CN103113411A - Preparation method of mono-chiral metallic organic frame material with function of splitting chiral amine - Google Patents
Preparation method of mono-chiral metallic organic frame material with function of splitting chiral amine Download PDFInfo
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Abstract
The invention provides a preparation method of a mono-chiral metallic organic frame material with a function of splitting chiral amine. The method comprises the following steps of: dissolving manganese salt and mono-chiral ligand (S)-3,3'-di-tert-butyl-5,5'-di(3,5-dicarboxylphenyl)-6,6'-dimethyl-2,2'-dihydroxyl-1,1'-bipheny into methanol and N,N-dimethyl formamide according to certain proportions, stirring for 10 minutes and then heating up to 80-85 DEG C, reacting for about 24 hours to generate colorless needle-like crystals, and then washing with aether to obtain the structurally stable mono-chiral metallic organic frame material with the function of splitting the chiral amine. The preparation method provided by the invention has the characteristics that the preparation condition is mild, the operation is simple, the separation ee value of the chiral amine is higher than 90%, and the chiral amine is reusable.
Description
Technical field
That the present invention relates to is a kind of preparation method of chemical technology field, is specifically related to a kind of preparation method with unidextrality metal organic frame material (MOFs) of resolving chiral amine functions.
Background technology
In recent years, along with the development of solid state chemistry, unidextrality metal organic frame material chiral recognition with separate, the field such as chirality fluorescence, Heterogeneous asymmetric catalysis shows application prospect widely.Show after deliberation, as long as the bore hole size of metal organic frame material and form and target molecule are complementary, frame material with amphiphilic hole may demonstrate very strong avidity to those amphiphilic guest molecules, and this type of metal organic frame material can carry out chiral recognition and separate some chiral molecules.Current, the weighting material that is used for the Chiral gas chromatography post of Chiral Amine separation is mainly the derivative of cyclodextrin, there are two deficiencies in the derivative type Chiral gas chromatography post of cyclodextrin: one is derivative synthetic more loaded down with trivial details of cyclodextrin, the filling more complicated of the derivative type Chiral gas chromatography post of cyclodextrin; The another one deficiency is the price comparison costliness of the derivative type Chiral gas chromatography post of cyclodextrin.
At present in numerous unidextrality metal organic frame materials, only about the report of the metal organic coordination polymer of chiral alcohol separation function, as, Y.M.Song etc. are used for splitting a kind of small molecular alcohol at Resolution of a Racemic Small Molecular Alcohol by a Chiral Metal-Organic Coordination Polymer through Intercalation(chiral metal organic coordination polymer by insertion), Crystal Growth﹠amp; Propose in Design (crystal growth and design, 2006 6 phase 14 pages) with a kind of unidextrality metal organic coordination polymer as framework, split the 2-butanols with the method for absorption.But the stability of the skeleton construction in this technology can't satisfy existing industrial needs, and its effect to the fractionation of 2-butanols is lower, can't be used for resolution of racemic amine.
Zhao Li, once peace disclosed the synthetic method of multiple MOFs in " chiral metal organic framework materials (MOFs) synthetic and use " (" organic chemistry " 09 phase in 2012), but the technology synthesis step is comparatively complicated, is difficult to satisfy existing industry with regard to the fractionation needs of Chiral Amine.
Summary of the invention
The present invention is directed to the prior art above shortcomings, a kind of unidextrality metal organic frame material preparation method with resolving chiral amine functions is proposed, by the Hyarogen-bonding of nitrogen-atoms on chirality function functional group and Chiral Amine, thereby can carry out chiral separation to the small molecules racemic amines well.The present invention operation is relatively simple, processing ease, Chiral Amine separating effect are desirable.
The present invention is achieved by the following technical solutions:
The present invention relates to a kind of unidextrality metal organic frame material preparation method with resolving chiral amine functions, at first synthetic unidextrality part (S)-H
4L:(S)-3,3 '-di-t-butyl-5,5 '-two (3,5-dicarboxyl phenyl)-6,6 '-dimethyl-2,2 '-dihydroxyl-1,1 '-biphenyl is then with part (S)-H
4L mixes with metal-salt, and with DMF and dissolve with methanol and react, reaction is cooled to room temperature after finishing, with drying and get final product after ether wash cooling after product several.
Described synthetic unidextrality part (S)-H
4L:(S)-3,3 '-di-t-butyl-5,5 '-two (3,5-dicarboxyl phenyl)-6,6 '-dimethyl-2,2 '-dihydroxyl-1,1 '-biphenyl comprises following two-step reaction altogether:
Concrete steps are:
1. take (S)-3, 3 '-di-t-butyl-5, 5 '-two bromo-6, 6 '-dimethyl-2, 2 '-dihydroxyl-1, 1 '-biphenyl, 5-pinacol ester m-phthalic acid methyl esters, three water potassiumphosphates, [1, two (diphenylphosphine) ferrocene of 1'-] palladium chloride is in reaction flask, the mixed solvent that adds dioxane and water, back flow reaction, precipitation after reaction finishes, extraction, washing, dry, filter, be spin-dried for, crude product namely gets target product (S)-3 through column chromatographic isolation and purification, 3 '-di-t-butyl-5, 5 '-two (3, 5-dimethoxycarbonyl phenyl)-6, 6 '-dimethyl-2, 2 '-dihydroxyl-1, 1 '-biphenyl.
2. gained target product of upper step is dissolved with tetrahydrofuran (THF), then add methyl alcohol, splash into lithium hydroxide solution, react the rear concentration of reaction solution that spends the night under 70 ℃, use the dilute hydrochloric acid adjust pH, stirring for some time under room temperature is that the adularescent solid is separated out, and filters, washes, is drying to obtain unidextrality part (S)-H
4L:(S)-3,3 '-di-t-butyl-5,5 '-two (3,5-dicarboxyl phenyl)-6,6 '-dimethyl-2,2 '-dihydroxyl-1,1 '-biphenyl.
described step 1., be specially: take (S)-3 according to mol ratio 1:2.8:4.5:0.05, 3 '-di-t-butyl-5, 5 '-two bromo-6, 6 '-dimethyl-2, 2 '-dihydroxyl-1, 1 '-biphenyl, 5-pinacol ester m-phthalic acid methyl esters, three water potassiumphosphates, [1, two (diphenylphosphine) ferrocene of 1'-] palladium chloride is in reaction flask, the mixed solvent that adds dioxane: water=9:1 under nitrogen protection, back flow reaction 10 hours, precipitation after reaction finishes, extraction, washing, dry, filter, be spin-dried for, crude product namely gets target product (S)-3 through column chromatographic isolation and purification, 3 '-di-t-butyl-5, 5 '-two (3, 5-dimethoxycarbonyl phenyl)-6, 6 '-dimethyl-2, 2 '-dihydroxyl-1, 1 '-biphenyl.
Described step 2., be specially: gained biphenyl of upper step is dissolved with tetrahydrofuran (THF), then the methyl alcohol that adds tetrahydrofuran (THF) 1/1 volume, splash into lithium hydroxide solution the pH value is transferred to 13～14, the lower rear concentration of reaction solution that spends the night that reacts refluxes, with dilute hydrochloric acid adjust pH to 1～2, stirring 8 hours under room temperature is that the adularescent solid is separated out, and filters, washes, is drying to obtain unidextrality part (S)-H
4L:(S)-3,3 '-di-t-butyl-5,5 '-two (3,5-dicarboxyl phenyl)-6,6 '-dimethyl-2,2 '-dihydroxyl-1,1 '-biphenyl.
Described reaction refers to: take metal-salt and unidextrality part (S)-H according to mol ratio 2:1
4L is in sample bottle, and every 0.05 mmole part adds 1 milliliter of DMF, every 0.05 mmole part 5 ml methanol, fully screws bottle cap after dissolving, and sample bottle is placed in 80 ℃ of baking oven heating 1 day.Take out sample bottle after 1 day, to be cooled to room temperature elimination reaction solution, the gained crystal is placed in air with the ether washing for several times dries, namely get a kind of unidextrality metal organic frame material with chiral separation function.
Described metal-salt is four hydration Manganous chloride tetrahydrates.
The present invention relates to a kind of synthetic unidextrality part (S) for the preparation of unidextrality metal organic frame material-H
4L:(S)-3,3 '-di-t-butyl-5,5 '-two (3,5-dicarboxyl phenyl)-6,6 '-dimethyl-2,2 '-dihydroxyl-1,1 '-biphenyl, its molecular structure is:
The present invention relates to the unidextrality metal organic frame material with chiral separation function that aforesaid method prepares, its structural formula is [Mn
2L (DMF)
2(H
2O)
2] 3DMF2H
2O。
The present invention relates to the application of above-mentioned unidextrality metal organic frame material, be used for selective one-time or repeat to adsorb Chiral Amine.[0017] described absorption comprises the following steps: 30mg is had the unidextrality metal organic frame material of chiral separation function through placing 2 hours under the vacuum of 80 ℃ after exchange of solvent, then under-10 ℃, be dissolved with in the methyl alcohol of racemic amines at 5mL and soaked one day, filter, with methanol wash for several times, then soaked one day in tetrahydrofuran (THF), filter, filtrate is used Chiralcel OD-H type liquid phase chiral separation post after the Benzoyl chloride derivatize, at 25 ℃, normal hexane/Virahol=90/10, 1.0mL/min under flow velocity, the Chiral Amine of measuring is separated ee (enantiomeric excess, enantiomeric excess) value reaches more than 90%.
Described racemic amines comprises: (Rac)-1-phenyl-ethyl amine, (Rac)-1-(4-fluorophenyl) ethamine, (Rac)-1-(4-bromophenyl) ethamine, (Rac)-1-(4-p-methoxy-phenyl) ethamine and (Rac)-2-butylamine
Technique effect
Compared with prior art, beneficial effect of the present invention comprises:
1) because the present invention adopts the solvent-thermal method temperature of reaction low, only have 80～85 ℃, the reaction times is shorter, approximately need 24 hours, reaction raw materials is relatively cheap and be easy to get, as manganese salt, anhydrous methanol, tetrahydrofuran (THF), DMF, ether, deionized water commonly used.Thereby the present invention is simple to operate, efficient is higher, and the unidextrality metal organic frame material internal diameter of preparation reaches 1.0nm.
2) have chirality function functional group thereby can ideally carry out chiral separation to racemic amines due to the unidextrality metal organic frame material internal with chiral separation function.To the ee value of the selective adsorption of (Rac)-1-phenyl-ethyl amine, (Rac)-1-(4-fluorophenyl) ethamine, (Rac)-1-(4-bromophenyl) ethamine, (Rac)-1-(4-p-methoxy-phenyl) ethamine and (Rac)-2-butylamine respectively up to 91.0%, 98.7%, 91.5%, 90.3% and 85.1%, it is also more stable that this kind has the internal structure of unidextrality metal organic frame material of chiral separation function, to the ee value of the reusable selective adsorption of secondary of (Rac)-4-fluorophenethylamine also up to 98.3%.Therefore the unidextrality metal organic frame material of this kind with chiral separation function can extraordinary selective adsorption separate (Rac)-1-phenyl-ethyl amine, (Rac)-1-(4-fluorophenyl) ethamine, (Rac)-1-(4-bromophenyl) ethamine, (Rac)-1-(4-p-methoxy-phenyl) ethamine and (Rac)-racemic amines such as 2-butylamine, and can repeated application.
Description of drawings
Fig. 1 is product schematic perspective view of the present invention;
In figure: (a) part (S)-H
4Coordination mode (c) the four strip metal coiled strands of the coordination mode of L (b) metal ion are through part (S)-H
4L formed 4
1Spiral hole (d) 1 schematic three dimensional views along the c-axis direction.
Fig. 2 is the liquid chromatogram of resulting unidextrality metal organic frame material selectivity absorption (Rac)-1-phenyl-ethyl amine;
In figure: (a) be the liquid chromatogram of (Rac)-1-phenyl-ethyl amine; (b) be the liquid chromatogram of (R)-1-phenyl-ethyl amine;
Fig. 3 is the liquid chromatogram of resulting unidextrality metal organic frame material selectivity absorption (Rac)-1-(4-fluorophenyl) ethamine;
In figure: (a) be the liquid chromatogram of (Rac)-1-(4-fluorophenyl) ethamine; (b) be the liquid chromatogram of (R)-1-(4-fluorophenyl) ethamine;
Fig. 4 is the liquid chromatogram of resulting unidextrality metal organic frame material selectivity absorption (Rac)-1-(4-bromophenyl) ethamine;
In figure: (a) be the liquid chromatogram of (Rac)-1-(4-bromophenyl) ethamine; (b) be the liquid chromatogram of (R)-1-(4-bromophenyl) ethamine;
Fig. 5 is the liquid chromatogram of resulting unidextrality metal organic frame material selectivity absorption (Rac)-1-(4-p-methoxy-phenyl) ethamine;
In figure: (a) be the liquid chromatogram of (Rac)-1-(4-p-methoxy-phenyl) ethamine; (b) be the liquid chromatogram of (R)-1-(4-p-methoxy-phenyl) ethamine;
Fig. 6 is the liquid chromatogram of resulting unidextrality metal organic frame material selectivity absorption (Rac)-2-butylamine;
In figure: (a) be the liquid chromatogram of (Rac)-2-butylamine; (b) be the liquid chromatogram of (R)-2-butylamine;
Fig. 7 is the x-ray diffractogram of powder of resulting unidextrality metal organic frame material.
Embodiment
The below elaborates to embodiments of the invention, and the present embodiment is implemented under take technical solution of the present invention as prerequisite, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
step 1, with (S)-3, 3 '-di-t-butyl-5, 5 '-two bromo-6, 6 '-dimethyl-2, 2 '-dihydroxyl-1, 1 '-biphenyl [Eur.J.Org.Chem.2010, 3027] (1.0g, 2mmol), 5-pinacol ester m-phthalic acid methyl esters [Cryst.Growth Des., 2010, 2775] (1.7g, 5.6mmol), three water potassiumphosphate (1.9g, 9mmol), [1, 1 '-two (diphenylphosphine) ferrocene] palladium chloride (80mg, 0.1mmol) be placed in reaction flask, the mixed solvent that adds dioxane/water=9:1(60mL) under nitrogen protection, back flow reaction was cooled to room temperature after 10 hours, after the reaction solution precipitation with ethyl acetate extraction for several times, wash for several times with saturated sodium-chloride after merging organic phase, filter with Büchner funnel after anhydrous sodium sulfate drying, be spin-dried for, crude product is through column chromatographic isolation and purification (silicagel column, eluent is sherwood oil: ethyl acetate=10:1), get target product (S)-3, 3 '-di-t-butyl-5, 5 '-two (3, 5-dimethoxycarbonyl phenyl)-6, 6 '-dimethyl-2, 2 '-dihydroxyl-1, 1 '-biphenyl 1.3g (productive rate: 88%).
1H?NMR(CDCl
3，400MHz)δ：8.66(s，2H，ArH)，8.19-8.20(d，4H，ArH)，7.22(s，2H，ArH)，5.17(s，2H，OH)，3.97(s，12H，OCH
3)，1.84(s，6H，CH
3)，1.43(s，18H，C(CH
3)
3)。
13CNMR(CDCl
3)δ:166.54，152.45，143.28，135.03，134.73，133.48，133.09，130.77，129.60，129.12，121.18，52.66，34.99，29.70，17.37。IR (KBr compressing tablet, ν/cm
-1): 3511 (m), 3448 (w), 3000 (w), 2955 (m), 2918 (w), 2870 (w), 1729 (s), 1600 (w), 1438 (m), 1361 (m), 1336 (s), 1294 (m), 1245 (s), 1146 (m), 1107 (w), 1032 (w), 1003 (w), 963 (w), 920 (w), 897 (w), 875 (w), 758 (m), 724 (w), 705 (w), 637 (w), 585 (w).ESI-MS:m/z732.1(Calcd?m/z710.31for[L+Na-H])。
The step 1 reaction formula is:
Step 2, gained 1.3g of upper step biphenyl is dissolved in the mixed solvent of 30 milliliters of tetrahydrofuran (THF)/methyl alcohol=1/1, add and be dissolved with 5 milliliters of 0.77g lithium hydroxide aqueous solutions, after spending the night, 70 ℃ of lower stirring reactions revolve majority of organic solvent, add 2M dilute hydrochloric acid that the pH value is transferred to 1～2, continue under room temperature and reacted 8 hours, visible white solid is separated out, it is leached with Büchner funnel, be drying to obtain unidextrality part (S)-H in 80 ℃ of baking ovens after washed several times with water
4L:(S)-3,3 '-di-t-butyl-5,5 '-two (3,5-dicarboxyl phenyl)-6,6 '-dimethyl-2,2 '-dihydroxyl-1,1 '-biphenyl 1.2g(productive rate: 86%).
1H?NMR(CDCl
3，400MHz)δ：8.40(s，2H，ArH)，8.10-8.11(d，4H，ArH)，7.45(s，2H，ArH)，7.05(s，2H，OH)，1.68(s，6H，CH
3)，1.40(s，18H，C(CH
3)
3)。
13CNMR(CDCl
3)δ:167.42，153.73，144.14，134.80，134.37，133.23，131.85，128.54，128.52，128.02，124.86，35.02，30.28，17.80。IR (KBr compressing tablet, ν/cm
-1): 3517 (m), 3431 (m), 2960 (m), 2922 (m), 2879 (m), 1704 (s), 1604 (m), 1445 (m), 1415 (m), 1395 (m), 1365 (m), 1271 (m), 1254 (m), 1176 (m), 1034 (w), 920 (m), 873 (w), 762 (w), 703 (w), 673 (w), 660 (w), 632 (w), 589 (w).ESI-MS:m/z653.2(Calcd?m/z654.2for[L-H]
-)。
The step 2 reaction formula is:
Step 3 takes 15.8mg four hydration Manganous chloride tetrahydrate (MnCl
24H
2O) and 20mg part (S)-H
4L is in 10 ml sample bottles, add 1 milliliter of N in sample bottle, dinethylformamide and 5 ml methanol, until fully screwing bottle cap after dissolving, sample bottle is placed in 80 ℃ of baking ovens heating 1 day, takes out sample bottle after 1 day, to be cooled to the room temperature the elimination reaction solution, the gained crystalline solid is placed in air with the ether washing for several times dries, (its structural formula is [Mn namely to get 28mg unidextrality metal organic frame material
2L (DMF)
2(H
2O)
2] 3DMF2H
2O), productive rate 78%.
The crystalline structure schematic diagram of the unidextrality metal organic frame material of gained as shown in Figure 1.
The unidextrality metal organic frame material crystallization of gained is in cubic chirality spacer P4 as seen from Figure 1
12
12, comprise a part (S)-H in asymmetric cell
4L and two manganese atom Mn1 and Mn3 that are in the independent crystallization on screw diad.Mn1 and part (S)-H
4Two of bridging Sauerstoffatoms, two water moleculess and two DMF coordinations in L, Mn2 and four bridge ligands (S)-H
4Five Sauerstoffatoms and a DMF coordination of L, and Mn3 and four bridge ligands (S)-H
4Four Sauerstoffatoms and two water molecules coordinations of L.Three Mn atoms are all taked the octahedral coordination pattern of distortion, and the bond distance of Mn-O is in normally [2.245 (6)-2.358 (6)
].Mn1 and Mn2 be by a bidentate carboxylic acid bridging, and the carboxylic acid of Mn2 by a chelating is connected with Mn3.Thus, the hydroxy-acid group of Mn center by bridging formed on the c-axis direction and had [Mn
2(CO
2)
2] the one-dimensional metal chain of n structure, this metallic bond is as secondary construction unit.Part (S)-H
4L adopts a kind of exo-seven tooth coordination modes, and wherein carboxylic acid is taked respectively doube bridge connection, bidentate chelating and monodentate ligand pattern, and its carboxylic acid phenyl ring is along axle 1,1 ' key rotation and phenyl ring and 1 of biphenyl, and the interfacial angle between 1 ' key is 74 (1) °.Four adjacent metal-carboxylic acid chains are by the skeleton bridging of biphenyl ligand, have formed the chirality nano pore that the one dimension size is about 1.5nm * 1.0nm on the c-axis direction.Adjacent chirality nano pore is by three-dimensional unidextrality porous metal organic framework materials of the final formation of chiral metal chain.
step 4, resulting 30mg in step 3 had the unidextrality metal organic frame material of chiral separation function through placing 2 hours after exchange of solvent under the vacuum of 80 ℃, then under-10 ℃, be dissolved with in the methyl alcohol of racemize 1-phenyl-ethyl amine at 5mL and soaked one day, Büchner funnel filters, with methanol wash for several times, then soaked one day in tetrahydrofuran (THF), Büchner funnel filters, filtrate is used Chiralcel OD-H type liquid phase chiral separation post after the Benzoyl chloride derivatize, at 25 ℃, normal hexane/Virahol=90/10, under the 1mL/min flow velocity, the Chiral Amine of measuring is separated the ee value and is reached 90.9%, as shown in Figure 2.Analytical results in Fig. 2 is as follows:
Embodiment 2
resulting 30mg in embodiment 1 step 3 had the unidextrality metal organic frame material of chiral separation function through placing 2 hours after exchange of solvent under the vacuum of 80 ℃, then under-10 ℃, be dissolved with in the methyl alcohol of racemize 1-(4-fluorophenyl) ethamine at 5mL and soaked one day, Büchner funnel filters, with methanol wash for several times, then soaked one day in tetrahydrofuran (THF), Büchner funnel filters, filtrate is used Chiralcel OD-H type liquid phase chiral separation post after the Benzoyl chloride derivatize, at 25 ℃, normal hexane/Virahol=90/10, 0.6mL/min under flow velocity, the Chiral Amine of measuring is separated the ee value and is reached 98.7%, as shown in Figure 3.Analytical results in Fig. 3 is as follows:
Embodiment 3
resulting 30mg in embodiment 1 step 3 had the unidextrality metal organic frame material of chiral separation function through placing 2 hours after exchange of solvent under the vacuum of 80 ℃, then under-10 ℃, be dissolved with in the methyl alcohol of racemize 1-(4-bromophenyl) ethamine at 5mL and soaked one day, Büchner funnel filters, with methanol wash for several times, then soaked one day in tetrahydrofuran (THF), Büchner funnel filters, filtrate is used Chiralcel OD-H type liquid phase chiral separation post after the Benzoyl chloride derivatize, at 25 ℃, normal hexane/Virahol=90/10, 1.0mL/min under flow velocity, the Chiral Amine of measuring is separated the ee value and is reached 91.5%, as shown in Figure 4.Analytical results in Fig. 4 is as follows:
Embodiment 4
resulting 30mg in embodiment 1 step 3 had the unidextrality metal organic frame material of chiral separation function through placing 2 hours after exchange of solvent under the vacuum of 80 ℃, then under-10 ℃, be dissolved with in the methyl alcohol of racemize 1-(4-p-methoxy-phenyl) ethamine at 5mL and soaked one day, Büchner funnel filters, with methanol wash for several times, then soaked one day in tetrahydrofuran (THF), Büchner funnel filters, filtrate is used Chiralcel OD-H type liquid phase chiral separation post after the Benzoyl chloride derivatize, at 25 ℃, normal hexane/Virahol=90/10, 1.0mL/min under flow velocity, the Chiral Amine of measuring is separated the ee value and is reached 90.3%, as shown in Figure 5.Analytical results in Fig. 5 is as follows:
The unidextrality metal organic frame material that resulting 30mg in embodiment 1 step 3 is had to the chiral separation function was placed 2 hours under the vacuum of 80 ℃ after exchange of solvent, then under-10 ℃, at 5mL, be dissolved with in the methyl alcohol of racemic sec-butylamine and soaked one day, Buchner funnel filters, with methanol wash for several times, then in oxolane, soaked one day, Buchner funnel filters, filtrate is used Chiralcel OD-H type liquid phase chiral separation post after the chlorobenzoyl chloride derivatization, 25 ℃, n-hexane/isopropyl alcohol=93/7
0.6mL/min under flow velocity, the Chiral Amine of mensuration is separated the ee value and is reached 85.1%, as shown in Figure 6.Analytical results in Fig. 6 is as follows:
The filtration that relates in this specification sheets, washing, drying, all adopt the routine operation method to realize.
Claims (12)
1. the unidextrality metal organic frame material preparation method with resolving chiral amine functions, is characterized in that, at first synthetic unidextrality part (S)-H
4L:(S)-3,3 '-di-t-butyl-5,5 '-two (3,5-dicarboxyl phenyl)-6,6 '-dimethyl-2,2 '-dihydroxyl-1,1 '-biphenyl is then with part (S)-H
4L mixes with metal-salt, and with DMF and dissolve with methanol and react, reaction is cooled to room temperature after finishing, with drying and get final product after ether wash cooling after product several.
2. method according to claim 1, is characterized in that, described synthetic unidextrality part (S)-H
4L:(S)-3,3 '-di-t-butyl-5,5 '-two (3,5-dicarboxyl phenyl)-6,6 '-dimethyl-2,2 '-dihydroxyl-1,1 '-biphenyl comprises following two-step reaction altogether:
3. method according to claim 1 and 2, is characterized in that, described synthetic unidextrality part (S)-H
4L:(S)-3,3 '-di-t-butyl-5,5 '-two (3,5-dicarboxyl phenyl)-6,6 '-dimethyl-2,2 '-dihydroxyl-1,1 '-biphenyl concrete steps are:
1. take (S)-3, 3 '-di-t-butyl-5, 5 '-two bromo-6, 6 '-dimethyl-2, 2 '-dihydroxyl-1, 1 '-biphenyl, 5-pinacol ester m-phthalic acid methyl esters, three water potassiumphosphates, [1, two (diphenylphosphine) ferrocene of 1'-] palladium chloride is in reaction flask, the mixed solvent that adds dioxane and water, back flow reaction, precipitation after reaction finishes, extraction, washing, dry, filter, be spin-dried for, crude product namely gets target product (S)-3 through column chromatographic isolation and purification, 3 '-di-t-butyl-5, 5 '-two (3, 5-dimethoxycarbonyl phenyl)-6, 6 '-dimethyl-2, 2 '-dihydroxyl-1, 1 '-biphenyl,
2. gained target product of upper step is dissolved with tetrahydrofuran (THF), then add methyl alcohol, splash into lithium hydroxide solution, react the rear concentration of reaction solution that spends the night under 70 ℃, use the dilute hydrochloric acid adjust pH, stirring for some time under room temperature is that the adularescent solid is separated out, and filters, washes, is drying to obtain unidextrality part (S)-H
4L:(S)-3,3 '-di-t-butyl-5,5 '-two (3,5-dicarboxyl phenyl)-6,6 '-dimethyl-2,2 '-dihydroxyl-1,1 '-biphenyl.
4. method according to claim 3, it is characterized in that, described step 1., be specially: take (S)-3 according to mol ratio 1:2.8:4.5:0.05, 3 '-di-t-butyl-5, 5 '-two bromo-6, 6 '-dimethyl-2, 2 '-dihydroxyl-1, 1 '-biphenyl, 5-pinacol ester m-phthalic acid methyl esters, three water potassiumphosphates, [1, two (diphenylphosphine) ferrocene of 1'-] palladium chloride is in reaction flask, the mixed solvent that adds dioxane: water=9:1 under nitrogen protection, back flow reaction 10 hours, precipitation after reaction finishes, extraction, washing, dry, filter, be spin-dried for, crude product namely gets target product (S)-3 through column chromatographic isolation and purification, 3 '-di-t-butyl-5, 5 '-two (3, 5-dimethoxycarbonyl phenyl)-6, 6 '-dimethyl-2, 2 '-dihydroxyl-1, 1 '-biphenyl.
5. method according to claim 3, it is characterized in that, described step 2., be specially: gained biphenyl of upper step is dissolved with tetrahydrofuran (THF), then add the methyl alcohol of tetrahydrofuran (THF) 1/1 volume, splash into lithium hydroxide solution the pH value is transferred to 13～14, the lower rear concentration of reaction solution that spends the night that reacts refluxes, with dilute hydrochloric acid adjust pH to 1～2, stirring 8 hours under room temperature is that the adularescent solid is separated out, and filters, washes, is drying to obtain unidextrality part (S)-H
4L:(S)-3,3 '-di-t-butyl-5,5 '-two (3,5-dicarboxyl phenyl)-6,6 '-dimethyl-2,2 '-dihydroxyl-1,1 '-biphenyl.
6. method according to claim 1, is characterized in that, described reaction refers to: take metal-salt and unidextrality part (S)-H according to mol ratio 2:1
4L is in sample bottle, and every 0.05 mmole part adds 1 milliliter of DMF, every 0.05 mmole part 5 ml methanol, fully screws bottle cap after dissolving, and sample bottle is placed in 80 ℃ of baking oven heating 1 day.Take out sample bottle after 1 day, to be cooled to room temperature elimination reaction solution, the gained crystal is placed in air with the ether washing for several times dries, namely get a kind of unidextrality metal organic frame material with chiral separation function.
7. method according to claim 1, is characterized in that, described metal-salt is four hydration Manganous chloride tetrahydrates.
8. synthetic unidextrality part for the preparation of unidextrality metal organic frame material, (S)-H
4L:(S)-3,3 '-di-t-butyl-5,5 '-two (3,5-dicarboxyl phenyl)-6,6 '-dimethyl-2,2 '-dihydroxyl-1,1 '-biphenyl is characterized in that, molecular structure is:
9. the unidextrality metal organic frame material with chiral separation function for preparing according to the described method of above-mentioned arbitrary claim, is characterized in that, its structural formula is [Mn
2L (DMF)
2(H
2O)
2] 3DMF2H
2O。
10. the application according to the described unidextrality metal organic frame of above-mentioned arbitrary claim material, is characterized in that, is used for selective one-time or repeats to adsorb Chiral Amine.
11. application according to claim 10, it is characterized in that, described absorption comprises the following steps: 30mg is had the unidextrality metal organic frame material of chiral separation function through placing 2 hours under the vacuum of 80 ℃ after exchange of solvent, then under-10 ℃, be dissolved with in the methyl alcohol of Chiral Amine at 5mL and soaked one day, filter, with methanol wash for several times, then soaked one day in tetrahydrofuran (THF), filter, filtrate is used Chiralcel OD-H type liquid phase chiral separation post after the Benzoyl chloride derivatize, at 25 ℃, normal hexane/Virahol=90/10, 1.0mL/min under flow velocity, the Chiral Amine of measuring is separated the ee value and is reached more than 90%.
12. according to the described application of above-mentioned arbitrary claim, it is characterized in that, described racemic amines comprises: (Rac)-1-phenyl-ethyl amine, (Rac)-1-(4-fluorophenyl) ethamine, (Rac)-1-(4-bromophenyl) ethamine, (Rac)-1-(4-p-methoxy-phenyl) ethamine and (Rac)-2-butylamine.
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