CN105218585A - A kind of preparation method of genistein chromic compound - Google Patents

A kind of preparation method of genistein chromic compound Download PDF

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Publication number
CN105218585A
CN105218585A CN201510601671.8A CN201510601671A CN105218585A CN 105218585 A CN105218585 A CN 105218585A CN 201510601671 A CN201510601671 A CN 201510601671A CN 105218585 A CN105218585 A CN 105218585A
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China
Prior art keywords
genistein
preparation
chromic compound
reaction
precipitate
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徐暾海
李朋收
刘铜华
徐雅娟
解生旭
张曼祺
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Beijing University of Chinese Medicine
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Beijing University of Chinese Medicine
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Abstract

The preparation method of a kind of genistein chromic compound of the present invention, adds concentration 60% ethanol in genistein; Heated and stirred adds CrCl again 36H 2o; Dropwise add sodium hydroxide adjust ph to 7 ~ 9 again, solution transition is blackish green suspending system; Suction filtration will be precipitated; With deionized water and dehydrated alcohol respectively by after washing of precipitate for several times, collecting precipitation, vacuum-drying, to obtain final product.The invention provides a kind of new genistein chromic compound preparation method, under the condition not adding catalyzer, first genistein is alkalized into sodium salt, then genistein sodium salt and chromium chloride are carried out ligand substituting, thus obtain its metal complexes, the temperature of reaction of genistein sodium salt and chromium chloride controls at 60 ~ 70 DEG C, and the reaction times is 3 ~ 4 hours, and productive rate is 60%.Compared with bibliographical information, reduce temperature of reaction, also substantially reduce the reaction times, significantly improve products collection efficiency.

Description

A kind of preparation method of genistein chromic compound
Technical field
The present invention relates to a kind of preparation method of genistein chromic compound, further there is provided a kind of new preparation method, there is shortening preparation time, and improve the features such as productive rate, belong to compou nd synthesis technical field.
Background technology
Genistein (Genistein) is that one has multiple bioactive flavonoid compound, chemical name is Genistein, extensively be present in traditional medicinal plant such as soybean and trifolium, Flower of Chinese Peashrub, Chinese honey locust, the Fructus Sophorae, there is very high pharmaceutical use.
The molecular formula of genistein chromic compound: [C 15h 9o 5] 3cr2H 2o; Molecular weight: 895.5; Called after: genistein chromic compound; Structural formula is:
The preparation method of existing genistein chromic compound is the method adopting genistein and chromium acetate direct reaction, and shortcoming is that the time is longer, reaction needed 18 hours, and needs the ageing of 48 hours, and productive rate is lower.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of genistein chromic compound, be that existing lignin chromic compound preparation method is improved, improve productive rate, shorten preparation time.
The preparation method of a kind of genistein chromic compound of the present invention, comprises the following steps:
1, in genistein in quality: volume is that the ratio of 1:37 ~ 50 adds concentration 60% ethanol;
2, be heated to 60 ~ 70 DEG C stir 0.5 ~ 1.0 hour, then add CrCl 36H 2o, adding proportion is for being 1:1 ~ 1:2 with genistein mol ratio;
3, dropwise add sodium hydroxide adjust ph to 7 ~ 9 of 2mol/L again, solution transition is blackish green suspending system;
4, there is a large amount of grass green to precipitate after 3 ~ 4h to generate, will suction filtration be precipitated;
5, use deionized water and dehydrated alcohol respectively by after washing of precipitate for several times, collecting precipitation, vacuum-drying, obtains graminaceous pulverulent solids.
positively effect of the present invention is:provide a kind of new genistein chromic compound preparation method, under the condition not adding catalyzer, first genistein is alkalized into sodium salt, then genistein sodium salt and chromium chloride are carried out ligand substituting, thus obtain its metal complexes, the temperature of reaction of genistein sodium salt and chromium chloride controls at 60 ~ 70 DEG C, and the reaction times is 3 ~ 4 hours, and productive rate is 60%.Compared with bibliographical information, reduce temperature of reaction, also substantially reduce the reaction times, significantly improve products collection efficiency.
Accompanying drawing explanation
Fig. 1 is the ultraviolet spectrogram of embodiment 1;
Fig. 2 is the infrared spectrogram of embodiment 1;
Fig. 3 is the TG-DTA spectrogram of embodiment 1;
Fig. 4 is the ultraviolet spectrogram of embodiment 2;
Fig. 5 is the infrared spectrogram of embodiment 2;
Fig. 6 is the TG-DTA spectrogram of embodiment 2;
Fig. 7 is the ultraviolet spectrogram of embodiment 3;
Fig. 8 is the infrared spectrogram of embodiment 3;
Fig. 9 is the TG-DTA spectrogram of embodiment 3.
Embodiment
Below by way of specific embodiment, the present invention is further described, but these embodiments are not limited to protection scope of the present invention.
embodiment 1
Take genistein 1.35g(5mmol) in 100mL there-necked flask, add the ethanol of 50mL60%, 65 DEG C of heated and stirred 0.5 hour, add 1.23g(5mmol afterwards) CrCl 36H 2o, dropwise adding the sodium hydroxide adjust ph to 7.5 of 2mol/L, solution transition is blackish green suspending system, has a large amount of grass green to precipitate and generate after 3.5h.To precipitate suction filtration, with deionized water and dehydrated alcohol respectively by after washing of precipitate for several times, collecting precipitation, vacuum-drying, obtains graminaceous pulverulent solids, and productive rate is 60%.Before improving far above existing synthetic method 41%, and the reaction times greatly shorten, by 18 ~ 20h(before improving and need the ageing of 48h) taper to current 3.5h.
embodiment 2
Take genistein 1.35g(5mmol) in 100mL there-necked flask, add the ethanol of 60mL60%, 67 DEG C of heated and stirred 0.5 hour, add 1.23g(5mmol afterwards) CrCl 36H 2o, dropwise adding the sodium hydroxide adjust ph to 8 of 2mol/L, solution transition is blackish green suspending system, has a large amount of grass green to precipitate and generate after 3h.To precipitate suction filtration, with deionized water and dehydrated alcohol respectively by after washing of precipitate for several times, collecting precipitation, vacuum-drying, obtains graminaceous pulverulent solids, and productive rate is 60%.Before improving far above existing synthetic method 41%, and the reaction times greatly shorten, by 18 ~ 20h(before improving and need the ageing of 48h) taper to current 3h.
embodiment 3
Take genistein 1.35g (5mmol) in 100mL there-necked flask, add the ethanol of 55mL60%, 70 DEG C of heated and stirred 0.5 hour, add 1.23g (5mmol) CrCl afterwards 36H 2o, dropwise adding the sodium hydroxide adjust ph to 9 of 2mol/L, solution transition is blackish green suspending system, has a large amount of grass green to precipitate and generate after 4h.To precipitate suction filtration, with deionized water and dehydrated alcohol respectively by after washing of precipitate for several times, collecting precipitation, vacuum-drying, obtains graminaceous pulverulent solids, and productive rate is 60%.Before improving far above existing synthetic method 41%, and the reaction times greatly shorten, by 18 ~ 20h(before improving and need the ageing of 48h) taper to current 4h.
genistein chromic compound test example to prepared by the embodiment of the present invention 1 ~ embodiment 3:
1. title complex physico-chemical property and ultimate analysis
Genistein chromic compound is grass green pulverulent solids, can be dissolved in dimethyl sulfoxide (DMSO) (DMSO), DMF, be slightly soluble in methyl alcohol, acetone, be insoluble in water, CCl4.With VarioEL type elemental analyser, C, the H in genistein chromic compound is measured, the content EDTA method titration of chromium.Mass spectroscopy (electrospray ionization source ESI) is carried out with ThermoLQTOrbitrapXL LC-MS instrument.
The ultimate analysis of table 1 title complex of the present invention
2. differential thermal and thermogravimetric analysis
Under fluidizing air, heat-up rate 10 DEG C/min, measures the thermography of title complex.Can find out that chromium is combined with two zero-g periods from TG-DTA spectrogram.The weightlessness of title complex first stage is at about 75 DEG C, and rate of weight loss is 3.94%, and with the amount suitable (theoretical rate of weight loss is 4.02%) losing 2 water moleculess, corresponding have very little absorption peak on DTA curve, illustrates that title complex has the crystal water of 2 molecules.Second stage is from 320 DEG C to 420 DEG C, rate of weight loss is 86.99%, with lose 3 ligand moleculars quite (theoretical rate of weight loss is 87.5%), correspondence shows as a very large exothermic peak on DTA curve, for the oxygenolysis peak of title complex, wherein about 400 DEG C very exothermic, show that 3 molecule ligands decompose rapidly, chromium is then oxidized in atmosphere.The resistates that title complex obtains after decomposing is the oxide compound Cr of chromium 2o 3, (embodiment 1-3 prepares sample TG-DTA spectrogram and sees accompanying drawing).
3. Infrared spectroscopy
At 400-4000cm -1in scope, measure the infrared spectrogram of ligands and complexes with Thermo-NicoletNexus type Fourier transformation infrared spectrometer (KBr compressing tablet).Dominant spectral data list in table 2.
The major infrared spectrum modal data of table 2 genistein and chromic compound and ownership (cm thereof -1)
Compound V(O-H) V(C=O) V(C=C) V(C-O-C) V(O-M)
Genistein(L) 3412 1652 1616 1259
CrL 3·2H 2O 3438 1629 1612 1263 498
The infrared spectra of part and chromic compound is compared: 4 carbonylic stretching vibration frequency v (C=O) of genistein are positioned at 1652cm from table 2 data -1, after forming title complex, move to 1629cm -1, the 23cm to the displacement of lower wave number direction -1, as can be seen here, 4 ketonic oxygens of part participate in coordination.The stretching vibration v(C=C of 5-OH place phenyl ring skeleton) obviously weaken in title complex, wave number also has minimizing; The 3412cm of genistein -1stretching vibration frequency wave number after formation title complex of left and right hydroxyl adds 26cm -1, this is all that 5-OH participation coordination causes.In part, the stretching vibration v (C-O-C) of aryl oxide key is with to form change in location after title complex little, illustrates that the oxygen on genistein aryl oxide key does not participate in coordination (embodiment 1-3 prepares sample infrared spectrogram and sees accompanying drawing).
4. the UV spectrum of title complex
At DMSO:CH 3in OH=1:9 solvent there are two feature ultraviolet absorption peaks at 260nm and 330nm in genistein.Form latter two peak band of title complex all to move to long wave direction, it is weak that maximum absorption wavelength is respectively 269nm and 393nm().Wherein, strong absorption band II by after 260nm red shift 9nm to 269nm, and weak absorbing band I also has larger displacement, its reason be in genistein molecule B ring can not with the unsaturated carbonyl conjugation of C ring, make its with I absorption intensity weaken, be an acromion; And because 3 genistein molecules are by 4 carbonyls and 5 hydroxyls and chromium coordination in title complex, the flush type of whole molecule being strengthened, conjugated system increases, and causes band I red shift, intensity summary increasing.Ultraviolet data also demonstrate 4 carbonyls of genistein and 5 hydroxyls take part in coordination (embodiment 1-3 prepares sample ultraviolet spectrogram and sees accompanying drawing).

Claims (1)

1. a preparation method for genistein chromic compound, comprises the following steps:
1) in genistein in quality: volume is that the ratio of 1:37 ~ 50 adds concentration 60% ethanol;
2) be heated to 60 ~ 70 DEG C stir 0.5 ~ 1.0 hour, then add CrCl 36H 2o, adding proportion is for being 1:1 ~ 1:2 with genistein mol ratio;
3) dropwise add sodium hydroxide adjust ph to 7 ~ 9 of 2mol/L again, solution transition is blackish green suspending system;
4) there is a large amount of grass green to precipitate after 3 ~ 4h to generate, will suction filtration be precipitated;
5) use deionized water and dehydrated alcohol respectively by after washing of precipitate for several times, collecting precipitation, vacuum-drying, obtains graminaceous pulverulent solids.
CN201510601671.8A 2015-09-21 2015-09-21 A kind of preparation method of genistein chromic compound Pending CN105218585A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106187973A (en) * 2016-07-15 2016-12-07 北京中医药大学 The compositions of a kind of many isoflavone derivatives and preparation method and medical application
CN110305165A (en) * 2019-08-22 2019-10-08 福建农林大学 A kind of guanidine radicals luteolin-chromium (III) complex compound and preparation method thereof
CN110437284A (en) * 2019-08-22 2019-11-12 福建农林大学 A kind of 5', 8- bis- (dimethylbiguanide base) luteolin-chromium (III) complex compound
CN110684004A (en) * 2018-10-24 2020-01-14 荆门医药工业技术研究院 Genistein palladium chelate as well as preparation method and application thereof

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CN101857583A (en) * 2009-04-08 2010-10-13 温州医学院 Method for preparing isoflavone metal complexes and anti-tumor medical application

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106187973A (en) * 2016-07-15 2016-12-07 北京中医药大学 The compositions of a kind of many isoflavone derivatives and preparation method and medical application
CN110684004A (en) * 2018-10-24 2020-01-14 荆门医药工业技术研究院 Genistein palladium chelate as well as preparation method and application thereof
CN110305165A (en) * 2019-08-22 2019-10-08 福建农林大学 A kind of guanidine radicals luteolin-chromium (III) complex compound and preparation method thereof
CN110437284A (en) * 2019-08-22 2019-11-12 福建农林大学 A kind of 5', 8- bis- (dimethylbiguanide base) luteolin-chromium (III) complex compound
CN110305165B (en) * 2019-08-22 2022-01-11 福建农林大学 Guanidino luteolin-chromium (III) complex and preparation method thereof
CN110437284B (en) * 2019-08-22 2022-01-11 福建农林大学 5', 8-di (dimethyldiguanidino) luteolin-chromium (III) complex

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Application publication date: 20160106