GB2155012A - Preparation of 2,3-pyridinedicarboxylic acid from 5-halo-8-hydroxyquinoline - Google Patents
Preparation of 2,3-pyridinedicarboxylic acid from 5-halo-8-hydroxyquinoline Download PDFInfo
- Publication number
- GB2155012A GB2155012A GB08504956A GB8504956A GB2155012A GB 2155012 A GB2155012 A GB 2155012A GB 08504956 A GB08504956 A GB 08504956A GB 8504956 A GB8504956 A GB 8504956A GB 2155012 A GB2155012 A GB 2155012A
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- United Kingdom
- Prior art keywords
- acid
- hydroxyquinoline
- solution
- halo
- pyridinedicarboxylic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/803—Processes of preparation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/80—Acids; Esters in position 3
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
1 GB 2 155 012A 1
SPECIFICATION
A process for the preparation of 2,3-pyridinedicarboxylic acid The present invention relates to a novel process for the preparation of pyridine-2, 3-carboxylic 5 acid by catalytic oxidation of a 5-halo-8-hydroxyquinoline and, in particular, of 5-chloro-8 hydroxyquinoline.
The preparation of 2,3-pyridinedicarboxylic acid by oxidation of 8hydroxyquinoline with nitric acid at 0' to 5'C is known (q.v. Houben-Weyl, Methoden der organischen Chemie, 4/1 a (1955), pp. 731-732). According to the teaching of DE-B-455 386, 2,3- pyridinedicarboxylic 10 acid can also be obtained by treating 6-chloro-8-hydroxyquinoline with nitric acid at elevated temperature in the range from 70 to 90C.
It is also known from the same Houben-Weyl reference cited above that quinoline can be degraded to nicotinic acid with nitric acid/sulfuric acid using ammonium vanadate as catalyst.
It has now been found the 2,3-pyridinedicarboxylic acid can be prepared in good yield and 15 high quality by oxidising 5-halo-8-hydroxyquinoline with nitric acid using specific catalysts.
Accordingly, the present invention relates to a process for the preparation of 2,3-pyridinedicarboxylic acid, which comprises catalytically oxidising a 5-halo-8-hydroxyquinoline, or a salt thereof, wherein halogen denotes bromine, flourine, iodine or, preferably, chlorine, with nitric acid in the presence of a vanadium compound and in the temperature range from 70 to 20 1 10C.
The principal feature of the invention is that an 8-hydroxyquinoline which contains a halogen atom, preferably a chlorine atom, in the 5-position, is oxidised with nitric acid. The characteristic feature of the invention is that the oxidation is carried out, under the stated conditions, in the presence of a catalyst selected from the series of the vanadium compounds. The oxidation is preferably carried out in the presence of hydrochloric acid.
The vanadium compounds suitable for use as catalysts are conveniently those that are soluble in nitric acid or in a mixture of nitric acid and hydrochloric acid. Particularly suitable catalysts are vanadium sulfate, alkali metal vanadates, for example the potassium or sodium salts thereof, or, in particular, ammonium vanadate.
The vanadium compounds eligible for use in the process of this invention have an excellent catalytic effect and can be used in low amounts. After the oxidation, the catalyst can be easily separated by filtering off the resultant, 2,3-pyridinedicarboxylic acid and washing with water, thus affording the 2,3-pyridinedicarboxylic acid in excellent purity. In addition, the filtrate containing the catalyst is concentrated to dryness and can be re-used in a continous oxidation 35 process to give a substantially improved yield.
The amount of catalyst is conveniently in the range from 0.001 to 10% by weight or 0.01 to 10% by weight, preferably from 0. 1 to 5% by weight, based on the amount of starting material employed. It is preferred to use ammonium vanadate in an amount of 1 to 3. 5% by weight, based on the amount of starting material.
The starting 5-halo-8-hydroxyquinolines can be in the form of free bases or of salts, preferably acid salts, e.g. hydrogen sulfates or hydrohalides, as for example hydrobromides or, preferably, hydrochlorides. Suitable salt-forming acids are organic or, preferably, inorganic acids, for example formic acid, acetic acid, sulfuric acid, hydrobromic acid or, in particular, hydrochloric acid.
Exemplary of suitable starting materials are: 5-bromo-8-hydroxyquinoline, 5-fluoro-8-hydroxy quinoline, 5-iodo-8-hydroxyquinoline and, in particular, 5-chloro-8- hydroxyquinoline as well as the corresponding quinolinium hydrogen sulfates, quinolinium hydrochlorides or quinolinium hydrobromides.
Isomeric 6-halo-8-hydroxyquinoline and salts thereof, however, do not yield, 2,3-pyridinedicar- 50 boxylic acid under the reaction conditions of this invention.
In the process of the invention, nitric acid is employed as oxidising agent. The nitric acid may be in the form of an aqueous solution having a concentration in the range from 40 to 90% by weight, or of a mixture of 64-68% nitric acid with 100% nitric acid. The actual amount of oxidising agent is conveniently in the range from 1.1 to 4, preferably 1. 2 to 1.9, molar 55 equivalents, based on the 5-halo-8-hydroxyquinoline or a salt thereof.
The nitric acid is preferably employed in admixture with concentrating hydrochloric acid (35-40%), with the ratio of HN03 to HC1 being conveniently from 5:1 to 1:1, preferably from 3:1 to 2: 1.
As the reaction is exothermic, it is usually advantageous to carry out the process in the 60 temperature range from 70 to 11 O'C, preferably from 80' to 1 00C and, most preferably, from 90 to 95'C. It is possible to exceed the temperature range of 11 O'C, but this has the disadvantage of a more complicated cooling procedure and involves the risk of a decarboxylation to nicotinic acid.
The 2,3-pyridinedicarboxylic acid obtainable by the process of this invention is a valuable 65 2 GB 2155 012A 2 starting material for a very wide range of chemical syntheses. In particular, it is a starting material for the preparation of 1-azaanthraquinone dyes or of 3,3- disubstituted azaphthalides or of azafluoranes which are substituted by basic groups, which compounds are suitable for use as colour formers in pressure-sensitive or heat-sensitive recording materials.
The following non-limitative Examples illustrates the invention in more detail. Percentages are 5 by weight.
Example 1: With stirring, 1.0 9 of ammonium vanadate is dissolved in 300 m] of concentrated (64%) nitric acid. Then 30 g of powdered 5-chloro-8-hydroxyquinoline are added and the temperature rises to 40'-45'C. After about 1 minute the reaction commences, accompanied by 10 the evolution of nitrous gases, and the temperature rises slowly to 91 93C. The reaction mixture is cooled to 25C and the solution is concentrated to dryness on a rotary evaporator.
Then two 150 m] portions of water are added the solution is again concentrated to dryness. The residue is crystallised by addition of 50 m] of ice-water and the crystals are collected by filtration, washed with 50 mi of ice-water and dried in vacuo over phosphorus pentoxide, 15 affording 22.3 g of 2,3-pyridinedicarboxylic acid. The yield is 79.7% of theory.
Analysis of the 2,3-pyridinedicarboxylic acid (CH,N04) cal.: C 50.31 % H 3.02% N 8.38% found: C 49.9 % H 3.1 % N 8.4 % Example 2: The catalyst solution obtained by filtration in Example 1 is also concentrated to dryness and the residue is dissolved in 300 mi of concentrated hydrochloric acid. To this solution are added 30 9 of 5-chloro-8-hydroxyquinoline and the temperature rises to WC over the course of 5-10 minutes. The solution is then cooled at 25C and worked up as described in 25 Example 1. The product is then dried, affording 27.5 g of 2,3- pyridinedicarboxylic acid with a melting point of 183'- 1 86'C. The yield is 98% of theory.
The filtered catalyst solution can be re-used after being concentrated to dryness once more.
Example 3:1 g of vanadium pentoxide is suspended in 5 ml of concentrated sulfuric acid and, 30 with stirring, the suspension is heated to 1 55C, whereupon the vanadium pentoxide goes into solution to form vanadium sulfate. This solution is added to 300 ml of concentrated (64 %) nitric acid to form a clear yellow solution. To this new solution are added 30 g of 5-chloro-8 hydroxyquinoline at 20-25C and the procedure of Example 1 is carried out, giving 20 g of 2,3-pyridinedicarboxylic acid. The yield is 75.5 % of theory.
Example 4: To a solution of 1 9 of ammonium vanadate in 300 mi of 64% nitric acid are added 30 9 of 5-bromo-8-hydroxyquinoline, the temperature rising to 45'-50C. The reaction then commences, accompanied by the formation of nitrous gases, and the temperature rises to 93C The reaction mixture is cooled to room temperature and the resultant solution is worked up as 40 described in Example 1, affording 22 g of 2,3-pyridinedicarboxylic acid. The yield is 79 % of theory.
Example 5: To a solution of 1.5 g of ammonium vanadate in 300 ml of 64 % nitric acid are added 54 g of 5-chloro-8-hydroxyquinolinium hydrogen sulfate, the temperature rising to 88C accompanied by the evolution of nitrous gases. Upon completion of the reaction, the solution is cooled and concentrated on a rotary evaporator. The residue is treated with a solution of 35 g of sodium bicarbonate in 200 ml of water to give a beigecoloured precipitate which is isolated by filtration and washed with 50 ml of ice-water. The yield of 2,3-pyridinedicarboxylic acid is 17 g.
Example 6: To a solution of 1 g of ammonium vanadate in 300 mi of 64 % nitric acid are added 30 g of 5-chloro-8-hydroxyquinolinium hydrochloride, the temperature rising to 45C.
The temperature then rises further to 93C accompanied by the evolution of nitrous gases. The solution is then cooled and worked up as described in Example 1, affording 2,3-pyridinedicar boxylic acid in a yield of 22 g.
The filtrate obtained during working up that contains the catalyst is concentrated to dryness and re-used in a further batch for obtaining 2,3-pyridinedicarboxylic acid.
Example 7: 0.1 g of ammonium vanadate is dissolved in a mixture of 100 mi of 100% nitric acid and 200 mi of 64 % nitric acid. This mixture is cooled to WC and then 30 g of 5-chloro-8- 60 hydroxyquinoline is slowly stirred in, with external cooling, so that the temperature does not rise above 25C. The cooling bath is then removed and the temperature rises to 50-55C, whereupon vigorous evolution of nitrous gases ensues and the temperature rises further to 87'C. The solution is cooled and concentrated to dryness at 70C/39 mbar. The residual crystals are washed with 50 mi of ice-water, isolated by filtration and dried, affording 25.2 g of 2,3- 65 GB2155012A 3 pyridinedicarboxylic acid with a melting point of 182'C (decomposition).
Example 8: To a solution of 20 mg of ammonium vanadate in 90 mi of 64 % nitric acid and 30 mi of concentrated (38 %) hydrochloric acid are added 30 g of 5-chloro-8-hydroxyquinoline at 22'-25'C over 15 minutes, the temperature rising to 43'C over 20 minutes. The mixture is heated to 6WC over 20 minutes, whereupon evolution of gas commences and crystals precipitate from the solution. The temperature rises to 75-80'C. Upon cessation of the gas evolution, the temperature is maintained by heating for 1 1 /2 hours to 7W-75'C. The acids are then removed by evaporation at 7TC/39 mbar. The crystalline residue is stirred in 50 mi of10 ice-water, isolated by filtration and dried, affording 27.6 g of 2,3pyridinedicarboxylic acid with a melting point of 181 - 1 82T (decomposition).
If external cooling is not applied at the onset of the reaction, then the temperature rises to 85C. Working up in similar manner then yields 28.5 g of 2,3-pyridinedicarboxylic acid with a melting point of 182C (decomposition).
Example 9: 20 mg of ammonium vanadate are added to a solution of 90 ml of 64 % nitric acid and 30 ml of concentrated (38 %) hydrochloric acid. With stirring, 44 g of 5-chloro-8hydroxyquinoline hydrogen sulfate are added at room temperature. The mixture is slowly heated to 60C to give a clear solution, the reaction commencing with evolution of gas and the temperature rising to 84C. After the temperature has fallen, it is maintained at 72-73C for 1 hour by heating. The resultant suspension is concentrated by evaporation and a solution of 5 g of sodium hydroxide in 60 ml of water is added to the semi-solid residue. The suspension is cooled in ice-water and the precipitated crystals are isolated by filtration and dried, affording 17.3 g of 2,3-pyridinedicarboxylic acid with a melting point of 1 82'C (decomposition).
Example 10: 20 mg of sodium vanadate are added to a mixture of 90 mi of 64 % nitric acid and- 30 mi of concentrated (38 %) hydrochloric acid. With cooling and stiring, 30 g of 5-chloro8-hydroxyquinoline are added to the solution. Stirring is continued for 30 minutes at increasing temperature (25-40C) and the solution is heated to 65C. The reaction commences accompanied by evolution of gas and a rise in temperature up to 87,C. The reaction mixture is maintained for 15 minutes at 85'-87% and the product is isolated as described in Example 8, affording 27 g of 2,3pyridinedicarboxylic acid in the form of yellowish crystals with a melting point of 181 -1 82C.
Claims (7)
1. A process for the preparation of 2,3-pyridinedicarboxylic acid, which comprises catalytically oxidising 5-halo-8-hydroxyquinoline or a salt thereof, wherein halogen denotes bromine, chlorine, fluorine or iodine, with nitric acid in the presence of a vanadium compound and in the temperature range from 70 to 11 WC.
2. A process according to claim 1, wherein the oxidation is carried out in the presence of hydrochloric acid, the ratio of HN03 to I-IC1 being from 5:1 to 1A.
3. A process according to either claim 1 or claim 2, wherein the vanadium compound is employed in an amount of 0.001 to 10 % by weight, based on the amount of 5-halo-8- hydroxyquinoline or a salt thereof.
4. A process according to claim 1, wherein 5-chloro-8-hydroxyquinoline is oxidised to 2,3 pyridinedicarboxylic acid.
5. A process according to any one of claims 1 to 4, wherein the oxidation is carried out in the presence of ammonium vanadate, an alkali metal vanadate or vanadium sulfate.
6. A process according to any one of claims 1 to 5, wherein the oxidation is carried out in 50 the temperature range from 90 to 9WC.
7. 2,3-Pyridinedicarboxylic acid prepared by a process as claimed in any one of claims 1 to 6.
Printed in the United Kingdom for Her Majesty's Stationery Office, Dd 8818935. 1985. 4235. Published at The Patent Office, 25 Southampton Buildings, London, WC2A l AY, from which copies may be obtained-
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH101184 | 1984-03-01 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8504956D0 GB8504956D0 (en) | 1985-03-27 |
| GB2155012A true GB2155012A (en) | 1985-09-18 |
| GB2155012B GB2155012B (en) | 1987-03-18 |
Family
ID=4200361
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08504956A Expired GB2155012B (en) | 1984-03-01 | 1985-02-26 | Preparation of 2,3-pyridinedicarboxylic acid from 5-halo-8-hydroxyquinoline |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0153908A1 (en) |
| JP (1) | JPS60202863A (en) |
| DE (1) | DE3506681A1 (en) |
| GB (1) | GB2155012B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3614756A1 (en) * | 1986-04-30 | 1987-11-05 | Ruetgerswerke Ag | METHOD FOR THE PRODUCTION OF 5-ALKYLCHINOLIN ACIDS AND AGENT FOR IMPLEMENTING THE METHOD |
| US5371229A (en) * | 1992-10-28 | 1994-12-06 | American Cyanamid Company | Method for the preparation of 2,3-pyridine-dicarboxylic acids and derivatives thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE455386C (en) * | 1924-09-09 | 1928-02-01 | Chemische Ind Ges | Process for the preparation of pyridine-2,3-dicarboxylic acid (quinoline acid) |
| DE945147C (en) * | 1945-03-29 | 1956-07-05 | Riedel De Haeen Ag | Process for the preparation of pyridine-2,3-dicarboxylic acid |
| DE3150005A1 (en) * | 1981-12-17 | 1983-06-23 | Rütgerswerke AG, 6000 Frankfurt | METHOD FOR PRODUCING CHINOLIN ACID |
-
1985
- 1985-02-25 EP EP85810075A patent/EP0153908A1/en not_active Withdrawn
- 1985-02-26 DE DE19853506681 patent/DE3506681A1/en not_active Withdrawn
- 1985-02-26 GB GB08504956A patent/GB2155012B/en not_active Expired
- 1985-03-01 JP JP3894185A patent/JPS60202863A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| EP0153908A1 (en) | 1985-09-04 |
| GB8504956D0 (en) | 1985-03-27 |
| DE3506681A1 (en) | 1985-09-12 |
| JPS60202863A (en) | 1985-10-14 |
| GB2155012B (en) | 1987-03-18 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |