CN1793096A - Process for catalyzing oxidating synthesizing 2,5-dichlorophenol - Google Patents
Process for catalyzing oxidating synthesizing 2,5-dichlorophenol Download PDFInfo
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- CN1793096A CN1793096A CN 200610049124 CN200610049124A CN1793096A CN 1793096 A CN1793096 A CN 1793096A CN 200610049124 CN200610049124 CN 200610049124 CN 200610049124 A CN200610049124 A CN 200610049124A CN 1793096 A CN1793096 A CN 1793096A
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- heteropolyacid
- chlorophenesic acid
- catalyzed oxidation
- salt
- oxidation synthetic
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Abstract
The invention relates to a method to compound 2, 5-dichlorophenol by catalytic oxidation. The feature is that 1, 4-dichlorobenzene adopts heteropolyacid, heteropolyacid salt or the load of heteropolyacid as catalyst, uses H<SUB>2</SUB>O<SUB>2</SUB> as oxidant to take catalytic oxidation reaction solution. After reacting, decreasing pressure and distilling, the 2, 5-dichlorophenol would be gained. The method has short reaction way, simple technology, and is benefit to environment protection.
Description
Technical field
The invention belongs to the compounds process for production thereof technical field, be specially a kind of catalyzed oxidation Synthetic 2, the method for 5-chlorophenesic acid.
Background technology
2, the 5-chlorophenesic acid is a kind of important pesticide intermediate, and nitrogen fertilizer potentiating agent and leather are prevented the enzyme agent.By 2, the 5-chlorophenesic acid synthesizes 3, and the 6-dichlorosalicylic acid can prepare 3 by the O-alkylated reaction then, 6-two chloro-O-Anisic Acids.3,6-two chloro-O-Anisic Acids are a kind of M-nitro benzoic acid serial herbicides, and trade name Dicamba (Dicamba) is mainly used in gramineous crop fields such as wheat and prevents and kill off annual one-tenth or perennial broadleaf weeds.
Traditional 2,5-chlorophenesic acid synthetic method has trichlorobenzene hydrolysis method, dichlorphenamide bulk powder diazonium hydrolysis method, trichlorobenzene sulfonation alkali solution technique.Yet this several method all exists the common shortcoming, is exactly that reaction scheme is longer, complex process, and equipment corrosion is serious, all can residual a large amount of spent acid or salkali waste after reaction finishes, environmental pollution is very big.The reactant 1 that patent application of the present invention relates to, 4-dichlorobenzene structural formula is as follows:
Summary of the invention
The present invention is directed to the problems referred to above that prior art exists, design provides a kind of catalyzed oxidation Synthetic 2, the technical scheme of the method for 5-chlorophenesic acid, and its reaction scheme is shorter, and technology is simple, and equipment can not be corroded, and environmental pollution is little.
Described catalyzed oxidation Synthetic 2, the method for 5-chlorophenesic acid is characterized in that 1, the 4-dichlorobenzene adopts heteropolyacid, heteropolyacid salt or its loading type to make catalyzer, with H in solvent
2O
2Make oxygenant, carry out catalytic oxidation, reaction finishes the back underpressure distillation and goes out 2, the 5-chlorophenesic acid.
Described catalyzed oxidation Synthetic 2, the method of 5-chlorophenesic acid, it is characterized in that 1, the 4-dichlorobenzene fully dissolves the back and adds catalyzer, under stirring, brute force slowly adds oxygenant, temperature of reaction is 0～150 ℃, and described solvent is 1,2-ethylene dichloride, methylene dichloride, chloroform, acetate, propionic acid, acetonitrile, acetone, butanone, methyl alcohol, ethanol or water.
Described catalyzed oxidation Synthetic 2, the method for 5-chlorophenesic acid is characterized in that described catalyzer is: H
4SiMo
12O
40, H
4SiW
12O
40, H
3PW
12O
40, H
3PMo
12O
40, H
4GeW
12O
40, H
4PMo
11VO
40, H
6PMo
9V
3O
40, H
5PMo
10V
2O
40Or H
6P
2W
18O
62, or its heteropolyacid salt, or the loaded catalyst of corresponding heteropolyacid, heteropolyacid salt.
Described catalyzed oxidation Synthetic 2, the method of 5-chlorophenesic acid, it is characterized in that heteropolyacid or heteropolyacid salt and 1, the mass ratio of 4-dichlorobenzene is 1: 0.0001～0.1, is preferably: 1: 0.001～0.1, more preferably: 1: 0.01～0.1, the loaded catalyst of heteropolyacid or heteropolyacid salt and 1, the mass ratio of 4-dichlorobenzene is 1: 0.001～1, is preferably: 1: 0.01～1, more preferably: 1: 0.1～1.
Described catalyzed oxidation Synthetic 2, the method for 5-chlorophenesic acid is characterized in that oxygenant H
2O
2With 1, the mol ratio of 4-dichlorobenzene is 1: 0.1～10, preferred 1: 0.3～5, more preferably 1: 0.3～3.
Described catalyzed oxidation Synthetic 2, the method for 5-chlorophenesic acid is characterized in that the time of oxidizing reaction is 1～48 hour, is preferably: 3～36, more preferably: 5～24.
Described catalyzed oxidation Synthetic 2, the method for 5-chlorophenesic acid is characterized in that oxygenant H
2O
2Weight concentration is 3%～90%, is preferably 30%～70%, more preferably: 30%～50%.
Described catalyzed oxidation Synthetic 2, the method for 5-chlorophenesic acid is characterized in that temperature of reaction is 0～90 ℃, is preferably: 20～90 ℃, more preferably: 50～90 ℃.
Described catalyzed oxidation Synthetic 2, the method for 5-chlorophenesic acid is characterized in that oxygenant H
2O
2The middle stablizer that adds, described stablizer is zinc salt, phosphoric acid salt, pyrophosphate salt, xitix, 2,6 di tert butyl 4 methyl phenol, 5-tertiary butyl-4-hydroxy-2-toluenesulfonate or oxine and tin-oxide.
Described catalyzed oxidation Synthetic 2, the method for 5-chlorophenesic acid is characterized in that adding siccative in reaction solvent, and described siccative is molecular sieve, silica gel, calcium sulfate or sal epsom.
Described catalyzed oxidation Synthetic 2; the method of 5-chlorophenesic acid is characterized in that reaction system with the protection of nitrogen or rare gas, in addition; also can suppress the generation of by product under the dark condition, can also in reaction system, add suitable phase-transfer catalyst under some situation.
The pH value of reaction system is controlled at 1～6, is generally 1～5, is preferably 1～3, and low pH value can promote reaction, adds some and can improve yield, when making solvent with acetate, adds sodium acetate and can promote reaction in reaction system.
The heteropolyacid general structure that the present invention relates to is:
HnMmOy or HnXxMmOy
Wherein, M joins atom, and X is a heteroatoms, and M is Mo, W, V, Nb, Co, Zn, Cr, Sg; X is Si, Ge, P, As, B, Sn, Pb, As, Sb, Bi; H is a hydrogen; O is an oxygen.Concrete heteropolyacid comprises: H
4SiMo
12O
40, H
4SiW
12O
40, H
3PW
12O
40, H
3PMo
12O
40, H
4GeW
12O
40, H
4PMo
11VO
40, H
6PMo
9V
3O
40, H
5PMo
10V
2O
40, H
6P
2W
18O
62Deng polyacid compound with Keggin structure or Well-Dawson structure.
The oxidation of corresponding heteropolyacid salt santochlor has katalysis equally.Suitable salt comprises inorganic salt such as Na salt, Mg salt, K salt, Ca salt, Li salt, Be salt, Rb salt, Sr salt, Cs salt, Ba salt, Fr salt, Ra salt, and the form of salt can also be organic salt such as bromohexadecane yl pyridines salt, ammonium salt, quaternary ammonium salt.
There are problems such as catalyst recovery difficulty and pollution to a certain degree, corrosion in the heteropolyacid homogeneous catalysis, and the heteropolyacid specific surface area is less, is unfavorable for giving full play to catalytic activity.Therefore, heteropolyacid is carried on the porous support effectively, improves its specific surface area greatly, carry out heterogeneous catalytic reaction.Can heteropolyacid or heteropolyacid salt be loaded on the big or aperture of certain specific surface area by pickling process, coprecipitation method, ion exchange method, hybrid system, spraying method and maybe can improve on the carrier of catalyst performance greatly, maturing temperature is 40～500 ℃ during load.Suitable carrier comprises gac, molecular sieve, SiO
2, Al
2O
3, TiO
2, silica gel, diatomite, wilkinite and ion exchange resin.
Above-mentioned catalyzed oxidation Synthetic 2, the method for 5-chlorophenesic acid, reaction scheme is short, and technology is simple, and equipment corrosion is little, can residual a large amount of spent acid or salkali waste, help environment protection, and product yield and purity improve a lot compared with prior art.
Embodiment
The present invention is further described below in conjunction with concrete embodiment.
1) preparation of heteropolyacid:
A) H
4SiMo
12O
40Preparation
With 50g Na
2MoO
42H
2O (0.21mol) is dissolved in the 200ml water, and make solution be heated to 80 ℃, in solution, add the 20ml concentrated hydrochloric acid, the powerful stirring down drips sodium metasilicate solution (0.045mol) in the 30min, this moment, solution became yellow, continued to stir, and dripped the 60ml concentrated hydrochloric acid with dropping funnel, extracted with diethyl ether is used in filtrate cooling back, vapors away ether and obtains heteropolyacid H
4SiMo
12O
40
B) H
4SiW
12O
40Preparation
With 20gNa
2WO
42H
2O (0.061mol) is dissolved in the 40ml water, adds the 0.0071mol Starso then in solution, and mixture stirs and be warming up to boiling, drip the 12ml concentrated hydrochloric acid with dropping funnel, joining day is 90min, and extracted with diethyl ether is used in filtrate cooling back, vapors away ether and obtains heteropolyacid H
4SiW
12O
40
2) load of heteropolyacid or heteropolyacid salt
A) get 50g Al
2O
32H
2Continue behind 300 ℃ of roasting 2h of O to get 10gH at 600 ℃ of following roasting 4h
4SiMo
12O
40Be dissolved in the carrier impregnation 24h after the adding roasting in the 100ml water, leach solid oven dry 4h under 120 ℃ and promptly get loading type H
4SiMo
12O
40
3) 2, the preparation of 5-chlorophenesic acid
A) under 0 ℃, with 14.7g 1,4-dichlorobenzene (0.1mol) is dissolved in the 30ml acetone, and the dissolving back adds 0.5g H fully
4SiMo
12O
40, the powerful H of the interior 30ml 30% of dropping of 8h down that stirs
2O
2, behind the reaction 24h, underpressure distillation goes out 2,5-chlorophenesic acid (under the 2mm, 70 ℃ of boiling points).2, the fusing point of 5-chlorophenesic acid is 57～59 ℃.
B) under 70 ℃, with 14.7g 1,4-dichlorobenzene (0.1mol) is dissolved in the 120ml acetone, and the dissolving back adds 0.8g H fully
4SiW
12O
40, the powerful H of the interior 60ml 30% of dropping of 4h down that stirs
2O
2, behind the reaction 12h, underpressure distillation goes out 2, the 5-chlorophenesic acid.
C) under 40 ℃, with 14.7g 1,4-dichlorobenzene (0.1mol) is dissolved in the 80ml acetone, and the dissolving back adds 1.2g Na fully
4SiW
12O
40, the powerful H of the interior 30ml 50% of dropping of 6h down that stirs
2O
2, behind the reaction 24h, underpressure distillation goes out 2, the 5-chlorophenesic acid.
D) under 85 ℃, with 14.7g 1,4-dichlorobenzene (0.1mol) is dissolved in the 60ml acetone, and the dissolving back adds 2.5g loading type H fully
4SiMo
12O
40, the powerful H of the interior 40ml 50% of dropping of 4h down that stirs
2O
2, behind the reaction 6h, underpressure distillation goes out 2, the 5-chlorophenesic acid.
Claims (10)
1. catalyzed oxidation Synthetic 2, the method for 5-chlorophenesic acid is characterized in that 1, the 4-dichlorobenzene adopts heteropolyacid, heteropolyacid salt or its loading type to make catalyzer, with H in solvent
2O
2Make oxygenant, carry out catalytic oxidation, reaction finishes the back underpressure distillation and goes out 2, the 5-chlorophenesic acid.
2. catalyzed oxidation Synthetic 2 as claimed in claim 1, the method of 5-chlorophenesic acid, it is characterized in that 1, the 4-dichlorobenzene fully dissolves the back and adds catalyzer, under stirring, brute force slowly adds oxygenant, temperature of reaction is 0～150 ℃, and described solvent is 1,2-ethylene dichloride, methylene dichloride, chloroform, acetate, propionic acid, acetonitrile, acetone, butanone, methyl alcohol, ethanol or water.
3. catalyzed oxidation Synthetic 2 as claimed in claim 1, the method for 5-chlorophenesic acid is characterized in that described catalyzer is: H
4SiMo
12O
40, H
4SiW
12O
40, H
3PW
12O
40, H
3PMo
12O
40, H
4GeW
12O
40, H
4PMo
11VO
40, H
6PMo
9V
3O
40, H
5PMo
10V
2O
40Or H
6P
2W
18O
62, or its heteropolyacid salt, or the loaded catalyst of corresponding heteropolyacid, heteropolyacid salt.
4. catalyzed oxidation Synthetic 2 as claimed in claim 1, the method of 5-chlorophenesic acid, it is characterized in that heteropolyacid or heteropolyacid salt and 1, the mass ratio of 4-dichlorobenzene is 1: 0.0001～0.1, is preferably: 1: 0.001～0.1, more preferably: 1: 0.01～0.1, the loaded catalyst of heteropolyacid or heteropolyacid salt and 1, the mass ratio of 4-dichlorobenzene is 1: 0.001～1, is preferably: 1: 0.01～1, more preferably: 1: 0.1～1.
5. catalyzed oxidation Synthetic 2 as claimed in claim 1, the method for 5-chlorophenesic acid is characterized in that oxygenant H
2O
2With 1, the mol ratio of 4-dichlorobenzene is 1: 0.1～10, preferred 1: 0.3～5, more preferably 1: 0.3～3.
6. catalyzed oxidation Synthetic 2 as claimed in claim 1, the method for 5-chlorophenesic acid is characterized in that the time of oxidizing reaction is 1～48 hour, is preferably: 3～36 hours, more preferably: 5～24 hours.
7. catalyzed oxidation Synthetic 2 as claimed in claim 1, the method for 5-chlorophenesic acid is characterized in that temperature of reaction is 0～90 ℃, is preferably: 20～90 ℃, more preferably: 50～90 ℃.
8. catalyzed oxidation Synthetic 2 as claimed in claim 1, the method for 5-chlorophenesic acid is characterized in that oxygenant H
2O
2The middle stablizer that adds, described stablizer is zinc salt, phosphoric acid salt, pyrophosphate salt, xitix, 2,6 di tert butyl 4 methyl phenol, 5-tertiary butyl-4-hydroxy-2-toluenesulfonate or oxine and tin-oxide.
9. catalyzed oxidation Synthetic 2 as claimed in claim 1, the method for 5-chlorophenesic acid is characterized in that adding siccative in reaction solvent, and described siccative is molecular sieve, silica gel, calcium sulfate or sal epsom.
10. catalyzed oxidation Synthetic 2 as claimed in claim 1, the method for 5-chlorophenesic acid is characterized in that reaction system is with the protection of nitrogen or rare gas.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100491244A CN1329357C (en) | 2006-01-17 | 2006-01-17 | Process for catalyzing oxidating synthesizing 2,5-dichlorophenol |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100491244A CN1329357C (en) | 2006-01-17 | 2006-01-17 | Process for catalyzing oxidating synthesizing 2,5-dichlorophenol |
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| Publication Number | Publication Date |
|---|---|
| CN1793096A true CN1793096A (en) | 2006-06-28 |
| CN1329357C CN1329357C (en) | 2007-08-01 |
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|---|---|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104591973A (en) * | 2015-01-06 | 2015-05-06 | 安徽雪郎生物科技股份有限公司 | Preparation method of 2,5-dichlorophenol |
| CN104961630A (en) * | 2015-06-15 | 2015-10-07 | 江苏蓝丰生物化工股份有限公司 | Preparation method of 2, 5-dichlorophenol |
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01175948A (en) * | 1987-12-28 | 1989-07-12 | Mitsui Petrochem Ind Ltd | Production of 3,5-dichlorophenol |
-
2006
- 2006-01-17 CN CNB2006100491244A patent/CN1329357C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104591973A (en) * | 2015-01-06 | 2015-05-06 | 安徽雪郎生物科技股份有限公司 | Preparation method of 2,5-dichlorophenol |
| CN104961630A (en) * | 2015-06-15 | 2015-10-07 | 江苏蓝丰生物化工股份有限公司 | Preparation method of 2, 5-dichlorophenol |
| CN104961630B (en) * | 2015-06-15 | 2017-03-22 | 江苏蓝丰生物化工股份有限公司 | Preparation method of 2, 5-dichlorophenol |
| 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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| CN1329357C (en) | 2007-08-01 |
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