含硫烷基芳香硝基化合物的CO选择性还原
摘要
芳香硝基物还原成芳香胺是工业生产中使用最为广泛而又经典的一个有机化
学反应。但是含硫烷基的芳香硝基物的还原却一直是工业生产的难点所在。本论
文首次应用过渡金属催化的CO选择性还原含硫烷基的芳香硝基物合成芳胺。
本论文首次将Ru_3（CO）_(12)/NEt_3、Ru_3（TPP）_3和Ru_3（CO）_(12)/PEO-DPPPA三种
催化剂应用于催化还原合硫烷基的芳香硝基化合物4-丙硫基-2-硝基苯胺，得出
在最佳反应条件下，三种催化剂催化反应底物的转化率依次为90％，83％和70％并
且产物的选择性都高达98％。其中具有表面活性的膦配体PEO-DPPPA配合十二
羰基三钌生成的催化剂具有一定的回收循环催化效果。
本论文还对阿苯达唑的重要中间体，即4-丙硫基-邻苯二胺的前体4-丙硫基-
2-硝基苯胺的合成方法进行了实验研究与相对比较。实验结果表明，采用氢氧化
钠法制备4-丙硫基-2-硝基苯胺的效果最佳，收率达95％。
The reduction of nitroarenes to corresponding amines is such a kind of classical organic reaction that it was widely applied in industry. However, the existence of alkylthio group in the nitroarenes deactivates most catalysts and degrades the reaction selectivity for the target products. Here in this paper, the CO selective reduction of nitroarenes was firstly introduced to reduce the alkylthio nitroarenes.
The CO selective reduction of 4-propylthio-2-nitroaniline catalyzed by Ru3(CO)12 complex with NEt3, TPP or thermoregulated phase transfer phosphine ligand PEO-DPPPA were studied. Under their optimal conditions, the conversions of the substrate are respectively 90%,83%and 70%, while the selectivity of the product up-reaches 98%. When Ru3(CO)12 / PEO-DPPPA was used for the reaction, it could be recovered in aqueous phase and recycled several times.
Three procedures to prepare 4-propylthio-2-nitro-aniline, a key intermediate for Albendazole, were also investigated in the paper. The results shown that the procedure catalyzed by sodium hydroxide was the best as the conversion of the substrate under this condition out-rival others to be 95%.
学反应。但是含硫烷基的芳香硝基物的还原却一直是工业生产的难点所在。本论
文首次应用过渡金属催化的CO选择性还原含硫烷基的芳香硝基物合成芳胺。
本论文首次将Ru_3（CO）_(12)/NEt_3、Ru_3（TPP）_3和Ru_3（CO）_(12)/PEO-DPPPA三种
催化剂应用于催化还原合硫烷基的芳香硝基化合物4-丙硫基-2-硝基苯胺，得出
在最佳反应条件下，三种催化剂催化反应底物的转化率依次为90％，83％和70％并
且产物的选择性都高达98％。其中具有表面活性的膦配体PEO-DPPPA配合十二
羰基三钌生成的催化剂具有一定的回收循环催化效果。
本论文还对阿苯达唑的重要中间体，即4-丙硫基-邻苯二胺的前体4-丙硫基-
2-硝基苯胺的合成方法进行了实验研究与相对比较。实验结果表明，采用氢氧化
钠法制备4-丙硫基-2-硝基苯胺的效果最佳，收率达95％。
The reduction of nitroarenes to corresponding amines is such a kind of classical organic reaction that it was widely applied in industry. However, the existence of alkylthio group in the nitroarenes deactivates most catalysts and degrades the reaction selectivity for the target products. Here in this paper, the CO selective reduction of nitroarenes was firstly introduced to reduce the alkylthio nitroarenes.
The CO selective reduction of 4-propylthio-2-nitroaniline catalyzed by Ru3(CO)12 complex with NEt3, TPP or thermoregulated phase transfer phosphine ligand PEO-DPPPA were studied. Under their optimal conditions, the conversions of the substrate are respectively 90%,83%and 70%, while the selectivity of the product up-reaches 98%. When Ru3(CO)12 / PEO-DPPPA was used for the reaction, it could be recovered in aqueous phase and recycled several times.
Three procedures to prepare 4-propylthio-2-nitro-aniline, a key intermediate for Albendazole, were also investigated in the paper. The results shown that the procedure catalyzed by sodium hydroxide was the best as the conversion of the substrate under this condition out-rival others to be 95%.
引文
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[32]刘志东，陈昌藻，催化学报，1996，17(6)，554．
[33]姜恒，徐筠，廖世健，余道容．石油化工，1996，25(11)，757．
[34]杨斌，徐筠，廖世健，余道容．分子催化，1996，10(5)，339．
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[37]Roberts,B.D.;Carrick,W.J.;Thakur, D.S. WO 9,700,131.,1997
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[40]Tafesh,A.M.; Weiguny, J. J. Chem. Rev. 96,1996,2035.
[41]Cole,T.;Ramage,R.;Cann,K.;Pettit,R., J.Am. Chem. Soc.,1980,102,6182.
[42]Takemura, Y.;Onodera,K.;Ouchi, K.,Chem. Prod. Res. Dev.,1983,22,539.
[43]Nomura, K.;Ishino,M.;Hazama,M., J. Mol. Catal., 1993, 78,273-282.
[44] Nomura,K.;Ishino,M.;Hazama,M.,J.Mol. Catal.. 1991, 65, L5．
[45] Okano,T.;Fujiwara,K.;Konishi,H.;Kiji,J.,Chem.Lett.1981,1083．
[46] Nomura,K.,Ishino,M.;Hazama,M..,Bull.Chem.Soc.Jpn.,1991,64,2624．
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[48] Grate,J.H.;Hamm,D.R., US 4,687,872． , 1987．
[49] Grate,J.H.;Hamm,D.R., US 4,709,073． , 1987．
[50] Cenini,S.;Pizzotti.;Crotti,C.;Ragaini,F.;Porta,F.J.Mol.Catal.,1988,59, 59．
[51] Cenini,S.;Ragaini,F.;Pizzotti,M.;Porta,F.;etal.,J,Mol. Catal., 1991, 64, 179．
[52] Hashem,K.E.;Petrignani,J.F.;Alper,H.,7． Mol. Cotol., 1984, 26, 285．
[53] Joo,F.;Alper,H., Can. J. Chem. 1985, 63, 1157．
[54] Miura,M.;Shinohara,M.;Nomura,M.,J.Mol. Catal., 1988,45, 151-3．
[55] Bremer,J.;Madeja,K.;Dexheimer,V., DD 146,287, 1981．
[56] Watanabe,Y.;Tsuji,Y;Ohsumi,T.;Takeuchi,R., Tett. Lett, 1983, 24 (38) , 4121．
[57] Watanabe,Y.;TsujisY.;Ohsumi,T.;Takeuchi,R.Bull.Chem.Soc.Jpn., 1984, 57, 2867．
[58] Tafesh,A.;Beller,M., Tett.Lett., 1995, 36, 9305．
[59] Falicki,S.;Alper,H., Organometallics, 1988,7, 2548．
[60] Kaneda,K.;Hiraki,M.;Imanaka,T.,y. Mol. Catal., 1981, 12, 385．
[61] Nomura,K. J. Mol.Catal.,1995,95,203．
[62] Alper,H.;Amaratuga,S., Tett. Lett. 1980,21,2603．
[63] Alessio,E. ;Zassinovich,G. ;Metroni,G. ; J.Mol. Catal. 1988,18． 113．
[64] Tafesh,A.;Beller,M.;kohlpaintner,C.;Naumann,C.,EP96,102,416． ,1996
[65] Herrmann,W.;Kohlpainter,C.Angew.Chem.Int.Ed.Engl.1993,32． 1524．
[67] Kaneda,K.;Kuwahara,H.;Imanaka,T.,J.Mol.Catal..1994,88． L267．
[68]Thomas,J.W.;,Baton,R.L., US 4,152,522.
[69]黄之涛，陈玉书，吴新坚等，医药工业 1986，17(11)，3：483．
[70]张长利，医药工业 1988，19(8)：379
[71]Oyamada, K.Tobizuka,J., JP 74-117460
[72]Szoke,S.;Lugosi,G.;Bakonyi,M.;etal., EP 31,473.
[73]Bakonyi,M.;Lugosi,G.;Kallai,T.;etal., EP 191,940.
[74]Helya,G.;Palosi,E.;Korbonits,D.;etal., HU 52,755 (1991)
[75]Zilin,Jin;Xiaolai,Zheng;Bernhard,Fell., J.Mol. Catal. 116 (1997) 55
[76]金子林等，高等学校化学学报，21(6)，2000，941
[77]梅建庭，蒋景阳等，国际网上化学学报，2(1)2000，41．
[78]梅建庭，蒋景阳等，高等学校化学学报，21(6)，2000，89
[2] Khan,M.S.;Abdul,H.Muhammad,A. J.Nat.Sci.Math.,1990,30(1) ,63．
[3] Prajapati,D.;Boarh,H.N.;Sandhu,J.S.;Ghosh,A.C.,Synth.Commun.1995,25(24) ,4025
[4] Redemann,C.T.;Redemann,C.E. Org.Syn., 1955,3,69．
[5] Robertson,G.R. Org.Syn.,194l,1,52．
[6] Hartman,W.W.;Silloway,H.L. Org.Syn.,1955,3,82
[7] Boyer,J.H.;Buriks,R.S. Org.Syn.1960,40,96
[8] Griffin,K.P.;Peterson,W.D. Org.Syn. 1955,3,242
[9] Idoux,J.P.J.Chem.Soc.,1970,66,437．
[10] Dizey,S.S. Synthetic Reagents,1974,1,205
[11] Neilson,J.Chem.Soc.,1962,58,371
[12] Satoh,T.;Suzuki,S. Tett.Lett.,1969,10,4555．
[13] Cnopchenko,A. J.Org.Chem.,1979,44,1233．
[14] Lalancette,J.M.;Brindle,J.R. Can.J.Chem,1971,49,2990．
[15] Furst,A. Chem.Rev.,1965,65,51．
[16] Hirshima,T.;Manabe,O. Chem.Lett,1975,51(3) ,259．
[17] Braude,E.A. J.Chem.Soc.,1954,50,3568．
[18] Clendinning,R.A.;Rauscher,W.H. J.Org.Chem.,1961,26,2963．
[19] Kozlov,N.S.;Tovshtein,M.N.Zh.Org.Khim.,1967,3,318．
[20] Kozlov,N.S.;Vestsi;Akad.Navuk,Balarus,Ser.Khim.Navuk,1970,(1) ,101
[21] Selena,R.B. and Michael,A.K. Tett. Lett. 36(14) 1995,2411
[22]Jacek,K.; Pol. 165,527.,1995.
[23]Naoki,T.;Lu,P. Chem. Lett.,1996,(9),729.
[24]Kotohiro,N.;Massaru,I.J.Mol. Catal.,1991,65,(3),5
[25]姚蒙正，程侣柏，王家儒 精细化工产品合成原理 中石化出版社 1992 P．353
[26]Greenfield,H.;Frederick,S.D.J. Org. Chem.,32,3670(1967)
[27]Hildreth,J.D.;Haslam,D.G.. EP 0,805.
[28]Bird,A.J.;Ferrier,G.G. DE 3,006,748.
[29]Karakhanov,E.A. Neftekhimya,1991,31 (3),312.
[30]Yu,Z.K.,Liao,S.J.;Xu,Y.;et.al., J. Chem. Soc.Chem.Commun.1995,1155.
[31]Sasykova,L.R.;Masenova,A.T.;Bizhanov, F.B.Izv. Nats.Akad.Nauk. Resp. Kaz.,Ser. Khim. 1995,(1).
[32]刘志东，陈昌藻，催化学报，1996，17(6)，554．
[33]姜恒，徐筠，廖世健，余道容．石油化工，1996，25(11)，757．
[34]杨斌，徐筠，廖世健，余道容．分子催化，1996，10(5)，339．
[35]Baumeister,P.;Siegrist, V. WO 9,636,588,1996
[36]Jebarathinam,N.J.;Eswarammorthy, M.;Krishnasamy, V.React Kinet. Catal. Lett.,1991,58,(2),291.
[37]Roberts,B.D.;Carrick,W.J.;Thakur, D.S. WO 9,700,131.,1997
[38]Woonphil,B.;Jeong,L.H.;KI,C.L. etal. Tett. Lett., 35,1994,3965.
[39]Cann,K.;Cole,T.; Slegeir,W.;Pettit,R.J .Am. Chem. Soc. 100,1978,3969.
[40]Tafesh,A.M.; Weiguny, J. J. Chem. Rev. 96,1996,2035.
[41]Cole,T.;Ramage,R.;Cann,K.;Pettit,R., J.Am. Chem. Soc.,1980,102,6182.
[42]Takemura, Y.;Onodera,K.;Ouchi, K.,Chem. Prod. Res. Dev.,1983,22,539.
[43]Nomura, K.;Ishino,M.;Hazama,M., J. Mol. Catal., 1993, 78,273-282.
[44] Nomura,K.;Ishino,M.;Hazama,M.,J.Mol. Catal.. 1991, 65, L5．
[45] Okano,T.;Fujiwara,K.;Konishi,H.;Kiji,J.,Chem.Lett.1981,1083．
[46] Nomura,K.,Ishino,M.;Hazama,M..,Bull.Chem.Soc.Jpn.,1991,64,2624．
[47] Nomura,K.;Ishino,M.;Hazama,M., J. Mol. Catal., 1991, 66, L1
[48] Grate,J.H.;Hamm,D.R., US 4,687,872． , 1987．
[49] Grate,J.H.;Hamm,D.R., US 4,709,073． , 1987．
[50] Cenini,S.;Pizzotti.;Crotti,C.;Ragaini,F.;Porta,F.J.Mol.Catal.,1988,59, 59．
[51] Cenini,S.;Ragaini,F.;Pizzotti,M.;Porta,F.;etal.,J,Mol. Catal., 1991, 64, 179．
[52] Hashem,K.E.;Petrignani,J.F.;Alper,H.,7． Mol. Cotol., 1984, 26, 285．
[53] Joo,F.;Alper,H., Can. J. Chem. 1985, 63, 1157．
[54] Miura,M.;Shinohara,M.;Nomura,M.,J.Mol. Catal., 1988,45, 151-3．
[55] Bremer,J.;Madeja,K.;Dexheimer,V., DD 146,287, 1981．
[56] Watanabe,Y.;Tsuji,Y;Ohsumi,T.;Takeuchi,R., Tett. Lett, 1983, 24 (38) , 4121．
[57] Watanabe,Y.;TsujisY.;Ohsumi,T.;Takeuchi,R.Bull.Chem.Soc.Jpn., 1984, 57, 2867．
[58] Tafesh,A.;Beller,M., Tett.Lett., 1995, 36, 9305．
[59] Falicki,S.;Alper,H., Organometallics, 1988,7, 2548．
[60] Kaneda,K.;Hiraki,M.;Imanaka,T.,y. Mol. Catal., 1981, 12, 385．
[61] Nomura,K. J. Mol.Catal.,1995,95,203．
[62] Alper,H.;Amaratuga,S., Tett. Lett. 1980,21,2603．
[63] Alessio,E. ;Zassinovich,G. ;Metroni,G. ; J.Mol. Catal. 1988,18． 113．
[64] Tafesh,A.;Beller,M.;kohlpaintner,C.;Naumann,C.,EP96,102,416． ,1996
[65] Herrmann,W.;Kohlpainter,C.Angew.Chem.Int.Ed.Engl.1993,32． 1524．
[67] Kaneda,K.;Kuwahara,H.;Imanaka,T.,J.Mol.Catal..1994,88． L267．
[68]Thomas,J.W.;,Baton,R.L., US 4,152,522.
[69]黄之涛，陈玉书，吴新坚等，医药工业 1986，17(11)，3：483．
[70]张长利，医药工业 1988，19(8)：379
[71]Oyamada, K.Tobizuka,J., JP 74-117460
[72]Szoke,S.;Lugosi,G.;Bakonyi,M.;etal., EP 31,473.
[73]Bakonyi,M.;Lugosi,G.;Kallai,T.;etal., EP 191,940.
[74]Helya,G.;Palosi,E.;Korbonits,D.;etal., HU 52,755 (1991)
[75]Zilin,Jin;Xiaolai,Zheng;Bernhard,Fell., J.Mol. Catal. 116 (1997) 55
[76]金子林等，高等学校化学学报，21(6)，2000，941
[77]梅建庭，蒋景阳等，国际网上化学学报，2(1)2000，41．
[78]梅建庭，蒋景阳等，高等学校化学学报，21(6)，2000，89