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Synthesis and isomerization of acridine substituted 1,3-thiazolidin-4- ones and 4-oxo-1,3-thiazolidin-5-ylidene acetates. An experimental and computational study

Result description

Acridine thiosemicarbazones 3aeg, obtained through a two-step reaction between aromatic isothiocyanates and hydrazine followed by the treatment with acridin-9-carbaldehyde, in reaction with bifunctional reagents; methyl bromoacetate (MBA) and diethyl acetylenedicarboxylate (DEAD) afforded acridin-thiazolidinone derivatives 4aeg and 7aef and not their regioisomers 6aeg and 9aef. Derivatives 4aeg and 7aef exhibit ZC2N6EN7C8 configuration. Upon standing in DMSO-d6 the thiazolidinones 4aeg and 7aef spontaneously isomerized into ZC2N6ZN7C8 isomers 5aeg and 8aef to give a mixture of the both stereoisomers. All compounds were fully characterized by multinuclear NMR, mass spectrometry (MS) and X-ray crystal structure of 4b is also described. X-ray diffraction study revealed that the representative compound 4b crystallized in the monoclinic crystal system with the C2/c space group and Z ¼ 4. Intramolecular C10eH10/N-7 hydrogen bond between the acridine proton H-10 and nitrogen N-7 of linker existed. This hydrogen bond is responsible for the E isomerism on C-8 atom which was observed in the NMR experiments. Quantum-chemical calculations and NOESY experiments confirmed ZC2N6ZN7C8 configuration of the transformed stereoisomers 5aeg and 8aef.

Keywords

AcridineThiazolidinoneE/Z isomerNMR spectroscopySingle crystal X-ray study

The result's identifiers

Alternative languages

  • Result language

    angličtina

  • Original language name

    Synthesis and isomerization of acridine substituted 1,3-thiazolidin-4- ones and 4-oxo-1,3-thiazolidin-5-ylidene acetates. An experimental and computational study

  • Original language description

    Acridine thiosemicarbazones 3aeg, obtained through a two-step reaction between aromatic isothiocyanates and hydrazine followed by the treatment with acridin-9-carbaldehyde, in reaction with bifunctional reagents; methyl bromoacetate (MBA) and diethyl acetylenedicarboxylate (DEAD) afforded acridin-thiazolidinone derivatives 4aeg and 7aef and not their regioisomers 6aeg and 9aef. Derivatives 4aeg and 7aef exhibit ZC2N6EN7C8 configuration. Upon standing in DMSO-d6 the thiazolidinones 4aeg and 7aef spontaneously isomerized into ZC2N6ZN7C8 isomers 5aeg and 8aef to give a mixture of the both stereoisomers. All compounds were fully characterized by multinuclear NMR, mass spectrometry (MS) and X-ray crystal structure of 4b is also described. X-ray diffraction study revealed that the representative compound 4b crystallized in the monoclinic crystal system with the C2/c space group and Z ¼ 4. Intramolecular C10eH10/N-7 hydrogen bond between the acridine proton H-10 and nitrogen N-7 of linker existed. This hydrogen bond is responsible for the E isomerism on C-8 atom which was observed in the NMR experiments. Quantum-chemical calculations and NOESY experiments confirmed ZC2N6ZN7C8 configuration of the transformed stereoisomers 5aeg and 8aef.

  • Czech name

  • Czech description

Classification

  • Type

    Jimp - Article in a specialist periodical, which is included in the Web of Science database

  • CEP classification

  • OECD FORD branch

    10403 - Physical chemistry

Result continuities

Others

  • Publication year

    2018

  • Confidentiality

    S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Data specific for result type

  • Name of the periodical

    JOURNAL OF MOLECULAR STRUCTURE

  • ISSN

    0022-2860

  • e-ISSN

  • Volume of the periodical

    1154

  • Issue of the periodical within the volume

    FEB

  • Country of publishing house

    NL - THE KINGDOM OF THE NETHERLANDS

  • Number of pages

    13

  • Pages from-to

    152-164

  • UT code for WoS article

    000418212000019

  • EID of the result in the Scopus database

    2-s2.0-85031714368