CN101333232B - Method for preparing modified glucose chelator - Google Patents
Method for preparing modified glucose chelator Download PDFInfo
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- CN101333232B CN101333232B CN2008100329456A CN200810032945A CN101333232B CN 101333232 B CN101333232 B CN 101333232B CN 2008100329456 A CN2008100329456 A CN 2008100329456A CN 200810032945 A CN200810032945 A CN 200810032945A CN 101333232 B CN101333232 B CN 101333232B
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Abstract
The invention discloses a preparation method for a modified glucose chelator: D-glucose and anhydrous ethylenediamine are added into three containers based on a molar ratio of 2:1; anhydrous methanol is taken as solvent, and the D-glucose is completely dissolved through stirring at 50-80 DEG C; then, anhydrous acetic acid is added as catalyst; the dosage of the catalyst takes up 1% of the mole number of the D-glucose; the reaction time is 3 hours; the white sediment is washed with anhydrous ethanol and anhydrous methanol, and then dried through vacuum leaching and vacuum drying at 55 DEG C; the obtained white crystal is aminated glucose. The composition of the aminated glucose prepared with the method of the invention is C14H 28O10N2. In the UV spectrum, the aminated glucose is not obviously absorbed in the UV area; when the aminated glucose forms a complex with Cu (II), the maximum absorption peak appears near 236nm. In the aminated glucose-Cu (II) complex, the complexing ratio between Cu2+ and the aminated glucose is close to 1:1; the stability constant of the complex is 6.8 by 107.
Description
Technical field
The present invention relates to a kind of preparation method of modified glucose chelator, relate in particular a kind of can be as the preparation method of the amination glucose of sequestrant.
Background technology
No matter sugar and derivative thereof are aspect the research of the synthetic and catalyzed reaction of stereospecificity compound, still are at aspects such as biomedicine, daily-use chemical industries important meaning to be arranged all.Carbohydrate derivative to human temperature and, biological degradation is fast and safety has eco-friendly characteristics.Replace hydroxyl on the sugar ring with the strong functional group of coordination abilities such as nitrogenous, sulphur, but the modified glucose chelator of processability excellence is having a wide range of applications aspect medicine, food, the functional material.
Summary of the invention
Technical problem to be solved by this invention provides a kind of preparation method of amination glucose of easy, easy row, and this amination glucose can good complex reaction take place as modified glucose chelator and Cu (II) ion.
The technical solution used in the present invention: a kind of preparation method of modified glucose chelator, comprise the following steps: thermometer is being housed, in three mouthfuls of containers of reflux condensing tube and electric mixer, added D-glucose and anhydrous ethylenediamine in 2: 1 in molar ratio, with anhydrous methanol as solvent, under 50～80 ℃ of temperature, stir, D-glucose is dissolved fully, add anhydrous Glacial acetic acid then and make catalyzer, catalyst consumption is 1% of a D-glucose mole number, reaction 3h, the adularescent throw out generates, to the white depositions dehydrated alcohol, the anhydrous methanol washing, vacuum filtration, 55 ℃ of vacuum-dryings, the gained white crystal is amination glucose.
D-glucose should pass through vacuum drying treatment before dropping into three mouthfuls of container reactions.
The process of whole preparation modified glucose chelator should be carried out under anhydrous condition.
Beneficial effect of the present invention: the modified glucose chelator of the present invention's preparation is an amination glucose, consists of C
14H
28O
10N
2The present invention is that raw material and reacting ethylenediamine form amination glucose with glucose, simple, the easy row of reaction.The structure employing FTIR of product,
1H-NMR spectrum characterizes, in the FTIR spectrum, at 1629～1608cm
-1δ appears in the place
NHAbsorption peak;
1In the H-NMR spectrum, the chemical shift at 4.82～4.79ppm place corresponds respectively to glucose C
1On proton and and C
1Directly the proton on the amino of the quadrol of Xiang Lianing shows that quadrol has replaced glucose C when reacting
1On hydroxyl, formed amination glucose.In UV spectrum, amination glucose does not obviously absorb at ultraviolet region, but after forming title complex with Cu (II), maximum absorption band occurs near 236nm.In amination glucose-Cu (II) title complex, Cu
2+Be similar to 1: 1, this title complex stability constant 6.8 * 10 with the complexing ratio of amination glucose
7
Description of drawings
Fig. 1 is the infrared spectrogram of glucose and amination glucose;
Fig. 2 is an amination glucose
1H NMR wave spectrogram;
Fig. 3 is amination glucose and Cu thereof
2+The uv absorption spectra of title complex;
Fig. 4 is the abosrption spectrogram of amination glucose-Cu (II) title complex;
Fig. 5 is A-[Cu
2+]/[R] graphic representation.
Embodiment
Below by drawings and Examples the present invention is described in further detail: a kind of preparation method of modified glucose chelator, comprise the following steps: thermometer is being housed, in three mouthfuls of containers of reflux condensing tube and electric mixer, added D-glucose and anhydrous ethylenediamine in 2: 1 in molar ratio, with anhydrous methanol as solvent, under 50～80 ℃ of temperature, stir, D-glucose is dissolved fully, add anhydrous Glacial acetic acid then and make catalyzer, catalyst consumption is 1% of a D-glucose mole number, reaction 3h, the adularescent throw out generates, to the white depositions dehydrated alcohol, the anhydrous methanol washing, vacuum filtration, 55 ℃ of vacuum-dryings, the gained white crystal is amination glucose.D-glucose should pass through vacuum drying treatment before dropping into three mouthfuls of container reactions.The process of whole preparation modified glucose chelator should be carried out under anhydrous condition.
Preparation embodiment
Get D-glucose 18g (being 0.1mol), 55 ℃ of vacuum-dryings.In the there-necked flask that thermometer, reflux condensing tube and electric mixer are housed, add 100mL anhydrous methanol solvent earlier, add dried 18g D-glucose and anhydrous ethylenediamine 3g (being 0.05mol) again, be heated to 65 ℃, add 2～3 anhydrous Glacial acetic acid (be about D-glucose mole number 1%) after treating to dissolve fully again, reaction 3h, the adularescent throw out generates in the there-necked flask.White depositions with dehydrated alcohol, anhydrous methanol washing, vacuum filtration, 55 ℃ of vacuum-dryings, is got white crystal, be amination glucose.
1. the diffuse reflectance infrared spectroscopy of glucose and amination glucose
The diffuse reflectance infrared spectroscopy of glucose and amination glucose is seen Fig. 1, and glucose is that A, amination glucose are B, as can be seen from Figure 1 at 3500～3000cm
-1Be glucose hydroxyl and ν
N-HCharacteristic absorbance, broad peak demonstrates the association feature of hydroxyl, 2944～2890cm
-1Be ν
C-HCharacteristic peak.At 1700～1500cm
-1In the scope, glucose has only 1 1631cm
-1Absorption peak, this is the δ by crystal water
HOHCaused, and amination glucose is at 1629～1608cm
-1δ appears in the place
NHAbsorption peak.At 1500～1250cm
-1In the scope, glucose has occurred 1461,1383,1340,1297cm
-1Four absorption peaks, this is by CH
2Flexural vibration and several angle vibrational couplings such as OCH, CCH, COH form, their variation has reflected the variation of glycan molecule conformation.After forming aminate, only occurred 1385 in this zone, 1269cm
-1Two absorption peaks correspond respectively to ν (C-N) and τ (C-H) vibration.At 1250～1100cm
-1In the scope, glucose has 1225,1204,1149,1111cm
-1Four absorption peaks.2 spikes are caused by two kinds of C-O stretching vibrations, wherein a kind of ν that belongs among the COH
CO(1111cm
-1), another kind belongs to the ν on the sugar ring
CO(1149cm
-1), all the other 2 absorption peaks are caused by the OCH formation vibration.After forming aminate, only at 1096cm
-11 peak occurs, the reason of variation may be because reaction has taken place for oh group and quadrol.At 1100～900cm
-1In the scope, glucose has 1050,1025,1002,916cm
-1Four absorption peaks.1002cm wherein
-1Absorption peak belong to C-O-H formation vibration, 916cm
-1Absorption peak is caused by asymmetric ring vibration, and all the other 2 peaks belong to C-C-H, the vibration of O-C-H angle.1050cm behind the formation aminate
-1The peak to high wave number displacement, shift to 1057cm
-1, 1025,1002,916cm
-1The peak to the lower wave number displacement, shift to 1022,978 respectively, 898cm
-1At 900～400cm
-1In the scope, glucose has occurred 839,774,618,559cm
-1Four peaks appear at 839cm in the sugar
-1Absorption peak be to cause 774cm by the vibration of the O-C-H angle of α-end group isomery
-1The peak belong to the symmetrical stretching vibration of sugar ring, and 618,559cm
-1The absorption peak at place is mainly caused by skeletal vibration.After forming aminate, appear at 839cm in the raw sugar
-1Absorption peak shifted to lower wave number, be displaced to 810cm
-1, infer that amino has replaced C
1On hydroxyl; 774cm
-1The peak disappeared, 618,559cm
-1The peak shifted to high wave number, be displaced to 635 respectively, 593cm
-1The ring texture that shows sugar still exists, but because amino replacement makes the position of skeletal vibration absorption peak shift to high wave number.
2. amination glucose ultimate analysis
In order further to determine the composition of amination glucose, it has been carried out ultimate analysis, test result sees Table 1.Results of elemental analyses is averaged, and the mol ratio that gets carbon, hydrogen, nitrogen as calculated is
The C that consists of of this amination glucose is described
14H
28O
10N
2
Table 1 ultimate analysis table
| N(％)? | C(％)? | H(％)? |
| 7.115? | 43.30? | 6.908? |
| 7.019? | 43.02? | 7.607? |
3. the proton nmr spectra of amination glucose
Fig. 2 is an amination glucose
1H NMR wave spectrogram.As can be seen from Figure 2, in the chemical shift at 4.82～4.79ppm place corresponding to C
1On proton be a position and and C
1The direct proton e position on the amino of the quadrol of Xiang Lianing; Chemical shift at 4.51～4.34ppm place is C
2, C
3, C
4, C
6Proton d position in the last hydroxyl, two peaks only appear in the ripple in the drawings because proton in the hydroxyl is relatively lived; Chemical shift at 3.67～3.64ppm place is and C
1Proton f position on another amino of the quadrol that links to each other; Displacement at 3.42～3.32 places is C
6Last two proton c positions; At 3.14～3.03ppm and 2.50～2.49ppm place is C
2, C
3, C
4, C
5On proton b position; At 2.90～2.84ppm and 2.63～2.51ppm place respectively corresponding to C
1The CH of the quadrol that links to each other
2On proton g position and h position.From amination glucose
1H NMR spectrogram as can be known, quadrol has replaced glucose C
1On hydroxyl.Existing lot of documents reports that also aliphatic amide is easy to replace C
1On hydroxyl form amination glucose.In conjunction with results of elemental analyses, this amination glucose structural formula is as follows:
4. the UV spectrum of amination glucose and Cu thereof (II) title complex
Fig. 3 is the ultra-violet absorption spectrum of amination glucose and Cu (II) title complex thereof, 1-amination glucose, 2-amination glucose-Cu
2+Title complex.Amination glucose does not have obvious absorption in the ultraviolet region as can be seen from Figure 3, and its Cu (II) title complex has maximum absorption band near the 236nm of ultraviolet region, this is that n → σ takes place the electronics in the complex molecule because Cu (II) adds back and amination glucose generation complex reaction
*The required energy of transition more coordinate amination glucose low due to.Because the copper complex of amination glucose has absorption in the ultraviolet region,,, measure different concns Cu by fixed ligands concentration in order to understand the complex ability of this amination glucose and cupric ion
2+Ion and part form the absorbancy (is reference with the ligand solution) behind the title complex, have measured this part and Cu
2+Form the composition and the stability constant of title complex.Fig. 4 is the absorption spectrum of amination glucose-Cu (II) title complex, and blank reagent is a reference, [amination glucose]=2.3 * 10
-5MolL
-1, [Cu
2+] (* 10
-5MolL
-1): 1-1.2,2-1.4,3-1.6,4-1.8,5-2.0,6-2.2,7-2.4.Fig. 4 shows: fixedly the amination glucose concn is 2.3 * 10
-5Mol.L
-1, along with Cu
2+Concentration increases, and the absorption peak of title complex increases gradually near 236nm, and curve 6,7 is overlapping, illustrates that complex reaction reaches capacity, at this moment [Cu
2+Amination]/[glucose] ratio approached 1: 1, illustrate that the complex compound type is 1: 1 type.May be in this complex reaction, not only the amino nitrogen on the amination glucose has participated in complexing, and complex reaction has also taken place with Cu (II) in hydroxyl oxygen.In order further to ask the composition of calculating this complex compound, fixedly the amination glucose concn is 2.3 * 10
-5MolL
-1, Cu progressively increases respectively
2+Concentration is also measured the absorbancy at 236nm place, draws A-[Cu
2+Amination]/[glucose] curve, Fig. 5 is A-[Cu
2+]/[R] graphic representation, blank reagent is a reference, [R]=2.3 * 10
-5MolL
-1Amination glucose, curve break is similar to 1.0, confirms that thus the complex compound type is 1: 1 type.According to document as can be known: β=[MR
n]/[M] [R]
n=(A/ ε)/| [M]-A/ ε | ([R]-nA/ ε)
n, A is the absorbancy of complex compound maximum absorption wave strong point in the formula, and ε is a molar absorptivity, and [M] is the concentration of metal ion, and [R] is ligand concentration, n is the complexing ratio.Wherein ε can calculate by saturated absorbance A max (i.e. [M]＞＞when [R], ε=nAmax/[R], A is recorded by experiment, n, [M] and [R] are given value, thereby can calculate necessarily stability constant (table 2) of [R] time complex compound.Get the mean value of twice experimental result, this copper complex stability constant β is 6.8 * 10
7, table 2 is calculated values of copper complex stability constant β.
Table 2 copper complex stability constant β
| [amination glucose] | A max | [Cu 2+](×10 -5mol·L -1) | A? | β? |
| 2.3×10 -5mol·L -1 | 0.0702? | 2.2? | 0.0686? | 9.0×10 7 |
| 2.4? | 0.0691? | 4.6×10 7 | ? | ? |
Conclusion
(1) with glucose be raw material, form amination glucose with reacting ethylenediamine, its structure employing FTIR,
1H-NMR spectrum characterizes.In the FTIR spectrum, at 1629～1608cm
-1δ appears in the place
NHAbsorption peak;
1In the H-NMR spectrum, the chemical shift at 4.82～4.79ppm place corresponds respectively to glucose C
1On proton and and C
1Directly the proton on the amino of the quadrol of Xiang Lianing shows that quadrol has replaced glucose C when reacting
1On hydroxyl, formed amination glucose.
(2) in UV spectrum, amination glucose does not obviously absorb at ultraviolet region, but after forming title complex with Cu (II), maximum absorption band occurs near 236nm.In amination glucose-Cu (II) title complex, Cu
2+Be similar to 1: 1, this title complex stability constant 6.8 * 10 with the complexing ratio of amination glucose
7
Above said content only is the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.
Claims (3)
1. the preparation method of a modified glucose chelator, comprise the following steps: thermometer is being housed, in three mouthfuls of containers of reflux condensing tube and electric mixer, added D-glucose and anhydrous ethylenediamine in 2: 1 in molar ratio, with anhydrous methanol as solvent, under 50～80 ℃ of temperature, stir, D-glucose is dissolved fully, add anhydrous Glacial acetic acid then and make catalyzer, catalyst consumption is 1% of a D-glucose mole number, reaction 3h, the adularescent throw out generates, to the white depositions dehydrated alcohol, the anhydrous methanol washing, vacuum filtration, 55 ℃ of vacuum-dryings, the gained white crystal is amination glucose.
2. according to the preparation method of the described a kind of modified glucose chelator of claim 1, it is characterized in that: D-glucose is the process vacuum drying treatment before dropping into three mouthfuls of container reactions.
3. according to the preparation method of the described a kind of modified glucose chelator of claim 1, it is characterized in that: whole process of preparation is carried out under anhydrous condition.
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Non-Patent Citations (5)
| Title |
|---|
| J.MARTIN MACLEOD.synthesis and hydrolysis of N,N"-diglycopyranosylethyl-enediamines.Carbohydrate Research.1979,7571-81. * |
| J.MARTINMACLEOD.synthesisandhydrolysisofN N"-diglycopyranosylethyl-enediamines.Carbohydrate Research.1979 |
| SHIGENOBU YANO ET AL.antifungal nickel(II) complexes derived from amino sugars against pathogenic yeast, candida albicans.Journal of Inorganic Biochemistry.1998,6915-23. * |
| SHIGENOBUYANOETAL.antifungalnickel(II)complexesderivedfromaminosugarsagainstpathogenicyeast candida albicans.Journal of Inorganic Biochemistry.1998 |
| 张炜等.金属-糖胺配合物的合成，光谱表征及催化脂类水解的动力学研究.光谱学与光谱分析.2005,25(6),975-978. * |
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Effective date of registration: 20141222 Address after: 200090 Pingliang Road, Shanghai, No. 2103, No. Patentee after: Shanghai University of Electric Power Patentee after: State Grid Shanghai Municipal Electric Power Company Address before: 200090 Pingliang Road, Shanghai, No. 2103, No. Patentee before: Shanghai University of Electric Power |