CN1706785A - O-ethoxyl phenol synthesizing process - Google Patents
O-ethoxyl phenol synthesizing process Download PDFInfo
- Publication number
- CN1706785A CN1706785A CN 200510016842 CN200510016842A CN1706785A CN 1706785 A CN1706785 A CN 1706785A CN 200510016842 CN200510016842 CN 200510016842 CN 200510016842 A CN200510016842 A CN 200510016842A CN 1706785 A CN1706785 A CN 1706785A
- Authority
- CN
- China
- Prior art keywords
- pyrocatechol
- water
- toluene
- sodium hydroxide
- monochloroethane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The o-ethoxyl phenol synthesizing process with catechol and ethyl chloride as material includes the following steps: adding toluene and water into high pressure reactor, starting stirrer and water cooling the shaft of the high pressure reactor; adding catechol, sodium carbonate, alkyl amine bromide catalyst, solid sodium hydroxide, ethyl chloride in required amount successively; sealing, heating and maintaining at 100-139 deg.c and 0.1-1.1 MPa for 2-6 hr. The weight proportion among catechol, sodium hydroxide, sodium carbonate, ethyl chloride, alkyl amine bromide, water and toluene is 1 to 0.364-0.509 to 0.045-0.273 to 0.591-0.938 to 0.0091-0.0682 to 1.591-2.730 to 1.820-4.545. The present invention has yield of 86 %, and compared with other process, the present invention has lowered product cost, less sewage exhaust, low sewage COD, short technological process and less investment.
Description
Technical field
The present invention relates to a kind of synthetic method of Pyrocatechol monoethyl ether, relating in particular to pyrocatechol and monochloroethane is raw material, in the presence of phase-transfer catalyst, and the method for synthetic Pyrocatechol monoethyl ether.
Background technology
Pyrocatechol monoethyl ether claims 2-ethoxy-phenol again, and ethylguaiacol is synthetic vanirone important source material, also is the important intermediate that pharmaceutical industries can not lack.The method of synthetic Pyrocatechol monoethyl ether mainly contains two kinds both at home and abroad at present, i.e. o-phenetidine method and pyrocatechol method:
1, o-phenetidine method:
This method be o-phenetidine method in the presence of sulfuric acid, carry out diazotization reaction at low temperatures with Sodium Nitrite, hydrolysis under the copper sulfate effect again generates Pyrocatechol monoethyl ether.This process application is morning and relatively wider, technical maturity, and raw material is easy to get, and reaction conditions is not harsh, and yield is higher.But this operational path is longer, and complicated operation is seriously polluted.
2, pyrocatechol method: this method mainly contains following three kinds of routes:
(1) pyrocatechol, Ethanol Method: LI XUEMEI, Zhu Xiaomei, Zhang Wenxiang, etc. ethanol and pyrocatechol gas phase synthesizing 2-ethoxy-phenol research [J]. Ningxia University's journal, 2001, (6): 114～115. document once had report; This method need prepare the catalyzer of specific composition and shape, and is pollution-free, and once through yield is low, and the raw material usefulness that can circulate is suitable for large-scale plant.But cost is higher;
(2) pyrocatechol, ethyl sulfate method:
T M Jyothi, T paja, M B talawar, etal.Seoective o-methylation of catechol usingdimethyo carbonate over calcined Mg-Al Hydrotalcites[J] .Applied Catalysis A:General, 2001, (211): 41～46. document once had report; This method is that pyrocatechol reacts in the presence of phase-transfer catalyst and makes.This method yield height, selectivity is good; Yet ethyl sulfate toxicity is big, and environmental pollution is more serious.
(3) pyrocatechol, monochloroethane method:
Zhang Zhenming. the polyoxyethylene glycol phase-transfer catalysis is synthesized ethylguaiacol [J]. prints during chemical industry, 2000, (12): 54～56.The document once had report; This method is that pyrocatechol and monochloroethane are under the phase-transfer catalyst effect, through processes such as condensation, reduced pressure distillations and make.Its chemical equation is as follows:
Summary of the invention
The objective of the invention is to overcome the deficiency that prior art exists, providing a kind of is raw material with pyrocatechol and monochloroethane, and the flow process under the phase-transfer catalyst effect is short, yield height, the method for the synthetic adjacent guoethol that cost is low.
The objective of the invention is to be achieved by following technical scheme:
The synthetic method of Pyrocatechol monoethyl ether, in autoclave, add toluene, water, start agitator, after opening autoclave axle water coolant, the pyrocatechol, yellow soda ash, alkyl ammonium bromide catalyzer, solid sodium hydroxide, the monochloroethane that add requirement successively in autoclave behind the airtight autoclave, heat up and are 100-139 ℃ in temperature, pressure is under the 0.1-1.1Mpa, keeps 2-6 hour; Wherein in mass, pyrocatechol: sodium hydroxide: yellow soda ash: monochloroethane: alkyl ammonium bromide: water: toluene is 1: 0.364-0.509: 0.045-0.273: 0.591-0.938: 0.0091-0.0682: 1.591-2.730: 1.820-4.545.
Above-mentioned method, in mass, pyrocatechol: sodium hydroxide: yellow soda ash: monochloroethane: alkyl ammonium bromide: water: toluene is 1: 0.364-0.473: 0.045-0.227: 0.591-0.880: 0.0091-0.0545: 1.591-2.500: 2.273-4.545.
Above-mentioned method, its temperature of reaction are 110-139 ℃, and pressure is 0.2-1.0Mpa, keep 2-5 hour.
Above-mentioned method, in mass, pyrocatechol: sodium hydroxide: yellow soda ash: monochloroethane: quaternary ammonium salts phase-transfer catalyst: water: toluene is 1: 0.364-0.473: 0.045-0.227: 0.591-0.880: 0.0091-0.0545: 1.591-2.500: 2.273-4.545, in temperature of reaction is 110-139 ℃, pressure is 0.2-1.0Mpa, keeps 2-5 hour.
Above-mentioned method, its described alkyl ammonium bromide are tetramethyl-amine bromide, tetraethyl-amine bromide or four butyl bromation amine.
Raw material and product analysis method adopt vapor-phase chromatography and chemical analysis.
The present invention compared with prior art has following obvious improvement:
1. yield of the present invention is 86% (in pyrocatechol).
2. compare with additive method, cost decreases 3000～5000 yuan/ton;
3. sewage quantity only is 1/3 times of o-phenetidine method, and the COD of sewage amount only is 1/4 of an o-phenetidine method.
4. flow process of the present invention is short, and one-time investment is few.
Embodiment
Now the present invention is further described as follows by embodiment:
Embodiment 1
In autoclave, add toluene 800g, water 480g opens stirring, open autoclave axle water coolant, add pyrocatechol 176g, yellow soda ash 8g, four butyl bromation amine 12g, solid sodium hydroxide 89.6g, monochloroethane 165g again, seal lid after, inflated with nitrogen is to 1.0Mpa, kept 2 minutes, check whether leak gas,, put pressure as air tight.Begin to heat up, keeping 2 hours under 130～139 ℃ of temperature, under 0.1～1.1MPa pressure, reaction is cooled to room temperature after finishing, and opens autoclave after the pressure release, feed liquid is poured in the separating funnel into separatory.Water adds hydrochloric acid and transfers pH value 5～6, after fully extracting with toluene, merges oil phase.Oil reservoir gets the O-ethoxyl phenolic product of purity 〉=98.0% through normal pressure distillation, underpressure distillation.Distillation recovered solvent recycled.Products obtained therefrom is weighed and analyzed its purity, calculated yield.The results are shown in Table the test lot number of example 1 correspondence in 1.
The yield method of calculation are:
Total recovery is mole number * 100% of the mole number pyrocatechol that ÷ drops into of=products obtained therefrom
Embodiment 2
In autoclave, add toluene 800g, water 500g opens stirring, open autoclave axle water coolant, add pyrocatechol 220g, yellow soda ash 20g, tetraethyl-amine bromide 9g, solid caustic soda 104g, monochloroethane 180g again, seal lid after, inflated with nitrogen is to 1.0Mpa, kept 2 minutes, check whether leak gas,, put pressure as air tight.Begin to heat up, keeping 4 hours under 120～130 ℃ of temperature, under 0.1～1.1MPa pressure, reaction is cooled to room temperature after finishing, and opens autoclave after the pressure release, feed liquid is poured in the separating funnel into separatory.Water adds hydrochloric acid and transfers pH value 5～6, after fully extracting with toluene, merges oil phase.Oil reservoir gets the O-ethoxyl phenolic product of purity 〉=98.0% through normal pressure distillation, underpressure distillation.Distillation recovered solvent recycled.Products obtained therefrom is weighed and analyzed its purity, calculated yield.The results are shown in Table the test lot number of example 2 correspondences in 1.The yield method of calculation are with example 1.
Embodiment 3
In autoclave, add toluene 500g, water 350g opens stirring, open autoclave axle water coolant, add pyrocatechol 220g, yellow soda ash 60g, tetramethyl-amine bromide 2g, solid caustic soda 80g, monochloroethane 130g again, seal lid after, inflated with nitrogen is to 1.0Mpa, kept 2 minutes, check whether leak gas,, put pressure as air tight.Begin to heat up, keeping 6 hours under 100～120 ℃ of temperature, under 0.2～1.0MPa pressure, reaction is cooled to room temperature after finishing, and opens autoclave after the pressure release, feed liquid is poured in the separating funnel into separatory.Water adds hydrochloric acid and transfers pH value 5～6, after fully extracting with toluene, merges oil phase.Oil reservoir gets the O-ethoxyl phenolic product of purity 〉=98.0% through normal pressure distillation, underpressure distillation.Distillation recovered solvent recycled.Products obtained therefrom is weighed and analyzed its purity, calculated yield.The results are shown in Table the test lot number of example 3 correspondences in 1.The yield method of calculation are with example 1.
Table 1 synthesizes the Pyrocatechol monoethyl ether test-results with the invented technology route
| Batch | Example 1 | Example 2 | Example 3 | |||
| ??1 | ??2 | ??3 | ??4 | ??5 | ??6 | |
| Transformation efficiency/% | ??91.6 | ??91.6 | ??91.3 | ??91.6 | ??91.6 | ??91.6 |
| Selectivity/% | ??94.0 | ??94.1 | ??94.2 | ??94.1 | ??94.1 | ??94.2 |
| Yield/% | ??86.1 | ??86.2 | ??86.0 | ??86.2 | ??86.2 | ??86.2 |
More than the raw materials used industrial goods that are, more easily buy from market.
Claims (5)
1, the synthetic method of Pyrocatechol monoethyl ether: in autoclave, add toluene, water, start agitator, after opening autoclave axle water coolant, the pyrocatechol, yellow soda ash, alkyl ammonium bromide catalyzer, solid sodium hydroxide, the monochloroethane that in autoclave, add requirement successively, behind the airtight autoclave, heat up and be under the 0.1-1.1Mpa condition, kept 2-6 hour in 100-139 ℃, pressure; , wherein in mass, pyrocatechol: sodium hydroxide: yellow soda ash: monochloroethane: alkyl ammonium bromide: water: toluene is 1: 0.364-0.509: 0.045-0.273: 0.591-0.938: 0.0091-0.0682: 1.591-2.730: 1.820-4.545.
2, method according to claim 1, in mass, pyrocatechol: sodium hydroxide: yellow soda ash: monochloroethane: quaternary ammonium salts phase-transfer catalyst: water: toluene is 1: 0.364-0.473: 0.045-0.227: 0.591-0.880: 0.0091-0.0545: 1.591-2.500: 2.273-4.545.
3, method according to claim 1, temperature of reaction are 110-139 ℃, and pressure is 0.2-1.0Mpa, keep 2-5 hour.
4, method according to claim 1, in mass, pyrocatechol: sodium hydroxide: yellow soda ash: monochloroethane: quaternary ammonium salts phase-transfer catalyst: water: toluene is 1: 0.364-0.473: 0.045-0.227: 0.591-0.880: 0.0091-0.0545: 1.591-2.500: 2.273-4.545, temperature of reaction is 110-139 ℃, pressure is 0.2-1.0Mpa, keeps 2-5 hour.
5, method according to claim 1 is characterized in that: described alkyl ammonium bromide is tetramethyl-amine bromide, tetraethyl-amine bromide or four butyl bromation amine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510016842 CN1706785A (en) | 2005-05-24 | 2005-05-24 | O-ethoxyl phenol synthesizing process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510016842 CN1706785A (en) | 2005-05-24 | 2005-05-24 | O-ethoxyl phenol synthesizing process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1706785A true CN1706785A (en) | 2005-12-14 |
Family
ID=35580922
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200510016842 Pending CN1706785A (en) | 2005-05-24 | 2005-05-24 | O-ethoxyl phenol synthesizing process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1706785A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101811941A (en) * | 2010-03-12 | 2010-08-25 | 重庆欣欣向荣精细化工有限公司 | Preparation method for o-hydroxy-phenyl alkyl ether |
| CN102351774A (en) * | 2011-08-31 | 2012-02-15 | 常州市阳光药业有限公司 | Preparation method for indole-4-formaldehyde |
-
2005
- 2005-05-24 CN CN 200510016842 patent/CN1706785A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101811941A (en) * | 2010-03-12 | 2010-08-25 | 重庆欣欣向荣精细化工有限公司 | Preparation method for o-hydroxy-phenyl alkyl ether |
| CN102351774A (en) * | 2011-08-31 | 2012-02-15 | 常州市阳光药业有限公司 | Preparation method for indole-4-formaldehyde |
| CN102351774B (en) * | 2011-08-31 | 2014-03-26 | 常州市阳光药业有限公司 | Preparation method for indole-4-formaldehyde |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103073405B (en) | A kind of method of catalysis of pimelinketone oxime hydrolysis reaction in acidic ionic liquid | |
| CN1857767A (en) | Multifunctional reactor for preparing ionic liquid | |
| CN110256476B (en) | Method for synthesizing 1,1,1,3,5,5, 5-heptamethyltrisiloxane by using hydrogen-containing silicone oil low-boiling-point substance | |
| CN1706785A (en) | O-ethoxyl phenol synthesizing process | |
| CN102757312B (en) | High-selectivity and low-energy-consumption preparation method for benzyl alcohol | |
| CN112876371B (en) | Method for simultaneously producing bis (dimethylaminoethyl) ether and tetramethyl ethylenediamine | |
| CN114105805A (en) | Method for preparing formamide compound under catalysis of titanium dioxide | |
| CN102002020A (en) | Method for refining piperazine | |
| CN106397080B (en) | ɑ, a kind of preparation method of alpha, beta-unsaturated ketone | |
| CN101481330A (en) | Preparation of N-(4-ethoxy carbonyl phenyl)-N'-methyl-N'-phenyl formamidine | |
| CN104876788A (en) | Benzene-propyl alcohol azeotrope continuous extractive distillation technology based on choline chloride/urea low co-melting solvent | |
| CN108586243B (en) | Method for indirectly synthesizing organic carbonate from carbon dioxide and organic amine | |
| CN114478339B (en) | Preparation method of xanthate collector | |
| CN104804032A (en) | Solvent method synthetic process of Si-75 | |
| CN112745252B (en) | H catalysis with ionic liquid as catalyst2Method for synthesizing high-added-value mercaptoacid by addition reaction of S and olefine acid | |
| CN1706784A (en) | O-ethoxyl phenol refining process | |
| CN100349861C (en) | Ethyl carbamate and its preparation method | |
| CN108558610B (en) | Enrichment and purification process of low-content 2,3, 5-trimethylphenol | |
| CN114007735A (en) | Preparation system and preparation method of diester-based composition | |
| CN1289476C (en) | Method of preparing dimethyl thioether using methyl sodium sulphate | |
| CN111377798B (en) | Purification equipment and process of 3-methyl-3-butene-1-ol | |
| CN1660767A (en) | Method for preparing 3-methoxy methyl propionate | |
| CN101205174B (en) | Method for preparing p-alkoxy phenol | |
| CN113735797B (en) | Extracting agent for extracting, rectifying and purifying dimethyl oxalate, preparation method thereof and purifying method of dimethyl oxalate | |
| CN115337961B (en) | Catalyst for synthesizing N-allyl thiourethane compounds and synthetic method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |