Novel Synthesis of5-Ethoxycarbonyl-1H-azuleno[8,1-cd]pyridazines
| Autor: | CHung-hao Chang, 張中豪 |
|---|---|
| Rok vydání: | 2010 |
| Druh dokumentu: | 學位論文 ; thesis |
| Popis: | 98 4 - ethoxy -1 - ethoxycarbonyl azulene and α, β unsaturated ketone function, methyl vinyl ketone, cyclohex-2-enone, for Michael Addition reaction, obtained in high yields 95 ~ 97% ethyl 4-ethoxy - 3 -( 3-oxobutyl ) azulene-1-carboxylate 6 and ethyl 4-ethoxy - 3 -( 3-oxocyclohexyl ) azulene-1-carboxylate 3; of which the first compound 6 and reduction with NaBH4, then the first carbon of the third position of azulene ring was oxidated into carbonyl group(C=O) by DDQ,we can afford ethyl 3 - (2 - hydroxypropyl) -1H - azuleno[8,1-cd]pyridazine-5-carboxylate 9 yield 75% by addition of hydrazine.In addition,the compound 3 undergo oxidation with DDQ and then react with hydrazine can afford ethyl 3 - (4 - oxopentyl) -1H - azuleno[8,1-cd]pyridazine 12, the yield 58%. 1H-NMR spectrum displayed that the pyridazine has the fulvene structure,the part of the hydrogen chemical shifts move to high magnetic field about 0.8 ~ 1 ppm, the electronic density of the second carbon of the azulene will be polarity reversal, which is good to undergo electrophilic substitution. The compound 12, since there is carbonyl group at the third position,can undergo intramolecular electrophilic substitution and catalyze by the p-TSA, afford the compound 15, the yield 85%.React with POCl3/DMF will undergo intermolecular electrophilic substitution, we can afford ethyl -4-formyl- 3 - (4 - oxopentyl) -1H - azuleno[8,1-cd]pyridazine 16. |
| Databáze: | Networked Digital Library of Theses & Dissertations |
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