Study on the synthesis and reaction ofethyl 4-dialkylmethylidenehydrazino-3-alkylazulene-1-caboxylate

• Main Authors: Tien-Shyang Chen, 陳天祥
• Other Authors: 吳吉輝
• Format: Others
• Language: zh-TW
• Published: 2008
• Online Access: http://ndltd.ncl.edu.tw/handle/47845565928230998962

碩士 === 中原大學 === 化學研究所 === 96 === 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.