第26卷第2期稀 Vol. 26,No.22005年4月 Chinese Rare Earths April 2005氯化鈰催化合成苯甲醛乙二醇縮醛郭春燕,黃占凱,劉春生,羅根祥(遼寧石油化工大學(xué)石油化工學(xué)院,遼寧撫順113001)摘要:以環(huán)境友好試劑氯化鈰為催化劑,對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、醇醛摩爾比、帶水劑等因素對苯甲醛與乙二醇縮醛收率的影響。實驗結(jié)果表明,氯化鈰有較好的催化活性。在回流條件下,催化劑用量約占醛用量的0.8%摩爾分?jǐn)?shù),醇醛摩爾比為1.5:1,帶水劑環(huán)己烷的用量為10mL時反應(yīng)120min,苯甲醛與乙二醇縮醛收率達(dá)79.6%關(guān)鍵詞:苯甲醛乙二醇縮醛氯化鈰;催化中圖分類號:O614.33;0643.3文獻(xiàn)標(biāo)識碼:A文章編號:1004-0277(2005)02-0019-03苯甲醛性質(zhì)活潑,空氣中就可緩慢氧化成苯凝管加熱回流。待分水器中不再有水分出,再反應(yīng)甲酸而其縮醛形式卻相對穩(wěn)定得多且具有優(yōu)于母15分鐘為止。反應(yīng)結(jié)束后,并分水器中的有機(jī)層體的花果香味,因此,其縮醛的合成與應(yīng)用研究日和反應(yīng)液,水洗兩次(每次10mL),無水MgSO4受到人們重視12。縮醛傳統(tǒng)的合成方法是在無機(jī)燥,常壓蒸餾,收集222C~228C的餾分,計算收酸[3催化下反應(yīng),但該法后處理產(chǎn)生大量酸性廢水,率。造成環(huán)境污染。隨著人們生活水平的提高和環(huán)保意識的增強,環(huán)境友好綠色催化劑的研究與應(yīng)用日益2結(jié)果與討論受到人們的關(guān)注本文探討了以無毒無腐蝕、2.1醇醛摩爾比對縮醛收率的影響易處理的綠色路易斯酸CeCl3·7H2O7為催化劑催按實驗方法取苯甲醛0.1moL,催化劑氯化鈰化合成苯甲醛乙二醇縮醛,得到了滿意的結(jié)果。實驗.0003mol,10mL環(huán)己烷作帶水劑,改變乙二醇的表明,該催化劑可使苯甲醛乙二醇縮醛收率達(dá)用量分別反應(yīng),實驗結(jié)果見表1。由表1可見,乙二79.6%醇用量對收率的影響顯著,增大乙二醇用量有利于1實驗部分收率的提高。但當(dāng)醇醛摩爾比達(dá)到1.5:1以后,收1.1主要試劑及儀器率反而有所下降,這可能是由于過量的乙二醇在催苯甲醛(分析純,武漢有機(jī)合成化工廠);之二醇化劑存在下分子間脫水生成二氧六環(huán)副產(chǎn)物的緣(分析純,沈陽試劑一廠);氯化鈰(CeCl3·7H2O,分故因此最佳醇醛摩爾比為1.5:1析純,中國醫(yī)藥集團(tuán)上?；瘜W(xué)試劑公司);環(huán)己烷(分析純,沈陽沈一精細(xì)化學(xué)品有限公司); Spectrum表1醇醛摩爾比對縮醛收率的影響GX紅外光譜儀(Perkin-Elmer-);wzs-1阿貝折 Table Effect of the reactant ratio on the光儀(上海)。 yield of acetalization1.2實驗方法醇醛摩爾比1.2:11.3:11.4:11.5:11.6:1在50mL圓底燒瓶中,加入一定比例的苯甲收率/%49.363.166.969.067.1醛、乙二醇、催化劑和帶水劑,裝上分水器和回流冷20稀土第26卷2.2催化劑用量對縮醛收率的影響件同2.4,結(jié)果見表5。由表5可知,隨反應(yīng)時間的增改變催化劑用量,選定醇醛摩爾比為1.5:1,加,縮醛產(chǎn)率隨之增加,但超過2h后變化不大故綜其余條件同上,實驗結(jié)果見表2由表2可見僅用合考慮反應(yīng)時間以2h為宜少量催化劑就可獲得較高收率,且隨著CeCl37H2O用量增加,縮醛收率提高。當(dāng)催化劑用量為苯表5反應(yīng)時間對縮醛收率的影響甲醛的0.8%(摩爾分?jǐn)?shù))時具有最佳的催化效果, Table 5 Effect of reaction time on the yield因此合適的催化劑摩爾分?jǐn)?shù)為0.8%。 of acetalization反應(yīng)時間/min6090120150表2催化劑用量對縮醛收率的影響收率/%72.873.579.675.9 Table 2 Effect of the amount of catalysis on the yield of acetalization2.6產(chǎn)品的表征催化劑用量/%0.30.40.60.81.0所得產(chǎn)品為無色透明液體,其折射率np20=收率/%69.070.176.777.967.71.5270(文獻(xiàn)值1.5268)。其IR(,cm-1)主要顯示:3038(其環(huán)CH),2963,2889(烴CH),1608,1459(苯2.3帶水劑用量對收率的影響環(huán)骨架),1225,1087(CO),757,702(一取代苯),未用量對縮醛的收率也有一定的影響,在10mL時收3結(jié)吸收峰。采用最佳醇醛摩爾比和催化劑摩爾分?jǐn)?shù),改變見羰基和羥環(huán)己烷用量,實驗結(jié)果見表3。由表3可見,環(huán)己烷率最大。若環(huán)己烷用量過少,起不到較好的帶水效1.稀土化合物CeCl·7H2O是一種合成苯甲果;過多則會降低反應(yīng)體系的回流溫度,率反而下醛環(huán)縮醛的良好催化劑具有反應(yīng)條件溫和,分離簡降。故帶水劑環(huán)己烷的用量以10mL為宜。單,產(chǎn)率高且無污染、無腐蝕等優(yōu)點,在綠色化學(xué)進(jìn)程中具有良好的應(yīng)用前景。表3帶水劑用量對縮醛收率的影響2.以氯化鈰為催化劑合成苯甲醛乙二醇縮醛 Table 3 Effect of the amount of cyclohexane的最佳條件為:醇醛摩爾比為1.5:1,催化劑占苯 on the yield of acetalization甲醛摩爾分?jǐn)?shù)的0.8%,帶水劑環(huán)己烷的用量為環(huán)己烷用量/mL68910111210mL時,反應(yīng)120min后苯甲醛乙二醇縮醛收率達(dá)66.477.978.079.675.673.579.6%2.4不同帶水劑對縮醛收率的影響參考文獻(xiàn):選定帶水劑用量10mL,醇醛摩爾比為1.5:[1]張克福,孫寶國苯甲醛正丁硫醇縮醛的合成研究1,催化劑摩爾分?jǐn)?shù)為0.8%,改變帶水劑的種類,分J].精細(xì)化工,1998,18(3):23-25.別考察環(huán)己烷、苯、甲苯、二甲苯對縮醛收率的影響,[2]田志新龔健,李菊仁,鈮酸催化縮醛反應(yīng)[]精細(xì)石油化工,2000,(2):23-25.實驗結(jié)果見表4由表4可見,該縮合反應(yīng)環(huán)己烷為3]李述文范如霖實用有機(jī)化學(xué)手冊M]上海:上?？七m宜的帶水劑,不僅收率高,且毒性較其余三種小。技出版社,1981.319.[4]余協(xié)卿.用環(huán)境友好催化劑合成氯乙酸酯的研究[J]表4不同帶水劑對縮醛收率的影響精細(xì)石油化工進(jìn)展,2002,3(5):9-11.[5]羅玉梅,羅義,呂寶蘭,等,磷鎢酸催化合成丁酮乙二 Table 4 Effect of different water-carrying醇縮酮[J]化學(xué)推進(jìn)劑與高分子材料,2003,1(5):9- agents on the yield of acetalization10.帶水劑環(huán)己烷苯甲苯二甲苯[6]胥勃,吳越雜多酸(鹽)一種多用途的催化劑[收率/%79.670.861.346.5化學(xué)通報,1985,(4):34-40. [7] Paquette L. A. Encylopedia of Organic Synthesis [M]. New York: John Wiley 8. Sons, 1995.1031.第2期郭春燕等:氯化鈰催化合成苯甲醛乙醇縮醛21 Catalytic Synthesis of Benzaldehyde Ethylene Glycol Acetal by Cerous()Chloride Heptahydrate GUO Chun-yan, HUANG Zhan-kai, LIU Chun-sheng, LUO Gen-xiang (Petrochemical Engineering School, Liaoning University of Petroleum and Chemical Technology Fushun 113001. China) Abstract: The acetal was synthesized in high yield by the reaction of benzaldehyde with ethylene glycol in the presence of a new environmentally friendly catalyst CeCls. 7H2O. The obtained results indicated that CeCls.7H2O possessed a fairly high catalytic activity for this acetalization reaction. In this article the factors influencing the syn thesis were discussed and the best conditions were determinded. The optimum conditions are as follows: the molar atio of ethylene glycol to benzaldehyde is1.5:1 the molar ratio of catalyst to benzaldehyde is0.8%; cyclohexane better water-carrying agent to the reaction is 10 mL; reaction time is 120 min. Under the above conditions the yield of benazldehyde ethylene glycol acetal is up to 79. 6 % The results showed CeCls 7H2 O is an excellent catalyst for synthesizing benazldehyde ethylene glycol acetal. Key words: benazldehyde ethylene glycol acetal CeCl3. 7H,O:catalyst cecccecececeeecececeeeeeeceeceeeceeee eececccecececececeeeeeceeecceeceeeeeceee(上接第18頁) -side cyclodextrin binding sites [JJ. J Am Chem Soc.有很好的效果,提示PACC也能水解其它含有磷酸1988110:8553-8561.二酯鍵的化合物如有機(jī)磷農(nóng)藥等并且,PAcc的配3 Condorelli Costanzo Guidi De Inhibition of體實質(zhì)是能裝成層析柱的瓊脂糖凝膠。在實際應(yīng)用 photohemolysis by copper() complexes with sod-中,利用PACC層析柱過濾含有有害磷酸酯類化合 like activity [J]. J Inorg Biochem, 1994, 54: 257-262.物如有機(jī)磷農(nóng)藥的廢水果汁、蔬菜汁等,使化合物[4]高飛,陰彩霞楊頻核酸酶催化磷酸二酯鍵水解斷裂作用的配位化學(xué)模擬[J]科學(xué)通報,2004,49(15):中的磷酸二酯鍵水解,并且PACC中的Ce(Ⅳ)不會1471-1483.從PACC上解離下來,這樣就不會造成目標(biāo)物質(zhì)如5]汪東風(fēng),須磨岡淳,王常紅,等褐藻多糖鈰配合物對果汁的二次污染,從而達(dá)到去除有害物質(zhì)的目的。應(yīng)質(zhì)粒DNA及牛血清白蛋白的裂解作用[]中國稀土用PACC降解果蔬汁中有機(jī)磷農(nóng)藥的實驗結(jié)果將學(xué)報,2002,20(3):283-285.另文報道。[6]汪東風(fēng),羅軼,杜德紅,等,鈰配合物對有機(jī)磷農(nóng)藥的降解作用[]中國海洋大學(xué)學(xué)報,2004,34(4):577-參考文獻(xiàn):581. [1] Tabushi, Kuroda Y. Bis (histamino) cyclodextrin-zinc [7] Per-Erik Gustaysson, Per-Olof Larsson. Super- -imidazde complex as an artificial carbonic anhydrase porous agarose, a new material for chromatographyCJ]. Am Chem Soc,1984,106:4580-4583 [J]. Journal of Chromatography, 1996,734: 231- [2] Akkaya E. Czarnik A W. Synthesis and reactivity of240. cobalt(m) complexes bearing primary-and- secondary[8]汪東風(fēng),趙貴文茶葉中稀土總量的快速測定法[J茶葉科學(xué),1998,18(2):151-154. Preparation of the Particle of Agarose-C()Complexes and their Effects on Catalyzing the Hydrolysis of PNPP2Na YU Li-na, WANG Dong-feng, SU Lin, SUN Li-ping (Department of Food Science and Engineering Ocean University of China, Qingdao 266003, China) Abstract: The particle of agarose-Ce( complexesPACC) have been prepared using superporous agarose as supporting ligands in this paper, and the physical stability of PACC was investigated. The results indicated that PACC should been used less than 40C or pH 12.0. The PACC could also catalyze the hydrolysis of phosphate diester