CN107778153A - The preparation method of the dihydroxy benaophenonel of 4 chlorine 4 ' - Google Patents
The preparation method of the dihydroxy benaophenonel of 4 chlorine 4 ' Download PDFInfo
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- CN107778153A CN107778153A CN201610770157.1A CN201610770157A CN107778153A CN 107778153 A CN107778153 A CN 107778153A CN 201610770157 A CN201610770157 A CN 201610770157A CN 107778153 A CN107778153 A CN 107778153A
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- preparation
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- dihydroxy benaophenonels
- chlorophenyl nitrile
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/44—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reduction and hydrolysis of nitriles
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of preparation method of the dihydroxy benaophenonel of 4 chlorine 4 ', appropriate dichloroethanes is added in a kettle, phenol, to 6-chlorophenyl nitrile, anhydrous zinc chloride and gel-type strong-acid ion exchange resin are stirred, temperature control is continuously passed through dry hydrogen chloride gas at 50 DEG C~120 DEG C, until to the complete reaction of 6-chlorophenyl nitrile, it is cooled to room temperature and adds appropriate aqueous hydrochloric acid solution, temperature rising reflux reacts 5h~7h, it is subsequently cooled to room temperature, layering, dichloroethanes is reclaimed in organic layer, residue adds alkali soluble solution, decolourized with activated carbon, acid out, filter, drying obtains the dihydroxy benaophenonel of 4 chlorine 4 '.The preparation method route of the dihydroxy benaophenonel of 4 chlorine 4 ' of the present invention is succinct and high income.
Description
Technical field
The present invention relates to a kind of preparation method of compound, the preparation side of especially a kind of chloro- 4 '-dihydroxy benaophenonels of 4-
Method.
Background technology
The chloro- 4 '-dihydroxy benaophenonels of 4- are a kind of important medicine intermediates.The preparation of the chloro- 4 '-dihydroxy benaophenonels of 4-
The shortcomings of method has a variety of, but raw material sources difficulty all be present, and route is complicated, and yield is low, and industrialization cost is high..
How to provide that a kind of route is succinct and the preparation method of the chloro- 4 '-dihydroxy benaophenonels of 4- of high income is this area
Technical staff's technical issues that need to address.
The content of the invention
Succinct and the chloro- 4 '-hydroxy benzophenones of 4- of high income the technical problem to be solved in the present invention is to provide a kind of route
The preparation method of ketone.
The present invention is to solve a kind of technical scheme that above-mentioned technical problem proposes to be：A kind of chloro- 4 '-dihydroxy benaophenonels of 4-
Preparation method, add appropriate dichloroethanes, phenol in a kettle, to 6-chlorophenyl nitrile, anhydrous zinc chloride and gel-type strong acid
Property ion exchange resin be stirred, temperature control is continuously passed through dry hydrogen chloride gas at 50 DEG C~120 DEG C, until to chlorine
Cyanophenyl is reacted completely, is cooled to room temperature and is added appropriate aqueous hydrochloric acid solution, temperature rising reflux reaction 5h~7h, is subsequently cooled to room
Temperature, it is layered, dichloroethanes is reclaimed in organic layer, residue adds alkali soluble solution, decolourized with activated carbon, acid out, filters, dries
To the chloro- 4 '-dihydroxy benaophenonels of 4-.
The gel-type strong-acid ion exchange resin is Dowex 50W resins.
The parts by weight of the phenol are 18~25, and the parts by weight to 6-chlorophenyl nitrile are 28~35, the anhydrous zinc chloride
Parts by weight be 3~6, the parts by weight of the gel-type strong-acid ion exchange resin are 1~2.
The quality of the dichloroethanes is 300 times~500 times to 6-chlorophenyl nitrile quality.
The concentration of the aqueous hydrochloric acid solution is 25%~35%, the quality of the hydrochloric acid be to the 90% of 6-chlorophenyl nitrile quality~
110%。
The alkali added in the residue is the sodium hydrate aqueous solution that concentration is 15%.
A kind of preferable scheme is that temperature control is continuously passed through dry hydrogen chloride gas at 80 DEG C~110 DEG C.
A kind of further preferred scheme is that temperature control is continuously passed through dry hydrogen chloride gas at 90 DEG C~100 DEG C.
The present invention has positive effect：The preparation method of the chloro- 4 '-dihydroxy benaophenonels of 4- of the present invention is with to 6-chlorophenyl nitrile
It is raw material with phenol, under conditions of zinc chloride, hydrogen chloride and catalyst, is reacted, raw material easily obtains, and cost is relatively low, instead
Should be succinct, efficiency high.Using gel-type strong-acid ion exchange resin Dowex 50W as catalyst and by reaction temperature control
System is in 90 DEG C~100 DEG C yields that can significantly improve reaction so that yield reaches more than 85%, if using cation exchange
Resin, yield can only achieve 60%.In addition, dichloroethanes, which is solvent, is easily recycled reusable edible, cost is advantageously reduced.This
The preparation method of the chloro- 4 '-dihydroxy benaophenonels of 4- of invention is suitable to industrial mass production.
Embodiment
Embodiment 1
The specific steps of the preparation method of the chloro- 4 '-dihydroxy benaophenonels of 4- of the present embodiment include：Dichloro is added in a kettle
Ethane 500ml, phenol 100g, the Dowex 50W resin 5g to the production of 6-chlorophenyl nitrile 146g, anhydrous zinc chloride 20g and DOW Chemical,
It is stirred, temperature control is continuously passed through dry hydrogen chloride gas at 95 DEG C, and the reaction of material is detected in venting process intermediate gap
Situation, until to the complete reaction of 6-chlorophenyl nitrile, it is cooled to room temperature and adds concentration as 30% aqueous hydrochloric acid solution 400ml, temperature rising reflux,
6h is reacted, has been hydrolyzed to intermediate, has been subsequently cooled to room temperature, is layered, is washed, reclaims dichloroethanes in organic layer, residue adds
The sodium hydrate aqueous solution 200ml that concentration is 15% dissolves, and is decolourized with activated carbon 8g, acid out, filters, and drying obtains yellowish
Color solid is the chloro- 4 '-dihydroxy benaophenonels of 4-, content 99.3%, yield 87.6%.
Reaction equation is as follows：
Embodiment 2
The specific steps of the preparation method of the chloro- 4 '-dihydroxy benaophenonels of 4- of the present embodiment include：Dichloro is added in a kettle
Ethane 600ml, phenol 120g, the Dowex 50W resin 8g to the production of 6-chlorophenyl nitrile 146g, anhydrous zinc chloride 25g and DOW Chemical,
It is stirred, temperature control is continuously passed through dry hydrogen chloride gas at 90 DEG C, and the reaction of material is detected in venting process intermediate gap
Situation, until to the complete reaction of 6-chlorophenyl nitrile, it is cooled to room temperature and adds concentration as 30% aqueous hydrochloric acid solution 500ml, temperature rising reflux,
5h is reacted, has been hydrolyzed to intermediate, has been subsequently cooled to room temperature, is layered, is washed, reclaims dichloroethanes in organic layer, residue adds
The sodium hydrate aqueous solution 250ml that concentration is 15% dissolves, and is decolourized with activated carbon 8g, acid out, filters, and drying obtains yellowish
Color solid is the chloro- 4 '-dihydroxy benaophenonels of 4-, content 99.5%, yield 86.7%.
Embodiment 3
The specific steps of the preparation method of the chloro- 4 '-dihydroxy benaophenonels of 4- of the present embodiment include：Dichloro is added in a kettle
Ethane 550ml, phenol 120g, the Dowex 50W resin 7g to the production of 6-chlorophenyl nitrile 146g, anhydrous zinc chloride 22g and DOW Chemical,
It is stirred, temperature control is continuously passed through dry hydrogen chloride gas at 90 DEG C, and the reaction of material is detected in venting process intermediate gap
Situation, until to the complete reaction of 6-chlorophenyl nitrile, it is cooled to room temperature and adds concentration as 30% aqueous hydrochloric acid solution 450ml, temperature rising reflux,
7h is reacted, has been hydrolyzed to intermediate, has been subsequently cooled to room temperature, is layered, is washed, reclaims dichloroethanes in organic layer, residue adds
The sodium hydrate aqueous solution 200ml that concentration is 15% dissolves, and is decolourized with activated carbon 8g, acid out, filters, and drying obtains yellowish
Color solid is the chloro- 4 '-dihydroxy benaophenonels of 4-, content 99.2%, yield 88.1%.
Raw materials used in the present invention is bought-in article unless otherwise specified, and concentration is that chemistry is pure.
Obviously, above-described embodiment is only intended to clearly illustrate example of the present invention, and is not to the present invention
The restriction of embodiment.For those of ordinary skill in the field, it can also be made on the basis of the above description
Its various forms of changes or variation.There is no necessity and possibility to exhaust all the enbodiments.And these belong to this hair
Among the obvious changes or variations that bright spirit is extended out is still in protection scope of the present invention.
Claims (8)
- A kind of 1. preparation method of the chloro- 4 '-dihydroxy benaophenonels of 4-, it is characterised in that：Appropriate dichloro is added in a kettle Ethane, phenol, 6-chlorophenyl nitrile, anhydrous zinc chloride and gel-type strong-acid ion exchange resin are stirred, temperature control is 50 DEG C~120 DEG C be continuously passed through dry hydrogen chloride gas, until to the complete reaction of 6-chlorophenyl nitrile, be cooled to room temperature and add appropriate salt Aqueous acid, temperature rising reflux reaction 5h~7h, is subsequently cooled to room temperature, is layered, reclaim dichloroethanes in organic layer, residue adds Alkali soluble solution, is decolourized with activated carbon, acid out, is filtered, and drying obtains the chloro- 4 '-dihydroxy benaophenonels of 4-.
- 2. the preparation method of the chloro- 4 '-dihydroxy benaophenonels of 4- according to claim 1, it is characterised in that：The gel-type Strong-acid ion exchange resin is Dowex 50W resins.
- 3. according to the preparation method of the chloro- 4 '-dihydroxy benaophenonels of 4- described in claim 2, it is characterised in that：The weight of the phenol It is 18~25 to measure part, and the parts by weight to 6-chlorophenyl nitrile are 28~35, and the parts by weight of the anhydrous zinc chloride are 3~6, described solidifying The parts by weight of glue-type strong-acid ion exchange resin are 1~2.
- 4. the preparation method of the chloro- 4 '-dihydroxy benaophenonels of 4- according to claim 3, it is characterised in that：Two chloroethene The quality of alkane is 300 times~500 times to 6-chlorophenyl nitrile quality.
- 5. the preparation method of the chloro- 4 '-dihydroxy benaophenonels of 4- according to claim 4, it is characterised in that：The hydrochloric acid water The concentration of solution is 25%~35%, and the quality of the hydrochloric acid is 90%~110% to 6-chlorophenyl nitrile quality.
- 6. the preparation method of the chloro- 4 '-dihydroxy benaophenonels of 4- according to claim 5, it is characterised in that：The residue In plus alkali be concentration be 15% sodium hydrate aqueous solution.
- 7. the preparation method of the chloro- 4 '-dihydroxy benaophenonels of 4- according to any one of claim 1 to 5, its feature exist In：Temperature control is continuously passed through dry hydrogen chloride gas at 80 DEG C~110 DEG C.
- 8. the preparation method of the chloro- 4 '-dihydroxy benaophenonels of 4- according to claim 7, it is characterised in that：Temperature control exists 90 DEG C~100 DEG C are continuously passed through dry hydrogen chloride gas.
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| CN201610770157.1A CN107778153A (en) | 2016-08-31 | 2016-08-31 | The preparation method of the dihydroxy benaophenonel of 4 chlorine 4 ' |
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| CN201610770157.1A CN107778153A (en) | 2016-08-31 | 2016-08-31 | The preparation method of the dihydroxy benaophenonel of 4 chlorine 4 ' |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63141942A (en) * | 1986-12-03 | 1988-06-14 | Asahi Chem Ind Co Ltd | Production of chlorohydroxybenzophenones |
| JPH03127753A (en) * | 1989-10-09 | 1991-05-30 | Mitsubishi Kasei Corp | Production of 4-chloro-4'-hydroxybenzophenones |
| CN103896754A (en) * | 2014-03-25 | 2014-07-02 | 徐州工业职业技术学院 | Method for clean preparation of 4-hydroxyl-4'-chlorobenzophenone |
| CN104030911A (en) * | 2014-06-10 | 2014-09-10 | 金坛德培化工有限公司 | Method for preparing 4-chloro-4'-hydroxybenzophenone |
-
2016
- 2016-08-31 CN CN201610770157.1A patent/CN107778153A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63141942A (en) * | 1986-12-03 | 1988-06-14 | Asahi Chem Ind Co Ltd | Production of chlorohydroxybenzophenones |
| JPH03127753A (en) * | 1989-10-09 | 1991-05-30 | Mitsubishi Kasei Corp | Production of 4-chloro-4'-hydroxybenzophenones |
| CN103896754A (en) * | 2014-03-25 | 2014-07-02 | 徐州工业职业技术学院 | Method for clean preparation of 4-hydroxyl-4'-chlorobenzophenone |
| CN104030911A (en) * | 2014-06-10 | 2014-09-10 | 金坛德培化工有限公司 | Method for preparing 4-chloro-4'-hydroxybenzophenone |
Non-Patent Citations (1)
| Title |
|---|
| 李敢: "4 － 羟基－ 4" － 氯二苯甲酮的合成研究", 《广州化工》 * |
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