CN110078613A - A kind of synthetic method of 2- halogen -5- iodo-benzoic acid - Google Patents
A kind of synthetic method of 2- halogen -5- iodo-benzoic acid Download PDFInfo
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- CN110078613A CN110078613A CN201910469871.0A CN201910469871A CN110078613A CN 110078613 A CN110078613 A CN 110078613A CN 201910469871 A CN201910469871 A CN 201910469871A CN 110078613 A CN110078613 A CN 110078613A
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- iodo
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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
Abstract
The invention discloses a kind of synthetic methods of 2- halogen -5- iodo-benzoic acid.The following steps are included: o-Halogen benzoic acids carry out a step iodo in iodo reagent can obtain 2- halogen -5- iodo-benzoic acid.Post-processing is by pouring into reaction solution after cold reproducibility aqueous solution is quenched, solvent evaporated, and recrystallizes, and filtering can obtain product.This 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 a kind of high product 2- halogen -5- iodo-benzoic acid
Synthetic method.
Background technique
2- halogen -5- iodo-benzoic 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- iodo-benzoic 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- iodo-benzoic acid is less, it is now known that have clearly report be Journal
Of Medicinal Chemistry, 5 (2006), 1506-1508. is using o-fluorobenzoic acid as raw material, using NIS/ sulfuric acid as iodo
Reagent carries out the synthesis fluoro- 5- iodo-benzoic acid of 2-；CN106748721 is nitrified with 0-chloro-benzoic acid, reduction, diazotising, iodo four
The step reaction synthesis chloro- 5- iodo-benzoic acid of 2-；Ye Fei etc. using methyl anthranilate as raw material, through iodo, sandmeyer reaction,
It hydrolyzes three-step reaction and synthesizes the chloro- 5- iodo-benzoic acid of 2-；Organic Chemistry, 10 (2008), 1797-1801. is to bromine iodine
Benzene is that raw material synthesizes the bromo- 5- iodo-benzoic acid of 2- with carbon dioxide reaction；Deng similar reaction.
Above scheme is analyzed, finds above method, although product can be obtained in NIS, but higher cost, economy are imitated
Benefit is low, and nitrification and diazo-reaction belong to dangerization reaction, are not easy industrialized production, and reaction step is long.Use carbon dioxide
Although when comparison it is green, reaction condition is harsher, reacted at -70 DEG C with butyl lithium, butyl lithium meet water meet oxygen easily send out
Raw exothermic reaction, humid air easily burns rapidly butyl lithium solution high concentration (being greater than 1.0M) in case of wet, and the solvent in packing container is general
All over being low boiling point flammable and combustible liquids, once expanded by heating is easy to cause explosion, and product yield is lower, is unfavorable for industrializing
Production.
Pertinent literature: carrying out iodo with sodium metaperiodate/potassium iodide/sulfuric acid in CA2735130A1, with a large amount of sulphur in reaction
Acid causes the three wastes more, and yield is lower, is unfavorable for industrializing.US2009/0143352A1 and Tetrahedron, 60
(2004), iodide reaction is carried out with sodium metaperiodate/iodine/sulfuric acid in 9113-9119, but its substrate and the application are different.
The applicant attempts using its reaction condition for synthesizing 2- halogen -5- iodo-benzoic acid, i.e., using o-Halogen benzoic acids as raw material, is added high
Sodium iodate/iodine carries out iodide reaction (see embodiment 1), has a small amount of product to generate in reaction as the result is shown, and reaction solution is carbonarius,
Impurity is more, the iodo- 2- halogen-benzoic acid (a) and 3 of 3-, and the iodo- 2- halogen-benzoic acid (b) of 5- bis- is larger.
For green, low cost and industry is suitble to be combined to 2- halogen -5- iodo-benzoic acid, the present invention is provided by repeatedly attempting
A kind of green synthesis method preparing 2- halogen -5- iodo-benzoic acid.
Summary of the invention
The present invention provides a kind of synthetic methods of 2- halogen -5- iodo-benzoic 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- iodo-benzoic acid, comprising the following steps:
Under the action of sulfuric acid, o-Halogen benzoic acids and iodo reagent carry out iodide reaction, fully reacting in organic solvent
Obtain the 2- halogen -5- iodo-benzoic acid after post treatment afterwards；
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- iodo-benzoic acid:
In formula (I)~(II), X is selected from-F ,-Cl ,-Br or-I.
Reaction route is as follows:
Preferably, the iodo reagent is made of oxidant and iodine.
The type of oxidant can generate large effect to reaction result, preferably, the oxidant is selected from high iodine
One or more of sour potassium, sodium metaperiodate, Potassiumiodate, sodium iodate, acid iodide.Wherein, the o-Halogen benzoic acids, oxidant and
The molar ratio of iodine is 1:0.1~0.2:0.5~0.6.
Preferably, the mass ratio of the o-Halogen benzoic acids and sulfuric acid dosage is 1:0.5~50；As further excellent
The mass ratio of choosing, the o-Halogen benzoic acids and sulfuric acid dosage is 1:0.5~20.
Preferably, the organic solvent is one of methylene chloride, chloroform, carbon tetrachloride, 1,2- dichloroethanes
Or it is a variety of.
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 post-processing includes: that reaction solution is poured into cold reproducibility aqueous solution to be quenched, it is evaporated molten
Agent is recrystallized, and the 2- halogen -5- iodo-benzoic acid is obtained by filtration.
Preferably, the reproducibility aqueous solution is selected from sodium hypophosphite, sodium hydrogensulfite, sodium dithionite, sulphur
One or more of sodium thiosulfate aqueous solution.
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 iodine atom utilization rate height in iodo 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, it is molten in 320.0g90% sulfuric acid that 15.6g 0-chloro-benzoic acid is added
3.8g sodium metaperiodate and 13.0g iodine are added in reaction solution Xie Hou, open stirring, control 25~30 DEG C of reaction temperature, heat preservation is anti-
1h, reaction solution blackening are answered, raw material after completion of the reaction, reaction solution is poured into cold sodium thiosulfate solution and is quenched, will
Reaction solution is spin-dried for, filtering, crude product purity 65%, a content 18%, b content 10%.With 46.8ml recrystallizing methanol, it is thick to obtain 12.6g
Product.Yield 45%.Purity 98.2%.
When using Tetrahedron, 60 (2004), when the reaction condition application 0-chloro-benzoic acid of 9113-9119, reaction solution
For black, product quality is poor, and impurity is more.
Embodiment 2
In equipped with thermometer, blender four-hole boiling flask, 15.6g 0-chloro-benzoic acid is added in 78.0g sulfuric acid and 62.4g
After being dissolved in DCM, 3.8g sodium metaperiodate and 13.0g iodine are added in reaction solution, open stirring, controls reaction temperature 25~30
DEG C, insulation reaction 1h is precipitated violet solid in reaction solution, and after completion of the reaction, product content 88% in reaction solution, 3- is iodo- for raw material
2- halogen-benzoic acid (a) content 8%, 3,5- bis- iodo- 2- halogen-benzoic acid (b) contents 2%.Reaction solution is poured into cold thiosulfuric acid
It is quenched in sodium water solution, reaction solution is spin-dried for, filtered, with 46.8ml recrystallizing methanol, the chloro- 5- iodine of 19.3g 2- can be obtained
Benzoic acid.Yield 68.6%, purity 99.1%.1H NMR(CDCl3,400MHz),δ:11.26(s,1H)；8.32(d,1H)；
7.77(dd,1H)；7.23(d,1H).
Embodiment 3
In equipped with thermometer, blender four-hole boiling flask, 15.6g 0-chloro-benzoic acid is added in 78.0g sulfuric acid and 62.4g
After being dissolved in DCM, 4.0g Potassiumiodate and 13.0g iodine are added in reaction solution, open stirring, controls 25~30 DEG C of reaction temperature,
Insulation reaction 1h, is precipitated violet solid in reaction solution, raw material after completion of the reaction, product content 89% in reaction, the iodo- 2- halogen-of 3-
Benzoic acid (a) content 9%, 3,5- bis- iodo- 2- halogen-benzoic acid (b) contents 0.5%.Reaction solution is poured into cold sodium thiosulfate
It is quenched in aqueous solution, reaction solution is spin-dried for, filtered, with 46.8ml recrystallizing methanol, the chloro- 5- iodobenzene of 19.6g2- can be obtained
Formic acid.Yield 69.6%, purity 99.3%.
Embodiment 4-6
Sodium iodate, potassium metaperiodate and acid iodide are attempted respectively as oxidant, and other conditions are same as Example 3.Raw material is thrown
Entering amount is all 15.6g, and raw material is 0-chloro-benzoic acid.
It was found that various oxidants are made obtaining yield and be not much different, economically, select sodium iodate more particularly suitable.
Embodiment 7
In equipped with thermometer, blender four-hole boiling flask, 13.9g o-fluorobenzoic acid is added in 69.5g sulfuric acid and 55.6g
After being dissolved in DCM, 4.5g sodium iodate and 13.0g iodine are added in reaction solution, open stirring, controls 25~30 DEG C of reaction temperature,
Violet solid is precipitated in reaction solution in insulation reaction 1h, and it is water-soluble that raw material pours into cold sodium thiosulfate after completion of the reaction, by reaction solution
It is quenched in liquid, reaction solution is spin-dried for, filtered, with 41.7ml recrystallizing methanol, the fluoro- 5- iodo-benzoic acid of 20g 2- can be obtained.
Yield 75.8%, purity 99.0%.1H NMR(CDCl3,400MHz),δ:11.24(s,1H)；8.41(d,1H)；7.86(dd,
1H)；7.13(d,1H).
Embodiment 8-10
Chloroform, carbon tetrachloride and 1 are attempted respectively, and 2- dichloroethanes makees solvent, and other conditions are same as Example 7, raw material
For o-fluorobenzoic acid.
| Solvent | Product weight/g | Yield/% | Purity/% |
| Chloroform | 19.4 | 73.5% | 99.29% |
| Carbon tetrachloride | 19.2 | 72.8% | 99.13% |
| 1,2- dichloroethanes | 18.7 | 70.8% | 99.06% |
Therefore, because chloroform and carbon tetrachloride category control class solvent, and 1,2- dichloroethanes yield is lower, is more toxic.
Methylene chloride is selected to be tested as solvent.
Embodiment 11
In equipped with thermometer, blender four-hole boiling flask, 20.0g o-bromobenzoic acid is added in 100.0g sulfuric acid and 80.0g
After being dissolved in DCM, 4.5g sodium iodate and 13.0g iodine are added in reaction solution, open stirring, controls 25~30 DEG C of reaction temperature,
Violet solid is precipitated in reaction solution in insulation reaction 1h, and it is water-soluble that raw material pours into cold sodium thiosulfate after completion of the reaction, by reaction solution
It is quenched in liquid, reaction solution is spin-dried for, filtered, with 40ml recrystallizing methanol, the bromo- 5- iodo-benzoic acid of 21.4g 2- can be obtained.
Yield 65.8%, purity 98.3%.1H NMR(CDCl3,400MHz),δ:11.26(s,1H)；8.22(d,1H)；7.58(dd,
1H)；7.37(d,1H).
Embodiment 12
Tested 24.8g o-iodobenzoic acid equipped with thermometer, in blender four-hole boiling flask, is added, other conditions with
Embodiment 8 is identical, obtains 18.7g 2,5- diiodo acid.Yield 50.1%, purity 98.5%.1H NMR(CDCl3,
400MHz),δ:11.25(s,1H)；8.02(d,1H)；7.47(dd,1H)；7.53(d,1H).
Embodiment 13
In equipped with thermometer, blender four-hole boiling flask, 20.0g o-bromobenzoic acid is added in 40g sulfuric acid and 80g DCM
After dissolution, 4.5g sodium iodate and 13.0g iodine are added in reaction solution, open stirring, controls 25~30 DEG C of reaction temperature, heat preservation is anti-
Answer 1h, be precipitated violet solid in reaction solution, raw material after completion of the reaction, reaction solution is poured into cold sodium thiosulfate solution into
Row is quenched, and reaction solution is spin-dried for, and filters, with 60ml recrystallizing methanol, can obtain the bromo- 5- iodo-benzoic acid of 21.7g 2-.Yield
66.7%, purity 99.0%.
Therefore, which, which can be used less sulfuric acid and solvent, can be obtained both economical technique.
Claims (10)
1. a kind of synthetic method of 2- halogen -5- iodo-benzoic acid, which comprises the following steps:
Under the action of sulfuric acid, o-Halogen benzoic acids and iodo reagent carry out iodide reaction in organic solvent, pass through after fully reacting
Later processing obtains the 2- halogen -5- iodo-benzoic 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- iodo-benzoic acid:
In formula (I)~(II), X is selected from-F ,-Cl ,-Br or-I.
2. the synthetic method of 2- halogen -5- iodo-benzoic acid according to claim 1, which is characterized in that the iodo reagent
It is made of oxidant and iodine.
3. the synthetic method of 2- halogen -5- iodo-benzoic acid according to claim 2, which is characterized in that the oxidant choosing
From one or more of potassium metaperiodate, sodium metaperiodate, Potassiumiodate, sodium iodate, acid iodide.
4. the synthetic method of 2- halogen -5- iodo-benzoic acid according to claim 1, which is characterized in that the adjacent halobenzene first
The mass ratio of acid and sulfuric acid dosage is 1:0.5~50.
5. the synthetic method of 2- halogen -5- iodo-benzoic 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.
6. the synthetic method of 2- halogen -5- iodo-benzoic acid according to claim 1 or 5, which is characterized in that neighbour's halobenzene first
The mass ratio of acid and organic solvent is 1:0.5~50.
7. the synthetic method of 2- halogen -5- iodo-benzoic acid according to claim 1, which is characterized in that the post-processing packet
It includes: reaction solution being poured into cold reproducibility aqueous solution and is quenched, solvent evaporated is recrystallized, and the 2- halogen -5- is obtained
Iodo-benzoic acid.
8. the synthetic method of 2- halogen -5- iodo-benzoic acid according to claim 7, which is characterized in that the reproducibility water
Solution be selected from sodium hypophosphite, sodium hydrogensulfite, sodium dithionite, sodium thiosulfate one of aqueous solution or more
Kind.
9. the synthetic method of 2- halogen -5- iodo-benzoic acid according to claim 7, which is characterized in that molten used in recrystallizing
Agent is halogenated hydrocarbon solvent, alcohols solvent, acetonitrile or ether solvent.
10. the synthetic method of 2- halogen -5- iodo-benzoic acid according to claim 9, which is characterized in that molten used in recrystallizing
Agent is methanol, ethyl alcohol, DCM, acetonitrile or MTBE.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110590541A (en) * | 2019-10-16 | 2019-12-20 | 吕东 | Preparation method of 5-bromo-2-chlorobenzoic acid |
| CN112194661A (en) * | 2020-10-22 | 2021-01-08 | 威海同丰海洋生物科技有限公司 | Preparation method of 4-amino-7-iodopyrrolo [2, l-f ] [ l,2,4] triazine |
| CN113582847A (en) * | 2021-07-16 | 2021-11-02 | 湖北工业大学 | Method for preparing iodobenzoic acid (ester) by improving sandmeyer reaction |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101525322A (en) * | 2009-01-20 | 2009-09-09 | 中国药科大学 | New technology for synthesizing Corey lactonic acid by pan boiling method |
| CN103539662A (en) * | 2013-10-18 | 2014-01-29 | 雅本化学股份有限公司 | Preparation and recovery method of 2-methyl-5-iodobenzoic acid |
| CN104086361A (en) * | 2014-07-25 | 2014-10-08 | 南通市华峰化工有限责任公司 | Preparation method of 2-chloro-5-iodobenzoic acid |
| CN106748721A (en) * | 2016-11-17 | 2017-05-31 | 山东铂源药业有限公司 | A kind of preparation method of the iodo-benzoic acid of 2 chlorine 5 |
| WO2018089904A1 (en) * | 2016-11-11 | 2018-05-17 | 3-V Biosciences, Inc. | Heterocyclic modulators of lipid synthesis |
| WO2018112094A1 (en) * | 2016-12-15 | 2018-06-21 | Amgen Inc. | 1,4-thiazine dioxide and 1,2,4-thiadiazine dioxide derivatives as beta-secretase inhibitors and methods of use |
-
2019
- 2019-05-31 CN CN201910469871.0A patent/CN110078613B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101525322A (en) * | 2009-01-20 | 2009-09-09 | 中国药科大学 | New technology for synthesizing Corey lactonic acid by pan boiling method |
| CN103539662A (en) * | 2013-10-18 | 2014-01-29 | 雅本化学股份有限公司 | Preparation and recovery method of 2-methyl-5-iodobenzoic acid |
| CN104086361A (en) * | 2014-07-25 | 2014-10-08 | 南通市华峰化工有限责任公司 | Preparation method of 2-chloro-5-iodobenzoic acid |
| WO2018089904A1 (en) * | 2016-11-11 | 2018-05-17 | 3-V Biosciences, Inc. | Heterocyclic modulators of lipid synthesis |
| CN106748721A (en) * | 2016-11-17 | 2017-05-31 | 山东铂源药业有限公司 | A kind of preparation method of the iodo-benzoic acid of 2 chlorine 5 |
| WO2018112094A1 (en) * | 2016-12-15 | 2018-06-21 | Amgen Inc. | 1,4-thiazine dioxide and 1,2,4-thiadiazine dioxide derivatives as beta-secretase inhibitors and methods of use |
Non-Patent Citations (6)
| Title |
|---|
| A. I. KOVALEV ET AL.: "Selective cross-coupling of 1-ethynyl-4-iodobenzenes with activated arylacetylenes", 《RUSSIAN CHEMICAL BULLETIN, INTERNATIONAL EDITION》 * |
| CARL J. KLEMME ET AL.: "SYNTHESIS OF IODOHIPPURIC ACIDS.I.2,5-,3,5-AND 3,4-DIIODOHIPPURIC ACIDS", 《J. ORG. CHEM》 * |
| CHRISTOPH LAMBERT ET AL.: "Heterogeneous Electron Transfer Processes in Self-Assembled Monolayers of Amine Terminated Conjugated Molecular Wires", 《LANGMUIR》 * |
| MARIANA FLORES-JARILLO ET AL.: "Synthesis of Fluorescent oligo(p-phenyleneethynylene) (OPE3) via Sonogashira Reactions", 《JOURNAL OF THE MEXICAN CHEMICAL SOCIETY》 * |
| MIN-TSANG HSIEH ET AL.: "Synthesis of fluazolate via the application of regioselective [3+2] cyclocondensation and nucleophilic substitution-cyclization strategies", 《TETRAHEDRON》 * |
| 葛秀涛主编: "《物理化学》", 31 August 2014, 中国科学技术大学出版社 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110590541A (en) * | 2019-10-16 | 2019-12-20 | 吕东 | Preparation method of 5-bromo-2-chlorobenzoic acid |
| CN112194661A (en) * | 2020-10-22 | 2021-01-08 | 威海同丰海洋生物科技有限公司 | Preparation method of 4-amino-7-iodopyrrolo [2, l-f ] [ l,2,4] triazine |
| CN113582847A (en) * | 2021-07-16 | 2021-11-02 | 湖北工业大学 | Method for preparing iodobenzoic acid (ester) by improving sandmeyer reaction |
| CN113582847B (en) * | 2021-07-16 | 2023-09-12 | 湖北工业大学 | Improved method for preparing iodo-benzoic acid (ester) by sandmeyer reaction |
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