DE972976C - Process for the production of pyridine-‰ - or -ª † -carboxylic acid - Google Patents
Process for the production of pyridine-‰ - or -ª † -carboxylic acidInfo
- Publication number
- DE972976C DE972976C DEB20838A DEB0020838A DE972976C DE 972976 C DE972976 C DE 972976C DE B20838 A DEB20838 A DE B20838A DE B0020838 A DEB0020838 A DE B0020838A DE 972976 C DE972976 C DE 972976C
- Authority
- DE
- Germany
- Prior art keywords
- nitric acid
- pyridine
- pyridines
- carboxylic acid
- production
- 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
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title claims description 5
- 238000000034 method Methods 0.000 title claims description 5
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 150000003222 pyridines Chemical class 0.000 claims description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- TWBYWOBDOCUKOW-UHFFFAOYSA-N isonicotinic acid Chemical compound OC(=O)C1=CC=NC=C1 TWBYWOBDOCUKOW-UHFFFAOYSA-N 0.000 description 4
- 229910001868 water Inorganic materials 0.000 description 4
- NTSLROIKFLNUIJ-UHFFFAOYSA-N 5-Ethyl-2-methylpyridine Chemical compound CCC1=CC=C(C)N=C1 NTSLROIKFLNUIJ-UHFFFAOYSA-N 0.000 description 2
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical class OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229960003512 nicotinic acid Drugs 0.000 description 1
- 235000001968 nicotinic acid Nutrition 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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 Pyridin-f- oder -y-carbonsäure Man hat bereits vorgeschlagen, Pyridin und daneben gegebenenfalls Pyridincarbonsäuren dadurch zu gewinnen, @daß. man homologe Pyridine mit verdünnter Salpetersäure unter Druck erhitzte.Process for the preparation of pyridine-f- or -y-carboxylic acid One has already proposed, pyridine and possibly also pyridinecarboxylic acids thereby to win @ that. one homologous pyridines with dilute nitric acid under pressure heated.
Es wurde nun gefunden, daß man Pyridin-f-oder -y-carbonsäure durch Oxydation von Pyridinen, die in ß- oder y-Stellung und daneben gegebenenfalls in a-Stellung Alkylgruppen tragen, mittels etwa 5- bis 4o°/oiger Salpetersäure unter Druck bei Temperaturen über 200° C im kontinuierlichen Betrieb vorteilhaft erhält, wenn man die Pyridine unddie Salpetersäure je für sich gleichzeitig oder im Gemisch miteinander ohne besondere Vorwärmun.g oder allenfalls unter Vorwärmung durch die entgegenströmenden, im wesentlichen aus Wasserdampf, Kohlendioxyd und Stickoxyden bestehenden Gase in das obere Ende eines stehenden Druckrohr einpumpt, das etwa zur Hälfte mit dem zu gewinnenden Reaktionsprodukt gefüllt ist und dessen Flüssigkeitsstand durch ein Überlaufrohr ständig auf der erwähnten Höhe gehalten wird, wobei man die Zufuhr so regelt, daß die Verweilzeit in der auf etwa 26o bis 300° C gehaltenen Reaktionszone, die sich etwa in der Mitte des Rohres befindet, etwa io bis 30 Minuten beträgt.It has now been found that pyridine-f- or -y-carboxylic acid can be added by means of about 5- to 40% strength nitric acid by oxidation of pyridines which carry alkyl groups in the β- or γ-position and also optionally in the α-position Pressure at temperatures above 200 ° C is advantageously obtained in continuous operation if the pyridines and the nitric acid are each separately or in a mixture with one another without special preheating or, if necessary, with preheating by the countercurrent gases consisting essentially of water vapor, carbon dioxide and nitrogen oxides is pumped into the upper end of a standing pressure pipe which is about half full with the reaction product to be recovered and whose liquid level is constantly kept at the mentioned level by an overflow pipe, the supply being regulated so that the residence time in the to about 26o to 300 ° C held reaction zone, which is located approximately in the middle of the tube, is about 10 to 30 minutes.
Diese Arbeitsweise gestattet, in kontinuierlichem Verfahren unter weitgehender Schonung der Apparatur hohe Durchsätze zu erzielen und unmittelbar verhältnismäßig reine Pyridin-ß- und -y-carbonsäure zu gewinnen. Infolge der kurzen Verweilzeit im heißen Reaktionsraum wird ein zu weiter Abbau des Ausgangsmoleküls verhindert und in sehr guter Ausbeute die gewünschte Pyridincarbonsäure gewonnen.This mode of operation allows in a continuous process under Achieve high throughputs and immediately, while protecting the equipment as much as possible relatively to obtain pure pyridine-ß- and -y-carboxylic acid. As a result of the short dwell time Excessive degradation of the starting molecule is prevented in the hot reaction space and obtained the desired pyridinecarboxylic acid in very good yield.
Als Material für die Apparatur verwendet man zweckmäßig korrosionsbeständige Stahllegierungen, z. B. Chromnickelstahl, insbesondere mit austenitischem Gefüge.Corrosion-resistant material is expediently used as the material for the apparatus Steel alloys, e.g. B. Chrome-nickel steel, especially with an austenitic structure.
Der anzuwendende Druck richtet sich nach der Temperatur in der heißen Zone und beträgt etwa 5o bis zoo at und darüber. Bei Ingangsetzung des kontinuierlich durchgeführten Verfahrens wird die heiße Zone durch Wärmezufuhr von außen, z. B. durch elektrische Heizung, erzeugt. Da dieReaktion s.tarkexotherm ist, kanndie Heizung nach kurzer Zeit abgestellt werden.. Durch. Regulierung der Menge, Temperatur und Strömungsgeschwindigkeit des zugeführten Gemisches sowie durch Zugabe von 'Wasser bzw. Verdünnung der Salpetersäure hat man es in der Hand, die Temperatur ständig auf der gewünschten Höhe zu halten. Im übrigen läßt sich die etwa zu hoch steigende Temperatur in der heißen Zone, d. h. die frei werdende Reaktionswärme, auch durch äußere Kühlung mit Wasser, Dampf oder Luft herabmindern.The pressure to be used depends on the temperature in the hot Zone and is about 50 to zoo at and above. When starting the continuously carried out process, the hot zone by supplying heat from the outside, z. B. by electric heating. Since the reaction is strongly exothermic, the heating can be used be turned off after a short time .. By. Regulation of the amount, temperature and Flow rate of the supplied mixture as well as by adding 'water or dilution of nitric acid you have it in your hand, the temperature constant to keep at the desired height. Otherwise, the too high rising Temperature in the hot zone, d. H. the heat of reaction released, also through Reduce external cooling with water, steam or air.
Die Mischung der beiden Komponenten erfolgt in einem -zweckmäßig gekühlten - besonderen Gefäß. Im allgemeinen wird die Salpetersäure im Überschuß, d. h. in Mengen von über 2 Mol, verwendet: Man pumpt sodann das Gemisch aus demerwähnten Gefäß: oder die beiden Komponenten für sich direkt und gleichzeitig in das Druckgefäß ein; als solches verwendet man ein stehendes Rohr, vorteilhaft aus Chromnickelstahl. Die heiße Zone ist etwa in der Mitte des Rohres vorgesehen. Diese Zone, in der die Oxydation vorzugsweise stattfindet, wird in der Weise fixiert, daß man den Flüssigkeitsstand auf eben dieser Höhe hält.The two components are mixed in an appropriately cooled - special vessel. In general, the nitric acid is used in excess, i. H. in Amounts in excess of 2 moles are used: The mixture is then pumped out of the aforementioned Vessel: or both components directly and simultaneously in the pressure vessel a; a standing pipe, advantageously made of chrome-nickel steel, is used as such. The hot zone is provided approximately in the middle of the pipe. This zone in which the Oxidation preferably takes place, is fixed in such a way that the liquid level is reached holds at this height.
Die bei der Oxydation entstehenden Gase werden am oberen Flansch des Rohres abgeführt. Ihr Hauptbestandteil ist Stickoxyd neben Wasserdampf und Kohlendioxyd; deshalb eignet sich das Abgas besonders für die Regeneration zu Salpetersäure, wie sie für die Oxydation erwünscht ist..The gases produced during the oxidation are released from the upper flange of the Pipe discharged. Its main component is nitrogen oxide, along with water vapor and carbon dioxide; therefore the exhaust gas is particularly suitable for regeneration to nitric acid, such as it is desired for the oxidation ..
Beispiel y-Picolin und 3o%ige Salpetersäure werden im Verhältnis von 8o Gewichtsteilen y-Picolin zu 42o Gewichtsteilen 3o%iger Salpetersäure unter Kühlung miteinander gemischt und unter zoo at Druck kontinuierlich in das obere Ende eines stehenden Druckrohres, das zur Hälfte mit dem zu gewinnenden Reaktionsprodukt gefüllt ist, derart gepumpt, daß pro Stunde etwa 5oo Teile des Gemisches eingepumpt werden. Der Flüssigkeitsstand wird durch ein Überlaufrohr ständig auf der erwähnten Höhe gehalten. Die Zufuhr des umzusetzenden Gemisches wird so geregelt, daß die Verweilzeit in der auf etwa 2j8o° gehaltenen heißen Zone, die sich oberhalb des Flüssigkeitsstandes, also etwa in der Mitte des Rohres, befindet, etwa 2o Minuten beträgt. Die bei der Reaktion entstehenden, Stickoxyd, Wasser und Kohlendioxyd enthaltenden Gase werden durch ein am oberen Ende des Reaktionsgefäßes befindliches Ventil entspannt. Das aus dem Überlauf entspannte Oxydationsprodukt besteht zu etwa 25,% aus Isonicotinsäure, die vom wäßrigen Teil abgeschleudert wird. Durch Waschen mit Wasser und Umkristallisieren wird die reine Isonicotinsäure vom Schmelzpunkt 326° gewonnen. Die Ausbeute beträgt 82% der Theorie.Example y-picoline and 3o% nitric acid are used in a ratio of 8o parts by weight of y-picoline to 42o parts by weight of 3o% nitric acid with cooling mixed together and under zoo at pressure continuously into the top of a standing pressure tube, which is half filled with the reaction product to be obtained is, pumped in such a way that about 500 parts of the mixture are pumped in per hour. The liquid level is constantly at the mentioned height through an overflow pipe held. The supply of the mixture to be converted is regulated so that the residence time in the hot zone, which is kept at about 2j8o °, which is above the liquid level, that is about in the middle of the tube, is about 20 minutes. The at the The resulting reaction will be gases containing nitrogen oxide, water and carbon dioxide expanded through a valve located at the upper end of the reaction vessel. That The oxidation product released from the overflow consists of about 25% isonicotinic acid, which is thrown off from the aqueous part. By washing with water and recrystallizing pure isonicotinic acid with a melting point of 326 ° is obtained. The yield is 82% of theory.
In analoger Weise verfährt man, wenn man als Ausgangsprodukt 2-Methyl-5-äthylpyridin verwendet. In diesem Falle entsteht Nicotinsäure, die durch Auskristallisieren aus dem wäßrigen Reaktionsgemisch erhalten wird. Freie Salpetersäure befindet sich im umgesetzten Gemisch nur in Spuren.The procedure is analogous if 2-methyl-5-ethylpyridine is used as the starting material used. In this case nicotinic acid is produced, which crystallizes out the aqueous reaction mixture is obtained. Free nitric acid is in the converted mixture only in traces.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEB20838A DE972976C (en) | 1952-06-18 | 1952-06-18 | Process for the production of pyridine-‰ - or -ª † -carboxylic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEB20838A DE972976C (en) | 1952-06-18 | 1952-06-18 | Process for the production of pyridine-‰ - or -ª † -carboxylic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE972976C true DE972976C (en) | 1959-11-12 |
Family
ID=6960442
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEB20838A Expired DE972976C (en) | 1952-06-18 | 1952-06-18 | Process for the production of pyridine-‰ - or -ª † -carboxylic acid |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE972976C (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR892871A (en) * | 1941-12-31 | 1944-05-23 | Ig Farbenindustrie Ag | Process for obtaining pyridine and pyridine-carboxylic acids |
-
1952
- 1952-06-18 DE DEB20838A patent/DE972976C/en not_active Expired
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR892871A (en) * | 1941-12-31 | 1944-05-23 | Ig Farbenindustrie Ag | Process for obtaining pyridine and pyridine-carboxylic acids |
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