CN102344345A - Preparation method of arylene ether compound - Google Patents
Preparation method of arylene ether compound Download PDFInfo
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- CN102344345A CN102344345A CN2011102127319A CN201110212731A CN102344345A CN 102344345 A CN102344345 A CN 102344345A CN 2011102127319 A CN2011102127319 A CN 2011102127319A CN 201110212731 A CN201110212731 A CN 201110212731A CN 102344345 A CN102344345 A CN 102344345A
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Abstract
The invention relates to a preparation method of arylene ether compound. The preparation method is characterized in that phenol is added into aqueous solution of sodium hydroxide or potassium hydroxide to prepare sodium salt or potassium salt of phenol, halohydrocarbon is added dropwise at the temperature of 0-20 DEG C, reaction is carried out for a period of time while the temperature is maintained, temperature is increased to 40-100 DEG C, reaction is continued, cooling is carried out, and separation is carried out to obtain arylene ether. The preparation method of the arylene ether compound in water phase has simple process, short reaction time, good product quality and high yield. Only water is taken as reaction solvent in a reaction process, no organic solvent is adopted, no solvent recovery or aftertreatment is required to be carried out, and the preparation method is environmentally friendly.
Description
Technical field
The present invention relates to a kind of preparation method of aryl oxide compound, be specifically related to carry out in the aqueous solution method of aryl oxide compounds preparation.
Background technology
Aryl oxide is the ethers that contains aromatic base.General formula of molecular structure is Ar-O-Ar ' or Ar-O-R, and Ar and Ar ' are aromatic base in the formula, and R is an alkyl.Aryl oxide is important fine-chemical intermediate, is used for synthetic dyestuff, agricultural chemicals, pharmaceuticals etc.Wherein alkyl aromatic ether is important basic medicine chemical material, and bromo aryl oxide compounds can be used as the good fire retardant of character.
Usually produce Ar-O-R ether (Williamson is synthetic) by phenol and haloalkane reaction, in the presence of copper catalyst, react system Ar-O-Ar ' ether (Ullmann reaction) by phenol and aromatic halide.(He Ganwu. the preparation of alkyl aromatic ether under the cesium carbonate catalysis. Shaoyang institute journal (natural science edition); 2007; 4 (1): 90-92) preparation of aryl oxide generally adopts phenol sodium in solvent, to prepare under catalyst action with halohydrocarbon; Usually handle phenol with alkali aqueous solution; Make it become water-soluble phenol sodium (potassium) salt; Again with the toluene of halohydrocarbon; Solution such as halogeno-benzene add in phenol sodium (potassium) salt brine solution; Under certain temperature; Under the effect of catalyzer, react; There is catalyzer in aforesaid method; Solvent is selected and isolating problem; Aftertreatment loaded down with trivial details (Liu Shuheng. press the synthetic aryl oxide of salt catalysis chitosan season. Cangzhou teacher training school journal. 2002,18 (3): 52).
CN200410084425.1 has disclosed a kind of method of synthesizing dihalogenated aromatic ether by phase transfer, is raw material with dihalo phenol, in the HaOH aqueous solution; Add phase-transfer catalyst; Drip hydrobromic ether and react, generate the dihalo aromatic oxide, separation is purified and is got finished product again.Only add entry as solvent in this method reaction, do not add any other organic solvent.Since not with an organic solvent, therefore on technology, reduced steps such as organic solvent recovery and rectifying in the reaction, environmentally friendly, be easy to suitability for industrialized production.And, owing to do not contain organic solvent, can be heated in the mixture of dihalo phenol, the NaOH aqueous solution and phase-transfer catalyst than higher temperature (more than 90 ℃), accelerated the speed of response with hydrobromic ether greatly, and yield is improved.Produce the dihalo aryl oxide with method of the present invention, yield can reach more than 90%, and gas chromatographic analysis purity can reach more than 95%.
CN200310116688.1 discloses a kind of preparation method of ethylene glycol bisthioglycolate aryl oxide of suitable suitability for industrialized production, promptly in reactor, adds substituted phenol, alkaline solution, stirring reaction; Add excessive ethylene dichloride and phase-transfer catalyst, 70-100 ℃ of back flow reaction, the reaction times is 15-35 hour; Concentrate at 95-130 ℃ then and divide water, make to react completely; After adding the abundant dissolve inorganic salts of water, discard water layer, resistates gets product behind recrystallization, and yield is greater than 80%, and purity is greater than 99%.
Adopt the mixed solvent of water and organic solvent; Though reduced the usage quantity of organic solvent; Make product cost reduce; But because the toxicity and the inflammableness of organic solvent; Still there is potential safety hazard in entire reaction course; And catalyzer need use phase-transfer catalyst; Adopt phase-transfer catalyst can improve speed of reaction really; But make product have color easily; Have a strong impact on quality product; In production practice, needing increases postprocessing working procedures to remove color, causes reducing in the production process productive rate, implements difficulty and strengthens.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of aryl oxide compound; Can overcome the deficiency of prior art; The aryl oxide compound prepares at aqueous phase; Entire reaction course only with water as solvent; Not not with an organic solvent and phase-transfer catalyst; Technology is simple, does not have solvent recuperation and aftertreatment problem, and is environmentally friendly.
Realize that the object of the invention adopts following technical scheme:
A kind of preparation method of aryl oxide compound; It is characterized in that: phenol is added sodium salt or the sylvite of processing phenol in the aqueous solution of sodium hydroxide or potassium hydroxide; 0 ℃-20 ℃ drip halohydrocarbon; After keeping this thermotonus certain hour; Elevated temperature to 40 ℃～100 ℃ continues reaction; After reaction finished, cooling separated making aryl oxide.
Described phenol comprises monohydric phenol or dihydric phenol.Monohydric phenol comprises phenol, alkylphenol, alkylene phenol or halogenated phenol, preferred phenol, C
1-C
4Alkylphenol, phenyl-monobromide phenol, dibrominated phenol or tribromo-benzene phenol.Dihydric phenol comprises dihydroxyphenyl propane, alkyl dihydroxyphenyl propane, halogenated bisphenol A, dihydroxy-benzene or halogeno-benzene diphenol, preferred dihydroxyphenyl propane, tetrabromo-bisphenol, pyrocatechol, Resorcinol, Resorcinol and (single, many) bromobenzene diphenol.
The preferred chlorallylene of described halohydrocarbon, allyl bromide 98, benzyl chlorine, benzyl bromine, alkyl benzyl chlorine, alkyl benzyl bromine or uncle's halogenated alkane.
The inventive method can prepare single phenol aryl oxide or polyphenol aryl oxide.The preparation method of single phenol aryl oxide is following: after the aqueous solution of phenol or (single, many) fortified phenol and sodium hydroxide (or potassium) is processed phenol sodium (or potassium) salts solution; Controlled temperature adds halohydrocarbon for 0 ℃-20 ℃; After keeping the low-temp reaction certain hour; Elevated temperature continues reaction; After reaction finished, cooling separated.
The preparation method of polyphenol aryl oxide is following: after the aqueous solution of dihydroxy-benzene, (single, many) substituted benzene diphenol or (replacement) dihydroxyphenyl propane and sodium hydroxide (or potassium) is processed phenol sodium (or potassium) salts solution; Controlled temperature adds halohydrocarbon for 0 ℃-20 ℃; After keeping the low-temp reaction certain hour; Elevated temperature continues reaction; After reaction finished, cooling separated.
In the described method, wherein the mol ratio of phenolic hydroxyl group and sodium hydroxide or potassium hydroxide is 1:1.05-1.2.The preferred proportion that the present invention recommends is 1:1.08-1.12.
In said sodium hydroxide or the potassium hydroxide aqueous solution, the mass concentration of sodium hydroxide or potassium hydroxide is 0.01～0.5g/mL.
In the described method, wherein the mol ratio of unit phenol and halohydrocarbon is 1:1-1.5, and the mol ratio of dihydric phenol and halohydrocarbon is 1:2.0-2.6, and the preferred proportion that the present invention recommends is 1:1-1.3 and 1:2.0-2.2.
Need not adopt phase-transfer catalyst in the described method.
Described method is controlled at 0 ℃-20 ℃, and keeps this thermotonus in halohydrocarbon dropping process, the time of keeping reaction is 0.5～3 h.
Described method, heating back 40 ℃～100 ℃ reaction times is 2～4h.Preferred temperature of reaction is 40 ℃～60 ℃.
With single-substituted phenol is example (suitable equally to bis-phenol), and the inventive method synthetic main route can be represented as follows (R=C wherein
1-C
4Alkyl or alkylene):
Reaction formula 1
Reaction formula 2
Reaction process is reduced to room temperature after accomplishing, and can pass through separatory or filtration, directly obtains product after the washing.
Beneficial effect of the present invention:
1, the overall yield of method products obtained therefrom of the present invention can reach more than 90% 85 ~ 98% usually.
2, do not use phase-transfer catalyst in the inventive method, directly can react with water as solvent, temperature is low, and reaction conditions is gentle, and is easy to control.
3, the quality of the prepared aryl oxide product of the present invention is good, and product purity is high, and color and luster is better, does not need other decolouring to handle.
4, method of the present invention can prepare the aryl oxide (like the product in the reaction formula 1) that has two keys, and product can be used as reactive flame retardant, or can obtain the body flame retarded polymeric material with olefin-copolymerization, and its flame retardant properties is better, and is more lasting.
5, the inventive method is only reacted at aqueous phase, separates simply, does not have the recovery and the aftertreatment problem of organic solvent, environmental protection and with low cost more in process of production.
In a word, the inventive method technology is simple, and the reaction times is short, good product quality, and yield is high, and is environmentally friendly.
Describe the present invention below in conjunction with specific embodiment.Protection scope of the present invention is not exceeded with embodiment, but is limited claim.
Embodiment
Embodiment 1
In four-hole boiling flask, add entry 150g, sodium hydroxide 2.6g, temperature adds tribromophenol 20g after reducing to room temperature; Place cryosel to bathe this solution; Treat that temperature reduces to below 20 ℃, begin to drip benzyl chlorine 7.7 g, controlled temperature is lower than 20 ℃; Drip and finish back low-temp reaction 30 mim; Elevated temperature to 60 ℃ reaction 2h, stopped reaction, cooling; Phase-splitting, wash the finished product.Product yield 96%, purity 98%.
Embodiment 2
In four-hole boiling flask, add entry 150g, sodium hydroxide 2.6g, temperature adds tribromophenol 20g after reducing to room temperature; Place cryosel to bathe this solution; Treat that temperature reduces to below 20 ℃, begin to drip benzyl chlorine 11.5 g, controlled temperature is lower than 20 ℃; Drip and finish back low-temp reaction 30 mim; Elevated temperature to 60 ℃ reaction 2h, stopped reaction, cooling; Phase-splitting, wash the finished product.Product yield 97.5%, purity 98%.
Embodiment 3
In four-hole boiling flask, add entry 150g, sodium hydroxide 2.6g, temperature adds tribromophenol 20g after reducing to room temperature; Place cryosel to bathe this solution; Treat that temperature reduces to below 20 ℃, begin to drip benzyl chlorine 10 g, controlled temperature is lower than 20 ℃; Drip and finish back low-temp reaction 30 mim; Elevated temperature to 60 ℃ reaction 2h, stopped reaction, cooling; Phase-splitting, wash the finished product.Product yield 98%, purity 99%.
Embodiment 4
In four-hole boiling flask, add entry 150g, sodium hydroxide 2.6g, temperature adds tribromophenol 20g after reducing to room temperature; Place cryosel to bathe this solution; Treat that temperature reduces to below 20 ℃, begin to add benzyl bromine 12g, controlled temperature is lower than 20 ℃; Drip and finish back low-temp reaction 60 mim; Behind elevated temperature to the 50 ℃ reaction 2h, stopped reaction, cooling; Filter, wash the finished product.
Embodiment 5
In four-hole boiling flask, add entry 150g, sodium hydroxide 2.6g, temperature adds tribromophenol 20g after reducing to room temperature; Place cryosel to bathe this solution; Treat that temperature reduces to below 20 ℃, begin to drip allyl bromide 98 8 g, controlled temperature is lower than 15 ℃; Drip and finish back low-temp reaction 60 mim; Elevated temperature to 40 ℃ reaction 2h, stopped reaction, cooling; Filter, wash the finished product.
Embodiment 6,7,8 is changed to tribromophenol dihydroxyphenyl propane 13.8 g respectively with embodiment 1,2,3.
Embodiment 9,10,11 is changed to tribromophenol tetrabromo-bisphenol 32.9 g respectively with embodiment 1,2,3.
Embodiment 12, with embodiment 1, tribromophenol replaced with ethylphenol 7.4g.
Embodiment 13, with embodiment 1, tribromophenol replaced with phenyl-monobromide phenol 10.5g.
Embodiment 14
In four-hole boiling flask, add entry 300g, sodium hydroxide 3g, temperature adds Resorcinol 4.3g after reducing to room temperature; Place cryosel to bathe this solution; Treat that temperature reduces to below 20 ℃, begin to drip benzyl chlorine 10g, controlled temperature is lower than 20 ℃; Drip and finish back low-temp reaction 30 mim; Elevated temperature to 50 ℃ reaction 2h, stopped reaction, cooling; Phase-splitting, wash the finished product.
Embodiment 15
In four-hole boiling flask, add entry 50g, sodium hydroxide 3 g, temperature adds Resorcinol 4.3g after reducing to room temperature; Place cryosel to bathe this solution; Treat that temperature reduces to below 20 ℃, begin to drip benzyl chlorine 10g, controlled temperature is lower than 20 ℃; Drip and finish back low-temp reaction 30 mim; Elevated temperature to 50 ℃ reaction 2h, stopped reaction, cooling; Phase-splitting, wash the finished product.
Claims (10)
1. the preparation method of an aryl oxide compound; It is characterized in that: phenol is added sodium salt or the sylvite of processing phenol in the aqueous solution of sodium hydroxide or potassium hydroxide; 0 ℃-20 ℃ drip halohydrocarbon; After keeping this thermotonus certain hour; Elevated temperature to 40 ℃～100 ℃ continues reaction; After reaction finished, cooling separated making aryl oxide.
2. the preparation method of aryl oxide compound according to claim 1 is characterized in that: described phenol comprises phenol, alkylphenol, alkylene phenol, halogenated phenol, dihydroxyphenyl propane, alkyl dihydroxyphenyl propane, halogenated bisphenol A, dihydroxy-benzene or halogeno-benzene diphenol.
3. the preparation method of aryl oxide compound according to claim 2 is characterized in that: described phenol comprises phenol, C
1-C
4Alkylphenol, phenyl-monobromide phenol, dibrominated phenol, tribromo-benzene phenol, dihydroxyphenyl propane, tetrabromo-bisphenol, pyrocatechol, Resorcinol, Resorcinol or bromobenzene diphenol.
4. the preparation method of aryl oxide compound according to claim 1 is characterized in that: described halohydrocarbon comprises chlorallylene, allyl bromide 98, benzyl chlorine, benzyl bromine, alkyl benzyl chlorine, alkyl benzyl bromine or uncle's halogenated alkane.
5. the preparation method of aryl oxide compound according to claim 1 is characterized in that: the mol ratio of described phenolic hydroxyl group and sodium hydroxide or potassium hydroxide is 1:1.05-1.2.
6. the preparation method of aryl oxide compound according to claim 1 is characterized in that: in described sodium hydroxide or the potassium hydroxide aqueous solution, the mass concentration of sodium hydroxide or potassium hydroxide is 0.01～0.5 g/ mL.
7. the preparation method of aryl oxide compound according to claim 1 is characterized in that: described phenol, and wherein the mol ratio of monohydric phenol and halohydrocarbon is 1:1-1.5, the mol ratio of dihydric phenol and halohydrocarbon is 1:2.0-2.6.
8. the preparation method of aryl oxide compound according to claim 1 is characterized in that: in the described method, 0 ℃-20 ℃ times of keeping reaction are 0.5～3 h.
9. the preparation method of aryl oxide compound according to claim 1 is characterized in that: in the described method, 40 ℃～100 ℃ reaction times are 2～4h.
10. the preparation method of aryl oxide compound according to claim 1 is characterized in that: in the described method, reaction is reduced to room temperature after finishing, and through phase-splitting or filtering separation, obtains the aryl oxide product after the washing.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105418388A (en) * | 2015-12-18 | 2016-03-23 | 钱立军 | Preparation method for flame retardant of 2,2-bis [3,5-dibromo-4-(2,3-dibromo-2-methyl propoxy) phenyl] propane |
| CN106083539A (en) * | 2016-06-15 | 2016-11-09 | 郑州泰基鸿诺医药股份有限公司 | A kind of single fluorine methoxyl group or the synthetic method of single fluorine deuterated methoxyl group compounds |
| CN109761762A (en) * | 2019-01-25 | 2019-05-17 | 盐城锦明药业有限公司 | A kind of preparation method of two fragrant pyridyl ethers compounds |
| CN112979612A (en) * | 2021-02-21 | 2021-06-18 | 苏州大学 | Method for preparing 2-iodo-heterocyclic aromatic ether at room temperature |
| CN112979497A (en) * | 2021-02-21 | 2021-06-18 | 苏州大学 | Method for preparing 2-iodoaryl ether based on o-haloiodobenzene without catalyst |
| WO2022117071A1 (en) * | 2020-12-04 | 2022-06-09 | 福建海创医药科技有限公司 | Method for synthesizing benzyl ether from polyhydric phenol |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102030620A (en) * | 2010-12-07 | 2011-04-27 | 尹华芳 | Method for preparing 2,2',6,6'-tetrabromobisphenol A diallyl ether |
-
2011
- 2011-07-28 CN CN2011102127319A patent/CN102344345A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102030620A (en) * | 2010-12-07 | 2011-04-27 | 尹华芳 | Method for preparing 2,2',6,6'-tetrabromobisphenol A diallyl ether |
Non-Patent Citations (2)
| Title |
|---|
| 王彦林等: "水相合成四溴双酚A-双烯丙基醚的研究", 《盐业与化工》 * |
| 王红等: "双酚A合成四溴双酚A双(2,3一二溴丙基)醚的工艺研究", 《广东化工》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105418388A (en) * | 2015-12-18 | 2016-03-23 | 钱立军 | Preparation method for flame retardant of 2,2-bis [3,5-dibromo-4-(2,3-dibromo-2-methyl propoxy) phenyl] propane |
| CN105418388B (en) * | 2015-12-18 | 2020-09-01 | 山东兄弟科技股份有限公司 | Preparation method of flame retardant 2, 2-bis [3, 5-dibromo-4- (2, 3-dibromo-2-methylpropyloxy) phenyl ] propane |
| CN106083539A (en) * | 2016-06-15 | 2016-11-09 | 郑州泰基鸿诺医药股份有限公司 | A kind of single fluorine methoxyl group or the synthetic method of single fluorine deuterated methoxyl group compounds |
| CN106083539B (en) * | 2016-06-15 | 2018-10-23 | 郑州泰基鸿诺医药股份有限公司 | A kind of synthetic method of list fluorine methoxyl group or the deuterated methoxy base class compound of single fluorine |
| CN109761762A (en) * | 2019-01-25 | 2019-05-17 | 盐城锦明药业有限公司 | A kind of preparation method of two fragrant pyridyl ethers compounds |
| CN109761762B (en) * | 2019-01-25 | 2022-11-18 | 盐城师范学院 | Preparation method of diaryl ether compound |
| WO2022117071A1 (en) * | 2020-12-04 | 2022-06-09 | 福建海创医药科技有限公司 | Method for synthesizing benzyl ether from polyhydric phenol |
| CN114867708A (en) * | 2020-12-04 | 2022-08-05 | 泉州海创医药科技有限公司 | Method for synthesizing benzyl ether from polyhydroxyphenol |
| CN114867708B (en) * | 2020-12-04 | 2024-07-23 | 泉州海创医药科技有限公司 | Method for synthesizing benzyl ether from polyhydroxy phenol |
| CN112979612A (en) * | 2021-02-21 | 2021-06-18 | 苏州大学 | Method for preparing 2-iodo-heterocyclic aromatic ether at room temperature |
| CN112979497A (en) * | 2021-02-21 | 2021-06-18 | 苏州大学 | Method for preparing 2-iodoaryl ether based on o-haloiodobenzene without catalyst |
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Application publication date: 20120208 |