Synthesis, characterization and derivatizations of quinazolin-3-oxides
Date
2021-09-21
Authors
Samandram, Rashinikumar Singh
Journal Title
Journal ISSN
Volume Title
Publisher
Bursa Uludağ Üniversitesi
Abstract
2-Aminobenzaldehit, 1-(2-aminofenil)etanon ve 2-aminofenil fenil metanon oksimler 1, karşılık gelen 1,2-dihidrokinazolin-3-oksitleri vermek üzere aromatik aldehitlerle reaksiyona sokuldu. Oda sıcaklığında çevreye zarar vermeyen H2O2-tungstat oksidan sistemi kullanılarak yüksek verimlerle bir dizi kinazolin-3-oksit 3’e dönüştürüldü. Bileşik 3'ün sentezi için yüksek verimli tek kap prosedürü de geliştirilmiştir. 2-Arilkinazolin 3-oksitlerin arilboronik asitlerle C-4 arilasyonlarında oksidan bileşen olarak manganez triasetatın kullanımı rapor edilmiştir. Yeni yöntem, iyi ila yüksek verimlerde yeni 2,4-diarillenmiş kinazolin 3-oksitler hazırlamak için uygulanmıştır. Yöntemin, her iki aromatik halka üzerinde çeşitli sübstitüentleri tolere ettiği, oksijensizleşme ve kinazolin-4(3H)-one'ye yeniden düzenleme gibi dezavantajları olmadığı gösterilmiştir. Kinazolin-3-oksitler 3'ün, karşılık gelen N-(2-(((hidroksiimino)metil)fenil)-benzamidler 9'u vermek üzere ZrOCl2 varlığında hidrolitik halka açılmasına maruz kaldıkları gösterilmiştir. 9 bileşikleri, katalitik miktarlarda bir asit beraberinde DMSO içinde tekrar halkalaştırılmıştır.
2-Aminobenzaldehyde, 1-(2-aminophenyl)ethanone and 2-aminophenyl phenyl methanone oximes 1 were reacted with aromatic aldehydes to give the corresponding 1,2- dihydroquinazoline-3-oxides 2. The latter were converted in high yields to a series of quinazoline-3-oxides 3 using environmentally benign H2O2-tungstate oxidant system at room temperature. High yielding one-pot procedure was also developed for the synthesis of compounds 3. The use of manganese triacetate as an oxidant component in the C-4 arylations of 2-aryl-quinazoline 3-oxides with arylboronic acids is reported. The new protocol was applied to prepare new 2,4-diarylated quinazoline 3-oxides in good to high yields. The method was shown to tolerate variety of substituents on both aromatic rings and no complications as deoxygenation and rearrangement to quinazolin-4(3H)-one were observed. Quinazoline-3-oxides 3 were shown to undergo hydrolytic ring opening in the presence of ZrOCl2 to give the corresponding N-(2-((hydroxyimino)methyl)phenyl)- benzamides 9. The latter can be recyclized in DMSO using catalytic amounts of an acid.
2-Aminobenzaldehyde, 1-(2-aminophenyl)ethanone and 2-aminophenyl phenyl methanone oximes 1 were reacted with aromatic aldehydes to give the corresponding 1,2- dihydroquinazoline-3-oxides 2. The latter were converted in high yields to a series of quinazoline-3-oxides 3 using environmentally benign H2O2-tungstate oxidant system at room temperature. High yielding one-pot procedure was also developed for the synthesis of compounds 3. The use of manganese triacetate as an oxidant component in the C-4 arylations of 2-aryl-quinazoline 3-oxides with arylboronic acids is reported. The new protocol was applied to prepare new 2,4-diarylated quinazoline 3-oxides in good to high yields. The method was shown to tolerate variety of substituents on both aromatic rings and no complications as deoxygenation and rearrangement to quinazolin-4(3H)-one were observed. Quinazoline-3-oxides 3 were shown to undergo hydrolytic ring opening in the presence of ZrOCl2 to give the corresponding N-(2-((hydroxyimino)methyl)phenyl)- benzamides 9. The latter can be recyclized in DMSO using catalytic amounts of an acid.
Description
Keywords
1,2-dihidrokinazolin-3-oksit, H2O2 oksidasyonu, N-oksitler, Kinazolin, Kinazolin-3-oksit, Kinazolin-4(3H)-on, C-H aktivasyonu, Mn(OAc)3, 1,2-dihydroquinazoline-3-oxide, H2O2 oxidation, N-oxides, Quinazoline, Quinazoline-3-oxide, Quinazolin-4(3H)-one, C-H activation, Mn(OAc)3
Citation
Samandram, R. S. (2021). Synthesis, characterization and derivatizations of quinazolin-3-oxides. Yayınlanmamış doktora tezi. Bursa Uludağ Üniversitesi Fen Bilimleri Enstitüsü.