CN1062905A - 4-hydroxyl-7-chloro-quinolinic acid synthetic method - Google Patents
4-hydroxyl-7-chloro-quinolinic acid synthetic method Download PDFInfo
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- CN1062905A CN1062905A CN 91100048 CN91100048A CN1062905A CN 1062905 A CN1062905 A CN 1062905A CN 91100048 CN91100048 CN 91100048 CN 91100048 A CN91100048 A CN 91100048A CN 1062905 A CN1062905 A CN 1062905A
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- quinolinic acid
- amidine
- chloro
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- ester
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Abstract
4-hydroxyl-7-chloro-quinolinic acid synthetic method, be a kind of organic substance synthetic technology, present technique mainly solves the existing 4-of production hydroxyl-7-chloro-quinolinic acid method, and the raw materials consumption height of existence, price are expensive, the while present technique is suitable for pushes to production, is a kind of significant practical technique that takes effect.
Description
Quinolinic acid is a kind of widespread use industrial chemicals, mainly uses dyestuffs industries and pharmaceutical industry
At present, the industrial production synthetic method of 4-hydroxyl-7-chloro-quinolinic acid generally adopts, Price, C.C.Rolerts, R.M.L.Am, Chem, Soc, 1964,68,1255 and Shen Shenshen, the improvement report of chloroquine intermediate 4-hydroxyl 7-chloro-quinolinic acid preparation, 1965.This method is called for short, improved diethyl ethoxymethylene method, used triethyl orthoformate, with diethyl malonate, reflux through the manufacturing of amidine ester with m-chloro aniline, quinolinic acid is made two step operations, and there is the raw materials consumption height in this method, and price is expensive is unfavorable for reducing the industrial chemicals price and improves the export market competitive power.
The objective of the invention is to, a kind of synthetic method of new 4-hydroxyl-7-chloro-quinolinic acid is provided, it is characterized in that adopting trimethyl orthoformate and dimethyl malonate, replace triethyl orthoformate and diethyl malonate, thereby reduce the cost of materials consumed.
Described 4-hydroxyl of the present invention-7-chloro-quinolinic acid synthetic method is made and two step of quinolinic acid manufacturing operations through the amidine ester, and its technological process is as follows:
1, the amidine ester is made
(1) ratio of components (weight ratio)
M-chloro aniline: trimethyl orthoformate: dimethyl malonate: boron trifluoride diethyl etherate=1: 0.902: 1.321: 0.012.
(2) technological process
At this moment m-chloro aniline and half trimethyl orthoformate of measuring are added the reaction flask internal heating had methyl alcohol to generate in 3 hours to 75-85 ℃ of backflow, boil off methyl alcohol up to steaming to the greatest extent, at this moment temperature is to 110 ℃ in, add dimethyl malonate then, the trimethyl orthoformate and the boron trifluoride diethyl etherate of other half amount, reheat refluxed 6 hours to 105-110 ℃, there is methyl alcohol to generate, boil off methyl alcohol and finish, during interior temperature to 130 ℃, be incubated 6 hours, about 30 ℃ of adding toluene are finished in insulation, adding 30% hcl acidifying PH is 3, and layering, toluene liquid wash PH6-7 with water, steam toluene to the greatest extent amidine ester yield 89%.
2, quinolinic acid manufacturing
(1) ratio of components (weight ratio)
Amidine ester: Valelinum Liquidum: hydrochloric acid=1: 2.5: 1.8
(2) technological process
A certain amount of Valelinum Liquidum of suction in the there-necked flask stirs and heats up, when interior temperature to 270 ℃ adding amidine ester, keep 270 ℃ 30 minutes, pour Valelinum Liquidum and be cooled to 110 ℃ and add 30% hydrochloric acid,, be cooled to that 30C filters, dry quinolinic acid yield 85% 105 ℃ of-110 ℃ of hydrolysis 8 hours.
Example
1, the amidine ester is made
For better explanation, example is as follows: m-chloro aniline 100g and trimethyl orthoformate 45g are added three mouthfuls of reaction flasks, be heated to backflow, kept 3 hours, and boiled off methyl alcohol then, temperature is to 110 ℃ in treating, add dimethyl malonate 132g and 45g trimethyl orthoformate and boron trifluoride diethyl etherate liquid 1.2g again, the temperature rising reflux reaction is 6 hours again, and backflow finishes, and boils off methyl alcohol, when interior temperature to 130 ℃, be incubated 6 hours, pour into beaker and add about 30 ℃ of toluene, add hydrochloric acid again, transferring PH is 3, layering, it is 6-7 that toluene liquid is washed with water to PH, and toluene liquid only flows out with being atmospherically distilled to no toluene, gets amidine ester 188g yield 89%.
2, quinolinic acid manufacturing
Valelinum Liquidum 125g is added there-necked flask stir, interior temperature rise to 270 ℃ adds 50g amidine ester again, be incubated 30 minutes, pour cold Valelinum Liquidum, be cooled to 110 ℃ and add 30% hydrochloric acid accent PH2.5g, 108 ℃ of insulation reaction 8 hours are chilled to 30 ℃ of suction filtrations, dry quinolinic acid 35g yield 85%.
One, the chemical formula of amidine ester
Claims (6)
1, a kind of compound 4--hydroxyl--method of 7--chloro-quinolinic acid of synthetic following structural formula.
This method comprises that the manufacturing of amidine fat and quinolinic acid make two-step, and the technological process of amidine ester is carried out the m-chloro aniline methyl esters class thing that spreads out, back flow reaction, boil off methyl alcohol then after, insulation again, acidifying, the solubilizing agent layering, the washing of solvent liquid promptly gets the amidine ester.
The quinolinic acid manufacturing is stirred intensification with Valelinum Liquidum, adds the amidine ester, pours Valelinum Liquidum after the insulation reaction and gets cyclocomplex, and the cyclocomplex cooling adds hydrochloric acid again, hydrolysis, suction filtration, the dry quinolinic acid that gets.
2, according to claim 1, methoxyl group methyne diethyl malonate is selected in the manufacturing of amidine ester for use, oxyethyl group methyne dimethyl malonate, and methoxyl group methyne dimethyl malonate and m-chloro aniline reflux, and use the toluene layering, and toluene is steamed in washing, gets the amidine ester.
3, according to claim 1, select trimethyl orthoformate or dimethyl malonate for use in the manufacturing of amidine ester, the solvent of layering extraction is selected for use, benzene, toluene, pentamethylene, ring alkane in the sixth of the twelve Earthly Branches, sherwood oil.
4, according to claim 1,75 ℃-110 ℃ of reflux temperatures.
5, according to claim 1,250 ℃-270 ℃ of cyclization temperature.
6, according to claim 1, catalyzer is selected for use in the manufacturing of amidine ester: boron trifluoride diethyl etherate liquid, ammonia chloride, ammonium nitrate, inferior ammonium nitrate, aluminum chloride, zinc chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91100048 CN1062905A (en) | 1991-01-01 | 1991-01-01 | 4-hydroxyl-7-chloro-quinolinic acid synthetic method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91100048 CN1062905A (en) | 1991-01-01 | 1991-01-01 | 4-hydroxyl-7-chloro-quinolinic acid synthetic method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1062905A true CN1062905A (en) | 1992-07-22 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 91100048 Pending CN1062905A (en) | 1991-01-01 | 1991-01-01 | 4-hydroxyl-7-chloro-quinolinic acid synthetic method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1062905A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103113298A (en) * | 2013-02-27 | 2013-05-22 | 北京格林凯默科技有限公司 | Preparation method of 7-bromo-4-hydroxy-3-quinoline carboxylic acid |
| CN111747890A (en) * | 2020-07-03 | 2020-10-09 | 重庆医药高等专科学校 | Preparation method of 4, 7-dichloroquinoline |
-
1991
- 1991-01-01 CN CN 91100048 patent/CN1062905A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103113298A (en) * | 2013-02-27 | 2013-05-22 | 北京格林凯默科技有限公司 | Preparation method of 7-bromo-4-hydroxy-3-quinoline carboxylic acid |
| CN111747890A (en) * | 2020-07-03 | 2020-10-09 | 重庆医药高等专科学校 | Preparation method of 4, 7-dichloroquinoline |
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| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |