DE491681C - Process for the preparation of iodine substitution products of pyridine derivatives - Google Patents

Process for the preparation of iodine substitution products of pyridine derivatives

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Publication number
DE491681C
DE491681C DER71416D DER0071416D DE491681C DE 491681 C DE491681 C DE 491681C DE R71416 D DER71416 D DE R71416D DE R0071416 D DER0071416 D DE R0071416D DE 491681 C DE491681 C DE 491681C
Authority
DE
Germany
Prior art keywords
preparation
pyridine derivatives
substitution products
iodine substitution
solution
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
DER71416D
Other languages
German (de)
Inventor
Dr Kurl Raeth
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.)
Schering Kahlbaum AG
Original Assignee
Schering Kahlbaum AG
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 Schering Kahlbaum AG filed Critical Schering Kahlbaum AG
Priority to DER71416D priority Critical patent/DE491681C/en
Application granted granted Critical
Publication of DE491681C publication Critical patent/DE491681C/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
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C07D213/64—One oxygen atom attached in position 2 or 6
    • 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
    • C07D213/61—Halogen atoms or nitro radicals
    • 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
    • C07D213/72—Nitrogen atoms
    • C07D213/73—Unsubstituted amino or imino radicals

Description

Verfahren zur Darstellung von Jodsubstitutionsprodukten von Pyridinderivaten Es ist bereits bekannt, durch Diazotierung von 2-Chlor-3-Aminopyridin in Gegenwart von Bromwasserstoffsäure das 2-Chlor-3-brompyridin herzustellen (vgl. Chem. Zentralblatt 1923, 11I, S. xo2o letzter Abs.).Process for the preparation of iodine substitution products of pyridine derivatives It is already known that 2-chloro-3-bromopyridine can be produced by diazotizing 2-chloro-3-aminopyridine in the presence of hydrobromic acid (cf. Chem. Zentralblatt 1923, 11I, p. Xo2o last paragraph .).

Die auf diesem Wege gewonnene Bromverbindung besitzt keine therapeutische Bedeutung. Es wurde nun gefunden, daß man zu Verbindungen von ganz besonderem therapeutischem Wert gelangt, wenn man in Derivaten des 3-Aminopyridins die Aminogruppe über den Diazorest gegen Jod ersetzt. Hierzu läßt man auf die 3-Diazoniumsalze von Pyridinderivaten in saurer Lösung Alkalijodide einwirken. Vorteilhaft verwendet man als Ausgangsstoffe solche Derivate des 3- (5-) Aminopyridins, welche neben der Aminogruppe noch elektronegative Substituenten, wie die Hydroxylgruppe oder Chlor, enthalten.The bromine compound obtained in this way is not therapeutic Meaning. It has now been found that compounds of very special therapeutic Value comes when the amino group in derivatives of 3-aminopyridine via the Diazorest replaced with iodine. To this end, the 3-diazonium salts of pyridine derivatives are left on act in acidic solution alkali iodides. It is advantageous to use the starting materials those derivatives of 3- (5-) aminopyridine which, in addition to the amino group, are also electronegative Substituents such as the hydroxyl group or chlorine contain.

Die nach dem Verfahren erhältlichen Jodverbindungen, wie z. B. die Oxyjodverbindungen, besitzen stark baktericide Eigenschaften. Sie haben sich u. a. zur Bekämpfung von Strepto-und Staphylokokkenkrankheiten als ausgezeichnet geeignet erwiesen.The iodine compounds obtainable by the process, such as. B. the Oxyiodine compounds have strong bactericidal properties. You have u. a. excellent for combating streptococcal and staphylococcal diseases proven.

Beispiel r 36 g 2, 5-Diaminopyridin-hydrochlorid werden in 150 ccm Wasser gelöst und mit 200 ccm zoprozentiger Schwefelsäure versetzt. Man diazotiert sodann in üblicher Weise durch Zugabe einer Lösung von =q. g Natriumnitrit und 250 ccm Wasser. In die erhaltene saure Diazolösung läßt man dann eine Lösung von zo g Jodkalium in 40 ccm Wasser allmählich einfließen. Nach Beendigung der Reaktion, die sich durch starkes Schäumen bemerkbar macht, läßt man längere Zeit stehen, gegebenenfalls unter Erwärmen. Alsdann wird die Flüssigkeit mit konzentrierter Natronlauge stark alkalisch gemacht und das 2-Amino-5-jodpyridin mit Wasserdampf abgetrieben. Hierbei scheidet sich die Verbindung in weißen Kristallblättchen ab, die nach dem Erkalten des Destillates abgesaugt werden und nach dem Trocknen im Vakuum den Schmelzpunkt 129' besitzen. Die noch im Destillat gelösten Anteile kann man z. B. durch Extraktion mit Äther gewinnen.Example r 36 g of 2,5-diaminopyridine hydrochloride are dissolved in 150 cc of water and treated with 200 cc of zo percent sulfuric acid. It is then diazotized in the usual way by adding a solution of = q. g sodium nitrite and 250 cc water. A solution of ten g of potassium iodide in 40 cc of water is then gradually run into the acidic diazo solution obtained. After the reaction, which is noticeable by vigorous foaming, is left to stand for a long time, if necessary with heating. The liquid is then made strongly alkaline with concentrated sodium hydroxide solution and the 2-amino-5-iodopyridine is driven off with steam. The compound separates out in white crystal flakes, which are suctioned off after the distillate has cooled down and, after drying in vacuo, have a melting point of 129 '. The shares still dissolved in the distillate can be z. B. win by extraction with ether.

Beispiel 2 zoo g 2-Oxy-5-aminopyridin-hydrochlorid werden in 300 ccm Wasser gelöst und sodann mit 300 ccm konzentrierter Salzsäure versetzt. Das Amin wird dann durch Zugabe von 47 g Natriumnitrit in Zoo ccm Wasser in der üblichen Weise diazotiert. In die Diazolösung läßt man in dünnem Strahl eine Lösung von 350 g Kaliumjodid in 350 ccm Wasser unter kräftigem Rühren einfließen. Hierauf wird kurze Zeit auf dem Wasserbade erwärmt und das Reaktionsgemisch dann mehrere Stunden stehengelassen. Hierbei scheidet sich ein dunkelgefärbtes Produkt ab, welches durch Behandeln mit konzentrierter Natronlauge in das Natriumsalz des 2-Oxy-5-jodpyridins übergeführt wird. Durch Umkristallisieren aus Wasser erhält man das Natriumsalz in reiner Form.'-Durch Behandeln des Salzes mit Säuren, zweckmäßig durch Einleiten von Kohlensäure in die wässrige Lösung des Salzes, wird das freie 2-Oxy-5-jodpyridin ausgefällt. Schmelzpunkt xgz-=g2 °.Example 2 zoo g of 2-oxy-5-aminopyridine hydrochloride are dissolved in 300 cc of water and then 300 cc of concentrated hydrochloric acid are added. The amine is then diazotized in the usual way by adding 47 g of sodium nitrite to zoo cc of water. A solution of 350 g of potassium iodide in 350 cc of water is poured into the diazo solution in a thin stream while stirring vigorously. This is followed by heating on the water bath for a short time and then allowing the reaction mixture to stand for several hours. A dark colored product separates out, which is converted into the sodium salt of 2-oxy-5-iodopyridine by treatment with concentrated sodium hydroxide solution. The sodium salt is obtained in pure form by recrystallization from water. By treating the salt with acids, expediently by introducing carbonic acid into the aqueous solution of the salt, the free 2-oxy-5-iodopyridine is precipitated. Melting point xgz- = g2 °.

Beispiel 3 2-Chlor-5-aminopyridin wird in üblicher Weise in saurer Lösung mit Natriumnitrit diazotiert. Die erhaltene Diazolösung wird in eine Lösung von Jodkalium gegeben. Die Reaktion setzt sofort unter stürmischer Stickstoffentwicklung ein. Durch Alkalischmachen und Destillation mit Wasserdampf gewinnt man das 2-Chlor-5-jodpyridin in weißen Blättchen vom Schmelzpunkt 99 '. Beispiel q. 2-Oxy-3-aminopyridin wird in üblicher Weise diazotiert. Durch Behandlung der Diazolösung in der beim Beispie13 beschriebenen Weise erhält man das bei x7o ° schmelzende 2-Oxy-3-jodpyridin, dessen Natriumsalz im Wasser leicht lösliche Kristalle bildet.Example 3 2-chloro-5-aminopyridine is diazotized in the usual way in acidic solution with sodium nitrite. The diazo solution obtained is poured into a solution of potassium iodide. The reaction starts immediately with a violent evolution of nitrogen. By making alkaline and distilling with steam, the 2-chloro-5-iodopyridine is obtained in white flakes with a melting point of 99 '. Example q. 2-Oxy-3-aminopyridine is diazotized in the usual way. By treating the diazo solution in the manner described in Example 13, 2-oxy-3-iodopyridine, which melts at × 70 ° and whose sodium salt forms easily soluble crystals in water, is obtained.

Claims (1)

PATENTANSPRUCH: Verfahren zur Darstellung von jodsubstitutionsprodukten von Pyridinderivaten, dadurch gekennzeichnet, daß man auf 3-DiazoniumsalzevonDerivaten des Pyridins, zweckmäßig solche mit negativen Substituenten, wie der Hydroxylgruppe oder Chlor, in saurer Lösung Alkalijodide einwirken läßt. Claim: Process for the preparation of iodine substitution products of pyridine derivatives, characterized in that alkali iodides are allowed to act on 3-diazonium salts of derivatives of pyridine, expediently those with negative substituents such as the hydroxyl group or chlorine, in acidic solution.
DER71416D 1924-07-01 1924-07-01 Process for the preparation of iodine substitution products of pyridine derivatives Expired DE491681C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DER71416D DE491681C (en) 1924-07-01 1924-07-01 Process for the preparation of iodine substitution products of pyridine derivatives

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DER71416D DE491681C (en) 1924-07-01 1924-07-01 Process for the preparation of iodine substitution products of pyridine derivatives

Publications (1)

Publication Number Publication Date
DE491681C true DE491681C (en) 1930-02-19

Family

ID=7414156

Family Applications (1)

Application Number Title Priority Date Filing Date
DER71416D Expired DE491681C (en) 1924-07-01 1924-07-01 Process for the preparation of iodine substitution products of pyridine derivatives

Country Status (1)

Country Link
DE (1) DE491681C (en)

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