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DE1082267B - Process for the preparation of new derivatives of pyrimidine - Google Patents

Process for the preparation of new derivatives of pyrimidine

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Publication number
DE1082267B
DE1082267B DES30698A DES0030698A DE1082267B DE 1082267 B DE1082267 B DE 1082267B DE S30698 A DES30698 A DE S30698A DE S0030698 A DES0030698 A DE S0030698A DE 1082267 B DE1082267 B DE 1082267B
Authority
DE
Germany
Prior art keywords
pyrimidine
ethyl
preparation
chlorophenyl
chloro
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.)
Pending
Application number
DES30698A
Other languages
German (de)
Inventor
Robert Michel Jacob
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.)
Rhone Poulenc SA
Original Assignee
Rhone Poulenc SA
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 Rhone Poulenc SA filed Critical Rhone Poulenc SA
Publication of DE1082267B publication Critical patent/DE1082267B/en
Pending legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D239/00Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24Heterocyclic 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
    • C07D239/28Heterocyclic 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
    • C07D239/46Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/48Two nitrogen atoms

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Description

Verfahren zur Herstellung von neuen Derivaten des Pyrimidins Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von neuen Derivaten des Pyrimidins der allgemeinen Formel worin R den Rest n-C, He oder - (CH,), - C H (C H3) 2 bedeutet.Process for the preparation of new derivatives of pyrimidine The present invention relates to a process for the preparation of new derivatives of pyrimidine of the general formula where R denotes the radical nC, He or - (CH,), - CH (C H3) 2.

Diese Produkte werden erfindungsgemäß erhalten, indem man ein primäres Amin R - N 112 auf 2-Amino-4-chlor-5-(4'-chlor-phenyl)-6-äthyl-pyrimidin oder sein N-acetyliertes Derivat, nämlich 2-Acetylamino-4-chlor-5-(4'-chlor-phenyl)-6-äthyl-pyrimidin, einwirken läßt; im letztgenannten Falle findet gleichzeitig Entacetylierung des Acetylaminorestes statt.According to the invention, these products are obtained by using a primary Amine R - N 112 on 2-amino-4-chloro-5- (4'-chloro-phenyl) -6-ethyl-pyrimidine or be N-acetylated derivative, namely 2-acetylamino-4-chloro-5- (4'-chlorophenyl) -6-ethyl-pyrimidine, lets act; in the latter case, deacetylation of the takes place at the same time Acetylaminorestes instead.

Die Umsetzung wird durchgeführt, indem man auf Temperaturen über 100°C, vorzugsweise zwischen 150 und 200°C, erhitzt. Vorteilhaft wird ein Überschuß an primärem Amin verwendet; bei Verwendung von niedrigen aliphatischen Aminen arbeitet man im Autoklav, im Falle von Aminen mit genügend hohem Siedepunkt unter Erhitzen am Rückflußkühler.The reaction is carried out by heating to temperatures above 100 ° C, preferably between 150 and 200 ° C, heated. An excess of is advantageous primary amine used; works when using lower aliphatic amines one in the autoclave, in the case of amines with a sufficiently high boiling point with heating on the reflux condenser.

Es ist auch möglich, die Umsetzung des 2-Amino-4-chlor-5-(4'-chlor-phenyl)-6-äthyl-pyrimidins nicht nur mit einem primären Amin R - N H2, sondern auch mit einem Salz derartiger Amine, wie z. B. dem Hydrochlorid oder dem Acetat, durchzuführen. In diesem Fall kann man ohne Lösungsmittel bei einer Temperatur über 150°C und vorzugsweise bei etwa 200°C arbeiten. Diese Methode weist im besonderen den Vorteil auf, daß man in allen Fällen ohne Autoklav arbeiten kann.It is also possible to implement the 2-amino-4-chloro-5- (4'-chlorophenyl) -6-ethyl-pyrimidine not only with a primary amine R - N H2, but also with a salt of such Amines such as B. the hydrochloride or the acetate to perform. In this case can be used without a solvent at a temperature above 150 ° C and preferably at work around 200 ° C. This method has the particular advantage that one can work without an autoclave in all cases.

Die Herstellung des als Ausgangsmaterial verwendeten 2-Amino-4-chlor-5-(4'-chlor-phenyl)-6-äthyl-pyrimidins bzw. seines N-acetylierten Derivats ist in der Patentanmeldung S 28810 IVc/12p beschrieben.The preparation of the 2-amino-4-chloro-5- (4'-chlorophenyl) -6-ethyl-pyrimidine used as starting material or its N-acetylated derivative is described in patent application S 28810 IVc / 12p.

Die erfindungsgemäß erhaltenen Produkte besitzen interessante antiparasitäre Eigenschaften; insbesondere auf Grund ihrer Antimalariawirksamkeit sind sie in der Human- und Veterinärtherapie verwendbar.The products obtained according to the invention have interesting anti-parasitic properties Properties; especially because of their antimalarial effectiveness, they are in the Can be used in human and veterinary therapy.

In der untenstehenden Tabelle sind die chemotherapeutischen Eigenschaften der erfindungsgemäß hergestellten Substanzen mit denjenigen des bekannten 2,4-Diamino-5-(4'-chlor-phenyl)-6-äthyl pyrimidins verglichen: DClao an mit DL., an P. Berghei Cg*) Produkt R = Mäusen in infizierten CK X**) mg/kgp.o. Mäusen in mg/kg p.o. H 60 0,25 1 n-C,H9 220 0,4 2,3 -(CHICH(CH3)2 600 1,25 2 *) CK =chemotherapeutischer Koeffizient. **) X = 2,4-Diamino-5-(4'-chlor-phenyl)-6-äthyl-pyrimidin. Die folgenden Beispiele sollen die Erfindung näher erläutern. Die angegebenen Schmelzpunkte wurden im Kofler-Block bestimmt. Beispiel 1 Man erhitzt eine Mischung aus 10g 2-Acetylamino-4-chlor-5-(4'-chlor-phenyl)-6-äthyl-pyrimidin, 15 g n-Butylamin und 10 ccm Äthanol 8 Stunden auf 160° C. Man nimmt das Reaktionsgemisch in 200 ccm Wasser auf, saugt das gebildete Produkt ab, wäscht mit Wasser und trocknet im Vakuum. Man erhält so 7,9 g 2-Amino-4-butylamino-5-(4'-chlor-phenyl)-6-äthyl-pyrimidin vom F. =133°C. Sein Hydrochlorid schmilzt bei 200 bis 205°C.In the table below, the chemotherapeutic properties of the substances prepared according to the invention are compared with those of the known 2,4-diamino-5- (4'-chlorophenyl) -6-ethyl pyrimidine: DClao on with DL., To P. Berghei Cg *) product R = mice in infected CK X **) mg / kgp.o. Mice in mg / kg po H 60 0.25 1 nC, H9 220 0.4 2.3 - (CHICH (CH3) 2 600 1.25 2 *) CK = chemotherapeutic coefficient. **) X = 2,4-diamino-5- (4'-chlorophenyl) -6-ethyl-pyrimidine. The following examples are intended to explain the invention in more detail. The melting points given were determined in a Kofler block. Example 1 A mixture of 10 g of 2-acetylamino-4-chloro-5- (4'-chloro-phenyl) -6-ethyl-pyrimidine, 15 g of n-butylamine and 10 cc of ethanol is heated to 160 ° C. for 8 hours the reaction mixture is taken up in 200 cc of water, the product formed is filtered off with suction, washed with water and dried in vacuo. 7.9 g of 2-amino-4-butylamino-5- (4'-chlorophenyl) -6-ethyl-pyrimidine with a melting point of 133 ° C. are thus obtained. Its hydrochloride melts at 200 to 205 ° C.

In analoger Weise kann man das 2-Amino-4-(3'-rnethylbutylamino) - 5 - (4"- chlor - phenyl) - 6 - äthyl - pyrimidin vom F. = 143°C erhalten. Beispiel 2 2 g 2-Amino-4-chlor-5-(4'-chlor-phenyl)-6-äthyl-pyrimidin vom F. =163°C und 1,26 g n-Butylarnin-chlorhydrat werden 1 Stunde auf 200°C erhitzt. Man nimmt die erhaltene Masse in Wasser auf, wäscht mit Wasser und trocknet im Vakuum. Man erhält 2,1 g rohes 2-Amino-4-n-butylamino-5- (4'-chlor-phenyl) -6-äthyl-pyrimidin vom F. = 120 bis 122°C. Nach dem Umkristallisieren aus Dioxan ist dieses Produkt rein und schmilzt bei 132 bis 133°C.The 2-amino-4- (3'-methylbutylamino) - 5 - (4 "- chlorophenyl) - 6 - ethyl - pyrimidine obtained with a melting point of 143 ° C. Example 2 2 g of 2-amino-4-chloro-5- (4'-chloro-phenyl) -6-ethyl-pyrimidine with a melting point of 163 ° C and 1.26 g of n-butylamine chlorohydrate are heated to 200 ° C. for 1 hour. One takes the one received The mass is dissolved in water, washed with water and dried in vacuo. 2.1 g are obtained Crude 2-amino-4-n-butylamino-5- (4'-chlorophenyl) -6-ethyl-pyrimidine with a melting point of 120 up to 122 ° C. After recrystallization from dioxane, this product is pure and melts at 132 to 133 ° C.

In analoger Weise kann man das 2-Amino-4-(3'-methylbutylamino)-5-(4"-chlor-phenyl)-6-äthyl-pyrimidin vom F. =143°C erhalten.2-Amino-4- (3'-methylbutylamino) -5- (4 "-chlorophenyl) -6-ethyl-pyrimidine can be used in an analogous manner obtained from the F. = 143 ° C.

Claims (2)

PATENTANSPRÜCHE: 1. Verfahren zur Herstellung von neuen Derivaten des Pyrimidins der allgemeinen Formel worin R den Rest n-C4H9 oder -(CH2)2-CH(CH3)2 bedeutet', dadurch gekennzeichnet, daß man 2 Amino-4-chlor-5-(4'-chlor-phenyl)-6-äthyl-pyrimidin oder sein N-acetyliertes Derivat mit einem primären Amin R - N H2 oder einem Salz desselben, z. B. dem Hydrochlorid oder Acetat, kondensiert. PATENT CLAIMS: 1. Process for the preparation of new derivatives of pyrimidine of the general formula wherein R denotes the radical n-C4H9 or - (CH2) 2-CH (CH3) 2 ', characterized in that 2 amino-4-chloro-5- (4'-chlorophenyl) -6-ethyl-pyrimidine or its N-acetylated derivative with a primary amine R - N H2 or a salt thereof, e.g. B. the hydrochloride or acetate, condensed. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man die Umsetzung bei Verwendung eines Salzes eines primären Amins bei einer Temperatur von über 150°C, vorzugsweise bei etwa 200°C, durchführt. In Betracht gezogene Druckschriften: Britische Patentschrift Nr. 583 815; Journal of the American Chemical Society, Bd.73 (1951), S. 3768; Journal of the Chemical Society, 1946, S. 359.2. The method according to claim 1, characterized in that the reaction when using a salt of a primary amine at a temperature of over 150 ° C, preferably at about 200 ° C, is carried out. References considered: British Patent No. 583815; Journal of the American Chemical Society, 73, 3768 (1951); Journal of the Chemical Society, 1946, p. 359.
DES30698A 1951-11-06 1952-10-16 Process for the preparation of new derivatives of pyrimidine Pending DE1082267B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR1082267X 1951-11-06

Publications (1)

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DE1082267B true DE1082267B (en) 1960-05-25

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DES30698A Pending DE1082267B (en) 1951-11-06 1952-10-16 Process for the preparation of new derivatives of pyrimidine

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DE (1) DE1082267B (en)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB583815A (en) * 1944-05-18 1946-12-31 Francis Henry Swinden Curd New pyrimidine compounds

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB583815A (en) * 1944-05-18 1946-12-31 Francis Henry Swinden Curd New pyrimidine compounds

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