V. M. Muzalevskiy

Halogen-bonded tris(2,4-bis(trichloromethyl)-1,3,5-triazapentadienato)-M(III) [M = Mn, Fe, Co] complexes and their catalytic activity in the peroxidative oxidation of 1-phenylethanol to acetophenone

One-pot template condensation of CCl3CN with ammonia on a metal source [MnCl2·4H2O, FeCl3·6H2O or Co(CH3COO)2·4H2O] in DMSO led to the formation of tris{2,4-bis(trichloromethyl)-1,3,5-triazapentadienato}-M(III) complexes, [M{NHC(CCl3)NC(CCl3)NH}3]·n(CH3)2SO [M = Mn, n = 1 (1); M = Fe, n = 2 (2); M = Co, n = 2 (3)], which were characterized using elemental analysis, and IR, ESI-MS and single-crystal X-ray analysis. The role of inter- and intramolecular non-covalent halogen and hydrogen bonds in the synthesis of 1–3 is discussed. It is shown that the crystal ionic radii of the metal ions [68.5 (Co) 3.155 (2) > 3.133 (1) A]. Compounds 1–3 and the related di(triazapentadienato)-Cu(II) complex [Cu{NHC(CCl3)NC(CCl3)NH}2]·2(CH3)2SO (4) act as catalyst precursors for the additive-free microwave (MW) assisted homogeneous oxidation of 1-phenylethanol with tert-butylhydroperoxide (TBHP), leading to the formation of acetophenone with yields up to 99% and TONs up to 5.0 × 103 after 1 h of low power (10 W) MW irradiation.

New approach to the synthesis of trifluoromethylvinyl sulfides

Nucleophilic substitution reaction of halogen atom in β-chloro-and β-bromo-β-trifluoromethylstyrenes by thiolates was studied. Stereo-and regioselectivity of the reaction with respect to the electronic and sterical properties of substituents in the aromatic ring of starting styrenes was investigated. Regioisomer with geminal trifluoromethyl and alkyl-or arylthio groups was found to be formed predominantly or exclusively. The reaction proceeds stereoselectively in nearly quantitative yields. On this basis, a new convenient stereoselective method for the synthesis of trifluoromethylvinyl sulfides was elaborated.

Design and synthesis of a new family of fluorinated liquid crystals.

A convenient and simple three-step pathway to the new family of CF(2)CF(2)S-bridged alkanes and CF(2)S-, CF(2)O-bridged alkenes and alkynes was elaborated by using catalytic olefination reaction as a key step of the synthetic sequence. The obtained compounds revealed attractive liquid crystalline characteristics.

Reactions of trifluoromethyl-substituted arylacetylenes with arenes in superacids

Protonation of the C≡C bond in trifluoromethyl-substituted arylacetylenes ArC≡CCF3 by the action of superacids (CF3SO3H or HSO3F) generates vinyl cations ArC+=CHCF3 which react with arenes Ar′H to give alkenes Ar(Ar′)C=CHCF3. Protonation of the latter at the C=C bond in the reaction medium yields stable cations Ar(Ar′)C+-CH2CF3 which are converted into E/Z-isomeric alkenes Ar(Ar′)C=CHCF3 and/or alcohols Ar(Ar′)C(OH)CH2CF3 as a result of quenching of superacid reaction solution.

Freons in catalytic olefination reaction. Synthesis of fluorinated compounds from the products of olefination

Application of freons in catalytic olefination for production of fluorinated alkenes is discussed and also the synthesis of versatile fluorinated compounds on this basis.

Synthesis of bis(halovinyl)benzenes by catalytic olefination

Catalytic olefination of hydrazines of terephthalic and isophthalic aldehydes with polyhaloalkanes afforded the corresponding p- and m-divinylbenzene derivatives bearing halogen atoms and various functional groups at the double bonds. Stereochemical features of the reaction were studied.

Catalytic olefination reaction. Synthesis of fluorinated ethers and thioethers

Novel synthetic approaches involving catalytic olefination to access fluorinated propyl, allyl, and propargyl ethers and thioethers were developed.

Unusual reaction of bromoalkyl trifluoromethyl ketones with symmetrically disubstituted ethylenediamines. Theoretic investigation applying methods of density functional and multiparticle perturbation theory МР-2

Mechanism of a multistage reaction between α-bromotrifluoromethylenones and N,N′-dialkylethylenediamines was examined in detail using quantum chemical methods of density functional (non-empirical functional РВЕ, extended split TZp-basis) and multiparticle perturbation theory МР-2, basis 6-311+G(d,p), in the gas phase approximation, and also including solvents molecules (water and 2,2,2-trifluoroethanol). The specific solvation of transition states owing to the hydrogen bonds formation with solvent molecules is the main factor governing the direction of the reaction. Trifluoroethanol forms a strong H-bond with the carbonyl oxygen atom of the trifluoroacetyl group increasing its electrophilicity. It also solvates the departing bromide anion facilitating the occurrence of the SN2-substitution reaction. An essential but less important factor is the ability of trifluoroethanol to play the role of a nucleophilic partner by forming hydrogen bonds at the expense of the unshared electron pair of the hydroxyl oxygen facilitating the proton abstraction from the nitrogen atom of the diamine attacking the carbon atom in the course of SN2-substitution.

A new approach to ferrocene derived alkenes via copper-catalyzed olefination

Summary A new approach to ferrocenyl haloalkenes and bis-alkenes was elaborated. The key procedure involves copper catalyzed olefination of N-unsubstituted hydrazones, obtained from ferrocene-containing carbonyl compounds and hydrazine, with polyhaloalkanes. The procedure is simple, cheap and could be applied for the utilization of environmentally harmful polyhalocarbons. The cyclic voltammetry study of the representative examples of the synthesized ferrocenyl alkenes shows the strong dependence of the cathodic behavior on the amount of vinyl groups: while for the monoalkene containing molecules no reduction is seen, the divinyl products are reduced in several steps.

Synthesis of bis-heterocyclic compounds with a phenylene bridge from 1,4- and 1,3-bis(2-chloro-2-cyanovinyl)benzenes

Reaction of binucleophiles with 1,4- and 1,3-bis(2-chloro-2-cyanovinyl)benzenes, synthesized using a catalytic olefination of terephthalic and isophthalic aldehydes, gave high yields of aminopyrazoles, 3-amino-5-arylthiophene-2-carboxylic acid esters, and 2,4-diamino-6-arylpyrimidines.