CN103980113B - A kind of preparation method of 4-bromophthalic acid - Google Patents
A kind of preparation method of 4-bromophthalic acid Download PDFInfo
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- CN103980113B CN103980113B CN201410244731.0A CN201410244731A CN103980113B CN 103980113 B CN103980113 B CN 103980113B CN 201410244731 A CN201410244731 A CN 201410244731A CN 103980113 B CN103980113 B CN 103980113B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/363—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/083—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid anhydrides
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Abstract
The invention discloses a kind of preparation method of 4-bromophthalic acid, the present invention is taking phthalic anhydride, NaOH and sodium bromide as raw material, phthalic anhydride is mixed with NaOH, under ultrasound condition, add aqueous sodium hypochlorite solution to react, control the pH value of reactant liquor simultaneously, obtain target product 4-bromophthalic acid. The 4-bromophthalic acid purity obtaining by the inventive method is greater than 98.5%, and yield is greater than 80%, meets the requirement of environmental protection. The present invention compared with prior art, evade the use of high toxicity, volatile high price bromine, the utilization rate of bromine reaches more than 90%, and recyclable unreacted phthalic acid, meets the requirement of green chemical industry, the present invention carries out under ultrasound condition, selectively good, reaction relaxes easy to control, and yield is high, constant product quality, is suitable for suitability for industrialized production.
Description
Technical field
The present invention relates to a kind of preparation method of 4-bromophthalic acid.
Background technology
4-bromophthalic acid is important chemical intermediate, is widely used in dyestuff, polymer workThe aspects such as industry, the polyurethane using 4-bromophthalic acid as raw material is used in a large number as encapsulating materialIn microelectronic industry. Along with the increase of polyamide and phthalocyanine dye consumption, cause one's own profession in recent yearsThe concern of industry professional to 4-bromophthalic acid.
In prior art, the multiplex bromine (Br of the preparation method of 4-bromophthalic acid2) react,The utilization rate of bromine is low, and remaining bromine easily causes environmental pollution and handling safety hidden danger, and needing increasesEquipment, to reclaim unnecessary bromine, increases operating procedure, and the utilization rate of its bromine atoms is only 40% left sideRight.
In prior art, " fine-chemical intermediate " " Vol.31.No.2, April2001,10-12Reported " the synthetic and application of 4-bromophthalic acid acid anhydride ", it is by disodium phthalate saltThe aqueous solution reacts at 70-75 DEG C with bromine, and then makes reactant mixture acidifying, then uses methyl iso-butyl ketone (MIBK)Extraction obtains the method for 4-bromophthalic acid, but the operation of 4-bromophthalic acid preparation process is numerousThe defects such as the utilization rate of trivial, easy contaminated environment, bromine is low, the at present domestic adjacent benzene two of similar 4-bromo that has noThe preparation method of formic acid.
Summary of the invention
Problem to be solved by this invention is to provide a kind of preparation method of 4-bromophthalic acid,To overcome 4-bromophthalic acid preparation process complex operation in prior art, easy contaminated environment, bromineThe low deficiency of element utilization rate.
Technical conceive of the present invention is such:
The present invention is taking phthalic anhydride, NaOH and sodium bromide as raw material, by phthalic anhydrideSodium hydroxide solution mix with sodium bromide, under ultrasound condition, add aqueous sodium hypochlorite solution to enterRow reacts, and controls the pH value of reactant liquor simultaneously, obtains target product 4-bromophthalic acid.
Technical scheme of the present invention comprises the steps:
In phthalic anhydride and solid sodium hydroxide being dissolved in to pure water successively under ultrasound condition, generateBeginning reactant liquor in room temperature, adds sodium bromide and mixes under stirring in initial action liquid, ultrasonicUnder be warming up to 40-70 DEG C, slowly splash into the aqueous solution of clorox, add watery hydrochloric acid control reaction simultaneouslyThe pH value of liquid is 5-8; Ultrasonic insulation was warming up to 80-90 DEG C after 1-2 hour, continued ultrasonic 1-2 hour,Then reactant liquor is cooled to-5-5 DEG C to ultrasonic processing 0.5-1.0 hour, the 4-bromo obtaining after filtrationO-phthalic acid crude is recrystallized with pure water, obtains 4-bromophthalic acid.
Further, described ultrasound condition refers to that frequency is the ultrasound bath condition of 20-40KHz.
The mass ratio of phthalic anhydride of the present invention and NaOH is: phthalic anhydride:NaOH=1.0:0.26-0.28, g/g.
The mass ratio of phthalic anhydride of the present invention and sodium bromide is: phthalic anhydride: bromineChange sodium=1.0:0.70-0.77, g/g.
The mass ratio of phthalic anhydride of the present invention and clorox is: phthalic anhydride:Clorox=1.0:0.50-0.55, g/g.
In initial action liquid of the present invention, the mass volume ratio of phthalic anhydride and pure water is 1:4-6,g/ml。
It is that the solution of 2-3mol/L adds reaction again that clorox of the present invention is made into concentration with pure waterIn liquid; The concentration of watery hydrochloric acid is 5-10wt%.
The present invention utilizes sodium bromide as brominated reagent, under the condition existing, completes liquor natrii hypochloritisReaction, reaction equation is:
The 4-bromophthalic acid purity obtaining by the inventive method is greater than 98.5%. Yield is greater than80％。
Beneficial effect of the present invention:
For the present invention, inorganic acid cheap and that low toxicity is harmless, alkali, salt are (as NaOH, brominationSodium, clorox, watery hydrochloric acid etc.), make brominated reagent with sodium bromide, evade conventional use bromineBromination process, meet the requirement of environmental protection.
The present invention compared with prior art, has evaded the use of high toxicity, volatile high price bromine,The utilization rate of bromine reaches more than 90%, and in reaction, unreacted phthalic anhydride can phthalic acidForm reclaim, greatly reduce the processing intensity of environmental protection COD.
Preparation method of the present invention is selectively good, and under ultrasound condition, reaction relaxes easy to control, yieldHeight, constant product quality, is suitable for suitability for industrialized production.
Detailed description of the invention
Below by specific embodiment, the present invention is described further, but embodiment does not limit thisThe protection domain of invention.
Embodiment 1
148g phthalic anhydride, 40g NaOH are slowly added successively under ultrasonic in 690g water,Be placed in the 2000ml four-hole reaction bulb with condenser pipe, thermometer, then add 106g sodium bromide,Ultrasonic mixing. Be heated to 55 DEG C, the ultrasonic lower aqueous solution (concentration slowly splashing into containing 77g cloroxFor 2mol/L), regulate pH value between 5-8 with 5wt% watery hydrochloric acid simultaneously. Feed intake complete, insulation 1Hour, be then warming up to 80 DEG C of reactions 2 hours. Be cooled to 2 DEG C, ultrasonic lower processing 0.5 hour, quietPut, filter, obtain crude product 236.2g (HPLC purity is 92%).
Crude product obtains 198.3g4-bromophthalic acid with pure water recrystallization, and HPLC detection level is98.9%, yield is 81%.
Filtrate adds hydrochloric acid and is acidified to pH2 left and right, cooling, reclaims unreacted phthalic acid.
Embodiment 2
100g phthalic anhydride, 26g NaOH are slowly added successively under ultrasonic in 600g water,Be placed in the 1000ml four-hole reaction bulb with condenser pipe, thermometer, then add 77g sodium bromide,Ultrasonic mixing. Be heated to 65 DEG C, the ultrasonic lower aqueous solution (concentration slowly splashing into containing 50g cloroxFor 3mol/L), regulate pH value between 5-8 with 10wt% watery hydrochloric acid simultaneously. Feed intake complete, insulation 2Hour, be then warming up to 90 DEG C of reactions 1 hour. Be cooled to-2 DEG C, ultrasonic lower processing 1 hour, quietPut, filter, obtain crude product 161.5g (HPLC purity is 93%).
Crude product obtains 137.3g4-bromophthalic acid with pure water recrystallization, and HPLC detection level is98.6%, yield is 83%.
Filtrate adds hydrochloric acid and is acidified to pH2 left and right, cooling, reclaims unreacted phthalic acid.
It should be noted that, above embodiment is only unrestricted in order to technical scheme of the present invention to be described.Although the present invention is had been described in detail with reference to preferred embodiment, those of ordinary skill in the art shouldWork as understanding, can modify or be equal to replacement the technical scheme of invention, and not depart from the present inventionThe scope of technical scheme, it all should be encompassed in claim scope of the present invention.
Claims (7)
1. a preparation method for 4-bromophthalic acid, is characterized in that, comprises the steps:Under ultrasound condition, phthalic anhydride and solid sodium hydroxide are dissolved in successively in pure water, generate initialReactant liquor in room temperature, adds sodium bromide and mixes under stirring in initial action liquid, superUnder sound, be warming up to 40-70 DEG C, splash into the aqueous solution of clorox, add watery hydrochloric acid control anti-simultaneouslyThe pH value of answering liquid is 5-8; Ultrasonic insulation was warming up to 80-90 DEG C after 1-2 hour, continued ultrasonic1-2 hour, is then cooled to reactant liquor-5-5 DEG C, ultrasonic processing 0.5-1.0 hour, after filtrationObtain 4-bromophthalic acid crude product, be recrystallized with pure water, obtain the adjacent benzene two of 4-bromoFormic acid.
2. preparation method according to claim 1, is characterized in that, described ultrasound condition refers toFrequency is the ultrasound bath condition of 20-40KHz.
3. preparation method according to claim 1, is characterized in that, described phthalic anhydrideWith the mass ratio of NaOH be: phthalic anhydride: NaOH=1.0:0.26-0.28, g/g.
4. preparation method according to claim 1, is characterized in that, described phthalic anhydrideWith the mass ratio of sodium bromide be: phthalic anhydride: sodium bromide=1.0:0.70-0.77, g/g.
5. preparation method according to claim 1, is characterized in that, described phthalic anhydrideWith the mass ratio of clorox be: phthalic anhydride: clorox=1.0:0.50-0.55, g/g.
6. preparation method according to claim 1, is characterized in that, adjacent in described initial action liquidThe mass volume ratio of phthalate anhydride and pure water is 1:4-6, g/mL.
7. preparation method according to claim 1, is characterized in that, described clorox water-solubleLiquid is that clorox pure water is made into the solution that concentration is 2-3mol/L; The concentration of watery hydrochloric acid is5-10wt％。
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105315135A (en) * | 2015-06-23 | 2016-02-10 | 国药集团化学试剂有限公司 | 2-bromine-4-tert-butylphenol preparing method |
| CN105315127B (en) * | 2015-07-02 | 2017-10-27 | 国药集团化学试剂有限公司 | A kind of preparation method of 4 tert-butyl group bromobenzyl |
| CN106397185B (en) * | 2015-07-29 | 2020-11-10 | 国药集团化学试剂有限公司 | Environment-friendly preparation method of m-bromobenzoic acid |
| CN106432037B (en) * | 2015-08-05 | 2021-04-20 | 国药集团化学试剂有限公司 | Pollution-free preparation method of N-bromosuccinimide |
| CN105111153B (en) * | 2015-08-11 | 2019-09-24 | 绍兴文理学院 | A kind of preparation method of 5-bromouracil |
| CN105483750B (en) * | 2015-11-27 | 2017-09-12 | 北京工业大学 | The method that phthalylhydrazine electrochemical oxidation prepares phthalic acid |
| CN108947763A (en) * | 2018-08-07 | 2018-12-07 | 国药集团化学试剂有限公司 | A kind of preparation method of 3,4,5- trifluorobromobenzene |
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| US2028383A (en) * | 1933-06-12 | 1936-01-21 | Monsanto Chemicals | Chlorination of phthalic anhydride |
| US2211465A (en) * | 1939-09-22 | 1940-08-13 | Max Factor & Co | Manufacture of brominated phthalic acid |
| US3160653A (en) * | 1959-08-22 | 1964-12-08 | Bergwerksverband Gmbh | Method of producing benzene ring-halogenated aromatic hydrocarbons |
| CN87106482A (en) * | 1986-09-19 | 1988-03-30 | 拜尔公司 | Process for preparing benzoic acid derivatives |
| CN1431990A (en) * | 2000-06-05 | 2003-07-23 | 日产化学工业株式会社 | Process for prepn. of bromoisophthalic acid compounds |
| CN101671272A (en) * | 2009-07-15 | 2010-03-17 | 杭州吉华江东化工有限公司 | Synthetic method of 2-cyanogroup-4-nitro-6-bromaniline diazosalt |
| CN101671266A (en) * | 2009-07-15 | 2010-03-17 | 杭州吉华江东化工有限公司 | Synthetic method of 2,6-dibromo-4-nitroaniline diazosalt |
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- 2014-06-04 CN CN201410244731.0A patent/CN103980113B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2028383A (en) * | 1933-06-12 | 1936-01-21 | Monsanto Chemicals | Chlorination of phthalic anhydride |
| US2211465A (en) * | 1939-09-22 | 1940-08-13 | Max Factor & Co | Manufacture of brominated phthalic acid |
| US3160653A (en) * | 1959-08-22 | 1964-12-08 | Bergwerksverband Gmbh | Method of producing benzene ring-halogenated aromatic hydrocarbons |
| CN87106482A (en) * | 1986-09-19 | 1988-03-30 | 拜尔公司 | Process for preparing benzoic acid derivatives |
| CN1431990A (en) * | 2000-06-05 | 2003-07-23 | 日产化学工业株式会社 | Process for prepn. of bromoisophthalic acid compounds |
| CN101671272A (en) * | 2009-07-15 | 2010-03-17 | 杭州吉华江东化工有限公司 | Synthetic method of 2-cyanogroup-4-nitro-6-bromaniline diazosalt |
| CN101671266A (en) * | 2009-07-15 | 2010-03-17 | 杭州吉华江东化工有限公司 | Synthetic method of 2,6-dibromo-4-nitroaniline diazosalt |
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