CN107954878A - A kind of synthetic method of intermediate 3- fluoro-4-nitrophenols - Google Patents
A kind of synthetic method of intermediate 3- fluoro-4-nitrophenols Download PDFInfo
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- CN107954878A CN107954878A CN201711246902.3A CN201711246902A CN107954878A CN 107954878 A CN107954878 A CN 107954878A CN 201711246902 A CN201711246902 A CN 201711246902A CN 107954878 A CN107954878 A CN 107954878A
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- nitrophenols
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
Abstract
The invention discloses a kind of synthetic method of 3 fluorine of intermediate, 4 nitrophenol, comprise the following steps：(1) after 2,4 two bromo nitrobenzenes are mixed with water, 50 60 DEG C are heated to; under inert gas shielding, add cobalt acetate and be uniformly mixed, ammonium hydroxide is added dropwise afterwards and carries out back flow reaction; after being added dropwise to complete, continue to be stirred at reflux 1 2h of reaction, centrifuged after the completion of reaction; liquid separation, collects organic phase, vacuum distillation; the mixture of 3 bromine, 4 nitrophenol and 5 bromine 2 nitrophenol is made, after through steam distillation, ether extraction; recrystallization, separates isomer, and 3 bromine, 4 nitrophenol is made；(2) 3 bromine, 4 nitrophenol is added in DMSO and added after polyethylene glycol 400 is uniformly mixed, 40 50 DEG C are heated to, adds potassium fluoride, 4 5h of stirring reaction thereto, after reaction, vacuum distillation, after recrystallization, obtained 3 fluorine, the 4 nitrophenol synthetic method is easy to operate, mild condition, accessory substance is less, and product purity is high, and product yield is higher.
Description
Technical field
The present invention relates to medicine intermediate field, more particularly to a kind of synthesis side of intermediate 3- fluoro-4-nitrophenols
Method.
Background technology
Fluoro-aromatic compounds refer to the compound with fluoro substituents group on aromatic organic compounds, such compound
It is the important source material of synthesis medicine, pesticide and dyestuff etc..It is right with the rapid development of medical in recent years, pesticide and dye industry
The demand of aromatic series Organic fluoride intermediate increases sharply, thus cause industrial sector to aromatic series organic fluoride research with
The extensive concern of exploitation.The purposes of aromatic halide is quite varied, such compound can be used for synthetic herbicide, fungicide
And Functional dye etc..Wherein 3- fluoro-4-nitrophenols are a kind of quite varied fluoro-aromatic compounds of application, are synthesis
The necessary intermediate of a variety of insecticides, antiseptic, antidepressants and liquid crystal material etc..
It is several below the preparation method of existing research report 3- fluoro-4-nitrophenols：1st, m fluorophenol is in acetic acid medium
Middle nitrification process, using m fluorophenol as raw material, acetic acid is solvent, and concentrated nitric acid carries out nitration reaction for nitrating agent, then by complexity
3- fluoro-4-nitrophenols are made after post-processing step, this method yield is relatively low；2nd, m fluorophenol is in the concentrated sulfuric acid and sodium nitrate medium
Middle nitrification, using m fluorophenol as raw material, forms nitration mixture by nitrate and concentrated sulfuric acid effect generation nitric acid and excessive sulfuric acid, carries out
Nitration reaction, there are safety problem for this method operating process；3rd, m fluorophenol is through N- acylations, nitrification, hydrolysis, diazotising and water
Target product is prepared after solution, this method process route is longer, and product is not readily separated, and overall yield is relatively low；4th, m-fluoroaniline with
Benzaldehyde is through being condensed, nitrify, hydrolyze, prepares target product after diazotising and hydrolysis, this method equally exist process route compared with
The shortcomings that length, yield is relatively low.Therefore, research and development are a kind of operates relatively simple, the preparation side of the higher 3- fluoro-4-nitrophenols of yield
Method has important practical value.
Chinese patent CN200810053707.3 discloses a kind of preparation method of 3- fluoro-4-nitrophenols, including following
Step：M fluorophenol is dissolved in water-insoluble organic solvent, solvent CH2Cl2Or 1,2- dichloroethanes, solvent and a fluorine
The quality parts ratio of phenol is 10-20:1；At 0 DEG C -15 DEG C, 65% concentrated nitric acid of concentration, 65% concentrated nitric acid and a fluorobenzene are added dropwise to
The quality parts ratio of phenol is 1.5-1.8:1.When stirring reaction 0.5-1.5 is small at 0-15 DEG C after dripping off；Reactant is subjected to water
Steam distillation, solvent first steam, after distillate yellow dirty solution；After no grease distillates, stop distillation；With ether extraction kettle
Liquid, is washed with saturated sodium bicarbonate solution, then is washed with saturated nacl aqueous solution, and after anhydrous magnesium sulfate drying, filtering, is evaporated off second
Ether obtains faint yellow solid 3- fluoro-4-nitrophenols.The technique nitrification yield significantly improve, post-process simply, technological process it is short, molten
Agent is easily recycled, cost is low.
The content of the invention
The object of the present invention is to provide a kind of synthetic method of intermediate 3- fluoro-4-nitrophenols, synthetic method operation
Simply, mild condition, accessory substance is less, and product purity is high, and product yield is higher.
To achieve the above object, the present invention uses following technical scheme：
A kind of synthetic method of intermediate 3- fluoro-4-nitrophenols, comprises the following steps：
(1) after 2,4-, bis- bromo nitrobenzenes are mixed with water, 50-60 DEG C is heated to, under inert gas shielding, adds acetic acid
Cobalt is uniformly mixed, and ammonium hydroxide is added dropwise afterwards and carries out back flow reaction, after being added dropwise to complete, continues to be stirred at reflux reaction 1-2h, reaction
After the completion of centrifuge, liquid separation, collects organic phase, vacuum distillation, is made the mixed of the bromo- 4- nitrophenols of 3- and the bromo- 2- nitrophenols of 5-
Compound, after through steam distillation, ether extraction, recrystallization, separates isomer, and the bromo- 4- nitrophenols of 3- are made；
(2) the bromo- 4- nitrophenols of obtained 3- are added in DMSO and added after polyethylene glycol-400 is uniformly mixed, added
Heat adds potassium fluoride, stirring reaction 4-5h, after reaction, vacuum distillation, after recrystallization, is made thereto to 40-50 DEG C
3- fluoro-4-nitrophenols.
Preferably, the use molal volume ratio of 2,4-, bis- bromo nitrobenzenes and water is 0.4-0.6mol/L in the step (1).
Preferably, inert gas is helium or argon gas in the step (1).
Preferably, the use molar ratio of 2,4-, bis- bromo nitrobenzenes and cobalt acetate is 1.2-1.4 in the step (1):1.
Preferably, the use molal volume ratio of 2,4-, bis- bromo nitrobenzenes and ammonium hydroxide is 0.6-0.8mol/ in the step (1)
L, the concentration of ammonium hydroxide is 1mol/L.
Preferably, the use molal volume ratio of the bromo- 4- nitrophenols of 3- and DMSO are 0.2- in the step (2)
0.4mol/L。
Preferably, the usage amount volume ratio of DMSO and polyethylene glycol-400 is 11 in the step (2):2.
Preferably, the use molar ratio of the bromo- 4- nitrophenols of 3- and potassium fluoride is 1 in the step (2):1.2-1.5.
The invention has the advantages that being starting material using 2,4-, bis- bromo nitrobenzenes, substitute through perhydroxyl radical, fluorine takes
Target product 3- fluoro-4-nitrophenols are made after generation, preparation method raw material sources of the invention are wider, cheap and easy to get, prepare
Cheng Chengben is relatively low, and easy to operate, is very suitable for industrialized production popularization.The present invention uses cobalt acetate as catalyst
Hydroxyl substitutes, and has good selectivity, the conversion ratio of the preparation generation bromo- 4- nitrophenols of 3- is higher, and utilizes it as
The temperature conditionss needed for substitution reaction that catalyst carries out are more gentle, have higher security.In reaction process of the present invention
Catalyst fluorine substitution reaction is used as using polyethylene glycol-400 so that the reaction can be carried out without high temperature, energy consumption
Amount is few, economizes on resources.
Embodiment
In order to be better understood from the present invention, below by embodiment, the present invention is further described, and embodiment is served only for solving
The present invention is released, any restriction will not be formed to the present invention.
Embodiment 1
A kind of synthetic method of intermediate 3- fluoro-4-nitrophenols, comprises the following steps：
(1) after 2,4-, bis- bromo nitrobenzenes are mixed with water, 50 DEG C are heated to, under inert gas shielding, adds cobalt acetate
It is uniformly mixed, ammonium hydroxide is added dropwise afterwards and carries out back flow reaction, after being added dropwise to complete, continues to be stirred at reflux reaction 1h, reaction is completed
After centrifuge, organic phase is collected in liquid separation, vacuum distillation, and the mixture of the bromo- 4- nitrophenols of 3- and the bromo- 2- nitrophenols of 5- is made,
After through steam distillation, ether extraction, recrystallization, separates isomer, and the bromo- 4- nitrophenols of 3- are made；
(2) the bromo- 4- nitrophenols of obtained 3- are added in DMSO and added after polyethylene glycol-400 is uniformly mixed, added
Heat adds potassium fluoride, stirring reaction 4h, after reaction, vacuum distillation, after recrystallization, it is fluoro- to be made 3- thereto to 40 DEG C
4- nitrophenols.
The use molal volume ratio of bis- bromo nitrobenzenes of 2,4- and water is 0.4mol/L in the step (1)；Inert gas is
Helium or argon gas；The use molar ratio of bis- bromo nitrobenzenes of 2,4- and cobalt acetate is 1.2:1；Bis- bromo nitrobenzenes of 2,4- and ammonium hydroxide make
It is 0.6mol/L with molal volume ratio, the concentration of ammonium hydroxide is 1mol/L.
The use molal volume ratio of the bromo- 4- nitrophenols of 3- and DMSO are 0.2mol/L in the step (2)；DMSO is with gathering
The usage amount volume ratio of ethylene glycol -400 is 11:2；The use molar ratio of the bromo- 4- nitrophenols of 3- and potassium fluoride is 1:1.2.
The yield of obtained 3- fluoro-4-nitrophenols is 61.5%, purity 99.1%, HNMR:5.35,1h, 6.80,
1H, 7.38,1H, 8.09,1H.
Embodiment 2
A kind of synthetic method of intermediate 3- fluoro-4-nitrophenols, comprises the following steps：
(1) after 2,4-, bis- bromo nitrobenzenes are mixed with water, 60 DEG C are heated to, under inert gas shielding, adds cobalt acetate
It is uniformly mixed, ammonium hydroxide is added dropwise afterwards and carries out back flow reaction, after being added dropwise to complete, continues to be stirred at reflux reaction 2h, reaction is completed
After centrifuge, organic phase is collected in liquid separation, vacuum distillation, and the mixture of the bromo- 4- nitrophenols of 3- and the bromo- 2- nitrophenols of 5- is made,
After through steam distillation, ether extraction, recrystallization, separates isomer, and the bromo- 4- nitrophenols of 3- are made；
(2) the bromo- 4- nitrophenols of obtained 3- are added in DMSO and added after polyethylene glycol-400 is uniformly mixed, added
Heat adds potassium fluoride, stirring reaction 5h, after reaction, vacuum distillation, after recrystallization, it is fluoro- to be made 3- thereto to 50 DEG C
4- nitrophenols.
The use molal volume ratio of bis- bromo nitrobenzenes of 2,4- and water is 0.6mol/L in the step (1)；Inert gas is
Helium or argon gas；The use molar ratio of bis- bromo nitrobenzenes of 2,4- and cobalt acetate is 1.4:1；Bis- bromo nitrobenzenes of 2,4- and ammonium hydroxide make
It is 0.8mol/L with molal volume ratio, the concentration of ammonium hydroxide is 1mol/L.
The use molal volume ratio of the bromo- 4- nitrophenols of 3- and DMSO are 0.4mol/L in the step (2)；DMSO is with gathering
The usage amount volume ratio of ethylene glycol -400 is 11:2；The use molar ratio of the bromo- 4- nitrophenols of 3- and potassium fluoride is 1:1.5.
The yield of obtained 3- fluoro-4-nitrophenols is 63.3%, purity 99.0%, HNMR:5.34,1h, 6.81,
1H, 7.38,1H, 8.10,1H.
Embodiment 3
A kind of synthetic method of intermediate 3- fluoro-4-nitrophenols, comprises the following steps：
(1) after 2,4-, bis- bromo nitrobenzenes are mixed with water, 50 DEG C are heated to, under inert gas shielding, adds cobalt acetate
It is uniformly mixed, ammonium hydroxide is added dropwise afterwards and carries out back flow reaction, after being added dropwise to complete, continues to be stirred at reflux reaction 2h, reaction is completed
After centrifuge, organic phase is collected in liquid separation, vacuum distillation, and the mixture of the bromo- 4- nitrophenols of 3- and the bromo- 2- nitrophenols of 5- is made,
After through steam distillation, ether extraction, recrystallization, separates isomer, and the bromo- 4- nitrophenols of 3- are made；
(2) the bromo- 4- nitrophenols of obtained 3- are added in DMSO and added after polyethylene glycol-400 is uniformly mixed, added
Heat adds potassium fluoride, stirring reaction 5h, after reaction, vacuum distillation, after recrystallization, it is fluoro- to be made 3- thereto to 40 DEG C
4- nitrophenols.
The use molal volume ratio of bis- bromo nitrobenzenes of 2,4- and water is 0.4mol/L in the step (1)；Inert gas is
Helium or argon gas；The use molar ratio of bis- bromo nitrobenzenes of 2,4- and cobalt acetate is 1.4:1；Bis- bromo nitrobenzenes of 2,4- and ammonium hydroxide make
It is 0.6mol/L with molal volume ratio, the concentration of ammonium hydroxide is 1mol/L.
The use molal volume ratio of the bromo- 4- nitrophenols of 3- and DMSO are 0.4mol/L in the step (2)；DMSO is with gathering
The usage amount volume ratio of ethylene glycol -400 is 11:2；The use molar ratio of the bromo- 4- nitrophenols of 3- and potassium fluoride is 1:1.2.
The yield of obtained 3- fluoro-4-nitrophenols is 66.2%, purity 99.2%, HNMR:5.35,1h, 6.81,
1H, 7.37,1H, 8.09,1H.
Embodiment 4
A kind of synthetic method of intermediate 3- fluoro-4-nitrophenols, comprises the following steps：
(1) after 2,4-, bis- bromo nitrobenzenes are mixed with water, 60 DEG C are heated to, under inert gas shielding, adds cobalt acetate
It is uniformly mixed, ammonium hydroxide is added dropwise afterwards and carries out back flow reaction, after being added dropwise to complete, continues to be stirred at reflux reaction 1h, reaction is completed
After centrifuge, organic phase is collected in liquid separation, vacuum distillation, and the mixture of the bromo- 4- nitrophenols of 3- and the bromo- 2- nitrophenols of 5- is made,
After through steam distillation, ether extraction, recrystallization, separates isomer, and the bromo- 4- nitrophenols of 3- are made；
(2) the bromo- 4- nitrophenols of obtained 3- are added in DMSO and added after polyethylene glycol-400 is uniformly mixed, added
Heat adds potassium fluoride, stirring reaction 4h, after reaction, vacuum distillation, after recrystallization, it is fluoro- to be made 3- thereto to 50 DEG C
4- nitrophenols.
The use molal volume ratio of bis- bromo nitrobenzenes of 2,4- and water is 0.6mol/L in the step (1)；Inert gas is
Helium or argon gas；The use molar ratio of bis- bromo nitrobenzenes of 2,4- and cobalt acetate is 1.2:1；Bis- bromo nitrobenzenes of 2,4- and ammonium hydroxide make
It is 0.8mol/L with molal volume ratio, the concentration of ammonium hydroxide is 1mol/L.
The use molal volume ratio of the bromo- 4- nitrophenols of 3- and DMSO are 0.2mol/L in the step (2)；DMSO is with gathering
The usage amount volume ratio of ethylene glycol -400 is 11:2；The use molar ratio of the bromo- 4- nitrophenols of 3- and potassium fluoride is 1:1.5.
The yield of obtained 3- fluoro-4-nitrophenols is 65.7%, purity 99.1%, HNMR:5.36,1h, 6.81,
1H, 7.39,1H, 8.11,1H.
Embodiment 5
A kind of synthetic method of intermediate 3- fluoro-4-nitrophenols, comprises the following steps：
(1) after 2,4-, bis- bromo nitrobenzenes are mixed with water, 55 DEG C are heated to, under inert gas shielding, adds cobalt acetate
It is uniformly mixed, ammonium hydroxide is added dropwise afterwards and carries out back flow reaction, after being added dropwise to complete, continues to be stirred at reflux reaction 2h, reaction is completed
After centrifuge, organic phase is collected in liquid separation, vacuum distillation, and the mixture of the bromo- 4- nitrophenols of 3- and the bromo- 2- nitrophenols of 5- is made,
After through steam distillation, ether extraction, recrystallization, separates isomer, and the bromo- 4- nitrophenols of 3- are made；
(2) the bromo- 4- nitrophenols of obtained 3- are added in DMSO and added after polyethylene glycol-400 is uniformly mixed, added
Heat adds potassium fluoride, stirring reaction 5h, after reaction, vacuum distillation, after recrystallization, it is fluoro- to be made 3- thereto to 45 DEG C
4- nitrophenols.
The use molal volume ratio of bis- bromo nitrobenzenes of 2,4- and water is 0.5mol/L in the step (1)；Inert gas is
Helium or argon gas；The use molar ratio of bis- bromo nitrobenzenes of 2,4- and cobalt acetate is 1.3:1；Bis- bromo nitrobenzenes of 2,4- and ammonium hydroxide make
It is 0.7mol/L with molal volume ratio, the concentration of ammonium hydroxide is 1mol/L.
The use molal volume ratio of the bromo- 4- nitrophenols of 3- and DMSO are 0.3mol/L in the step (2)；DMSO is with gathering
The usage amount volume ratio of ethylene glycol -400 is 11:2；The use molar ratio of the bromo- 4- nitrophenols of 3- and potassium fluoride is 1:1.3.
The yield of obtained 3- fluoro-4-nitrophenols is 62.7%, purity 99.2%, HNMR:5.36,1h, 6.80,
1H, 7.39,1H, 8.10,1H.
Claims (8)
1. a kind of synthetic method of intermediate 3- fluoro-4-nitrophenols, it is characterised in that comprise the following steps：
(1) after 2,4-, bis- bromo nitrobenzenes are mixed with water, 50-60 DEG C is heated to, under inert gas shielding, cobalt acetate is added and stirs
Mix uniformly mixed, ammonium hydroxide is added dropwise afterwards and carries out back flow reaction, after being added dropwise to complete, continues to be stirred at reflux reaction 1-2h, reaction is completed
After centrifuge, organic phase is collected in liquid separation, vacuum distillation, and the mixture of the bromo- 4- nitrophenols of 3- and the bromo- 2- nitrophenols of 5- is made,
After through steam distillation, ether extraction, recrystallization, separates isomer, and the bromo- 4- nitrophenols of 3- are made；
(2) the bromo- 4- nitrophenols of obtained 3- are added in DMSO and added after polyethylene glycol-400 is uniformly mixed, is heated to
40-50 DEG C, potassium fluoride is added thereto, stirring reaction 4-5h, after reaction, vacuum distillation, after recrystallization, is made 3-
Fluoro-4-nitrophenol.
2. the synthetic method of intermediate 3- fluoro-4-nitrophenols according to claim 1, it is characterised in that：The step
(1) the use molal volume ratio of bis- bromo nitrobenzenes of 2,4- and water is 0.4-0.6mol/L in.
3. the synthetic method of intermediate 3- fluoro-4-nitrophenols according to claim 1, it is characterised in that：The step
(1) inert gas is helium or argon gas in.
4. the synthetic method of intermediate 3- fluoro-4-nitrophenols according to claim 1, it is characterised in that：The step
(1) the use molar ratio of bis- bromo nitrobenzenes of 2,4- and cobalt acetate is 1.2-1.4 in:1.
5. the synthetic method of intermediate 3- fluoro-4-nitrophenols according to claim 1, it is characterised in that：The step
(1) the use molal volume ratio of 2,4-, bis- bromo nitrobenzenes and ammonium hydroxide is 0.6-0.8mol/L in, and the concentration of ammonium hydroxide is 1mol/L.
6. the synthetic method of intermediate 3- fluoro-4-nitrophenols according to claim 1, it is characterised in that：The step
(2) the use molal volume ratio of the bromo- 4- nitrophenols of 3- and DMSO are 0.2-0.4mol/L in.
7. the synthetic method of intermediate 3- fluoro-4-nitrophenols according to claim 1, it is characterised in that：The step
(2) the usage amount volume ratio of DMSO and polyethylene glycol-400 is 11 in:2.
8. the synthetic method of intermediate 3- fluoro-4-nitrophenols according to claim 1, it is characterised in that：The step
(2) the use molar ratio of the bromo- 4- nitrophenols of 3- and potassium fluoride is 1 in:1.2-1.5.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114560771A (en) * | 2022-03-07 | 2022-05-31 | 中北大学 | Method for selective nitration of bromophenol by photocatalysis |
-
2017
- 2017-12-01 CN CN201711246902.3A patent/CN107954878A/en not_active Withdrawn
Non-Patent Citations (2)
| Title |
|---|
| 伍丹 等: "《有机化学合成反应原理及新技术研究》", 31 October 2014 * |
| 赵继周: "《高等无机化学》", 31 July 1987 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114560771A (en) * | 2022-03-07 | 2022-05-31 | 中北大学 | Method for selective nitration of bromophenol by photocatalysis |
| CN114560771B (en) * | 2022-03-07 | 2023-10-27 | 中北大学 | Method for photocatalytic selective nitration of bromophenol |
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