Synthesis, reactions and DFT study of tropolone N,N-dimethylthiocarbamate
Küçük Resim Yok
Tarih
2015
Dergi Başlığı
Dergi ISSN
Cilt Başlığı
Yayıncı
Pergamon-Elsevier Science Ltd
Erişim Hakkı
info:eu-repo/semantics/closedAccess
Özet
A new tropolone derivative namely O-(7-oxocyclohepta-1,3,5-trienyl) dimethylthiocarbamate was synthesized from tropolone and N,N-dimethylthiocarbamoyl chloride and its reactions with lithium halides in acidic media were examined. The product of each lithium halide treatment was identical and identified as S-(3-oxocyclohepta-1,4,6-trienyl) dimethylcarbamothioate. Eventually it was converted to 3-mercapto 2,4,6-cycloheptatrien-1-one on treatment with base. DFT calculations at the B3LYP/6-311++G** level were performed on the key elimination step of the mechanism, which was proposed by Ponaras et al. on analogous five-membered ring systems. The experimentally observed regioselectivity was correlated to the calculated activation barriers on five and seven-membered systems in the elimination step such that in both cases, experimentally observed product was favored over the alternative one. Thus, quantum mechanical calculations have provided insights into the synthetic pathway and regioselectivity of the reaction in this study, in comparison to the analogous five-membered system. (C) 2015 Elsevier Ltd. All rights reserved.
Açıklama
Anahtar Kelimeler
Tropolone, Thiocarbamate, Thiole, Dimethylthiocarbamoyl Chloride, DFT, B3LYP, Replacement, Diosphenols, Elaboration
Kaynak
Tetrahedron
WoS Q Değeri
Q2
Scopus Q Değeri
Q2
Cilt
71
Sayı
33
