CH560197A5 - 2-alkylthio-4,6-bis (subst amino)-5-nitropyrimidines - - herbicides - Google Patents

2-alkylthio-4,6-bis (subst amino)-5-nitropyrimidines - - herbicides

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Publication number
CH560197A5
CH560197A5 CH1703673A CH1703673A CH560197A5 CH 560197 A5 CH560197 A5 CH 560197A5 CH 1703673 A CH1703673 A CH 1703673A CH 1703673 A CH1703673 A CH 1703673A CH 560197 A5 CH560197 A5 CH 560197A5
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Switzerland
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nitro
methylthio
pyrimidine
ethylamino
isopropylamino
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CH1703673A
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German (de)
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Ciba Geigy Ag
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Priority to CH1703673A priority Critical patent/CH560197A5/en
Publication of CH560197A5 publication Critical patent/CH560197A5/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • 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
    • C07D239/48—Two nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond

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  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dentistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Plant Pathology (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)

Abstract

Title cpds. of formula (I):- where R1 = (2-6C) alkyl, (3-5C) alkenyl, (3-5C) alkinyl, alkoxyalkyl, alkylaminoalkyl, trialkylammonioalkyl, (1-4C) alkyl substd. by OH or CN, or (3-6C) cycloalkyl; R2 and R3 = H or (1-6C) alkyl; R4 = H, (1-6C) alkyl, or (3-6C) cycloalkyl; R1 + R2 and/or R3 + R4 = polymethylene opt. substd. by O, S or N (l.alkyl); and R5 = (1-6C) alkyl; and salts of (I) are prepd. e.g. from 2,4,6-trihalo-5-nitropyrimidine by substituting the 3 hal atoms as required and in any convenient order.

Description

       

  
 



   Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung neuer Pyrimidin-Derivate. Diese haben   pflanzenbeeinfiussende    Wirkung.



   Bestimmte   2,4Bis(subst.aminoYpyrimidine    werden in der französischen Patentschrift Nr. 1572620 als Fungizide und Insektizide beschrieben. In der niederländischen Auslegeschrift Nr. 68. 14057 werden substituierte Pyrimidine genannt, die fungizide Wirkung vor allem gegen phytopatogene Pilze an Obstund Gemüsepflanzen aufweisen.



   Es wurde nun überraschenderweise gefunden, dass die neuen 5-Nitropyrimidine der Formel I sowie ihre Additionssalze oder ihre durch Quaternierung gewonnenen Salze den Pflanzenstoffwechsel zu beeinflussen vermögen, ohne aufgelaufene Pflanzen nennenswert im Sinne eines Nachauflauf-Herbizids zu schädigen:
Die neuen Pyrimidin-Derivate entsprechen der Formel I.
EMI1.1     




  und umfassen ebenfalls die Additionssalze und quaternäre Ammoniumsalze dieser Pyrimidine.



  In dieser Formel bedeutet:
R1 einen Alkyl-Rest mit 2 bis 6 Kohlenstoffatomen, einen Alkenyl-Rest mit 3 bis 5 Kohlenstoffatomen, einen Alkoxyalkyl-, Alkylaminoalkyl-, Trialkylammonio-alkyl-Rest einen Hydroxyalkyl- oder Cyanoalkyl-Rest mit 1 bis 4 Kohlenstoffatomen, einen Cycloalkyl-Rest mit 3 bis 6 Kohlenstoffatomen,
R2 und R3 unabhängig   voneinanderje    Wasserstoff oder einen niederen Alkyl-Rest,
R4 Wasserstoff, einen niederen Alkyl-Rest, einen Cycloalkyl Rest mit 3 bis 6 Kohlenstoffatomen und die Symbole-Paare
R1 und R2 und/oder R3 und R4 ausserdem zusammen ein Polymethylenbrückenglied, in dem eine Methylengruppe durch Sauerstoff, die -NH-Gruppe oder die Gruppe
N-R' ersetzt sein kann, in der R' für einen niederen Alkylrest steht,    Rs    einen niederen Alkylrest.



   Unter Alkyl-Resten bzw. unter niederen Alkyl-Resten sind in Formel 1, soweit nicht anders definiert, geradkettige oder verzweigte Reste mit 1 bis 6 Kohlenstoffatomen zu verstehen, wie z.B.   Methyl-,    Äthyl-, n-Propyl, Isopropyl, n-Butyl, Isobutyl, sec.



  Butyl, tert. Butyl-, n-Pentyl, n-Hexyl, und die Isomeren der C5 und C6 - Alkylreste. Die niederen geradkettigen oder verzweigten Alkylreste mit bzw. 2 bis 6 Kohlenstoffatomen bilden auch den Alkylteil von Alkoxy-, Alkylthio-, Dialkylamino-, Alkylamino-, Trialkylammonio-Substituenten. Unter Alkenyl-Resten werden in Formel I geradkettige oder verzweigte Reste mit 3 bis 5 Kohlenstoffatomen verstanden, z.B. Propenyl-, Butenyl-, Pentenyl-Reste, bevorzugt sind der Allyl-, Methallyl, 3-Methyl-butenyl- oder n-Butenyl-Rest. Als Cycloalkyl-Reste mit 3 bis 6 Ringkohlenstoffatomen sind z.B. Cyclopropyl, Cyclobutyl, Cyclopentyl, Cyclohexyl zu nennen. Diese Ringe können durch Methyl oder Äthyl substituiert sein.



   Ein durch die Symbolpaare   RI/R2    und R3/R4 mit dem benachbarten Stickstoffatom gebildeter Heterocyclus weist 3 resp.



  5 bis 7 Ringglieder auf. Solche Heterocyclen sind beispielsweise Aziridin, Pyrrolidin, Piperidin, Hexahydroazepin, Piperazin, N-Methylpiperazin und N-Phenylpiperazin oder Morpholin.



   Unter Additionssalzen sind die Salze mit anorganischen und organischen starken Säuren zu verstehen, vorzugsweise Chlorwasserstoffsäure, Bromwasserstoffsäure, Phosphorsäure, Schwefelsäure, Salpetersäure, Fluorborsäure   (HDF4),    Perchlorsäure, Methyl- oder Äthylschwefelsäure, Halogenbenzoesäuren, Trichloressigsäure und aromatische Sulfonsäuren, wie Methansulfonsäure oder p-Toluolsulfonsäure. Für die Bildung von quaternären Salzen der Pyrimidin-Derivate der Formel I, in denen R1 einen Trialkylammonio-alkyl-Rest darstellen, kommen die entsprechenden Anionen anorganischer oder organischer Säuren der genannten Art sowie schwache Säuren wie Naphtoesäure, Benzoesäure, Essigsäure, Aminoessigsäure, Propionsäure, Halogenpropionsäure, aliphatische Dicarbonsäuren z.B. Oxalsäure, Weinsäure oder Maleinsäure in Frage.



   Die neuen Pyrimidin-Derivate beeinflussen das Pflanzenwachstum in verschiedener Weise. So hemmen, verzögern oder unterbinden sie in erster Linie die Keimung. Die Pyrimidin-Derivate der Formel I sind in den üblichen Aufwandmengen, wie erwähnt, praktisch nicht phytotoxisch gegenüber den aufgelaufenen Pflanzen, hemmen aber das Längenwachstum bei verschiedenen Pflanzenarten. Bei sehr hohen Dosierungen von über 10 kg AS/ha können die Pflanzen auch nach dem Auflaufen unterschiedlich geschädigt werden und sogar eingehen. Die Wirkstoffe der   Formeln    besitzen auch fungizide, insbesondere pflanzenfungizide Wirkung.



   Die neuen Nitropyrimidin-Derivate der   Formeln    werden gemäss vorliegender Erfindung hergestellt, indem man ausgehend von einem entsprechenden   2-Alkylthio-4,6-dihalogen-5-nitropyrimidin    der Formel IV
EMI1.2     
 worin R5 die unter Formel I angegebene Bedeutung hat, die in   4    und 6-Stellung befindlichen Halogenatome, vorzugsweise Chloratome, nacheinander in Gegenwart eines säurebindenden Mittels gegen Reste von Aminen der Formeln II und/oder III
EMI1.3     
 austauscht. In den Formeln II und III haben R1 bis R4 die unter Formel I angegebenen Bedeutungen. Die Reaktionstemperatur   kann im Bereich bon - 60" und + 120 C, liegen, wobei vorteil-    hafterweise der Austausch des 1. Halogenatoms   zwischen - 60"      und + 20 C und der des 2.

  Halogenatoms zwischen 10 und 50 C    oder höher vorgenommen wird. Der bei Einführung unterschiedlicher Amine II oder III notwendige stufenweise Austausch ist, wie aus analogen chemischen Prozessen bekannt, sowohl temperatur- als auch zeit- und lösungsmittelabhängig.



   Als Lösungs- oder Verdünnungsmittel kommen für die erfindungsgemässen Umsetzungen Wasser, Ketone wie Aceton oder Methyläthylketon, Äther und ätherartige Verbindungen wie Dioxan oder Tetrahydrofuran, aliphatische und aromatische Kohlenwasserstoffe und Halogenkohlenwasserstoffe, ferner Nitrile wie Acetonitril, N,N-dialkylierte Amide wie Dimethylformamid oder Sulfoxide wie Dimethylsulfoxid sowie Gemische solcher Lösungsmittel untereinander in Betracht.



   Als säurebindende Mittel sind für das erfindungsgemässe Verfahren anorganische Basen wie Alkalimetall- und Erdalkalimetall-hydroxide, -hydrogencarbonate und -carbonate am besten geeignet. Es kommen aber auch als organische Basen tertiäre Amine  wie Trialkylamine, Dialkylaniline, Pyridin und Pyridinbasen in Frage. Ebenso kann die jeweilige Aminkomponente der Formel II oder III im Überschuss eingesetzt als säurebindendes Mittel dienen. Bevorzugt werden Natriumhydroxid oder Kaliumhydroxid.



   Als Zwischenprodukte lassen sich nach der 1. Austauschstufe mit einem Amin II oder III Verbindungen der Formel V
EMI2.1     
 isolieren, von denen ein Teil noch nicht in der Literatur beschrieben ist.



   Die Ausgangsprodukte der Formel IV können nach an sich bekannten Verfahren durch Alkylierung von 2-Mercapto-4,5dihydroxy-pyrimidin mit einem üblichen Alkylierungsmittel wie Alkylhalogenid oder Dialkylschwefelsäureester, anschliessender Nitrierung des erhalten 2-Alkylthio-4,6-dihydroxy-pyrimidins mit Salpetersäure oder Nitriergemisch und Ersatz der beiden Hydroxygruppen durch die gewünschten Halogenatome mit Hilfe von Phosphorylhalogeniden wie   POL3,      Pol5,      Pur^,      PC13    oder mit Thionylchlorid bzw. Thionylbromid.



   Für die Herstellung von Additionssalzen setzt man die Pyrimidin-Derivate der Formel I in an sich bekannter Weise mit anorganischen und organischen Säuren um. Bevorzugt sind für die Pyrimidin-Derivate der Formel I, in der R1 eine von Alkylaminoalkyl verschiedene Bedeutung besitzt, die starken Säuren, wie Halogenwasserstoffsäuren. Schwefelsäure, Fluoborsäure, Phosphorsäuren, Alkylschwefelsäuren etc.



   Für die Herstellung von quaternären Salzen der neuen Pyrimidin-Derivate kommen insbesondere diejenigen Verbindungen der Formel I in Betracht, in denen R1 einen Dialkylaminoalkyl-Rest darstellt. Solche Pyrimidine werden mit einem Alkylierungsmittel, wie z.B. einem Alkylhalogenid oder Dialkylsulfaten, umgesetzt. Das Anion der so erhaltenen Ammoniumsalze kann leicht gegen das Anion jeder beliebigen anorganischen oder organischen Säure ausgetauscht werden und zwar: a) durch Neutralisieren und anschliessende Umsetzung mit der entsprechenden Säure, oder b) mit Hilfe eines Anionenaustauschers.



   Die folgenden Beispiele dienen zur Veranschaulichung des erfindungsgemässen Verfahrens und seiner Variante. Anschliessend an die Beispiele sind weitere von Formel I umfasste Pyrimidin Derivate mit ihren physikalischen Daten aufgeführt. In einer weiteren Tabelle sind die Zwischenprodukte aufgeführt, die bei der Herstellung der Verbindungen der Formel I erhalten wurden.



   Die Herstellung der tabellarisch aufgeführten Pyrimidin Derivate erfolgte analog dem in den Beispielen beschriebenen Weg.



  Beispiel 1: a) In eine Lösung von 120,1 g 2-Methylthio-4,6-dichlor-5-nitro pyrimidin und 50,5 g Triäthylamin in 2200 ml absolutem  Äthanol werden unter Kühlung   bei -90"      bis - 10 C    22,5 g  Äthylamin-Gas eingeleitet. Nach Abklingen der Reaktion wird die Mischung zur Trockene eingedampft, der Rückstand wird in kaltem Wasser aufgeschlemmt, gewaschen und abgetrennt.



   Nach Umkristallisieren aus Hexan erhält man das    2-Methylthio-4 chlor-5-nitro-6-äthylamino-pyrimidin    vom
Fp:   100    bis   101"C.   



  b) In eine Lösung von   2-Methylthio-4-chlor-5-nitro-6-äthylamino-    pyrimidin in 100 ml absolutem Äthanol werden bei   35    bis   45 (   
10 g sec. Butylamin getropft. Nach 18 stündigem Rühren bei    25    wird das Reaktionsgemisch zur Trockene eingedampft und der Rückstand mit Äther extrahiert. Nach dem Trocknen und
Abdestillieren des Äthers wird der Rückstand aus einem 2:1
Pentan/Hexan-Gemisch unkristallisiert.



   Das   2-Methyfthio-4sec.butylamino-5-nitro-6äthylamino    pyrimidin hat den Fp.:   45"    bis   57"    C. (Verb. Nr. 1).



  Beispiel 2:
In eine Lösung von 60,0 g 2-Methylthio-4,6-dichlor-5-nitropyrimidin in 750 ml absolutem Äthanol werden bei ca.   35 C    ohne Kühlung 50 g (1,11 Mol) Äthylamin-Gas langsam eingeleitet.



  Anschliessend wird die Mischung 2 Stunden bei Raumtemperatur gerührt und bei   45"    im Vakuum zur Trockene eingeengt. Der Rückstand wird mit 500 ml Wasser aufgeschlemmt, abgetrennt und mit Wasser gewaschen. Das Produkt wird aus einem Gemisch von Hexan und Pentan im Verhältnis 10:1 umkristalisiert. Das 2-Methylthio-4,6-bis-äthylamino-5-nitro-pyrimidin hat den Fp: 130 bis   131"C.    (Verb. Nr. 2) Ber.: C42,01 H 5,88 N 27,22 S 12,46% Gef.: C42,00 H 5,83 N 27,17   S 12,31%    Beispiel 3: a) 144,2 g   2-Mercapto-4,6-dihydroxy-pyrimidin,    gelöst in 1000 ml
2 n wässriger Natriumhydroxid-Lösung, werden mit 184,1 g n-Butyljodid versetzt und 2 Stunden auf   85-90 C    erhitzt. Nach dem Erkalten wird das Reaktionsgemisch mit Eis und konzentrierter Salzsäure kongosauer gestellt.

  Das als Nieder schlag ausgefallene 2-n-Butylthio-4,6-dihydroxy-pyrimidin wird abgetrennt und getrocknet.



  b) 20 g 2-n-Butylthio-4,6-dihydroxy-pyrimidin werden unter Eis
Kochsalzkühlung langsam in 60 ml rauchende Salpetersäure eingetragen. Das Reaktionsgemisch wird 30 Minuten bei   0     gerührt und anschliessend in Eiswasser gegeben. Der braue
Niederschlag wird dann abgetrennt mit Wasser gewaschen und getrocknet. Das 2-Butylthio-4,6-dihydroxy-5-nitropyrimidin hat den Fp.:   155-157"C.   



  c) 110 g   2-n-Butylthio-4,6-dihydroxy-5-nitro-pyrimidin    werden zusammen mit 500 ml Phosphoroxychlorid auf   80     erhitzt und vorsichtig mit 146 ml Diäthylanilin, so dass die ein setzende, starke exotherme Reaktion kontrollierbar bleibt.



   Anschliessend wird das Gemisch 90 Minuten auf   150 C    Bad temperatur erhitzt und nach dem Erkalten in Eiswasser gegeben.



   Die wässrige Lösung wird dann mehrmals   rnit    Äther extrahiert.



   Die Ätherauszüge werden nach dem Trocknen über
Magnesiumsulfat vom Lösungsmittel befreit. Der Rückstand wird in Petroläther aufgenommen und von dem öligen Anteil abgetrennt. Nach dem Abdestillieren des Petroläthers wird das  Öl destilliert. Das 2-n-Butylthio-4,6-dichlor-5-nitropyrimidin hat den Kp.   135-140"C/0,001    Torr.

 

  d) In die Lösung von 10 g 2-n-Butylthio-4,6-dichlor-5-nitro pyrimidin in 100 ml absolutem Äthanol werden bei   45-50    
7,7 g Äthylamin-Gas eingeleitet. Die Reaktionsmischung wird dann am Vakuum zur Trockene eingeengt und der Rückstand mit Wasser aufgeschlemmt. Der ungelöste Niederschlag wird abgetrennt aus Hexan umkristallisiert. Das 2-n-Butylthio-4,6 diäthylamino-5-nitropyrimidin hat den Fp.   112 C.    (Verb. Nr. 3)
Tabelle 1: Verbindungen: Schmelz punkte in
Grad
Celsius    2-Methylthio-4-n-propylamino-5-nitro-6-äthyl- amino-pyrimidin . . .... .... . . 114    2-Methylthio-4-äthylamino-5-nitro-6-dimethyl amino-pyrimidin .   173-175      Verbindungen: Schmelz punkte in
Grad
Celsius 2-Methylthio-4-isopentylamino-5-nitro-6-äthyl amino-pyrimidin ................

  .......... 26  2-Methylthio-4-äthylamino-5-nitro-6-methylamino pyrimidin.................................. 119-121  2-Methylthio-4-äthylamino-5-nitro-6-amino pyrimidin.................................. 117  2-Methylthio-4-tert.butylamino-5-nitro-6-äthyl amino-pyrimidin ........................... 62-64  2-Methylthio-4-(1,1-dimethyl-1-cyano-methyl) amino-5-nitro-6-äthylamino-pyrimidin......... 120-122  2-Methylthio-4-äthylamino-5-nitro-6-cyclopropyl amino-pyrimidin ........................ . 128-130  2-Methylthio-4-allylamino-5-nitro-6-äthyl-amino pyrimidin................... .............. 110  2-Methylthio-4-sec.butylamino-5-nitro-6-dimethyl amino-pyrimidin .............. ............ 178  2-Methylthio-4-isopropylamino-5-nitro-6-dimethyl amino-pyrimidin ..... ...... .......... 181-182  2-Methylthio-4-isopropylamino-5-nitro-6-äthyl amino-pyrimidin .... ......

  ............. 80-81  2-Methylthio-4-sec.butylamino-5-nitro-6-methyl amino-pyrimidin ........................... 85-87  2-Methylthio-4-isopropylamino-5-nitro-6-methyl amino-pyrimidin ..... ..................... 108-110  2-Butylthio-4-isopropylamino-5-nitro-6-äthyl-amino
Pyrimidin ....... ...... ........... ... 76-77  2-Butylthio-4-methylamino-5-nitro-6-äthylamino pyrimidin ............................. ... 88-89  2-Methylthio-4-(3-methyl-2-butenylamino)-5 nitro-6-methylamino-pyrimidin ............... 60-62  2-Methylthio-4-isopentylamino-5-nitro-6-methyl amino-pyrimidin ..... ............... ... 60-61  2-Methylthio-4-diäthylamino-5-nitro-6-äthyl-amino pyrimidin .......... .............. ... ... 67-69  2-Methylthio-4-(2-methoxy-äthylamino)-5-nitro
6-äthylamino-pyrimidin ..... ..........

  . 112  2-Methylthio-4-äthanolamino-5-nitro-6-äthyl amino-pyrimidin ........................... 147  2-Methylthio-4-isobutylamino-5-nitro-6-äthyl amino-pyrimidin ........... ............ . 60-61  2-Methylthio-4-methylamino-5-nitro-6-n-butyl amino-pyrimidin ........... .... ....... 75-77  2-Methylthio-4-methylamino-5-nitro-6-n-propyl amino-pyrimidin ......... ........ . .... 106-108  2-Methylthio-4-methylamino-5-nitro-6-cyclo propylamino-pyrimidin...... ............... 103-105  2-Methylthio-4-dimethylamino-5-nitro-6-cyclo propylamino-pyrimidin.......... ... ..... 125-126  2-Äthylthio-4,6-bis-isopropylamino-5-nitro pyrimidin..... ....... .... .. .. .. 102-104  2-Äthylthio-4,6-bis-äthylamino-5-nitro-pyrimidin... 87-88  2-Methylthio-4-äthylamino-5-nitro-6-hydroxy methylamino-pyrimidin.... ........... . 128-130  2-Methylthio-4-äthylamino-5-nitro-6-n-butyl-amino pyrimidin...................

  ..... .... 58-60  2-Methylthio-4,6-bis-butylamino-5-nitro-pyrimidin 66  2-Methylthio-4,6-bis-sec.butylamino-5-nitro pyrimidin....... .... .. .... 45-46  2-Methylthio-4,6-bis-propylamino-5-nitro-pyrimidin 103  2-Methylthio-4,6-bis-isopropylamino-5-nitro pyrimidin......... ........ ....... ..... 123-124  Verbindungen: Schmelz punkte in
Grad
Celsius 2-n-Propylthio-4,6-bis-(n-propylamino)-5-nitro pyrimidin............... ..... 90-92  2-Methylthio-4,6-bis-cyclopentylamino-5-nitro pyrimidin...................... ...... 76-78  2-Methylthio-4,6-bis-cyclopropylamino-5-nitro pyrimidin...... ........................ 155  2-Methylthio-4,6-bis-cyclohexylamino-5-nitro pyrimidin............................... 105  2-Methylthio-4,6-bis-dimethylamino-5-nitro pyrimidin..... .... ..... 183-184  2-Butylthio-4,6-bis-isopropylamino-5-nitro pyrimidin..............

  ................. 92-93  2-Methylthio-4,6-bis-(äthylamino)-5-nitro-pyrimidin 148-150  2-Methylthio-4-äthylamino-5-nitro-6-sec.



   butylamino-pyrimidin.. ...... ........... 45-47  2-n-Butylthio-4,6-bis(äthylamino)-5-nitro-pyrimidin 112  2-Methylthio-4,6-bis(äthylamino)-5-nitro-pyrimidin, p-Toluolsulfonat....................... . 117  N,N,N-Trimethyl-ss-[(2-methylthio-4-äthylamino
5-nitropyrimidin-6)-amino]-äthylammonium jodid.................................... 230-232  2-Methylthio-4-äthylamino-5-nitro-6-cyano methylamino-pyrimidin... ...... ...... ... 177  2-Methylthio-4-äthylamino-5-nitro-6-äthylenimino pyrimidin........ .... ............ .. 130  2-Methylthio-4-äthylamino-5-nitro-6-sec.amylamino pyrimidin.................. ......... . viskoses Öl nD20 1.6099 2-Methylthio-4-äthylamino-5-nitro-6-(pent-3'-yl) amino-pyrimidin. ...................... Smp:45-47  2-Methylthio-4-äthylamino-5-nitro-6-cyclohexyl amino-pyrimidin....... ........... 116-117  2-Methyl-4-isopropylamino-5-nitro-6-sec.



   butylamino-pyrimidin... . viskoses Öl nD25 1.6051 2-Methyl-4-isopropylamino-5-nitro-6-n propylamino-pyrimidin.............. ........ 68  2-Methylthio-4-äthylamino-5-nitro-6  (2',4'-dimethylpent-3'-yl)amino-pyrimidn....... viskoses Öl nD22 1.6071 2-Methylthio-4-äthylamino-5-nitro-6-(4'-methyl hex-2'-yl)amino-pyrimidin............... . viskoses Öl nD22 1.6072 2-Methylthio-4-äthylamino-5-nitro-6-neopentyl amino-pyrimidin . .. . ........ ..... 64-65  2-Methylthio-4-äthylamino-5-nitro-6-(3'-methyl pent-2'-yl)amino-pyrimidin........ ........ viskoses Öl nD22 1.6082 2-Methylthio-4-äthylamino-5-nitro-6-(2'-methyl cyclopropylamino)-pyrimidin.............. 70-71  2-Methylthio-4-äthylamino-5-nitro-6-isohexalamino pyrimidin.. ..... ............. viskoses Öl nD22 1.6065 2-Methylthio-4-äthylamino-5-nitro-6-isoheptyl amino-pyrimidin..... ..... .

  ........ viskoses Öl nD22 1.5973 2-Methylthio-4-äthylamino-5-nitro-6-sec.pentyl amino-pyrimidin. ..... ....... . viskoses Öl nD22 1.6161 2-Methylthio-4-äthylamino-5-nitro-6-(2'-hydroxy prop-1'-ylamino)-pyrimidin . ......... 96    Verbindungen: Brechungs indices bzw.



   Schmelz punkte in
Grad
Celsius 2-Methylthio-4-äthylamino-5-nitro-6-cyclobutyl amino-pyrimidin ..... ... .... ...... 105-106 2-Methylthio-4-isopropylamino-5-nitro-6-(1',2'-di    methylpropylaminotpyrimidin    . . . viskoses Öl nD24.5 1.6000 2-Methylthio-4-isopropylamino-5-nitro-6-(1'-cyclo propyl-äthylamino)-pyrimidin............ . nD25 1.6143   2-Methylthio-4-äthylamino-5-nitro-6-(1'-cyclo-       propyl-äthylamino Spyrimidin    . ..... .....   57-62     2-Methylthio-4-isopropylamino-5-nitro-6-(pent-2' ylamino)-pyrimidin. .... ............. . nD25 1.6008 2-Methylthio-4-äthylamino-5-nitro-6-(3'-methyl but-2'-ylamino)-pyrimidin.. ..... ...... . 68-69    2-Methylthio-4-methylamino-5-nitro-6-(pent-2'-    ylamino)-pyrimidin . ... ...........

  .. nD25 1.6310 2-Methylthio-4-methylamino-5-nitro-6-(1'-cyclo propyl-äthylamino)-pyrimidin . .... . . . 91-93  2-Methylthio-4-isopropylamino-5-nitro-6-tert.



   butylamino-pyrimidin.... ........ ...... . nD25.5 1.6032 2-Methylthio-4-äthylamino-5-nitro-6-(N'-methyl    sec.butylaminotpyrimidin      ...    ... Öl   2-Methylthio-4-äthylamino-5-nitro-6-piperidino-    pyrimidin......... ..... .......... ..... Öl 2-Methylthio-4-äthylamino-5-nitro-6-(1',1'-dimethyl    2'-hydroxy-äthylamino tpyrimidin 96-98"    2-Methylthio-4-äthylamino-5-nitro-6-1'-äthyl  (2'-hydroxy-äthylamino)-pyrimidin .. ...... . 110-111  2-Methylthio-4-äthylamino-5-nitro-6-(3 '-methyl but-2'-ylamino)-pyrimidin.... ............. 75-77  2-Methylthio-4-dimethylamino-5-nitro-6-isobutyl amino-pyrimidin . .... ........ . ..... 178  2-Methylthio-4-äthylamino-5-nitro-6-cyclopentyl amino-pyrimidin . . . 80-81" 2-Methylthio-4-methylamino-5-nitro-6-(pent-3'-yl amino)-pyrimidin. . ... .

  . 47-54  2-Methylthio-4-methylamino-5-nitro-6-cyclopentyl amino-pyrimidin . . . . 99-102"
2-Methylthio-4-dimethylamino-5-nitro
6-cyclopentylamino-pyrimidin .   ..      nD4    1.6412
2-Methylthio-4-dimethylamino-5-nitro-6-(pent-3'-yl    amino pyrimidin. . 45-47"   
2-Methylthio-4-isopropylamino-5-nitro-6-(pent-3' yl-amino)-pyrimidin. nD24 1.6033
2-Methylthio-4-isopropylamino-5-nitro
6-cyclopentylamino-pyrimidin . . 72-74 
2-Methylthio-4-äthylamino-5-nitro-6    (N'-methylpiperazinotpyrimidin . . 72-74"   
2-Methylthio-4-äthylamino-5-nitro-6-pyrrolidino pyrimidin........ .. . .... . 59-61 
2-Methylthio-4-äthylamino-5-nitro-6 morpholino-pyrimidin......... ..... .. .. 65-70 
N,N-Dimethyl-N'-[2-methylthio-4-äthyl-amino-5    nitropyrimidin-63-piperazoniumjodid .

  .    .   210" (Zers.)   
Folgende bisher noch nicht beschriebene Zwischenprodukte der Formel V wurden auf dem in Beispiel 3a bis c beschriebenen
Wege erhalten:
Tabelle 2: Verbindungen: Physikalische
Daten: 2-Methylthio-4-amino-5-nitro-6-chlor pyrimidin ... ..... .... ............ Fp: 175  2-Methylthio-4-methylamino-5-nitro-6-chlor pyrimidin ...... . . . .... Fp: 120-121  2-Methylthio-4-sec.butylamino-5-nitro-6-chlor pyrimidin ... .... .... ....... Fp: 77    2-Methylthio-4-n-propylamino-5-nitro-6-chlor-    pyrimidin ...... .............. ... Fp: 82    2-Butylthio-4-äthylamino-5-nitro-6-chlor    pyrimidin . ........ ............ . Kp: 145 /0,01
Torr 2-Methylthio-4-dimethylamino-5-nitro-6-chlor pyrimidin ...... ... ...... ... Fp: 104-106  2-Methylthio-4-äthylamino-5-nitro-6-chlor pyrimidin . . ... . .... ......

  Fp: 95-97  2-Methylthio-4-isopropylamino-5-nitro-6-chlor pyrimidin .... .... ... ..... Fp: 84-86  2-Methylthio-4-di-n-propyl-amino-5-nitro-6    chlor-pyrimidin . Fp: 50-51"   
PATENTANSPRUCH 1
Verfahren zur Herstellung neuer Pyrimidin-Derivate der Formel   1   
EMI4.1     
 in der
R1 einen Alkyl-Rest mit 2 bis 6 Kohlenstoffatomen,' einen Alkenyl-Rest mit 3 bis 5 Kohlenstoffatomen, einen Alkoxyalkyl-, Alkylaminoalkyl-, Trialkylammonio-alkyl-Rest, einen Hydroxyalkyl- oder Cyanoalkylrest mit 1 bis 4 Kohlenstoffatomen, einen Cycloalkyl-Rest mit 3 bis 6 Kohlenstoffatomen,
R2 und R3 unabhängig voneinander je Wasserstoff oder einen niederen Alkyl-Rest,
R4 Wasserstoff, einen niederen Alkylrest, einen Cycloalkyl-Rest mit 3 bis 6 Kohlenstoffatomen und die Symbol-Paare
R1 und R2 und/oder R3 und R4 ausserdem zusammen ein Polymethylenbrückenglied, 

   in dem eine Methylengruppe durch Sauerstoff, die -NH-Gruppe oder die Gruppe
N-R', ersetzt sein kann, in der R' für einen niederen Alkylrest steht, und R5 einen niederen Alkylrest bedeuten, dadurch gekennzeichnet, dass man in einer Verbindung der   Formel IV    

**WARNUNG** Ende DESC Feld konnte Anfang CLMS uberlappen**.



   



  
 



   The present invention relates to a process for the preparation of new pyrimidine derivatives. These have a plant-influencing effect.



   Certain 2,4 bis (subst.aminoYpyrimidines are described in French patent specification No. 1572620 as fungicides and insecticides. In the Dutch patent application No. 68.14057, substituted pyrimidines are mentioned, which have fungicidal activity, especially against phytopathogenic fungi on fruit and vegetable plants.



   It has now been found, surprisingly, that the new 5-nitropyrimidines of the formula I and their addition salts or their salts obtained by quaternization are able to influence the plant metabolism without causing any significant damage to emerged plants in the sense of a post-emergence herbicide:
The new pyrimidine derivatives correspond to the formula I.
EMI1.1




  and also include the addition salts and quaternary ammonium salts of these pyrimidines.



  In this formula:
R1 is an alkyl radical with 2 to 6 carbon atoms, an alkenyl radical with 3 to 5 carbon atoms, an alkoxyalkyl, alkylaminoalkyl, trialkylammonio-alkyl radical, a hydroxyalkyl or cyanoalkyl radical with 1 to 4 carbon atoms, a cycloalkyl radical with 3 to 6 carbon atoms,
R2 and R3 independently of one another are hydrogen or a lower alkyl radical,
R4 is hydrogen, a lower alkyl radical, a cycloalkyl radical with 3 to 6 carbon atoms and the symbol pairs
R1 and R2 and / or R3 and R4 also together form a polymethylene bridge member in which a methylene group is replaced by oxygen, the -NH group or the group
N-R 'can be replaced in which R' stands for a lower alkyl radical, Rs a lower alkyl radical.



   Unless otherwise defined, alkyl radicals or lower alkyl radicals in formula 1 are to be understood as meaning straight-chain or branched radicals with 1 to 6 carbon atoms, e.g. Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec.



  Butyl, tert. Butyl, n-pentyl, n-hexyl, and the isomers of the C5 and C6 alkyl radicals. The lower straight-chain or branched alkyl radicals with or 2 to 6 carbon atoms also form the alkyl part of alkoxy, alkylthio, dialkylamino, alkylamino, trialkylammonio substituents. In formula I, alkenyl radicals are understood to mean straight-chain or branched radicals with 3 to 5 carbon atoms, e.g. Propenyl, butenyl, pentenyl radicals, preferred are the allyl, methallyl, 3-methyl-butenyl or n-butenyl radical. Cycloalkyl radicals with 3 to 6 ring carbon atoms are e.g. Cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl should be mentioned. These rings can be substituted by methyl or ethyl.



   A heterocycle formed by the symbol pairs RI / R2 and R3 / R4 with the adjacent nitrogen atom has 3 or



  5 to 7 ring links. Such heterocycles are, for example, aziridine, pyrrolidine, piperidine, hexahydroazepine, piperazine, N-methylpiperazine and N-phenylpiperazine or morpholine.



   Addition salts are to be understood as meaning the salts with inorganic and organic strong acids, preferably hydrochloric acid, hydrobromic acid, phosphoric acid, sulfuric acid, nitric acid, fluoroboric acid (HDF4), perchloric acid, methyl or ethylsulfuric acid, halobenzoic acids, trichloroacetic acid and aromatic sulfonic acids, such as methanesulfonic acid, or p-toluenesulfonic acid . For the formation of quaternary salts of the pyrimidine derivatives of the formula I, in which R1 represent a trialkylammonio-alkyl radical, the corresponding anions of inorganic or organic acids of the type mentioned as well as weak acids such as naphthoic acid, benzoic acid, acetic acid, aminoacetic acid, propionic acid, Halopropionic acid, aliphatic dicarboxylic acids, for example Oxalic acid, tartaric acid or maleic acid in question.



   The new pyrimidine derivatives influence plant growth in various ways. They primarily inhibit, delay or prevent germination. As mentioned, the pyrimidine derivatives of the formula I are practically non-phytotoxic to the emerged plants in the usual application rates, but they inhibit the growth in length in various plant species. At very high doses of over 10 kg AS / ha, the plants can be damaged and even die in different ways after emergence. The active ingredients of the formulas also have a fungicidal, in particular plant-fungicidal, effect.



   The new nitropyrimidine derivatives of the formulas are prepared according to the present invention by starting from a corresponding 2-alkylthio-4,6-dihalo-5-nitropyrimidine of the formula IV
EMI1.2
 wherein R5 has the meaning given under formula I, the halogen atoms in the 4 and 6-position, preferably chlorine atoms, one after the other in the presence of an acid-binding agent against residues of amines of the formulas II and / or III
EMI1.3
 exchanges. In formulas II and III, R1 to R4 have the meanings given under formula I. The reaction temperature can be in the range from −60 "to + 120 ° C., the exchange of the 1st halogen atom being advantageously between −60" and + 20 ° C. and that of the 2nd halogen atom.

  Halogen atom between 10 and 50 C or higher is made. The gradual exchange necessary when introducing different amines II or III is, as known from analogous chemical processes, dependent on both temperature, time and solvent.



   Suitable solvents or diluents for the reactions according to the invention are water, ketones such as acetone or methyl ethyl ketone, ethers and ethereal compounds such as dioxane or tetrahydrofuran, aliphatic and aromatic hydrocarbons and halogenated hydrocarbons, and also nitriles such as acetonitrile, N, N-dialkylated amides such as dimethylformamide or sulfoxides such as dimethylformamide or sulfoxides Dimethyl sulfoxide and mixtures of such solvents with one another are suitable.



   Inorganic bases such as alkali metal and alkaline earth metal hydroxides, bicarbonates and carbonates are most suitable as acid-binding agents for the process according to the invention. However, tertiary amines such as trialkylamines, dialkylanilines, pyridine and pyridine bases are also suitable as organic bases. The respective amine component of the formula II or III, used in excess, can also serve as an acid-binding agent. Sodium hydroxide or potassium hydroxide are preferred.



   Compounds of the formula V can be used as intermediate products after the 1st exchange stage with an amine II or III
EMI2.1
 isolate some of which are not yet described in the literature.



   The starting materials of the formula IV can be obtained by methods known per se by alkylating 2-mercapto-4,5 dihydroxypyrimidine with a customary alkylating agent such as alkyl halide or dialkylsulfuric acid ester, then nitrating the 2-alkylthio-4,6-dihydroxypyrimidine with nitric acid or Nitration mixture and replacement of the two hydroxyl groups by the desired halogen atoms with the help of phosphoryl halides such as POL3, Pol5, Pur ^, PC13 or with thionyl chloride or thionyl bromide.



   For the preparation of addition salts, the pyrimidine derivatives of the formula I are reacted in a manner known per se with inorganic and organic acids. For the pyrimidine derivatives of the formula I in which R1 has a meaning different from alkylaminoalkyl, preference is given to the strong acids, such as hydrohalic acids. Sulfuric acid, fluoroboric acid, phosphoric acids, alkyl sulfuric acids etc.



   For the preparation of quaternary salts of the new pyrimidine derivatives, those compounds of the formula I are particularly suitable in which R1 is a dialkylaminoalkyl radical. Such pyrimidines are made with an alkylating agent such as e.g. an alkyl halide or dialkyl sulfates. The anion of the ammonium salts obtained in this way can easily be exchanged for the anion of any desired inorganic or organic acid, namely: a) by neutralization and subsequent reaction with the corresponding acid, or b) with the aid of an anion exchanger.



   The following examples serve to illustrate the process according to the invention and its variant. Following the examples, further pyrimidine derivatives encompassed by formula I are listed with their physical data. The intermediates which were obtained in the preparation of the compounds of the formula I are listed in a further table.



   The pyrimidine derivatives listed in the table were prepared analogously to the route described in the examples.



  Example 1: a) In a solution of 120.1 g of 2-methylthio-4,6-dichloro-5-nitro-pyrimidine and 50.5 g of triethylamine in 2200 ml of absolute ethanol, while cooling at -90 "to -10 C 22 , 5 g of ethylamine gas are passed in. After the reaction has subsided, the mixture is evaporated to dryness, the residue is suspended in cold water, washed and separated off.



   After recrystallization from hexane, 2-methylthio-4-chloro-5-nitro-6-ethylamino-pyrimidine is obtained
M.p .: 100 to 101 "C.



  b) In a solution of 2-methylthio-4-chloro-5-nitro-6-ethylaminopyrimidine in 100 ml of absolute ethanol at 35 to 45 (
10 g sec. Butylamine added dropwise. After stirring at 25 for 18 hours, the reaction mixture is evaporated to dryness and the residue is extracted with ether. After drying and
Distilling off the ether, the residue is from a 2: 1
Pentane / hexane mixture uncrystallized.



   2-Methyfthio-4sec.butylamino-5-nitro-6ethylamino pyrimidine has the melting point: 45 "to 57" C. (Comp. No. 1).



  Example 2:
50 g (1.11 mol) of ethylamine gas are slowly introduced into a solution of 60.0 g of 2-methylthio-4,6-dichloro-5-nitropyrimidine in 750 ml of absolute ethanol at about 35 ° C. without cooling.



  The mixture is then stirred for 2 hours at room temperature and concentrated to dryness at 45 "in vacuo. The residue is suspended in 500 ml of water, separated off and washed with water. The product is recrystallized from a mixture of hexane and pentane in a ratio of 10: 1 2-Methylthio-4,6-bis-ethylamino-5-nitro-pyrimidine has the melting point: 130 to 131 ° C. (Comp. No. 2) Calc .: C42.01 H 5.88 N 27.22 S 12.46% Found: C42.00 H 5.83 N 27.17 S 12.31% Example 3: a) 144.2 g of 2-mercapto-4,6-dihydroxypyrimidine, dissolved in 1000 ml
2 N aqueous sodium hydroxide solution, 184.1 g of n-butyl iodide are added and the mixture is heated to 85-90 ° C. for 2 hours. After cooling, the reaction mixture is acidified to Congo with ice and concentrated hydrochloric acid.

  The 2-n-butylthio-4,6-dihydroxypyrimidine precipitated as a precipitate is separated off and dried.



  b) 20 g of 2-n-butylthio-4,6-dihydroxy-pyrimidine are under ice
Saline cooling slowly added to 60 ml of fuming nitric acid. The reaction mixture is stirred for 30 minutes at 0 and then poured into ice water. The brew
The precipitate is then separated off, washed with water and dried. The 2-butylthio-4,6-dihydroxy-5-nitropyrimidine has a m.p .: 155-157 "C.



  c) 110 g of 2-n-butylthio-4,6-dihydroxy-5-nitro-pyrimidine are heated to 80 together with 500 ml of phosphorus oxychloride and carefully with 146 ml of diethylaniline, so that the strong exothermic reaction that sets in remains controllable.



   The mixture is then heated to a bath temperature of 150 ° C. for 90 minutes and, after cooling, poured into ice water.



   The aqueous solution is then extracted several times with ether.



   The ether extracts are over after drying
Magnesium sulfate freed from the solvent. The residue is taken up in petroleum ether and separated from the oily fraction. After the petroleum ether has been distilled off, the oil is distilled. The 2-n-butylthio-4,6-dichloro-5-nitropyrimidine has a boiling point of 135-140 "C / 0.001 Torr.

 

  d) In the solution of 10 g of 2-n-butylthio-4,6-dichloro-5-nitro pyrimidine in 100 ml of absolute ethanol are at 45-50
7.7 g ethylamine gas initiated. The reaction mixture is then concentrated to dryness in vacuo and the residue is suspended in water. The undissolved precipitate is separated off and recrystallized from hexane. The 2-n-butylthio-4,6 diethylamino-5-nitropyrimidine has the melting point 112 C. (Comp. No. 3)
Table 1: Compounds: Melting points in
Degree
Celsius 2-methylthio-4-n-propylamino-5-nitro-6-ethylamino-pyrimidine. . .... ..... . 114 2-Methylthio-4-ethylamino-5-nitro-6-dimethylamino-pyrimidine. 173-175 compounds: melting points in
Degree
Celsius 2-methylthio-4-isopentylamino-5-nitro-6-ethylamino-pyrimidine ................

  .......... 26 2-Methylthio-4-ethylamino-5-nitro-6-methylamino pyrimidine ....................... ........... 119-121 2-Methylthio-4-ethylamino-5-nitro-6-amino pyrimidine .................... .............. 117 2-Methylthio-4-tert-butylamino-5-nitro-6-ethylamino-pyrimidine ............... ............ 62-64 2-Methylthio-4- (1,1-dimethyl-1-cyano-methyl) amino-5-nitro-6-ethylamino-pyrimidine ..... .... 120-122 2-methylthio-4-ethylamino-5-nitro-6-cyclopropylamino-pyrimidine ......................... 128-130 2-Methylthio-4-allylamino-5-nitro-6-ethyl-amino pyrimidine ................... .......... .... 110 2-Methylthio-4-sec.butylamino-5-nitro-6-dimethylamino-pyrimidine .............. ........... 178 2-Methylthio-4-isopropylamino-5-nitro-6-dimethylamino-pyrimidine ..... ...... .......... 181-182 2-Methylthio-4- isopropylamino-5-nitro-6-ethylamino-pyrimidine .... ......

  ............. 80-81 2-Methylthio-4-sec.butylamino-5-nitro-6-methylamino-pyrimidine .............. ............. 85-87 2-Methylthio-4-isopropylamino-5-nitro-6-methylamino-pyrimidine ..... ........... .......... 108-110 2-butylthio-4-isopropylamino-5-nitro-6-ethyl-amino
Pyrimidine ....... ...... ........... ... 76-77 2-Butylthio-4-methylamino-5-nitro-6-ethylamino pyrimidine ... .......................... ... 88-89 2-Methylthio-4- (3-methyl-2-butenylamino) -5 nitro -6-methylamino-pyrimidine ............... 60-62 2-methylthio-4-isopentylamino-5-nitro-6-methylamino-pyrimidine ..... ... ............ ... 60-61 2-Methylthio-4-diethylamino-5-nitro-6-ethylamino pyrimidine .......... .... .......... ... ... 67-69 2-methylthio-4- (2-methoxy-ethylamino) -5-nitro
6-ethylamino-pyrimidine ..... ..........

  . 112 2-Methylthio-4-ethanolamino-5-nitro-6-ethylamino-pyrimidine ........................... 147 2-Methylthio -4-isobutylamino-5-nitro-6-ethylamino-pyrimidine ........... ............. 60-61 2-Methylthio-4-methylamino-5-nitro-6-n-butylamino-pyrimidine ........... .... ....... 75-77 2- Methylthio-4-methylamino-5-nitro-6-n-propylamino-pyrimidine ......... ......... .... 106-108 2-Methylthio-4-methylamino-5-nitro-6-cyclopropylamino-pyrimidine ...... ............... 103-105 2 -Methylthio-4-dimethylamino-5-nitro-6-cyclo propylamino-pyrimidine .......... ... ..... 125-126 2-Ethylthio-4,6-bis-isopropylamino- 5-nitro pyrimidine ..... ....... .... .. .. .. 102-104 2-ethylthio-4,6-bis-ethylamino-5-nitro-pyrimidine ... 87 -88 2-Methylthio-4-ethylamino-5-nitro-6-hydroxy methylamino-pyrimidine .... ............ 128-130 2-Methylthio-4-ethylamino-5-nitro-6-n-butyl-amino pyrimidine ...................

  ..... .... 58-60 2-Methylthio-4,6-bis-butylamino-5-nitro-pyrimidine 66 2-Methylthio-4,6-bis-sec.butylamino-5-nitro pyrimidine .. ..... .... .. .... 45-46 2-Methylthio-4,6-bis-propylamino-5-nitro-pyrimidine 103 2-Methylthio-4,6-bis-isopropylamino-5- nitro pyrimidine ......... ........ ....... ..... 123-124 compounds: melting points in
Degree
Celsius 2-n-propylthio-4,6-bis- (n-propylamino) -5-nitro pyrimidine ............... ..... 90-92 2-methylthio- 4,6-bis-cyclopentylamino-5-nitro pyrimidine ...................... ...... 76-78 2-methylthio-4,6 -bis-cyclopropylamino-5-nitro pyrimidine ...... ........................ 155 2-methylthio-4,6-bis- cyclohexylamino-5-nitro pyrimidine ............................... 105 2-methylthio-4,6-bis-dimethylamino- 5-nitro pyrimidine ..... .... ..... 183-184 2-butylthio-4,6-bis-isopropylamino-5-nitro pyrimidine ............. .

  ................. 92-93 2-methylthio-4,6-bis- (ethylamino) -5-nitro-pyrimidine 148-150 2-methylthio-4-ethylamino- 5-nitro-6-sec.



   butylamino-pyrimidine .. ...... ........... 45-47 2-n-butylthio-4,6-bis (ethylamino) -5-nitro-pyrimidine 112 2-methylthio- 4,6-bis (ethylamino) -5-nitro-pyrimidine, p-toluenesulfonate ........................ 117 N, N, N-trimethyl-ss - [(2-methylthio-4-ethylamino
5-nitropyrimidine-6) -amino] -äthylammonium iodid .................................... 230- 232 2-methylthio-4-ethylamino-5-nitro-6-cyano methylamino-pyrimidine ... ...... ...... ... 177 2-methylthio-4-ethylamino-5-nitro- 6-Ethylenimino pyrimidine ........ .... ............ .. 130 2-Methylthio-4-ethylamino-5-nitro-6-sec.amylamino pyrimidine. ................. .......... viscous oil nD20 1.6099 2-methylthio-4-ethylamino-5-nitro-6- (pent-3'-yl) aminopyrimidine. ...................... m.p .: 45-47 2-methylthio-4-ethylamino-5-nitro-6-cyclohexylamino-pyrimidine ..... .. ........... 116-117 2-methyl-4-isopropylamino-5-nitro-6-sec.



   butylamino-pyrimidine .... viscous oil nD25 1.6051 2-methyl-4-isopropylamino-5-nitro-6-n propylamino-pyrimidine .............. ........ 68 2-methylthio-4 -äthylamino-5-nitro-6 (2 ', 4'-dimethylpent-3'-yl) amino-pyrimidn ....... viscous oil nD22 1.6071 2-methylthio-4-ethylamino-5-nitro-6- (4'-methyl hex-2'-yl) amino-pyrimidine ................ viscous oil nD22 1.6072 2-methylthio-4-ethylamino-5-nitro-6-neopentylamino-pyrimidine. ... ........ ..... 64-65 2-methylthio-4-ethylamino-5-nitro-6- (3'-methyl pent-2'-yl) amino-pyrimidine ..... ... ........ viscous oil nD22 1.6082 2-methylthio-4-ethylamino-5-nitro-6- (2'-methyl cyclopropylamino) pyrimidine ............ .. 70-71 2-methylthio-4-ethylamino-5-nitro-6-isohexalamino pyrimidine .. ..... ............. viscous oil nD22 1.6065 2-methylthio-4 -äthylamino-5-nitro-6-isoheptylamino-pyrimidine ..... ......

  ........ viscous oil nD22 1.5973 2-methylthio-4-ethylamino-5-nitro-6-sec.pentylamino-pyrimidine. ..... ........ viscous oil nD22 1.6161 2-methylthio-4-ethylamino-5-nitro-6- (2'-hydroxy-prop-1'-ylamino) -pyrimidine. ......... 96 compounds: refractive indices resp.



   Melting points in
Degree
Celsius 2-methylthio-4-ethylamino-5-nitro-6-cyclobutylamino-pyrimidine ..... ... .... ...... 105-106 2-methylthio-4-isopropylamino-5- nitro-6- (1 ', 2'-dimethylpropylaminotpyrimidine... viscous oil nD24.5 1.6000 2-methylthio-4-isopropylamino-5-nitro-6- (1'-cyclopropyl-ethylamino) -pyrimidine ... .......... nD25 1.6143 2-Methylthio-4-ethylamino-5-nitro-6- (1'-cyclo-propyl-ethylamino-spyrimidine. ..... ..... 57-62 2-Methylthio-4-isopropylamino-5-nitro-6- (pent-2 'ylamino) -pyrimidine. .... .............. ND25 1.6008 2-Methylthio-4- ethylamino-5-nitro-6- (3'-methyl-but-2'-ylamino) -pyrimidine .. ..... ....... 68-69 2-methylthio-4-methylamino-5-nitro -6- (pent-2'-ylamino) -pyrimidine. ... ...........

  .. nD25 1.6310 2-Methylthio-4-methylamino-5-nitro-6- (1'-cyclopropyl-ethylamino) -pyrimidine. .... . . 91-93 2-Methylthio-4-isopropylamino-5-nitro-6-tert.



   butylamino-pyrimidine .... ........ ....... nD25.5 1.6032 2-methylthio-4-ethylamino-5-nitro-6- (N'-methyl sec.butylaminotpyrimidine ... ... oil 2-methylthio-4-ethylamino-5-nitro-6-piperidino-pyrimidine ......... ..... .......... ..... oil 2-methylthio-4-ethylamino-5-nitro-6- (1 ', 1' -dimethyl 2'-hydroxy-ethylamino pyrimidine 96-98 "2-methylthio-4-ethylamino-5-nitro-6-1'-ethyl (2'-hydroxy-ethylamino) -pyrimidine .. ....... 110-111 2-Methylthio-4-ethylamino-5-nitro-6- (3'-methyl-but-2'-ylamino) -pyrimidine .... ............. 75- 77 2-Methylthio-4-dimethylamino-5-nitro-6-isobutylamino-pyrimidine. .... ......... ..... 178 2-Methylthio-4-ethylamino-5-nitro -6-cyclopentylamino-pyrimidine... 80-81 "2-Methylthio-4-methylamino-5-nitro-6- (pent-3'-ylamino) pyrimidine.. ....

  . 47-54 2-Methylthio-4-methylamino-5-nitro-6-cyclopentylamino-pyrimidine. . . . 99-102 "
2-methylthio-4-dimethylamino-5-nitro
6-cyclopentylamino-pyrimidine. .. nD4 1.6412
2-methylthio-4-dimethylamino-5-nitro-6- (pent-3'-ylamino pyrimidine.. 45-47 "
2-methylthio-4-isopropylamino-5-nitro-6- (pent-3 'yl-amino) pyrimidine. nD24 1.6033
2-methylthio-4-isopropylamino-5-nitro
6-cyclopentylamino-pyrimidine. . 72-74
2-methylthio-4-ethylamino-5-nitro-6 (N'-methylpiperazinotpyrimidine.. 72-74 "
2-Methylthio-4-ethylamino-5-nitro-6-pyrrolidino pyrimidine ........ ... .... 59-61
2-methylthio-4-ethylamino-5-nitro-6 morpholino-pyrimidine ......... ..... .. .. 65-70
N, N-Dimethyl-N '- [2-methylthio-4-ethyl-amino-5-nitropyrimidine-63-piperazonium iodide.

  . . 210 "(dec.)
The following intermediates of the formula V, which have not yet been described, were based on that described in Examples 3a to c
Get ways:
Table 2: Connections: Physical
Data: 2-Methylthio-4-amino-5-nitro-6-chloro pyrimidine ... ..... .... ............ Mp: 175 2-Methylthio-4 -methylamino-5-nitro-6-chloro pyrimidine ....... . . .... mp: 120-121 2-methylthio-4-sec.butylamino-5-nitro-6-chloro pyrimidine ... .... .... ....... mp: 77 2- Methylthio-4-n-propylamino-5-nitro-6-chloropyrimidine ...... .............. ... Mp: 82 2-butylthio-4-ethylamino -5-nitro-6-chloro pyrimidine. ........ ............. Bp: 145 / 0.01
Torr 2-Methylthio-4-dimethylamino-5-nitro-6-chloropyrimidine ...... ... ...... ... Mp: 104-106 2-Methylthio-4-ethylamino-5- nitro-6-chloro pyrimidine. . ... .... ......

  Mp: 95-97 2-Methylthio-4-isopropylamino-5-nitro-6-chloropyrimidine .... .... ... ..... Mp: 84-86 2-Methylthio-4-di- n-propyl-amino-5-nitro-6-chloro-pyrimidine. Fp: 50-51 "
PATENT CLAIM 1
Process for the preparation of new pyrimidine derivatives of formula 1
EMI4.1
 in the
R1 is an alkyl radical with 2 to 6 carbon atoms, an alkenyl radical with 3 to 5 carbon atoms, an alkoxyalkyl, alkylaminoalkyl, trialkylammonio-alkyl radical, a hydroxyalkyl or cyanoalkyl radical with 1 to 4 carbon atoms, a cycloalkyl radical with 3 to 6 carbon atoms,
R2 and R3 independently of one another are each hydrogen or a lower alkyl radical,
R4 is hydrogen, a lower alkyl radical, a cycloalkyl radical with 3 to 6 carbon atoms and the symbol pairs
R1 and R2 and / or R3 and R4 also together form a polymethylene bridge member,

   in which a methylene group is replaced by oxygen, the -NH group or the group
N-R ', in which R' stands for a lower alkyl radical and R5 stands for a lower alkyl radical, characterized in that in a compound of the formula IV

** WARNING ** End of DESC field could overlap beginning of CLMS **.

Claims (1)

**WARNUNG** Anfang CLMS Feld konnte Ende DESC uberlappen **. Verbindungen: Brechungs indices bzw. ** WARNING ** Beginning of CLMS field could overlap end of DESC **. Connections: refractive indices or Schmelz punkte in Grad Celsius 2-Methylthio-4-äthylamino-5-nitro-6-cyclobutyl amino-pyrimidin ..... ... .... ...... 105-106 2-Methylthio-4-isopropylamino-5-nitro-6-(1',2'-di methylpropylaminotpyrimidin . . . viskoses Öl nD24.5 1.6000 2-Methylthio-4-isopropylamino-5-nitro-6-(1'-cyclo propyl-äthylamino)-pyrimidin............ . nD25 1.6143 2-Methylthio-4-äthylamino-5-nitro-6-(1'-cyclo- propyl-äthylamino Spyrimidin . ..... ..... 57-62 2-Methylthio-4-isopropylamino-5-nitro-6-(pent-2' ylamino)-pyrimidin. .... ............. . nD25 1.6008 2-Methylthio-4-äthylamino-5-nitro-6-(3'-methyl but-2'-ylamino)-pyrimidin.. ..... ...... . 68-69 2-Methylthio-4-methylamino-5-nitro-6-(pent-2'- ylamino)-pyrimidin . ... ........... Melting points in Degree Celsius 2-methylthio-4-ethylamino-5-nitro-6-cyclobutylamino-pyrimidine ..... ... .... ...... 105-106 2-methylthio-4-isopropylamino-5- nitro-6- (1 ', 2'-dimethylpropylaminotpyrimidine... viscous oil nD24.5 1.6000 2-methylthio-4-isopropylamino-5-nitro-6- (1'-cyclopropyl-ethylamino) -pyrimidine ... .......... nD25 1.6143 2-Methylthio-4-ethylamino-5-nitro-6- (1'-cyclo-propyl-ethylamino-spyrimidine. ..... ..... 57-62 2-Methylthio-4-isopropylamino-5-nitro-6- (pent-2 'ylamino) -pyrimidine. .... .............. ND25 1.6008 2-Methylthio-4- ethylamino-5-nitro-6- (3'-methyl-but-2'-ylamino) -pyrimidine .. ..... ....... 68-69 2-methylthio-4-methylamino-5-nitro -6- (pent-2'-ylamino) -pyrimidine. ... ........... .. nD25 1.6310 2-Methylthio-4-methylamino-5-nitro-6-(1'-cyclo propyl-äthylamino)-pyrimidin . .... . . . 91-93 2-Methylthio-4-isopropylamino-5-nitro-6-tert. .. nD25 1.6310 2-Methylthio-4-methylamino-5-nitro-6- (1'-cyclopropyl-ethylamino) -pyrimidine. .... . . 91-93 2-Methylthio-4-isopropylamino-5-nitro-6-tert. butylamino-pyrimidin.... ........ ...... . nD25.5 1.6032 2-Methylthio-4-äthylamino-5-nitro-6-(N'-methyl sec.butylaminotpyrimidin ... ... Öl 2-Methylthio-4-äthylamino-5-nitro-6-piperidino- pyrimidin......... ..... .......... ..... Öl 2-Methylthio-4-äthylamino-5-nitro-6-(1',1'-dimethyl 2'-hydroxy-äthylamino tpyrimidin 96-98" 2-Methylthio-4-äthylamino-5-nitro-6-1'-äthyl (2'-hydroxy-äthylamino)-pyrimidin .. ...... . 110-111 2-Methylthio-4-äthylamino-5-nitro-6-(3 '-methyl but-2'-ylamino)-pyrimidin.... ............. 75-77 2-Methylthio-4-dimethylamino-5-nitro-6-isobutyl amino-pyrimidin . .... ........ . ..... 178 2-Methylthio-4-äthylamino-5-nitro-6-cyclopentyl amino-pyrimidin . . . 80-81" 2-Methylthio-4-methylamino-5-nitro-6-(pent-3'-yl amino)-pyrimidin. . ... . butylamino-pyrimidine .... ........ ....... nD25.5 1.6032 2-methylthio-4-ethylamino-5-nitro-6- (N'-methyl sec.butylaminotpyrimidine ... ... oil 2-methylthio-4-ethylamino-5-nitro-6-piperidino-pyrimidine ......... ..... .......... ..... oil 2-methylthio-4-ethylamino-5-nitro-6- (1 ', 1' -dimethyl 2'-hydroxy-ethylamino pyrimidine 96-98 "2-methylthio-4-ethylamino-5-nitro-6-1'-ethyl (2'-hydroxy-ethylamino) -pyrimidine .. ....... 110-111 2-Methylthio-4-ethylamino-5-nitro-6- (3'-methyl-but-2'-ylamino) -pyrimidine .... ............. 75- 77 2-Methylthio-4-dimethylamino-5-nitro-6-isobutylamino-pyrimidine. .... ......... ..... 178 2-Methylthio-4-ethylamino-5-nitro -6-cyclopentylamino-pyrimidine... 80-81 "2-Methylthio-4-methylamino-5-nitro-6- (pent-3'-ylamino) pyrimidine.. .... . 47-54 2-Methylthio-4-methylamino-5-nitro-6-cyclopentyl amino-pyrimidin . . . . 99-102" 2-Methylthio-4-dimethylamino-5-nitro 6-cyclopentylamino-pyrimidin . .. nD4 1.6412 2-Methylthio-4-dimethylamino-5-nitro-6-(pent-3'-yl amino pyrimidin. . 45-47" 2-Methylthio-4-isopropylamino-5-nitro-6-(pent-3' yl-amino)-pyrimidin. nD24 1.6033 2-Methylthio-4-isopropylamino-5-nitro 6-cyclopentylamino-pyrimidin . . 72-74 2-Methylthio-4-äthylamino-5-nitro-6 (N'-methylpiperazinotpyrimidin . . 72-74" 2-Methylthio-4-äthylamino-5-nitro-6-pyrrolidino pyrimidin........ .. . .... . 59-61 2-Methylthio-4-äthylamino-5-nitro-6 morpholino-pyrimidin......... ..... .. .. 65-70 N,N-Dimethyl-N'-[2-methylthio-4-äthyl-amino-5 nitropyrimidin-63-piperazoniumjodid . . 47-54 2-Methylthio-4-methylamino-5-nitro-6-cyclopentylamino-pyrimidine. . . . 99-102 " 2-methylthio-4-dimethylamino-5-nitro 6-cyclopentylamino-pyrimidine. .. nD4 1.6412 2-methylthio-4-dimethylamino-5-nitro-6- (pent-3'-ylamino pyrimidine.. 45-47 " 2-methylthio-4-isopropylamino-5-nitro-6- (pent-3 'yl-amino) pyrimidine. nD24 1.6033 2-methylthio-4-isopropylamino-5-nitro 6-cyclopentylamino-pyrimidine. . 72-74 2-methylthio-4-ethylamino-5-nitro-6 (N'-methylpiperazinotpyrimidine.. 72-74 " 2-Methylthio-4-ethylamino-5-nitro-6-pyrrolidino pyrimidine ........ ... .... 59-61 2-methylthio-4-ethylamino-5-nitro-6 morpholino-pyrimidine ......... ..... .. .. 65-70 N, N-Dimethyl-N '- [2-methylthio-4-ethyl-amino-5-nitropyrimidine-63-piperazonium iodide. . . 210" (Zers.) Folgende bisher noch nicht beschriebene Zwischenprodukte der Formel V wurden auf dem in Beispiel 3a bis c beschriebenen Wege erhalten: Tabelle 2: Verbindungen: Physikalische Daten: 2-Methylthio-4-amino-5-nitro-6-chlor pyrimidin ... ..... .... ............ Fp: 175 2-Methylthio-4-methylamino-5-nitro-6-chlor pyrimidin ...... . . . .... Fp: 120-121 2-Methylthio-4-sec.butylamino-5-nitro-6-chlor pyrimidin ... .... .... ....... Fp: 77 2-Methylthio-4-n-propylamino-5-nitro-6-chlor- pyrimidin ...... .............. ... Fp: 82 2-Butylthio-4-äthylamino-5-nitro-6-chlor pyrimidin . ........ ............ . Kp: 145 /0,01 Torr 2-Methylthio-4-dimethylamino-5-nitro-6-chlor pyrimidin ...... ... ...... ... Fp: 104-106 2-Methylthio-4-äthylamino-5-nitro-6-chlor pyrimidin . . ... . .... ...... . . 210 "(dec.) The following intermediates of the formula V, which have not yet been described, were based on that described in Examples 3a to c Get ways: Table 2: Connections: Physical Data: 2-Methylthio-4-amino-5-nitro-6-chloro pyrimidine ... ..... .... ............ Mp: 175 2-Methylthio-4 -methylamino-5-nitro-6-chloro pyrimidine ....... . . .... mp: 120-121 2-methylthio-4-sec.butylamino-5-nitro-6-chloro pyrimidine ... .... .... ....... mp: 77 2- Methylthio-4-n-propylamino-5-nitro-6-chloropyrimidine ...... .............. ... Mp: 82 2-butylthio-4-ethylamino -5-nitro-6-chloro pyrimidine. ........ ............. Bp: 145 / 0.01 Torr 2-Methylthio-4-dimethylamino-5-nitro-6-chloropyrimidine ...... ... ...... ... Mp: 104-106 2-Methylthio-4-ethylamino-5- nitro-6-chloro pyrimidine. . ... .... ...... Fp: 95-97 2-Methylthio-4-isopropylamino-5-nitro-6-chlor pyrimidin .... .... ... ..... Fp: 84-86 2-Methylthio-4-di-n-propyl-amino-5-nitro-6 chlor-pyrimidin . Fp: 50-51" PATENTANSPRUCH 1 Verfahren zur Herstellung neuer Pyrimidin-Derivate der Formel 1 EMI4.1 in der R1 einen Alkyl-Rest mit 2 bis 6 Kohlenstoffatomen,' einen Alkenyl-Rest mit 3 bis 5 Kohlenstoffatomen, einen Alkoxyalkyl-, Alkylaminoalkyl-, Trialkylammonio-alkyl-Rest, einen Hydroxyalkyl- oder Cyanoalkylrest mit 1 bis 4 Kohlenstoffatomen, einen Cycloalkyl-Rest mit 3 bis 6 Kohlenstoffatomen, R2 und R3 unabhängig voneinander je Wasserstoff oder einen niederen Alkyl-Rest, R4 Wasserstoff, einen niederen Alkylrest, einen Cycloalkyl-Rest mit 3 bis 6 Kohlenstoffatomen und die Symbol-Paare R1 und R2 und/oder R3 und R4 ausserdem zusammen ein Polymethylenbrückenglied, Mp: 95-97 2-Methylthio-4-isopropylamino-5-nitro-6-chloropyrimidine .... .... ... ..... Mp: 84-86 2-Methylthio-4-di- n-propyl-amino-5-nitro-6-chloro-pyrimidine. Fp: 50-51 " PATENT CLAIM 1 Process for the preparation of new pyrimidine derivatives of formula 1 EMI4.1 in the R1 is an alkyl radical with 2 to 6 carbon atoms, an alkenyl radical with 3 to 5 carbon atoms, an alkoxyalkyl, alkylaminoalkyl, trialkylammonio-alkyl radical, a hydroxyalkyl or cyanoalkyl radical with 1 to 4 carbon atoms, a cycloalkyl radical with 3 to 6 carbon atoms, R2 and R3 independently of one another are each hydrogen or a lower alkyl radical, R4 is hydrogen, a lower alkyl radical, a cycloalkyl radical with 3 to 6 carbon atoms and the symbol pairs R1 and R2 and / or R3 and R4 also together form a polymethylene bridge member, in dem eine Methylengruppe durch Sauerstoff, die -NH-Gruppe oder die Gruppe N-R', ersetzt sein kann, in der R' für einen niederen Alkylrest steht, und R5 einen niederen Alkylrest bedeuten, dadurch gekennzeichnet, dass man in einer Verbindung der Formel IV EMI5.1 in which a methylene group is replaced by oxygen, the -NH group or the group N-R ', in which R' stands for a lower alkyl radical and R5 stands for a lower alkyl radical, characterized in that in a compound of the formula IV EMI5.1 die in Stellung und in 6-Stellung befindlichen Halogenatome in Gegenwart eines säurebindenden Mittels nacheinander gegen Reste von Aminen der Formeln II und III EMI5.2 austauscht, wobei die Substituenten R1 bis R5 die für Formel I gegebene Bedeutung haben und Hal ein Halogenatom darstellt. the halogen atoms in position and in 6-position in the presence of an acid-binding agent successively against residues of amines of formulas II and III EMI5.2 exchanges, where the substituents R1 to R5 have the meaning given for formula I and Hal represents a halogen atom. UNTERANSPRÜCHE 1. Verfahren gamäss Patentanspruch I, wobei der Austausch der Halogenatome in Gegenwart eines Lösungs- und/oder Verdünnungsmittels durchgeführt wird. SUBCLAIMS 1. The method according to claim I, wherein the halogen atoms are replaced in the presence of a solvent and / or diluent. 2. Verfahren gemäss Patentanspruch I, dadurch gekennzeichnet, dass man die Pyrimidinderivate der Formeln anschliessend noch in eines ihrer Salze überführt. 2. The method according to claim I, characterized in that the pyrimidine derivatives of the formulas are then converted into one of their salts. PATENTANSPRUCH II Die Verwendung der gemäss Patentanspruch I erhaltenen Nitro-Pyrimidine der Formel I und deren Salze zur Beeinflussung des Pflanzenwachstums. PATENT CLAIM II The use of the nitro-pyrimidines of the formula I and their salts obtained according to patent claim I for influencing plant growth.
CH1703673A 1971-05-17 1971-05-17 2-alkylthio-4,6-bis (subst amino)-5-nitropyrimidines - - herbicides CH560197A5 (en)

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US8293751B2 (en) 2003-01-14 2012-10-23 Arena Pharmaceuticals, Inc. 1,2,3-trisubstituted aryl and heteroaryl derivatives as modulators of metabolism and the prophylaxis and treatment of disorders related thereto such as diabetes and hyperglycemia
US8933083B2 (en) 2003-01-14 2015-01-13 Arena Pharmaceuticals, Inc. 1,2,3-trisubstituted aryl and heteroaryl derivatives as modulators of metabolism and the prophylaxis and treatment of disorders related thereto such as diabetes and hyperglycemia
US7470699B2 (en) 2003-07-11 2008-12-30 Arena Pharmaceuticals, Inc. Trisubstituted aryl and heteroaryl derivatives as modulators of metabolism and the prophylaxis and treatment of disorders related thereto
US7838525B2 (en) 2003-07-11 2010-11-23 Arena Pharmaceuticals, Inc. Trisubstituted aryl and heteroaryl derivatives as modulators of metabolism and the prophylaxis and treatment of disorders related thereto
US8546429B2 (en) 2003-07-11 2013-10-01 Arena Pharmaceuticals, Inc. 1,2,3-trisubstituted aryl and heteroaryl derivatives as modulators of metabolism and the prophylaxis and treatment of disorders related thereto
US7812159B2 (en) 2005-01-10 2010-10-12 Arena Pharamaceuticals, Inc. Processes for preparing aromatic ethers
US8362248B2 (en) 2005-01-10 2013-01-29 Arena Pharmaceuticals, Inc. Substituted pyridinyl and pyrimidinyl derivatives as modulators of metabolism and the treatment of disorders related thereto
WO2006136442A1 (en) * 2005-06-23 2006-12-28 Novartis Ag Pyrimidine derivatives for the treatment op gaba b mediated nervous system disorders
JP2008546731A (en) * 2005-06-23 2008-12-25 ノバルティス アクチエンゲゼルシャフト Pyrimidine derivatives for the treatment of GABAB-mediated nervous system disorders
US10894787B2 (en) 2010-09-22 2021-01-19 Arena Pharmaceuticals, Inc. Modulators of the GPR119 receptor and the treatment of disorders related thereto
US11007175B2 (en) 2015-01-06 2021-05-18 Arena Pharmaceuticals, Inc. Methods of treating conditions related to the S1P1 receptor
US11884626B2 (en) 2015-06-22 2024-01-30 Arena Pharmaceuticals, Inc. Crystalline L-arginine salt of (R)-2-(7-(4-cyclopentyl-3-(trifluoromethyl)benzyloxy)-1,2,3,4-tetrahydrocyclo-penta [b]indol-3-yl)acetic acid(Compound1) for use in S1P1 receptor-associated disorders

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