CN102432641A - Diacetone-D-galactose modified heteropoly acid hybrid and preparation method thereof - Google Patents
Diacetone-D-galactose modified heteropoly acid hybrid and preparation method thereof Download PDFInfo
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- CN102432641A CN102432641A CN2011102849230A CN201110284923A CN102432641A CN 102432641 A CN102432641 A CN 102432641A CN 2011102849230 A CN2011102849230 A CN 2011102849230A CN 201110284923 A CN201110284923 A CN 201110284923A CN 102432641 A CN102432641 A CN 102432641A
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Abstract
The invention provides a diacetone-D-galactose modified heteropoly acid hybrid which has a chemical formula of [(n-Bu)4N]3{MnMo6O18[(OCH2)3CNHCOC15H23O7]2}. A preparation method for the hybrid is as follows: diacetone-D-galactose is used as a starting material to react with succinic anhydride so as to prepare an intermediate product; the intermediate product reacts with molybdenum-containing polyoxometallate having an Anderson structure so as to obtain a hybrid compound connected through covalent bonds. The invention has the following advantages: an organic-inorganic hybridization method is employed for chemical modification of molybdenum-containing polyoxometallate, so connection of molybdenum-containing polyoxometallate with diacetone-D-galactose through covalent bonds is realized for the first time; conditions of the preparation method are not severe, purification is easy to carry out, an obtained product has high yield and purity, it is convenient to popularize and apply the method, and the hybrid compound has a potential application value in the fields of medicine, biology, catalysts, surfactants, etc.
Description
Technical field
The present invention relates to the synthetic technology of hybrid inorganic-organic macromolecular cpd, particularly a kind of two acetone-D-semi-lactosi modification heteropolyacid hybrid and preparation method thereof.
Background technology
Cancer serious threat all the time human beings'health, and current environment pollutes aggravation day by day, and human living environment constantly worsens, and is more and more tightr with contacting of carcinogenic factor, causes the human mortality ratio that causes because of cancer to rise rapidly.The treatment for cancer method generally has operative treatment, radiotherapy and chemotherapy etc. at present, but still is main method at present with the chemotherapy.Chemotherapy is to take the medicine intravascular to whole body, and is all influential to the health all cells.This therapy is also referred to as " born of the same parents poison therapy " sometimes because institute's medicament all is harmful, or even be with toxic, cells in vivo, whether no matter malignant cell all be damaged, even some cancer therapy drug is to be difficult for being absorbed by specific cells.Therefore to having clinical efficacy but spinoff is big or the chemically modified of the cancer therapy drug that is difficult for absorbing; To seek target positioning action to drug target; Improve simultaneously non-absorption or a little less than the cell absorption intensity that absorbs the drug, be the task of top priority of present cancer therapy drug research.
Heteropolyacid is claimed polyoxometallate again, is the one type of negatively charged ion unit molecule cluster compound with definite structure that is formed through oxygen coordination bridging by the early transition metal atom, serves as main representative with elements such as vanadium, molybdenum, tungsten wherein.The size of polyoxometallate has abundant chemical ingredients and various topological framework about 0.5nm-5nm, and all shows excellent character at aspects such as catalysis, light, electricity, magnetic functional materials and medicine.Aspect biological medicine: 1971, people such as French scientist Raynaud at first reported the SiW of Keggin structure
12O
40Have antiviral activity, started the pharmaceutical chemical research boom of polyoxometallate thus.The Hungarian Jozsef of late nineteen eighties has used (NH first in anticancer patent prescription
4)
6[Mo
7O
24] 6H
2O is as cancer therapy drug.The nineties Japan Yamase etc. proposes (NH
3Pri)
6[Mo
7O
24] 3H
2The redox mechanism of O (pH=8) antitumor action.The biological activity of polyoxometallate mainly comprises the following aspects: the height of enzyme function is selected to suppress; The anti-tumor activity of vivo and vitro; Antiviral activity and anti-AIDS cytotoxic activity, polyoxometallate have significant application value and good DEVELOPMENT PROSPECT aspect pharmaceutical chemistry.
Carbohydrate is as the necessary nutrient substance of human body; Be familiar with by people already, along with the deep development of biology, medicine and pharmacology, the biological function of saccharide compound is disclosed by people gradually; It is one of most important drug kinds always, and the research of saccharide compound is a hot fields always.The many verivates that experiment showed, saccharide compound are biologically active also, is demonstrating huge prospect aspect the diseases such as treatment various inflammation, cardiovascular system diseases and cancer; Can be used to treat disease [Kamisango K, Nagaoka M, Fujii H such as osteo-arthritis, rheumatic arthritis, arthritis ache and gout like 1-amino-1-deoxyglucose alcohol; Azuma I.Journal of clinical microbiology, 1985,21 (1): 135-137]; Miglitol can be as glycosidase inhibitor and treatment mellitus [Fouace S, Therisod M.Tetrahedron Letters, 2000; 41:7313-7315], chebulinic acid has HIV-resistant activity [Han Q, Song J; Qiao C, etal.J.Sep.Sci.2006,29 (11): 1653-1657.].
The present invention utilizes two acetone-D-semi-lactosi to be initial feed; Adopt the method for hybrid inorganic-organic; With contain molybdenum multi-metal oxygen hydrochlorate covalent linkage and be connected, the mode through covalent linkage of having realized first will contain being connected of molybdenum multi-metal oxygen hydrochlorate and two acetone-D-semi-lactosi.Purpose is with two acetone-D-semi-lactosi as targeting vector; Through with have potential cancer therapy drug characteristic to contain molybdenum multi-metal oxygen hydrochlorate target molecule covalently bound, to improving vitals such as liver the receptivity of target molecule and target molecule are had important potential using value to the target positioning action of organ.
Summary of the invention
The objective of the invention is provides a kind of two acetone-D-semi-lactosi modification heteropolyacid hybrid and preparation method thereof to above-mentioned technical Analysis, and not harsh, the easy purification of this preparing method's condition, product yield and purity are higher, easy to utilize.
Technical scheme of the present invention:
A kind of two acetone-D-semi-lactosi modification heteropolyacid hybrid is characterized in that chemical formula is:
[(n-Bu)
4N]
3{MnMo
6O
18[(OCH
2)
3CNHCOC
15H
23O
7]
2}。
The compound method of a kind of two acetone-D-semi-lactosi modification heteropolyacid hybrid, synthesis step is following:
1) two acetone-D-semi-lactosi, 4-Dimethylamino pyridine, succinyl oxide and triethylamine are dissolved in the toluene solvant, stirred refluxed 3 hours, reaction solution drops to room temperature; Revolve driedly, solids is dissolved in the chloroform, with deionized water extraction three times; Organic phase after the separation is with anhydrous magnesium sulfate drying, revolves driedly, and crude product is dissolved in ETHYLE ACETATE; In normal hexane, precipitate, the product after the separation is dissolved in ETHYLE ACETATE, secondary sedimentation in ethanol; Obtain white powder after the vacuum-drying and be 6-O-(3-carboxyl propionyl)-1,2:3,4-two-O-isopropylidene-D-galactopyranose;
2) with 2-oxyethyl group-1-ethoxy carbonic acyl radical-1, the 2-EEDQ joins in the acetonitrile solvent, under the reflux conditions, adds 6-O-(3-carboxyl propionyl)-1,2:3, and 4-two-O-isopropylidene-D-galactopyranose reaction added [(n-Bu) after 30-50 minute
4N]
3{ MnMo
6O
18[(OCH
2)
3CNH
2]
2, refluxed 48 hours;
3) cool to room temperature concentrates, and in ETHYLE ACETATE, precipitates; Product behind the suction filtration is dissolved in the acetonitrile solvent, and slowly deposition was separated out orange solids after 24-72 hour in ether steam; Suction filtration, dried in vacuum promptly gets two acetone-D-semi-lactosi modification heteropolyacid hybrid.
The mol ratio of said two acetone-D-semi-lactosi, 4-Dimethylamino pyridine, succinyl oxide and triethylamine is 1.0: 0.1: 1.2: 1.2.
The amount ratio of said two acetone-D-semi-lactosi and toluene solvant is 20mg two acetone-D-semi-lactosi/1mL toluene solvant.
Said 2-oxyethyl group-1-ethoxy carbonic acyl radical-1, the amount ratio of 2-EEDQ and acetonitrile solvent is the 2mg/1mL acetonitrile solvent.
Said 2-oxyethyl group-1-ethoxy carbonic acyl radical-1,2-EEDQ, 6-O-(3-carboxyl propionyl)-1,2:3,4-two-O-isopropylidene-D-galactopyranose with [(n-Bu)
4N]
3{ MnMo
6O
18[(OCH
2)
3CNH
2]
2Mol ratio be 3.0～6.5: 3.0～4.5: 1.0.
The product behind the said suction filtration and the amount ratio of acetonitrile solvent are 150mg/ acetonitrile 1mL solvent.
The synthetic route of said two acetone-D-semi-lactosi modification heteropolyacid hybrid is represented as follows:
Advantage of the present invention is: the present invention is a starting raw material with two acetone-D-semi-lactosi; Adopt the method for hybrid inorganic-organic; Carry out chemical modification to containing molybdenum multi-metal oxygen hydrochlorate; Synthesized a kind of two acetone-D-semi-lactosi modification heteropolyacid hybrid, the present invention will contain molybdenum multi-metal oxygen hydrochlorate and two acetone-D-semi-lactosi hydridization through covalent linkage first; Not harsh, the easy purification of this preparing method's condition, product yield and purity are higher, easy to utilize.
Description of drawings
Fig. 1 is 6-O-(3-carboxyl propionyl)-1,2:3, the H of 4-two-O-isopropylidene-D-galactopyranose
1The nuclear magnetic resonance, spectrum spectrogram.
Fig. 2 is [(n-Bu)
4N]
3{ MnMo
6O
18[(OCH
2)
3CNHCOC
15H
23O
7]
2FT-IR ir spectra spectrogram.
Fig. 3 is [(n-Bu)
4N]
3{ MnMo
6O
18[(OCH
2)
3CNHCOC
15H
23O
7]
2H
1The nuclear magnetic resonance, spectrum spectrogram.
Embodiment
Below in conjunction with embodiment the present invention is made further explanation, but the present invention is not limited to this embodiment.
Embodiment: prepare two acetone-D-semi-lactosi modification heteropolyacid hybrid, step is following:
1) 2g two acetone-D-semi-lactosi, 94mg 4-Dimethylamino pyridine, 922mg succinyl oxide and 933mg triethylamine are joined in the container, be dissolved in the 100mL toluene solvant, stirred refluxed 3 hours, reaction solution drops to room temperature; Revolve driedly, solids is dissolved in the chloroform, and with deionized water extraction three times, the organic phase after the separation is with anhydrous magnesium sulfate drying; Revolve driedly, crude product is dissolved in 10mL ETHYLE ACETATE, in the 300mL normal hexane, precipitates; Filter out product, be dissolved in 7mL ETHYLE ACETATE, secondary sedimentation in 350mL ethanol; Obtain white powder after the vacuum-drying and be 6-O-(3-carboxyl propionyl)-1,2:3,4-two-O-isopropylidene-D-galactopyranose;
2) with 2-oxyethyl group-1-ethoxy carbonic acyl radical-1,2-EEDQ 258mg and 130mL acetonitrile solvent under refluxad, add 6-O-(3-carboxyl propionyl)-1,2:3, and 4-two-O-isopropylidene-D-galactopyranose 250mg reacted after 35 minutes, added [(n-Bu)
4N]
3{ MnMo
6O
18[(OCH
2)
3CNH
2]
2327mg, refluxed 48 hours;
3) behind the cool to room temperature, concentrate, in 350mL ETHYLE ACETATE, precipitate; To remove residual 2-oxyethyl group-1-ethoxy carbonic acyl radical-1 in the dereaction, 2-EEDQ, the product behind the suction filtration are dissolved in the 2.5mL acetonitrile solvent; Slowly deposition is separated out orange solids, suction filtration two days later in ether steam; Dried in vacuum promptly gets two acetone-D-semi-lactosi modification heteropolyacid hybrid, productive rate 76.0%.
With the 6-O-(3-carboxyl propionyl)-1 of preparation, 2:3,4-two-O-isopropylidene-D-galactopyranose passes through H
1Nuclear magnetic resonance spectrometer detects, and the result is following:
Fig. 1 is 6-O-(3-carboxyl propionyl)-1,2:3, the H of 4-two-O-isopropylidene-D-galactopyranose
1The nuclear magnetic resonance, spectrum spectrogram, all there is good ownership at each peak among the figure, and wherein ☆ representes solvent peak, thereby has confirmed the 6-O-(3-carboxyl propionyl)-1 of preparation, 2:3,4-two-O-isopropylidene-D-galactopyranose purity is higher.
Two acetone-D-semi-lactosi modification heteropolyacid the hybrid of preparation is passed through FT-IR IR and H respectively
1Nuclear magnetic resonance spectrometer detects, and the result is following:
Fig. 2 is the FT-IR ir spectra spectrogram of two acetone-D-semi-lactosi modification heteropolyacid hybrid, and this infrared spectrogram shows: 1030,941,921,904,667,563cm
-1The characteristic peak of the polyoxometallate at place has obtained good reservation in the hydridization molecule, confirmed that polyoxometallate structure after the reaction neutralization reaction has all kept complete; 3346cm
-1The peak be the stretching vibration peak of N-H, 1738 and 1688cm
-1Be the stretching vibration peak of C=O, 1511cm
-1Be the flexural vibration peak of N-H, 1255cm
-1Be the stretching vibration peak of C-N, these peaks have proved the existence of amido linkage in the hydridization molecule, thereby confirm polyoxometallic acid molecules of salt and 6-O-(3-carboxyl propionyl)-1, and 2:3 is covalently bound between 4-two-O-isopropylidene-D-galactopyranose.
Fig. 3 is the H of two acetone-D-semi-lactosi modification heteropolyacid hybrid
1The nuclear magnetic resonance, spectrum spectrogram, all there is good ownership at each peak among the figure, and wherein ☆ representes solvent peak, and * representes the water peak, thereby has confirmed the integrity and the higher degree of two acetone-D-semi-lactosi modification heteropolyacid hybrid structure.
Claims (7)
1. two acetone-D-semi-lactosi modification heteropolyacid hybrid is characterized in that chemical formula is:
[(n-Bu)
4N]
3{MnMo
6O
18[(OCH
2)
3CNHCOC
15H
23O
7]
2}。
2. compound method of two acetone-D-semi-lactosi modification heteropolyacid hybrid according to claim 1 is characterized in that synthesis step is following:
1) two acetone-D-semi-lactosi, 4-Dimethylamino pyridine, succinyl oxide and triethylamine are dissolved in the toluene solvant, stirred refluxed 3 hours, reaction solution drops to room temperature; Revolve driedly, solids is dissolved in the chloroform, with deionized water extraction three times; Organic phase after the separation is with anhydrous magnesium sulfate drying, revolves driedly, and crude product is dissolved in ETHYLE ACETATE; In normal hexane, precipitate, the product after the separation is dissolved in ETHYLE ACETATE, secondary sedimentation in ethanol; Obtain white powder after the vacuum-drying and be 6-O-(3-carboxyl propionyl)-1,2:3,4-two-O-isopropylidene-D-galactopyranose;
2) with 2-oxyethyl group-1-ethoxy carbonic acyl radical-1, the 2-EEDQ joins in the acetonitrile solvent, under the reflux conditions, adds 6-O-(3-carboxyl propionyl)-1,2:3, and 4-two-O-isopropylidene-D-galactopyranose reaction added [(n-Bu) after 30-50 minute
4N]
3{ MnMo
6O
18[(OCH
2)
3CNH
2]
2, refluxed 48 hours;
3) cool to room temperature concentrates, and in ETHYLE ACETATE, precipitates; Product behind the suction filtration is dissolved in the acetonitrile solvent, and slowly deposition was separated out orange solids after 24-72 hour in ether steam; Suction filtration, dried in vacuum promptly gets two acetone-D-semi-lactosi modification heteropolyacid hybrid.
3. according to the compound method of said two acetone of claim 2-D-semi-lactosi modification heteropolyacid hybrid, it is characterized in that: the mol ratio of said two acetone-D-semi-lactosi, 4-Dimethylamino pyridine, succinyl oxide and triethylamine is 1.0: 0.1: 1.2: 1.2.
4. according to the compound method of said two acetone of claim 2-D-semi-lactosi modification heteropolyacid hybrid, it is characterized in that: the amount ratio of said two acetone-D-semi-lactosi and toluene solvant is 20mg two acetone-D-semi-lactosi/1mL toluene solvant.
5. according to the compound method of said two acetone of claim 2-D-semi-lactosi modification heteropolyacid hybrid, it is characterized in that: said 2-oxyethyl group-1-ethoxy carbonic acyl radical-1, the amount ratio of 2-EEDQ and acetonitrile solvent is the 2mg/1mL acetonitrile solvent.
6. according to the compound method of said two acetone of claim 2-D-semi-lactosi modification heteropolyacid hybrid; It is characterized in that: said 2-oxyethyl group-1-ethoxy carbonic acyl radical-1; 2-EEDQ, 6-O-(3-carboxyl propionyl)-1,2:3,4-two-O-isopropylidene-D-galactopyranose with [(n-Bu)
4N]
3{ MnMo
6O
18[(OCH
2)
3CNH
2]
2Mol ratio be 3.0～6.5: 3.0～4.5: 1.0.
7. according to the compound method of said two acetone of claim 2-D-semi-lactosi modification heteropolyacid hybrid, it is characterized in that: the product behind the said suction filtration and the amount ratio of acetonitrile solvent are 150mg/ acetonitrile 1mL solvent.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103145978A (en) * | 2013-03-25 | 2013-06-12 | 南开大学 | Pegylation polyoxometallate and preparation method thereof |
| CN106750538A (en) * | 2016-12-07 | 2017-05-31 | 中北大学 | A kind of polyoxomolybdate polyethylene glycol hybrid and preparation method thereof |
| CN116870177A (en) * | 2022-09-29 | 2023-10-13 | 山东第一医科大学(山东省医学科学院) | Podophyllotoxin modified polyoxometallate hybrid compound and preparation method and application thereof |
-
2011
- 2011-09-23 CN CN2011102849230A patent/CN102432641A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103145978A (en) * | 2013-03-25 | 2013-06-12 | 南开大学 | Pegylation polyoxometallate and preparation method thereof |
| CN106750538A (en) * | 2016-12-07 | 2017-05-31 | 中北大学 | A kind of polyoxomolybdate polyethylene glycol hybrid and preparation method thereof |
| CN116870177A (en) * | 2022-09-29 | 2023-10-13 | 山东第一医科大学(山东省医学科学院) | Podophyllotoxin modified polyoxometallate hybrid compound and preparation method and application thereof |
| CN116870177B (en) * | 2022-09-29 | 2024-03-08 | 山东第一医科大学(山东省医学科学院) | Podophyllotoxin modified polyoxometallate hybrid compound and preparation method and application thereof |
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Application publication date: 20120502 |