含薁核α-羥基酯類之合成研究

Study on Synthesis of α-hydroxyl Esters Containing Azulenic Ring

魏明雄(Ming-Hsiung Wei)

指導教授 ： 吳吉輝

中原大學/理學院/化學研究所/碩士(2002年)

https://doi.org/10.6840/cycu200200459

摘要

本篇主要是研究含薁核α-羥基酯類及其前驅物含薁核α-酮基酯類之合成，因α-羥基酯類衍生物具有抗精神病效果（antipsychotics），及含薁核衍生物具有降低膽固醇、抗潰瘍、抗發炎、抗高血質的效果。應用Friedel-Crafts醯化(acylation)的方法合成3-(乙氧羰基甲醯基)薁-1-羧酸酯類衍生物，係將自行製備之薁-1-羧酸酯類的衍生物原料，溶於氯苯中，然後加入三氯化鋁催化劑，再加入草酸氯乙酯，在120℃下反應4小時，而得3-(乙氧羰基甲醯基)薁-1-羧酸乙酯、2-乙氧基-3-(乙氧羰基甲醯基)薁-1-羧酸乙酯、2-羥基-3-(乙氧羰基甲醯基)薁-1-羧酸乙酯、3-(乙氧羰基甲醯基)薁-1-羧酸甲酯、2,4-二乙氧基-1-(乙氧羰基甲醯基)薁及2,4-二乙氧基-1,3-二(乙氧羰基甲醯基)薁等含薁核α-酮基酯類前驅物；其中前驅物2-乙氧基-3-(乙氧羰基甲醯基)薁-1-羧酸乙酯和3-(乙氧羰基甲醯基)薁-1-羧酸甲酯分別與格林納(Grignard)試劑（異丙基鎂氯）於0℃下反應40分鐘，可得到3-(1-乙氧羰基-2-甲基-1-羥基丙基)薁-1-羧酸甲酯和2-乙氧基-3-(1-乙氧羰基-2-甲基-1-羥基丙基)薁-1-羧酸乙酯等含薁核α-羥基酯類。以上化合物及前驅物結構的決定依紅外線光譜（IR）、核磁共振光譜（NMR）及質譜（Mass）鑑定之。

關鍵字

酯 ； 羥基 ； 薁

並列摘要

The aim of this study is to synthesize α-xyl hydroesters azulene and it's precursor α-keto esters azulene. The α-hydroxyl ester derivatives have long been known for their antipsychotics effect，and azulene derivatives have long been known for their hypocholesterolemic effect and anti-ulcerative, anti-inflammatory and antihyperlipidemic activity. The reaction we apply to synthesize ethyl 3-(ethoxycarbonylformyl)azulene -1-carboxylate derivatives is Friedel-Crafts Acylation. These derivatives were prepared by reaction of azulene-1-carboxylate derivatives with aluminium chloride (AlCl3) and ethyl chloro glyoxylate in chlorobenzene at 120℃ for 4hrs. The precusors reported in this thesis include ethyl 3-(ethoxycarbonylformyl) azulene-1- carboxylate, ethyl 2-ethoxy-3-(ethoxycarbonylformyl) azulene-1-carboxylate, 2-hydroxy-3-(ethoxycarbonylformyl) azulene-1-carboxylate, methyl 3-(ethoxycarbonylformyl)azulene -1-carboxylate, 2,4-diethoxy-3-(ethoxycarbonylformyl)azulene and 2,4-diethoxy-1,3-di(ethoxycarbonylformyl)azulene. Reactions of the precursors ethyl 2-ethoxy-3- (ethoxycarbonylformyl)azulene-1-carboxylate and methyl 3-(ethoxycarbonylformyl)azulene-1-carboxylate reacted with isopropylmagnesium chloride at 0℃ for 40 min. afforded methyl 3-(1-ethoxycarbonyl-2- methyl -1- hydroxylpropyl) azulene-1-carboxylate and ethyl 2-ethoxy-3- (1-ethoxycarbonyl- 2-methyl -1- hydroxylpropyl)azulene-1-carboxylate, respectively. These new compounds were characterized by IR, NMR and Mass spectra.

並列關鍵字

azulene ； ester ； hydroxyl

參考文獻

20. 吳姝嫻碩士論文 , 中原大學化學研究所(2001).

3. T. Nozoe, S. Seto,S. Matsumura and T. Asano，Proc. Jap. Acad.，32，339(1956).

4. T. Nozoe, S. Seto, K.Takase，S. Matsumura and T. Nakazawa，Nippon Kagaku Zasshi，86，346(1965).

7. P. W. Yang, M. Yasunami, and K. Takase, Tetrahedron Lett., 4275(1971).

1. D.Piesse, Compt. Rend., 57,106(1964).