CN1830799A - Carboxymethyl-beta-cyclodextrin intercalated water talc used for chiral resolution racemic modification and its preparation method - Google Patents
Carboxymethyl-beta-cyclodextrin intercalated water talc used for chiral resolution racemic modification and its preparation method Download PDFInfo
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- CN1830799A CN1830799A CN 200610011386 CN200610011386A CN1830799A CN 1830799 A CN1830799 A CN 1830799A CN 200610011386 CN200610011386 CN 200610011386 CN 200610011386 A CN200610011386 A CN 200610011386A CN 1830799 A CN1830799 A CN 1830799A
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Abstract
A carboxymethyl-beta-cyclodextin intercalated hydrotalcite for chiral resolving raceme is prepared through using LDHs as template to insert the carboxymethyl-beta- cyclodextrin anions in between the layers of hydrotalcite by ion change. Its chemical formula is also disclosed.
Description
Affiliated field
The invention belongs to the chiral separation field of racemic modification, a kind of carboxymethyl-beta-cyclodextrin intercalated hydrotalcite that is used for the chiral separation racemic modification and preparation method thereof particularly is provided.
Background technology
Chemical constitution, molecular formula are identical, but form the atom of compound or atomic group at the different ghosted compound of spatial orientation enantiomorph.Because they can not overlap each other as two hands of people, are called chipal compounds again.Enantiomorph particularly more and more is familiar with by people at the not same-action of pharmaceutical field in bioprocess.In vivo, biomacromolecule all is among the chiral environment of high complexity, and enantiomer of drugs enters in the organism and can produce significant difference at pharmacologically active, metabolic process and meta-bolites, the aspects such as toxic side effect that cause.Under normal conditions, have only an enantiomorph to have pharmacological action, another enantiomorph does not then have effect, even also can produce very strong toxicity or side effect.Therefore, chiral intermediate and disassemble technique are the emphasis that many pharmacy and chemical company are are researching and developing.The physico-chemical property of enantiomorph is very close, and the chiral separation difficulty is big.Chromatographic technique is the main method of present chiral separation, comprising thin-layer chromatography, gas-chromatography, high performance liquid chromatography etc.The chiral stationary phase high performance liquid chromatography is with the most use a kind of, and its main drawback is: pillar costs an arm and a leg, and performance is often low than common liquid phase post; Range of application is narrower, needs the different chirality liquid-phase chromatographic column of several classes to satisfy a certain specific analysis requirement usually.
Cyclodextrin (cyclodextrin, CD) be by α-1 by α-D-glucopyranose unit, the member cyclic oligosaccharides that the 4-glycosidic link is formed because cyclodextrin and derivative thereof have special chiral ring cavity, can provide good chiral environment, they not only are widely used in the separating optical isomeric body, also be used to separate various geometrical isomers, as the neighbour of aromatic hydrocarbons,, para-isomeride, the positional isomers of terpene and polycyclic aromatic hydrocarbons etc.Document T.Kossielski, D.Sybilska, J.Jurczak, J Chromatogr., 1983,280,131 just adopt on the stationary phase packed column that α-CD and methane amide are formed and have realized the gas-chromatography Chiral Separation, split α-, beta-pinene enantiomer, (Z.Juvancz in 1987, H.-P.Nowotny, J.Szejtli, HRC, 1987,10,105) Hungarian Szejtli study group has prepared full methyl-β-CD coated capillary first, high post capillaceous is imitated and the highly selective of cyclodextrin combines, and makes the vapor-phase chromatography enantiomer separation obtain to use widely and develop.
The bimetal complex hydroxide is called hydrotalcite (Layered Double Hydroxides again, be abbreviated as LDHs) be a kind of novel multifunctional stratified material, its chemical stability is good, has strong heat resistanceheat resistant performance, but and LDHs laminate metal ion modulation, interlayer anion has interchangeability, multiple functional negatively charged ion all can enter interlayer by ion-exchange, obtain various functional composite materials, therefore can be with it as template, regulate and control laminate metal and interlayer anion as required simultaneously, obtain functional composite material.
Summary of the invention
The object of the invention is: a kind of carboxymethyl-beta-cyclodextrin intercalated hydrotalcite that is used for the chiral separation racemic modification and preparation method thereof is provided.With carboxymethyl-beta-cyclodextrin intercalated hydrotalcite is sorbent material, the method for chiral separation racemic modification.Utilize the controlled and veneer structure orientation effect of interlayer ion interchangeability, laminate of LDHs, carboxymethyl-beta-cyclodextrin is introduced interlayer with anionic form, make inorganic-organic composite material.Carry out the chiral separation of racemize phenylglycol and phenylethyl alcohol then with the intercalation product that makes.But this material preferentially adsorbed (R) type phenylglycol and phenylethyl alcohol, thereby the chiral separation of realization racemize phenylglycol and phenylethyl alcohol.
Of the present inventionly be used for consisting of of the carboxymethyl-beta-cyclodextrin intercalated hydrotalcite of chiral separation racemic modification: interlayer anion is NO
3 -Perhaps Cl
-The hydrotalcite precursor, carboxymethyl-beta-cyclodextrin is replaced NO through ion-exchange
3 -Perhaps Cl
-Enter hydrotalcite layers, constitute the anionic supramolecule stratified material that the carboxymethyl-beta-cyclodextrin negatively charged ion accounts for interlayer anion total moles 20～100%.
The chemical formula that is used for the carboxymethyl-beta-cyclodextrin intercalated hydrotalcite of chiral separation racemic modification that the present invention is prepared is:
[(M
2+)
1-x(M
3+)
x(OH)
2]
X+(CMCD
N-)
X/nMH
2O, CMCD are carboxymethyl-beta-cyclodextrin;
0.2≤x≤0.33 wherein, n=0.5-4, m=3-6 are interlayer crystal water molecule number,
M
2+Representing divalent-metal ion, can be Mg
2+, Zn
2+, Ca
2+, Cu
2+Any, M
2+Preferred Zn
2+
M
3+Representing trivalent metal ion, can be Al
3+, Cr
3+Any, M
3+Preferred Al
3+
The preparation process of carboxymethyl-beta-cyclodextrin intercalated hydrotalcite of the present invention is as follows:
A. preparing interlayer anion is NO
3 -Perhaps Cl
-, laminate divalence, Tricationic mol ratio M
2+/ M
3+=2～3 hydrotalcite precursor;
B. the sodium salt with carboxymethyl-beta-cyclodextrin is dissolved in except that CO
2Deionized water in, make saturated solution;
C. the precursor of hydrotalcite described in a is joined among the solution b, at N
2Protection is also stirred down, and 50～70 ℃ are reacted 12～48h down, and product spends CO
2Water washing, centrifugal 6 times can obtain carboxymethyl-beta-cyclodextrin intercalated hydrotalcite [(M after 40～70 ℃ of following dryings
2+)
1-x(M
3+)
x(OH)
2]
X+(CMCD
N-)
X/nMH
2O.
Hydrotalcite main body laminate of the present invention is selected divalent metal Mg
2+, Zn
2+, Ca
2+, Cu
2+In any and trivalent metal cation Al
3+, Cr
3+In any combination.
The intercalation product that makes is carried out XRD, IR, elemental analysis, and study its chiral selectivity absorption property.By X-ray diffractogram as can be known, it is big that interlamellar spacing obviously becomes, and shows that carboxymethyl-beta-cyclodextrin is after ion-exchange enters the LDHs interlayer; The IR spectrogram shows that the CMCD-LDHs for preparing is at 1606cm
-1, 1420cm
-1COO has appearred in the place
-Characteristic peak, also prove carboxymethyl-beta-cyclodextrin intercalated success.And behind the intercalation product absorption phenylglycol, the UV-vis analysis revealed is 265,256, the strong triple feature ultraviolet absorption peaks of phenyl ring appear near the 251nm, analyze filtrate with chiral high performance liquid chromatography and show the amount of the amount of (S) type phenylglycol in the filtrate greater than (R) type phenylglycol, carboxymethyl-beta-cyclodextrin intercalated hydrotalcite preferentially adsorbed (R) type phenylglycol is described, shows that more than CMCD-LDHs has the effect of chiral separation to the racemize phenylglycol.
Advantage of the present invention is:
1, first the hydrotalcite of intercalation cyclodextrin is applied to the chiral separation field; But the controlled and veneer structure orientation effect of the intercalation assembleability, the laminate that utilize the hydrotalcite stratified material, cyclodextrin with excellent chiral separation performance is assembled into hydrotalcite layers, realize the immobilization of cyclodextrin molecular and in the high dispersing of interlayer, but obtain a kind of composite organic-inorganic material of chiral separation racemize phenylglycol.
2, the preparation method's technology that is adopted is simple, and cost is low, and reaction is easy to carry out;
3, by anionic kind and mol ratio in the control hydrotalcite, the chiral separation performance of adjustable hydrotalcite.
Description of drawings
Fig. 1 is the X-ray powder diffraction figure of the carboxymethyl-beta-cyclodextrin intercalated hydrotalcite of embodiment 1 preparation.Wherein, a is the hydrotalcite precursor; B is carboxymethyl-beta-cyclodextrin intercalated hydrotalcite.
Fig. 2 is the uv atlas before and after the embodiment 1 carboxymethyl-beta-cyclodextrin intercalated hydrotalcite absorption racemize phenylglycol.Wherein, c is a phenylglycol; D is the preceding hydrotalcite uv atlas of absorption phenylglycol; E is a hydrotalcite uv atlas behind the absorption phenylglycol.
Fig. 3 is the high-efficient liquid phase chromatogram of embodiment 1 carboxymethyl-beta-cyclodextrin intercalated hydrotalcite absorption racemize phenylglycol rear filtrate.Wherein, r is (R) type phenylglycol; S is (S) type phenylglycol
Embodiment:
Embodiment 1
Steps A: take by weighing 35.6g Zn (NO
3)
26H
2O, 22.6g Al (NO
3)
39H
2O and 9.06gNaNO
3Be dissolved in 200ml and remove CO
2Water preparation mixing salt solution, other gets 11.2g NaOH and is dissolved in 100ml and removes CO
2Prepare alkaline solution in the water, N under the room temperature
2Protection adopts two methods of dripping that salts solution and alkaline solution are slowly added in the four-hole bottle violent stirring.Regulating the pH value with 0.1mol/LNaOH solution is 7.The gained slurries are in 70 ℃ of crystallization 24h, and the product centrifuge washing is to neutral; Take out sample and characterize behind the dry 20h down for 70 ℃, obtain Zn
2Al-NO
3LDHs, its Zn
2+/ Al
3+=2.
Step B: with the sodium salt [C of 20.6g carboxymethyl-beta-cyclodextrin
42H
70-nO
35(C
2H
2O
2Na)
n] solid adds and to fill in the four-hole bottle of hydrotalcite precursor N
2Protection is heated to 70 ℃, stirs reaction 48h down, and liquid becomes light yellow.The product centrifuge washing is to neutral, and 70 ℃ of following dry 20h can obtain carboxymethyl-beta-cyclodextrin intercalated hydrotalcite Zn
2Al-CMCD LDHs.
Step C: accurate a certain amount of carboxymethyl-beta-cyclodextrin intercalated hydrotalcite (Zn of weighing
2Al-CMCD LDHs) and the racemize phenylglycol, add 20ml and remove CO
2Deionized water in, make sample.As benchmark,, make other series of samples according to the usage quantity that same ratio is progressively dwindled phenylglycol.It is placed vibrator under nitrogen protection, 30 ℃ of 24h that vibrate down filter, and get filtrate and do ultraviolet and efficient liquid phase chromatographic analysis, with formula (C
0-C) V/m calculates adsorptive capacity.
By X-ray diffractogram as can be known, carboxymethyl-beta-cyclodextrin is after ion-exchange enters the LDHs interlayer, and its laminate spacing increases to 1.644nm by the 0.887nm of precursor; Two kinds of LDHs have the obvious diffraction peak near 2 θ are 61 °, and corresponding unit cell parameters a is approximately 0.305nm, illustrates that carboxymethyl-beta-cyclodextrin intercalated front and back LDHs laminate electric density does not change, and the LDHs laminate obtains more complete maintenance.The IR spectrogram shows that the CMCD-LDHs for preparing is at 1606cm
-1, 1420cm
-1COO has appearred in the place
-Characteristic peak, at 643cm
-1The stretching vibration peak of Zn-O has appearred in the place, proves carboxymethyl-beta-cyclodextrin intercalated success.And behind the intercalation product absorption phenylglycol, the UV-vis analysis revealed is 265,256, the strong triple feature ultraviolet absorption peaks of phenyl ring appear near the 251nm, analyze filtrate with chiral high performance liquid chromatography and show the amount of the amount of (S) type phenylglycol in the filtrate greater than (R) type phenylglycol, carboxymethyl-beta-cyclodextrin intercalated hydrotalcite preferentially adsorbed (R) type phenylglycol is described, shows that more than CMCD-LDHs has the effect of chiral separation to the racemize phenylglycol.
Embodiment 2
Steps A: take by weighing 30.7g Mg (NO
3)
26H
2O and 22.6g Al (NO
3)
39H
2O is dissolved in 200ml and removes CO
2Water preparation mixing salt solution, other gets 11.2g NaOH and is dissolved in 100ml and removes CO
2Prepare alkaline solution in the water, N under the room temperature
2Protection adopts two methods of dripping that salts solution and alkaline solution are slowly added in the four-hole bottle, and dripping off the back is 10 with 0.1mol/LNaOH solution adjust pH, the following 70 ℃ of crystallization 24h of gained slurries, and the product centrifuge washing is to neutral; Take out small amount of sample and characterize behind the dry 20h down for 70 ℃, obtain Mg
2Al-NO
3LDHs, its Mg
2+/ Al
3+=2.
Step B: by the method for step B in the similar embodiment 1, with the sodium salt [C of 20.6g carboxymethyl-beta-cyclodextrin
42H
70-nO
35(C
2H
2O
2Na)
n] solid adds and to fill in the four-hole bottle of sample N
2Protection is heated to 70 ℃ of reaction 48h, and liquid becomes light yellow.The product centrifuge washing is to neutral, and 70 ℃ of following dry 20h can obtain carboxymethyl-beta-cyclodextrin intercalated hydrotalcite Mg
2Al-CMCD LDHs.
Step C: take step C method in the similar embodiment 1, accurately a certain amount of carboxymethyl-beta-cyclodextrin intercalated hydrotalcite (Mg of weighing
2Al-CMCD LDHs) and the racemize phenylglycol, add 20ml and remove CO
2Deionized water in, make sample.As benchmark,, make other series of samples according to the usage quantity that same ratio is progressively dwindled phenylglycol.It is placed vibrator under protection of nitrogen gas, 30 ℃ of 24h that vibrate down filter, and get filtrate and do ultraviolet and efficient liquid phase chromatographic analysis, with formula (C
0-C) V/m calculates adsorptive capacity.
By X-ray diffractogram as can be known, Mg
2Al-CMCD LDHs laminate spacing increases to 1.632nm by the 0.874nm of precursor, the unit cell parameters a of the charateristic avsorption band correspondence of two kinds of LDHs is approximately 0.304mn near 2 θ are 61 °, LDHs laminate electric density did not change before and after the CMCD intercalation was described, the LDHs laminate obtains more complete maintenance.The IR spectrogram shows that the intercalation product is at 1610cm
-1, 1400cm
-1COO has appearred in the place
-Characteristic peak, prove title complex CMCD intercalation success.And behind the intercalation product absorption phenylglycol, the UV-vis analysis revealed is 265,256, the strong triple feature ultraviolet absorption peaks of phenyl ring appear near the 251nm, analyze filtrate with chiral high performance liquid chromatography and show the amount of the amount of (S) type phenylglycol in the filtrate greater than (R) type phenylglycol, carboxymethyl-beta-cyclodextrin intercalated hydrotalcite preferentially adsorbed (R) type phenylglycol is described, shows that more than CMCD-LDHs has the effect of chiral separation to the racemize phenylglycol.
Embodiment 3
Steps A: take by weighing 16.4g ZnCl
2With 14.5g AlCl
36H
2O is dissolved in 200ml and removes CO
2Water preparation mixing salt solution, other gets 11.2g NaOH and is dissolved in 100ml and removes CO
2Prepare alkaline solution in the water, N under the room temperature
2Protection adopts two methods of dripping that salts solution and alkaline solution are slowly added in the four-hole bottle, and dripping off the back is 6 with 0.1mol/LNaOH solution adjust pH, the following 70 ℃ of crystallization 24h of gained slurries, and the product centrifuge washing is to neutral; Take out small amount of sample and characterize behind the dry 20h down for 70 ℃, obtain Zn
2Al-Cl LDHs, its Zn
2+/ Al
3+=2.
Step B: by the method for step B in the similar embodiment 1, with the sodium salt [C of 20.6g carboxymethyl-beta-cyclodextrin
42H
70-nO
35(C
2H
2O
2Na)
n] solid adds and to fill in the four-hole bottle of sample N
2Protection is heated to 70 ℃ of reaction 48h, and liquid becomes light yellow.The product centrifuge washing is to neutral, and 70 ℃ of following dry 20h can obtain carboxymethyl-beta-cyclodextrin intercalated hydrotalcite Zn
2Al-CMCD LDHs.
Step C: take step C method in the similar embodiment 1, accurately a certain amount of carboxymethyl-beta-cyclodextrin intercalated hydrotalcite of weighing (CMCD-LDHs) and racemize phenylethyl alcohol add 20ml and remove CO
2Deionized water in, make sample.As benchmark,, make other series of samples according to the usage quantity that same ratio is progressively dwindled phenylethyl alcohol.It is placed vibrator under protection of nitrogen gas, 30 ℃ of 24h that vibrate down filter, and get filtrate and do ultraviolet and efficient liquid phase chromatographic analysis, with formula (C
0-C) V/m calculates adsorptive capacity.
By X-ray diffractogram as can be known, Zn
2Al-CMCD LDHs laminate spacing increases to 1.643nm by the 0.884nm of precursor, the unit cell parameters a of the charateristic avsorption band correspondence of two kinds of LDHs is approximately 0.304nm near 2 θ are 61 °, LDHs laminate electric density did not change before and after the CMCD intercalation was described, the LDHs laminate obtains more complete maintenance.The IR spectrogram shows that the intercalation product is at 1610cm
-1, 1420cm
-1COO has appearred in the place
-Characteristic peak, prove title complex CMCD intercalation success.And behind the intercalation product absorption phenylethyl alcohol, the UV-vis analysis revealed is 265,256, the strong triple feature ultraviolet absorption peaks of phenyl ring appear near the 251nm, analyze filtrate with chiral high performance liquid chromatography and show the amount of the amount of (S) type phenylethyl alcohol in the filtrate greater than (R) type phenylethyl alcohol, carboxymethyl-beta-cyclodextrin intercalated hydrotalcite preferentially adsorbed (R) type phenylethyl alcohol is described, shows that more than CMCD-LDHs has the effect of chiral separation to the racemize phenylethyl alcohol.
Claims (4)
1, a kind of carboxymethyl-beta-cyclodextrin intercalated hydrotalcite that is used for the chiral separation racemic modification, it is characterized in that: chemical formula is: [(M
2+)
1-x(M
3+)
x(OH)
2]
X+(CMCD
N-)
X/nMH
2O, CMCD are carboxymethyl-beta-cyclodextrin, 0.2≤x≤0.33 wherein, and n=0.5-4, m=3-6 are interlayer crystal water molecule number, M
2+Represent divalent-metal ion Mg
2+, Zn
2+, Ca
2+, Cu
2+Any, M
3+Represent trivalent metal ion Al
3+, Cr
3+Any; Interlayer anion is NO
3 -Perhaps Cl
-The hydrotalcite precursor, carboxymethyl-beta-cyclodextrin is replaced NO through ion-exchange
3 -Perhaps Cl
-Enter hydrotalcite layers, constitute the anionic supramolecule stratified material that the carboxymethyl-beta-cyclodextrin negatively charged ion accounts for interlayer anion total moles 20～100%.
2, according to the described intercalated houghite of claim 1, it is characterized in that: M
2+Select Zn
2+, M
3+Preferred Al
3+
3, a kind of prepare the described carboxymethyl-beta-cyclodextrin intercalated hydrotalcite that is used for the chiral separation racemic modification of claim 1 and method, it is characterized in that:
A. preparing interlayer anion is NO
3 -Perhaps Cl
-, laminate divalence, Tricationic mol ratio M
2+/ M
3+=2～3 hydrotalcite precursor;
B. the sodium salt of carboxymethyl-beta-cyclodextrin is dissolved in except that CO
2Deionized water in, make saturated solution;
C. the precursor of hydrotalcite described in a is joined among the solution b, at N
2Protection is also stirred down, and 50～70 ℃ are reacted 12～48h down, and product spends CO
2Water washing, centrifugal obtains carboxymethyl-beta-cyclodextrin intercalated hydrotalcite [(M after 40～70 ℃ of following dryings
2+)
1-x(M
3+)
x(OH)
2]
X+(CMCD
N-)
X/nMH
2O.
4, in accordance with the method for claim 3, it is characterized in that: described hydrotalcite main body laminate is selected divalent metal Mg
2+, Zn
2+, Ca
2+, Cu
2+In any and trivalent metal cation Al
3+, Cr
3+In any combination.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010003336A1 (en) * | 2008-07-11 | 2010-01-14 | 北京化工大学 | A cyclodextrin intercalated hydrotalcite thin-film vertically grown on a substrate, and a method for producing the same |
| CN101972676A (en) * | 2010-09-17 | 2011-02-16 | 北京化工大学 | Chiral oxidation catalyst and preparation method thereof |
| CN103191746A (en) * | 2013-03-20 | 2013-07-10 | 北京化工大学 | Carbon supported core-shell structure nano metal catalyst as well as preparation method and application thereof |
-
2006
- 2006-02-28 CN CN 200610011386 patent/CN1830799A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010003336A1 (en) * | 2008-07-11 | 2010-01-14 | 北京化工大学 | A cyclodextrin intercalated hydrotalcite thin-film vertically grown on a substrate, and a method for producing the same |
| CN101972676A (en) * | 2010-09-17 | 2011-02-16 | 北京化工大学 | Chiral oxidation catalyst and preparation method thereof |
| CN103191746A (en) * | 2013-03-20 | 2013-07-10 | 北京化工大学 | Carbon supported core-shell structure nano metal catalyst as well as preparation method and application thereof |
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