I. G. Mamedov

Investigation of the Molecular Dynamics of Some Phenols and Their Acetyl Isomers in Solutions by NMR Relaxation

The dynamics of relaxations and Fries rearrangements in phenol acetates and their acetyl isomers was studied by the NMR relaxation technique in acetone-d6. The results of 13C and 1H spin-lattice nuclear relaxation measurements show that these experiments can be used for determining the mobility and activation energies of the molecular motions of compounds in different systems.

One-pot insertion of chalcones into the benzoylacetone backbone

Interaction of 1-phenylbutane-1,3-dione and chalcones in the presence of a base gives, in one step, good to high yields cyclic and unusual acyclic insertion products in ratios which depend on substrate, catalyst, and reaction conditions. All the synthesized compounds are characterized using IR, 1H and 13C NMR spectroscopies, ESI–MS, and single-crystal X-ray diffraction (for one compound) analysis.

Molecular dynamics of (Z)-1-(2-hydroxy-5-methyl-3-nitrophenyl)ethanone oxime and (E)-2-hydroxy-5-methylacetophenone thiosemicarbazone in solution studied by NMR spectroscopy

The formation of hydrogen bonds and the molecular dynamics for molecules (Z)-1-(2-hydroxy-5-methyl-3-nitrophenyl)ethanone oxime and (E)-2-hydroxy-5-methylacetophenone thiosemicarbazone, (E)-4-bromoacetophenone thiosemicarbazone have been investigated in solution using NMR. The results confirm the formation of different O-H…O type intramolecular hydrogen bonds in the oxime molecule. The rotational barrier energy and energy of intramolecular hydrogen bonds have been determined.

Molecular dynamics of cis‐1‐(2‐hydroxy‐5‐ methylphenyl)ethanone oxime and N‐(2‐hydroxy‐4‐methylphenyl)acetamide in solution studied by NMR spectroscopy

The formation of hydrogen bonds and molecular dynamics for the molecules cis‐1‐(2‐hydroxy‐5‐methylphenyl)ethanone oxime (I) and N‐(2‐hydroxy‐4‐methylphenyl)acetamide (II) have been investigated in solution using NMR. The results confirm the formation of OH···O, OH···N and O···HN type inter‐ and intramolecular hydrogen bonds. Spin‐lattice relaxation times (T1), activation energy of molecular dynamics and energy of intramolecular hydrogen bonds have been determined. Copyright

Molecular dynamics of (E)‐6‐acetyl‐3‐(2‐hydroxy‐5‐methylphenyl)‐5‐styryl cyclohex‐2‐en‐1‐one and (E)‐6‐ethylcarboxylate‐3‐(2‐hydroxy‐5‐methylphenyl)‐5‐styryl cyclohex‐2‐en‐1‐one in a solution studied by NMR spectroscopy

Molecular dynamics of cyclohexenone derivatives of (2E,4E)‐1‐(2‐hydroxy‐5‐methylphenyl)‐5‐phenyl‐2,4‐pentadiene‐1‐one (chalcone) has been investigated in solutions using NMR. The results confirm the formation of O‐H⋯O intramolecular hydrogen bond and the presence of keto–enol tautomeric transitions in the (E)‐6‐acetyl‐3‐(2‐hydroxy‐5‐methylphenyl)‐5‐styryl cyclohex‐2‐en‐1‐one. The free energy of activation for the keto–enol tautomeric transitions has been calculated. The keto–enol tautomerism in the investigated compound has been also confirmed by chemical method. Copyright

Synthesis of a new 1,2,3,4,5-pentasubstituted cyclohexanol and determining its stereochemistry by NMR spectroscopy and quantum-chemical calculations

The presence of substituents in cyclohexane can influence to the ratio of conformers; for some cases, the boat form is preferable. The new six‐membered cyclohexanol derivative 2 has been obtained by the synthesis of (E)‐1‐(bromophenyl)‐3‐phenylpropen‐2‐one (1). The NMR and quantum‐chemical conformational analysis for the 2 have carried out, and its possible mechanism of formation was given. Copyright

New synthesis on the basis 2‐allyloxy chalcone and NMR studies its some derivatives

Synthesis and NMR investigations of cyclohexenone, flavanone, isoxazol and indazole derivatives of (2E)‐3‐[2‐(allyloxy)‐5‐bromophenyl]‐1‐(2‐hydroxy‐5‐methylphenyl)‐2‐propen‐1‐one (I, chalcone) have been carried out. The results confirm the formation of O–H•••O type intramolecular hydrogen bond and intramolecular cyclization in the (2E)‐3‐[2‐(allyloxy)‐5‐bromophenyl]‐1‐(2‐hydroxy‐5‐methylphenyl)‐2‐propen‐1‐one (I), the presence of conformational and keto–enol tautomeric transitions in the 6‐acetyl‐5‐[2‐(allyloxy)‐5‐bromophenyl]‐3‐(2‐hydroxy‐5‐methylphenyl)‐2‐cyclohexen‐1‐one (II), conformational transitions in the 2‐{4‐[2‐(allyloxy)‐5‐bromophenyl]‐3‐methyl‐4.5‐dihydro‐1.2‐benzisoxazol‐6‐yl}‐4‐methylphenol (III) and 2‐{4‐[2‐(allyloxy)‐5‐bromophenyl]‐3‐methyl‐4.5‐dihydro‐1H‐indazol‐6‐yl}‐4‐methylphenol (IV). The conformational and keto–enol tautomerism in the investigated compounds have been also confirmed by chemical methods. Copyright

Molecular dynamics of 6‐methyl‐2‐phenyl‐2,3‐dihydro‐4H‐chromen‐4‐one and 6‐methyl‐2‐(4‐nitrophenyl)‐2,3‐dihydro‐4H‐chromen‐4‐one (flavanone) derivatives in a solution studied by NMR spectroscopy

Molecular dynamics of benzoxazepin, oxime, pyrazole, and thiosemicarbazone derivatives of some flavanones have been investigated in a solution using NMR. The results confirm the formation of different O–H···O, O–H···N, N···H–N type intramolecular hydrogen bonds in the pyrazole and oxime molecules. The rotational barrier energy and energy of intramolecular hydrogen bonds have been determined. Copyright

Reaction of 3-chloro-1-(2,4,6-trimethylphenyl)propan-2-one with amines

While continuing our studies in the fields of synthesis and transformations of 1,2-chlorohydrins [1] obtained by reaction of arenes with 3-chloro-1,2-epoxypropane in the presence of aluminum chloride, we performed oxidation of 3-chloro-1-(2,4,6-trimethylphenyl)propan-2-ol (I) with chromium(VI) oxide and isolated 3-chloro-1-(2,4,6-trimethylphenyl)propan-2one (II). α-Chloro ketone II was brought into reaction with various primary amines in aqueous potassium hydroxide at room temperature. The reaction time was 20–45 min. Regardless of the amine nature, in all cases the products were the corresponding N-substituted 3-(2,4,6-trimethylphenyl)propionamides III–IX which were isolated in 50–97% yield as colorless crystalline substances and were recrystallized from ethanol.

The molecular mobility of 2-propenylphenols capable of hydrogen bonding

Hydrogen bonding and molecular mobility of 2-propenylphenols containing an aminomethyl fragment in the ortho position were studied by NMR. The results confirmed the importance of using relaxation times as a sensitive test for molecular dynamics studies.