CONVENIENT SYNTHESIS OF NITRILES VIA DEHYDRATION OF ALDOXIMES USING TOSYLCHLORIDE AND SODIUM HYDRIDE IN AMBIENT CONDITIONS

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Asutay O., ERDEM S.

Bulletin of the Chemical Society of Ethiopia, cilt.40, sa.7, ss.1529-1542, 2026 (SCI-Expanded, Scopus)

  • Yayın Türü: Makale / Tam Makale
  • Cilt numarası: 40 Sayı: 7
  • Basım Tarihi: 2026
  • Doi Numarası: 10.4314/bcse.v40i7.11
  • Dergi Adı: Bulletin of the Chemical Society of Ethiopia
  • Derginin Tarandığı İndeksler: Science Citation Index Expanded (SCI-EXPANDED), Scopus, Directory of Open Access Journals
  • Sayfa Sayıları: ss.1529-1542
  • Anahtar Kelimeler: Aldoxime, Dehydration, DFT calculations, Nitrile, Sodium hydride, Tosylchloride
  • Açık Arşiv Koleksiyonu: AVESİS Açık Erişim Koleksiyonu
  • Marmara Üniversitesi Adresli: Evet

Özet

An efficient and general synthetic procedure was developed for the conversion of aldoximes to nitriles. A series of aldoximes was converted into nitriles using commercially available reagents NaH and TsCl at room temperature. The successive addition of NaH and TsCl to the solution of the aldoxime in THF provided the corresponding nitriles in high yields in a very short time. In the case of 1H-pyrrole-2-carbaldehyde oxime 1-tosyl-1H-pyrrole-2-carbonitrile was isolated. However, increasing the amount of NaH provided the detosylated 1H-pyrrole-2-carbaldehyde nitrile in high yield. This new, simple method offers several advantages. It has a wide scope covering alkyl, alkenyl, aryl, and hetaryl aldoximes. The reaction is very fast at room temperature, requires no catalyst, and produces a very high yield using readily available, environmentally friendly reagents. DFT calculations on the prototype aldoxime elucidated the proposed mechanism, which consists of three steps: deprotonation of the aldoxime, SN2-type substitution with TsCl, and E2 elimination of tosylate. The calculated energy profiles verified that the reaction is extremely facile and exergonic with a continuously downhill potential energy surface but almost no activation energy barrier. These computational findings elucidate the experimental results.