Study of rotational isomerism in arylmethanesulfonates

Conclusions In solution, the arylmethanesulfonates exist as two conformers with the methyl and aryl radicals in gauche and trans configurations.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2006–2009, September, 1978.     

Synthesis of 1,3-disubstituted hydantoins as possible anticonvulsants

Seven newer 1,3-disubstituted hydantoins ( 17–23 ) were synthesized from 4-alkoxyanilines. The anticonvulsant activity of these substituted hydantoins and their precursor carbamides ( 10–16 ) was reflected by their ability to provide 28–80% and 30–70% protection, respectively, against pentylenetetrazol-induced convulsions in mice. In general, substituted hydantoins possessed greater anticonvulsant activity than their corresponding precursor carbamides.     

超声波作用下5, 5-二取代乙内酰脲的合成

本文以氰化钠水溶液、碳酸铵和相应的醛或酮为原料, 于25℃~45℃超声波作用3~4h合成八种5, 5-二取代乙内酰脲, 收率30.1~100%。与传统方法比较, 反应时间缩短, 产品收率提高。     

Study of the rotational isomerism about the C-O bond in six-membered secondary-tertiary diols

We have determined the spectroscopic characteristics, the dipole moments, and the Kerr constants of the stereoisomers of the secondary-tertiary diols of the cyclohexane and bicyclo [4.1.0]pentane series: 3,4-dihydroxy-3-carane (I), 3,4-dihydroxy-3-methylnorcarane (II), 3,4-dihydroxy-3-methylnorcarane (III), 4, 5-dihydroxy-3-methylcyclohexene (IV), 3,4-dihydroxy-3-carane (V), 3,4-dihydroxy-3-methylnorcarane (VI), 3, 4-dihydroxy-3-carane (VII), and 3,4-dihydroxy-4-methyl-3-carane (VIII). It was found that the cis diols are more polar than their trans isomers. It was shown by electrical and electrooptical methods that rotamers with a gauche orientation with respect to the tertiary C-O are stable relative to those containing the diol at the ordinary C-C bond of the ring.Deceased.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 619–625, March, 1991.     

Reaction of 1,3,4-oxadiazolones with free L-α-amino acids: A facile synthesis of novel 3,5-disubstituted hydantoins

A series of novel 3,5-disubstituted hydantoins 3a-1 were easily synthesized in one-step from the reaction of 2-phenyl-1,3,4-oxadiazolin-5-ones 1a-h with various free L-α-amino acids 2a-e in m-cresol at 150°. An alternative route leading to the formation of 3-benzamido-5-isopropylhydantoin 3c was also developed to make clear the reaction mechanism.     

NOE difference spectroscopy of some 5-substituted and 5,5-disubstituted hydantoins

The nOe difference (NOED) spectra of twelve 5-substituted- and 5,5-disubstituted hydantoins were recorded in deuteriochloroform. The nOe's observed from the interaction of substituents on C-5 with the proton on N-1 are more reliable than the chemical shift of the N-1 proton for structure determination.     

Solvent influence on the rotational isomerism in terephthalaldehyde

Experimental and theoretical studies were carried out in order to investigate the rotational isomerism of terephthalaldehyde. The dipole moment measurements and infrared spectroscopy in Ar matrix and using various solvents were performed experimentally. In order to supplement the experimental study, both static and dynamical theoretical calculations were performed. IR spectra and potential energy distribution (PED) were calculated for both cis and trans isomers of terephthalaldehyde in gas phase using B3LYP/6-31G(d,p) level of theory. Further calculations consisted of conformational analysis were performed in order to estimate the rotational barrier and relative stabilities of isomers. The DFT theory with B3LYP functional and four double-zeta and triple-zeta basis sets served as framework for this part of calculations. Semiempirical AM1 and PM3 methods were also used for gas-phase modeling. Molecular dynamics using MM3 force field was applied to study the preferences of solvent molecules’ orientation around the studied molecule. Additionally, the effect of solvent polarity on the Gibbs energy of the trans ⇌ cis equilibrium was analyzed in terms of the continuum dielectric medium models.     

Vibrational spectra and rotational isomerism of fluoroacetone

Infrared spectra have been redetermined for fluoroacetone in the vapor, liquid, and solid states, and Raman spectra have been obtained for the liquid. There are two rotational isomers present in the liquid, but only the more polar form is present in the crystalline solid and only the less polar form is present in the vapor. Vibrational assignments were made for the two rotamers with the aid of normal coordinate calculations that utilized a twenty-five parameter valence force field.     

Synthesis and nitrosation of 3- and 3,5-substituted hydantoins

The cyclization of N-alkylated (arylated) -ureidocarboxylic acids gives a series of 3-mono- and 3,5-disubstituted hydantoins, and nitrosation of the latter yields their nitroso derivatives. The rotational isomerism of 3-(-naphthyl)hydantoins has been studied by PMR spectroscopy.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1404–1406, October,Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1404–1406, October,     

Cis–trans isomerism shown by the polymer containing chalcone moiety in its side chain

Polymer containing chalcone moiety showed a cis–trans isomerism. Two novel acrylate monomers, 4‐[3‐(2,4‐dichloro‐phenyl)3‐oxoprop‐1‐en‐1‐yl]phenylacrylate (DCP) and 4‐(3‐(4‐((4‐(4‐(3‐(2,4‐dichlorophenyl)‐3‐oxoprop‐1‐en‐1‐yl)phenoxy)‐6‐((4‐nitrophenyl)amino)‐1,3,5‐triazin‐2‐yl)oxy)phenyl)‐3‐oxoprop‐1‐en‐1‐yl)phenyl acrylate (TCP) were synthesized and copolymer with acrylic acid. All the monomers and polymer were characterized by IR, NMR and UV techniques. The M_w of the DCP based polymer and TCP based polymer were 4000 and 10,000 g/mol respectively. DCP and TCP based polymer showed double stage and single stage decomposition respectively. The reactivity ratio of the polymers showed that the poly(DCP‐co‐AA) formed random polymerization whereas poly(TCP‐co‐AA) formed alternate copolymerization. The poly(TCP‐co‐AA) showed excellent photoisomerism whereas poly(DCP‐co‐AA) showed photocycloaddition reaction. Copyright © 2016 John Wiley & Sons, Ltd.     

Study of molecular rotational isomerism using deuterium NMR in chiral oriented solvents

Deuterium NMR in polypeptide chiral liquid crystals is used for the first time to investigate the internal rotational isomerism phenomenon, illustrated by the interconversion between conformers of 1-(2,6-dideutero-4-methylphenyl)naphthalene     

Vibrational spectra and rotational isomerism of ethyl trichloroacetate

The IR and Raman spectra of ethyl trichloroacetate (E-TCA) and its deuterate (E-TCA-d₅) have been measured in the liquid, glassy and crystalline states. Vibrational assignment was made by referring to isotopic wavenumber-shift, characteristic group frequencies of related esters and with the aid of a normal coordinate calculation on E-TCA and E-TCA-d₅. It is suggested that in the liquid and glassy states there exist two molecular forms (trans—trans—trans and trans—trans—gauche) with regard to the internal rotations about the ClC---C---O---CH₂CH₃ axis, and that the former persists in the crystalline state. The band pairs of E-TCA and the other ethyl esters are discussed in relation to the nature and number of rotational axes, effect of the heavy trichloromethyl group, and enhancement of band intensity by vibrational coupling.     

Structure and rotational isomerism of chloroacetyl chloride molecules

The structure of chloroacetyl chloroide (CH₂ClCOCl) molecule in different conformations arising from rotation of the CH₂Cl group about the C-C bond was determined by the Hartree-Fock RHF/6-31G(d) quantum-chemical calculations. The energy difference between the two stable rotamers was estimated at 5.9 kJ mol^?1, and barriers to intramolecular reorientations of the CH₂Cl group were calculated.     

Vibrational spectra and rotational isomerism of triallyl amine

The infrared spectra of triallyl amine in the vapour and liquid phases (as solutions in CS₂, CCl₄, CH₃Cl and CH₃CN), and in the solid state at low temperature were measured from 250 to 4000 cm⁻¹. The Raman spectrum of the liquid was recorded and qualitative depolarization measurements were made. It is shown that in the liquid and vapour phases the molecule exists as a mixture of at least two rotational isomers, while in the crystalline phase it assumes a single configuration having point-group symmetry C₃. A vibrational assignment for the observed bands in the infrared and Raman spectra is proposed on the basis of the C₃ point group symmetry for the more stable form of the molecule.     

Divergent asymmetric synthesis of 3,5-disubstituted piperidines

A divergent synthesis of various 3,5-dioxygenated piperidines with interesting pharmacological properties is described. A mixture of the achiral cis- and racemic trans-3,5-piperidine diol could be efficiently obtained from N-benzylglycinate in five steps by the use of chemoenzymatic methods. In the subsequent enzyme- and Ru-catalyzed reaction, the rac/meso diol mixture was efficiently transformed to the cis-(3R,5S)-diacetate with excellent diastereoselectivity and in high yield. Further transformations of the cis-diacetate selectively delivered the cis-piperidine diol and the cis-(3R,5S)-hydroxy acetate. Alternatively, the DYKAT could be stopped at the monoacetate stage to give the trans-(3R,5R)-hydroxy acetate.