CN1911887A - Method of synthesizing aromatic ether without solvent - Google Patents
Method of synthesizing aromatic ether without solvent Download PDFInfo
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- CN1911887A CN1911887A CN 200610053106 CN200610053106A CN1911887A CN 1911887 A CN1911887 A CN 1911887A CN 200610053106 CN200610053106 CN 200610053106 CN 200610053106 A CN200610053106 A CN 200610053106A CN 1911887 A CN1911887 A CN 1911887A
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- phenol sodium
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- aryl oxide
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- ionic liquid
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Abstract
The no-solvation aromatic ether synthesizing process with sodium phenolate or substituted sodium phenolate as main material includes adding small amount of ionic liquid as catalyst and adding halocarbon for reaction to produce aromatic ether. The product aromatic ether is heated to smelt and added into the reaction system as the solvent. The no-solvation aromatic ether synthesizing process has high reactant concentration, high reaction speed, high product yield up to 90 %, high product purity up to 98 %, no use of other solvent, no sewage draining and environment friendship, and is easy use in industrial production.
Description
Technical field
The present invention relates to a kind of method for preparing aryl oxide, the method for the synthetic aryl oxide of a kind of solvent free.
Background technology
2,4 dichloro benzene base isopropyl ether and 5-nitro-aryl oxides such as 2,4 dichloro benzene base isopropyl ether are the important organic intermediates of a class.Prepare this class aryl oxide and can use the phase-transfer catalysis synthesis method, carry out at aqueous phase.For example, the method that under phase-transfer catalysis, uses water as the synthetic aryl oxide of solvent that Chinese patent 200410084425.1 is introduced, the catalysis building-up process is promptly carried out at aqueous phase, and the purity of product can reach more than 95%, and yield is more than 86%.Though this method not with an organic solvent, has been omitted solvent distillation and has been reclaimed technology, owing to use water as solvent, brought the handling problem of factory effluent, raw material and product have produced loss because of dissolving in water simultaneously, and the by product Sodium Bromide can't be separated owing to good water solubility.
Summary of the invention
The present invention is intended to propose a kind of method that does not need any other solvent to prepare aryl oxide, the method for the synthetic aryl oxide of a kind of solvent free.
The method of the synthetic aryl oxide of this solvent free is to be raw material with phenol sodium or substituted phenol sodium, in phenol sodium or substituted phenol sodium, add small amount of ionic liquid and make catalyzer, adding halohydrocarbon reacts, generate aryl oxide, before adding halohydrocarbon, in the mixture of phenol sodium or substituted phenol sodium and ionic liquid catalyst, add this reaction product aryl oxide earlier, and heating makes the aryl oxide fusing, in reaction process, no longer add any other solvent, and be solvent with this product aryl oxide.
The method of the synthetic aryl oxide of solvent free of the present invention, in the reaction owing to do not use other solvents, therefore steps such as organic solvent recovery and rectifying on technology, have been reduced, the solid sodium halide and the aryl oxide that generate can obtain respectively, water not, thereby do not have sewage discharge, organic solvent-free yet yet, environmentally friendly, be easy to suitability for industrialized production.Phenol sodium or substituted phenol sodium react in the mixing liquid that ionic liquid catalyst, product ether and halohydrocarbon are formed, owing to there are not other solvents, the reaction density height, accelerated the speed of response of phenol sodium and halohydrocarbon greatly, and quality is improved, product inorganic salt are separable obtains for Fan Ying another simultaneously, recyclable Sodium Bromide or sodium iodide when using hydrobromic ether or idohydrocarbon.Compared with the prior art, produce aryl oxide with method of the present invention, product yield and purity all are greatly improved, and yield reaches more than 90%, can reach more than 98% through gas chromatographic analysis purity.
Embodiment
The method of the synthetic aryl oxide of this solvent free is to be raw material with phenol sodium or substituted phenol sodium, in product ether bed material, adds ionic liquid catalyst, adds halohydrocarbon and reacts, and generates aryl oxide.Can slough unnecessary halohydrocarbon and be pure product by filtering the halide crystal of removing sodium after the finished product discharging.This etherification method is a nucleophilic substitution, and organic phase is halohydrocarbon and product ether, and phenol sodium or substituted phenol sodium become an inorganic phase as a nucleophilic reagent, is carried in the organic phase by ionic liquid catalyst and carries out nucleophilic substitution reaction with halohydrocarbon.The inorganic salt that the reaction back generates are not owing to there is this polar solvent of water, and inorganic salt will be separated out in the crystal mode, and organic phase is the high aryl oxide product of purity.Method of the present invention without any other solvent, has solved the problem that side reaction takes place in the reaction owing to except product ether, product yield height, and purity is also high, has simplified technology simultaneously, has reduced environmental pollution again.
In the method for the synthetic aryl oxide of solvent free of the present invention, the amount that each raw material adds can be phenol sodium or substituted phenol sodium: halohydrocarbon=1: 1～1.5, in mol; Ionic liquid catalyst: phenol sodium or substituted phenol sodium=0.01～0.1: 1, by weight.
The reaction formula of the method for the synthetic aryl oxide of this solvent free is as follows:
In the formula: R=C
nH
2n+1, as sec.-propyl, n-propyl, normal-butyl, ethyl etc.; X=Br, Cl; A=H, NO
2, SO
3H, b=H, Cl, c=H, Cl.
Ionic liquid catalyst is the imidazoles quaternary ammonium salt, has following structure:
In the formula: R
1=C
nH
2n+1(n=2,3,4.....8), R
2=C
nH
2n+1(n=2,3,4.....8).
In the method for this law invention, phenol sodium or substituted phenol sodium can add step by step, its process is: add phenol sodium or substituted phenol sodium, ionic liquid catalyst and product ether in reactor, heat temperature raising also stirs, when temperature reaches 60-120 ℃, slowly add halohydrocarbon RX, controlled temperature is 60-100 ℃ in the dropping process, behind the stirring 4-5h, adds phenol sodium or substituted phenol sodium again, reaction can be carried out repeatedly continuously, and product can be emitted by the reactor bottom.
Raw material in the method for the synthetic aryl oxide of solvent free of the present invention adopts 2, and when 4-dichloro fortified phenol sodium, halohydrocarbon employing bromo propane, prepared aryl oxide is a 2,4 dichloro benzene base isopropyl ether.
Raw material in the method for the synthetic aryl oxide of solvent free of the present invention adopts 5-nitro 2,4 dichloro benzene substituted phenol sodium, when halohydrocarbon is n-propyl bromide, prepared aryl oxide is a 5-nitro 2,4 dichloro benzene n-propyl ether.
Raw material in the method for the synthetic aryl oxide of solvent free of the present invention adopts sodium phenylate, when halohydrocarbon is bromo propane, prepared aryl oxide is a propyloxy phenyl base ether
Embodiment 1:
Get 2,4-dichloro-phenol sodium 18.5g (0.1mol), ionic liquid 1g, 2,4-dichloro-phenyl isopropyl ether 50g adds in the reactor.On reactor, set up reflux condensing tube, whipping appts, dropper and thermometer, heating also makes 2, the fusing of 4-dichloro-phenyl isopropyl ether, temperature rises to more than 60 ℃, begins to drip 18.5g bromo propane (0.15mol) by dropping funnel, dropwises behind the 1h, temperature of reaction is about 60-120 ℃, back flow reaction 3h, cooling back discharging 30g 2,4-dichloro-phenyl isopropyl ether.Add 2 again, 4-dichloro-phenol sodium 18.5g drips the 18.5g bromo propane, and circulation is reacted.Proceed reaction through adding ionic liquid 1g after 15 cyclically charging reactions.The product ether of bottom discharge is through gas chromatographic analysis, purity 99.5%, yield 99%.
Embodiment 2:
Get 5-nitro 2,4-dichloro-phenol sodium 22.8g (0.1mol), ionic liquid 3g adds in the reactor, adds 50g5-nitro-2,4-dichloro-phenyl isopropyl ether.On reactor, set up reflux condensing tube, whipping appts, dropper and thermometer, heating also makes 5-nitro-2, the fusing of 4-dichloro-phenyl n-propyl ether, temperature rises to more than 60 ℃, begin to drip 14.8g (0.12mol) n-propyl bromide by dropping funnel, dropwise behind the 1h, temperature of reaction is about 60-120 ℃, back flow reaction 3h, cooling back discharging 30g.Continue above-mentioned cyclically charging reaction, proceed reaction through adding ionic liquid 1g behind 20 secondary responses.The product 5-nitro-2 of bottom discharge, 4-dichloro-phenyl n-propyl ether be through gas chromatographic analysis purity 99%, yield 98%.
Embodiment 3:
Get sodium phenylate 11.6g (0.1mol), ionic liquid 0.5g adds in the reactor, adds 50g propyloxy phenyl base ether.Set up reflux condensing tube, whipping appts, dropper and thermometer on reactor, heat and make propyloxy phenyl base ether fusing, temperature rises to more than 60 ℃, begins to drip 16g (0.13mol) bromo propane by dropping funnel.Dropwise behind the 1h, temperature of reaction is about 60-120 ℃, and back flow reaction 3h cools off back discharging 20g.Continue above-mentioned cyclically charging reaction, proceed reaction through adding ionic liquid 1g behind 15 secondary responses.Product is through gas chromatographic analysis purity 98.5%, yield 97%.
Embodiment 4:
Get sodium phenylate 11.6g (0.1mol), ionic liquid 2g adds in the reactor, adds 50g propyloxy phenyl base ether.Set up reflux condensing tube, whipping appts, dropper and thermometer on reactor, heat and make propyloxy phenyl base ether fusing, temperature rises to more than 60 ℃, begins to drip 9.4g (0.12mol) chloroisopropane by dropping funnel.Dropwise behind the 1h, temperature of reaction is about 60-120 ℃, and back flow reaction 3h cools off back discharging 20g.Continue above-mentioned cyclically charging reaction, proceed reaction through adding ionic liquid 1g behind 20 secondary responses.Product is through gas chromatographic analysis purity 98.2%, yield 92%.
Embodiment 5:
5-nitro 2,4-dichloro-phenol sodium 22.8g (0.1mol), ionic liquid 1.5g adds in the reactor, adds 50g5-nitro-2,4-dichloro-phenyl isopropyl ether.On reactor, set up reflux condensing tube, whipping appts, dropper and thermometer, heat and make 5-nitro-2, the fusing of 4-dichloro-phenyl isopropyl ether, temperature rises to more than 60 ℃, begins to drip 7.8g (0.1mol) chloroisopropane by dropping funnel.Dropwise behind the 1h, temperature of reaction is about 60-120 ℃, and back flow reaction 3h cools off back discharging 30g.Continue above-mentioned cyclically charging reaction, proceed reaction through adding ionic liquid 1g behind 20 secondary responses.Product is through gas chromatographic analysis purity 98.5%, yield 90%.
Claims (2)
1, the method for the synthetic aryl oxide of a kind of solvent free, with phenol sodium or substituted phenol sodium is raw material, in phenol sodium or substituted phenol sodium, add small amount of ionic liquid and make catalyzer, add halohydrocarbon and react, generate aryl oxide, it is characterized in that before adding halohydrocarbon, the product aryl oxide that in the mixture of phenol sodium and ionic liquid catalyst, adds this reaction earlier, and heating makes aryl oxide fusing, no longer adds any other solvent in reaction process, and is solvent with this product aryl oxide.
2, the method for the synthetic aryl oxide of solvent free as claimed in claim 1 is characterized in that the add-on of each raw material is: phenol sodium or substituted phenol sodium: halohydrocarbon=1: 1～1.5, in mol; Ionic liquid catalyst: phenol sodium or substituted phenol sodium=0.01～0.1: 1, by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610053106 CN1911887A (en) | 2006-08-23 | 2006-08-23 | Method of synthesizing aromatic ether without solvent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610053106 CN1911887A (en) | 2006-08-23 | 2006-08-23 | Method of synthesizing aromatic ether without solvent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1911887A true CN1911887A (en) | 2007-02-14 |
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|---|---|---|---|
| CN 200610053106 Pending CN1911887A (en) | 2006-08-23 | 2006-08-23 | Method of synthesizing aromatic ether without solvent |
Country Status (1)
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|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104447220A (en) * | 2014-12-08 | 2015-03-25 | 上海应用技术学院 | Preparation method of 4-phenoxybutyl bromide |
| CN112979612A (en) * | 2021-02-21 | 2021-06-18 | 苏州大学 | Method for preparing 2-iodo-heterocyclic aromatic ether at room temperature |
-
2006
- 2006-08-23 CN CN 200610053106 patent/CN1911887A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104447220A (en) * | 2014-12-08 | 2015-03-25 | 上海应用技术学院 | Preparation method of 4-phenoxybutyl bromide |
| CN104447220B (en) * | 2014-12-08 | 2016-11-30 | 上海应用技术学院 | A kind of preparation method of 4-phenoxy group n-butyl bromide |
| CN112979612A (en) * | 2021-02-21 | 2021-06-18 | 苏州大学 | Method for preparing 2-iodo-heterocyclic aromatic ether at room temperature |
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