CN108558935B - Vanadic anhydride crystalline material and its synthetic method based on the modification of tartaric acid chiral derivatives - Google Patents
Vanadic anhydride crystalline material and its synthetic method based on the modification of tartaric acid chiral derivatives Download PDFInfo
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- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 238000010189 synthetic method Methods 0.000 title claims abstract description 22
- 239000002178 crystalline material Substances 0.000 title claims abstract description 17
- 238000012986 modification Methods 0.000 title claims abstract description 12
- 230000004048 modification Effects 0.000 title claims abstract description 12
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 235000002906 tartaric acid Nutrition 0.000 title claims abstract description 9
- 239000011975 tartaric acid Substances 0.000 title claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 48
- 239000000376 reactant Substances 0.000 claims description 40
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 36
- 150000001875 compounds Chemical class 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 239000012046 mixed solvent Substances 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 12
- 238000002425 crystallisation Methods 0.000 claims description 10
- 230000008025 crystallization Effects 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- FEWJPZIEWOKRBE-LWMBPPNESA-N levotartaric acid Chemical compound OC(=O)[C@@H](O)[C@H](O)C(O)=O FEWJPZIEWOKRBE-LWMBPPNESA-N 0.000 claims description 8
- OTXHZHQQWQTQMW-UHFFFAOYSA-N (diaminomethylideneamino)azanium;hydrogen carbonate Chemical compound OC([O-])=O.N[NH2+]C(N)=N OTXHZHQQWQTQMW-UHFFFAOYSA-N 0.000 claims description 7
- 229960001367 tartaric acid Drugs 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 229960001270 d- tartaric acid Drugs 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 2
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 claims 2
- 239000003446 ligand Substances 0.000 abstract description 22
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical group [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052720 vanadium Inorganic materials 0.000 abstract description 8
- 239000000047 product Substances 0.000 description 55
- 239000013078 crystal Substances 0.000 description 26
- 230000015572 biosynthetic process Effects 0.000 description 23
- 238000003786 synthesis reaction Methods 0.000 description 22
- 238000004458 analytical method Methods 0.000 description 14
- 239000012467 final product Substances 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 150000003852 triazoles Chemical class 0.000 description 12
- 239000000843 powder Substances 0.000 description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 10
- 239000000706 filtrate Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 238000009825 accumulation Methods 0.000 description 4
- 229960000583 acetic acid Drugs 0.000 description 4
- 238000002050 diffraction method Methods 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 239000012265 solid product Substances 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 241000388479 Physochlaina Species 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000002447 crystallographic data Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920002338 polyhydroxyethylmethacrylate Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- PNXOJQQRXBVKEX-UHFFFAOYSA-N iron vanadium Chemical compound [V].[Fe] PNXOJQQRXBVKEX-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/005—Compounds of elements of Group 5 of the Periodic Table without metal-carbon linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
- C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D249/14—Nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Plural Heterocyclic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses two vanadic anhydride crystalline materials based on the modification of tartaric acid chiral derivatives, specially complex 1 or complex 2, shown in the chemical formula of the complex 1 for example following (1), [(V2O5)(L-bate)](1)；Belong to monoclinic system, C2Space group；Shown in the chemical formula of the complex 2 for example following (2): [(V2O5)(D-bate)](2)；Belong to monoclinic system, C2Space group.Two complexs remain the script structure of vanadic anhydride, are by a V respectively2O5Molecule and a L-bate ligand or D-bate ligands form double-core vanadium structure, and vanadium atom takes the trigonal biyramid configuration of pentacoordinate.Synthetic method of the present invention is simple to operation, and raw material is easy to get.
Description
Technical field
The present invention relates to the vanadic anhydride crystalline materials and its synthetic method modified based on tartaric acid chiral derivatives, belong to
In organometallic chemistry technical field.
Background technique
Vanadium is VB race, and First Transition series elements have 3d34s2Valence electron constructure, the d track of outer layer sky can join
With bonding, the compound of the vanadium of+3 ,+4 ,+5 equivalent states is formed, is also easy to and formation V-O, V-N, V-S keys such as oxygen, nitrogen, sulphur.
Common vanadic anhydride in the market is presented+5 valences, is a kind of orange-yellow powder, is widely used in smelting vanadium
Iron, chemical industry etc., and organic catalysis, nano material, biology, in terms of have a wide range of applications.Five oxidations two
Vanadium does not dissolve in ethyl alcohol, is slightly soluble in water, is soluble in strong acid and strong base.
The applicant has found that a pair of of enantiomer chirality of introducing is organic on the basis of vanadic anhydride matches during the experiment
Body obtains the complex type crystalline material of a pair of of enantiomerism.
Summary of the invention
The technical problem to be solved in the present invention is to provide two structure novels based on the modification of tartaric acid chiral derivatives
Vanadic anhydride crystalline material and its synthetic method.
It is of the present invention based on tartaric acid chiral derivatives modification vanadic anhydride crystalline material, be complex 1 or
Complex 2, shown in the chemical formula of the complex 1 for example following (1), shown in the chemical formula of the complex 2 for example following (2):
Complex 1:[(V2O5)(L-bate)](1)；
Wherein, -1,2-ethanediol, i.e. L L-bate L-1,2-bis (5-amion-1H-1,2,4-triazole)
Bis- (5- amino -1H-1,2,4- the triazole) -1,2- ethylene glycol of type 1,2-；
The vanadic anhydride crystalline material belongs to monoclinic system, C2Space group, cell parameter are as follows:α=90.00 °, β=107.629 (10) °,
γ=90.00 °；
Complex 2:[(V2O5)(D-bate)](2)；
Wherein, -1,2-ethanediol, i.e. D D-bate D-1,2-bis (5-amion-1H-1,2,4-triazole)
Bis- (5- amino -1H-1,2,4- the triazole) -1,2- ethylene glycol of type 1,2-；
The vanadic anhydride crystalline material belongs to monoclinic system, C2Space group, cell parameter are as follows: α=90.00 °, β=107.599 (6) °, γ=
90.00°。
In above-mentioned technical proposal, the complex 1 is the vanadic anhydride modified based on L-TARTARIC ACID chiral derivatives
Crystalline material, by a V2O5Molecule and a L-bate ligands form double-core vanadium structure, and vanadium atom takes the three of pentacoordinate
Angle bipyramid configuration.The material is not soluble in water, ethyl alcohol, strong acid (when pH=1 static two hours all insoluble), is soluble in highly basic (pH
Then dissolved when >=13.6) and dimethyl sulfoxide.The complex 2 is five oxidations modified based on D- tartaric acid chiral derivatives
Two vanadium crystalline materials are by a V2O5Molecule and a D-bate ligands form double-core vanadium structure, and vanadium atom takes pentacoordinate
Trigonal biyramid configuration.The material is not soluble in water, ethyl alcohol, strong acid (when pH=1 static two hours all insoluble), is soluble in highly basic
(then being dissolved when pH >=13.6) and dimethyl sulfoxide.
The synthetic method of vanadic anhydride crystalline material of the present invention based on the modification of tartaric acid chiral derivatives are as follows:
Take V2O5It is dissolved with the compound as shown in following formula (I) or the compound as shown in following formula (II) with mixed solvent, adjusts acquired solution
PH=4.0-6.0, gained mixed liquor react under heating condition, and reactant is cooling, stand crystallization, respectively obtain 1 He of complex
Complex 2；Wherein, the mixed solvent is the composition of water and acetonitrile；
In above-mentioned synthetic method, V2O5With the molar ratio of the compound as shown in following formula (I) or the compound as shown in following formula (II)
Usually stoichiometric ratio specifically can be 1:1.5-2.0.
In above-mentioned synthetic method, in the composition of mixed solvent, ratio of the acetonitrile shared by the mixed solvent is preferably 30-
40v/v%.The dosage of the mixed solvent can determine as needed, be usually advisable with that can dissolve the raw material participated in and reacted, specifically
Ground is calculated on the basis of compound or the compound as shown in following formula (II) shown in the formula (I) of 1mmol, the mixing used of whole raw materials
Total dosage of solvent is generally 12-15mL.In specific the step of dissolving, it can will participate in after the raw material reacted mix again
Mixed solvent is added to be dissolved, remixes after can also dissolving the raw material for participating in reaction with mixed solvent respectively and carries out together
Reaction.
In above-mentioned synthetic method, solution can be adjusted using existing common alkaline matter (such as pyridine or triethylamine)
PH value.In technical solution of the present invention, the pH=4.5-5.5 of solution is preferably adjusted.
In above-mentioned synthetic method, whether reaction can use thin-layer chromatography (TLC) tracing detection completely.Reaction preferably exists
It is carried out under the conditions of 40-100 DEG C, the time control reacted at this time is appropriate in 2-8h；Reaction is further preferably in 60-100 DEG C of item
It carries out under part, is more preferably carried out under the conditions of 60-80 DEG C.
Compound shown in compound shown in formula involved in above-mentioned synthetic method (I) or formula (II) can refer to existing literature
((A.A.Dippold,T.M.And N.Winter.Eur.J.Inorg.Chem., 2012,3474-3484) into
Row synthesis or the synthesis of designed, designed route.It is preferred that being prepared as follows:
Compound shown in compound shown in the formula (I) or formula (II) is prepared as follows:
1) it takes L-TARTARIC ACID or D- tartaric acid and aminoguanidin carbonate to be placed in reaction vessel, concentrated hydrochloric acid is added, in 70-
It is reacted under the conditions of 90 DEG C, until solution is in faint yellow clear liquid, stops reaction, it is cooling, obtain reactant A；
2) pH >=12.0 for adjusting reactant A, then react under the conditions of 100-110 DEG C, until occurring white in solution
Precipitating and solution are in yellowish-brown turbid, stop reaction, cooling, obtain reactant B；
3) pH=3.0-4.0 for adjusting reactant B, there is a Precipitation, collects precipitating, washing, dry to get arriving formula (I)
Compound shown in shown compound or formula (II).
In the step 1) of compound shown in compound shown in above-mentioned synthesis formula (I) or formula (II), L-TARTARIC ACID or D- winestone
The molar ratio of acid and aminoguanidin carbonate is usually stoichiometric ratio, specifically can be 1:2-3.With the L-TARTARIC ACID of 1mmol
On the basis of, the concentrated hydrochloric acid of 10-12ml is added in the whole raw materials for participating in reaction.In the step, react under the conditions of 70-90 DEG C to molten
Liquid is usually 15-24h in the time of faint yellow clear liquid.
It, can be using existing common in the step 2) of compound shown in compound shown in above-mentioned synthesis formula (I) or formula (II)
Alkaline matter (such as ammonium hydroxide, sodium acetate, sodium carbonate, sodium phosphate, sodium bicarbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, hydrogen-oxygen
Change calcium etc.) adjust the pH value of reactant A, preferably selection sodium hydroxide is adjusted；Further preferably adjust the pH=of reactant A
12.0-14.0.In the step, being reacted under the conditions of 100-110 DEG C to the time that solution is in yellowish-brown turbid is 15-24h.
It, can be using existing common in the step 3) of compound shown in compound shown in above-mentioned synthesis formula (I) or formula (II)
Acidic materials (such as acetic acid or phosphoric acid), preferably adjusting reactant B pH acidic materials be acetic acid.In the step, usually
It is to be washed with cold water, the product after washing is dry under the conditions of being usually placed in 60-80 DEG C.
Compared with prior art, the present invention introduces a paratartaric acid chiral derivatives respectively on the basis of vanadic anhydride
Ligand L-bate and ligand D-bate obtains two new crystalline materials, respectively complex 1 and complex 2, they retain
The script structure of vanadic anhydride, is by a V respectively2O5Molecule and a L-bate ligand or a ligand D-bate are matched
Position forms double-core vanadium structure, and vanadium atom takes the trigonal biyramid configuration of pentacoordinate.Synthetic method is simple to operation, and raw material is easy to get,
Resulting materials not soluble in water, ethyl alcohol, strong acid (all not dissolving for static two hours when pH=1) are synthesized, highly basic (pH >=13.6 are soluble in
When then dissolve) and dimethyl sulfoxide, may biology, catalysis, in terms of have potential application, be expected to will
It is confirmed in the research come.
Detailed description of the invention
Fig. 1 is the structure chart of final product made from the embodiment of the present invention 4；
Fig. 2 is the accumulation graph of final product made from the embodiment of the present invention 4；
Fig. 3 is the infrared spectrogram of final product made from the embodiment of the present invention 4；
Fig. 4 is the CD spectrogram of final product made from final product made from the embodiment of the present invention 4 and embodiment 12,
Middle solid line indicates that final product made from embodiment 4, dotted line indicate final product made from embodiment 12；
Fig. 5 is the hot weight curve of final product made from the embodiment of the present invention 4；
Fig. 6 is the powder diagram of final product made from the embodiment of the present invention 4；
Fig. 7 is the structure chart of final product made from the embodiment of the present invention 12；
Fig. 8 is the accumulation graph of final product made from the embodiment of the present invention 12；
Fig. 9 is the infrared spectrogram of final product made from the embodiment of the present invention 12；
Figure 10 is the hot weight curve of final product made from the embodiment of the present invention 12；
Figure 11 is the powder diagram of final product made from the embodiment of the present invention 12.
Specific embodiment
The present invention is described in further detail combined with specific embodiments below, content to better understand the invention, but
The present invention is not limited to following embodiments.
Embodiment 1: the synthesis of ligand L-bate
By following route synthetic ligands L-bate:
Specific synthetic method the following steps are included:
1) 3.0g (19.8mmol) L-TARTARIC ACID and 5.4g (39.6mmol) aminoguanidin carbonate is taken to be placed in the circle of 250ml
In the flask of bottom, 12ml concentrated hydrochloric acid is added, reacts for 24 hours, is cooled to room temperature under the conditions of being warming up to 80 DEG C, obtain reactant A；
2) pH=14.0 of reactant A is adjusted with NaOH, then is reacted for 24 hours under the conditions of being warming up to 110 DEG C, is cooled to room temperature,
Obtain reactant B；
3) pH=4.0 that reactant B is adjusted with glacial acetic acid, has a large amount of white precipitates to generate, and filters, ice water washing, later
It is dried in vacuo 4h under the conditions of being placed in 80 DEG C, obtains white solid product, yield 90%.
To white solid product obtained by the present embodiment, specific spectral data is as follows:
(1) infrared:
PerkinElmer company, U.S. PE SpectrumOne FT-IR Spectrometer fourier-transform infrared light
Spectrometer (KBr tabletting).IR(KBr,cm-1)3433.25(s),3329.13(w),3191.88(s),2696.71(w),1652.36
(s)、1599.95(s)、1534.27(s)、1470.90(m)、1413.26(m)、1342.40(m)、1244.12(m)、1139.97
(s)、1102.47(m)、1075.63(m)、1048.08(w)、924.85(w)、848.47(m)、785.85(m)、697.30(m)、
502.41(w)、425.41(w)。
(2) mass spectrum:
ESI-MS m/z:225.08[M-H]-, wherein M is the molecular weight of L-bate.
Accordingly, it can be determined that above-mentioned product is ligand L-bate, shown in structural formula such as following formula (I):
Embodiment 2: the synthesis of ligand L-bate
Embodiment 1 is repeated, unlike:
In step 1), the molar ratio of L-TARTARIC ACID and aminoguanidin carbonate is changed to 1:2.5, and the dosage of concentrated hydrochloric acid is changed to
12ml, reaction carry out under the conditions of 70 DEG C, reaction time 20h；
In step 2), the pH=12.0 of reactant A is adjusted, reaction carries out under the conditions of 100 DEG C；
In step 3), the pH=3.0 of reactant B is adjusted.
The present embodiment products therefrom is characterized, the ligand L-bate of structure shown in formula (I) is determined as.
Embodiment 3: the synthesis of ligand L-bate
Embodiment 1 is repeated, unlike:
In step 1), the dosage of concentrated hydrochloric acid is changed to 10ml, and reaction carries out under the conditions of 90 DEG C, reaction time 22h；
In step 2), the pH=13.0 of reactant A is adjusted, reaction carries out under the conditions of 70 DEG C, reaction time 20h；
In step 3), the pH=3.5 of reactant B is adjusted.
The present embodiment products therefrom is characterized, the ligand L-bate of structure shown in formula (I) is determined as.
Embodiment 4:[(V2O5) (L-bate)] and synthesis
It is synthesized by following routes:
Weigh V2O5(0.2mmol, 0.0364g) and L-bate (0.3mmol, 0.0678g) are placed in the round-bottomed flask of 25mL
In, the mixed solvent (acetonitrile proportion is 33v/v%) that 12ml is made of water and acetonitrile, dissolution is added；It is adjusted with triethylamine
The pH=5.0 of acquired solution, gained mixed liquor react 3h under 60 DEG C of water bath conditions, and reactant filters while hot, and filtrate stands analysis
Crystalline substance has light yellow strip crystal to generate, yield 70%.
The present embodiment products therefrom is characterized:
(1) structural characterization of product
The light yellow strip crystal for choosing suitable dimension is placed on SuperNova single crystal diffractometer, using graphite monochromatic
Change MoK alpha rayProduct is under the conditions of 298 (2) K, within the scope of certain θ, collects diffraction point data.
Structure is solved with direct method, mixed hydrogenation, and hydrogen atom uses isotropism thermal parameter；Non-hydrogen atom uses anisotropy physochlaina infudibularis
Number.Structure is corrected through complete matrix least square method, and the parsing of crystal structure and structural modifications are respectively by SHELX97
(Sheldrick, 1990) and SHELXL97 (Sheldrick, 1997) program bag are completed, in relation to crystallography and structural modifications data
As described in Table 1, part bond distance bond angle is as described in Table 2, and the structure of products therefrom is as shown in Figure 1, accumulation graph such as Fig. 2 institute
Show.
Table 1: crystallographic data
Table 2: part bond distanceWith bond angle (°)
(2) IR Characterization
PerkinElmer company, U.S. PE Spectrum One FT-IR Spectrometer fourier-transform infrared light
Spectrometer (KBr tabletting).IR (KBr, the cm of products therefrom-1): 3421w, 3321w, 1659s, 1557m, 1471m, 1388w,
1341w, 1107m, 922s, 677m, 621m, spectrogram are as shown in Figure 3.
(3) CD spectrogram
Products therefrom is L-configuration, has apparent positive Cotton effect in CD spectrogram at 305nm.The CD of products therefrom
Spectrum spectrogram is as shown by the bold lines in fig.
(4) thermal stability analysis
Experimental temperature control in room temperature between 800 DEG C, flow velocity 15cm3/ min nitrogen atmosphere protection under, with 5 DEG C/
The heating rate of min has carried out thermal stability determination to products therefrom.The thermogravimetric curve of products therefrom is as shown in Figure 5.Thermogravimetric point
Analysis shows: it is slowly weightless between 36-182 DEG C, a hydrone (experiment value 5.06%, theoretical value 4.43%) is lost, is connect
From 182 DEG C to 218 DEG C dramatic decrease, lose two hydrones (experiment value 7.25%, theoretical value 8.86%), then have occurred
The collapsing of molecular skeleton terminates until 798 DEG C of pyrolysis.
(5) powder diffraction analysis
In order to study a large amount of samples of products therefrom and the uniformity of single crystal, i.e. pure phase substance.The applicant is by institute
It obtains product to be tested using powder diffraction under normal temperature conditions, test scope is 5-55 °, and sweep speed is 5 °/min.Then
Simulated by mercury software, the CIF file analogy of products therefrom mono-crystalline structures obtained into powder map, then with practical spectrogram
It compares, it can be seen that the position of characteristic peak and peak type are almost the same, show that big quantity of material is pure phase.The powder of products therefrom spreads out
It is as shown in Figure 6 to penetrate spectrogram.
Pass through above-mentioned characterization, it may be determined that the present embodiment products therefrom is an object of the application product complex 1, i.e. [(V2O5)
(L-bate)], wherein L-bate is L-1, -1,2-ethanediol, i.e. L 2-bis (5-amion-1H-1,2,4-triazole)
Bis- (5- amino -1H-1,2,4- the triazole) -1,2- ethylene glycol of type 1,2-.
Embodiment 5:[(V2O5) (L-bate)] and synthesis
Embodiment 4 is repeated, unlike:
1) in the composition of mixed solvent, acetonitrile proportion is changed to 40v/v%)；
2) pH=6.0 of acquired solution is adjusted with triethylamine；
3) gained mixed liquor reacts 3h under 80 DEG C of water bath conditions.
Reactant filters while hot, and filtrate stands crystallization, has light yellow strip crystal to generate.
The analysis such as single crystal diffraction, infrared is carried out to the present embodiment products therefrom, is determined as target product [(V2O5)(L-
Bate)], wherein L-bate is L-1, -1,2-ethanediol, i.e. L-type 2-bis (5-amion-1H-1,2,4-triazole)
Bis- (5- amino -1H-1,2,4- the triazole) -1,2- ethylene glycol of 1,2-.
Embodiment 6:[(V2O5) (L-bate)] and synthesis
Embodiment 4 is repeated, unlike:
1) in the composition of mixed solvent, acetonitrile proportion is changed to 30v/v%)；
2) pH=4.0 of acquired solution is adjusted with triethylamine；
3) gained mixed liquor reacts 8h under 40 DEG C of water bath conditions.
Reactant filters while hot, and filtrate stands crystallization, has light yellow strip crystal to generate.
The analysis such as single crystal diffraction, infrared is carried out to the present embodiment products therefrom, is determined as target product [(V2O5)(L-
Bate)], wherein L-bate is L-1, -1,2-ethanediol, i.e. L-type 2-bis (5-amion-1H-1,2,4-triazole)
Bis- (5- amino -1H-1,2,4- the triazole) -1,2- ethylene glycol of 1,2-.
Embodiment 7:[(V2O5) (L-bate)] and synthesis
Embodiment 4 is repeated, unlike:
1) in the composition of mixed solvent, acetonitrile proportion is changed to 38v/v%)；
2) pH=4.5 of acquired solution is adjusted with triethylamine；
3) gained mixed liquor reacts 2h under 100 DEG C of water bath conditions.
Reactant filters while hot, and filtrate stands crystallization, has light yellow strip crystal to generate.
The analysis such as single crystal diffraction, infrared is carried out to the present embodiment products therefrom, is determined as target product [(V2O5)(L-
Bate)], wherein L-bate is L-1, -1,2-ethanediol, i.e. L-type 2-bis (5-amion-1H-1,2,4-triazole)
Bis- (5- amino -1H-1,2,4- the triazole) -1,2- ethylene glycol of 1,2-.
Embodiment 8:[(V2O5) (L-bate)] and synthesis
Embodiment 4 is repeated, unlike:
1) by V2O51:2.0 is changed to the molar ratio of L-bate；
2) dosage of mixed solvent is changed to 15ml, and wherein acetonitrile proportion is changed to 38v/v%)；
3) pH=5.5 of acquired solution is adjusted with triethylamine；
4) gained mixed liquor reacts 5h under 70 DEG C of water bath conditions.
Reactant filters while hot, and filtrate stands crystallization, has light yellow strip crystal to generate.
The analysis such as single crystal diffraction, infrared is carried out to the present embodiment products therefrom, is determined as target product [(V2O5)(L-
Bate)], wherein L-bate is L-1, -1,2-ethanediol, i.e. L-type 2-bis (5-amion-1H-1,2,4-triazole)
Bis- (5- amino -1H-1,2,4- the triazole) -1,2- ethylene glycol of 1,2-.
Embodiment 9: the synthesis of ligand D-bate
By following route synthetic ligands D-bate:
Specific synthetic method the following steps are included:
1) 3.0g (19.8mmol) D- tartaric acid and 5.4g (39.6mmol) aminoguanidin carbonate is taken to be placed in the circle of 250ml
In the flask of bottom, 12ml concentrated hydrochloric acid is added, reacts for 24 hours, is cooled to room temperature under the conditions of being warming up to 80 DEG C, obtain reactant A；
2) pH=14.0 of reactant A is adjusted with NaOH, then is reacted for 24 hours under the conditions of being warming up to 110 DEG C, is cooled to room temperature,
Obtain reactant B；
3) pH=4.0 that reactant B is adjusted with glacial acetic acid, has a large amount of white precipitates to generate, and filters, ice water washing, later
It is dried in vacuo 4h under the conditions of being placed in 80 DEG C, obtains white solid product, yield 93%.
White solid product obtained by the present embodiment is characterized, specific spectral data is as follows:
(1) infrared:
PerkinElmer company, U.S. PE Spectrum One FT-IR Spectrometer fourier-transform infrared light
Spectrometer (KBr tabletting).IR(KBr,cm-1):3433.60(s),3328.87(w),3191.29(s),2695.96(w),
1651.67(s)、1599.24(s)、1534.39(s)、1470.61(m)、1412.02(m)、1342.16(m)、1244.15(m)、
1140.32(s)、1102.25(m)、1075.63(m)、1047.71(w)、925.02(w)、848.54(m)、785.75(m)、
696.94(m)、424.46(w)。
(2) mass spectrum:
ESI-MS m/z:225.08[M-H]-, wherein M is the molecular weight of D-bate.
Accordingly, it can be determined that above-mentioned product is ligand D-bate, shown in structural formula such as following formula (II):
Embodiment 10: the synthesis of ligand D-bate
Embodiment 9 is repeated, unlike:
In step 1), the molar ratio of D- tartaric acid and aminoguanidin carbonate is changed to 1:2.2, and the dosage of concentrated hydrochloric acid is changed to
12ml, reaction carry out under the conditions of 70 DEG C, reaction time 20h；
In step 2), the pH=12.0 of reactant A is adjusted, reaction carries out under the conditions of 100 DEG C；
In step 3), the pH=3.0 of reactant B is adjusted.
The present embodiment products therefrom is characterized, the ligand D-bate of structure shown in formula (II) is determined as.
Embodiment 11: the synthesis of ligand D-bate
Embodiment 9 is repeated, unlike:
In step 1), the dosage of concentrated hydrochloric acid is changed to 10ml, and reaction carries out under the conditions of 90 DEG C, reaction time 22h；
In step 2), the pH=13.0 of reactant A is adjusted, reaction carries out under the conditions of 70 DEG C, reaction time 20h；
In step 3), the pH=3.5 of reactant B is adjusted.
The present embodiment products therefrom is characterized, the ligand D-bate of structure shown in formula (II) is determined as.
Embodiment 12:[(V2O5) (D-bate)] and synthesis
It is synthesized by following routes:
Weigh V2O5(0.2mmol, 0.0364g) and D-bate (0.3mmol, 0.0678g) are placed in the round-bottomed flask of 25mL
In, the mixed solvent (acetonitrile proportion is 33v/v%) that 12ml is made of water and acetonitrile, dissolution is added；It is adjusted with triethylamine
The pH=5.0 of acquired solution, gained mixed liquor react 3h under 60 DEG C of water bath conditions, and reactant filters while hot, and filtrate stands analysis
Crystalline substance has light yellow strip crystal to generate, yield 60%.
The present embodiment products therefrom is characterized:
(1) structural characterization of product
The light yellow strip crystal for choosing suitable dimension is placed on SuperNova single crystal diffractometer, using graphite monochromatic
Change MoK alpha rayProduct is under the conditions of 298 (2) K, within the scope of certain θ, collects diffraction point data.
Structure is solved with direct method, mixed hydrogenation, and hydrogen atom uses isotropism thermal parameter；Non-hydrogen atom uses anisotropy physochlaina infudibularis
Number.Structure is corrected through complete matrix least square method, and the parsing of crystal structure and structural modifications are respectively by SHELX97
(Sheldrick, 1990) and SHELXL97 (Sheldrick, 1997) program bag are completed, in relation to crystallography and structural modifications data
As described in Table 3, part bond distance bond angle is as described in Table 4, and the structure of products therefrom is as shown in fig. 7, accumulation graph such as Fig. 8 institute
Show.
Table 3: crystallographic data
Table 4: part bond distanceWith bond angle (°)
(2) IR Characterization
PerkinElmer company, U.S. PE Spectrum One FT-IR Spectrometer fourier-transform infrared light
Spectrometer (KBr tabletting).IR (KBr, the cm of products therefrom-1): 3424s, 3336w, 1648s, 1530w, 1473w, 1380w,
1306w, 1235w, 1116s, 1042w, 619m, 447w；621m, spectrogram are as shown in Figure 9.
(3) CD spectrogram
Products therefrom is D configuration.There is at 305nm apparent negative Cotton effect, the CD of products therefrom in CD spectrogram
Spectrum spectrogram is as shown in phantom in figure 4.And the CD curve of the present embodiment products therefrom and 4 products therefrom of above-described embodiment is substantially
In mirror symmetry, therefore, it is determined that being the enantiomter of chiral coordination compound.
(4) thermal stability analysis
Experimental temperature control in room temperature between 800 DEG C, flow velocity 15cm3/ min nitrogen atmosphere protection under, with 5 DEG C/
The heating rate of min has carried out thermal stability determination to products therefrom.The thermogravimetric curve of products therefrom is as shown in Figure 10.Thermogravimetric point
Analysis shows: it is slowly weightless between 36-178 DEG C, a hydrone (experiment value 5.1%, theoretical value 4.43%) is lost, then
DEG C dramatic decrease from 178 DEG C to 227 loses two hydrones (experiment value 8.01%, theoretical value 8.86%), is then divided
The collapsing of sub- skeleton terminates until 798 DEG C of pyrolysis.
(5) powder diffraction analysis
In order to study a large amount of samples of products therefrom and the uniformity of single crystal, i.e. pure phase substance.The applicant is by institute
It obtains product to be tested using powder diffraction under normal temperature conditions, test scope is 5-55 °, and sweep speed is 5 °/min.Then
Simulated by mercury software, the CIF file analogy of products therefrom mono-crystalline structures obtained into powder map, then with practical spectrogram
It compares, it can be seen that the position of characteristic peak and peak type are almost the same, show that big quantity of material is pure phase.The powder of products therefrom spreads out
It is as shown in figure 11 to penetrate spectrogram.
Pass through above-mentioned characterization, it may be determined that the present embodiment products therefrom is an object of the application product complex 2, i.e. [(V2O5)
(D-bate)], wherein D-bate is D-1, -1,2-ethanediol, i.e. D 2-bis (5-amion-1H-1,2,4-triazole)
Bis- (5- amino -1H-1,2,4- the triazole) -1,2- ethylene glycol of type 1,2-.
Embodiment 13:[(V2O5) (D-bate)] and synthesis
Embodiment 12 is repeated, unlike:
1) in the composition of mixed solvent, acetonitrile proportion is changed to 40v/v%)；
2) pH=6.0 of acquired solution is adjusted with triethylamine；
3) gained mixed liquor reacts 3h under 80 DEG C of water bath conditions.
Reactant filters while hot, and filtrate stands crystallization, has light yellow strip crystal to generate.
The analysis such as single crystal diffraction, infrared is carried out to the present embodiment products therefrom, is determined as target product [(V2O5)(D-
Bate)], wherein D-bate is D-1,2-bis (5-amion-1H-1,2,4-triazole) -1,2-ethanediol, i.e. D type
Bis- (5- amino -1H-1,2,4- the triazole) -1,2- ethylene glycol of 1,2-.
Embodiment 14:[(V2O5) (D-bate)] and synthesis
Embodiment 12 is repeated, unlike:
1) in the composition of mixed solvent, acetonitrile proportion is changed to 30v/v%)；
2) pH=4.0 of acquired solution is adjusted with triethylamine；
3) gained mixed liquor reacts 8h under 40 DEG C of water bath conditions.
Reactant filters while hot, and filtrate stands crystallization, has light yellow strip crystal to generate.
The analysis such as single crystal diffraction, infrared is carried out to the present embodiment products therefrom, is determined as target product [(V2O5)(D-
Bate)], wherein D-bate is D-1,2-bis (5-amion-1H-1,2,4-triazole) -1,2-ethanediol, i.e. D type
Bis- (5- amino -1H-1,2,4- the triazole) -1,2- ethylene glycol of 1,2-.
Embodiment 15:[(V2O5) (D-bate)] and synthesis
Embodiment 12 is repeated, unlike:
1) in the composition of mixed solvent, acetonitrile proportion is changed to 38v/v%)；
2) pH=4.5 of acquired solution is adjusted with triethylamine；
3) gained mixed liquor reacts 2h under 100 DEG C of water bath conditions.
Reactant filters while hot, and filtrate stands crystallization, has light yellow strip crystal to generate.
The analysis such as single crystal diffraction, infrared is carried out to the present embodiment products therefrom, is determined as target product [(V2O5)(D-
Bate)], wherein D-bate is D-1,2-bis (5-amion-1H-1,2,4-triazole) -1,2-ethanediol, i.e. D type
Bis- (5- amino -1H-1,2,4- the triazole) -1,2- ethylene glycol of 1,2-.
Embodiment 16:[(V2O5) (D-bate)] and synthesis
Embodiment 12 is repeated, unlike:
1) by V2O51:2.5 is changed to the molar ratio of D-bate；
2) dosage of mixed solvent is changed to 15ml, and wherein acetonitrile proportion is changed to 38v/v%；
3) pH=5.5 of acquired solution is adjusted with triethylamine；
4) gained mixed liquor reacts 5h under 70 DEG C of water bath conditions.
Reactant filters while hot, and filtrate stands crystallization, has light yellow strip crystal to generate.
The analysis such as single crystal diffraction, infrared is carried out to the present embodiment products therefrom, is determined as target product [(V2O5)(D-
Bate)], wherein D-bate is D-1,2-bis (5-amion-1H-1,2,4-triazole) -1,2-ethanediol, i.e. D type
Bis- (5- amino -1H-1,2,4- the triazole) -1,2- ethylene glycol of 1,2-.
Claims (10)
1. described to match for complex 1 or complex 2 based on the vanadic anhydride crystalline material of tartaric acid chiral derivatives modification
Shown in the chemical formula for example following (1) for closing object 1, shown in the chemical formula of the complex 2 for example following (2):
Complex 1:[(V2O5)(L-bate)] (1)；
Wherein, -1,2-ethanediol, i.e. L L-bate L-1,2-bis (5-amion-1H-1,2,4-triazole-3-yl)
Bis- (5- amino -1H-1,2,4- triazole -3- the base) -1,2- ethylene glycol of type 1,2-；
The vanadic anhydride crystalline material belongs to monoclinic system, C2Space group, cell parameter are as follows:α=90.00 °, β=107.629
(10) °, γ=90.00 °；
Complex 2:[(V2O5)(D-bate)] (2)；
Wherein, -1,2-ethanediol, i.e. D D-bate D-1,2-bis (5-amion-1H-1,2,4-triazole-3-yl)
Bis- (5- amino -1H-1,2,4- triazole -3- the base) -1,2- ethylene glycol of type 1,2-；
The vanadic anhydride crystalline material belongs to monoclinic system, C2Space group, cell parameter are as follows: α=90.00 °, β=107.599 (6) °, γ=
90.00°。
2. the synthetic method of the vanadic anhydride crystalline material described in claim 1 based on the modification of tartaric acid chiral derivatives,
It is characterized by: taking V2O5It is dissolved, is adjusted with mixed solvent with the compound as shown in following formula (I) or the compound as shown in following formula (II)
The pH=4.0-6.0 of acquired solution is saved, gained mixed liquor reacts under heating condition, and reactant is cooling, crystallization is stood, respectively
To complex 1 and complex 2；Wherein, the mixed solvent is the composition of water and acetonitrile；
3. synthetic method according to claim 2, it is characterised in that: the in the mixed solvent, acetonitrile is in mixed solvent
In shared ratio be 30-40v/v%.
4. synthetic method according to claim 2, it is characterised in that: reaction carries out under the conditions of 60-80 DEG C.
5. synthetic method according to claim 2, it is characterised in that: adjust the pH value of solution with triethylamine.
6. the synthetic method according to any one of claim 2-5, it is characterised in that: compound shown in the formula (I) or
Compound shown in formula (II) is prepared as follows:
1) it takes L-TARTARIC ACID or D- tartaric acid and aminoguanidin carbonate to be placed in reaction vessel, concentrated hydrochloric acid is added, in 70-90 DEG C
Under the conditions of react, until solution is in faint yellow clear liquid, stop reaction, it is cooling, obtain reactant A；
2) pH >=12.0 for adjusting reactant A, then react under the conditions of 100-110 DEG C, until there is white precipitate in solution
And solution is in yellowish-brown turbid, stops reaction, and it is cooling, obtain reactant B；
3) pH=3.0-4.0 for adjusting reactant B, there is Precipitation, collects precipitating, and washing is dry to get to shown in formula (I)
Compound shown in compound or formula (II).
7. synthetic method according to claim 6, it is characterised in that: in step 1), using the L-TARTARIC ACID of 1mmol as base
The concentrated hydrochloric acid of 10-12ml is added in standard, the whole raw materials for participating in reaction.
8. synthetic method according to claim 6, it is characterised in that: in step 1), react under the conditions of 70-90 DEG C to molten
Liquid is 15-24h in the time of faint yellow clear liquid.
9. synthetic method according to claim 6, it is characterised in that: in step 2), adjust the pH=12.0- of reactant A
14.0。
10. synthetic method according to claim 6, it is characterised in that: in step 2), reacted under the conditions of 100-110 DEG C
It is 15-24h to the time that solution is in yellowish-brown turbid.
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| CN101967159A (en) * | 2009-12-17 | 2011-02-09 | 辽宁师范大学 | Amino acid Schiff base ligand-containing vanadium oxide compound |
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| CN103232486A (en) * | 2013-05-07 | 2013-08-07 | 山西大学 | Vanadium oxide complex as well as preparation method and application thereof |
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