CN107868006B - A kind of method of purification of the chloro- 4,6- dinitroresorcinol of 2- - Google Patents
A kind of method of purification of the chloro- 4,6- dinitroresorcinol of 2- Download PDFInfo
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- CN107868006B CN107868006B CN201610855683.8A CN201610855683A CN107868006B CN 107868006 B CN107868006 B CN 107868006B CN 201610855683 A CN201610855683 A CN 201610855683A CN 107868006 B CN107868006 B CN 107868006B
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- dinitroresorcinol
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/16—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/08—Preparation of nitro compounds by substitution of hydrogen atoms by nitro groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
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- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to organic chemistry fileds, and in particular to a kind of method that highly acid impurity (Acidity is relative to chloro- 4, the 6- dinitroresorcinol of 2-) is removed from the acetic acid ethyl acetate extract of chloro- 4, the 6- dinitroresorcinol of 2-.The present invention is by using strong base weak acid saline solution chloro- to the 2- containing highly acid impurity 4, the ethyl acetate solution of 6- dinitroresorcinol mixed, separating treatment, effectively remove 2- chloro- 4, highly acid impurity in 6- dinitroresorcinol solution, improve the purity of chloro- 4, the 6- dinitroresorcinol of 2-.
Description
Technical field
The present invention relates to organic chemistry fileds, and in particular to a kind of acetic acid second from chloro- 4, the 6- dinitroresorcinol of 2-
The method of highly acid impurity (Acidity is relative to the chloro- 4,6- dinitroresorcinol of 2-) is removed in ester extract liquor.
Background technique
Polyparaphenylene's benzo dioxazole (hereinafter referred PBO) is a kind of high-performance fiber, has been used for military affairs, space flight etc. at present
Field, 4,6-diaminoresorcinol (hereinafter referred DAR) hydrochloride are one of the important monomer of synthetic fibers PBO, DAR preparation
It is with 1,2,3- trichloro-benzenes for raw material, is prepared through nitrification, hydrolysis plus the reaction of the processes such as hydrogen and recrystallization.Specific steps are such as
Under: 1,2,3- trichloro-benzenes obtains 1,2,3- tri- chloro- 4,6- dinitrobenzenes (A) after nitration reaction, and A obtains 2- through hydrolysis, acidification reaction
Chloro- 4,6- dinitroresorcinol (CDNR) acidifying solution, acidifying solution obtain hydrolysis extraction liquid, hydrolysis extraction after extracting with ethyl acetate
Up to hydrolysis finished product CDNR after liquid distillation.
1,2,3- trichloro-benzenes in addition to generating target product A, while having 1 during nitration reaction, 2,3- tri- chloro- 4- nitre
Base benzene and 1,2,3- tri- two kinds of chloro- 5- nitrobenzene nitrification impurity generate, both impurity in sequential hydrolysis reaction process simultaneously
Hydrolysis occurs, generates corresponding hydroxyl impurity, due to the difference of molecular structure, these hydroxyl impurity and CDNR are shown
The acidity shown is variant, using the difference of acidity, can carry out the separation of impurity.
The processing method of the impurity generated at present to hydrolytic process includes: that (1) is carried out at recrystallization with methanol or n-butanol
Reason；(2) ethyl alcohol and water carry out dissolved processing；(3) reaction product is washed with methanol, such processing method purification mechanism is
By impurity and CDNR, dissolubility difference passes through the dissolving crystallized raising chloro- 4,6- dinitroresorcinol of 2- in organic solvent
Purity can partially reduce the impurity content in CDNR.
Summary of the invention
The technical problem to be solved in the present invention: the highly acid impurity in above-mentioned hydrolysis extraction liquid is removed.This method will hydrolyze
Strong base weak acid salting liquid, stirring, after standing that organic phase is separated from the water, realization removal chloro- 4, the 6- bis- of 2- are added in extract liquor
The purpose of nitro-resorcinol middle strong acidity impurity.Chloro- 4, the 6- dinitro isophthalic of 2- can be improved in processing by the method for the invention
The purity of diphenol.
Main technical schemes of the invention: the method for purification of chloro- 4, the 6- dinitroresorcinol of 2- is from 2- chloro- 4,6-
The method that highly acid impurity is removed in dinitroresorcinol extract liquor, 1,2,3- trichloro-benzenes obtain 1,2,3- tri- after nitration reaction
Chloro- 4,6- dinitrobenzene, 1,2,3- tri- chloro- 4,6- dinitrobenzene obtain chloro- 4, the 6- dinitro isophthalic two of 2- through hydrolysis, acidification reaction
Phenol anaerobic hydrolysate, anaerobic hydrolysate are obtained hydrolysis extraction liquid, hydrolyzed after the distillation of hydrolysis extraction liquid after being extracted with ethyl acetate
Chloro- 4, the 6- dinitroresorcinol of finished product 2-, it is characterised in that strong base weak acid salting liquid is stirred with hydrolysis extraction liquid, is quiet
It sets, separate, the highly acid impurity in hydrolysis extraction liquid is separated to water phase, purifying 2-chloro -4,6- dinitroresorcinol is reached
Purpose, it is characterised in that the following steps are included:
A) strong base weak acid salting liquid is added into hydrolysis extraction liquid, stands, be layered after stirring；Form oil phase and water phase；
B) to ethyl acetate is added in separation water phase in a), add dilute hydrochloric acid acidification, stand, be layered after stirring, to point
It is extracted from chloro- 4, the 6- dinitroresorcinol of part 2- in water phase, extract liquor is incorporated into the anaerobic hydrolysate of lower batch.
Generally, selected strong base-weak acid salt is sodium carbonate or solution of potassium carbonate.
Selected strong base weak acid concentration of salt solution is 5~10%.
It is that DAR prepares the 5~10% of starting material 1,2,3- trichloro-benzenes molal quantity that molal quantity, which is added, in the strong acid weak base salt.
Selected concentration of hydrochloric acid solution is 5~15%.
The acidification hydrochloric acid additional amount molal quantity is the 30~50% of strong acid weak base salt amount molal quantity.
Beneficial effects of the present invention: compared with prior art, the present invention has the following advantages: the present invention is by being added on a small quantity
Strong base-weak acid salt handles hydrolysis extraction liquid, and the highly acid impurity in hydrolysis extraction liquid is removed, and reaches purification CDNR's
Purpose, while the water phase containing impurity generated after the processing of strong base weak acid salting liquid is acidified, is extracted, it reduces because purification is led
The loss of material of cause.
Specific embodiment
The present invention is further illustrated combined with specific embodiments below.
Embodiment 1
On four-hole bottle device with stirring, chloro- 4, the 6- dinitroresorcinol (CDNR) of 200mL2- is added into four-hole bottle
Ethyl acetate solution (including CDNR about 0.092mol), add 10 grams of 10% aqueous sodium carbonate, stratification after stirring,
Detect content of organics in oily phase and water phase respectively with high performance liquid chromatography, water phase middle strong acidity impurity content is 5.98%, 2-
Chloro- 4,6- dinitroresorcinol content is 94.01%, is not detected highly acid impurity in oily phase, between chloro- 4, the 6- dinitro of 2-
Benzenediol content is 98.56%.
Device is same as above.The separation water phase in example 1 is added in four-hole bottle, ethyl acetate 20mL is added, adds 15%
1 gram of hydrochloric acid, stratification after stirring analyzes content of organics in oily phase and water phase, water phase middle strong acidity with liquid chromatogram respectively
Impurity content is that chloro- 4, the 6- dinitroresorcinol content of 11.74%, 2- is 88.26%, and oily phase middle strong acidity impurity is 0.05%,
The chloro- 4,6- dinitroresorcinol content of 2- is 98.48%.
Embodiment 2
The acetic acid second of chloro- 4, the 6- dinitroresorcinol (CDNR) of 200mL2- is added into four-hole bottle with example 1 for device
Ester solution (includes CDNR about 0.092mol), adds 10 grams of 5% aqueous sodium carbonate, stratification after stirring, with efficient liquid phase
Chromatography detects content of organics in oily phase and water phase respectively, and water phase middle strong acidity impurity content is chloro- 4, the 6- dinitro of 4.23%, 2-
Base resorcinol content is 95.77%, highly acid impurity is not detected in oily phase, chloro- 4, the 6- dinitroresorcinol content of 2- is
98.56%。
Device is same as above.The separation water phase in example 1 is added in four-hole bottle, ethyl acetate 20mL is added, adds 5%
10 grams of hydrochloric acid, stratification after stirring analyzes content of organics in oily phase and water phase, water phase middle strong acidity with liquid chromatogram respectively
Impurity content is that chloro- 4, the 6- dinitroresorcinol content of 8.26%, 2- is 91.73%, and oily phase middle strong acidity impurity is 0.07%,
The chloro- 4,6- dinitroresorcinol content of 2- is 98.35%.
Embodiment 3
The acetic acid second of chloro- 4, the 6- dinitroresorcinol (CDNR) of 200mL2- is added into four-hole bottle with example 1 for device
Ester solution (includes CDNR about 0.092mol), adds 12 grams of 10% wet chemical, stratification after stirring, with efficient liquid
Phase chromatography detects content of organics in oily phase and water phase respectively, and water phase middle strong acidity impurity content is chloro- 4, the 6- bis- of 5.95%, 2-
Nitro-resorcinol content is 94.05%, and highly acid impurity, chloro- 4, the 6- dinitroresorcinol content of 2- is not detected in oily phase
It is 98.50%.
Device is same as above.The separation water phase in example 1 is added in four-hole bottle, ethyl acetate 20mL is added, adds 10%
1 gram of hydrochloric acid, stratification after stirring analyzes content of organics in oily phase and water phase, water phase middle strong acidity with liquid chromatogram respectively
Impurity content is that chloro- 4, the 6- dinitroresorcinol content of 11.80%, 2- is 88.20%, and oily phase middle strong acidity impurity is 0.07%,
The chloro- 4,6- dinitroresorcinol content of 2- is 98.42%.
Above example shows:, can be with by being stirred, being separated to hydrolysis extraction liquid with sodium carbonate or wet chemical
The highly acid impurity in hydrolysis extraction liquid is effectively removed, and the aqueous solution by generating to processing carries out acidification and extraction processing,
Can chloro- 4, the 6- dinitroresorcinol component of 2- in partially recycled extract liquor, loss of material caused by reducing because of purification.
Claims (6)
1. a kind of method of purification of chloro- 4, the 6- dinitroresorcinol of 2- is from chloro- 4, the 6- dinitroresorcinol extract liquor of 2-
It is middle removal highly acid impurity method, 1,2,3- trichloro-benzenes after nitration reaction 1,2,3- tri- chloro- 4,6- dinitrobenzenes, 1,2,
Chloro- 4, the 6- dinitrobenzene of 3- tri- obtains chloro- 4, the 6- dinitroresorcinol anaerobic hydrolysate of 2-, hydrolysis acid through hydrolysis, acidification reaction
Change and obtain hydrolysis extraction liquid after liquid is extracted with ethyl acetate, up to hydrolysis chloro- 4, the 6- dinitro of finished product 2- after the distillation of hydrolysis extraction liquid
Resorcinol, it is characterised in that strong base weak acid salting liquid is stirred with hydrolysis extraction liquid, stands, separates, by hydrolysis extraction liquid
In highly acid impurity separate to water phase, reach the purpose of purifying 2-chloro -4,6- dinitroresorcinol, comprising the following steps:
A) strong base weak acid salting liquid is added into hydrolysis extraction liquid, stands, be layered after stirring；Form oil phase and water phase；
B) to ethyl acetate is added in separation water phase in a), dilute hydrochloric acid acidification is added, stands, be layered after stirring, to separation water
Chloro- 4, the 6- dinitroresorcinol of part 2- in phase is extracted, and extract liquor is incorporated into the anaerobic hydrolysate of lower batch.
2. the method according to claim 1, wherein selected strong base-weak acid salt is sodium carbonate or solution of potassium carbonate.
3. method according to claim 1 or 2, which is characterized in that selected strong base weak acid concentration of salt solution is 5~10%.
4. the method according to claim 1, wherein it is prepared by DAR that molal quantity, which is added, in the strong acid weak base salt
The 5~10% of beginning raw material 1,2,3- trichloro-benzenes molal quantity.
5. the method according to claim 1, wherein selected concentration of hydrochloric acid solution is 5~15%.
6. method according to claim 1 or 5, it is characterised in that acidification hydrochloric acid additional amount molal quantity is strong acid weak base salt amount
The 30~50% of molal quantity.
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| CN201610855683.8A CN107868006B (en) | 2016-09-28 | 2016-09-28 | A kind of method of purification of the chloro- 4,6- dinitroresorcinol of 2- |
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| CN201610855683.8A CN107868006B (en) | 2016-09-28 | 2016-09-28 | A kind of method of purification of the chloro- 4,6- dinitroresorcinol of 2- |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101811972A (en) * | 2010-04-23 | 2010-08-25 | 哈尔滨工业大学 | Method for separating and purifying 2-chlorine-4,6-dinitroresorcinol in dilution crystallization method |
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- 2016-09-28 CN CN201610855683.8A patent/CN107868006B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101811972A (en) * | 2010-04-23 | 2010-08-25 | 哈尔滨工业大学 | Method for separating and purifying 2-chlorine-4,6-dinitroresorcinol in dilution crystallization method |
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Address after: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 699 Patentee after: China Petroleum & Chemical Corp. Patentee after: SINOPEC NANJING CHEMICAL RESEARCH INSTITUTE Co.,Ltd. Address before: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 699 Patentee before: China Petroleum & Chemical Corp. Patentee before: Nanhua Group Research Institute |