摘要
通过HCl对雷公藤内酯醇(triptolide)的12-C进行选择性亲核进攻,将雷公藤植物中分离获得的雷公藤内酯醇(triptolide)和雷公藤内酯酮(triptonide)结构,改造为具有强抗炎、免疫抑制和雄性抗生育活性的雷藤氯内酯醇(tripchlorolide)。并通过二维NMR谱和选择性远程DFPT等图谱分析,归属了雷公藤内酯醇、雷公藤内酯酮和表雷公藤内酯醇(epitriptolide)NMR谱的全部碳和氢的信号。
Tripchlorolide (Ⅰ) is a diterpenoid epoxide isolated from Tripteryguium wilfordii Hook. f. (TW). In the pharmacologic assay, it showed definite anti-inflammatory action and strong immunosuppressive and antffertile activities. Since the yield of tripchlorolide is very low from TW, we semi-synthesized it by structural modification of triptolide (Ⅱ) and triptonide (Ⅲ) isolated from TW. Triptolide suffered selective nucloophilic attach by hydrogen chloride at C-12, and tripchlorolide was obtained in 91% yield. In this reaction, 'Pyridine hydrochloride' was a convenient reagent to us. Reduction of compound triptonide (NaBH_4/CH_3 CH_2 OH) give triptolide (22%) and epitriptolide (Ⅳ, 68%) that were separated by chromatography column on silica gel. Although undesired isomer epitriptolide is the major product from borohydride reduction of troptonide, epitriptolide can be oxidized back to triptonide in 96% yield with Beckmann's chromic acid. The chemical structures of triptolide and triptonide isolated from TW and epitriptolide were established on the basis of spectral (UV, IR, MS and NMR) analyses. All ~1H-NMR and ^(13)C-NMR spectral peaks of these compounds were assigned by ~1H-~1 H cosy, ~1H- ^(13)C cosy and Selective Long-range DEPT NMR spectral analysis (Table 1, 2 and Figer 1). The NMR and IR spectra and R_f value of TLC of semi-synthesized tripchlorolide were identical with that of the natural products that were isolated from TW by our laboratory.
出处
《中国药科大学学报》
CAS
CSCD
北大核心
1992年第3期135-139,共5页
Journal of China Pharmaceutical University
基金
卫生部科学研究基金资助
关键词
雷公藤
雷藤氯内酯醇
Tripterygium wolfordii
Tripchlorolide
Triptolide
Triptonide
Epitriptolide
Semi-synthesis of tripchlorolide
