CN109651120A - A kind of preparation method of 4- (4- formvlphenoxv) benzaldehyde - Google Patents
A kind of preparation method of 4- (4- formvlphenoxv) benzaldehyde Download PDFInfo
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Abstract
The present invention relates to technical field of chemical synthesis, specifically disclose a kind of preparation method of 4- (4- formvlphenoxv) benzaldehyde.The preparation method use first 4- hydroxy benzaldehyde and potassium carbonate existing for the polymerization inhibitor and antioxidant under the conditions of react and generate sylvite; the water generated by azeotropic reflux elimination reaction; then the sylvite for removing water is reacted again with 4- fluorobenzaldehyde, 4- (4- formvlphenoxv) benzaldehyde product is made.The purity of 4- (4- formvlphenoxv) benzaldehyde product produced by the present invention can reach 99% or more; molar yield can reach 97% or more; the industrialized production for realizing 4- (4- formvlphenoxv) benzaldehyde, has broad application prospects.
Description
Technical field
The present invention relates to the preparations of technical field of chemical synthesis more particularly to a kind of 4- (4- formvlphenoxv) benzaldehyde
Method.
Background technique
4- (4- formvlphenoxv) benzaldehyde, structural formula are as follows:
It is the important raw material for preparing novel phenolic resins, using it as phenolic resin prepared by raw material, has excellent
Insulating properties, heat resistance and processability are widely used in the various necks such as electronics, solar energy, photovoltaic power generation, Aeronautics and Astronautics
Domain.
Currently, mainly having by the method for synthesis 4- (4- formvlphenoxv) benzaldehyde: (1) with parahydroxyben-zaldehyde and
P-bromobenzoic acid is raw material, and 4- (4- formvlphenoxv) benzaldehyde is prepared by way of being first etherified and restoring, still, this
Lithium aluminium hydride and tetrahydrofuran are used in synthetic method, risk is higher, and operation difficulty is big, it is difficult to realize industrialized production；
(2) using 4- hydroxy benzaldehyde as raw material, self-condensation reaction occurs under the effect of the catalyst and obtains 4- (4- formvlphenoxv)
Benzaldehyde, still, the yield of 4- (4- formvlphenoxv) benzaldehyde that the method obtains only have 79%；(3) with 4,4 '-oxygen two
Chlorobenzoyl chloride is raw material, and using tetrahydrofuran as catalyst, hydrogenation tributyl lithium aluminium is reducing agent, obtains 4- (4- through reduction reaction
Formvlphenoxv) benzaldehyde, this method raw material corrosivity is big, safety is poor, the receipts of 4- (4- formvlphenoxv) benzaldehyde
Rate only has 84%.Therefore, in order to improve the yield of 4- (4- formvlphenoxv) benzaldehyde, and security risk is reduced, it is necessary to
Find a kind of production technology safer, capable of being industrialized.
Summary of the invention
For prior art preparation 4- (4- formvlphenoxv) benzaldehyde technique there are yield is low and risk compared with
Greatly, it is difficult to realize that industrialized problem, the present invention provide a kind of preparation method of 4- (4- formvlphenoxv) benzaldehyde.
In order to solve the above technical problems, present invention provide the technical scheme that
A kind of preparation method of 4- (4- formvlphenoxv) benzaldehyde, includes the following steps:
Step 1: 4- hydroxy benzaldehyde, potassium carbonate, polymerization inhibitor, antioxidant and water entrainer are added in solvent, it is heated to back
Stream, is stirred to react, obtains intermediary solution；
Step 2: 4- fluorobenzaldehyde is added into the intermediary solution carries out etherification reaction, 4- (4- formoxyl benzene oxygen is obtained
Base) benzaldehyde solution；
Step 3: water entrainer in 4- (4- formvlphenoxv) benzaldehyde solution is removed, filter, decrease temperature crystalline obtains 4-
(4- formvlphenoxv) benzaldehyde product.
The reaction equation of above-mentioned preparation process is as follows:
Compared with the existing technology, the preparation method of 4- (4- formvlphenoxv) benzaldehyde provided by the invention, with 4- hydroxyl
Benzaldehyde and 4- fluorobenzaldehyde are raw material, and 4- hydroxy benzaldehyde and carbonic acid nak response are first generated potassium before the two reaction
Salt, the water generated by azeotropic reflux elimination reaction, then the sylvite for removing water is reacted, avoid 4- with 4- fluorobenzaldehyde again
Side reaction occurs for fluorobenzaldehyde and water, improves the conversion ratio of 4- fluorobenzaldehyde, the conversion ratio of 4- fluorobenzaldehyde can reach
99.5%；The polymerization inhibitor of addition can reduce the generation of the polymeric by-products such as aldol condensation；The antioxidant of addition protects preparation
The aldehyde radical of 4- (4- formvlphenoxv) benzaldehyde product improves the appearance of product while reducing oxidation side reaction.This
Invention product 4- (4- formvlphenoxv) benzaldehyde is that white to off-white color crystallizes, and HPLC content is greater than 99%, molar yield
Greater than 97%, and raw material is easy to get, easy to operate, highly-safe, realizes the industrialization of 4- (4- formvlphenoxv) benzaldehyde
Production.
Preferably, in step 1, the time being stirred to react is 2-4h.
The time being preferably stirred to react can be such that 4- hydroxy benzaldehyde sufficiently reacts with potassium carbonate, and the water for generating reaction
Removing completely avoids 4- fluorobenzaldehyde and water that side reaction occurs, and product yield and purity is caused to reduce.
Preferably, in step 2, the temperature of etherification reaction is 110-130 DEG C, reaction time 14-17h.
Preferred reaction temperature and reaction time, the sylvite prepared in step 1 can be made sufficiently to react with 4- fluorobenzaldehyde,
The generation of side reaction can also be reduced simultaneously, improve the conversion ratio of 4- fluorobenzaldehyde.
Preferably, in step 2,4- fluorobenzaldehyde is added in the intermediary solution by the way of being added dropwise, time for adding
For 20-40min.
The adding manner that preferred 4- fluorobenzaldehyde uses can react fully progress, reduce the generation of side reaction.
Preferably, in step 1, the polymerization inhibitor is phenthazine.
Preferred polymerization inhibitor can reduce the generation of the polymeric by-products such as aldol condensation, improve the conversion ratio and product of raw material
Purity.
Preferably, the antioxidant is 2,6-di-tert-butyl p-cresol (BHT).
Preferred antioxidant can effectively protect the aldehyde radical of product, while reducing oxidation side reaction, improves the outer of product
It sees, keeps 4- prepared by the present invention (4- formvlphenoxv) benzaldehyde product quality more preferable.
Preferably, the water entrainer is one or both of toluene or dimethylbenzene.
The solvent is at least one of N,N-dimethylformamide, DMAC N,N' dimethyl acetamide or dimethyl sulfoxide.
Preferred solvent can be such that 4- hydroxy benzaldehyde, polymerization inhibitor, antioxidant sufficiently dissolves, and preferred water entrainer can make 4- hydroxyl
The water fast eliminating that benzaldehyde and carbonic acid nak response generate.
Preferably, the mass ratio of the polymerization inhibitor and 4- hydroxy benzaldehyde is 0.0001-0.0005:1.
Preferably, the mass ratio of the antioxidant and 4- hydroxy benzaldehyde is 0.0002-0.0005:1.
Preferred polymerization inhibitor, antioxidant additional amount can be effectively reduced under the premise of guaranteeing introducing impurity few as far as possible
The side reaction that may occur under high temperature, to improve the purity of 4- (4- formvlphenoxv) benzaldehyde product.
Preferably, the molar ratio of the potassium carbonate and 4- hydroxy benzaldehyde is 0.6-0.8:1.
Preferably, the molar ratio of the 4- fluorobenzaldehyde and 4- hydroxy benzaldehyde is 1:1.01-1.05.
Ratio between preferred each reactant, can be improved the utilization rate of raw material, to improve 4- (4- formoxyl benzene oxygen
Base) benzaldehyde product yield.
Preferably, the mass ratio of the solvent and water entrainer is 1:0.1-0.3.
Preferably, the solvent is n,N-Dimethylformamide, and the water entrainer is toluene.
Preferably, the mass ratio of the solvent and 4- hydroxy benzaldehyde is 3-5:1.
The additional amount of preferred water entrainer and solvent, can be such that 4- hydroxy benzaldehyde, polymerization inhibitor, antioxidant sufficiently dissolves, keep away
Exempt from uneven due to mixing, makes that raw material reaction is not thorough and polymerization inhibitor and antioxidant cannot play going out for abundant problems in role
It is existing.Simultaneously, moreover it is possible to which when making to reach reflux temperature, 4- hydroxy benzaldehyde is sufficiently reacted with potassium carbonate generates sylvite, and is conducive to
The water fast eliminating generated is reacted, the reaction time is shortened, improves the conversion ratio of 4- hydroxy benzaldehyde.
Preferably, in step 3, the step of the decrease temperature crystalline are as follows: to filtering in resulting filtrate plus water, be cooled to 10-
20 DEG C, heat preservation crystallization 2-4h.
Preferred crystallization temperature and crystallization time can be such that 4- (4- formvlphenoxv) benzaldehyde is sufficiently precipitated, and improve product
Yield, and the precipitation of metal ion can also be avoided, improve the purity of product.
Preferably, in step 3, the mass ratio 0.9-1.2:1 of added water and the solvent in filtrate.
Preferably, the hot water that water added in filtrate is 80-90 DEG C.
N,N-Dimethylformamide has preferable solubility to 4- (4- formvlphenoxv) benzaldehyde crude product, can be abundant
4- (4- formvlphenoxv) benzaldehyde crude product is dissolved, the solution formed after water is added to 4- (4- formvlphenoxv) benzaldehyde
There are also preferable solvabilities for the inorganic impurities such as remaining metal ion in crude product, can sufficiently remove 4- (4- formvlphenoxv)
Impurity in benzaldehyde crude product improves the yield and purity of product.
Optionally, in step 3, the condition of water entrainer is removed are as follows: air-distillation, distillation to gas phase temperature stop when being 145 DEG C
Only.
Purpose of this step operation is but to retain the N, N- bis- in solution to remove the toluene or dimethylbenzene in solution
Methylformamide, one of the solvent as later crystallization.
Optionally, it in step 3, filters by the way of filtering while hot, the reaction solution for removing water entrainer is cooled to
It 80-90 DEG C, filters while hot.
It is filtered using 80-90 DEG C, it is ensured that 4- (4- formvlphenoxv) is avoided under the premise of dissolution of benzaldehyde degree is higher
Metal ion is precipitated with the formation of salt, improves the purity of product.
The preparation method of 4- (4- formvlphenoxv) benzaldehyde provided through the invention, it is raw materials used for common examination
Agent, cheap, production cost is low, and easy to operate, highly-safe, 4- (4- formvlphenoxv) benzaldehyde being prepared
It is crystallized for white to off-white color, HPLC content is greater than 99%, and molar yield is greater than 97%, realizes 4- (4- formvlphenoxv)
The industrialized production of benzaldehyde.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
Embodiment 1
A kind of preparation method of 4- (4- formvlphenoxv) benzaldehyde:
Step 1: by 303kg4- hydroxy benzaldehyde, 240kg potassium carbonate, 90.9g phenthazine, 121.2gBHT, 1212kgN,
In the enamel reaction still of dinethylformamide and 242.4kg toluene investment with reflux unit, stirring is warming up to 120 DEG C of heat preservations,
Reflux dewatering 3h obtains intermediary solution；
Step 2: 299g4- fluorobenzaldehyde is added dropwise into the intermediary solution, time for adding 0.5h continues to keep
120 DEG C of reaction 16h, less than 0.2%, reaction terminates sampling HPLC detection 4- fluorobenzaldehyde content, obtains 4- (4- formoxyl benzene oxygen
Base) benzaldehyde solution；
Toluene, distillation to 145 DEG C of gas phase temperature stoppings are steamed under step, normal pressure；85 DEG C are cooled to, keeps the temperature filters pressing while hot,
With 200kgN, dinethylformamide washs filter cake, merging filtrate and cleaning solution, and 85 DEG C of hot water 1212kg, drop is added in stirring
Temperature is to 15 DEG C, and heat preservation crystallization 3h is centrifuged, washing, and filter cake is the crystallization of white 4- (4- formvlphenoxv) benzaldehyde, and HPLC contains
Amount 99.7%, molar yield 98.6%.
Embodiment 2
A kind of preparation method of 4- (4- formvlphenoxv) benzaldehyde:
Step 1: by 303kg4- hydroxy benzaldehyde, 205.8kg potassium carbonate, 151.5g phenthazine, 60.6gBHT,
In the enamel reaction still of 909kgN, N- dimethyl acetamide and 272.2kg toluene investment with reflux unit, stirring is warming up to 130
DEG C heat preservation, reflux dewatering 2h obtains intermediary solution；
Step 2: 304.9kg4- fluorobenzaldehyde, time for adding 0.5h, after continuation of insurance are added dropwise into the intermediary solution
130 DEG C of reaction 14h are held, less than 0.2%, reaction terminates sampling HPLC detection 4- fluorobenzaldehyde content, obtains 4- (4- formoxyl benzene oxygen
Base) benzaldehyde solution；
Toluene, distillation to 145 DEG C of gas phase temperature stoppings are steamed under step, normal pressure；90 DEG C are cooled to, keeps the temperature filters pressing while hot,
With 200kgN, dinethylformamide washs filter cake, merging filtrate and cleaning solution, and 90 DEG C of hot water 1091kg, drop is added in stirring
Temperature is to 20 DEG C, and heat preservation crystallization 2h is centrifuged, washing, and filter cake is the crystallization of white 4- (4- formvlphenoxv) benzaldehyde, and HPLC contains
Amount 99.3%, molar yield 97.6%.
Embodiment 3
Step 1: by 303kg4- hydroxy benzaldehyde, 274.3kg potassium carbonate, 33g phenthazine, 151.5gBHT, 1515kgN,
The mixture of the mixture (mass ratio 1:1) and 151.5kg toluene and dimethylbenzene of dinethylformamide and dimethyl sulfoxide
(mass ratio 1:1) is put into the enamel reaction still with reflux unit, stirring is warming up to 110 DEG C of heat preservations, reflux dewatering 4h, is obtained
Between object solution；
Step 2: 293.3kg4- fluorobenzaldehyde, time for adding 0.5h, after continuation of insurance are added dropwise into the intermediary solution
110 DEG C of reaction 17h are held, less than 0.2%, reaction terminates sampling HPLC detection 4- fluorobenzaldehyde content, obtains 4- (4- formoxyl benzene oxygen
Base) benzaldehyde solution；
Toluene, distillation to 145 DEG C of gas phase temperature stoppings are steamed under step, normal pressure；80 DEG C are cooled to, keeps the temperature filters pressing while hot,
With 200kgN, dinethylformamide washs filter cake, merging filtrate and cleaning solution, and 80 DEG C of hot water 1364kg, drop is added in stirring
Temperature is to 10 DEG C, and heat preservation crystallization 4h is centrifuged, washing, and filter cake is the crystallization of white 4- (4- formvlphenoxv) benzaldehyde, and HPLC contains
Amount 99.5%, molar yield 98.6%.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modification, equivalent replacement or improvement etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. a kind of preparation method of 4- (4- formvlphenoxv) benzaldehyde, which comprises the steps of:
Step 1: 4- hydroxy benzaldehyde, potassium carbonate, polymerization inhibitor, antioxidant and water entrainer are added in solvent, it is heated to flowing back,
It is stirred to react, obtains intermediary solution；
Step 2: 4- fluorobenzaldehyde is added into the intermediary solution carries out etherification reaction, 4- (4- formvlphenoxv) is obtained
Benzaldehyde solution；
Step 3: water entrainer in 4- (4- formvlphenoxv) benzaldehyde solution is removed, filter, decrease temperature crystalline obtains 4- (4- first
Acyl group phenoxy group) benzaldehyde product.
2. the preparation method of 4- (4- formvlphenoxv) benzaldehyde as described in claim 1, which is characterized in that step 1
In, the time being stirred to react is 2-4h；And/or
In step 2, the temperature of etherification reaction is 110-130 DEG C, reaction time 14-17h.
3. the preparation method of 4- (4- formvlphenoxv) benzaldehyde as described in claim 1, which is characterized in that the polymerization inhibitor
Agent is phenthazine；And/or
The antioxidant is DBPC 2,6 ditertiary butyl p cresol；And/or
The water entrainer is one or both of toluene or dimethylbenzene；And/or
The solvent is at least one of N,N-dimethylformamide, DMAC N,N' dimethyl acetamide or dimethyl sulfoxide.
4. the preparation method of 4- (4- formvlphenoxv) benzaldehyde as claimed in claim 1 or 3, which is characterized in that described
The mass ratio of polymerization inhibitor and 4- hydroxy benzaldehyde is 0.0001-0.0005:1；And/or
The mass ratio of the antioxidant and 4- hydroxy benzaldehyde is 0.0002-0.0005:1.
5. the preparation method of 4- (4- formvlphenoxv) benzaldehyde as described in claim 1, which is characterized in that the carbonic acid
The molar ratio of potassium and 4- hydroxy benzaldehyde is 0.6-0.8:1；And/or
The molar ratio of the 4- fluorobenzaldehyde and 4- hydroxy benzaldehyde is 1:1.01-1.05.
6. the preparation method of 4- (4- formvlphenoxv) benzaldehyde as described in claim 1, which is characterized in that the solvent
Mass ratio with water entrainer is 1:0.1-0.3.
7. the preparation method of 4- (4- formvlphenoxv) benzaldehyde as claimed in claim 6, which is characterized in that the solvent
For n,N-Dimethylformamide, the water entrainer is toluene.
8. the preparation method of 4- (4- formvlphenoxv) benzaldehyde as claimed in claim 6, which is characterized in that the solvent
Mass ratio with 4- hydroxy benzaldehyde is 3-5:1.
9. the preparation method of 4- (4- formvlphenoxv) benzaldehyde as described in claim 1, which is characterized in that step 3
In, the step of the decrease temperature crystalline are as follows: to filtering in resulting filtrate plus water, be cooled to 10-20 DEG C, heat preservation crystallization 2-4h.
10. the preparation method of 4- (4- formvlphenoxv) benzaldehyde as claimed in claim 9, which is characterized in that in filtrate
The mass ratio 0.9-1.2:1 of added water and the solvent.
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