CN105646176A - Preparation method of 4,5-dibromophthalic acid - Google Patents
Preparation method of 4,5-dibromophthalic acid Download PDFInfo
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- CN105646176A CN105646176A CN201610001336.9A CN201610001336A CN105646176A CN 105646176 A CN105646176 A CN 105646176A CN 201610001336 A CN201610001336 A CN 201610001336A CN 105646176 A CN105646176 A CN 105646176A
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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
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D237/00—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings
- C07D237/26—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings condensed with carbocyclic rings or ring systems
- C07D237/30—Phthalazines
- C07D237/32—Phthalazines with oxygen atoms directly attached to carbon atoms of the nitrogen-containing ring
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Abstract
The invention discloses a preparation method of 4,5-dibromophthalic acid. The preparation method comprises the following steps: (1) after dissolving phthalylhydrazine into glacial acetic acid, adding N-bromo-succinimide (NBS), heating the mixture to 80 to 100 DEG C and reacting for 0.5 to 1 hour; after the reaction is finished, cooling the system to a room temperature and pouring the mixture into ice water; separating out solids and filtering to obtain dibromophthalhydrazide and filtrate; (2) dissolving the dibromophthalhydrazide into a sodium hydroxide water solution, and heating the mixture to 60 to 70 DEG C and carrying out a hydrolysis reaction; after the hydrolysis reaction is finished, adjusting the pH of the hydrolysis reaction system to be 6 to 7; separating out white solids, and filtering and washing with water to prepare the 4,5-dibromophthalic acid. The preparation method of the 4,5-dibromophthalic acid has the advantages that the cost is low; products of two steps are both separated out in a solid manner; reaction is easy to treat and the purity of the products is high; industrial requirements on the products can be met completely, and sufficient raw materials are provided for research and development of downstream chemical products and materials.
Description
Technical field
The invention belongs to synthetic organic chemical art, it is specifically related to the preparation method of a kind of 4,5-bis-phthalate bromine.
Background technology
O-phthalic acid compounds is excellent metal ligand and valuable organic intermediate, and be the important source material of synthetic phthalocyanine compound, phthalocyanine has big pi-conjugated aroma system, have a wide range of applications in fields such as sensor, the treatment of cancer fluorescence, dyestuff, optical recording, electrochromic intelligent material and solar photovoltaic devices, especially two phthalate bromines are the raw materials that synthetic bromide is needed badly for phthalocyanine-like compound, but 4,5-bis-phthalate bromine is being sold without batch on the market substantially, the synthetic method reported mostly is early literatures (Chem.Ber.1884, 17:2494-2496; J.Chem.Soc.,1952, 4615-4618; J.Amer.Chem.Soc.,1942, 64:2639-2641), many employing nitric acid is oxidized at high temperature 170 DEG C, and method falls behind, and it is unfavorable for environmental protection. Next has is that raw material sulfuric acid and bromine element are at high temperature prepared taking acid phthalic anhydride, there is severe corrosive and environmental issue equally, and these method receipts rates are low, pollutes big, not easily operates, cannot adapt to the batch demand of modern material already.
4,5-bis-phthalate bromine is seldom produced on the market, and expensive, has important purposes, the especially important source material of synthetic phthalocyanine compounds in prepared by coordination chemistry and functional materials. Therefore the batch of 4,5-bis-phthalate bromine, cheapness, easy preparation method have important value.
Summary of the invention
It is an object of the invention to provide the preparation method of a kind of 4,5-bis-phthalate bromine, this preparation method is simple, easily operation, pollution-free and cost is low, can prepare in batches, is applicable to suitability for industrialized production.
For achieving the above object, the present invention is by the following technical solutions:
A preparation method for 4,5-bis-phthalate bromine, step is as follows:
The synthesis of (1) two bromine Phthalocyclohydrazide: after Phthalocyclohydrazide is dissolved in glacial acetic acid, add N-bromine for succimide (NBS), it is heated to 80 ~ 100 DEG C of reactions 0.5 ~ 1 hour, system is cooled to after having reacted room temperature then pour in frozen water, precipitate out solid, filter and obtain two bromine Phthalocyclohydrazide and filtrates;
(2) 4, the synthesis of 5-bis-phthalate bromine: two bromine Phthalocyclohydrazides are dissolved in aqueous sodium hydroxide solution, it is heated to 60 ~ 70 DEG C of reactions 1 ~ 2 hour that are hydrolyzed, after hydrolysis reaction terminates, the pH regulating hydrolysis reaction system is 6 ~ 7, precipitating out white solid, filtration, washing obtain 4,5-bis-phthalate bromine.
In described step (1), Phthalocyclohydrazide is 2.1:1 ~ 2.2:1 with the ratio of the amount of substance of NBS.
The concentration of the aqueous sodium hydroxide solution in described step (2) is 10mol/L.
In described step (2), in the amount of substance of sodium hydroxide and step (1), the ratio of the amount of substance of Phthalocyclohydrazide is 2.5:1 ~ 3:1.
Washing in described step (2) adopts the water of 0 DEG C.
Synthesis syntheti c route of the present invention is as follows:
Described step (2) regulate the pH of hydrolysis reaction system to be 6 ~ 7 with the filtrate in step (1).
The useful effect of the present invention: the 4 of (1) the present invention, the preparation method of 5-bis-phthalate bromine cheapness is easy, taking the industry byproduct Phthalocyclohydrazide of cheapness as main raw material (market price is about per kilogram 30 yuan), in glacial acetic acid solution, prepare 4,5-bis-phthalate bromine with NBS, this method receipts rate can reach 97%, product purity reaches 99%, purity height, with low cost, it is easy to operation, can large-batch industrial prepare; (2) the gentle bromizating agent NBS that present method adopts, the spent acid that simultaneous reactions produces and salkali waste just neutralize utilization, and having prepared rear wastewater pH is neutral substantially, decreases the environmental issue of sewage discharge; (3) the present invention provides that this kind of method steps is few, receipts rate height, is a kind of rare way being applicable to big batch preparation, can meet the industrial requirement of this series products completely, for downstream Chemicals and investigation of materials exploitation provide sufficient raw material.
Embodiment
Embodiment 1
The preparation method of 4,5-bis-phthalate bromine of the present embodiment, step is as follows:
The synthesis of (1) two bromine Phthalocyclohydrazide: add 16.20g Phthalocyclohydrazide in the 250mL tri-mouthfuls of round-bottomed flasks with reflux condensing tube, then 100mL glacial acetic acid is poured into, adopt mechanical stirring, after solid all dissolves, add 37.94gNBS wherein, this process has a little heat and releases. After system is stable, opening heating, temperature control 85 DEG C, along with the carrying out of reaction, the color of solution is deepened gradually, turns into yellow gradually from faint yellow. After reaction 1h, reaction solution is cooled, then pours in frozen water, after ice melts, the solid of precipitation is taken out filter, obtains white solid. By drying, claiming its dried quality to be 31.8g, its receipts rate is 99%
(2) 4, the synthesis of 5-bis-phthalate bromine: solid two bromine Phthalocyclohydrazide 31.8g step (1) obtained is dissolved in 10mol/L aqueous sodium hydroxide solution 300 milliliters, then it is heated to 65 DEG C, reacts after 2 hours, cooling, then regulate pH to being 6 with the filtrate of previous step, precipitating out a large amount of white solid, filter, frozen water washs, 31.7g, receipts rate 98% is obtained after dry.
HPLC:98.22% (214nm), 99.12% (254nm). LC-MS:m/z (%): 324.9;1HNMR(400MHz,D2O): 8.07 (s, 1H). Ultimate analysis C10H9NO3S theoretical value (%): C, 29.66; H, 1.24; Br, 49.34; Observed value: C, 29.75; H, 1.12; Br, 49.37
Embodiment 2
The preparation method of 4,5-bis-phthalate bromine of the present embodiment, step is as follows:
The synthesis of (1) two bromine Phthalocyclohydrazide: add 16.20g Phthalocyclohydrazide in the 250mL tri-mouthfuls of round-bottomed flasks with reflux condensing tube, then 100mL glacial acetic acid is poured into, adopt mechanical stirring, after solid all dissolves, add 35.6gNBS wherein, this process has a little heat and releases. After system is stable, opening heating, temperature control 85 DEG C, along with the carrying out of reaction, the color of solution is deepened gradually, turns into yellow gradually from faint yellow. After reaction 1h, reaction solution is cooled, then pours in frozen water, after ice melts, the solid of precipitation is taken out filter, obtains white solid. By drying, claiming its dried quality to be 30g, its receipts rate is 94%;
(2) synthesis of 4,5-bis-phthalate bromine: solid two bromine Phthalocyclohydrazide that step (1) is obtained (1) 30g is dissolved in 10mol/L aqueous sodium hydroxide solution 300 milliliters, is then heated to 65 DEG C, reacts after 2 hours, cooling, then regulates pH to being 6 with the filtrate of previous step, precipitates out a large amount of white solid, filter, frozen water washs, after dry 29.8g, receipts rate 98%.
Embodiment 3
The preparation method of 4,5-bis-phthalate bromine of the present embodiment, step is as follows:
The synthesis of (1) two bromine Phthalocyclohydrazide: add 16.20g Phthalocyclohydrazide in the 250mL tri-mouthfuls of round-bottomed flasks with reflux condensing tube, then 100mL glacial acetic acid is poured into, adopt mechanical stirring, after solid all dissolves, add 37.94gNBS wherein, this process has a little heat and releases. After system is stable, opening heating, temperature control 85 DEG C, along with the carrying out of reaction, the color of solution is deepened gradually, turns into yellow gradually from faint yellow. After reaction 0.5h, reaction solution is cooled, then pours in frozen water, after ice melts, the solid of precipitation is taken out filter, obtains white solid. By drying, claiming its dried quality to be 28.8g, its receipts rate is 90%;
(2) 4, the synthesis of 5-bis-phthalate bromine: solid two bromine Phthalocyclohydrazide 28.8g step (1) obtained is dissolved in 10mol/L aqueous sodium hydroxide solution 300 milliliters, then it is heated to 65 DEG C, reacts after 2 hours, cooling, then regulate pH to being 6 with the filtrate of previous step, precipitating out a large amount of white solid, filter, frozen water washs, 28.6g, receipts rate 98% is obtained after dry.
Embodiment 4
The preparation method of 4,5-bis-phthalate bromine of the present embodiment, step is as follows:
The synthesis of (1) two bromine Phthalocyclohydrazide: add 16.20g Phthalocyclohydrazide in the 250mL tri-mouthfuls of round-bottomed flasks with reflux condensing tube, then 100mL glacial acetic acid is poured into, adopt mechanical stirring, after solid all dissolves, add 37.94gNBS wherein, this process has a little heat and releases. After system is stable, opening heating, temperature control 80 DEG C, along with the carrying out of reaction, the color of solution is deepened gradually, turns into yellow gradually from faint yellow. After reaction 1h, reaction solution is cooled, then pours in frozen water, after ice melts, the solid of precipitation is taken out filter, obtains white solid. By drying, claiming its dried quality to be 30.7g, its receipts rate is 96%;
(2) 4, the synthesis of 5-bis-phthalate bromine: solid two bromine Phthalocyclohydrazide 30.7g step (1) obtained is dissolved in 10mol/L aqueous sodium hydroxide solution 300 milliliters, then it is heated to 65 DEG C, reacts after 2 hours, cooling, then regulate pH to being 6 with the filtrate of previous step, precipitating out a large amount of white solid, filter, frozen water washs, 30.5g, receipts rate 98% is obtained after dry.
Embodiment 5
The preparation method of 4,5-bis-phthalate bromine of the present embodiment, step is as follows:
The synthesis of (1) two bromine Phthalocyclohydrazide: add 16.20g Phthalocyclohydrazide in the 250mL tri-mouthfuls of round-bottomed flasks with reflux condensing tube, then 100mL glacial acetic acid is poured into, adopt mechanical stirring, after solid all dissolves, add 37.94gNBS wherein, this process has a little heat and releases. After system is stable, opening heating, temperature control 100 DEG C, along with the carrying out of reaction, the color of solution is deepened gradually, turns into yellow gradually from faint yellow. After reaction 1h, reaction solution is cooled, then pours in frozen water, after ice melts, the solid of precipitation is taken out filter, obtains white solid. By drying, claiming its dried quality to be 30.1g, its receipts rate is 94%;
(2) 4, the synthesis of 5-bis-phthalate bromine: solid two bromine Phthalocyclohydrazide 30.1g step (1) obtained is dissolved in 10mol/L aqueous sodium hydroxide solution 300 milliliters, then it is heated to 65 DEG C, reacts after 2 hours, cooling, then regulate pH to being 6 with the filtrate of previous step, precipitating out a large amount of white solid, filter, frozen water washs, 29.8g, receipts rate 98% is obtained after dry.
Embodiment 6
The preparation method of 4,5-bis-phthalate bromine of the present embodiment, step is as follows:
The synthesis of (1) two bromine Phthalocyclohydrazide: add 16.20g Phthalocyclohydrazide in the 250mL tri-mouthfuls of round-bottomed flasks with reflux condensing tube, then 100mL glacial acetic acid is poured into, adopt mechanical stirring, after solid all dissolves, add 37.94gNBS wherein, this process has a little heat and releases. After system is stable, opening heating, temperature control 85 DEG C, along with the carrying out of reaction, the color of solution is deepened gradually, turns into yellow gradually from faint yellow. After reaction 1h, reaction solution is cooled, then pours in frozen water, after ice melts, the solid of precipitation is taken out filter, obtains white solid. By drying, claiming its dried quality to be 31.8g, its receipts rate is 99%;
(2) 4, the synthesis of 5-bis-phthalate bromine: solid two bromine Phthalocyclohydrazide 31.8g step (1) obtained is dissolved in 10mol/L aqueous sodium hydroxide solution 300 milliliters, then it is heated to 60 DEG C, reacts after 2 hours, cooling, then regulate pH to being 6 with the filtrate of previous step, precipitating out a large amount of white solid, filter, frozen water washs, 29g, receipts rate 90% is obtained after dry.
Embodiment 7
The preparation method of 4,5-bis-phthalate bromine of the present embodiment, step is as follows:
The synthesis of (1) two bromine Phthalocyclohydrazide: add 16.20g Phthalocyclohydrazide in the 250mL tri-mouthfuls of round-bottomed flasks with reflux condensing tube, then 100mL glacial acetic acid is poured into, adopt mechanical stirring, after solid all dissolves, add 37.94gNBS wherein, this process has a little heat and releases. After system is stable, opening heating, temperature control 85 DEG C, along with the carrying out of reaction, the color of solution is deepened gradually, turns into yellow gradually from faint yellow. After reaction 1h, reaction solution is cooled, then pours in frozen water, after ice melts, the solid of precipitation is taken out filter, obtains white solid. By drying, claiming its dried quality to be 31.8g, its receipts rate is 99%;
(2) 4, the synthesis of 5-bis-phthalate bromine: solid two bromine Phthalocyclohydrazide 31.8g step (1) obtained is dissolved in 10mol/L aqueous sodium hydroxide solution 300 milliliters, then it is heated to 65 DEG C, reacts after 1 hour, cooling, then regulate pH to being 6 with the filtrate of previous step, precipitating out a large amount of white solid, filter, frozen water washs, 28g, receipts rate 87% is obtained after dry.
Embodiment 8
The preparation method of 4,5-bis-phthalate bromine of the present embodiment, step is as follows:
The synthesis of (1) two bromine Phthalocyclohydrazide: add 16.20g Phthalocyclohydrazide in the 250mL tri-mouthfuls of round-bottomed flasks with reflux condensing tube, then 100mL glacial acetic acid is poured into, adopt mechanical stirring, after solid all dissolves, add 37.94gNBS wherein, this process has a little heat and releases. After system is stable, opening heating, temperature control 85 DEG C, along with the carrying out of reaction, the color of solution is deepened gradually, turns into yellow gradually from faint yellow. After reaction 1h, reaction solution is cooled, then pours in frozen water, after ice melts, the solid of precipitation is taken out filter, obtains white solid. By drying, claiming its dried quality to be 31.8g, its receipts rate is 99%;
(2) 4, the synthesis of 5-bis-phthalate bromine: solid two bromine Phthalocyclohydrazide 31.8g step (1) obtained is dissolved in 10mol/L aqueous sodium hydroxide solution 300 milliliters, then it is heated to 65 DEG C, reacts after 1 hour, cooling, then regulate pH to being 7 with the filtrate of previous step, precipitating out a large amount of white solid, filter, frozen water washs, 27g, receipts rate 84% is obtained after dry.
Embodiment 9
The preparation method of 4,5-bis-phthalate bromine of the present embodiment, step is as follows:
The synthesis of (1) two bromine Phthalocyclohydrazide: add 162g Phthalocyclohydrazide in the 1000mL tri-mouthfuls of round-bottomed flasks with reflux condensing tube, then 600mL glacial acetic acid is poured into, adopt mechanical stirring, after solid all dissolves, add 380gNBS wherein, after system is stable, open heating, temperature control 85 DEG C, along with the carrying out of reaction, the color of solution is deepened gradually, turns into yellow gradually from faint yellow. After reaction 1h, reaction solution is cooled, then pours in frozen water, after ice melts, the solid of precipitation is taken out filter, obtains white solid. By drying, claiming its dried quality to be 319g, its receipts rate is 99%;
(2) 4, the synthesis of 5-bis-phthalate bromine: solid two bromine Phthalocyclohydrazide 319g step (1) obtained is dissolved in 10mol/L aqueous sodium hydroxide solution 3000 milliliters, then it is heated to 70 DEG C, reacts after 1.5 hours, cooling, then regulate pH to being 6 with the filtrate of previous step, precipitating out a large amount of white solid, filter, frozen water washs, 320g, receipts rate 98% is obtained after dry.
Embodiment 10
The preparation method of 4,5-bis-phthalate bromine of the present embodiment, step is as follows:
The synthesis of (1) two bromine Phthalocyclohydrazide: add 1.6kg Phthalocyclohydrazide in the 5000mL tri-mouthfuls of round-bottomed flasks with reflux condensing tube, then pour 3L glacial acetic acid into, adopts mechanical stirring, adds 3.8kgNBS after solid all dissolves wherein. After system is stable, opening heating, temperature control 85 DEG C, along with the carrying out of reaction, the color of solution is deepened gradually, turns into yellow gradually from faint yellow. After reaction 1h, reaction solution is cooled, then pours in frozen water, after ice melts, the solid of precipitation is taken out filter, obtains white solid. By drying, claiming its dried quality to be 3.19kg, its receipts rate is 99%;
(2) 4, the synthesis of 5-bis-phthalate bromine: solid two bromine Phthalocyclohydrazide 3.19kg step (1) obtained is dissolved in 10mol/L aqueous sodium hydroxide solution 30 liters, then it is heated to 65 DEG C, reacts after 1 hour, cooling, then regulate pH to being 6 with the filtrate of previous step, precipitating out a large amount of white solid, filter, frozen water washs, 3.2kg, receipts rate 98% is obtained after dry.
More than show and describe the ultimate principle of the present invention and the advantage of main feature and the present invention. The technician of the industry should understand; the present invention is not restricted to the described embodiments; the principle that the present invention is just described described in above-described embodiment and specification sheets; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention. The claimed scope of the present invention is defined by appending claims and equivalent thereof.
Claims (6)
1. the preparation method of 4,5-bis-phthalate bromine, it is characterised in that step is as follows:
The synthesis of (1) two bromine Phthalocyclohydrazide: after Phthalocyclohydrazide is dissolved in glacial acetic acid, add N-bromine for succimide, it is heated to 80 ~ 100 DEG C of reactions 0.5 ~ 1 hour, system is cooled to after having reacted room temperature then pour in frozen water, precipitate out solid, filter and obtain two bromine Phthalocyclohydrazide and filtrates;
(2) 4, the synthesis of 5-bis-phthalate bromine: two bromine Phthalocyclohydrazides are dissolved in aqueous sodium hydroxide solution, it is heated to 60 ~ 70 DEG C of reactions 1 ~ 2 hour that are hydrolyzed, after hydrolysis reaction terminates, the pH regulating hydrolysis reaction system is 6 ~ 7, precipitating out white solid, filtration, washing obtain 4,5-bis-phthalate bromine.
2. the preparation method of 4,5-bis-phthalate bromine according to claim 1, it is characterised in that: in described step (1), Phthalocyclohydrazide and N-bromine are 2.1:1 ~ 2.2:1 for the ratio of the amount of substance of succimide.
3. the preparation method of 4,5-bis-phthalate bromine according to claim 1, it is characterised in that: dense DEG C of the aqueous sodium hydroxide solution in described step (2) is 10mol/L.
4. the preparation method of 4,5-bis-phthalate bromine according to claim 1, it is characterised in that: in described step (2), in the amount of substance of sodium hydroxide and step (1), the ratio of the amount of substance of Phthalocyclohydrazide is 2.5:1 ~ 3:1.
5. the preparation method of 4,5-bis-phthalate bromine according to claim 1, it is characterised in that: the washing in described step (2) adopts the water of 0 DEG C.
6. the preparation method of 4,5-bis-phthalate bromine according to claim 1, it is characterised in that: described step (2) regulate the pH of hydrolysis reaction system to be 6 ~ 7 with the filtrate in step (1).
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110357775A (en) * | 2019-08-23 | 2019-10-22 | 四川武胜春瑞医药化工有限公司 | A kind of preparation method and preparation facilities of phthalic acid |
| CN115057767A (en) * | 2022-07-06 | 2022-09-16 | 山东泓瑞医药科技股份公司 | Preparation method of phthalic acid |
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| GB1238224A (en) * | 1967-12-04 | 1971-07-07 | ||
| CN102372626A (en) * | 2011-11-23 | 2012-03-14 | 济南诚汇双达化工有限公司 | Preparation method of phthalic acid |
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2016
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| Publication number | Priority date | Publication date | Assignee | Title |
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| GB1238224A (en) * | 1967-12-04 | 1971-07-07 | ||
| CN102372626A (en) * | 2011-11-23 | 2012-03-14 | 济南诚汇双达化工有限公司 | Preparation method of phthalic acid |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110357775A (en) * | 2019-08-23 | 2019-10-22 | 四川武胜春瑞医药化工有限公司 | A kind of preparation method and preparation facilities of phthalic acid |
| CN115057767A (en) * | 2022-07-06 | 2022-09-16 | 山东泓瑞医药科技股份公司 | Preparation method of phthalic acid |
| CN115057767B (en) * | 2022-07-06 | 2023-12-12 | 山东泓瑞医药科技股份公司 | Preparation method of phthalic acid |
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Inventor after: Jin Qingxian Inventor after: Wu Lei Inventor after: Hu Xianmei Inventor after: Chen Shuyu Inventor after: Chen Sanxu Inventor after: Wang Fulin Inventor after: Zhang Hongpei Inventor after: Li Zhengguang Inventor after: Li Yajie Inventor before: Jin Qingxian Inventor before: Liu Yingfan Inventor before: Wu Shide Inventor before: Xiao Yuanhua Inventor before: Fang Shaoming Inventor before: Ding Ruimin Inventor before: Zhang Yuening Inventor before: Li Lulu |
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