过渡金属锰、铜、锌与嘧啶胺类配合物的研究
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摘要
在文献的基础上，对嘧啶胺类化合物2-氨基-4,6二甲氧基嘧啶(AMP)及2-氨基-4,6二甲基嘧啶(DMPA)的合成方法进行了改良，使其产率达到95％以上。以这两种嘧啶胺类的化合物为配体，分别制备了其与锰盐、铜盐、锌盐等9种未见报道的金属配合物。通过化学分析、元素分析确定化合物分子组成分别为Mn(DMPA)_2Cl_2，Mn(AMP)_2Cl_2，Cu(DMPA)_2Cl_2·2H_2O，Cu(DMPA)(NO_3)_2·H_2O，Cu(DMPA)(CH_3COO)_2，Zn(DMPA)_2Cl_2，Zn(DMPA)_2(NO_3)_2·4H_2O，Zn(DMPA)SO_4和Zn(AMP)_4(NO_3)_2；借助IR、~1H NMR和XPS对化合物的键型特征进行了表征，运用X-射线单晶衍射分析法测定了个别化合物的晶体结构；以TG-DTG技术研究了化合物的热稳定性，阐明了它们的热分解机理；用精密转动弹热量计测定了化合物在298.15 K的恒容燃烧能，并计算了它们的标准燃烧焓和标准生成焓；选取1～2种病菌，初步测定了化合物的杀菌活性，进而研究了它们的生物活性。
Based on the literatures, the syntheses method concerning aminopyrimidine involed 2 - amino - 4, 6 - dimethoxy-pyrimidine (AMP) and 2 - amino - 4, 6 -dimethyl-pyrimidine (DMPA) were amalierated and the yields of the compounds were improved to 95 % above. Nine solid complexes were initially synthesized by the reactions of AMP and DMPA with Manganese (II), Copper (II) and Zinc (II). The compositions of complexes were determined as, by chemical and elemental analyses, Mn(DMPA)2CI2, Mn(AMP)2Cl2, Cu(DMPA)2Cl2-2H2O, Cu(DMPA)(NO3)2-H2O, Cu(DMPA)(CH3COO)2, Zn(DMPA)2Cl2, Zn(DMPA)2(NO3)2-4H2O,Zn(DMPA)SO4 and Zn(AMP)4(NO3)2, respectively. These complexes were characterized by IR, 'H NMR and XPS. The crystal structures of these complexes were determined by single crystal X-ray diffraction techniques. The thermstability of the complexes was investigated by TG-DTG and the processes of their thermal decomposition were
speculated. The constant-volume combustion energies of complexes, cU, were determined by a precision rotating bomb calorimeter at 298.15 K. Their standard enthalpies of formation, Hm, were calculated respectively. Finally, their biological
activity was researched after the bactericidal activity was determined by selection of 1-2 bacteria.
Based on the literatures, the syntheses method concerning aminopyrimidine involed 2 - amino - 4, 6 - dimethoxy-pyrimidine (AMP) and 2 - amino - 4, 6 -dimethyl-pyrimidine (DMPA) were amalierated and the yields of the compounds were improved to 95 % above. Nine solid complexes were initially synthesized by the reactions of AMP and DMPA with Manganese (II), Copper (II) and Zinc (II). The compositions of complexes were determined as, by chemical and elemental analyses, Mn(DMPA)2CI2, Mn(AMP)2Cl2, Cu(DMPA)2Cl2-2H2O, Cu(DMPA)(NO3)2-H2O, Cu(DMPA)(CH3COO)2, Zn(DMPA)2Cl2, Zn(DMPA)2(NO3)2-4H2O,Zn(DMPA)SO4 and Zn(AMP)4(NO3)2, respectively. These complexes were characterized by IR, 'H NMR and XPS. The crystal structures of these complexes were determined by single crystal X-ray diffraction techniques. The thermstability of the complexes was investigated by TG-DTG and the processes of their thermal decomposition were
speculated. The constant-volume combustion energies of complexes, cU, were determined by a precision rotating bomb calorimeter at 298.15 K. Their standard enthalpies of formation, Hm, were calculated respectively. Finally, their biological
activity was researched after the bactericidal activity was determined by selection of 1-2 bacteria.
引文
1．阎隆飞，张玉麟，分子生物学，北京：中国农业出版社，1997
2. Heye, U. J. et al., Crop Protection, 13(7),541(1994)
3．化学工业部农药情报中心站，《国外农药品种手册》3，174(1981)
4. Godwin J R, et al. Brighton Crop Prot. Conf.- pests and Diseases. 1992,435～437
5. Beautement K, et al.Pestic. Sci., 1991,31,499～519
6. Kleschich W A, Costales M J, Dunbar J E, et al. Pestic. Sci.,1990,29,341～355
7．罗宣干，高等学校化学学报，1996，17(9)，1416～1420
8．化学工业部农药情报中心站，《国外农药品种手册》2，46、48(1981)
9．尚尔才，刘长令，杜英娟，化工进展，1995，5，8～15
10．刘长令，中国化工报，1998—05—11(4)
11．刘长令，精细与专用化学品，2000，6，1
12. ACROW, ISO proposed names, 1999,No 338,26
13. Angerstein, St.,Ber.,34,3956(1901)
14. GB 1245085(1968)
15. Ger (East)151404(1981)
16. CA102 162065
17. Maeno, S.et al., Brighton Crop Prot. Conf. Pests and diseases, 5-3,415(1990)
18. Neumann, G. L. et al., Brighton Crop Prot. Conf. Pests and diseases,5-1,395(1992)
19．马忠华，叶钟音，农药译丛，1997，19(3)，11～13
20. Harry J. J.Amer. Chem. Soc. 1932, 54, 727
21．孔繁蕾，化学世界，1991，32(6)，254～257
22. Haley CAC, Maitland P.J.Chem. Soc., 1951,3155
23. Hussain, Shaheen A., Pak. J. Sci.Ind.Res. 1998,41(2),63-67
24．薛思佳，化学研究与应用，1998，10(1)，74～78
25．薛思佳，化学试剂，1999，21(2)，73～75
26．张宗涛，王岩，农药，1988，27(3)40～45
27． Beasley,M.L.&Collins,R.L.,Science,169(1970) 769-70
28． Clifford,D.P.&Carson,C.M.,Pestic.Sci.,23(1988) 93-102
29． Nepera Chemical Co.Inc.Brit.564,315,9,22,1944
30． Junichi Ishii,J.Chem.Soc.Japan,Ind.Chem.Sect.1951,54,87
31． Singh P.P.Indian,J.Chem.Sect.A,1976,14(10) ,812-813
32． Singh P.P.Indian,J.Chem.Sect.A,1976,14 A(9) ,684-687
33． Stetsenko A.I.Koord.Khim,1976,2(6) ,834-840(Russ)
34． Kong Pi-Chang.Can.J.Chem,1979,57(5) ,526-529
35． Bhasin S.K.Tran SAEST,1979,14(3) ,145-149
36． Allan J.R.J.Therm.Anal,1981,21(1) ,3-12
37． Lumme Paavo.Finn.Chem.Lett.,1981,13(4) ,25-28
38． ADEGBOYE ADEYEMO,Inorganica Chimica Acta 51(1981) ,19-22
39． Homer L.Werkst Rorros,1982,33(4) ,189-193
40． Mishra L.K.J.Indian.Chem.Soc.,1982,59(3) ,408-409
41． Lavrenova L.GIzv.Sib.Otd.Akad.Nauk.SSSR Ser.Khim.Nauk,1985,3,59-64(Russ)
42． Singh E.B.J.Indian.Chem.Soc.,1987,64(6) ,359-360
43． Kovala-Demertzi D.Bull.Soc.Chim.Belg,1987,96(1) ,7-14
44． Kulig Jacek.POL.J.Chem,1988,62(4-6) ,351-358
45． AL-Hajjar F.H.Corros.Sci.,1988,28(2) ,163-171
46． Kovala-Demerzi,D.Transition Met.Chem.,1990,15(1) ,23-26
47． GRAHAM SMITH,Polyhedron,1991,8,873-876
48． Kovala-Demertzi.Bull.Chem.Soc.Jpn,1991,64(2) ,744-746
49． Bhasin S.K.Bull.Electrochem,1991,7(3) ,146-148
50． Contreras.J.Spectrochim.ActaPart.A,1992,48A(4) ,525-532
51． 姚学斌，应用化学，1994，11(6) ，6-11
52． Xuebin Yao,J.Solid State Chem,1995,117(2) ,333-336
53． 张培志，化学研究与应用，1997，9(1) ，92-94
54． Kovala-Demertzi D.,Spectrochim.Acta Part.A,1998,54A(12) ,1801-1809
55． 张培志，应用化学，2000，17(5) ，558-560
56． Gandhi,Orient.J.Chem.2000,16(2) ,353-354
57． Van Albada,Gerard A,J.Chem.Crystallogr.2000,30(1) ,11-16
58． Miao,Q.Appl.Surf.Sci.2001,171(1-2) 49-56
59． Van Albada,Gerard A,Inorganica Chimica Acta 2002,327,134-139
60． 徐克勋。精细有机化工原料及中间体手册，99～100
61． 薛思佳。化学试剂，1993，15(3) ，181
62． Dong Q.N.Infrared Spectrometry.Beijing Chemical and Indusreial Press,1979．
63． NaKamoto,K.,Written,Huang D.J.;et al.,Translated.Infrared and Roman Specera of Inorganic and Coordination compounds.Bei Jing Chemical and Industrial Press(4th Edi).,1991．
64． Wang J.Q.;et al.Instruction to x-ray Photoelectron spectroscopy(XPS / XAES / UPS).Bei Jing National Defence Industry Press.,1992．
65． 张祖德，张雄，刘清亮；XPS在配位化学中的应用．大学化学，1999，14(4) ，27～31
66． Yang X.W,Chen S.P,Gao S.L,et al.Instrumentation Sci.& techn.2002,30,311
67． Popov,M.M.Thermometry and Calorimetry.Moscow Univ.,Publishing House,Moscow,1954,382
68． Cox,J.D.J.Chem.Thermodyn.1978,10,903
69． Wangman,D.S,Evans,W.H,Pariker,V.B.In The NBS of Chemical Thermodynamic Properties,Translated by Liu,T.H,Zhao,M.K,Chinese standards Press,Beijing,1998
2. Heye, U. J. et al., Crop Protection, 13(7),541(1994)
3．化学工业部农药情报中心站，《国外农药品种手册》3，174(1981)
4. Godwin J R, et al. Brighton Crop Prot. Conf.- pests and Diseases. 1992,435～437
5. Beautement K, et al.Pestic. Sci., 1991,31,499～519
6. Kleschich W A, Costales M J, Dunbar J E, et al. Pestic. Sci.,1990,29,341～355
7．罗宣干，高等学校化学学报，1996，17(9)，1416～1420
8．化学工业部农药情报中心站，《国外农药品种手册》2，46、48(1981)
9．尚尔才，刘长令，杜英娟，化工进展，1995，5，8～15
10．刘长令，中国化工报，1998—05—11(4)
11．刘长令，精细与专用化学品，2000，6，1
12. ACROW, ISO proposed names, 1999,No 338,26
13. Angerstein, St.,Ber.,34,3956(1901)
14. GB 1245085(1968)
15. Ger (East)151404(1981)
16. CA102 162065
17. Maeno, S.et al., Brighton Crop Prot. Conf. Pests and diseases, 5-3,415(1990)
18. Neumann, G. L. et al., Brighton Crop Prot. Conf. Pests and diseases,5-1,395(1992)
19．马忠华，叶钟音，农药译丛，1997，19(3)，11～13
20. Harry J. J.Amer. Chem. Soc. 1932, 54, 727
21．孔繁蕾，化学世界，1991，32(6)，254～257
22. Haley CAC, Maitland P.J.Chem. Soc., 1951,3155
23. Hussain, Shaheen A., Pak. J. Sci.Ind.Res. 1998,41(2),63-67
24．薛思佳，化学研究与应用，1998，10(1)，74～78
25．薛思佳，化学试剂，1999，21(2)，73～75
26．张宗涛，王岩，农药，1988，27(3)40～45
27． Beasley,M.L.&Collins,R.L.,Science,169(1970) 769-70
28． Clifford,D.P.&Carson,C.M.,Pestic.Sci.,23(1988) 93-102
29． Nepera Chemical Co.Inc.Brit.564,315,9,22,1944
30． Junichi Ishii,J.Chem.Soc.Japan,Ind.Chem.Sect.1951,54,87
31． Singh P.P.Indian,J.Chem.Sect.A,1976,14(10) ,812-813
32． Singh P.P.Indian,J.Chem.Sect.A,1976,14 A(9) ,684-687
33． Stetsenko A.I.Koord.Khim,1976,2(6) ,834-840(Russ)
34． Kong Pi-Chang.Can.J.Chem,1979,57(5) ,526-529
35． Bhasin S.K.Tran SAEST,1979,14(3) ,145-149
36． Allan J.R.J.Therm.Anal,1981,21(1) ,3-12
37． Lumme Paavo.Finn.Chem.Lett.,1981,13(4) ,25-28
38． ADEGBOYE ADEYEMO,Inorganica Chimica Acta 51(1981) ,19-22
39． Homer L.Werkst Rorros,1982,33(4) ,189-193
40． Mishra L.K.J.Indian.Chem.Soc.,1982,59(3) ,408-409
41． Lavrenova L.GIzv.Sib.Otd.Akad.Nauk.SSSR Ser.Khim.Nauk,1985,3,59-64(Russ)
42． Singh E.B.J.Indian.Chem.Soc.,1987,64(6) ,359-360
43． Kovala-Demertzi D.Bull.Soc.Chim.Belg,1987,96(1) ,7-14
44． Kulig Jacek.POL.J.Chem,1988,62(4-6) ,351-358
45． AL-Hajjar F.H.Corros.Sci.,1988,28(2) ,163-171
46． Kovala-Demerzi,D.Transition Met.Chem.,1990,15(1) ,23-26
47． GRAHAM SMITH,Polyhedron,1991,8,873-876
48． Kovala-Demertzi.Bull.Chem.Soc.Jpn,1991,64(2) ,744-746
49． Bhasin S.K.Bull.Electrochem,1991,7(3) ,146-148
50． Contreras.J.Spectrochim.ActaPart.A,1992,48A(4) ,525-532
51． 姚学斌，应用化学，1994，11(6) ，6-11
52． Xuebin Yao,J.Solid State Chem,1995,117(2) ,333-336
53． 张培志，化学研究与应用，1997，9(1) ，92-94
54． Kovala-Demertzi D.,Spectrochim.Acta Part.A,1998,54A(12) ,1801-1809
55． 张培志，应用化学，2000，17(5) ，558-560
56． Gandhi,Orient.J.Chem.2000,16(2) ,353-354
57． Van Albada,Gerard A,J.Chem.Crystallogr.2000,30(1) ,11-16
58． Miao,Q.Appl.Surf.Sci.2001,171(1-2) 49-56
59． Van Albada,Gerard A,Inorganica Chimica Acta 2002,327,134-139
60． 徐克勋。精细有机化工原料及中间体手册，99～100
61． 薛思佳。化学试剂，1993，15(3) ，181
62． Dong Q.N.Infrared Spectrometry.Beijing Chemical and Indusreial Press,1979．
63． NaKamoto,K.,Written,Huang D.J.;et al.,Translated.Infrared and Roman Specera of Inorganic and Coordination compounds.Bei Jing Chemical and Industrial Press(4th Edi).,1991．
64． Wang J.Q.;et al.Instruction to x-ray Photoelectron spectroscopy(XPS / XAES / UPS).Bei Jing National Defence Industry Press.,1992．
65． 张祖德，张雄，刘清亮；XPS在配位化学中的应用．大学化学，1999，14(4) ，27～31
66． Yang X.W,Chen S.P,Gao S.L,et al.Instrumentation Sci.& techn.2002,30,311
67． Popov,M.M.Thermometry and Calorimetry.Moscow Univ.,Publishing House,Moscow,1954,382
68． Cox,J.D.J.Chem.Thermodyn.1978,10,903
69． Wangman,D.S,Evans,W.H,Pariker,V.B.In The NBS of Chemical Thermodynamic Properties,Translated by Liu,T.H,Zhao,M.K,Chinese standards Press,Beijing,1998