1-乙氧羰基-3-烷基-4-二烷基甲亞基肼基薁
的合成與反應之研究

摘要薁(Azulene)藍紫色物質，屬於非苯環芳香族之碳氫化合物，其構造為具有十個π電子的雙環共軛結構，薁的特性為五圓環上的1,3－位置傾向帶負電荷，容易進行親電性取代反應，七圓環上的4,6,8－位置傾向帶正電荷，容易進行親核性取代反應。本論文研究由3-乙氧羰基-8-乙氧基-2H-環庚-[b]-呋喃-2-酮21與醛類化合物及嗎啡琳，於乙醇迴流下進行反應，可得到1-乙氧羰基-3-烷基-4-乙氧基薁22，接著用聯胺於乙醇迴流下對薁核第四位置之乙氧基進行取代反應，可得到1-乙氧羰基-3-烷基-4-肼基薁23。將1-乙氧羰基-3-烷基-4-肼基薁23分別與丙酮、3-甲基-2-丁烯醛、4-甲氧基苯甲醛、2,3-丁二酮、乙醯乙酸乙酯、2,4-戊二酮共六種羰基化合物，於乙醇迴流下進行縮合反應，可得到十個不同的1-乙氧羰基-3-烷基-4-二烷基甲亞基肼基薁類化合物，其中與2,4-戊二酮反應得到1-乙氧羰基-3-甲基-4-(3,5-二甲基吡唑基)薁29其薁核第四位置已形成一個五圓環，以及與4-甲氧基苯甲醛反應得到1-乙氧羰基-3-甲基-4-[N-(4-甲氧基-苄亞基)]甲亞基肼基薁26因產率偏低故不使用。接著八個1-乙氧羰基-3-烷基-4-二烷基甲亞基肼基薁類化合物則以DDQ(2,3-dichloro-5,6-dicyan-p-benzochinon)與丙酮水溶液於室溫下進行反應，可將薁類化合物之第三位置烷基氧化，分別得到了六個不同的1-乙氧羰基-3-醯基-4-二烷基甲亞基肼基薁類化合物，以及兩個形成三圓環的薁類化合物1-乙氧羰基-5H-薁倂[8,1-c,d]噠嗪33a和2-(2-乙氧羰基-1-甲基-乙烯基)-5-乙氧羰基-2H-薁倂[8,1-c,d]-噠嗪36a。最後嘗試將1-乙氧羰基-3-醯基-4-二烷基甲亞基肼基薁類化合物與DBU(1,5-Diazabicyclo[5,4,0]undec-7-ene)進行反應，在甲醇或乙醇為溶劑下得到了三圓環的薁類化合物2-(2-乙氧羰基-1-甲基-乙烯基)-3-甲基-5-乙氧羰基-2H-薁倂[8,1-c,d]噠嗪36b、2-(1-甲氧基-1-甲基-2-酮-丙基)-5-乙氧羰基-2H-薁倂[8,1-c,d]噠嗪38a、2-(1-乙氧基-1-甲基-2-酮-丙基)-5-乙氧羰基-2H-薁倂[8,1-c,d]噠嗪38b、2-乙氧羰基-7,8-二胺-9,10-二甲基-9-甲氧基-10-羥基四環薁化合物39a、2-乙氧羰基-7,8-二胺-9,10-二甲基-9-乙氧基-10-羥基四環薁化合物39b、1-乙氧羰基-3-甲基-5H-薁倂[8,1-c,d]噠嗪33b。另一方面實驗由1-乙氧羰基-3-甲基-4-異丙亞基肼基薁24a溶於甲醇與I2及DBU進行反應，可得到薁核第四位置含偶氮官能基之1-乙氧羰基-3-甲基-4-(1-甲氧基-1-甲基-乙基偶氮基)薁化合物30。

關鍵字

薁；噠嗪；偶氮

並列摘要

Abstract Azulene is a blue color non-benzenoid aromatic molecule with a two-ring polar resonance structure. One of the features is the electron drift from the seven -membered ring toward the five-membered ring. The research use 3-ethoxycarbonyl-8-ethoxy-2H-cyclohepta[b]furan-2-one21 reacts with morpholine and propionaldehyde or butyraldehyde, the product 4-ethoxy-1-ethoxycarbonyl-3-alkylazulenes22.Then reacts with hydrazine the product of the reaction is 1-ethoxycarbonyl-3-alkyl-4-hydrazinoazulenes23. The 1-ethoxycarbonyl-3-alkyl-4-hydrazinoazulenes23 to condensation reacts with six kind of the carbonyl compounds, will obtain 10 different 1-ethoxy-carbonyl-3-alkyl-4-dialkylmethylidenehydrazinoazulenes. two of the product compounds 1-ethoxycarbonyl-3-methyl-4-(3,5-dimethyl-1H-pyraz-1-yl)-azulene29 form a new five-membered, and 1-ethoxycarbonyl-3-methyl-4-(4-methoxybenzyl)methylidenehydrazinoazulene26 due to low yield is not used. Then use the DDQ(2,3-dichloro-5,6-dicyan-p-benzochinon) as a oxidative reagent to reacts with 8 different 1-ethoxycarbonyl-3-alkyl-4-dialkylmethylidene-hydrazinoazulenes, will obtain 6 different 1-ethoxycarbonyl-3-acyl-4-dialkyl-methylidenehydrazinoazulenes, and 2 kind of three-ring compounds 1-ethoxy-carbonyl-5H-azuleno[8,1-c,d]pyridazine33a, 2-(2-ethoxycarbonyl-1-methyl-vinyl)-5-ethoxycarbonyl-2H-azuleno[8,1-c,d]pyridazine36a. To continue 1-ethoxycarbonyl-3-acyl-4-dialkyl-methylidenehydrazino-azulenes reacts with DBU(1,5-Diazabicyclo[5,4,0]undec-7-ene), the product of the reaction are 2-(2-ethoxycarbonyl-1-methyl-vinyl)-3-methyl-5-ethoxy-carbonyl-2H-azuleno-[8,1-c,d]pyridazine36b, 2-(1-methoxy-1-methyl-2-oxo-propyl)-5-ethoxycarbonyl-2H-azuleno-[8,1-c,d]pyridazine38a, 2-(1-ethoxy-1-methyl-2-oxo-propyl)-5-ethoxycarbonyl-2H-azuleno-[8,1-c,d]pyridazine38b, 2-ethoxycarbonyl-7,8-diaza-9,10-dimethyl-9-methoxy-10-hydroxytricyclo-azulene39a, 2-ethoxycarbonyl-7,8-diaza-9,10-dimethyl-9-ethoxy-10-hydroxytricycloazulene39b, 1-ethoxy-carbonyl-3-methyl-5H-azuleno[8,1-c,d]pyridazine 33b. The path of reaction shows the 1-ethoxycarbonyl-3-methyl-4-isopropylidene-hydrazinoazulene24a dissolve in methanol, then reacts with I2 and DBU in reflux, the product of the reaction is 1-ethoxycarbonyl-3-methyl-4-(1-meth-oxy-1-methyl-ethylazo)azulene30.