摘要
微波技术是二十世纪八十年代兴起的一项有机合成新技术，与常规加热方法相比，具有反应体系受热均匀，增加分子间的碰撞几率，缩短反应时间，提高反应收率等特点。杂多酸环境友好，并具有低温高活性、热稳定性好以及独特的“假液相”行为、多功能(酸、氧化、光电催化)等优点，从而在催化研究领域中受到研究者们的广泛重视。利用微波技术促进杂多酸催化合成精细有机化学品，文献报道较少(只是最近几年才有少量文献报道)。本文对微波促进杂多酸催化合成精细有机化学品进行了研究。
1．微波促进杂多酸催化剂催化缩羰基化反应研究
(1)研究了在微波辐射条件下活性炭负载杂多酸催化合成季戊四醇单缩醛(酮)、双缩醛(酮)以及不同醛(酮)的季戊四醇二缩醛(酮)反应，合成了34种季戊四醇缩醛(酮)，其中有2种季戊四醇单缩醛、5种季戊四醇双缩醛和10种不同醛(酮)的季戊四醇二缩醛(酮)属首次报道的新化合物，并进行了IR、~1HNRM和元素分析表征。结果表明：活性炭负载杂多酸对季戊四醇缩醛(酮)的合成具有催化活性高、催化剂用量少、产率高、催化剂可重复使用、不腐蚀设备等优点，同时利用微波技术可极大地加快反应速率，与常规加热法相比，微波法普遍要快(?)0～600倍以上，且不用或少用溶剂，具有广泛的工业应用前景。
(2)研究了含1，3-二噁烷环的双磺酸盐的可裂解表面活性剂的微波合成及临界胶束浓度(CMC)测定和酸性条件下的水解作用、微波促进杂多酸催化合成乙酰乙酸乙酯缩酮的反应。以活性炭负载磷钨酸作催化剂，利用微波辐射技术合成乙酰乙酸乙酯乙二醇缩酮，比常规加热法要快20倍以上，催化剂用量减少，且不用溶剂。
2．微波辐射杂多酸催化剂催化酯化反应研究
研究了微波辐射超稳Y沸石负载硅钨酸催化合成肉桂酸β-苯乙酯和苯乙酸β-苯乙酯，微波辐射活性炭负载磷钨酸催化合成苯乙酸β-苯乙酯以及微波辐射SiO_2负载磷钨酸催化合成丙酸苄酯。结果表明：以HSW／USY和HPW／C为催化剂，将微波技术应用于肉桂酸与β-苯乙醇和苯乙酸与β-苯乙醇的酯化反应，反应时间短，酸醇比小，酯化率高，操作简便，不用溶剂，有利于环境保护，催化剂可重复使用。同样，微波辐射对SiO_2负载磷钨酸催化剂催化合成丙酸苄酯具有显著的促进作用，与传统加热方法相比，反应速率提高45倍，酯化收率提高7.1％，带水剂用量减少50.0％，催化剂可重复使用。
3．微波促进杂多酸及SnCl_4催化α-蒎烯异构化反应研究
研究了微波促进杂多酸及SnCl_4催化α-蒎烯异构化反应，研究表明：微波辐射对活性炭负载磷钨酸和SnCl_4催化α-蒎烯异构化反应具有很大的促进作用。催化剂负载量增大、催化剂用量增加、微波辐射功率增大和辐射时间延长都能增加反应速率和提高转化率，同
Microwave technique has been a novel method of organic synthesis since 1980s. Compared with the conventional heating way, the microwave technique has been proved to be more useful, for example, more average heated in reaction system, more collision factor of probability in intermolecular, shorter reaction time, higher yield. Since heteropoly acid possesses numerous merits, such as an environmental amity, and an excellent activity in low temperature, a good hot stability, a unique pseudofluid phase behavior, a multifunction catalysis for acid, oxidize, and photoelectricity heteropoly acid has extensively been attracted attention in the field of catalysis by catalytic researchers. Up to now, it has been limited to report the use of microwave technique to accelerate the heteropoly acid catalytic synthesis of fine organic chemicals. In this thesis, the use of microwave technique to accelerate the heteropoly acid catalytic synthesis of fine organic chemicals has in detail been studied as follow:
1. Study of microwave irradiation promoting the heteropoly acid catalytic function for condensation reaction of carbonyl compoubds
(1) Based on the microwave irradiation, mono-acetal (ketal) of pentaerythritol and diacetal (diketal) of pentaerythritol, and different kinds of diacetal (diketal) of pentaerythritol were synthesized by active carbon loading heteropoly acids. 34 kinds of such products were obtained and characterized by IR, ~1HNRM and element analysis. Among these products, such compounds were for the first time reported as two kinds of mono-acetal of pentaerythritol, five kinds of diacetal of pentaerythritol, and ten kinds of different kinds of diacetal (diketal) of pentaerythritol. The results demonstrate that the active carbon loading heteropoly acids possess good catalytic reactions, small dosage, high yield, repeated use, and incorrosive equipments in these synthetic processes. Meanwhile microwave techniques importantly have expediting reaction rates where these rates based on these microwave techniques have 30 to 600 times as many as those rates by the conventional heating ways and it is unnecessary to use solvent (if need, only a little of solvent is needed) in these catalytic reactions. So the microwave techniques are provided with potential applications in large-scale industry produces.
(2) The microwave synthesis of disulfonate salt-type surfactants with a 1,3-dioxane ring and the determinations of critical micelle concentration (CMC), and hydrolyzation reactions in acidic conditions, and the promoting heteropoly acid catalytic syntheses of acetoacetic ester ketal by microwave techniques were researched. During the microwave techniques, based on these
引文
[1] 金钦汉，戴树珊，黄卡玛．微波化学[M]．北京：科学出版社，2001：1-6．
[2] H. P. Broida, J. W. Moyer. The microwave induces plasma (MIP)[J]. J. Opt. Soc. Am., 1952, 42, 37-45.
[3] 凌笑梅，张寒琦，邴贵德，金钦汉，田家乐．微波等离子体原子吸收光谱法的研究[J]．化学学报，1989，48，909-912．
[4] Y. Duan, X. Kong, H. zhang, J. Liu, Q. Jin. Evaluation of a low-powered argon microwave plasma discharge as an atomizer for the determination of mercury by atomic fluorescence spectrometry[J]. J. Anal. At. Spectrom. 1992. 7(1), 7-10.
[5] Y. Duan. Y. Li. Z. Du. Q. Jin. Application of commercial microwave ovens to organic synthesis[J]. Appl. Spectrosc. 1996, 50. 977-979.
[6] A. A. Samra, J. S. Morris, S. R. Koirtyohann. Wet ashing of some biological samples in a microwave oven[J]. Anal. Chem., 1975, 47(8): 1475-1477.
[7] R. J. Giguere, T. L. Bray, S. M. Duncan, G. Majetich. Application of commercial microwave ovens to organic synthesis[J]. Tetrahedron Lett.. 1986, 27(41), 4945-4948.
[8] R. Gedye, E. Smith, K. Westaway, H. Ali, L. Baldisera, The use of microwave ovens for rapid organic synthesis[J], Tetrahedron Lett.. 1986, 27(3): 279-282.
[9] A. G. Whittaker, D. M. P. Mingos. Synthetic reactions using metal powders under microwave irradiation[J]. Journal of Microwave Power and Electromagnetic Energy, 1994, 29(4): 195-198.
[10] 彭金辉，杨红鹃．微波加热技术在陶瓷坯体干燥上的应用[J]．现代化工，1993，(11)，38-41．
[11] R. Gedye. F. Smith. K. Westaway. Microwaves in Organic and Organometallic Synthesis[J]. Journal of Microwave Power and Electromagnetic Energy, 1991, 26(1): 3-17.
[12] K. Huang, J. Tang, Y. Liu. Interference of electromagnetic waves in dynamic metabolism[J]. Chinese Science Bulletin, 1996, 41(15), 1259-1260.
[13] D. M. P. Mingos, D. R. Baghurst. Synthesis of aromatic ethers under microwave irradiation in dry media[J]. Chem. Soc. Rev., 1991, 20: 1-5
[14] K. D. Raner, C. R. Strauss. Influence of microwaves on the rate of esterification of 2, 4, 6-trimethylbenzoic acid with 2-propanol[J].J. Org. Chem., 1992, 57(8): 6232-6234.
[15] K. D. Raner, C. R. Strauss, R. W. Trainor. A new microwave reactor for batchwise organic synthesis[J]. J. Org. Chem., 1995, 60(8): 2456-2460.
[16] A. K. Bose, M. S. Manhas, M. Ghose. Microwave-induced organic reaction enhancement chemistry. 2. Simplified techniques[J]. J. Org. Chem., 1991, 56(25): 6968-6970.
[17] 刘福安，徐文国．微波化学研讨会在长春召开[J]．高等等学校化学学报，1993，14(11)：1517．
[18] S. Chen, S. Chiou, K. Wang. Synthesis of oximes in the microwave oven[J]. J. Chem. Soc. Chem. Commun, 1990, 56: 807-808.
[19] T. Cablewski, A. F. Faux, C. R. Strauss. Development and Application of a Continuous Microwave Reactor for Organic Synthesis[J]. J. Org. Chem.. 1994, 59(12): 3408-3412.
[20] H. M. Kingston, L. B. Jassie(郭振库等译)．分析化学中的微波制样技术-原理及应用[M]．北京：气象出版社，1992：1-15．
[21] 龚盛昭，杨卓如．微波提取黄芩甙的协同效应研究[J]．精细化工，2003，20(7)：427-433．
[22] 郑汝骊，王恩波．钼钨酸的多酸化学[J]．化学通报，1984，(9)：12-15．
[23] 王恩波，胡长文，许林著．多酸化学导论[M]．北京：化学工业出版社，1998：1-20
[24] M. Misono. Recent Progress in Catalytic Techology in Japan[J]. Appl. Catal, 1990, 64: 1.
[25] 梁娟，王善均．催化剂新材料[M]．北京：化学工业出版社，1990：79-86．
[26] I. V. Kozhevnikov. Heteropoly Acids and Related Conpounds as Catalysts for Fine Chemical Synthesis[J]. Catal. Rev. Sci. Eng., 1995, 37(2): 311-352.
[27] E. A. Kazhevnikov, S. Y. Narin, T. Filippova. On the mechanism of catalytic hydroxylation of aromatic hydrocarbons by hydrogen peroxide[J]. Neftekhimiya, 1987, 27(6): 791-793.
[28] 王恩波，牛景扬，许林．杂多钨酸盐热性质研究[J]．东北师范大学学报自然科学版，1994，2(2)：138-143．
[29] T. Kitane, Y. Kuroda, A. Itoh. One-step gas-phase catalytic oxidation of benzene to phenol with molecular oxygen over Cu-supported ZSM-5 zeolites[J]. J. Chem. Soc., Perkin Trans., 1990, (2): 1991.
[30] H. Hayashi, J. B. Moffat. Oxidation Processes on Stoichiometric and Nonstoichiometric Hydroxyapatites[J]. J. Catal., 1982, 77: 473-484.
[31] I. V. Kzhevnikov. Heteropoly Acid and Related Compounds as Catalysts for Fine Chemical Synthesis[J]. Catal. Rev. -Sci, Eng., 1995, 37(2): 311-352.
[32] 许林，胡长文，王恩波．杂多酸型催化剂研究进展[J]．石油化工，1997，26(9)：632-636．
[33] T. Okuhara, N. Mizuno, M. Misono. Catalytic Chemistry of Heteropoly Compounds[C]. Advances in Catalysis, London: Acdemic Press, 1996: 41, 113-252.
[34] 赵忠奎，李宗石，王桂茹，等．杂多酸催化剂及其在精细化学品合成中的应用[J]．化学进展，2004，16(4)：620-630．
[35] 马建伟，叶兴凯，吴越．杂多化合物催化性能的研究—单过渡金属配位的磷钨杂多化合的合成、性质及其对H_2O_2分解反应的催化作用[J]．催化学报，1991，12(6)：443-449．
[36] 何奕工，李奋，王蓬，杜泽学．杂多酸催化剂的吸附、酸性和物化性质[J]．石油炼制与化工，1996，27(8)：12-16．
[37] 陈霄榕，李永丹，康慧敏，等．SiO_2 与 Keggin 杂多酸相互作用的研究[J]．分子催化，2002：16(1)：60-64．
[38] 温朗友，沈师孔，闵恩泽．二氧化硅负载磷钨杂多酸催化剂的表征及催化性质[J]．催化学报，2000，21(6)：524-527．
[39] M. Misono. Heterogeneous Catalysis by Heteropoly Compounds of Molybdenum and Tungsten[J]. Catal. Rev. Sci. Eng., 1987, 29: 269-321.
[40] J. F. Kniflon. Alkylphenol Synthesis Using Heteropoly acid Catalysts[P]. US Patent: 5300703, 1994-04-05.
[41] T. Bara, Y. Ono. Heteropoly acids and their salts supported on acidic Ion-exchange Resin As Highly Active Solid-Acid Catalysts[J]. Appl. Catal., 1986, 22: 321-324.
[42] T. Kwon, T. J. Pinnavvaia, Synthesis and Properties of Anionic Clays Pillared by[XM_(12)O_(40)]~(n-) Keggin ions[J]. J. MOL. Catal., 1992, 74: 23-33.
[43] 王新平，叶兴凯，吴越．活性炭表面固载十二硅钨酸的表征[J]．催化学报，1995，16(6)：510-513．
[44] 吴越，叶兴凯，杨向光，等．杂多酸的固载化—关于制备负载型酸催化剂的一般原理[J]．分子催化，1996，10(4)：299-309．
[45] S. Soled, S. Miseo, G. Mcvicker. Heteropoly compounds and use in Aromatic Alkylation[J]. Catal. Today, 1997, 36: 441-450.
[46] 金英杰，沈健，任杰．苯-长链烯烃烷基化固体酸催化剂的研究Ⅰ．中孔分子筛固载杂多酸催化剂的制备及表征[J]．石油化工，2000，29(7)：479-483．
[47] 杜泽学，何奕工，闵恩泽．结晶水的性质及其对含钨杂多酸酸性的影响[J]．石油学报(石油加工)。1999，15(1)：61-65．
[48] 金英杰，任杰，袁兴东．负载型中孔分子筛上苯与长链烯烃烷基化反应[J]．燃料化学学报，1999，27(6)：490-493．
[49] P. G. Vazquez, M. N. Blanco, C. V. Caceres. Catalysts Based on Supported 12-Molybdophosphoric Acids[J]. Catal. Lett., 1999, 60(4): 205-215.
[50] 陈霄榕，李永丹，康慧敏，等．制备条件对负载型杂多酸性质的影响[J]．天然气化工，2001，26：50-53．
[51] 侯文华，颜其洁．负载杂多酸催化剂H_4SiMo_(12-n)W_nO_(40)／SiO_2 表征[J]．分子催化，1990，4(1)：13-19．_
[52] 张汉鹏，张小明，索继栓，等．固载型杂多酸的合成与表征及催化异丙醇气相脱水反应的活性[J]．精细石油化工，2002，(1)：19-23．
[53] 孙渝，乐英红，李惠云，等．MCM-41负载钨磷杂多酸催化剂的性能研究[J]．化学学报，1999，57(7)：746-753．
[54] K. Satito, M. Nomura, S. Ohgoshi. Arteriovenous Oximeter for O sub-2 content Difference[J]. Preprints, 1997, (4): 719-721.
[55] C. W. Hu, Y. F. Zhang, L. Xu. Continuous Syntheses of Octyl Phenol and Nonane Phenol on Supported Heteropoly Acid Catalysts[J]. Appl. Catal. A, 1999, 177(2): 2237-2244.
[56] Z. V. Kozhevnikov, A. Sinnema, R. J. Jansen, et al. Mesoporous Silica Supported Solid Acid Catalysts[J]. Catal. Lett., 1994, 30(14): 241-252.
[57] S. Soled, S. Miseo, M. Vicker, et al. Efficient Synthesis of Polyhydroxylated Fullerene[J]. Chemical Engineering Joumai, 1996, 64: 247-254.
[58] S. Choi, Y. Wang, Z. Nei, et al. Preparation of Highly Dispersed Cs-Tungstophosphoric Acid Salt on MCM-41 Silica[J]. Catal. Today, 2000, 55: 117-124.
[59] S. Soled, S. Misio, G. Mc Ricker, et al. Highly Active and Stable Rh/MgO-AI2O3 Catalysts for Methane Steam Reforming[J]. Catal. Today, 1997, 36: 441-450.
[60] Y. Izumi, K. Hisano, T. Hida. Support Effects on Bronsted Acid Site Densities and Alcohol Dehydration Turnover Rates on Tungsten Oxide Domains[J]. Appl. Catal. A, 1999, 181: 277-282.
[61] 泉有亮．芳香族新规気相合成[J]．触媒，1997，39(4)：292-297．
[62] Y. Izumi, W. Nohara, M. Ogawa, et al. Preparation of Highly Dispersed Cs-Tungstophosphoric Acid Salt on MCM-41 Silica[J]. Catal. Lett., 1992, 28(10): 1987-1990.
[63] Y. Izumi, M. Ono,, M. Kitagawa, M. Yoshida, K. Urabe. Structural study of the sol-gel transition of branched polyethylene in toluene[J]. Microporour Mater., 1995, 5: 255.
[64] 张维萍，韩秀文，包信和，等．超细分子筛的的合成、结构特性及在催化中的应用[J]．分子催化，1999，13(5)：393-400．
[65] M. Misono. Recent Progress in Catalytic Technology in Japan[J]. Appl. Catal., 1990, 64: 1-30.
[66] Y. Ono. Heteropoly Acid Catalysis-A Unique Blend of Acid-Base and Redox Properties[J]. Perspect Catal, 1992, 34(2): 431-464.
[67] 杜少兵，徐元植．杂多酸及其盐的催化研究新进展[J]．石油化工，1993，22(8)：694-702．
[68] F. Cavani. A Blend of Acid and Oxidizing Properties[J]. Catal Today, 1998, 41: 73-86.
[69] 王恩波，胡长文，许林著．多酸化学导论[M]．北京：化学工业出版社，1998：14-15．
[70] S. L. Altenau, M. T. Pope. Models for Heteropoly Blues. Degress of Valence Trapping in Vanadium(Ⅳ) and Molybenum(Ⅴ)-titated keggin Anions[J]. Inorg. Chem., 1975, 2: 417.
[71] P. E. Katsolis, M. T. Pope. New Chemistry for Heteropolyanions in Anhydrous Nonpolar Solvents. Coordinative Unsaturation of Surface Atoms Polyanion Oxygen Carriers[J]. J. Am. Chem. Soc., 1984, 106: 2737.
[72] 王恩波，胡长文，许林著．多酸化学导论[M]．北京：化学工业出版社，1998：181．
[73] N. Mizuno, D. J. Suh. Selective Oxidative Dehy-drogenation of Propane at 380 ℃ by Cs_(2.5)Cu_(0.08)H_(3.34)PMo_9V_3O_(40)Catalyst Pre-cursor[J]. Appl. Catal. A, 1996, 146: 249-254.
[74] R. Neumann, I. Dror, Oxidative Dehydrogenation of 4-Vinyl cyclo--hexene to Styrene Catalyzed by PMo_(10)V_2O_(40) Heteropoly acids[J]. Appl. Catal. A, 1998, 172: 67-72.
[75] W. Li, W. Ueda, Catalytic Oxidation of Isobutane toMethacrylic Acid with Molecular Oxygen over Activated Pyridinium 12-Molybdophosphate[J]. Catal. Lett, 1997, 46: 261-265.
[76] 王建坤，杨锐．铝钒磷杂多酸催化氧化饱和烃[J]．北华大学学报(自然科学版)，2002，3(3)：199-201．
[77] Y. Seki, N. Mizuno, M. Misono, et al. High-Yield Liquid-Phase Oxygenation of Methane with Hydrogen Peroxide Catalyzed by 12-Molybdovanadophosphoric Acid Catalyst Precursor[J]. Appl Catal A, 1997, 158: 47-51.
[78] K. Nowinska, D. Dudko, Transtion Metal Salts of Heteropoly Acids as Palladium Cocatalysts for Wack-er Oxidationof Ethene[J]. Appl. Catal. A, 1997, 159: 75-87.
[79] K. Nowinska, D. Dudko. Transtion Metal Salts of Heteropoly Acids as Palladium co-Catalysts for Wacker oxidation of butene-1 to MEK[J]. Catal. Lett., 1997, 49: 43-48.
[80] 毛萱，段元骐，王浩，等．丙烯选择氧化制丙烯酸杂多酸催化剂的探索[J]．分子催化，2000，14(5)：384-387．
[81] 黄世煜，丁云杰，张连中，等．乙烯直接氧化制乙酸的研究Ⅰ．Pd Ru／HPA／SiO2 双金属催化剂的催化性能[J]．催化学报，2001，26(2)：579-581．
[82] 蔡铁军，陈亚中，彭振山，等．MNaPMoV／SO_2 系列催化剂对异丁烯氧化反应的催化性能[J]．催化学报，2002，23(3)：285-288．
[83] 单玉华，邬国英，鱼蓉，等．反应萃取法合成戊二醛中H_3PMo_xW_(12-x)O_(40) 的催化作用[J]．分子催化，1999，13(1)．54-58．
[84] 丁彤，郝金库，杨恩翠，等．杂多酸及其盐催化苯氧化合成苯酚反应研究[J]．天津化工，2000，6：14-16．
[85] 余雅琴，李小晶，林深，等．镧钼钒磷杂多配合物催化乙苯选择性氧化制苯乙酮[J]．化学研究与应用，2000，12(6)：654-657．
[86] 王海英，王晓丹，姜恒等．杂多酸催化下苯甲醇氧化合成苯甲醛反应研究[J]．科研开发，2002，10(3)：7-9．
[87] 韩伟，龚剑．杂多酸催化制备丙三醇的研究[J]．吉林化工学院学报，1995，12(3)：16-18．
[88] 于剑锋，杨宇，吴通好．Dawson结构钼钒磷杂多化合物对苯酚过氧化氢羟化作用的研究[J]．高等学校化学学报，1996，17：126．
[89] 钱东，张敏，王开毅．杂多酸固载催化剂催化氧化合成 2，3，5-三甲基苯醌[J]．合成化学，1998，6(2)：111-112．
[90] 陈春生．异丁醛—步氧化制甲基丙烯酸的技术开发[J]．化工设计，1994，1：40-44．
[91] O. Watzenberger, G. Emig, D. T. Lynch. Oxydehydrogenation of Isobutyric Acid with Heteropoly Acid Catalysts: Experimental Observations of Deactivation[J]. J. Catal., 1990, 124: 247-258.
[92] G. B. M. Garvey, J. B. Moffat. The Oxidative Dehydrogenation of Isobutyric Acid to Methacrylic Acid on Ion-exchange Modified 12-Heteropoly Oxometalates[J]. J. Catal., 1991, 132: 100.
[93] 马荣华，刘春涛，梁敏．杂多配合物异构体在马来酸环氧化反应中的催化活性[J]．合成化学，2002，10(3)：277-280．
[94] K. Nakayama, M. Hamamoto, Y. Nishiyama. Oxidation of Benzylic Derivatives with Dioxygen Catalyzed by Mixed Addenda Metallophosphate Containing Vanadium and Molybdenum[J]. Chem. Lett., 1993, 67: 1699.
[95] G. Oeztuerk, B. Guemguem, O. Akba. Synthesis of Ester under Microwave Irradiation Using Heteropoly Acids as Aatalysts[J]. Catalysis Letters, 2002, 82(3-4): 233-235.
[96] G. Oeztuerk, B. Guemguem. Etherification of Benzyl Alcohol under Microwave Irradiation Using Heteropoly Acids as Catalysts[J]. Reaction Kinetics and Catalysis Letters, 2004, 82(2): 395-399.
[97] M. J. Grormow, D. J. Macquarrie, J. H. Clark, P. Ravenscroft. A Study into the Use of Microwaves and Solid Acid Catalysts for Friedel-Crafts Acetylations[J]. Joumal of Molecular Catalysis A: Chemical, 2005, 231(1～2): 47-51.
[98] 盛军凤．微波辐射硅钨酸催化合成乙酸异戊酯研究[J]．江苏化工，2004，32(6)：35-36．
[99] 胡玉才，林洁，李敏．微波辐射杂多酸催化合成乙酸丁酯的研究[J]．化学工程师，2004，(10)：1-2．
[100] 刘玮炜，钱保华，纪延光，张国华．微波加热磷钨酸催化合成对羟基苯甲酸丁酯[J]．淮南工学院学报，1999，8(3)：45-46．
[101] 李静，王淑敏．微波辐射磷钨酸催化合成肉桂酸乙酯[J]．化学试剂，2004，26(1)：43-44．
[102] 谭志斗．微波辐射磷钨酸催化合成丙酸苄酯[J]．安徽化工，2003，(3)：14-16．
[103] 农兰平．活性炭负载磷钨酸铝催化合成柠檬酸三丁酯[J]．精细化工中间体，2004，35(3)：50-54．
[104] 程景雄，施用晖，乐国伟．微波合成寡糖新工艺研究[J]．河南工业大学学报(自然科学版)，2005，26(1)：46-49．
[105] M. Misono. Heteropolyacids Versatile green catalysts usable[J]. Appl. Catal., 1990, 64: 1.
[106] 奥原敏夫．一种新型催化剂[J]．表面(日)，1989，27(8)：629．
[107] Y. Izumi, K. Urabe. Direct Condensation of Carboxylic Acids with Alcohols Catalyzed by Hafnium(Ⅳ) Salts[J]. Chem. Lett., 1981, 67: 663.
[108] M. A. Schwegler, P. Vinke, et. al. Oxidation Occurs More Readily at Room Temperature on Pure[J]. Appl. Catal., A: General, 1992, 80: 41.
[109] 张敏，尹笃林．活性炭负载磷钨酸催化α-蒎烯的异构化反应[J]．林产化学与工业，2001，21(3)：11-15．
[110] 王新平，叶新凯，吴越．活性炭表面杂多酸的稳定和酸性[J]．催化学报，1994，15(4)：314-317．
[111]．贾向东，柳海橙，王金希．钨钼钒硅杂多酸盐的的合成及表征[J]．无机化学学报，1988，4(3)：89-95．
[112] 刘琪英，武文良，王延儒，王军．超稳Y沸石负载杂多酸催化剂的制备、表征及催化性能 Ⅰ．制备及表征[J]．石油化工，2003，32(5)：387-391．
[113] 袁晓红，姚源，周斌，等．改性Y型分子筛孔结构研究[J]．现代科学仪器，2001，(1)：42-44．
[114] B. Sulikowski, J. Haber, et al, In Situ Solid-State NMR Studies of the Catalytic Conversion of Methanol[J]. Catal. Lett., 1996, 39: 27-31.
[115] K. Pamin, A. Kubacka, et al. Immobilization of Dodecatungstophosphoric Acid on Dealuminated Zeolite Y: a Physicochemical Study[J]. Appl. Catal., A, 2000, 194/195: 137-146.
[116] 武文良，刘琪英，王延儒，王军．超稳Y沸石负载杂多酸催化剂的制备、表征及催化性能Ⅱ．萘的丙基化反应[J]．石油化工，2003，32(6)：453-457．
[117] 温朗友，沈师孔，闵恩泽．二氧化硅负载磷钨杂多酸催化剂的表征及催化性质[J]．催化学报，2000，21(6)：524-527．
[118] 济南市轻工业研究所编译．合成食用香料手册[M]．北京：中国轻工业出版社，1985：625-626．
[119] 刘树文编著．合成香料技术手册[M]．北京：中国轻工业出版社，2000：583-584．
[120] 陈新，徐永廷，金春霞．季戊四醇双缩醛的合成与表征[J]．合成化学，1997，5(2)：212-214．
[121] J. Pemer, G. Frey, K. Stork. Interactions of Carboxylated Polymer Latexes with Polyethoxylated. Nonionic. Surfactants[J]. Tenside Deterged. 1977, 14: 180.
[122] 陆绍荣．多聚磷酸催化化合成季戊四醇双缩醛[J]．吉林化工学院学报，1999，16(4)：20-22．
[123] 袁先友，张敏，王小勇．脱铝超稳Y沸石催化合成季戊四醇双缩醛[J]．化学研究与应用，1997，9(6)：600-603．
[124] 袁先友，张敏．2，2-二羟甲基-1，3-丙二醇单缩醛的合成[J]．化学研究与应用，1998，10(6)：636-638．
[125] S. F. Marrian. The Chemical Reactions of Pentaerythritol and its Derivatives[J]. Chem. Rev., 1948, 43: 149-198.
[126] 刘清福，钟桂云，谈廷凤．微波照射硫酸氢铵催化季戊四醇双缩醛、酮的合成[J]．精细化工，2005，22(6)：434-435．
[127] S. Mager, M. HornI. Grosu, et al. Synthesis of acetalization of pentaerythritol[J]. Monatsch. Chem., 1989, 120: 735.
[128] G. W. Wang, X. Y. Yuan, Y. C. Liu, X. G. Lei. Preparation and Properties of Sulfonate Salt-Type Cleavable Surfactants with a 1, 3-Dioxane Ring[J]. J. Am. Oil Chem. Soc, 1994, 71: 727-730.
[129] Z. H. Zhang, T. S. Li, T. S. Jin, J. T. Li. Montmorillonite Clays Catalysis. Part 12. An Efficient and Practical Procedure for Synthesis of Diacetals from 2, 2-Bis (hydroxymethyl)Propane-1, 3-diol with Carbonyl Compounds[J], J. Chem. Research(S), 1998, 18: 640-641.
[130] C. D. Wang, X. Zhong, and R. J. Xie. Synthesis of Diacals of 2, 2-Bis(hydroxymethyl) Propane-1, 3-diol Under Microwave irradiation[J]. Synthetic Communications, 1997, 27(14): 2517-2520.
[131] E. J. Corey, J. W. Suggs, Pyridinium Chlorochromate. an Efficient Reagent for Oxidation of Primary and Secondary Alcohols to Carbonyl Compounds[J]. Tetrahedron Lett., 1975, 31(49): 2647-2650.
[132] R. W. Ratcliffe. Novel Synthetic Approach to Carbapenems Utilizing aza-Cope Mannich Cyclization[J]. Org. Synth., 1976, 55: 84.
[133] W. E. Conrad, B. D. Gesner, L. A. Levasseur. Acetals and Ketals of 1, 3-Diols[J]. J. Org. Chem., 1961, 26: 3571-3574.
[134] S. F. Marrian, The Chemical Reactions of Pentaerythritol and its Derivatives[J]. Chem. Rev., 1948, 43: 149-198.
[135] Z. H. Zhang, T. S. Li, T. S. Jin, J. T. Li. Synthesis of Diacetals by Condensation of Carbonyl Compounds with Bis(hydroxymethyl)-1, 3-Propanediol[J]. J. Chem. Res. Synop, 1998, (10): 640.
[136] S. F. Marrian, The Chemical Reactions of Pentaerythritol and its Derivatives[J], Chem. Rev., 1948, 43: 149-198.
[137] 王官武，袁先友，雷学工，刘有成．季戊四醇双缩醛的合成[J]．应用化学，1994，11(1)：114-115．
[138] T. S. Jin, T. S. Li, Z. H. Zhang, Y. J. Yuan. Synthesis of Diacetals by Condensation of Carbonyl Compounds with Bis(hydroxymethyl)-1, 3-Propanediol Catalysed by Expansive Graphite[J]. Synth. Commun, 1999, 29(9): 1601-1606.
[139] S. F. Marrian. The Chemical Reactions of Pentaerythritol and its Derivatives[J]. Chem. Rev., 1948, 43, 149-198.
[140] D. A. Jaeger, M. R. Frey, Preparation and Characterization of Destructible Surfactants[J]. J. Org. Chem., 1982, 47(2): 311-315.
[141] D. A. Jaeger, Y. M. Sayed, A. K. Dutta. Second Generation Single-chain Cleaveable Surfactants[J]. Tetrahedron Lett., 1990, 31(4): 449-450.
[142] D. A. Jaeger, Y. M. Sayed, Synthesis and Characterization of Single-chain Second Generation Cleavable Surfactants[J]. J. Org. Chem., 1993, 58(9): 2619-2627.
[143] S. Y. amamura, M. Nakamura, T. Takeda. Quantitation of Cholesterol Oxidation Products in Unirradiated and Irradiated Meats[J]. J. Am. Oil Chem. Soc., 1989, 64: 1165-1169.
[144] K. A. Wilk, A. Bienicki, B. Burczyk, A. Sokolowski. Lipase-catalyzed Synthesis of Methyl[J]. J. Am. Oil Chem. Soc., 1994, 71: 81-86.
[145] D. Ono, A. Masuyama, Y. Nakatsuji, M. Okahara, S. Yamarnura, T. Takeda. Synthesis and Properties of Soap Types of Cleavable Surfactants Bearing a 1, 3-Dioxolane Ring[J]. J. Am. Oil Chem. Soc., 1993, 70: 29.
[146] D. A. Jaeger, C. A. Martin, T. G. Golich."Destructible" Surfactants Based on a Ketal Group[J]. J. Org. Chem., 1984, 49(23): 4545-4547.
[147] D. A. Jaeger, T. G. Golich. Commercially Prepared Alkyl Bonded Silica Materials Exhibited Low Base Adsorp[J]. J. Am. Oil Chem. Soc., 1987, 64: 1550.
[148] D. A. Jaeger, P. K. Chou, D. Bolikal, D. Ok, K. Y. Kim. Kinetics of Amphiphilic Ketone Epimerizations in Cleavable Surfactant Hosts[J]. J. Am. Chem. Soc., 1988, 110(15): 5123-5129.
[149] D. A. Jaeger, J. Jamrozik, T. G. Golich, M. W. Clennan, J. Mohebalian. Preparation and Characterization of Glycerol-based Cleavable Surfactants and Derived Vesicles[J]. J. Am. Chem. Soc., 1989, 111(8): 3001-3006.
[150] D. A. Jaeger, J. Mohebalian, P. L. Rose, Acid-catalyzed hydrolysis and monolayer properties of ketal-based cleavable surfactants[J]. Langmuir, 1990, 6(3): 547-554.
[151] G. W. Wang, X. Y. Yuan, Y. C. Liu, Q. X. Guo, X. G. Lei. Synthesis, Characterization and Hydrolytic Property of Cleavable Surfactant with Two 1, 3-Dioxane Rings[J]. Indian J. Chem., Sect. B, 1996, 35: 583-585.
[152] T. S. Takeda, S. Yamamura, K. Tanaka, M. Nakajima, T. Takeda. Applications of Mass Spectrometry to Organic Stereochemistry[J]. J. Jpn. Oil Chem. Soe.(YUkAGAKU), 1991, 40: 16.
[153] S. Yamamura, M. Nakamura, K. Tanaka, T. Takeda. Complete Determination of Polarization State in the Hard X-Ray Region[J]. J. Jpn. Oil Chem. Soc(YUKAGAKU). 1991, 40: 104.
[154] S. Yamamura, M. Nakamura, K. Kasai, H. Sato, T. Takeda. In Situ 57Fe Mossbauer Spectroscopy and X-ray Differaction on CaFeO3(Fe4: t32el) under Pressure[J], J. Jpn. Oil Chem. Soc. (YUKAGAKU), 1991, 40: 1002.
[155] D. A. Ono, A. Masuyama, Y. Nakatsuji, M. Okahara, S. Yamamura, T. Takeda. Molecular Genetic Analysis of a Novel Parkin Gene[J]. J. Am. Oil Chem. Soc., 1993, 70: 29.
[156] B. Burczyk, M. Banaszczyk, A. Sokolowski, A. Piasecki. Source Core: from the Point of View of Preparation of Brachytherapy Radiation Sources[J]. J. Am. Oil Chem. Soc., 1988, 65: 1204.
[157] A. Sokolowski, A. Piasecki, B. Burczyk. An Approach to the Preparation of Iodine-125 Seed-type Sources[J]. J. Am. Oil Chem. Soc., 1992, 69: 633.
[158] T. Kida, A. Masuyama, M. Okahara. Preparation of Trihydroxycarboxylates Bearing a Long-chain Alkyl Acetal Group from Glucono-1, 5-Lactone[J]. Tetrahedron Lett., 1990, 31(41), 5939-5942.
[159] G. W. Wang, X. Y. Yuan, Y. C. Liu, X. G. Lei. Synthesis and Characterization of Cleavable Cationic Surfactants with a 1, 3-Dioxane Ring[J]. J. Am. Oil Chem. Soc., 1995, 72: 83-87.
[160] G. W. Wang, Y. C. Liu, X. Y. Yuan, X. G. Lei. Preparation, Properties, and Applications of Vesicle-Forming Cleavable Surfactants with a1, 3-Dioxane Ring[J], J. Colloid Interface Sci., 1995, 173: 49,
[161] G. W. Wang, X. G. Lei, Y. C. Liu. Preparation and Properties of Cleavable Dianionic Surfactants with a 1,3-Dioxane Ring[J].J.Am.Oil Chem.Soc.,1993,70:731.
[162] N.J.Turro,P.L.Kuo,P.Somasundaran,K.Wong.Surface and Bulk Interactions of Ionic and Nonionic Surfactants[J].J. Phys. Chem., 1986,90(2):288-291.
[163] 北京日用化学工业学会编．化工产品手册(第一版)[M]．北京：化学工业出版社，1989，361-362．
[164] 王存德，周璇．苹果酯-β的合成[J]．精细化工，1998，15(3)：30-31．
[165] 王建平．硅钨酸催化实用香料苹果酯-β的合成研究[J]．化学研究与应用，2001，13(2)：208-210．
[166] 杨仕豪，兰柳波，李移．苹果酯和苹果酯-β的合成研究[J]．化学世界，1999，40(2)：90-92．
[167] 谭日红．苹果酯的合成[J]．精细化工，1995，12(4)：40-41．
[168] 程永浩．SO_4~(2-)／TiO_2固体超强酸催化合成苹果酯的研究[J]．化学世界，2000，41(7)：356-357．
[169] 张敏，袁先友．活性炭负载磷钨酸催化合成苹果酯[J]，化学试剂，2002，24(2)：115-116．
[170] Z.H.Zhang,T.S.Li,T.S.Jin,J.T.Li,Montmorillonite Clays Catalysis. Part 12.An Efficient and Practical Procedure for Synthesis of Diacetals from 2,2-Bis (hydroxymethyl) Propane-1,3-diol with Carbonyl Compounds[J],J.Chem.Research(S), 1998,78:640-641.
[171] 杨启云，戚建英，曹晋荣．超细固体酸TiO_2-SO_4~(2-)催化α-蒎烯异构化反应的研究[J]．1997，9(3)：250-253．
[172] 王石发，安鑫南，程芝．α-蒎烯催化异构制各双戊烯的研究[J]．林产化学与工业，1996，16(3)：32-38．
[173] 谭志新，余金权，肖树德．TiO_2／SO_4~(2-)催化的α-蒎烯异构化反应[J]．林产化学与工业，1994，14(2)：1-9．
[174] 吴晓刚，程芝，伍忠萌．固体超强酸催化α-蒎烯异构化反应研究[J]．林产化学与工业，1993，13(2)：155-158．
[175] 王亚明，王辉，魏云波．化学气相沉积法修饰13X分子筛上α-蒎烯的异构化反应[J]．1995，15(4)：8-12．
[176] 刘尧权，陈庆之，李允隆，刘铸晋．丝光沸石催化的α-蒎烯异构化反应[J]．林产化学与工业，1988，8(4)：10-16．
[177] M.A.Harmer.Preparation of an MCM-41/Nafion(?) Composite Material; a Selective Catalyst for A-Methylstyrene Dimerization[J].Applied Catalysis A,2001,221(1-2):45-62.
[178] K.Arata.Engelhard Corporation Press Release[J].Adv. Catal., 1990,37: 165-204.
[179] J.R.Sohn, T.D.Kwon,S.B.Kin.Etude des Petits Cycles—ⅩⅩⅧ: Regression de Preparation of New Solid Super-acid Catalyst, Titanium Sulfate Supported on Zirconia and its Acid Catalytic Properties [J].Bull Korean Chem. Soc.,2001,22(12): 1309-1315.
[180] 袁先友，尹笃林，李谦和，伏再辉．脱铝超稳Y沸石催化α-蒎烯异构化反应[J]．分子催 化，1996，10(6)：435-439．
[181] 欧阳玉祝，邹晓勇，彭清静．活性炭吸附硅钨酸催化合成丁酸丁酯[J]．化学世界，2000，(12)：653-654．
[182] 中国化工商品大全编委会编．中国化工商品大全(上册)[M]．北京：中国物质出版社，1993：232-233．
[183] 化学工业部科学技术情报研究所编．化工产品手册—有机化工原料(上册)[M]．北京：化学工业出版社，1985：617-618．
[184] 陈海生，陈庆之，郑淑贞，等．天然丝光沸石催化环己醇脱水制环己烯[J]．化学试剂，1997，19(4)：242-244．
[185] 郭俊胜．环己醇催化脱水制备环己烯[J]．化学试剂，2001，23(3)：178-179．
[186] 张敏，袁先友．脱铝超稳Y沸石催化环己醇催化脱水制备环己烯[J]．精细化工，2000，17(5)：287-289．
[187] 张敏．磷钨酸催化合成环己烯[J]．现代化工，2000，20(4)：26-28．
[188] 袁先友，张敏，刘元圆．SnCl_4催化合成环己烯[J]．化学试剂，2001，23(3)：182-183．
[189] 俞志明．中国化工商品大全(上册)[M]．北京：中国物质出版社，1993：720．
[190] 王箴．化工辞典(第四版)[M]．北京：化学工业出版社，2001：672．
[191] A.Mckillop,J.C.Faud,R.P.Hug.Etude des Peters Cycles—ⅩⅩⅧ·Regression de Cycle Generale de Cyclobutanols—Ⅰ. Halohydrines-1,2, Diols-1,2 et Epoxydes Correspondants[J]. Tetrahedron, 1974,30(11): 1397-1403.
[192] 刘树文．合成香料技术手册[M]．北京：中国轻工业出版社，2000：141．
[193] 俞善信，俞超源．氯化铁催化合成β-萘甲醚[J]．现化化工，1996，16(7)：29-30．
[194] 张敏．磷钨酸催化合成环己烯[J]．现代化工，2000，20(4)：26-28．
[195] 张敏．活性炭负载磷钨酸催化合成环己酮1，2-丙二醇[J]．精细石油化工，2002，1：36-38．
[196] 张敏，袁先友．磷钨酸催化合成三醋酸甘油酯[J]．合成化学，2001，9(5)：469-472．
[197] G.Stork.The Base Effect in Catalytic Hydrogenation. A Simple Synthesis of 6-Methoxy-α-tetralone[J].J.Am.Chem.Soc., 1947,69(3):576-579.
[198] 吴越．催化化学(下册)(第二版)[M]．北京：科学出版社，1998：1070．
[199] 王恩波，胡长文，许林著．多酸化学导论[M]．北京：化学工业出版社，1998：19．
[200] 魏文德．有机化工原料大全(下卷)(第二版)[M]．北京：化学工业出版社，1999：457-469．
[201] 郑箐英，刘荣华，季慰红，等．以混合轻稀土硝酸盐催化剂由葸氧化制备蒽醌[J]．北京工业大学学报，1990，16(3)：94-95．
[202] 张永华．氧气液相氧化葸制取蒽醌的研究[J]．现代化工，1999，19(11)：29-31．
[203] 陈忠秀，彭耀丽，宗志敏，等．硝酸氧化蒽制备蒽醌[J]．精细石油化工，1999，(3)：20-22．
[204] G.A.Tsigdinos,C.Hallada.Molybdovanadophosphoric Acids and Characterization[J].J. Inorg. Chem., 1968,7(3):437-441.
[205] James F.,et al.Chirality of Oxidized and Reduced Octadecamoly- bdodiphosphate Anions.Observation of a Pfeiffer Effect[J].J.Inorg.chem., 1978,17(5): 1115-1121.
[206] 李铭铀，刘景福，王恩波，等．电解酸化法合成钼钒磷杂多酸[J]．东北师大学报(自然科学版)，1985，(3)：51-57．
[207] 陈亚光，王恩波，赵世良，等．高含量钼钒磷杂多化合物的合成和性质研究[J]．东北师大学报(自然科学版)，1985，(3)：127-128．