CN1169982A - Preparation of p-formacyl phenylethyl ester - Google Patents
Preparation of p-formacyl phenylethyl ester Download PDFInfo
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- CN1169982A CN1169982A CN 96115854 CN96115854A CN1169982A CN 1169982 A CN1169982 A CN 1169982A CN 96115854 CN96115854 CN 96115854 CN 96115854 A CN96115854 A CN 96115854A CN 1169982 A CN1169982 A CN 1169982A
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- formylbenzoic acid
- methyl esters
- acid methyl
- formylbenzoic
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Abstract
A process for preparing methyl p-formylbenzoate from the by-product generated in production of p-benzenedicarboxaldehyde includes such technological steps as concentrating the by-product to obtain solid as raw material, extracting p-formyl benzoic acid with the solation of sodium sulfite, pressurizing and esterificating with methanol under the catalysis of lewis acids, and refining. The process is also suitable to prepare meta-or o-formyl benzoates.
Description
Involved in the present invention is a kind of method for preparing the p formylbenzoic acid methyl esters, and the by product of terephthalaldehyde is produced in this method utilization, and purifying is a p formylbenzoic acid, prepares the p formylbenzoic acid methyl esters with methanol esterification then.(Methyl?Terephthalaldehydate.Methyl?4-formybenzoate.OHC-O-COOCH
3)
The document relevant with invention has: day disclosure JP5857343; GerDE3149021; J, A, C, S, 64; 1180-1182 (1940); day disclosure JP82; 24; 321 in these pertinent literatures the preparation force method of mentioned p formylbenzoic acid methyl esters; its raw material all is to be starting raw material by ready-made p formylbenzoic acid; and its esterification force method is that its process for refining and purifying also is to carry out in organic solvent with organic solvent catalytic esterification under normal pressure; the cost height with an organic solvent brings all inconvenience.
The by product that the objective of the invention is to produce terephthalaldehyde with chlorination one oxidation style by p-Xylol is a raw material, through separation purify p formylbenzoic acid, then with the esterification of methyl alcohol pressurized catalysis, refining once again p formyl benzoic acid methyl esters.Changed preparation technology in the past.
Be described as follows about enrichment p formylbenzoic acid from the waste liquid of producing terephthalaldehyde: producing terephthalaldehyde is to make starting raw material with p-Xylol than method in common; logical chlorine under the illumination; get corresponding contraposition benzyl chlorine; can be replaced by a plurality of chlorine with hydrogen on two methyl of difference of chlorization condition; through hydrolysis, nitric acid or other oxygenant oxidations just get terephthalaldehyde again
, can add little amount of catalyst during oxidation, can not add sometimes yet.Oxide compound (the V that adds a small amount of vanadium during nitric acid oxidation
2O
5) make catalyzer.Because restive degree of depth chlorination and oxidation, no matter be force methods such as recrystallization or washing when obtaining terephthalaldehyde, the by product p formylbenzoic acid
And terephthalic acid
-COOH) grade produces simultaneously.Design of the present invention is based on the crystalline mother solution or the washings of collection, purifying terephthalaldehyde, and the acidifying enrichment is a solid materials, gets p formylbenzoic acid with the solid materials purifying, just gets the p formylbenzoic acid methyl esters with methanol esterification.
The approach that obtains the by-product refuse in the process of preparation terephthalaldehyde comprises crystalline mother solution or the washings of isolating terephthalaldehyde from be bordering on neutral yellow soda ash or sodium hydrogen carbonate solution, the used alcohols of purification terephthalaldehyde generally is methyl alcohol or alcoholic acid crystalline mother solution, with water lotion of dilute sodium carbonate or the impure terephthalaldehyde of sodium bicarbonate water washing solid state etc.Above-mentioned these liquid all can be separately or accumulation collect, behind mineral acid or low molecular organic acids acid precipitation, but after filtration, centrifugal, drying or non-drying all enrichment be solid materials.The main component of this solid materials butt is generally (percent by weight, hereinafter also together)
Terephthalic acid 2-50%
P formylbenzoic acid (TAA) 40-90%
Terephthalaldehyde (TDA) 2-8%
Other not clear thing 1-2%
Raw material of the present invention is above-mentioned moisture or water-free solid materials, and generally more easily obtains with moisture 10-90%, can be scaled the butt meter during use.
The detailed preparation method of this invention is: with above-mentioned production terephthalaldehyde by-product solid materials is raw material, A, with alkali metal sulfite or bisulfite salt brine solution dissolved solids material, and sulfuric acid acidation, separation, purifying get p formylbenzoic acid; B, p formylbenzoic acid and the esterification of anhydrous methanol pressurized catalysis get thick p formylbenzoic acid methyl esters; C, crude product further wash, filter, dry p formylbenzoic acid methyl esters highly finished product.
The purifying of p formylbenzoic acid is earlier solid materials to be dissolved with 5-30% S-WAT or aqueous solution of sodium bisulfite; also can use corresponding sylvite or ammonium salt during dissolving; the consumption of its S-WAT or sodium bisulfite is 0.9-1.5 a times of solids butt, adds 10-50%H after the stirring and dissolving
2SO
4Acidifying makes PH at 3.5-5, and the elimination precipitation is collected filtrate, and the 0.7-1.3 by solids butt weight extraordinarily goes into H again
2SO
4, (with 98%H
2SO
4Meter) thermal degradation, the SO of generation
2In resorber, get Na with the 5-15%NaOH solution absorption
2SO
3Reuse again, decomposition temperature 90-105 ℃, resolving time 0.5-5 hour, cold filtration afterwards, collecting precipitation is washed to nearly neutrality, dry p formylbenzoic acid.Purity generally can reach 98.0-99.0%.
The pressurization esterification is that p formylbenzoic acid, anhydrous methanol and the catalyzer with purifying mixes by a certain percentage and add in the anti-corrosion autoclave pressure, and the suitable percent by weight of three is:
Anhydrous methanol 50-80%
P formylbenzoic acid 10-40%
Catalyzer 0.2-10%
As 400-16009 with the total charging capacity of the anti-corrosion autoclave pressure of 2L, the logical rare gas element in the reinforced back that finishes, generally logical N
2Drive O
22-5 minute; valve-off starts stirring; intensification also is incubated in 110-125 ℃; pressure 0.4-1.0MPa reaction times 2.5-8 hour, cools off 20-40 ℃ afterwards; discharging also leaches catalyzer or impurity; steam the methyl alcohol in the filtrate in the distiller of another band condenser, emit debris while hot, cooling promptly gets thick p formylbenzoic acid methyl esters.Esterification yield is generally at 85-95%.
Employed catalysis is for providing the Lewis acid of proton, as p-methyl benzenesulfonic acid, Hydrogen butt strong-acid cation-exchange resin, large porous strong acid styrene type cation exchange resin, aluminum trichloride (anhydrous) etc. in the reaction.
The washing of p formylbenzoic acid methyl esters is refining
Because esterification is reversible reaction; unreacted intact p formylbenzoic acid and other impurity are still arranged in thick p formylbenzoic acid methyl esters; for removing above-mentioned impurity; the available rare alkaline carbonate or the solution washing of supercarbonate; and with the sodium bicarbonate optimum; washing purified step is that thick p formyl benzoic acid methyl esters is joined in the aqueous solution that contains methyl alcohol 75-90%; its solid content is pressed 40-90% control; slowly add in the 0.4-4% sodium hydrogen carbonate solution that has prepared after the low-grade fever dissolving; the weight ratio of the sodium hydrogen carbonate solution of its thick p formylbenzoic acid methyl esters and 0.4-4% is 1: 8-26; adding the back that finishes stirred 10-20 minute; filter; and discard filtrate; filter cake is washed to neutrality, and 30-50 ℃ of following vacuum or cryodrying get finished product p formylbenzoic acid methyl esters.Purity 96-99%; Refining yield 85-90%.
Between, adjacent formyl radical benzoates can be with reference to preparing with method.
The p formylbenzoic acid methyl esters is the organic synthesis important intermediate owing to have active aldehyde radical, can synthesize multiple fine chemical product.As the p formylbenzoic acid methyl esters is the indispensable intermediate of important white dyes 5.6-dimethyl-2-(4 '-methyl-formiate vinylbenzene) benzoxazoles (Hostalux ET) of polyester material and fiber; it also be the fluorescent monomer 4,4 used of special synthetic materials '-stilbenedicarboxylicacid acid methyl esters (CH
3OOC-O-CH=CH-O-COOCH
3) one of raw material, so it has use value widely.
The present invention utilizes the by-product waste material of producing terephthalaldehyde to be raw material, reduces environmental pollution, brings good to and remove all evil, the simple and easy practicality of purifying process, esterification technique no longer add benzene class organic solvent, direct and methyl alcohol pressurization esterification, washing is refining simple, and finished product is the fine chemical product of high added value.So the present invention has considerable economy and society benefit.
Embodiment 1
The p formylbenzoic acid purifying;
In the reaction flask that the 2000ml band stirs, add sodium sulphite anhydrous 99.3 200g, water 800ml, dissolving.Add moisture 75% enrichment by-product waste material 790g, under agitation make it whole dissolvings, add 15%H
2SO
4In lysate, adjust PH ≈ 4, filter and collect filtrate.
Filtrate added 2000ml band condenser and link with the 500ml gas absorber and be equipped with in the reactor of stirring, add 10%NaOH300ml in the resorber, stir down slowly heating, and slowly add 50%H
2SO
4198g, Heating temperature 95-102 ℃, 4.5 hours time.Decompose the SO that emits
2Import in the absorption bottle that the NaOH absorption liquid is housed by condenser and to be absorbed as Na
2SO
3After finishing, decomposition is chilled to room temperature, vacuum filtration, and collecting precipitation is washed to nearly neutrality, and 75-95 ℃ of drying gets pure p formylbenzoic acid 136g, purity 98.5%.
The pressurization esterification
With anhydrous methanol 1200g, with the p formylbenzoic acid 400g of aforesaid method purifying, p-methyl benzenesulfonic acid 5g, mix the back and add in the anti-corrosion autoclave pressure of 2L, fill N after opening exhaust-valve
23 minutes; close all valves; start and stir, intensification also is incubated at 118-120 ℃ pressure 0.5-0.75MPa; 5 hours time; react postcooling to the 30 ℃ discharging that finishes, elimination impurity steams and reclaims methyl alcohol in another distiller in case of necessity; emit debris while hot, cool off thick p formylbenzoic acid methyl esters 440g.
Making with extra care of p formylbenzoic acid methyl esters
2000ml band stirs in three mouthfuls of anti-device bottles, adds water 1200ml, adds sodium bicarbonate 20g, and it is standby to start stirring and dissolving under the room temperature.
In another 500ml reactor, add the thick p formylbenzoic acid methyl esters 95g that 80% methanol aqueous solution 120g and aforesaid method make, slowly be heated to 50 ℃ and treat that material all slowly adds in the sodium hydrogen carbonate solution of having got ready after the dissolving while hot.Add fashionable should constantly the stirring, feed liquid adds the back and stirred 10 minutes, and filter cake is all collected in vacuum filtration, is washed to neutrality, and 40-44 ℃ of vacuum-drying gets product 89g, purity 97.5%.
Embodiment 2
The p formylbenzoic acid purifying is identical with example 1; the pressurization esterification is: with anhydrous methanol 1200g; thick p formylbenzoic acid methyl esters 400g; dry hydrogen Zeo-karb 18g mixes the back and adds in the 21 anti-corrosion autoclave pressures, opens vent valve; filled N23 minute; close all valves, start and stir, 118-121 ℃ of intensification and insulation; pressure 0.56-0.79MPa; 5 hours time, finish postcooling to 30 ℃ of reaction, discharging and elimination catalyzer and impurity; filtrate is to another matrass; steam recovery methyl alcohol, emit raffinate while hot and stay liquid, cool off slightly to formyl radical methyl-formiate 445g.Making with extra care of its p formylbenzoic acid methyl esters with example 1.
Claims (5)
1, a kind of preparation method of p formylbenzoic acid methyl esters, it is characterized in that this method is a raw material with the by-product solid materials of producing terephthalaldehyde, A, with alkali metal sulfite or bisulfite salt brine solution dissolved solids material, sulfuric acid acidation, separation, purifying get p formylbenzoic acid; B, p formylbenzoic acid and the esterification of anhydrous methanol pressurized catalysis get thick p formylbenzoic acid methyl esters; C, crude product further wash, filter, dry p formylbenzoic acid methyl esters highly finished product.
2, press the preparation method of the described p formylbenzoic acid methyl esters of claim 1; it is characterized in that and to produce the by-product solid materials of terephthalaldehyde enrichment with 5-30% S-WAT or aqueous solution of sodium bisulfite dissolving; also can use the dissolving of corresponding sylvite or ammonium salt aqueous solution; the consumption of its S-WAT or sodium bisulfite is 0.9-1.5 a times of solids butt, adds 10-50%H after the stirring and dissolving
2SO
4, acidifying makes PH at 3.5-5.0, and the elimination precipitation is collected filtrate, and the 0.7-1.3 by solids butt weight extraordinarily goes into H again
2SO
4, thermal degradation, the sulfurous gas of generation gets Na with the 5-15%NaOH solution absorption in resorber
2SO
3Reuse again, decomposition temperature 90-105 ℃, resolving time 0.5-5 hour, cold filtration afterwards, collecting precipitation is washed to nearly neutrality, dry p formylbenzoic acid.
3, the preparation method according to the said p formylbenzoic acid methyl esters of claim 1 is characterized in that the pressurized catalysis esterification of this force method is p formylbenzoic acid, anhydrous methanol and catalyzer to be mixed by a certain percentage add in the anti-corrosion autoclave pressure, and the suitable percent by weight of three is:
Anhydrous methanol 50-80%;
P formylbenzoic acid 10-40%;
Catalyzer 0.2-10%
The logical rare gas element in the reinforced back that finishes, generally logical N
22-5 minute; valve-off starts and stirs, and intensification also keeps 110-125 ℃; pressure 0.4-1.0MPa; reaction times 2.5-8 hour, be cooled to 20-40 ℃ afterwards, discharging also leaches catalyzer or impurity; in the distiller of another band condenser; steam the methyl alcohol in the filtrate, emit debris while hot, cooling promptly gets thick p formylbenzoic acid methyl esters.
4, according to the wherein said catalyzer of the preparation method of right 1,3, said p formylbenzoic acid methyl esters for the Lewis acid of proton can be provided; as p-methyl benzenesulfonic acid, Hydrogen butt strong-acid cation-exchange resin, large porous strong acid styrene type cation exchange resin, aluminum trichloride (anhydrous) etc.
5; according to claim 1; the preparation method of said p formylbenzoic acid methyl esters; it is characterized in that washing refining is with rare alkaline carbonate or the washing of supercarbonate dilute aqueous soln; and with the sodium bicarbonate optimum; washing purified step is that thick p formylbenzoic acid methyl esters is joined in the aqueous solution that contains methyl alcohol 75-90%; its solid content is pressed 40-90% control; under agitation slowly add after the low-grade fever dissolving and prepared in the 0.4-4% sodium hydrogen carbonate solution; the weight ratio of its thick p formylbenzoic acid methyl esters and 0.4-4% sodium hydrogen carbonate solution is 1: 8-26; adding the back that finishes stirred 10-20 minute; filter; discard filtrate; filter cake is washed to neutrality, and 30-50 ℃ of following vacuum or cryodrying get finished product p formylbenzoic acid methyl esters.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96115854A CN1067978C (en) | 1996-06-21 | 1996-06-21 | Preparation of P-formacyl phenylethyl ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96115854A CN1067978C (en) | 1996-06-21 | 1996-06-21 | Preparation of P-formacyl phenylethyl ester |
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| Publication Number | Publication Date |
|---|---|
| CN1169982A true CN1169982A (en) | 1998-01-14 |
| CN1067978C CN1067978C (en) | 2001-07-04 |
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ID=5123063
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96115854A Expired - Fee Related CN1067978C (en) | 1996-06-21 | 1996-06-21 | Preparation of P-formacyl phenylethyl ester |
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|---|---|
| CN (1) | CN1067978C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111747841A (en) * | 2019-03-29 | 2020-10-09 | 北京博诺安科科技有限公司 | Preparation method of 4-formylbenzoic acid and obtained 4-formylbenzoic acid |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5071641A (en) * | 1973-10-31 | 1975-06-13 | ||
| JPS5857343A (en) * | 1981-10-02 | 1983-04-05 | Nippon Ester Co Ltd | Preparation of alkyl 4-formylbenzoate |
| DE3302127A1 (en) * | 1983-01-22 | 1984-07-26 | Dynamit Nobel Ag, 5210 Troisdorf | Method for the recovery of a fraction enriched with methyl terephthalaldehydate |
-
1996
- 1996-06-21 CN CN96115854A patent/CN1067978C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111747841A (en) * | 2019-03-29 | 2020-10-09 | 北京博诺安科科技有限公司 | Preparation method of 4-formylbenzoic acid and obtained 4-formylbenzoic acid |
| CN111747841B (en) * | 2019-03-29 | 2022-09-06 | 北京博诺安科科技有限公司 | Preparation method of 4-formylbenzoic acid and obtained 4-formylbenzoic acid |
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| Publication number | Publication date |
|---|---|
| CN1067978C (en) | 2001-07-04 |
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