CN106397209A - Preparation method of 2-chloride-5-nitrobenzoic acid - Google Patents
Preparation method of 2-chloride-5-nitrobenzoic acid Download PDFInfo
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- CN106397209A CN106397209A CN201610769451.0A CN201610769451A CN106397209A CN 106397209 A CN106397209 A CN 106397209A CN 201610769451 A CN201610769451 A CN 201610769451A CN 106397209 A CN106397209 A CN 106397209A
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- chloro
- chloride
- preparation
- acid
- nitrobenzoic acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/08—Preparation of nitro compounds by substitution of hydrogen atoms by nitro groups
Abstract
The invention provides a preparation method of 2-chloride-5-nitrobenzoic acid. The preparation method comprises the following steps: mixing concentrated nitric acid and fuming sulphuric acid with the SO3 concentration of 20 percent according to the mass ratio of 1:(2-3), and controlling the temperature of the solution to be less than 10 DEG C in a mixing process; dripping 2-chloride trichlorotoluene, controlling the temperature of reaction liquid to be 0 to 10 DEG C, and continuously stirring at the end of dripping till the reaction is completed; pouring the reaction liquid into ice water, extracting with dichloromethane, washing an organic phase with a saturated sodium bicarbonate solution, and concentrating and drying to obtain 2-chloride-5-nitro trichlorotoluene; preparing concentrated sulfuric acid with the concentration of 85 weight percent, heating to 60 to 65 DEG C, adding the 2-chloride-5-nitro trichlorotoluene in batches, and preserving the heat till the reaction is completed; cooling the reaction liquid, adding water into the reaction liquid for dilution, extracting with ethyl acetate, taking an organic phase, and performing washing and concentration to obtain 2-chloride-5-nitrobenzoic acid. The technological steps are more reasonable in design and high in operability; the number of byproducts is small; the prepared product is relatively high in purity and can meet the requirement on industrial application.
Description
Technical field
The present invention relates to a kind of preparation method of 2- chloro-5-nitrobenzoic acid.
Background technology
The method preparing 2- chloro-5-nitrobenzoic acid in prior art is using refined side after 0-chloro-benzoic acid nitrification
Method, but produce more 2- chloro- 3- nitrobenzoic acid during due to nitrification, it is extremely difficult to relatively using conventional process for purification
High purity, typically can only control 99.0% about it is impossible to meet the needs using.
Content of the invention
The technical problem to be solved is for the deficiencies in the prior art, provides that a kind of technique is more reasonable, institute
The production technology of the high 2- chloro-5-nitrobenzoic acid of product purity producing.
The present invention is realized in：
A kind of preparation method of 2- chloro-5-nitrobenzoic acid, comprises the following steps：
(1) by mass ratio be 1:2～3 red fuming nitric acid (RFNA) and SO3Oleum mixing for 20%, mixed process controls solution
Temperature is less than 10 DEG C；Dropping 2- chlorobenzotrichloride, between controlling reacting liquid temperature to be 0～10 DEG C, after being added dropwise to complete, continues stirring
Complete to reacting；Reactant liquor is poured in frozen water, with dichloromethane extraction, organic phase is washed with saturated sodium bicarbonate solution, dense
Contracting, is dried, obtains 2- chloro- 5- nitrotrichloromethane benzene；
(2) configure the concentrated sulfuric acid of 85wt%, be warming up to 60～65 DEG C, be dividedly in some parts prepared 2- chloro- 5- nitrotrichloromethane
Benzene, then heats to 90～95 DEG C, is incubated to reaction completely；Cooling reactant liquor is less than 50 DEG C to temperature, reactant liquor is added water dilute
Release, be extracted with ethyl acetate, take organic phase, washing, concentrate, obtain final product.
Preferably, in step 1,2- chlorobenzotrichloride and red fuming nitric acid (RFNA) and SO3Oleum mixed liquor In quality for 20%
Than for 1:3～4.
Present invention also offers the 2- chloro-5-nitrobenzoic acid being prepared from using above-mentioned preparation method.
Compared with prior art, the advantage of the technology of the present invention is：Present invention process step designs more reasonable, operability
By force, accessory substance is few, and the purity of obtained product is higher, can meet the needs of commercial Application.
Specific embodiment
With reference to specific embodiment, the present invention is further illustrated, to more fully understand the present invention.Embodiment 1
The 500ml four round flask be equipped with mechanical stirring device, cooling device, thermometer and dropping funel adds
Enter the red fuming nitric acid (RFNA) that mass ratio is 1～3 and SO3Oleum for 20%, mixed process controls solution temperature to be less than 10 DEG C.About
2- chlorobenzotrichloride (2- chlorobenzotrichloride and red fuming nitric acid (RFNA) and SO is added in 2.5 hours introversive sulfonitric mixture obtaining3For
The mass ratio of 20% oleum mixed liquor is 1:4), between controlling reacting liquid temperature to be 0～10 DEG C, after being added dropwise to complete, protect
Hold temperature and continue stirring reaction in 2 hours completely.Then reactant liquor is poured into and in frozen water, may be immediately observed that solids of sedimentation.To this mixing
Dichloromethane is added to be extracted in thing, organic phase saturation NaHCO3Solution washs, and is then dried with magnesium sulfate, filters and steam
It is sent to drying.Obtain 2- chloro- 5- nitrotrichloromethane benzene (GC titer=99.6%, molar yield 98%).
The concentrated sulfuric acid taking mass fraction to be 96%, the adjustment acid concentration that adds water to 85wt%.By sour temperature adjustment to about 60
DEG C, and start to be added portionwise into the 2- chloro- 5- nitrotrichloromethane benzene of purification.Then temperature adjustment it is 90 DEG C it is noted that gradually shape
Become to be dispersed in the solid product in described mixture.Keep this temperature about 3 hours, then reactant mixture is cooled to about 50 DEG C
And be diluted with adding water, it is extracted with ethyl acetate product at room temperature.Separate each phase, and wash organic phase with water.Finally, steam
Send out solvent and obtain 2- chloro-5-nitrobenzoic acid (titer=98.5% of HPLC, molar yield 94%).
Embodiment 1
The 500ml four round flask be equipped with mechanical stirring device, cooling device, thermometer and dropping funel adds
Entering mass ratio is 1:2 red fuming nitric acid (RFNA) and SO3Oleum for 20%, mixed process controls solution temperature to be less than 10 DEG C.About
2- chlorobenzotrichloride (2- chlorobenzotrichloride and red fuming nitric acid (RFNA) and SO is added in 2.5 hours introversive sulfonitric mixture obtaining3For
The mass ratio of 20% oleum mixed liquor is 1:3), between controlling reacting liquid temperature to be 0～10 DEG C, after being added dropwise to complete, protect
Hold temperature and continue stirring reaction in 2 hours completely.Then reactant liquor is poured into and in frozen water, may be immediately observed that solids of sedimentation.To this mixing
Dichloromethane is added to be extracted in thing, organic phase saturation NaHCO3Solution washs, and is then dried with magnesium sulfate, filters and steam
It is sent to drying.Obtain 2- chloro- 5- nitrotrichloromethane benzene (GC titer=99.2%, molar yield 99.1%).
The concentrated sulfuric acid taking mass fraction to be 96%, the adjustment acid concentration that adds water to 85wt%.By sour temperature adjustment to about 65
DEG C, and start to be added portionwise into the 2- chloro- 5- nitrotrichloromethane benzene of purification.Then temperature adjustment it is 95 DEG C it is noted that gradually shape
Become to be dispersed in the solid product in described mixture.Keep this temperature about 3 hours, then reactant mixture is cooled to about 50 DEG C
And be diluted with adding water, it is extracted with ethyl acetate product at room temperature.Separate each phase, and wash organic phase with water.Finally, steam
Send out solvent and obtain 2- chloro-5-nitrobenzoic acid (titer=98.7% of HPLC, molar yield 95%).
Above the specific embodiment of the present invention is described in detail, but it has been intended only as example, the present invention has not limited
It is formed on particular embodiments described above.To those skilled in the art, any equivalent modifications that the present invention is carried out and
Substitute also all among scope of the invention.Therefore, the impartial conversion made without departing from the spirit and scope of the invention and
Modification, all should cover within the scope of the invention.
Claims (3)
1. a kind of preparation method of 2- chloro-5-nitrobenzoic acid is it is characterised in that comprise the following steps：
(1) by mass ratio be 1:2～3 red fuming nitric acid (RFNA) and SO3Oleum mixing for 20%, mixed process controls solution temperature
Less than 10 DEG C；Dropping 2- chlorobenzotrichloride, between controlling reacting liquid temperature to be 0～10 DEG C, after being added dropwise to complete, continues stirring to anti-
Should be completely；Reactant liquor is poured in frozen water, with dichloromethane extraction, organic phase is washed with saturated sodium bicarbonate solution, concentrates, and does
Dry, obtain 2- chloro- 5- nitrotrichloromethane benzene；
(2) configure the concentrated sulfuric acid of 85wt%, be warming up to 60～65 DEG C, be dividedly in some parts prepared 2- chloro- 5- nitrotrichloromethane benzene, so
After be warming up to 90～95 DEG C, be incubated to reaction completely；Cooling reactant liquor is less than 50 DEG C to temperature, and reactant liquor is diluted with water, and uses
Ethyl acetate extracts, and takes organic phase, washing, concentrates, obtains final product.
2. a kind of preparation method of 2- chloro-5-nitrobenzoic acid according to claim 1 is it is characterised in that in step 1,
2- chlorobenzotrichloride and red fuming nitric acid (RFNA) and SO3The mass ratio of the oleum mixed liquor for 20% is 1:3～4.
3. a kind of 2- chloro-5-nitrobenzoic acid being prepared from using preparation method as claimed in claim 1 or 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610769451.0A CN106397209A (en) | 2016-08-30 | 2016-08-30 | Preparation method of 2-chloride-5-nitrobenzoic acid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610769451.0A CN106397209A (en) | 2016-08-30 | 2016-08-30 | Preparation method of 2-chloride-5-nitrobenzoic acid |
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| CN106397209A true CN106397209A (en) | 2017-02-15 |
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| CN201610769451.0A Pending CN106397209A (en) | 2016-08-30 | 2016-08-30 | Preparation method of 2-chloride-5-nitrobenzoic acid |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111253261A (en) * | 2020-03-02 | 2020-06-09 | 杭州沈氏节能科技股份有限公司 | Preparation method of 3, 5-dinitrobenzoic acid |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0751115A1 (en) * | 1995-06-27 | 1997-01-02 | Bayer Ag | Process for the preparation of 5-fluoro-2-nitrobenzoic acid |
| CN101142168A (en) * | 2005-02-22 | 2008-03-12 | 巴斯福股份公司 | Process for the preparation of benzoic acid derivatives via a new intermediate of synthesis |
| CN102329237A (en) * | 2011-06-24 | 2012-01-25 | 灌南伊斯特化工有限公司 | Production process of 2-chloro-5-nitrobenzoic acid |
-
2016
- 2016-08-30 CN CN201610769451.0A patent/CN106397209A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0751115A1 (en) * | 1995-06-27 | 1997-01-02 | Bayer Ag | Process for the preparation of 5-fluoro-2-nitrobenzoic acid |
| CN101142168A (en) * | 2005-02-22 | 2008-03-12 | 巴斯福股份公司 | Process for the preparation of benzoic acid derivatives via a new intermediate of synthesis |
| CN102329237A (en) * | 2011-06-24 | 2012-01-25 | 灌南伊斯特化工有限公司 | Production process of 2-chloro-5-nitrobenzoic acid |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111253261A (en) * | 2020-03-02 | 2020-06-09 | 杭州沈氏节能科技股份有限公司 | Preparation method of 3, 5-dinitrobenzoic acid |
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