CN1052300A - By p-nitrobenzoic acid synthetic 4,4 '-the phenyl ether dioctyl phthalate - Google Patents
By p-nitrobenzoic acid synthetic 4,4 '-the phenyl ether dioctyl phthalate Download PDFInfo
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- CN1052300A CN1052300A CN 89109210 CN89109210A CN1052300A CN 1052300 A CN1052300 A CN 1052300A CN 89109210 CN89109210 CN 89109210 CN 89109210 A CN89109210 A CN 89109210A CN 1052300 A CN1052300 A CN 1052300A
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- phenyl ether
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- dioctyl phthalate
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Abstract
The present invention is the monomeric synthetic method of a kind of organic polymer.It is raw material with the p-nitrobenzoic acid that the present invention has designed a kind of, through three steps of cyaniding, condensation, hydrolysis produce 4,4 '-route of phenyl ether dioctyl phthalate.Facts have proved that this synthetic route good product quality can reach 99% without its purity of purifying, total recovery reaches 73.5%.Synthesis device is simple, easy to operate, and raw material is easy to get.Compare 4,4 with condensation, the oxidation route in past '-cost of phenyl ether dioctyl phthalate had significantly and reduced, and provides condition for developing this product widely.
Description
The present invention is the monomeric synthetic method of a kind of organic polymer.
In the laboratory, manufacture experimently 4 since the sixties abroad, 4 '-phenyl ether dioctyl phthalate (hereinafter to be referred as ether acid), so far the synthetic method of being reported is concluded two big classes, one class is to be that the ULLmann reaction of raw material footpath makes 4 with p-cresol with to toluene iodide or para-bromo toluene, 4 '-the dimethyl phenyl ether, with oxygenants such as potassium permanganate or sodium dichromate 99 or air methyl oxidation is become carboxyl again.Another kind of is that to be raw material with chlorobenzene and phenol make phenyl ether through ULLmann reaction condensation, connects corresponding group by electrophilic substitution reaction, changes into carboxyl again, compare this two classes synthetic method, when last class was made oxygenant with potassium permanganate, the ether acid that makes was purer, but yield is low, the cost height.Back one class methods have isomer inevitably and produce, separation difficulty, and the purity of ether acid is influenced.And this two classes synthetic method all adopted the ULLmann reaction, the temperature of reaction height, and side reaction is many, the product purification difficult, yield is not high.
On February 18th, 1986, the inventor once proposed " 4,4 '-synthetic method of phenyl ether dioctyl phthalate " patent application, and open on September 9th, 87.The synthetic method of this application is to be raw material with para-bromo toluene and p-cresol, the reform catalyzer, and through condensation, steps such as second oxidation make purity greater than 99% ether acid, and its synthetic total recovery can reach 65%, has improved 2.4 times than the yield of external similar route.But the price of this synthetic method raw material is more expensive, para-bromo toluene particularly, and domestic have only SILVER REAGENT not have industrial goods, makes the cost of ether acid very high.Therefore reform the synthetic route of ether acid, reduce cost, just become current urgent task.
It is raw material that the present invention has designed with the p-nitrobenzoic acid, produces the route of ether acid through oxidation, condensation, three steps of hydrolysis.It is good that practice shows that this synthetic route can obtain purity, the ether acid that yield is high.
Details are as follows for synthetic route of the present invention:
One, cyanogenation:
Cyanogenation carries out in solution, can adopt organic solvent such as aromatic hydrocarbons and halides and some ethers to reactionlessness.The solvent decompression can be steamed after reaction finishes, recovery set is used.Raw materials used is the industrial goods p-nitrobenzoic acid, and reagent has the industrial goods phosphorus oxychloride, and liquefied ammonia.Temperature of reaction is controlled at 115～130 ℃.Its reaction formula is as follows:
Two, condensation reaction:
The p-nitrophenyl formonitrile HCN that obtains with cyanogenation is a raw material, adds reagent potassium nitrite and yellow soda ash, at DMAC(N, N-N,N-DIMETHYLACETAMIDE) react in the solvent.Its proportioning is (1M) p-nitrophenyl formonitrile HCN: (0.4～1M) potassium nitrite: (0.2～0.5M) yellow soda ash.Control reaction temperature is at 170～175 ℃.After finishing, reaction removes solvent under reduced pressure.Its reaction formula is as follows:
Three, hydrolysis reaction
Be reflected in the autoclave and carry out, autoclave needs withstand voltage 4～5 kilograms per centimeter
2Hydrolysis needs to carry out under alkalescence or acidic conditions, and what hydrolysis obtained in basic solution is carboxylate salt, needs further acidifying that acid out is gone out.Because the process that acid out goes out can make impurity stay in the mother liquor, has improved sour purity, so the present invention's hydrolysis in basic solution, its basicity is 8～12% sodium hydroxide solutions.Temperature of reaction is between 130～150 ℃.Reaction formula is as follows:
The present invention compares with existing synthetic method and has the following advantages.
1. yield height, cyaniding, condensation, the average yield in each step of hydrolysis reach 89%, 86% and 96% respectively, and total recovery reaches 73.5%.
2. good product quality can both reach 99% without its purity of purification.
3. only need a kind of raw material, and be easy to get, do not need special reagent and equipment.
4. easy and simple to handle, except that one step of cyaniding is wanted the controlled temperature when leading to ammonia,, two steps of back all are to reflux under constant temperature.
5. with ULLmann condensation in the past, the potassium permanganate oxidation synthetic route is compared, and the cost of ether acid has had reduction significantly.
Be that example illustrates synthetic route of the present invention now with the small-sized production in laboratory.
Add 300 milliliters of Mixed XYLENEs in 0.5 liter of four-hole boiling flask successively, 16.7 gram p-nitrobenzoic acids and 30.7 gram phosphorus oxychloride stir, and are heated to boiling.Treat that raw material dissolves the back substantially and feeds ammonia, control reaction temperature is at 115～130 ℃, after gas that the condensation mouth of pipe is emerged is alkalescence, continues logical ammonia half an hour, is incubated 1～2 hour, stopped reaction.Remove dimethylbenzene recovery set usefulness under reduced pressure, solid in the reactor is carried out steam distillation, the p-nitrophenyl formonitrile HCN is overflowed with steam, filters, and washing is dry, promptly obtains pale yellow crystals.
In there-necked flask, add the p-nitrophenyl formonitrile HCN successively, 3.84 gram anhydrous sodium saltpetre, 2.41 gram anhydrous sodium carbonate and 49 milliliters of DMAC.Heated and stirred, control reaction temperature, remove the DMAC recovery set under reduced pressure and use till reddish-brown gas disappears substantially at 170～175 ℃.With brown solid remaining in the reactor with hot wash 3～4 times, filtering drying, obtain khaki 4,4 '-the dicyano phenyl ether.
In autoclave, add 4,4 successively '-the dicyano phenyl ether, 8.65 gram sodium hydroxide and 80 ml waters are heated to 140～150 ℃, stop heating after six hours, reactant is taken out use activated carbon decolorizing.Then in hot solution with excessive 50% concentrated hydrochloric acid acidifying.This moment, the ether acid precipitation of adularescent was separated out, and with little fiery heated and boiled half an hour, was cooled to the room temperature suction filtration, and washed with water to filtrate and do not have chlorion, placed the vacuum drying oven drying to obtain 9.47 humid ether acid and restrained finished products.
This ether acid fusing point is 332～333 ℃ (secondary mark meters) after measured, and HPLC analytical results purity is greater than 99%.
Claims (3)
1, a kind of 4,4 '-synthetic route of phenyl ether dioctyl phthalate, it is characterized in that with the p-nitrobenzoic acid being raw material, through cyanogenation, condensation reaction and three steps of hydrolysis reaction make 4,4 '-the phenyl ether dioctyl phthalate.
2, be at solvent DMAC(N by the described condensation reaction of claim 1, N-dimethyl acetyl by) in carry out.Raw material and reagent proportioning are (1M) p-nitrophenyl formonitrile HCN: (0.4～1M) potassium nitrite: (0.2～0.5M) yellow soda ash.After finishing, reaction removes solvent under reduced pressure.
3, be to carry out in basic solution by the described hydrolysis reaction of claim 1, its basicity is 8～12% sodium hydroxide solutions, 130～150 ℃ of temperature of reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89109210 CN1019484B (en) | 1989-12-08 | 1989-12-08 | Synthesizing 4,4' diphenyl ether diformic acid from p-nitrophenyl formic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89109210 CN1019484B (en) | 1989-12-08 | 1989-12-08 | Synthesizing 4,4' diphenyl ether diformic acid from p-nitrophenyl formic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1052300A true CN1052300A (en) | 1991-06-19 |
| CN1019484B CN1019484B (en) | 1992-12-16 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 89109210 Expired CN1019484B (en) | 1989-12-08 | 1989-12-08 | Synthesizing 4,4' diphenyl ether diformic acid from p-nitrophenyl formic acid |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1211235A3 (en) * | 2000-11-30 | 2004-01-02 | JFE Chemical Corporation | Preparation process of 4,4'-Dicarboxydiphenyl ethers or derivatives thereof |
| JP2013159585A (en) * | 2012-02-07 | 2013-08-19 | Air Water Inc | Method of producing 3,3',4,4'-tetracyano diphenyl ether |
| CN104311408A (en) * | 2014-09-12 | 2015-01-28 | 沈阳化工研究院有限公司 | Preparation method of 4,4'-oxybisbenzoic acid |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101774909B (en) * | 2010-02-24 | 2012-10-03 | 常州市阳光医药原料有限公司 | Method for preparing 4, 4'-diphenyl ether dicarboxylic acid |
-
1989
- 1989-12-08 CN CN 89109210 patent/CN1019484B/en not_active Expired
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1211235A3 (en) * | 2000-11-30 | 2004-01-02 | JFE Chemical Corporation | Preparation process of 4,4'-Dicarboxydiphenyl ethers or derivatives thereof |
| JP2013159585A (en) * | 2012-02-07 | 2013-08-19 | Air Water Inc | Method of producing 3,3',4,4'-tetracyano diphenyl ether |
| CN104311408A (en) * | 2014-09-12 | 2015-01-28 | 沈阳化工研究院有限公司 | Preparation method of 4,4'-oxybisbenzoic acid |
| CN104311408B (en) * | 2014-09-12 | 2019-11-08 | 沈阳化工研究院有限公司 | The preparation method of 4,4 '-oxydibenzoic acids |
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| Publication number | Publication date |
|---|---|
| CN1019484B (en) | 1992-12-16 |
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