CN106365950A - Preparation method of pentafluoroiodobenzene - Google Patents
Preparation method of pentafluoroiodobenzene Download PDFInfo
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- CN106365950A CN106365950A CN201610739583.9A CN201610739583A CN106365950A CN 106365950 A CN106365950 A CN 106365950A CN 201610739583 A CN201610739583 A CN 201610739583A CN 106365950 A CN106365950 A CN 106365950A
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- Prior art keywords
- iodosuccinimide
- phenyl
- pentafluoride
- sulphuric acid
- concentrated sulphuric
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- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method of pentafluoroiodobenzene and belongs to the technical field of chemical industry, particularly to the field of chemical synthesis. The preparation method enables pentafluorobenzene and iodosuccinimide to react in concentrated sulfuric acid, wherein a molar ratio of the pentafluorobenzene, the iodosuccinimide and the concentrated sulfuric acid is 1:(1-1.5):(5-7.5). The pentafluoroiodobenzene prepared by using the method provided herein has high purity and yield, and the method produces little three wastes, is simple to performance and is easy to industrialize.
Description
Technical field
The present invention relates to a kind of preparation method of five fluorine iodobenzenes, belong to chemical technology field, particularly belong to chemosynthesis neck
Domain.
Background technology
Five fluorine iodobenzenes, its structural formula is:
In prior art, its synthetic method is the two-step synthesis method with five bromofluorobenzenes or five fluorochlorobenzenes as raw material, Chinese patent
Mention in cn102827614, cn102153454, cn104194800, raw material is made grignard reagent by such method first, then profit
Carry out the two-step method of iodate with iodine, the method products obtained therefrom yield is 64%, and complex steps yield is low, high cost, three-protection design
Complicated.organic letters 11(2)；421-423；A kind of phenyl-pentafluoride and iodine is disclosed in secondary phosphorus in 2009supporting
The method that under sour potassium effect, reaction under high pressure synthesizes five fluorine iodobenzenes, the method products obtained therefrom yield is 40%, and the method yield is low, adopts
With high pressure equipment, congenial rate is low, high cost, and the three wastes are many.
Content of the invention
Method product for overcoming prior art to synthesize five fluorine iodobenzenes with five bromofluorobenzenes or five fluorochlorobenzenes for raw material two step is received
Rate is low, the problem of high cost, and the present invention provides a kind of product purity height, high income, raw material to be easy to get, and course of industrialization is simple, one-tenth
The method of this low one-step synthesis five fluorine iodobenzene.
A kind of preparation method of five fluorine iodobenzenes, the method makes phenyl-pentafluoride and n- N-iodosuccinimide anti-in concentrated sulphuric acid
Should, wherein, phenyl-pentafluoride, n- N-iodosuccinimide, the mol ratio of concentrated sulphuric acid are 1:1～1.5:5～7.5.
The phenyl-pentafluoride described in preparation method of five fluorine iodobenzenes of the present invention, n- N-iodosuccinimide, concentrated sulphuric acid mole
Than the h referring in phenyl-pentafluoride and n- N-iodosuccinimide, concentrated sulphuric acid2so4Mol ratio.
The sulfuric acid solution that term " concentrated sulphuric acid " of the present invention is 98% for sulphuric acid mass fraction.
Phenyl-pentafluoride of the present invention, n- N-iodosuccinimide, the mol ratio of concentrated sulphuric acid are preferably 1:1～1.2:5～6,
Most preferably 1:1:5.
The preparation method of five fluorine iodobenzenes of the present invention is preferred: by phenyl-pentafluoride and n- N-iodosuccinimide in concentrated sulphuric acid
Reaction, gained mix products are layered after terminating by reaction, extract and distill, obtain product.
Further, described " layering, extraction and distillation " is preferably gained mix products static layering, obtains upper strata acid
Layer adds dichloromethane extraction, the oil reservoir being obtained by extraction and gas producing formation to merge, and normal pressure concentrates dichloromethane solvent, is subsequently adding Asia
Sodium bisulphate solution, steam distillation removes the tar in product, and the product that steam distillation obtains carries out rectification again, obtains five fluorine iodine
Benzene.
Preferably react in all technical schemes of preparation method of five fluorine iodobenzenes of the present invention and carry out under stirring, enter
The preferred mixing speed of one step is 300～500r/min.
At preferably 30～40 DEG C in all technical schemes of preparation method of five fluorine iodobenzenes of the present invention, make phenyl-pentafluoride and n-
N-iodosuccinimide reacts in concentrated sulphuric acid.
Especially, preferably phenyl-pentafluoride is added dense sulfur in all technical schemes of preparation method of five fluorine iodobenzenes of the present invention
In acid；N- N-iodosuccinimide is added in above-mentioned gained mixed solution.
Further, preferably by n- iodo succinyl in all technical schemes of preparation method of five fluorine iodobenzenes of the present invention
Imines is at the uniform velocity added in mixed solution, and further, preferably n- N-iodosuccinimide is to be at the uniform velocity added to mixed solution
In and added in 5～8 hours.
One exemplary aspect of the invention is:
A kind of preparation method of five fluorine iodobenzenes, at 30～40 DEG C, n- N-iodosuccinimide is at the uniform velocity added to phenyl-pentafluoride
In the mixed liquor being formed with concentrated sulphuric acid；Charging terminates to be incubated at least 2h after 30～40 DEG C.
Further, a kind of preparation method of five fluorine iodobenzenes, at 30～40 DEG C, the mixing speed of 300～500r/min
Under, n- N-iodosuccinimide is at the uniform velocity added in the mixed liquor that phenyl-pentafluoride is formed with concentrated sulphuric acid；Charging terminates after 30～
40 DEG C, be incubated at least 2h under the mixing speed of 300～500r/min.
The invention has the benefit that the method tool with phenyl-pentafluoride for raw material one-step synthesis five fluorine iodobenzene that the present invention provides
There are following characteristics: one is that product purity is high, and content is 99%；Two is high income, and yield, in terms of phenyl-pentafluoride, is 85%；Three is three
Useless few；Four is without organic solvent, and sulphuric acid is reactant and solvent；Five is simple to operate, is conducive to industrialization.
Specific embodiment
Following non-limiting examples can make those of ordinary skill in the art that the present invention is more fully understood, but not with
Any mode limits the present invention.
Test method described in following embodiments, if no special instructions, is conventional method；Described reagent and material, such as
No specified otherwise, all commercially obtains.
Embodiment 1
Put into 504.2 grams of phenyl-pentafluorides, 1512 grams of concentrated sulphuric acids into 2000ml reactor, open stirring, control mixing speed
300r/min, controls temperature to be 38 DEG C, at the uniform velocity adds 675 grams of n- N-iodosuccinimides to take 5 hours altogether, adds per hour
135 grams, add to finish the 38 DEG C of insulations of control kettle temperature and be incubated for 2 hours and terminate, static layering, obtain upper strata acid layer and add dichloromethane extraction
Take, the oil reservoir being obtained by extraction and gas producing formation merge, and normal pressure concentrates dichloromethane solvent, is subsequently adding aqueous solution of sodium bisulfite,
Steam distillation removes the tar in product, and the product that steam distillation obtains carries out rectification again, obtains 750 grams of product, and five fluorine iodobenzenes contain
Amount 99%, yield, in terms of phenyl-pentafluoride, is 85%
Embodiment 2
Put into 504.2 grams of phenyl-pentafluorides, 2250 grams of concentrated sulphuric acids into 2000ml reactor, open stirring, control mixing speed
350r/min, controls temperature to be 35 DEG C, at the uniform velocity adds 1012.5 grams of n- N-iodosuccinimides to take 6 hours altogether, per hour plus
Enter 168.75 grams, add to finish the 35 DEG C of insulations of control kettle temperature and be incubated for 2 hours and terminate, static layering, obtain upper strata acid layer and add dichloro
Methane extracts, and the oil reservoir being obtained by extraction and gas producing formation merge, and normal pressure concentrates dichloromethane solvent, is subsequently adding sodium sulfite water
Solution, steam distillation removes the tar in product, and the product that steam distillation obtains carries out rectification again, obtains 775 grams of product, five fluorine iodine
Benzene content 99%, yield, in terms of phenyl-pentafluoride, is 87%
Embodiment 3
Put into 504.2 grams of phenyl-pentafluorides, 1800 grams of concentrated sulphuric acids into 2000ml reactor, open stirring, control mixing speed
360r/min, controls temperature to be 37 DEG C, at the uniform velocity adds 810 grams of n- N-iodosuccinimides to take 6 hours altogether, adds per hour
135 grams, add to finish the 37 DEG C of insulations of control kettle temperature and be incubated for 2 hours and terminate, static layering, obtain upper strata acid layer and add dichloromethane extraction
Take, the oil reservoir being obtained by extraction and gas producing formation merge, and normal pressure concentrates dichloromethane solvent, is subsequently adding aqueous solution of sodium bisulfite,
Steam distillation removes the tar in product, and the product that steam distillation obtains carries out rectification again, obtains 766 grams of product, and five fluorine iodobenzenes contain
Amount 99%, yield, in terms of phenyl-pentafluoride, is 86%.
Claims (8)
1. a kind of preparation method of five fluorine iodobenzenes, the method makes phenyl-pentafluoride and n- N-iodosuccinimide react in concentrated sulphuric acid,
Wherein, phenyl-pentafluoride, n- N-iodosuccinimide, the mol ratio of concentrated sulphuric acid are 1:1～1.5:5～7.5.
2. method according to claim 1 it is characterised in that: described phenyl-pentafluoride, n- N-iodosuccinimide, concentrated sulphuric acid
Mol ratio is 1:1～1.2:5～6.
3. method according to claim 2 it is characterised in that: described phenyl-pentafluoride, n- N-iodosuccinimide, concentrated sulphuric acid
Mol ratio is 1:1:5.
4. method according to claim 1 it is characterised in that: described reaction is carried out at a temperature of 30～40 DEG C.
5. the method according to claim 1 or 4 it is characterised in that: by phenyl-pentafluoride add concentrated sulphuric acid in；Mix to above-mentioned gained
Close and in solution, add n- N-iodosuccinimide.
6. method according to claim 5 it is characterised in that: at 30～40 DEG C, by n- N-iodosuccinimide add five
In the mixed liquor that fluorobenzene is formed with concentrated sulphuric acid；Charging terminates to be incubated at least 2h after 30～40 DEG C.
7. method according to claim 1 it is characterised in that: reaction terminate after gained mix products are layered, extraction
Take and distill, obtain product.
8. method according to claim 1 it is characterised in that: described reaction is carried out under stirring, and mixing speed is
300～500r/min.
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| CN201610739583.9A CN106365950B (en) | 2016-08-26 | 2016-08-26 | A kind of preparation method of five fluorine iodobenzene |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0995753A2 (en) * | 1998-10-23 | 2000-04-26 | Nippon Shokubai Co., Ltd. | Method for manufacturing fluoroaryl magnesium halide |
| CN102827614A (en) * | 2012-09-24 | 2012-12-19 | 上海天问化学有限公司 | Negative liquid crystal containing 2, 3, 5, 6-tetra-fluorine phenylene, as well as synthesis method and application of negative liquid crystal |
| CN103333697A (en) * | 2013-07-16 | 2013-10-02 | 上海天问化学有限公司 | Nematic negative liquid crystal containing 2,3,5,6-tetrafluorotolane, synthetic method and application |
| CN104194800A (en) * | 2014-08-11 | 2014-12-10 | 福建省邵武市永晶化工有限公司 | Fluorine-containing diphenyldiacetylene nematic negative liquid crystal, synthesis method and application |
-
2016
- 2016-08-26 CN CN201610739583.9A patent/CN106365950B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0995753A2 (en) * | 1998-10-23 | 2000-04-26 | Nippon Shokubai Co., Ltd. | Method for manufacturing fluoroaryl magnesium halide |
| CN102827614A (en) * | 2012-09-24 | 2012-12-19 | 上海天问化学有限公司 | Negative liquid crystal containing 2, 3, 5, 6-tetra-fluorine phenylene, as well as synthesis method and application of negative liquid crystal |
| CN103333697A (en) * | 2013-07-16 | 2013-10-02 | 上海天问化学有限公司 | Nematic negative liquid crystal containing 2,3,5,6-tetrafluorotolane, synthetic method and application |
| CN104194800A (en) * | 2014-08-11 | 2014-12-10 | 福建省邵武市永晶化工有限公司 | Fluorine-containing diphenyldiacetylene nematic negative liquid crystal, synthesis method and application |
Non-Patent Citations (6)
| Title |
|---|
| CHAIKOVSKI, VITOLD K. 等: "N-Iodoimines in H2SO4 as the most powerful iodination agents for deactivated arenes", 《PROCEEDINGS-KORUS 2000, THE KOREA-RUSSIA INTERNATIONAL SYMPOSIUM ON SCIENCE AND TECHNOLOGY, 4TH, ULSAN, REPUBLIC OF KOREA》 * |
| CHAIKOVSKII,V.K. 等: "Superactivity and dual reactivity of the system N-iodosuccinimide-H2SO4 in the iodination of deactivated arenes", 《RUSSIAN JOURNAL OF ORGANIC CHEMISTRY》 * |
| CHAIKOVSKII,V.K. 等: "Synthesis of N-iodosuccinimide and its application in H2SO4 as efficient iodination reagent for deactivated aromatic compounds", 《RUSSIAN JOURNAL OF ORGANIC CHEMISTRY》 * |
| KRASNOKUTSKAYA,E.A. 等: "Comparative Study of the Reactivity of Iodinating Agents in Solution and Solid Phase", 《RUSSIAN JOURNAL OF ORGANIC CHEMISTRY》 * |
| PRAKASH,G.K.SURYA 等: "N-Halosuccinimide/BF3-H2O,Efficient Electrophilic Halogenating Systems for Aromatics", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
| 古双喜 等: "N-碘代丁二酰亚胺在有机合成中的应用", 《化学试剂》 * |
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Inventor after: Han Xiaodong Inventor after: Jiang Dianbao Inventor after: Zhang Hongxue Inventor after: Pei Xiong Inventor before: Han Xiaodong Inventor before: Jiang Dianping Inventor before: Zhang Hongxue Inventor before: Pei Xiong |
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