CN105523906A - Method for preparing o-methallyloxyphenol - Google Patents
Method for preparing o-methallyloxyphenol Download PDFInfo
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- CN105523906A CN105523906A CN201610024313.XA CN201610024313A CN105523906A CN 105523906 A CN105523906 A CN 105523906A CN 201610024313 A CN201610024313 A CN 201610024313A CN 105523906 A CN105523906 A CN 105523906A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
- C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
- C07C17/208—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being MX
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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Abstract
The invention provides a method for preparing o-methallyloxyphenol. According to the method, catechol and 3-chloro-2-methylpropene serving as raw materials are catalyzed under specific solvent, acid-binding agent, catalyst and proper reaction condition to prepare o-methallyloxyphenol, wherein the solvent is isobutyl methyl ketone, the acid-binding agent is alkali carbonate or alkali bicarbonate, and the catalyst is an arbitrary one or mixture of sodium iodide and potassium iodide; and the reaction is conducted at 98-108 DEG C for 7-13 hours. After an etherification reaction, water serving as a solvent is used for reclaiming the catalyst by adopting a circulation method, and the reclaimed catalyst is used as a reacting product to prepare the o-methallyloxyphenol. The o-methallyloxyphenol prepared by the process has the advantages of high conversion rate, high selectivity and high yield, and can realize recycling of the catalyst, so that the industrial feasibility can be greatly improved.
Description
[technical field]
The present invention relates to a kind of preparation method of o-methyl allyloxyphenol.
[background technology]
Benzofuranol, chemical name 2,3-dihydro-2,2-dimethyl-7-hydroxyl benzofuran (2,3-dihydro-2,2-Dimethyl-7-hydroxybenzof), molecular formula C
10h
12o
2, molecular weight 164, colourless or yellow liquid, is dissolved in the organic solvents such as methylene dichloride, toluene, alcohol, ether, water insoluble.Benzofuranol produces Furadan (carbofuran), and pacify prestige well, the important intermediate of benfuracarb, can be used as medicine intermediate simultaneously, is the fine chemical product with high added value.Pyrocatechol method take pyrocatechol as the typical method that starting raw material prepares benzofuranol, and this technics comparing is ripe, easy handling, is the main method of producing benzofuranol at present both at home and abroad.
Pyrocatechol etherification reaction product o-methyl allyloxyphenol (being called for short monoether, o-methallyoxyphenol), molecular weight 164, colourless transparent liquid, irritant smell.Current industrial o-methyl allyloxyphenol preparation method obtains with pyrocatechol and methylallyl chloride reaction usually.Due to have in pyrocatechol two can the hydroxyl of etherificate, therefore, in reactant except the monoether needed, also have by product 1,2-diformazan to generate for allyloxy benzene (abbreviation bis ether).Due to the generation of bis ether, the yield of monoether is declined, how to improve the selectivity of monoether, have many patents to report.As Chinese patent CN02139611, with pyrocatechol, methylallyl chloride is raw material (pyrocatechol: methylallyl chloride=1:1.1 ~ 1.6), at the mixed solvent that alcohol ether solvent and hydro carbons or aromatic hydrocarbons or halohydrocarbon form, o-methyl allyloxyphenol is prepared under acid binding agent and suitable reaction conditions, this technique adopts degree of depth etherification technology, by excessive for the methylallyl chloride transformation efficiency of pyrocatechol that makes is reached 99.9%, but the production this promoting by product bis ether causes selectivity to only have about 85%, cause the waste of a large amount of pyrocatechols.As Chinese patent CN101215227, pyrocatechol carries out conversion reaction (pyrocatechol: methylallyl chloride=1:0.8 ~ 1.8) in reaction solvent with methylallyl chloride, and the transformation efficiency controlling pyrocatechol is 60 ~ 85%; After reaction solution removes reaction solvent, then with non-aqueous solvent wiring solution-forming; Extract with extraction agent the pyrocatechol that in this solution, unreacted is complete to recycle, and obtain the extracting phase containing reaction product o-methyl allyloxyphenol, selectivity reaches more than 95%.US Patent No. 3474171 discloses and refluxes 30 hours under salt of wormwood and potassiumiodide existence condition, pyrocatechol and methylallyl chloride react under anhydrous propanone equimolar amount prepares o-methyl allyloxyphenol, the recovery method of the potassiumiodide of the unexposed costliness of this patent.Reclaimed by the difference of the solubleness concentrating and utilize them in water from containing Repone K and unreacted salt of wormwood, need to consume comparatively multi-energy, and potassiumiodide can not be recovered completely.
[summary of the invention]
Above-mentioned disclosed method all relates to prepares o-methyl allyloxyphenol with pyrocatechol and methylallyl chloride, these methods by methylallyl chloride excessive improve pyrocatechol transformation efficiency or by the excessive selectivity improving pyrocatechol of pyrocatechol, all do not relate to the technical scheme simultaneously obtaining higher transformation efficiency, selectivity and yield.The invention provides a kind of Catalytic processes, equally with pyrocatechol and methylallyl chloride for raw material, hexone selected by solvent, to obtain the method preparing o-methyl allyloxyphenol of tool high conversion, highly selective and high yield as catalyzer by adding sodium iodide in alkaline metal iodide or potassiumiodide or both mixtures, be simultaneously solvent recuperation catalyzer with water, and be that methallyl iodide participates in etherification reaction again as reactant using catalytic conversion, to realize recovery and the recycle of catalyzer, ensure the feasibility of this preparation method.
The invention provides a kind of preparation method of o-methyl allyloxyphenol, with pyrocatechol, methylallyl chloride for raw material, under specific solvent, acid binding agent, catalyzer and suitable reaction conditions, prepare o-methyl allyloxyphenol; Wherein, described solvent is hexone, and described acid binding agent is alkaline carbonate or alkali metal hydrocarbonate, and described catalyzer is the mixture of any one or both in sodium iodide, potassiumiodide, temperature of reaction is 98 ~ 108 DEG C, and the reaction times is 7 ~ 13 hours.
In preparation method one preferred embodiment of o-methyl allyloxyphenol provided by the invention, the mol ratio of described pyrocatechol and described methylallyl chloride is 1:1.0 ~ 1.5, the mol ratio of described pyrocatechol and described acid binding agent is 1:0.5 ~ 0.8, the mol ratio of described pyrocatechol and described hexone is 1:6 ~ 14, and the mol ratio of described pyrocatechol and described catalyzer is 1:0.08 ~ 0.40.
In preparation method one preferred embodiment of o-methyl allyloxyphenol provided by the invention, the mol ratio of described pyrocatechol and described hexone is 1:8 ~ 12, and the mol ratio of described pyrocatechol and described catalyzer is 1:0.12 ~ 0.30.
In preparation method one preferred embodiment of o-methyl allyloxyphenol provided by the invention, described acid binding agent is the mixture of any one or two kinds in sodium carbonate, salt of wormwood, sodium bicarbonate, saleratus.
In further embodiment, the invention provides a kind of preparation method of o-methyl allyloxyphenol, comprising:
Step one, with pyrocatechol, methylallyl chloride for raw material, under specific solvent, acid binding agent, catalyzer and appropriate reaction condition, prepare o-methyl allyloxyphenol;
Wherein, described solvent is hexone, and described acid binding agent is alkaline carbonate or alkali metal hydrocarbonate, and described catalyzer is the mixture of any one or both in sodium iodide, potassiumiodide, temperature of reaction is 98 ~ 108 DEG C, and the reaction times is 7 ~ 13 hours;
The recovery of step 2, catalyzer: by the product cooled and filtered of step one, obtain solid salt slag, the catalyzer wherein added containing step one in solid salt slag, is then dissolved in water, then adds methylallyl chloride and react, and obtains methallyl iodide.
In preparation method one preferred embodiment of o-methyl allyloxyphenol provided by the invention, in described step one, the mol ratio of described pyrocatechol and described methylallyl chloride is 1:1.0 ~ 1.5, the mol ratio of described pyrocatechol and described acid binding agent is 1:0.5 ~ 0.8, the mol ratio of described pyrocatechol and described hexone is 1:8 ~ 12, and the mol ratio of described pyrocatechol and described catalyzer is 1:0.12 ~ 0.30.
In preparation method one preferred embodiment of o-methyl allyloxyphenol provided by the invention, in described step 2, the mol ratio of described methylallyl chloride and water is 1:15 ~ 40, and the mol ratio of described methylallyl chloride and described catalyzer is 2.5 ~ 7.2:1.
In preparation method one preferred embodiment of o-methyl allyloxyphenol provided by the invention, in described step 2, temperature of reaction is 51 DEG C ~ 80 DEG C, and the reaction times is 5 ~ 8 hours.
In preparation method one preferred embodiment of o-methyl allyloxyphenol provided by the invention, also comprise:
The methallyl iodide that step 3, recycling step 2 reclaim, carries out etherification reaction and prepares o-methyl allyloxyphenol.
Compared to correlation technique, the preparation method of o-methyl allyloxyphenol provided by the invention has following beneficial effect:
One, the present invention adopts Catalytic processes to prepare o-methyl allyloxyphenol, take methyl iso-butyl ketone (MIBK) as solvent, potassiumiodide in alkaline metal iodide or sodium iodide or both mixtures are catalyzer, when the transformation efficiency of pyrocatechol is about 94%, reaction terminates, selectivity reaction later stage (in 7 ~ 13 hours) Absorbable organic halogens between 90 ~ 96%, what yield was best reaches more than 90%, in reaction system, unreacted pyrocatechol can continue to reclaim use, compared with the existing technique not adding catalyzer, although add the raw materials cost of catalyzer, but the present invention is by circulation and stress catalyzer, achieve the recycling of catalyzer, the present invention has high conversion, the advantage of highly selective and high yield.
Two, the present invention is by the reaction product cooled and filtered of etherification reaction, take water as solvent recuperation catalyzer, the high-recovery of catalyzer can be realized by 2 ~ 3 circulations, catalytic conversion is methallyl iodide, catalyst recovery yield can reach more than 97%, compared with reclaiming the technical scheme of catalyzer, can reduce the separation costs cost of Separation of Organic and methallyl iodide with employing organic solvent, use water as recycling design is the method for most simple economy simultaneously, more easily realize suitability for industrialized production.
Three, the present invention is when reclaiming catalyzer alkaline metal iodide, first be dissolved in water after reaction product being filtered, directly in reaction solution, dissolved salt is added if do not filtered, because have the pyrocatechol of part and unreacted also soluble in waterly can be not easy to the recovery of pyrocatechol, in addition because the o-methyl allyloxyphenol generated need be used for the preparation of benzofuranol, also can avoid directly introducing other impurity in subsequent reactions.The simple convenient operation of filtration process simultaneously, if also have the unreacted methallyl iodide of minute quantity in reaction solution, also can realize it by the recovery of reaction solvent and reclaim in industrial subsequent technique.
Four, catalyst recovery product methallyl iodide is carried out etherification reaction as reactant and prepares o-methyl allyloxyphenol, in halohydrocarbon, the activity of methallyl iodide is far better than methylallyl chloride, for the molecule that polarizability is strong, under ambient conditions impact, molecule easily changes shape, with the needs of adaptive response, so the existence that methallyl iodide does not need catalyzer in etherification reaction process just can directly and pyrocatechol generation etherification reaction, the selectivity of this etherification reaction can be stabilized in about 94%, pyrocatechol transformation efficiency is more than 90%, the yield of o-methyl allyloxyphenol is more than 85%.
Five, the present invention with the potassiumiodide in alkaline metal iodide or sodium iodide or both mixtures for catalyzer, after etherification reaction, be that solvent adopts circulation method to reclaim catalyzer again with water, and the catalyzer of recovery is prepared o-methyl allyloxyphenol as reactant, this technique is not when introducing new reactant, the recycle of alkaline metal iodide catalyzer can be realized, while greatly reducing enterprise's production cost, owing to not needing special conversion unit, substantially increase commercial viability.
[embodiment]
Be clearly and completely described the technical scheme in the embodiment of the present invention below, obviously, described embodiment is only a part of embodiment of the present invention, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making other embodiments all obtained under creative work prerequisite, belong to the scope of protection of the invention.
Etherification reaction
In the method for the invention, with pyrocatechol and methylallyl chloride for raw material, be solvent with hexone, and add catalyzer and acid binding agent prepares o-methyl allyloxyphenol under suitable reaction conditions, belong to Catalytic processes and prepare o-methyl allyloxyphenol.Wherein main reaction is that pyrocatechol and methylallyl chloride react and generate o-methyl allyloxyphenol, and side reaction primary product is two methylallyl oxygen base benzene (abbreviation bis ether).
In the present reaction, the effect of acid binding agent is the HCl that neutralization reaction produces, and plays a driving role to etherification reaction.In addition, acid binding agent also can react with pyrocatechol and generate basic metal list phenates, and then with alkylating agent generation etherification reaction, therefore the existence of acid binding agent plays a driving role equally to generating the side reaction of bis ether equally.A lot of inorganic salt can use as the acid binding agent of etherification reaction, as sodium carbonate, salt of wormwood, sodium bicarbonate, saleratus, calcium carbonate and Calcium hydrogen carbonate etc.Etherification reaction needs the acid binding agent adopting weak acid strong alkali salt as reaction, and to increase the impellent of process, and alkalescence is too high, can increase the speed of side reaction, and may cause the side reaction of other types.In the present invention, described acid binding agent is alkaline carbonate or alkali metal hydrocarbonate, is specially the mixture of a kind of in sodium carbonate, salt of wormwood, sodium bicarbonate, saleratus or two kinds, preferred sodium carbonate.In an embodiment of the present invention, acid binding agent selects sodium carbonate.
In the present reaction, catalyzer is alkaline metal iodide, and be specially a kind of in sodium iodide, potassiumiodide or both mixtures, what work is iodide ion.In an embodiment of the present invention, potassiumiodide selected by catalyzer.
The recovery of catalyzer
In the recovery method of catalyzer provided by the invention, taking water as the solid salt slag after dissolution with solvents is filtered, take methylallyl chloride as reactant, circulation and stress catalyzer.In halogenated alkane, because the electronegativity of halogen atom is larger than carbon atom, so the share electron pair of carbon-halogen bond is partial to halogen atom, carbon ribbon is made to have part positive charge, therefore carbon electrode is vulnerable to the attack of nucleophilic reagent, halogen atom is then left away with the form of negative ion with pair of electrons, and then completes the nucleophilic substitution reaction of halohydrocarbon.Catalyzer potassiumiodide is the nucleophilic reagent that a kind of activity is stronger, and methylallyl chloride is the halohydrocarbon that a kind of activity is stronger, very easily there is chemical reaction and generate methallyl iodide in both, and the activity of methallyl iodide is far better than methylallyl chloride in halohydrocarbon, for the molecule that polarizability is strong, under ambient conditions impact, molecule easily changes shape, with the needs of adaptive response, so methallyl iodide do not need in etherification reaction process the existence of catalyzer just can directly and pyrocatechol generation etherification reaction generate o-methyl allyloxyphenol, and can potassiumiodide be reverted to after etherification reaction, catalyzer again as etherification reaction uses.The recycle of catalyzer can be realized according to aforesaid method, can greatly reduce enterprise's production cost, realize suitability for industrialized production.
In the examples below, transformation efficiency (%), selectivity (%), yield (%) and the potassiumiodide rate of recovery (%) are as given a definition:
Transformation efficiency (%)=100 × [(mole number of the pyrocatechol of supply)-(unreacted pyrocatechol mole)]/(mole number of the pyrocatechol of supply)
Selectivity (%)=100 × (generating the mole number of the pyrocatechol that o-methyl allyloxyphenol consumes)/[(mole number of the pyrocatechol of supply)-(mole number of unreacted pyrocatechol)]
Yield (%)=100 × (generating the mole number of the pyrocatechol that o-methyl allyloxyphenol consumes)/(mole number of the pyrocatechol of supply)
The potassiumiodide rate of recovery (%)=100 × (the potassiumiodide mole number reacted with the methylallyl chloride)/mole number of potassiumiodide (in the salt slag)
Etherification reaction (embodiment 1-8)
Embodiment 1
One be equipped with stirring, thermometer, condenser 1500mL be with magnetic agitation glass reaction still in, pyrocatechol 110 grams (1mol), potassiumiodide 13.3 grams (0.08mol) and 53 grams, sodium carbonate (0.5mol) is added in 600 grams of (6mol) hexone solvents, after stirring is warming up to 98 DEG C, start to drip methylallyl chloride 90.5 grams (1mol), dropwise in 90min, react 9 hours, cooling, reacts complete.
Cooling pours product into suction funnel later, negative pressure is produced by liquid suction filter flask by vacuum pump, solid salt slag remains in funnel, solid salt cinder ladle draws together sodium-chlor, Repone K and potassiumiodide, and then with hexone cleaning solid salt slag, liquid is again by vacuum pump suction filter flask, weigh up the weight of mother liquor in filter flask, analyze the content of pyrocatechol, o-methyl allyloxyphenol, by reservation of weighing after the drying of solid salt slag, use in order to catalyst recovery.
Through efficient liquid phase chromatographic analysis, the transformation efficiency of pyrocatechol is 92.71%, and the selectivity of pyrocatechol is 93.07%, and the yield of o-methyl allyloxyphenol is 86.29%.
Except by as shown in table 1 for reaction conditions change like that except, other all same with embodiment 1 modes carry out reacting and measuring, and obtain embodiment 2-8.The reaction conditions of embodiment 2-8 and result are as Table 1 and Table 2 below.
Table 1
Table 2
Potassiumiodide reclaims (embodiment 9-15)
Embodiment 9
One be equipped with stirring, thermometer, condenser 500mL be with magnetic agitation glass reactor in, add solid salt slag to be recycled, wherein contain potassiumiodide 23.24 grams (0.14mol) in solid salt slag, add methylallyl chloride 90.5 grams (1mol) and 270 grams, water (15mol) simultaneously, stirring is warming up to 51 DEG C, react after 8 hours, the solution separating obtained is become oil reservoir and water layer, methallyl iodide place layer is oil reservoir, measure the content of the potassiumiodide in water layer, the rate of recovery calculating potassiumiodide is 95.28%;
Except by as shown in table 3 for reaction conditions change like that except, other all same with embodiment 9 modes carry out reacting and measuring.Reaction conditions and result are as shown in embodiment 10-12 in table 3:
Table 3
| Embodiment 9 | Embodiment 10 | Embodiment 11 | Embodiment 12 | |
| Water (mol) | 15 | 20 | 30 | 40 |
| Methylallyl chloride (mol) | 1 | 1 | 1 | 1 |
| Potassiumiodide (mol) | 0.14 | 0.2 | 0.3 | 0.4 |
| Temperature of reaction (DEG C) | 51 | 60 | 70 | 80 |
| Reaction times (hour) | 8 | 7 | 6 | 5 |
| The potassiumiodide rate of recovery (%) | 95.28 | 97.30 | 97.57 | 94.79 |
Take water as solvent, once circulation, secondary circulation and the experiment condition circulated for three times and experimental result detailed in Example 13-15.
Embodiment 13
Embodiment 11 is reclaimed the water solution cycle containing potassiumiodide after potassiumiodide to use, recording potassiumiodide in water is 1.21 grams (0.007mol), add methylallyl chloride 3.7 grams (0.04mol) and 16.5 grams, water (0.92mol), after stirring is warming up to 55 DEG C, react after 5 hours, the solution separating obtained is become oil reservoir and water layer, methallyl iodide place layer is oil reservoir, measure the content of the potassiumiodide in water layer, calculate the rate of recovery of potassiumiodide.
By once circulating, potassiumiodide total yield is 98.22%.
Embodiment 14
First set reaction: one be equipped with stirring, thermometer, condenser 500mL be with magnetic agitation glass reactor in, add solid salt slag to be recycled, contain potassiumiodide 12 grams (0.072mol) in solid salt slag, add methylallyl chloride 37 grams (0.40mol) and 160 grams, water (8.9mol) simultaneously, after stirring is warming up to 55 DEG C, react after 5 hours, the solution separating obtained is become oil reservoir and water layer, methallyl iodide place layer is oil reservoir, measure the content of the potassiumiodide in water layer, the rate of recovery calculating potassiumiodide is 91.12%;
Once circulate: lower batch of solid salt slag is dissolved in the aqueous solution after first set reaction recovery potassiumiodide, record potassiumiodide in the aqueous solution to be 13.1 grams (0.079mol), to add methylallyl chloride 39 grams (0.43mol) again, stirring is warming up to 55 DEG C, react after 5 hours, the solution separating obtained is become oil reservoir and water layer, methallyl iodide place layer is oil reservoir, and measure the content of the potassiumiodide in water layer, the rate of recovery calculating potassiumiodide is 90.17%;
Secondary circulation: the water solution cycle containing potassiumiodide after a circulation and stress potassiumiodide is used, record potassiumiodide in the aqueous solution to be 1.29 grams (0.008mol), to add methylallyl chloride 3.9 grams (0.043mol) again, stirring is warming up to 55 DEG C, react after 5 hours, the solution separating obtained is become oil reservoir and water layer, methallyl iodide place layer is oil reservoir, and measure the content of the potassiumiodide in water layer, the rate of recovery calculating potassiumiodide is 90.23%.
By secondary circulation, potassiumiodide total yield is 99.00%.
Embodiment 15
First set reaction: one be equipped with stirring, thermometer, condenser 500mL be with magnetic agitation glass reactor in, add solid salt slag to be recycled, containing potassiumiodide 12 grams (0.072mol) in solid salt slag, add methylallyl chloride 37 grams (0.04mol) and 160 grams, water (8.9mol) simultaneously, after stirring is warming up to 55 DEG C, react after 5 hours, the solution separating obtained is become oil reservoir and water layer, methallyl iodide place layer is oil reservoir, measure the content of the potassiumiodide in water layer, the rate of recovery calculating potassiumiodide is 90.76%;
Once circulate: the dissolving aqueous solution (containing potassiumiodide 1.1 grams) after recovery potassiumiodide being cycled to used in next batch solid salt slag (containing potassiumiodide 12 grams), record potassiumiodide in the aqueous solution to be 13.1 grams (0.079mol), to add methylallyl chloride 39 grams (0.43mol) again, stirring is warming up to 55 DEG C, react after 5 hours, the solution separating obtained is become oil reservoir and water layer, methallyl iodide place layer is oil reservoir, measure the content of the potassiumiodide in water layer, the rate of recovery calculating potassiumiodide is 90.25%;
Secondary circulation: the dissolving aqueous solution (containing potassiumiodide 1.28 grams) after a circulation and stress potassiumiodide being cycled to used in again next batch solid salt slag (containing potassiumiodide 12 grams), record potassiumiodide in the aqueous solution to be 13.28 grams (0.08mol), to add methylallyl chloride 39 grams (0.43mol) again, stirring is warming up to 55 DEG C, react after 5 hours, the solution separating obtained is become oil reservoir and water layer, methallyl iodide place layer is oil reservoir, measure the content of the potassiumiodide in water layer, the rate of recovery calculating potassiumiodide is 91.33%.
Three circulations: secondary circulation is reclaimed the aqueous solution (containing potassiumiodide 1.15 grams) containing potassiumiodide after potassiumiodide and recycle, record potassiumiodide in the aqueous solution to be 1.15 grams (0.007mol), to add methylallyl chloride 3.6 grams (0.04mol) again, stirring is warming up to 55 DEG C, react after 5 hours, the solution separating obtained is become oil reservoir and water layer, methallyl iodide place layer is oil reservoir, measure the content of the potassiumiodide in water layer, calculate the rate of recovery of potassiumiodide.By three circulations, the rate of recovery of potassiumiodide is 99.33%.
Therefore, be solvent with water, add methylallyl chloride reaction, adopt 2 ~ 3 circulations that the total yield of potassiumiodide can be made to reach more than 99.00%.
The catalyzer reclaimed is used to carry out etherification reaction
Embodiment 16
One be equipped with stirring, thermometer, condenser 500mL be with magnetic agitation glass reaction still in, pyrocatechol 110 grams (1mol) and 63.6 grams, sodium carbonate (0.6mol) is added in reaction solvent hexone 800 grams (8mol), after stirring is warming up to 98 DEG C, start to drip Halocarbon blends, described Halocarbon blends is methylallyl chloride 90.5 grams (1mol) and the mixture reclaiming gained methallyl iodide 18.2 grams (0.1mol), dropwise in 90min, react 10 hours, cooling, reacts complete.Methallyl iodide is converted into potassiumiodide again, can again use as catalyst recirculation.
Cooling pours product into suction funnel later, and produce negative pressure by liquid suction filter flask by vacuum pump, solid salt slag remains in funnel, and solid salt cinder ladle draws together sodium-chlor, Repone K and potassiumiodide.Then with hexone cleaning solid salt slag, liquid is again by vacuum suction filter flask.Weigh up the weight of mother liquor in filter flask, analyze the content of pyrocatechol, o-methyl allyloxyphenol, by reservation of weighing after the drying of solid salt slag, use in order to catalyst recovery.
Through efficient liquid phase chromatographic analysis, the transformation efficiency of pyrocatechol is 91.12%, and the selectivity of pyrocatechol is 95.2%, and the yield of o-methyl allyloxyphenol is 86.75%.
The preparation method that the invention provides o-methyl allyloxyphenol has following beneficial effect:
One, the present invention adopts Catalytic processes to prepare o-methyl allyloxyphenol, take methyl iso-butyl ketone (MIBK) as solvent, when the transformation efficiency of pyrocatechol is about 94%, reaction terminates, selectivity reaction later stage Absorbable organic halogens between 90 ~ 96%, what yield was best reaches more than 90%, in reaction system, unreacted pyrocatechol can continue to reclaim use, compared with the existing technique not adding catalyzer, add the raw materials cost of catalyzer, but the present invention is by circulation and stress potassiumiodide, achieve it to recycle, the present invention has the advantage of highly selective and high yield.
Two, the present invention is by the reaction product cooled and filtered of etherification reaction, take water as solvent recuperation catalyzer, the high-recovery of catalyzer can be realized by 2 ~ 3 circulations, catalytic conversion is methallyl iodide, catalyst recovery yield can reach more than 97%, compared with reclaiming the technical scheme of catalyzer, can reduce the separation costs of Separation of Organic and methallyl iodide with employing organic solvent, use water as the method that catalyzer is most simple economy simultaneously, more easily realize suitability for industrialized production.
Three, the present invention is when reclaiming catalyzer alkaline metal iodide, first reaction product is filtered and be dissolved in water again, directly in reaction solution, dissolved salt is added if do not filtered, because have the pyrocatechol of part and unreacted also soluble in waterly can be not easy to the recovery of pyrocatechol, in addition because the o-methyl allyloxyphenol generated need be used for the preparation of benzofuranol, also can avoid directly introducing other impurity in subsequent reactions.The simple convenient operation of filtration process simultaneously, reclaims if also have the unreacted methallyl iodide of minute quantity also can realize it by the recovery of reaction solvent in reaction solution in industrial subsequent technique.
Four, catalyst recovery product methallyl iodide is prepared o-methyl allyloxyphenol as reactant generation etherification reaction, in halohydrocarbon, the activity of methallyl iodide is far better than methylallyl chloride, for the molecule that polarizability is strong, under ambient conditions impact, molecule easily changes shape, with the needs of adaptive response, so the existence that methallyl iodide does not need catalyzer in etherification reaction process just can directly and pyrocatechol generation etherification reaction, the selectivity of this etherification reaction can be stabilized in about 94%, pyrocatechol transformation efficiency is more than 90%, the yield of o-methyl allyloxyphenol is more than 85%.
Five, the present invention take alkaline metal iodide as catalyzer, after etherification reaction, be that solvent adopts circulation method to reclaim catalyzer again with water, and the catalyzer of recovery is prepared o-methyl allyloxyphenol as reactant, this technique, not introducing in new reactive material situation, can realize the recycle of alkaline metal iodide catalyzer, while greatly reducing enterprise's production cost, owing to not needing special conversion unit, substantially increase commercial viability.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (9)
1. a preparation method for o-methyl allyloxyphenol, is characterized in that, with pyrocatechol, methylallyl chloride for raw material, under specific solvent, acid binding agent, catalyzer and suitable reaction conditions, prepares o-methyl allyloxyphenol; Wherein, described solvent is hexone, and described acid binding agent is alkaline carbonate or alkali metal hydrocarbonate, and described catalyzer is the mixture of any one or both in sodium iodide, potassiumiodide, temperature of reaction is 98 ~ 108 DEG C, and the reaction times is 7 ~ 13 hours.
2. the preparation method of o-methyl allyloxyphenol according to claim 1, it is characterized in that, the mol ratio of described pyrocatechol and described methylallyl chloride is 1:1.0 ~ 1.5, the mol ratio of described pyrocatechol and described acid binding agent is 1:0.5 ~ 0.8, the mol ratio of described pyrocatechol and described hexone is 1:6 ~ 14, and the mol ratio of described pyrocatechol and described catalyzer is 1:0.08 ~ 0.40.
3. the preparation method of o-methyl allyloxyphenol according to claim 2, it is characterized in that, the mol ratio of described pyrocatechol and described hexone is 1:8 ~ 12, and the mol ratio of described pyrocatechol and described catalyzer is 1:0.12 ~ 0.30.
4. the preparation method of o-methyl allyloxyphenol according to claim 1, is characterized in that, described acid binding agent is the mixture of any one or two kinds in sodium carbonate, salt of wormwood, sodium bicarbonate, saleratus.
5. a preparation method for o-methyl allyloxyphenol, is characterized in that, comprising:
Step one, with pyrocatechol, methylallyl chloride for raw material, under specific solvent, acid binding agent, catalyzer and appropriate reaction condition, prepare o-methyl allyloxyphenol;
Wherein, described solvent is hexone, and described acid binding agent is alkaline carbonate or alkali metal hydrocarbonate, and described catalyzer is the mixture of any one or both in sodium iodide, potassiumiodide, temperature of reaction is 98 ~ 108 DEG C, and the reaction times is 7 ~ 13 hours;
The recovery of step 2, catalyzer: by the product cooled and filtered of step one, obtain solid salt slag, wherein in solid salt slag containing the catalyzer added in step one, be then dissolved in water, then add methylallyl chloride and react, obtain methallyl iodide.
6. the preparation method of o-methyl allyloxyphenol according to claim 5, it is characterized in that, in described step one, the mol ratio of described pyrocatechol and described methylallyl chloride is 1:1.0 ~ 1.5, the mol ratio of described pyrocatechol and described acid binding agent is 1:0.5 ~ 0.8, the mol ratio of described pyrocatechol and described hexone is 1:8 ~ 12, and the mol ratio of described pyrocatechol and described catalyzer is 1:0.12 ~ 0.30.
7. the preparation method of o-methyl allyloxyphenol according to claim 5, it is characterized in that, in described step 2, the mol ratio of described methylallyl chloride and water is 1:15 ~ 40, and the mol ratio of described methylallyl chloride and described catalyzer is 2.5 ~ 7.2:1.
8. the preparation method of o-methyl allyloxyphenol according to claim 5, is characterized in that, in described step 2, temperature of reaction is 51 DEG C ~ 80 DEG C, and the reaction times is 5 ~ 8 hours.
9. the preparation method of o-methyl allyloxyphenol according to claim 5, is characterized in that, also comprises:
The methallyl iodide that step 3, recycling step 2 reclaim, carries out etherification reaction and prepares o-methyl allyloxyphenol.
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| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4465868A (en) * | 1981-07-17 | 1984-08-14 | Otsuka Kagaku Yakuhin Kabushiki Kaisha | Process for preparing o-methallyloxyphenol |
| US4465876A (en) * | 1983-02-07 | 1984-08-14 | Air Products And Chemicals, Inc. | Nitration of aromatics with nitrogen oxides in trifluoroacetic acid |
| CN101215227A (en) * | 2007-12-29 | 2008-07-09 | 湘潭大学 | Integration method for preparing o-methyl allyloxyphenol |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4465868A (en) * | 1981-07-17 | 1984-08-14 | Otsuka Kagaku Yakuhin Kabushiki Kaisha | Process for preparing o-methallyloxyphenol |
| US4465876A (en) * | 1983-02-07 | 1984-08-14 | Air Products And Chemicals, Inc. | Nitration of aromatics with nitrogen oxides in trifluoroacetic acid |
| CN101215227A (en) * | 2007-12-29 | 2008-07-09 | 湘潭大学 | Integration method for preparing o-methyl allyloxyphenol |
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| V. B. DEODHAR等: "AN IMPROVED SYNTHESIS OF 2-METHALLYLOXYPHENOL", 《OPPI BRIEFS》 * |
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| 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 |
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