CN104262109B - A kind of synthetic method of resorcinol - Google Patents
A kind of synthetic method of resorcinol Download PDFInfo
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- CN104262109B CN104262109B CN201410439377.7A CN201410439377A CN104262109B CN 104262109 B CN104262109 B CN 104262109B CN 201410439377 A CN201410439377 A CN 201410439377A CN 104262109 B CN104262109 B CN 104262109B
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- Prior art keywords
- resorcinol
- acid
- diaminobenzene
- raw material
- solid supported
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
- C07C37/045—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis by substitution of a group bound to the ring by nitrogen
- C07C37/05—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis by substitution of a group bound to the ring by nitrogen by substitution of a NH2 group
Abstract
The invention discloses the synthetic method of a kind of resorcinol, specifically with m-diaminobenzene. as raw material, at NaNO2Resorcinol is prepared with next pot of effect of solid supported acid.The method reaction condition is gentle, another product is that nitrogen does not affect product purity, without expensive catalyst, and the response time is shorter, environmentally friendly, the acid catalyst of its solid supported used can reuse, and also reduces the consumption of acid in reactions steps while reducing cost.
Description
Technical field
The present invention relates to the synthetic method of a kind of resorcinol, be further the synthesis of a kind of acid catalyzed resorcinol
Method, moreover a kind of with solid acid catalysis, the method being Material synthesis resorcinol with m-diaminobenzene..
Background technology
Resorcinol is a kind of application fine Organic Chemicals widely, it agricultural, dyestuff, coating, medicine,
Plastics, rubber and electronic chemical product field suffer from extremely important effect.At field of medicaments, resorcinol has and necessarily kills
Bacterium effect, can treat the dermatosis of fungal infection or be used as intestinal disinfectant, in addition resorcinol or a weight
The medicine intermediate wanted, such as it is the initial feed of antitubercular agent para-aminosalicylic acid medicine.
At present, there are Si Peike chemical company of Germany and Britain of the U.S. and SUMITOMO CHEMICAL in the enterprise that can produce more than ten thousand tons in the world per year
Chemistry.The U.S. the consumption figure of domestic resorcinol in 2004 reach 1.6 ten thousand tons, the resorcinol consumption figure of Japan be 6 kilotons
Estimating will be with annual 3.5% speed increment.Along with the raising of people's living standard, the domestic demand to resorcinol is not yet
Disconnected increase, this sought-after resorcinol price is risen sharply, the domestic upsurge in construction having risen resorcinol.
The industrial process of domestic resorcinol includes: benzene sulfonated alkali fusion method, group method of substitution, arylation method, phenol
Hydroxylating method, m-Diisopropylbenzene oxidizing process.
Benzene sulfonated alkali fusion method is using benzene as initiation material, and process conditions are simple, and technology is the most ripe, but environmental pollution
Greatly.In the production process of product, need a large amount of strong acid, highly basic, produce substantial amounts of inorganic salt Na2SO4, Na2SO3, environment simultaneously
Pressure is bigger.
M-Diisopropylbenzene oxidizing process is developed by Stanford University, and this process contamination is little, low cost, and by-product acetone is easy
Also it is an important fine chemical product in separating simultaneously.The present Japanese industry of the method, but China there is presently no work
The device of industry.The method with m-Diisopropylbenzene under certain condition, acts on lower life by oxygen, hydrogen peroxide, the common of sulphuric acid
Become peroxide, then hydrolysis obtains resorcinol.The defect of this method is, generates a peroxide in oxidation step
Less stable, is susceptible to danger, has special requirement to testing equipment, limits answering of the method to a certain extent
With.
Group method of substitution is the group on hydroxyl-substituted ring, the general designation of a class reaction of the resorcinol of system.The method
Raw material include o-dichlorohenzene, m-dichlorobenzene, m-diaminobenzene..In the method, o-dichlorohenzene is to utilize substitution reaction to reset to produce
Resorcinol, its another product is o-phenol, and this limits this reaction application industrially greatly.And with a dichloro
Benzene is that raw material production resorcinol needs High Temperature High Pressure, rare metal lanthanum makees catalyst and productivity is the lowest, is not suitable for carrying out work
Industry metaplasia is produced.A kind of production resorcinol method of being widely applied at home is: between being first reduced to by m-nitro
, at high temperature under high pressure, there is the resorcinol of substitution reaction with water and acid in phenylenediamine.But, m-diaminobenzene. in the method
Two amido reactivities are poor, generally require longer response time and more acid Jie during preparing resorcinol
Matter is to promote the carrying out of reaction.Another kind of group method of substitution is to be hydrolyzed under certain temperature and pressure by m-diaminobenzene.
To resorcinol (patent No.: 200510117199.7), the defect of the method is, needs higher reaction temperature and longer
Response time, the inwall of reaction vessel also need plate last layer rare metal, cost is high.
Arylation method is to be prepared in the effect of 170 DEG C, the dehydrogenation such as Pd with hydroresorcinol.This reaction work
It is not required to for process flow is short, reaction condition compares additive method use strong acid, highly basic or strong oxidizer, technique green ring
Protect.But, prepare the raw material 1 of resorcinol, the productivity that hydroresorcinol is industrially prepared is relatively low, is vulnerable to price fluctuation shadow
Ring, and need use to be similar to the most expensive catalyst of Pd in process of production, limit this reaction industrially
Application.(patent No.: CN2007100076588).
At present, the production technology of China's resorcinol also exists some problems, such as: need a large amount of use strong acid and strong base or
Strong oxidizer；Technical process energy consumption is relatively big, produce needed for appointed condition high；Product yield is too low；Raw materials for production are expensive.
Transformation to resorcinol technique, reduces or eliminates this problem above, can improve the life of China's resorcinol greatly
Production capacity power and the minimizing pollution to environment.
Being connected with diazo by alkyl and the organic compound that generates additionally, diazonium compound is a class, formula is
R3C-N=N-.It is typically under the effect of mineral acid and sodium nitrite, to be generated diazonium compound by aromatic amine, mostly has explosivity.
Therefore, diazo-reaction is seldom applied in big commercial production.
Summary of the invention:
The present invention puies forward a kind of new resorcinol synthetic method much of that, and the method existing method that compares has bigger excellent
Gesture, can obtain product resorcinol with the condition of milder, shorter response time.
The synthetic route of the present invention is as follows:
。
The present invention seeks to be achieved through the following technical solutions:
The synthetic method of a kind of resorcinol, comprises raw material, reagent and catalyst dissolution, stirs, reacts, extracts, subtracts
Pressure distills to obtain the step of finishing room Benzodiazepines, it is characterised in that with m-diaminobenzene. as raw material, under solid supported acid catalysis, will
M-diaminobenzene. and NaNO2 hybrid reaction, hydrolysis, one kettle way generates Resorcino.
Further, in said method, the mass ratio range that feeds intake of raw material m-diaminobenzene. and solid supported acid is at 1:1-
1.8。
Further, in said method, the molar ratio example scope of raw material m-diaminobenzene. and sodium nitrite is at 1:1-2.
Further, in said method, solid supported acid is sulfuric acid-silica.
Finding through applicant's many experiments, the present invention is with m-diaminobenzene. as initiation material, under solid supported sulfuric acid catalysis
Defining a diazointermediate with sodium nitrite, this intermediate general diazonium compound that compares is more stable, after hydrolysis
Produce phenol.The stable reason of this intermediate is in the middle of the diazonium that amine is formed probably as solid supported acid catalyst
Time, diazo-moieties is played a Stabilization by the lone pair electrons part on its siliceous and sulfur.The mild condition of this reaction,
By-product is nitrogen, it is not necessary to expensive catalyst, and the response time is shorter, environmentally friendly.Its solid supported used
Acid catalyst is after making to be finished, by reusing, while reducing cost after the operations such as acid and water alternately washing, drying
Also reduce the consumption of acid in reactions steps.
It addition, in the present invention, described stirring course of reaction can also be carried out under conditions of heating.
One feasible solid supported processed with acid Preparation Method is as follows:
Weigh the silica gel of 150g, in silica gel, under conditions of being then stirred at room temperature, add 200ml concentrated sulphuric acid slowly,
Room temperature stands overnight.Filtering, rinse filter cake with dehydrated alcohol, filter cake is dried 8h at 110 DEG C, standby.
One feasible complete resorcinol synthetic method is as follows:
1. the sulphuric acid solid catalyst of m-diaminobenzene. and above-mentioned solid supported is joined in solvent deionized water,
Stir under room temperature.
2., to the NaNO2 aqueous solution that reaction system dropping is appropriate, after dropping, continue stirring reaction under this condition.
3. after reaction terminates, adding ethyl acetate extraction to reaction system, the organic facies after extraction merges.
Decompression distillation at 4.30 DEG C, recycling design ethyl acetate, remainder is with after A4 molecular sieve drying, under 30mmHg
Decompression distillation, collects product.
The beneficial effects of the present invention is:
Resorcinol synthetic method the most disclosed in this invention is one pot reaction, greatly simplify reactions steps, contracting
Short operation, the most industrial application and popularization；
2. use sodium nitrite as reaction promoter, greatly reduce m-diaminobenzene. and be changed into temperature and the pressure of resorcinol
Power so that it is can react at normal temperatures and pressures, the most also shortens the response time；
3. the present invention uses solid supported sulphuric acid as catalyst, and this catalyst can make reaction condition more heat
With, controlled and cheap；
Method the most disclosed by the invention has higher productivity and product purity.
Detailed description of the invention
Several specific embodiment is set forth below to further illustrate the present invention program.Should be appreciated that following any enforcement
The further restriction to the present invention of the most non-any form of example.
Embodiment 1
Weigh the silica gel of 150g, in silica gel, under conditions of being then stirred at room temperature, add 200ml concentrated sulphuric acid slowly,
Room temperature stands overnight.Filtering, rinse filter cake with dehydrated alcohol, filter cake is dried 8h at 110 DEG C, standby.
Embodiment 2
The solid supported acid of 11.00g m-diaminobenzene. and 11.00g is joined in 200ml water, is stirred at room temperature
30min.In reaction system, it is slowly added to the aqueous solution 50ml containing 27.56g sodium nitrite, the most at room temperature reacts 5h.Cross
Filter, filter cake is by appropriate ethyl acetate rinse.Filtrate is extracted with ethyl acetate, and extract and the ethyl acetate rinsed merge.
At reduced pressure, remove solvent and water, then by A4 molecular sieve drying 2h.Under 30mmHg, decompression distillation, obtains between 8.41g
Benzodiazepines, productivity 75%, purity is more than 99%.
Embodiment 3
The solid supported acid of 11.00g m-diaminobenzene. and 15.00g is joined in 200ml water, is stirred at room temperature
30min.In reaction system, it is slowly added to the aqueous solution 50ml containing 27.56g sodium nitrite, the most at room temperature reacts 5h.Cross
Filter, filter cake is by appropriate ethyl acetate rinse.Filtrate is extracted with ethyl acetate, and extract and the ethyl acetate rinsed merge.
At reduced pressure, remove solvent and water, then by A4 molecular sieve drying 2h.Under 30mmHg, decompression distillation, obtains between 8.96g
Benzodiazepines, productivity 80%, purity is more than 99%.
Embodiment 4
The solid supported acid of 11.00g m-diaminobenzene. and 20.00g is joined in 200ml water, is stirred at room temperature
30min.In reaction system, it is slowly added to the aqueous solution 50ml containing 27.56g sodium nitrite, the most at room temperature reacts 5h.Cross
Filter, filter cake is by appropriate ethyl acetate rinse.Filtrate is extracted with ethyl acetate, and extract and the ethyl acetate rinsed merge.
At reduced pressure, remove solvent and water, then by A4 molecular sieve drying 2h.Under 30mmHg, decompression distillation, obtains between 8.06g
Benzodiazepines, productivity 72%, purity is more than 99%.
Embodiment 5
The solid supported acid of 11.00g m-diaminobenzene. and 15.00g is joined in 200ml water, is stirred at room temperature
30min.In reaction system, it is slowly added to the aqueous solution 50ml containing 14.04g sodium nitrite, the most at room temperature reacts 5h.Cross
Filter, filter cake is by appropriate ethyl acetate rinse.Filtrate is extracted with ethyl acetate, and extract and the ethyl acetate rinsed merge.
At reduced pressure, remove solvent and water, then by A4 molecular sieve drying 2h.Under 30mmHg, decompression distillation, obtains between 7.90g
Benzodiazepines, productivity 70.5%, purity is more than 95%.
Embodiment 6
The solid supported acid of 11.0kg m-diaminobenzene. and 15.0kg is joined in 200L water, is stirred at room temperature 30min.
In reaction system, it is slowly added to the aqueous solution 50L containing 35.1kg sodium nitrite, the most at room temperature reacts 4.5h.Filter, filter
Cake is by appropriate ethyl acetate rinse.Filtrate is extracted with ethyl acetate, and extract and the ethyl acetate rinsed merge.In decompression
Under conditions of, remove solvent and water, then be dried 2h with the drying tower that A4 is molecular sieve filled.Under 30mmHg, decompression distillation, obtains
8.56kg resorcinol, productivity 76.5%, purity is more than 95%.
Embodiment 7
Used solid acid catalyst in Example 3, through pickling, wash, be dried, described in embodiment 3
Method Reusability 10 times, every time at solid acid catalyst with finishing, is both needed to pickling, washing, drying for standby.Tenth secondary response obtains
Resorcinol 8.91g, productivity is 79.5%, and purity is more than 99%.
Claims (3)
1. a synthetic method for resorcinol, comprises raw material, reagent and catalyst dissolution, stirs, reacts, extracts, reduces pressure
Distill to obtain the step of finishing room Benzodiazepines, it is characterised in that with m-diaminobenzene. as raw material, under solid supported acid catalysis, will between
Phenylenediamine and NaNO2Mixed dissolution, stirring reaction hydrolysis, one kettle way generates Resorcino；
Wherein said solid supported acid is sulfuric acid-silica solid acid, wherein resorcinol and NaNO2It is stirred at room temperature anti-
Should.
2. according to the method described in claim 1, it is characterised in that raw material m-diaminobenzene. and the quality that feeds intake of solid supported acid
Proportion is at 1:1-1.8.
3. according to the method described in claim 1, it is characterised in that raw material m-diaminobenzene. and the molar ratio of sodium nitrite
Example scope is at 1:2-5.
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| CN107262150B (en) * | 2017-06-06 | 2018-10-16 | 青岛科技大学 | A kind of preparation method of m-phenylene diamine (MPD) hydrolysis load-type solid acid catalyst |
| CN107285344B (en) * | 2017-07-26 | 2023-07-21 | 沈阳化工研究院有限公司 | Treatment process and device for byproduct mixed waste salt in phenol production process |
| CN109422659B (en) * | 2017-08-23 | 2022-02-11 | 中国石油化工股份有限公司 | Method for preparing m-aminophenol by hydrolyzing m-phenylenediamine |
| CN114591146A (en) * | 2020-12-03 | 2022-06-07 | 中国科学院大连化学物理研究所 | Method for preparing hydroquinone from p-aminophenol |
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| CN103848724B (en) * | 2014-03-18 | 2016-04-13 | 南京工业大学 | The technique of Resorcinol is produced in a kind of mphenylenediamine hydrolysis |
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| 间苯二酚的低污染合成工艺研究;田璇;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20080115(第01期);摘要 * |
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