CN111099959B - Industrial production method of 1, 4-dibromo-2, 5-diiodobenzene - Google Patents
Industrial production method of 1, 4-dibromo-2, 5-diiodobenzene Download PDFInfo
- Publication number
- CN111099959B CN111099959B CN201911394699.3A CN201911394699A CN111099959B CN 111099959 B CN111099959 B CN 111099959B CN 201911394699 A CN201911394699 A CN 201911394699A CN 111099959 B CN111099959 B CN 111099959B
- Authority
- CN
- China
- Prior art keywords
- diiodobenzene
- dibromo
- industrial production
- dibromobenzene
- production method
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
- C07C17/12—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms in the ring of aromatic compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses an industrial production method of 1, 4-dibromo-2, 5-diiodobenzene, belonging to the technical field of organic synthesis and comprising the following steps: taking 1, 4-dibromobenzene as a raw material, and carrying out iodination reaction at 68-72 ℃ under the action of trifluoroacetic acid and N-iodosuccinimide to prepare 1, 4-dibromo-2, 5-diiodobenzene; compared with the existing synthesis method of 1, 4-dibromo-2, 5-diiodobenzene, the method avoids the use of concentrated sulfuric acid, has mild synthesis conditions, simple operation and safe process, and is convenient for industrial production.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to an industrial production method of 1, 4-dibromo-2, 5-diiodobenzene.
Background
The 1, 4-dibromo-2, 5-diiodobenzene contains two halogens of bromine and iodine, and the same halogens are mutually para-positioned to form a completely symmetrical compound; the halogen has higher reactivity, and can realize the growth of chain segments through reactions such as Suzuki, Stille, Buchwald-Hartwig and the like. 1, 4-dibromo-2, 5-diiodobenzene is used as a starting material, is widely used for synthesizing compounds with conjugated structures, and has wide application in the fields of solar cells, organic light-emitting diodes, field effect transistors and the like.
At present, 1, 4-dibromo-2, 5-diiodobenzene is synthesized by using 1, 4-dibromobenzene as a raw material, and the specific synthesis methods mainly include two methods: 1) iodination with iodine under the action of concentrated sulfuric acid (such as CN 108117563A); 2) iodination with periodic acid and potassium iodide (CN 106543216A) is carried out under the action of concentrated sulfuric acid. A large amount of concentrated sulfuric acid is used in the synthesis process of the two types of 1, 4-dibromo-2, 5-diiodobenzene, and the concentrated sulfuric acid is strong acid, so that the danger is high in industrial production and the post-treatment is difficult. In addition, when iodine is used for iodination, the reaction temperature is high, 1, 4-dibromobenzene is easy to sublimate at high temperature, and raw materials are easy to desublimate on the wall of a reaction kettle in the reaction process. When periodic acid and potassium iodide are used for iodination, the reaction temperature is low, 1, 4-dibromobenzene is difficult to dissolve, the method is complex to operate, and the risk of industrial production and the difficulty of post-treatment are greatly increased.
Disclosure of Invention
In order to solve the problems, the invention discloses an industrial production method of 1, 4-dibromo-2, 5-diiodobenzene, which avoids the use of concentrated sulfuric acid in the synthetic process, is simple and safe to operate, is easy to carry out post-treatment and is suitable for industrial production.
An industrial production method of 1, 4-dibromo-2, 5-diiodobenzene comprises the following steps: taking 1, 4-dibromobenzene as a raw material, and carrying out iodination reaction at 68-72 ℃ under the action of trifluoroacetic acid and N-iodosuccinimide to prepare 1, 4-dibromo-2, 5-diiodobenzene;
the synthetic route is as follows:
preferably, the industrial production method of the 1, 4-dibromo-2, 5-diiodobenzene specifically comprises the following steps:
mixing trifluoroacetic acid and 1, 4-dibromobenzene, heating to 68-72 ℃, adding N-iodosuccinimide, keeping the temperature at 68-72 ℃, reacting for 15-25 h, cooling to 20-30 ℃, diluting, filtering and recrystallizing to obtain 1, 4-dibromo-2, 5-diiodobenzene;
the dosage ratio of the 1, 4-dibromobenzene to the trifluoroacetic acid is 1 g: 20-40 mL, wherein the molar ratio of the 1, 4-dibromobenzene to the N-iodosuccinimide is 1: 2.0-2.6.
Preferably, the N-iodosuccinimide is added in 2 portions, each 2h apart.
Preferably, the reagent used in the dilution process is water.
Preferably, the reagent used for recrystallization is methylcyclohexane.
Compared with the prior art, the invention has the following beneficial effects:
compared with the existing synthesis method of 1, 4-dibromo-2, 5-diiodobenzene, the invention adopts 1, 4-dibromobenzene as a raw material to carry out iodination reaction under the action of trifluoroacetic acid and N-iodosuccinimide, avoids the use of concentrated sulfuric acid in the existing synthesis method, and has the advantages of lower reaction temperature, mild synthesis conditions, simple operation, safe process, easy post-treatment and convenient industrial production.
Drawings
FIG. 1 shows the preparation of 1, 4-dibromo-2, 5-diiodobenzene obtained in example 1 1 H NMR spectrum;
FIG. 2 shows the reaction scheme of 1, 4-dibromo-2, 5-diiodobenzene produced in example 1 13 C NMR spectrum;
FIG. 3 is a mass spectrum of 1, 4-dibromo-2, 5-diiodobenzene obtained in example 1.
Detailed Description
In order to make the technical solutions of the present invention better understood and implemented by those skilled in the art, the present invention is further described below with reference to the following specific embodiments and the accompanying drawings, but the embodiments are not meant to limit the present invention.
Example 1
An industrial production method of 1, 4-dibromo-2, 5-diiodobenzene specifically comprises the following steps:
adding 3000mL of trifluoroacetic acid and 100.00g (423.89mmol) of 1, 4-dibromobenzene into a 5000mL three-neck round-bottom flask in sequence, stirring and heating to 68 ℃, adding 209.82g (932.56mmol) of N-iodosuccinimide twice at intervals of 2h, keeping the temperature at 68 ℃ for reacting for 20h, cooling to 20 ℃, adding 3000mL of water into the system for diluting, filtering, and recrystallizing a filter cake with methylcyclohexane to obtain 148.39g of white-like solid with the yield of 71.78%. As shown in FIGS. 1-3, 1 H NMR(500MHz,d 6 -DMSO):δ8.19(2H,s). 13 C NMR(500MHz,d 6 -DMSO):δ103.09,129.02,141.83.GC-MS:calcd for C 6 H 2 Br 2 I 2 (M + ) 488; found,488, thus, the successful synthesis of 1, 4-dibromo-2, 5-diiodobenzene can be proved.
Example 2
An industrial production method of 1, 4-dibromo-2, 5-diiodobenzene specifically comprises the following steps:
sequentially adding 4000mL of trifluoroacetic acid and 100.00g (423.89mmol) of 1, 4-dibromobenzene into a 5000mL three-neck round-bottom flask, stirring and heating to 72 ℃, adding 190.73g (847.78mmol) of N-iodosuccinimide twice at intervals of 2h, keeping the temperature for reacting at 72 ℃ for 15h, cooling to 30 ℃, adding 4000mL of water into a system for diluting, filtering, and recrystallizing a filter cake by methylcyclohexane to obtain 135.16g of white-like solid with yield of 135.16g65.38％。GC-MS:calcd for C 6 H 2 Br 2 I 2 (M + ),488；found,488. 1 H NMR(500MHz,d 6 -DMSO):δ8.19(2H,s). 13 C NMR(500MHz,d 6 -DMSO):δ103.09,129.02,141.83.
Example 3
An industrial production method of 1, 4-dibromo-2, 5-diiodobenzene specifically comprises the following steps:
2000mL of trifluoroacetic acid and 100.00g (423.89mmol) of 1, 4-dibromobenzene are sequentially added into a 5000mL three-neck round-bottom flask, the mixture is stirred and heated to 70 ℃, 247.95g (1102.11mmol) of N-iodosuccinimide is added in two times at intervals of 2h, the temperature is kept at 70 ℃ for reaction for 25h, the temperature is reduced to 25 ℃, 2000mL of water is added into the system for dilution, the filtration is carried out, and a filter cake is recrystallized by methylcyclohexane, so that 108.56g of white-like solid is obtained, and the yield is 52.51%. 1 H NMR(500MHz,d 6 -DMSO):δ8.19(2H,s). 13 C NMR(500MHz,d 6 -DMSO):δ103.09,129.02,141.83.GC-MS:calcd for C 6 H 2 Br 2 I 2 (M + ),488；found,488.
Compared with the existing synthesis method of 1, 4-dibromo-2, 5-diiodobenzene, the method disclosed by the invention has the advantages that 1, 4-dibromobenzene is adopted as a raw material, iodination reaction is carried out under the action of trifluoroacetic acid and N-iodosuccinimide, 1, 4-dibromo-2, 5-diiodobenzene is successfully synthesized, the use of concentrated sulfuric acid in the existing synthesis method is avoided in the synthesis process, the reaction temperature is low, the synthesis condition is mild, the operation is simple, the process is safe, the post-treatment is easy, and the industrial production is facilitated.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, it is intended that such changes and modifications be included within the scope of the appended claims and their equivalents.
Claims (5)
1. An industrial production method of 1, 4-dibromo-2, 5-diiodobenzene is characterized by comprising the following steps: taking 1, 4-dibromobenzene as a raw material, and carrying out iodination reaction at 68-72 ℃ under the action of trifluoroacetic acid and N-iodosuccinimide to prepare 1, 4-dibromo-2, 5-diiodobenzene;
the synthetic route is as follows:
2. the industrial production method of 1, 4-dibromo-2, 5-diiodobenzene according to claim 1, comprising the following steps:
mixing trifluoroacetic acid and 1, 4-dibromobenzene, heating to 68-72 ℃, adding N-iodosuccinimide, keeping the temperature at 68-72 ℃, reacting for 15-25 h, cooling to 20-30 ℃, diluting, filtering and recrystallizing to obtain 1, 4-dibromo-2, 5-diiodobenzene;
the dosage ratio of the 1, 4-dibromobenzene to the trifluoroacetic acid is 1 g: 20-40 mL, wherein the molar ratio of the 1, 4-dibromobenzene to the N-iodosuccinimide is 1: 2.0-2.6.
3. The method for industrially producing 1, 4-dibromo-2, 5-diiodobenzene according to claim 2, wherein the N-iodo succinimide is added in 2 portions at intervals of 2 hours.
4. The industrial production method of 1, 4-dibromo-2, 5-diiodobenzene according to claim 2, wherein the reagent used in the dilution process is water.
5. The method for industrially producing 1, 4-dibromo-2, 5-diiodobenzene according to claim 2, wherein the reagent for recrystallization is methylcyclohexane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911394699.3A CN111099959B (en) | 2019-12-30 | 2019-12-30 | Industrial production method of 1, 4-dibromo-2, 5-diiodobenzene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911394699.3A CN111099959B (en) | 2019-12-30 | 2019-12-30 | Industrial production method of 1, 4-dibromo-2, 5-diiodobenzene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111099959A CN111099959A (en) | 2020-05-05 |
| CN111099959B true CN111099959B (en) | 2022-09-02 |
Family
ID=70425051
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911394699.3A Active CN111099959B (en) | 2019-12-30 | 2019-12-30 | Industrial production method of 1, 4-dibromo-2, 5-diiodobenzene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111099959B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112537996B (en) * | 2020-12-25 | 2022-05-27 | 大连金点生物科技有限公司 | Method for green synthesis of 2, 5-dibromo-1, 4-diiodobenzene intermediate |
| CN115959969A (en) * | 2022-12-19 | 2023-04-14 | 安徽科技学院 | Synthetic method of 1,4-dibromo-2,5-diiodobenzene and homolog thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1161960A (en) * | 1996-02-22 | 1997-10-15 | 赫彻斯特股份公司 | Ortho-substituted benzoylguanidine, preparation method, use as medicine or diagnostic reagent and medicine containing same |
| CN106543216A (en) * | 2016-10-27 | 2017-03-29 | 天津大学 | A kind of benzene, naphtho- thiophene cough up derivative organic photoelectrical material and preparation method thereof |
| CN108117563A (en) * | 2017-11-28 | 2018-06-05 | 华南协同创新研究院 | A kind of Organic micromolecular semiconductor material of the Dithiophene containing anthra and its preparation method and application |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110207114A1 (en) * | 2008-10-29 | 2011-08-25 | Indian Institute Of Technology Mumbai | Amplified Fluorescence Polymers and Sensor Thereof |
-
2019
- 2019-12-30 CN CN201911394699.3A patent/CN111099959B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1161960A (en) * | 1996-02-22 | 1997-10-15 | 赫彻斯特股份公司 | Ortho-substituted benzoylguanidine, preparation method, use as medicine or diagnostic reagent and medicine containing same |
| CN106543216A (en) * | 2016-10-27 | 2017-03-29 | 天津大学 | A kind of benzene, naphtho- thiophene cough up derivative organic photoelectrical material and preparation method thereof |
| CN108117563A (en) * | 2017-11-28 | 2018-06-05 | 华南协同创新研究院 | A kind of Organic micromolecular semiconductor material of the Dithiophene containing anthra and its preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111099959A (en) | 2020-05-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111099959B (en) | Industrial production method of 1, 4-dibromo-2, 5-diiodobenzene | |
| CN103992225B (en) | A kind of salicylaldehyde derivatives and preparation method thereof | |
| CN109776381B (en) | Preparation method of spiro indolone compound in aqueous phase | |
| CN110343064B (en) | Synthesis method of [60] fullerene-tetrahydrocyclopenta [2,3-b ] indole derivative | |
| CN101928233A (en) | Cholromethylation method of benzoic acid derivative | |
| CN108358868B (en) | Preparation method of 2-substituted benzothiazole compound | |
| CN102584686A (en) | Water soluble terpyridyl fluorescent compound and preparation method thereof | |
| CN110317132B (en) | Preparation method of sodium phenylbutyrate | |
| CN104926785A (en) | Selenium aromatic heterocycte derivative and preparation method thereof | |
| EP0076639B1 (en) | Production of 11,11,12,12-tetracyano-9,10-anthraquinodimethane and derivatives thereof | |
| CN104230966A (en) | Benzimidazole binuclear zinc metal complex and application of complex in PVC (polyvinyl chloride) thermal stabilizer | |
| CN107235853A (en) | It is a kind of to be used to prepare Canton love-pea vine A prime and its synthetic method of isomers | |
| CN113582843A (en) | Preparation method of 5-chloro-2-fluoro-3-hydroxybenzoic acid ethyl ester | |
| CN108083963B (en) | Synthetic method of diarylethene | |
| TW202106663A (en) | Method for producing arylsulfonic acid ester compound | |
| CN113004248A (en) | Method for synthesizing carbazole compound by catalyzing hydrocarbon amination reaction with cobalt | |
| JP2006193444A (en) | Method for producing 4,4'-dicarboxy-2,2'-bipyridine | |
| JP2006206516A (en) | Method for producing 4,4'-dicarboxy-2,2'-bipyridine | |
| JPH0782207A (en) | Production of fluorenone and oxidation catalyst used therein | |
| CN112679361B (en) | Synthetic method of 3-fluoro-5-nitropyridine-2-formaldehyde | |
| CN110483494B (en) | Chiral bisoxazoline-hydrogenated imidazole carbene salt compound, and synthetic method and application thereof | |
| CN102633606B (en) | 3,3'-dimethoxy-5,5'-dibromo-6,6'-diiodobiphenyl and synthesis method thereof | |
| CN116813525B (en) | Synthesis method of polyacetyl substituted oxindole compound | |
| CN1031083A (en) | The preparation method of compounds with antiulcer action | |
| KR101251625B1 (en) | Novel manufacturing method of dutasteride using novel intermediates |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |