CN107935842A - A kind of preparation method of 2 chlorine, 4 bromine, 6 methyl benzoic acid - Google Patents
A kind of preparation method of 2 chlorine, 4 bromine, 6 methyl benzoic acid Download PDFInfo
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- CN107935842A CN107935842A CN201711439877.0A CN201711439877A CN107935842A CN 107935842 A CN107935842 A CN 107935842A CN 201711439877 A CN201711439877 A CN 201711439877A CN 107935842 A CN107935842 A CN 107935842A
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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
- C07C51/15—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction of organic compounds with carbon dioxide, e.g. Kolbe-Schmitt synthesis
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- C—CHEMISTRY; METALLURGY
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- C07B49/00—Grignard reactions
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Abstract
The invention belongs to technical field of organic synthesis, more particularly to a kind of preparation method of 2 chlorine, 4 bromine, 6 methyl benzoic acid, using 2 chlorine, 4 bromine, 6 methyl iodobenzene as raw material, the Grignard Reagent of phenyl-magnesium-chloride is made with isopropylmagnesium chloride generation grignard exchange reaction for 2 chlorine, 4 bromine, 6 methyl iodobenzene, gained phenyl-magnesium-chloride Grignard Reagent reacts with carbon dioxide, 2 chlorine, 4 bromine, 6 methyl benzoic acid crude product is obtained after dilute hydrochloric acid hydrolyzes again, last purified up to 2 chlorine, 4 bromine, 6 methyl benzoic acid finished product, the solvent of reaction is tetrahydrofuran.The advantages of 2 chlorine, 4 bromine, 6 methyl benzoic acid preparation method of the invention, is cheap and easy to get using raw material, and reaction condition is gentle, and post-processing operation is simple, and production cost is relatively low, reduces reaction cost, is adapted to industrialized production.
Description
Technical field
The present invention relates to technical field of organic synthesis, and in particular to a kind of preparation side of the bromo- 6- methyl benzoic acids of the chloro- 4- of 2-
Method.
Background technology
The character of the bromo- 6- methyl benzoic acids of the chloro- 4- of 2- is cream-white crystals, is among a kind of very extensive chemical industry of purposes
Body, is widely used in medicine and the synthesis of other fine chemical products.
The content of the invention
The technical problems to be solved by the invention are to provide the chloro- 4- of 2- that a kind of purity is high, technique is simple and cost is low
The preparation method of bromo- 6- methyl benzoic acids.
The technical problems to be solved by the invention are realized using following technical solution.
Using the bromo- 6- methyl iodobenzenes of the chloro- 4- of 2- as raw material, with isopropylmagnesium chloride lattice occur for the bromo- 6- methyl iodobenzenes of the chloro- 4- of 2-
The Grignard Reagent of phenyl-magnesium-chloride is made in family name's exchange reaction, and gained phenyl-magnesium-chloride Grignard Reagent reacts with carbon dioxide,
The bromo- 6- methyl benzoic acids crude products of the chloro- 4- of 2- are obtained after dilute hydrochloric acid hydrolyzes again, it is last purified up to the bromo- 6- methyl of the chloro- 4- of 2-
Benzoic acid finished product, the solvent of reaction is tetrahydrofuran.
A kind of preparation method of the bromo- 6- methyl benzoic acids of the chloro- 4- of 2-, comprises the following steps.
(1) under nitrogen protection, first by magnesium chips, and in a small amount of 2 cbloropropane isopropyl chloride input reaction vessel, tetrahydrofuran, heating are added
To 30~40 DEG C, with bromoethane initiation reaction, the 2 cbloropropane isopropyl chloride mixed liquor being dissolved in tetrahydrofuran is then added dropwise, is added dropwise
After carry out insulation reaction, isopropylmagnesium chloride solution is made.
(2) the bromo- 6- methyl iodobenzene solids of the chloro- 4- of 2- are put into reaction vessel, adds tetrahydrofuran dissolving, cool down, so
Isopropylmagnesium chloride solution is added dropwise afterwards, insulation reaction is carried out after being added dropwise, the bromo- 6- methyl-magnesium-chlorides grignard of the chloro- 4- of 2- is made
Reagent.
(3) dry carbon dioxide is passed through in the solution of Grignard Reagent obtained above, stopped after completion of the reaction
Ventilation.
(4) the hydrochloric acid stirring of mass concentration 10% is added into reaction system after reaction, by the pH value tune of reaction solution
To 3 ~ 4, then stratification, through extraction, merges organic layer, dry, precipitation, it is thick to obtain the bromo- 6- methyl benzoic acids of the chloro- 4- of 2-
Product.
(5) the bromo- 6- methyl benzoic acids crude products of the chloro- 4- of 2- are obtained into the bromo- 6- methylbenzenes first of the chloro- 4- of 2- by recrystallization purification
Sour sterling.
The molar ratio of the bromo- 6- methyl iodobenzenes of the chloro- 4- of 2- and isopropylmagnesium chloride is in the step (2):1:(1.0-
1.5), preferably:1:(1.0-1.3), the concentration of isopropylmagnesium chloride is 1.0mol/L.
The reaction temperature of the bromo- 6- methyl iodobenzenes of the chloro- 4- of 2- and isopropylmagnesium chloride is -20~20 DEG C in the step (2),
Insulation reaction temperature is -20~20 DEG C, and preferable reaction temperature is 0~10 DEG C, and holding temperature is 0~10 DEG C, and soaking time is small for 2
When.
The bromo- 6- methyl-magnesium-chlorides Grignard Reagent of the chloro- 4- of 2- and the reaction temperature of carbon dioxide are -20 in the step (2)
~20 DEG C, insulation reaction temperature is -20~20 DEG C, and preferable reaction temperature is 0~10 DEG C, and holding temperature is 0~10 DEG C.
In order to make the technical means, the creative features, the aims and the efficiencies achieved by the present invention easy to understand, tie below
Specific embodiment is closed, the present invention is further explained.
Embodiment 1.
(1) prepared by isopropylmagnesium chloride Grignard Reagent:20mL tetrahydrofurans and 3g2- are first added in 50mL single-necked flasks
Solution is made in chloropropane stirring, spare.Under nitrogen protection, in the three-necked flask of 50mL dryings, 1.1g magnesium chips, a small amount of 2- are added
Chloropropane, adds tetrahydrofuran solvent, 30~40 DEG C is warming up to, with bromoethane initiation reaction.Then it is added dropwise the four of 2 cbloropropane isopropyl chloride
Hydrogen tetrahydrofuran solution, carries out insulation reaction after being added dropwise, obtained isopropylmagnesium chloride grignard reagent concentration is 1mol/L.
(2) grignard exchanges:Under nitrogen protection, the bromo- 6- methyl of the chloro- 4- of 5g2- is added in the three-necked flask of 100ml dryings
Iodobenzene, 20ml tetrahydrofurans.0 DEG C is cooled to, is slowly added dropwise isopropylmagnesium chloride Grignard Reagent 20ml, the process that is added dropwise maintains 0~
10 DEG C, be added dropwise insulation reaction 2 it is small when, the chloro- 4- of 2- bromo- 6- methyl-magnesium-chlorides Grignard Reagent is made.
(3) it is carbonylated:Dry carbon dioxide is passed through in grignard reagent solution obtained above, in venting process
It is 0~10 DEG C to keep reacting liquid temperature, and reaction terminates to stop ventilation.Mass concentration is added into reaction system after reaction
10% hydrochloric acid stirring, is transferred to 3 ~ 4, then stratification by the pH value of reaction solution, through extraction, merges organic layer, dry, takes off
It is molten, obtain the bromo- 6- methyl benzoic acids crude products of the chloro- 4- of 2.25g2-, yield 60%.
(4) purify:The bromo- 6- methyl benzoic acids crude products of the chloro- 4- of 2.25g2- are added in 25ml conical flasks, add ethyl acetate
Hot melt, add 10ml petroleum ethers, cooling, crystallization, centrifuge the bromo- 6- methyl benzoic acids products of the chloro- 4- of 1.92g2-, yield are
51%.
Embodiment 2.
(1) prepared by isopropylmagnesium chloride Grignard Reagent:20mL tetrahydrofurans and 3g2- are first added in 50mL single-necked flasks
Solution is made in chloropropane stirring, spare.Under nitrogen protection, in the three-necked flask of 50mL dryings, 1.1g magnesium chips, a small amount of 2- are added
Chloropropane, adds tetrahydrofuran solvent, 30~40 DEG C is warming up to, with bromoethane initiation reaction.Then it is added dropwise the four of 2 cbloropropane isopropyl chloride
Hydrogen tetrahydrofuran solution, carries out insulation reaction after being added dropwise, obtained isopropylmagnesium chloride grignard reagent concentration is 1mol/L.
(2) grignard exchanges:Under nitrogen protection, the bromo- 6- methyl of the chloro- 4- of 5g2- is added in the three-necked flask of 100ml dryings
Iodobenzene, 20ml tetrahydrofurans.- 20 DEG C are cooled to, is slowly added dropwise isopropylmagnesium chloride Grignard Reagent 15ml, the process that is added dropwise maintains-
20~-10 DEG C, be added dropwise insulation reaction 2 it is small when, the chloro- 4- of 2- bromo- 6- methyl-magnesium-chlorides Grignard Reagent is made.
(3) it is carbonylated:Dry carbon dioxide is passed through in grignard reagent solution obtained above, in venting process
It is -20~-10 DEG C to keep reacting liquid temperature, and reaction terminates to stop ventilation.It is dense that quality is added into reaction system after reaction
The hydrochloric acid stirring of degree 10%, is transferred to 3 ~ 4, then stratification by the pH value of reaction solution, through extraction, merges organic layer, dry, takes off
It is molten, obtain the bromo- 6- methyl benzoic acids crude products of the chloro- 4- of 1.73g2-, yield 46%.
(4) purify:The bromo- 6- methyl benzoic acids crude products of the chloro- 4- of 2- of 1.39g are added in 25ml conical flasks, add acetic acid second
Ester heat, add 6ml petroleum ethers, cooling, crystallization, centrifuge the bromo- 6- methyl benzoic acids products of the chloro- 4- of 1.8g2-, yield are
37%.
Embodiment 3.
(1) prepared by isopropylmagnesium chloride Grignard Reagent:20mL tetrahydrofurans and 3g2- are first added in 50mL single-necked flasks
Solution is made in chloropropane stirring, spare.Under nitrogen protection, in the three-necked flask of 50mL dryings, 1.1g magnesium chips, a small amount of 2- are added
Chloropropane, adds tetrahydrofuran solvent, 30~40 DEG C is warming up to, with bromoethane initiation reaction.Then it is added dropwise the four of 2 cbloropropane isopropyl chloride
Hydrogen tetrahydrofuran solution, carries out insulation reaction after being added dropwise, obtained isopropylmagnesium chloride grignard reagent concentration is 1mol/L.
(2) grignard exchanges:Under nitrogen protection, the bromo- 6- methyl of the chloro- 4- of 5g2- is added in the three-necked flask of 100ml dryings
Iodobenzene, 20ml tetrahydrofurans.0 DEG C is cooled to, is slowly added dropwise isopropylmagnesium chloride Grignard Reagent 23ml, the process that is added dropwise maintains 0~
10 DEG C, be added dropwise insulation reaction 2 it is small when, the chloro- 4- of 2- bromo- 6- methyl-magnesium-chlorides Grignard Reagent is made.
(3) it is carbonylated:Dry carbon dioxide is passed through in grignard reagent solution obtained above, in venting process
It is 0~10 DEG C to keep reacting liquid temperature, and reaction terminates to stop ventilation.Mass concentration is added into reaction system after reaction
10% hydrochloric acid stirring, is transferred to 3 ~ 4, then stratification by the pH value of reaction solution, through extraction, merges organic layer, dry, takes off
It is molten, obtain the bromo- 6- methyl benzoic acids crude products of the chloro- 4- of 2.07g2-, yield 55%.
(4) purify:The bromo- 6- methyl benzoic acids crude products of the chloro- 4- of 2.07g2- are added in 25ml conical flasks, add ethyl acetate
Hot melt, add 8ml petroleum ethers, cooling, crystallization, centrifuge the bromo- 6- methyl benzoic acids products of the chloro- 4- of 1.77g2-, yield are
47%.
Embodiment 4.
(1) prepared by isopropylmagnesium chloride Grignard Reagent:20mL tetrahydrofurans and 3g2- are first added in 50mL single-necked flasks
Solution is made in chloropropane stirring, spare.Under nitrogen protection, in the three-necked flask of 50mL dryings, 1.1g magnesium chips, a small amount of 2- are added
Chloropropane, adds tetrahydrofuran solvent, 30~40 DEG C is warming up to, with bromoethane initiation reaction.Then it is added dropwise the four of 2 cbloropropane isopropyl chloride
Hydrogen tetrahydrofuran solution, carries out insulation reaction after being added dropwise, obtained isopropylmagnesium chloride grignard reagent concentration is 1mol/L.
(2) grignard exchanges:Under nitrogen protection, the bromo- 6- methyl of the chloro- 4- of 5g2- is added in the three-necked flask of 100ml dryings
Iodobenzene, 20ml tetrahydrofurans.0 DEG C is cooled to, is slowly added dropwise isopropylmagnesium chloride Grignard Reagent 20ml, the process that is added dropwise maintains 0~
10 DEG C, be added dropwise insulation reaction 2 it is small when, the chloro- 4- of 2- bromo- 6- methyl-magnesium-chlorides Grignard Reagent is made.
(3) it is carbonylated:Dry carbon dioxide is passed through in grignard reagent solution obtained above, in venting process
It is 10~20 DEG C to keep reacting liquid temperature, and reaction terminates to stop ventilation.Mass concentration is added into reaction system after reaction
10% hydrochloric acid stirring, is transferred to 3 ~ 4, then stratification by the pH value of reaction solution, through extraction, merges organic layer, dry, takes off
It is molten, obtain the bromo- 6- methyl benzoic acids crude products of the chloro- 4- of 1.5g2-, yield 40%.
(4) purify:The bromo- 6- methyl benzoic acids crude products of the chloro- 4- of 1.5g2- are added in 25ml conical flasks, add ethyl acetate hot
It is molten, add 4ml petroleum ethers, cooling, crystallization, centrifuge to obtain the bromo- 6- methyl benzoic acids products of the chloro- 4- of 1.2g2-, yield 32%.
The basic principles, main features and the advantages of the invention have been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and modifications of the present invention are possible, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent thereof.
Claims (5)
- A kind of 1. preparation method of the bromo- 6- methyl benzoic acids of the chloro- 4- of 2-, it is characterised in that:With the bromo- 6- methyl iodobenzenes of the chloro- 4- of 2- For raw material, the grignard of phenyl-magnesium-chloride is made with isopropylmagnesium chloride generation grignard exchange reaction for the bromo- 6- methyl iodobenzenes of the chloro- 4- of 2- Reagent, gained phenyl-magnesium-chloride Grignard Reagent react with carbon dioxide, then to obtain after dilute hydrochloric acid hydrolyzes the chloro- 4- of 2- bromo- 6- methyl benzoic acid crude products, last purified up to the bromo- 6- methyl benzoic acids finished products of the chloro- 4- of 2-, the solvent of reaction is tetrahydrochysene furan Mutter, synthetic route is as follows:。
- 2. a kind of preparation method of the bromo- 6- methyl benzoic acids of the chloro- 4- of 2-, it is characterised in that comprise the following steps:(1) under nitrogen protection, first by magnesium chips, and in a small amount of 2 cbloropropane isopropyl chloride input reaction vessel, tetrahydrofuran is added, is warming up to 30 ~40 DEG C, with bromoethane initiation reaction, the 2 cbloropropane isopropyl chloride mixed liquor being dissolved in tetrahydrofuran is then added dropwise, is added dropwise laggard Row insulation reaction, is made isopropylmagnesium chloride solution;(2) by the bromo- 6- methyl iodobenzene solid input reaction vessels of the chloro- 4- of 2-, tetrahydrofuran dissolving is added, cooling, then drips Add isopropylmagnesium chloride solution, insulation reaction is carried out after being added dropwise, the bromo- 6- methyl-magnesium-chlorides Grignard Reagent of the chloro- 4- of 2- is made;(3) dry carbon dioxide is passed through in the solution of Grignard Reagent obtained above, stops ventilation after completion of the reaction;(4) the hydrochloric acid stirring of mass concentration 10% is added into reaction system after reaction, the pH value of reaction solution is transferred to 3 ~ 4, then stratification, through extraction, merges organic layer, dry, precipitation, obtains the bromo- 6- methyl benzoic acids crude products of the chloro- 4- of 2-;(5) that the bromo- 6- methyl benzoic acids crude products of the chloro- 4- of 2- are obtained the bromo- 6- methyl benzoic acids of the chloro- 4- of 2- by recrystallization purification is pure Product.
- 3. the preparation method of the bromo- 6- methyl benzoic acids of the chloro- 4- of 2- according to claim 2, it is characterised in that:The 2- The molar ratio of the bromo- 6- methyl iodobenzene of chloro- 4- and isopropylmagnesium chloride is:1:(1.0-1.5), preferably:1:(1.0-1.3), The concentration of isopropylmagnesium chloride is 1.0mol/L.
- 4. the preparation method of the bromo- 6- methyl benzoic acids of the chloro- 4- of 2- according to claim 2, it is characterised in that:The chloro- 4- of 2- The reaction temperature of bromo- 6- methyl iodobenzene and isopropylmagnesium chloride is -20~20 DEG C, and insulation reaction temperature is -20~20 DEG C, preferably Reaction temperature is 0~10 DEG C, and holding temperature is 0~10 DEG C, when soaking time is 2 small.
- 5. the preparation method of the bromo- 6- methyl benzoic acids of the chloro- 4- of 2- according to claim 2, it is characterised in that:The 2- The bromo- 6- methyl-magnesium-chlorides Grignard Reagent of chloro- 4- and the reaction temperature of carbon dioxide are -20~20 DEG C, and insulation reaction temperature is -20 ~20 DEG C, preferable reaction temperature is 0~10 DEG C, and holding temperature is 0~10 DEG C.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112047829A (en) * | 2020-08-31 | 2020-12-08 | 成都艾必克医药科技有限公司 | Synthetic method of hydrochloric acid Alininib intermediate 2- (4-ethyl-3-iodophenyl) -2-methylpropanoic acid |
CN112239402A (en) * | 2020-10-28 | 2021-01-19 | 爱斯特(成都)生物制药股份有限公司 | Preparation method of 2, 5-dimethoxy phenylacetic acid |
CN116425623A (en) * | 2023-04-10 | 2023-07-14 | 大连凯飞化学股份有限公司 | Method for synthesizing 3,5-dichloro-4-methylbenzoic acid by one-pot method |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102532038A (en) * | 2011-12-22 | 2012-07-04 | 吉安市东庆精细化工有限公司 | Method for preparing 2-methyl-1-pyrimidine-5-yl-1-(4-fluoroform methoxyl phenyl) allene-1-alcohol |
CN102791706A (en) * | 2010-01-07 | 2012-11-21 | 阿斯利康(瑞典)有限公司 | Process for making a metabotropic glutamate receptor positive allosteric modulator-874 |
CN104853757A (en) * | 2012-08-15 | 2015-08-19 | 默沙东公司 | 4-heteroaryl substituted benzoic acid compounds as rorgammat inhibitors and uses thereof |
-
2017
- 2017-12-27 CN CN201711439877.0A patent/CN107935842A/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102791706A (en) * | 2010-01-07 | 2012-11-21 | 阿斯利康(瑞典)有限公司 | Process for making a metabotropic glutamate receptor positive allosteric modulator-874 |
CN102532038A (en) * | 2011-12-22 | 2012-07-04 | 吉安市东庆精细化工有限公司 | Method for preparing 2-methyl-1-pyrimidine-5-yl-1-(4-fluoroform methoxyl phenyl) allene-1-alcohol |
CN104853757A (en) * | 2012-08-15 | 2015-08-19 | 默沙东公司 | 4-heteroaryl substituted benzoic acid compounds as rorgammat inhibitors and uses thereof |
Non-Patent Citations (1)
Title |
---|
YOSHIHIDE HATTORI等: "Synthesis and evaluation as MRI probe of the trifluoromethylated p-boronophenylalanine and its alcohol derivative", 《BIOORGANIC & MEDICINAL CHEMISTRY》 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112047829A (en) * | 2020-08-31 | 2020-12-08 | 成都艾必克医药科技有限公司 | Synthetic method of hydrochloric acid Alininib intermediate 2- (4-ethyl-3-iodophenyl) -2-methylpropanoic acid |
CN112047829B (en) * | 2020-08-31 | 2023-05-26 | 成都艾必克医药科技有限公司 | Synthesis method of alcaine intermediate 2- (4-ethyl-3-iodophenyl) -2-methylpropanoic acid |
CN112239402A (en) * | 2020-10-28 | 2021-01-19 | 爱斯特(成都)生物制药股份有限公司 | Preparation method of 2, 5-dimethoxy phenylacetic acid |
CN116425623A (en) * | 2023-04-10 | 2023-07-14 | 大连凯飞化学股份有限公司 | Method for synthesizing 3,5-dichloro-4-methylbenzoic acid by one-pot method |
CN116425623B (en) * | 2023-04-10 | 2024-02-13 | 大连凯飞化学股份有限公司 | Method for synthesizing 3,5-dichloro-4-methylbenzoic acid by one-pot method |
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