2,3-Disübstitue benzobarrelenlerin fotokimyasal düzenlemesi
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Abstract
I ÖZET 2,3-Disübstitüe benzobarrelen türevlerini hazırlamak için uygun bir bileşik olan 2,3-dibromobenzobarrelen (119) çeşitli kimyasal transformasyonlarla 2- siyano-3-metilbenzobarrelen (122), 2-karbometoksi-3-metilbenzobarrelen (148), 2-formil-3-metilbenzobarrelen (170), 2-karbometoksi-3-siyanobenzo- barrelen (181) çevrildi. X=CH3 Y=CN 1 2 2 X=CH3 Y=CHO 1 7 0 X=CH3 Y=C02CH3 1 4 8 x=CN Y=CXD2CH3 1 8 1 hv Aseton ca>o^+oix;omcYx X=CN 1 g 7 Y=C02CH3 X=CH3 Y=CN 1 3 9 X=CH3 Y=CN 1 4 0 X=CH3 Y^C02CH3 1 6 2 X=CH3 Y=CHO 17 4 X=CH3 Y=CHO 1 7 3 X=CH3 1 6 5 YrıCOjO-b 2-Siyano-3-metilbenzobarrelenin (122) aseton sensitize fotolizinden vinil-vinil köprüleşmesiyle 1-siyano-8-metilbenzosemibulvalen (139) ve 1-siyano-6- metilbenzosemibulvalen (140) elde edilirken, 2-formil-3-metilbenzobarrelenin (170) fotolizinden 1-formil-8-metilbenzosemibulvalen (173) ile 1-formil-6- metilbenzosemibulvalen (174) elde edildi. 2-Karbometoksi-3-metilbenzo barrelenin (148) aynı şartlarda yapılan fotolizinden 1 -karbometoksi-8-metil- benzosemibulvalen (162) ve 7-karbometoksi-6-metilbenzosemibulvalen (165) oluştu. 2-Karbometeoksi-3-siyanobenzobarrelenin (181) aseton sensitizerliğinde yapılan fotolizinden de iki vinil grubu arasında intramoleküler [2+2] siklokatı İmayla 7-karbometoksi-8-siyanobenzosiklooktatetraen (197) elde edildi. II SUMMARY In order to prepare 2,3-disubstituted benzobarrelene derivatives such as 2- cyano-3-methylbenzobarrelene (1 22), 2-carbomethoxy-3-methylbenzobarre- lene (148), 2-formyl-3-methylbenzobarrelene (170) and 2-carbomethoxy-3- cyanobenzobarrelene (181) we reacted 2,3-dibromobenzobarrelene (119), which serves as a key compound, with suitable reagents. X=Br 1 1 9 X=CH3 y=CN 122 X=CH3 Y=CHO 170 X=CH3 Y=COsCH3 1 4 8 x=CN YrCCfcCHs 1 8 1 hv Aseton ax-oi-cdb.;om: x X=CN 1 g 7 Y=CXD2CH3 X=CH3 Y=CN 1 3 9 X=CH3 Y=CN 1 4 0 X=CH3 Y=C02CH3 1 6 2 X=CH3 Y=CHO 1 7 4 X=CH3 Y=CHO 1 7 3 X=CH3 i 6 5 Y=CC»2CH3 While aceton sensitized photolysis of 2-cyano-3-methylbenzobarrelene (122) was giving 1-cyano-8-methylbenzosemibullvalene (139) and 1-cyano-6- methylbenzosemibullvalene (140) involving vinyl-vinyl bridging, the photolysis of 2-formyl-3-methylbenzobarrelene (170) afforded 1-formyl-8- methylbenzosemibullvalene (173) and 1-formyl-6-methylbenzosemibullva- lene (174). 1-Carbomethoxy-8-methylbenzosemibullvalene (162) and 1- carbomethoxy-8-methylbenzosemibullvalene (165) were obtained by the photolysis of 2-carbomethoxy-3-methylbenzobarrelene (148) performed under the same reaction conditions. Aceton sensitized photolysis of 2-carbomethoxy-3-cyanobenzobarrelene (181) gave 7-carbomethoxy*8-cyanobenzocyclooctatetraene (197) by a [2+2] intramolecular cycloaddition reaction between two vinyl groups.
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