EP0946522A1 - Procede pour la preparation de derives de 1-phenyl-uracyle - Google Patents

Procede pour la preparation de derives de 1-phenyl-uracyle

Info

Publication number
EP0946522A1
EP0946522A1 EP97954360A EP97954360A EP0946522A1 EP 0946522 A1 EP0946522 A1 EP 0946522A1 EP 97954360 A EP97954360 A EP 97954360A EP 97954360 A EP97954360 A EP 97954360A EP 0946522 A1 EP0946522 A1 EP 0946522A1
Authority
EP
European Patent Office
Prior art keywords
chlorine
cyano
fluorine
substituted
formula
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.)
Withdrawn
Application number
EP97954360A
Other languages
German (de)
English (en)
Inventor
Heinz-Jürgen Wroblowsky
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.)
Bayer AG
Original Assignee
Bayer 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 Bayer AG filed Critical Bayer AG
Publication of EP0946522A1 publication Critical patent/EP0946522A1/fr
Withdrawn legal-status Critical Current

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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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C255/58—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the carbon skeleton
    • C07C255/60—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the carbon skeleton at least one of the singly-bound nitrogen atoms being acylated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
    • C07D265/04—1,3-Oxazines; Hydrogenated 1,3-oxazines
    • C07D265/06—1,3-Oxazines; Hydrogenated 1,3-oxazines not condensed with other rings

Definitions

  • the present invention relates to a new process for the preparation of known 1-phenyl-urac ⁇ l derivatives.
  • the invention also relates to new intermediates and a process for their preparation
  • phenyl uracils can be prepared by reacting corresponding aminoalkenoic esters with substituted pheny socyanates or with substituted phenyl urethanes in the presence of bases, such as, for example, sodium hydride (cf. EP-A 0 408 382, EP-A 0 648 749 and WO 95-
  • R 1 represents hydrogen, cyano, nitro or halogen
  • R 2 represents cyano, nitro, halogen or optionally substituted alkyl or alkoxy
  • R 3 for hydrogen, hydroxy, mercapto, amino, hydroxyamino, halogen, or for one of the radicals -R 7 , -QR 7 , -NH-R 7 , -NH-OR 7 , -NH-SO 2 -R 7 , - N (SO 2 - R 7) 2J -CQl-R 7 , -CQi-Q ⁇ R 7 , -CQi-NH-R 7 , -Q ⁇ CQ ⁇ R 7 , -NH-CQ ⁇ R 7 , - N ( SO 2 -R 7 ) (CQ 1 -R 7 ), or -Q 2 -CQ 1 -NH- R 7 ,
  • Q 1 and Q 2 independently of one another represent oxygen or sulfur
  • R 7 represents optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, aryl, arylalkyl, heterocyclyl or heterocyclylalkyl,
  • R 4 represents hydrogen, halogen or optionally substituted alkyl
  • R 5 represents alkyl substituted by fluorine and / or chlorine
  • R 6 represents hydrogen, hydroxy or in each case optionally substituted alkyl, alkoxy, alkenyl or alkynyl,
  • R 1 , R 2 , R 3 , R 4 and R 5 have the meanings given above,
  • 1-phenyl-uracil derivatives of the formula (I) can be prepared by the process according to the invention, because based on the prior art it was assumed that only those 1,3-oxazine-2 , 4 (3H) -diones, which contain a non-electron-withdrawing substituent adjacent to the oxygen atom, react with primary amines to form uracil. It is also unexpected that 1-phenyl-uracile can be prepared in a significantly higher yield by the process according to the invention than by the most similar previously known methods.
  • the method according to the invention is characterized by a number of advantages. So the required starting materials are easily accessible and also in larger quantities. Furthermore, the implementation of the reaction and the isolation of the desired substances pose no problems. It is particularly favorable that the 1-phenyluracil derivatives are obtained in very high yield and excellent purity. Otherwise, the method is widely applicable.
  • Formula (II) provides a general definition of the phenyloxazin-diones required as starting materials when carrying out the process according to the invention.
  • R 1 represents hydrogen, cyano, nitro, fluorine, chlorine or bromine
  • R 2 represents cyano, nitro, fluorine, chlorine, bromine or in each case optionally substituted by fluorine and / or chlorine alkyl or alkoxy having 1 to 4 carbon atoms,
  • R 3 for hydrogen, hydroxy, mercapto, amino, hydroxyamino, halogen, or for one of the radicals -R 7 , -QR 7 , -NH-R 7 , -NH-OR 7 , -NH-SO 2 -R 7 , - N (SO 2 -
  • R7 2) -CQl-R 7 , -CQi-Q ⁇ R 7 , -CQ! -NH-R 7 , -Q 2 -CQ 1 -R 7 , -NH-CQ i -R 7 , -
  • Q represents O, S, SO or SO 2 ,
  • Q 1 and Q 2 independently of one another represent oxygen or sulfur
  • R 7 for optionally substituted by cyano, halogen, C1-C4-alkoxy, C1-C4-alkylthio, -C-C4-alkyl-carbonyl, C ⁇ -C4-alkoxy-carbonyl or Ci - C4-alkylamino-carbonyl alkyl with 1 to 6 carbon atoms,
  • R 4 represents hydrogen, fluorine, chlorine, bromine or alkyl which has 1 to 6 carbon atoms and is optionally substituted by fluorine and / or chlorine and
  • R 5 represents fluorine and / or chlorine-substituted alkyl having 1 to 6 carbon atoms.
  • R 1 represents hydrogen, fluorine or chlorine
  • R 2 represents cyano, fluorine, chlorine, bromine, methyl or trifluoromethyl, for hydroxy, mercapto, amino, fluorine, chlorine, bromine or for one of the radicals -R 7 , -QR 7 , -NH-R 7 , -NH-OR 7 , -NH-SO 2 -R 7 , -N (SO 2 -R 7 ) 2 , -CQ ! -R 7 , -CQ! -Q 2 -R 7 , -CQ! -NH-R 7 , -Q -CQ!
  • Q represents O, S, SO or SO 2 ,
  • Q 1 and Q 2 independently of one another represent oxygen or sulfur
  • R 7 for each methyl, ethyl, n- or i-propyl, n-, i- , s- or t-butyl,
  • cyano carboxy, fluorine, chlorine, bromine, acetyl, propionyl, n- or i-butyroyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, methylaminocarbonyl, ethylaminocarbonyl, n- or i-propylaminocarbonyl penyl, butenyl, propynyl or butynyl, or for cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexyl- optionally substituted by cyano, carboxy, fluorine, chlorine, bromine, acetyl, propionyl, methoxycarbonyl or ethoxycarbonyl is methyl, or in each case optionally up to three
  • R 4 represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl or trifluoromethyl
  • R 5 represents trifluoromethyl, chlorodifluoromethyl, fluorodichloromethyl or pentafluoroethyl.
  • a 1 represents fluorine or chlorine
  • a 2 represents cyano
  • a 3 represents fluorine or chlorine
  • a 4 represents hydrogen, fluorine, chlorine or methyl
  • a 5 represents trifluoromethyl, chlorodifluoromethyl, fluorodichloromethyl or pentafluoroethyl.
  • the substituted phenyloxazin-diones of the formula (Ila) can be prepared by
  • a 1 , A 2 , A 3 , A 4 and A 5 have the meanings given above,
  • Z 1 and Z 2 are the same or different and represent halogen, alkoxy, aryloxy,
  • Imidazolyl or triazolyl if appropriate in the presence of an acid binder, such as sodium hydride, pyridine or 4-dimethylaminopyridine, and optionally in the presence of a diluent, such as toluene or tetrahydrofuran, at temperatures between -20 ° C and + 150 ° C (see the preparation examples)
  • an acid binder such as sodium hydride, pyridine or 4-dimethylaminopyridine
  • a diluent such as toluene or tetrahydrofuran
  • substituted phenyloxazin-diones of the formula (II) can be prepared in the same way by substituting substituted ⁇ -keto-carboxylic acid anilides of the formula
  • R 1 , R 2 , R 3 , R 4 and R 5 have the meanings given above,
  • Formula (V) provides a general definition of the carbonic acid derivatives required as reaction components in process (a).
  • Z 1 and Z 2 are the same or different and are preferably chlorine, methoxy, ethoxy, phenoxy, imidazol-1-yl or 1,2,4-triazol-l-yl.
  • the carbonic acid derivatives of the formula (V) are known.
  • R 1 , R 2 , R 3 , R 4 and R 5 preferably have those
  • a 1 represents fluorine or chlorine
  • a 2 represents cyano
  • a 6 represents fluorine, chlorine, methylsulfonylamino or ethylsulfonylamino
  • a 4 represents hydrogen, fluorine, chlorine or methyl
  • a 5 represents trifluoromethyl, chlorodifluoromethyl, fluorodichloromethyl or pentafluoroethyl.
  • a 4 and A 5 have the meanings given above and
  • R represents alkyl having 1 to 4 carbon atoms
  • a 1 , A 2 and A 6 have the meanings given above,
  • a diluent e.g. N, N-dimethylformamide or N-methyl-pyrrolidone, at temperatures between 50 ° C and 150 ° C, or if one
  • a 1 , A 2 , A 3 , A 4 and A 6 have the meanings given above,
  • an acid catalyst such as hydrochloric acid, sulfuric acid or methanesulfonic acid
  • an organic solvent such as methanol, ethanol, n- or i-propanol, n-, i-, s- or t-butanol, at temperatures between 0 ° C and 100 ° C (see the manufacturing examples)
  • R preferably represents methyl or ethyl
  • R 6 for hydrogen, hydroxyl, each optionally with hydroxyl, cyano,
  • Halogen substituted alkenyl or alkynyl each having 2 to 6 carbon atoms
  • R 6 for hydrogen, hydroxy, for each optionally by hydroxy, cyano,
  • amino compounds of the formula (III) can also be used in the form of their acid adducts, preference being given to addition salts with hydrochloric acid
  • amino compounds of the formula (III) and also their acid addition salts are known or can be prepared by known methods.
  • Suitable acid acceptors for carrying out the process according to the invention are all customary inorganic or organic bases.
  • Alkali metal or alkaline earth metal acetates, amides, carbonates, hydrogen bicarbonates, hydrides, hydroxides or alkanolates, such as sodium, potassium or calcium acetate, lithium, sodium or potassium, are preferably used - or calcium amide, sodium, potassium or calcium carbonate, sodium, potassium or calcium hydrogen carbonate, lithium, sodium, potassium or calcium hydride, lithium, sodium,
  • Potassium or calcium hydroxide sodium or potassium methoxide, ethanolate, n- or -i-propanolate, -n-, -i-, -s- or -t-butanolate; basic organic nitrogen compounds, such as trimethylamine, triethylamine, tripropylamine, tributylamine, ethyldiisopropylamine, N, N-dimethylcyclohexylamine, dicyclohexylamine, ethyldicyclohexylamine, N, N-dimethylaniline, N, N- Dimethylbenzylamine,
  • basic organic nitrogen compounds such as trimethylamine, triethylamine, tripropylamine, tributylamine, ethyldiisopropylamine, N, N-dimethylcyclohexylamine, dicyclohexylamine, ethyldicyclohexylamine, N, N-dimethylaniline
  • Pyridine 2-methyl, 3-methyl, 4-methyl, 2,4-dimethyl, 2,6-dimethyl, 3,4-dimethyl and 3,5-dimethyl-pyridine, 5- Ethyl-2-methyl-pyridine, 4-dimethylamino-pyridine, N-methyl-piperidine, 1,4-diazabicyclo [2,2,2] octane (DABCO), 1,5-diazabicyclo-
  • DBN non-5-ene
  • DBU diazabicyclo [5,4,0] -undec-7-ene
  • Suitable diluents for carrying out the process according to the invention are all customary inert, organic solvents and also water.
  • Aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons such as, for example, gasoline, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride, can preferably be used;
  • Ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether;
  • Ketones such as acetone, butanone or methyl isobutyl ketone; Nitriles such as acetonitrile, propionitrile or butyronitrile; Amides such as N, N-dimethylformamide, N, N-d
  • Methyl acetate or ethyl acetate sulfoxides such as dimethyl sulfoxide, alcohols such as methanol, ethanol, n- or i-propanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, their mixtures with water or pure water.
  • the reaction temperatures can be varied within a substantial range when carrying out the process according to the invention. In general, temperatures between -50 ° C. and + 100 ° C., preferably between -30 ° C. and + 80 ° C.
  • the procedure is generally carried out under atmospheric pressure.
  • elevated pressure or, if no volatile components are used, under reduced pressure
  • the substituted phenyloxazinedione of the formula (II) is placed in a suitable diluent and the amino compound of the formula (III) is slowly metered in.
  • the reaction mixture is then stirred - if appropriate at elevated temperature - until the end of the reaction.
  • the processing takes place according to usual methods (see the manufacturing examples)
  • Butanol is stirred for 20 hours at room temperature (approx. 20 ° C). Then the organic phase is separated off, washed twice with 150 ml of water each time, dried over sodium sulfate and filtered. The solvent is carefully distilled off from the filtrate in a water jet vacuum. The residue is mixed with 200 ml of cyclohexane - Stirs, and the crystalline product is isolated by suction

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un nouveau procédé pour la préparation de dérivés de 1-phényl-uracyle de la formule (I) dans laquelle R?1, R2, R3, R4, R5 et R6¿ ont les significations indiquées dans la description. Dans ce procédé, on fait réagir des phényloxazin-diones substituées de la formule (II) avec des composés amino de la formule (III) H¿2N-R?6 ou bien avec des produits d'addition d'acide des composés amino de la formule (III), éventuellement en présence d'un accepteur d'acide et éventuellement en présence d'un diluant.
EP97954360A 1996-12-17 1997-12-05 Procede pour la preparation de derives de 1-phenyl-uracyle Withdrawn EP0946522A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19652433 1996-12-17
DE19652433A DE19652433A1 (de) 1996-12-17 1996-12-17 Verfahren zur Herstellung von 1-Phenyl-uracil-Derivaten
PCT/EP1997/006821 WO1998027067A1 (fr) 1996-12-17 1997-12-05 Procede pour la preparation de derives de 1-phenyl-uracyle

Publications (1)

Publication Number Publication Date
EP0946522A1 true EP0946522A1 (fr) 1999-10-06

Family

ID=7814962

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97954360A Withdrawn EP0946522A1 (fr) 1996-12-17 1997-12-05 Procede pour la preparation de derives de 1-phenyl-uracyle

Country Status (7)

Country Link
EP (1) EP0946522A1 (fr)
JP (1) JP2001506247A (fr)
AU (1) AU5854598A (fr)
BR (1) BR9714407A (fr)
DE (1) DE19652433A1 (fr)
IL (1) IL130205A0 (fr)
WO (1) WO1998027067A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IL139899A (en) 1999-12-07 2005-06-19 Sumitomo Chemical Co Uracil compounds and use thereof
JP2001322986A (ja) * 1999-11-15 2001-11-20 Sumitomo Chem Co Ltd ３−フェニルウラシル化合物の製造方法
IL167957A (en) 2000-02-04 2009-07-20 Sumitomo Chemical Co Hydroxypyridine compounds
ITMI20022758A1 (it) 2002-12-23 2004-06-24 Isagro Ricerca Srl Nuovi uracili ad attivita' erbicida.
US20220411381A1 (en) 2019-10-01 2022-12-29 Bayer Aktiengesellschaft Pyrimidinedione derivatives

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2734895A (en) * 1994-05-27 1995-12-21 Ciba-Geigy Ag Process for the preparation of 3-aryluracils

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9827067A1 *

Also Published As

Publication number Publication date
DE19652433A1 (de) 1998-06-18
AU5854598A (en) 1998-07-15
JP2001506247A (ja) 2001-05-15
IL130205A0 (en) 2000-06-01
BR9714407A (pt) 2000-04-18
WO1998027067A1 (fr) 1998-06-25

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