新型吡咯类农药溴虫腈的合成研究
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摘要
溴虫腈是20世纪后期出现的一种新型的芳基吡咯类杀虫、杀螨剂，其作用机制新颖，具有杀虫谱广，低毒，高效等特点
本文重点研究了溴虫腈及其中间体的合成。合成出中间体对氯苯甘氨酸、4-(对-氯苯基)-2-三氟甲基-3-恶唑-5-酮、2-(对-氯苯基)-5-三氟甲基吡咯-3-腈、4-溴-2-(对-氯苯基)-5-三氟甲基吡咯-3-腈和目标产物溴虫腈，并对其结构进行了表征。
本文通过查阅大量的文献，对杀虫剂溴虫腈的多种合成路线进行了较深入的比较研究，重点研究了由对氯苯甲醛为起始原料，经Bucherer-Bergs反应、环加成、溴化、烷基化后得到溴虫腈的方法，并得出较佳的合成工艺条件。
在制备对氯苯甘氨酸的过程中，有大量的红色油状物质生成，经大量的实验得出了减少红色油状物出现的优惠工艺条件，红色油状物的分离与否对收率没有影响。制备4-(对-氯苯基)-2-三氟甲基-3-(口恶)唑-5-酮时，可进行简单的处理后直接进行下一步反应，为工业化连续生产溴虫腈提供了可靠的实验数据。
The chlorfenapyr is part of one kind of arylpyrrole pesticide acariasis and has'
primarily pesticide properties.
In this paper,the study of preparation for chlorfenapyr and its intermidates is emphaticallydiscussed.The intermidates of p-chlorophenylglycine, 4-(p-chlorophenyl) 2-trifluoromethyl-3-oxazolin-5-one,2-(p-chlorophenyl)-5-(trifluoromethyl)pyrrole3-carb onitrile, 4-bromo-2-(p-chlorophenyl)- 5-(trifluoromethyl)pyrrole-3-carbonitrile and chlorfenapyr are synthesized and their compounds'structure are characterized.
In this paper,Several methods are elaborated for the synthesis of chlorfenapyr, corresponding methods are emphatically discussed . Corresponding methods are.begined with p-chlorophenylglycine,proceeding from Bucherer-Bergs reaction bromate reaction and obtaining better ways to stnthesize chlorfenapyr at last.
According to these results, with corresponding methods, by-product happening during preparing p-chlorophenylglycine was inquired and producing p-chlorophenylglycine with coherent methods was discussed and 6btaining better process to prevent red oily compound from happening.. This has given a strating point for industrial applying. The separate or not is not effect the yield of p-chlorophenylgly cine. Preparing 4-(p-chlorophenyl)-2-trifluoromethyl-3-oxazolin-5-one can simply disposed and be directly used the next reaction.This provide the reliable data for the industry.
本文重点研究了溴虫腈及其中间体的合成。合成出中间体对氯苯甘氨酸、4-(对-氯苯基)-2-三氟甲基-3-恶唑-5-酮、2-(对-氯苯基)-5-三氟甲基吡咯-3-腈、4-溴-2-(对-氯苯基)-5-三氟甲基吡咯-3-腈和目标产物溴虫腈，并对其结构进行了表征。
本文通过查阅大量的文献，对杀虫剂溴虫腈的多种合成路线进行了较深入的比较研究，重点研究了由对氯苯甲醛为起始原料，经Bucherer-Bergs反应、环加成、溴化、烷基化后得到溴虫腈的方法，并得出较佳的合成工艺条件。
在制备对氯苯甘氨酸的过程中，有大量的红色油状物质生成，经大量的实验得出了减少红色油状物出现的优惠工艺条件，红色油状物的分离与否对收率没有影响。制备4-(对-氯苯基)-2-三氟甲基-3-(口恶)唑-5-酮时，可进行简单的处理后直接进行下一步反应，为工业化连续生产溴虫腈提供了可靠的实验数据。
The chlorfenapyr is part of one kind of arylpyrrole pesticide acariasis and has'
primarily pesticide properties.
In this paper,the study of preparation for chlorfenapyr and its intermidates is emphaticallydiscussed.The intermidates of p-chlorophenylglycine, 4-(p-chlorophenyl) 2-trifluoromethyl-3-oxazolin-5-one,2-(p-chlorophenyl)-5-(trifluoromethyl)pyrrole3-carb onitrile, 4-bromo-2-(p-chlorophenyl)- 5-(trifluoromethyl)pyrrole-3-carbonitrile and chlorfenapyr are synthesized and their compounds'structure are characterized.
In this paper,Several methods are elaborated for the synthesis of chlorfenapyr, corresponding methods are emphatically discussed . Corresponding methods are.begined with p-chlorophenylglycine,proceeding from Bucherer-Bergs reaction bromate reaction and obtaining better ways to stnthesize chlorfenapyr at last.
According to these results, with corresponding methods, by-product happening during preparing p-chlorophenylglycine was inquired and producing p-chlorophenylglycine with coherent methods was discussed and 6btaining better process to prevent red oily compound from happening.. This has given a strating point for industrial applying. The separate or not is not effect the yield of p-chlorophenylgly cine. Preparing 4-(p-chlorophenyl)-2-trifluoromethyl-3-oxazolin-5-one can simply disposed and be directly used the next reaction.This provide the reliable data for the industry.
引文
[1] 唐触痴等编著，《农药化学》，南开大学，1998．
[2] 冯坚译，2001年全球农药市场令人沮丧，农药快讯，2002，(7)：31.。
[3] 徐苏酩．磷化氢熏杀剂对贮藏农产品的影响．农药译丛，1996，18(4)：58-59．
[4] 胡世华．农业害虫的综合防治．四川环境．1995，14(3)：70-74．
[5] 张延坤，刘国中．杀虫剂及其在家庭与环境卫生害虫防治中的应用．日用化学品工业，2000．5期．
[6] 中山医学院．药理学．北京：人民卫生出版社，1981，140-142．
[7] 张一宾．杀虫剂的特性及其应用上的问题．农药译丛．1997，19(5)：1-6．
[8] 南开大学元素有机化学研究所编译，国外农药进展，化学工业出版社，1987．
[9] 罗万春，慕立义．杀虫剂现状及发展前景。农药1997，36(9)：10-12．
[10] 张一宾．对中国农药发展之浅见．农药．1999，37(5)：1-2．
[11] 程铸生主编．《精细化学品化学》．华东理工大学出版社．1996．
[12] 贺红武．新农药创制途经及研究．湖北化工．1996年增刊．
[13] 赵国锋，等．有机磷生物活性物质研究进展(上)农药译丛．1996，18(4)：1-7．
[14] 王晓光，李海屏．我国高毒有机磷替代品种开发进展．农药，2001，40(2)：10-13．
[15] 扬春河．害虫化学防治农用杀虫剂的进展．农药译丛，1996，18(1)：1-5．
[16] 徐尚成，蒋木庚．吡咯类农药活性化合物的研究进展．农药学学报．2002，4(2)：1-8。
[17] Copping L G.,Menn J J. Biopesticides:a review of their action, application and efficacy. Pest Manag Sci, 2000,56:651-676.
[18] 张仲贞，张一丙．含吡咯环农药的研究开发概述．上海化工．2001，5：19-22．
[19] 刘长令．含氟农药的创制途径．农药．1998，37(8)：1-5．
[20] 徐尚成．烟碱类杀虫剂的研究与开发进展．精细与专用化学品，2001，9(5)：3-5．
[21] 屠豫钦．天然源农药的研究利用—机遇与挑战．世界农药，199，，21(4)：4-12．
[22] the Pesticide Manual. 11th ed. 1997, 209.
[23] 周善波，张海．从溴从腈的结构来探讨型杀虫剂创新思路．上海化工．2000，5：17-19．
[24] 张仲贞，张一丙．含吡咯环农药的研究开发概述．上海化工，2001，1：19-22．
[25] 田伟生，罗雍容，陈毓群．中国化学通讯，1991，2(3)：217-220．
[26] 田伟生，罗雍容，陈毓群．CN1074439．
[27] 田伟生，罗雍容，陈毓群．化学学报，1994，52：1126-1132．
[28] Cater, G., Neitsche, J., Goodman, J., Torray, M., Dunn, T., Borders, D..Antibiotics. 1982, 40: 233-236.
[29] 张芝平．吡咯类杀虫剂的构效关系和作用机理研究．世界农药，1999，21(6)：12-16．
[30] 李再峰．杀虫剂结构与昆虫抗药性．宁夏农学院学报．1994，15(1)：71-74．
[31] Lovell J B, Wright D P, Gard I E, etal. AC303630 Aninsecticide/acaricide from a novel class of chemistry. Brighton Corp Prot. Conf-pest and Dieases. Brighton:British Crop Prot Council, 1990,1:41-45.
[32] J.B.Lovell, D.P.Wright. AC303630—一种新型杀虫、杀螨剂．农药译丛．1992，14(6)：57-59．
[33] 陶贤鉴，谭本祝．新农药AC303630的合成与应用．农药译丛 1998，20(5)：15-17．
[34] 谭本祝．含氟杀虫剂溴虫腈的合成．1999，38(12)：7-9．
[35] AU TSIEN MING (SG); CHIA YAN WAH.RF identification transponder US5945938.1999-8-31.
[36] FARLOW ROBERI A(US); REID BYRON L. Arylpyrroles for subterranean termite control.US6071951.2000-6-6.
[37] Addor R., Brown D., Babcock T In Synthesis and Chemistry of Agrochemicals. 1192: 283-97.
[38] David G.kuhnt, Victor M.Kamhi, Joseph A.Furch..The Synthesis of Pyrroles with Insecticidal.Pestic.sci..1994, 41: 279-286.
[39] FARLOW ROBERT A(US); REID BYRON L. Arylpyrroles for subterranean termite control. US6071951.2000-6-6.
[40] KAMESWARAN VENKATARAMAN . Process for the manufacture of2-aryl-5-perfluoroalkylpyrrole derivatives and intermediates useful therefore.US5750726． 1998-5-12．
[41] BROWN DALE G (US); SIDDENS JACK K (US); DIEHL ROBERT E (US); WRIGHT JR DONALD P .Arylpyrrole insecticidal acaricidal and nematicidal agents and methods for the preparation thereof. US5010098． 1991-4-23．
[42] 何玉仙，杨秀娟．10％除尽防治甜菜夜蛾和小菜蛾．PESTICIDES．1999，38(9) ： 18-19．
[43] 陈修会，陈振峰．除尽等农药防治茶树甜菜夜蛾药效试验．农药．2001，40(4) ： 27．
[44] Kameswaran. Synthesis of 2-aryl-5-trifluoromethyl)Pyrroces useful as spesticical agents and as intermediates for the preparation of said agents. US:5128485, 1992-7-7．
[45] KAMESWARAN VENKATARAMAN; BARTON JERRY MICHAEL . PROCESS FOR THE MANUFACTURE OF PESTICIDAL 1-(ALKOXYMETHYL) PYRROLE COMPOUNDS US:5151536． 1992-6-24．
[46] Venkataraman Kameswaran, Princton Junction,N.J ..Method for the preparation of 2-aryl-5-trifluoromethylpyrrole compoundes. US:5256796． 1992-12-11．
[47] Kameswaram, Process for the manufacture of pesticidal 1-(alkoxymethyl)p pyrrole compounds .EP:0492171A1． 1992-6-24．
[48] Kameswaram, venkataraman.2-aryl-5-(trifluorornethyl)-2-pyrroline compounds and process for the manufacture of insecticidal. EP:0492171A1． 1992-1-7．
[49] RoberetF. Doehner, Jr.; Jerry M. Barton, David G.Kuhn,newtown,Pa.. 2-aryl-5-(trifluoromethyl)-2-pyrroline compounds useful in the manufacture of insecticidal, nematocidal and acaricidal arylpyrroles.US:5118816． 1990-12-26．
[50] DOEHNER JR ROBERT F; BARTON JERRY M (US); KUHN DAVID G 2-aryl-5-(trifluoromethyl)-2-pyrroline compounds useful in the manufacture of insecticidal, nematocidal and acaricidal arylpyrrolesUS:5288901． 1994．
[51] DOEHNER JR ROBERT F (US); KAMESWARAN VENKATARAMAN Process for the manufacture of insecticidal2-aryl-1insecticidal2-aryl-1-(al koxymethyl)-4-halo-5-(triflu
oromethyl)pyrrolesUS:5194630． 1993-3-16．
[52] Venkataraman Kameswaran, Princton Junction, N.J .Synthesis of 2-aryl-5-(trifluoromethyl)pyroles useful as pesticidal agents and as intermediates for the preparation of said agents. US:5128485． 190-12-17．
[53] Roberet F. Doehner,Jr.,Eastwindsor,N.J..Process for the preparation of 2-aryl-l-substitted-5-(trifluoromethyl)pyrrole compounds useful as insecticidal and nematocidal agents and as intermediates for the manfacture of said agents. US:5144041． 1992-3-20．
[54] 陶贤签，谭本祝．含氟杀虫剂的制备．湖南化工．2000，30(5) ：29-31．
[55] Robert F. Doehner, Jr.; Jerry M.Barton; David GKuhn,Newtown. 2-Aryl-5-(trifluoromethyl)-2-pyrroline compounds useful in the manufacture of insecticidal and acaricidal arylpyrroles. US:5288901． 1992-4-8．
[56] Venkataraman Kameswaran, Princton Junction,N.J; Jerry M.Barton,East Windsor,N.J.Process for the manufature of pesticidal 1-(alkoxymethyl)pyrrle compounds.US:5151536． 1990-12-7．
[57] Venkataraman Kameswaran, Princton Junction,N.J. Ammonium oxazole and amino oxazolium intermediates,methods for the preparation thereof and the use thereof in the manufacture of insecticidal arylpyrroles. US:5925773． 1997-6-27．
[58] Venkataraman Kameswaran, Princton Junction,N.J. Oxazole amines as intermediates in the manufacture of insecticidal pyrroles. US:5631379． 1997-3-20．
[59] DOEHNER JR ROBERT F. Process for the preparation of 2-aryl-1-substituted-5-(trifluoromethyl) pyrrole compounds useful as insecticidal, acaricidal and nematocidal US :5144041． 1992-9-1．
[60] Venkataraman Kameswaran, Princton Junction,N.J. Perfluoroalkanoyl aminonttriles. US:5426225． 1995-6-20．
[61] KING STEPHEN WAYNE. Reductive amination catalystsUS:5750790． 1998-5-12．
[62] ADDOR ROGER W (US); FURCH JOSEPH A (US); KUHN DAVID G .Process for the preparation of insecticidal, acaricidal and nematicidal 2-aryl-5-(trifluoromethyl) pyrrole compoundsUS:5030735． 1991-7-9．
[63] KAMESWARAN VENKATARAMAN .Method for the preparation of
2-aryl-5-trifluoromethylpyrrole compounds.US:5256796． 1993-10-26．
[64] RobertF.Doehner,E.Windsor,N. J.; Jerry M.Barton,Langhorne,Pa.. Alkoxymethylation of pyrroles.US:5359090． 1993-12-29．
[65] KNAPP JR PAUL W .Manufacture of 4-aryl-2-perfluoroalkyl-3-oxazolin-5-one from arylglycine. US5453508． 1995-9-26．
[66] 田伟生，罗雍容．从容易制备的三氟甲基恶唑酮直接合成三氟甲基吡咯及其 有关化合物．化学学报．1994，52：1126-1132．
[67] 田伟生，罗雍容，陈敏毓．一种从三氟甲基恶唑酮合成三氟甲基吡咯类化合 物的方法．CN：1074439A．1993-7-21．
[68] DOEHNER JR ROBERT F (US); KAMESWARAN VENKATARAMAN .Process for the manufacture of insecticidal 2-aryl-1-(alkoxymethyl)-4-halo-5-(trifluoromethyl)pyrroles US:5194630． 1993-3-16．
[69] YAMASAKI TETSURO (JP); KUMOBAYASHI HIDENORI (JP); SAYO NOBORU (JP); MURAYAMA TOSHIYUKI (JP); SANO NOBORU (JP); ISHIZAKI TAKERO. Process for producing optically active diaminohexanone derivative. US:5631397． 1997-5-20．
[70] Venkataraman Kameswaran,Princton Junction; N.J. Precess for the manufacture of 2-aryl-5-perfluoroalklpyrrole derivatives. US:5777132． 1998-7-7．
[71] KAMESWARAN VENKATARAMAN.N-(arylmethylene)-1-chloro-1-(perfluoroalkyl) methylamine compounds.US6034273． 2000-3-7．
[72] KAMESWARAN VENKATARAMAN .Perfluoroalkanoyl aminonitrilesUS5426225． 1995-6-20．
[73] KAMESWARAN VENKATARAMAN Ammonium oxazole and amino oxazolium intermediates, methods for the preparation thereof and the use thereof in the manufacture of insecticidaUS5925773． 1999-7-20．
[74] KAMESWARAN VENKATARAMAN PROCESS FOR THE PREPARATION OF INSECTICIDAL,NEMATICIpAL AND ACARICIDAL4-SUBSTITUTED-5-METHYL)PYRROLE-3-CARBONITRILE COMPOUNDS.US5106985． 1992-5-20．
[75] KAMESWARAN VENKATARAMAN .Process for the preparation of insecticidal, acaricidal and nematicidal 2-aryl-3-substituted-5-(trifluoromethyl)pyrrole compounds. US5225568． 1993-7-6．
[76] Venkataraman Kameswaran, Princton Junction; N.J. Process for the preparation of 2-aryl-5-(perfluoro-alkyl)pyrrole compounds from N-arylimidoyl chlorode compounds. US:5817834.1998-2-9.
[77] Venkataraman Kameswaran, Trenton, N.J.. Precess for the preparation of 2-aryl-5-(perfpluoroalkyl)pyrrole compounds from N-(perfiuorothyl)arylimidoyl alkylme chloride compounds. US:5965773.1999-10-12.
[78] Venkataraman Kameswaran,Princton Junction; N.J.; David G.Kuhn,Newtown, Pa..Process for the manufacture of insecticidal, nematicidal and acaricidal 2-aryl-3-substitued-5-(trifluoromethyl)pyrrle compounds from N-(substitutedbenzl)-2,2,2-trifluoro-acetimidoylchloride compounds. US:5145986.1992-9-8.
[79] KAMESWARAN VENKATARAMAN PROCESS FOR THE PREPARATION OF INSECTICIDAL, NEMATICIDAL AND ACARICIDAL 4-SUBSTITUTED-5-(TRIFLUOROMETHYL)PYRROLE-3-CARBONITRILE COMPOUNDS. US5106985.1992-5-20.
[80] 俞凌翀．有机化学中的人名反应．北京科学出版社．1984：326．
[81] Edward L. COMPERE, Jr., David A. WEINSTEIN. Synthesis of α-Aminoarylacetic Acids from Bromoform, Aryaldehydes, and Ammonia, with Potassium Hydroxide/Lithium Amid Cmbination as Catalyst. SYNTHESIS. 1977(852-853).
[82] Kazuo Matsumoto.A New Synthesis of α-Amino Acids. J.Org. Chem., 1973, 88(11): 45-49.
[83] 王素青．芳基甘氨酸的不对称合成．北京师范大学学报．1994，30(3)．
[84] 李记太，李立军，张能芳，李慧章．DL-α-苯甘氨酸合成方法的改进．合成化学(HECHENGHUAXUE) 1997，5(2)
[85] 李记太，张能芳，李慧章．DL-α-苯甘氨酸合成的合成研究．河北大学学报 1994，14(4)：74-77．
[86] 俞凌翀．有机化学中的人名反应．北京科学出版社．1984，86．
[87] 俞凌翀．有机化学中的人名反应．北京科学出版社．1984，592-594．
[88] Kobayashi Y., Kamadaki I..Tetrahedron Lett., 1982, 3929. 2 Kobayashi Y., Kamadaki I., OhsawaA..Chem. Pharm. Bull., 1978, 26: 1247.
[89] 胡卫国．温度对合成甘氨酸反应的影响．化学世界，2001年4期．p189-191．
[90] 温辉梁，刘崇波，邓瑞红，等．一种高产率制备甘氨酸的方法．南昌大学学报 2000，24(3)：295-297．
[91] 正交试验法．中国科学院数学研究所数理统计组编．人民教育出版社．
[92] 史达清，周龙虎．溴代反应中的选择性溴化剂．化学试剂．1995，17(4)：345-350．
[93] 董志超．N-取代吡咯的简便合成方法．中国医药工业杂志．1996，27(6)：268-269．
[2] 冯坚译，2001年全球农药市场令人沮丧，农药快讯，2002，(7)：31.。
[3] 徐苏酩．磷化氢熏杀剂对贮藏农产品的影响．农药译丛，1996，18(4)：58-59．
[4] 胡世华．农业害虫的综合防治．四川环境．1995，14(3)：70-74．
[5] 张延坤，刘国中．杀虫剂及其在家庭与环境卫生害虫防治中的应用．日用化学品工业，2000．5期．
[6] 中山医学院．药理学．北京：人民卫生出版社，1981，140-142．
[7] 张一宾．杀虫剂的特性及其应用上的问题．农药译丛．1997，19(5)：1-6．
[8] 南开大学元素有机化学研究所编译，国外农药进展，化学工业出版社，1987．
[9] 罗万春，慕立义．杀虫剂现状及发展前景。农药1997，36(9)：10-12．
[10] 张一宾．对中国农药发展之浅见．农药．1999，37(5)：1-2．
[11] 程铸生主编．《精细化学品化学》．华东理工大学出版社．1996．
[12] 贺红武．新农药创制途经及研究．湖北化工．1996年增刊．
[13] 赵国锋，等．有机磷生物活性物质研究进展(上)农药译丛．1996，18(4)：1-7．
[14] 王晓光，李海屏．我国高毒有机磷替代品种开发进展．农药，2001，40(2)：10-13．
[15] 扬春河．害虫化学防治农用杀虫剂的进展．农药译丛，1996，18(1)：1-5．
[16] 徐尚成，蒋木庚．吡咯类农药活性化合物的研究进展．农药学学报．2002，4(2)：1-8。
[17] Copping L G.,Menn J J. Biopesticides:a review of their action, application and efficacy. Pest Manag Sci, 2000,56:651-676.
[18] 张仲贞，张一丙．含吡咯环农药的研究开发概述．上海化工．2001，5：19-22．
[19] 刘长令．含氟农药的创制途径．农药．1998，37(8)：1-5．
[20] 徐尚成．烟碱类杀虫剂的研究与开发进展．精细与专用化学品，2001，9(5)：3-5．
[21] 屠豫钦．天然源农药的研究利用—机遇与挑战．世界农药，199，，21(4)：4-12．
[22] the Pesticide Manual. 11th ed. 1997, 209.
[23] 周善波，张海．从溴从腈的结构来探讨型杀虫剂创新思路．上海化工．2000，5：17-19．
[24] 张仲贞，张一丙．含吡咯环农药的研究开发概述．上海化工，2001，1：19-22．
[25] 田伟生，罗雍容，陈毓群．中国化学通讯，1991，2(3)：217-220．
[26] 田伟生，罗雍容，陈毓群．CN1074439．
[27] 田伟生，罗雍容，陈毓群．化学学报，1994，52：1126-1132．
[28] Cater, G., Neitsche, J., Goodman, J., Torray, M., Dunn, T., Borders, D..Antibiotics. 1982, 40: 233-236.
[29] 张芝平．吡咯类杀虫剂的构效关系和作用机理研究．世界农药，1999，21(6)：12-16．
[30] 李再峰．杀虫剂结构与昆虫抗药性．宁夏农学院学报．1994，15(1)：71-74．
[31] Lovell J B, Wright D P, Gard I E, etal. AC303630 Aninsecticide/acaricide from a novel class of chemistry. Brighton Corp Prot. Conf-pest and Dieases. Brighton:British Crop Prot Council, 1990,1:41-45.
[32] J.B.Lovell, D.P.Wright. AC303630—一种新型杀虫、杀螨剂．农药译丛．1992，14(6)：57-59．
[33] 陶贤鉴，谭本祝．新农药AC303630的合成与应用．农药译丛 1998，20(5)：15-17．
[34] 谭本祝．含氟杀虫剂溴虫腈的合成．1999，38(12)：7-9．
[35] AU TSIEN MING (SG); CHIA YAN WAH.RF identification transponder US5945938.1999-8-31.
[36] FARLOW ROBERI A(US); REID BYRON L. Arylpyrroles for subterranean termite control.US6071951.2000-6-6.
[37] Addor R., Brown D., Babcock T In Synthesis and Chemistry of Agrochemicals. 1192: 283-97.
[38] David G.kuhnt, Victor M.Kamhi, Joseph A.Furch..The Synthesis of Pyrroles with Insecticidal.Pestic.sci..1994, 41: 279-286.
[39] FARLOW ROBERT A(US); REID BYRON L. Arylpyrroles for subterranean termite control. US6071951.2000-6-6.
[40] KAMESWARAN VENKATARAMAN . Process for the manufacture of2-aryl-5-perfluoroalkylpyrrole derivatives and intermediates useful therefore.US5750726． 1998-5-12．
[41] BROWN DALE G (US); SIDDENS JACK K (US); DIEHL ROBERT E (US); WRIGHT JR DONALD P .Arylpyrrole insecticidal acaricidal and nematicidal agents and methods for the preparation thereof. US5010098． 1991-4-23．
[42] 何玉仙，杨秀娟．10％除尽防治甜菜夜蛾和小菜蛾．PESTICIDES．1999，38(9) ： 18-19．
[43] 陈修会，陈振峰．除尽等农药防治茶树甜菜夜蛾药效试验．农药．2001，40(4) ： 27．
[44] Kameswaran. Synthesis of 2-aryl-5-trifluoromethyl)Pyrroces useful as spesticical agents and as intermediates for the preparation of said agents. US:5128485, 1992-7-7．
[45] KAMESWARAN VENKATARAMAN; BARTON JERRY MICHAEL . PROCESS FOR THE MANUFACTURE OF PESTICIDAL 1-(ALKOXYMETHYL) PYRROLE COMPOUNDS US:5151536． 1992-6-24．
[46] Venkataraman Kameswaran, Princton Junction,N.J ..Method for the preparation of 2-aryl-5-trifluoromethylpyrrole compoundes. US:5256796． 1992-12-11．
[47] Kameswaram, Process for the manufacture of pesticidal 1-(alkoxymethyl)p pyrrole compounds .EP:0492171A1． 1992-6-24．
[48] Kameswaram, venkataraman.2-aryl-5-(trifluorornethyl)-2-pyrroline compounds and process for the manufacture of insecticidal. EP:0492171A1． 1992-1-7．
[49] RoberetF. Doehner, Jr.; Jerry M. Barton, David G.Kuhn,newtown,Pa.. 2-aryl-5-(trifluoromethyl)-2-pyrroline compounds useful in the manufacture of insecticidal, nematocidal and acaricidal arylpyrroles.US:5118816． 1990-12-26．
[50] DOEHNER JR ROBERT F; BARTON JERRY M (US); KUHN DAVID G 2-aryl-5-(trifluoromethyl)-2-pyrroline compounds useful in the manufacture of insecticidal, nematocidal and acaricidal arylpyrrolesUS:5288901． 1994．
[51] DOEHNER JR ROBERT F (US); KAMESWARAN VENKATARAMAN Process for the manufacture of insecticidal2-aryl-1insecticidal2-aryl-1-(al koxymethyl)-4-halo-5-(triflu
oromethyl)pyrrolesUS:5194630． 1993-3-16．
[52] Venkataraman Kameswaran, Princton Junction, N.J .Synthesis of 2-aryl-5-(trifluoromethyl)pyroles useful as pesticidal agents and as intermediates for the preparation of said agents. US:5128485． 190-12-17．
[53] Roberet F. Doehner,Jr.,Eastwindsor,N.J..Process for the preparation of 2-aryl-l-substitted-5-(trifluoromethyl)pyrrole compounds useful as insecticidal and nematocidal agents and as intermediates for the manfacture of said agents. US:5144041． 1992-3-20．
[54] 陶贤签，谭本祝．含氟杀虫剂的制备．湖南化工．2000，30(5) ：29-31．
[55] Robert F. Doehner, Jr.; Jerry M.Barton; David GKuhn,Newtown. 2-Aryl-5-(trifluoromethyl)-2-pyrroline compounds useful in the manufacture of insecticidal and acaricidal arylpyrroles. US:5288901． 1992-4-8．
[56] Venkataraman Kameswaran, Princton Junction,N.J; Jerry M.Barton,East Windsor,N.J.Process for the manufature of pesticidal 1-(alkoxymethyl)pyrrle compounds.US:5151536． 1990-12-7．
[57] Venkataraman Kameswaran, Princton Junction,N.J. Ammonium oxazole and amino oxazolium intermediates,methods for the preparation thereof and the use thereof in the manufacture of insecticidal arylpyrroles. US:5925773． 1997-6-27．
[58] Venkataraman Kameswaran, Princton Junction,N.J. Oxazole amines as intermediates in the manufacture of insecticidal pyrroles. US:5631379． 1997-3-20．
[59] DOEHNER JR ROBERT F. Process for the preparation of 2-aryl-1-substituted-5-(trifluoromethyl) pyrrole compounds useful as insecticidal, acaricidal and nematocidal US :5144041． 1992-9-1．
[60] Venkataraman Kameswaran, Princton Junction,N.J. Perfluoroalkanoyl aminonttriles. US:5426225． 1995-6-20．
[61] KING STEPHEN WAYNE. Reductive amination catalystsUS:5750790． 1998-5-12．
[62] ADDOR ROGER W (US); FURCH JOSEPH A (US); KUHN DAVID G .Process for the preparation of insecticidal, acaricidal and nematicidal 2-aryl-5-(trifluoromethyl) pyrrole compoundsUS:5030735． 1991-7-9．
[63] KAMESWARAN VENKATARAMAN .Method for the preparation of
2-aryl-5-trifluoromethylpyrrole compounds.US:5256796． 1993-10-26．
[64] RobertF.Doehner,E.Windsor,N. J.; Jerry M.Barton,Langhorne,Pa.. Alkoxymethylation of pyrroles.US:5359090． 1993-12-29．
[65] KNAPP JR PAUL W .Manufacture of 4-aryl-2-perfluoroalkyl-3-oxazolin-5-one from arylglycine. US5453508． 1995-9-26．
[66] 田伟生，罗雍容．从容易制备的三氟甲基恶唑酮直接合成三氟甲基吡咯及其 有关化合物．化学学报．1994，52：1126-1132．
[67] 田伟生，罗雍容，陈敏毓．一种从三氟甲基恶唑酮合成三氟甲基吡咯类化合 物的方法．CN：1074439A．1993-7-21．
[68] DOEHNER JR ROBERT F (US); KAMESWARAN VENKATARAMAN .Process for the manufacture of insecticidal 2-aryl-1-(alkoxymethyl)-4-halo-5-(trifluoromethyl)pyrroles US:5194630． 1993-3-16．
[69] YAMASAKI TETSURO (JP); KUMOBAYASHI HIDENORI (JP); SAYO NOBORU (JP); MURAYAMA TOSHIYUKI (JP); SANO NOBORU (JP); ISHIZAKI TAKERO. Process for producing optically active diaminohexanone derivative. US:5631397． 1997-5-20．
[70] Venkataraman Kameswaran,Princton Junction; N.J. Precess for the manufacture of 2-aryl-5-perfluoroalklpyrrole derivatives. US:5777132． 1998-7-7．
[71] KAMESWARAN VENKATARAMAN.N-(arylmethylene)-1-chloro-1-(perfluoroalkyl) methylamine compounds.US6034273． 2000-3-7．
[72] KAMESWARAN VENKATARAMAN .Perfluoroalkanoyl aminonitrilesUS5426225． 1995-6-20．
[73] KAMESWARAN VENKATARAMAN Ammonium oxazole and amino oxazolium intermediates, methods for the preparation thereof and the use thereof in the manufacture of insecticidaUS5925773． 1999-7-20．
[74] KAMESWARAN VENKATARAMAN PROCESS FOR THE PREPARATION OF INSECTICIDAL,NEMATICIpAL AND ACARICIDAL4-SUBSTITUTED-5-METHYL)PYRROLE-3-CARBONITRILE COMPOUNDS.US5106985． 1992-5-20．
[75] KAMESWARAN VENKATARAMAN .Process for the preparation of insecticidal, acaricidal and nematicidal 2-aryl-3-substituted-5-(trifluoromethyl)pyrrole compounds. US5225568． 1993-7-6．
[76] Venkataraman Kameswaran, Princton Junction; N.J. Process for the preparation of 2-aryl-5-(perfluoro-alkyl)pyrrole compounds from N-arylimidoyl chlorode compounds. US:5817834.1998-2-9.
[77] Venkataraman Kameswaran, Trenton, N.J.. Precess for the preparation of 2-aryl-5-(perfpluoroalkyl)pyrrole compounds from N-(perfiuorothyl)arylimidoyl alkylme chloride compounds. US:5965773.1999-10-12.
[78] Venkataraman Kameswaran,Princton Junction; N.J.; David G.Kuhn,Newtown, Pa..Process for the manufacture of insecticidal, nematicidal and acaricidal 2-aryl-3-substitued-5-(trifluoromethyl)pyrrle compounds from N-(substitutedbenzl)-2,2,2-trifluoro-acetimidoylchloride compounds. US:5145986.1992-9-8.
[79] KAMESWARAN VENKATARAMAN PROCESS FOR THE PREPARATION OF INSECTICIDAL, NEMATICIDAL AND ACARICIDAL 4-SUBSTITUTED-5-(TRIFLUOROMETHYL)PYRROLE-3-CARBONITRILE COMPOUNDS. US5106985.1992-5-20.
[80] 俞凌翀．有机化学中的人名反应．北京科学出版社．1984：326．
[81] Edward L. COMPERE, Jr., David A. WEINSTEIN. Synthesis of α-Aminoarylacetic Acids from Bromoform, Aryaldehydes, and Ammonia, with Potassium Hydroxide/Lithium Amid Cmbination as Catalyst. SYNTHESIS. 1977(852-853).
[82] Kazuo Matsumoto.A New Synthesis of α-Amino Acids. J.Org. Chem., 1973, 88(11): 45-49.
[83] 王素青．芳基甘氨酸的不对称合成．北京师范大学学报．1994，30(3)．
[84] 李记太，李立军，张能芳，李慧章．DL-α-苯甘氨酸合成方法的改进．合成化学(HECHENGHUAXUE) 1997，5(2)
[85] 李记太，张能芳，李慧章．DL-α-苯甘氨酸合成的合成研究．河北大学学报 1994，14(4)：74-77．
[86] 俞凌翀．有机化学中的人名反应．北京科学出版社．1984，86．
[87] 俞凌翀．有机化学中的人名反应．北京科学出版社．1984，592-594．
[88] Kobayashi Y., Kamadaki I..Tetrahedron Lett., 1982, 3929. 2 Kobayashi Y., Kamadaki I., OhsawaA..Chem. Pharm. Bull., 1978, 26: 1247.
[89] 胡卫国．温度对合成甘氨酸反应的影响．化学世界，2001年4期．p189-191．
[90] 温辉梁，刘崇波，邓瑞红，等．一种高产率制备甘氨酸的方法．南昌大学学报 2000，24(3)：295-297．
[91] 正交试验法．中国科学院数学研究所数理统计组编．人民教育出版社．
[92] 史达清，周龙虎．溴代反应中的选择性溴化剂．化学试剂．1995，17(4)：345-350．
[93] 董志超．N-取代吡咯的简便合成方法．中国医药工业杂志．1996，27(6)：268-269．