CN100384860C - Process for preparing tungsten complex crystal with multiple channel structure characteristic - Google Patents
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- CN100384860C CN100384860C CNB2006100911698A CN200610091169A CN100384860C CN 100384860 C CN100384860 C CN 100384860C CN B2006100911698 A CNB2006100911698 A CN B2006100911698A CN 200610091169 A CN200610091169 A CN 200610091169A CN 100384860 C CN100384860 C CN 100384860C
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Abstract
The present invention is tungsten complex crystal with multiple pore channel structure and its preparation process. The preparation process includes the reaction of tungsten compound or tungsten polymer, organic amine and catechol benzene or substitution derivative in organic solvent and/or inorganic solvent; filtering the reacted solution; adding ethyl ether to the filtrate and stilling at room temperature or even lower temperature to crystallize. The said process can prepare micron or nanometer level multilayer assembled tubular, strip and lamellar lower dimensional tungsten complex crystal with multiple pore channel structure. The said process has the advantages of controllable product shape and simple technological process.
Description
Technical field
The present invention relates to the preparation method of tungsten complex crystalline substance, especially design has the preparation method of the tungsten complex crystalline substance of multiple channel structure characteristic.
Background technology
20 end of the centurys, because the rise of nanotechnology, nano material is because self small-size effect, surface effects, quantum size effect and macroscopical tunnel effect etc., it demonstrates the character that many conventional particles do not have at aspects such as magnetic, light, electricity, heat and catalysis, shows special physical and chemical performance.People begin exploration nanotechnology are applied to each ambit, because tungsten has many outstanding physics, chemical properties such as high-density, high-melting-point, high rigidity, high-wearing feature, be widely used in various fields such as machinery, electronics, chemical industry, nuclear power, military aviation, the tungsten complex nano material of exploitation and development novel texture and new function has caused that people pay close attention to widely.
Continued since the discovery of carbon fullerene and carbon nanotube, Tenne in 1992 and 1993 etc. have delivered the WS with similar Fuller olefin structure at Nature first
2And MoS
2, started the brand-new field of non-carbon inorganic fullerene nano materials research.
The Chen Wei of department of chemistry of Zhejiang University is auspicious to wait the people to report employing " machinery-physics solid state reaction " device, carries out chemical treatment in high temperature H2S atmosphere, has synthesized inorganic fullerene tungsten sulfide nano material.
Human machinery-physics solid state reaction devices such as the applicating physical system Sun Ke of Central South University brightness have prepared nanometer WS2 lubricant, and have analyzed its microtexture.
Britain Yan Qiu Zhu reports that under given conditions hot spots can be obtained micron order tree structure tungsten oxide by the tungsten paper tinsel that silicon-dioxide wraps up, and through ultra-sonic oscillation, this tree structure can be decomposed into needle-like, sheet and polyhedron nanoparticle.
Application number is the preparation method that the Chinese patent application of CN200510011520.3 discloses a kind of nano tungsten trioxide, blue tungsten and tungsten powder.
The application's applicant has proposed in April 6 calendar year 2001 that application number is 01110359.0, name is called " the octahedra molybdenum tungsten complex of chirality, their synthetic method and the purposes in cancer therapy drug " application, and this application discloses general formula and has been the octahedra molybdenum of the chirality of (I) or tungsten or molybdenum tungsten complex:
Wherein M is the mixture of molybdenum or tungsten or molybdenum tungsten;
Wherein
Be selected from adjacent fragrant diphenol and substitutive derivative thereof, ortho position substituted aroma diamino and substitutive derivative thereof, ortho position substituted aroma dithiol and substitutive derivative thereof, adjacent amino fragrant phenol and substitutive derivative thereof, adjacent hydroxyl aromatic thiophenol and substitutive derivative thereof, substituting group is selected from hydroxyl, the five Yuans single heterocycles of alpha-substitution and the substitutive derivative thereof of amino and sulfydryl, substituting group is selected from hydroxyl, the six Yuans single heterocycles of alpha-substitution and the substitutive derivative thereof of amino and sulfydryl, substituting group is selected from hydroxyl, the five Yuans single heterocycles of alpha-substitution benzo and the substitutive derivative thereof of amino and sulfydryl, substituting group is selected from hydroxyl, the six Yuans single heterocycles of alpha-substitution benzo and the substitutive derivative thereof of amino and sulfydryl, purine series and substitutive derivative thereof, pterin series and substitutive derivative thereof and flavine series and substitutive derivative thereof; M is 4,5 or 6, and n is the arbitrary integer of 1-4.
The contriver finds through a large amount of tests, can the part of compounds of above general formula compound be made nano crystal material by certain method.
Up to now, also forming the report that tungsten complex is built into nano material then about being cooperated with organic ligand by the tungsten metal ion, is that patent documentation or scientific paper are not all reported in this respect.
Summary of the invention
The object of the present invention is to provide the method for preparing tungsten complex crystal, using the prepared tungsten complex of the inventive method is the flaky low-dimensional tungsten complex crystal of tubulose, strip and thin layer with multiple channel structure characteristic.
Having that the inventive method is prepared many (micrometer/nanometer) pore passage structure feature the coordination anion of the flaky low-dimensional tungsten complex of tubulose, strip and thin layer crystalline substance have following general structure:
W wherein
(q+)Be W
(IV), W
(V), W
(VI)Coordination metal center ion, six-ring is a phenyl ring, R is substituting groups such as halogen, alkyl, amino or nitro, alkyl is preferably C1～C5 alkyl, the phenyl ring that this R replaces can be mono-substituted or dibasic or more multidigit replacement, for example three replace or quaternary, replace speech substituting group ortho position, contraposition or a position each other for two, and promptly part is that pyrocatechol aromatics or its benzene ring hydrogen are by single replacement such as halogen, alkyl, amino or nitro or polysubstituted derivative;
The counter cation of coordination anion is a protonated quadrol positively charged ion, protonated 1 in the above-mentioned tungsten complex crystal, 2-propylene diamine or protonated 1,3-propylene diamine positively charged ion.
For preparing above-mentioned nanometer tungsten complex compound, the present invention proposes to be prepared as follows method, and this method comprises tungsten compound or tungsten polymer and organic ligand and organic amine reacted in solvent and prepares the above-mentioned flaky low-dimensional tungsten complex crystal of tubulose, strip and thin layer with many (micrometer/nanometer) pore passage structure feature.
Synthetic route is as follows:
Particularly, the above-mentioned method for preparing the nanometer tungsten complex comprises: under normal temperature or high temperature, tungsten compound or tungsten polymer, organic amine and pyrocatechol or pyrocatechol substitutive derivative are reacted in organic phase solvent, inorganic phase solvent or organic phase and inorganic mixed phase solvent mutually, with reacting liquid filtering, filtrate directly or add ether in filtrate after is left standstill crystallization.Wherein, preferably in filtrate, leave standstill crystallization behind the adding ether, can improve crystallization rate, improve productive rate because add ether, and make crystal formation better.
Above-mentioned preparation method preferably includes following steps:
1. at normal temperatures, tungsten compound or tungsten polymer, organic amine and pyrocatechol aromatics or its substitutive derivative are dissolved in organic phase solvent, inorganic phase solvent or the organic-inorganic mixed phase solvent stirring reaction;
2. reacted solution is filtered and obtain clarifying filtrate, filtrate places container, and the volume of preferred filtrate is smaller or equal to 1/4th of container volume;
3. slowly add ether in filtrate, preferably its volume is not less than 1/6 of filtrate volume;
4. leave standstill crystallization, separating out the crystal that is the low-dimensional pattern in wall of container and bottom is final product, leaves standstill the crystalline temperature preferably in-15 ℃～room temperature range, and it is preferred more than 24 hours to leave standstill crystallization time.
This method also preferably includes following steps:
1. in organic phase solvent, inorganic phase solvent or organic-inorganic mixed phase solvent, tungsten compound or tungsten polymer, organic amine and pyrocatechol aromatics or its substitutive derivative are put into autoclave, autoclave is put into baking oven;
2. the temperature in the adjusting baking oven is 30 ℃-180 ℃, isothermal reaction certain hour under a certain therein temperature, preferred 8～12 hours, cool to room temperature then;
3. reacting liquid filtering is obtained precipitation and filtrate, the reject precipitation;
4. clear filtrate is placed container, the volume of preferred filtrate is smaller or equal to 1/4th of container volume;
5. slowly add ether in filtrate, preferably its volume is not less than 1/6 of filtrate volume;
6. leave standstill crystallization, separating out the crystal that is the low-dimensional pattern in wall of container and bottom is final product, leaves standstill the crystalline temperature preferably in-15 ℃～room temperature range, and it is preferred more than 24 hours to leave standstill crystallization time.
Wherein, select corresponding pyrocatechol or pyrocatechol substitutive derivative according to the structure of part in the coordination anion of required preparation tungsten complex;
The organic phase solvent is methyl alcohol, acetonitrile, acetone or their any mixture, inorganic phase solvent is a water, and organic phase is any mixture of described organic phase solvent (being methyl alcohol, acetonitrile, acetone or their any mixture) and described inorganic phase solvent (being water) with inorganic mixed phase solvent mutually;
Tungsten compound or tungsten polymer are a kind of in sodium wolframate, ammonium tungstate, sulfo-ammonium tungstate, the positive tetrabutyl ten ammonium tungstates, seven ammonium tungstates, two ammonium tungstate, tungsten hexacarbonyl and the tungsten hexachloride;
Organic amine is a quadrol sun, 1,2-propylene diamine or 1,3-propylene diamine.
Use the inventive method can obtain the tungsten complex crystal with multiple channel structure characteristic of nano-scale, this crystal has multi-level assembling characteristic, the wire crystal tiling that is nanoporous obtains nanometer sheet, continue tiling or pile up the crystal that becomes micron level, the micron level crystal further is piled into a millimeter rank crystal.
The present invention utilizes this country's high yield elemental tungsten resource, tungstenic chemical reagent with cheapness is a raw material, with simple reactor, glassware etc. is container, can prepare the flaky low-dimensional tungsten complex crystal of tubulose, strip and thin layer of the multi-level assembling with multiple channel structure characteristic of micron, nanoscale.Such low-dimensional tungsten complex crystalline substance has porous road structure, at Nano grade is nano pore, in micron level is the micron duct, on macro morphology in a tubular form, strip or thin layer sheet, the cavity of its tubulose match crystal and peripheral yardstick from nano level to the millimeter rank, length is from nano level to centimetre rank, and strip match crystal breadth wise dimension is from the nano level to the micron order
Length is an extremely millimeter rank of nano level, and to the millimeter level, the thickness of individual layer is nano level to thin layer sheet match crystal thickness from nano level, and length and width are extremely centimetre rank of nano level.Preparation method provided by the invention has technology and equipment is simple, the advantage of controllable product shape.
Description of drawings
Fig. 1 is that coordination anion structure iron (a), the EPR of tungsten complex crystalline substance 1 among the embodiment 1 schemes (b) and structure cell accumulation graph (c).
Fig. 2 be among the embodiment 1 tungsten complex crystalline substance 1 SEM figure: (a) strip tungsten complex crystalline substance; (b) the brilliant sectional view of strip tungsten complex; (c) tubulose tungsten complex crystalline substance; (d) the brilliant sectional view of tubulose tungsten complex; (e) sheet tungsten complex crystalline substance; (f) the brilliant sectional view of sheet tungsten complex.
Fig. 3 is the TEM figure of tungsten complex crystalline substance 1: (a) brilliant 1 nanotube of tungsten complex; (b) axial, cross-sectional view of brilliant 1 nanotube of tungsten complex.
Fig. 4 is the coordination anion structure iron (a) and the structure cell accumulation graph (b) of tungsten complex crystalline substance 2 among the embodiment 2.
Fig. 5 be tungsten complex crystalline substance 2 among the embodiment 2 SEM figure (a) with and cross-sectional view (b).
Fig. 6 is the TEM figure (a) of tungsten complex crystalline substance 2 among the embodiment 2 and the nanometer line chart (b) that is arranged in parallel.
Fig. 7 is the anion structure (a) and the structure cell accumulation graph (b) of tungsten complex crystalline substance 3 among the embodiment 3.
Fig. 8 be tungsten complex crystalline substance 3 among the embodiment 3 SEM figure (a) with and sectional view (b).
Fig. 9 is TEM figure (a) and the cross section honeycomb figure (b) of tungsten complex crystalline substance 3 among the embodiment 3.
Figure 10 is the molecular structure (a) and the structure cell accumulation graph (b) of tungsten complex crystalline substance 4 among the embodiment 3.
Figure 11 is the SEM figure of tungsten complex crystalline substance 4 among the embodiment 3.
Figure 12 is the TEM figure of tungsten complex crystalline substance 4 among the embodiment 3.
Embodiment
Further describe the present invention below in conjunction with specific embodiment; but embodiment is used for illustrative explanation technical scheme; protection scope of the present invention is not constituted any restriction; it will be understood by those skilled in the art that the replacement of making according to spirit of the present invention any of equal value or revise and all fall within the scope of protection of the present invention.
Embodiment 1
Take by weighing 0.4 gram sodium wolframate (perhaps positive tetrabutyl wolframic acid ammonium salt) and 0.8 gram pyrocatechol respectively and put into the round-bottomed flask of 50ml, in flask, add quadrol 8ml, acetonitrile 10ml, anhydrous methanol 10ml then successively, with magnetic stirrer reaction 8 hours.Reaction solution is filtered with glass funnel, filtrate is placed test tube, slowly add the 4ml ether and carry out the layering diffusion.Left standstill under the room temperature 5 days, the crystal of yellow tubulose, strip and sheet pattern is arranged at test tube wall and bottom is that tungsten complex brilliant 1 generates.
The ultimate analysis value (%) of tungsten complex crystalline substance (tubulose, bar dress and sheet) 1 is (being theoretical value in the bracket): C, 35.17 (35.28); H, 5.70 (5.69); N, 13.60 (13.61).
1H NMR (D
2O is a solvent), 6.59～6.81 (m, ArH), 2.90 (s, NH
3CH
2CH
2NH);
13C NMR (D
2O is a solvent), 156.00 (C), 120.87 (CH on the phenyl ring), 116.65 (CH on the phenyl ring), 113.90 (CH on the phenyl ring), 40.05 (CH
2).Ir data (cm
-1) be: N-H:3362m; Ar-H:3048m; C-O:1479s, 1262s; W-O:892s, 853m, 861s.
X-ray crystal structure is resolved:
Brilliant 1 molecular formula of tungsten complex is (NH
3CH
2CH
2NH
2)
3[WO
2(C
6H
4O
2)
2], molecular weight 615.3, oblique system belongs to P2
1/ c space point group, a=7.1354 (4)
B=30.7781 (16)
C=9.8145 (5)
β=102.696 (2) °, V=2102.70 (11)
R (wR2)=0.0357 (0.0815).
The coordination anion structure of tungsten complex crystalline substance 1, EPR spectrogram and structure cell are piled up and are seen the (a) and (b) of Fig. 1 and (c) respectively.
The stereoscan photograph of tubulose, strip and sheet tungsten complex crystalline substance is seen Fig. 2: (a) strip tungsten complex crystalline substance; (b) the brilliant sectional view of strip tungsten complex; (c) tubulose tungsten complex crystalline substance; (d) the brilliant sectional view of tubulose tungsten complex; (e) sheet tungsten complex crystalline substance; (f) the brilliant sectional view of sheet tungsten complex.Fig. 2 clearly discloses tungsten complex crystalline substance 1 in the porous road of micron level structural performance.The transmission electron microscope photo of tubulose, strip and sheet tungsten complex crystalline substance is seen Fig. 3: (a) brilliant 1 nanotube of tungsten complex; (b) axial, cross-sectional view of brilliant 1 nanotube of tungsten complex.Fig. 3 clearly discloses tungsten complex crystalline substance 1 in the porous road of Nano grade structural performance;
Embodiment 2
Take by weighing the 0.4 gram positive tetrabutyl ten wolframic acid ammonium salts (perhaps ammonium tungstate) and 0.8 gram pyrocatechol respectively and put into the round-bottomed flask of 50ml, in flask, add 1 successively then, 2-propylene diamine 8ml, acetonitrile 10ml, anhydrous methanol 10ml were with magnetic stirrer reaction 10 hours.To react back solution and filter, filtrate will be placed test tube, and slowly add the 3ml ether and carry out the layering diffusion with glass funnel.Left standstill under the room temperature 5 days, xanchromatic strip crystal is arranged at test tube wall and bottom is that tungsten complex brilliant 2 generates.
The ultimate analysis value (%) of tungsten complex crystalline substance 2 is (being theoretical value in the bracket): C, 37.12 (37.13); H, 5.10 (5.06); N, 9.62 (9.67).
1H NMR (D
2O is a solvent): 6.46 (m, ArH), 1.25 (b, CH
3); 2.89,2.93 (m, CH
aH
b *); 3.32 (m, CH);
13C NMR (D
2O is a solvent): 156.02 (C), 121.12 (CH), 116.89 (CH), 113.99 (CH), 49.06 (NCH), 20.38 (NCH
2).Ir data (cm
-1) be: N-H:3362m; Ar-H:3048m; C-O:1479s, 1262s; W-O:892s, 853m, 861s.
X-ray crystal structure is resolved:
The molecular formula of match crystal 2 is: (NH
3CH
2CHCH
2NH
2)
2[WO
2(C
6H
1O
2)
2], molecular weight is 583.32, oblique system belongs to P2
1/ n spacer.Unit cell parameters: a=1.1099 (3) nm, b=1.0416 (3) nm, c=1.8874 (5) nm, β=96.492 (5) °, V=2.1679 (2) nm
3, Z=4, Dc=1.787g/cm
-3, R=0.0455, Rw=0.682.
The coordination anion structure of tungsten complex crystalline substance 2 and structure cell are piled up and are seen Fig. 4 (a) and (b) respectively, and stereoscan photograph is seen Fig. 5, and transmission electron microscope picture is seen Fig. 6.
Embodiment 3
Take by weighing the positive tetrabutyl ten wolframic acid ammonium salts of 0.4 gram (perhaps two ammonium tungstate) and 0.8 gram pyrocatechol respectively and put into the round-bottomed flask of dress 50ml, in flask, add 1 successively then, 3-propylene diamine 8ml, acetonitrile 10ml, anhydrous methanol 10ml were with magnetic stirrer reaction 20 hours.To react back solution and filter, filtrate will be placed test tube, and slowly add the 4ml ether and carry out the layering diffusion with glass funnel.Left standstill under the room temperature 6 days, test tube wall and bottom have xanchromatic strip tungsten complex brilliant 3 and tabular crystal tungsten complex brilliant 4 to generate.
The ultimate analysis value (%) of strip tungsten complex crystalline substance 3 is (being theoretical value in the bracket): C, 37.15 (37.13); H, 5.09 (5.06); N, 9.68 (9.67).
1H NMR (D
2O is a solvent): 6.46 (m, ArH), 2.07 (t, CCH
2), 3.08 (m, NCH
2);
13C NMR (D
2O is a solvent): 158.80 (CH), 122.42 (CH), 119.13 (CH), 117.80 (CH), 116.79 (CH), 40.68 (CCH
2), 32.17 (NCH
2).Ir data (cm
-1) be: N-H:3362m; Ar-H:3048m; C-O:1479s, 1262s; W-O:892s, 853m, 861s.
The x-ray crystal structure of tungsten complex crystalline substance 3 is resolved:
The molecular formula of strip tungsten complex crystalline substance 3 is: (NH
3CH
2CH
2CH
2NH
2)
2[WO
2(C
6H
4O
2)
2], molecular weight is 583.32, rhombic system belongs to the Pbna spacer, unit cell parameters: a=0.7480 (2) nm, b=1.3975 (6) nm, c=1.2181 (6); R=0.0289, Rw=0.0683.
The molecular structure of tungsten complex crystalline substance 3 and structure cell accumulation graph are seen Fig. 7 (a) and (b) respectively, and sem photograph sees 8, and transmission electron microscope photo is seen Fig. 9.
The ultimate analysis value (%) of sheet tungsten complex crystalline substance 4 is (being theoretical value in the bracket): C, 37.15 (37.13); H, 5.09 (5.06); N, 9.68 (9.67).
1H NMR (D
2O is a solvent): 6.46 (m, ArH), 2.07 (t, CCH
2), 3.08 (m, NCH
2);
13C NMR (D
2O is a solvent): 158.80 (CH), 122.42 (CH), 119.13 (CH), 117.80 (CH), 116.79 (CH), 40.68 (CCH
2), 32.17 (NCH
2).Ir data (cm
-1) be: N-H:3362m; Ar-H:3048m; C-O:1479s, 1262s; W-O:892s, 853m, 861s.
The x-ray crystal structure of tungsten complex crystalline substance 4 is resolved:
The molecular formula of sheet tungsten complex crystalline substance 4 is: (NH
3CH
2CH
2CH
2NH
2)
2[WO
2(C
6H
4O
2)
2], molecular weight is 583.32, oblique system belongs to P2
1/ c space point group, unit cell parameters: a=0.7069 (2) nm, b=2.3552 (6) nm, c=1.3016 (6), β=98.178 (5) °, R=0.0272, Rw=0.0663.
The molecular structure of tungsten complex crystalline substance 4 and structure cell accumulation graph are seen Figure 10 (a) and (b) respectively, and sem photograph sees 11, and transmission electron microscope photo is seen Figure 12.
Embodiment 4
With the pyrocatechol among the ortho position chlorine pyrocatechol replacement embodiment 1, other conditions are identical with embodiment 1, make (NH
3CH
2CH
2NH
2)
3[WO
2(o-Cl-C
6H
3O
2)
2].
Embodiment 5
With the pyrocatechol among the position chlorine pyrocatechol replacement embodiment 1, other conditions are identical with embodiment 1, make (NH
3CH
2CH
2NH
2)
3[WO
2(m-Cl-C
6H
3O
2)
2].
Embodiment 6
With the pyrocatechol among the position chlorine pyrocatechol replacement embodiment 2, other conditions are identical with embodiment 2, make (NH
3CH
2CHCH
2NH
2)
2[WO
2(m-Cl-C
6H
3O
2)
2].
Embodiment 7
With the pyrocatechol among the position methyl pyrocatechol replacement embodiment 2, other conditions are identical with embodiment 2, make (NH
3CH
2CHCH
2NH
2)
2[WO
2(m-CH
3-C
6H
3O
2)
2].
Embodiment 8
With the pyrocatechol among the contraposition methyl pyrocatechol replacement embodiment 2, other conditions are identical with embodiment 2, make (NH
3CH
2CHCH
2NH
2)
2[WO
2(m-CH
3-C
6H
3O
2)
2].
Embodiment 9
With the pyrocatechol among the position methyl pyrocatechol replacement embodiment 3, other conditions are identical with embodiment 3, make (NH
3CH
2CH
2CH
2NH
2)
2[WO
2(p-CH
3-C
6H
3O
2)
2].
Pyrocatechol with among the contraposition methyl pyrocatechol replacement embodiment 3 places test tube not add ether filtrate and directly leaves standstill crystallization in 10 days, and other conditions are identical with embodiment 3, make (NH
3CH
2CH
2CH
2NH
2)
2[WO
2(m-CH
3-C
6H
3O
2)
2].
Claims (12)
1. preparation has the method for tungsten complex crystal of porous road structure, and this method comprises reacts tungsten compound or tungsten polymer and organic ligand and organic amine in organic solvent, and the general structure of the coordination anion of described tungsten complex crystal is:
W wherein
(q+)Be W
(IV), W
(V), W
(VI)Coordination metal center ion, six-ring are phenyl ring, and R is hydrogen, halogen, alkyl, amino or nitro;
The counter cation of coordination anion is a protonated quadrol positively charged ion, protonated 1 in the above-mentioned tungsten complex crystal, 2-propylene diamine or protonated 1,3-propylene diamine positively charged ion.
2. the method for claim 1 is characterized in that, described alkyl is C1～C5 alkyl.
3. the method for claim 1, it is characterized in that, this method comprises: under normal temperature or high temperature, tungsten compound or tungsten polymer, organic amine and pyrocatechol or the pyrocatechol that replaced by halogen, alkyl, amino or nitro are reacted at the organic phase solvent, with reacting liquid filtering, filtrate directly or add ether in filtrate after is left standstill crystallization.
4. the method for claim 1 is characterized in that, this method comprises:
(1) at normal temperatures, tungsten compound or tungsten polymer, organic amine and pyrocatechol or the pyrocatechol that replaced by halogen, alkyl, amino or nitro are dissolved in the organic phase solvent stirring reaction;
(2) the reacted solution filtration is obtained clarifying filtrate, filtrate places container;
(3) in filtrate, slowly add ether;
(4) leave standstill crystallization, separating out the crystal that is the low-dimensional pattern in wall of container and bottom is final product.
5. method as claimed in claim 4 is characterized in that:
In the step (1), the volume of described filtrate is smaller or equal to 1/4th of container volume;
And/or in the step (3), the volume of described ether is not less than 1/6 of filtrate volume;
And/or in the step (4), the described crystalline temperature that leaves standstill is in-15 ℃～room temperature range, and leaving standstill crystallization time is more than 24 hours.
6. the method for claim 1 is characterized in that, this method comprises:
(1) in the organic phase solvent, put into autoclave with tungsten compound or tungsten polymer, organic amine and pyrocatechol or by the pyrocatechol that halogen, alkyl, amino or nitro replace, autoclave is put into baking oven;
(2) temperature of regulating in the baking oven is 30 ℃-180 ℃, isothermal reaction, cool to room temperature then under a certain therein temperature;
(3) reacting liquid filtering is obtained precipitation and filtrate, the reject precipitation;
(4) clarifying filtrate is placed container;
(5) in filtrate, slowly add ether;
(6) leave standstill crystallization, separating out the crystal that is the low-dimensional pattern in wall of container and bottom is final product.
7. method as claimed in claim 6 is characterized in that:
In the step (2), described reaction was carried out 8～12 hours;
And/or in the step (4), the volume of described filtrate is smaller or equal to 1/4th of container volume;
And/or in the step (5), the volume of described ether is not less than 1/6 of filtrate volume;
And/or in the step (6), the described crystalline temperature that leaves standstill is in-15 ℃～room temperature range, and leaving standstill crystallization time is more than 24 hours.
8. as each described method of claim 1-7, it is characterized in that described organic phase solvent is methyl alcohol, acetonitrile, acetone or its any mixture.
9. as each described method of claim 1-7, it is characterized in that described tungsten compound or tungsten polymer are a kind of in sodium wolframate, ammonium tungstate, sulfo-ammonium tungstate, the positive tetrabutyl ten ammonium tungstates, seven ammonium tungstates, two ammonium tungstate, tungsten hexacarbonyl and the tungsten hexachloride.
10. as each described method of claim 1-7, it is characterized in that described organic amine is a quadrol, 1,2-propylene diamine or 1,3-propylene diamine.
11., it is characterized in that the pyrocatechol of selecting corresponding pyrocatechol or being replaced according to the part in the coordination anion of required preparation tungsten complex as each described method of claim 1-7 by halogen, alkyl, amino or nitro.
12. tungsten complex crystal with multiple channel structure characteristic according to each described method preparation of claim 1-11.
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|---|---|---|---|---|
| CN1321644A (en) * | 2001-04-06 | 2001-11-14 | 鲁晓明 | Chiral octahedral Mo-W complexes, their synthesis method and application for preparing anticancer medicine |
| CN1634944A (en) * | 2004-12-02 | 2005-07-06 | 首都师范大学 | Molybdenum, wolfram, molybdenum and wolfram complex, method for making and use in preparing anticancer, antitumor medicament |
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2006
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1321644A (en) * | 2001-04-06 | 2001-11-14 | 鲁晓明 | Chiral octahedral Mo-W complexes, their synthesis method and application for preparing anticancer medicine |
| CN1634944A (en) * | 2004-12-02 | 2005-07-06 | 首都师范大学 | Molybdenum, wolfram, molybdenum and wolfram complex, method for making and use in preparing anticancer, antitumor medicament |
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