Electrochemically induced processes of formation of phosphoric acid derivatives. 3. Electrosynthesis from white phosphorus in alcohol-water solutions

It has been established that the process of splitting of the P-P bonds of the white phosphorus molecules is initiated by cathode-generated nucleophiles (HO^–, RO^–), while functionalization of the P-H bond formed in phosphoric oligomers occurs under the action only of alcohol. The primary product after splitting of all the P-P bonds in phosphoric oligomers is dialkylphosphite (in alcohol-water media), or trialkylphosphite (in absolute alcohol), in the course of electrolysis being transformed into trialkylphosphate. Formation of esters of pyrophosphoric acid with reduced protogenic character of the medium was examined. It is proposed that under these conditions nucleophilic reagents of the type (P)_c-O^– form and participate in splitting of the P-P bonds.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center of the Russian Academy of Sciences, 420083 Kazan. V. I. Ul'yanov-Lenin State University, 420008 Kazan. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 9, pp. 2033–2038, September, 1992.     

立窑法利用中低品位磷矿石生产工业磷酸的研究

本文介绍了在一个特殊的立窑内,利用中低品位磷矿粉和辅料,并利用反应过程中磷元素自身氧化还原的化学热能,生产出市场紧俏的工业级磷酸,磷酸的收率可达90%以上.这是一种新的磷酸生产工艺路线和方法.试验取得了较满意的结果.     

Deep Eutectic Solvents and Multicomponent Reactions: Two Convergent Items to Green Chemistry Strategies

One of the highlights of green chemistry is the development of techniques and procedures with low environmental impact. In the last years, deep eutectic solvents (DES) have become an important alternative to conventional organic solvents. For a period ionic liquids have provoked remarkable interest, but they have been displaced by DES because they show easier preparation methods, lower prices, many of them are biodegradable and compatible with biological systems. In addition, they show adjustable physicochemical properties, high thermal stability, low volatility and are compatible with water. In this paper is reviewed the state of the art of the use of DES paying special attention to the role of reaction media in organic synthesis.     

含羟基中环二胺及其衍生物的合成

合成了一类含羟基中环二胺及其羧酸、磷酸衍生物,且利用强酸型阳离子交换树脂分离得到了游离的含羟基中环二胺羧酸衍生物。     

手性磷酸催化的吲哚与乙醛酸乙酯亚胺的不对称傅克烷基化反应

在20%手性磷酸催化下,吲哚及其衍生物与乙醛酸乙酯亚胺发生不对称傅克烷基反应,合成了9个吲哚取代的甘氨酸衍生物(其中两个为新化合物),其结构经1H NMR表征。     

Synthesis of Terpineol from Alpha-Pinene Catalyzed by α-Hydroxy Acids

We report the use of five alpha-hydroxy acids (citric, tartaric, mandelic, lactic and glycolic acids) as catalysts in the synthesis of terpineol from alpha-pinene. The study found that the hydration rate of pinene was slow when only catalyzed by alpha-hydroxyl acids. Ternary composite catalysts, composed of AHAs, phosphoric acid, and acetic acid, had a good catalytic performance. The reaction step was hydrolysis of the intermediate terpinyl acetate, which yielded terpineol. The optimal reaction conditions were as follows: alpha-pinene, acetic acid, water, citric acid, and phosphoric acid, at a mass ratio of 1:2.5:1:(0.1–0.05):0.05, a reaction temperature of 70 °C, and a reaction time of 12–15 h. The conversion of alpha-pinene was 96%, the content of alpha-terpineol was 46.9%, and the selectivity of alpha-terpineol was 48.1%. In addition, the catalytic performance of monolayer graphene oxide and its composite catalyst with citric acid was studied, with acetic acid used as an additive.     

Sustainable Approaches to the Synthesis of Metallophthalocyanines in Solution

This work aims to investigate more sustainable reaction conditions for the synthesis of metallophthalocyanines. Anisole, glycerol and their mixtures have been investigated as reaction media for the tetramerization of phthalonitriles. Acetates of three divalent first-transition metal cations, Co(II), Cu(II) and Zn(II), were used and several bases were tested, depending on the chosen substrates and reaction conditions, with a view to making the whole process more sustainable while ensuring its scalability. Unsubstituted phthalocyanines were synthesized to analyze the behavior of the different metal ions in terms of reactivity in the new reaction media, resulting in a general Cu > Co > Zn trend, while the nonpolar tetra-tert-butyl substitution was investigated to evaluate the synthesis of soluble derivatives in the new conditions. Furthermore, the potassium hydroxide (KOH)-aided statistical synthesis of the unsymmetrical 9(10), 16(17), 23(24)-tri-tert-butyl-2-iodophthalocyaninato zinc(II), starting from 4-tert-butylphthalonitrile and 4-iodophthalonitrile in a glycerol/anisole mixture, proceeded with a satisfactory 26% yield. Our results provide insights into the investigation of new reaction environments and the understanding of their strengths and weaknesses, with a view to further increasing the sustainability of the synthesis of metallomacrocycles with high added value while lowering their production cost.     

Flow Synthesis in Hot Water: Synthesis of the Atypical Antipsychotic Iloperidone

Inductively heated steel reactors continuously perform organic transformations in water under high temperature conditions, utilizing the unique physiochemical properties of water at subcritical conditions. We demonstrated the power of this set‐up in the continuous synthesis of the atypical antipsychotic drug iloperidone, in which we performed four out of five steps under aqueous conditions.     

Olefin Metathesis at the Dawn of Implementation in Pharmaceutical and Specialty‐Chemicals Manufacturing

The recent uptake of molecular metathesis catalysts in specialty‐chemicals and pharmaceutical manufacturing is reviewed.