CN106008174A - Preparation method of 4,4'-dialkoxy methyl diphenyl ether - Google Patents
Preparation method of 4,4'-dialkoxy methyl diphenyl ether Download PDFInfo
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- CN106008174A CN106008174A CN201610349492.4A CN201610349492A CN106008174A CN 106008174 A CN106008174 A CN 106008174A CN 201610349492 A CN201610349492 A CN 201610349492A CN 106008174 A CN106008174 A CN 106008174A
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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
- C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
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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
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/22—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of halogens; by substitution of halogen atoms by other halogen atoms
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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
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/40—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation
- C07C41/42—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation by distillation
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Abstract
The invention provides a preparation method of 4,4'-dialkoxy methyl diphenyl ether. The method comprises the following steps: conducting a bromination reaction of bromine, 4,4'-dimethyl diphenyl ether and an initiator in an organic solvent to obtain a brominated product; cooling the brominated product with sodium alcoholate to obtain an etherification reaction system; and heating the etherification reaction system for an etherification reaction to obtain the 4,4'-dialkoxy methyl diphenyl ether. Compared with the prior art, the preparation method provided by the invention can greatly increase the product purity on the premise of guaranteeing the yield. The result of the embodiment of the invention indicates that the yield of 4,4'-dialkoxy methyl diphenyl ether prepared by the method is over 50%, and the product purity is higher than 99.5%.
Description
Technical field
The present invention relates to technical field of organic synthesis, particularly relate to a kind of 4,4 '-dialkoxymethyl diphenyl ether
Preparation method.
Background technology
4,4 '-dialkoxymethyl diphenyl ether is that a class produces high-performance poly diphenyl ether and derivant compound inslation thereof
Material, diazo photographic material, foundry goods binding agent, veneer bonding agent, radiosensitive recording materials, high speed water
Property print the important monomer of the NEW TYPE OF COMPOSITE macromolecular materials such as emulsion, its function admirable, of many uses, industrial
Using value has a high potential.Such as by 4,4 '-dialkoxymethyl diphenyl ether monomer and various aromatic compounds
Fourier catalyst leave through polycondensation, cross-link, solidify and prepare polydiphenyl ether resin, have high temperature resistant,
The premium properties such as corrosion-resistant, electrical insulating property good, cohesive force is strong, is that a kind of novel high temperature resistant (H level) is exhausted
Edge material.4,4 '-dialkoxymethyl diphenyl ether monomer and aromatic diazo compound obtain through polycondensation for another example
High-performance diazonium photosensitive resin, can be used for making imaging plate, printing PS plate and producing positivity or negative photo
Glue.
Disclosing more preparation 4 in prior art, the method for 4 '-dialkoxymethyl diphenyl ether, such as Publication No.
The United States Patent (USP) of US 4413149 discloses the preparation method of a kind of 4,4 '-dialkoxymethyl diphenyl ether: with
4,4 '-dimethyl diphenyl ether is raw material, first passes through electrochemistry alkoxylate and prepares 4,4 '-diphenyl ether dicarbaldehyde dialkyl group
Acetal, then prepare 4 through the catalytic hydrogenolysis of cobalt carbonyl catalyst, 4 '-dialkoxymethyl diphenyl ether.Though
So nitrogen-containing heterocycle compound (such as pyridine, pyrroles, ketopyrrolidine, piperidines etc.) is joined carbonyl by this patent
In Co catalysts, significantly improve the selectivity of catalytic hydrogenolysis, make the yield of catalytic hydrogenolysis bring up to 85%,
But prepared by the method 4, the purity of 4 '-dialkoxymethyl diphenyl ether is inadequate, only up to reach
Reach 95%.
Summary of the invention
In view of this, it is an object of the invention to provide a kind of 4, the preparation side of 4 '-dialkoxymethyl diphenyl ether
Method, improves 4, the purity of 4 '-dialkoxymethyl diphenyl ether.
In order to realize foregoing invention purpose, the present invention provides techniques below scheme:
The invention provides one 4, the preparation method of 4 '-dialkoxymethyl diphenyl ether, comprise the following steps:
By bromine, 4,4 '-dimethyl diphenyl ether and initiator carry out bromo-reaction in organic solvent, obtain bromo
Product；
Mix with sodium alkoxide after described bromination product is cooled down, obtain etherification reaction system；
Described etherification reaction system is heated up, carries out etherification reaction, obtain 4,4 '-dialkoxymethyl diphenyl ether.
Preferably, the one during described organic solvent is carbon tetrachloride, hexamethylene, normal hexane, benzene and chlorobenzene
Or it is several；
The mass ratio of described organic solvent and 4,4 '-dimethyl diphenyl ether is (1.5～4.5): 1.
Preferably, described initiator is peroxide type initiators and/or azo-initiator；
The mol ratio of described initiator and 4,4 '-dimethyl diphenyl ether is (0.01～0.1): 1.
Preferably, described peroxide type initiators be di-tert-butyl peroxide, tert-butyl hydroperoxide,
One or more in dibenzoyl peroxide and dicumyl peroxide.
Preferably, described azo-initiator is azodiisobutyronitrile and/or AMBN.
Preferably, described bromine and 4, the mol ratio of 4 '-dimethyl diphenyl ether is (2～3): 1.
Preferably, one or more during described sodium alkoxide is Feldalat NM, Sodium ethylate and sodium propoxide；
The mol ratio of described sodium alkoxide and 4,4 '-dimethyl diphenyl ether is (2.25～3.5): 1.
Preferably, the reaction temperature of described bromo-reaction is 70～90 DEG C；
The response time of described bromo-reaction is 1～3h.
Preferably, the temperature of described cooling is 40～50 DEG C.
Preferably, the temperature of described etherification reaction is 70～90 DEG C；
The time of described etherification reaction is 1～3h.
The invention provides one 4, the preparation method of 4 '-dialkoxymethyl diphenyl ether, comprise the following steps:
By bromine, 4,4 '-dimethyl diphenyl ether and initiator carry out bromo-reaction in organic solvent, obtain bromination product；
Mix with sodium alkoxide after described bromination product is cooled down, obtain etherification reaction system；By described etherification reaction system
Heat up, carry out etherification reaction, obtain 4,4 '-dialkoxymethyl diphenyl ether.The present invention is because have employed selection bromine
Generation and rectification and purification so that products obtained therefrom purity of the present invention is high.Compared with prior art, the present invention provides
Preparation method can be greatly improved the purity of product on the premise of ensureing productivity.The result of the embodiment of the present invention
Showing, the method that the application provides prepares 4, and the productivity of 4 '-dialkoxymethyl diphenyl ether is all higher than 50%, produces
Thing purity is above 99.5%.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of 4,4 '-dimethoxy-methyl diphenyl ether that the embodiment of the present invention 1 obtains；
Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of 4,4 '-dimethoxy-methyl diphenyl ether that the embodiment of the present invention 1 obtains；
Fig. 3 is the carbon-13 nmr spectra figure of 4,4 '-dimethoxy-methyl diphenyl ether that the embodiment of the present invention 1 obtains；
Fig. 4 is the infrared spectrogram of 4,4 '-diethoxymethyl diphenyl ether that the embodiment of the present invention 9 obtains；
Fig. 5 is the hydrogen nuclear magnetic resonance spectrogram of 4,4 '-diethoxymethyl diphenyl ether that the embodiment of the present invention 9 obtains；
Fig. 6 is the carbon-13 nmr spectra figure of 4,4 '-diethoxymethyl diphenyl ether that the embodiment of the present invention 9 obtains；
Fig. 7 is the infrared spectrogram of 4,4 '-diisopropoxy methyl diphenyl ether that the embodiment of the present invention 10 obtains；
Fig. 8 is the proton nmr spectra of 4,4 '-diisopropoxy methyl diphenyl ether that the embodiment of the present invention 10 obtains
Figure；
Fig. 9 is the carbon-13 nmr spectra of 4,4 '-diisopropoxy methyl diphenyl ether that the embodiment of the present invention 10 obtains
Figure.
Detailed description of the invention
The invention provides one 4, the preparation method of 4 '-dialkoxymethyl diphenyl ether, comprise the following steps:
By bromine, 4,4 '-dimethyl diphenyl ether and initiator carry out bromo-reaction in organic solvent, obtain bromo
Product；
Mix with sodium alkoxide after described bromination product is cooled down, obtain etherification reaction system；
Described etherification reaction system is heated up, carries out etherification reaction, obtain 4,4 '-dialkoxymethyl diphenyl ether.
The present invention by bromine, 4,4 '-dimethyl diphenyl ether and initiator carry out bromo-reaction in organic solvent,
To bromination product.Described bromine, 4,4 '-dimethyl diphenyl ether, initiator and organic solvent are being reacted by the present invention
Front material order by merging does not has special restriction, uses the anti-of organic system well known to those skilled in the art
Answer charging sequence.4,4 '-dimethyl diphenyl ether, initiator and organic solvent are the most first mixed by the present invention,
Obtain mixed organic solvents system；Bromine is joined to carry out bromo in described mixed organic solvents system anti-again
Should.The present invention is to 4,4 '-dimethyl diphenyl ether, initiator and organic solvent in described mixed organic solvents system
Charging sequence there is no any particular restriction, three can mix with random order.
In the present invention, described bromo-reaction is the most under reflux conditions carried out, and the present invention is to described backflow
Detailed description of the invention does not has particular/special requirement, uses reflux operation well-known to those skilled in the art to carry out.
The present invention is to described 4, and the source of 4 '-dimethyl diphenyl ether is not particularly limited, and uses people in the art
Known to Yuan 4,4 '-dimethyl diphenyl ether, concrete can be the commercially available product of 4,4 '-dimethyl diphenyl ether
Product.
In the present invention, described organic solvent is preferably carbon tetrachloride, hexamethylene, normal hexane, benzene and chlorobenzene
In one, two kinds, three kinds, four kinds or five kinds.In the present invention, described organic solvent and 4,4 '-diformazan
The mass ratio of yl diphenyl ether is preferably (1.5～4.5): 1, more preferably (2～4): 1, most preferably (2.5～3.5): 1.
In the present invention, described initiator is preferably peroxide type initiators and/or azo-initiator.Enter
One step ground, in the present invention, described peroxide type initiators is preferably di-tert-butyl peroxide, tertiary fourth
One in base hydrogen peroxide, dibenzoyl peroxide and dicumyl peroxide, two kinds, three kinds or
Four kinds；Described azo-initiator is preferably azodiisobutyronitrile and/or AMBN.
In the present invention, described initiator and 4, the mol ratio of 4 '-dimethyl diphenyl ether is preferably (0.01～0.1): 1,
More preferably (0.02～0.9): 1, most preferably (0.03～0.07): 1.
The source of described bromine is not particularly limited by the present invention, uses bromine well-known to those skilled in the art
Element, concrete can be the commercially available prod of bromine.In the present invention, described bromine and 4,4 '-dimethyl
The mol ratio of diphenyl ether is preferably (2～3): 1, more preferably (2.1～2.6): 1, most preferably (2.2～2.4): 1.?
In the present invention, the bromine that described bromo process is added can successfully replace 4, on 4 '-dimethyl diphenyl ether methyl
Hydrogen atom, generate 4,4 '-dibromo methyl diphenyl ether.
The feed postition of described bromine is not particularly limited by the present invention, uses well known to those skilled in the art
Add chemical raw material mode be added.The present invention preferably selects the mode of dropping and adds bromine,
The speed of described dropping is not particularly limited by the present invention.In the present invention, the time of described dropping bromine is excellent
Choosing less than 2h, more preferably less than 1.8h, most preferably less than 1.5h.
In the present invention, the reaction temperature of described bromo-reaction is preferably 70～90 DEG C, more preferably 75～85 DEG C,
Most preferably 79 DEG C.In the present invention, the response time of described bromo-reaction is preferably 1～3h, and concrete can
Think 1h, 1.5h, 2h, 2.5h or 3h.
The present invention does not has particular/special requirement to the control mode of the reaction temperature of described bromo-reaction, uses this area
The temperature control mode of the organic reaction known to technical staff is carried out.In the present invention, described bromo-reaction
The control of reaction temperature preferably carry out under water bath condition.
After completing described bromo-reaction, the present invention mixes with sodium alkoxide after being cooled down by described bromination product, obtains ether
Change reaction system.The present invention before described bromination product is mixed with sodium alkoxide preferably by described bromination product
Solvent removes.The present invention does not has special restriction to the method for described removing solvent, uses people in the art
The technical scheme removing solvent known to Yuan, as in an embodiment of the present invention, to described bromo-reaction
The bromination product obtained carries out distillation process, steams solvent therein.The tool that described distillation is processed by the present invention
Body mode is not particularly limited, and uses the operation of distillation agent well-known to those skilled in the art, specifically
Can be air-distillation.In the present invention, the solvent distilled out described in can directly recycle.
After obtaining bromination product, described bromination product is cooled down by the present invention.In the present invention, described cold
But temperature is preferably 40～50 DEG C, more preferably 42～48 DEG C, most preferably 44～46 DEG C.The present invention is to institute
The control mode stating cooling does not has particular/special requirement, uses the temperature of organic reaction well-known to those skilled in the art
Prosecutor formula is carried out.In the present invention, described cooling is preferably carried out under water bath condition.
After described cooling, the bromination product after described cooling is mixed by the present invention with sodium alkoxide, obtains etherification reaction
System.
Sodium alkoxide is preferably added in the bromination product after described cooling by the present invention, obtains etherification reaction system.This
Invent the feed postition to described sodium alkoxide to be not particularly limited, use interpolation well-known to those skilled in the art
The mode of chemical raw material is added.The present invention preferably selects the mode of dropping and adds sodium alkoxide, the present invention
The speed of described dropping is not particularly limited.In the present invention, the time of described dropping is preferably less than 1h,
More preferably less than 0.8h, most preferably less than 0.5h.
In the present invention, one during described sodium alkoxide is preferably Feldalat NM, Sodium ethylate and sodium propoxide, two kinds or
Three kinds, more preferably the one in Feldalat NM, Sodium ethylate and sodium isopropylate, two or three.Concrete,
The present invention prepare 4,4 '-dialkoxymethyl diphenyl ether is respectively 4,4 '-dimethoxy-methyl diphenyl ether,
4,4 '-diethoxymethyl diphenyl ether and 4,4 '-diisopropoxy methyl diphenyl ether, corresponding described 4,4 '-two
Alkoxyl in alkoxy methyl diphenyl ether is respectively methoxyl group, ethyoxyl and isopropoxy.
In the present invention, described sodium alkoxide and 4, the mol ratio of 4 '-dimethyl diphenyl ether is preferably (2.25～3.5): 1,
More preferably (2.5～3.25): 1, most preferably (2.6～3): 1.
The present invention preferably using alcohol sodium solution as reaction raw materials, mixes with the bromination product after described cooling,
To etherification reaction system.In the present invention, described alcohol sodium solution is preferably sodium methoxide solution, alcohol sodium solution
With the one in sodium isopropylate solution, two or three.In the present invention, the solvent in described alcohol sodium solution
Be preferably the one in alcohols solvent, more preferably methanol, ethanol and isopropanol, two or three.This
Bright preferably sodium alkoxide is dissolved in the alcohol compound identical with its alkyl, such as methanol solution, the ethanol of Feldalat NM
The ethanol solution of sodium, the aqueous isopropanol of sodium isopropylate.In the present invention, the quality of described alcohol sodium solution is dense
Degree preferably 10～40%, more preferably 15～35%, most preferably 20～30%.
Described etherification reaction system is heated up, carries out etherification reaction, obtain 4,4 '-dialkoxymethyl diphenyl ether.
In the present invention, the temperature of described etherification reaction is preferably 70～90 DEG C, more preferably 75～85 DEG C, most preferably
It it is 78～82 DEG C.The heating rate of described intensification is not particularly limited by the present invention, uses those skilled in the art
The known warming temperature during organic reaction is carried out.The present invention reaction to described etherification reaction
The control mode of temperature does not has particular/special requirement, uses the temperature control of organic reaction well-known to those skilled in the art
Mode is carried out.In the present invention, the control of the reaction temperature of described etherification reaction is preferably in water bath condition
Under carry out.
In the present invention, the time of described etherification reaction is preferably 1～3h, concrete can be 1h, 1.5h, 2h,
2.5h or 3h.In the present invention, described etherification reaction is the most under reflux conditions carried out, and the present invention is to described
The detailed description of the invention of etherification reaction does not has particular/special requirement, uses backflow behaviour well-known to those skilled in the art
Make to carry out.
After completing described etherification reaction, the etherification reaction solution obtained preferably is carried out post processing by the present invention,
Sterling to 4,4 '-dialkoxymethyl diphenyl ether.In the present invention, described post processing preferably specifically include with
Lower step:
Remove the alcohol in described etherification reaction solution, obtain primary product；
Described primary product is mixed with water and carries out split-phase process, obtain oil phase；
Described oil phase is carried out successively air-distillation process and decompression distillation processes, obtain thick product；
Described thick product is carried out distillation process, obtains 4, the sterling of 4 '-dialkoxymethyl diphenyl ether.
The present invention preferably removes the alcohol in described etherification reaction solution, obtains primary product.The present invention is to described
The method removing the alcohol in described etherification reaction solution does not has special restriction, uses those skilled in the art ripe
The technical scheme removing solvent known, as in an embodiment of the present invention, is carried out described reaction solution
Distillation processes, and steams alcohol therein.Distillation described herein is same as above, no longer repeats at this.?
In the present invention, the alcohol steamed can recycle, and again prepares sodium alkoxide.
After obtaining described primary product, described primary product is preferably mixed with water and carries out split-phase process by the present invention,
Obtain oil phase.Concrete mixes described primary product with Part I water, stands split-phase.The present invention is preferred
It is stirred after described primary product is mixed with Part I water.The speed of described stirring is not had by the present invention
There is particular/special requirement, use the alr mode of chemical field well-known to those skilled in the art to be stirred.
The present invention preferably stirs 5～15 minutes, preferred stirring 8～12 minutes, most preferably stirring 10 minutes.
The present invention does not has particular/special requirement to the time of described standing, it is possible to make aqueous phase and separation of oil.
After described standing split-phase, the oil phase obtained preferably is washed twice with water by the present invention.The present invention is to described
The mode of washing does not has particular/special requirement, uses washing means well-known to those skilled in the art.At this
In invention, described twice slurry amount is preferably respectively the half of Part I water.In the present invention,
Described Part I water and twice slurry sum are total water consumption, described total water consumption and 4,4 '-diformazan
The mass ratio of yl diphenyl ether is (7～12): 1, and that concrete can be 7:1,8:1,9:1,10:1,11:1 or 12:1.
The present invention does not has particular/special requirement to the kind of described water, uses water well-known to those skilled in the art,
Concrete can be pure water, deionized water or distilled water.
After obtaining oil phase, described oil phase is preferably carried out at air-distillation process and decompression distillation by the present invention successively
Reason, obtains thick product.In the present invention, the temperature in the kettle of described air-distillation is 100～120 DEG C, gas phase temperature
Degree is 90～100 DEG C.In the present invention, the pressure that described decompression distillation processes is preferably 1～2mmHg, specifically
Can be 1mmHg, 1.5mmHg or 2mmHg；The temperature in the kettle that described decompression distillation processes is preferably
200～280 DEG C, more preferably 220～260 DEG C, most preferably 230～250 DEG C；Described decompression distillation processes
Gas phase temperature is preferably 190～240 DEG C, more preferably 200～230 DEG C, most preferably 210～220 DEG C.
After obtaining described thick product, described thick product is preferably carried out rectification process by the present invention, obtain 4,4 '-
The sterling of dialkoxymethyl diphenyl ether.The present invention does not has particular/special requirement to the concrete mode of described rectification process,
Use the rectification mode known to chemical processing skilled person.
The device that preparation and the last handling process of above-mentioned 4,4 '-dialkoxymethyl diphenyl ether are used by the present invention
Have no requirement, use the application of disclosure satisfy that well-known to those skilled in the art to operate the device of requirement
?.Concrete, due to the fact that the experiment being to carry out in laboratory, use in embodiments of the present invention
250mL is with thermometer, Dropping funnel, condenser and churned mechanically four-hole boiling flask.If by the application
Technical scheme is applied to commercial production, then apply and well-known to those skilled in the art disclosure satisfy that the application skill
The commercial plant that art requires.
The invention provides one 4, the preparation method of 4 '-dialkoxymethyl diphenyl ether, comprise the following steps:
By bromine, 4,4 '-dimethyl diphenyl ether and initiator carry out bromo-reaction in organic solvent, obtain bromination product；
Mix with sodium alkoxide after described bromination product is cooled down, obtain etherification reaction system；By described etherification reaction system
Heat up, carry out etherification reaction, obtain 4,4 '-dialkoxymethyl diphenyl ether.Compared with prior art, this
The preparation method of bright offer can be greatly improved the purity of product on the premise of ensureing productivity.The present invention implements
The result of example shows, the method that the application provides prepares 4, and the productivity of 4 '-dialkoxymethyl diphenyl ether is all higher than
50%, product purity is above 99.5%.
4,4 '-dialkoxymethyl the diphenyl ether provided the present invention below in conjunction with embodiment is carried out specifically
Bright, but they can not be interpreted as limiting the scope of the present invention.
Embodiment 1
By 4,4 '-dimethyl diphenyl ether of 20g (0.1mol), 60g carbon tetrachloride and 0.45g (0.005mol) tertiary fourth
Base hydrogen peroxide joins 250mL with thermometer, Dropping funnel, condenser and churned mechanically four mouthfuls of burnings
In Ping, by heating in water bath material, after being heated to 70 DEG C with stirring, drip 36.8g (0.23mol) bromine
Element, 1.5h drips off, and drips off rear back flow reaction 2.0h.
Reactant liquor normal pressure back flow reaction obtained steams carbon tetrachloride, subsequently material is cooled to 40 DEG C, to
Dripping 64.8g (0.3mol) mass concentration in material after cooling is 25% methanol solution of sodium methylate, and 60min drips
Complete, it is heated to reflux 2.0h, steams methanol afterwards.The carbon tetrachloride amount of steaming is 54.5g, through being washed to neutrality also
Dried carbon tetrachloride 53.5g, is 99.3% through gas chromatographic analysis purity, and the response rate is 89.2%.Return
The carbon tetrachloride reuse received.The methanol amount of steaming is 43.5g, is 94.6% through gas chromatographic analysis purity, reclaims
Rate is 84.7%.The methanol reclaimed can be used for Feldalat NM processed after rectification.
To steaming, the product of etherification reaction adds after methanol 100mL water, stand after stirring 10min and divide
Phase, oil phase washes twice with remaining 100mL water, each slurry 50mL.
Oil phase elder generation normal pressure after washing is steamed water, then decompression distillation under the pressure condition of 1～2mmHg,
Obtaining thick product 18.8g, the boiling point of this thick product is 190～200 DEG C/1～2mmHg.
The thick product obtained is carried out rectification under vacuum process, obtains the sterling of product.Through gas chromatographic analysis,
Product purity is 99.6%.Being computed, productivity is 89.2%.
The bottom temperature of rectification is 200～250 DEG C, and tower top temperature is 196～200 DEG C, and pressure is 1～2mmHg.
Gas chromatographic analysis uses VARIAN CP-3800 chromatographic.Chromatographiccondition is as follows: post
Type: DB-5；Vaporizer temperature: 250 DEG C；Temperature programming: 40 DEG C/1min → 30 DEG C/min → 250 DEG C/30
min。
The pure product that the present embodiment is also obtained by the present invention has carried out infrared and nuclear magnetic resonance, NMR sign, characterizes knot
The most as shown in Figures 1 to 3, Fig. 1 is 4 that the embodiment of the present invention 1 obtains to fruit, 4 '-dimethoxy-methyl diphenyl ether red
External spectrum figure；Fig. 2 is 4 that the embodiment of the present invention 1 obtains, the nuclear magnetic resonance, NMR of 4 '-dimethoxy-methyl diphenyl ether
Hydrogen spectrogram；Fig. 3 is 4 that the embodiment of the present invention 1 obtains, the nuclear magnetic resonance, NMR carbon of 4 '-dimethoxy-methyl diphenyl ether
Spectrogram.
In Fig. 1: 3034cm-1For (=C-H) hydrocarbon stretching vibration peak on phenyl ring；2983cm-1, 2852cm-1
For methyl (CH3-) hydrocarbon asymmetric and symmetrical stretching vibration peak；2925cm-1, 2820cm-1For methylene
(-CH2-) hydrocarbon asymmetric and symmetrical stretching vibration peak；1602cm-1, 1502cm-1Stretch for phenyl ring skeleton
Vibration peak；1239cm-1C-O-C asymmetrical stretching vibration peak for aromatic ether；1097cm-1For methyl ether
C-O-C symmetrical stretching vibration peak；832cm-1For the out-of-plane bending vibration of on phenyl ring two adjacent hydrogen, show benzene
Ring is para-orientation.
In Fig. 2:1H NMR(CDCl3, δ):
δ=3.4258 (3H, s, CH3-)×2；
δ=4.4529 (2H, s ,-CH2-)×2；
δ=7.0120～7.3436 (4H, q, Ar-) × 2.
In Fig. 3:13C NMR(CDCl3, δ):
δ1=58.04 is methyl 1#Carbon atom；
δ2=74.21 is the 2 of methylene#Carbon atom；
δ3=133.11 is 3 on the phenyl ring being connected with methylene#Carbon atom；
δ4=129.38 is 4 on phenyl ring#Carbon atom；
δ5=118.75 is 5 on phenyl ring#Carbon atom；
δ6=156.80 is 6 on phenyl ring#Carbon atom.
According to Fig. 1～3 it is recognised that the target product that the present invention obtains has 4,4 '-dimethoxy-methyl hexichol
The characteristic peak of all groups of ether normal structure, it was demonstrated that the product that the present invention obtains is 4,4 '-dimethoxy-methyl two
Phenylate.
Embodiment 2
A kind of 4, the preparation method of 4 '-dimethoxy-methyl diphenyl ether, comprise the following steps:
By 20g (0.1mol) 4,4 '-dimethyl diphenyl ether, 60g carbon tetrachloride and 0.73g (0.005mol) two uncle
Butylperoxide joins in above-mentioned four-hole boiling flask, by heating in water bath material, and heat temperature raising with stirring
Dripping 36.8g (0.23mol) bromine after 72 DEG C, 1.6h drips off, and drips off rear back flow reaction 2.0h.
Reactant liquor normal pressure back flow reaction obtained steams carbon tetrachloride, subsequently material is cooled to 41 DEG C, to
Dripping 64.8g (0.3mol) mass concentration in material after cooling is 25% methanol solution of sodium methylate, and 55min drips
Complete, it is heated to reflux 1.0h, steams methanol afterwards.The carbon tetrachloride amount of steaming is 54.7g, through being washed to neutrality also
Dried carbon tetrachloride 53.1g, is 99.3% through gas chromatographic analysis purity, and the response rate is 88.5%.First
The alcohol amount of steaming is 43.8g, is 94.2% through gas chromatographic analysis purity, and the response rate is 84.9%.
In above-mentioned material, add 100mL water, after stirring 10min, stand split-phase, the remaining washing of oil phase
Wash twice, each slurry 50mL.
Oil phase elder generation normal pressure after washing is steamed water, then decompression distillation under the pressure condition of 1～2mmHg,
Obtaining thick product 17.4g, the boiling point of this thick product is 190～200 DEG C/1～2mmHg.
After obtaining described thick product, the present invention carries out rectification under vacuum process to described thick product, is produced
The sterling of thing.Through gas chromatographic analysis, product purity is 99.6%.Being computed, productivity is 87.4%.
The bottom temperature of rectification is 200～250 DEG C, and tower top temperature is 196～200 DEG C, and pressure is 1～2mmHg.
Gas chromatographic analysis uses VARIAN CP-3800 chromatographic.Chromatographiccondition is as follows: post
Type: DB-5；Vaporizer temperature: 250 DEG C；Temperature programming: 40 DEG C/1min → 30 DEG C/min → 250 DEG C/30
min。
According to the characteristic manner in embodiment 1, the product of the present embodiment is detected, it was demonstrated that the present embodiment obtains
To product be target product.
Embodiment 3
A kind of 4, the preparation method of 4 '-dimethoxy-methyl diphenyl ether, comprise the following steps:
By 20g (0.1mol) 4,4 '-dimethyl diphenyl ether, 60g carbon tetrachloride and 1.22g (0.005mol) hexichol
Formyl peroxide joins in above-mentioned four-hole boiling flask, by heating in water bath material, and heat temperature raising with stirring
Dripping 36.8g (0.23mol) bromine after 74 DEG C, 1.7h drips off, and drips off rear back flow reaction 2.0h.
Reactant liquor normal pressure back flow reaction obtained steams carbon tetrachloride, subsequently material is cooled to 42 DEG C, to
Dripping 64.8g (0.3mol) mass concentration in material after cooling is 25% methanol solution of sodium methylate, and 50min drips
Complete, it is heated to reflux 3.0h, steams methanol afterwards.The carbon tetrachloride amount of steaming is 53.4g, through being washed to neutrality also
Dried carbon tetrachloride 52.5g, is 99.6% through gas chromatographic analysis purity, and the response rate is 87.2%.First
The alcohol amount of steaming is 44.5g, is 94.9% through gas chromatographic analysis purity, and the response rate is 86.9%.
In above-mentioned material, add 100mL water, after stirring 10min, stand split-phase, the remaining washing of oil phase
Wash twice, each slurry 50mL.
Oil phase elder generation normal pressure after washing is steamed water, then decompression distillation under the pressure condition of 1～2mmHg,
Obtaining thick product 17.9g, the boiling point of this thick product is 190～200 DEG C/1～2mmHg.
After obtaining described thick product, the present invention carries out distillation process of reducing pressure to described thick product, is produced
The sterling of thing.Through gas chromatographic analysis, product purity is 99.7%.Being computed, productivity is 87.7%.
The bottom temperature of rectification is 200～250 DEG C, and tower top temperature is 196～200 DEG C, and pressure is 1～2mmHg.
Gas chromatographic analysis uses VARIAN CP-3800 chromatographic.Chromatographiccondition is as follows: post
Type: DB-5；Vaporizer temperature: 250 DEG C；Temperature programming: 40 DEG C/1min → 30 DEG C/min → 250 DEG C/30
min。
According to the characteristic manner in embodiment 1, the product of the present embodiment is detected, it was demonstrated that the present embodiment obtains
To product be target product.
Embodiment 4
A kind of 4, the preparation method of 4 '-dimethoxy-methyl diphenyl ether, comprise the following steps:
By 20g (0.1mol) 4,4 '-dimethyl diphenyl ether, 60g carbon tetrachloride and 0.82g (0.005mol) azo
Isopropyl cyanide joins in above-mentioned four-hole boiling flask, by heating in water bath material, is heated to 76 DEG C with stirring
Rear dropping 36.8g (0.23mol) bromine, 1.8h drips off, and drips off rear back flow reaction 1.0h.
Reactant liquor normal pressure back flow reaction obtained steams carbon tetrachloride, subsequently material is cooled to 43 DEG C, to
Dripping 64.8g (0.3mol) mass concentration in material after cooling is 25% methanol solution of sodium methylate, and 45min drips
Complete, it is heated to reflux 2.0h, steams methanol afterwards.The carbon tetrachloride amount of steaming is 54.9g, through being washed to neutrality also
Dried carbon tetrachloride 54.4g, is 99.2% through gas chromatographic analysis purity, and the response rate is 89.9%.First
The alcohol amount of steaming is 44.1g, is 95.3% through gas chromatographic analysis purity, and the response rate is 86.5%.
In above-mentioned material, add 100mL water, after stirring 10min, stand split-phase, the remaining washing of oil phase
Wash twice, each slurry 50mL.
Oil phase elder generation normal pressure after washing is steamed water, then decompression distillation under the pressure condition of 1～2mmHg,
Obtaining thick product 18.7g, the boiling point of this thick product is 190～200 DEG C/1～2mmHg.
After obtaining described thick product, the present invention carries out rectification under vacuum process to described thick product, is produced
The sterling of thing.Through gas chromatographic analysis, product purity is 99.8%.Being computed, productivity is 89.3%.
The bottom temperature of rectification is 200～250 DEG C, and tower top temperature is 196～200 DEG C, and pressure is 1～2mmHg.
Gas chromatographic analysis uses VARIAN CP-3800 chromatographic.Chromatographiccondition is as follows: post
Type: DB-5；Vaporizer temperature: 250 DEG C；Temperature programming: 40 DEG C/1min → 30 DEG C/min → 250 DEG C/30
min。
According to the characteristic manner in embodiment 1, the product of the present embodiment is detected, it was demonstrated that the present embodiment obtains
To product be target product.
Embodiment 5
A kind of 4, the preparation method of 4 '-dimethoxy-methyl diphenyl ether, comprise the following steps:
By 20g (0.1mol) 4,4 '-dimethyl diphenyl ether, 30g hexamethylene and 0.82g (0.005mol) azo are different
Butyronitrile joins in above-mentioned four-hole boiling flask, by heating in water bath material, after being heated to 78 DEG C with stirring
Dropping 36.8g (0.23mol) bromine, 1.9h drips off, and drips off rear back flow reaction 1.0h.
Reactant liquor normal pressure back flow reaction obtained steams hexamethylene, subsequently material is cooled to 44 DEG C, Xiang Leng
But dripping 64.8g (0.3mol) mass concentration in the material after is 25% methanol solution of sodium methylate, and 40min drips off,
It is heated to reflux 1.0h, steams methanol afterwards.The hexamethylene amount of steaming is 26.5g, through being washed to neutrality dried
Obtaining hexamethylene 26.2g, be 99.4% through gas chromatographic analysis purity, the response rate is 87.3%.The hexamethylene reclaimed
Alkane reuse.The methanol amount of steaming is 44.4g, is 94.5% through gas chromatographic analysis purity, and the response rate is 86.3%.
In above-mentioned material, add 100mL water, after stirring 10min, stand split-phase, the remaining washing of oil phase
Wash twice, each slurry 50mL.
Oil phase elder generation normal pressure after washing is steamed water, then decompression distillation under the pressure condition of 1～2mmHg,
Obtaining thick product 18.9g, the boiling point of this thick product is 190～200 DEG C/1～2mmHg.
After obtaining described thick product, the present invention carries out rectification under vacuum process to described thick product, is produced
The sterling of thing.Through gas chromatographic analysis, product purity is 99.5%.Being computed, productivity is 90.4%.
The bottom temperature of rectification is 200～250 DEG C, and tower top temperature is 196～200 DEG C, and pressure is 1～2mmHg.
Gas chromatographic analysis uses VARIAN CP-3800 chromatographic.Chromatographiccondition is as follows: post
Type: DB-5；Vaporizer temperature: 250 DEG C；Temperature programming: 40 DEG C/1min → 30 DEG C/min → 250 DEG C/30
min。
According to the characteristic manner in embodiment 1, the product of the present embodiment is detected, it was demonstrated that the present embodiment obtains
To product be target product.
Embodiment 6
A kind of 4, the preparation method of 4 '-dimethoxy-methyl diphenyl ether, comprise the following steps:
By 20g (0.1mol) 4,4 '-dimethyl diphenyl ether, 30g benzene and 0.82g (0.005mol) azo isobutyronitrile
Join in above-mentioned four-hole boiling flask, by heating in water bath material, drip after being heated to 80 DEG C with stirring
36.8g (0.23mol) bromine, 2h drips off, and drips off rear back flow reaction 1.0h.
Reactant liquor normal pressure back flow reaction obtained steams benzene, subsequently material is cooled to 45 DEG C, after cooling
Material in drip 64.8g (0.3mol) mass concentration be 25% methanol solution of sodium methylate, 35min drips off, and adds
Hot reflux 2.0h, steams methanol afterwards.The benzene amount of steaming is 25.6g, through being washed to neutral and dried benzene
25.3g, is 99.4% through gas chromatographic analysis purity, and the response rate is 84.3%.The benzene reuse reclaimed.Methanol steams
Output is 44.7g, is 94.3% through gas chromatographic analysis purity, and the response rate is 86.7%.
In above-mentioned material, add 100mL water, after stirring 10min, stand split-phase, the remaining washing of oil phase
Wash twice, each slurry 50mL.
Oil phase elder generation normal pressure after washing is steamed water, then decompression distillation under the pressure condition of 1～2mmHg,
Obtaining thick product 17.1g, the boiling point of this thick product is 190～200 DEG C/1～2mmHg.
After obtaining described thick product, the present invention carries out rectification under vacuum process to described thick product, is produced
The sterling of thing.Through gas chromatographic analysis, product purity is 99.6%.Being computed, productivity is 92.8%.
The bottom temperature of rectification is 200～250 DEG C, and tower top temperature is 196～200 DEG C, and pressure is 1～2mmHg.
Gas chromatographic analysis uses VARIAN CP-3800 chromatographic.Chromatographiccondition is as follows: post
Type: DB-5；Vaporizer temperature: 250 DEG C；Temperature programming: 40 DEG C/1min → 30 DEG C/min → 250 DEG C/30
min。
According to the characteristic manner in embodiment 1, the product of the present embodiment is detected, it was demonstrated that the present embodiment obtains
To product be target product.
Embodiment 7
A kind of 4, the preparation method of 4 '-dimethoxy-methyl diphenyl ether, comprise the following steps:
By 20g (0.1mol) 4,4 '-dimethyl diphenyl ether, 60g carbon tetrachloride and 0.82g (0.005mol) azo
Isopropyl cyanide joins in above-mentioned four-hole boiling flask, by heating in water bath material, is heated to 80 DEG C with stirring
Rear dropping 35.2g (0.22mol) bromine, 1.4h drips off, and drips off rear back flow reaction 1.0h.
Reactant liquor normal pressure back flow reaction obtained steams carbon tetrachloride, subsequently material is cooled to 46 DEG C, to
Dripping 64.8g (0.3mol) mass concentration in material after cooling is 25% methanol solution of sodium methylate, and 30min drips
Complete, it is heated to reflux 3.0h, steams methanol afterwards.The carbon tetrachloride amount of steaming is 55.2g, through being washed to neutrality also
Dried carbon tetrachloride 54.6g, is 99.2% through gas chromatographic analysis purity, and the response rate is 91.0%.Return
The carbon tetrachloride reuse received.The methanol amount of steaming is 44.3g, is 94.5% through gas chromatographic analysis purity, reclaims
Rate is 86.1%.
In above-mentioned material, add 100mL water, after stirring 10min, stand split-phase, the remaining washing of oil phase
Wash twice, each slurry 50mL.
Oil phase elder generation normal pressure after washing is steamed water, then decompression distillation under the pressure condition of 1～2mmHg,
Obtaining thick product 17.7g, the boiling point of this thick product is 190～200 DEG C/1～2mmHg.
After obtaining described thick product, the present invention carries out distillation process of reducing pressure to described thick product, is produced
The sterling of thing.Through gas chromatographic analysis, product purity is 99.8%.Being computed, productivity is 87.4%.
The bottom temperature of rectification is 200～250 DEG C, and tower top temperature is 196～200 DEG C, and pressure is 1～2mmHg.
Gas chromatographic analysis uses VARIAN CP-3800 chromatographic.Chromatographiccondition is as follows: post
Type: DB-5；Vaporizer temperature: 250 DEG C；Temperature programming: 40 DEG C/1min → 30 DEG C/min → 250 DEG C/30
min。
According to the characteristic manner in embodiment 1, the product of the present embodiment is detected, it was demonstrated that the present embodiment obtains
To product be target product.
Embodiment 8
A kind of 4, the preparation method of 4 '-dimethoxy-methyl diphenyl ether, comprise the following steps:
By 20g (0.1mol) 4,4 '-dimethyl diphenyl ether, 60g carbon tetrachloride and 0.82g (0.005mol) azo
Isopropyl cyanide joins in above-mentioned four-hole boiling flask, by heating in water bath material, is heated to 80 DEG C with stirring
Rear dropping 38.4g (0.24mol) bromine, 1.3h drips off, and drips off rear back flow reaction 3.0h.
Reactant liquor normal pressure back flow reaction obtained steams carbon tetrachloride, subsequently material is cooled to 47 DEG C, to
Dripping 64.8g (0.3mol) mass concentration in material after cooling is 25% methanol solution of sodium methylate, and 30min drips
Complete, it is heated to reflux 3.0h, steams methanol afterwards.The carbon tetrachloride amount of steaming is 55.2g, through being washed to neutrality also
Dried carbon tetrachloride 54.5g, is 99.1% through gas chromatographic analysis purity, and the response rate is 90.8%.First
The alcohol amount of steaming is 44.6g, is 94.3% through gas chromatographic analysis purity, and the response rate is 86.5%.
In above-mentioned material, add 100mL water, after stirring 10min, stand split-phase, the remaining washing of oil phase
Wash twice, each slurry 50mL.
Oil phase elder generation normal pressure after washing is steamed water, then decompression distillation under the pressure condition of 1～2mmHg,
Obtaining thick product 17.7g, the boiling point of this thick product is 190～200 DEG C/1～2mmHg.
After obtaining described thick product, the present invention carries out rectification under vacuum process to described thick product, is produced
The sterling of thing.Through gas chromatographic analysis, product purity is 99.8%.Being computed, productivity is 89.8%.
The bottom temperature of rectification is 200～250 DEG C, and tower top temperature is 196～200 DEG C, and pressure is 1～2mmHg.
Gas chromatographic analysis uses VARIAN CP-3800 chromatographic.Chromatographiccondition is as follows: post
Type: DB-5；Vaporizer temperature: 250 DEG C；Temperature programming: 40 DEG C/1min → 30 DEG C/min → 250 DEG C/30
min。
According to the characteristic manner in embodiment 1, the product of the present embodiment is detected, it was demonstrated that the present embodiment obtains
To product be target product.
Embodiment 9
A kind of 4, the preparation method of 4 '-diethoxymethyl diphenyl ether, comprise the following steps:
By 20g (0.1mol) 4,4 '-dimethyl diphenyl ether, 60g carbon tetrachloride and 0.82g (0.005mol) azo
Isopropyl cyanide joins in above-mentioned four-hole boiling flask, by heating in water bath material, is heated to 80 DEG C with stirring
Rear dropping 36.8g (0.23mol) bromine, 1.2h drips off, and drips off rear back flow reaction 3.0h.
Reactant liquor normal pressure back flow reaction obtained steams carbon tetrachloride, subsequently material is cooled to 48 DEG C, to
Dripping 81.6g (0.3mol) mass concentration in material after cooling is 25% alcohol sodium alcohol solution, and 30min drips
Complete, it is heated to reflux 2.0h, steams ethanol afterwards.The carbon tetrachloride amount of steaming is 55.0g, through being washed to neutrality also
Dried carbon tetrachloride 54.3g, is 99.3% through gas chromatographic analysis purity, and the response rate is 90.5%.Second
The alcohol amount of steaming is 55.1g, is 95.6% through gas chromatographic analysis purity, and the response rate is 86.1%.The second reclaimed
Alcohol can be used for Sodium ethylate processed after rectification and drying and dehydrating.
In above-mentioned material, add 100mL water, after stirring 10min, stand split-phase, the remaining washing of oil phase
Wash twice, each slurry 50mL.
Oil phase elder generation normal pressure after washing is steamed water, then decompression distillation under the pressure condition of 1～2mmHg,
Obtaining thick product 21.7g, the boiling point of this thick product is 210～220 DEG C DEG C/1～2mmHg.
After obtaining described thick product, the present invention carries out rectification under vacuum process to described thick product, is produced
The sterling of thing.Through gas chromatographic analysis, product purity is 99.6%.Being computed, productivity is 91.2%.
The bottom temperature of rectification is 210～270 DEG C, and tower top temperature is 216～220 DEG C, and pressure is 1～2mmHg.
Gas chromatographic analysis uses VARIAN CP-3800 chromatographic.Chromatographiccondition is as follows: post
Type: DB-5；Vaporizer temperature: 250 DEG C；Temperature programming: 40 DEG C/1min → 30 DEG C/min → 250 DEG C/30
min。
The pure product that the present embodiment is also obtained by the present invention has carried out infrared and nuclear magnetic resonance, NMR sign, characterizes knot
The most as shown in figures 4-6, Fig. 4 is 4 that the embodiment of the present invention 9 obtains to fruit, 4 '-diethoxymethyl diphenyl ether red
External spectrum figure；Fig. 5 is 4 that the embodiment of the present invention 9 obtains, the nuclear magnetic resonance, NMR of 4 '-diethoxymethyl diphenyl ether
Hydrogen spectrogram；Fig. 6 is 4 that the embodiment of the present invention 9 obtains, the nuclear magnetic resonance, NMR carbon of 4 '-diethoxymethyl diphenyl ether
Spectrogram.
In Fig. 4: 3034cm-1For (=C-H) hydrocarbon stretching vibration peak on phenyl ring；2974cm-1, 2862cm-1
For methyl (CH3-) hydrocarbon asymmetric and symmetrical stretching vibration peak；2930cm-1For methylene (-CH2-) hydrocarbon
Stretching vibration peak；1602cm-1, 1501cm-1For phenyl ring skeleton stretching vibration peak；1238cm-1For aromatic ether
C-O-C asymmetrical stretching vibration peak；1096cm-1C-O-C symmetrical stretching vibration peak for ethylether；828
cm-1For the out-of-plane bending vibration of on phenyl ring two adjacent hydrogen, show that phenyl ring is para-orientation.
In Fig. 5:1H NMR (Acetone, δ):
δ=1.106～1.144 (3H, t, CH3-)×2；
δ=3.445～3.485 (2H, q ,-CH2-)×2；
δ=4.409 (2H, s, Ar-CH2-)×2；
δ=6.918～7.307 (4H, q, Ar-) × 2.
In Fig. 6:13C NMR (Acetone, δ):
δ1=15.73 is the 1 of methyl#Carbon atom；
δ2=66.22 is the 2 of the methylene being connected with methyl#Carbon atom；
δ3=72.60 is the 3 of the methylene being connected with phenyl ring#Carbon atom；
δ4=135.23 is 4 on the phenyl ring being connected with methylene#Carbon atom；
δ5=130.16 is 5 on phenyl ring#Carbon atom；
δ6=119.43 is 6 on phenyl ring#Carbon atom；
δ7=157.62 is 7 on phenyl ring#Carbon atom.
According to Fig. 4～6 it is recognised that the product that the present invention obtains has 4,4 '-diethoxymethyl diphenyl ether mark
The characteristic peak of all groups of quasi-structure, it was demonstrated that the structure that the present invention obtains is 4,4 '-diethoxymethyl diphenyl ether.
Embodiment 10
A kind of 4, the preparation method of 4 '-diisopropoxy methyl diphenyl ether, comprise the following steps:
By 20g (0.1mol) 4,4 '-dimethyl diphenyl ether, 60g carbon tetrachloride and 0.82g (0.005mol) azo
Isopropyl cyanide joins in above-mentioned four-hole boiling flask, by heating in water bath material, is heated to 80 DEG C with stirring
Rear dropping 36.8g (0.23mol) bromine, 1.1h drips off, and drips off rear back flow reaction 3.0h.
Reactant liquor normal pressure back flow reaction obtained steams carbon tetrachloride, subsequently material is cooled to 50 DEG C, to
Dripping 98.4g (0.3mol) mass concentration in material after cooling is 25% sodium isopropylate aqueous isopropanol, 35min
Drip off, be heated to reflux 3.0h, steam isopropanol afterwards.The carbon tetrachloride amount of steaming is 54.8g, in being washed to
Property and dried carbon tetrachloride 54.2g, be 99.1% through gas chromatographic analysis purity, the response rate is 90.3%.
The isopropanol amount of steaming is 67.1g, is 95.6% through gas chromatographic analysis purity, and the response rate is 86.9%.Reclaim
Isopropanol after rectification and drying and dehydrating, can be used for preparing isopropanol sodium.
In above-mentioned material, add 100mL water, after stirring 10min, stand split-phase, the remaining washing of oil phase
Wash twice, each slurry 50mL.
Oil phase elder generation normal pressure after washing is steamed water, then decompression distillation under the pressure condition of 1～2mmHg,
Obtaining thick product 23.8g, the boiling point of this thick product is 220～230 DEG C/1～2mmHg.
After obtaining described thick product, the present invention carries out rectification under vacuum process to described thick product, is produced
The sterling of thing.Through gas chromatographic analysis, product purity is 99.8%.Being computed, productivity is 92.8%.
The bottom temperature of rectification is 220～280 DEG C, and tower top temperature is 226～230 DEG C, and pressure is 1～2mmHg.
Gas chromatographic analysis uses VARIAN CP-3800 chromatographic.Chromatographiccondition is as follows: post
Type: DB-5；Vaporizer temperature: 250 DEG C；Temperature programming: 40 DEG C/1min → 30 DEG C/min → 250 DEG C/30
min。
The pure product that the present embodiment is also obtained by the present invention has carried out infrared and nuclear magnetic resonance, NMR sign, characterizes knot
As shown in figs. 7-9, Fig. 7 is 4 that the embodiment of the present invention 10 obtains to fruit, 4 '-diisopropoxy methyl diphenyl ether
Infrared spectrogram；Fig. 8 is 4 that the embodiment of the present invention 10 obtains, 4 '-diisopropoxy methyl diphenyl ether
Hydrogen nuclear magnetic resonance spectrogram；Fig. 9 is 4 that the embodiment of the present invention 10 obtains, 4 '-diisopropoxy methyl diphenyl ether
Carbon-13 nmr spectra figure.
In Fig. 7: 3034cm-1For (=C-H) hydrocarbon stretching vibration peak on phenyl ring；2971cm-1, 2866cm-1
For methyl (CH3-) hydrocarbon asymmetric and symmetrical stretching vibration peak；2930cm-1For methylene (-CH2-) hydrocarbon
Symmetrical stretching vibration peak；1603cm-1, 1501cm-1For phenyl ring skeleton stretching vibration peak；1240cm-1For virtue
The C-O-C asymmetrical stretching vibration peak of fragrant ether；1067cm-1C-O-C symmetrical stretching vibration for isopropyl ether
Peak；816cm-1For the out-of-plane bending vibration of on phenyl ring two adjacent hydrogen, show that phenyl ring is para-orientation.
In Fig. 8:1H NMR (Acetone, δ):
δ=1.878～1.890 (6H, d, CH3–×2)×2；
δ=4.361～4.410 (1H, m, CH) × 2；
δ=5.181 (2H, s, CH2–)×2；
δ=7.663～8.061 (4H, q, Ar) × 2.
In Fig. 9:13C NMR (Acetone, δ):
δ1=δ3=15.73 is methyl 1#With 3#Carbon atom；
δ2=66.22 is 2 be connected with methyl#Carbon atom；
δ4=72.60 is 4 on the methylene being connected with phenyl ring#Carbon atom；
δ5=135.23 is 5 on phenyl ring#Carbon atom；
δ6=130.16 is 6 on phenyl ring#Carbon atom；
δ7=119.43 is 7 on phenyl ring#Carbon atom.
δ8=157.62 is 8 on phenyl ring#Carbon atom.
According to Fig. 7～9 it is recognised that the product that the present invention obtains has 4,4 '-diisopropoxy methyl diphenyl ether
The characteristic peak of all groups of normal structure, it was demonstrated that the structure that the present invention obtains is 4,4 '-diisopropoxy methyl two
Phenylate.
As seen from the above embodiment, the present invention by bromine, 4,4 '-dimethyl diphenyl ether and initiator are at organic solvent
In carry out bromo-reaction, obtain bromination product；Mix with sodium alkoxide after described bromination product is cooled down, obtain ether
Change reaction system；Described etherification reaction system is heated up, carries out etherification reaction, obtain 4,4 '-dialkoxy first
Yl diphenyl ether.Compared with prior art, the preparation method that the present invention provides can on the premise of ensureing productivity
It is greatly improved the purity of product.The result of the embodiment of the present invention shows, the method that the application provides prepares 4,4 '-
The productivity of dialkoxymethyl diphenyl ether is all higher than 50%, and product purity is above 99.5%.
The above is only the preferred embodiment of the present invention, it is noted that common for the art
For technical staff, under the premise without departing from the principles of the invention, it is also possible to make some improvements and modifications,
These improvements and modifications also should be regarded as protection scope of the present invention.
Claims (10)
1. one kind 4, the preparation method of 4 '-dialkoxymethyl diphenyl ether, comprise the following steps:
By bromine, 4,4 '-dimethyl diphenyl ether and initiator carry out bromo-reaction in organic solvent, obtain bromo
Product；
Mix with sodium alkoxide after described bromination product is cooled down, obtain etherification reaction system；
Described etherification reaction system is heated up, carries out etherification reaction, obtain 4,4 '-dialkoxymethyl diphenyl ether.
Preparation method the most according to claim 1, it is characterised in that described organic solvent is four chlorinations
One or more in carbon, hexamethylene, normal hexane, benzene and chlorobenzene；
The mass ratio of described organic solvent and 4,4 '-dimethyl diphenyl ether is (1.5～4.5): 1.
Preparation method the most according to claim 1, it is characterised in that described initiator is peroxide
Class initiator and/or azo-initiator；
The mol ratio of described initiator and 4,4 '-dimethyl diphenyl ether is (0.01～0.1): 1.
Preparation method the most according to claim 3, it is characterised in that described peroxide type initiators
For di-tert-butyl peroxide, tert-butyl hydroperoxide, dibenzoyl peroxide and diisopropylbenzene (DIPB) peroxidating
One or more in thing.
Preparation method the most according to claim 3, it is characterised in that described azo-initiator is even
Nitrogen bis-isobutyronitrile and/or AMBN.
Preparation method the most according to claim 1, it is characterised in that described bromine and 4,4 '-dimethyl
The mol ratio of diphenyl ether is (2～3): 1.
Preparation method the most according to claim 1, it is characterised in that described sodium alkoxide is Feldalat NM, second
One or more in sodium alkoxide and sodium propoxide；
The mol ratio of described sodium alkoxide and 4,4 '-dimethyl diphenyl ether is (2.25～3.5): 1.
Preparation method the most according to claim 1, it is characterised in that the reaction temperature of described bromo-reaction
Degree is 70～90 DEG C；
The response time of described bromo-reaction is 1～3h.
Preparation method the most according to claim 1, it is characterised in that the temperature of described cooling is
40～50 DEG C.
Preparation method the most according to claim 1, it is characterised in that the temperature of described etherification reaction
It it is 70～90 DEG C；
The time of described etherification reaction is 1～3h.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA732641A (en) * | 1966-04-19 | B. Trapp Walter | Ar-poly(hydroxymethyl)diphenyl ethers and their method of preparation | |
| US4413149A (en) * | 1980-12-24 | 1983-11-01 | Hoechst Aktiengesellschaft | Process for the catalytic hydrogenolysis of p-substituted benzaldehyde-dimethylacetals to produce the corresponding benzyl methyl ether derivatives |
| EP0171443A1 (en) * | 1984-08-11 | 1986-02-19 | Chemische Fabrik Kalk GmbH | Nuclear-brominated mixtures of dimethyldiphenyl ether isomers, their preparation and their use as flame retardants for synthetics |
| EP1349218A2 (en) * | 2002-03-28 | 2003-10-01 | National Institute for Materials Science | Nb3Ga multifilamentary superconducting wire and process for preparing the same |
| CN101182338A (en) * | 2007-12-17 | 2008-05-21 | 浙江大学 | Dinuclear metallocene compounds and uses thereof |
| CN101774909A (en) * | 2010-02-24 | 2010-07-14 | 常州市阳光医药原料有限公司 | Method for preparing 4, 4'-diphenyl ether dicarboxylic acid |
| CN104086377A (en) * | 2014-07-07 | 2014-10-08 | 太仓博亿化工有限公司 | Synthesis method of polymethoxy substituted diphenyl ether compound |
| CN105461904A (en) * | 2015-11-27 | 2016-04-06 | 浙江大学 | Novel method for preparing polymer on basis of carbon free radical coupling reaction |
-
2016
- 2016-05-24 CN CN201610349492.4A patent/CN106008174A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA732641A (en) * | 1966-04-19 | B. Trapp Walter | Ar-poly(hydroxymethyl)diphenyl ethers and their method of preparation | |
| US4413149A (en) * | 1980-12-24 | 1983-11-01 | Hoechst Aktiengesellschaft | Process for the catalytic hydrogenolysis of p-substituted benzaldehyde-dimethylacetals to produce the corresponding benzyl methyl ether derivatives |
| EP0171443A1 (en) * | 1984-08-11 | 1986-02-19 | Chemische Fabrik Kalk GmbH | Nuclear-brominated mixtures of dimethyldiphenyl ether isomers, their preparation and their use as flame retardants for synthetics |
| EP1349218A2 (en) * | 2002-03-28 | 2003-10-01 | National Institute for Materials Science | Nb3Ga multifilamentary superconducting wire and process for preparing the same |
| CN101182338A (en) * | 2007-12-17 | 2008-05-21 | 浙江大学 | Dinuclear metallocene compounds and uses thereof |
| CN101774909A (en) * | 2010-02-24 | 2010-07-14 | 常州市阳光医药原料有限公司 | Method for preparing 4, 4'-diphenyl ether dicarboxylic acid |
| CN104086377A (en) * | 2014-07-07 | 2014-10-08 | 太仓博亿化工有限公司 | Synthesis method of polymethoxy substituted diphenyl ether compound |
| CN105461904A (en) * | 2015-11-27 | 2016-04-06 | 浙江大学 | Novel method for preparing polymer on basis of carbon free radical coupling reaction |
Non-Patent Citations (2)
| Title |
|---|
| 张田林等: "4,4’-二溴甲基二苯醚的合成", 《江苏化工》 * |
| 文生雷等: "4,4’-二甲氧基甲基二苯醚的性能、用途及合成工艺", 《精细石油化工进展》 * |
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