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Thermolysis of 4‐Diazotetrahydrofuran‐3‐ones: Total Change of Reaction Course Compared to Photolysis
Author(s) -
Rodina Ludmila L.,
Medvedev Jury J.,
Galkina Olesia S.,
Nikolaev Valerij A.
Publication year - 2014
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201400161
Subject(s) - chemistry , thermal decomposition , alkyl , aryl , substituent , photodissociation , medicinal chemistry , decomposition , photochemistry , yield (engineering) , organic chemistry , materials science , metallurgy
Thermolysis of 2,2,5,5‐tetrasubstituted 4‐diazodihydrofuran‐3‐ones in protic (BnOH) and aprotic (DMSO) media, in contrast to photolysis, gives rise to the formation of 2,2,4,5‐substituted 3(2 H )‐furanones as a result of 1,2‐alkyl (aryl) shift. The thermal stability of diazodihydrofuranones in these processes is determined by the nature of the substituents at the C‐5 atom of the heterocyclic structure: alkyl and electron‐donating groups in the para ‐position of the aryl substituent notably reduce the persistence of diazodihydrofuranones, whereas aryl groups and electron‐withdrawing substituents increase their stability considerably. Thermolysis of substituted 4‐diazodihydrofuran‐3‐ones in DMSO solution is a first‐order reaction that furnishes higher yields of furanones than thermolysis in BnOH. The reaction can serve as a preparative method for the synthesis of tetrasubstituted‐3(2 H )‐furanones.