CN100534994C - Production of metallic molecule large ring with chirality separation function and method of use thereof - Google Patents
Production of metallic molecule large ring with chirality separation function and method of use thereof Download PDFInfo
- Publication number
- CN100534994C CN100534994C CNB2007101721479A CN200710172147A CN100534994C CN 100534994 C CN100534994 C CN 100534994C CN B2007101721479 A CNB2007101721479 A CN B2007101721479A CN 200710172147 A CN200710172147 A CN 200710172147A CN 100534994 C CN100534994 C CN 100534994C
- Authority
- CN
- China
- Prior art keywords
- alcohol
- chiral separation
- metallic molecule
- separation function
- big ring
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of metal molecular large ring with chiral separation function, and a relative application method, wherein the invention uses chemical solvent heating method to prepare metal molecular large ring with chiral separation function. The invention mixes the chemical solvent heating-type reaction solution of zinc salt, ligand and guest molecule solvents, increases temperature to 80DEG C to react, and slowly cools to room temperature to obtain light-yellow bar crystals, washes via alcohol and dries, to obtain two kinds of metal molecular large rings with chiral separation function. The invention has mild conditions, simple operation, low cost, and repeatable applicaton, while the chiral alcohol separation ee value reaches more than 99%.
Description
Technical field
The present invention relates to a kind of preparation and application method thereof of chemical technology field, be specifically related to a kind of preparation and application method thereof with big ring of metallic molecule of chiral separation function.
Background technology
The internal structure of nano-tube material has very large influence to the performance and the application of nano-tube material, and preparing the nano-tube material with specific internal has significant meaning for the frontier of developing the nano-tube material function.Because the nanotube internal structure has bigger internal diameter thereby good application prospects is arranged.Nanotube is carbon nanotube particularly, has been widely used in aspects such as photocatalyst, molecule vessel, ion-exchange and transmitter.At present in numerous chiral nanotubes materials, also seldom about the report of the big ring of metallic molecule with chiral separation function.Although single wall chiral carbon nano-tube material has outside spirane structure, nearest theoretical investigation shows single wall chiral carbon nano-tube material because inside does not have function functional group and can not carry out chiral separation to the enantiomorph material.And the weighting material that is used for the isolating chirality gas chromatographic column of chiral alcohol now mainly is the derivative of cyclodextrin, there are three deficiencies in the derivative type chirality gas chromatographic column of cyclodextrin: one is derivative synthetic more loaded down with trivial details of cyclodextrin, the filling more complicated of the derivative type chirality gas chromatographic column of cyclodextrin; The another one deficiency is that the derivative type chirality gas chromatographic column of cyclodextrin can not well directly separate the 2-butanols, and the general derivative that generates sec-butyl alcohol earlier that adopts separates then; The price comparison costliness of the derivative type chirality gas chromatographic column that to also have a deficiency in addition be cyclodextrin.The big ring of the metallic molecule of chiral separation function is inner to have chirality function functional group and a weak force by Sauerstoffatom on atoms metal and the chiral alcohol and our synthetic has, thereby can particularly carry out chiral separation well to the small molecules chiral alcohol to (R)-2-butanols.
Find Power, T.D. through literature search to prior art; Skoulidas, A.I.; Sholl, D.S.J.Am.Chem.Soc (American Chemical Society's periodical) .2002 (time), 124 (issues), 1858 (start pages), article name: Can Chiral Single Walled Carbon Nanotubes Be Used asEnantiospecific Adsorbents? can (single wall chiral carbon nanotube be used to selective adsorption mapping material? although) proposed single wall chiral carbon nano-tube material in this article and have outside spirane structure, nearest theoretical investigation shows that single wall chiral carbon nano-tube material does not have function functional group and can not carry out chiral separation to the enantiomorph material owing to inside.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of preparation and application method thereof with big ring of metallic molecule of chiral separation function is provided, makes that its part synthetic method is simple relatively, processing ease, lower, two kinds of the big rings of metallic molecule of chiral alcohol separating effect ideal of cost with chiral separation function.
The present invention is achieved by the following technical solutions:
The preparation method of the big ring of metallic molecule with chiral separation function involved in the present invention, adopt the get everything ready big ring of metallic molecule of chiral separation function of the hot legal system of chemical solvents: after the hot method reaction solution of chemical solvents of zinc salt, part and guest molecule solvent is stirred, be warming up to 80 ℃, after reaction under 80 ℃ of temperature, reduce to room temperature, obtain light yellow bar shaped crystal,, promptly obtain the big ring of metallic molecule that two kinds of tetra-atomic ring and six-rings have the chiral separation function then with drying after the washing with alcohol.
The present invention has the preparation method of the big ring of metallic molecule of chiral separation function, comprises the steps:
1. the preparation of the hot method reaction solution of chemical solvents: the 60mg part is dissolved in 5mL N, dinethylformamide, the 34mg zinc salt is dissolved in the 1mL deionized water, the two mixing, in mixed solution, add 5mL acetonitrile or alcohol or chiral alcohol or tetrahydrofuran (THF) again, at room temperature stir then.
Described zinc salt is a zinc nitrate hexahydrate.
Described part be (R, R)-(-)-N, two (the 3-tertiary butyl-5-(4-pyridine) salicylidenes)-1 of N-, 2-hexamethylene diimine.
Described alcohol is methyl alcohol or ethanol.
Described chiral alcohol is 2-butanols, 3-methyl-2-butanols or 2-amylalcohol.
Described stirring, its time is 10 minutes.
2. the big ring of metallic molecule synthetic that has the chiral separation function: the hot method reaction solution of chemical solvents that 1. step is prepared is warming up to 80 ℃, reacts under 80 ℃ temperature, and reaction is reduced to room temperature after finishing, and obtains light yellow bar shaped crystal.With drying after the washing with alcohol, can obtain the big ring of metallic molecule that two kinds of tetra-atomic ring and six-rings have the chiral separation function respectively then.
Describedly be warming up to 80 ℃, its temperature rise rate is 15 ℃/min.
The described room temperature of reducing to, 1015 ℃/min of its reduction of speed rate～15 ℃/min.
Described reaction, its time is 24 hours.
The described washing with alcohol of using is meant with ethanol 10mL 95% (v/v) ethanol and washes five times that wherein 95% (v/v) is the volume ratio per-cent of second alcohol and water.
The big ring of the metallic molecule with chiral separation function that the present invention is prepared has nano tube structure, and the internal diameter with big ring of metallic molecule of six-membered ring structure reaches 1.2nm.
The application method of the big ring of metallic molecule with chiral separation function involved in the present invention comprises following two kinds:
First kind: the mensuration with the big ring material separating chiral alcohol of metallic molecule ee value of chiral separation function: the big ring material of metallic molecule that 30mg is had the chiral separation function soaked one day in the 5mL chloroform, filter, filtrate is separated the ee value and is reached more than 99% with Chiraldex G-TA type (Astec company) the gas phase chiral separation post of 30m * 0.5mm, the chiral alcohol of mensuration;
Described chiral alcohol ee value is (R type alcohol-S type alcohol)/(R type alcohol+S type alcohol) * 100%.
Second kind: have the mensuration that the big ring material of the metallic molecule of chiral separation function is reused separating chiral alcohol ee value: 30mg and have the big ring of metallic molecule that tetra-atomic ring or six-membered ring structure contain different guest molecules and under 40 ℃ vacuum, placed 2 hours, then under the room temperature, in the chiral alcohol of 5mL, soaked one day, after 10 * 10mL95% (v/v) washing with alcohol, in the 5mL chloroform, soaked one day, filter, filtrate is separated the ee value and is reached more than 90% with Chiraldex G-TA type (Astec company) the gas phase chiral separation post of 30m * 0.5mm, the chiral alcohol of mensuration.
Compared with prior art, the invention has the beneficial effects as follows:
1. because the present invention adopts the hot method temperature of reaction of chemical solvents low, have only 80 ℃, reaction times is shorter, approximately need 24 hours, reaction raw materials is relatively more cheap and be easy to get, as zinc salt, 95% (v/v) ethanol, tetrahydrofuran (THF), N commonly used, dinethylformamide, deionized water and (R, R)-(-)-and N, N-two (the 3-tertiary butyl-5-(4-pyridine) salicylidene)-1,2-hexamethylene diimine.Thereby the present invention is simple to operate, cost is lower, efficient is higher, and the internal diameter of the big ring of metallic molecule with six-membered ring structure of preparation reaches 1.2nm.
2. have chirality function functional group thereby can very desirablely carry out chiral separation owing to the big ring material of metallic molecule inside chiral alcohol with chiral separation function.To (R)-2-butanols, (R)-the ee value of the selective adsorption of 3-methyl-2-butanols and (R)-2-amylalcohol is respectively up to 99.2%, 99.4% and 99.5%, the internal structure of two kinds of big ring materials of metallic molecule with chiral separation function is also more stable, the big ring material of metallic molecule that wherein has a tetra-atomic ring structure to the ee value of the reusable selective adsorption of secondary of (R)-3-methyl-2-butanols also up to 92.7%, and the big ring material of the metallic molecule with six-membered ring structure to the ee value of the selective adsorption of (R)-3-methyl-2-butanols and 2-butanols also respectively up to 95.6% and 98.4%.Therefore two kinds of big ring materials of metallic molecule with chiral separation function can extraordinary selective adsorption (R)-2-butanols, (R)-3-methyl-2-butanols and (R)-2-amylalcohol, and can repeated application.
Description of drawings
Fig. 1: the X-ray diffraction spectrogram that contains different guest molecules for the embodiment of the invention 1 resulting big ring of metallic molecule with tetra-atomic ring structure.
Fig. 2: the X-ray diffraction spectrogram that contains different guest molecules for the embodiment of the invention 1 resulting big ring of metallic molecule with six-membered ring structure.
Fig. 3: be the embodiment of the invention 1 resulting crystalline structure figure with big ring of metallic molecule of tetra-atomic ring structure.
Fig. 4: be the embodiment of the invention 1 resulting crystalline structure figure with big ring of metallic molecule of six-membered ring structure.
Fig. 5: be the embodiment of the invention 1 resulting gas chromatogram with the big ring selective adsorption of metallic molecule (R)-2-butanols of tetra-atomic ring structure.
Fig. 6: be the embodiment of the invention 1 resulting gas chromatogram with the big ring selective adsorption of metallic molecule (R)-3-methyl-2-butanols of tetra-atomic ring structure.
Fig. 7: be the embodiment of the invention 1 resulting gas chromatogram with the big ring selective adsorption of metallic molecule (R)-2-amylalcohol of six-membered ring structure.
Fig. 8: the gas chromatogram of reusing selective adsorption (R)-3-methyl-2-butanols for the embodiment of the invention 1 resulting big ring secondary of metallic molecule with tetra-atomic ring structure.
Fig. 9: be the embodiment of the invention 1 resulting gas chromatogram with the big ring selective adsorption of metallic molecule (R)-2-butanols of six-membered ring structure.
Figure 10: be the embodiment of the invention 1 resulting gas chromatogram with big the selecting property of ring of metallic molecule absorption (R)-3-methyl-2-butanols of six-membered ring structure.
Embodiment
Below in conjunction with accompanying drawing embodiments of the invention are elaborated: present embodiment is being to implement under the prerequisite with the technical solution of the present invention, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment one:
1. with 60mg (R, R)-(-)-N, N-two (the 3-tertiary butyl-5-(4-pyridine) salicylidene)-1,2-hexamethylene diimide ligand is dissolved in 5mL N, dinethylformamide, and the 34mg zinc nitrate hexahydrate is dissolved in the 1mL deionized water, the two is mixed in the 50mL white sample bottle, add 5mL 2-butanols again, stirred 10 minutes, after just be prepared into the reaction solution of the big ring of metallic molecule with tetra-atomic ring structure.
2. the hot method reaction solution of chemical solvents for preparing is put into and be warming up to 80 ℃ in the baking oven, 15 ℃/min of temperature rise rate, reaction is about 24 hours under 80 ℃ temperature, and reaction is slowly reduced to room temperature after finishing, and 15 ℃/min of reduction of speed rate obtains light yellow bar shaped crystal.Dry after using 5 * 10mL 95% (v/v) washing with alcohol then, can obtain to have the big ring of metallic molecule that the tetra-atomic ring structure contains (R)-2-butanols guest molecule.
The resulting big ring x-ray diffraction pattern of metallic molecule such as Fig. 1 with tetra-atomic ring structure.In order further to understand the internal structure of the big ring of metallic molecule, product has been carried out the single crystal diffraction analysis with tetra-atomic ring structure.Fig. 3 is the crystalline structure figure with big ring of metallic molecule of tetra-atomic ring structure, and as seen from the figure, four atoms metals form a tetrahedron, contain four (R) 2-butanols guest molecules in each tetrahedron, and intermolecular π-π reactive force is piled into space structure.
Embodiment two:
1. with 60mg (R, R)-(-)-N, N-two (the 3-tertiary butyl-5-(4-pyridine) salicylidene)-1,2-hexamethylene diimide ligand is dissolved in 5mL N, dinethylformamide, and the 34mg zinc nitrate hexahydrate is dissolved in the 1mL deionized water, the two is mixed in the 50mL white sample bottle, add 5mL methyl alcohol again, stirred 10 minutes, after just be prepared into the reaction solution of the big ring of metallic molecule with tetra-atomic ring structure.
2. the hot method reaction solution of chemical solvents for preparing is put into and be warming up to 80 ℃ in the baking oven, 15 ℃/min of temperature rise rate, reaction is about 24 hours under 80 ℃ temperature, and reaction is slowly reduced to room temperature after finishing, and 15 ℃/min of reduction of speed rate obtains light yellow bar shaped crystal.Dry after using 5 * 10mL 95% (v/v) washing with alcohol then, can obtain to have the big ring of metallic molecule that the tetra-atomic ring structure contains the methyl alcohol guest molecule.
Resulting have the big ring x-ray diffraction pattern of metallic molecule such as Fig. 1 that the tetra-atomic ring structure contains the methyl alcohol object.As seen from the figure, product has the structure with the same big ring of metallic molecule with tetra-atomic ring structure of embodiment one.
Embodiment three
1. with 60mg (R, R)-(-)-N, N-two (the 3-tertiary butyl-5-(4-pyridine) salicylidene)-1,2-hexamethylene diimide ligand is dissolved in 5mL N, dinethylformamide, and the 34mg zinc nitrate hexahydrate is dissolved in the 1mL deionized water, the two is mixed in the 50mL white sample bottle, add 5mL ethanol again, stirred 10 minutes, after just be prepared into the reaction solution of the big ring of metallic molecule with tetra-atomic ring structure.
2. the hot method reaction solution of chemical solvents for preparing is put into and be warming up to 80 ℃ in the baking oven, 15 ℃/min of temperature rise rate, reaction is about 24 hours under 80 ℃ temperature, and reaction is slowly reduced to room temperature after finishing, and 15 ℃/min of reduction of speed rate obtains light yellow bar shaped crystal.Dry after using 5 * 10mL 95% (v/v) washing with alcohol then, can obtain to have the big ring of metallic molecule that the tetra-atomic ring structure contains the ethanol guest molecule.
Resulting have the big ring x-ray diffraction pattern of metallic molecule such as Fig. 1 that the tetra-atomic ring structure contains the ethanol guest molecule.As seen from the figure, product has the structure with the same big ring of metallic molecule with tetra-atomic ring structure of embodiment one.
Embodiment four:
1. with 60mg (R, R)-(-)-N, N-two (the 3-tertiary butyl-5-(4-pyridine) salicylidene)-1,2-hexamethylene diimide ligand is dissolved in 5mL N, dinethylformamide, and the 34mg zinc nitrate hexahydrate is dissolved in the 1mL deionized water, the two is mixed in the 50mL white sample bottle, add the 5mL acetonitrile again, stirred 10 minutes, after just be prepared into the reaction solution of the big ring of metallic molecule with tetra-atomic ring structure.
2. the hot method reaction solution of chemical solvents for preparing is put into and be warming up to 80 ℃ in the baking oven, 15 ℃/min of temperature rise rate, reaction is about 24 hours under 80 ℃ temperature, and reaction is slowly reduced to room temperature after finishing, and 15 ℃/min of reduction of speed rate obtains light yellow bar shaped crystal.Dry after using 5 * 10mL 95% (v/v) washing with alcohol then, can obtain to have the big ring of metallic molecule that the tetra-atomic ring structure contains the acetonitrile guest molecule.
Resulting have the big ring x-ray diffraction pattern of metallic molecule such as Fig. 1 that the tetra-atomic ring structure contains the acetonitrile guest molecule.As seen from the figure, product has the structure with the same big ring of metallic molecule with tetra-atomic ring structure of embodiment one.
Embodiment five:
1. with 60mg (R, R)-(-)-N, N-two (the 3-tertiary butyl-5-(4-pyridine) salicylidene)-1,2-hexamethylene diimide ligand is dissolved in 5mL N, dinethylformamide, and the 34mg zinc nitrate hexahydrate is dissolved in the 1mL deionized water, the two is mixed in the 50mL white sample bottle, add 5mL 3-methyl-2-butanols again, stirred 10 minutes, after just be prepared into the reaction solution of the big ring of metallic molecule with tetra-atomic ring structure.
2. the hot method reaction solution of chemical solvents for preparing is put into and be warming up to 80 ℃ in the baking oven, 15 ℃/min of temperature rise rate, reaction is about 24 hours under 80 ℃ temperature, and reaction is slowly reduced to room temperature after finishing, and 15 ℃/min of reduction of speed rate obtains light yellow bar shaped crystal.Dry after using 5 * 10mL 95% (v/v) washing with alcohol then, can obtain to have the big ring of metallic molecule that the tetra-atomic ring structure contains (R)-3-methyl-2-butanols guest molecule.
Resulting have the big ring x-ray diffraction pattern of metallic molecule such as Fig. 1 that the tetra-atomic ring structure contains (R)-3-methyl-2-butanols guest molecule.As seen from the figure, product has the structure with the same big ring of metallic molecule with tetra-atomic ring structure of embodiment one.
Embodiment six:
1. with 60mg (R, R)-(-)-N, N-two (the 3-tertiary butyl-5-(4-pyridine) salicylidene)-1,2-hexamethylene diimide ligand is dissolved in 5mL N, dinethylformamide, and the 34mg zinc nitrate hexahydrate is dissolved in the 1mL deionized water, the two is mixed in the 50mL white sample bottle, add the 5mL tetrahydrofuran (THF) again, stirred 10 minutes, after just be prepared into the reaction solution of the big ring of metallic molecule with six-membered ring structure.
2. the hot method reaction solution of chemical solvents for preparing is put into and be warming up to 80 ℃ in the baking oven, 15 ℃/min of temperature rise rate, reaction is about 24 hours under 80 ℃ temperature, and reaction is slowly reduced to room temperature after finishing, and 15 ℃/min of reduction of speed rate obtains light yellow bar shaped crystal.Dry after using 5 * 10mL 95% (v/v) washing with alcohol then, can obtain to have the big ring of metallic molecule that six-membered ring structure contains the tetrahydrofuran (THF) guest molecule.
Resulting have the big ring x-ray diffraction pattern of metallic molecule such as Fig. 2 that six-membered ring structure contains the tetrahydrofuran (THF) guest molecule.In order further to understand the internal structure of the big ring of metallic molecule with six-membered ring structure, product has been carried out the single crystal diffraction analysis, Fig. 4 is the crystalline structure figure with big ring of metallic molecule of six-membered ring structure, as seen from the figure, six atoms metals form a hexahedron, contain six tetrahydrofuran (THF) guest molecules in each hexahedron, intermolecular π-π reactive force is piled into space structure, and the internal diameter with big ring of metallic molecule of six-membered ring structure reaches 1.2nm.
Embodiment seven:
1. with 60mg (R, R)-(-)-N, N-two (the 3-tertiary butyl-5-(4-pyridine) salicylidene)-1,2-hexamethylene diimide ligand is dissolved in 5mL N, dinethylformamide, and the 34mg zinc nitrate hexahydrate is dissolved in the 1mL deionized water, the two is mixed in the 50mL white sample bottle, add 5mL 2-amylalcohol again, stirred 10 minutes, after just be prepared into the reaction solution of the big ring of metallic molecule with six-membered ring structure.
2. the hot method reaction solution of chemical solvents for preparing is put into and be warming up to 80 ℃ in the baking oven, 15 ℃/min of temperature rise rate, reaction is about 24 hours under 80 ℃ temperature, and reaction is slowly reduced to room temperature after finishing, and 15 ℃/min of reduction of speed rate obtains light yellow bar shaped crystal.Dry after using 5 * 10mL 95% (v/v) washing with alcohol then, can obtain to have the big ring of metallic molecule that six-membered ring structure contains (R)-2-amylalcohol guest molecule.
Resulting have the big ring x-ray diffraction pattern of metallic molecule such as Fig. 2 that six-membered ring structure contains (R)-2-amylalcohol guest molecule.As seen from the figure, product has the structure with the same big ring of metallic molecule with six-membered ring structure of embodiment six.
Embodiment eight:
The 30mg that embodiment one is obtained has the big ring material of metallic molecule that the tetra-atomic ring structure contains (R)-2-butanols guest molecule and soaked one day in the 5mL chloroform, filter, filtrate is used the Chiraldex G-TA type gas phase chiral separation post of 30m * 0.5mm, under 26 ℃, hydrogen flow rate 0.5mL/min and nitrogen flow rate 0.5mL/min, (R)-2-butanols of measuring separates the ee value up to 99.2%, as shown in Figure 5.
Embodiment nine:
The 30mg that embodiment five is obtained has the big ring material of metallic molecule that the tetra-atomic ring structure contains (R)-3-methyl-2-butanols guest molecule and soaked one day in the 5mL chloroform, filter, filtrate is used Chiraldex G-TA type (Astec company) the gas phase chiral separation post of 30m * 0.5mm, under 30 ℃, hydrogen flow rate 0.75mL/min and nitrogen flow rate 1mL/min, (R)-3-methyl of measuring-2-butanols separates the ee value up to 99.4%, as shown in Figure 6.
Embodiment ten:
The 30mg that embodiment seven is obtained has the big ring material of metallic molecule that six-membered ring structure contains (R)-2-amylalcohol guest molecule and soaked one day in the 5mL chloroform, filter, filtrate is used Chiraldex G-TA type (Astec company) the gas phase chiral separation post of 30m * 0.5mm, under 40 ℃, hydrogen flow rate 1mL/min and nitrogen flow rate 1.5mL/min, (R)-2-amylalcohol of measuring separates the ee value up to 99.5%, as shown in Figure 7.
Embodiment 11:
The 30mg that embodiment one or embodiment two or embodiment three or embodiment four or embodiment five are obtained has the big ring material of metallic molecule that the tetra-atomic ring structure contains different guest molecules and placed 2 hours under 40 ℃ vacuum, then under the room temperature, in 5mL 3-methyl-2-butanols, soaked one day, after 10 * 10mL 95% (v/v) washing with alcohol, in the 5mL chloroform, soaked one day, filter, filtrate is used Chiraldex G-TA type (Astec company) the gas phase chiral separation post of 30m * 0.5mm, at 30 ℃, under hydrogen flow rate 0.75mL/min and the nitrogen flow rate 1mL/min, (R)-3-methyl of mensuration-2-butanols separates the ee value and reaches more than 92.7%.As shown in Figure 8.
Embodiment 12:
The 30mg that embodiment six or embodiment seven are obtained has the big ring material of metallic molecule that six-membered ring structure contains different guest molecules and placed 2 hours under 40 ℃ vacuum, then under the room temperature, in the 3-of 5mL methyl-2-butanols, soaked one day, after 10 * 10mL 95% (v/v) washing with alcohol, in the 5mL chloroform, soaked one day, filter, filtrate is used Chiraldex G-TA type (Astec company) the gas phase chiral separation post of 30m * 0.5mm, at 30 ℃, under hydrogen flow rate 0.75mL/min and the nitrogen flow rate 1mL/min, (R)-3-methyl of mensuration-2-butanols separates the ee value and reaches more than 95.6%.As shown in Figure 9.
Embodiment 13:
The 30mg that embodiment six or embodiment seven are obtained has the big ring material of metallic molecule that six-membered ring structure contains different guest molecules and placed 2 hours under 40 ℃ vacuum, then under the room temperature, in the 2-of 5mL butanols, soaked one day, after 10 * 10mL 95% (v/v) washing with alcohol, in the 5mL chloroform, soaked one day, filter, filtrate is used Chiraldex G-TA type (Astec company) the gas phase chiral separation post of 30m * 0.5mm, under 26 ℃, hydrogen flow rate 0.5mL/min and nitrogen flow rate 0.5mL/min, (R)-2-butanols of mensuration separates the ee value and reaches more than 98.4%.As shown in figure 10.
Claims (8)
1, a kind of preparation method with big ring of metallic molecule of chiral separation function is characterized in that, comprises the steps:
1. the preparation of the hot method reaction solution of chemical solvents: the 60mg part is dissolved in 5mL N, dinethylformamide, the 34mg zinc salt is dissolved in the 1mL deionized water, the two mixing, in mixed solution, add 5mL acetonitrile or alcohol or chiral alcohol or tetrahydrofuran (THF) again, at room temperature stir then;
2. the big ring of metallic molecule synthetic that has the chiral separation function: the hot method reaction solution of chemical solvents that 1. step is prepared is warming up to 80 ℃～85 ℃, under 80 ℃～85 ℃ temperature, react, after reaction finishes, reduce to room temperature, obtain light yellow bar shaped crystal, with drying after the washing with alcohol, can obtain the big ring of metallic molecule that two kinds of tetra-atomic ring and six-rings have the chiral separation function respectively then;
Described zinc salt is a zinc nitrate hexahydrate;
Described part be (R, R)-(-)-N, two (the 3-tertiary butyl-5-(4-pyridine) salicylidenes)-1 of N-, 2-hexamethylene diimine;
Described alcohol is methyl alcohol or ethanol; Described chiral alcohol is 2-butanols, 3-methyl-2-butanols or 2-amylalcohol.
2, the preparation method with big ring of metallic molecule of chiral separation function according to claim 1 is characterized in that, step 1. in, described stirring, its time is 10 minutes.
3, the preparation method with big ring of metallic molecule of chiral separation function according to claim 1 is characterized in that, step 2. in, describedly be warming up to 80 ℃～85 ℃, its temperature rise rate is 10 ℃/min～15 ℃/min; The described room temperature of reducing to, 1015 ℃/min of its reduction of speed rate～15 ℃/min.
4, according to claim 1 or 3 described preparation methods, it is characterized in that with big ring of metallic molecule of chiral separation function, step 2. in, described reaction, its time is 24 hours; The described washing with alcohol of using is meant with ethanol 10mL, volume ratio to be that 95% ethanol is washed five times.
5, a kind of application method with big ring of metallic molecule of chiral separation function as claimed in claim 1 is characterized in that, described mensuration with the big ring material separating chiral alcohol of metallic molecule ee value of chiral separation function.
6, the application method with big ring of metallic molecule of chiral separation function according to claim 5, it is characterized in that, described mensuration is meant: the big ring material of metallic molecule that 30mg is had the chiral separation function soaked one day in the 5mL chloroform, filter, filtrate is separated the ee value and is reached more than 99% with the Chiraldex G-TA type gas phase chiral separation post of 30m * 0.5mm, the chiral alcohol of mensuration.
7, a kind of application method with big ring of metallic molecule of chiral separation function as claimed in claim 1 is characterized in that, the described big ring material of metallic molecule with chiral separation function is reused the mensuration of separating chiral alcohol ee value.
8, the application method with big ring of metallic molecule of chiral separation function according to claim 7, it is characterized in that, described mensuration is meant: 30mg has the big ring of metallic molecule that tetra-atomic ring or six-membered ring structure contain different guest molecules and placed 2 hours under 40 ℃ vacuum, then under the room temperature, in the chiral alcohol of 5mL, soaked one day, after 10 * 10mL 95% (v/v) washing with alcohol, in the 5mL chloroform, soaked one day, filter, filtrate is separated the ee value and is reached more than 90% with the Chiraldex G-TA type gas phase chiral separation post of 30m * 0.5mm, the chiral alcohol of mensuration.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007101721479A CN100534994C (en) | 2007-12-13 | 2007-12-13 | Production of metallic molecule large ring with chirality separation function and method of use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007101721479A CN100534994C (en) | 2007-12-13 | 2007-12-13 | Production of metallic molecule large ring with chirality separation function and method of use thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101195631A CN101195631A (en) | 2008-06-11 |
| CN100534994C true CN100534994C (en) | 2009-09-02 |
Family
ID=39546273
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007101721479A Expired - Fee Related CN100534994C (en) | 2007-12-13 | 2007-12-13 | Production of metallic molecule large ring with chirality separation function and method of use thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100534994C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103113411B (en) * | 2013-02-28 | 2015-02-25 | 上海交通大学 | Preparation method of mono-chiral metallic organic frame material with function of splitting chiral amine |
| CN104119267B (en) * | 2014-07-21 | 2016-10-26 | 上海交通大学 | A kind of preparation method of the metal organic macrocycle crystalline material for resolving chiral amine |
-
2007
- 2007-12-13 CN CNB2007101721479A patent/CN100534994C/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| Can Chiral Single Walled Carbon Nanotubes Be Used asEnantiospecific Adsorbents? Power,T.D et.J.Am.Chem.Soc.,No.124. 2002 |
| Can Chiral Single Walled Carbon Nanotubes Be Used asEnantiospecific Adsorbents? Power,T.D et.J.Am.Chem.Soc.,No.124. 2002 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101195631A (en) | 2008-06-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107011145B (en) | Method for preparing 2-iodopent-2-ene-1, 4-dione derivative by visible light catalysis | |
| US9067957B2 (en) | Metal nickel-imidazolate chiral nano clathrate complex and preparation method thereof | |
| CN111995635B (en) | Method for preparing organosilicon compound by catalyzing chitosan loaded copper film material | |
| Tang et al. | A chiral metal-organic cage used as the stationary phase for gas chromatography separations | |
| CN103193831B (en) | Preparation method of single chiral metal-organic framework material with chiral separation and photoinduction functions | |
| CN100534994C (en) | Production of metallic molecule large ring with chirality separation function and method of use thereof | |
| Guo et al. | The biomimetic engineering of metal–organic frameworks with single-chiral-site precision for asymmetric hydrogenation | |
| CN104248950A (en) | Palladium/carbon nanotube catalyst and preparation and application thereof | |
| CN104119267B (en) | A kind of preparation method of the metal organic macrocycle crystalline material for resolving chiral amine | |
| Cui et al. | Engineering noble-metal-free metal–organic framework composite catalyst for efficient CO2 conversion under ambient conditions | |
| CN108976249B (en) | Preparation method of cycloindene corrole-fullerene star-shaped compound | |
| Yang et al. | Alkylzirconocenes in Organic Synthesis: An Overview | |
| CN102993206A (en) | Method for synthesising tetraphenylporphyrin metal complex via one-step process | |
| Wang et al. | Efficient transfer hydrogenation of ketones using molybdenum complexes by comprehensively verifying the auxiliary ligands | |
| CN102500418B (en) | Preparation method of magnetic bidentate imide palladium ligand catalyst | |
| Lü et al. | Influence of TiO 2 impregnated with a novel copper (II) carboxylic porphyrin and its application in photocatalytic degradation of 4-Nitrophenol | |
| CN108948055B (en) | 8-methylquinoline gem-diboron compound and preparation method thereof | |
| CN111286035A (en) | Zn (II) complex based on 4, 4' -dicarboxylic acid dimethyl azobenzene and adenine and synthetic method and application thereof | |
| CN104513281B (en) | Method for efficiently preparing high-purity n-octyl ferrocene through mixed solvent recrystallization | |
| CN104941681A (en) | Fluorescence sensing material based on naphthalimides derivative and application thereof | |
| CN104974192B (en) | synthetic method and application of thiophene amide substituted chiral phosphine ferrocene catalyst | |
| You et al. | Catalytic Enantioselective Inverse-Electron-Demand Diels–Alder Reaction of 2-Pyrones and Vinyl Selenides | |
| Zhao et al. | Enantioselective reductive aryl-benzylation of alkenes by a nickel-titanium bimetallic system | |
| CN107629049B (en) | Synthesis method of pyridine [2,1-a ] isoindole compound | |
| CN110668960A (en) | Preparation method of alpha-aryl alpha-aminoketone compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090902 Termination date: 20111213 |