CN102585040B - Beta-cyclodextrin derivative based on annular alkamine as well as preparation method and application of beta-cyclodextrin derivative - Google Patents
Beta-cyclodextrin derivative based on annular alkamine as well as preparation method and application of beta-cyclodextrin derivative Download PDFInfo
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Abstract
The invention discloses a beta-cyclodextrin derivative based on annular alkamine as well as a preparation method and an application of the beta-cyclodextrin derivative. The beta-cyclodextrin derivative is mono (6-(2-hydroxyl hexanaphthene amino)-6-deoxidation)-beta-cyclodextrin (CD-1), mono (6-(3-hydroxyl hexanaphthene amino)-6-deoxidation)-beta-cyclodextrin (CD-2), mono (6-(4-hydroxyl hexanaphthene amino)-6-deoxidation)-beta-cyclodextrin (CD-3), mono (6-(2-hydroxyl cyclopentyl amino)-6-deoxidation)-beta-cyclodextrin (CD-4) and mono (6-(3-hydroxyl-4-amino tetrahydrofuran)-6-deoxidation)-beta-cyclodextrin (CD-5). The beta-cyclodextrin derivative can be prepared from mono (6-O-p-tosyl group)-beta-cyclodextrin and corresponding annular alkamine to take nucleophilic substitution reaction in polar aprotic solvents. A synthetic method has the advantages that the operation is simple, the reaction condition is mild, the yield is high, and the like. The beta-cyclodextrin derivative can be used as a water-soluble ligand of metal imitation enzymes to be applied to water phase metal catalytic organic synthesis, water phase molecular recognition and water phase photosensitive materials.
Description
Technical field
The present invention relates to a kind of based on cyclic amino alcohols
β-cyclodextrine derivatives and its preparation method and application, belongs to catalysis organic synthesis field.
Background technology
Cyclodextrin (cyclodextrin, be called for short CD) be by
d-(+)-glucopyranose units is passed through
αthe cyclic oligosaccharide that-Isosorbide-5-Nitrae-glycosidic bond is formed by connecting, in truncated cones shape, has special construction and the character of " inner chamber is hydrophobic, and outer wall is hydrophilic ".Only has a kind of functional group of hydroxyl in the molecule thereof, easily intramolecular hydrogen bond is formed between hydroxyl, thus cyclodextrin molecular structure has very strong rigidity, and when interacting with the guest molecule with various shape and functional group, the structure of cyclodextrin is difficult to corresponding change in topology occurs.Meanwhile, cyclodextrin is only soluble in water and the strong polar organic solvent of minority, limit its application in organic solvent (
chem. Rev. 2003,
103, 4147).In order to change the physics and chemistry character of cyclodextrin, optionally can carry out chemical modification to the hydroxyl of cyclodextrin, conversion of hydroxyl is become target group, and then be built into various artificial imitative enzyme or artificial metal imitates enzyme.
The artificial metal constructed based on cyclodextrin imitates enzyme, mainly will through the cyclodextrine derivatives modified as the part of metal ion, by the inclusion of cyclodextrin cavity and substrate, organic synthesis is transferred to aqueous phase from organic phase, environmental protection.Simultaneously Inclusion property also relatively furthered substrate and catalytic active center distance and secure the two relative position, often can significantly improve the reaction rate of organic synthesis, regioselectivity and enantioselectivity.
Breslow etc. are respectively to have two or four
βthe derivatives of porphyrin of-cyclodextrin units is as the part of metal ions M n (III), be applied to the hydroxylating of catalysis sterid as cytochrome P-450 analogue enztme, high selectivity achieve sterid C-9 position hydroxylating (
j. Am. Chem. Soc. 1997,
119, 4535.;
angew. Chem. Int. Edit. 2000,
39, 2692.).Cyclic amino alcohols is compared with general straight chain amino alcohol, water-soluble poor, greatly sterically hindered between amino and hydroxyl, modifies through it
β-cyclodextrin can not only well with metal ion generation complexing, and modification group has stronger rigidity, and chiral induction is effective.Therefore, develop synthesis of cyclic amino alcohol to modify
β-cyclodextrin is imitated enzyme water soluble ligand as metal and is had stronger theoretical research value and using value.
Summary of the invention
The object of the present invention is to provide a kind of based on cyclic amino alcohols
β-cyclodextrine derivatives and its preparation method and application.
One provided by the invention is based on cyclic amino alcohols
β-cyclodextrine derivatives is that 2-aminocyclohexanol is modified
β-cyclodextrin (CD-1), 3-aminocyclohexanol are modified
β-cyclodextrin (CD-2), 4-aminocyclohexanol are modified
β-cyclodextrin (CD-3), 2-amino cyclopentyl alcohol are modified
β-cyclodextrin (CD-4) and 3-amino-4-hydroxy oxolane are modified
β-cyclodextrin (CD-5), it is modified position and is
β-cyclodextrin C-6 position, modification group is cyclic amino alcohols, and its structural formula is as follows:
CD-1 CD-2 CD-3 CD-4 CD-5
Wherein:
For
β-cyclodextrin parent fraction.
The present invention also provides described based on cyclic amino alcohols
βthe preparation method of-cyclodextrine derivatives, said method comprising the steps of: will single (6-
o-
p-tosyl)-
β-cyclodextrin and cyclic amino alcohols are dissolved in anhydrous polar aprotic solvent, under nitrogen atmosphere, react at the reaction temperatures, after gained reactant mixture cool to room temperature, be slowly added drop-wise in acetone, suction filtration, with absolute ethanol washing gained solid, and be recrystallized in pure water, respectively through acetone, washing, obtained product after vacuum drying.
Above-mentioned based on cyclic amino alcohols
βin the preparation method of-cyclodextrine derivatives, described list (6-
o-
p-tosyl)-
βthe mol ratio of-cyclodextrin and cyclic amino alcohols is 1:1 ~ 1:500; Described anhydrous polar aprotic solvent is the one in acetonitrile, sulfolane, hexamethyl phosphoramide, DMF and dimethyl sulfoxide (DMSO); Reaction temperature is 50 ° of C ~ 160 ° C; Reaction time is 6.0h ~ 96.0h.
Present invention also offers described based on cyclic amino alcohols
βthe application of-cyclodextrine derivatives, should
β-cyclodextrine derivatives can be used as the water soluble ligand that metal imitates enzyme and is applied to aqueous metal catalysis organic synthesis, aqueous phase molecular recognition or aqueous phase photosensitive material aspect.
In the applications described above, preferably should
β-cyclodextrine derivatives is applied in the asymmetric oxidation of aqueous metal catalysis thioether, it is characterized in that comprising the following steps: will
β-cyclodextrine derivatives CD-1 ~ CD-5 and slaine are dissolved in CH
3in COONa-HCl buffer solution, stirred at ambient temperature, then adds thioether, is stirred by reactant mixture, adds 30% H
2o
2the aqueous solution, CH
2cl
2extract and merge organic layer, the saturated NaCl aqueous solution washes gained organic layer, anhydrous Na
2sO
4drying, decompression precipitation, obtain yellow oily liquid, described thioether is the compound with following formula:
Wherein, R
1and R
2be selected from methyl, ethyl, propyl group, butyl, isopropyl, the tert-butyl group, phenyl, 1-naphthyl, 2-naphthyl, methoxyl group, ethyoxyl, hydroxyl, sulfydryl, amino, methylamino, ethylamino, dimethylamino, 1-hydroxyethyl, chlorine, bromine, iodine etc., R
1, R
2can be identical, also can be different.
Beneficial effect of the present invention is mainly reflected in: relate to based on cyclic amino alcohols
β-cyclodextrine derivatives CD-1 ~ CD-5 novel structure, its synthetic route is simple, and yield is high, and application is wide, can carry out ligand complex with many kinds of metal ions, shows excellent enantioselectivity, product in the organic asymmetric catalysis synthesis of catalysis
ee% value is high, and is easy to reclaim.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in this:
What embodiment 1-6 illustrated is cyclic amino alcohols
βthe application of-cyclodextrine derivatives in aqueous metal catalysis organic synthesis.
What embodiment 7 illustrated is cyclic amino alcohols
βthe application of-cyclodextrine derivatives in aqueous phase molecular recognition or aqueous phase photosensitive material.
Embodiment 1
In 250mL eggplant shaped reaction bottle, by single for 32.23g (25.0mmol) (6-
o-
p-tosyl)-
β-cyclodextrin and 2.88g (25.0mmol) 2-aminocyclohexanol are dissolved in the anhydrous HMPA of 100mL, in N
2under atmosphere, 120 ° of C stirring reaction 60.0h.After gained reactant mixture cool to room temperature, slowly be added drop-wise in 400mL acetone, suction filtration, gained solid washed by 200mL absolute ethyl alcohol, and be recrystallized in 2 × 150mL water secondary, and washed by 100mL acetone by gained solid, 50mL washes, vacuum drying 3.0h under 120 ° of C, obtains white solid (CD-1) 27.87g, yield 90.48%.
CD-1: m.p. >265°C;
1H NMR(DO
2, 400 MHz)
δ: 5.25~5.17(m, 7H), 4.06~3.88(m, 26H), 3.82~3.67(m, 14H), 3.53(t, 1H), 3.18(d, 1H), 2.98~2.93(m, 1H), 2.74~2.66(m, 1H), 1.89~1.33 ppm (m, 8H);
13C NMR (DMSO-
d 6 , 400 MHz)
δ: 101.94~101.71, 82.81, 82.00~81.40, 72.88~71.87, 70.77, 67.30, 59.73, 58.15, 46.08, 30.64, 26.79, 22.39, 20.97 ppm; MS (ESI):
m/z: 1232.4([M+1]
+), 1254.5([M+Na]
+).
Embodiment 2
In 250mL eggplant shaped reaction bottle, by single for 32.23g (25.0mmol) (6-
o-
p-tosyl)-
β-cyclodextrin and 2.88g (25.0mmol) 3-aminocyclohexanol are dissolved in the anhydrous HMPA of 100mL, in N
2under atmosphere, 120 ° of C stirring reaction 60.0h.After gained reactant mixture cool to room temperature, slowly be added drop-wise in 400mL acetone, suction filtration, gained solid washed by 200mL absolute ethyl alcohol, and be recrystallized in 2 150mL water secondary, and washed by 100mL acetone by gained solid, 50mL washes, vacuum drying 3.0h under 120 ° of C, obtains white solid (CD-2) 28.45g, yield 92.36%.
CD-2: m.p. >265°C;
1H NMR (DO
2, 400 MHz)
δ: 5.18~5.07(m, 7H), 4.14~3.80(m, 26H), 3.70~3.58(m, 14H), 3.48~3.38(m, 1H), 3.22~3.12(m, 1H), 2.93~2.76(m, 1H), 2.65~2.55(m, 1H), 2.22~0.98 ppm (m, 8H); MS (ESI):
m/z: 1232.4([M+1]
+), 1254.4([M+Na]
+).
Embodiment 3
In 250mL eggplant shaped reaction bottle, by single for 32.23g (25.0mmol) (6-
o-
p-tosyl)-
β-cyclodextrin and 2.88g (25.0mmol) 4-aminocyclohexanol are dissolved in the anhydrous HMPA of 100mL, in N
2under atmosphere, 120 ° of C stirring reaction 60.0h.After gained reactant mixture cool to room temperature, slowly be added drop-wise in 400mL acetone, suction filtration, gained solid washed by 200mL absolute ethyl alcohol, and be recrystallized in 2 × 150mL water secondary, and washed by 100mL acetone by gained solid, 50mL washes, vacuum drying 3.0h under 120 ° of C, obtains white solid (CD-3) 28.22g, yield 91.61%.
CD-3: m.p. >275°C;
1H NMR (DO
2, 400 MHz)
δ: 5.18~5.09(m, 7H), 3.98~3.84(m, 26H), 3.71~3.58(m, 14H), 3.47(t, 1H), 3.19(d, 1H), 2.84(t, 1H), 2.57(t, 1H), 2.02~1.95(m, 4H), 1.36~1.18 ppm(m, 4H); MS (ESI):
m/z: 1232.5([M+1]
+), 1254.5([M+Na]
+).
Embodiment 4
In 250mL eggplant shaped reaction bottle, by single for 32.23g (25.0mmol) (6-
o-
p-tosyl)-
β-cyclodextrin and 2.53g (25.0mmol) 2-amino cyclopentyl alcohol are dissolved in the anhydrous HMPA of 100mL, in N
2under atmosphere, 120 ° of C stirring reaction 60.0h.After gained reactant mixture cool to room temperature, slowly be added drop-wise in 400mL acetone, suction filtration, gained solid washed by 200mL absolute ethyl alcohol, and be recrystallized in 2 × 150mL water secondary, and washed by 100mL acetone by gained solid, 50mL washes, vacuum drying 3.0h under 120 ° of C, obtains white solid (CD-4) 27.51g, yield 90.34%.
CD-4: m.p. >265°C;
1H NMR (DO
2, 400 MHz)
δ: 5.11~5.04(m, 7H), 3.97~3.79(m, 26H), 3.70~3.53(m, 14H), 3.45~3.35(m, 1H), 3.18~3.01(m, 1H), 2.95~2.88(m, 1H), 2.83~2.76(m, 1H), 2.03~1.33 ppm (m, 6H); MS (ESI):
m/z: 1218.4([M+1]
+), 1240.4([M+Na]
+).
Embodiment 5
In 250mL eggplant shaped reaction bottle, by single for 32.23g (25.0mmol) (6-
o-
p-tosyl)-
β-cyclodextrin and 2.58g (25.0mmol) 3-amino-4-hydroxy oxolane are dissolved in the anhydrous HMPA of 100mL, in N
2under atmosphere, 120 ° of C stirring reaction 60.0h.After gained reactant mixture cool to room temperature, slowly be added drop-wise in 400mL acetone, suction filtration, gained solid washed by 200mL absolute ethyl alcohol, and be recrystallized in 2 × 150mL water secondary, and washed by 100mL acetone by gained solid, 50mL washes, vacuum drying 3.0h under 120 ° of C, obtains white solid (CD-5) 28.36g, yield 92.98%.
CD-5: m.p. >250°C;
1H NMR (DO
2, 400 MHz)
δ: 5.09~5.06(m, 7H), 4.31~4.23(m, 1H), 4.13~4.08(m, 1H), 3.98~3.85(m, 26H), 3.75~3.70(m, 1H), 3.66~3.55(m, 14H), 3.50~3.44(m, 1H), 3.25~3.21(m, 1H), 3.13~3.07(m, 1H), 2.93~2.79(m, 1H), 2.58 ppm(s, 1H); MS (ESI):
m/z: 1220.3([M+1]
+), 1242.4([M+Na]
+).
Embodiment 6
In 250mL two mouthfuls of kieldahl flasks, by 10mmol
β-cyclodextrine derivatives CD-1 ~ CD-5 and 0.85g (5.0mmol) CuCl
22H
2o is dissolved in 100mL pH=9.5 4.0M CH
3in COONa-HCl buffer solution, stirred at ambient temperature 1.0h.Then aminomethyl phenyl thioether 62.11g (500mmol) is added, stirred at ambient temperature 1.0h.Stir under reactant mixture being placed in-20 ° of C, add 50mL 30% H
2o
2the aqueous solution, stirring reaction 3.0h under-20 ° of C.3 × 100mL CH
2cl
2extract and merge organic layer, the saturated NaCl aqueous solution of 100mL washes gained organic layer, anhydrous Na
2sO
4drying, decompression precipitation, obtains yellow oily liquid.HPLC analyzes (V
n-hexane: V
isopropyl alcohol=4:1,0.9mL/min, 254nm).Yield, 96%.
ee%，92%(
S)。
Embodiment 7
At NaOH-KH
2pO
4in buffer solution, fixing
pthe concentration (5.0 × 10 of-tolyl aldehyde
-5mol/L or 4.0 × 10
-5mol/L),
βthe concentration of-cyclodextrine derivatives CD-1 ~ CD-5 gets (0.2 × 10 successively
-3mol/L, 0.4 × 10
-3mol/L, 0.6 × 10
-3mol/L, 0.8 × 10
-3mol/L and 1.0 × 10
-3and (1.0 × 10 mol/L)
-3mol/L, 2.0 × 10
-3mol/L, 3.0 × 10
-3mol/L, 4.0 × 10
-3mol/L and 5.0 × 10
-3mol/L), leave standstill after about 36.0 h under 25 ° of C, with respective concentration
β-cyclodextrine derivatives solution is reference, measures its ultra-violet absorption spectrum and change successively.
Fixing
pthe concentration of-tolyl aldehyde is 5.0 × 10
-5the concentration of mol/L, CD-1 gets 0, and 1.0,2.0,3.0,4.0,5.0 × 10
-3mol/L, measures successively
pthe ultra-violet absorption spectrum of-tolyl aldehyde.At absorption maximum 261nm place, UV absorption is followed successively by 0.8093,0.7880,0.7787,0.7743,0.7717 and 0.7687, describes ultra-violet absorption spectrum intensity and declines successively along with the increase of CD-1 concentration.This is because CD-1 is in aqueous phase
pthe molecular recognition of-tolyl aldehyde result in aqueous phase
pthe change of-tolyl aldehyde ultra-violet absorption spectrum.
Claims (2)
1. one kind based on cyclic amino alcohols
βthe application of-cyclodextrine derivatives in aqueous metal catalysis thioether asymmetric oxidation, is characterized in that,
Described based on cyclic amino alcohols
β-cyclodextrine derivatives comprises: 3-aminocyclohexanol is modified
β-cyclodextrin (CD-2), 4-aminocyclohexanol are modified
β-cyclodextrin (CD-3), 2-amino cyclopentyl alcohol are modified
β-cyclodextrin (CD-4) and 3-amino-4-hydroxy oxolane are modified
β-cyclodextrin (CD-5), it is modified position and is
β-cyclodextrin C-6 position, modification group is cyclic amino alcohols, and its structural formula is as follows:
CD-2 CD-3 CD-4 CD-5
Wherein:
For
β-cyclodextrin parent fraction;
Described based on cyclic amino alcohols
βthe preparation method of-cyclodextrine derivatives, for inciting somebody to action single (6-
o-
p-tosyl)-
β-cyclodextrin and cyclic amino alcohols are dissolved in anhydrous polar aprotic solvent, under nitrogen atmosphere, react at the reaction temperatures, after gained reactant mixture cool to room temperature, be slowly added drop-wise in acetone, suction filtration, with absolute ethanol washing gained solid, and be recrystallized in pure water, respectively through acetone, washing, obtained product after vacuum drying;
Described list (6-
o-
p-tosyl)-
βthe mol ratio of-cyclodextrin and cyclic amino alcohols is 1:1 ~ 1:500;
Described anhydrous polar aprotic solvent is the one in acetonitrile, sulfolane, hexamethyl phosphoramide, DMF and dimethyl sulfoxide (DMSO);
Described reaction temperature is 50 ° of C ~ 160 ° C, and the reaction time is 6.0h ~ 96.0h;
Described based on cyclic amino alcohols
βthe application of-cyclodextrine derivatives, comprises the following steps: will
β-cyclodextrine derivatives CD-2 ~ CD-5 and slaine are dissolved in CH
3in COONa-HCl buffer solution, stirred at ambient temperature, then adds thioether, is stirred by reactant mixture, adds 30% H
2o
2the aqueous solution, CH
2cl
2extract and merge organic layer, the saturated NaCl aqueous solution washes gained organic layer, anhydrous Na
2sO
4drying, decompression precipitation, obtains yellow oily liquid.
2. application according to claim 1, is characterized in that, described thioether is the compound with following formula:
Wherein, R
1and R
2be selected from methyl, ethyl, propyl group, butyl, isopropyl, the tert-butyl group, phenyl, 1-naphthyl, 2-naphthyl, methoxyl group, ethyoxyl, hydroxyl, sulfydryl, amino, methylamino, ethylamino, dimethylamino, 1-hydroxyethyl, chlorine, bromine and iodine, R
1, R
2can be identical, also can be different.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101195662A (en) * | 2007-12-20 | 2008-06-11 | 山东大学 | 6-(2-glucosyl amido)-beta- cyclodextrin derivant and method for producing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101195662A (en) * | 2007-12-20 | 2008-06-11 | 山东大学 | 6-(2-glucosyl amido)-beta- cyclodextrin derivant and method for producing the same |
Non-Patent Citations (3)
| Title |
|---|
| Synthesis of _-cyclodextrin derivative bearing a cyclohexylamino moiety and its inclusion complexation with organic dye molecules;Yu Liu et al;《Microchemical Journal》;20011130;第70卷(第2期);第115-121页 * |
| Synthesis of water-soluble multidentate aminoalcohol b-cyclodextrin;K. Martina et al;《Carbohydrate Research》;20110922;第346卷;第2677-2682页 * |
| β-环糊精超分子催化剂用于液相有机合成;纪红兵等;《有机化学》;20081215;第28卷(第12期);第2072-2080页 * |
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