DE936447C - Process for the preparation of isocinchomeronic acid - Google Patents
Process for the preparation of isocinchomeronic acidInfo
- Publication number
- DE936447C DE936447C DED11529A DED0011529A DE936447C DE 936447 C DE936447 C DE 936447C DE D11529 A DED11529 A DE D11529A DE D0011529 A DED0011529 A DE D0011529A DE 936447 C DE936447 C DE 936447C
- Authority
- DE
- Germany
- Prior art keywords
- acid
- isocinchomeronic
- oxidation
- copper
- preparation
- 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.)
- Expired
Links
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
Description
Verfahren zur Herstellung von Isocinchomeronsäure Es ist bekannt, Isocinchomeronsäure, das ist Pyridin-2, 5-dicarbonsäure, durch Oxydation von 2, 5-Dialkyl-pyridinen, besonders von 2-Methyl-5-äthyl-pyridin, mit konzentrierter Salpetersäure von q.o bis 950/, bei Temperaturen zwischen 75 und 2oo° unter Druck herzustellen. Dabei erhält man im günstigsten Falle eine Ausbeute von 72,7 "% der Theorie.Process for the preparation of isocinchomeronic acid It is known Isocinchomeronic acid, that is pyridine-2, 5-dicarboxylic acid, by oxidation of 2, 5-Dialkyl-pyridines, especially of 2-methyl-5-ethyl-pyridine, with concentrated Nitric acid from q.o to 950 /, at temperatures between 75 and 200 ° under pressure to manufacture. In the most favorable case, this gives a yield of 72.7% of the Theory.
Es wurde nun die überraschende Feststellung gemacht, daß man Isocinchomeronsäure in ausgezeichneter Ausbeute erhält, wenn man 2,5-Dialkyl-pyridine, insbesondere 2-Methyl-5-äthyl-pyridin, unter Druck mit Salpetersäure bei Temperaturen von 16o bis 25o°, vorzugsweise zwischen Zoo und 225°, in Gegenwart einer solchen Menge von Kupfersalzen oxydiert, die mindestens zur salzartigen Bindung einer Carboxylgruppe der entstehenden Pyridindicarbonsäure ausreicht. Die gemäß der Erfindung anzuwendende Salpetersäurekonzentration beträgt zweckmäßig 5 bis 63 °/o, vorzugsweise 2o bis 50 °/o. Auf diese Weise wird erreicht, daß die aus dem Dialkylpyridin zuerst immer entstehende Isocinchomeronsäure sofort aus der Reaktionslösung ausfällt.The surprising discovery has now been made that one isocinchomeronic acid obtained in excellent yield if 2,5-dialkyl-pyridines, in particular 2-methyl-5-ethyl-pyridine, under pressure with nitric acid at temperatures of 16o to 25o °, preferably between Zoo and 225 °, in the presence of such an amount of Copper salts are oxidized, which at least lead to the salt-like bond of a carboxyl group the resulting pyridinedicarboxylic acid is sufficient. The one to be used according to the invention The nitric acid concentration is expediently 5 to 63%, preferably 20 to 50 ° / o. In this way it is achieved that the dialkylpyridine always comes first resulting isocinchomeronic acid precipitates out of the reaction solution immediately.
Das gebildete Kupfersalz hat, wie gefunden wurde, die Zusammensetzung Cu (C,H404N)2, d. h. ein Molekül Isocinchomeronsäure hält nur 1/Z Atom Kupfer gebunden. Wenn man annimmt, daß die in a-Stellung zum Stickstoffatom stehende Carboxylgruppe unter den angewandten Umsetzungsbedingungen besonders reaktionsfähig ist, muß man folgern, daß eben diese Gruppe durch Kupfer gebunden wird.The copper salt formed has been found to have the composition Cu (C, H404N) 2, i.e. H. one molecule of isocinchomeronic acid only holds 1 / Z atom of copper bound. Assuming that the carboxyl group in a-position to the nitrogen atom is particularly reactive under the reaction conditions used, one must conclude that this very group is bound by copper.
Das gebildete Kupfersalz ist in saurem Medium bei p$-Werten um i stabil. Daraus kann man nach allgemein bekannten Methoden die Isocinchomeronsäure in Freiheit setzen, z. B. durch Erwärmen mit überschüssigem wäßrigem Alkali, Abtrennung des gebildeten Kupferoxyds und Ansäuern der Lösung des Alkalisalzes. Stellt man diese Lösung auf den isoelektrischen Punkt der Isocinchomeronsäure ein (pH 1,5), so erhält man die freie Säure fast quantitativ in analysenreiner Form. Der Schmelzpunkt beträgt 25q.°, im Gegensatz zu der in der USA.-Patentschrift 2 524 957 angeführten Isocinchomeronsäure vom F. 238°.The copper salt formed is stable in an acidic medium at p $ values around i. From this one can generally look known methods isocinchomeronic acid set free, z. B. by heating with excess aqueous alkali, separation of the copper oxide formed and acidification of the solution of the alkali salt. If you ask this solution to the isoelectric point of isocinchomeronic acid (pH 1.5), in this way the free acid is obtained almost quantitatively in analytically pure form. The melting point is 25q. ° as opposed to that cited in U.S. Patent 2,524,957 Isocinchomeronic acid with a melting point of 238 °.
Die Isocinchomeronsäure kann als wertvolles Zwischenprodukt beider Herstellung von Vitaminen dienen.Isocinchomeronic acid can be used as a valuable intermediate product of both Serving manufacture of vitamins.
Die Herstellung kann diskontinuierlich im Autoklav oder kontinuierlich im Druckrohr durchgeführt werden. Man muß in beiden Fällen dafür sorgen, daß die bei der Oxydation auftretende starke Wärme durch entsprechende Kühlung abgeführt wird. Beispiel i Man bereitet eine Mischung von 6oo g 63°/oiger Salpetersäure, i2i g 2-Methyl-5-äthyl-pyridin, i2i g Kupfernitrat (Cu [NO,], + 3H20) und iooo ccm Wasser.The production can be discontinuous in the autoclave or continuously be carried out in the pressure pipe. In both cases one must ensure that the The strong heat generated during the oxidation is dissipated by appropriate cooling will. EXAMPLE 1 A mixture of 600 g of 63% nitric acid is prepared g of 2-methyl-5-ethyl-pyridine, i2i g of copper nitrate (Cu [NO,], + 3H20) and 100 cc of water.
Das Gemisch. gibt man in einen 4-1-Autoklav. Dieser wird auf etwa 18o° erhitzt. Bei dieser Temperaturbeginnt die Oxydation. Die Temperatur steigt schnell an. Durch geeignete Kühlung sorgt man dafür, daß sie 215° nicht übersteigt. Man hält noch 30 Minuten bei dieser Temperatur, kühlt dann ab, öffnet den Autoklav und. filtriert die Oxydationslösung. Der Filterrückstand ist isocinchomeronsaures Kupfer. Blaues Kristallpulver. Menge: 188 g = 95 % der Theorie, -bezogen auf eingesetztes 2-Methyl-5-äthylpyridin.The mixture. are placed in a 4-1 autoclave. This is heated to around 180 °. At this temperature the oxidation starts. The temperature rises quickly. Suitable cooling ensures that it does not exceed 215 °. It is held at this temperature for a further 30 minutes, then cooled, the autoclave is opened and. filters the oxidation solution. The filter residue is isocinchomeronic acid copper. Blue crystal powder. Amount: 188 g = 95% of theory, based on the 2-methyl-5-ethylpyridine used.
Das Kupfersalz gibt man in eine warme Lösung von iöo g Natriumhydroxyd in 500 ccm Wasser, erwärmt kurze Zeit, filtriert das Filtrat mit Schwefelsäure oder Salzsäure auf PH 1,5 ein. Dabei fällt Isocinchomeronsäure als schneeweißes Kristallpulver aus, das abgenutscht und mit eiskaltem Wasser ausgewaschen wird. Die Säure wird bei 1o5° getrocknet. Man erhält 15i,1 g Säure vom F. 254° (= 9o>5 °/o Ausbeute). Aus der Mutterlauge können noch 6 g Isocinchomeronsäure als Kupfersalz isoliert werden. Beispiel 2 Eine Mischung von 121 g 2-Methyl-5-äthyl-pyridin, igoo g 2o°/piger Salpetersäure und i2i g Kupfernitrat (Cu [N03]2 -E- 3 H20) pumpt man kontinuierlich in einen druckfesten Reaktionsturm, der im oberen Teil geheizt, im unteren Teil gekühlt wird. Die Oxydation wird bei einer Ofentemperatur von etwa 2io° durchgeführt. Die entstehenden Gase werden durch ein Überdruckventil kontinuierlich abgeführt.The copper salt is added to a warm solution of 10 g sodium hydroxide in 500 cc of water, warmed for a short time, and the filtrate is filtered with sulfuric acid or hydrochloric acid to pH 1.5. Isocinchomeronic acid precipitates as a snow-white crystal powder, which is sucked off and washed out with ice-cold water. The acid is dried at 1o5 °. 15.1 g of acid with a melting point of 254 ° are obtained (= 90> 5% yield). 6 g of isocinchomeronic acid can still be isolated as copper salt from the mother liquor. Example 2 A mixture of 121 g of 2-methyl-5-ethyl-pyridine, igoo g of 2o ° / piger nitric acid and i2i g of copper nitrate (Cu [NO3] 2 -E- 3 H20) is pumped continuously into a pressure-resistant reaction tower, which is in the The upper part is heated and the lower part is cooled. The oxidation is carried out at an oven temperature of about 20 °. The resulting gases are continuously discharged through a pressure relief valve.
Durch eine geeignete Filtriervorrichtung wird das bei der Umsetzung anfallende isocinchomeronsaure Kupfer laufend abgezogen. Gesamtmenge: 182 g = 92,1% der Theorie. Beispiel 3 i2i g 2-Methyl-5-äthyl-pyridin werden mit goo g 42o/oiger Salpetersäure und 125 g Kupfernitrat (Cu [N03]2 -f- 3 H20) im Druckgefäß erhitzt. Die Reaktion setzt bei etwa i8o° ein, dabei steigen Temperatur und Druck. Man hält 15 Minuten bei 2io bis 215°, kühlt ab und arbeitet auf Kupfersalz auf.A suitable filter device makes this possible during the implementation accumulating isocinchomeronic acid copper is continuously deducted. Total amount: 182 g = 92.1% the theory. Example 3 i2i g of 2-methyl-5-ethyl-pyridine are mixed with goo g 42o / oiger Heated nitric acid and 125 g of copper nitrate (Cu [N03] 2 -f- 3 H20) in a pressure vessel. The reaction begins at about 180 °, and the temperature and pressure rise. One holds 15 minutes at 2io to 215 °, cools down and works on copper salt.
Es werden so =83,3 g Kupfer-isocinchomeronat erhalten.This gives = 83.3 g of copper isocinchomeronate.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DED11529A DE936447C (en) | 1952-02-08 | 1952-02-08 | Process for the preparation of isocinchomeronic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DED11529A DE936447C (en) | 1952-02-08 | 1952-02-08 | Process for the preparation of isocinchomeronic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE936447C true DE936447C (en) | 1955-12-15 |
Family
ID=7033789
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DED11529A Expired DE936447C (en) | 1952-02-08 | 1952-02-08 | Process for the preparation of isocinchomeronic acid |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE936447C (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2513099A (en) * | 1947-09-09 | 1950-06-27 | Allied Chem & Dye Corp | Oxidation of heterocyclic aromatic nitrogen compounds |
| US2524957A (en) * | 1950-10-10 | Isocinchomeronic acid by oxidation |
-
1952
- 1952-02-08 DE DED11529A patent/DE936447C/en not_active Expired
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2524957A (en) * | 1950-10-10 | Isocinchomeronic acid by oxidation | ||
| US2513099A (en) * | 1947-09-09 | 1950-06-27 | Allied Chem & Dye Corp | Oxidation of heterocyclic aromatic nitrogen compounds |
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