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WO1997033876A1 - Procede de fabrication d'amides aromatiques substitues de l'acide thiocarboxylique - Google Patents

Procede de fabrication d'amides aromatiques substitues de l'acide thiocarboxylique Download PDF

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Publication number
WO1997033876A1
WO1997033876A1 PCT/EP1997/001061 EP9701061W WO9733876A1 WO 1997033876 A1 WO1997033876 A1 WO 1997033876A1 EP 9701061 W EP9701061 W EP 9701061W WO 9733876 A1 WO9733876 A1 WO 9733876A1
Authority
WO
WIPO (PCT)
Prior art keywords
alkyl
diyl
chlorine
fluorine
optionally substituted
Prior art date
Application number
PCT/EP1997/001061
Other languages
German (de)
English (en)
Inventor
Heinz-Jürgen Wroblowsky
Rudolf Thomas
Original Assignee
Bayer Aktiengesellschaft
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 Aktiengesellschaft filed Critical Bayer Aktiengesellschaft
Priority to JP9532243A priority Critical patent/JP2000506177A/ja
Priority to EP97906156A priority patent/EP0888314A1/fr
Priority to BR9708186A priority patent/BR9708186A/pt
Priority to AU20949/97A priority patent/AU2094997A/en
Priority to IL12609897A priority patent/IL126098A0/xx
Publication of WO1997033876A1 publication Critical patent/WO1997033876A1/fr

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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
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D249/12—Oxygen or sulfur atoms

Definitions

  • the invention relates to a new process for the preparation of substituted aromatic thiocarboxamides, which are known as herbicidally active compounds.
  • thiocarboxamides can be obtained by reacting nitriles with an alcoholic solution of an alkali metal hydrogen sulfide or ammonium hydrogen sulfide under elevated pressure (cf. Justus Liebigs
  • Hydrogen sulfide in pyridine in the presence of a strong base e.g. Triethylamine
  • the work-up is carried out by pouring the reaction mixture into water and suction.
  • a disadvantage of this method is the occurrence of an aqueous mother liquor containing pyridine and auxiliary base, from which the organic
  • Components can only be separated in a relatively complex process.
  • thiocarboxamides can also be obtained by reacting nitriles with thioacetamide in the presence of gaseous hydrogen chloride (hydrogen chloride) in dimethylformamide (cf. J. Am. Chem. Soc. £ 2
  • thiocarboxamides can be obtained by reacting nitriles with thioacetic acid (cf. Chem. Ber. 4 & (1915),
  • Hydrogen sulfide hydrogen sulfide, H 2 S
  • thioacetamide can be produced (cf. WO 95/30661).
  • the mixture is concentrated under reduced pressure and the product remaining in the residue is obtained in crystalline form by treatment with aqueous hydrochloric acid and / or with a suitable organic solvent.
  • the problem of recovering the organic reaction components remains unsolved.
  • R 1 represents hydrogen or halogen
  • R 2 represents the grouping below
  • a 4 stands for hydrogen, hydroxy, alkyl, alkoxy, aryl, alkylsulfonyl or arylsulfonyl, or (A 1 ) for optionally substituted alkanediyl.
  • a 2 represents a single bond, oxygen, sulfur, -SO-, -SO 2 -, -CO- or the grouping -NA 4 -, wherein A 4 represents hydrogen, hydroxy, alkyl, aryl, alkoxy, alkylsulfonyl or Arylsulfonyl, or (A 2 ) stands for optionally substituted alkanediyl, alkenediyl, alkynediyl, cycloalkanediyl, cycloalkenediyl or arendiyl, and
  • R 3 represents hydrogen, halogen or together with R 2 represents an alkanediyl or an alkenediyl group, which may be at the beginning (or
  • Z represents in each case optionally substituted monocyclic or bicyclic, saturated or unsaturated heterocyclyl, heterocyclylamino or heterocycliclimino,
  • R 1 , R 2 . R 3 and Z have the meanings given above,
  • aromatic thioamides of the general formula (I) which have been substituted by the process according to the invention can be described in considerably higher yields than hitherto and can be obtained in very good quality, it being possible to use inexpensive and technically manageable catalysts and diluents and the work-up and Isolation of the reaction products in a very simple manner - generally by simple suction - is possible.
  • the method according to the invention thus represents a valuable enrichment of the prior art.
  • the process according to the invention preferably relates to the preparation of compounds of the formula (I) in which
  • R 1 represents hydrogen, fluorine, chlorine or bromine
  • R represents the grouping below
  • a 1 stands for a single bond, for oxygen, sulfur, -SO-, -SO 2 -, -CO- or the grouping -NA 4 -, in which A 4 stands for water toff, hydroxy, C, -C 4 alkyl, C, -C 4 alkoxy, phenyl, C, -C 4 alkyl sulfonyl or phenyl sulfonyl, or (A 1 ) for each optionally substituted by fluorine or chlorine C, -C 6 -alkanediyl, C 2 -C 6 - alkenediyl, C 2 -C 6 alkynediyl, C 3 -C 6 -cycloalkanediyl, C 3 -C 6 -cycloalkyl is alkenediyl or phenylene,
  • a 2 represents a single bond, represents oxygen, sulfur, -SO-, -SO 2 -, -CO- or the grouping -NA 4 -, wherein A 4 represents hydrogen, hydroxy, C, -C 4 alkyl, C, -C 4 -alkoxy, phenyl, C r C 4 -alkylsulfonyl or phenylsulfonyl, or (A 2 ) for each optionally substituted by fluorine or chlorine substituted C r C 6 - alkanediyl, C 2 -C 6 - Alkenediyl, C 2 -C 6 , alkindiyl, C 3 -C 6 cycloalkanediyl, C 3 -C 6 cycloalkenediyl or phenylene,
  • Carbon atoms in the alkyl groups or if appropriate by nitro, cyano, carboxy, halogen, C, -C 4 alkyl, C r C 4 haloalkyl, C r C 4 alkyloxy, C, -C 4 haloalkyloxy and / or C j -C 4 alkoxy-carbonyl substituted phenyl, phenyloxy, phenyl-C ] -C 4 alkyl, phenyl-C r C 4 alkoxy, phenyloxycarbonyl or
  • R 3 represents hydrogen, fluorine, chlorine, bromine or together with R 2 represents an alkanediyl or alkenediyl group, each having up to 4 carbon atoms, which may optionally be at the beginning (or end) or within the
  • Hydrocarbon chain contains an oxygen atom, a sulfur atom, an NH group, an NC j -C 4 alkyl group, a carbonyl group and / or a thiocarbonyl group, and
  • Heterocyclyl, heterocyclylamino or heterocyclylimino each having 2 to 6 carbon atoms and 1 to 4 nitrogen atoms in the heterocyclic ring system, which optionally additionally contains an oxygen or sulfur atom and / or optionally up to three groups from the series -CO-, -CS-, -SO- and / or SO 2 -, and which is optionally substituted by one or more groups from the series nitro, hydroxy, amino, cyano, carboxy, carbamoyl, thiocarbamoyl, halogen, C r C 6 alkyl (which is optionally substituted by Halogen or C j -C 4 alkoxy is substituted), C 2 -C 6 alkenyl or C 2 -C 6 alkynyl (which are each optionally substituted by halogen), C, -C 6 alkoxy or C, -C 6 -
  • Alkoxy-carbonyl (which are each optionally substituted by halogen or C ] -C 4 alkoxy), C 2 -C 6 alkenyloxy or C 2 -C 6 alkynyloxy (which are each optionally substituted by halogen), C j -C 6 - alkylthio, C 2 -C 6 alkenylthio or C 2 -C 6 alkynylthio (which are each optionally substituted by halogen), C j -C 6 alkylamino or DHC j -
  • C 4 alkyl amino, C 3 -C 6 -cycloalkyl or C 3 -C 6 -cycloalkyl-C r C 4 -alkyl (which are in each case stituiert sub ⁇ optionally substituted by halogen and / or C j -C 4 alkyl ), Phenyl. Phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl or phenylamino (each of which may be nitro, cyano, halogen, C r C 4 alkyl, C r C 4 haloalkyl, C r C 4 alkyloxy, C r C 4 -
  • R 1 represents hydrogen, fluorine or chlorine
  • R 2 represents the grouping below
  • a 1 stands for a single bond, for oxygen, sulfur, -SO-, -SO 2 -, -CO- or the grouping -NA 4 -, wherein A 4 stands for hydrogen, hydroxy, methyl, ethyl, n- or i Propyl, methoxy, ethoxy, n- or i-propoxy, methylsulfonyl or ethylsulfonyl, or
  • a 4 represents hydrogen, hydroxy, methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl or phenylsulfonyl, or (A 2 ) is methylene, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,1-diyl, propane-1,2-diyl, Propane-
  • n-, i-, s- or t-butylamino dimethylamino, diethylamino, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, dimethoxyphosphoryl, diethoxyphosphoryl, dipropoxyphosphoryl or diisopropoxyphosphoryl, for propenyl, butenyl, propenyl, each optionally substituted by fluorine or chlorine
  • Fluorine, chlorine or together with R 2 represents an alkanediyl or alkenediyl grouping each having 1 to 3 carbon atoms, which optionally has an oxygen atom, a sulfur atom, an NH-- at the beginning (or end) or within the hydrocarbon chain.
  • Heterocyclyl, heterocyclylamino or heterocyclylimino each having 2 to 5 carbon atoms and 1 to 3 nitrogen atoms in the heterocyclic ring system, which optionally additionally contains an oxygen or sulfur atom and / or optionally up to two groups from the
  • Butynyloxy (which are optionally substituted by fluorine or chlorine); Methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, propenylthio, butenylthio, propynylthio or butynylthio (which are each optionally substituted by fluorine or chlorine); Methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino,
  • Formula (II) provides a general definition of the substituted aromatic nitriles to be used as starting materials in the process according to the invention for the preparation of the compounds of the general formula (I).
  • R 1 , R 2 , R 3 and Z preferably or in particular have those meanings which have already been mentioned above in connection with the description of the compounds of the formula (I) as preferred or as particularly preferred for R 1 , R 2 , R 3 and Z were given.
  • the starting materials of the formula (II) are known and / or can be prepared by known processes (cf. EP 370 332; EP 597 360; EP 609 734; EP 648 749).
  • the thioacetic acid to be used in the process according to the invention is a known synthetic chemical.
  • Non-polar or moderately polar organic solvents are particularly suitable as diluents. 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, methylcyclohexane, dichloromethane, chloroform, carbon tetrachloride; Ethers, such as diethyl ether, diisopropyl ether, diisobutyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether; Ketones such as acetone, butanone, methyl isopropyl ketone or methyl is
  • Toluene is particularly preferably used as the solvent in the process according to the invention.
  • the process according to the invention is optionally carried out in the presence of a catalyst.
  • Protonic acids are preferably used as catalysts. These include in particular mineral acids, such as. Hydrogen fluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide or sulfuric acid, but also organic acids, such as acetic acid, methanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid.
  • reaction temperatures can be varied within a substantial range when carrying out the process according to the invention. In general, temperatures between 0 ° C and 150 ° 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.
  • the substituted aromatic nitrile and the thioacetic acid - optionally together with a catalyst - are mixed in a suitable solvent, and the mixture is then - preferably at elevated
  • the substituted aromatic thiocarboxamides of the formula (I) to be prepared by the process according to the invention are already known as herbicidally active compounds (cf. WO 95/30661). Her $ teHunt.sbeispje

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

Abstract

L'invention concerne un nouveau procédé permettant de fabriquer des amides aromatiques substitués de l'acide thiocarboxylique, de formule (I), où R?1, R2, R3¿ et Z ont la signification mentionnée dans la description. Selon ce procédé, on fait réagir des nitriles aromatiques substitués de formule (II) avec de l'acide thioacétique éventuellement en présence d'un diluant et d'un catalyseur, à des températures comprises entre 0° et 150 °C.
PCT/EP1997/001061 1996-03-14 1997-03-03 Procede de fabrication d'amides aromatiques substitues de l'acide thiocarboxylique WO1997033876A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
JP9532243A JP2000506177A (ja) 1996-03-14 1997-03-03 置換芳香族チオカルボン酸アミドの製造方法
EP97906156A EP0888314A1 (fr) 1996-03-14 1997-03-03 Procede de fabrication d'amides aromatiques substitues de l'acide thiocarboxylique
BR9708186A BR9708186A (pt) 1996-03-14 1997-03-03 Processo para preparação de tiocarboxamidas aromáticas substituídas
AU20949/97A AU2094997A (en) 1996-03-14 1997-03-03 Process for producing substituted aromatic thiocarboxylic acid amides
IL12609897A IL126098A0 (en) 1996-03-14 1997-03-03 Process for preparing substituted aromatic thiocarboxamides

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19610786A DE19610786A1 (de) 1996-03-14 1996-03-14 Verfahren zur Herstellung von substituierten aromatischen Thiocarbonsäureamiden
DE19610786.5 1996-03-14

Publications (1)

Publication Number Publication Date
WO1997033876A1 true WO1997033876A1 (fr) 1997-09-18

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PCT/EP1997/001061 WO1997033876A1 (fr) 1996-03-14 1997-03-03 Procede de fabrication d'amides aromatiques substitues de l'acide thiocarboxylique

Country Status (9)

Country Link
EP (1) EP0888314A1 (fr)
JP (1) JP2000506177A (fr)
AU (1) AU2094997A (fr)
BR (1) BR9708186A (fr)
CZ (1) CZ293098A3 (fr)
DE (1) DE19610786A1 (fr)
HU (1) HUP9902109A2 (fr)
IL (1) IL126098A0 (fr)
WO (1) WO1997033876A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6451740B2 (en) 1999-12-07 2002-09-17 Sumitomo Chemical Company, Limited Uracil compounds and use thereof
US6537948B1 (en) 2000-02-04 2003-03-25 Sumitomo Chemical Company, Limited Uracil compounds and use thereof

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19962017A1 (de) * 1999-09-30 2001-04-05 Bayer Ag Selektive Herbizide auf Basis von N-Aryl-triazolin(thi)onen
JP2003510258A (ja) * 1999-09-30 2003-03-18 バイエル アクチェンゲゼルシャフト Ｎ−アリール−トリアゾリン（チ）オン類を基礎とした選択性除草剤
CA2383858C (fr) * 2000-05-04 2010-06-29 Basf Aktiengesellschaft Carboxamides de phenylsulfamoyle substitues
BRPI0315932B1 (pt) * 2002-10-30 2019-08-13 Basf Ag processo para a preparação de iso(tio)cianatos de fenila, compostos, e, processo para a preparação do composto sendo amida do ácido aminobenzoilsulfâmico

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995030661A1 (fr) * 1994-05-04 1995-11-16 Bayer Aktiengesellschaft Amides aromatiques substitues d'acides thiocarboxyliques et leur utilisation comme herbicides

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995030661A1 (fr) * 1994-05-04 1995-11-16 Bayer Aktiengesellschaft Amides aromatiques substitues d'acides thiocarboxyliques et leur utilisation comme herbicides

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 85, no. 9, 30 August 1976, Columbus, Ohio, US; abstract no. 62904m, page 548; XP002033448 *
GAUTHIER; LEBEL: "A remarkably simple conversion of nitriles to thioamides", PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS, vol. 95&96, no. 1-4, 1994, pages 325 - 326, XP000654912 *
MOERKVED ET AL.: "Reactions of 1,2,5-thiadiazole-3,4-dicarbonitrile", ACTA CHEMICA SCANDINAVICA, vol. 48, 1994, pages 372 - 376, XP000654421 *
SUVOROV ET AL.: "thioamides of indolylalkanoic acids", KHIM.-FARM.ZH., vol. 10, no. 4, 1976, pages 41 - 42 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6451740B2 (en) 1999-12-07 2002-09-17 Sumitomo Chemical Company, Limited Uracil compounds and use thereof
US6667413B2 (en) 1999-12-07 2003-12-23 Sumitomo Chemical Company, Limited Uracil compounds and use thereof
US6537948B1 (en) 2000-02-04 2003-03-25 Sumitomo Chemical Company, Limited Uracil compounds and use thereof

Also Published As

Publication number Publication date
BR9708186A (pt) 1999-07-27
HUP9902109A2 (hu) 1999-11-29
AU2094997A (en) 1997-10-01
IL126098A0 (en) 1999-05-09
DE19610786A1 (de) 1997-09-18
EP0888314A1 (fr) 1999-01-07
CZ293098A3 (cs) 1999-01-13
JP2000506177A (ja) 2000-05-23

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