中國醫(yī)藥1業(yè)朵態(tài) Chinese journal of pharmaceuticals2003,3410)文章編號:10ul8255(2003)10-0487-013-溴代丁醛縮乙二醇的合成改進(jìn)袁春良,葉和玨中國科學(xué)院廣州化學(xué)研究所藥物研究室廣東廣州510650)摘要:巴豆醛先與溴化氡加成,再與乙二醇縮醛化得到3溴代丁醛縮乙二醇,收率80.8%。關(guān)鍵詞:3-溴代丁醛縮乙二醇;巴豆醛;縮醛化;加成;合成中圖分類號:0626.29文獻(xiàn)標(biāo)識碼:A3-溴代丁醛縮醇是有機(jī)合成的重要中間體、尤20C下加入無水乙二醇(26ml,0.466mol)和干燥其在萜類化合物的合成中應(yīng)用廣泛其 grignard試的4A分子篩(35g),混合物20~25C攪拌過夜。劑與α}烯酮等不飽和羰基化合物進(jìn)行1,4-加成將 NaHCO3(24g,0.286mol)和 Na,co3反應(yīng)后,在酸催化下羥醛縮合是合成含環(huán)化合物的(12g,0.113mol)混合后緩慢加至如上反應(yīng)液中,重要途徑3-溴代丙醛縮二醇的合成可用內(nèi)烯劇烈攪拌,以免產(chǎn)生大量氣泡而外溢。加畢后抽濾,醛與乙二醇的飽和HBr溶液反應(yīng)制得,但收率僅濾液依次用適量飽和 NahCo3溶液和飽和氯化鈉61%:本文參照類似報道以巴豆醛(2)在飽和溶液洗滌兩次用尢水硫酸鎂干燥,過濾后減壓蒸餾HBr的乙醚溶液中反應(yīng),加成得3-溴丁醛,再加人收集69~7lC/798Pa餾分,得淡黃色油狀液體乙二醇縮合即得3溴代丁醛縮乙一醇(1)。操作簡(21.9g,80.8%)IR和HNMR證實結(jié)構(gòu)。便易行,收率80.8%。反應(yīng)式如下:elohexeme annulation via copper-catalyzed conjugate實驗部分addition of acetal-containing Grignard reagents[J].JKFX65 AFTIR型紅外光譜儀(美國 Analect公司)Org Chem,1982,47(26):5045-5050Brucker-6n0平核磁共振儀。[2 Paquette IA, I conc- Bay A. TriquInane sesquiter-在500m三頸瓶中加入無水醚(90ml),冰penes. An iterative. highly stereocontrolled synthesisof(+)silphinene [J1.Am Chem Soc,1983,105浴冷至(,攪拌下導(dǎo)人由五氧化二磷與40%氫溴25);73527358酸產(chǎn)生的HBt氣體,30min后,乙醚溶液呈淡黃色。3] Buchi G, Wuest H. Synthesis of(-) nucifera [ j1J另取2(12m1.0.117mol),用無水乙醚(70ml)稀Org Chena,l969,34:11221123釋,冰浴冷至0(,滴至如上所得飽和HHr的乙醚溶41S10Y, Sugasawa S. An improved preparation nf 8.液中,約1.5h加畢,0C攪拌反應(yīng)2h。撤去冰浴hloropropionaldehyde acetal [J]. Iror pn Acad SerB,198056(9):573-575.An Improved Preparation of 3-Bromobutyraldehyde Ethylene AcetalYUAN Chun- Liang, YE He-Jue(Guangzhu Institute of Chemstry, Chinese Academy o/ Sciences. Guangzhou 510650)ABSTRACT: 3- Bromobutyraldehyde ethylene acetal was synthesized from crotonaldehyde by addiith hydrogen bromide and then acetalation with ethylene glycol with an overall yield of 80. 8%Key Words: 3 bromobutyraldehyde ethylene acetal; crotonaldehyde; acetalation; addition; synthesis收稿日期:200208-22s3454羧酸制備酰基疊氮物的簡法 Gumaste vK等[了e基金項目:國家自然科學(xué)基金資助項目(39970865)trihedron Lett. 2002.43: 134作者簡介:哀春良(1977),男,碩土研究生,專業(yè)方向:藥物合成將三光氣的丙酮溶液于0CF滴加至羧酸、疊氮化鈉及Te:(20-85232189乙胺的內(nèi)酮溶液中,室溫反應(yīng)24h,制徘相應(yīng)的酰基疊氮E-mail: YeHejuc@ mail gie.Heen物。12例收率50%~96%。L黃偉摘