CN117263962A - Bis (hexafluoroacetylacetone) (tetramethyl ethylenediamine) magnesium complex and preparation method thereof - Google Patents
Bis (hexafluoroacetylacetone) (tetramethyl ethylenediamine) magnesium complex and preparation method thereof Download PDFInfo
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- hexafluoroacetylacetone
- tetramethyl ethylenediamine
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- QAMFBRUWYYMMGJ-UHFFFAOYSA-N hexafluoroacetylacetone Chemical compound FC(F)(F)C(=O)CC(=O)C(F)(F)F QAMFBRUWYYMMGJ-UHFFFAOYSA-N 0.000 title claims abstract description 79
- -1 (tetramethyl ethylenediamine) magnesium Chemical compound 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000010668 complexation reaction Methods 0.000 title description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 86
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 74
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims abstract description 44
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000047 product Substances 0.000 claims abstract description 33
- 239000012043 crude product Substances 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000000967 suction filtration Methods 0.000 claims abstract description 13
- 239000000706 filtrate Substances 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000725 suspension Substances 0.000 claims abstract description 11
- 238000001953 recrystallisation Methods 0.000 claims abstract description 10
- 238000004440 column chromatography Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 35
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 32
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 239000013078 crystal Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 239000003480 eluent Substances 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000000741 silica gel Substances 0.000 claims description 6
- 229910002027 silica gel Inorganic materials 0.000 claims description 6
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- QWDJLDTYWNBUKE-UHFFFAOYSA-L magnesium bicarbonate Chemical compound [Mg+2].OC([O-])=O.OC([O-])=O QWDJLDTYWNBUKE-UHFFFAOYSA-L 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 10
- 229910052751 metal Inorganic materials 0.000 abstract description 9
- 239000002184 metal Substances 0.000 abstract description 9
- 150000001412 amines Chemical class 0.000 abstract description 5
- 238000001914 filtration Methods 0.000 abstract description 4
- 239000012295 chemical reaction liquid Substances 0.000 abstract description 3
- 238000000605 extraction Methods 0.000 abstract description 3
- 229910021645 metal ion Inorganic materials 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 20
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 16
- 238000005303 weighing Methods 0.000 description 14
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 11
- 239000000395 magnesium oxide Substances 0.000 description 10
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000001514 detection method Methods 0.000 description 9
- 239000010408 film Substances 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000007735 ion beam assisted deposition Methods 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 230000005311 nuclear magnetism Effects 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000000231 atomic layer deposition Methods 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 3
- 239000000347 magnesium hydroxide Substances 0.000 description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000010815 organic waste Substances 0.000 description 2
- 238000004549 pulsed laser deposition Methods 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- PKZCRWFNSBIBEW-UHFFFAOYSA-N 2-n,2-n,2-trimethylpropane-1,2-diamine Chemical compound CN(C)C(C)(C)CN PKZCRWFNSBIBEW-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002887 superconductor Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
- 229910021521 yttrium barium copper oxide Inorganic materials 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
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic System
- C07F3/02—Magnesium compounds
Abstract
The invention discloses a bis (hexafluoroacetylacetone) (tetramethyl ethylenediamine) magnesium complex and a preparation method thereof, and relates to the field of organic metal synthesis. The method comprises the following steps: slowly dropwise adding an ethanol solution containing N-propylamine and hexafluoroacetylacetone into an N, N, N ', N' -tetramethyl ethylenediamine magnesium suspension, stirring overnight, carrying out suction filtration, extracting the filtrate, mixing the extract with filter residues, re-dissolving, removing the solvent from the filtrate to obtain a final crude product, purifying by column chromatography, and carrying out low-temperature recrystallization treatment by using N-hexane to obtain the target product. The target product has better solubility in ethanol and water, the yield of the product can be further improved by using the reaction liquid after extraction and filtration of dichloromethane, and the organic amine n-propylamine is used as an alkaline reagent, so that other metal ions cannot be introduced into a reaction system, the improvement of the metal purity of the product is facilitated, the crude product is purified by column chromatography and a low-temperature recrystallization method of n-hexane, and the purity of the product can be further improved.
Description
Technical Field
The invention relates to the field of organic metal synthesis, in particular to a bis (hexafluoroacetylacetone) (tetramethyl ethylenediamine) magnesium complex and a preparation method thereof.
Background
Magnesium oxide (MgO) is widely used for insulating and buffer layers of multilayer electronic/photonic devices because it has a very large band gap (7.2 eV), excellent thermal stability (melting point 2900 ℃), electrical insulation properties (dielectric constant 9.8), and it is easy to form a thin film having a textured microstructure with a high MgO (100) orientation due to a simple cubic rock salt crystal structure. MgO films with a highly biaxial structure have been successfully prepared using Ion Beam Assisted Deposition (IBAD) techniques for use as template/buffer layer coatings for YBCO superconductors to facilitate the template process, prevent electrical cross-talk, and minimize interface diffusion and lattice mismatch. MgO textured films are also commonly used to increase the crystallinity of films in magnetic storage media while reducing the cost of the substrate. Single crystal MgO wafers are excellent substrates for growing epitaxial films due to good surface conditions, with the microstructure texture required for propagation from substrate to film. In addition, the MgO thin film has excellent fire resistance and a low sputtering rate, and plays an important role as a protective layer in improving discharge characteristics of an AC plasma display panel and panel lifetime defects.
Heretofore, there are several deposition techniques for MgO films, including sol-gel, sputtering, pulsed Laser Deposition (PLD), ion Beam Assisted Deposition (IBAD), chemical Vapor Deposition (CVD), and the like. Among these techniques, metal Organic Chemical Vapor Deposition (MOCVD) has advantages of relatively simple equipment, suitability for mass production, wide conformal coverage, wide application range of deposition materials, metastable phase accessibility, and the like. The MgO film grown on the amorphous glass substrate is usually polycrystalline, the key factor for successful film growth by MOCVD is the availability of efficient metal organic precursors, and high purity bis (hexafluoroacetylacetone) (tetramethyl ethylenediamine) magnesium can be used as a precursor source material for preparing MgO films by atomic layer deposition.
The bis (hexafluoroacetylacetone) (tetramethyl ethylenediamine) magnesium precursor improves the volatility and the thermal stability of the precursor through saturated coordination, and solves the defects of the current Mg precursor. However, the synthesis method of bis (hexafluoroacetylacetone) (tetramethyl ethylenediamine) magnesium precursor still has the problem of low yield and purity at present, and needs to be solved.
Disclosure of Invention
The invention provides a bis (hexafluoroacetylacetone) (tetramethyl ethylenediamine) magnesium complex and a preparation method thereof, which can improve the yield and purity of a synthesized target product.
In order to solve the technical problems, one of the purposes of the invention is to provide a preparation method of a bis (hexafluoroacetylacetone) (tetramethyl ethylenediamine) magnesium complex, which comprises the following steps:
(1) Slowly dropwise adding N, N, N ', N' -tetramethyl ethylenediamine into the magnesium nitrate aqueous solution to obtain N, N, N ', N' -tetramethyl ethylenediamine magnesium suspension;
(2) Slowly dropwise adding an ethanol solution or an aqueous solution containing N-propylamine and hexafluoroacetylacetone into the N, N, N ', N' -tetramethyl ethylenediamine magnesium suspension under the stirring condition, and stirring overnight after the dropwise addition is finished;
(3) Extracting the filtrate by using an extracting agent, removing the extracting agent to obtain a crude product, adding an organic solvent into filter residues after the suction filtration to dissolve the filter residues, collecting the filtrate after the suction filtration, and removing the organic solvent to obtain the crude product;
(4) Mixing and dissolving all crude products, then placing the crude products into a chromatographic column for column chromatography purification, using a mixed solution of normal hexane and dichloromethane as eluent, collecting a second chromatographic band, and removing eluent solvent to obtain a product A;
(5) Slowly dripping n-hexane into the product A at 50-70 ℃ to completely dissolve the solid, and placing the solid in an environment of minus 35 ℃ to minus 50 ℃ for recrystallization treatment, and collecting crystals to obtain the target product.
By adopting the scheme, as the target product has certain solubility in ethanol and water, the yield of the product can be further improved by using the dichloromethane extraction reaction liquid, and the organic amine n-propylamine is used as an alkaline reagent to replace other metal-containing alkali, so that other metal ions are not introduced into a reaction system, the improvement of the metal purity of the product is facilitated, and the organic amine reagent is removed by heating, so that no residue can be produced, the product purity is higher, and the requirement of an ALD precursor preparation process is met; the purity of the product can be further improved by column chromatography and low-temperature recrystallization of normal hexane, and dichloromethane and normal hexane solvents used in the reaction process can be recycled, so that the treatment of organic waste liquid is reduced.
As a preferred embodiment, in the step (2), the ethanol solution containing n-propylamine and hexafluoroacetylacetone is prepared by: n-propylamine is slowly added dropwise into an ethanol solution containing hexafluoroacetylacetone at 0 ℃ under stirring to obtain an ethanol solution containing n-propylamine and hexafluoroacetylacetone.
Preferably, in the step (4), the silica gel powder number in the chromatographic column is 200-300 mesh.
In the step (4), the volume ratio of n-hexane to dichloromethane in the eluent is (20-30): 1.
preferably, in the step (1), the molar ratio of magnesium nitrate to N, N, N ', N' -tetramethyl ethylenediamine is 1:1.
5. the method for producing bis (hexafluoroacetylacetone) (tetramethyl ethylenediamine) magnesium complex according to claim 1, wherein in step (2), the molar ratio of n-propylamine to hexafluoroacetylacetone in the ethanol solution containing n-propylamine and hexafluoroacetylacetone is 1:1.
preferably, in the step (2), the molar ratio of magnesium nitrate, N' -tetramethyl ethylenediamine and hexafluoroacetylacetone is 1:1:2.
preferably, in the step (1), 1-3mL of water is added for every 1mmol of magnesium nitrate in the magnesium nitrate aqueous solution.
Preferably, in the step (2), 1mL-3mL of the ethanol solution is added for every 1mmol of hexafluoroacetylacetone in the ethanol solution or the aqueous solution containing hexafluoroacetylacetone.
Preferably, in the step (2), the volume fraction of ethanol in the ethanol solution containing hexafluoroacetylacetone is 15% -20%.
Preferably, in step (3), the extractant is dichloromethane, 1, 2-dichloroethane or ethyl acetate, and the extractant is selected mainly from the aspects of solubility of the product and boiling point, wherein the dichloromethane boiling point is much lower than that of 1, 2-dichloroethane and ethyl acetate, and is easier to remove.
As a preferred scheme, in the step (3), the volume ratio of the filtrate to the extractant is 10: (3-4.5).
Preferably, in step (3), the organic solvent is dichloromethane, 1, 2-dichloroethane, ethyl acetate or acetone, and the solubility of the organic solvent to the target product is better than that of other organic solvents.
Preferably, in step (5), the recrystallization time is 10h to 15h.
In order to solve the technical problems, the second object of the present invention is to provide a bis (hexafluoroacetylacetone) (tetramethyl ethylenediamine) magnesium complex, wherein the organic content of the bis (hexafluoroacetylacetone) (tetramethyl ethylenediamine) magnesium complex is above 99.99% and the inorganic purity is above 6N.
Compared with the prior art, the embodiment of the invention has the following beneficial effects:
1. according to the method, the target product has certain solubility in ethanol and water, the yield of the product can be further improved by using the reaction liquid after extraction and filtration of dichloromethane, and the organic amine n-propylamine is used as an alkaline reagent to replace other metal-containing alkali, so that other metal ions cannot be introduced into a reaction system, the improvement of the metal purity of the product is facilitated, and the organic amine reagent is removed by heating, so that no residue can be produced, the product purity is higher, and the requirement of an ALD precursor preparation process is met.
2. The crude product is purified by the column chromatography and the low-temperature recrystallization method of the n-hexane, so that the purity of the product can be further improved, and the methylene dichloride and the n-hexane solvent used in the reaction process can be recycled, so that the treatment of organic waste liquid is reduced.
Drawings
Fig. 1: the invention relates to a chemical reaction formula in a preparation method of a bis (hexafluoroacetylacetone) (tetramethyl ethylenediamine) magnesium complex.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
A preparation method of bis (hexafluoroacetylacetone) (tetramethyl ethylenediamine) magnesium complex has a chemical reaction formula shown in figure 1, and comprises the following steps:
(1) Weighing 236mmol of Mg (NO) 3 ) 2 ·6H 2 Adding 400mL of deionized water into a three-neck flask, stirring and dissolving by using a magnetic stirrer at the rotating speed of 450r/min to obtain a magnesium nitrate aqueous solution, weighing 236mmol of N, N, N ', N' -tetramethyl ethylenediamine in a constant-pressure dropping funnel, slowly dropping the N, N, N ', N' -tetramethyl ethylenediamine into the magnesium nitrate aqueous solution at the speed of 2 drops/s, and fully reacting to obtain N, N, N ', N' -tetramethyl ethylenediamine magnesium suspension;
(2) Weighing 472mmol of hexafluoroacetylacetone in a three-neck flask, adding 100mL of ethanol and 500mL of pure water to prepare an ethanol solution containing hexafluoroacetylacetone, immediately weighing 472mmol of n-propylamine in another constant-pressure dropping funnel, slowly dropping the solution into the ethanol solution containing hexafluoroacetylacetone at a speed of 2 drops/s under the stirring condition at 0 ℃ to avoid incomplete component precipitation reaction and obtain an ethanol solution containing n-propylamine and hexafluoroacetylacetone;
(3) Then slowly adding an ethanol solution containing N-propylamine and hexafluoroacetylacetone into the N, N, N ', N' -tetramethyl ethylenediamine magnesium suspension at a speed of 3 drops/s under stirring, and continuously stirring the reaction mixture overnight after the dripping is finished;
(4) After the reaction is finished, carrying out suction filtration, extracting filtrate by using dichloromethane at room temperature, wherein the volume ratio of the filtrate to the extractant is 10:4, removing dichloromethane solvent from the extract to obtain a crude product, adding 100mL of dichloromethane into filter residue after suction filtration to dissolve, removing insoluble substances such as magnesium hydroxide and the like after suction filtration, and then removing dichloromethane solvent to obtain the crude product;
(5) All crude products are mixed, completely dissolved by a small amount of dichloromethane and then placed in a chromatographic column filled with 300-mesh silica gel powder, wherein the height of the silica gel powder is 30cm, and the volume ratio of 2L is 20:1, performing column chromatography purification by using a mixed solution of n-hexane and dichloromethane as an eluent, collecting a second chromatographic band, and removing a solvent after eluting to obtain a product A;
(6) Slowly dripping N-hexane into the product A at 50 ℃ to completely dissolve the solid, then placing the product A in an environment of minus 35 ℃ for recrystallization treatment, recrystallizing at low temperature for 10 hours to obtain white crystals in the N-hexane solution, namely the target product bis (hexafluoroacetylacetone) (tetramethyl ethylenediamine) magnesium, filtering and flushing the white crystals by using the N-hexane solution at minus 35 ℃, weighing 0.2706mol bis (hexafluoroacetylacetone) (tetramethyl ethylenediamine) magnesium after normal-temperature vacuum drying, calculating to obtain 80.2% of yield based on N, N, N ', N' -tetramethyl ethylenediamine, detecting the organic content of 99.99% by nuclear magnetism, detecting the inorganic purity of 6N by ICP-OES, and obtaining the nuclear magnetic resonance hydrogen spectrum result of 6N 1 H NMR(δ,C6D6):1.74[s,4H],1.85[s,12H],6.31[s,2H]。
Example two
The preparation method of bis (hexafluoroacetylacetone) (tetramethyl ethylenediamine) magnesium complex, the steps and the reagents and process parameters used in each step are the same as those in the first embodiment, except that in the step (5), the volume ratio of eluent is 5:1 in a mixed solution of n-hexane and dichloromethane; in the step (6), 0.1791mol of bis (hexafluoroacetylacetone) (tetramethyl ethylenediamine) magnesium is prepared, the yield is 75.9%, the organic content is 99.99% by nuclear magnetic resonance detection, the inorganic purity is 6N by ICP-OES detection, and the nuclear magnetic resonance hydrogen spectrum result is 1 H NMR(δ,C6D6):1.74[s,4H],1.85[s,12H],6.31[s,2H]。
Comparative example one
A preparation method of a bis (hexafluoroacetylacetone) (tetramethyl ethylenediamine) magnesium complex, which comprises the following steps:
(1) Weighing and weighing236mmol Mg(NO 3 ) 2 ·6H 2 Adding 400mL of deionized water into a three-neck flask, stirring and dissolving by using a magnetic stirrer at the rotating speed of 450r/min to obtain a magnesium nitrate aqueous solution, weighing 236mmol of N, N, N ', N' -tetramethyl ethylenediamine in a constant-pressure dropping funnel, and slowly dropping the N, N, N ', N' -tetramethyl ethylenediamine into the magnesium nitrate aqueous solution at the speed of 2 drops/s to obtain a N, N, N ', N' -tetramethyl ethylenediamine magnesium suspension;
(2) Weighing 472mmol of hexafluoroacetylacetone in a three-neck flask, adding 100mL of ethanol and 500mL of pure water to prepare an ethanol solution containing hexafluoroacetylacetone, immediately weighing 472mmol of NaOH, dissolving in 200mL of pure water, placing in another constant-pressure dropping funnel, and slowly dropping into the ethanol solution containing hexafluoroacetylacetone at a speed of 2 drops/s under the stirring condition at 0 ℃ to obtain an ethanol solution containing NaOH and hexafluoroacetylacetone;
(3) Then adding ethanol solution containing NaOH and hexafluoroacetylacetone slowly into the N, N, N ', N' -tetramethyl ethylenediamine magnesium suspension at a speed of 3 drops/s under stirring, and continuously stirring the reaction mixture overnight after the dripping is finished;
(4) After the reaction is finished, carrying out suction filtration, extracting filtrate by using dichloromethane, wherein the volume ratio of the filtrate to the extractant is 10:4, removing dichloromethane solvent from the extract to obtain a crude product, adding 100mL of dichloromethane into filter residue after suction filtration to dissolve, removing insoluble substances such as magnesium hydroxide and the like after suction filtration, and then removing dichloromethane solvent to obtain the crude product;
(5) All crude products are mixed, completely dissolved by a small amount of dichloromethane and then placed in a chromatographic column filled with 300-mesh silica gel powder, wherein the height of the silica gel powder is 30cm, and the volume ratio of 2L is 20:1, performing column chromatography purification by using a mixed solution of n-hexane and dichloromethane as an eluent, collecting a second chromatographic band, and removing a solvent after eluting to obtain a product A;
(6) Slowly dripping n-hexane into the product A at 50deg.C to dissolve the solid completely, recrystallizing at-35deg.C for 10 hr to obtain white crystal, i.e. target product bis (hexafluoroacetylacetone) (tetramethyl ethylenediamine) magnesium, suction filtering, and making into solid preparationWashing white crystal with-35deg.C N-hexane solution, vacuum drying at normal temperature, weighing to obtain 0.1888mol bis (hexafluoroacetylacetone) (tetramethyl ethylenediamine) magnesium, calculating to obtain 80.0% based on N, N, N ', N' -tetramethyl ethylenediamine, detecting by nuclear magnetic resonance to obtain 99.95% organic content, detecting by ICP-OES to obtain inorganic purity 4N, and detecting by nuclear magnetic resonance to obtain hydrogen spectrum result 1 H NMR(δ,C6D6):1.74[s,4H],1.85[s,12H],6.31[s,2H]。
Comparative example two
The preparation method of bis (hexafluoroacetylacetone) (tetramethyl ethylenediamine) magnesium complex comprises the steps, reagents and process parameters used in the steps are the same as those in the first embodiment, and the difference is that in the step (4), 100mL of dichloromethane is added into filter residues for dissolution after the reaction is finished, insoluble matters such as magnesium hydroxide and the like are removed by suction filtration, and then dichloromethane solvent is removed to obtain a final crude product.
In the step (6), 0.1529mol of bis (hexafluoroacetylacetone) (tetramethyl ethylenediamine) magnesium is prepared, the yield is 64.8%, the organic content is 99.99% by nuclear magnetic resonance detection, the inorganic purity is 6N by ICP-OES detection, and the nuclear magnetic resonance hydrogen spectrum result is 1 H NMR(δ,C6D6):1.74[s,4H],1.85[s,12H],6.31[s,2H]。
Comparative example three
The preparation method of bis (hexafluoroacetylacetone) (tetramethyl ethylenediamine) magnesium complex comprises the steps and the reagents and process parameters used by the steps are the same as those of the first embodiment, except that the operation of the step (5) is not carried out, in the step (6), N-hexane is slowly dripped into the final crude product obtained in the step (4) at 50 ℃ to just dissolve the solid completely, then the solid is placed in the environment of minus 35 ℃ for recrystallization treatment, the low-temperature recrystallization is carried out for 10 hours, white crystals are obtained in the N-hexane solution, namely the target product bis (hexafluoroacetylacetone) (tetramethyl ethylenediamine) magnesium is obtained, the white crystals are washed by the N-hexane solution of minus 35 ℃, 0.1897mol of bis (hexafluoroacetylacetone) (tetramethyl ethylenediamine) magnesium is weighed after the constant-temperature vacuum drying, the calculated yield is 80.4% based on N, N ', N' -tetramethyl ethylenediamine, the organic content of the final product is detected to be 99.9% by nuclear magnetism, and the inorganic purity of the final product is detected by ICP-OES5N, the nuclear magnetic resonance hydrogen spectrum result is 1 H NMR(δ,C6D6):1.74[s,4H],1.85[s,12H],6.31[s,2H]。
Comparative example four
A preparation method of bis (hexafluoroacetylacetone) (tetramethyl ethylenediamine) magnesium complex, the reagent and technological parameters used in each step and each step are the same as those of the first embodiment, except that in the step (5), the obtained product A is dried under vacuum at normal temperature, 0.1902mol of bis (hexafluoroacetylacetone) (tetramethyl ethylenediamine) magnesium is weighed, the calculated yield is 80.6% based on N, N, N ', N' -tetramethyl ethylenediamine, the detected organic content is 99.5% by nuclear magnetism, the inorganic purity is 4N by ICP-OES detection, and the nuclear magnetic resonance hydrogen spectrum result is that 1 H NMR(δ,C6D6):1.74[s,4H],1.85[s,12H],6.31[s,2H]。
Comparative example five
A preparation method of a bis (hexafluoroacetylacetone) (tetramethyl ethylenediamine) magnesium complex, which comprises the following steps:
(1) Weighing 236mmol of Mg (NO) 3 ) 2 ·6H 2 Adding 400mL of deionized water into a three-neck flask, stirring and dissolving by using a magnetic stirrer at the rotating speed of 450r/min to obtain a magnesium nitrate aqueous solution, weighing 236mmol of N, N, N ', N' -tetramethyl ethylenediamine in a constant-pressure dropping funnel, and slowly dropping the N, N, N ', N' -tetramethyl ethylenediamine into the magnesium nitrate aqueous solution at the speed of 2 drops/s to obtain a N, N, N ', N' -tetramethyl ethylenediamine magnesium suspension;
(2) Weighing 472mmol of hexafluoroacetylacetone in a three-neck flask, adding 100mL of ethanol and 500mL of pure water to prepare an ethanol solution containing hexafluoroacetylacetone, immediately weighing 472mmol of n-propylamine in another constant-pressure dropping funnel, and slowly dropping the solution into the ethanol solution containing hexafluoroacetylacetone at a speed of 2 drops/s under the stirring condition at 0 ℃ to obtain an ethanol solution containing n-propylamine and hexafluoroacetylacetone;
(3) Then slowly adding an ethanol solution containing N-propylamine and hexafluoroacetylacetone into the N, N, N ', N' -tetramethyl ethylenediamine magnesium suspension at a speed of 3 drops/s under stirring, and continuously stirring the reaction mixture overnight after the dripping is finished;
(4) After the reaction is finished, suction filtration is carried out, filter residues are dried on a P205 desiccant, white solid is sublimated and purified at the condition of 60 ℃/1.3MTorr, 0.1551mol of bis (hexafluoroacetylacetone) (tetramethyl ethylenediamine) magnesium is obtained, the calculated yield is 65.7 percent based on N, N, N ', N' -tetramethyl ethylenediamine, the organic content is 99.5 percent through nuclear magnetism detection, the inorganic purity is 4N through ICP-OES detection, and the nuclear magnetic resonance hydrogen spectrum result is 1 H NMR(δ,C6D6):1.74[s,4H],1.85[s,12H],6.31[s,2H]。
Comparative example six
The preparation method of bis (hexafluoroacetylacetone) (tetramethyl ethylenediamine) magnesium complex, the steps and the reagents and process parameters used in each step are the same as those in the first embodiment, except that in the step (6), acetone is adopted for replacing n-hexane; in the step (6), 0.2063mol of bis (hexafluoroacetylacetone) (tetramethyl ethylenediamine) magnesium was obtained in a yield of 87.4%, the organic content thereof was 96% by nuclear magnetic resonance detection, the inorganic purity thereof was 2N by ICP-OES detection, and the nuclear magnetic resonance hydrogen spectrum thereof was as follows 1 H NMR(δ,C6D6):1.74[s,4H],1.85[s,12H],6.31[s,2H]。
The foregoing embodiments have been provided for the purpose of illustrating the general principles of the present invention, and are not to be construed as limiting the scope of the invention. It should be noted that any modifications, equivalent substitutions, improvements, etc. made by those skilled in the art without departing from the spirit and principles of the present invention are intended to be included in the scope of the present invention.
Claims (10)
1. A method for preparing a bis (hexafluoroacetylacetone) (tetramethyl ethylenediamine) magnesium complex, which is characterized by comprising the following steps:
(1) Slowly dropwise adding N, N, N ', N' -tetramethyl ethylenediamine into the magnesium nitrate aqueous solution to obtain N, N, N ', N' -tetramethyl ethylenediamine magnesium suspension;
(2) Slowly dropwise adding an ethanol solution or an aqueous solution containing N-propylamine and hexafluoroacetylacetone into the N, N, N ', N' -tetramethyl ethylenediamine magnesium suspension under the stirring condition, and stirring overnight after the dropwise addition is finished;
(3) Extracting the filtrate by using an extracting agent, removing the extracting agent to obtain a crude product, adding an organic solvent into filter residues after the suction filtration to dissolve the filter residues, collecting the filtrate after the suction filtration, and removing the organic solvent to obtain the crude product;
(4) Mixing and dissolving all crude products, then placing the crude products into a chromatographic column for column chromatography purification, using a mixed solution of normal hexane and dichloromethane as eluent, collecting a second chromatographic band, and removing eluent solvent to obtain a product A;
(5) Slowly dripping n-hexane into the product A at 50-70 ℃ to completely dissolve the solid, and placing the solid in an environment of minus 35 ℃ to minus 50 ℃ for recrystallization treatment, and collecting crystals to obtain the target product.
2. The method for producing a bis (hexafluoroacetylacetone) (tetramethyl ethylenediamine) magnesium complex according to claim 1, wherein in the step (2), the method for producing an ethanol solution containing n-propylamine and hexafluoroacetylacetone comprises: n-propylamine is slowly added dropwise into an ethanol solution containing hexafluoroacetylacetone at 0 ℃ under stirring to obtain an ethanol solution containing n-propylamine and hexafluoroacetylacetone.
3. The method for producing bis (hexafluoroacetylacetone) (tetramethyl ethylenediamine) magnesium complex according to claim 1, wherein in the step (4), the silica gel powder is 200-300 mesh in size.
4. The method for preparing bis (hexafluoroacetylacetone) (tetramethyl ethylenediamine) magnesium complex according to claim 1, wherein in step (4), the volume ratio of n-hexane to dichloromethane in the eluent is (20-30): 1.
5. the process for preparing a magnesium bis (hexafluoroacetylacetone) (tetramethyl ethylenediamine) complex according to claim 1, wherein in step (1), the molar ratio of magnesium nitrate to N, N' -tetramethyl ethylenediamine is 1:1.
6. the method for producing bis (hexafluoroacetylacetone) (tetramethyl ethylenediamine) magnesium complex according to claim 1, wherein in step (2), the molar ratio of n-propylamine to hexafluoroacetylacetone in the ethanol solution containing n-propylamine and hexafluoroacetylacetone is 1:1.
7. a process for the preparation of bis (hexafluoroacetylacetone) (tetramethyl ethylenediamine) magnesium complex according to claim 1, wherein at least one of the following a) -d) is satisfied:
a) In the step (2), the molar ratio of magnesium nitrate, N, N, N ', N' -tetramethyl ethylenediamine and hexafluoroacetylacetone is 1:1:2;
b) In the step (1), 1-3mL of water is added for every 1mmol of magnesium nitrate in the magnesium nitrate aqueous solution;
c) In the step (2), 1mL-3mL of ethanol solution or aqueous solution is added for every 1mmol of hexafluoroacetylacetone in the ethanol solution or aqueous solution containing hexafluoroacetylacetone;
d) In the step (2), the volume fraction of ethanol in the ethanol solution containing hexafluoroacetylacetone is 15% -20%.
8. The method for preparing bis (hexafluoroacetylacetone) (tetramethyl ethylenediamine) magnesium complex according to claim 1, wherein in the step (3), the extractant is dichloromethane, 1, 2-dichloroethane or ethyl acetate, and the volume ratio of the filtrate to the extractant is 10: (3-4.5).
9. The method for preparing bis (hexafluoroacetylacetone) (tetramethyl ethylenediamine) magnesium complex according to claim 1, wherein in the step (3), the organic solvent is dichloromethane, 1, 2-dichloroethane, ethyl acetate, or acetone.
10. A bis (hexafluoroacetylacetone) (tetramethyl ethylenediamine) magnesium complex obtained by the process according to any one of claims 1 to 9, wherein the bis (hexafluoroacetylacetone) (tetramethyl ethylenediamine) magnesium complex has an organic content of 99.99% or more and an inorganic purity of 6N or more.
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