CN110452203A - A kind of preparation method of 1- oxo -1,3- dihydro-3-hydroxy benzofuran -5- formic acid - Google Patents
A kind of preparation method of 1- oxo -1,3- dihydro-3-hydroxy benzofuran -5- formic acid Download PDFInfo
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- CN110452203A CN110452203A CN201910809442.3A CN201910809442A CN110452203A CN 110452203 A CN110452203 A CN 110452203A CN 201910809442 A CN201910809442 A CN 201910809442A CN 110452203 A CN110452203 A CN 110452203A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
- C07D307/89—Benzo [c] furans; Hydrogenated benzo [c] furans with two oxygen atoms directly attached in positions 1 and 3
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Abstract
The invention discloses a kind of preparation methods of 1- oxo -1,3- dihydro-3-hydroxy benzofuran -5- formic acid.2,5- halogeno toluene is dissolved in tetrahydrofuran solution by the present invention, under catalysis of iodine, corresponding Grignard Reagent is prepared with magnesium metal reaction, is passed through carbon dioxide and obtains 2- methylterephthalic acid；Then make 2- methylterephthalic acid that 1- oxo -1,3- dihydro-3-hydroxy benzofuran -5- formic acid be prepared through chromium trioxide oxidation and dilute hydrochloric acid hydrolysis in the presence of glacial acetic acid, acetic anhydride, the concentrated sulfuric acid.Preparation method synthesis of the invention is simple, raw material is cheap and easy to get, is convenient for large-scale preparation, and reaction treatment of the invention is simple, only needs washing, extraction and filtering that can obtain pure target product；The present invention is simple to reaction kit equipment requirement, since raw material is cheap and easy to get, so there is very big advantage in reaction cost, improves economic benefit, has outstanding industrialization prospect.
Description
Technical field
The present invention relates to organic compound preparation technical fields, and in particular to a kind of 1- oxo -1,3- dihydro-3-hydroxy benzene
And the preparation method of furans -5- formic acid.
Background technique
Terephthaldehyde's acids compound is a kind of important dyestuff, drug and chemical intermediate.In multi-functional metal
The synthesis field of organic frame (MOFs) has potential application.Organic active function is carried out in the side of terephthalic acid (TPA) position
The pre- modification of group is a kind of common research strategy, and the introducing of the active group of new functional group especially chemical property is to this kind of new
Material bring new property.
BaogangWang et al. reported the synthesis 2- formoxyl of the 2- formylbenzoate of different substituents in 2014
Terephthalic acid (TPA), but it is 20% that the yield of 2- formoxyl terephthalic acid (TPA) synthesis is very low, the nuclear magnetic data provided from author
From the point of view of, obtain the interior ester isomer (FTPA) that material is also 2- formoxyl terephthalic acid (TPA), i.e. 1- oxo -1,3- dihydro -3-
Hydroxyl benzofuran -5- formic acid.
StephenJ.D. in 2016 with 2,5- dibromo benzaldehyde for raw material, in bis- (diphenylphosphine) -9 palladium acetate, 4,5-,
Under the conditions of 9- xanthphos and carbon monoxide etc., 2- formoxyl terephthaldehyde acid lactone isomers is synthesized.
The synthesis of 1- oxo -1,3- dihydro-3-hydroxy benzofuran -5- formic acid is reported at present, it is domestic not yet at
Ripe the relevant technologies.Therefore the 1- oxo -1,3- dihydro-3-hydroxy benzofuran -5- formic acid of a kind of high yield, high-purity is studied
Preparation method the technical issues of being those skilled in the art's urgent need to resolve.
Summary of the invention
In view of this, the present invention is that raw material has obtained a kind of new 1- oxygen by studying for a long period of time with 2,5- halogeno toluene
The preparation method of generation -1,3- dihydro-3-hydroxy benzofuran -5- formic acid；
To achieve the goals above, the present invention adopts the following technical scheme:
The preparation method of 1- oxo -1,3- dihydro-3-hydroxy benzofuran -5- formic acid, the specific steps are as follows:
(1) under protective gas or dry protection of pipe, 2,5- halogeno toluene is dissolved in tetrahydrofuran, then to tetrahydro furan
It mutters and magnesium metal and initiator is added in solution, green reagent is made under initiator initiation；
(2) after being passed through carbon dioxide to green reagent obtained in step (1) and hydrochloric acid acidification is added, 2- methyl pair is obtained
Phthalic acid；
(3) the 2- methylterephthalic acid that step (2) obtains is added to the mixed liquor of glacial acetic acid, acetic anhydride and the concentrated sulfuric acid
In, chromium trioxide is added into mixed liquor under water bath condition and is aoxidized, then to mixed liquor to be quenched, except deicing vinegar
To get 1- oxo -1,3- dihydro-3-hydroxy benzofuran -5- first after acid and acetic anhydride, extraction, washing, drying and concentration
Acid.
Compared with prior art the beneficial effects of the present invention are: (1) reaction treatment of the invention is simple, only need washing,
Extraction and filtering can obtain pure target product；(2) preparation method of the invention synthesis is simple, raw material is cheap and easy to get,
It is convenient for large-scale preparation, there is outstanding industrialization prospect；(3) present invention is simple to reaction kit equipment requirement, due to raw material
It is cheap and easy to get, so there is very big advantage in reaction cost, improve economic benefit.
Further, the protective gas in above-mentioned steps (1) is nitrogen or inert gas.
Be using above-mentioned further beneficial effect: Grignard Reagent prepared by the present invention is to water sensitive, using indifferent gas
Body protection can guarantee that Grignard Reagent is successfully prepared.
Further, 2,5- halogeno toluene is 2,5- dichlorotoleune or 2,5- dibromomethylbenzene in above-mentioned steps (1).
Further, magnesium metal is magnesium chips or magnesium powder in above-mentioned steps (1)；The molar ratio of magnesium metal and 2,5- halogeno toluene is
5-6:1。
Be using above-mentioned further beneficial effect: the present invention can guarantee all 2,5- dihalo- first using excessive magnesium
Benzene being capable of fully reacting.
Further, the reaction temperature of initiation reaction is 50~65 DEG C in above-mentioned steps (1), and the reaction time is 2~8h.
Be using above-mentioned further beneficial effect: improving reaction temperature can be improved the yield of product, reaction time
Longer yield is also higher.
Further, glacial acetic acid, acetic anhydride, the concentrated sulfuric acid rub with starting 2,5- halogeno toluene in above-mentioned steps (3) mixed liquor
You are than being 21:12.5:5:1.
Be using above-mentioned further beneficial effect: above-mentioned raw materials ratio can guarantee reaction in the present invention sufficiently into
Row.
Further, when into mixed liquor, addition chromium trioxide is aoxidized in above-mentioned steps (3), chromium trioxide is slowly added to
Into mixed liquor, reaction temperature is 0-5 DEG C, reaction time 2-24h when addition, and reacting liquid temperature is 5 DEG C.
Further, the molar ratio of above-mentioned chromium trioxide and starting 2,5- halogeno toluene is 3-5:1.
It is using above-mentioned further beneficial effect: the chromium trioxide and originate 2,5- halogeno toluene that the present invention limits
Molar ratio can be avoided the methyl in raw material mix for 3-5:1 and be melted into carboxyl by peroxide.
Further, quenching operation method is that reaction solution is poured slowly into a large amount of ice water in above-mentioned steps (3)；The ice
The removing method of acetic acid and acetic anhydride is water washing removal；The extractant can choose ethyl acetate or methylene chloride；
The washing of organic phase common distilled water or deionized water, are finally washed with saturated sodium chloride solution；In the drying process
It is dried using anhydrous sodium sulfate, anhydrous magnesium sulfate or anhydrous calcium chloride.
Be using above-mentioned further beneficial effect: massive laundering washs away glacial acetic acid and acetic anhydride facilitates processing；Extraction
It takes solvent boiling point low, is easy to be distilled off；Distilled water or deionized water washing can further remove glacial acetic acid and acetic anhydride, satisfy
The water in organic phase is removed with NaCl, it is advantageous dry in next step；Anhydrous sodium sulfate, anhydrous magnesium sulfate and anhydrous calcium chloride
Dry and remove remaining trace water.
Detailed description of the invention
Fig. 1 is the core for the 1- oxo -1,3- dihydro-3-hydroxy benzofuran -5- formic acid that the embodiment of the present invention 1 is prepared
Magnetic resonance hydrogen composes spectrogram.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
Embodiment 1
The preparation method synthetic route of 1- oxo -1,3- dihydro-3-hydroxy benzofuran -5- formic acid is as follows:
Steps are as follows:
First step reaction
4.4g magnesium powder, elemental iodine and magneton are added in the three-necked flask of 500mL, bottleneck is plus reflux among three-necked flask
It manages, connects nitrogen ball using threeway on return pipe；Bottleneck installs constant pressure funnel, constant pressure funnel dress on the left of three-necked flask
There is the tetrahydrofuran solution of the 2,5- dibromomethylbenzene containing 9.075g；Bottleneck is sealed with anti-mouth rubber stopper on the right side of three-necked flask, and pumping is set
Change nitrogen three times；The tetrahydrofuran solvent 150mL newly handled is added from right side bottleneck, reaction solution is heated to 50 DEG C, and will contain 2,
The tetrahydrofuran solution of 5- dibromomethylbenzene is slowly added dropwise in reaction solution, and reaction temperature is increased after being added dropwise to 65 DEG C of reaction 6h
Afterwards；Carbon dioxide gas is slowly blasted into reaction solution, is opened simultaneously threeway connection atmosphere, is stopped air-blowing after reacting 1h；To anti-
It answers liquid to be cooled to room temperature, the hydrochloric acid 150mL of 4mol/L is added, the reaction was continued 1h；Vacuum distillation is taken out after removing tetrahydrofuran
Filter, by filter cake 200mL water washing, filter cake is dried to obtain faint yellow solid 5.5g, calculated yield 84% for 60 DEG C in an oven.
Second step reaction
3.6g2- methyl para Toluic Acid is dissolved in glacial acetic acid, acetic anhydride and concentrated sulfuric acid mixed solution, in mixed solution
Containing glacial acetic acid 25.2g, acetic anhydride 25.9g, concentrated sulfuric acid 10.3g, reaction system is cooled to 0~5 DEG C by ice-water bath, stirring condition
Under.6.0g chromium trioxide is slowly added into mixed liquor, adition process continues 40min；Reaction solution is at 25 DEG C after charging
Lower stirring 4h；Then reaction solution is poured slowly into 300mL ice water, and quickly stirred, the mixed liquor 150mL after stirring
Ethyl acetate extracts in three times, combined ethyl acetate phase, respectively successively with 200mL deionized water and 200mL saturated salt solution
It washed once, be then dried with anhydrous calcium chloride, vacuum distillation removes solvent up to target compound 1.6g, meter after filtering
Calculating yield is 41%.
Embodiment 2
First step reaction
5.3g magnesium chips, elemental iodine and magneton are added in the three-necked flask of 500mL, bottleneck is plus reflux among three-necked flask
It manages, connects drying tube on return pipe；Bottleneck installs constant pressure funnel on the left of three-necked flask, and constant pressure funnel, which is equipped with, to be contained
The tetrahydrofuran solution of the 2,5- dichlorotoleune of 5.847g；The tetrahydrofuran solvent 150mL newly handled is added from right side bottleneck, instead
Liquid is answered to be heated to 65 DEG C, and the tetrahydrofuran solution that will contain 2,5- dichlorotoleune is slowly added dropwise in reaction solution, after being added dropwise
Continue after 65 DEG C of reaction 8h；Carbon dioxide gas is slowly blasted into reaction solution, is opened simultaneously threeway connection atmosphere, is reacted 1h
After stop air-blowing；It is cooled to room temperature to reaction solution, the hydrochloric acid 150mL of 4mol/L is added, continue to stir 1h；Vacuum distillation removes four
It is filtered after hydrogen furans, by filter cake 200mL water washing, filter cake is dried to obtain faint yellow solid 5.1g for 60 DEG C in an oven,
Calculated yield is 73%.
Second step reaction is that chromium trioxide is 10.0g, reaction with the difference of the second step reaction in embodiment 1
The time reacted at 25 DEG C extends to for 24 hours, and extractant is methylene chloride, and desiccant is anhydrous sodium sulfate, obtains target chemical combination
Object 1.3g, calculated yield 34%.
Embodiment 3
The first step reaction reacted with 1 first step of embodiment the difference is that, take 2,5-, bis- iodotoluene of 12.4881g
Instead of 2,5- dibromomethylbenzene；Reaction carries out under protection of argon gas, and the reaction time is 2h at 65 DEG C, obtains yellow solid 4.2g, counts
Calculating yield is 60%.
Second step reaction react with 1 second step of embodiment the difference is that, be that chromium trioxide for 8.0g, reacts and exists
The time reacted at 25 DEG C extends to 12h, and extractant is methylene chloride, and desiccant is anhydrous magnesium sulfate, obtains target compound
1.5g, calculated yield 39%.
Product nuclear magnetic resonance spectroscopy is as follows:
1HNMR(400MHz,DMSO-d6) δ 13.61 (br, 1H), 8.50-8.0 (br, 1H), 8.20 (d, J=8.0Hz,
1H), 8.17 (s, 1H), 7.95 (d, J=8.0Hz, 1H), 6.77 (s, 1H), spectrogram is as shown in Figure 1.
Claims (9)
1. a kind of preparation method of 1- oxo -1,3- dihydro-3-hydroxy benzofuran -5- formic acid, which is characterized in that specific steps
It is as follows:
(1) under protective gas or dry protection of pipe, 2,5- halogeno toluene is dissolved in tetrahydrofuran, it is then molten to tetrahydrofuran
Magnesium metal and initiator are added in liquid, green reagent is made under initiator initiation；
(2) after being passed through carbon dioxide to green reagent obtained in step (1) and hydrochloric acid acidification is added, 2- methyl is obtained to benzene two
Formic acid；
(3) the 2- methylterephthalic acid that step (2) obtains is added in the mixed liquor of glacial acetic acid, acetic anhydride and the concentrated sulfuric acid,
Chromium trioxide is added into mixed liquor under water bath condition to be aoxidized, then to mixed liquor to be quenched, remove glacial acetic acid
With after acetic anhydride, extraction, washing, drying and concentration to get 1- oxo -1,3- dihydro-3-hydroxy benzofuran -5- formic acid.
2. a kind of preparation method of 1- oxo -1,3- dihydro-3-hydroxy benzofuran -5- formic acid according to claim 1,
It is characterized in that, protective gas described in step (1) is nitrogen or inert gas.
3. a kind of preparation method of 1- oxo -1,3- dihydro-3-hydroxy benzofuran -5- formic acid according to claim 1,
It is characterized in that, 2,5- halogeno toluene described in step (1) is 2,5- dichlorotoleune, 2,5- dibromomethylbenzene and 2, bis- iodotoluene of 5-.
4. a kind of preparation method of 1- oxo -1,3- dihydro-3-hydroxy benzofuran -5- formic acid according to claim 1,
It is characterized in that, magnesium metal described in step (1) is magnesium chips or magnesium powder；The molar ratio of magnesium metal and 2,5- halogeno toluene is 5-6:1.
5. a kind of preparation method of 1- oxo -1,3- dihydro-3-hydroxy benzofuran -5- formic acid according to claim 1,
It is characterized in that, the reaction temperature of initiation reaction described in step (1) is 50~65 DEG C, and the reaction time is 2~8h.
6. a kind of preparation method of 1- oxo -1,3- dihydro-3-hydroxy benzofuran -5- formic acid according to claim 1,
It is characterized in that, glacial acetic acid, acetic anhydride, the concentrated sulfuric acid and the molar ratio for originating 2,5- halogeno toluene are in step (3) described mixed liquor
21:12.5:5:1。
7. a kind of preparation method of 1- oxo -1,3- dihydro-3-hydroxy benzofuran -5- formic acid according to claim 1,
It is characterized in that, when into mixed liquor, addition chromium trioxide is aoxidized described in step (3), chromium trioxide is slowly added to mixing
In liquid, reaction temperature is 0-5 DEG C, reaction time 4-24h when addition, and reacting liquid temperature is 25 DEG C.
8. a kind of preparation method of 1- oxo -1,3- dihydro-3-hydroxy benzofuran -5- formic acid according to claim 7,
It is characterized in that, the molar ratio of the chromium trioxide and starting 2,5- halogeno toluene is 2~5:1.
9. a kind of preparation method of 1- oxo -1,3- dihydro-3-hydroxy benzofuran -5- formic acid according to claim 1,
It is characterized in that, quenching operation method described in step (3) is that reaction solution is poured slowly into ice water；The glacial acetic acid and acetic anhydride
Removing method be using water washing organic phase method remove；The extractant can choose ethyl acetate or dichloromethane
Alkane；The washing operation is after being washed with distilled water or deionized water, to be washed with saturated sodium chloride solution；The drying process
It is middle to be dried using anhydrous sodium sulfate, anhydrous magnesium sulfate or anhydrous calcium chloride.
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| CN111234210A (en) * | 2020-02-28 | 2020-06-05 | 青岛农业大学 | Covalent organic framework material with benzofuran structure, synthetic method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111234210A (en) * | 2020-02-28 | 2020-06-05 | 青岛农业大学 | Covalent organic framework material with benzofuran structure, synthetic method and application |
| CN111234210B (en) * | 2020-02-28 | 2022-05-13 | 青岛农业大学 | Covalent organic framework material with benzofuran structure, synthetic method and application |
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