CN104610244A - Halogen cyclic regeneration technology applied to dehydrogenation and hydrolysis reaction - Google Patents
Halogen cyclic regeneration technology applied to dehydrogenation and hydrolysis reaction Download PDFInfo
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- CN104610244A CN104610244A CN201410826737.9A CN201410826737A CN104610244A CN 104610244 A CN104610244 A CN 104610244A CN 201410826737 A CN201410826737 A CN 201410826737A CN 104610244 A CN104610244 A CN 104610244A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
- C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
- C07D407/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- C07—ORGANIC CHEMISTRY
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- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/22—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4
- C07D311/26—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3
- C07D311/28—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3 with aromatic rings attached in position 2 only
- C07D311/30—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3 with aromatic rings attached in position 2 only not hydrogenated in the hetero ring, e.g. flavones
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H17/00—Compounds containing heterocyclic radicals directly attached to hetero atoms of saccharide radicals
- C07H17/04—Heterocyclic radicals containing only oxygen as ring hetero atoms
- C07H17/06—Benzopyran radicals
- C07H17/065—Benzo[b]pyrans
- C07H17/07—Benzo[b]pyran-4-ones
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Abstract
The invention discloses a halogen cyclic regeneration technology applied to dehydrogenation and hydrolysis reaction. The method comprises the following steps: using a dehydrogenized flavonoids compound as a raw material, performing halogen substitution, dehydrogenizing the raw material, performing the hydrolysis one-step reaction, adopting a halogen in-situ cyclic regeneration method to synchronously regenerating the halogen consumed in the reaction, so that the halogen dosage in the reaction process is greatly reduced by 5% of the theoretic halogen dosage; meanwhile the reaction time is greatly shortened by 30% of the theoretic reaction time; through adjustment of the pH value, as for the substance containing glucoside, in the halogen in-situ cyclic regeneration dehydrogenation process, the glucoside can be synchronously hydrolyzed, so that original two-step reaction can be changed to one step; the halogen cyclic regeneration technology can be widely applied to dehydrogenation and hydrolysis reaction of the flavonoids compound.
Description
Technical field
The present invention relates to a kind of halogen cycle regeneration techniques be applied in dehydrogenation and hydrolysis reaction.
Background technology
Dehydrogenation removes the reaction process of hydrogen atom from the molecule of organic compound.Carbon-hydrogen during dehydrogenation in compound molecule, oxygen-hydrogen or nitrogen-hydrogen bond rupture, hydrogen is dissociated and generates hydrogen molecule (H
2).Catalytic dehydrogenation-main catalyzer that uses makes carbon in organism-hydrogen splitting of chain, reaches the object of dehydrogenation, also will maintain the carbon carbon bond more easily ruptured simultaneously, do not make it rupture, therefore must select suitable catalyzer.If hydrogen atom is simultaneously oxidized, such as generate water or by other receptor as the acceptance such as halogen and Nitrogen or sulfur-compounds, then claim oxydehydrogenation, when this method is mainly used in organism and the water reaction of dehydrogenation product discord thereof.The result of dehydrogenation is the degree of unsaturation of augmenting response thing, makes product have higher reactive behavior, is the significant process be widely used in organic synthesis.Just achieved by the industrial production of methanol dehydrogenation formaldehyde as far back as 1889.The twenties in 20th century rises, and successively achieves the industrial production of dehydrogenation of isopropanol acetone, ethyl benzene dehydrogenation preparation of styrene, butane dehydrogenation butylene, butylene dehydrogenation divinyl, n-butene oxydehydrogenation divinyl etc.Dehydrogenation be reversible, heat absorption, molecule number increase reaction, high temperature and low pressure be conducive to react carrying out.Dehydrogenation generally just has certain speed of response at higher temperature (300 ~ 800 DEG C), but correspondingly cracking side-reaction speed also can be accelerated.
The catalyzer that catalytic dehydrogenation must adopt selectivity good, and with decompression operation to reduce temperature of reaction as far as possible.But the low voltage operated danger having leaking-in air to set off an explosion, industrial is generally pass into water vapour to reactive system, to reduce the dividing potential drop of reactant, and can provide the heat needed for reaction, eliminate and alleviate the coking of catalyzer.Catalytic dehydrogenating reaction device has fixed-bed reactor, as shell and tube, cylinder shape adiabatic reactor single hop or multistage reactor and radial reactor, and fluidized-bed reactor.The material of reactor will have ability that is high temperature resistant and resistant to hydrogen erosion.Select suitable catalyzer, be improve dehydrogenation reaction speed and optionally key.Dehydrogenation is the inverse process of hydrogenation, and hydrogenation catalyst also can use as dehydrogenation catalyst in principle.But, because dehydrogenation is different with hydrogenation conditions, when selecting catalyst, except attention catalytic activity except, should also be noted that following some: 1. good heat resistance, ensures not to be sintered in dehydrogenation hot environment; 2. chemical stability is good, has the ability of anti-hydrogen reducing and vapour resistant erosion at relatively high temperatures; 3. dehydrogenation is easier than hydrogenation makes catalyst surface coking, should be easy to carry out catalyst regeneration.Conventional catalyzer is various metal oxide (as ferric oxide, oxidation, zinc oxide, magnesium oxide) and various metal (as copper, silver, nickel, platinum) etc.Oxy-dehydrogenation catalyst, except the performance with dehydrogenation catalyst, also should have catalytic oxidation performance, and conventional is mixed oxide catalyst (as the oxide compound of molybdenum, bismuth, the oxide compound etc. of iron, antimony), also available metal catalyzer.
Catalytic dehydrogenation can be divided into: 1. C-H catalytic dehydrogenation, as the dehydrogenation of alkane, alkene, aromatic hydrocarbons and naphthenic hydrocarbon etc.; 2. the catalytic dehydrogenation of the key such as oxygen-hydrogen and nitrogen-hydrogen, as the dehydrogenation of alcohol (straight chain alcohol, cycloalkanol) and amine.
Oxydehydrogenation, can make the hydrogen of generation be oxidized to water and remove, and impels reaction to shift to dehydrogenation direction, to improve transformation efficiency; A large amount of heat is released in simultaneous oxidation, can supply the needs of dehydrogenation heat absorption.Reaction is oxydehydrogenation heat release by dehydrogenation endothermic transition, and not only reaction conversion ratio is high, and temperature of reaction can reduce.The shortcoming of oxydehydrogenation easily causes oxidation side reaction, and the dehydrogenation reaction (oxydehydrogenation) having oxidizing reaction to participate in, as butenc becomes divinyl.
The acid that the hydrolysis reaction of glucosides is conventional has hydrochloric acid, sulfuric acid, formic acid, acetic acid etc., and reaction is generally carried out in water or dilute alcohol solution.The difficulty or ease of acid-catalyzed hydrolysis and the electron density of glycosidic bond atom and space environment thereof have substantial connection.It is protonated that aglycone structure is conducive to glycosidic bond atom, is easy to hydrolysis.1) by the difference of glycosidic bond atom, acid hydrolysis is from the easier to the more advanced: N-glycosides > O-glycosides > S-glycosides > C-glycosides is (because N easily accepts proton, facile hydrolysis, C is upper without shared electron pair, not easily protonated); 2) different by the kind of sugar in glycosides, acid hydrolysis order is from the easier to the more advanced: 1. furanoside > pyranoside.2. ketoside > aldoside.3. in pyranoside, five-carbon sugar glycosides > methyl five-carbon sugar glycosides > hexose glycosides > glycuronide.4. 2,6-deoxidation glucosides > 2-deoxidation glucosides > 6-deoxidation glucosides > 2-hydroxyl glucosides > 2-aminoglycosides; 3) time different by the kind of aglycon: 1. the more fatty glycosides of fragrant glycosides is easy to hydrolysis.2. when aglycon is little group: glycosidic bond is e key comparatively a key facile hydrolysis; When aglycon is macoradical: glycosidic bond be a key comparatively e key be easy to hydrolysis.3. the most facile hydrolysis of aforementioned N-glycosides, but when N is in acid amides N or pyrimidine N position in aglycon, N-glycosides is difficult hydrolysis also.The aglycon of some glycoside is unstable to acid, can not obtain real aglycon after acid hydrolysis, but obtains the artifact that chemical structure changed.Now, mitigation acid-hydrolysis method, enzymolysis process or Smith edman degradation Edman etc. should be adopted.The most common be divided into according to aglycone structure type, phenolic glycoside, alcohol glycosides, anthra-glucoside, flavonoid glycoside, saponin(e, cardiac glycoside, coumarin glycoside and iridoid glycoside etc.; Also oxygen glycosides, sulphur glycosides, nitrogen glycosides, carbon glycosides etc. can be divided into.
This invention is for the compound without glucosides of dehydrogenation can directly adopt the oxydehydrogenation of halogen original position cyclic regeneration method, for the compound of dehydrogenation adopting halogen original position cyclic regeneration method containing glucosides, regulate the potential of hydrogen of halogen cycle regeneration system, dehydrogenation is synchronously carried out with hydrolysis, significantly reduce halogen consumption, reduce the reaction times.Being widely used in can dehydrogenation or in the dehydrogenation hydrolysis reaction of dehydrogenation hydrolyzable compound again, greatly can reduce production cost.
Summary of the invention
The selection of the first reaction medium.
The adjustment of the second reaction system acid-basicity.
The selection of the 3rd catalyzer.
4th dehydrogenation and hydrolysis reaction
The control of the 5th reaction end and reaction solution process
Concentrating of 6th reactant.
The process of the 7th enriched material.
8th product purification.
Embodiment
Mode one: in a kettle., add one or both in the chemical reagent of 1.4 ~ 1.6 of solvent specific refractory power, the mixed solution of three kinds, is made into reaction solvent, regulate potential of hydrogen, stir evenly rear input silibinin, reaction mass and solvent feed intake with 1: 5 ~ 1: 8 (W/W) ratio, at 90 ~ 100 DEG C of reaction 1 ~ 3h, with high performance liquid chromatography detection reaction liquid, content of hesperidin, lower than 0.5% stopped reaction, is cooled to 50 ~ 70 DEG C, regulates pH6 ~ 7 with liquid caustic soda.Concentrated under 90 DEG C of vacuum tightnesss are-0.092Mpa, after 30min, temperature is upgraded to 68 DEG C, is heated to 80 DEG C, vacuum tightness is concentrated 5-8h under-0.094Mpa, and concentrated solution proportion 1.16, adds the ethanolic soln of pH8 ~ 10, backflow 1h, press filtration, adds purified water in filter cake input reactor and stirs evenly, regulate pH to 1 ~ 5,1h is heated at 80 DEG C, press filtration, is washed to neutrality, obtains dehydro-silibinin.
Mode two: in 2000kg reactor, adds one or both in the chemical reagent of 1.4 ~ 1.6 of 1500L specific refractory power, the mixed solution of three kinds, be made into reaction solvent, slowly add silibinin 300.0kg, under stirring, be slowly heated to 90 ~ 100 DEG C, at this temperature, react 1 ~ 3h.Sample thief detects the content of silibinin, stopped reaction after silibinin content is lower than 0.5%.Be cooled to 50 ~ 70 DEG C, regulate pH6 ~ 7 with liquid caustic soda.Vacuum tightness be-(0.092 ~ 0.095) Mpa under recycling design, in residue, add methanol solution 500 ~ 1000L that pH is 2 ~ 4, reflux 2h, filter after fully stirring into pasty state, obtain filter cake, filter cake is joined in 500 ~ 1000L 10% (W/W) sodium hydroxide solution, abundant stirring and dissolving, be heated to 60 ~ 80 DEG C of insulation 30min, filter, filtrate adjust ph is 2 ~ 6, precipitation, press filtration, is washed to neutrality, obtains dehydro-silibinin.
In mode three: 1000Kg reactor, add 800L specific refractory power 1.4 ~ 1.5 chemical reagent be made into reaction solvent, Hesperidin 100kg is slowly added in reactor, abundant stirring and dissolving, and then add auxiliary material 2.0 ~ 3.0kg, fully stir, slowly be heated to 90 ~ 100 DEG C, react 1 ~ 4h at this temperature, the content of Hesperidin in detection reaction liquid, lower than 0.5% rear stopped reaction.Be cooled to 50 ~ 70 DEG C, regulate pH6 ~ 7 with liquid caustic soda.Vacuum tightness be-(0.092 ~ 0.094) Mpa under recycling design, obtain diosmin concentrated solution, add 1000kg ethanol, adjust ph is 7 ~ 9, reflux 1h, and press filtration obtains diosmin crude product.Diosmin crude product is dropped in reactor and adds the abundant stirring and dissolving of 500kg5% sodium hydroxide, at 50 ~ 80 DEG C, heat 1 ~ 5h, adjust ph 8-10, precipitation, press filtration, filter cake fully stirs evenly with the sour water of pH value 2 ~ 4, heats 1h at 80 DEG C, press filtration, is washed to neutrality, obtains diosmin product.
In mode four: 500Kg reactor, add 300L specific refractory power 1.4 ~ 1.5 chemical reagent be made into reaction solvent, add naringin 100.0kg, adjust ph is 2 ~ 10, is slowly heated to 90 ~ 100 DEG C under stirring, reacts 3h at this temperature.The content of naringin in detection reaction liquid, stopped reaction after naringin content is lower than 0.5%, obtains the reaction solution of apigenin, is cooled to 50 ~ 70 DEG C, regulates pH6 ~ 7 with liquid caustic soda.Be concentrated in 60 ~ 90 DEG C of vacuum tightnesss with dual-effect concentrator and be concentrated into enriched material proportion 1.15 ~ 1.20 under-(0.092-0.095) Mpa.Add ethanol 300L reflux 1h, press filtration collect filtrate, by filtrate with 5 ~ 10% (W/W) gac 60 ~ 70 DEG C decolouring 30 ~ 60min, filter, filtrate is concentrated into dry, and adding sherwood oil (60-90 DEG C) heated and stirred is suspended matter, slowly add a small amount of ethyl acetate, one of or methyl alcohol, ethanol, in acetone, a small amount of pigment impurity is made to be dissolved in mixed solution, centrifugal, with a small amount of sherwood oil rinsing, obtain the apigenin product refined.
Claims (9)
1. be applied to the halogen cycle regeneration techniques in dehydrogenation and hydrolysis reaction, it is characterized in that, with can dehydrogenation compound or containing glucosides can the compound of dehydrogenation for raw material, the method is successively through following steps:
(1) selection of reaction medium.
(2) adjustment of reaction system acid-basicity.
(3) selection of catalyzer.
(4) dehydrogenation and hydrolysis reaction
(5) control of reaction end and reaction solution process
(6) reactant is concentrated.
(7) process of enriched material.
(8) product purification.
2. a kind of halogen cycle regeneration techniques be applied in dehydrogenation and hydrolysis reaction according to right 1, is characterized in that, solvent for use is one or both in the chemical reagent of 1.4 ~ 1.6 of specific refractory power in step (1), the mixed solution of three kinds.
3. a kind of halogen cycle regeneration techniques be applied in dehydrogenation and hydrolysis reaction according to right 1, is characterized in that, only for dehydrogenation in step (2), pH is adjusted to 5 ~ 6; Both dehydrogenation had hydrolysis, and pH is adjusted to 2 ~ 4.One of acid used is hydrochloric acid, sulfuric acid, phosphoric acid, in Glacial acetic acid.
4. a kind of halogen cycle regeneration techniques be applied in dehydrogenation and hydrolysis reaction according to right 1, is characterized in that, in step (3), catalyzer is oxygenant, the oxygenant of oxidation price 7 ~ 3.
5. a kind of halogen cycle regeneration techniques be applied in dehydrogenation and hydrolysis reaction according to right 1, it is characterized in that, in step (4), reaction mass and solvent feed intake with 1: 5 ~ 1: 8 (W/W) ratio, at 90 ~ 100 DEG C of reaction 1 ~ 4h.
6. a kind of halogen cycle regeneration techniques be applied in dehydrogenation and hydrolysis reaction according to right 1, it is characterized in that, measuring material content with high performance liquid phase in step (5) is less than 0.5% stopped reaction, is cooled to 50 ~ 70 DEG C, regulates pH6 ~ 7 with liquid caustic soda.
7. a kind of halogen cycle regeneration techniques be applied in dehydrogenation and hydrolysis reaction according to right 1, it is characterized in that, be concentrated in 60 ~ 90 DEG C of vacuum tightnesss with dual-effect concentrator in step (6) and be concentrated into enriched material proportion 1.15 ~ 1.20 under-(0.092-0.095) Mpa.
8. a kind of halogen cycle regeneration techniques be applied in dehydrogenation and hydrolysis reaction according to right 1, it is characterized in that, in step (7), in enriched material, add methyl alcohol, ethanol, dimethyl sulfoxide (DMSO) one of them, or the two mixture, adjust ph 2 ~ 10, heating for dissolving, press filtration, if dehydrogenation separately, then collect filter cake, obtain reaction product; If dehydrogenation is synchronously carried out with hydrolysis, then filtrate is dehydrogenation hydrolysising product solution.
9. a kind of halogen cycle regeneration techniques be applied in dehydrogenation and hydrolysis reaction according to right 1, it is characterized in that, step (8) if in independent dehydrogenation adopt alkali extraction-acid precipitation to refine, crude product thing is dissolved with 5 ~ 30% (W/W) sodium hydroxide or hydroxide agent solution, prepares 1; The hydrochloric acid solution of 1 (V/V), wherein adds the dimethyl formamide of hydrochloric acid solution volume 50%, is heated to 50 ~ 70 DEG C, solvent alkali lye is heated to 50 ~ 70 DEG C simultaneously, alkali lye is slowly joined in hydrochloric acid solution, make pH value be 8 ~ 10, be heated to 80 ~ 90 DEG C, insulation 1h, precipitation 6 ~ 8h, press filtration, filter cake stirs evenly with the sour water of pH1-4, is heated to 80 ~ 90 DEG C, insulation 1h, filters, is washed to neutrality, collect filter cake, obtain dehydrogenation product; If dehydrogenation is hydrolyzed the product synchronously carried out, by extracting solution with 5 ~ 10% (W/W) gac 60 ~ 70 DEG C decolouring 30 ~ 60min, filter, filtrate is concentrated into dry, adding sherwood oil (60-90 DEG C) heated and stirred is suspended matter, slowly adds a small amount of ethyl acetate, or methyl alcohol, ethanol, one of in acetone, make a small amount of pigment impurity be dissolved in mixed solution, centrifugal, with a small amount of sherwood oil rinsing, obtain the dehydrogenation hydrolysis prods refined.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113292618A (en) * | 2021-04-06 | 2021-08-24 | 湖南圆通药业有限公司 | Low-cost preparation method of diosmin |
Citations (3)
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| CN103772336A (en) * | 2014-02-23 | 2014-05-07 | 闻永举 | Semi-synthesis method of phenolic hydroxyl flavonoid compounds and iodine recycling method |
| CN103819438A (en) * | 2014-01-21 | 2014-05-28 | 李玉山 | Novel technology for preparing apigenin from by one-step method |
| CN103819521A (en) * | 2014-02-24 | 2014-05-28 | 罗懿 | Method for preparing flavonoid compound from flavanone compound |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103819438A (en) * | 2014-01-21 | 2014-05-28 | 李玉山 | Novel technology for preparing apigenin from by one-step method |
| CN103772336A (en) * | 2014-02-23 | 2014-05-07 | 闻永举 | Semi-synthesis method of phenolic hydroxyl flavonoid compounds and iodine recycling method |
| CN103819521A (en) * | 2014-02-24 | 2014-05-28 | 罗懿 | Method for preparing flavonoid compound from flavanone compound |
Non-Patent Citations (1)
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| 李玉山等: "地奥司明的合成工艺", 《实验室研究与探索》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113292618A (en) * | 2021-04-06 | 2021-08-24 | 湖南圆通药业有限公司 | Low-cost preparation method of diosmin |
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