β-萘甲醚合成新工藝

第32卷第6期現代化工June 20122012年6月Modern Chemical industry·47β-荼甲醚合成新工藝位青聰,葉文濤,宋輝,呂雯雯,趙敏,吳范宏(華東理工大學(xué)化學(xué)與分子工程學(xué)院,上海200237)摘要:對B-萘甲醚的現有合成工藝進(jìn)行改進(jìn)。結合工業(yè)生產(chǎn),得到一條新的工藝,即采用一水合硫酸氫鈉作為催化劑B荼酚和甲醇于130~140℃下回流反應14h。反應收率最高達954%,與現有工藝相當,且隨著(zhù)B-萘酚投量的增加,收率趨于穩定(910%)。該工藝避免了現有工藝中的催化劑濃硫酸對設備的嚴重腐蝕和環(huán)境污染,可以應用于工業(yè)化生產(chǎn)。關(guān)鍵詞-茶甲醚;合成;新工藝中圖分類(lèi)號:0625322;TQ031.2文獻標識碼:A文章編號:0253-4320(2012)06-0047-02New synthesis process of B-naphthyl methyl etherWEI Qing-cong, YE Wen-tao, SONG Hui. Lv Wen-wen, ZHAO Min. WU Fan-hong. pSchooi of Chemistry and Molecular Engineering, East China University of Science and TechnologyShanghai 200237, China)Abstract: The existing synthetic process of B-naphthyl methyl ether is improved in this study Based on literaturesndustrial production, a new synthetic process is obtained, that is, B-naphthol reacts with methanol under refluxbetween 130-140C for 14 hours with sodium bisulfate monohydrate as the catalyst. The highest yield is 95.4%. Thestable yield(91. 0%)tends to be achieved with increasing the amount of B-naphthol. The new process avoids somedrawbacks in the existing route such as severe corrosion and environmental pollution caused by concentrated sulfuricid It makes the new process have great potential to be applied in industrial productionKey words: B-naphthyl methyl ether; synthesis; new processβ-萘甲醚又名橙花醚,具有橙花香味。作為口燒瓶中,加分水器冷凝管恒壓滴液漏斗,在磁力種合成香料,常用于食用香精和香皂中,也是合成萘攪拌下升溫至回流,然后一邊滴加甲醇,一邊將甲醇普生炔諾孕酮和米非可酮等藥物的中間體。工業(yè)蒸出,使得反應體系的溫度相對穩定。反應數小時(shí),上常釆用濃硫酸催化β-萘酚與甲醇反應或硫酸二然后冷卻,加入30mL乙酸乙酯和30m水,攪拌至甲酯與甲醇反應來(lái)制備,但是這2種方法的收率不固體全溶,分液,有機相用質(zhì)量分數為5%的氫氧化高,由于濃硫酸的腐蝕性和強氧化性,容易造成設備鈉水溶液洗滌,分液,有機相再用水洗后用無(wú)水硫酸的腐蝕,產(chǎn)生氧化偶聯(lián)的副產(chǎn)物,且硫酸二甲酯具有鈉干燥,得粗品,用無(wú)水乙醇重結晶后得白色鱗片狀劇毒性,因此開(kāi)發(fā)新的B-萘甲醚的合成方法對于節固體,熔點(diǎn)為72-~73℃;水相合并后用稀鹽酸酸化約成本和環(huán)保都具有積極的意義2。筆者以一水回收β-茶酚。合硫酸氫鈉作為催化劑,甲醇和B-茶酚為原料,對工藝進(jìn)行了改進(jìn)。2結果與討論實(shí)驗2.1加料方式對反應收率的影響1.1實(shí)驗藥品及儀器實(shí)驗中,B-茶酚和一水合硫酸氫鈉的摩爾比參β-萘酚、甲醇、硫酸氫鈉、無(wú)水硫酸鈉、氫氧化考文獻[3]中的比例。在實(shí)驗中發(fā)現,甲醇的用量鈉、濃鹽酸(以上藥品均為分析純)及乙酸乙酯(化對回流反應的溫度有影響,亦對反應的收率有影響。學(xué)純)。當采用傳統回流方式——即在反應瓶上裝回流冷凝WRS-1B型熔點(diǎn)儀, Brucker am400(400MHz)管的方式,由于甲醇的沸點(diǎn)較低(64.8℃),反應體核磁共振儀。系不能夠升到較高的溫度(100℃以上),因此,為了1.2β萘甲醚的合成繼續提高反應體系的溫度,采用了不同的加料方式,將14.4g(0.100mol)B-萘酚、5.0g(0.0362即對甲醇邊蒸出邊滴加的方式,通過(guò)控制滴加的速mol)→水合硫酸氫鈉和一定量甲醇放入100mL三率來(lái)間接調整反應體系的溫度。收稿日期:2012-01-10作者簡(jiǎn)介:位青聰(1985-),男,碩上生, hanxia016@ o sina. corn;趙敏(1965-),男,副教授,研究方向為有機合成和藥物合成,021-64253530,haomin6502@sina.com;吳范宏(1968-),男,博土,教授,研究方向為有機氟化學(xué)及藥物和中間體合成,通訊聯(lián)系人,wh@eust現代化工第32卷第6期22反應溫度對收率的影響2.5產(chǎn)品結構的表征以0.0250mlB-萘酚投料質(zhì)量為基準,在不同實(shí)驗合成所得的β-萘甲醚粗品用無(wú)水乙醇重的溫度范圍內反應6h,B-萘甲髒的收率見(jiàn)表1。結晶后得到白色鱗片狀固體,熔點(diǎn)為72~73℃,與表1溫度對收率的影響文獻值相符4;產(chǎn)品結構經(jīng)H-NMR和紅外光譜確溫度/℃70~8090~100110~120130~140150~160認:H-NMR(400MHz,CDCl13),8:3.93(s,3H,收率/%60.565.471.575.374.5CH3),7.14(m,2H,ArH),7.34(m,1H,ArH),7. 44(m, IH, ArH), 7. 76(m, 3H, ArH ) IR( KBr),vr從表1可以看出,當反應溫度在130~140℃時(shí)cm:3055.0、300.6(ArH);2961.0、294.9收率較高,且溫度繼續增加后收率相對穩定,故選擇288282835.5(C—H);1629.4、1596.1、15058此溫度進(jìn)行后續實(shí)驗。1472.8(Ar);1259.6、1216.8、1029.1(C-0)。2.3反應時(shí)間對收率的影響3結論以0.0250moB-萘酚投料質(zhì)量為基準,在130140℃下反應,反應時(shí)間對收率的影響見(jiàn)表2。以n(B-萘酚):n(一水合硫酸氡鈉)=1:0.29表2反應時(shí)間對收率的影響比例進(jìn)行投料反應,對甲醇采用邊滴加邊蒸出的加時(shí)間/h61214料方式,控制反應溫度在130~140℃,反應14h,收收率%75.380.688.791.294.893.5率最高達95.4%。產(chǎn)物收率隨著(zhù)β-萘酚的投料質(zhì)量的增加趨于穩定(91.0%)。該工藝在工業(yè)生產(chǎn)上操作可行,且一水合硫酸氫鈉價(jià)廉易得,對設備腐從表2可以看出,當反應溫度為14h時(shí),收率蝕小,可以取代濃硫酸應用于工業(yè)化生產(chǎn)。最高,故選擇反應時(shí)間為14ho2.4B-酚投料質(zhì)量對收率的影響參考文獻β-萘酚投料質(zhì)量對收率的影響見(jiàn)表3「1]吳飛陳天云4A分子篩在合成2-萘甲醚中的應用[J].化學(xué)反表3B酚投料質(zhì)量對收率的影響應工程與工藝,2002,18(2):149-152投料質(zhì)量/g3.67.214.421.628.857.6[2]曾慶欂.β-萘甲醚的相轉移催化合成[J].中國醫藥工業(yè)雜志,收率/%94.895.095.491.291.191.01997,28(4):187[3]俞善信,管仕斌倇酸氪鈉催化合成β-萘甲醚[J].湘南學(xué)院學(xué)報,2004,25(5):從表3可以看出,隨著(zhù)β-萘酚投料質(zhì)量的增[4]俞善信,俞超源氯化鐵催化合成β-萘甲醚[J].現代化工,加,產(chǎn)物的收率趨于穩定。199,(7):29-30.■凸4444畫(huà)小▲心卓心4心學(xué)(上接第46頁(yè))[ 22] Pinto M FC, Noronha F B, Borges L E P. 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