2,3-distibstitüebenzobarrelenlerin yeni ve uygun bir metodla sentezi ve 2,3-dimetoksibenzobarrelenin fotooksijenasyonu

Abstract

This study involves the synthesis of the disubstituebenzobarrelenes with a high yield and an available /Olay.T~erefore dicyanobenzobarrelene(57) was synthesized fromthe reaction of the 2, 3-dibromobenzobarrelene (64) /'1i thCuCN. After BuLi was added to dibromobenzobarreli?ne itsderivative containing methylbromo(65) was syn'thesizedwith CH3 I. Methylcyano derivative(66) was obtained reactionof this compound(65) with CuCN. After BuLi and CO2were added to dibromobenzobarrelene(64) and its derivativewith methylbromo(65) , their derivatives with bromoacid(68)and methylacid(67) were synthesized. 'rhe derivative withbromoacid (68) was reacted wi th diazomethane and Vias convertedto ,the it:' ester derivative(69) .Dimethoxybenzobarrelene (72) was obtained from tl1e reactionof the dibromobenzobarrelene(64) with CuI and sodiummethoxide. It was seen that the photooxygene'tion of thedimethoxybenzobarrelene gave exo-dioxetane (86), endo-dioxetane(87) and cis-l,4-dicarbomethoxy-I,4-dihydronaphtalene(89). These dioxetanes could not be isolated because theyare high unstable and are easily decomposed to the compound(88) on heating Vie expected that the reaction of thiscompound /'Ii th CoTPP sensi ti zed could give the compound (89)but the spectroscopic data indicated that ti1e compound(89)was not occured, this reaction gave only the compound (88) .1, 4-dicarbomethoxynaphtalene (96) Vias obtained from thereaction of DDQ and dihydronaphtalene(88) .