2-(1H-diazol-2-ylmethylene)indane-1-ones and 2-(1H-diazol-2-ylmethylene)-1H-indene-1,3(2H)-diones: Photoisomerization and hydrogen-bonding-induced association

Mark V. Sigalov; Bagrat A. Shainyan; Nina N. Chipanina; Larisa P. Oznobikhina; Irina V. Sterkhova

doi:10.1016/j.tet.2020.131755

2-(1H-diazol-2-ylmethylene)indane-1-ones and 2-(1H-diazol-2-ylmethylene)-1H-indene-1,3(2H)-diones: Photoisomerization and hydrogen-bonding-induced association

Mark V. Sigalov, Bagrat A. Shainyan, Nina N. Chipanina, Larisa P. Oznobikhina, Irina V. Sterkhova

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

3 Scopus citations

Abstract

The products of condensation of 2-imidazolyl-, 4-imidazolyl-, 3-pyrazolylcarbaldehydes with indan-1-one 1–3 and 1H-indene-1,3(2H)-dione 4–6 were synthesized. The E-isomers of 1–3 undergo UV-induced isomerization to the Z-isomers stabilized by intramolecular NH⋯O[dbnd]C hydrogen bond with the pyrrolic-type NH group. Theoretical analysis of all isomers, tautomers and rotamers showed that the degree of conjugation between the diazolyl group and the C[dbnd]O group decreases in the order 1 > 2>3. Spectroscopic study of 1–6 performed before and after UV irradiation allowed to conclude on the nature of the associates formed. A remarkably different association of the 2- and 4-imidazolyl derivatives 4 and 5 was revealed by X-ray and confirmed theoretically, leading to the formation of the chelate rings closed by NH⋯O[dbnd]C hydrogen bond in 4 or by N–H … N_pyridinic hydrogen bond in 5. Both chelate rings include two bifurcate H-bonds with bifurcation on the carbonyl oxygen and the pyrrolic NH hydrogen.

Original language	English
Article number	131755
Journal	Tetrahedron
Volume	77
DOIs	https://doi.org/10.1016/j.tet.2020.131755
State	Published - 1 Jan 2021

Keywords

Diazolylmethyleneindanones and -indenediones
Hydrogen bonding
IR and UV spectroscopy
NMR
Photoinduced E→Z-isomerization
QTAIM analysis
Quantum chemical calculations
X-ray structural analysis

ASJC Scopus subject areas

Biochemistry
Drug Discovery
Organic Chemistry

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10.1016/j.tet.2020.131755

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@article{256f7c4384134620805829f8efa19c82,

title = "2-(1H-diazol-2-ylmethylene)indane-1-ones and 2-(1H-diazol-2-ylmethylene)-1H-indene-1,3(2H)-diones: Photoisomerization and hydrogen-bonding-induced association",

abstract = "The products of condensation of 2-imidazolyl-, 4-imidazolyl-, 3-pyrazolylcarbaldehydes with indan-1-one 1–3 and 1H-indene-1,3(2H)-dione 4–6 were synthesized. The E-isomers of 1–3 undergo UV-induced isomerization to the Z-isomers stabilized by intramolecular NH⋯O[dbnd]C hydrogen bond with the pyrrolic-type NH group. Theoretical analysis of all isomers, tautomers and rotamers showed that the degree of conjugation between the diazolyl group and the C[dbnd]O group decreases in the order 1 > 2>3. Spectroscopic study of 1–6 performed before and after UV irradiation allowed to conclude on the nature of the associates formed. A remarkably different association of the 2- and 4-imidazolyl derivatives 4 and 5 was revealed by X-ray and confirmed theoretically, leading to the formation of the chelate rings closed by NH⋯O[dbnd]C hydrogen bond in 4 or by N–H … Npyridinic hydrogen bond in 5. Both chelate rings include two bifurcate H-bonds with bifurcation on the carbonyl oxygen and the pyrrolic NH hydrogen.",

keywords = "Diazolylmethyleneindanones and -indenediones, Hydrogen bonding, IR and UV spectroscopy, NMR, Photoinduced E→Z-isomerization, QTAIM analysis, Quantum chemical calculations, X-ray structural analysis",

author = "Sigalov, {Mark V.} and Shainyan, {Bagrat A.} and Chipanina, {Nina N.} and Oznobikhina, {Larisa P.} and Sterkhova, {Irina V.}",

note = "Funding Information: The authors are grateful to the Russian Foundation for Basic Research for the financial support of this work (Grant No. 19-03-00036). All instrumental measurements were performed using the equipment of the Baikal Analytical Center for Collective Use of Siberian Branch of Russian Academy of Sciences. Funding Information: The authors are grateful to the Russian Foundation for Basic Research for the financial support of this work (Grant No. 19-03-00036 ). Publisher Copyright: {\textcopyright} 2020 Elsevier Ltd",

year = "2021",

month = jan,

day = "1",

doi = "10.1016/j.tet.2020.131755",

language = "English",

volume = "77",

journal = "Tetrahedron",

issn = "0040-4020",

publisher = "Elsevier Ltd.",

}

TY - JOUR

T1 - 2-(1H-diazol-2-ylmethylene)indane-1-ones and 2-(1H-diazol-2-ylmethylene)-1H-indene-1,3(2H)-diones

T2 - Photoisomerization and hydrogen-bonding-induced association

AU - Sigalov, Mark V.

AU - Shainyan, Bagrat A.

AU - Chipanina, Nina N.

AU - Oznobikhina, Larisa P.

AU - Sterkhova, Irina V.

N1 - Funding Information: The authors are grateful to the Russian Foundation for Basic Research for the financial support of this work (Grant No. 19-03-00036). All instrumental measurements were performed using the equipment of the Baikal Analytical Center for Collective Use of Siberian Branch of Russian Academy of Sciences. Funding Information: The authors are grateful to the Russian Foundation for Basic Research for the financial support of this work (Grant No. 19-03-00036 ). Publisher Copyright: © 2020 Elsevier Ltd

PY - 2021/1/1

Y1 - 2021/1/1

N2 - The products of condensation of 2-imidazolyl-, 4-imidazolyl-, 3-pyrazolylcarbaldehydes with indan-1-one 1–3 and 1H-indene-1,3(2H)-dione 4–6 were synthesized. The E-isomers of 1–3 undergo UV-induced isomerization to the Z-isomers stabilized by intramolecular NH⋯O[dbnd]C hydrogen bond with the pyrrolic-type NH group. Theoretical analysis of all isomers, tautomers and rotamers showed that the degree of conjugation between the diazolyl group and the C[dbnd]O group decreases in the order 1 > 2>3. Spectroscopic study of 1–6 performed before and after UV irradiation allowed to conclude on the nature of the associates formed. A remarkably different association of the 2- and 4-imidazolyl derivatives 4 and 5 was revealed by X-ray and confirmed theoretically, leading to the formation of the chelate rings closed by NH⋯O[dbnd]C hydrogen bond in 4 or by N–H … Npyridinic hydrogen bond in 5. Both chelate rings include two bifurcate H-bonds with bifurcation on the carbonyl oxygen and the pyrrolic NH hydrogen.

AB - The products of condensation of 2-imidazolyl-, 4-imidazolyl-, 3-pyrazolylcarbaldehydes with indan-1-one 1–3 and 1H-indene-1,3(2H)-dione 4–6 were synthesized. The E-isomers of 1–3 undergo UV-induced isomerization to the Z-isomers stabilized by intramolecular NH⋯O[dbnd]C hydrogen bond with the pyrrolic-type NH group. Theoretical analysis of all isomers, tautomers and rotamers showed that the degree of conjugation between the diazolyl group and the C[dbnd]O group decreases in the order 1 > 2>3. Spectroscopic study of 1–6 performed before and after UV irradiation allowed to conclude on the nature of the associates formed. A remarkably different association of the 2- and 4-imidazolyl derivatives 4 and 5 was revealed by X-ray and confirmed theoretically, leading to the formation of the chelate rings closed by NH⋯O[dbnd]C hydrogen bond in 4 or by N–H … Npyridinic hydrogen bond in 5. Both chelate rings include two bifurcate H-bonds with bifurcation on the carbonyl oxygen and the pyrrolic NH hydrogen.

KW - Diazolylmethyleneindanones and -indenediones

KW - Hydrogen bonding

KW - IR and UV spectroscopy

KW - NMR

KW - Photoinduced E→Z-isomerization

KW - QTAIM analysis

KW - Quantum chemical calculations

KW - X-ray structural analysis

UR - http://www.scopus.com/inward/record.url?scp=85096122534&partnerID=8YFLogxK

U2 - 10.1016/j.tet.2020.131755

DO - 10.1016/j.tet.2020.131755

M3 - Article

AN - SCOPUS:85096122534

SN - 0040-4020

VL - 77

JO - Tetrahedron

JF - Tetrahedron

M1 - 131755

ER -

2-(1H-diazol-2-ylmethylene)indane-1-ones and 2-(1H-diazol-2-ylmethylene)-1H-indene-1,3(2H)-diones: Photoisomerization and hydrogen-bonding-induced association

Abstract

Keywords

ASJC Scopus subject areas

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