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AcCl veya Ac2O Kullanılarak Bazı Norkantarimid Türevlerinin Moleküler Kararlılık, Sentez Mekanizması ve Oluşumunlarının İncelenmesi: Mekanizma Tabanlı Bir Çalışma

Year 2023, Volume: 23 Issue: 3, 618 - 627, 28.06.2023
https://doi.org/10.35414/akufemubid.1207578

Abstract

Bu çalışmadaki amaç, ilk olarak norkantarimid türevlerinin AcCl ile eter parçalanmasından sonra oluşan diasetatların zamanla klorlu monoasetatlara dönüşümünü NMR tekniği yardımıyla detaylı olarak açıklamak ve ikinci olarak bu dönüşümü teorik ve hesaplamalı olarak doğrulamaktır. N-metil, N-benzil ve N-asetoksietil sübstitüe norkantarimid türevlerinin eter parçalanma reaksiyonları Ac2O veya AcCl ile H2SO4 varlığında gerçekleştirildi ve bu reaksiyonların mekanizmaları detaylı olarak açıklandı. AcCl ile yapılan reaksiyonlardan alınan örneklerin 1H NMR analizlerine göre, önce trans-1,4-diasetatlar oluştu. Reaksiyonun devam etmesi ile trans-1,4-diasetatlar, SN2' mekanizması yoluyla trans-1,2-kloroasetatlara dönüştü. İlave olarak, bu açıklama teorik ve fiziksel hesaplamalarla daha da desteklendi.

References

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  • Baran, A., Kazaz, C., Seçen, H. (2004). Stereoselective ring-opening reactions with AcBr and AcCl. A new method for preparation of some haloconduritols. Tetrahedron. 60, 4, 861-866. https://doi.org/10.1016/j.tet.2003.11.054
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  • Köse, A., Kaya, M., Kishalı, N.H., Akdemir, A., Şahin, E., Kara, Y., Şanlı-Mohamed, G. (2020). Synthesis and biological evaluation of New Chloro/Acetoxy Substituted Isoindole Analogues as new tyrosine kinase inhibitors. Bioorganic Chemistry. 94, 103421. https://doi.org/10.1016/j.bioorg.2019.103421
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  • Tan, A., Bozkurt, E., Kishali, N., Kara, Y. (2014). A New and Convenient Synthesis of Amino-phthalimide (1H-Isoindole1,3(2H)-dione) Derivatives and Their Photoluminescent Properties. Helvetica Chimica Acta. 97, 8, 1107-1114. https://doi.org/10.1002/hlca.201300394
  • Wang, G.S. (1989). Medical Uses of Mylabris in Ancient China and Recent Studies. Journal of Ethnopharmacology. 26, 2, 147-162. https://doi.org/10.1016/0378-8741(89)90062-7
  • https://doi.org/10.1016/0378-8741(89)90062-7

Investigation Into The Molecular Stability, Synthesis Mechanism, and Formation of Some Norcantharimide Derivatives Using AcCl or Ac2O: A Mechanism-Based Study

Year 2023, Volume: 23 Issue: 3, 618 - 627, 28.06.2023
https://doi.org/10.35414/akufemubid.1207578

Abstract

The aim in this study was first to explain, in detail the conversion of diacetates over time into chlorinated monoacetates following ether cleavage with AcCl of norcantharimide derivatives with the help of the NMR technique and second, to verify this conversion theoretically and computationally. Ether cleavage reactions of N-methyl, N-benzyl, and N-acetoxyethyl-substituted norcantharimide derivatives were performed with Ac2O or AcCl in the presence of H2SO4, and the mechanisms of these reactions were elucidated in detail. According to the 1H NMR analyses of aliquots from the reactions with AcCl, trans-1,4-diacetates formed firstly. Upon the continuation of the reaction, trans-1,4-diacetates transformed into trans-1,2-chloroacetates via an SN2' mechanism. Additionally, this explanation was further supported by the soft theoretical and physical calculations.

References

  • Baran, A., Kazaz, C., Seçen, H., Sütbeyaz, Y. (2003). Synthesis of haloconduritols from an endo-cycloadduct of furan and vinylene carbonate. Tetrahedron. 59, 20, 3643-3648. https://doi.org/10.1016/S0040-4020(03)00510-6
  • Baran, A., Kazaz, C., Seçen, H. (2004). Stereoselective ring-opening reactions with AcBr and AcCl. A new method for preparation of some haloconduritols. Tetrahedron. 60, 4, 861-866. https://doi.org/10.1016/j.tet.2003.11.054
  • Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Scalmani, G., Barone, V., Mennucci, B., Petersson, G.A., Nakatsuji, H., Caricato, M., Li, X., Hratchian, H. P., Izmaylov, A.F., Bloino, J., Zheng, G., Sonnenberg, J.L., Hada, M., Ehara, M., Toyota, K., Fukuda, R., Hasegawa, J., Ishida, M., Nakajima, T., Honda, Y., Kitao, O., Nakai, H., Vreven, T., Montgomery, J.A.Jr., Peralta, J. E., Ogliaro, F., Bearpark, M., Heyd, J.J., Brothers, E., Kudin, K.N., Staroverov, V.N., Kobayashi, R., Normand, J., Raghavachari, K., Rendell, A., Burant, J.C., Iyengar, S.S., Tomasi, J., Cossi, M., Rega, N.,.. et all (2009), Gaussian 09, Gaussian, Inc.: Wallingford, CT.
  • Köse, A., Bal, Y., Kishalı, N.H., Şanlı-Mohamed, G., Kara, Y. (2017). Synthesis and anticancer activity evaluation of new isoindole analogues. Medicinal Chemistry Research. 26, 4, 779-786. https://doi.org/10.1007/s00044-017-1793-1
  • Köse, A., Kaya, M., Kishalı, N.H., Akdemir, A., Şahin, E., Kara, Y., Şanlı-Mohamed, G. (2020). Synthesis and biological evaluation of New Chloro/Acetoxy Substituted Isoindole Analogues as new tyrosine kinase inhibitors. Bioorganic Chemistry. 94, 103421. https://doi.org/10.1016/j.bioorg.2019.103421
  • Lee, C., Yang, W. and Parr, R.G. Development of the Colic-Salvetti correlation-energy formula into a functional of the electron density. (1988). Physical Review B. 37, 2, 785-789. https://doi.org/10.1103/PhysRevB.37.785
  • Lin, P.Y., Shi, S.J., Hsu, F.L., Chen, C.F. (1998). New Cantharidinimides from Cantharidin and 2-Arylethylamines: Efficient Synthesis under High Pressure.. Journal of the Chinese Chemical Society. 45, 2, 323-326. https://doi.org/10.1002/jccs.199800052
  • Nickolls, L.C., and Teare, D. (1954). Poisoning By Cantharidin. British Medical Journal. 1954; 2, 4901, 1384-1386. https://www.jstor.org/stable/20361797
  • Tagwireyi, D., Ball, D.E., Loga, P.J., Moyo, S. (2000). Cantharidin poisoning due to “Blister beetle” ingestion. Toxicon. 38, 12, 1865-1869. https://doi.org/10.1016/s0041-0101(00)00093-3
  • Tan, A., Koc, B., Sahin, E., Kishali, N.H., Kara, Y. (2011). Synthesis of New Cantharimide Analogues Derived from 3-Sulfolene. Synthesis. 7, 1079- https://doi.org/10.1055/s-0030-1258466
  • Tan, A., Bozkurt, E., Kishali, N., Kara, Y. (2014). A New and Convenient Synthesis of Amino-phthalimide (1H-Isoindole1,3(2H)-dione) Derivatives and Their Photoluminescent Properties. Helvetica Chimica Acta. 97, 8, 1107-1114. https://doi.org/10.1002/hlca.201300394
  • Wang, G.S. (1989). Medical Uses of Mylabris in Ancient China and Recent Studies. Journal of Ethnopharmacology. 26, 2, 147-162. https://doi.org/10.1016/0378-8741(89)90062-7
  • https://doi.org/10.1016/0378-8741(89)90062-7
There are 13 citations in total.

Details

Primary Language English
Subjects Organic Chemistry
Journal Section Articles
Authors

Aytekin Köse 0000-0003-2448-3716

Early Pub Date June 22, 2023
Publication Date June 28, 2023
Submission Date November 20, 2022
Published in Issue Year 2023 Volume: 23 Issue: 3

Cite

APA Köse, A. (2023). Investigation Into The Molecular Stability, Synthesis Mechanism, and Formation of Some Norcantharimide Derivatives Using AcCl or Ac2O: A Mechanism-Based Study. Afyon Kocatepe Üniversitesi Fen Ve Mühendislik Bilimleri Dergisi, 23(3), 618-627. https://doi.org/10.35414/akufemubid.1207578
AMA Köse A. Investigation Into The Molecular Stability, Synthesis Mechanism, and Formation of Some Norcantharimide Derivatives Using AcCl or Ac2O: A Mechanism-Based Study. Afyon Kocatepe Üniversitesi Fen Ve Mühendislik Bilimleri Dergisi. June 2023;23(3):618-627. doi:10.35414/akufemubid.1207578
Chicago Köse, Aytekin. “Investigation Into The Molecular Stability, Synthesis Mechanism, and Formation of Some Norcantharimide Derivatives Using AcCl or Ac2O: A Mechanism-Based Study”. Afyon Kocatepe Üniversitesi Fen Ve Mühendislik Bilimleri Dergisi 23, no. 3 (June 2023): 618-27. https://doi.org/10.35414/akufemubid.1207578.
EndNote Köse A (June 1, 2023) Investigation Into The Molecular Stability, Synthesis Mechanism, and Formation of Some Norcantharimide Derivatives Using AcCl or Ac2O: A Mechanism-Based Study. Afyon Kocatepe Üniversitesi Fen Ve Mühendislik Bilimleri Dergisi 23 3 618–627.
IEEE A. Köse, “Investigation Into The Molecular Stability, Synthesis Mechanism, and Formation of Some Norcantharimide Derivatives Using AcCl or Ac2O: A Mechanism-Based Study”, Afyon Kocatepe Üniversitesi Fen Ve Mühendislik Bilimleri Dergisi, vol. 23, no. 3, pp. 618–627, 2023, doi: 10.35414/akufemubid.1207578.
ISNAD Köse, Aytekin. “Investigation Into The Molecular Stability, Synthesis Mechanism, and Formation of Some Norcantharimide Derivatives Using AcCl or Ac2O: A Mechanism-Based Study”. Afyon Kocatepe Üniversitesi Fen Ve Mühendislik Bilimleri Dergisi 23/3 (June 2023), 618-627. https://doi.org/10.35414/akufemubid.1207578.
JAMA Köse A. Investigation Into The Molecular Stability, Synthesis Mechanism, and Formation of Some Norcantharimide Derivatives Using AcCl or Ac2O: A Mechanism-Based Study. Afyon Kocatepe Üniversitesi Fen Ve Mühendislik Bilimleri Dergisi. 2023;23:618–627.
MLA Köse, Aytekin. “Investigation Into The Molecular Stability, Synthesis Mechanism, and Formation of Some Norcantharimide Derivatives Using AcCl or Ac2O: A Mechanism-Based Study”. Afyon Kocatepe Üniversitesi Fen Ve Mühendislik Bilimleri Dergisi, vol. 23, no. 3, 2023, pp. 618-27, doi:10.35414/akufemubid.1207578.
Vancouver Köse A. Investigation Into The Molecular Stability, Synthesis Mechanism, and Formation of Some Norcantharimide Derivatives Using AcCl or Ac2O: A Mechanism-Based Study. Afyon Kocatepe Üniversitesi Fen Ve Mühendislik Bilimleri Dergisi. 2023;23(3):618-27.