Ring-Chain Tautomerism of the Condensation Products of 2-Mercaptobenzohydrazide with Aliphatic and Aromatic Aldehydes: Influence of Electronic and Steric Factors

doi:10.4236/oalib.1103584

OALib Journal期刊
ISSN: 2333-9721
费用：99美元

查看量	下载量

Open Access Library Journal 4 2017

查看所有领域

Ring-Chain Tautomerism of the Condensation Products of 2-Mercaptobenzohydrazide with Aliphatic and Aromatic Aldehydes: Influence of Electronic and Steric Factors

DOI: 10.4236/oalib.1103584, PP. 1-10

Andrei Yu Ershov, Igor V. Lagoda, Marina Yu Vasileva, Stanislav I. Yakimovich, Boris V. Chernitsa, Lyudmila Yu Kuleshova, Lyudmila V. Pavlova, Aleksandr V. Yakimansky

Subject Areas: Organic Chemistry

Keywords: Hammett and Taft Equations, Ring-Chain Tautomerism 2-Mercaptobenzoylhydrazones, Benzo-1,3,4-Thiadiazepines

Full-Text Cite this paper Add to My Lib

Abstract

It has been shown by ¹H and ¹³C NMR spectroscopy that 2-mercaptobenzoyl-hydrazones of aliphatic and aromatic aldehydes exist in solution as tautomeric mixtures of linear and cyclic benzo-1,3,4-thiadiazepine forms. The linear hydrazone form is represented by (E,E')-and (E,Z')-conformational isomers, differing in the disposition relative to the amide C–N bond. Growing bulk of the alkyl substituent at the C=N bond of the aliphatic aldehydes derivatives decreases the fraction of the cyclic tautomer; therewith the logarithms of the constants of the chain-ring tautomeric equilibrium correlate with the E_S steric constants of the alkyl substituents. In the series of the aromatic aldehydes 2-mercaptobenzoylhydrazones the linear tautomer prevails, and the logarithms of the tautomeric equilibrium constants K_T correlate with the σ-constants of the substituents in the aromatic nucleus.

Cite this paper

Ershov, A. Y. , Lagoda, I. V. , Vasileva, M. Y. , Yakimovich, S. I. , Chernitsa, B. V. , Kuleshova, L. Y. , Pavlova, L. V. and Yakimansky, A. V. (2017). Ring-Chain Tautomerism of the Condensation Products of 2-Mercaptobenzohydrazide with Aliphatic and Aromatic Aldehydes: Influence of Electronic and Steric Factors. Open Access Library Journal, 4, e3584. doi: http://dx.doi.org/10.4236/oalib.1103584.

References

[1]	Majumdar, P., Pati, A., Patra, M., Behera, R.K. and Behera, A.K. (2014) Acid Hydrazides, Potent Reagents for Synthesis of Oxygen-, Nitrogen-, and/or Sulfur-Containing Heterocyclic Rings. Chemical Reviews, 114, 2942-2977. https://doi.org/10.1021/cr300122t
[2]	El-Barbary, A.A., El-Ezz, A.Z.A., Sharaf, A.M. and Nielsen, C. (2006) The Synthesis of Some New Quinazolone Derivatives of Potential Biological Activity. Phosphorus, Sulfur, and Silicon and the Related Elements, 181, 1895-1912. https://doi.org/10.1080/10426500500543834
[3]	Ershov, A.Yu., Chernitsa, B.V., Doroshenko, V.A., Yakimovich, S.I., Alekseev, V.V., Lagoda, I.V., Pakalnis, V.V., Zerova, I.V. and Shamanin, V.V. (2011) N-2-Amino-benzoyl-N-Methylhydrazones of Aldehydes and Aldoses and Their Cyclization into Benzo-1,3,4-Triazepine Derivatives. Chemistry of Heterocyclic Compounds, 46, 1838-1848. https://doi.org/10.1007/s10593-011-0697-0
[4]	Valters, R.E. and Flitsch, W. (1985) Ring-Chain Tautomerism. Plenum Press, New York, 290 p. https://doi.org/10.1007/978-1-4684-4883-2
[5]	Elguero, J., Marzin, C., Katrizky, A.R. and Linda, P. (1976) The Tautomerism of Heterocycles. Academic Press, New York, London, 655 p.
[6]	Lázár, L. and Fülop, F. (2003) Recent Developments in the Ring-Chain Tautomerism of 1,3-Heterocycles. European Journal of Organic Chemistry, 16, 3025-3042. https://doi.org/10.1002/ejoc.200300142
[7]	Ershov, A.Yu., Lagoda, I.V., Yakimovich, S.I., Pakalnis, V.V. and Shamanin, V.V. (2007) Ring-Chain Tautomerism of the Condensation Product of Acetone with 2- Sulfanylbenzohydrazide. Russian Journal of Organic Chemistry, 43, 1745-1746. https://doi.org/10.1134/S1070428007110310
[8]	Flegontov, S.A., Titova, Z.S., Stolyarov, A.P., Buzykin, B.I. and Kitaev, Yu.P. (1979) Hydrazones 62. The Structures of Aroylhydrazones with Intramolecular Hydrogen Bonding. Bulletin of the Academy of Sciences of the USSR, Division of Chemical Science, 28, 948-953. https://doi.org/10.1007/BF00963303
[9]	Neuvonen, K., Fülop, F., Neuvonen, H., Simeonov, M. and Pihlaja, K. (1997) Correlation Analysis of the ¹³C Chemical Shifts of Substituted Benzaldehyde 2-Amino-benzoylhydrazones. Study of the Propagation of Substituent Effects along a Heteroatomic Chain. Journal of Physical Organic Chemistry, 10, 55-66. https://doi.org/10.1002/(SICI)1099-1395(199701)10:1<55::AID-POC854>3.0.CO;2-D
[10]	Kitaev, Yu.P. and Buzykin, B.I. (1974) Hydrazones. Nauka, Moscow, 381 p. (In Russian)
[11]	Parpiev, N.A., Yusupov, V.G., Yakimovich, S.I. and Sharipov, Kh.T. (1988) Acylhydrazones and Their Complexes with Transition Metals. Fan, Tashkent, 163 p. (In Russian)
[12]	Ershov, A.Yu., Lagoda, I.V., Yakimovich, S.I., Pakalnis, V.V., Zerova, I.V., Dobrodumov, A.V. and Shamanin, V.V. (2009) Tautomerism and Conformational Isomerism of Mercaptoacetylhydrazones of Aliphatic and Aromatic Aldehydes. Russian Journal of Organic Chemistry, 45, 660-666. https://doi.org/10.1134/S1070428009050030
[13]	Ershov, A.Yu., Lagoda, I.V., Yakimovich, S.I., Zerova, I.V., Pakalnis, V.V. and Shamanin, V.V. (2009) Structure of the Condensation Products of 3-Sulfanylpropionic acid Hydrazide with Aldehydes, Ketones, and Aldoses. Russian Journal of Organic Chemistry, 45, 1488-1495. https://doi.org/10.1134/S107042800910011X
[14]	Karabatsos, G.J., Draham, J.D. and Vane, F.M. (1962). syn-anti Isomer Determination of 2,4-Dinitrophenylhydrazones and Semicarbazones by N.M.R. Journal of American Chemical Society, 84, 753-755. https://doi.org/10.1021/ja00864a015
[15]	Taft, R.W. (1952) Linear Free Energy Relationships from Rates of Esterification and Hydrolysis of Aliphatic and Ortho-Substituted Benzoate Esters. Journal of American Chemical Society, 74, 2729-2732. https://doi.org/10.1021/ja01131a010
[16]	Zhdanov, Yu.A. and Minkin, V.I. (1966) Correlation Analysis in Organic Chemistry. Rostov University, Rostov-on-Don, 470 p. (In Russian)
[17]	Charton, M. (1975) Steric Effects. I. Esterification and Acid-Catalyzed Hydrolysis of Esters. Journal of American Chemical Society, 97, 1552-1556. https://doi.org/10.1021/ja00839a047
[18]	Palm, V.A. (1977) Fundamentals of the Quantitative Theory of Organic Reactions. Khimia, Leningrad, 360 p. (In Russian)
[19]	Hammett, L.P. (1937) The Effect of Structure upon the Reactions of Organic Compounds. Benzene Derivatives. Journal of American Chemical Society, 59, 96-103. https://doi.org/10.1021/ja01280a022
[20]	Brown, H.C. and Okamoto, Y. (1958) Electrophylic Substituent Constants. Journal of American Chemical Society, 80, 4979-4987. https://doi.org/10.1021/ja01551a055
[21]	Zelenin, K.N., Alekseev, V.V., Kuznetsova, O.B., Terentev, P.B., Lashin, V.V., Ovcharenko, V.V. and Khorseeva, L.A. (1993) Thiosemicarbazones, thiobenzoylhydrazones and Thiocarbonohydrazones of Monoses. Russian Journal of Organic Chemistry, 29, 278-286.
[22]	Katz, L., Karger, L.S., Schroeder, W. and Cohen, M.S. (1953) Hydrazine Derivatives. I. Benzalthio- and Bisbenzaldi-Thiosalicylhydrazides. Journal of Organic Chemistry, 18, 1380-1402. https://doi.org/10.1021/jo50016a019
[23]	Ershov, A.Yu., Lagoda, I.V., Mokeev, M.V., Yakimovich, S.I., Zerova, I.V., Pakalnis, V.V. and Shamanin, V.V. (2008) Thiosalicyloylhydrazones of Alyphatic Aldehydes and Their Cyclization into 1,3,4-Benzothiadiazepine Derivatives. Chemistry of Heterocyclic Compounds, 44, 356-359. https://doi.org/10.1007/s10593-008-0052-2
[24]	Chernitsa, B.V., Ershov, A.Yu., Doroshenko, V.A., Yakimovich, S.I., Lagoda, I.V., Zerova, I.V., Pakal’nis, V.V. and Shamanin, V.V. (2010) Ring-Chain Tautomerism of 2-Mercaptobenzoylhydrazones of Aromatic Aldehydes. Chemistry of Heterocyclic Compounds, 46, 1133-1137. https://doi.org/10.1007/s10593-010-0638-3

Full-Text

comments powered by Disqus

Contact Us

service@oalib.com

QQ:3279437679

WhatsApp +8615387084133

WeChat 1538708413