CN105523906B - The preparation method of o-methyl allyloxyphenol - Google Patents
The preparation method of o-methyl allyloxyphenol Download PDFInfo
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- CN105523906B CN105523906B CN201610024313.XA CN201610024313A CN105523906B CN 105523906 B CN105523906 B CN 105523906B CN 201610024313 A CN201610024313 A CN 201610024313A CN 105523906 B CN105523906 B CN 105523906B
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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
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Abstract
The present invention provides a kind of preparation method of o-methyl allyloxyphenol.The preparation method of the o-methyl allyloxyphenol uses Catalytic processes, and using catechol, methylallyl chloride as raw material, o-methyl allyloxyphenol is prepared under specific solvent, acid binding agent, catalyst and appropriate reaction condition；Wherein, the solvent is hexone, and the acid binding agent is alkali carbonate or alkali metal hydrogencarbonate, and the catalyst is the mixture of any one in sodium iodide, KI or both, reaction temperature is 98~108 DEG C, and the reaction time is 7~13 hours.After etherification reaction, then using water be solvent using round-robin method recovery catalyst, and the catalyst of recovery is prepared into o-methyl allyloxyphenol as reactant.O-methyl allyloxyphenol is prepared by the technique, have high conversion, high selectivity and in high yield the advantages of, and recycling for catalyst can be realized, substantially increase commercial viability.
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 benzofurans (2,3-dihydro-2,2-
Dimethyl-7-hydroxybenzof), molecular formula C10H12O2, molecular weight 164, colourless or yellow liquid, be dissolved in dichloromethane,
The organic solvents such as toluene, alcohol, ether, it is not soluble in water.Benzofuranol is production Furadan (carbofuran), pacifies prestige well, Benfuracard micro
Important intermediate, it is the fine chemical product with high added value at the same time as medicine intermediate.Catechol method is with neighbour
Benzenediol is the typical method that initiation material prepares benzofuranol, and this technics comparing is ripe, easily operated, is production both at home and abroad at present
The main method of benzofuranol.
Catechol etherification reaction product o-methyl allyloxyphenol (abbreviation monoether, o-methallyoxyphenol),
Molecular weight 164, colourless transparent liquid, irritant smell.Industrial o-methyl allyloxyphenol preparation method is usual at present
It is made with catechol and methylallyl chloride reaction.Due to there is two hydroxyls that can be etherified in catechol, therefore, reaction
In thing in addition to the monoether of needs, also accessory substance 1,2- diformazans generate for allyloxy benzene (abbreviation bis ether).Due to the life of bis ether
Into so that the yield of monoether declines, and how to improve the selectivity of monoether, has many patents to be reported.Such as Chinese patent
CN02139611, using catechol, methylallyl chloride as raw material (catechol：Methylallyl chloride=1：1.1~1.6),
Prepared under the mixed solvent of alcohol ethers solvent and hydro carbons or aromatic hydrocarbons or halogenated hydrocarbons composition, acid binding agent and appropriate reaction condition adjacent
Methyl allyloxyphenol, the technique use depth etherification technology, by by the excessive catechol of methylallyl chloride
Conversion ratio reaches 99.9%, but the production for so promoting accessory substance bis ether causes selectivity only 85% or so, causes
The waste of substantial amounts of catechol.Such as Chinese patent CN101215227, catechol in reaction dissolvent with methylallyl chloride
Carry out conversion reaction (catechol：Methylallyl chloride=1：0.8~1.8), control the conversion ratio of catechol for 60~
85%；After reaction solution elimination reaction solvent, then with nonaqueous solvents wiring solution-forming；It is complete that unreacted in the solution is extracted with extractant
Catechol recycles, and obtains the raffinate phase of the o-methyl allyloxyphenol containing reaction product, has selectively reached 95%
More than.United States Patent (USP) US3474171 discloses to flow back 30 hours under potassium carbonate and KI existence condition, catechol and first
For allyl chloride, reaction prepares o-methyl allyloxyphenol under anhydrous propanone equimolar amounts, the undisclosed expensive iodine of the patent
Change the recovery method of potassium.By concentrating and utilizing their solubility in water from containing potassium chloride and unreacted potassium carbonate
Difference reclaim, it is necessary to consume compared with multi-energy, and KI can not be recovered completely.
【The content of the invention】
Method disclosed above all refers to prepare o-methyl allyloxyphenol with catechol and methylallyl chloride, this
A little methods are excessively improved the conversion ratio of catechol or excessively improve adjacent benzene by catechol by methylallyl chloride
The selectivity of diphenol, without reference to the technical scheme for obtaining higher conversion ratio, selectivity and yield simultaneously.The present invention provides
A kind of Catalytic processes, equally using catechol and methylallyl chloride as raw material, solvent selection hexone, by adding
The mixture for entering the sodium iodide in alkaline metal iodide or KI or both obtains tool high conversion, high selection as catalyst
Property and the method for preparing o-methyl allyloxyphenol in high yield, while using water as solvent recovery catalyst, and by catalyst
It is converted into methallyl iodide and participates in etherification reaction again as reactant, to realize the recovery of catalyst and recycle, protects
Demonstrate,prove the feasibility of the preparation method.
The present invention provides a kind of preparation method of o-methyl allyloxyphenol, using catechol, methylallyl chloride as
Raw material, o-methyl allyloxyphenol is prepared under specific solvent, acid binding agent, catalyst and appropriate reaction condition；Wherein,
The solvent is hexone, and the acid binding agent is alkali carbonate or alkali metal hydrogencarbonate, the catalyst
For the mixture of any one in sodium iodide, KI or both, reaction temperature is 98~108 DEG C, and the reaction time is 7~13
Hour.
In the preferred embodiment of preparation method one of o-methyl allyloxyphenol provided by the invention, the catechol
Mol ratio with the methylallyl chloride is 1：1.0~1.5, the mol ratio of the catechol and the acid binding agent is
1：0.5~0.8, the mol ratio of the catechol and the hexone is 1：6~14, the catechol with
The mol ratio of the catalyst is 1：0.08~0.40.
In the preferred embodiment of preparation method one of o-methyl allyloxyphenol provided by the invention, the catechol
Mol ratio with the hexone is 1：8~12, the mol ratio of the catechol and the catalyst is
1：0.12~0.30.
In the preferred embodiment of preparation method one of o-methyl allyloxyphenol provided by the invention, the acid binding agent is
The mixture of any one or two kinds in sodium carbonate, potassium carbonate, sodium acid carbonate, saleratus.
In further embodiment, the present invention provides a kind of preparation method of o-methyl allyloxyphenol, bag
Include：
Step 1: using catechol, methylallyl chloride as raw material, in specific solvent, acid binding agent, catalyst and appropriate
O-methyl allyloxyphenol is prepared under reaction condition；
Wherein, the solvent is hexone, and the acid binding agent is alkali carbonate or alkali metal hydrogen carbonate
Salt, the catalyst are the mixture of any one in sodium iodide, KI or both, and reaction temperature is 98~108 DEG C, instead
It is 7~13 hours between seasonable；
Step 2: the recovery of catalyst：By the product cooled and filtered of step 1, solid salt slag, wherein solid salt are obtained
The catalyst added in slag containing step 1, is then dissolved in water, adds methylallyl chloride and reacted, obtain methallyl
Base iodine.
In the preferred embodiment of preparation method one of o-methyl allyloxyphenol provided by the invention, in the step 1
In, the mol ratio of the catechol and the methylallyl chloride is 1：1.0~1.5, the catechol is tied up with described
The mol ratio of sour agent is 1：0.5~0.8, the mol ratio of the catechol and the hexone is 1：8~
12, the mol ratio of the catechol and the catalyst is 1：0.12~0.30.
In the preferred embodiment of preparation method one of o-methyl allyloxyphenol provided by the invention, in the step 2
In, the mol ratio of the methylallyl chloride and water is 1：15~40, the methylallyl chloride rubs with the catalyst
Your proportioning is 2.5~7.2：1.
In the preferred embodiment of preparation method one of o-methyl allyloxyphenol provided by the invention, in the step 2
In, reaction temperature is 51 DEG C~80 DEG C, and the reaction time is 5~8 hours.
In the preferred embodiment of preparation method one of o-methyl allyloxyphenol provided by the invention, in addition to：
Step 3: the methallyl iodide of recycling step 2 recovery, carries out etherification reaction and prepares adjacent methallyl oxygen
Base phenol.
Compared to correlation technique, the preparation method of o-methyl allyloxyphenol provided by the invention has below beneficial to effect
Fruit：
First, the present invention prepares o-methyl allyloxyphenol using Catalytic processes, using methyl iso-butyl ketone (MIBK) as solvent, alkali gold
The mixture of KI or sodium iodide or both in category iodide is catalyst, when the conversion ratio of catechol is 94% or so
Shi Fanying terminates, and selectivity can be stablized between 90~96% in the later stage of reaction (in 7~13 hours), best reachable of yield
To more than 90%, unreacted catechol can continue recovery and use in reaction system, with the existing technique phase for being not added with catalyst
Than although adding the cost of material of catalyst, for the present invention by circulation and stress catalyst, the recovery for realizing catalyst is sharp
With, the present invention have high conversion, high selectivity and in high yield the advantages of.
2nd, the reaction product cooled and filtered of the invention by etherification reaction, using water as solvent recovery catalyst, passes through 2~3
The high-recovery of catalyst can be achieved in secondary circulation, and catalyst is converted into methallyl iodide, and catalyst recovery yield can reach 97%
More than, compared with using the technical scheme of organic solvent recovery catalyst, Separation of Organic and methallyl iodide can be reduced
Separation expense cost, while be the method for most simple economy by the use of water as recycling design, be more easy to realize industrialized production.
3rd, the present invention is dissolved in water when reclaiming catalyst alkaline metal iodide after reaction product is filtered first, if
Do not filter and dissolving salt is directly added in reaction solution, because having the catechol of part and unreacted soluble in water can be also not easy to
The recovery of catechol, additionally since the o-methyl allyloxyphenol of generation can also avoid required to the preparation of benzofuranol
Other impurities are introduced directly into subsequent reactions.Filtering technique is simply easy to operation simultaneously, if also very small amount is not in reaction solution
The methallyl iodide of reaction, its recovery can also be realized by the recovery of reaction dissolvent in industrial subsequent technique.
4th, catalyst recovery product methallyl iodide is subjected to etherification reaction as reactant and prepares adjacent methallyl oxygen
Base phenol, the activity of methallyl iodide is the strong molecule of polarizability, outside much stronger than methylallyl chloride in halogenated hydrocarbons
Under the influence of boundary's condition, molecule easily changes shape, with the needs of adaptive response, so methallyl iodide is in etherification reaction process
In do not need catalyst presence can directly with catechol occur etherification reaction, the selectivity of the etherification reaction can be steady
94% or so is scheduled on, catechol conversion ratio is more than 90%, and the yield of o-methyl allyloxyphenol is more than 85%.
5th, the present invention is using the KI in alkaline metal iodide or the mixture of sodium iodide or both as catalyst, etherificate
After reaction, then using water be solvent using round-robin method recovery catalyst, and prepare adjacent first generation using the catalyst of recovery as reactant
Allyloxy phenol, the technique can realize following for alkaline metal iodide catalyst in the case where not introducing new reactant
Ring utilizes, and while enterprise's production cost is substantially reduced, due to not needing special consersion unit, substantially increasing industry can
Row.
【Embodiment】
The technical scheme in the embodiment of the present invention is clearly and completely described below, it is clear that described embodiment
Only it is the part of the embodiment of the present invention, rather than whole embodiments.Based on the embodiment in the present invention, the common skill in this area
All other embodiment that art personnel are obtained under the premise of creative work is not made, belong to the model that the present invention protects
Enclose.
Etherification reaction
In the method for the invention, using catechol and methylallyl chloride as raw material, using hexone to be molten
Agent, and add catalyst and acid binding agent and prepare o-methyl allyloxyphenol under appropriate reaction condition, belong to Catalytic processes
Prepare o-methyl allyloxyphenol.Wherein main reaction is that catechol generates adjacent methallyl oxygen with methylallyl chloride reaction
Base phenol, side reaction primary product are two methylallyl epoxide benzene (abbreviation bis ether).
In the present reaction, the effect of acid binding agent is HCl caused by neutralization reaction, and etherification reaction is played a driving role.In addition,
Acid binding agent can also react generation alkali metal list phenates with catechol, etherification reaction then occur with alkylating agent again, therefore tie up acid
The presence of agent equally equally plays a driving role to the side reaction for generating bis ether.Many inorganic salts can serve as tiing up for etherification reaction
Sour agent uses, such as sodium carbonate, potassium carbonate, sodium acid carbonate, saleratus, calcium carbonate and calcium bicarbonate.Etherification reaction needs
Using acid binding agent of the weak acid strong alkali salt as reaction, to increase the motive force of process, and alkalescence is too high, can increase side reaction
Speed, and other kinds of side reaction may be caused.In the present invention, the acid binding agent is alkali carbonate or alkali metal carbon
One kind or two kinds of mixture in sour hydrogen salt, specially sodium carbonate, potassium carbonate, sodium acid carbonate, saleratus, preferably carbonic acid
Sodium.In an embodiment of the present invention, acid binding agent selects sodium carbonate.
In the present reaction, catalyst is alkaline metal iodide, and specially one or both of sodium iodide, KI is mixed
Compound, what is worked is iodide ion.In an embodiment of the present invention, catalyst selects KI.
The recovery of catalyst
In the recovery method of catalyst provided by the invention, using water as the solid salt slag after solvent dissolution filter, with first
It is reactant for allyl chloride, circulation and stress catalyst.In halogenated alkane, because the electronegativity of halogen atom is bigger than carbon atom,
So the share electron pair of carbon-halogen bond is partial to halogen atom, carbon ribbon is set to have part positive charge, therefore carbon electrode is vulnerable to nucleopilic reagent
Attack, halogen atom then left away with pair of electrons in the form of anion, and then completes the nucleophilic substitution of halogenated hydrocarbons.Urge
Agent KI is a kind of stronger nucleopilic reagent of activity, and methylallyl chloride is a kind of stronger halogenated hydrocarbons of activity, both
Chemical reaction generation methallyl iodide easily occurs, and the activity of methallyl iodide is much stronger than methylallyl in halogenated hydrocarbons
Chlorine, it is the strong molecule of polarizability, under the influence of external condition, molecule easily changes shape, with the needs of adaptive response, so
It is anti-that methallyl iodide does not need the presence can of catalyst that etherificate directly occurs with catechol during etherification reaction
O-methyl allyloxyphenol should be generated, and KI can be reverted to after etherification reaction, again the catalyst as etherification reaction
Use.Recycling for catalyst can be realized according to the above method, enterprise's production cost can be substantially reduced, realize industrial metaplasia
Production.
In the examples below, conversion ratio (%), selectivity (%), yield (%) and the KI rate of recovery (%) are fixed as follows
Justice：
Conversion ratio (%)=100 × [(molal quantity of the catechol of supply)-(mole of unreacted catechol)]/
(molal quantity of the catechol of supply)
Selectivity (%)=100 × (molal quantity of the catechol of generation o-methyl allyloxyphenol consumption)/[(supply
The molal quantity for the catechol given)-(molal quantity of unreacted catechol)]
Yield (%)=100 × (molal quantity of the catechol of generation o-methyl allyloxyphenol consumption)/(supply
The molal quantity of catechol)
The KI rate of recovery (%)=100 × (the KI molal quantity with methylallyl chloride reaction)/(iodate in salt slag
The molal quantity of potassium)
Etherification reaction (embodiment 1-8)
Embodiment 1
One equipped with stirring, thermometer, condenser glass reaction kettles of the 1500mL with magnetic agitation in, at 600 grams
Catechol 110 grams (1mol), KI 13.3 grams (0.08mol) and carbonic acid are added in (6mol) hexone solvent
Sodium 53 grams (0.5mol), after stirring is warming up to 98 DEG C, starts that methylallyl chloride 90.5 grams (1mol) is added dropwise, be added dropwise in 90min
Finish, react 9 hours, cooling, reaction finishes.
Product is poured into suction funnel after cooling, producing negative pressure by vavuum pump draws fluid into bottle,suction, solid
Salt slag is remained in funnel, and solid salt cinder ladle includes sodium chloride, potassium chloride and KI, is then cleaned with hexone solid
Body salt slag, liquid are pumped into bottle,suction by vacuum again, weigh up the weight of mother liquor in bottle,suction, analysis catechol, adjacent first generation
The content of allyloxy phenol, reservation of being weighed after solid salt slag is dried, in case catalyst recovery uses.
Through efficient liquid phase chromatographic analysis, the conversion ratio of catechol is 92.71%, and the selectivity of catechol is
93.07%, the yield of o-methyl allyloxyphenol is 86.29%.
In addition to reaction condition is changed as shown in table 1, other are all carried out with the same mode of embodiment 1
React and be measured, obtain embodiment 2-8.Embodiment 2-8 reaction condition and result is as Table 1 and Table 2 below.
Table 1
Table 2
KI reclaims (embodiment 9-15)
Embodiment 9
One equipped with stirring, thermometer, condenser glass reactors of the 500mL with magnetic agitation in, add and treat back
23.24 grams (0.14mol) containing KI in the solid salt slag of receipts, wherein solid salt slag, while add methylallyl chloride 90.5
Gram (1mol) and water 270 grams (15mol), stirring are warming up to 51 DEG C, after reaction 8 hours, by obtained solution be separated into oil reservoir and
Water layer, layer where methallyl iodide is oil reservoir, measures the content of the KI in water layer, and the rate of recovery of KI is calculated
For 95.28%；
In addition to reaction condition is changed as shown in table 3, other are all carried out with the same mode of embodiment 9
React and be measured.Reaction condition 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 |
| KI (mol) | 0.14 | 0.2 | 0.3 | 0.4 |
| Reaction temperature (DEG C) | 51 | 60 | 70 | 80 |
| Reaction time (hour) | 8 | 7 | 6 | 5 |
| The KI rate of recovery (%) | 95.28 | 97.30 | 97.57 | 94.79 |
Using water as solvent, one cycle, secondary cycle and the experiment condition circulated three times and experimental result detailed in Example
13-15。
Embodiment 13
Embodiment 11 is reclaimed to the water solution cycle containing KI after KI to use, it is 1.21 to measure KI in water
Gram (0.007mol), adds methylallyl chloride 3.7 grams (0.04mol) and water 16.5 grams (0.92mol), and stirring is warming up to 55 DEG C
Afterwards, after reacting 5 hours, obtained solution is separated into oil reservoir and water layer, layer where methallyl iodide is oil reservoir, measures water layer
In KI content, the rate of recovery of KI is calculated.
By one cycle, KI overall recovery is 98.22%.
Embodiment 14
First set reaction：Stirring, thermometer, glass reactors of the 500mL with magnetic agitation of condenser are housed at one
In, solid salt slag to be recycled is added, KI 12 grams (0.072mol) is contained in solid salt slag while adds methylallyl chloride
37 grams (0.40mol) and water 160 grams (8.9mol), after stirring is warming up to 55 DEG C, after reacting 5 hours, obtained solution is separated
Into oil reservoir and water layer, layer where methallyl iodide is oil reservoir, measures the content of the KI in water layer, KI is calculated
The rate of recovery be 91.12%；
One cycle：Lower batch of solid salt slag is dissolved in the aqueous solution after first set reaction recovery KI, measures water
KI is 13.1 grams (0.079mol), adds methylallyl chloride 39 grams (0.43mol) in solution, and stirring is warming up to 55
DEG C, after reacting 5 hours, obtained solution is separated into oil reservoir and water layer, layer where methallyl iodide is oil reservoir, measures water layer
In KI content, be calculated KI the rate of recovery be 90.17%；
Secondary cycle：One cycle is reclaimed to the water solution cycle containing KI after KI to use, measures the aqueous solution
Middle KI is 1.29 grams (0.008mol), adds methylallyl chloride 3.9 grams (0.043mol), and stirring is warming up to 55 DEG C,
After reaction 5 hours, obtained solution is separated into oil reservoir and water layer, layer where methallyl iodide is oil reservoir, is measured in water layer
KI content, be calculated KI the rate of recovery be 90.23%.
By secondary cycle, KI overall recovery is 99.00%.
Embodiment 15
First set reaction：Stirring, thermometer, glass reactors of the 500mL with magnetic agitation of condenser are housed at one
In, add solid salt slag to be recycled, 12 grams (0.072mol) containing KI in solid salt slag, while add methylallyl chloride
37 grams (0.04mol) and water 160 grams (8.9mol), after stirring is warming up to 55 DEG C, after reacting 5 hours, obtained solution is separated
Into oil reservoir and water layer, layer where methallyl iodide is oil reservoir, measures the content of the KI in water layer, KI is calculated
The rate of recovery be 90.76%；
One cycle：The aqueous solution (containing 1.1 grams of KI) after recovery KI is circulated for next group solid salt slag
The dissolving of (containing 12 grams of KI), measure KI in the aqueous solution and be 13.1 grams (0.079mol), add methylallyl chloride
39 grams (0.43mol), stirring are warming up to 55 DEG C, after reacting 5 hours, obtained solution are separated into oil reservoir and water layer, first is for alkene
Layer where propyl iodide is oil reservoir, measures the content of the KI in water layer, and the rate of recovery that KI is calculated is 90.25%；
Secondary cycle：The aqueous solution (containing 1.28 grams of KI) after one cycle recovery KI is circulated again under being used for
The dissolving of a collection of solid salt slag (containing 12 grams of KI), measure KI in the aqueous solution and be 13.28 grams (0.08mol), add
Methylallyl chloride 39 grams (0.43mol), stirring are warming up to 55 DEG C, after reaction 5 hours, by obtained solution be separated into oil reservoir and
Water layer, layer where methallyl iodide is oil reservoir, measures the content of the KI in water layer, and the rate of recovery of KI is calculated
For 91.33%.
Circulate three times：Secondary cycle is reclaimed to the aqueous solution (containing 1.15 grams of KI) containing KI after KI to circulate
Use, measure KI in the aqueous solution and be 1.15 grams (0.007mol), add methylallyl chloride 3.6 grams (0.04mol), stir
Mix and be warming up to 55 DEG C, after reacting 5 hours, obtained solution is separated into oil reservoir and water layer, layer where methallyl iodide is oil
Layer, the content of the KI in water layer is measured, the rate of recovery of KI is calculated.By circulating three times, the recovery of KI
Rate is 99.33%.
Therefore, using water as solvent, methylallyl chloride reaction is added, the total recovery that can make KI is circulated using 2~3 times
Rate reaches more than 99.00%.
Etherification reaction is carried out using the catalyst of recovery
Embodiment 16
One equipped with stirring, thermometer, condenser glass reaction kettles of the 500mL with magnetic agitation in, reaction it is molten
Catechol 110 grams (1mol) and sodium carbonate 63.6 grams (0.6mol) are added in 800 grams of agent hexone (8mol),
After stirring is warming up to 98 DEG C, start that Halocarbon blends are added dropwise, the Halocarbon blends are 90.5 grams of methylallyl chloride
(1mol) and recovery gained methallyl iodide 18.2 grams (0.1mol) mixture, it is added dropwise in 90min, reaction 10 is small
When, cooling, reaction finishes.Methallyl iodide is re-converted into KI, can be recycled again as catalyst.
Product is poured into suction funnel after cooling, producing negative pressure by vavuum pump draws fluid into bottle,suction, solid
Salt slag is remained in funnel, and solid salt cinder ladle includes sodium chloride, potassium chloride and KI.Then cleaned with hexone solid
Body salt slag, liquid are pumped into bottle,suction by vacuum again.The weight of mother liquor in bottle,suction is weighed up, analysis catechol, adjacent first are for alkene
The content of propoxyl group phenol, reservation of being weighed after solid salt slag is dried, in case catalyst recovery uses.
Through efficient liquid phase chromatographic analysis, the conversion ratio of catechol is 91.12%, and the selectivity of catechol is
95.2%, the yield of o-methyl allyloxyphenol is 86.75%.
The preparation method that the present invention provides o-methyl allyloxyphenol has the advantages that：
First, the present invention prepares o-methyl allyloxyphenol using Catalytic processes, using methyl iso-butyl ketone (MIBK) as solvent, works as neighbour
Reaction terminates when the conversion ratio of benzenediol is 94% or so, and selectivity can be stablized between 90~96% in the later stage of reaction, receives
Rate it is best can reach more than 90%, unreacted catechol can continue recovery and use in reaction system, be not added with urging with existing
The technique of agent is compared, and adds the cost of material of catalyst, but the present invention realizes its recovery by circulation and stress KI
Utilize, the present invention have high selectivity and in high yield the advantages of.
2nd, the reaction product cooled and filtered of the invention by etherification reaction, using water as solvent recovery catalyst, passes through 2~3
The high-recovery of catalyst can be achieved in secondary circulation, and catalyst is converted into methallyl iodide, and catalyst recovery yield can reach 97%
More than, compared with using the technical scheme of organic solvent recovery catalyst, Separation of Organic and methallyl iodide can be reduced
Separation costs, while with water be the method for most simple economy as catalyst, be more easy to realize industrialized production.
3rd, reaction product filtering is added water dissolving by the present invention first when reclaiming catalyst alkaline metal iodide, if
Do not filter and dissolving salt is directly added in reaction solution, because having the catechol of part and unreacted soluble in water can be also not easy to
The recovery of catechol, additionally since the o-methyl allyloxyphenol of generation can also avoid required to the preparation of benzofuranol
Other impurities are introduced directly into subsequent reactions.Filtering technique is simply easy to operation simultaneously, if also very small amount is not in reaction solution
The methallyl iodide of reaction can also realize its recovery in industrial subsequent technique by the recovery of reaction dissolvent.
4th, as reactant etherification reaction is occurred into for catalyst recovery product methallyl iodide and prepares adjacent methallyl oxygen
Base phenol, the activity of methallyl iodide is the strong molecule of polarizability, outside much stronger than methylallyl chloride in halogenated hydrocarbons
Under the influence of boundary's condition, molecule easily changes shape, with the needs of adaptive response, so methallyl iodide is in etherification reaction process
In do not need catalyst presence can directly with catechol occur etherification reaction, the selectivity of the etherification reaction can be steady
94% or so is scheduled on, catechol conversion ratio is more than 90%, and the yield of o-methyl allyloxyphenol is more than 85%.
5th, the present invention using alkaline metal iodide as catalyst, after etherification reaction, then using water be solvent using round-robin method recovery
Catalyst, and the catalyst of recovery is prepared into o-methyl allyloxyphenol as reactant, the technique do not introduce it is new anti-
In the case of answering material, recycling for alkaline metal iodide catalyst can be realized, is substantially reducing the same of enterprise's production cost
When, due to not needing special consersion unit, substantially increase commercial viability.
The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the invention, for the skill of this area
For art personnel, the present invention can have various modifications and variations.Within the spirit and principles of the invention, that is made any repaiies
Change, equivalent substitution, improvement etc., should be included in the scope of the protection.
Claims (5)
- A kind of 1. preparation method of o-methyl allyloxyphenol, it is characterised in that including：Step 1: using catechol, methylallyl chloride as raw material, in specific solvent, acid binding agent, catalyst and appropriate reaction Under the conditions of prepare o-methyl allyloxyphenol；Wherein, the solvent is hexone, and the acid binding agent is alkali carbonate or alkali metal hydrogencarbonate, institute The mixture of any one of catalyst for sodium iodide, in KI or both is stated, reaction temperature is 98~108 DEG C, during reaction Between be 7~13 hours；Step 2: the recovery of catalyst：By the product cooled and filtered of step 1, solid salt slag is obtained, wherein in solid salt slag The catalyst added containing step 1, is then dissolved in water, adds methylallyl chloride and reacted, will reaction after the completion of reaction Solution is separated into the oil reservoir containing methallyl iodide and the water layer containing unreacted KI, then using excessive methylallyl chloride as Reactant, add water as solvent, using KI unrecovered in 2~3 circulation and stress water layers.
- 2. the preparation method of o-methyl allyloxyphenol according to claim 1, it is characterised in that in the step 1 In, the mol ratio of the catechol and the methylallyl chloride is 1：1.0~1.5, the catechol is tied up with described The mol ratio of sour agent is 1：0.5~0.8, the mol ratio of the catechol and the hexone is 1：8~ 12, the mol ratio of the catechol and the catalyst is 1：0.12~0.30.
- 3. the preparation method of o-methyl allyloxyphenol according to claim 1, it is characterised in that in the step 2 In, the mol ratio of the methylallyl chloride and water is 1：15~40, the methylallyl chloride rubs with the catalyst Your proportioning is 2.5~7.2：1.
- 4. the preparation method of o-methyl allyloxyphenol according to claim 1, it is characterised in that in the step 2 In, reaction temperature is 51 DEG C~80 DEG C, and the reaction time is 5~8 hours.
- 5. the preparation method of o-methyl allyloxyphenol according to claim 1, it is characterised in that also include：Step 3: the methallyl iodide of recycling step 2 recovery, carries out etherification reaction and prepares adjacent methallyl epoxide benzene Phenol.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4465876A (en) * | 1983-02-07 | 1984-08-14 | Air Products And Chemicals, Inc. | Nitration of aromatics with nitrogen oxides in trifluoroacetic acid |
| US4465868A (en) * | 1981-07-17 | 1984-08-14 | Otsuka Kagaku Yakuhin Kabushiki Kaisha | Process for preparing o-methallyloxyphenol |
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| AN IMPROVED SYNTHESIS OF 2-METHALLYLOXYPHENOL;V. B. Deodhar等;《OPPI BRIEFS》;19931231;第25卷(第5期);第583-585页 * |
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