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

Definitions

• the invention relates to a new process for the preparation of l-amino-3-aryl-uranium, which are known as agrochemical active substances or as intermediates for the preparation of active substances.
• R 1 represents optionally substituted alkyl
• R 2 represents hydrogen, nitro, cyano, halogen or optionally substituted alkyl
• R 3 represents hydrogen, nitro, cyano or halogen
• R 4 represents hydrogen, nitro, cyano, carbamoyl, thiocarbamoyl, hydroxy, halogen or in each case optionally substituted alkyl, alkoxy or benzoyloxy, and
• R 5 For hydrogen, hydroxy, mercapto, amino, hydroxyamino, nitro, cyano,
• Q represents O, S, SO or SO 2 ,
• Q 1 and Q 2 are independently O or S, and
• R 6 for optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, aryl, arylalkyl, heterocyclyl or
• reaction auxiliary optionally in the presence of a reaction auxiliary and optionally in the presence of a reaction auxiliary
• the l-amino-3-aryl-uracils of the general formula (I) can be obtained in significantly better yields by the process according to the invention with a considerably shorter reaction time (compared with the known process using l-aminooxy-2,4-dinitro- benzene) can be obtained.
• R 1 preferably represents alkyl with 1 to 4 carbon atoms optionally substituted by halogen.
• R 2 preferably represents hydrogen, nitro, cyano, halogen or optionally alkyl substituted by halogen with 1 to 4 carbon atoms.
• R preferably represents hydrogen, nitro, cyano, fluorine, chlorine or bromine.
• R 4 preferably represents hydrogen, nitro, cyano, carbamoyl, thiocarbamoyl,
• Alkyl or alkoxy each having 1 to 4 carbon atoms, or substituted for halogen, C 1 -C 4 alkyl or C 1 -C 4 alkoxy, if appropriate
• R 5 preferably represents hydrogen, hydroxy, mercapto, amino, hydroxyamino, nitro, cyano, carboxy, carbamoyl, thiocarbamoyl, halogen, or one of the groups below
• Q represents O, S, SO or SO 2 .
• Q 1 and Q are independently O or S, and for alkyl optionally substituted by cyano, halogen, C1-C4-alkoxy, C ] -C4-alkylthio, -C-C-4-alkyl-carbonyl, -C-C4-alkoxy-carbonyl or C ⁇ - C4-alkylammocarbonyl with 1 is up to 6 carbon atoms,
• cycloalkyl or cycloalkylalkyl each of which is optionally substituted by cyano, carboxy, halogen, C 4 -C 4 alkylcarbonyl or C 4 -C 4 alkoxycarbonyl, each having 3 to 6 carbon atoms in the cycloalkyl group and optionally 1 to 4 carbon atoms in the alkyl part,
• R 1 particularly preferably represents methyl, ethyl, n- or i-propyl which is optionally substituted by fluorine and / or chlorine.
• R 2 particularly preferably represents hydrogen, nitro, cyano, fluorine, chlorine, bromine, or in each case optionally substituted by fluorine and / or chlorine
• R 3 particularly preferably represents hydrogen, fluorine or chlorine.
• R 4 particularly preferably represents hydrogen, nitro, cyano, carbamoyl, thiocarbamoyl, hydroxy, fluorine, chlorine, bromine, or methyl or methoxy which is optionally substituted by fluorine and / or chlorine.
• R 5 particularly preferably represents hydrogen, hydroxy, mercapto, amino, hydroxyamino, nitro, cyano, carboxy, carbamoyl, thiocarbamoyl, fluorine,
• Q represents O, S, SO or SO 2 ,
• Q 1 and Q 2 are independently O or S, and for each methyl, ethyl, n- or i-propyl, n-, i-, s - or t-butyl,
• R 1 very particularly preferably represents fluorine or chlorine.
• R 2 very particularly preferably represents hydrogen, chlorine or methyl.
• R 3 very particularly preferably represents fluorine or chlorine.
• R 4 very particularly preferably represents cyano, carbamoyl, thiocarbamoyl,
• R 5 very particularly preferably represents hydrogen, hydroxyl, amino, nitro, cyano, carboxy, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine, or one of the groups below
• Q stands for O, S, SO or SO.
• Q 1 and Q 2 are independently O or S, and
• R 6 represents in each case methyl, ethyl, n- or i-propyl which is optionally substituted by cyano, fluorine, chlorine, methoxy, ethoxy, methylthio, ethylthio, acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl, methylaminocarbonyl or ethylaminocarbonyl,
• R most preferably represents hydrogen.
• R J most preferably represents fluorine.
• R 4 most preferably represents cyano, bromine or trifluoromethyl. If, for example, 1- (2-chloro-4-cyano-5-ethoxy-phenyl) -3,6-dihydro-2,6-dioxo-4-difluoromethyl-1 (2H) -pyrimidine and 2-aminooxysulfonyl-1 are used, 3,5-trimethyl-benzene as starting materials, the course of the reaction in the process according to the invention can be outlined using the following formula:
• Formula (II) provides a general definition of the 3-aryl-uracils to be used as starting materials in the process according to the invention for the preparation of compounds of the general formula (I).
• R 1 , R 2 , R 3 , R and R " preferably have those meanings which are preferred, particularly preferred, particularly preferred, particularly preferred in connection with the description of the compounds of the general formula (I) according to the invention preferably or most preferably for R 1 , R ⁇ R " , R 4 and R 5 .
• the starting materials of the general formula (II) are known and / or can be prepared by processes known per se (cf. EP-A-408382, FP-A-47355 1, EP-A-648749, US-A-5169430, WO -A- 1/00278, WO-A-95/291 8, YVO-A-95/30661, WO-A-96/35679).
• the compound 2-aminooxysulfonyl-1,3,5-trimethyl-benzene (O-mesitylenesulfonylhydroxylamine) of the formula (III) to be used further as a starting material in the process according to the invention is also known and / or can be prepared by processes known per se ( see J. Org. Chem. 1973 (38), 1239-1241; Synthesis 1972, 140; loc. cit. 1975, 788-789).
• reaction aids are generally suitable as reaction aids. These include, for example
• Alkali metal or alkaline earth metal acetates, amides, carbonates, bicarbonates, hydrides, hydroxides or alkanolates such as sodium, potassium or calcium acetate, lithium, sodium, potassium or calcium amide , Sodium, potassium or calcium carbonate, sodium, potassium or calcium hydrogen carbonate, lithium, sodium, potassium or calcium hydride, lithium, sodium, potassium or
• basic organic nitrogen compounds such as trimethylamine, triethylamine, tripropylamine, tri-butylamine, ethyl-diisopropylamine, N, N-dimethyl-cyclohexylamine, dicyclohexylamine, ethyl-dicyclohexylamine, N, N-dimethyl-aniline, N, N-
• 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-diaza-b ⁇ cyclo [4,3, 0] -non-5-ene (DBN), or 1.8 diazabicyclo [5,4,0] -undec-7-ene (DBU).
• DABCO 1,4-diazabicyclo [2,2,2] octane
• DBU 1,5-diaza-b ⁇ cyclo [4,3, 0] -non-5-ene
• DBU diazabicyclo [5,4,0] -undec-7-ene
• Sodium and potassium carbonate and sodium and potassium bicarbonate may be mentioned as preferred reaction auxiliaries.
• the process according to the invention for the preparation of the compounds of the general formula (I) is preferably carried out using a diluent.
• the main diluents are inert organic solvents. These include in particular 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; Ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-pentyl ether,
• Dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether Dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether; Ketones such as acetone, butanone, methyl isobutyl ketone; Nitriles such as acetonitrile, propionitrile or butyronitrile; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-formanilide, N-methyl-pyrrolidone or hexamethylphosphoric triamide; Esters such as 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
• Solvents such as e.g. Dichloromethane, chloroform, diisopropyl ether, methyl t-butyl ether, methyl t-pentyl ether, dioxane, tetrahydrofuran, ethylene glycol dimethyl or diethyl ether, acetone, butanone, methyl isobutyl ketone, acetonitrile, propionitrile, butyronitrile, N, N-dimethylformamide N, N-dimethylacetamide, N-methyl-formanilide, N-methyl-pyrrolidone, hexamethylphosphoric triamide, methyl acetate,
• 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 + 80 ° C, preferably between -30 ° C and
• the process according to the invention is generally carried out under normal pressure. However, it is also possible to carry out the process according to the invention under elevated or reduced pressure - generally between 0.1 bar and 10 bar.
• elevated or reduced pressure generally between 1 and 3 mol, preferably between 1.5 and 2.5 mol, of 2-aminooxy-1,3,5-trimethyl- are generally used per mol of 3-aryl-uracil of the general formula (II).
• benzene O-mesitylene-sulfonyl-hydroxylamine
• the 3-aryl-uracil of the general formula (II) is initially introduced with a reaction auxiliary in a suitable diluent and the 2-aminooxy-1,3,5-trimethyl-benzene (O-mesitylenesulfonylhydroxylamine) of the formula ( III) is added slowly. The addition can also take place in several portions over several hours. The reaction mixture is stirred until the reaction has ended.
• the workup can be carried out according to customary methods.
• the reaction mixture is poured onto approximately the same volume of 10% aqueous ammonium chloride solution and then shaken with an organic solvent that is practically immiscible with water.
• the organic phase is then washed with water or with a saturated aqueous sodium chloride solution, dried and filtered.
• the solvent is carefully distilled off from the filtrate under reduced pressure.
• the crude product obtained as a residue can be further purified in the usual way.
• the l-amino-3-aryl-uracils to be prepared by the process according to the invention can be used as agrochemical active substances or as intermediates for the preparation of active substances (cf. WO-A-94/0451 1, WO-A-95/29168, WO- A-
• Example 1 The logP value given in Example 1 was determined in accordance with EEC Directive 79/831 Annex V.A8 by HPLC (High Performance Liquid Chromatography) on a phase reversal column (C 18). Temperature: 43 ° C. - 14 -
• the calibration was carried out with unbranched alkan-2-ones (with 3 to 16 carbon atoms) whose logP values are known (determination of the logP values using the
• the filtrate is concentrated in a water jet vacuum and the residue (1.4 g) is subjected to column chromatography (kiesig el, chloroform / acetic acid - ethyl ester, vol 2/1) purified After the eluents have been distilled off in a water jet vacuum, the residue (1.0 g) is digested with diethyl ether / diisopropyl ether and the crystalline product is isolated by suction
• the reaction mixture is stirred at room temperature for 18 hours. Then 0.2 g (0.9 mmol) of 2-aminooxysulfonyl-1,3,5-trimethyl-benzene are added and the mixture is stirred for a further 2 hours at room temperature. Then another 0.2 g (0.9 mmol) of 2-aminooxysulfonyl-1,3,5-trimethyl-benzene are added once more and the mixture is stirred for a further 2 hours at room temperature. The mixture is then poured onto approximately the same volume of 1N hydrochloric acid. It is then extracted three times with ethyl acetate; the combined organic phases are dried with sodium sulfate and filtered. The filtrate is concentrated in a water jet vacuum, the residue (1.3 g) is digested with diethyl ether and the crystalline product is isolated by suction.
• reaction mixture After adding a further 0.45 g of ethanesulfonic acid chloride, the reaction mixture is stirred for a further 18 hours at room temperature (approx. 20 ° C.). Then it is shaken with 1N aqueous hydrochloric acid / dichloromethane, the organic phase is washed with 1N hydrochloric acid, dried with sodium sulfate and filtered. The filtrate is concentrated in a water jet vacuum, the residue is digested with diisopropyl ether and the crystalline product is isolated by suction.
• Aminooxysulfonyl-1,3,5-trimethyl-benzene was added and the mixture was stirred for a further 30 minutes. The addition of 2-aminooxysulfonyl-l, 3,5-trimethylbenzene and the 30-minute stirring are repeated two more times. The mixture is then stirred for a further 15 hours at room temperature. Then it is poured onto approximately the same volume of 1N hydrochloric acid and extracted twice with ethyl acetate. The organic extraction solutions are combined, dried with sodium sulfate and filtered. The filtrate is concentrated under reduced pressure, the residue is digested with diethyl ether / petroleum ether and the crystalline product is isolated by suction.

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• 2000
  • 2000-02-07 DE DE10005284A patent/DE10005284A1/de not_active Withdrawn
• 2001
  • 2001-01-25 WO PCT/EP2001/000795 patent/WO2001058883A1/de not_active Application Discontinuation
  • 2001-01-25 JP JP2001558434A patent/JP2003522762A/ja active Pending
  • 2001-01-25 EP EP01902351A patent/EP1257540A1/de not_active Withdrawn
  • 2001-01-25 US US10/182,966 patent/US20030032807A1/en not_active Abandoned
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