缩醛交换反应制备双二乙二醇丁醚缩甲醛

doi:10.16085/j.issn.1000-6613.2017-2230

化工进展 ›› 2018, Vol. 37 ›› Issue (09): 3592-3598.DOI: 10.16085/j.issn.1000-6613.2017-2230

缩醛交换反应制备双二乙二醇丁醚缩甲醛

邵冲¹, 王大卫², 沈雯雯¹, 刘洋¹, 张小祥¹, 朱新宝^1,3

1 南京林业大学化学工程学院, 江苏南京 210037;
2 澳大利亚交易管理集团南京航空航天大学项目部, 江苏南京 211106;
3 江苏省醇醚工程技术研究中心, 江苏江阴 214400

收稿日期:2017-10-31 修回日期:2017-12-04 出版日期:2018-09-05 发布日期:2018-09-05
通讯作者: 朱新宝,教授,博士生导师,研究方向为精细有机合成。
作者简介:邵冲(1992-),男,硕士研究生。E-mail:916031215@qq.com。
基金资助:
国家林业局948项目（2015-4-55）及江苏高校优势学科建设工程项目。

Preparation of bis(diethylene glycol butyl ether) formal by acetal exchange reactions

SHAO Chong¹, WANG Dawei², SHEN Wenwen¹, LIU Yang¹, ZHANG Xiaoxiang¹, ZHU Xinbao^1,3

1 College of Chemical Engineering, Nanjing Forestry University, Nanjing 210037, Jiangsu, China;
2 Australia Education Management Group Nanjing University of Aeronautics and Astronautics Branch, Nanjing 211106, Jiangsu, China;
3 Jiangsu Engineering Research Center of Alcohol Ether, Jiangyin 214400, Jiangsu, China

Received:2017-10-31 Revised:2017-12-04 Online:2018-09-05 Published:2018-09-05

摘要/Abstract

摘要： 报道了一种以二乙二醇丁醚（DEGB）和二乙氧基甲烷（DEM）为原料，通过磷钨酸催化下的缩醛交换反应，合成双二乙二醇丁醚缩甲醛（BDEGBF）的新方法；与甲醛相比，二乙氧基甲烷可作为一种绿色的反应试剂应用于缩醛交换反应。考察了催化剂种类、催化剂用量、原料配比、反应温度、反应时间等因素对缩醛交换反应的影响。结果表明：当磷钨酸催化剂用量为二乙二醇丁醚质量的1.0%，原料配比n（DEM）：n（DEGB）=3：1，反应温度为80℃，反应时间为90min时，DEGB的转化率达到最高为84.9%。磷钨酸催化剂回收方便，可重复使用6次。通过FTIR和¹H NMR对产物结构进行表征，并提出了缩醛交换反应可能的反应机理。本缩醛制备方法具有多个优点，例如反应条件温和、环境友好、操作简便，还具有一定的醇醚类底物普适性。

关键词: 双二乙二醇丁醚缩甲醛, 磷钨酸, 二乙氧基甲烷, 二乙二醇丁醚, 缩醛交换反应

Abstract: A novel approach for the synthesis of bis(diethylene glycol butyl ether) formal via acid-catalyzed acetal exchange reactions with diethylene glycol butyl ether and diethoxymethane was reported. Compared with formaldehyde, diethoxymethane was greener as thereagent. The effects of catalyst type, dosage of the catalyst, the ratio of the reactants, reaction temperature and reaction time on acetal exchange reaction were investigated. The results showed that the maximum conversion of 84.9% could be obtained with diethylene glycol butyl ether:diethoxymethane=1:3 in mole and in the presence of 1.0% phosphotungstic acid at 80℃ for 90min. The phosphotungstic acid catalyst could be reused for 6 times. The product was characterized by FTIR and ¹H NMR.The reaction mechanism of the exchange reaction was also provided. The method for the preparation of bis(glycol ether) acetals has several advantages, such as mild reaction conditions, friendly environment, simple operation and wide glycol ether substrates scope.

Key words: bis (diethylene glycol butyl ether) formal, phosphotungstic acid, diethoxymethane, diethylene glycol butyl ether, acetal exchange reaction

中图分类号:

TQ413.25

邵冲, 王大卫, 沈雯雯, 刘洋, 张小祥, 朱新宝. 缩醛交换反应制备双二乙二醇丁醚缩甲醛[J]. 化工进展, 2018, 37(09): 3592-3598.

SHAO Chong, WANG Dawei, SHEN Wenwen, LIU Yang, ZHANG Xiaoxiang, ZHU Xinbao. Preparation of bis(diethylene glycol butyl ether) formal by acetal exchange reactions[J]. Chemical Industry and Engineering Progress, 2018, 37(09): 3592-3598.

参考文献

[1] 申艳霞, 江焕峰, 汪朝阳. 缩醛化反应研究进展[J]. 有机化学, 2008, 28(5):782-790. SHEN Yanxia, JIANG Hanfeng, WANG Chaoyang. Research progress in acetalization[J]. Chinese Journal of Organic Chemistry, 2008, 28(5):782-790.
[2] 廉海昆, 龙慧敏. 甲缩醛生产技术和应用进展[J]. 天然气化工(C1化学与化工), 2012, 37(5):68-70. LIAN Haikun, LONG Minhui.Production technology and application of methylaldehyde[J]. Natural Gas Chemical (C1), 2012, 37(5):68-70.
[3] SAETORI G, BALLINI R, BIGI F, et al. Protection (and deprotection) of functional groups in organic synthesis by heterogeneous catalysis[J]. Chemical Reviews, 2004, 35(16):199-250.
[4] CLIMENT M J, CORMA A, IBORRA S, et al. Designing the adequate base solid catalyst with Lewis or Bronsted basic sites or with acid-base pairs[J]. Journal of Molecular Catalysis A:Chemical, 2002, 182(1):327-342.
[5] HAN X, YAN W, CHEN K, et al. Heteropolyacid-based ionic liquids as effective catalysts for the synthesis of benzaldehyde glycol acetal[J]. Applied Catalysis A:General, 2014, 485:149-156.
[6] 刘洪忠, 马昱博, 沈鑫权, 等. 连续萃取催化精馏制备高纯度甲缩醛[J]. 化工进展, 2012, 31(7):1620-1624. LIU Hongzhong, MA Yubo, SHEN Xinquan, et al. Continuous extractive catalytic distillation to synthesize high-purity methylal[J]. Chemical Industry and Engineering Progress, 2012, 31(7):1620-1624.
[7] 朱新宝, 王琳, 魏民, 等. 一种采用硫酸改性处理纳米级HZSM-5催化剂制备二低碳烷氧基甲烷的方法:CN104974021A[P]. 2015-06-29. ZHU Xinbao, WANG Lin, WEI Ming, et al. Method using sulfuric acid modified nano-level HSZM-5 catalyst to prepare bis(low-carbon alkyloxy)methane:CN104974021A[P]. 2015-06-29.
[8] 王康, 吴之强, 何康丽, 等. 碳化硅基碳复合核壳固体酸的制备及催化合成苯甲醛-1,3-丙二醇缩醛[J]. 化工进展, 2016, 35(7):2103-2108. WANG Kang, WU Zhiqiang, HE Kangli, et al. Preparation of silicon carbide based carbon composite core-shell structure solid acid catalyst for the synthesis of benzaldehyde 1,3-propanediol acetal[J]. Chemical Industry and Engineering Progress, 2016, 35(7):2103-2108.
[9] SMITH B M, GRAHAM A E. Indium triflate mediated acetalization of aldehydes and ketones[J]. Tetrahedron Letters, 2006, 47(52):9317-9319.
[10] BUENO A C, GONCALVES J A, GUSEVSKAYA E V. Palladium-catalyzed oxidation of primary alcohols:highly selective direct synthesis of acetals[J]. Applied Catalysis A:General, 2007, 329(10):1-6.
[11] GOPINATH R, HAQUE S J, PATEL B K. Tetrabutylammonium tribromide (TBATB) as an efficient generator of HBr for an efficient chemoselective reagent for acetalization of carbonyl compounds[J]. Journal of Organic Chemistry, 2002, 67(16):5842-5845.
[12] 梁学正, 高珊, 于心玉, 等. FeCl₃ 催化合成缩醛(酮)[J]. 化工进展, 2006, 25(6):684-686. LIANG Xuezheng, GAO Shan, YU Xinyu, et al. Catalytic synthesis of acetals (ketals) by FeCl₃[J]. Chemical Industry and Engineering Progress, 2006, 25(6):684-686.
[13] DHAKSHINAMOORTHY A, ALVARO M, GARCIA H. Aerobic oxidation of thiols to disulfides using iron metal-organic frameworks as solid redox catalysts[J]. Chemical Communications, 2010, 46(35):6476-6478.
[14] BASU M K, SAMAJDAR S, BECKER F F, et al. A new molecular Iodine-catalyzed acetalization of carbonyl compounds[J]. Synlett, 2002(02):0319-0321.
[15] WANG B, GU Y, SONG G, et al. An efficient procedure for protection of carbonyls catalyzed by sulfamic acid[J]. Journal of Molecular Catalysis A:Chemical, 2005, 233(1-2):121-126.
[16] 曹小华, 王原平, 徐常龙, 等. H₆P₂W₁₈O₆₂/C催化合成环己烯[J]. 化工进展, 2014, 33(3):685-688. CAO Xiaohua, WANG Yuanpin, XU Changlong, et al. Dehydration of cyclohexanol to cyclohexene over H₆P₂W₁₈O₆₂/C catalyst[J]. Chemical Industry and Engineering Progress, 2014, 33(3):685-688.
[17] 王恩波. 多酸化学导论[M]. 北京:化学工业出版社, 1998. WANG Enbo. Introduction of polyacid chemistry[M]. Beijing:Chemical Industry Press, 1998.
[18] JERMY B R, PANDURANGAN A. Catalytic application of Al-MCM-41 in the esterification of acetic acid with various alcohols[J]. Applied Catalysis A:General, 2005, 288(1/2):25-33.
[19] VARGAFTIK M N, MOISEEV I I, SYRKIN Y K. Formation of mixed allyl esters during reaction of higher olefins with palladium chloride in anhydrous carboxylic acid solutions[J]. Bulletin of the Academy of Sciences of the Ussr Division of Chemical Science, 1962, 11(5):868.
[20] 胡守印, 林东恩. 苯甲醛的缩醛反应研究[J]. 化学试剂, 2010, 32(2):173-176. HU Shouyin, LIN Dong'en. Study on acetal reaction of benzaldehyde[J]. Chemical Reagents, 2010, 32(2):173-176.
[21] CHAREONSIRIWAT L, CHAVASIRI W. Convenient method for the transformation of epoxide to aldehyde and acetonide mediated by Cr-PLM[J]. Synthetic Communications, 2016, 47(4):257-267.
[22] BOGERT M, RICHARD R J. Additions and corrections——the formation of cyclic acetals from aldehydes or ketones and alkylene oxides[J]. J. Am. Chem. Soc., 1933, 55(12):5077-5082.
[23] 樊晓娜, 魏明勇, 陈朝晖, 等. 增塑剂TP-95和TP-90B对丁腈橡胶性能的影响[J]. 特种橡胶制品, 2008, 29(4):8-11. FAN Xiaona, WEI Mingyong, CHEN Zhaohui, et al.Effect of plasticizer TP-95 and TP-90B on the properties of nitrile rubber[J]. Special Purpose Rubber Products, 2008, 29(4):8-11.
[24] 魏俊富, 姜勇, 王海峰. 用固体超强酸催化合成甲醛缩二乙二醇单丁醚[J]. 精细石油化工, 2004(2):41-44. WEI Junfu, JIANG Yong, WANG Haifeng. Synthesis of 5,8,11,13,16,19-hexaoxatricosane catalyzed by solid superacid[J]. Speciality Petrochemicals, 2004(2):41-44.
[25] 康润华. 吡咯-2-甲醛化合物的缩醛交换反应和醚化反应研究[D]. 南昌:南昌大学, 2010. KANG Runhua. Research of the transacetalization and etherification of the 2-formylpyrole compounds[D]. Nanchang:Nanchang University, 2010.
[26] 王春梅, 顾正桂, 王延儒. 二乙氧基甲烷的应用及分离研究进展[J]. 化学世界, 2006, 47(12):759-761. WANG Chunmei, GU Zhenggui, WANG Yanru. Review of applications and separation methods of diethoxymethane[J]. Chemical World, 2006, 47(12):759-761.

缩醛交换反应制备双二乙二醇丁醚缩甲醛

Preparation of bis(diethylene glycol butyl ether) formal by acetal exchange reactions

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