CN105884582A - Synthesizing process of 2, 5-dichlorophenol - Google Patents
Synthesizing process of 2, 5-dichlorophenol Download PDFInfo
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- CN105884582A CN105884582A CN201610276428.8A CN201610276428A CN105884582A CN 105884582 A CN105884582 A CN 105884582A CN 201610276428 A CN201610276428 A CN 201610276428A CN 105884582 A CN105884582 A CN 105884582A
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- dichloro
- chlorophenesic acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
- C07C37/02—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis by substitution of halogen
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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
Abstract
The invention discloses synthesizing process of 2, 5-dichlorophenol and belongs to the technical field of fine chemical industry. The synthesizing process includes halogenation and hydrolysis. The synthesizing process has the advantages that bromine or iodine which can be substituted more easily than chlorine is used, the bromine or iodine substituent group is hydrolyzed into hydroxyl after dichlorobenzene is halogenated, and halogenation depth is controlled by controlling the adding amount of the bromine or iodine so as to reduce the content of 2, 5-dichloro-1, 4-dihalogen benzene in the halogenation product; the conversion rate of 2, 5-dichloro halobenzene reaches above 92.0%, and the synthesizing process is short in synthetic route, simple, low in cost, few in produced three wastes and suitable for large-scale production.
Description
Technical field
The present invention relates to one 2, the synthesis technique of 5-chlorophenesic acid, belong to technical field of fine.
Background technology
2,5-chlorophenesic acids are a kind of important pesticide, medicine, the intermediate of dyestuff, nitrogen fertilizer potentiating agent and leather fungicide
Deng.2,5-chlorophenesic acid sterlings are white needle-like crystals, have off-odor, are used for herbicide 3,6-bis-chloro-2-methoxy at present
The synthesis of yl benzoic acid (dicamba).By 2,5-chlorophenesic acid synthesis 3,6-dichlorosalicylic acid, then by O-alkylated reaction
The chloro-2-methoxybenzoic acid of 3,6-bis-can be prepared.3,6-bis-chloro-2-methoxybenzoic acid are a kind of benzoic acid system herbicides,
Trade name Mediben (Dicamba), being mainly used in the gramineous crop fields such as Semen Tritici aestivi, to prevent and kill off annual or perennial broad-leaved miscellaneous
Grass.Along with deepening continuously that anti-Mediben biotechnology and Mediben mixed herbicide are studied, its good market prospect.
Preparation 2 at present, the process route of 5-chlorophenesic acid mainly has following three kinds, and patent US2799714 proposes with 1, and 2,
4-trichloro-benzenes is raw material, prepares mixed dichlorobenzene phenol, then carry out isolated 2 under the conditions of alkalescence, 5-chlorophenesic acid.This technique road
Line is simple, but the separating difficulty of mixed dichlorobenzene phenol is relatively big, and industrial production cost is higher；Patent US4326882 propose with
2,5-dichloroanilines are raw material, prepare 2 through diazotising, hydrolysis, and 5-chlorophenesic acid, this technique is the most ripe 2,5-
Chlorophenesic acid synthesis technique, the shortcoming of its maximum is exactly that environmental pollution is serious, the most a large amount of mineral acids and the use of nitrite
The most serious to equipment corrosion；Patent US6586624 proposes with 1,4-dichloro-benzenes for raw material is direct and hydrogen peroxide carries out hydroxyl
Changing reaction preparation 2,5-chlorophenesic acid, this technique is greenization technique, and meets Atom economy, but feed stock conversion is very
Low, it is unsuitable for large-scale industrial production.
Summary of the invention
Present invention seek to address that above-mentioned the deficiencies in the prior art, propose a kind of new with paracide as raw material, pass through halogen
Change, hydrolysis 2, the technique of 5-chlorophenesic acid, there is the advantage that synthetic route is short, technique is simple, production cost is low.
In order to realize foregoing invention purpose, technical scheme is as follows:
A kind of 2, the synthesis technique of 5-chlorophenesic acid, it is characterised in that: comprise the following steps:
A. halogenation
Isosorbide-5-Nitrae-dichloro-benzenes is dissolved in organic solvent, after adding catalyst, at 30～50 DEG C, adds halogen X, after reaction 6～10h,
Removing residual halogens X, layering takes organic facies, and organic facies is concentrated, obtain intermediate product II after rectification；Described halogen X and 1,4-
The amount ratio of the material of dichloro-benzenes is 0.5～1:1；
B. hydrolyze
The intermediate product II step A obtained is dissolved in organic solvent, adds copper salt catalyst, inorganic base and water, in temperature is
150～210 DEG C, pressure be react 1～3h under conditions of 1～2MPa after, then by reactant liquor through alkali cleaning, be acidified, extract, at precipitation
2,5-chlorophenesic acid is obtained after reason；Described inorganic base is 2～6:1 with the amount ratio of the material of intermediate product II, and described water is with middle
The amount ratio of the material of product II is 0～8:1；
Described halogen X is the one in bromine, iodine；Described intermediate product II is 2,5-dichloro halobenzene, i.e. 2,5-dichloro-bromobenzene or 2,
5-bis-chloroiodobenzone.
Synthetic route is as follows:
Further, in step A, described catalyst is aluminum chloride or alchlor, the addition of described catalyst be Isosorbide-5-Nitrae-
The 1～10% of dichloro-benzenes weight.
In step A, described organic solvent is the one in carbon tetrachloride, dichloromethane or dichloroethanes, described organic molten
The addition of agent is 2～6 times of 1,4-dichloro-benzenes weight.
In step A, the method for described removal residual halogens in reactant liquor add mass fraction be 1% ~ 8% lay particular stress on Asia
Sodium sulfate or sodium sulfite solution, until solution become colourless after, layering, organic facies through rectification respectively obtain Isosorbide-5-Nitrae-dichloro-benzenes, 2,
5-dichloro halobenzene, 2,5-bis-chloro-Isosorbide-5-Nitrae-two halobenzene, aqueous phase the most recyclable halogen X.The concrete operations reclaiming halogen are:
In aqueous phase, it is passed through chlorine, can reclaim reoxidized for halide ion after distillation for halogen simple substance；Additionally, in course of reaction
In also can produce hydrogen halides, hydrogen halides with sodium hydrate aqueous solution absorb, toward absorbing liquid in, be passed through chlorine, equally can through distill after
Recovery obtains halogen simple substance.
In step B, described organic solvent is methanol, and the addition of described methanol is 2～8 times of intermediate product II weight.
In step B, described copper salt catalyst is the one in copper sulfate, copper chloride, copper nitrate；Described copper salt catalyst
Addition is the 0.1～1% of intermediate product II weight.
In step B, described inorganic base is sodium hydroxide or potassium hydroxide.
In step B, described reactant liquor through alkali cleaning, be acidified, extract, obtain 2 after carrying out precipitation treatment, 5-chlorophenesic acid, refer to by
After reactant liquor is cooled to room temperature, adding sodium hydrate aqueous solution, then with extraction into heptane, and acid adding tune pH value is to highly acid, then
Add methylene chloride extraction, after after distillation removing dichloromethane, obtain 2,5-chlorophenesic acid.
Described halogen X is bromine, and bromine feed postition is: drop in reactant liquor with the speed of 10～20 seconds/.
Beneficial effects of the present invention:
(1) present invention is easier to the bromine or iodine being replaced by selection than chlorine, after dichloro-benzenes halogenation, by hydrolysis by bromine or iodine
Substituent group is hydrolyzed into hydroxyl, and controls the degree of depth of halogenation by controlling the addition of bromine or iodine, reduces in halogenated products 2,5-
The content of two chloro-1,4-bis-halobenzenes；After testing, the conversion ratio of 2,5-dichloro halobenzenes has reached more than 92.0%, thus realizes high turning
Change, highly selective prepares 2,5-chlorophenesic acid.It addition, bromine or iodine recoverable in course of reaction, thus significantly reduce work
Skill three-protection design amount and production cost；To sum up the present invention have that synthetic route is short, technique simple, low cost, generation the three wastes few,
The advantage being suitable for large-scale production.
(2) in step A of the present invention, Isosorbide-5-Nitrae-dichloro-benzenes is dissolved in organic solvent, after adding catalyst, adds at 30～50 DEG C
Entering halogen X, react 6～10h, temperature too low halogenation substitution reaction speed is the slowest, and temperature is too high can cause again halogen volatilization too fast
And react bad, therefore this temperature range is optimal.
(3) in step A of the present invention, described halogen X is 0.5～1:1 with the amount ratio of the material of Isosorbide-5-Nitrae-dichloro-benzenes, and halogen X uses
Measuring conference causes the dihalo-substituent of by-product to generate in a large number, and halogen X consumption deficiency can make again the conversion ratio of a halogen substituent
Not.
(4) in step A of the present invention, described catalyst is aluminum chloride or alchlor, and the addition of described catalyst is
The 1～10% of Isosorbide-5-Nitrae-dichloro-benzenes weight, aluminum chloride and alchlor activity are the highest, but are also easy to inactivation, if added
Amount very little, does not then reach preferable catalytic effect；Addition is too big, can produce again substantial amounts of waste residue during post processing, pollutes environment
And increase production cost, therefore addition is Isosorbide-5-Nitrae-dichloro-benzenes weight 1～10% is optimum range.
(5), in step A of the present invention, described organic solvent is the one in carbon tetrachloride, dichloromethane or dichloroethanes, institute
State organic solvent 2～6 times that addition is Isosorbide-5-Nitrae-dichloro-benzenes weight, it is suitable anti-that this ratio just can make raw material be in
Answering concentration, addition to cross conference causes response speed too slow, and addition deficiency can be completely dissolved Isosorbide-5-Nitrae-dichloro-benzenes again and lead
Cause reaction effect is bad.
(6), in step A of the present invention, the method for described removal residual halogens is 1 ~ 8% for adding mass fraction in reactant liquor
Sodium metabisulfite or sodium sulfite solution, until solution become colourless after, layering, organic facies respectively obtains Isosorbide-5-Nitrae-two through rectification
Chlorobenzene, 2,5-dichloro halobenzene, 2, the chloro-Isosorbide-5-Nitrae-dibromobenzene of 5-bis-, aqueous phase reclaims halogen X, sodium metabisulfite or Asia after treatment
Sodium sulfate has stronger reproducibility, it is easy to halogen generation redox reaction thus got rid of by the halogen of residual；Return
Receiving halogen is logical chlorine in aqueous phase, is reclaimed by reoxidized for halide ion one-tenth halogen simple substance, can be greatly reduced and produce into
This.
(7), in step B of the present invention, described inorganic base is 2～6:1 with the amount ratio of the material of intermediate product II, described water with
The amount ratio of the material of intermediate product II is 0～8:1, and the addition of inorganic base and water can cause hydrolysis effect bad not,
Addition the most also can affect hydrolysis the most also can increase production cost, therefore this adding proportion scope is optimal.
(8) in step B of the present invention, described organic solvent is methanol, and the addition of described methanol is intermediate product II weight
2～8 times, methanol addition can cause hydrolysis effect bad not, and addition too much can increase production cost, therefore this adds
It is optimal for adding proportion.
(9), in step B of the present invention, described copper salt catalyst is the one in copper sulfate, copper chloride, copper nitrate；Addition
For the 0.1～1% of intermediate product II weight, it is inconspicuous to the catalytic effect of hydrolysis that catalyst loading is not enough, addition mistake
How can increase production cost, therefore this adding proportion is optimal.
(10) halogen of the present invention is bromine, and bromine feed postition is: drop to reactant liquor with the speed of 10～20 seconds/
In, bromine more superiority of effectiveness compared with iodine, so the preferred bromine of the present invention is as halogenating agent；Bromine is easy to volatilization, needs slowly
Drop in reactant liquor, make bromine have little time to react just to vapor away and cause material loss big if rate of addition is too fast, dropping
Speed is crossed and can be extended the response time slowly thus the reaction time of increase.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1
A kind of 2, the synthesis technique of 5-chlorophenesic acid, comprise the following steps:
A. halogenation
Isosorbide-5-Nitrae-dichloro-benzenes is dissolved in organic solvent, after adding catalyst, at 30 DEG C, adds bromine, after reaction 10h, remove system residual
Staying bromine, layering to take organic facies, organic facies is concentrated, rectification obtains 2,5-dichloro-bromobenzene；Described bromine and the material of 1,4-dichloro-benzenes
Amount than for 0.5:1,2,5-dichloro-bromobenzene conversion ratios 92.5%；
B. hydrolyze
2 step A obtained, 5-dichloro-bromobenzene is dissolved in organic solvent, adds copper salt catalyst, inorganic base and water, in temperature
Be 150 DEG C, pressure be react 1h under conditions of 1MPa after, by reactant liquor through alkali cleaning, be acidified, extract, obtain 2 after carrying out precipitation treatment,
5-chlorophenesic acid；Described inorganic base and 2, the amount of the material of 5-dichloro-bromobenzene is than for 2:1, described water and 2, the thing of 5-dichloro-bromobenzene
The amount of matter ratio for 3:1,2,5-chlorophenesic acids hydrolysis yields 83.0%.
In the present embodiment step A, described catalyst is aluminum chloride, and the addition of aluminum chloride is Isosorbide-5-Nitrae-dichloro-benzenes weight
3%.
Embodiment 2
A kind of 2, the synthesis technique of 5-chlorophenesic acid, comprise the following steps:
A. halogenation
Isosorbide-5-Nitrae-dichloro-benzenes is dissolved in organic solvent, after adding catalyst, at 50 DEG C, adds bromine, after reaction 6h, remove residual bromine,
Layering takes organic facies, and organic facies is concentrated, rectification obtains 2,5-dichloro-bromobenzene；The amount ratio of described bromine and the material of 1,4-dichloro-benzenes
For 0.7:1,2,5-dichloro-bromobenzene conversion ratios 95.3%；
B. hydrolyze
2 step A obtained, 5-dichloro-bromobenzene is dissolved in organic solvent, adds copper salt catalyst, inorganic base and water, in temperature
Be 210 DEG C, pressure be react 3h under conditions of 2MPa after, by reactant liquor through alkali cleaning, be acidified, extract, obtain 2 after carrying out precipitation treatment,
5-chlorophenesic acid；Described inorganic base and 2, the amount of the material of 5-dichloro-bromobenzene is than for 5:1, described water and 2, the thing of 5-dichloro-bromobenzene
The amount of matter ratio for 2:1,2,5-chlorophenesic acids hydrolysis yields 92.5%.
In the present embodiment step A, described catalyst is alchlor, and the addition of alchlor is Isosorbide-5-Nitrae-dichloro-benzenes weight
1%.
In the present embodiment step A, described organic solvent is carbon tetrachloride, and the addition of described carbon tetrachloride is Isosorbide-5-Nitrae-dichloro
2 times of benzene weight.
Embodiment 3
A kind of 2, the synthesis technique of 5-chlorophenesic acid, comprise the following steps:
A. halogenation
Isosorbide-5-Nitrae-dichloro-benzenes is dissolved in organic solvent, after adding catalyst, at 40 DEG C, adds iodine, after reaction 9h, remove residual iodine,
Layering takes organic facies, and organic facies is concentrated, rectification obtains 2,5-bis-chloroiodobenzone；The amount ratio of described iodine and the material of 1,4-dichloro-benzenes
For 0.6:1,2,5-bis-chloroiodobenzone conversion ratios 93.8%；
B. hydrolyze
2 step A obtained, 5-dichloro-bromobenzene is dissolved in organic solvent, adds copper salt catalyst and inorganic base, in temperature is
180 DEG C, pressure be react 3h under conditions of 1.5MPa after, by reactant liquor through alkali cleaning, be acidified, extract, obtain 2 after carrying out precipitation treatment,
5-chlorophenesic acid；The amount of described inorganic base and the material of 2,5-bis-chloroiodobenzone is than for 4:1；2,5-chlorophenesic acid hydrolysis yield
89.5%。
In the present embodiment step A, described catalyst is aluminum chloride, and the addition of aluminum chloride is Isosorbide-5-Nitrae-dichloro-benzenes weight
5%.
In the present embodiment step A, in step A, described organic solvent is carbon tetrachloride, and the addition of described carbon tetrachloride is
5 times of 1,4-dichloro-benzenes weight.
In step A, described remove residual iodine method be in reacted mixture, addition mass fraction be 1% inclined
Sodium bisulfite solution, until solution become colourless after, layering, organic facies through rectification respectively obtain Isosorbide-5-Nitrae-dichloro-benzenes, 2,5-dichloro
Halobenzene, 2, the chloro-Isosorbide-5-Nitrae-dibromobenzene of 5-bis-, aqueous phase reclaims iodine after treatment.
Embodiment 4
A kind of 2, the synthesis technique of 5-chlorophenesic acid, comprise the following steps:
A. halogenation
Isosorbide-5-Nitrae-dichloro-benzenes is dissolved in organic solvent, after adding catalyst, at 30 DEG C, adds iodine, after reaction 10h, remove residual
Iodine, layering takes organic facies, and organic facies is concentrated, rectification obtains 2,5-bis-chloroiodobenzone；The material of described iodine and 1,4-dichloro-benzenes
Amount ratio is 0.9:1,2,5-bis-chloroiodobenzone conversion ratios 95.1%；
B. hydrolyze
2 step A obtained, 5-bis-chloroiodobenzone is dissolved in organic solvent, adds copper salt catalyst, inorganic base and water, in temperature
Be 150 DEG C, pressure be react 2h under conditions of 1MPa after, by reactant liquor through alkali cleaning, be acidified, extract, obtain 2 after carrying out precipitation treatment,
5-chlorophenesic acid；Described inorganic base and 2, the amount of the material of 5-bis-chloroiodobenzone is than for 5:1, described water and 2, the thing of 5-bis-chloroiodobenzone
The amount of matter ratio for 8:1,2,5-chlorophenesic acids hydrolysis yields 84.6%.
In the present embodiment step A, described catalyst is aluminum chloride, and the addition of described aluminum chloride is Isosorbide-5-Nitrae-dichloro-benzenes
The 8% of weight；Described organic solvent is dichloromethane, and the addition of described dichloromethane is 6 times of Isosorbide-5-Nitrae-dichloro-benzenes weight.
In step A, the described method removing residual iodine is in reacted mixture, and adding mass fraction is the Asia of 3%
Metabisulfite solution, until solution become colourless after, layering, organic facies through rectification respectively obtain Isosorbide-5-Nitrae-dichloro-benzenes, 2,5-dichloro halobenzene,
2,5-bis-chloro-Isosorbide-5-Nitrae-dibromobenzenes, aqueous phase reclaims iodine after treatment.
In step B, described organic solvent is methanol, and the addition of described methanol is 2,2.5 times of 5-bis-chloroiodobenzone weight.
Embodiment 5
A kind of 2, the synthesis technique of 5-chlorophenesic acid, comprise the following steps:
A. halogenation
Isosorbide-5-Nitrae-dichloro-benzenes is dissolved in organic solvent, after adding catalyst, at 50 DEG C, adds iodine, after reaction 8h, remove residual iodine,
Layering takes organic facies, and organic facies is concentrated, rectification obtains 2,5-bis-chloroiodobenzone；The amount ratio of described iodine and the material of 1,4-dichloro-benzenes
For 0.6:1,2,5-bis-chloroiodobenzone conversion ratios 96.1%；
B. hydrolyze
2 step A obtained, 5-bis-chloroiodobenzone is dissolved in organic solvent, adds copper salt catalyst, inorganic base and water, in temperature
Be 210 DEG C, pressure be react 3h under conditions of 2MPa after, by reactant liquor through alkali cleaning, be acidified, extract, obtain 2 after carrying out precipitation treatment,
5-chlorophenesic acid；Described inorganic base and 2, the amount of the material of 5-bis-chloroiodobenzone than for 3.5:1, described water and 2,5-bis-chloroiodobenzone
The amount of material ratio for 5:1,2,5-chlorophenesic acids hydrolysis yields 89.2%.
In the present embodiment step A, described catalyst is aluminum chloride, and the addition of described aluminum chloride is Isosorbide-5-Nitrae-dichloro-benzenes
The 10% of weight, described organic solvent is dichloroethanes, and the addition of described dichloroethanes is 5 times of Isosorbide-5-Nitrae-dichloro-benzenes weight.
In step A, described remove residual iodine method be in reacted mixture, addition mass fraction be 8% inclined
Sodium bisulfite solution.
In step B, described organic solvent is methanol, and the addition of described methanol is 2,8 times of 5-bis-chloroiodobenzone weight.
In step B, described copper salt catalyst is copper sulfate, and addition is 2, the 0.1% of 5-bis-chloroiodobenzone weight.
Embodiment 6
A kind of 2, the synthesis technique of 5-chlorophenesic acid, comprise the following steps:
A. halogenation
Isosorbide-5-Nitrae-dichloro-benzenes is dissolved in organic solvent, after adding catalyst, with the speed dropping bromine of 20 seconds/, reaction at 42 DEG C
After 8.5h, removing residual bromine, layering takes organic facies, and organic facies is concentrated, rectification obtains 2,5-dichloro-bromobenzene；Described bromine and 1,4-
The amount of the material of dichloro-benzenes is than for 1:1,2,5-dichloro-bromobenzene conversion ratios 98.5%；
B. hydrolyze
2 step A obtained, 5-dichloro-bromobenzene is dissolved in organic solvent, adds copper salt catalyst, inorganic base and water, in temperature
Be 190 DEG C, pressure be react 2h under conditions of 1MPa after, by reactant liquor through alkali cleaning, be acidified, extract, obtain 2 after carrying out precipitation treatment,
5-chlorophenesic acid；Described inorganic base and 2, the amount of the material of 5-dichloro-bromobenzene than for 6.5:1, described water and 2,5-dichloro-bromobenzene
The amount of material ratio for 7:1,2,5-chlorophenesic acids hydrolysis yields 90.4%.
In the present embodiment step A, catalyst is alchlor, and the addition of described alchlor is Isosorbide-5-Nitrae-dichloro-benzenes weight
4%；Described organic solvent is carbon tetrachloride, and the addition of described carbon tetrachloride is 3.5 times of Isosorbide-5-Nitrae-dichloro-benzenes weight.
In step A, the described method removing residual bromine is in reacted mixture, and adding mass fraction is the Asia of 5%
Metabisulfite solution.
In step B, described organic solvent is methanol, and the addition of described methanol is 2,5 times of 5-dichloro-bromobenzene weight；Institute
Stating copper salt catalyst is copper chloride, and addition is 2, the 0.5% of 5-dichloro-bromobenzene weight.
In step B, described inorganic base is sodium hydroxide.
Embodiment 7
The present embodiment is on the basis of embodiment 6, further, in step B, described reactant liquor through alkali cleaning, be acidified, extract, de-
The method of molten process is: after reactant liquor is cooled to room temperature, adds sodium hydrate aqueous solution, then with extraction into heptane, and with sour
Regulation pH value is 1, after extracting with dichloromethane, after through distillation removing dichloromethane.
Embodiment 8
A kind of 2, the synthesis technique of 5-chlorophenesic acid, comprise the following steps:
A. halogenation
Isosorbide-5-Nitrae-dichloro-benzenes is dissolved in organic solvent, after adding catalyst, with the speed dropping bromine of 10 seconds/, reaction at 42 DEG C
After 9h, removing residual bromine, layering takes organic facies, and organic facies is concentrated, rectification obtains 2,5-dichloro-bromobenzene；Described bromine and 1,4-bis-
The amount of the material of chlorobenzene is than for 0.7:1,2,5-dichloro-bromobenzene conversion ratios 96.7%；
B. hydrolyze
2 step A obtained, 5-dichloro-bromobenzene is dissolved in organic solvent, adds copper salt catalyst, inorganic base and water, in temperature
Be 180 DEG C, pressure be react 2h under conditions of 1.5MPa after, by reactant liquor through alkali cleaning, be acidified, extract, obtain after carrying out precipitation treatment
2,5-chlorophenesic acid；Described inorganic base and 2, the amount of the material of 5-dichloro-bromobenzene is than for 4.5:1, described water and 2,5-dichloro-bromobenzene
The amount ratio of material for 3:1,2,5-chlorophenesic acids hydrolysis yields 89.3%.
In the present embodiment step A, catalyst is aluminum chloride, and the addition of described aluminum chloride is Isosorbide-5-Nitrae-dichloro-benzenes weight
6%；Described organic solvent is carbon tetrachloride, and the addition of described carbon tetrachloride is 4 times of Isosorbide-5-Nitrae-dichloro-benzenes weight.
In step A, described remove residual bromine method be in reacted mixture, addition mass fraction be 5% inclined
Sodium bisulfite solution.
In step B, described organic solvent is methanol, and the addition of described methanol is 2,2 times of 5-dichloro-bromobenzene weight；Institute
Stating copper salt catalyst copper nitrate, addition is 2, the 1% of 5-dichloro-bromobenzene weight.
In step B, described inorganic base is potassium hydroxide.
In step B, described reactant liquor through alkali cleaning, be acidified, extract, carrying out precipitation treatment, after referring to reactant liquor is cooled to room temperature,
Add sodium hydrate aqueous solution, then with extraction into heptane, and be 1 with acid for adjusting pH value, then the extraction that adds methylene chloride, after through steaming
2,5-chlorophenesic acid is obtained after evaporating removing dichloromethane.
Embodiment 9
The present embodiment produces 2 with raw material for 1mol Isosorbide-5-Nitrae-dichloro-benzenes, and as a example by 5-chlorophenesic acid, the present invention will be further described.
In reaction bulb, add 147.0g Isosorbide-5-Nitrae-dichloro-benzenes (purity 98%), add 515 g carbon tetrachloride and dissolved,
Then adding 7.35 g aluminum trichloride (anhydrous)s in solution, stirring starts to drip bromine with the speed of 15 seconds/after being warming up to 35 DEG C
Element totally 105.6 g, 9 h droppings are complete.
Adding the sodium metabisulfite solution of 200.0 g mass fractions 5% in reacted mixture, liquid to be mixed becomes
After colourless, being layered to obtain organic facies, concentrated by gained carbon tetrachloride layer, rectification obtains Isosorbide-5-Nitrae-dichloro-benzenes 73.0 g, 2,5-dichloros
Bromobenzene 111.5 g and 2,5-bis-chloro-1,4-dibromobenzene 7.1 g.Knowable to calculating, the conversion ratio of 2,5-dichloro-bromobenzene reaches
96.7%, and 2,5-dichloro-bromobenzene and 2, the amount of the material of the chloro-Isosorbide-5-Nitrae-dibromobenzene of 5-bis-, than for 24:1, has reached height the most simultaneously
Conversion ratio and high selectivity.
In reactor, add 111.5 g 2,5-dichloro-bromobenzene, add 300 g methanol and dissolved, under stirring, add 80g
Sodium hydroxide and 25 mL water, then add 0.5g copper nitrate in solution, and reactor is airtight, and stirring is warming up to 180 DEG C instead
Should, reaction pressure is 1.2 MPa, stopped reaction after 3 h.After being cooled to room temperature, in reacted mixed liquor, add 3 mL
5% sodium hydroxide solution, gained mixed liquor extraction into heptane twice, use pentane 50mL to remove do not reacted former every time
The by-product generated in material and reaction；Solution hydrochloric acid remaining after extraction is acidified to pH=1, the phenol dichloro of generation
Methane extracts, and extracts three times, uses dichloromethane 100 mL every time, merges organic facies, and anhydrous sodium sulfate is dried, and concentrates, rectification
Obtaining 2,5-chlorophenesic acid 66.82 g afterwards, yield is 85.4%.
The above, be only presently preferred embodiments of the present invention, and the present invention not does any pro forma restriction, every depends on
Any simple modification of being made above example according to the technical spirit of the present invention, equivalent variations, each fall within the protection of the present invention
Within the scope of.
Claims (9)
1. one kind 2, the synthesis technique of 5-chlorophenesic acid, it is characterised in that: comprise the following steps:
A. halogenation
Isosorbide-5-Nitrae-dichloro-benzenes is dissolved in organic solvent, after adding catalyst, at 30～50 DEG C, adds halogen X, after reaction 6～10h,
Removing residual halogens X, layering takes organic facies, and organic facies is concentrated, rectification obtains intermediate product II；Described halogen X Yu 1,4-bis-
The amount ratio of the material of chlorobenzene is 0.5～1:1；
B. hydrolyze
The intermediate product II step A obtained is dissolved in organic solvent, adds copper salt catalyst, inorganic base and water, in temperature is
150～210 DEG C, pressure be react 1～3h under conditions of 1～2MPa after, then by reactant liquor through alkali cleaning, be acidified, extract, at precipitation
2,5-chlorophenesic acid is obtained after reason；Described inorganic base is 2～6:1 with the amount ratio of the material of intermediate product II, and described water is with middle
The amount ratio of the material of product II is 0～8:1；
Described halogen X is the one in bromine, iodine；Described intermediate product II is 2,5-dichloro-bromobenzene or 2,5-bis-chloroiodobenzone.
2. one 2 as claimed in claim 1, the synthesis technique of 5-chlorophenesic acid, it is characterised in that: in step A, described catalysis
Agent is aluminum chloride or alchlor, and the addition of described catalyst is the 1～10% of Isosorbide-5-Nitrae-dichloro-benzenes weight.
3. one 2 as claimed in claim 1, the synthesis technique of 5-chlorophenesic acid, it is characterised in that: in step A, described organic
Solvent is the one in carbon tetrachloride, dichloromethane or dichloroethanes, and the addition of described organic solvent is Isosorbide-5-Nitrae-dichloro-benzenes weight
2～6 times of amount.
4. one 2 as claimed in claim 1, the synthesis technique of 5-chlorophenesic acid, it is characterised in that: in step A, described removal
The method of residual halogens is in reacted mixture, adds sodium metabisulfite or sodium sulfite that mass fraction is 1 ~ 8%
Solution.
5. one 2 as claimed in claim 1, the synthesis technique of 5-chlorophenesic acid, it is characterised in that: in step B, described organic
Solvent is methanol, and described organic solvent addition is 2～8 times of intermediate product II weight.
6. one 2 as claimed in claim 1, the synthesis technique of 5-chlorophenesic acid, it is characterised in that: in step B, described mantoquita
Catalyst is the one in copper sulfate, copper chloride, copper nitrate；The addition of described copper salt catalyst is intermediate product II weight
0.1～1%.
7. one 2 as claimed in claim 1, the synthesis technique of 5-chlorophenesic acid, it is characterised in that: in step B, described inorganic
Alkali is sodium hydroxide or potassium hydroxide.
8. one 2 as claimed in claim 1, the synthesis technique of 5-chlorophenesic acid, it is characterised in that: in step B, described reaction
Liquid through alkali cleaning, be acidified, extract, obtain 2 after carrying out precipitation treatment, 5-chlorophenesic acid, after referring to reactant liquor is cooled to room temperature, add hydrogen
Aqueous solution of sodium oxide, then with extraction into heptane, and acid adding adjust pH value to highly acid, then the extraction that adds methylene chloride, after through distilling
2,5-chlorophenesic acid is obtained after removing dichloromethane.
9. the one 2 as described in any one of claim 1～8, the synthesis technique of 5-chlorophenesic acid, it is characterised in that: described halogen
Element X is bromine, and bromine feed postition is: drop in reactant liquor with the speed of 10～20 seconds/.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108046996A (en) * | 2017-12-12 | 2018-05-18 | 安徽国星生物化学有限公司 | A kind of 2,5- chlorophenesic acids are continuously synthesizing to method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4094913A (en) * | 1977-01-07 | 1978-06-13 | Velsicol Chemical Corporation | Process for the preparation of 2,5-dichlorophenol |
-
2016
- 2016-04-29 CN CN201610276428.8A patent/CN105884582A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4094913A (en) * | 1977-01-07 | 1978-06-13 | Velsicol Chemical Corporation | Process for the preparation of 2,5-dichlorophenol |
Non-Patent Citations (1)
| Title |
|---|
| 高鸿宾: "《有机化学》", 31 May 2005 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108046996A (en) * | 2017-12-12 | 2018-05-18 | 安徽国星生物化学有限公司 | A kind of 2,5- chlorophenesic acids are continuously synthesizing to method |
| CN108046996B (en) * | 2017-12-12 | 2021-04-09 | 安徽国星生物化学有限公司 | Continuous synthesis method of 2, 5-dichlorophenol |
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