Intramolecular Cyclization of the ortho‐Substituted N‐arylquinone Imines under Basic and Thermal Conditions. Issue 3 (17th January 2023)

• Record Type: Journal Article
• Authors: Khodykina, Evgenia S.; Steglenko, Dmitry V.; Vetrova, Elena V.; Pugachev, Artem D.; Galkina, Maria S.; Borodkina, Inna G.; Lesin, Alexander V.; Demidov, Oleg P.; Metelitsa, Anatoly V.; Kolodina, Alexandra A.
• Is Part Of: ChemistrySelect. Volume 8:Issue 3(2023)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2023-01-17
• Subjects: N-arylquinone imines -- benzazines -- benzazoles -- cyclization -- spiro compounds; Chemistry -- Periodicals; 540.5
• DOI: 10.1002/slct.202204317
• Languages: English
• ISSNs: 2365-6549

Abstract

Abstract: The S ( O, N )‐benzyl ethers of N ‐arylquinone imines undergo cyclization under the action of bases to form products of the benzothiazol, benzoxazole, and benzimidazole series, while under thermal conditions they undergo a non‐catalyzed rearrangement to form spiro‐cyclohexadiene derivatives of benzazines. The benzimidazole, spirobenzothiazine, and spirobenzoxazine structures were supported by the x‐ray diffraction method. The possibility of intramolecular photochemical cyclization was investigated; ortho ‐ S ( O, N )‐benzyl‐substituted N ‐arylquinone imines show high photostability under UV irradiation. The features of the cyclization processes of quinone imine derivatives were revealed by DFT calculations using the wB97XD/6‐311++G** method. Abstract : The dependence of the N ‐arylquinone imines benzyl ethers cyclization reaction pathway on the conditions is established. Under basic conditions, cyclization proceeds through the formation of a dihydro azole ring; under thermal conditions, cyclization proceeds through the formation of a spirane azine ring; under photochemical conditions, neither direct cyclization nor reverse reaction occur.