CN107353185A - A kind of preparation method of the dihydroxy diphenyl ether of active bactericide 4,4` dichloros 2 - Google Patents
A kind of preparation method of the dihydroxy diphenyl ether of active bactericide 4,4` dichloros 2 Download PDFInfo
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- CN107353185A CN107353185A CN201710479187.1A CN201710479187A CN107353185A CN 107353185 A CN107353185 A CN 107353185A CN 201710479187 A CN201710479187 A CN 201710479187A CN 107353185 A CN107353185 A CN 107353185A
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- dihydroxy diphenyl
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/26—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of hydroxy or O-metal groups
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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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
- C07C245/20—Diazonium compounds
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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
- C07C37/64—Preparation of O-metal compounds with O-metal group bound to a carbon atom belonging to a six-membered aromatic ring
- C07C37/66—Preparation of O-metal compounds with O-metal group bound to a carbon atom belonging to a six-membered aromatic ring by conversion of hydroxy groups to O-metal groups
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Abstract
The invention discloses a kind of active bactericide 4, the preparation method of the dihydroxy diphenyl ether of 4' dichloros 2, parachlorophenol forms phenol metal salt in the presence of alkali lye, with 2,5 dichloronitrobenzenes are condensed, nitro reduces, diazotising hydrolysis, with solvent extraction product, product purifies by vacuum distillation, obtains high-quality active bactericide product.Preparation process of the present invention is easy to operate, production cost is low, and product purity is high, and the sterilised products of compounding are all largely effective to killing or suppressing Gram-positive and negative bacterium, and be easy to compound, can be with anion, nonionic, both sexes and cationic surfactant compatibility.
Description
Technical field
The invention belongs to chemical field, and in particular to a kind of active bactericide 4, the preparation of the chloro- 2- dihydroxy diphenyl ethers of 4'- bis-
Method.
Background technology
4,4'- bis- chloro- 2- dihydroxy diphenyl ethers are a kind of widely used active bactericides, available for coating, paint, bonding
Agent, detergent, thimerosal, the middle sterilization component of surface cleaner.It can effectively suppress gram-positive bacteria, Gram-negative
Bacterium, bacterium and mould etc., it can reach target spot with penetration cell wall and play bactericidal action.
Have been reported and use dichloro-benzenes acetylation, yield 65.3%, be condensed with parachlorophenol, yield 69.2%, then
Hydrolysis obtains product, and yield 72.7%, total recovery only has 32.85%.Dichloro-benzenes acetylation route reaction condition is harsh, total to receive
Rate is only 32.85%, and product purity is not high.
Using o-methoxyphenol as raw material, chlorination, yield 90.8% are carried out with chlorine, then with being condensed to bromochlorobenzene, receive
Rate is 20%, and reaction, yield 45.78% is then hydrolyzed, and total recovery is only 8.31%.Chloridization process route is difficult to control
System, causes chloride impurity more, and hardly possible separation, yield is very low, is a uneconomic synthetic route.
Domestic at present not carry out industrialized production also according to both the above synthetic route, foreign countries use o-methoxyphenol chlorine
It is high to change process costs, selling price is also high, does not possess market competition strength.
The content of the invention
Goal of the invention：In order to solve the deficiencies in the prior art, the invention provides a kind of active bactericide 4,4'- bis- are chloro-
The preparation method of 2- dihydroxy diphenyl ethers, the raw material being easy to get using in the market, industrialized synthetic route is easily realized, realized
Production operation is convenient, drops the purpose for the synthetic route that can save consumption, high income and good product quality.
Technical scheme：A kind of active bactericide 4, the preparation method of the chloro- 2- dihydroxy diphenyl ethers of 4'- bis-, parachlorophenol is in alkali
Phenol metal salt is formed in the presence of liquid, be condensed with 2,5- dichloronitrobenzenes, nitro reduction, diazotising hydrolysis, use is molten
Product is extracted in agent, and product purifies by vacuum distillation, obtains high-quality active bactericide product.
Wherein, alkali lye is is the alkali metal base solution such as sodium hydroxide or potassium hydroxide, alkali concn 30%-50%, to chlorine
The molar ratio of phenol and alkali lye is 1:1~1.5.
Wherein, the molar ratio of parachlorophenol and 2,5- dichloronitrobenzene is 1~1.5:1, setting-up point 120
DEG C -180 DEG C, condensation product yield is more than 99%, and condensation yield is more than 99%.
Wherein, using ferric trichloride and activated carbon or iron-oxygen thing etc. as catalyst, solvent is for nitro reduction in a solvent
Alcohol, chlorobenzene, dichloro-benzenes, carbon tetrachloride, dichloromethane, dichloroethanes, the amount of catalyst are the 5%-20% of reactant, reduction
Agent is 50%~85% hydrazine hydrate, and reduction temperature is 60 DEG C~95 DEG C, and amino substance yield is more than 98%, and condensation yield is more than
98%.
Wherein, diazo reagent can be the synthetic of natrium nitrosum and sulfuric acid, or directly use salt-free nitrosyl sulfuric acid,
The molar ratio of diazo reagent and amino substance is 1~1.1:1, diazo-reaction temperature is 25 DEG C~50 DEG C.
Wherein, hydrolysis uses 50%~90% sulfuric acid, and hydrolysising reacting temperature is controlled at 150 DEG C~200 DEG C.
Wherein, Extraction solvent can be chlorine benzene,toluene,xylene, dichloro-benzenes, carbon tetrachloride, dichloromethane, two chloroethenes
Alkane, Extracting temperature are controlled at 50 DEG C~80 DEG C.
Wherein, vacuum degree control is distilled to collect at 150 DEG C~200 DEG C in 150Pa~500Pa, distillation heating and temperature control
Gas phase temperature is 120 DEG C~170 DEG C of cut, and obtained product purity is more than 99.5%.
Wherein, the yield of diazo-reaction, hydrolysis and vacuum distillation purification is more than 80%, and total recovery is more than 77%.
Reaction equation in the present invention is：
1) into salt
2) condensation reaction
3) reduction reaction
4) diazo-reaction
5) hydrolysis
Beneficial effect：Preparation process of the present invention is easy to operate, and production cost is low, and product purity is high, the sterilised products of compounding
It is all largely effective to killing or suppressing Gram-positive and negative bacterium, and be easy to compound, can be with anion, nonionic, both sexes
And cationic surfactant compatibility.
Embodiment
The technical scheme in the embodiment of the present invention will be clearly and completely described below, so that the technology of this area
Personnel can be better understood from advantages and features of the invention, so as to make apparent boundary to protection scope of the present invention
It is fixed.Embodiment described in the invention is only part of the embodiment of the present invention, rather than whole embodiments, based on the present invention
In embodiment, the every other implementation that those of ordinary skill in the art are obtained on the premise of creative work is not made
Example, belongs to the scope of protection of the invention.
Embodiment 1
The sodium hydroxide solutions of 500kg 50% are added in the reactor, and the parachlorophenol streams of 740kg 99.2% of thawing are added
Enter in reactor, form sodium phenolate, when being warming up to 140 DEG C, start the 1000kg 99.5%2 thawing, 5- dichloronitrobenzene streams
It is added in reactor, adds in 140 DEG C of -150 DEG C of insulation reactions 4 hours, thin-layer chromatographic analysis 2,5- dichloronitrobenzenes have reacted
Afterwards, less than 60 DEG C are cooled to, filtering, it is condensation product to drain to obtain 1685kg light yellow solids, solid content 87.22%, purity
For 99.32%, the yield given money as a gift is 99.18%. (being calculated with 2,5- dichloronitrobenzenes), and fusing point is 76.3 DEG C~77.5 DEG C.
It is 87.22%1000kg condensation products to add 1000kg chlorobenzenes, 50kg ferriferous oxides, solid content in the reactor, is risen
Temperature is to 90 DEG C, stream plus the hydrazine hydrates of 286kg 80.01%, in 90 DEG C of -95 DEG C of insulation reactions 4 hours, thin-layer chromatographic analysis condensation product
After having reacted, heat filtering, filter cake continue to apply mechanically with next group reduction reaction, filtrate decompression distills to obtain 950kg chlorobenzenes, under getting
Layer amino substance 765kg, purity 99.13%, yield 98.74%., fusing point are 61.4 DEG C~62.6 DEG C.
The nitrosyl sulfuric acid solution of 840kg 42.31% is added in the reactor, 25 DEG C is warming up to, the 700kg melted
Slowly stream is added in reactor amino substance, reacts complete to amino substance within 2 hours in 25 DEG C~30 DEG C insulation reactions, diazotising liquid stream
Temperature is added on as reaction is hydrolyzed in 155 DEG C of sulfuric acid of 500kg 78%, is added in 1 hour, 30 minutes is incubated, is cooled to
100 DEG C, hydrolysis liquid stream is added in 1000kg dimethylbenzene, at 80 DEG C~90 DEG C, spent acid layer is disposed temperature control.
Diformazan benzene layer is washed to neutrality with diluted alkaline, and vacuum distillation recovery dimethylbenzene, it is at 95 DEG C -120 DEG C to collect temperature
Dimethylbenzene 950kg.Continue to be evaporated in vacuo, temperature is heated to 180 DEG C -190 DEG C, is 250Pa~400Pa in vacuum, collects gas
Phase temperature is 130 DEG C~160 DEG C of cut, obtains product 612kg, purity 99.65%, and yield is 87.54% (in terms of amino substance
Calculate), fusing point is 73.2 DEG C~74.5 DEG C.
Embodiment 2
The potassium hydroxide solutions of 700kg 48% are added in the reactor, and the parachlorophenol streams of 740kg 99.2% of thawing are added
Enter in reactor, form sodium phenolate, when being warming up to 135 DEG C, start the 1000kg 99.5%2 thawing, 5- dichloronitrobenzene streams
It is added in reactor, adds in 135 DEG C of -140 DEG C of insulation reactions 3.5 hours, thin-layer chromatographic analysis 2, the reaction of 5- dichloronitrobenzenes
After complete, less than 60 DEG C are cooled to, filtering, it is condensation product to drain to obtain 1662kg light yellow solids, and solid content 88.54% is pure
Spend for 99.56%, the yield given money as a gift is 99.53%. (being calculated with 2,5- dichloronitrobenzenes), and fusing point is 76.5 DEG C~77.4 DEG C.
It is 88.54%1000kg condensation products to add 800kg tetrachloro-ethylenes, 50kg ferriferous oxides, solid content in the reactor,
It is warming up to 75 DEG C, stream plus the hydrazine hydrates of 292kg 80.08%, in 75 DEG C of -80 DEG C of insulation reactions 4 hours, thin-layer chromatographic analysis condensation
After thing has reacted, heat filtering, filter cake continues to apply mechanically to be distilled to obtain 785kg tetrachloro-ethylenes with next group reduction reaction, filtrate decompression,
Get lower floor amino substance 789kg, purity 99.21%, yield 98.85%., fusing point is 61.6 DEG C~62.4 DEG C.
The nitrosyl sulfuric acid solution of 800kg 44.45% is added in the reactor, 25 DEG C is warming up to, the 700kg melted
Slowly stream is added in reactor amino substance, reacts complete to amino substance within 2 hours in 30 DEG C~35 DEG C insulation reactions, diazotising liquid stream
Temperature is added on as reaction is hydrolyzed in 165 DEG C of sulfuric acid of 500kg 78%, is added in 1 hour, 30 minutes is incubated, is cooled to
100 DEG C, hydrolysis liquid stream is added in 1000kg toluene, at 75 DEG C~80 DEG C, spent acid layer is disposed temperature control.
Toluene layer is washed to neutrality with diluted alkaline, and vacuum distillation recovery toluene, it is the toluene at 80 DEG C -100 DEG C to collect temperature
985kg.Continue to be evaporated in vacuo, temperature is heated to 160 DEG C -180 DEG C, is 200Pa~350Pa in vacuum, collects gas phase temperature
For 130 DEG C~155 DEG C of cut, product 616kg, purity 99.81% are obtained, yield is 88.19% (being calculated with amino substance), is melted
Point is 73.4 DEG C~74.6 DEG C.
Preparation process of the present invention is easy to operate, and production cost is low, and product purity is high, and the sterilised products of compounding are to killing or pressing down
Gram-positive and negative bacterium processed are all largely effective, and are easy to compound, can be with anion, nonionic, both sexes and cation
Surfactant compatibility.
Claims (9)
1. a kind of active bactericide 4, the preparation method of the chloro- 2- dihydroxy diphenyl ethers of 4'- bis-, it is characterized in that：Parachlorophenol is in alkali lye
In the presence of formed phenol metal salt, be condensed with 2,5- dichloronitrobenzenes, nitro reduction, diazotising hydrolysis, use solvent
Product is extracted, product purifies by vacuum distillation, obtains high-quality active bactericide product.
2. active bactericide 4 according to claim 1, the preparation method of the chloro- 2- dihydroxy diphenyl ethers of 4'- bis-, it is characterized in that：
Alkali lye can be the alkali metal base solution such as sodium hydroxide, potassium hydroxide, alkali concn 30%-50%, parachlorophenol and alkali lye
Molar ratio is 1:1~1.5.
3. active bactericide 4 according to claim 1, the preparation method of the chloro- 2- dihydroxy diphenyl ethers of 4'- bis-, it is characterized in that：
The molar ratio of parachlorophenol and 2,5- dichloronitrobenzenes is 1~1.5:1, setting-up point is 120 DEG C -180 DEG C, condensation product
Yield is more than 99%, and condensation yield is more than 99%.
4. active bactericide 4 according to claim 1, the preparation method of the chloro- 2- dihydroxy diphenyl ethers of 4'- bis-, it is characterized in that：
Using ferric trichloride and activated carbon or iron-oxygen thing etc. as catalyst, solvent is alcohol, chlorobenzene, dichloro for nitro reduction in a solvent
Benzene, carbon tetrachloride, dichloromethane, dichloroethanes, the amount of catalyst are the 5%-20% of reactant, and reducing agent is 50%~85%
Hydrazine hydrate, reduction temperature be 60 DEG C~95 DEG C, amino substance yield be more than 98%.
5. active bactericide 4 according to claim 1, the preparation method of the chloro- 2- dihydroxy diphenyl ethers of 4'- bis-, it is characterized in that：
Diazo reagent can be the synthetic of natrium nitrosum and sulfuric acid, or directly use salt-free nitrosyl sulfuric acid, diazo reagent with
The molar ratio of amino substance is 1~1.1:1, diazo-reaction temperature is 25 DEG C~50 DEG C.
6. active bactericide 4 according to claim 1, the preparation method of the chloro- 2- dihydroxy diphenyl ethers of 4'- bis-, it is characterized in that：
Hydrolysis uses 50%~90% sulfuric acid, and hydrolysising reacting temperature is controlled at 150 DEG C~200 DEG C.
7. active bactericide 4 according to claim 1, the preparation method of the chloro- 2- dihydroxy diphenyl ethers of 4'- bis-, it is characterized in that：
Extraction solvent can be chlorine benzene,toluene,xylene, dichloro-benzenes, carbon tetrachloride, dichloromethane, dichloroethanes, and Extracting temperature controls
At 50 DEG C~80 DEG C.
8. active bactericide 4 according to claim 1, the preparation method of the chloro- 2- dihydroxy diphenyl ethers of 4'- bis-, it is characterized in that：
Vacuum degree control is distilled in 150Pa~500Pa, and for distillation heating and temperature control at 150 DEG C~200 DEG C, it is 120 to collect gas phase temperature
DEG C~170 DEG C of cut, obtained product purity is more than 99.5%.
9. active bactericide 4 according to claim 1, the preparation method of the chloro- 2- dihydroxy diphenyl ethers of 4'- bis-, it is characterized in that：
The yield of diazo-reaction, hydrolysis and vacuum distillation purification is more than 80%, and total recovery is more than 77%.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109541069A (en) * | 2018-12-20 | 2019-03-29 | 上海开米科技有限公司 | The detection method of the chloro- 2- dihydroxy diphenyl ether content of 4,4- bis- in a kind of detergent |
| CN113666819A (en) * | 2020-05-14 | 2021-11-19 | 帕潘纳(北京)科技有限公司 | Method for preparing chlorofluoromethrizole intermediate |
| CN113717039A (en) * | 2020-05-21 | 2021-11-30 | 帕潘纳(北京)科技有限公司 | Method for preparing chlorofluoromethrizole intermediate |
| CN114507155A (en) * | 2022-02-16 | 2022-05-17 | 浙江欣禾生物股份有限公司 | Preparation method of m-trifluoromethyl acetophenone oxime |
| CN116444353A (en) * | 2023-06-14 | 2023-07-18 | 山东奥友化学有限责任公司 | Preparation method of 4,4' -dichloro-2-hydroxydiphenyl ether |
-
2017
- 2017-06-22 CN CN201710479187.1A patent/CN107353185B/en active Active
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109541069A (en) * | 2018-12-20 | 2019-03-29 | 上海开米科技有限公司 | The detection method of the chloro- 2- dihydroxy diphenyl ether content of 4,4- bis- in a kind of detergent |
| CN113666819A (en) * | 2020-05-14 | 2021-11-19 | 帕潘纳(北京)科技有限公司 | Method for preparing chlorofluoromethrizole intermediate |
| CN113717039A (en) * | 2020-05-21 | 2021-11-30 | 帕潘纳(北京)科技有限公司 | Method for preparing chlorofluoromethrizole intermediate |
| CN114507155A (en) * | 2022-02-16 | 2022-05-17 | 浙江欣禾生物股份有限公司 | Preparation method of m-trifluoromethyl acetophenone oxime |
| CN116444353A (en) * | 2023-06-14 | 2023-07-18 | 山东奥友化学有限责任公司 | Preparation method of 4,4' -dichloro-2-hydroxydiphenyl ether |
| CN116444353B (en) * | 2023-06-14 | 2023-09-08 | 山东奥友化学有限责任公司 | Preparation method of 4,4' -dichloro-2-hydroxydiphenyl ether |
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