Smectic Mesophases from Dihydroxy Derivatives of Quaternary Alkylammonium Salts

Long alkyl-chain quaternary ammonium salts bearing two hydroxyethyl groups at the polar head group form smectic A mesophases at high temperatures and ordered smectic T mesophases of tetragonal symmetry at lower temperatures. The latter phase resembles a supermolecular grid (figure); it is formed by a hydrogen-bonding network between the hydroxy groups themselves on the one hand, and between the hydroxy groups and the bromide anions on the other, which is perfectly congruous with the tetragonal packing of the quaternary ammonium groups.     

巧制无水硫酸铜

在中学化学实验中,通常用无水硫酸铜来检验少量水的存在,然而,无水硫酸铜的吸湿性很强,需要时现制现用.制取无水硫酸铜时,通常将硫酸铜晶体放在蒸发皿中用小火慢慢加热并用玻璃棒不停搅拌,往往由于加热时温度稍高便有少量硫酸铜分解,使得一部分变黑,而且易结块,操作比较麻烦,而笔者为了克服以上缺点,不需加热便能巧妙制得无水硫酸铜,不但操作简单,而且实验效果明显.     

Convenient Access to α‐Fluorinated Alkylammonium Salts

A series of novel α‐fluoroalkyl ammonium salts was obtained from the corresponding cyano compounds or nitriles by reaction with anhydrous HF. Room‐temperature stable trifluoromethyl ammonium salts were obtained in quantitative yield in a one‐step reaction at ambient temperature from the commercially available starting materials BrCN or ClCN. The novel cations [CF₃CF₂NH₃]⁺, [HCF₂CF₂NH₃]⁺, and [(NH₃CF₂)₂]²⁺ were obtained from CF₃CN, HCF₂CN, and (CN)₂, respectively, and anhydrous HF. The aforementioned fluorinated ammonium cations were isolated as room temperature stable [AsF₆]^? and/or [SbF₆]^? salts, and characterized by multi‐nuclear NMR and vibrational spectroscopy. The salts [HCF₂NH₃][AsF₆] and [CF₃NH₃][Sb₂F₁₁] were characterized by their X‐ray crystal structure.     

采用不同碳链长度的季铵盐型表面活性剂模板剂合成MCM-48分子筛

采用3种不同碳链长度的季铵盐型表面活性剂CnTAB(n=12、14、16),成功合成了具有不同孔径的MCM-48分子筛.XRD结果表明,所合成的分子筛均具有MCM-48的特征衍射峰,且结晶度良好;N2吸附-脱附实验表明,所得MCM-48的孔径实现了在1.86～2.6nm之间的调变,且其均有大于1200m2/g的比表面积.     

Anion‐Exchange Properties of Trifluoroacetate and Triflate Salts of N‐Alkylammonium Resorcinarenes

The synthesis of N‐benzyl‐ and N‐cyclohexylammonium resorcinarene trifluoroacetate (TFA) and triflate (OTf) salt receptors was investigated. Solid‐state analysis by single‐crystal X‐ray diffraction revealed that the N‐alkylammonium resorcinarene salts (NARSs) with different upper substituents had different cavity sizes and different affinities for anions. Anion‐exchange experiments by mixing equimolar amounts of N‐benzylammonium resorcinarene trifluoroacetate and N‐cyclohexylammonium resorcinarene triflate, as well as N‐benzylammonium resorcinarene triflate and N‐cyclohexylammonium resorcinarene trifluoroacetate showed that the NARS with flexible benzyl groups preferred the larger OTf anion, whereas the rigid cyclohexyl groups preferred the smaller TFA anions. The anion‐exchange processes were confirmed in the solid state by single‐crystal and powder X‐ray diffraction experiments and in the gas phase by electrospray ionization mass spectrometry.     

化学气相传输法制备无水稀土氯化物

以化学气相传输法制取无水EuCl3,ErCl3和LuCl3。稀土氧化物为原料 ,无水氯化铝为氯化剂和传输介质。Ln2 O3与过量的氯化铝在3 0 0℃反应 ,生成LnCl3。LnCl3在高温与氯化铝反应生成气态配合物 ,该配合物在低温分解。控制适当的温度梯度场 ,可实现LnCl3与其他固体分离。残余氯化铝在 2 0 0℃加热除去。产物收率 >90 % ,纯度 >99 5%。利用化学气相传输法可获得纯度较高的无水LnCl3。     

Preparation of Sec-Alkyl Isouronium Salts

Eight examples of sec-alkyl isouronium salts were readily prepared from sec-alcohols, cynamide, and methanesulfonic acid (or CF₃SO₃H or HBF₄).     

A Simple Preparation of 3-Formyl-Cycloalkenones

Recently, we required a convenient method for preparing the 3-formyl-cyclohexenone, 1, starting from dihydroresorcinol. The conversion of dihydroresorcinol into the cyclohexenone derivative 2, could be readily accomplished using the elegant method of Stork and Danheiser,¹ however, existing methods for the transformation of the ketone group of 2 into the formyl group of 1 did not prove satisfactory.² We describe here, a simple and general method for the transformation of 2 into 1 (Scheme I).     

Crystalline Transformation of Chitosan from Hydrated to Anhydrous Polymorph Via Chitosan Monocarboxylic Acid Salts

ABSTRACT

Spontaneous removal of monocarboxylic (formic, acetic, propionic or butyric) acids accompanying dehydration of the corresponding chitosan salts was observed from X-ray fiber diffraction diagrams obtained during the storage of these salts for a given period of time. The first three salts were prepared by immersing a tendon chitosan (a hydrated crystal) in an aqueous solution of respective monocarboxylic acid and 2-propanol. The salts showed similar fiber patterns not only to one another but also to the “Eight-fold” polymorph of the original chitosan, indicating that they are Type II salts, hydrated crystals, where the backbone chitosan molecule takes up an eight-fold helical conformation. The temperature required for the salt formation depended on the hydrophobicity of the acid, e.g., the chitosan formic acid salt could be prepared at room temperature, whereas, formation of the propionic acid salt was carried out at 4 °C. All the acids spontaneously evaporated accompanied by dehydration during storage of the salts, resulting in formation of anhydrous crystalline chitosan. Removal of the monocarboxylic acids was accelerated by increasing the hydrophobicity of the acid: at 100% relative humidity approximately 3 months for the formic, 1 month for the acetic and 3 weeks for the propionic acid salts. In the case of butyric acid the anhydrous polymorph of chitosan was obtained immediately after the reaction, suggesting that the water removing action of this acid was too fast to detect a Type II salt by the present X-ray method. The anhydrous crystals of chitosan were irreversibly prepared by annealing a hydrated crystal in water at a high temperature, such as 240 °C, leading to a little loss of orientation and to thermal decomposition of the sample specimen to some extent. But it was found that, through Type II salts of monocarboxylic acids, the hydrated crystals of chitosan can be dehydrated even at room temperature without any loss of orientation and decomposition of the chitosan specimen.     

A Simple Preparation Method for Phytochromobilin

Phytochromobilin (PΦB), the chromophore of plant phytochromes, is difficult to isolate because phytochromes occur at very low concentrations in plants. It is, therefore, frequently replaced in plant phytochrome studies by phycocyanobilin, which is abundant in cyanobacteria. PΦB is also an attractive chromophore for far‐red emitting chromoproteins. In this work, we design and optimize a simple method to efficiently isolate useful quantities of PΦB: The chromophore is generated in Escherichia coli and transiently bound to a tailored chromophore‐binding domain of ApcE2, the apo‐protein of a core‐membrane linker, from which it can subsequently be released. The ease and effectiveness of this method hinges not only on the enhanced biosynthesis of PΦB in the presence of the ApcE2 construct from Synechococcus sp. PCC7335, but also on the noncovalent binding of the pigment to its apo‐protein. The isolated PΦB was successfully incorporated into phytochrome‐related assemblies, and furthermore, the noncovalently bound PΦB could be transferred directly from the ApcE2 construct to the apo‐proteins of phytochromes, cyanobacteriochromes and phycobiliproteins, without loss of relevant biological activity.     

Stabilization of the Pentazolate Anion in Three Anhydrous and Metal‐Free Energetic Salts

According to previous reports, metal cations or water molecules are necessary for the stabilization of pentazolate anion (cyclo‐N₅^?) at ambient temperature and pressure. Seeking a new method to stabilize N₅^? is a big challenge. In this work, three anhydrous, metal‐free energetic salts based on cyclo‐N₅^? 3,9‐diamino‐6,7‐dihydro‐5 H‐bis([1,2,4]triazolo)[4,3‐e:3′,4′‐g][1,2,4,5] tetrazepine‐2,10‐diium, N‐carbamoylguanidinium, and oxalohydrazinium (oxahy⁺) pentazolate were synthesized and isolated. All salts were characterized by elemental analysis, IR spectroscopy, ¹H, ¹³C, and (in some cases) ¹⁵N NMR spectroscopy, thermal analysis (TGA and DSC), and single‐crystal XRD analysis. Computational studies associated with heats of formation and detonation performance were performed by using Gaussian 09 and Explo5 programs, respectively. The sensitivity of the salts towards impact and friction was determined, and overall the real N₅ explosives showed promising energetic properties.     

A Simple Preparation of Trimethylsilyl Acetic Acid

A facile access to trimethylsilyl acetic acid is described. The method involves the preparation of the corresponding trimethylsilyl ester in fairly good yield (70%).     

A Simple Preparation of 1-Substituted Uracils

Reaction of isocyanates with 3,3-diethoxypropionamide gives diethoxy acyl ureas which may be conveniently cyclized to 1-substituted uracils.     

A Simple Preparation of Dialkylsulfinyl- and Dialkylsulfonyl-Sulfides

A first general approach to sulfinyl-sulfides R¹-S(O)-(CH₂)_n-S-R² and sulfonyl-sulfides R¹-S(O₂)-(CH₂)_n-S-R² with variable and different alkyl substituents is described.     

有机溶剂法无水氯化镁的制备与表征

Ammonium carnallite was synthesized by hydrated magnesium chloride in salt lake and ammonium chloride solution. Dehydrated ammonium carnallite was dissolved in methanol under low temperature by feeding ammonia, to prepare anhydrous magnesium chloride. The results show that anhydrous magnesium chloride contains magnesium oxide in an amount less than 0.1% by weight, the yield of magnesium chloride was above 99.5%. Ammonium carnallite, ammoniation magnesium chloride and anhydrous magnesium chloride were characterized by thermoanalysis, X-ray powder diffraction and scanning electron microscopy.     

A Simple Preparation of 2-Pyrone Structural Unit

The synthesis of 4-substituted 2(5H)-furanones via organosilicon intermediates has been reported from this laboratory.¹ This method gave possibilities to extend the synthesis to include 2-pyrone species (e. g. 1), which are structure units of some natural products.