化學(xué)與黏合2012年第34卷第6期 CHEMISTRY AND ADHESION45氯化錫催化合成苯甲醛乙醇縮醛王俏1,張玉琦1,魏清波1,劉勇2(1.延安大學(xué)化學(xué)與化工學(xué)院,陜西延安71600:2安職業(yè)技術(shù)學(xué)院,陜西延安700)摘要以環(huán)境友好試劑氯化錫為催化劑,對(duì)苯甲醛與乙二醇的縮合反應(yīng)進(jìn)行了研究,考察了該綠色催化劑的用量、醛醇摩爾比、帶水劑等因素對(duì)苯甲醛乙二醇縮醛收率的影響。實(shí)驗(yàn)結(jié)果表明,氯化錫有較好的催化活性。在回流條件下,催化劑用量約占醛用量的2.83%質(zhì)量分?jǐn)?shù),醛醇物質(zhì)的量的比為1:1.5,帶水劑環(huán)己烷的用量為5mL時(shí),反應(yīng)0min,苯甲醛與乙二醇縮醛收率達(dá)77.3%關(guān)鍵詞:甲醛乙二醇縮醛;氯化錫;催化;縮醛化中圖分類(lèi)號(hào):TQ426.94文獻(xiàn)標(biāo)識(shí)碼:A文章編號(hào):1001-0017(201206-0045-03 Synthesis of Benzaldehyde Ethylene Acetal Catalyzed by SnCl.-5H2O WANG Qiao', ZHANG Yu-qi', WEI Qing-bo' and LIU Yong' (1.College of Chemistry and Chemical Engineering. Yan'an University, Yan'an 716000, China; 2. Yan' an Institute of Vocational Technology, Yan'an716000China) Abstract: The condensation reaction of benzaldehyde and ethylene glycol was studied in the presence of a new envi ntally friendly catalyst SnCL-5H0. The obtained results indicated that SnCL. possessed a fairly high catalytic activity for this ac reaction. The effects on the yield of benzaldehyde ethylene acetal were disc such as the catalyst amount, molar ratio of benzaldehyde to ethylene glycol and water carrying agent. The optimum conditions were obtained as follows: the molar ratio of benzaldehyde to ethylene glycol was 1: 1.5, the mass fraction of catalyst was 2.83% of benzaldehyde, the water carrying agent cyclohexane was 5mL and the reaction time was 90min. Under the above conditions, the yield of benzaldehyde ethylene acetal was up to 77.3%. Key words: Benzaldehyde ethylene acetal; SnCl.,O: catalys; acetalation得到了滿(mǎn)意的結(jié)果。前言1實(shí)驗(yàn)部分縮醛是在食品和日用香精中廣泛應(yīng)用的新型香料,也常用于有機(jī)合成中作為羰基保護(hù)劑或中間1.1主要試劑及儀器體還可用作溶劑。苯甲醛乙二醇縮醛有蘋(píng)果香味,苯甲醛(分析純);乙二醇(分析純);氯化錫可用于多種日化香精配方。其傳統(tǒng)的合成方法是在(SnCl.5H2O,化學(xué)純);環(huán)己烷(化學(xué)純);氯化鈉(分無(wú)機(jī)酸催化下由苯甲醛與乙二醇合成,但該法存在析純)。副反應(yīng)多、產(chǎn)品純度不高、設(shè)備腐蝕嚴(yán)重、后處理中JJ500型精密電子天秤(常熟雙杰測(cè)試儀器含有大量的酸性廢水易造成環(huán)境污染等缺點(diǎn)隨著廠),wzS-I阿貝折射儀(上海)生活水平的提高,人們對(duì)香精和食品的質(zhì)量以及環(huán)1.2實(shí)驗(yàn)方法境保護(hù)提出了越來(lái)越高的要求。因此研究和開(kāi)發(fā)合在250mL三頸燒瓶中,加入一定比例的苯甲成縮醛酮)的新方法具有一定的意義受到學(xué)者們的醛、乙二醇、催化劑(SnCl45H2O)和帶水劑(環(huán)烷)普遍關(guān)注和重視。目前使用較多的合成方法是在無(wú),裝上分水器和回流冷凝管加熱回流。待分水器中機(jī)鹽、雜多酸固體超強(qiáng)酸、離子交換樹(shù)脂、分子篩、不再有水分出為止41。反應(yīng)結(jié)束后,靜置冷卻,然后單質(zhì)碘等催化下由苯甲醛與乙二醇經(jīng)縮合合成。合并分水器中的有機(jī)層和反應(yīng)液,用飽和氯化鈉水本文探討了以無(wú)毒、無(wú)腐蝕易處理的路易斯酸溶液洗滌兩次(每次用量約與有機(jī)層體積相當(dāng)),再SnCl5h2O為催化劑催化合成苯甲醛乙二醇縮醛,用無(wú)水MgSO4干燥,常壓蒸餾,收集220℃~228℃收稿日期:2012-05-06作者簡(jiǎn)介:王俏(1964-),女,陜西子洲人,教授,主要研究方向?yàn)橛袡C(jī)合成及高分子合成。E46王俏等,氯化錫催化合成苯甲醛乙二醇縮醛Vol.34,No.6,2012的餾份,稱(chēng)量計(jì)算收率,測(cè)定其折光率。2.4帶水劑用量對(duì)收率的影響采用最佳醛醇物質(zhì)的量比、催化劑質(zhì)量分?jǐn)?shù)和2結(jié)果與討論反應(yīng)時(shí)間,改變環(huán)烷用量,實(shí)驗(yàn)結(jié)果見(jiàn)表4。表4帶水劑用量對(duì)縮醛收率的影響2.1醛醇物質(zhì)的量比對(duì)縮醛收率的影響 Table 4 The effect of the water carrying agent on the yield實(shí)驗(yàn)固定苯甲醛為0.15mol,催化劑用量為環(huán)己烷用量/mL358100.1g,加入8mL環(huán)已烷作帶水劑,改變乙二醇的用收率%75.777.374.2734量,回流反應(yīng)60min。考察不同醛醇摩爾比對(duì)產(chǎn)品收率的影響,實(shí)驗(yàn)結(jié)果見(jiàn)表1由表4可見(jiàn),環(huán)己烷用量對(duì)縮醛的收率也有一表1醛醇摩爾比對(duì)縮醛收率的影響定的影響,環(huán)烷用量為5mL時(shí)收率最高。若環(huán)己 Table 1 The effect of the molar ratio of benzaldehyde to烷用量過(guò)少,起不到較好的帶水效果;過(guò)多則會(huì)降 ethylene glycol on the yield低反應(yīng)體系的回流溫度,收率反而下降。故帶水劑環(huán)己烷的用量以5mL為宜。醛醇摩爾比1:1.41:1.51:1.61:1.82.5在最佳條件下的重復(fù)實(shí)驗(yàn)收率%63.067.664.163.6以上實(shí)驗(yàn)得到較佳實(shí)驗(yàn)條件為苯甲醛0.15mol,由表1可見(jiàn),乙二醇用量對(duì)收率的影響顯著,乙二醇0.23mol,氯化錫(Snl45h20)0.45g環(huán)己烷增大乙二醇用量有利于收率的提高。但當(dāng)醛醇物質(zhì)5mL,反應(yīng)時(shí)間90min,在以上較佳實(shí)驗(yàn)條件下做3的量比達(dá)到1:1.5以后,收率反而有所下降,這可次平行實(shí)驗(yàn),考察最佳實(shí)驗(yàn)條件下實(shí)驗(yàn)結(jié)果的穩(wěn)定能是由于過(guò)量的乙二醇在催化劑存在下分子間脫性結(jié)果見(jiàn)表5水生成二氧六環(huán)副產(chǎn)物的緣故5。因此最佳醛醇物表5在較佳實(shí)驗(yàn)條件下的重復(fù)實(shí)驗(yàn)質(zhì)的量比為1:1.5。 Table 5 The repetition experiment result under the optimum2.2催化劑用量對(duì)產(chǎn)物收率的影響 conditions選定醛醇物質(zhì)的量比為1:1.5,其余條件同實(shí)驗(yàn)次數(shù)上,改變催化劑用量,實(shí)驗(yàn)結(jié)果見(jiàn)表2。收率%77.31%77.14%76.94%表2催化劑用量對(duì)縮醛收率的影響 Table 2 The effect of the amount of catalyst on the yield由表5表可見(jiàn),在較佳實(shí)驗(yàn)條件下的重復(fù)實(shí)驗(yàn)催化劑用量g0.10.30.40.45穩(wěn)定性良好。收率%71.772370.12.6產(chǎn)品的分析鑒定由表2可見(jiàn),僅用少量催化劑就可獲得較高收率,且隨著SnCl45H2用量增加,縮醛收率提高。當(dāng)本實(shí)驗(yàn)制得的苯甲醛乙二醇縮醛,,為無(wú)色透催化劑用量為0.45g時(shí)具有最佳的催化效果,此時(shí)明液體,具有新鮮的果香香氣,并有淡雅的蘋(píng)果香催化劑約占苯甲醛用量的2.83%(質(zhì)量分?jǐn)?shù))。因韻測(cè)得其折射率為1.5270(文獻(xiàn)2=1.5268)與文獻(xiàn)此合適的催化劑用量為苯甲醛用量的2.83%(質(zhì)量值相符。分?jǐn)?shù))2.3反應(yīng)時(shí)間對(duì)產(chǎn)物收率的影響3結(jié)論催化劑取0.45g,其余條件同2.2,改變反應(yīng)時(shí)間,實(shí)驗(yàn)結(jié)果見(jiàn)表3。(1)以SnCl45H2O為催化劑合成苯甲醛乙二醇表3反應(yīng)時(shí)間對(duì)縮醛收率的影響縮醛的較佳條件為:苯甲醛取0.15mol,醛醇物質(zhì)的 Table 3 The effect of reaction time on the yield量比為1:1.5,催化劑占所用苯甲醛的質(zhì)量分?jǐn)?shù)為反應(yīng)時(shí)間/min60901051202.83%,帶水劑環(huán)己烷的用量為5mL,反應(yīng)90min苯收率%72.374.273.571.1甲醛乙二醇縮醛收率可達(dá)77.3%由表3可知,隨反應(yīng)時(shí)間的增加,縮醛收率隨(2)SnCl45H2O對(duì)合成苯甲醛乙二醇縮醛具有之增加,但超過(guò)90min后變化不大,到120min時(shí)產(chǎn)良好的催化活性,催化劑用量少苯甲醛乙二醇縮量明顯下降,這可能是發(fā)生的副反應(yīng)增加造成的,醛收率較高,并且無(wú)廢酸排放,工藝流程簡(jiǎn)單。因故綜合考慮反應(yīng)時(shí)間以90min為宜。此,SnC45H2O是合成苯甲醛乙二醇縮醛的優(yōu)良催(下轉(zhuǎn)第70頁(yè))70王露潯等,油品氧化脫硫機(jī)理研究進(jìn)展Vol.34,No.6,2012 HIRAI,et al.Desulfurization and denitrogenation process for與天然氣化工,2005,(6):498-500 light oils based on chemical oxidation followed by liquid-liq-39]趙地順李發(fā)堂劉文麗催化裂化汽油光化學(xué)氧化脫硫]石 uid extraction [].Ind Eng Chem Res, 2002,41(17): 4362-油化工,2006,35(10):963-9664375.[40]白石康浩.液液抽出法光化學(xué)反應(yīng)利用為輕油新L[29]趙地順,孫智敏,李發(fā)堂等功能化酸性離子液體催化柴油氧深度脫硫口[J].ヶ力ル工二ヤヶ2000化脫硫的研究[]燃料化學(xué)學(xué)報(bào)2008,36(5):194-197.23(6):483-48630]趙地順,周二鵬,王建龍,等離子液體脫除汽油中含硫化合[41 HIRAL, SHIRAISHI,OGAWA,et alEffect of photosensi物的研究[J].化學(xué)工程20,381:14 [31] ZHU W S,LI H M JIANG X,et al. 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