邻二甲苯的选择性硝化及低压液相催化加氢研究
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摘要
3，4-二甲基苯胺是一种重要的化工中间体，广泛地应用于医药、农药、染料等领域。本论文以邻二甲苯为起始物，采用选择性硝化制3，4-二甲基硝基苯和低压液相催化氢化制备3，4-二甲基苯胺。内容主要包括以下三部分。
第一部分，对3，4-二甲基苯胺的合成方法进行了较为系统的概述，并对各方法进行了比较和评述。对硝化理论、提高硝化选择性的方法和低压液相催化加氢理论进行了详细的讨论，并对于论文的目的和意义进行了阐述。
第二部分，提高邻二甲苯硝化选择性的研究思路和研究内容。实验结果显示，在多聚磷酸存在的情况下硝化邻二甲苯有较佳的对位选择性。在此条件下对多聚磷酸的浓度、用量和反应温度等条件进行了优化，异构体中3，4-二甲基硝基苯的比例可以由混酸硝化的45％左右提高到83％。同时用甲苯、乙苯等相似芳香族化合物进行了对比性实验，对多聚磷酸硝化选择性做了初步探讨，认为多聚磷酸的位阻是选择性提高的主要原因。
第三部分，利用改性镍催化剂在较低的压力下加氢还原3，4-二甲基硝基苯，加氢转化率可达99.9％，并与钯／碳催化剂进行了比较。对浓
浙江工业大学硕士学位论文
度、压力、温度和溶剂等影响因素在较低压力下镍催化氢化3，4一二甲
基硝基苯进行了简单的动力学研究。
In this thesis, 3,4-xylidine which is an important organic intermediates widely applied in pharmacy, pesticide, and dye industries, has been prepared by selective nitration and catalytic hydrogenatuion in low pressure, using o-xylene as start material. The main content consisted of three sections.
In the first section, the synthesis of 3,4-xylidine have been reviewed. Selective nitration of o-xylene and catalytic hydrogenation were also mainly discussed.
In the second section, the selective nitration of o-xylene had been studied. The experimental results showed that nitration of o-xylene has good para-position selectivity in the presence of polyphosphoric acid. And the technologic conditions such as concentration of phosphoric acid ,temperature and so on were optimized. Under the selected conditions, the ratio of 4-nitro-o-xylene in the product rised from 45% to about 83%. Some other similar aromatic compounds such as toluene and chlorobenzene are also studied.
In the third section, synthesis of 3,4-xylidine was studied by
hydrogenation of 4-nitro-o-xylene in nickel catalyst, the conversation of 4-nitro-o-xylene was more than 99.9%. Factors such as concentration of 4-nitro-o-xylene, hydrogen pressure, temperature and solvent were studied and simple dynamics of hydrogenation of 4-nitro-o-xylene in low pressure were discussed.
第一部分，对3，4-二甲基苯胺的合成方法进行了较为系统的概述，并对各方法进行了比较和评述。对硝化理论、提高硝化选择性的方法和低压液相催化加氢理论进行了详细的讨论，并对于论文的目的和意义进行了阐述。
第二部分，提高邻二甲苯硝化选择性的研究思路和研究内容。实验结果显示，在多聚磷酸存在的情况下硝化邻二甲苯有较佳的对位选择性。在此条件下对多聚磷酸的浓度、用量和反应温度等条件进行了优化，异构体中3，4-二甲基硝基苯的比例可以由混酸硝化的45％左右提高到83％。同时用甲苯、乙苯等相似芳香族化合物进行了对比性实验，对多聚磷酸硝化选择性做了初步探讨，认为多聚磷酸的位阻是选择性提高的主要原因。
第三部分，利用改性镍催化剂在较低的压力下加氢还原3，4-二甲基硝基苯，加氢转化率可达99.9％，并与钯／碳催化剂进行了比较。对浓
浙江工业大学硕士学位论文
度、压力、温度和溶剂等影响因素在较低压力下镍催化氢化3，4一二甲
基硝基苯进行了简单的动力学研究。
In this thesis, 3,4-xylidine which is an important organic intermediates widely applied in pharmacy, pesticide, and dye industries, has been prepared by selective nitration and catalytic hydrogenatuion in low pressure, using o-xylene as start material. The main content consisted of three sections.
In the first section, the synthesis of 3,4-xylidine have been reviewed. Selective nitration of o-xylene and catalytic hydrogenation were also mainly discussed.
In the second section, the selective nitration of o-xylene had been studied. The experimental results showed that nitration of o-xylene has good para-position selectivity in the presence of polyphosphoric acid. And the technologic conditions such as concentration of phosphoric acid ,temperature and so on were optimized. Under the selected conditions, the ratio of 4-nitro-o-xylene in the product rised from 45% to about 83%. Some other similar aromatic compounds such as toluene and chlorobenzene are also studied.
In the third section, synthesis of 3,4-xylidine was studied by
hydrogenation of 4-nitro-o-xylene in nickel catalyst, the conversation of 4-nitro-o-xylene was more than 99.9%. Factors such as concentration of 4-nitro-o-xylene, hydrogen pressure, temperature and solvent were studied and simple dynamics of hydrogenation of 4-nitro-o-xylene in low pressure were discussed.
引文
[1] Kaichi Sahashi, Hiroshi Akamatsu, Hidesaburo Genda, Synthetic flavin and its raw materials Ⅰ. Synthesis of D-araboflavin from p-nitrotoluene, Bull. Inst. Phys. Chem. Research(Tokyo), 1948, 24, 72
[2] V. M. Berezovskii, Trudy Vsesoyuz, Chemical studies in the field of vitaminB, Nauch. Issledovatel. Vitamin. Inst., 1954, 5, 12-17
[3] P. Karrer, B. Becker, E Benz, P. Frei, H. Salomon, K. Schopp, Synthesis of lactoflavin, Helv. Chim. Acta., 1935, 18, 1435-1448
[4] Robert C. Weast, Jeanette G. Grasselli, CRC Handbook of Data on Organic Compounds, 2nd edition, CRC Press. Inc., 1989
[5] 徐克勋，精细有机化工原料及中间体手册，化学工业出版社，1998
[6] Manabe Osamu, Nara Kenichi, Aromatic amines, Ger. Often. 2,165,456, 1972
[7] Nara Kenichi, Manabe Osamu, amination of aromatic compounds Ⅰ. Aminations of aromatic sulfonates with sodium amide, Nippon Kayaku Kaishi, 1974, (8), 1522-1525
[8] Yu. P. Sobolev, V. M. Berezovskii, 3,4-Xylidine, U.S.S.R. 118,129, 1959
[9] Yoshikazu Sahashi, Hiroshi Akamatsu, Hidesaburo Genda, Synthesis of flavin from various materials Ⅰ. Synthesis of D-araboflavin from p-nitrotoluene, Proc. Imp. Acad.(Tokyo), 1945, 21, No.1, 44-52
[10] Keiichi Sahashi, Xylidine from the condensation of bis(chloromethyl)ether and nitrotoluene, Japan 172,795, 1946
[11] W. A. Wisansky, S. Ausbacher, Preparation of 3,4-dimethylaniline, J. Am. Chem. Soc., 1941, 63, 2532
[12] W. A. Wisansky, S. Ausbacher, 3,4-Dimethylailine, Org. Syntheses, 1948, 28, 46-48
[13] Veksher M. A., Shersherskii A. A., Shentsis I. E., Mathematical description of the 3,4-Xylidine production process, Khim. -Farm. Zh, 1982, 16(1), 86-89
[14] Arzoumanidis Gregory G., Rauch Frank C., Aromatic amines from carboxylic acid and ammonia: A homogeneous catalytic process, J. Org. Chem., 1981, 46(19), 3930-3932
[15] Rauch Frances C., Arzoumanidis Gregory G., Aromatic and heterocylic amines from aromatic or hetercyclic acids, Ger. Often. 2,258,227, 1973
[16] Rauch Francis C., Arzoumanidis Gregory G., Catalytic production of aniline and other amines from carboxylic acids and ammonia, U.S. 3,812,137, 1974
[17] Hiroshi Yamamoto, Kazuo Yamaguchi, Bunzo Sekine, Yoshio Kawamura, 3,4-Dimethylaniline, Japan 9070, 1957
[18] R. N. Keller, Peter A. S. Smith, Direct aromatic amination: New reaction of hydroxylamine-O-sulfonic acid, J. Am. Chem. Soc., 1944, 66, 1122-1124
[19] Takeuchi Hiroshi, Adachi Taki, Nishiguchi Hideaki, Itou Katsutaka, Koyama Kikuhiko, Direct aromatic amination by azides: reactions of hydrazoic acid and butyl azides with aromatic compounds in the presence of both trifluoromethanesulfonic acid and trifluoroacetic acid, J. Chem. Soc., Perkin Trans.1, 1993, (7), 867-870
[20] Hwu Jih Ru, Wong Fung Fuh, Shiao Min Jen, Reduction of aromatic nitro compounds to aromatic amines by sodium trimethylsilanethiolate, J. Org. Chem., 1992, 57(19), 5254-5255
[21] Brinkman Herbert R., Miles William H., Hilborn Michael D., Smith Michael C., The Reduction of Nitrobenzenes by Triethylsilane using Wilkinson's catalyst, Synth. Commun., 1996, 26(5), 973-980
[22] He Yun, Zhao He, Pan Xinfu, Wang Shaofei, Reduction with metal borohydride-transition metal salt system: Ⅰ. Reduction of aromatic nitro compounds with potassium borohydride-copper(Ⅰ) chloride, Synth. Commun., 1989, 19(17), 3047-3050
[23] Manabe Osamu, Hirashima Tsuneaki, Reduction of aromatic nitro compounds, Japan Kokai 76,125,027, 1976
[24] Hirashima Tsuneaki, Manabe Osamu, Catalytic reduction of aromatic nitro
compounds with hydrazine in the presence of iron(Ⅲ) chloride and active carbon, Chem. Lett., 1975, (3), 259-260
[25] Braeuniger Harold, Kleinschmide E. G., Bromination with N-bromosuccinimide. Ⅰ. General preparation of 5,6-dimethylbenzimidazole and bromination with N-bromosuccinimide.,Pharmazie, 1969, 24(1), 24-28
[26] Saha Chitta R., Bhattacharya Somnath, Reduction of nitroaromatics with poly(vinytpyridine)complexes of palladium(Ⅱ) and platinum(Ⅱ), J. Chem. Technol. Biotechnol., 1987, 37(4), 233-245
[27] Knifton John E, Suggitt Robert M., Homogeneous catalysts usful in the reduction of nitroaromatics to amines, U.S. 3,832,401, 1974
[28] Knifton John Frederick, Suggitt Robert Murray, Catalytic reduction of aromatic nitro compounds, Ger. Often. 2,210,564, 1972
[29] Tarabrin M. B., Styskin E. L., Kosoglyad A. I., Sarycheva I. K., Bulychev E. Yu, Evstigneeva R. P., Synthesis and analysis of a mixture of isomeric xylidines, Khim. -Farm.Zh, 1976, 10(2), 120-121
[30] Knifton John F., Suggitt Robert M., Homogeneous ruthenium catalysts useful in the selective reduction of nitroaromatics to amines, U.S. 3,906,045,1975
[31] Lee Irvin Smith, J. W. Opie, The chemistry of vitaminE. Ⅹ Ⅹ Ⅷ.Synthesis of the three dimethylethylquinones, J. Org. Chem., 1941,6, 427-436
[32] E.Harold Farmer, Donald A. Sutton, Course of autoxidation reactions in polyisoprenes and allied compounds. Ⅺ. Double bond movement during the autoxidation of a monoolefin, J. Chem. Soc., 1946, 10-13
[33] 章思规，辛忠，精细有机化工制备手册，北京，科学技术文献出版社，1994
[34] 唐培堃，中间体化学及工艺学，北京，化学工业出版社，1984
[35] 孙荣康，魏运洋，硝基化合物炸药化学与工艺学，北京，兵器工业出版社，1992
[36] H．福伊尔，硝基和亚硝基化学，北京，国防工业出版社，1988
[37] Urbanski T., Chemistry and Technology of Explosives(Vol.4), Oxford, Pergamn
Pr, 1984
[38] Harris G. E P., Isomer control in the mononitration of toluene and Control of isomer ratio in the dinitration of toluene, ACS Symposium Ser., 1976, 22, 300-312, 313-319
[39] Coon Clifford L., Blucher William G., Hill Marion E., Aromatic nitration with nitric acid and trifluoromethanesulfonic acid, J. Org. Chem., 1973, 38(25), 4243-4248
[40] Goddard D. R., Hughe E. D., Ingold C. K., Chemistry of nitronium salts. Ⅰ. Isolation of some nitronium salts, J. Chem. Soc., 1950, 2559-2575
[41] Ishizuka Yoriyasu, 4-nitro-o-xlyene, Japan 71 24,690, 1971
[42] Neumann Karl Heinz, Fiege Helmut, Production of 4-nitro-o-xylene, Ger. Often. DE 19,702,432, 1998
[43] Fujiwara Ryozo, Nitta Kazunari, 4-Nitro-o-xylene, Japan 72 47,370, 1972
[44] Rauch E C., Blanc G. M., Fanelli A. J., Selective nitration: the catalyzed nitration of o-xylene in the presence of Hg(Ⅱ) salts, Appl. Catal., 1984, 9(1), 63-67
[45] Rauch Francis C., Fanelli Anthony J., Blank Gerlinde M., Levy Stephen David, Mononitration of o-xylene, Ger. Often. 2,525,374, 1976
[46] Olah George A.,Narang Subhash C., Synthetic methods and reactions. 49. Perfluorinated resinsulfonic acid (Nation-H) catalyzed nitration of aromatic compounds with butyl nitrate, Synthesis, 1978, (9), 690-691
[47] Olah George A., Malhotra Ripudaman, Narang Subhash C., Aromatic substitution. 43. Perfluorinated resinsulfonic acid catalyzed nitration of aromatics, J. Org. Chem., 1978, 43(24), 4628-4630
[48] Olah George A., Krishnamurthy V. V., Narang Subhash C., Aromatic substitution. 50. Mercury(Ⅱ)-promoted azeotropic nitration of aromtics over Nafion-H solid superacidic catalyst, J. Org. Chem., 1982, 47(3), 596-598
[49] Kameo Takashi, Hirashima Tsuneaki, Manabe Osamu, Studies on nitration of aromatic compounds. Ⅵ. Nitration of substituted benzenes with nitric acid in the presence of ion-exchange resins, Nippon Kagaku Kaishi, 1983, (3), 414-419
[50] Smith Keith, Musson Adam, Deboos Gareth A., A novel method for the nitration of simple aromatic compounds, J. Org. Chem., 1998, 63(23), 8448-8454
[51] Milczak Tomasz, Jacniacki Jaroslaw, Zawadzki Janusz, Malesa Monika, Skupinski Wincenty, Nitration of aromatic compounds on solid catalysts, Synth. Commun., 2001, 31(2), 173-187
[52] Milligan, Barton, Miller, Donald G., Selective nitration of aromatic and substituted aromatic compositions, U.S.3,957,889, 1976
[53] Tasneem, M. M. Ali, K. C. Rajanna, P. K. Saiparakash, Ammonium nickel sulphate mediated nitration of aromatic compounds with nitric acid, Synth. Commun., 2001, 31(7), 1123-1127
[54] L．F．奥尔布赖特，C．汉森，工业与实验室硝化，北京，化学工业出版社，1984
[55] Myhre Philip C., Nitro group migrations during aromatic nitration, J. Amer. Chem. Soc., 1972, 94(22), 7921-7923
[56] 申凯华，刘平芹，李宗石，液相催化加氢制芳胺的研究与应用，染料工业，1999，36(6)，18-21
[57] 唐培堃，精细有机合成化学及工艺学，天津，天津大学出版社，1993
[58] 金松寿等，有机催化，上海，上海科学技术出版社，1986
[59] 钟邦克，精细化工过程催化作用，北京，中国石化出版社，2002
[2] V. M. Berezovskii, Trudy Vsesoyuz, Chemical studies in the field of vitaminB, Nauch. Issledovatel. Vitamin. Inst., 1954, 5, 12-17
[3] P. Karrer, B. Becker, E Benz, P. Frei, H. Salomon, K. Schopp, Synthesis of lactoflavin, Helv. Chim. Acta., 1935, 18, 1435-1448
[4] Robert C. Weast, Jeanette G. Grasselli, CRC Handbook of Data on Organic Compounds, 2nd edition, CRC Press. Inc., 1989
[5] 徐克勋，精细有机化工原料及中间体手册，化学工业出版社，1998
[6] Manabe Osamu, Nara Kenichi, Aromatic amines, Ger. Often. 2,165,456, 1972
[7] Nara Kenichi, Manabe Osamu, amination of aromatic compounds Ⅰ. Aminations of aromatic sulfonates with sodium amide, Nippon Kayaku Kaishi, 1974, (8), 1522-1525
[8] Yu. P. Sobolev, V. M. Berezovskii, 3,4-Xylidine, U.S.S.R. 118,129, 1959
[9] Yoshikazu Sahashi, Hiroshi Akamatsu, Hidesaburo Genda, Synthesis of flavin from various materials Ⅰ. Synthesis of D-araboflavin from p-nitrotoluene, Proc. Imp. Acad.(Tokyo), 1945, 21, No.1, 44-52
[10] Keiichi Sahashi, Xylidine from the condensation of bis(chloromethyl)ether and nitrotoluene, Japan 172,795, 1946
[11] W. A. Wisansky, S. Ausbacher, Preparation of 3,4-dimethylaniline, J. Am. Chem. Soc., 1941, 63, 2532
[12] W. A. Wisansky, S. Ausbacher, 3,4-Dimethylailine, Org. Syntheses, 1948, 28, 46-48
[13] Veksher M. A., Shersherskii A. A., Shentsis I. E., Mathematical description of the 3,4-Xylidine production process, Khim. -Farm. Zh, 1982, 16(1), 86-89
[14] Arzoumanidis Gregory G., Rauch Frank C., Aromatic amines from carboxylic acid and ammonia: A homogeneous catalytic process, J. Org. Chem., 1981, 46(19), 3930-3932
[15] Rauch Frances C., Arzoumanidis Gregory G., Aromatic and heterocylic amines from aromatic or hetercyclic acids, Ger. Often. 2,258,227, 1973
[16] Rauch Francis C., Arzoumanidis Gregory G., Catalytic production of aniline and other amines from carboxylic acids and ammonia, U.S. 3,812,137, 1974
[17] Hiroshi Yamamoto, Kazuo Yamaguchi, Bunzo Sekine, Yoshio Kawamura, 3,4-Dimethylaniline, Japan 9070, 1957
[18] R. N. Keller, Peter A. S. Smith, Direct aromatic amination: New reaction of hydroxylamine-O-sulfonic acid, J. Am. Chem. Soc., 1944, 66, 1122-1124
[19] Takeuchi Hiroshi, Adachi Taki, Nishiguchi Hideaki, Itou Katsutaka, Koyama Kikuhiko, Direct aromatic amination by azides: reactions of hydrazoic acid and butyl azides with aromatic compounds in the presence of both trifluoromethanesulfonic acid and trifluoroacetic acid, J. Chem. Soc., Perkin Trans.1, 1993, (7), 867-870
[20] Hwu Jih Ru, Wong Fung Fuh, Shiao Min Jen, Reduction of aromatic nitro compounds to aromatic amines by sodium trimethylsilanethiolate, J. Org. Chem., 1992, 57(19), 5254-5255
[21] Brinkman Herbert R., Miles William H., Hilborn Michael D., Smith Michael C., The Reduction of Nitrobenzenes by Triethylsilane using Wilkinson's catalyst, Synth. Commun., 1996, 26(5), 973-980
[22] He Yun, Zhao He, Pan Xinfu, Wang Shaofei, Reduction with metal borohydride-transition metal salt system: Ⅰ. Reduction of aromatic nitro compounds with potassium borohydride-copper(Ⅰ) chloride, Synth. Commun., 1989, 19(17), 3047-3050
[23] Manabe Osamu, Hirashima Tsuneaki, Reduction of aromatic nitro compounds, Japan Kokai 76,125,027, 1976
[24] Hirashima Tsuneaki, Manabe Osamu, Catalytic reduction of aromatic nitro
compounds with hydrazine in the presence of iron(Ⅲ) chloride and active carbon, Chem. Lett., 1975, (3), 259-260
[25] Braeuniger Harold, Kleinschmide E. G., Bromination with N-bromosuccinimide. Ⅰ. General preparation of 5,6-dimethylbenzimidazole and bromination with N-bromosuccinimide.,Pharmazie, 1969, 24(1), 24-28
[26] Saha Chitta R., Bhattacharya Somnath, Reduction of nitroaromatics with poly(vinytpyridine)complexes of palladium(Ⅱ) and platinum(Ⅱ), J. Chem. Technol. Biotechnol., 1987, 37(4), 233-245
[27] Knifton John E, Suggitt Robert M., Homogeneous catalysts usful in the reduction of nitroaromatics to amines, U.S. 3,832,401, 1974
[28] Knifton John Frederick, Suggitt Robert Murray, Catalytic reduction of aromatic nitro compounds, Ger. Often. 2,210,564, 1972
[29] Tarabrin M. B., Styskin E. L., Kosoglyad A. I., Sarycheva I. K., Bulychev E. Yu, Evstigneeva R. P., Synthesis and analysis of a mixture of isomeric xylidines, Khim. -Farm.Zh, 1976, 10(2), 120-121
[30] Knifton John F., Suggitt Robert M., Homogeneous ruthenium catalysts useful in the selective reduction of nitroaromatics to amines, U.S. 3,906,045,1975
[31] Lee Irvin Smith, J. W. Opie, The chemistry of vitaminE. Ⅹ Ⅹ Ⅷ.Synthesis of the three dimethylethylquinones, J. Org. Chem., 1941,6, 427-436
[32] E.Harold Farmer, Donald A. Sutton, Course of autoxidation reactions in polyisoprenes and allied compounds. Ⅺ. Double bond movement during the autoxidation of a monoolefin, J. Chem. Soc., 1946, 10-13
[33] 章思规，辛忠，精细有机化工制备手册，北京，科学技术文献出版社，1994
[34] 唐培堃，中间体化学及工艺学，北京，化学工业出版社，1984
[35] 孙荣康，魏运洋，硝基化合物炸药化学与工艺学，北京，兵器工业出版社，1992
[36] H．福伊尔，硝基和亚硝基化学，北京，国防工业出版社，1988
[37] Urbanski T., Chemistry and Technology of Explosives(Vol.4), Oxford, Pergamn
Pr, 1984
[38] Harris G. E P., Isomer control in the mononitration of toluene and Control of isomer ratio in the dinitration of toluene, ACS Symposium Ser., 1976, 22, 300-312, 313-319
[39] Coon Clifford L., Blucher William G., Hill Marion E., Aromatic nitration with nitric acid and trifluoromethanesulfonic acid, J. Org. Chem., 1973, 38(25), 4243-4248
[40] Goddard D. R., Hughe E. D., Ingold C. K., Chemistry of nitronium salts. Ⅰ. Isolation of some nitronium salts, J. Chem. Soc., 1950, 2559-2575
[41] Ishizuka Yoriyasu, 4-nitro-o-xlyene, Japan 71 24,690, 1971
[42] Neumann Karl Heinz, Fiege Helmut, Production of 4-nitro-o-xylene, Ger. Often. DE 19,702,432, 1998
[43] Fujiwara Ryozo, Nitta Kazunari, 4-Nitro-o-xylene, Japan 72 47,370, 1972
[44] Rauch E C., Blanc G. M., Fanelli A. J., Selective nitration: the catalyzed nitration of o-xylene in the presence of Hg(Ⅱ) salts, Appl. Catal., 1984, 9(1), 63-67
[45] Rauch Francis C., Fanelli Anthony J., Blank Gerlinde M., Levy Stephen David, Mononitration of o-xylene, Ger. Often. 2,525,374, 1976
[46] Olah George A.,Narang Subhash C., Synthetic methods and reactions. 49. Perfluorinated resinsulfonic acid (Nation-H) catalyzed nitration of aromatic compounds with butyl nitrate, Synthesis, 1978, (9), 690-691
[47] Olah George A., Malhotra Ripudaman, Narang Subhash C., Aromatic substitution. 43. Perfluorinated resinsulfonic acid catalyzed nitration of aromatics, J. Org. Chem., 1978, 43(24), 4628-4630
[48] Olah George A., Krishnamurthy V. V., Narang Subhash C., Aromatic substitution. 50. Mercury(Ⅱ)-promoted azeotropic nitration of aromtics over Nafion-H solid superacidic catalyst, J. Org. Chem., 1982, 47(3), 596-598
[49] Kameo Takashi, Hirashima Tsuneaki, Manabe Osamu, Studies on nitration of aromatic compounds. Ⅵ. Nitration of substituted benzenes with nitric acid in the presence of ion-exchange resins, Nippon Kagaku Kaishi, 1983, (3), 414-419
[50] Smith Keith, Musson Adam, Deboos Gareth A., A novel method for the nitration of simple aromatic compounds, J. Org. Chem., 1998, 63(23), 8448-8454
[51] Milczak Tomasz, Jacniacki Jaroslaw, Zawadzki Janusz, Malesa Monika, Skupinski Wincenty, Nitration of aromatic compounds on solid catalysts, Synth. Commun., 2001, 31(2), 173-187
[52] Milligan, Barton, Miller, Donald G., Selective nitration of aromatic and substituted aromatic compositions, U.S.3,957,889, 1976
[53] Tasneem, M. M. Ali, K. C. Rajanna, P. K. Saiparakash, Ammonium nickel sulphate mediated nitration of aromatic compounds with nitric acid, Synth. Commun., 2001, 31(7), 1123-1127
[54] L．F．奥尔布赖特，C．汉森，工业与实验室硝化，北京，化学工业出版社，1984
[55] Myhre Philip C., Nitro group migrations during aromatic nitration, J. Amer. Chem. Soc., 1972, 94(22), 7921-7923
[56] 申凯华，刘平芹，李宗石，液相催化加氢制芳胺的研究与应用，染料工业，1999，36(6)，18-21
[57] 唐培堃，精细有机合成化学及工艺学，天津，天津大学出版社，1993
[58] 金松寿等，有机催化，上海，上海科学技术出版社，1986
[59] 钟邦克，精细化工过程催化作用，北京，中国石化出版社，2002