DE926248C - Process for the production of pellets of pyridine-4-carboxylic acid hydrazide - Google Patents

Process for the production of pellets of pyridine-4-carboxylic acid hydrazide

Info

Publication number
DE926248C
DE926248C DEM13820A DEM0013820A DE926248C DE 926248 C DE926248 C DE 926248C DE M13820 A DEM13820 A DE M13820A DE M0013820 A DEM0013820 A DE M0013820A DE 926248 C DE926248 C DE 926248C
Authority
DE
Germany
Prior art keywords
carboxylic acid
pyridine
production
acid hydrazide
pellets
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
Application number
DEM13820A
Other languages
German (de)
Inventor
Fritz Von Dr Werder
Otto Dr Zima
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EMANUEL MERCK oHG
Original Assignee
EMANUEL MERCK oHG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by EMANUEL MERCK oHG filed Critical EMANUEL MERCK oHG
Priority to DEM13820A priority Critical patent/DE926248C/en
Application granted granted Critical
Publication of DE926248C publication Critical patent/DE926248C/en
Expired legal-status Critical Current

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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
    • C07D213/86—Hydrazides; Thio or imino analogues thereof

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pyridine Compounds (AREA)

Description

Verfahren zur Herstellung von Abkömmlingen des Pyrid'in-4-carbonsäurehydrazids In neuerer Zeit hat das Pyridin-4-.carbonsäurehydrazid als hochwirksames Tuberculostaticum Bedeutung gewonnen. Es wurde gefunden, d.aß das .bisher nicht bekannte Pyri-din-4-carbonsäUreß-methylmercap,to-propy'l@i,de@nhydira,zid sowie das Sulfoxyd dieser Verbindung gegenüber dar Stammsubstanz den Vorzug besonders guter Verträglichkeit besitzen.Process for the preparation of derivatives of pyrid'yne-4-carboxylic acid hydrazide In recent times, the pyridine-4-carboxylic acid hydrazide has been used as a highly effective tuberculostatic Gained importance. It was found that the previously unknown pyri-din-4-carboxylic acid methylmercap, to-propy'l @ i, de @ nhydira, zid and the sulfoxide of this compound is particularly preferred over the parent substance have good tolerance.

Die vorliegende Erfindung besteht darin, daß man. Pyridin-4-carbonsäurehydrazid nach an sich üblichen Methoden mit ß-Methylme-rcapto-propionaldehyd kondensiert und gegebenenfalls das so erhaltene ß-M,ethylmercapto-propyl.id@enhydrazid durch Behandlung mit einem Oxydationsmittel, besonders mit Wasserstoffsuperoxyd, in das entsprechende Sulfoxyd überführt. Pyridin-4-carbonsäure-ß-methylmercapto-propylidenhydrazid kristallisiert aus Essigester in farblosen Blättchen., die bei 95 bis 96° schmelzen und sich weniger leicht in Wasser lösen als das Pyridin-4-carbonsäurehydrazid. Das bei I27° schmelzende, ebenfalls farblose Pyridin-4-carbonsäure-ß-methylsulfoxyd-propylidenhy drazid dagegen ist sehr leicht in Wasser löslich. Eine ioo/oige wäßrige Lösung hat ein pH von 6,2. Die neuen Verbindungen haben folgende Strukturformeln: Das Herstellungsverfahren für die beiden Verbindungen wird in folgendem durch Beispiele erläutert.The present invention consists in that one. Pyridine-4-carboxylic acid hydrazide is condensed with ß-methylme-rcapto-propionaldehyde according to conventional methods and the ß-M, ethylmercapto-propylid @ enhydrazide obtained in this way is converted into the corresponding sulfoxide by treatment with an oxidizing agent, especially hydrogen peroxide . Pyridine-4-carboxylic acid-ß-methylmercapto-propylidene hydrazide crystallizes from ethyl acetate in colorless flakes, which melt at 95 to 96 ° and are less readily soluble in water than pyridine-4-carboxylic acid hydrazide. On the other hand, the likewise colorless pyridine-4-carboxylic acid-ß-methylsulfoxydpropylidenehydrazide, which melts at 127 °, is very easily soluble in water. A 100% aqueous solution has a pH of 6.2. The new compounds have the following structural formulas: The production process for the two compounds is illustrated in the following by means of examples.

i. 13,7 Gewichtsteile Pyridin-q.-carbonsäurehydrazid werden mit 75 Gewichtsteilen Wasser verrührt und durch Erwärmen auf q.0° in Lösung gebracht. Unter dauerndem Rühren werden 10,45 Gewichtsteile ß-Methylmercapto-propionaldehyd zugesetzt. Es entsteht vorübergehend eine klare Lösung, die sich plötzlich durch ölige Ausscheidung der gewünschten Verbindung trübt. Das Reaktionsgefäß wird mit Eiswasser umgeben, und es wird so lange weitergerührt, bis das Reaktionsprodukt kristallisiert. Das isolierte Rohprodukt wird mit Wasser gewaschen, getrocknet und aus Essigester umkristallisiert, wobei 21,5 Gewichtsteile Pyridinq.-carbonsäure-ß-methylmercapto-propylidenhydrazid in farblosen Kristallen vom Schmelzpunkt 95 bis 96° erhalten werden.i. 13.7 parts by weight of pyridine-q.-carboxylic acid hydrazide are added with 75 Parts by weight of water are stirred and brought into solution by heating to q.0 °. Under Continuous stirring 10.45 parts by weight of β-methylmercapto-propionaldehyde are added. A clear solution is created temporarily, which suddenly changes due to oily excretion the desired connection is cloudy. The reaction vessel is surrounded with ice water, and stirring is continued until the reaction product crystallizes. That isolated crude product is washed with water, dried and recrystallized from ethyl acetate, wherein 21.5 parts by weight of pyridineq.-carboxylic acid-ß-methylmercapto-propylidene hydrazide can be obtained in colorless crystals with a melting point of 95 to 96 °.

2. In eine Suspension von 18 Gewichtsteilen Pyridin - q.-carbonsäure - ß-methylmercapto-propylidenhydrazid in 9o Gewichtsteilen Wasser werden unter Rühren 1o Gewichtsteile 3oo/odges Hydroperoxyd eingetragen, wobei man dafür Sorge trägt, daB die Temperatur des. Reaktionsgemisches 5o° nicht übersteigt. Es, entsteht eine klare Lösung, die im Vakuum eingedampft wird. Der Rückstand wird aus absolutem Alkohol umkristallisiert. Der Schmelzpunkt des so gewonnenenPyridin-q.-carbonsäure-ß-methylsulfoxyd-propylidenhydrazids liegt bei z27°.2. In a suspension of 18 parts by weight of pyridine - q.-carboxylic acid - ß-methylmercapto-propylidene hydrazide in 90 parts by weight of water are stirred 1o parts by weight 3oo / odges hydroperoxide entered, taking care to that the temperature of the reaction mixture does not exceed 50 °. There arises one clear solution which is evaporated in vacuo. The residue becomes from absolute alcohol recrystallized. The melting point of the pyridine-q.-carboxylic acid-ß-methylsulfoxydpropylidene hydrazide obtained in this way is at z27 °.

Claims (1)

PATENTANSPRUCH: Verfahren zur Herstellung von Abkömmlin-,gen des Pyridlin-q.-c2rbansäu zhydr,azids, dadurch gekennzeichnet, daB man diese Verbindung nach an sich bekannten Methoden mit ß-Methylmercapto-propionaldehyd kondensiert und gegebenenfalls das erhaltene ß-Methylmerca,pto-propyli:denhydrazid; durch Behandlung mit einem Oxydationsmittel, besonders mit Hydroperoxyd, in das entsprechende Sulfoxyd überführt.PATENT CLAIM: Process for the production of descendants of Pyridlin-q.-c2rbansäu zhydr, azids, characterized in that this compound is used according to known methods Methods with ß-methylmercapto-propionaldehyde condensed and optionally that obtained ß-methylmerca, pto-propyli: denhydrazid; by treatment with an oxidizing agent, especially with hydroperoxide, converted into the corresponding sulfoxide.
DEM13820A 1952-04-24 1952-04-24 Process for the production of pellets of pyridine-4-carboxylic acid hydrazide Expired DE926248C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DEM13820A DE926248C (en) 1952-04-24 1952-04-24 Process for the production of pellets of pyridine-4-carboxylic acid hydrazide

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEM13820A DE926248C (en) 1952-04-24 1952-04-24 Process for the production of pellets of pyridine-4-carboxylic acid hydrazide

Publications (1)

Publication Number Publication Date
DE926248C true DE926248C (en) 1955-04-14

Family

ID=7296409

Family Applications (1)

Application Number Title Priority Date Filing Date
DEM13820A Expired DE926248C (en) 1952-04-24 1952-04-24 Process for the production of pellets of pyridine-4-carboxylic acid hydrazide

Country Status (1)

Country Link
DE (1) DE926248C (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1191818B (en) * 1958-05-06 1965-04-29 Merck Ag E Process for the preparation of a sulfur-containing isonicotinoyl hydrazone
DE1191816B (en) * 1958-04-25 1965-04-29 Merck Ag E Process for the preparation of a sulfur-containing isonicotinoyl hydrazone
DE1191817B (en) * 1956-04-26 1965-04-29 Merck Ag E Process for the production of a sulfur-containing fragment of isonicotinic acid hydrazide

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1191817B (en) * 1956-04-26 1965-04-29 Merck Ag E Process for the production of a sulfur-containing fragment of isonicotinic acid hydrazide
DE1191816B (en) * 1958-04-25 1965-04-29 Merck Ag E Process for the preparation of a sulfur-containing isonicotinoyl hydrazone
DE1191818B (en) * 1958-05-06 1965-04-29 Merck Ag E Process for the preparation of a sulfur-containing isonicotinoyl hydrazone

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