characterization, and mesomorphic properties of a new type of liquid-crystalline compounds, (3Z,6Z)-3,6-bis(3,4-dialkoxybenzylidene)piperazine-2,5-diones are reported. These compounds were derived from unsaturated piperazine-2,5-dione as the core group, and were prepared by condensation reactions of 1,4-diacetylpiperazine-2,5-dione and 3,4-dialkoxybenzaldehydes. The products were characterized by ¹H- and ¹³C-NMR spectroscopy, and elemental analysis, and the phase behavior of these compounds was characterized and studied by differential scanning calorimetry (DSC) and polarization microscopy. The results indicate that these rod-like compounds exhibit smectic C (S_c) phases. However, for the derivatives with two flexible alkoxy side chains, highly ordered smectic G (S_G) phases were also formed and confirmed by X-ray powder diffraction. The liquid crystallinity of these molecules was attributed to the presence of intermolecular hydrogen bonds involving the NH groups of the heterocyclic rings. The correlation of phase behavior and molecular shape is also discussed.     

Directional Specificity in the Boronate Cleavage of Unsaturated 1,3-Diol Derivatives

Recently Miyashita, Yanami, and Yoshikoshi reported an apparent case of peripheral bond cleavage in the fragmentation of the boronate 2 derived from octalin 1 to give aldehyde 4 (Scheme I, Path a).¹ Since previous examples of related fragmentations had been shown to proceed with exclusive cleavage of the more highly substituted carbon-carbon bond² (i.e. 2 → 3) it was of interest to examine the above system in greater detail to determine if the neighboring hydroxyl substituent caused the unexpected bond cleavage or if an alternative pathway (Scheme I, Path b) might be operative in this case.³ To that end, we first examined the behavior of the methyl ether derivative (5) of alcohol 1 which was prepared along the lines described below for ether 15 (Scheme II). However hydroboration of unsaturated ether 5 followed by base treatment led to no identifiable product. Evidently steric factors retard the hydroboration and / or basic cleavage of the intermediate boronate.     

Cyanoacetylene and Its Derivatives. 29. New Data on Synthesis and Properties of Substituted 1,3-Oxathiolan-2-ones

We have determined the conditions for carrying out the reaction of 4-alkyl-4-hydroxy-2-alkynonitriles containing bulky or spirocyclic substituents with the KSCN-KHSO₄ system, leading to 5,5-dialkyl-4-cyanomethylene-1,3-oxathiolan-2-ones in quantitative yield (for this, we had to increase the reaction time and use a 10-fold excess of the hydrothiocyanating system compared with the known conditions). 5,5-Dimethyl-4-cyanomethyl-1,3-oxathiolan-2-one reacts with methanol in the presence of triethylamine (20±2°C), forming 2-cyanomethyl-4-cyanomethylene-2-[(1-methoxycarbonyloxyethyl-1-methyl)]-5,5-dimethyl-1,3-dithiolane (yield 90%).     

三苯胺类小分子的合成及其AIE性能研究

以二苯胺、碘苯、对碘甲苯以及对碘苯甲醚为原料,合成了三苯胺及其衍生物T1~T5(4-甲氧基三苯胺、4-甲基三苯胺、4-醛基三苯胺、4-乙烯基三苯胺),并对其紫外-可见吸收光谱与荧光光谱进行了检测。结果表明,连有甲氧基、甲基、乙烯基取代基的三苯胺化合物在甲醇/氯仿混合溶液中具有聚集诱导发光(AIE)性能;而醛基取代的4-醛基三苯胺表现出了聚集荧光猝灭(ACQ)现象。     

Synthesis and Properties of Functionally Substituted Unsaturated Polysulfones

High-temperature copolymerization of ethyl esters of vinyl- or isopropenylcyclopropanecarboxylic acids with SO₂ was studied as a route to functionally substituted unsaturated polysulfones. The composition, structure, and some properties of the polysulfones obtained were studied. The copolymerization mechanism was considered.     

1,3-二氢-1,3-二氧-2H-异吲哚类衍生物的合成及抗新生血管生成活性研究

根据整合素α_vβ₃受体内源性配基RGD三肽构效关系和作用机制,以沙利度胺为先导化合物,设计并合成了5个未见文献报道的5-羧基-1,3-二氢-1,3-二氧-2H-异吲哚类衍生物,其结构经元素分析、红外光谱及核磁共振谱确证.体外初步生物活性筛选实验结果表明,部分目标物对脐静脉血管内皮细胞株(ECV304)增殖有显著抑制活性.