CN102827210B - Naphthol aldehyde Schiff alkali cobalt coordination polymer and preparation method and application thereof - Google Patents
Naphthol aldehyde Schiff alkali cobalt coordination polymer and preparation method and application thereof Download PDFInfo
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- CN102827210B CN102827210B CN201210334292.3A CN201210334292A CN102827210B CN 102827210 B CN102827210 B CN 102827210B CN 201210334292 A CN201210334292 A CN 201210334292A CN 102827210 B CN102827210 B CN 102827210B
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Abstract
The invention discloses a naphthol aldehyde Schiff alkali cobalt coordination polymer. A preparation method of the naphthol aldehyde Schiff alkali cobalt coordination polymer comprises the following steps of: (1) enabling raw materials including 2-amino group-2-ethyl-1, 3-propylene glycol and 2-oxhydryl-1-naphthaldehyde to react in solvent carbinol for 3-5h, steaming out the solvent, and drying after freezing, so that 2-oxhydryl-1-naphthaldehyde-2-amino group-2-ethyl-1, 3-propylene glycol Schiff alkali ligand can be obtained; and (2) under room-temperature condition, enabling raw materials including Co(CH3COO)2.4H2O and 2-oxhydryl-1-naphthaldehyde-2-amino group-2-ethyl-1, 3-propylene glycol Schiff alkali ligand to react in solvent carbinol for 4-6h, filtering to obtain solid matter, dissolving in ethanol, and standing and volatilizing solution, thus obtaining a brick-red blocky crystal, i.e. the naphthol aldehyde Schiff alkali cobalt coordination polymer provided by the invention. The coordination polymer is higher in antitumor activity, and can be taken as the raw material to prepare the drug for curing human pulmonary adenocarcinoma and human chronic granulocytic leukemia erythroleukemia pathological change. Compared with the common-used cis-platinum anticancer drugs, the naphthol aldehyde Schiff alkali cobalt coordination polymer has the characteristics of being high in antitumor activity, stability, and the like.
Description
Technical field
The present invention relates to a kind of new naphthols aldehydes Schiff alkali cobalt ligand polymer of antitumour activity and ferromagnetic exchange and preparation method thereof that has, and this compound is mainly in the application of preparing in cancer therapy drug.
Background technology
Cancer is to threaten one of disease that human life is the most serious at present, and the morbidity of cancer has presented the trend of increase year by year and rejuvenation.According to WHO statistics, 2007, the cancer patient that newly make a definite diagnosis in the whole world reached more than 1,200 ten thousand, and in the past few years, the patient of cancer is died from up to more than 7,000,000 in the whole world, expects the year two thousand twenty cancer patients and will reach every year more than 2,000 ten thousand.At present remain traditional operative treatment, radiotherapy and pharmacological agent for the methods for the treatment of of cancer, remain to a great extent taking pharmacological agent as main, so research and development are efficient, the new type antineoplastic medicine tool of low toxicity is of great significance.
Started from for 16th century for metal complexes for the research of tumour, until reported first cis-platinum in 1969 has after anti-tumor activity, just make metal and metal coordinating polymer thereof develop rapidly in applied research pharmaceutically.Because ligand polymer has novel topological framework and various accumulation mode, organic ligand in molecule not only have the paramagnetic center interionic distance of shortening from, also there is good transmission electronic capability, so, ligand polymer is also the good member of molecular magnetic materials research system, and especially functional metal coordinating polymer has broad application prospects in medicine and material science.
For above-mentioned prior art, the invention provides a kind of new naphthols aldehydes Schiff alkali cobalt ligand polymer of antitumour activity and ferromagnetic exchange and preparation method thereof that has, and this compound is mainly in the application of preparing in cancer therapy drug.
The present invention is achieved by the following technical solutions:
A kind of naphthols aldehydes Schiff alkali cobalt ligand polymer, structural formula is as follows:
Wherein, n is positive integer.
The preparation method of described naphthols aldehydes Schiff alkali cobalt ligand polymer, comprises the following steps:
(1) reaction raw materials APED and 2-hydroxyl-1-naphthalene Formaldehyde react 3～5 hours in solvent methanol, heated and stirred backflow (reflux temperature of methyl alcohol) in reaction process; After reaction, steam solvent, freezing rear dry, obtain 2-hydroxyl-1-naphthalene Formaldehyde contracting-APED Schiff aar ligand;
Wherein, the ratio of the amount of substance of described APED and 2-hydroxyl-1-naphthalene Formaldehyde is: 1.0:1.0～2.5; The consumption of described methyl alcohol is APED and 2-hydroxyl-1-naphthalene Formaldehyde total mass 20～25 times;
(2) under room temperature condition, reaction raw materials Co (CH
3cOO)
2.4H
22-hydroxyl-1-naphthalene Formaldehyde contracting-2-amino-2-ethyl-1 prepared by O and step (1), ammediol Schiff aar ligand reacts 4～6 hours in solvent methanol, in reaction process, ceaselessly stir, filter to obtain solid substance, dissolve with ethanol obtains solution, etoh solvent is removed in solution left standstill volatilization, obtains bulk crystals, is naphthols aldehydes Schiff alkali cobalt ligand polymer;
Wherein, described Co (CH
3cOO)
2.4H
2the ratio of the amount of substance of O and 2-hydroxyl-1-naphthalene Formaldehyde contracting-APED Schiff aar ligand is: 1.0～2.0:1.0;
The consumption of described methyl alcohol is Co (CH
3cOO)
2.4H
2o and 2-hydroxyl-1-naphthalene Formaldehyde contracting-APED Schiff aar ligand total mass 15～25 times.
Preferably, in described step (1), reaction raw materials 2-amino-2-ethyl-1, the specific implementation that ammediol and 2-hydroxyl-1-naphthalene Formaldehyde react 3～5 hours in solvent methanol is: in reactor, add 2-amino-2-ethyl-1, the methanol solution of ammediol, and the methanol solution of 2-hydroxyl-1-naphthalene Formaldehyde, heated and stirred refluxes 3～5 hours.
Preferably, in described step (1), evaporating solvent adopts Rotary Evaporators evaporation.
Preferably, in described step (1), freezing is at 0 DEG C of carry out below freezing.
Preferably, in described step (2), reaction raw materials Co (CH
3cOO)
2.4H
2the specific implementation that 2-hydroxyl-1-naphthalene Formaldehyde contracting-APED Schiff aar ligand prepared by O and step (1) reacts 4～6 hours in solvent methanol is: by Co (CH
3cOO)
2.4H
2the methanol solution of O, under agitation adds in the methanol solution of 2-hydroxyl-1-naphthalene Formaldehyde contracting-APED Schiff aar ligand stirring at room temperature 4～6 hours.
The product that described step (1) obtains is khaki color solid, yield: 81.6～83.4%, and fusing point: 138～141 DEG C.Through Infrared spectroscopy, ultimate analysis, nuclear-magnetism and ultraviolet spectral analysis, result is as follows:
Infrared spectra (KBr compressing tablet: cm
-1): 3444(vO-H), 2923(vArC-H), 1644(vC=N), 1542(vArC=C) and, 1384(δ ArC-H), 1252(vAr-O).
Ultimate analysis C
16h
19nO
3(Mw:273.33): calculated value: C 70.31, H 7.01, N 5.12%; Measured value: C 70.38, H 7.09, N 5.21%.
1h nuclear-magnetism (CDCl
3, δ/ppm): 8.907(s, 1H ,-CH=N), 7.694-7.695(d, 1H, AR-H), 7.322-7.370(t, 1H, AR-H), 7.245-7.291(m, 2H, AR-H), 7.073-7.110(t, 1H, AR-H), 6.657-6.602 (d, 1H, AR-H), 4.677 (br, 2H,-OH), 3.934-4.00(t, 4H ,-CH
2oH), 1.62-1.783(m, 2H ,-CH
2cH
3), 0.935-0.975(t, 3H ,-CH
3).
UV spectrum (λ
max methanol, nm): 231,248,305,398.
Can determine that its structural formula is:
Naphthols aldehydes Schiff alkali cobalt ligand polymer of the present invention, for brick-red bulk crystals, belongs to tetragonal system, and spacer is I4 (1)/a, and fusing point is 189～192 DEG C, while adopting aforesaid method to prepare, and productive rate 77.8～80.1%.Product is through Infrared spectroscopy, ultimate analysis and ultraviolet spectral analysis, and result is as follows:
Infrared spectra (KBr compressing tablet, cm
-1): 3430(-OH), 1618 (vC=N), 1540 (vasCOO
-), 1436 (vsCOO
-), 1084(Ph-O), 545(Co-N), 485(Co-O).
Ultimate analysis C
35h
43co
2n
2o
10(Mw:769.59): calculated value: C 54.62, H 5.63, N 3.64%; Measured value: C54.58, H 5.46, the product that N 3.49%(obtains is characterized by ligand polymer through x-ray diffractometer, the molecular formula that molecular formula is herein repeating unit; In addition, for the polymerization degree n of this polymkeric substance, belong to polymer chemistry research category, and Research Significance is little, therefore applicant does not measure, but does not affect the confirmation of its structure and the checking of function)
UV spectrum (λ
max methanol, nm): 269,361.
Crystallographic data: crystallographic system belongs to tetragonal system, spacer is I4 (1)/a, unit cell parameters is
α=90 °, β=90 °, γ=90 °,
z=4, D=1.465g.cm
-3, F (000)=6416, crystalline size size is 0.13 × 0.10 × 0.07mm.
Described naphthols aldehydes Schiff alkali cobalt ligand polymer has antitumour activity, can be for the preparation of the medicine for the treatment of human lung adenocarcinoma and the change of human chronic myelogenous leukemia's erythroleukemia.Naphthols aldehydes Schiff alkali cobalt ligand polymer of the present invention is that the Sauerstoffatom in Sauerstoffatom, nitrogen-atoms and the acetate moiety in four tooth Schiff aar ligands is combined with the form of hexa-coordinate with cobalt (II) and cobalt (III) ion, form the octoploids structure of two distortions, the structural unit of ligand polymer connects into one dimensional helical chain shape structure by acetic acid anion, and molecular formula is C
35h
43co
2n
2o
10, molecular weight is 769.59.Naphthols aldehydes Schiff alkali cobalt ligand polymer of the present invention has higher antitumour activity, can its medicine becoming for raw material preparation treatment human lung adenocarcinoma and human chronic myelogenous leukemia's erythroleukemia, compared with the cis-platinum kind anti-cancer drugs generally using, have that antitumour activity is high, a feature such as good stability, preparation method is simple, cost is low,, environmentally safe corrosion-free to equipment.And this ligand polymer molecular memory is in ferromagnetic exchange character, and this provides new way for developing PTS and ligand polymer magnetic molecule material.
Brief description of the drawings
Fig. 1 is the structural formula of naphthols aldehydes Schiff alkali cobalt ligand polymer of the present invention.
Fig. 2 is the temperature variant XMT-T curve of susceptibility of naphthols aldehydes Schiff alkali cobalt ligand polymer.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated.
Embodiment 1: prepare naphthols aldehydes Schiff alkali cobalt ligand polymer
Step is as follows:
(1) in 100mL round-bottomed flask, add 2-hydroxyl-1-naphthalene Formaldehyde 1.722g(10.0mmol) and 20ml methyl alcohol, stirring and dissolving.Then under agitation drip the methanol solution of 15ml APED (1.196g, 10.0mmol), heating, refluxes, and stirs 4.0 hours, and rotation steams solvent, and the freezing khaki color solid of separating out, obtains naphthols aldehydes Schiff aar ligand.Yield: 81.6%, fusing point: 138～140 DEG C.
Synthetic naphthols aldehydes Schiff aar ligand is through Infrared spectroscopy, ultimate analysis, nuclear-magnetism and ultraviolet spectral analysis, and result is as follows:
Infrared spectra (KBr compressing tablet: cm
-1): 3444(vO-H), 2923(vArC-H), 1644(vC=N), 1542(vArC=C) and, 1384(δ ArC-H), 1252(vAr-O).
Ultimate analysis C
16h
19nO
3(Mw:273.33): calculated value: C 70.31, H 7.01, N 5.12%; Measured value: C 70.38, H 7.09, N 5.21%.
1h nuclear-magnetism (CDCl
3, δ/ppm): 8.907(s, 1H ,-CH=N), 7.694-7.695(d, 1H, AR-H), 7.322-7.370(t, 1H, AR-H), 7.245-7.291(m, 2H, AR-H), 7.073-7.110(t, 1H, AR-H), 6.657-6.602 (d, 1H, AR-H), 4.677 (br, 2H,-OH), 3.934-4.00(t, 4H ,-CH
2oH), 1.62-1.783(m, 2H ,-CH
2cH
3), 0.935-0.975(t, 3H ,-CH
3).
UV spectrum (λ
max methanol, nm): 231,248,305,398.
Can determine that its structural formula is:
(2) in reactor, add 0.273g(1.0mmol) Schiff aar ligand and 10ml methyl alcohol, stir and make its dissolving.Again by 0.249g(1.0mmol) Co (CH
3cOO)
2.4H
2methyl alcohol (10ml) solution of O is slowly added drop-wise in Schiff aar ligand solution, stirring at room temperature 4.0 hours.Filter, with anhydrous alcohol solution, leave standstill solvent flashing, obtain brick-red bulk crystals, be naphthols aldehydes Schiff alkali cobalt ligand polymer of the present invention, productive rate 77.8%, fusing point: 189～190 DEG C.
Product is through Infrared spectroscopy, ultimate analysis and ultraviolet spectral analysis, and result is as follows:
Infrared spectra (KBr compressing tablet, cm
-1): 3430(-OH), 1618 (vC=N), 1540 (vasCOO
-), 1436 (vsCOO
-), 1084(Ph-O), 545(Co-N), 485(Co-O).
Ultimate analysis C
35h
43co
2n
2o
10(Mw:769.59): calculated value: C 54.62, H 5.63, N 3.64%; Measured value: C54.58, H 5.46, N 3.49%.
UV spectrum (λ
max methanol, nm): 269,361.
Crystallographic data: crystallographic system belongs to tetragonal system, spacer is I4 (1)/a, unit cell parameters is
α=90 °, β=90 °, γ=90 °,
z=4, D=1.465g.cm
-3, F (000)=6416, crystalline size size is 0.13 × 0.10 × 0.07mm.
Can determine that its structural formula is for (as shown in Figure 1):
Embodiment 2: prepare naphthols aldehydes Schiff alkali cobalt ligand polymer
Step is as follows:
(1) in 100mL round-bottomed flask, add 2-hydroxyl-1-naphthalene Formaldehyde 1.722g(10.0mmol) and 18ml methyl alcohol, stirring and dissolving.Then under agitation drip the methanol solution of 18ml APED (0.957g, 8.0mmol), heating, refluxes, and stirs 3.0 hours, and rotation steams solvent, and the freezing khaki color solid of separating out, obtains naphthols aldehydes Schiff aar ligand.Yield: 82.7%, fusing point: 138～140 DEG C.
(2) in reactor, add 0.273g(1.0mmol) Schiff aar ligand and 10ml methyl alcohol, stirring and dissolving.Again by 0.374g(1.5mmol) Co (CH
3cOO)
2.4H
2methyl alcohol (15ml) solution of O is slowly added drop-wise in Schiff aar ligand solution, stirring at room temperature 4.5 hours.Filter, with anhydrous alcohol solution, leave standstill solvent flashing.Obtain brick-red bulk crystals, be naphthols aldehydes Schiff alkali cobalt ligand polymer of the present invention, productive rate 79.4%, fusing point: 189～191 DEG C.
Embodiment 3: prepare naphthols aldehydes Schiff alkali cobalt ligand polymer
Step is as follows:
(1) in 100mL round-bottomed flask, add 2-hydroxyl-1-naphthalene Formaldehyde 2.583g(15.0mmol) and 30ml methyl alcohol, stirring and dissolving.Then under agitation drip the methanol solution of 15ml APED (0.718g, 6.0mmol), heating, refluxes, and stirs 3.5 hours, and rotation steams solvent, and the freezing khaki color solid of separating out, obtains naphthols aldehydes Schiff aar ligand.Yield: 83.4%, fusing point: 138～141 DEG C.
(2) in reactor, add 0.546g(2.0mmol) Schiff aar ligand and 25ml methyl alcohol, stirring and dissolving.Again by 0.996g(4.0mmol) Co (CH
3cOO)
2.4H
2methyl alcohol (30ml) solution of O is slowly added drop-wise in Schiff aar ligand solution, stirring at room temperature 5.0 hours.Filter, with anhydrous alcohol solution, leave standstill solvent flashing.Obtain brick-red bulk crystals, be naphthols aldehydes Schiff alkali cobalt ligand polymer of the present invention, productive rate 78.6%, fusing point: 189～192 DEG C.
Embodiment 4: prepare naphthols aldehydes Schiff alkali cobalt ligand polymer
Step is as follows:
(1) in 100mL round-bottomed flask, add 2-hydroxyl-1-naphthalene Formaldehyde 2.067g(12.0mmol) and 25ml methyl alcohol, stirring and dissolving.Then under agitation drip the methanol solution of 20ml APED (1.196g, 10.0mmol), heating, refluxes, and stirs 4.5 hours, and rotation steams solvent, and the freezing khaki color solid of separating out, obtains naphthols aldehydes Schiff aar ligand.Yield: 82.7%, fusing point: 138～140 DEG C.
(2) in reactor, add 0.410g(1.5mmol) Schiff aar ligand and 20ml methyl alcohol, stirring and dissolving.Again by 0.747g(3.0mmol) Co (CH
3cOO)
2.4H
2methyl alcohol (30ml) solution of O is slowly added drop-wise in Schiff aar ligand solution, stirring at room temperature 5.0 hours.Filter, with anhydrous alcohol solution, leave standstill solvent flashing.Obtain brick-red bulk crystals, be naphthols aldehydes Schiff alkali cobalt ligand polymer of the present invention, productive rate 79.2%, fusing point: 189～191 DEG C.
Embodiment 5: prepare naphthols aldehydes Schiff alkali cobalt ligand polymer
Step is as follows:
(1) in 100mL round-bottomed flask, add 2-hydroxyl-1-naphthalene Formaldehyde 2.583g(15.0mmol) and 30ml anhydrous methanol, stirring and dissolving.Then under agitation drip the methanol solution of 20ml APED (1.435g, 12.0mmol), heating, refluxes, and stirs 5.5 hours, and rotation steams solvent, and the freezing khaki color solid of separating out, obtains naphthols aldehydes Schiff aar ligand.Yield: 81.9%, fusing point: 138～141 DEG C.
(2) in reactor, add 0.273g(1.0mmol) Schiff aar ligand and 10ml methyl alcohol, stirring and dissolving.Again by 0.498g(2.0mmol) Co (CH
3cOO)
2.4H
2methyl alcohol (25ml) solution of O is slowly added drop-wise in Schiff aar ligand solution, stirring at room temperature 3.0 hours.Filter, with anhydrous alcohol solution, leave standstill solvent flashing.Obtain brick-red bulk crystals, be naphthols aldehydes Schiff alkali cobalt ligand polymer of the present invention, productive rate 78.0%, fusing point: 189～192 DEG C.
Embodiment 6: prepare naphthols aldehydes Schiff alkali cobalt ligand polymer
Step is as follows:
(1) in reactor, add 2-hydroxyl-1-naphthalene Formaldehyde 25.832g(150.0mmol) and 350ml methyl alcohol, stirring and dissolving.Then under agitation drip the absolute methanol solution of 200ml APED (11.964g, 100.0mmol), heating, refluxes, and stirs 5.0 hours, rotation steams solvent, and the freezing khaki color solid of separating out, obtains naphthols aldehydes Schiff aar ligand.Yield: 83.0%, fusing point: 138～141 DEG C.
(2) in reactor, add 2.730g(10.0mmol) Schiff aar ligand and 100ml methyl alcohol, stirring and dissolving.Again by 2.494g(10.0mmol) Co (CH
3cOO)
2.4H
2anhydrous methanol (150ml) solution of O is slowly added drop-wise in Schiff aar ligand solution, stirring at room temperature 5.0 hours.Filter, with anhydrous alcohol solution, leave standstill solvent flashing.Obtain brick-red bulk crystals, be naphthols aldehydes Schiff alkali cobalt ligand polymer of the present invention, productive rate 80.1%, fusing point: 189～191 DEG C.
Embodiment 7: prepare naphthols aldehydes Schiff alkali cobalt ligand polymer
Step is as follows:
(1) in reactor, add 2-hydroxyl-1-naphthalene Formaldehyde 25.832g(150.0mmol) and 380ml anhydrous methanol, stirring and dissolving.Then under agitation drip the absolute methanol solution of 160ml APED (9.560g, 80.0mmol), heating, refluxes, and stirs 4.5 hours, and rotation steams solvent, and the freezing khaki color solid of separating out, obtains naphthols aldehydes Schiff aar ligand.Yield: 82.6%, fusing point: 138～140 DEG C.
(2) in reactor, add 2.730g(10.0mmol) Schiff aar ligand and 120ml methyl alcohol, stirring and dissolving.Again by 4.982g(20.0mmol) Co (CH
3cOO)
2.4H
2anhydrous methanol (250ml) solution of O is slowly added drop-wise in Schiff aar ligand solution, stirring at room temperature 6.0 hours.Filter, with anhydrous alcohol solution, leave standstill solvent flashing.Obtain brick-red bulk crystals, be naphthols aldehydes Schiff alkali cobalt ligand polymer of the present invention, productive rate 79.8%, fusing point: 189～192 DEG C.
Naphthols aldehydes Schiff alkali cobalt ligand polymer of the present invention (prepared by embodiment 1), its Anticancer Activity in vitro is measured and is realized by MTT experimental technique, and its principle is:
MTT analytical method: with metabolism reduction 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl terrazoliumbromide is basis, has the desaturase relevant to NADP in viable cell plastosome, yellow MTT can be reduced into insoluble hepatic Formazan, dead cell is without this enzyme, MTT is not reduced, and with after DMSO dissolving Formazan, available microplate reader is measured the optical density(OD) of characteristic wavelength, carry out relevant data processing, reach a conclusion.
With MTT analytical method, human lung adenocarcinoma A-549 cell strain and human chronic myelogenous leukemia's erythroleukemia change K-562 cell strain are analyzed, measured its IC
50value, and with the IC of cis-platinum to A-549 cell strain and K-562 cell strain
50value (reference respectively: Y.S.Sohn, H.Baek, Y.H.ho, et.al., International Journal of Pharmaceutics[J], 1997, (153): 79 – 91; Han Chong, Li great Cheng, Dou Jianmin, phenanthroline sodium formiate fentin chloride compound and its preparation method and application [P], China, 201110350237.9,2011,11,08.) compare, result is as shown in table 1.Conclusion is: cancer therapy drug of the present invention, and to the external activity IC of human lung adenocarcinoma and the change of human chronic myelogenous leukemia's erythroleukemia
50be worth all IC lower than cis-platinum (DDP)
50value, illustrates that cancer therapy drug of the present invention has good Anticancer Activity in vitro, can be used as the candidate compound of cancer therapy drug.
Table 1 naphthols aldehydes Schiff alkali cobalt ligand polymer cancer therapy drug external activity test data
| Human lung adenocarcinoma | Human chronic myelogenous leukemia's erythroleukemia becomes | |
| Sample IC 50（μg/mL） | 0.7 | 2.0 |
| DDP IC 50（μg/mL） | 1.0 | 2.018 |
| Method | MTT | MTT |
| Cell strain | A-549 | K-562 |
Naphthols aldehydes Schiff alkali cobalt ligand polymer of the present invention (prepared by embodiment 1), its magnetic performance research is as follows:
The magnetic test of naphthols aldehydes Schiff alkali cobalt ligand polymer is used MPMS-XL-7SQUID instrument to complete, and all magnetic datas all use pascal constant to carry out diamagnetic correction, test the background data such as sample hose and sample thin film used and are deducted.The temperature variant χ of its susceptibility
mt-T curve is shown in Fig. 2.
Magnetic Measurement result shows: at room temperature χ of this ligand polymer
mt is 2.44cm
3mol
-1k, much larger than single Co
2+(g=2) spin state theoretical value 1.875cm of ion
3mol
-1k.Along with the reduction of temperature, χ
mt reduces gradually, reaches minimum value 1.62cm at 8.9K
3mol
-1k, rises subsequently gradually, reaches maximum 1.81cm when 2.0K
3mol
-1k.This is because the cobalt ion of octahedra has very strong spin orbital coupling, causes
4t
1gground state is split into six Kramers doublets, causes the χ of high-temperature zone
mthe decline of T value.Cold zone χ
mthe rising of T may be (reference: Y.G.Li, Q.Wu, L.Lecren, J.Mol.Struct.2008, (890): 339 – 345 of causing due to the iron magnetic action a little less than interchain or zero-field splitting.）。These magnetic features show that this ligand polymer molecular memory is in ferromagnetic exchange behavior.
Claims (10)
1. a naphthols aldehydes Schiff alkali cobalt ligand polymer, structural formula is as follows:
Wherein, n is positive integer.
2. the preparation method of naphthols aldehydes Schiff alkali cobalt ligand polymer claimed in claim 1, comprises the following steps:
(1) reaction raw materials APED and 2-hydroxyl-1-naphthalene Formaldehyde react 3～5 hours in solvent methanol, and in reaction process, heated and stirred refluxes; After reaction, steam solvent, freezing rear dry, obtain 2-hydroxyl-1-naphthalene Formaldehyde contracting-APED Schiff aar ligand;
Wherein, the ratio of the amount of substance of described APED and 2-hydroxyl-1-naphthalene Formaldehyde is: 1.0:1.0～2.5;
The volumetric usage of described methyl alcohol is APED and 2-hydroxyl-1-naphthalene Formaldehyde total mass 20～25 times;
(2) under room temperature condition, reaction raw materials Co (CH
3cOO)
2.4H
22-hydroxyl-1-naphthalene Formaldehyde contracting-2-amino-2-ethyl-1 prepared by O and step (1), ammediol Schiff aar ligand reacts 4～6 hours in solvent methanol, in reaction process, ceaselessly stir, filter to obtain solid substance, dissolve with ethanol obtains solution, etoh solvent is removed in solution left standstill volatilization, obtains bulk crystals, is naphthols aldehydes Schiff alkali cobalt ligand polymer;
Wherein, described Co (CH
3cOO)
2.4H
2the ratio of the amount of substance of O and 2-hydroxyl-1-naphthalene Formaldehyde contracting-APED Schiff aar ligand is: 1.0～2.0:1.0;
The volumetric usage of described methyl alcohol is Co (CH
3cOO)
2.4H
2o and 2-hydroxyl-1-naphthalene Formaldehyde contracting-APED Schiff aar ligand total mass 15～25 times.
3. the preparation method of naphthols aldehydes Schiff alkali cobalt ligand polymer according to claim 2, it is characterized in that: in described step (1), reaction raw materials 2-amino-2-ethyl-1, the specific implementation that ammediol and 2-hydroxyl-1-naphthalene Formaldehyde react 3～5 hours in solvent methanol is: in reactor, add 2-amino-2-ethyl-1, the methanol solution of ammediol, and the methanol solution of 2-hydroxyl-1-naphthalene Formaldehyde, heated and stirred refluxes 3～5 hours.
4. the preparation method of naphthols aldehydes Schiff alkali cobalt ligand polymer according to claim 2, is characterized in that: in described step (1), evaporating solvent adopts Rotary Evaporators evaporation.
5. the preparation method of naphthols aldehydes Schiff alkali cobalt ligand polymer according to claim 2, is characterized in that: in described step (1), freezing is at 0 DEG C of carry out below freezing.
6. the preparation method of naphthols aldehydes Schiff alkali cobalt ligand polymer according to claim 2, is characterized in that: in described step (2), and reaction raw materials Co (CH
3cOO)
2.4H
2the specific implementation that 2-hydroxyl-1-naphthalene Formaldehyde contracting-APED Schiff aar ligand prepared by O and step (1) reacts 4～6 hours in solvent methanol is: by Co (CH
3cOO)
2.4H
2the methanol solution of O, under agitation adds in the methanol solution of 2-hydroxyl-1-naphthalene Formaldehyde contracting-APED Schiff aar ligand stirring at room temperature 4～6 hours.
7. naphthols aldehydes Schiff alkali cobalt ligand polymer claimed in claim 1 becomes the application in medicine at preparation treatment human lung adenocarcinoma and human chronic myelogenous leukemia's erythroleukemia.
8. an intermediate for naphthols aldehydes Schiff alkali cobalt ligand polymer, structural formula is as follows:
9. the preparation method of the intermediate of naphthols aldehydes Schiff alkali cobalt ligand polymer claimed in claim 8, is characterized in that: step is as follows:
Reaction raw materials APED and 2-hydroxyl-1-naphthalene Formaldehyde react 3～5 hours in solvent methanol, and in reaction process, heated and stirred refluxes; After reaction, steam solvent, freezing rear dry, obtain 2-hydroxyl-1-naphthalene Formaldehyde contracting-APED Schiff aar ligand;
Wherein, the ratio of the amount of substance of described APED and 2-hydroxyl-1-naphthalene Formaldehyde is: 1.0:1.0～2.5;
The volumetric usage of described methyl alcohol is APED and 2-hydroxyl-1-naphthalene Formaldehyde total mass 20～25 times.
10. the intermediate of naphthols aldehydes Schiff alkali cobalt ligand polymer claimed in claim 8 is in the application of preparing in naphthols aldehydes Schiff alkali cobalt ligand polymer.
Priority Applications (1)
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| CN102399168A (en) * | 2011-09-20 | 2012-04-04 | 聊城大学 | Cu (II) coordination compound of Schiff base, preparation method, and application thereof |
| CN102408453A (en) * | 2011-09-20 | 2012-04-11 | 聊城大学 | Salicylaldehyde Schiff base binuclear cobalt coordination compound and preparation method and application thereof |
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| CN102399168A (en) * | 2011-09-20 | 2012-04-04 | 聊城大学 | Cu (II) coordination compound of Schiff base, preparation method, and application thereof |
| CN102408453A (en) * | 2011-09-20 | 2012-04-11 | 聊城大学 | Salicylaldehyde Schiff base binuclear cobalt coordination compound and preparation method and application thereof |
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| Title |
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| Li Li Hu et al..Synthesis, crystal structure and magnetic properties of a mixed-valence pentanuclear cobalt complex.《Dalton Transactions》.2008,第37卷第6113-6116页. * |
| LiLiHuetal..Synthesis crystal structure and magnetic properties of a mixed-valence pentanuclear cobalt complex.《Dalton Transactions》.2008 |
| Shyamapada Shit et al..A new tetranuclear copper(II) Schiff base complex containing Cu4O4 cubane core: Structural and spectral characterizations.《Journal of Molecular Structure》.2011,第911卷(第1-3期),第79-83页. * |
| Yan Qin Wang et al..Magnetic Systems with Mixed Carboxylate and Azide Bridges: Slow Relaxation in Co(II) Metamagnet and Spin Frustration in Mn(II) Compound.《Inorganic Chemistry》.2011,第50卷(第13期),第6314-6322页. * |
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