CN108929230A - A kind of ionic liquid-catalyzed method for preparing 5- nitrosalicylaldehyde of heteropolyacid acid - Google Patents
A kind of ionic liquid-catalyzed method for preparing 5- nitrosalicylaldehyde of heteropolyacid acid Download PDFInfo
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- CN108929230A CN108929230A CN201810884219.0A CN201810884219A CN108929230A CN 108929230 A CN108929230 A CN 108929230A CN 201810884219 A CN201810884219 A CN 201810884219A CN 108929230 A CN108929230 A CN 108929230A
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- ionic liquid
- nitrosalicylaldehyde
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
- B01J27/198—Vanadium
- B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of ionic liquid-catalyzed methods for preparing 5- nitrosalicylaldehyde of heteropolyacid acid, using p-nitrophenol and hexa as raw material, using heteropolyacid acid ionic liquid as catalyst, reaction preparation 5- nitrosalicylaldehyde, the yield of the 5- nitrosalicylaldehyde of acquisition can reach 90% or more, and purity HPLC can reach 98.5%.
Description
Technical field
The present invention relates to pharmaceutical intermediate synthesis technical fields, ionic liquid-catalyzed more particularly, to a kind of heteropolyacid acid
The method for preparing 5- nitrosalicylaldehyde.
Background technique
(also known as 2- hydroxy-nitro benzaldehyde, molecular formula: molecular weight: 167.12) C7H5O4N is 5- nitrosalicylaldehyde
A kind of fine-chemical intermediate being widely used in pesticide, medicine, dyestuff and production of flavor.
With the quickening of society advancement, the pressure that people bear is increasing, and the quantity of cardiovascular patient is also continuous
Increase, therefore, the research of cardiovascular drugs increasingly obtains the attention of people.Dronedarone
(dronedaronehydrochloride), entitled 2- normal-butyl -3- [4- (3- di-n-butyl amino propoxyl group) benzoyl of chemistry
Base]-methylsulfonyl amido benzofuran is a kind of polarization inhibitor researched and developed by Frenchman, clinic is mainly used for treating heart rate mistake
Often.
5- nitrosalicylaldehyde is one of the important source material for synthesizing dronedarone, in luminescent material and Coordinative Chemistry, 5- nitre
Base salicylide is also important synthetic intermediate.In recent years, the property of 5- nitrosalicylaldehyde series complex is the study found that this is
Column complex has certain anticancer and bacteriostatic activity, can be used as potential chemicals.Therefore, 5- nitro water is researched and developed
The new synthetic method and technique of poplar aldehyde has good economic benefit and social benefit.
There are two ways to common synthesis 5- nitrosalicylaldehyde, first is that salicylide nitrification process, can use in this preparation method
A large amount of nitration mixture nitrifies salicylide, and not only environmental pollution is big, and generates 3-5- nitrosalicylic aldehyde isomer, post-processing
It is not easy.Second is that p-nitrophenol formylated method, i.e. improvement Duff reaction.P-nitrophenol is under the catalysis of inorganic acid, with black Lip river
After tropine reaction, increase an aldehyde radical at the ortho position of hydroxyl, to generate 5- nitrosalicylaldehyde.Due to the original selected in the method
Material is cheap and is easy to get, and Chinese patent CN102633646A discloses another method for preparing 5- nitrosalicylaldehyde, this method
It is to be prepared using salicylide as raw material by improved low temperature nitrification process.During the reaction, used by hydrofluoric acid,
The completely new ternary mixed solvent system of acetic anhydride and acetic acid composition, maximum output in existing patent and document with regard to being related to preparing 5-
The problems such as yield of generally existing product is low in the method for nitrosalicylaldehyde, purity is low.Safe operation process has become industry
The main method of upper production 5- nitrosalicylaldehyde.
Chinese patent CN101967101A discloses a kind of side that 5- nitrosalicylaldehyde is prepared using p-nitrophenol as raw material
Method.This method is under the conditions of being stirred at room temperature, first by the concentrated sulfuric acid dissolution of catalyst poly 98% in acid flux material, then to
The mixture of hexa and p-nitrophenol is wherein added portionwise, after adding, is warming up to reflux, reacts 3~8 hours,
Finally reaction solution is transferred in water, obtains light yellow solid, filters, obtains 5- nitrosalicylaldehyde.Wherein with highest 68.8%
Yield has synthesized 5- nitrosalicylaldehyde, but the purity for obtaining product is relatively low, and only 91% or so.But the dense sulphur of poly 98%
The viscosity of acid is unfavorable for tracking and detects reaction, is not easy to realize industrialization, and hexa is added and reacts acute in the process
Strong heat release is easy material spray, and there are certain risk for reaction.Therefore, as can in product yield, purity, reaction raw materials with analogy
Face further increases, it will help the development of downstream fine chemistry industry.
Summary of the invention
Present invention aims at propose a kind of environmentally protective 5- nitrosalicylaldehyde preparation process.
A kind of ionic liquid-catalyzed preparation 5- nitre of heteropolyacid acid is being provided for the shortcomings of the prior art
The method of base salicylide, includes the following steps:
S1,80 DEG C will be warming up to after heteropolyacid acid ionic liquid vacuum dehydration, p-nitrophenol is then added and stirred
Uniformly, hexa is divided into more parts, hexa is added in batches, control reaction temperature at 100~110 DEG C；
S2, sufficiently reacted, added in 1~2 hour reacted after material material, reaction temperature control 80~90 DEG C it
Between (reaction temperature early period), subsequent 1~2 hour, reaction temperature control was entire anti-at 90~100 DEG C (reaction latter temperatures)
Control was 2~4 hours (reaction time) between seasonable；
S3, the temperature of mixture is down to room temperature after answering, stratification obtains product layer and ionic liquid layer, then
Ionic liquid layer, combined ethyl acetate extract liquor and product layer is extracted with ethyl acetate, water is then added and is stirred continuously, stirs
The temperature of mixture is reduced to 0~10 DEG C in the process, filter cake is obtained by filtration after stirring, with alkaline solution dissolving filter cake；
S4, with the solution ph that acid solution obtains dissolving filter cake 3~4 are adjusted to again, it is cooling after a large amount of solids are precipitated
To 0~10 DEG C, after heat preservation 1~4 hour, then it is filtered to obtain 5- nitrosalicylaldehyde；
The heteropolyacid acid ionic liquid is combined by heteropoly acid and acidic ion liquid and is made, and selected heteropoly acid is phosphorus
Molybdenum vanadium heteropoly acid is one of following three types: H4PMo11VO40Or H5PMo10V2O40；Selected acidic ion liquid is [Hmim]
HSO4。
Further, the heteropolyacid acid ionic liquid the preparation method is as follows:
1) a certain amount of N- methylimidazole is taken, is added in the bottle of three holes, is placed in ice-water bath and is cooled to 0~5 DEG C, violent
Under stirring, in the concentrated sulfuric acid and 10mL distilled water of using rubber head dropper to be added 98% in 30min, room temperature continues 2~4h of stirring；Reaction
Afterwards, mixed liquor rotary evaporation under conditions of 75 DEG C removes extra moisture, obtains target product [Hmim] HSO4；
2) it takes and takes ionic liquid [Hmim] HSO obtained by step 1)4, heteropoly acid H is added4PMo11VO40Or H5PMo10V2O40, add
Enter ethyl alcohol as solvent, using ethyl alcohol as solvent reaction 15~30 hours under conditions of 50~80 DEG C；After reaction, it stands,
Product is divided into two layers, removes lower layer's object, and upper layer substance is dried in vacuum desiccator to get heteropolyacid acid ionic liquid.
Further, it is washed the method also includes step S5, by the 5- nitrosalicylaldehyde of acquisition.
Further, the p-nitrophenol, hexa, heteropolyacid acid ionic liquid mass ratio be 1:
0.95~1.15:3.5~5.5.
Further, wherein the p-nitrophenol, hexa, heteropolyacid acid ionic liquid mass ratio be
1:1.03:4.3.
Further, wherein the alkaline solution is 10% sodium hydroxide.
Further, wherein the acid solution is 18% hydrochloric acid.
Beneficial effects of the present invention:
5- nitrosalicylaldehyde preparation method is provided through the invention, using p-nitrophenol and hexa as raw material,
Using heteropolyacid acid ionic liquid as catalyst, reaction preparation 5- nitrosalicylaldehyde can obtain 90% or more yield, purity
HPLC reaches 98.5% 5- nitrosalicylaldehyde.
Specific embodiment
The following is a clear and complete description of the technical scheme in the embodiments of the invention, it is clear that described embodiment
Only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field
Art personnel every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
[embodiment 1]
I, prepared by heteropolyacid acid ionic liquid:
1) the N- methylimidazole of 5g is taken, is added in the bottle of three holes, is placed in ice-water bath and is cooled to 0 DEG C, under violent stirring,
In the concentrated sulfuric acid and 10mL distilled water of using rubber head dropper to be added 98% in 30min, room temperature continues to stir 4h；After reaction, mixed liquor
Rotary evaporation removes extra moisture under conditions of 75 DEG C, obtains target product [Hmim] HSO4；
2) it takes and takes ionic liquid [Hmim] HSO obtained by step 1)4, 3g heteropoly acid H is added4PMo11VO40, ethyl alcohol conduct is added
Solvent, using ethyl alcohol as solvent reaction 20 hours under conditions of 65 DEG C；After reaction, it stands, product is divided into two layers, under removal
Layer object, upper layer substance are dried in vacuum desiccator to get heteropolyacid acid ionic liquid.
The preparation of II, 5- nitrosalicylaldehyde
S1,80 DEG C will be warming up to after heteropolyacid acid ionic liquid vacuum dehydration, p-nitrophenol is then added and stirred
Uniformly, hexa is divided into more parts, hexa is added in batches, control reaction temperature at 110 DEG C；It is described right
Nitrophenol, hexa, heteropolyacid acid ionic liquid mass ratio be 1:1.03:4.3；
S2, it is sufficiently reacted, is added in 1.5 hours reacted after material material, reaction temperature controls between 85 DEG C (anti-
Answer temperature early period), subsequent 1.5 hours, reaction temperature control existed in 95 DEG C (reaction latter temperatures), entire reaction time control
3 hours (reaction time)；
S3, the temperature of mixture is down to room temperature after answering, stratification obtains product layer and ionic liquid layer, then
Ionic liquid layer, combined ethyl acetate extract liquor and product layer is extracted with ethyl acetate, water is then added and is stirred continuously, stirs
The temperature of mixture is reduced to 0 DEG C in the process, filter cake is obtained by filtration after stirring, is dissolved and is filtered with 10% sodium hydroxide solution
Cake；
S4, with the solution ph that 18% hydrochloric acid solution obtains dissolving filter cake 3 are adjusted to again, it is cooling after a large amount of solids are precipitated
It to 5 DEG C, after heat preservation 1 hour, then is filtered, the 5- nitrosalicylaldehyde of acquisition is subjected to washing to obtain 5- nitrosalicylaldehyde
Product, yield 91.2%, HPLC purity are 98.6%.
[embodiment 2]
I, prepared by heteropolyacid acid ionic liquid:
1) the N- methylimidazole of 5g is taken, is added in the bottle of three holes, is placed in ice-water bath and is cooled to 0~5 DEG C, in violent stirring
Under, in the concentrated sulfuric acid and 10mL distilled water of using rubber head dropper to be added 98% in 30min, room temperature continues to stir 2h；After reaction, mixing
Liquid rotary evaporation under conditions of 75 DEG C removes extra moisture, obtains target product [Hmim] HSO4；
2) it takes and takes ionic liquid [Hmim] HSO obtained by step 1)4, heteropoly acid H is added5PMo10V2O40, ethyl alcohol conduct is added
Solvent, using ethyl alcohol as solvent reaction 15~30 hours under conditions of 60 DEG C；After reaction, it stands, product is divided into two layers, goes
Except lower layer's object, upper layer substance is dried in vacuum desiccator to get heteropolyacid acid ionic liquid.
The preparation of II, 5- nitrosalicylaldehyde
S1,80 DEG C will be warming up to after heteropolyacid acid ionic liquid vacuum dehydration, p-nitrophenol is then added and stirred
Uniformly, hexa is divided into more parts, hexa is added in batches, control reaction temperature at 100~110 DEG C；
The p-nitrophenol, hexa, heteropolyacid acid ionic liquid mass ratio be 1:0.96:4；
S2, it is sufficiently reacted, is added in 1.5 hours reacted after material material, reaction temperature controls between 85 DEG C (anti-
Answer temperature early period), subsequent 1.5 hours, reaction temperature control existed in 95 DEG C (reaction latter temperatures), entire reaction time control
3 hours (reaction time)；
S3, the temperature of mixture is down to room temperature after answering, stratification obtains product layer and ionic liquid layer, then
Ionic liquid layer, combined ethyl acetate extract liquor and product layer is extracted with ethyl acetate, water is then added and is stirred continuously, stirs
The temperature of mixture is reduced to 0 DEG C in the process, filter cake is obtained by filtration after stirring, is dissolved and is filtered with 10% sodium hydroxide solution
Cake；
S4, with the solution ph that 18% hydrochloric acid solution obtains dissolving filter cake 3 are adjusted to again, it is cooling after a large amount of solids are precipitated
It to 5 DEG C, after heat preservation 1 hour, then is filtered, the 5- nitrosalicylaldehyde of acquisition is subjected to washing to obtain 5- nitrosalicylaldehyde
Product, yield 92.6%, HPLC purity are 98.7%.
Above description sufficiently discloses a specific embodiment of the invention.It should be pointed out that being familiar with the field
Range of any change that technical staff does a specific embodiment of the invention all without departing from claims of the present invention.
Correspondingly, the scope of the claims of the invention is also not limited only to previous embodiment.
Claims (7)
1. a kind of ionic liquid-catalyzed method for preparing 5- nitrosalicylaldehyde of heteropolyacid acid, which is characterized in that including walking as follows
It is rapid:
S1,80 DEG C will be warming up to after heteropolyacid acid ionic liquid vacuum dehydration, p-nitrophenol is then added and stirred evenly,
Hexa is divided into more parts, hexa is added in batches, controls reaction temperature at 100~110 DEG C；
S2, it is sufficiently reacted, is added in 1~2 hour reacted after material material, reaction temperature controls between 80~90 DEG C
(reaction temperature early period), subsequent 1~2 hour, reaction temperature control was in 90~100 DEG C (reaction latter temperatures), entire reaction
Time controlled 2~4 hours (reaction time)；
S3, the temperature of mixture is down to room temperature after answering, stratification obtains product layer and ionic liquid layer, then uses second
Then acetoacetic ester extracting ionic liquid layer, combined ethyl acetate extract liquor and product layer are added water and are stirred continuously, whipping process
It is middle that the temperature of mixture is reduced to 0~10 DEG C, filter cake is obtained by filtration after stirring, with alkaline solution dissolving filter cake；
S4, with the solution ph that acid solution obtains dissolving filter cake 3~4 are adjusted to again, it is cooled to 0 after a large amount of solids are precipitated~
After 10 DEG C, heat preservation 1~4 hour, then it is filtered to obtain 5- nitrosalicylaldehyde；
The heteropolyacid acid ionic liquid is combined by heteropoly acid and acidic ion liquid and is made, and selected heteropoly acid is phosphorus molybdenum vanadium
Heteropoly acid is one of following three types: H4PMo11VO40Or H5PMo10V2O40；Selected acidic ion liquid is [Hmim] HSO4.
2. the ionic liquid-catalyzed method for preparing 5- nitrosalicylaldehyde of heteropolyacid acid according to claim 1, feature
Be, the heteropolyacid acid ionic liquid the preparation method is as follows:
1) a certain amount of N- methylimidazole is taken, is added in the bottle of three holes, is placed in ice-water bath and is cooled to 0~5 DEG C, in violent stirring
Under, in the concentrated sulfuric acid and 10mL distilled water of using rubber head dropper to be added 98% in 30min, room temperature continues 2~4h of stirring；After reaction,
Mixed liquor rotary evaporation under conditions of 75 DEG C removes extra moisture, obtains target product [Hmim] HSO4；
2) it takes and takes ionic liquid [Hmim] HSO4 obtained by step 1), heteropoly acid H is added4PMo11VO40Or H5PMo10V2O40, second is added
Alcohol is as solvent, using ethyl alcohol as solvent reaction 15~30 hours under conditions of 50~80 DEG C；After reaction, it stands, product
It is divided into two layers, removes lower layer's object, upper layer substance is dried in vacuum desiccator to get heteropolyacid acid ionic liquid.
3. the ionic liquid-catalyzed method for preparing 5- nitrosalicylaldehyde of heteropolyacid acid according to claim 1, feature
It is, is washed the method also includes step S5, by the 5- nitrosalicylaldehyde of acquisition.
4. the ionic liquid-catalyzed method for preparing 5- nitrosalicylaldehyde of heteropolyacid acid according to claim 1, feature
Be, the p-nitrophenol, hexa, heteropolyacid acid ionic liquid mass ratio be 1:0.95~1.15:
2.5~3.5.
5. the ionic liquid-catalyzed method for preparing 5- nitrosalicylaldehyde of heteropolyacid acid according to claim 1, feature
Be: wherein the p-nitrophenol, hexa, heteropolyacid acid ionic liquid mass ratio be 1:1.03:4.3.
6. the ionic liquid-catalyzed method for preparing 5- nitrosalicylaldehyde of heteropolyacid acid according to claim 1, feature
Be: alkaline solution described in step S3 is 10% sodium hydroxide.
7. the ionic liquid-catalyzed method for preparing 5- nitrosalicylaldehyde of heteropolyacid acid according to claim 1, feature
Be: in step S4, the acid solution is 18% hydrochloric acid.
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Citations (4)
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|---|---|---|---|---|
| CN1323286A (en) * | 1998-09-10 | 2001-11-21 | 埃克森化学专利公司 | Process for making aromatic aldehydes using ionic liquids |
| CN1583702A (en) * | 2003-08-19 | 2005-02-23 | 中国科学院兰州化学物理研究所 | Preparing method for benzaldehyde |
| CN103058874A (en) * | 2013-02-05 | 2013-04-24 | 上海煦旻化工科技发展有限公司 | Method for preparing 5-nitrosalicylaldehyde |
| CN104014369A (en) * | 2014-06-23 | 2014-09-03 | 山东大学 | Heteropolyacid acidic ionic liquid and application of heteropolyacid acidic ionic liquid in transesterification |
-
2018
- 2018-08-06 CN CN201810884219.0A patent/CN108929230A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1323286A (en) * | 1998-09-10 | 2001-11-21 | 埃克森化学专利公司 | Process for making aromatic aldehydes using ionic liquids |
| CN1583702A (en) * | 2003-08-19 | 2005-02-23 | 中国科学院兰州化学物理研究所 | Preparing method for benzaldehyde |
| CN103058874A (en) * | 2013-02-05 | 2013-04-24 | 上海煦旻化工科技发展有限公司 | Method for preparing 5-nitrosalicylaldehyde |
| CN104014369A (en) * | 2014-06-23 | 2014-09-03 | 山东大学 | Heteropolyacid acidic ionic liquid and application of heteropolyacid acidic ionic liquid in transesterification |
Non-Patent Citations (4)
| Title |
|---|
| AILONG SHI等: "Synthesis and bioevaluation of 2-phenyl-5-methyl-2H-1,2,3-triazole-4-carboxylic acid/carbohydrazide derivatives as potent xanthine oxidase inhibitors", 《RSC ADV.》 * |
| 李霞: "Brønsted酸性离子液体存在下乌洛托品和甲苯的硝化反应研究", 《南京理工大学硕士学位论文》 * |
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| 齐秀芳: "Brønsted酸性离子液体存在下的硝化(解)反应研究", 《南京理工大学博士学位论文》 * |
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