Шокол, Тетяна ВіталіївнаТетяна ВіталіївнаШоколГорбуленко, Н.Н.Горбуленко0000-0001-9438-572XХиля, Володимир ПетровичВолодимир ПетровичХиля2026-03-312026-03-312018Шокол, Т., Горбуленко, Н., & Хиля, В. (2018). Синтез 7-гідрокси-2,8-диметил-4-оксо-3-фенокси-4Н-6-хроменкарбальдегіду. Вісник київського національного університету імені Тараса Шевченка. Хімія, 1(55), 54-57. https://doi.org/10.17721/1728-2209.2018.1(55).13УДК 547.81410.17721/1728-2209.2018.1(55).13https://ir.library.knu.ua/handle/15071834/13896Ortho-hydroxyformylchromones are convenient syntones for the construction of linear and angular hetarenochromones. Usually, 7-hydroxy-6-formylchromones were synthesized by oxidation of natural linear furochromones: visnagin and kellin and their synthetic analogues. The Duff reaction, which is the formylation of phenols in the ortho-position by heating with hexamethylenetetramine followed by acidic hydrolysis of intermediate imine, was also used to convert 7-hydroxychromones into 7-hydroxy-6-formylchromones, but in this case there were some difficulties because of the passivity of position 6 in 7-hydroxychromones compared to position 8 to the electrophilic attack. Thus, for the preparation of 7-hydroxy-6-formylchromones, it is necessary to use 8-substituted derivatives and to provide formylation for a long time.A method for the synthesis of 7-hydroxy-6-formylchromones based on 8-substituted 7-hydroxy-6-dialkylaminomethylchromones and hexamethylenetetramine was developed using the Duff reaction conditions. This method was demonstrated on the synthesis of 7-hydroxy-2,8-dimethyl-4-oxo-3-phenoxy-4H-6-chromenecarbaldehyde from 6-dimethylaminomethyl-7-hydroxy-2,8-dimethyl-3-phenoxy-4H-4-chromenone and hexamethylenetetramine in glacial acetic acid at reflux. It should be noted that when carrying out this reaction under heating on a water bath with subsequent hydrochloric acid hydrolysis only Mannich basehydrochloride was isolated from the reaction mixture. The starting 6-dimethylaminomethyl-7-hydroxy-2,8-dimethyl-3-phenoxy-4H-4-chromenone was synthesized from 1-(2,4-dihydroxy-3-methylphenyl)-2-phenoxyethanone in three steps. Acylation of the latter with acetic anhydride in the presence of triethylamine followed by condensation afforded 2,8-dimethyl-4-оxо-3-phenoxy-4Н-7-chromenylаcetate. Subsequent removal of acetyl protection resulted in 7-hydroxy-2,8-dimethyl-3-phenoxy-4H-4-chromenone, which on introduction into the Mannich reaction with bisdimethylaminomethane in dioxane gave rise to the desired 6-dimethylaminomethyl derivative.Розроблено метод синтезу 7-гідрокси-6-формілхромонів на основі 7-гідрокси-6-діалкіламінометилхромонів та гексаметилентетраміну за умов реакції Даффа на прикладі синтезу 7-гідрокси-2,8-диметил-4-оксо-3-фенокси-4Н-6-хроменкарбальдегіду з 6-диметиламінометил-7-гідрокси-2,8-диметил-3-фенокси-4Н-4-хроменону. Вихідний 6-диметиламінометил-7-гідрокси-2,8-диметил-3-фенокси-4Н-4-хроменон було синтезовано з 1-(2,4-дигідрокси-3-метилфеніл)-2-феноксиетанону в три стадії: шляхом ацилювання оцтовим ангідридом в присутності триетиламіну, подальшого зняття ацетильного захисту та введення одержаного 7-гідроксихромону в реакцію Манніха з бісдиметиламінометаном.uk7-гідрокси-6-діалкіламінохромони7-гідрокси-6-формілхромониреакція Даффа6-dialkylaminomethyl-7-hydroxy-4H-4-chromenones7-hydroxy-4-oxo-4H-6-chromenecarbaldehydesDuff reactionСтаття