CN1169767C - Process for preparing o-methyl allyloxyphenol - Google Patents
Process for preparing o-methyl allyloxyphenol Download PDFInfo
- Publication number
- CN1169767C CN1169767C CNB021396116A CN02139611A CN1169767C CN 1169767 C CN1169767 C CN 1169767C CN B021396116 A CNB021396116 A CN B021396116A CN 02139611 A CN02139611 A CN 02139611A CN 1169767 C CN1169767 C CN 1169767C
- Authority
- CN
- China
- Prior art keywords
- solvent
- pyrocatechol
- ether
- kilograms
- allyloxyphenol
- 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.)
- Expired - Lifetime
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention discloses a method for preparing o-methallyloxy phenol. Pyrocatechol and methallyl chloride are used as raw materials, alkali metal or alkaline earth metal carbonate or hydrocarbonate is used as acid-binding agents, and proper mixed solvent is selected to prepare o-methallyloxy phenol. The present invention has the advantages of simple producing technology, convenient operation, high conversion rate of pyrocatechol and high yield of o-methallyloxy phenol, and the consumption of methallyl chloride which is main material can also be reduced greatly.
Description
Technical field:
The present invention relates to the preparation method of a kind of o-methyl allyloxyphenol (abbreviation monoether).
Technical background:
O-methyl allyloxyphenol is the important intermediate of producing benzofuranol.Benzofuranol is the important intermediate of producing many agricultural chemicals, as carbofuran, carbosulfan, benfuracarb, furathiocarb etc.The synthetic method of o-methyl allyloxyphenol normally makes with pyrocatechol and methylallyl chloride reaction.Since have in the pyrocatechol two can etherificate hydroxyl, therefore, except that the monoether of needs, also have by product 1 in the reactant, the 2-diformazan generates for allyloxy benzene (abbreviation bis ether).Because the generation of bis ether makes the yield of monoether descend, and how to improve the selectivity of monoether, has many patents to report.As Chinese patent CN86102956A, adopt the excessive way of pyrocatechol to suppress the generation of bis ether, we can see from its embodiment 1, the mol ratio of pyrocatechol and methylallyl chloride is 1.0: 0.6, the transformation efficiency of pyrocatechol has only about 50%, and mainly there is the deficiency of following several respects in this method; At first, have a large amount of pyrocatechols to need to reclaim, and the operation of recovery pyrocatechol is very loaded down with trivial details, and can produces a large amount of waste water.Secondly,, enter after the subsequent reactions, can influence the purity of benzofuranol if pyrocatechol reclaims not exclusively.For this reason, there is patent to adopt the excessive method of methylallyl chloride.This method can improve the transformation efficiency of pyrocatechol.As at United States Patent (USP) 4,982, in 012 the example 1, the mol ratio of pyrocatechol and methylallyl chloride is 1: 12.2, and the transformation efficiency of pyrocatechol is 100%, but the yield of monoether has only 58%.The weak point of this method is the consumption height of the lower and methylallyl chloride of the yield of monoether, is unfavorable for suitability for industrialized production.
Summary of the invention:
The purpose of this invention is to provide a kind of preparation method who can be applicable to the o-methyl allyloxyphenol of suitability for industrialized production, is raw material with pyrocatechol, methylallyl chloride promptly, prepares o-methyl allyloxyphenol in specific solvent.The mixed solvent that specific solvent is made up of pure ether solvent and hydro carbons or aromatic hydrocarbons or halohydrocarbon among the present invention, the alcohol ether solvent is meant one or more compositions in ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, the propylene glycol monomethyl ether, hydro carbons or aromatic hydrocarbons or halohydrocarbon are meant hexanaphthene, benzene, toluene, 1, one or more compositions in the 2-ethylene dichloride.Acid binding agent is that alkaline carbonate or alkali metal hydrocarbonate are meant one or more the mixture in yellow soda ash, salt of wormwood, sodium bicarbonate, the saleratus.
Pyrocatechol of the present invention and first for the mole proportioning of thiazolinyl chlorine are: 1: 1.1～1.6, and the equivalence ratio of pyrocatechol and acid binding agent is: 1: 1.12～1.54; The consumption of solvent is 3.6～5 times of pyrocatechol weight, and hydro carbons or aromatic hydrocarbons or halogenated hydrocarbon solvent account for 4%～10% of whole weight of solvent.
Temperature of reaction is 80 ℃～110 ℃, and the reaction times is 4～8 hours.
Because the present invention has selected suitable acid binding agent, solvent system, raw material ratio and suitable reaction conditions, the transformation efficiency of pyrocatechol can reach more than 99%, avoided the recovery of pyrocatechol and transformed not exclusively influence because of pyrocatechol product benzofuranol quality, and the yield of raising monoether, the consumption of having lowered the main raw material(s) methylallyl chloride.
Embodiment:
The invention will be further described below in conjunction with embodiment.
Embodiment 1:
In 500 liter enamel reaction stills that have stirring, thermometer, graphite condenser and a water trap, add content and be 98% 50 kilograms of pyrocatechols (0.4455KMol), content is 99% 36.9 kilograms in salt of wormwood (0.2643KMol), content is 99% 2 kilograms of saleratus (0.02KMol), 200 kilograms of solvent ethylene glycol monomethyl ethers, 15 kilograms of benzene.After stirring is warmed up to 80 ℃, begin to drip content and be 98% 61.7 kilograms of methylallyl chlorides (0.6683KMol), the dropping time is 1 hour.Reacted 6 hours down at 90 ℃ again after dropwising.There is water to generate in the reaction process, can the water that generate be removed by water trap.After reaction finishes, reaction mass is dropped to 20 ℃, the solid sodium chloride of generation is removed in centrifugation, and filter residue washs with 50 kilograms of ethylene glycol monomethyl ethers, and washings and reaction solution merge, and gets 341.1 kilograms of monoether solution.Through efficient liquid phase chromatographic analysis, wherein monoether content 18.40%, bis ether content 1.81%, pyrocatechol content 0.022%.The transformation efficiency of pyrocatechol is: 99.5%, and monoether yield: 85.9%.
Embodiment 2
In 500 liter enamel reaction stills that have stirring, thermometer, graphite condenser and a water trap, add content and be 98% 50 kilograms of pyrocatechols (0.4455KMol), content is 99% 35.3 kilograms in yellow soda ash (0.3296KMol), 250 kilograms of the single ether of solvent ethylene glycol, 30 kilograms of toluene.After stirring is warmed up to 110 ℃, begin to drip content and be 98% 53.5 kilograms of methylallyl chlorides (0.5793KMol), the dropping time is 1 hour, after dropwising again 110 ℃ of reactions 4 hours.In the dropwise reaction process, there is water to generate, can the water that generate be removed by water trap.After reaction finishes, reaction mass is dropped to 20 ℃, the solid sodium chloride of generation is removed in centrifugation, and filter residue washs with 50 kilograms of ethylene glycol monoethyl ethers, and washings and reaction solution merge, and obtain 420.1 kilograms of monoether solution.Through efficient liquid phase chromatographic analysis, wherein monoether content 14.70%, bis ether content 1.89%, pyrocatechol content 0.095%.The transformation efficiency of pyrocatechol is 99.1%, monoether yield 84.5%.
Embodiment 3
In 500 liter enamel reaction stills that have stirring, thermometer, graphite condenser and a water trap, add content and be 98% 50 kilograms of pyrocatechols (0.4455KMol), content is 99% 26.7 kilograms in yellow soda ash (0.2494KMol), 220 kilograms of solvent propylene glycol monomethyl ethers, 1,20 kilograms of 2--ethylene dichloride.After stirring is warmed up to 100 ℃, begin to drip content and be 98% 49.4 kilograms of methylallyl chlorides (0.5346KMol), the dropping time is 1.5 hours, after dropwising, 100 ℃～110 ℃ reactions 5 hours.There is water to generate in the reaction process, can the water that generate be removed by water trap.After reaction finishes, reaction mass is dropped to 20 ℃, the solid sodium chloride of generation is removed in centrifugation, and filter residue washs with 50 kilograms of propylene glycol monomethyl ethers, washings and reaction solution merge 374.5 kilograms of monoether solution.Through efficient liquid phase chromatographic analysis, wherein monoether content 16.90%, bis ether content 1.75%, pyrocatechol content 0.021%.The transformation efficiency of pyrocatechol is 99.8%, monoether yield 86.6%.
Embodiment 4
In 500 liter enamel reaction stills that have stirring, thermometer, graphite condenser and a water trap, add content and be 98% 50 kilograms of pyrocatechols (0.4455KMol), content is 99% 31.0 kilograms in yellow soda ash (0.2896KMol), content is 3 kilograms of 99% sodium bicarbonates (0.0354), 180 kilograms of solvent propylene glycol monomethyl ethers, 15 kilograms of hexanaphthenes.After stirring is warmed up to 90 ℃, begin to drip content and be 98% 57.6 kilograms of methylallyl chlorides (0.6237KMol), the dropping time is 2 hours.Dropwising the back reacted 3 hours at 90 ℃ again.There is water to generate in the reaction process, can the water that generate be removed by water trap.After reaction finishes, reaction mass is dropped to 20 ℃, the solid sodium chloride of generation is removed in centrifugation, and filter residue washs with 50 kilograms of propylene glycol monomethyl ethers, washings and reaction solution merge 340.5 kilograms of monoether solution.Through efficient liquid phase chromatographic analysis, wherein monoether content 18.40%, bis ether content 1.94%, pyrocatechol content 0.090%.The transformation efficiency of pyrocatechol is 99.3%, monoether yield 85.8%.
Embodiment 5
In 500 liter enamel reaction stills that have stirring, thermometer, graphite condenser and a water trap, add content and be 98% 50 kilograms of pyrocatechols (0.4455KMol), content is 99% 33.4 kilograms in yellow soda ash (0.3119KMol), 200 kilograms of solvent ethylene glycol monobutyl ethers, 15 kilograms of benzene.After stirring was warmed up to 110 ℃, the slow dropping of beginning content was 98% 65.8 kilograms of methylallyl chlorides (0.7128KMol), and the dropping time is 1 hour.Reacted 5 hours at 110 ℃ again after dropwising.There is water to generate in the reaction process, can the water that generate be removed by water trap.After reaction finishes, reaction mass is dropped to 20 ℃, the solid sodium chloride of generation is removed in centrifugation, and filter residue washs with 50 kilograms of ethylene glycol monobutyl ethers, and washings and reaction solution merge, and gets 358.8 kilograms of monoether solution.Through efficient liquid phase chromatographic analysis, wherein monoether content 17.30%, bis ether content 2.47%, pyrocatechol content 0.011%.The transformation efficiency of pyrocatechol is: 99.9%, and monoether yield: 85.0%.
Claims (2)
1, a kind of preparation method of o-methyl allyloxyphenol is characterized in that: with pyrocatechol, methylallyl chloride is raw material, prepares o-methyl allyloxyphenol under specific solvent, acid binding agent and appropriate reaction conditions; The mixed solvent that specific solvent is made up of pure ether solvent and hydro carbons or aromatic hydrocarbons or halohydrocarbon, the weight percentage that hydro carbons or aromatic hydrocarbons or halogenated hydrocarbon solvent account for whole solvent is 4%～10%, the consumption of mixed solvent is 3.6～5 times of pyrocatechol weight; Acid binding agent is alkaline carbonate or alkali metal hydrocarbonate; Temperature of reaction is 80 ℃ 1～110 ℃, and the reaction times is 3～6 hours, and pyrocatechol and first are 1: 1.0～1.6 for the mole proportioning of thiazolinyl chlorine, and the equivalence ratio of pyrocatechol and acid binding agent is 1: 1.12～1.54.
2, require the preparation method of described o-methyl allyloxyphenol according to right 1, it is characterized in that: specific solvent is made up of pure ether solvent and hydro carbons or aromatic hydrocarbons or halohydrocarbon, the alcohol ether solvent is meant wherein a kind of of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, hydro carbons or aromatic hydrocarbons or halohydrocarbon are meant hexanaphthene, benzene, toluene, 1, a kind of in the 2-ethylene dichloride; Alkaline carbonate or alkali metal hydrocarbonate acid binding agent are meant the mixture of a kind of in yellow soda ash, salt of wormwood, sodium bicarbonate, the saleratus or two kinds.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021396116A CN1169767C (en) | 2002-09-13 | 2002-09-13 | Process for preparing o-methyl allyloxyphenol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021396116A CN1169767C (en) | 2002-09-13 | 2002-09-13 | Process for preparing o-methyl allyloxyphenol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1401620A CN1401620A (en) | 2003-03-12 |
| CN1169767C true CN1169767C (en) | 2004-10-06 |
Family
ID=4750159
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021396116A Expired - Lifetime CN1169767C (en) | 2002-09-13 | 2002-09-13 | Process for preparing o-methyl allyloxyphenol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1169767C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114307217A (en) * | 2021-12-30 | 2022-04-12 | 江苏三吉利化工股份有限公司 | Device and method for extracting o-methallyloxyphenol from waste salt of furan phenol |
| CN117486695A (en) * | 2023-11-27 | 2024-02-02 | 山东泓瑞医药科技股份公司 | Veratone synthesis method based on claisen rearrangement and etherification reaction |
-
2002
- 2002-09-13 CN CNB021396116A patent/CN1169767C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1401620A (en) | 2003-03-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101010274B (en) | Polyglycerol monoethers and process for producing the same | |
| US4543430A (en) | Process for the preparation of addition products of epoxides and hydroxylated compounds | |
| CN102458658B (en) | Boron-based catalysts | |
| CN102459140B (en) | Process for the alkoxylation of alcohols | |
| CN1294111C (en) | Method for producing bisphenol alcoxylates | |
| CN100448864C (en) | Method for preparing vinylene carbonate | |
| CN101838249A (en) | Method for preparing high-purity guaiacol glycidyl ether | |
| CN101735029B (en) | Synthesis method of hellebore aldehyde | |
| CN1169767C (en) | Process for preparing o-methyl allyloxyphenol | |
| CN106565429B (en) | A kind of preparation method of meta-methoxy phenol | |
| IE47457B1 (en) | Selective monoetherification of pyrocatechol | |
| CN111072480A (en) | Method for producing methyl ethyl carbonate by using ionic liquid catalysis ester exchange method | |
| CN101434513B (en) | Preparation of 1-naphthalene bromide | |
| CN101659612B (en) | Selective esterification method | |
| CN111979287A (en) | Preparation method of 7-phenylacetylamino-3-nor-3-cephem-4-carboxylic acid | |
| EP0077635B1 (en) | Substituted esters and alcohols | |
| CN108727166B (en) | Refining method of chloromethyl hexafluoroisopropyl ether | |
| CN118405972B (en) | Preparation method of 5-fluoro salicylic acid | |
| CN115784847B (en) | New application of triphenylphosphine diiodide as reaction promoter | |
| CN109134250A (en) | A kind of synthetic method of β-iodo acetic acid esters compound | |
| CN117820095A (en) | Process method for synthesizing 2-fluoro-4-hydroxybenzaldehyde | |
| CN105237477A (en) | Preparation method for meptazinol impurity C | |
| CN101215227B (en) | Integration method for preparing o-methyl allyloxyphenol | |
| CN101723864A (en) | Method for preparing p-tert-butyl o-nitrothiophenol | |
| JP2002080471A (en) | Method of producing ether having oxetane ring |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20041006 |