CN102643298B - Amino-pyrazol title complex, its preparation method and application thereof - Google Patents
Amino-pyrazol title complex, its preparation method and application thereof Download PDFInfo
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Abstract
The present invention relates to a kind of amino-pyrazol title complex, its preparation method and application thereof.The general formula of this title complex is: M (AMP)
nl
m , wherein: M is transition metal ion, AMP is 3-methyl-5-amino-pyrazol, and L is Cl
-or containing carboxyl ligand, n be 1 or 2, m be 1 or 2.The present invention is in conjunction with the sterilization and disinfection effect of amino-pyrazol to the regulating effect of plant-growth and heavy metal ion, two kinds of components are made first to be combined into title complex, the disassociation of recycling title complex, coexist in same system after making two kinds of component segregations, act synergistically on and promote several seed germination, achieve good result.
Description
Technical field
The present invention relates to a kind of amino-pyrazol title complex, its preparation method and application thereof.
Background technology
There are some researches show that amino-pyrazol and derivative thereof have positive using value in agricultural insecticide and biological medicine.
As the people such as Bull, R.M. found a kind of amino-pyrazol-derivatives in 1994, be a kind of good Banana tree sterilant, its structural formula is:
The people such as Morimoto, K. have synthesized the intermediate of a kind of important medicine and agrochemicals in 1987, its molecular structure is:
The people such as Kordik, C.P. report several amino-pyrazol human nerve's p277 5 acceptor to avidity in calendar year 2001.And point out that this kind of amino-pyrazol has certain prospect on slimming medicine.
At present in the patent of invention promoting seed germination, used promotor mainly contains following several:
1 plant growth hormones class, as patent CN1391807, CN1210663, CN101142917, CN85100966, CN101099422, CN101336573, CN101385412, CN101530026, CN101715665A, CN101785382A, CN101548596, Plant hormones regulators,gibberellins in CN101836528A etc., PBI 58, indolylacetic acid, brassinolide, 6-benzyladenine etc., these hormones compounds have good biological regulation function, are applicable to various plants seed, suitability is strong, efficient height.But its source not easily, cost is higher, and the solvability of some dry powder compound in water is too poor, some time also first must add organic solvent dissolution, so troublesome poeration.
2 certain Plant Extracts, ginko pyroligneous disclosed in CN101273730.This ginkgo extract derives from rare tree species, and cost is high, bad adaptability, limited efficiency.
3 soak the pH value of water as the sulfuric acid in patent CN101292579, CN101411260 or sodium hydroxide etc. with common inorganic acid-alkali accommodation.The method of this change acid-basicity may be very effective to certain plants seed, but and be not suitable for common crop seeds.Its suitability is also limited.
4 are caused as CN85100966, CN101422098, CN101861771A etc. by special illumination.These class methods are very effective, but often need lighting box, and light irradiation apparatus cost is high, operates more complicated, and not easily realize operation in enormous quantities.
Organic swelling solvent CN101455139, CN101663934, the CN101720582A etc. such as 5 alcohol.Add solvent cost, and limited efficiency.
6 Macrogol 4000 polymeric PTC materials water-keeping materials etc.As CN101836529A, CN1177436, CN101366331 etc. need in the seed germination of adequate water.
7 some special mechanical means or physical wall breaking householder methods.As more complicated in the equipment in CN1032894, heated for controlling temperature complex operation, automatically controlled heating installation also more complicated in CN102177838A, the control of the CN101692761A controlled temperature conditions that wets is higher, manipulate the time long, CN101897255A needs incubator especially, is not suitable for a large amount of seed treatment of farm crop simultaneously, in CN101861771A, equipment is complicated, needs the solar panel that price is high.CN101960943A to be not suitable for the equipment of farm crop CN101971726A complicated, use cost is high.
8 inorganic salts are as CN101297623, CN101578995, CN101589726, CN1774971 etc.These class methods mainly because provide N, inorganic nutrients such as P, K, Ca and facilitate the growth of plant seedling.
On the other hand, in seed immersion process, normally used disinfection sanitizer is potassium permanganate, superoxide, heavy metallic salt (as bivalent mercury) or hypochlorite.And sterilization process and pregermination procedure generally all separate and carry out.This repeated multiple times treating processes not only complex operation, and easily certain destruction is produced to seed, affect its germinating growth.
Amino-pyrazol not only has stronger biological activity, and the leaded wastewater also due to amino-pyrazol is higher, can provide necessary supplementary nutrient, so amino-pyrazol should have certain biological regulation function for seed germination.But the research of title complex in biological regulation still not having amino-pyrazol and metal ion to be formed at present is reported.
Summary of the invention
An object of the present invention is to provide a kind of amino-pyrazol title complex, and this title complex take amino-pyrazol as major ligand, and the common and metal ion of auxiliary Ligands forms stable title complex.
Two of object of the present invention is the preparation method providing this title complex.
Three of object of the present invention is to provide this title complex promoting the application in seed germination.
For achieving the above object, mechanism of the present invention is: first can promote two of seed germination kinds of components by coordination method: the metal ion namely getting germicidal action to regulate and the amino-pyrazol of nutrition composition combines with getting, the metal complexes that forming component is single, then utilize the disassociation of title complex, two components are emanated in solution, jointly promotes the process of seed germination.
According to above-mentioned mechanism, the present invention adopts following technical scheme:
A kind of amino-pyrazol title complex, is characterized in that the composition general formula of this title complex is:
, wherein: M is transition metal ion, AMP is 3-methyl-5-amino-pyrazol, and L is Cl
-or containing dicarboxyl part, n be 1 or 2, m be 1 or 2.
Above-mentioned M can be Cu
2+, Cd
2+, Co
2+or Zn
2+; Described can be 2,6-dicarboxyl pyridine, 2,5-dicarboxyl pyridine or terephthalic acids containing dicarboxyl part.
Above-mentioned M is Cu
2+, L is chlorion.
Above-mentioned M is Cd
2+, L is 2,6-dicarboxyl pyridine.
Above-mentioned M is Co
2+, L is 2,5-dicarboxyl pyridine.
Above-mentioned M is Zn
2+, L is terephthalic acid.
A kind of method preparing above-mentioned amino-pyrazol title complex, it is characterized in that the concrete steps of the method are: mixed by the ethanolic soln of transition metal chloride solution with 3-amino-5-methylpyrazole, and the mol ratio controlling transition metal chloride and 3-amino-5-methylpyrazole is: 1 ︰ 1 ~ 1 ︰ 3, the volume ratio of ethanol and water is under the condition of 1 ︰ 1 ~ 1 ︰ 10; Stirring at room temperature 20 ~ 25h, backflow 1 ~ 3h, resolution of precipitate, filtered while hot, leaves standstill, has crystal to separate out; Crystal is washed with water, dry, namely obtain amino-pyrazol title complex.
A kind of method preparing above-mentioned amino-pyrazol title complex, it is characterized in that the concrete steps of the method are: mixed by the ethanolic soln of soluble transition metal salts solution with 3-amino-5-methylpyrazole, stirring at room temperature 0.5 ~ 1.5h, then the aqueous solution containing dicarboxyl part slowly adding that pH is 7, reflux 2.5 ~ 3.5h, filtered while hot, leave standstill, have crystal to separate out, by crystal washing with alcohol, drying, namely obtains amino-pyrazol title complex; Described soluble transition metal salt, 3-amino-5-methylpyrazole and the mol ratio containing dicarboxyl part are 1 ︰ 1 ︰ 1 ~ 1 ︰ 3 ︰ 1, and the volume ratio of ethanol and water is at 1 ︰ 1 ~ 1 ︰ 10.
A kind of method preparing above-mentioned amino-pyrazol title complex, it is characterized in that the concrete steps of the method are: pH be 7 containing dicarboxyl part the aqueous solution in, slowly add soluble transition metal salts solution, then add the aqueous solution of 3-amino-5-methylpyrazole, stirring at room temperature 20 ~ 30 hours, filter, leave standstill, have crystal to separate out, by crystal washing with alcohol, drying, namely obtains amino-pyrazol title complex; Described soluble transition metal salt, 3-amino-5-methylpyrazole and the mol ratio containing dicarboxyl part are 1 ︰ 1 ︰ 1 ~ 1 ︰ 3 ︰ 1, and the volume ratio of ethanol and water is at 1 ︰ 1 ~ 1 ︰ 10.
A kind of above-mentioned amino-pyrazol title complex is promoting the application in seed germination.
Above-mentioned seed can be mung bean seed, soya bean seed or rice paddy seed.
The present invention is in conjunction with the sterilization and disinfection effect of amino-pyrazol to the regulating effect of plant-growth and heavy metal ion, two kinds of components are made first to be combined into title complex, the disassociation of recycling title complex, coexist in same system after making two kinds of component segregations, act synergistically on and promote several seed germination, achieve good result.
Accompanying drawing explanation
fig. 1 is the structure iron of the embodiment of the present invention 1 gained title complex.
fig. 2 is the structure iron of the embodiment of the present invention 2 gained title complex.
fig. 3 is title complex (1) [Cd (C of different concns 4 h 7 n 3 ) 2 cl 2 ] n to the germination effect of soya bean, mung bean and paddy rice.(all seeds, all at indoor cultivation, do not accept direct illumination, and medial temperature is 12 DEG C.Average bud length is that to calculate the average bud of the seed germinateed long, error ± 1mm).
fig. 4 is title complex (2) [Cu (C 4 h 7 n 3 ) (C 7 h 3 o 4 n)] 2H 2 o is to soya bean and green germination of bean effect.all seeds, all at indoor cultivation, do not accept direct illumination, and medial temperature is 12 DEG C.Average bud length is that to calculate the average bud of the seed germinateed long.Error ± 1mm.
fig. 5 is the effect that 3-amino-5-methylpyrazole, cadmium chloride solution and water germinate to soya bean, mung bean and paddy rice.All seeds, all at indoor cultivation, do not accept direct illumination, and medial temperature is 12 DEG C.Average bud length is that to calculate the average bud of the seed germinateed long.Error ± 1mm.
(comparative example 1.1-1.9)
fig. 6 is the effect that copper nitrate solution germinates to soya bean and mung bean.All seeds, all at indoor cultivation, do not accept direct illumination, and medial temperature is 12 DEG C.Average bud length is that to calculate the average bud of the seed germinateed long.Error ± 1mm.
(comparative example 2.1-2.2).
Embodiment
Illustrate in greater detail the present invention by the following examples.When not being particularly limited in embodiment, the ratio of reactive material is mol ratio.Ultimate analysis CarloErba1106 type elemental analyser measures; Infrared spectra adopts KBr pressed disc method, with U.S. Buddhist nun's high-tensile strength company AVATAR370 type determination of infrared spectroscopy; Fusing point is measured by SGWX-4 micro-meldometer (Shanghai optical instrument factory), and thermometer is not calibrated.
Agents useful for same is analytical pure or chemical pure, does not purify further: 3-amino-5-methylpyrazole, CdCl before using
25/2H
2o, Cu (NO
3)
23H
2o, 2,6-dinicotinic acid, 2,5-dicarboxyl pyridine, terephthalic acid.Water is tap water, and soya bean, mung bean and paddy rice are all direct to be bought from supermarket, unprocessed.
crystal structure determination
Choose the top of sizeable single crystal sticky at glass fibre, be placed on BrukerSmartApex II CCD single X-ray diffractometer instrument and carry out structured testing, under 296 (2) K, collect diffraction data with ω scan mode with MoK ɑ (λ=0.71073) ray through graphite device monochromatization, diffracted intensity is through Lorentz-Polarization Summing Factor SADABS absorption correction.All data are through semiempirical absorption correction, and reduction of data and structure elucidation use SHELXL-97 and SHELXS-97 program to complete respectively, and the anisotropy of complete matrix method of least squares to non-hydrogen atom is revised, and adopts theoretical hydrogenation to hydrogen atom.
embodiment 1:title complex [Cd (C
4h
7n
3)
2cl
2]
n(
1) synthesis
In 25ml round-bottomed flask, add 2ml containing CdCl
25/2H
2o (0.1141g, aqueous solution 0.5mmol) and 2ml are containing 3-amino-5-methylpyrazole (0.0970g, ethanolic soln 1mmol), generates a small amount of yellow mercury oxide, stirring at room temperature 24h, reflux 2h, resolution of precipitate, filtered while hot, light yellow filtrate leaves standstill, slow volatilization, has a large amount of light yellow bulk crystals to separate out.Crystal is used a small amount of water washing, vacuum-drying.The productive rate of title complex (1) crystal is: 31%.The elemental analysis value (being theoretical value in bracket) of title complex (1) is C:25.74(25.45), H:4.12(3.74), N:22.75(22.26).Its fusing point is 212 DEG C (decomposition).In infared spectrum 3284.90,3211.35cm
-1belong to asymmetrical stretching vibration and the symmetrical stretching vibration of amino N-H.3131.55cm
-1n-H stretching vibration on ownership pyrazole ring.2922.17,2880.36cm
-1belong to C-H asymmetrical stretching vibration and the symmetrical stretching vibration of methyl.1621.79,1587.21,1493.93cm
-1belong to the skeletal vibration of pyrazole ring.777.60cm
-1belong to the formation vibration of amino N-H.1316.22cm
-1belong to C-N
nH2stretching vibration.Title complex (1) crystal belongs to oblique system, P2 (1)/c spacer, unit cell parameters: a=11.0005 (13), b=8.2028 (9), c=7.6172 (9); β=101.7300 (10) °, V=672.98 (13)
3, Z=2, Dc=1.863mg/m
3.This complex structure figure, see Fig. 1.
embodiment 2:title complex (
2) [Cu (C
4h
7n
3) (C
7h
3o
4n)] 2H
2the synthesis of O
In 25ml round-bottomed flask, add 3ml containing Cu (NO
3)
23H
2the ethanolic soln of O (0.0483g, 0.2mmol), then add 4ml containing 3-amino-5-methylpyrazole (0.0388g, ethanolic soln 0.4mmol), stirring at room temperature 1h, solution is blackish green, slowly add the aqueous solution that 4ml NaOH is adjusted to 2, the 6-dinicotinic acids (0.0334g, 0.2mmol) of PH=7 again, after dropwising, have blue-greenish colour to precipitate to generate, reflux 3h, resolution of precipitate, filtered while hot, has green platelet-type crystal to separate out immediately.By crystal washing with alcohol, vacuum-drying.Title complex (
2) productive rate be: 52%.Title complex (
2) [Cu (C
4h
7n
3) (C
7h
3o
4n)] 2H
2the elemental analysis value of O is (being theoretical value in bracket) C:36.33(36.52), H:3.77(3.90), N:15.72(15.49).Its fusing point > 250 DEG C.Infared spectrum has indicated the existence of part 3-amino-5-methylpyrazole and 2,6-dinicotinic acid.3069.75,3046.92cm
-1the absorption peak at place belongs to asymmetrical stretching vibration and the symmetrical stretching vibration of methyl in title complex.3324.94,3246.77cm
-1the absorption peak at place belongs to asymmetrical stretching vibration in title complex on amino and symmetrical stretching vibration.1633.09,1430.76cm
-1the absorption peak at place belongs to asymmetrical stretching vibration and the symmetrical stretching vibration of carboxyl in title complex, Δ v=202cm respectively
-1, illustrate that carboxyl is with the coordination of monodentate mode.1619.28,1594.58,1577.45,1513.14cm
-1the absorption peak at place belongs to the skeletal vibration of pyrazole ring and pyridine ring in title complex, 1313.42cm
-1c-N
nH2stretching vibration absorption peak.779.26cm
-1belong to the N-H key formation vibration in title complex on amino.3475.07,3382.97cm
-1the O-H key that the absorption peak located can be attributed to the lattice water of the existence in crystal forms the asymmetrical stretching vibration after associating and symmetrical stretching vibration.Title complex
(2)belong to oblique system, P2 (1)/c spacer, unit cell parameters: a=13.3754 (18), b=12.5047 (17), c=8.3925 (11); β=99.727 (2) °, V=1383.5 (3)
3, Z=4, Dc=1.737mg/m
3.The molecular structure of this title complex, see Fig. 2.
embodiment 3:title complex
(1)[Cd (C
4h
7n
3)
2cl
2]
ndilute solution effect that soya bean, mung bean and paddy rice are germinateed
The concentration being respectively charged into 10mL in the beaker of 50mL is respectively 0.05mgmL
-1, 0.1mgmL
-1, 0.5mgmL
-1, 1.0mgmL
-1title complex (
1) solution, join respectively after each 20 soya beans, mung bean and rice paddy seeds are rinsed one time in flowing water above-mentioned title complex (
1) in solution, room temperature leaves standstill soaks, the title complex that renews after 24 hours (
1) solution 10mL, measured every three days and to record each seed germination bud long, acquired results, see Fig. 3
.
embodiment 4:title complex
(2)[Cu (C
4h
7n
3) (C
7h
3o
4n)] 2H
2the dilute solution of O is to soya bean and mung bean germination effect
The concentration being respectively charged into 10mL in the beaker of 50mL is respectively 0.05mgmL
-1, 0.1mgmL
-1, 0.5mgmL
-1, 1.0mgmL
-1title complex (
2) solution, join respectively after each 20 soya beans and mung bean seed are rinsed one time in flowing water above-mentioned title complex (
2) in solution, room temperature leaves standstill soaks, the title complex that renews after 24 hours (
2) solution 10mL, measured every two to three days and to record each seed germination bud long, acquired results is see Fig. 4.
comparative example 1:the effect that 3-amino-5-methylpyrazole, cadmium chloride solution and water germinate to soya bean, mung bean and paddy rice
The concentration being respectively charged into 10mL in the beaker of 50mL is respectively 0.5mgmL
-13-amino-5-methylpyrazole solution, 0.5mgmL
-1cadmium chloride solution and water.Join in above-mentioned solution respectively after each 20 soya beans and mung bean seed are rinsed one time in flowing water, room temperature leaves standstill soaks, and the solution 10mL renewed after 24 hours, measured every two to three days and to record each seed germination bud long, and acquired results is see Fig. 5.
comparative example 2:the effect that cupric nitrate germinates to soya bean and mung bean
The concentration being respectively charged into 10mL in the beaker of 50mL is 0.5mgmL
-1copper nitrate solution.Join in above-mentioned solution respectively after each 20 soya beans and mung bean seed are rinsed one time in flowing water, room temperature leaves standstill soaks, and the solution 10mL renewed after 24 hours, measured every two to three days and to record each seed germination bud long, and acquired results, see Fig. 6.
Comparison diagram 3 and Fig. 5, as embodiment 3, soya bean: 3 days percentage of germination >90%, 9 days long >3.4cm of bud.Mung bean: 2 days percentage of germination >80%, 9 days long >2.4cm of bud.Paddy rice: 3 days percentage of germination 100%, 9 days long >1.8cm of bud.And at comparative example 1.2, soya bean in 1.5,1.8: 3 days percentage of germination 50%, 9 days long >2.2cm of bud.Mung bean: 2 days percentage of germination >40%, 9 days long 1.7cm of bud.Paddy rice: 3 days percentage of germination 40%, 9 days long 1.3cm of bud.According to this result: title complex (1) has promoter action when lower concentration to the germination of soya bean, mung bean and paddy rice, and Cadmium chloride fine powder (0.5mgmL
-1) germination slightly restraining effect to soya bean, mung bean and paddy rice.And 3-amino-5-methylpyrazole (0.5mgmL
-1) differing not obvious with the effect of water, the former is better than the latter slightly.Data in same comparison diagram 4 and 6 are known, and title complex (2) also has promoter action when lower concentration to soya bean and green germination of bean.
embodiment 5: title complex (3) [Co (C
4
h
7
n
3
) (C
7
h
3
o
4
n)]
n
synthesis
In 25ml round-bottomed flask, add 2ml containing Co (NO
3)
26H
2the ethanolic soln of O (0.0436g, 0.15mmol), then add 4ml containing 3-amino-5-methyl pyrazole (0.0582g, ethanolic soln 0.6mmol), stirring at room temperature 1h, solution takes on a red color, more slowly add that 4ml NaOH is adjusted to PH=7 2,5-dinicotinic acid (0.0251g, aqueous solution 0.15mmol), after dropwising, solution presents redness, after stirring 24h, leave standstill and obtain red crystals.Crystal is washed with water, vacuum-drying.Productive rate: 55%, fusing point > 250 DEG C.In IR, 3307.17,3148.84cm
-1the absorption peak at place belongs to asymmetrical stretching vibration and the symmetrical stretching vibration of the N-H key in title complex on amino.1640.78cm
-1the absorption peak at place belongs to the asymmetrical stretching vibration of carboxyl in title complex, and 1483.62,1413.52cm
-1the absorption peak at place belongs to the symmetrical stretching vibration of carboxyl.Elemental analysis value (being theoretical value in bracket) C:41.35(41.14), H:3.02(3.14), N:17.86(17.45).
embodiment 6: title complex (4) { [Zn (C
4
h
7
n
3
) (C
8
h
4
o
4
)] 2H
2
o}
n
synthesis
In 25ml round-bottomed flask, add the aqueous solution that 4ml NaOH is adjusted to the terephthalic acid (0.0416g, 0.25mmol) of PH=7, more slowly add 2ml containing Zn (NO
3)
26H
2the aqueous solution of O (0.0744g, 0.25mmol), generates a large amount of white precipitate, stirring at room temperature 1h, then add the aqueous solution of 4ml containing 3-amino-5-methyl pyrazole (0.0485g, 0.5mmol), after stirring at room temperature 24h, after evaporative removal solvent, namely obtain yellow mercury oxide.Wash with water after sedimentation and filtration, vacuum-drying.Productive rate: 65%, fusing point 70 DEG C.In IR, 3441.62,3274.45cm
-1the absorption peak at place belongs to asymmetrical stretching vibration and the symmetrical stretching vibration of the N-H key in title complex on amino.3163.97,3076.50cm
-1the absorption peak at place belongs to the unsaturated C-H stretching vibration absorption peak on phenyl ring and pyrazole ring.The stretching vibration absorption peak of methyl is 2982.52 and 2921.23cm
-1.1613.26,1425.65cm
-1the absorption peak at place belongs to C-O asymmetrical stretching vibration and the symmetrical stretching vibration of carboxyl in title complex respectively.Elemental analysis value (being theoretical value in bracket) C:40.27(39.74), H:4.34 (4.17), N:11.93 (11.59).
Claims (8)
1. an amino-pyrazol title complex, is characterized in that the composition general formula of this title complex is:
, n be 1 or 2, m be 1 or 2, AMP be 3-methyl-5-amino-pyrazol, L is 2,6-dicarboxyl pyridines, 2,5-dicarboxyl pyridine or terephthalic acids; M is Cu
2+, Cd
2+, Co
2+or Zn
2+.
2. amino-pyrazol title complex according to claim 1, is characterized in that described M is Cd
2+, L is 2,6-dicarboxyl pyridine.
3. amino-pyrazol title complex according to claim 1, is characterized in that described M is Co
2+, L is 2,5-dicarboxyl pyridine.
4. amino-pyrazol title complex according to claim 1, is characterized in that described M is Zn
2+, L is terephthalic acid.
5. prepare the method for amino-pyrazol title complex according to any one of claim 1 to 4 for one kind, it is characterized in that the concrete steps of the method are: mixed by the ethanolic soln of soluble transition metal salts solution with 3-amino-5-methylpyrazole, stirring at room temperature 0.5 ~ 1.5h, then the aqueous solution containing dicarboxyl part slowly adding that pH is 7, reflux 2.5 ~ 3.5h, filtered while hot, leave standstill, have crystal to separate out, by crystal washing with alcohol, drying, namely obtains amino-pyrazol title complex; Described soluble transition metal salt, 3-amino-5-methylpyrazole and the mol ratio containing dicarboxyl part are 1 ︰ 1 ︰ 1 ~ 1 ︰ 3 ︰ 1, and the volume ratio of ethanol and water is at 1 ︰ 1 ~ 1 ︰ 10.
6. prepare the method for amino-pyrazol title complex according to any one of claim 1 to 4 for one kind, it is characterized in that the concrete steps of the method are: pH be 7 containing dicarboxyl part the aqueous solution in, slowly add soluble transition metal salts solution, then add the aqueous solution of 3-amino-5-methylpyrazole, stirring at room temperature 20 ~ 30 hours, filter, leave standstill, have crystal to separate out, by crystal washing with alcohol, drying, namely obtains amino-pyrazol title complex; Described soluble transition metal salt, 3-amino-5-methylpyrazole and the mol ratio containing dicarboxyl part are 1 ︰ 1 ︰ 1 ~ 1 ︰ 3 ︰ 1, and the volume ratio of ethanol and water is at 1 ︰ 1 ~ 1 ︰ 10.
7. an amino-pyrazol title complex according to claim 1 is promoting the application in seed germination.
8. application according to claim 7, is characterized in that described seed is mung bean seed, soya bean seed or rice paddy seed.
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| "Transition metal complexes with pyrazole-based ligands. Part 6.: Synthesis, characterization and thermal decomposition of cadmium complexes with 3 (5)-amino-5 (3)-methylpyrazole";Mészáros Szécsényi K，et al.;《Thermochimica acta》;19981231;第316卷(第1期);第79-85页 * |
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