Sarvinoz I. Tirkasheva

Diols represent a structurally diverse class of compounds with considerable biological and functional significance. Herein, we describe the synthesis of 1,1-bis(4-ethylphenyl)propan-1,2-diol (BEPP) via a Grignard reaction. The structure of BEPP was unambiguously elucidated by ¹H and ¹³C nuclear magnetic resonance (NMR), heteronuclear multiple-bond correlation (HMBC), high-resolution mass spectrometry (HRMS), and infrared (IR) spectroscopy.

In this work the vinylation reactions of aromatic carboxylic acids with vinyl acetate, which contain various substituents, in the presence of 2-chloro-4,6-dimethoxy-1,3,5-triazine were studied for the first time. The influence of the nature of the starting materials, temperature, reaction duration, solvent and reagents - zinc triflate (Zn(OTf)2, 3,3-diphenylbinaphthol (3,3'-Ph2BINOL-2Li), tertiary potassium butylate (KOtrBu), butyllithium (BuLi) for the synthesis of vinyl esters. The synthesis of vinyl esters of aromatic carboxylic acids was carried out: benzoiс, 2-phenylacetic, 4-methylbenzoic, 4-methoxybenzoic, 3,4-dimethoxybenzoic, 2-brombenzoic, 4-brombenzoic, 4-fluorobenzoic, 3-nitrobenzoic, 4-nitrobenzoic, 4-tertiary butylbenzoic, 2-chlorobenzoic, 4-chlorobenzoic, 3-hydroxybenzoic and 4-hydroxybenzoic acids has been studied. The structure of synthesized vinyl esters has been determined by modern physical methods and a technological scheme for their production has been elaborated.

The purpose of the study is to develop a new catalytic system for the synthesis of internal acetylene alcohols from the Sonogastric coupling reaction of terminal acetylene alcohols and benzolchloride. For the first time in this work, internal acetylene alcohols have been synthesized based on reactions of some terminal acetylene alcohols – 3,4-dimethylpentin-1-ol-3, 3,4,4-trimethylpentin-1-ol-3, 1-ethynylcyclohexanol-1, 2-ethynyladamantanol-2, 2-phenylbutin-3-ol-2, 2-(naphthyl-2)butyn-3-ol-2, 2-(furanyl-2)butyn-3-ol-2 and 2-(pyridinyl-4)butyn-3-ol-2 with chloridebenzene. In order to achieve high product productivity in the Sonogashira reaction, alternative conditions have been identified by studying the molar ratios, spatial structure, induction effects of substituents, solvent and catalyst nature, as well as temperature, reaction duration effects, and the reaction mechanism has been proposed on the basis of literature sources.

The purpose of the research is to develop a method of synthesizing new acetylene diols, to determine their structure, physico-chemical properties and to create optimal conditions by studying the effect of various environments on product yield. For the first time, nucleophilic coupling reactions of 1-ethynylcyclohexanol with some ketones - cyclohexanone, acetophenone, para-chloroacetophenone, adamantanone, methylhexylketone and ethyl-n-butyl ketones were studied using the Bu4NOH/DMSO/H2O catalytic system. New acetylene diols – 1-(2-(1-hydro-xycyclohexyl)ethynyl)cyclohexanol (1), 1-(3-hydroxy-3-phenylbut-1-ynyl)cyclohexanol (2), 1-(3-(4-chlorophenyl)-3-hydroxybut-1-ynyl)cyclo-hexanol(3), 1-(2-(1-hydroxyadamantanyl)-ethynyl)cyclohexanol (4), 1-(3-hydroxy-3-methyldec-1-ynyl)cyclohexanol(5) and 1-(3-ethyl-3-hydroxyhept-1-ynyl)cyclohexanol (6) were synthesized in the process. The effects of the catalyst for the synthesis of acetylene diols, the nature of the solvent, the mole ratio of the starting materials, the temperature, and the duration of the reaction were systematically analyzed. The composition, structure and purity of the synthesized acetylene diols were determined by modern physical and chemical research methods.

A novel catalytic system for homocoupling terminal acetylenes was elaborated based on CuCl as a catalyst (10 mol%), TMEDA as a base and CCl₄ as an oxidant. The influence of the solvent, base, amount of catalyst and CCl₄ on the reaction was investigated. Methanol was found to be the solvent of choice. The broad synthetic scope of the reaction was demonstrated. Diynes with various substituents were prepared in up to 92% yields. The possible reaction mechanism is discussed.

The title compound, C₁₆H₂₂O₂, was synthesized in order to obtain its guest-free form because `wheel-and-axle'-shaped molecules tend to crystallize from solutions as solvates or host–guest molecules. It crystallizes in the monoclinic space group P2/c with two crystallographically non-equivalent molecules, one situated on an inversion center and the other on a twofold axis. The rod-like 1,3-diyne fragments have the usual linear geometry. In the crystal, O—H ... O bonds form eight-membered rings of the R ⁴ ₄(8) type, linking molecules into layers. The Hirshfeld surface analysis indicates that the largest contributions are from intermolecular H...H (ca 71%) and H...C/C...H (ca 19%) contacts. The energies of the frontier molecular orbitals were determined by DFT calculations at the B3LYP/def2-TZVP level of theory.

The protocol, 3-methyldec-1-yn-3-ol (1a) was chosen to perform the dimerization process. The optimal conditions for synthesis of 8,13-dimethylicosa-9,11-diyne-8,13 (2a) with high efficiency when using copper-catalyzed, N,N,N′N′-tetramethylethylenediamine as a ligand and CCl₄ and methanol solvents in atmospheric pressure were determined. The structure of the obtained compound was proved by IR, ¹H-NMR and ¹³C-NMR spectroscopy.