DE749148C - Process for the nitrosation of 4-aminouracil - Google Patents

Process for the nitrosation of 4-aminouracil

Info

Publication number
DE749148C
DE749148C DEB199886D DEB0199886D DE749148C DE 749148 C DE749148 C DE 749148C DE B199886 D DEB199886 D DE B199886D DE B0199886 D DEB0199886 D DE B0199886D DE 749148 C DE749148 C DE 749148C
Authority
DE
Germany
Prior art keywords
acid
aminouracil
nitrosation
vol
nitrite
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
DEB199886D
Other languages
German (de)
Inventor
Dr Walter Boehm
Dr Wilhelm Peschke
Dr Erich Rabald
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.)
Roche Diagnostics GmbH
CF Boehringer und Soehne GmbH
Original Assignee
Boehringer Mannheim GmbH
CF Boehringer und Soehne GmbH
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 Boehringer Mannheim GmbH, CF Boehringer und Soehne GmbH filed Critical Boehringer Mannheim GmbH
Priority to DEB199886D priority Critical patent/DE749148C/en
Application granted granted Critical
Publication of DE749148C publication Critical patent/DE749148C/en
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/52—Two oxygen atoms
    • C07D239/54—Two oxygen atoms as doubly bound oxygen atoms or as unsubstituted hydroxy radicals
    • C07D239/545—Two oxygen atoms as doubly bound oxygen atoms or as unsubstituted hydroxy radicals with other hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

Verfahren zur Nitrosierung des 4-Aminouracils Bei den bisher üblichen Verfahren zur N itrosierung von 4-Aminouracil, wobei man, wenn nicht dem Umsetzungsgemisch nachträglich alkalische Agenzien zugesetzt werden, das saure Natriumsalz des 5-Isonitroso-4-aminouracils erhält, wird zur Freimachung der salpetrigen Säure aus dem zum Einsatz gelangenden Natriumnitrit mindestens die äquivalente Menge Säure angewandt (vgl. z. B. Berichte der Deutschen Chem. Gesellschaft 33 11I, S. 304q., sowie journ. of the Am. Chem. SOC., vol. 55, 1933 I, S. z668). Wird vom @Tatriumsalz des 4-Aminouracils ausgegangen, so werden entsprechend mindestens a Mol Säure angewendet.Process for the nitrosation of 4-aminouracil in the hitherto customary Process for the nitrosation of 4-aminouracil, wherein if not the reaction mixture subsequently alkaline agents are added, the acidic sodium salt of 5-isonitroso-4-aminouracil received, is used to release the nitrous acid from the used Sodium nitrite used at least the equivalent amount of acid (see e.g. reports der Deutschen Chem. Gesellschaft 33 11I, S. 304q., as well as journ. of the Am. Chem. SOC., Vol. 55, 1933 I, p. Z668). If the @ sodium salt of 4-aminouracil is assumed, accordingly, at least a mole of acid is used.

Es .wurde nun gefunden, daß schon ein ganz geringer Zusatz -Von der zur Zerlegung des Natriumnitrits erforderlichen Säure genügt, um die Nitrosierung des 4-Aminoüracils vollständig durchzuführen. Offenbar reagiert die zunächst entstehende geringe Menge an Isonitrosoverbindung sauer genug, um von sich aus weitere Mengen salpetriger Säure in Freiheit zu setzen. Bei Verwendung von reinem 4-Aminouracil in wäßriger Suspension in Gegenwart von Natriumnitrit tritt auch beim Erhitzen keine Reaktion ein. Erst nach Zusatz einiger Tropfen Säure kommt die I#itrosierung in Gang, die Wirkung der Säure kann also gewissermaßen als eine katalytische betrachtet werden. Die Umsetzung erfolgt äußerst glatt und schnell und liefert, im Gegensatz zu den bisherigen Verfahren, das neutrale Salz in fast quantitativer Ausbeute; dabei herrscht stets neutrale Reaktion. Das erfindungsmäßige Verfahren mini als außerordentlich- -iiberraschend bezeichnet werden und besitzt infolge Ersparung an Säure und Abstuinpfungsmittel große praktische Bedeutung. Zudem ist (las Auftreten nitroser Gase, ilie sich bei den älteren Verfahren, insbesondere bei ihrer technischen Durchführung, leicht in störender Weise entwickeln können, vollkommen ausgeschlossen. Beispiele i. In eine Suspension voll i Mol .I-Aminouracil in 120o ccm Wasser «-erden ;7o- Natriuinnitrit eingebracht. Man erwärmt auf 850 und fügt etwa i ccm Eisessig hinzu. Nach kurzer Frist färbt sich das Umsetzungsgemisch rosarot und erstarrt schließlich zu einem dicken Kristallbrei. Es wird gut gekühlt und abgenutscht, wobei man nach kurzem Auswaschen das neutrale 1Tatriumsalz des 5-Isonitroso-4-aniinouracils, das in Wasser fast unlöslich ist, rein und in fast quantitativer Ausbeute erhält. a. Man verfährt wie in Beispiel i, nur werden all Stelle des Eisessigs o,$ ccm go°joige Ameisensäure angewandt. Man erhält auch auf diese Weise die Verbindung praktisch quantitativ und in reiner Form.It has now been found that even a very small addition of the acid required to decompose the sodium nitrite is sufficient to carry out the nitrosation of the 4-aminouracil completely. Apparently the small amount of isonitroso compound initially formed reacts acidic enough to release further amounts of nitrous acid on its own. When using pure 4-aminouracil in aqueous suspension in the presence of sodium nitrite, no reaction occurs even when heated. Only after a few drops of acid is added does itrosis start to occur; the acid can therefore be regarded as a kind of catalytic effect. The conversion takes place extremely smoothly and quickly and, in contrast to the previous processes, delivers the neutral salt in almost quantitative yield; there is always a neutral reaction. The mini process according to the invention can be described as extraordinarily surprising and is of great practical importance due to the saving of acid and detergent. In addition, the occurrence of nitrous gases, which can easily develop in a disruptive manner in the older processes, especially when they are carried out industrially, is completely excluded. It is heated to 850 and about 1 cc of glacial acetic acid is added. After a short period of time, the reaction mixture turns pinkish-red and finally solidifies to a thick crystal paste. It is well cooled and suction filtered, the neutral sodium salt being washed out for a short time of 5-isonitroso-4-aniinouracil, which is almost insoluble in water, is obtained in pure form and in almost quantitative yield In this way, too, the compound is obtained practically quantitatively and in pure form.

Ebenso gelingt die Umsetzung finit geringen Mengen Salzsäure oder Schwefelsäure.Likewise, the implementation succeeds finitely small amounts of hydrochloric acid or Sulfuric acid.

Claims (1)

PATENTANSPRUCH: Verfahren zur 1Titrosierung des q-Aminouracils mittels Nitrit und Säure, dadurch gekennzeichnet, daß nur geringe Bruchteile des jeweiligen Äquivalentgewichts (bezogen auf das eingesetzte Nitrit) an Säure angewendet werden. Zur Abgrenzung des Anmeldungsgegenstandes vom Stand der Technik sind im Erteilungsverfahren folgende Druckschriften in Betracht gezogen «-orden: Berichte der Deutschen Chemischen Gesellschaft, Bd. 33III, S.30.4; Journal of the Ainerican Chemical Society, Bd. 55, S. 1663.PATENT CLAIM: Process for 1titrosation of q-aminouracil by means of Nitrite and acid, characterized in that only small fractions of each Equivalent weight (based on the nitrite used) of acid are used. To distinguish the subject of the application from the state of the art, the granting procedure the following publications considered "order: Reports of the German Chemicals Society, Vol. 33III, p.30.4; Journal of the American Chemical Society, Vol. 55, p. 1663.
DEB199886D 1942-10-09 1942-10-09 Process for the nitrosation of 4-aminouracil Expired DE749148C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DEB199886D DE749148C (en) 1942-10-09 1942-10-09 Process for the nitrosation of 4-aminouracil

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEB199886D DE749148C (en) 1942-10-09 1942-10-09 Process for the nitrosation of 4-aminouracil

Publications (1)

Publication Number Publication Date
DE749148C true DE749148C (en) 1944-11-24

Family

ID=7012125

Family Applications (1)

Application Number Title Priority Date Filing Date
DEB199886D Expired DE749148C (en) 1942-10-09 1942-10-09 Process for the nitrosation of 4-aminouracil

Country Status (1)

Country Link
DE (1) DE749148C (en)

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

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