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

Yıl 2023, Cilt: 23 Sayı: 3, 618 - 627, 28.06.2023

Aytekin Köse

https://doi.org/10.35414/akufemubid.1207578

Öz

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.

Anahtar Kelimeler

Klorlanmış ürünler; Norkantarimid Aminler SN2' mekanizması

Kaynakça

  • 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

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

Yıl 2023, Cilt: 23 Sayı: 3, 618 - 627, 28.06.2023

Aytekin Köse

https://doi.org/10.35414/akufemubid.1207578

Öz

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.

Anahtar Kelimeler

Chlorinated products Norcantharimide Amines SN2' mechanism

Kaynakça

  • 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
Toplam 13 adet kaynakça vardır.

Ayrıntılar

Birincil Dil İngilizce
Konular Organik Kimya
Bölüm Makaleler
Yazarlar

Aytekin Köse 0000-0003-2448-3716

Erken Görünüm Tarihi 22 Haziran 2023
Yayımlanma Tarihi 28 Haziran 2023
Gönderilme Tarihi 20 Kasım 2022
Yayımlandığı Sayı Yıl 2023 Cilt: 23 Sayı: 3

Kaynak Göster

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. Haziran 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, sy. 3 (Haziran 2023): 618-27. https://doi.org/10.35414/akufemubid.1207578.
EndNote Köse A (01 Haziran 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, c. 23, sy. 3, ss. 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 (Haziran 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, c. 23, sy. 3, 2023, ss. 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.
 Kapak Resmi İndir