3-溴代丁醛縮乙二醇的合成改進(jìn)

中國醫藥業(yè)朵態(tài) Chinese Journal of Pharmaceutical2003,3410)文章編號:10ul8255(203)10-0487-0l3-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:巴豆醛先與溴化加成,再與乙一醇縮醛化得到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;縮幡化;加成;合成中圖分類(lèi)號:O626.29文獻標識碼:A3-溴代丁醛縮醇是有機合成的重要中問(wèn)體,尤20C下加入無(wú)水乙二醇(26ml,0.466mol)和干燥其在萜類(lèi)化合物的合成中應用廣泛,其 grignard試的4A分子篩(35g),混合物20~25C攪拌過(guò)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 Na2 CO反應后,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液中重要途徑3-溴代丙醛縮乙二醇的合成可用內烯劇烈攪拌,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溶液反應制得,但收率僅濾液依次用適量飽和 NaHCO2溶液和飽和氯化鈉61%,本文參照類(lèi)似報道…以巴豆醛(2)在飽和溶液洗滌兩次。用無(wú)水硫酸鎂干燥,過(guò)濾后減壓蒸餾HBr的乙醚溶液中反應,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溴代丁醉縮乙二醇(1)。操作簡(jiǎn)(21.9g,80.8%)。IR和HNMR證實(shí)結構。便易行,收率80.8%。反應式如下:入(10, HB EtO- ArcHo Hd參考文獻:1] Bal SA. Marfat A. Helquist P. Cyclopentene and cy-lohexene annulation via copper-catalyzed conjugate實(shí)驗部分ddition of acetal-containing Grignard reagents [J].JKFX65 AFTIR型紅外光譜儀(美國 Analect公司)Org Chem,1982,47(26):5045-5050.Brucker-600型核磁共振儀[2 Paquette LA, I conc- Bay A. Triquinane sesquiter在500m三頸瓶中加入無(wú)水醚(90ml),冰of (+)silphinene [J T. J Am Chem Soc,1983,105浴冷至0C,攪拌下導人由五氧化二磷與40%氫溴(25);73527358酸產(chǎn)生的HB氣體,30min后,乙醚溶液呈淡黃色。13] Buchi G, Wuest H. Synthesis of(+) nucifera[J1.J另取2(12ml,0.117mol),用無(wú)水乙醚(70ml)稀g Chen,1969,34:11221123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 of液中,約1.5h加畢,0C攪拌反應2h,撤去冰浴hloropropionaldehyde acetal[J]. Pror pn/ SerB,1980.56(9):573-57An Improved Preparation of 3-Bromobutyraldehyde Ethylene AcetalYUAN Chun-Liang, YE He-Jue(Guangzhou Institute of Chemstry, Chinese Ae ademty o/ Sciences. Guangzhou 510650ABSTRACT: 3-Bromobutyraldehyde ethylene acetal was synthesized from crotonaldehyde by additionwith 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》》》》》》》多》游》》》》》親收稿日期:200208-22S3454羧酸制備?；B氮物的簡(jiǎn)法 Gumaste vK等[了e基金項目:國家自然科學(xué)基金資助項目(3997065)。作者簡(jiǎn)介:袁春良(1977),男,碩士研究生,專(zhuān)業(yè)方向:藥物合T料:(20-85232189中國煤化工制得相應的基疊氮E-mail: YeHejuc@ mail gie.atenCNMHG L黃偉摘