CN1199930C - 3-Br-4-hydroxybenzaldehyde preparation - Google Patents
3-Br-4-hydroxybenzaldehyde preparation Download PDFInfo
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- CN1199930C CN1199930C CN 01127357 CN01127357A CN1199930C CN 1199930 C CN1199930 C CN 1199930C CN 01127357 CN01127357 CN 01127357 CN 01127357 A CN01127357 A CN 01127357A CN 1199930 C CN1199930 C CN 1199930C
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Abstract
The present invention relates to a method for preparing 3-bromine-4-hydroxy benzaldehyde, which is characterized in that 1 share of PHB, 9 to 20 shares of chloromethane solvent, 0 to 3 shares of cosolvent and 1.2 to 1.8 shares of bromine are collected to carry out bromination reaction at a temperature between 0 and 60 DEGC, then the solvents are recovered by carrying out treatment according to a specific process, and finished products of 3-bromine-4-hydroxy benzaldehyde can be obtained by carrying out treatment according to a conventional method finally. Additionally, the present invention overcomes the defect of high production cost in the prior art and has the advantages of less consumption of solvents, convenient recovery, simple device and convenience of realizing industrialization, and the present invention can be used for recovering bromide from mother liquid.
Description
One, technical field
The invention belongs to the Technology field of preparation 3-bromo-4-hydroxy benzaldehyde.
Two, background technology
3-bromo-4-hydroxy benzaldehyde (hereinafter to be referred as-bromal) be a kind of fine-chemical intermediate.At present, the comparatively advanced method of preparation-bromal is to make through bromination reaction for raw material with p-Hydroxybenzaldehyde (hereinafter to be referred as PHB).This technology introduced in the articles such as " synthesizing of 3-bromo-4-hydroxy benzaldehyde " of " Jiization science and technology " second phase in 1999 publication.By above-mentioned article as can be known the key step of this technology be: with CHCl
3For solvent (adding an amount of solubility promoter sometimes) makes the PHB dissolving, add bromine again and make its bromination.Bromination finishes the back and removes solvent under reduced pressure and reclaim under 0.093MPa and 40 ℃ of conditions, and raffinate is that solvent carries out Crystallization Separation and obtains a bromal again with water.The major defect of this technology is: (1) solvent load is big.The applicant simulates above-mentioned document in the laboratory during a synthetic bromal, and when finding to remove solvent under reduced pressure under the condition of 40 ℃ and 0.093MPa, solvent recovering yield is about 75%.By its rate of recovery is 80% calculating, produces 17.1gPHB and need consume CHCl
370ml (103.6g) promptly prepares one ton of one bromal and need consume solvent and reach 6 tons more than, and the solvent expense is higher.(2) solvent recuperation inconvenience.Because contain HBr and bromine in the solvent, during underpressure distillation, HBr and bromine and solvent steam together, so whole recovery equipment must use anti-HBr and bromine corrosive glass equipment and enamel equipment; And produced the secondary pollution waste water that contains methyl chloride when washing the tail gas of vacuum system with water, need handle the emission standard that just can reach regulation especially.These all are that industrial production has been brought inconvenience.Because above two aspects have limited this method in industrial application.
Three, summary of the invention
The novel process that the purpose of this invention is to provide a kind of preparation one bromal, solvent recovering rate height during with this prepared one bromal, solvent consumption is low, and convenient solvent reclaiming is convenient to realize suitability for industrialized production.
To achieve these goals, the technical scheme of the application's proposition is to prepare according to the following steps-bromal:
A. add the PHB of 1 weight part in bromination reactor, the bromine of the methyl chloride solvent of 9-20 weight part, the solubility promoter of 0-3 weight part, 1.2-1.8 weight part carries out bromination reaction under 0-60 ℃;
B. after bromination reaction is finished, in finishing liquid, add the PH=6 of 30% liquid caustic soda solution regulator solution earlier, and then add the water of 10-20 weight part;
C. solution is heated distillating recovering solvent, recovered solvent adds dewatering agent to carry out carrying out second distillation after the processed, and the solvent that obtains can supply the usefulness of bromination once more.
Said methyl chloride kind solvent refers to CHCl in the above-mentioned A step
3Or CCl
4, solubility promoter is an ethyl acetate; Said alkaline solution is meant NaOH solution or Na in the B step
2CO
3Solution; Said dewatering agent is anhydrous CaCl in the C step
2Or Sodium sulfate anhydrous.min(99).
Steaming enters the Crystallization Separation operation except the solution of solvent.An amount of water of adding is heated to and boils in solution, and the heat filter gets crude product 3, and 5-two bromo-, 4 hydroxy benzaldehydes and filtrate, filtrate place cold water cooling, the crystallization and filtration under the room temperature to get crude product one bromal.In crude product one bromal, add proper amount of deionized water and carry out recrystallization, get a white bromal crystallization, promptly get a bromal finished product after the drying.
When making a bromal by above-mentioned steps, but also by-product is a small amount of 3,5-two bromo-4-hydroxy benzaldehydes (hereinafter to be referred as two bromals).
Use prepared one bromal of the present invention, after liquid is finished in the neutralization of adding alkaline solution, utilize solvent and water to form constant boiling mixture and moisture less these characteristics, adopt the distillatory mode to reclaim solvent.Recovered solvent is through adding the anhydrous CaCl of dewatering agent
2Carry out the distillation second time after dewatering again, resulting solvent promptly can be used for the secondary bromination reaction.Used dewatering agent carries out also can reusing after the drying, and the form that the bromide that is contained in the bromal primary crystallization mother liquor then can bromine reclaims.This shows that the present invention has overcome the high shortcoming of production cost in the prior art, solvent-oil ratio is little, and it is convenient to reclaim, and is convenient to realize suitability for industrialized production.Specifically, the present invention mainly contains following advantage and positively effect:
1, can make the consumption of solvent be reduced to total input amount 5% within, the solvent-oil ratio of a bromal per ton is about 0.6 ton, thereby the manufacturing cost of a bromal is reduced greatly.
2, the recyclable bromine of making of bromides such as NaBr that a bromal primary crystallization mother liquor contains in the production process has further reduced the production cost of a bromal.
The secondary pollution waste water that contains methyl chloride that has produced because of washing process when 3, having eliminated vacuum distillation recovered solvent in the prior art.
4, the equipment of recovery solvent is simpler, and material is not had particular requirement.These all are that the industrial production of a bromal has been created condition.
Embodiment
Embodiment 1:
A. in the bromination reactor that agitator, reflux exchanger, thermometer and dropping funnel are housed, add 122gPHB and 1350mlCHCl
3, under stirring PHB is dissolved gradually.The 208g bromine is dissolved in 150mlCHCl
3In.Slowly add this solution in the reactor then and keep temperature of reaction below 10 ℃.Added behind the bromine earlier in 10-25 ℃ bromination reaction 3 hours, and heated up then and continued bromination reaction 6 hours down at 40-45 ℃.After bromination reaction is finished, add 30% liquid caustic soda and regulate bromination and finish liquid and make its PH-6, add entry 2000ml, heated solution is to boiling, and the fraction of collecting boiling point and being below 60 ℃ is standby.
Add entry 3000ml in reactor, continue cooked solution to boiling, filtered while hot gets filtrate I and filter residue I.Cool off in the filtrate I water at room temperature, separate out crystallization.Filter, get a mother liquor I and a bromal crude product.Add the 5000ml deionized water to this crude product, heated solution is to 85-90 ℃, and filtered while hot gets filtrate II and filter residue II.Cool off in the filtrate II water at room temperature, separate out crystallization, filter a mother liquor II and a bromal crystallization.This crystal is carried out drying and get a white bromal crystallization 166g under 70 ℃, fusing point 124-126 ℃, yield 82.6%.Filter residue I and filter residue II are merged, add 1500ml mother liquor II, boil, filter, get mother liquor III and filter residue III.Filter residue III is carried out the dry faint yellow two bromal 23.5g of getting, fusing point 182-184 ℃, yield 8.4% under 110-120 ℃.
With the anhydrous CaCl of fraction under collect 60 ℃
2Dehydration, the CHCl after the dehydration
3It is 58-62 ℃ CHCl that reheat distillation can obtain boiling point
31460ml can be for the usefulness of next bromination.A spot of boiling point carries out processed in the recovered solvent after the fraction below 58 ℃ is then incorporated the bromination second time into.
Mother liquor I behind the primary crystallization is multiplexing to send to the recovery bromine after once.Mother liquor II and mother liquor III merge the back to be used as handling when bromination is finished liquid for the second time.
B. in bromination reactor, drop into the CHCl that 122gPHB and 1350ml reclaim
3Solvent, stirring and dissolving.The 208g bromine is dissolved in the CHCl that 150ml reclaims
3In, by the technology described in the above-mentioned A example carry out bromination reaction again through neutralization, add water, distill, boil, filtration, recrystallization and a white bromal 166g (fusing point 124-126 ℃), yield 82.6%; Fusing point is 182 ℃ two bromal 24g, yield 8.6%.Also obtain boiling range simultaneously and be 58-62 ℃ recovery CHCl
31465ml can supply the usefulness of bromination once more.
Embodiment 2:
A. in bromination reactor, add 122gPHB and 1350mlCHCl
3, stirring and dissolving.The 176g bromine is dissolved in 150mlCHCl
3In, add this bromine solution in the reactor at leisure then and maintain the temperature at below 10 ℃.Adding heats up behind the bromine makes it 40-45 ℃ of following bromination reaction 8 hours.Handle according to the technology identical with embodiment 1A after bromination reaction is finished, obtain fusing point and be white-bromal 162.8g of 124-126 ℃, yield 81% is paid simultaneously and is produced two bromal 1g (182 ℃ of fusing points) yield 0.36%, also obtains the CHCl that reclaims
31456ml can be for the usefulness of secondary bromination.
B. in reactor, add the CHCl that 122gPHB and 1350ml reclaim
3, stirring and dissolving.The 176g bromine is dissolved in 150mlCHCl
3In.Carry out bromination reaction by the technology identical with above-mentioned 1A, reclaiming and obtaining fusing point after solvent and the Crystallization Separation is 124-126 ℃ white one bromal 163.2g, yield 81.2%; Fusing point is 182 ℃ two bromal 2g, yield 0.71%; Reclaim CHCl simultaneously
3Solvent 1450ml can supply the usefulness of bromination once more.
Embodiment 3:
A. in reactor, add PHB122g, CHCl
31000ml, ethyl acetate 250ml, stirring and dissolving is to 150ml CHCl
3In add bromine 192g, slowly add this bromine solutions in the reactor then and keep temperature of reaction below 15 ℃.Heat up gradually after adding bromine, reacted 8 hours down at 20-25 ℃.After bromination reaction is finished, add 30% liquid caustic soda and regulate the PH=6 that bromination is finished liquid, add the 2000ml deionized water then.Add thermal distillation.Collect 55-62 ℃ fraction earlier, regather 68-72 ℃ fraction and place standby respectively.In reactor, add entry 3000ml again, boil by the technology identical with embodiment 1A, heat filter, cooling, crystallization is filtered, and recrystallization obtains fusing point and is 124-126 ℃ white one bromal crystallization 152.8g, yield 76%; Fusing point is 182 ℃ faint yellow two bromal crystallization 28g, yield 10%.
With the boiling point of collecting different two kinds of solvents carry out processed respectively.Solvent after the dehydration carries out second distillation and obtains 1110ml CHCl respectively
3And the 245ml ethyl acetate, can supply the usefulness of bromination once more.
B. the CHCl that in reactor, adds PHB122g and recovery
3The ethyl acetate 250ml of 1000ml and recovery, stirring and dissolving.Reclaim CHCl to 150ml then
3The middle bromine 192g that adds slowly adds this bromine solutions in the reactor.According to obtaining fusing point with above-mentioned A step identical operations is 124-126 ℃ white one bromal crystal 152g, and yield 75.6%, fusing point are 182 ℃ two bromal crystal 3 1g, yield 11.1%.Also recyclable simultaneously CHCl
31115ml, ethyl acetate 245ml can supply the usefulness of bromination once more.
Embodiment 4:
A. in reactor, add PHB122g, CCl
41000ml and ethyl acetate 250ml stir, and PHB is dissolved gradually.The 200g bromine is dissolved in 250mlCCl
4In, slowly add bromine solution in the reactor then and the temperature that keeps reaction system below 18 ℃, add and heat up behind the bromine and maintain the temperature at 20-25 ℃ of reaction 8 hours down.Add 30% liquid caustic soda after bromination reaction is finished and make its PH=6, add water 2000ml, add thermal distillation.Collect the fraction below 68 ℃ earlier, regather 68-72 ℃ fraction and place standby respectively.
Add entry 3000ml again in reactor, be heated to and boil, filtered while hot is carried out Crystallization Separation and is got-bromal 156.8g yield 78%, (fusing point 124-126 ℃) by the technology identical with embodiment 1A; Pay and produce two bromal 15.7g, yield 5.6% (182 ℃ of fusing points).
Recovered solvent is used anhydrous CaCl respectively
2Processed is distilled respectively at last again, can obtain 1225mlCCl
4And the 245ml ethyl acetate, can be for the usefulness of next bromination.
B. feeding intake by the technology identical with above-mentioned 4A, to carry out second time bromination synthetic again, then can obtain a bromal 155g (fusing point 124-126 ℃), yield 77.1%; Two bromal 17g (182 ℃ of fusing points), yield 6.1%.Reclaim solvent C Cl
41226ml, ethyl acetate 245ml, the bromination that can be used for next round is synthetic.
Claims (4)
1. the preparation method of 3-bromo-4 hydroxy benzaldehydes comprises bromination reaction, and three operations of solvent recuperation and Crystallization Separation is characterized in that:
A. add 1 weight part p-Hydroxybenzaldehyde, 9-20 weight part methyl chloride solvent, 0-3 weight part solubility promoter in bromination reactor, 1.2-1.8 weight part bromine carries out bromination reaction under 0-60 ℃ temperature;
B. after bromination reaction is finished, in finishing liquid, add earlier the PH=6 of q.s alkaline solution regulator solution, and the content that makes water in the solution is 10 of the 3-bromo-4 hydroxy benzaldehyde weight that generate---15 times;
C. solution is heated distillating recovering solvent.Add dewatering agent in the recovered solvent and carry out carrying out second distillation again after the processed, the solvent that obtains can supply the usefulness of bromination once more.
2. according to the preparation method of the described 3-bromo-of claim 1 4-hydroxy benzaldehyde, it is characterized in that used methyl chloride solvent is CHCl
3Or CCl
4, solubility promoter is an ethyl acetate.
3. according to the preparation method of claim 1 or 2 described 3-bromo-4 hydroxy benzaldehydes, it is characterized in that said alkaline solution is NaOH solution or Na in the B step
2CO
3Solution.
4. according to the preparation method of claim 1 or 2 described 3-bromo-4 hydroxy benzaldehydes, it is characterized in that the dewatering agent in the C step is anhydrous CaCl
2Or Sodium sulfate anhydrous.min(99).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01127357 CN1199930C (en) | 2001-08-28 | 2001-08-28 | 3-Br-4-hydroxybenzaldehyde preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01127357 CN1199930C (en) | 2001-08-28 | 2001-08-28 | 3-Br-4-hydroxybenzaldehyde preparation |
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| Publication Number | Publication Date |
|---|---|
| CN1406918A CN1406918A (en) | 2003-04-02 |
| CN1199930C true CN1199930C (en) | 2005-05-04 |
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|---|---|---|---|
| CN 01127357 Expired - Fee Related CN1199930C (en) | 2001-08-28 | 2001-08-28 | 3-Br-4-hydroxybenzaldehyde preparation |
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| CN107382686A (en) * | 2017-07-19 | 2017-11-24 | 毕佳 | A kind of circulation preparation method of the hydroxy benzaldehyde of 3 bromine 4 |
| CN110746281B (en) * | 2019-10-23 | 2022-05-03 | 浙江新和成股份有限公司 | Preparation method of 3-bromo-4-hydroxybenzaldehyde |
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Address after: Dongfeng East Weifang University dormitory 261061 Shandong city of Weifang province (the big garden) No. 10 East unit area C Room 201 Patentee after: Qiu Guorong Address before: 261041 Adult Education College, Weifang University, 254 Shengli East Street, Kuiwei, Shandong, Weifang Patentee before: Qiu Guorong |
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