Synthesis of Acylated Steroidal Olefins and Their Derivatives

Acylation of cholest-5-ene and cholest-5-ene 3-one with anhydrides in the presence of zinc chloride and characterization of products thus obtained on the basis of elemental analysis, spectral data, and chemical transformations are reported.     

Preparation the Esters of Oleic Acid-Maleic Anhydride Copolymer and Their Evaluation as Flow Improvers for Waxy Crude Oil

Five comb-like copolymers derived from oleic acid-maleic anhydride were prepared and then esterified by long-chain fatty alcohol (POMA C_n), where n = 18, 20, 22. These polymers were characterized by FTIR and ¹H NMR analysis. The molecular weight was determined by using gel permeation chromatography (GPC). The prepared copolymers were investigated as flow improvers and pour point depressants (PPD) for crude oil. From the evaluation, it was found that, the maximum depression of PP was obtained by (POMA₂ C₂₂) with long-chain alcohol (C₂₂–OH) from 27°C to 15°C (ΔPP_3000ppm = ?12°C). On the other side, it was remarked that no depression obtained by (POMA₂ C₁₈), which esterified by alcohol (C₁₈–OH) at the same condition. The depression of pour point effectiveness was discussed on the light of polymers structure, molecular weights, and their concentrations. By analysis the results of the rheological flow properties, it was found that the POMA₂ C₂₂ enhanced the Bingham yield values (τ_β). The τ_β for crude oil without additives against 15, 27, and 39°C were 0.286, 0.131, and 0.075 Pa respectively, whereas the τβ for the treated crude oil with POMA₂ C₂₂ were 0.027, 0.022 and 0.010 Pa at 3000 ppm at the same temperatures. By using the photomicrography analysis, it was found that, the wax morphology was greatly modified to fine dispersed crystals of compact size.     

悬浮聚合制备大尺寸梭形聚苯乙烯粒子新方法及机理研究

利用氢氧化钾对苯乙烯-马来酸酐交替共聚物(SMA)进行水解,所得中等皂化程度的SMA水解产物(SMAA)在水溶液中具有刚性棒状直链构型;将此特殊结构的大分子作为分散剂用于苯乙烯悬浮聚合,通过控制搅拌速度和油水比,可得到梭形聚苯乙烯粒子;在优化条件下,粒子平均长度6.8 mm,宽度1.4 mm,厚度0.5 mm,长径比约5.0.其可能的机理为,中等皂化程度的刚棒直链型SMAA在聚合物"软粒子"表面能形成难以"回复"的有效保护层,使由剪切形成的变形聚合物"软粒子"在聚合过程中能保持形状和尺寸的稳定,从而得到梭形聚合物粒子.     

Glyoxylic acid in the reaction of isatoic anhydride with amines: a rapid synthesis of 3-(un)substituted quinazolin-4(3H)-ones leading to rutaecarpine and evodiamine

A dual reactant/catalyst role of glyoxylic acid in the reaction of isatoic anhydride with various amines afforded a novel, robust and rapid synthesis of 3-(un)substituted quinazolin-4(3H)-ones. This metal catalyst-free reaction proceeds via an unusual and unexpected cleavage of C–C bond. A shorter and common route to two alkaloids, that is, rutaecarpine and evodiamine is also accomplished.     

Two-Step Derivatization of Amino Acids for Stable-Isotope Dilution GC–MS Analysis: Long-Term Stability of Methyl Ester-Pentafluoropropionic Derivatives in Toluene Extracts

Analysis of amino acids by gas chromatography-mass spectrometry (GC–MS) requires at least one derivatization step to enable solubility in GC–MS-compatible water-immiscible organic solvents such as toluene, to make them volatile to introduce into the gas chromatograph and thermally stable enough for separation in the GC column and introduction into the ion-source, and finally to increase their ionization by increasing their electronegativity using F-rich reagents. In this work we investigated the long-term stability of the methyl esters pentafluoropropionic (Me-PFP) derivatives of 21 urinary amino acids prepared by a two-step derivatization procedure and extraction by toluene. In situ prepared trideuteromethyl ester pentafluoropropionic derivatives were used as internal standards. GC–MS analysis (injection of 1 µL aliquots and quantification by selected-ion monitoring of specific mass fragments) was performed on days 1, 2, 8, and 15. Measured peak areas and calculated peak area ratios were used to evaluate the stability of the derivatives of endogenous amino acids and their internal standards, as well as the precision and the accuracy of the method. All analyses were performed under routine conditions. Me-PFP derivatives of endogenous amino acids and their stable-isotope labelled analogs were stable in toluene for 14 days. The peak area values of the derivatives of most amino acids and their internal standards were slightly higher on days 8 and 15 compared to days 1 and 2, yet the peak area ratio values of endogenous amino acids to their internal standards did not change. Our study indicates that Me-PFP derivatives of amino acids from human urine samples can easily be prepared, are stable at least for 14 days in the extraction solvent toluene, and allow for precise and accurate quantitative measurements by GC–MS using in situ prepared deuterium-labelled methyl ester as internal standard.     

Synthesis,characterization and biological activity evaluation of new 3- methyl and 4- fluoro isoindoline-1, 3-dione/phthalimide analogues

The convenient route for the synthesis of a series of new Isoindoline-1, 3-dione/phthalimide analogues by condensation of substituted phthalic anhydride with an appropriate Ar-amine is described. Selective phthalimide derivatives were evaluated for their preliminary biological activities against Gram-positive, Gram-negative and fungi strains. These encouraging results could be helpful for the development of new antibacterial or antifungal agents.     

An efficient synthesis of medicinally important indole based triarylmethanes by using propylphosphonic anhydride (T3P®)

Abstract

We have developed an economical and efficient method for the synthesis of medicinally and synthetically important indole-based triarylmethanes by using indoles and benzhydrols in the presence of propylphosphonic anhydride (T3P^®). This methodology is an alternate approach for the C–C bond formation with good to excellent yields. In this T3P-mediated dehydration approach, the by-product is highly soluble in water, so that it can be done at larger scale also. In addition to that this efficient protocol has several advantages such as mild reaction conditions, short reaction time and operational simplicity. We have successfully synthesized pyrrole, imidazothiadiazole and imidazolo pyridine based triarylmethanes also.     

NaZnPO4催化碳酸二甲酯和丙氨酸“一锅法”合成N-羧基丙氨酸酸酐

以碳酸二甲酯（DMC）代替光气,一锅法合成α-氨基酸-N-羧酸酐（NCAs）是实现绿色制备多肽的重要途径.制备了酸碱协同催化剂NaZnPO₄,用该催化剂催化DMC和丙氨酸"一锅法"合成N-羧基丙氨酸酸酐（Ala-NCA）.在N,N-二甲基甲酰胺（DMF）溶剂中,150℃的反应条件反应8 h时,Ala-NCA的收率最高为46.84%,催化剂循环5次后收率仍达38.62%.NaZnPO₄中Zn²⁺和O-Na具有有效的酸碱协同催化作用,在反应过程中具有去质子化、精准酰基化和高效成环的作用.利用TG-MS-IR技术研究了催化剂表面上原料转化和中间体精准关环过程,并提出了可能的反应催化机理.     

A weak cation exchanger by encapsulating silica with maleic anhydride–modified polyvinyl alcohol

A novel weak cation exchanger is described by encapsulating silica with a (or multiple) layer(s) of maleic anhydride–modified polyvinyl alcohol coating(s). The preparation method is facile and fast, which is simply performed by dipping silica particles into maleic anhydride–modified polyvinyl alcohol solution as‐synthesized, then filtering and curing thermally, and finally generating a thin coating onto silica particles. Multiple layers of maleic anhydride–modified polyvinyl alcohol coatings can be generated by repeating above steps, offering an easy way to manipulate the capacity. The obtained weak cation exchanger demonstrated high separation efficiency and good selectivity toward common inorganic cations, for example, high plate count of 81 000 per meter was obtained for NH₄⁺. Simultaneous separation of alkali and alkaline earth metals could be achieved within 14 min under isocratic conditions.     

Development of GC–MS/MS method with programmable temperature vaporization large volume injection for monitoring of 17β-estradiol and 2-methoxyestradiol in plasma

Monitoring of estradiol and its metabolites in biological samples is essential for the accurate diagnosis of a number of endocrine diseases. In this study, a sensitive, precise and specific GC–MS/MS method for the quantification of 17β-estradiol (17-BE) and its main metabolite, 2-methoxyestradiol (2-MEOE), in plasma was developed and validated. Plasma concentrations of these steroids are currently investigated as diagnostic markers for pre-eclampsia, a systematic disorder of pregnancy and a leading cause of maternal and fetal morbidity and mortality worldwide.