ACETOLYSIS OF TECHNICAL OILS AS A BASIS FOR THEIR COMPLEX PROCESSING INTO ALTERNATIVE ONESBIOPRODUCTS OF THE FUEL AND LUBRICANTS INDUSTRY: AN INNOVATIVE METHOD AND TECHNOLOGY

The material of the article reflects the results of the next stage of the systematic study of a very important problem in finding effective methods for processing chemical (T) oils into alternative functionally high quality and high biodegradability bioproducts of the fuel and lubricants (PM) materials. The main object of experimental research is the method of acetolysis of oils as one of the practically unexplored methods in comparison with well-developed methods of alcoholysis and esterolysis of T-oils. Based on the considered mechanism of catalytic and reversible reaction of acetolysis of oils as specific preacylation of their triacetylglycerol molecules, chemical-technological bases of processes of acetolysis of oils of two types are developed, namely: basic – rapeseed (g) and composition on its basis with 20 %, castor oil the so-called "ripritsol-20" (years). The optimal technological parameters for achieving high efficiency of acetolysis processes to obtain high-quality intermediates - mixtures of the corresponding FFAs of the general formulas RрC(O)–OH or RррC(O)–OH have been established. The necessity of combining the process of acetolysis of oils (p) or (pp) as the basis of the first stage of processing technology with the next stage, namely the conversion of VJ acids into more active in the reactions of the next stage derivatives - acid chlorides, and by a known, simple and fast method almost quantitative yield of intermediate products - mixtures of HlAn-VZhK (r) or (rr). The conceptual idea of the complex technology indicates the directions of rational processing of mixtures of VZ acids and their anhydrides (mixtures of HlAn-VZhK) into biocomponents of a wide range of purposes. In the second stage of the complex process, it is proposed to process Hlan-IJK mixtures into main bioproducts - biofuels or basic bio-oils by the well-known technologically and perfect Schotten-Bauman method, which is based on the acylation reaction of alcohols of the appropriate structure with chlorides of a certain type. or HlAn-VZhK (pp). Emphasis is placed on the rather favorable course of the acylation reaction of alcohols by the chosen method, in particular on its irreversibility, high speed under standard conditions, under such conditions high technical and economic efficiency of the second stage technology of the complex process is provided. It is shown that the technological operations of the complex process can be modified, directing them to the production of certain bioproducts, such as biofuels or biooils on the basis of adapted selection of the necessary combinations of raw materials. Thus, new biofuels of ester structure are proposed to be obtained by acylation of methanol or ethanol with mixtures of VOR acid chlorides derived from ripol. While new basic biooils of diester structure are recommended to be obtained by acylation of glycolysis of industrial production (in particular ethylene glycol) with a mixture of HlAn-VZhK, derived from the composite oil ripritsol-20. The presented tables of the calculated material balances of each of the stages of the complex process characterize their technical and economic efficiency and environmental safety. The main functional properties and some operational indicators of the experimental samples of products obtained during the research are determined: both biofuels and basic biooils, and composite ones based on the best mineral and bioproducts, in particular biodiesel and motor min-biooils. The analysis of their characteristics convinces that they do not concede on the functional indicators of quality to the best traditional materials of branch of PM-materials. Bibl. 12, Tab. 5.

Halogen-Containing Fire Resistant Copolyesters

Copolyarylates based on a mixture of 2,2-bis (4'-hydroxyphenyl) propane, 3,3-bis (4'-hydroxyphenyl) phthalide, terephthalic and isophthalic acid chlorides and 3,5-dibromo-p-hydroxybenzoic acid chloride were synthesized by low-temperature acceptor-catalytic polycondensation. To study the structure of the obtained polyesters and study the physical and mechanical properties, infrared spectroscopy, elemental, thermogravimetric, X-ray structural and thermomechanical analyzes were used. The obtained polymers have high values ​​of strength characteristics, thermal and heat resistance, good fire resistance.

Synthesis and Reactions of 1,3,5-Tri- and 1,3,5,7-Tetracarbonyl Compounds

The reaction of 1,3-bis(silyloxy)-1,3-butadienes with functionalized and nonfunctionalized acid chlorides and bis(acid chlorides) gives rise to the formation of a great variety of 1,3,5-tri- and 1,3,5,7-tetracarbonyl compounds and cyclic products derived from them. Examples include functionalized and nonfunctionalized 3,5-dioxopentanoates, 3,5-dioxopimelates, 3-alkylidene-3H-isobenzofuran-1-ones, salicylates, 3(2H)furanones, and 3-oxo-4-sulfonylesters. Methylation and cyclopropanation reactions of 1,3,5-tri- and 1,3,5,7-tetracarbonyl compounds do not provide access to the expected permethylated and cyclopropanated polycarbonyl compounds. However, the latter could be prepared by stepwise protocols. The reaction of 1,3,5-tri- and 1,3,5,7-tetracarbonyl compounds with dinucleophiles resulted in cyclization reactions to give a variety of heterocyclic structures.1 Introduction2 Reactions of 1,3-Bis(silyloxy)-1,3-butadienes with Acid Chlorides3 Reactions of 1,3,5-Tri- and 1,3,5,7-Tetracarbonyl Compounds4 Conclusion

INVESTIGATION OF REACTIONS OF INTERACTION OF CELLULOSE NITRIC ESTERS WITH CARBOXYLIC ACID CHLORIDES

The chemical interaction of high-nitrogen cellulose ether with acetic, propionic, butyric and isobutyric acids has been studied. The general laws and features of the electrophilic substitution of functional groups of cellulose nitroesters are revealed. The preferred directions of the chemical interaction of cellulose nitrate with carboxylic acid chlorides are established: O-acylation of nitrate and hydroxyl groups; O-acylation of the glucopyranose ring; O-acylation of the ether bond with depolymerization of the chain of an SC molecule; hydrolysis of nitrate groups; destruction of the chain of a macromolecule of nitric acid ester with the formation of water-soluble organic compounds. The structure, properties and possibilities of using synthesized mixed cellulose ethers were studied. Effective methods have been developed for the chemical modification of cellulose nitrates with carboxylic acid chlorides. The probable directions of the reaction of the interaction of cellulose nitrates with electrophilic reagents are predicted based on quantum-chemical calculations of point charges on the atoms of the reacting molecules. The reactivity of highly substituted cellulose nitrates in reactions with carboxylic acid chlorides has been established. The optimal conditions for the interaction of cellulose nitrates with carboxylic acid chlorides have been identified and a mathematical model of the reaction kinetics has been constructed. The possibility of a directed change in the composition of chemically modified cellulose nitrates depending on the synthesis conditions has been established. As a result of the combined use of physicochemical research methods, the chemical composition was determined and the structure of the synthesized compounds was determined: cellulose acetyl nitrates, cellulose propionyl nitrates, cellulose butyryl nitrates, and cellulose isobutyryl nitrates. Using gel chromatography, it was found that the molecular weight characteristics of the synthesized samples are directly dependent on the conditions of their synthesis. It was found that electrophilic substitution of the functional groups of cellulose nitrate proceeds more intensively in the pyridine medium.

One-Pot Synthesis of (Z)-β-Halovinyl Ketones via the Cascade of Sonogashira Coupling and Hydrohalogenation

Herein, we report an efficient method for the synthesis of (Z)-β-halovinyl ketones through a one-pot Sonogashira coupling and hydrohalogenation reaction promoted by palladium-copper catalyst and Brønsted acid. The ynone intermediates are generated in situ from readily available acid chlorides and terminal alkynes at room temperature, which are directly converted to (Z)-β-halovinyl ketones by treating with triflic acid. This method avoids the use of an external halogen source and features broad substrate scope, high yield, and good to excellent stereoselectivity.