CN110105193A - A kind of synthetic method of 2- halogen -5- bromobenzoic acid - Google Patents
A kind of synthetic method of 2- halogen -5- bromobenzoic acid Download PDFInfo
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- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
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Abstract
The invention discloses a kind of synthetic methods of 2- halogen -5- bromobenzoic acid, comprising the following steps: under the action of sulfuric acid, o-Halogen benzoic acids and NBS carry out bromo-reaction in organic solvent, after reaction after post treatment, obtain the 2- halogen -5- bromobenzoic acid.Method reaction route of the invention is short, easy to operate, environmental-friendly, safer, economical, is with a wide range of applications.
Description
Technical field
The present invention relates to a kind of preparation methods of chemical intermediate, more particularly, to the 2- halogen -5- bromobenzene first of Gao Pin a kind of
The synthetic method of acid.
Background technique
2- halogen -5- bromobenzoic acid is that there are two types of the armaticity function monomers of different halogens and a carboxyl for band, using each
The activity difference of group is reacted from different groups, the compound that a variety of functional groups replace is synthesized, in medical Organometallic Chemistry etc.
Aspect is widely used.Such as: the chloro- 5- bromobenzoic acid of 2- is mainly used for newest hypoglycemic medicine dapagliflozin (BMS-
512148) synthesis of, sotagliflozin, Empagliflozin and Ertugliflozin.
Preparation method report about 2- halogen -5- bromobenzoic acid is less, it is now known that have clearly report be patent
WO2017/046318. using o-fluorobenzoic acid as raw material, using potassium bromate/sulfuric acid as brominated reagent, the synthesis fluoro- 5- bromobenzene of 2- is carried out
Formic acid.CN107954852 is using o-Halogen benzoic acids as raw material, with sodium metaperiodate/sodium bromide/sulfuric acid/for brominated reagent, acetic acid-water
2- halogen -5- bromobenzoic acid is synthesized for solvent.Tetrahedron Letters, 9 (1997), 1559-1562. to be to halogen bromobenzene
Raw material is similar with carbon dioxide reaction synthesis 2- halogen -5- bromobenzoic acid etc. to react.
Above scheme is analyzed, finds above method, although sodium metaperiodate/sodium bromide/sulfuric acid/can for brominated reagent
Product is obtained, but product yield is low, economic benefit is low.Potassium bromate/sulfuric acid is brominated reagent, and product can be obtained in reaction, but should
Impurity is more under technique, and product proportion is lower, the bromo- 2- halogen-benzoic acid (a) and 3 of 3-, and the bromo- 2- halogen-benzoic acid (b) of 5- bis- is larger.
Although green with comparison when carbon dioxide, reaction condition is harsher, reacts at -70 DEG C with butyl lithium, and butyl lithium is met
Water meets oxygen and exothermic reaction easily occurs, and humid air easily burns rapidly butyl lithium solution high concentration (being greater than 1.0M) in case of wet, packing container
Interior solvent is commonly low boiling point flammable and combustible liquids, once expanded by heating is easy to cause explosion, and product yield is lower, no
Conducive to industrialized production.
Pertinent literature: Tetrahedron Letters.6 (1993), 931-934. use C5H6Br2N2O2 as brominated reagent,
Product also can be obtained in reaction, but impurity is more, the bromo- 2- halogen-benzoic acid (a) and 3 of 3-, and the bromo- 2- halogen-benzoic acid (b) of 5- bis- is larger.
European Journal of Organic Chemistry, 5 (2018), 640-647. are used using o-iodobenzoic acid as raw material
NBS (N-bromosuccinimide) obtains bromination product under effect of sulfuric acid as brominated reagent.But its bromination product is not
Including 2- halogen -5- bromobenzoic acid, when its reaction condition is used to synthesize 2- halogen -5- bromobenzoic acid by the applicant, sulfuric acid is found
Dosage is big, and reaction temperature is high, will appear carbonization in reaction process (see embodiment 1).Although there is product generation, reaction solution is black
Color, impurity is more, the bromo- 2- halogen-benzoic acid (a) and 3 of 3-, and the bromo- 2- halogen-benzoic acid (b) of 5- bis- is larger.J.Org.Chem.60
(1995), 5328-5331. and CN107540648A. uses NBS as brominated reagent, and reaction obtains bromo production under polar solvent
Object, but its bromination product does not include 2- halogen -5- bromobenzoic acid, when its reaction condition is applied to synthesis o-bromobenzoic acid,
Product 2- halogen -5- bromobenzoic acid is not obtained (see embodiment 2).
For green, low cost and industry is suitble to be combined to 2- halogen -5- bromobenzoic acid, the present invention is provided by repeatedly attempting
A kind of green synthesis method preparing 2- halogen -5- bromobenzoic acid.
Summary of the invention
The present invention provides a kind of synthetic methods of 2- halogen -5- bromobenzoic acid, subtract while improving product quality quality
Few environmental pollution keeps production reaction easy, environmentally friendly, and product is more suitable for producing in enormous quantities.
A kind of synthetic method of 2- halogen -5- bromobenzoic acid, comprising the following steps:
Under the action of sulfuric acid, o-Halogen benzoic acids and NBS carry out bromo-reaction in organic solvent, pass through after reaction
Post-processing obtains the 2- halogen -5- bromobenzoic acid；
Shown in the structure of the o-Halogen benzoic acids such as formula (I):
Shown in the structure such as formula (II) of the 2- halogen -5- bromobenzoic acid:
In formula (I)~(II), X is selected from-F ,-Cl or-Br.
Synthetic route is as follows:
The type and dosage of organic solvent can generate large effect to reaction effect, preferably, described is organic molten
Agent is one or more of methylene chloride, chloroform, carbon tetrachloride, 1,2- dichloroethanes；
Preferably, the o-Halogen benzoic acids and the mass ratio of solvent usage are 1:0.5~50；As further preferred,
The mass ratio of the o-Halogen benzoic acids and solvent usage is 1:0.5~20.
Preferably, the mass ratio of the o-Halogen benzoic acids and sulfuric acid dosage is 1:0.5~50；As further preferred,
The mass ratio of the o-Halogen benzoic acids and sulfuric acid dosage is 1:0.5~20.
In the present invention, the dosage of NBS used is relative to o-Halogen benzoic acids, for slightly excess, generally
1.1equiv left and right.
Preferably, the temperature of the bromo-reaction be -10 DEG C~80 DEG C, the time be 1~for 24 hours.
Preferably, the process of the post-processing is as follows:
Reaction solution is quenched with ice water, recycling design, filters to obtain 2- halogen -5- bromobenzoic acid crude product, crude product is by recrystallization
Obtain sterling.
Preferably, solvent used in recrystallization is halogenated hydrocarbon solvent, alcohols solvent, acetonitrile or ether solvent.
Preferably, solvent used in recrystallization is methanol, ethyl alcohol, DCM, acetonitrile or MTBE.
Compared with the existing technology, the beneficial effects of the present invention are embodied in:
(1) method of the invention reduces environmental pollution while improving product quality quality, clean production,
Environmental protection makes product be more suitable for producing in enormous quantities.
(2) the used solvent of the present invention participates in reaction, makes bromine atom utilization rate height in brominated reagent, and sulfuric acid dosage is few, and three
It is useless few, product yield height and high financial profit.
Specific embodiment
The present invention is further explained in the light of specific embodiments, but protection scope of the present invention is not limited in
This.
Embodiment 1 (comparative example 1)
In equipped with thermometer, blender four-hole boiling flask, 15.6g 0-chloro-benzoic acid is added and is dissolved in 250.0g sulfuric acid
Afterwards, 19.8g NBS is added in reaction solution, opens stirring, control 25~30 DEG C of reaction temperature, insulation reaction 1h, reaction solution becomes
For black, raw material after completion of the reaction, reaction solution is poured into ice water and is quenched, reaction solution is spin-dried for, filtering, with 15.6ml second
Alcohol recrystallization, obtaining crude product is class black, obtains 11.7g crude product.Yield 50%.Purity 80%, the bromo- 2- halogen-benzoic acid a of 3- contain
Measure the bromo- 2- halogen of 8%, 3,5- bis--benzoic acid b content 9%.Product quality is poor, and impurity is more.
Embodiment 2 (comparative example 2)
In equipped with thermometer, blender four-hole boiling flask, 15.6g 0-chloro-benzoic acid is added and is dissolved in 124.8g solvent
Afterwards, 19.8g NBS is added in reaction solution, opens stirring, control 25~30 DEG C of reaction temperature, for 24 hours, reaction solution is not for insulation reaction
Reaction, no product generate.
Solvent attempts the halogenated alkanes solvents such as acetonitrile, DCM, chloroform, carbon tetrachloride, tetrahydrofuran, 1,2- dichloroethanes,
Equal unreacted.
Embodiment 3
In equipped with thermometer, blender four-hole boiling flask, 15.6g 0-chloro-benzoic acid is added in 46.8g sulfuric acid and 124.8g
After being dissolved in DCM, 19.8g NBS is added in reaction solution, opens stirring, controls 25~30 DEG C of reaction temperature, insulation reaction 1h,
Be precipitated off-white powder in reaction solution, raw material after completion of the reaction, product content 90% in reaction solution, a content 8%, b content
0.3%.Reaction solution is poured into ice water and is quenched, reaction solution is spin-dried for, filters, with 15.6ml ethyl alcohol recrystallization, can obtain
The chloro- 5- bromobenzoic acid of 16.5g2-.Yield 70.3%, purity 99.1%.1H NMR(CDCl3,400MHz),δ:11.16(s,1H)；
8.44(d,1H)；7.98(dd,1H)；7.33(d,1H).
Embodiment 4
In equipped with thermometer, blender four-hole boiling flask, 13.9g o-fluorobenzoic acid is added in 41.7g sulfuric acid and 111.2g
After being dissolved in DCM, 19.8g NBS is added in reaction solution, opens stirring, controls 25~30 DEG C of reaction temperature, insulation reaction 1h,
Off-white powder is precipitated in reaction solution, raw material after completion of the reaction, reaction solution is poured into ice water and is quenched, reaction solution is revolved
Dry, filtering with 13.9ml ethyl alcohol recrystallization, can obtain the fluoro- 5- bromobenzoic acid of 16.4g2-.Yield 75.5%, purity 99.0%.1H NMR(CDCl3,400MHz),δ:11.16(s,1H)；8.48(d,1H)；8.09(dd,1H)；7.24(d,1H).
Embodiment 5-7
Chloroform, carbon tetrachloride and 1 are attempted respectively, and 2- dichloroethanes makees solvent, and other conditions are same as Example 4, raw material
For o-fluorobenzoic acid.
| Solvent | Product weight/g | Yield/% | Purity/% |
| Chloroform | 15.3 | 70.4% | 99.39% |
| Carbon tetrachloride | 15.7 | 72.3% | 99.03% |
| 1,2- dichloroethanes | 15.9 | 73.2% | 99.16% |
Therefore, because chloroform and carbon tetrachloride category control class solvent, and 1,2- dichloroethanes is more toxic.Select dichloromethane
Alkane is tested as solvent.
Embodiment 8
In equipped with thermometer, blender four-hole boiling flask, 20.0g o-bromobenzoic acid is added in 60.0g sulfuric acid and 80.0g
After being dissolved in DCM, 19.8gNBS is added in reaction solution, opens stirring, controls 25~30 DEG C of reaction temperature, insulation reaction 2h,
Off-white powder is precipitated in reaction solution, raw material after completion of the reaction, reaction solution is poured into ice water and is quenched, reaction solution is revolved
Dry, filtering with 20ml ethyl alcohol recrystallization, can obtain 18.2g2,5- dibromobenzoic acid.Yield 65.4%, purity 98.1%.1H
NMR(CDCl3,400MHz),δ:11.16(s,1H)；8.24(d,1H)；7.69(dd,1H)；7.85(d,1H).
Embodiment 9
In equipped with thermometer, blender four-hole boiling flask, 20.0g o-bromobenzoic acid is added in 40.0g sulfuric acid and 80.0g
After being dissolved in DCM, 19.8g NBS is added in reaction solution, opens stirring, controls 25~30 DEG C of reaction temperature, insulation reaction 2h,
Off-white powder is precipitated in reaction solution, raw material after completion of the reaction, reaction solution is poured into ice water and is quenched, reaction solution is revolved
Dry, filtering with 60ml recrystallizing methanol, can obtain 18.5g2,5- dibromobenzoic acid.Yield 66.4%, purity 99.0%.
Therefore, which, which can be used less sulfuric acid and solvent, can be obtained both economical technique.
Claims (6)
1. a kind of synthetic method of 2- halogen -5- bromobenzoic acid, which comprises the following steps:
Under the action of sulfuric acid, o-Halogen benzoic acids and NBS carry out bromo-reaction in organic solvent, and temperature is -10 DEG C~80 DEG C,
Time is 1~for 24 hours, after reaction after post treatment, obtain the 2- halogen -5- bromobenzoic acid；
Shown in the structure of the o-Halogen benzoic acids such as formula (I):
Shown in the structure such as formula (II) of the 2- halogen -5- bromobenzoic acid:
In formula (I)~(II), X is selected from-F ,-Cl or-Br.
2. the synthetic method of 2- halogen -5- bromobenzoic acid according to claim 1, which is characterized in that the organic solvent
For one or more of methylene chloride, chloroform, carbon tetrachloride, 1,2- dichloroethanes；
The o-Halogen benzoic acids and the mass ratio of consumption of organic solvent are 1:0.5~50.
3. the synthetic method of 2- halogen -5- bromobenzoic acid according to claim 1, which is characterized in that the o-Halogen benzoic acids
Mass ratio with sulfuric acid dosage is 1:0.5~50.
4. the synthetic method of 2- halogen -5- bromobenzoic acid according to claim 1, which is characterized in that the post-processing
Process is as follows:
Reaction solution is quenched with ice water, recycling design, filters to obtain 2- halogen -5- bromobenzoic acid crude product, crude product is by being recrystallized to give
Sterling.
5. the synthetic method of 2- halogen -5- bromobenzoic acid according to claim 5, which is characterized in that molten used in recrystallizing
Agent is halogenated hydrocarbon solvent, alcohols solvent, acetonitrile or ether solvent.
6. the synthetic method of 2- halogen -5- bromobenzoic acid according to claim 6, which is characterized in that molten used in recrystallizing
Agent is methanol, ethyl alcohol, DCM, acetonitrile or MTBE.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110002989A (en) * | 2019-03-15 | 2019-07-12 | 河北合佳医药科技集团股份有限公司 | A kind of preparation method of the bromo- 2- chlorobenzoic acid of highly selective 5- |
| CN110590541A (en) * | 2019-10-16 | 2019-12-20 | 吕东 | Preparation method of 5-bromo-2-chlorobenzoic acid |
| CN111925289A (en) * | 2020-06-30 | 2020-11-13 | 浙江美诺华药物化学有限公司 | Preparation method of 5-bromo-2-chlorobenzoic acid |
| CN112250562A (en) * | 2020-10-22 | 2021-01-22 | 怀化宝华生物科技有限公司 | Synthetic method of 2-bromo-5-methoxybenzoic acid |
| WO2023019849A1 (en) | 2021-08-16 | 2023-02-23 | 浙江奥翔药业股份有限公司 | Method for preparing 5-bromo-2-chloro-benzoic acid as raw material in hypoglycemic drug synthesis |
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| CN110002989A (en) * | 2019-03-15 | 2019-07-12 | 河北合佳医药科技集团股份有限公司 | A kind of preparation method of the bromo- 2- chlorobenzoic acid of highly selective 5- |
| CN110002989B (en) * | 2019-03-15 | 2021-06-22 | 河北合佳医药科技集团股份有限公司 | Preparation method of high-selectivity 5-bromo-2-chlorobenzoic acid |
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| WO2023019849A1 (en) | 2021-08-16 | 2023-02-23 | 浙江奥翔药业股份有限公司 | Method for preparing 5-bromo-2-chloro-benzoic acid as raw material in hypoglycemic drug synthesis |
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