EP0888314A1 - Procede de fabrication d'amides aromatiques substitues de l'acide thiocarboxylique - Google Patents

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

Info

Publication number
EP0888314A1
EP0888314A1 EP97906156A EP97906156A EP0888314A1 EP 0888314 A1 EP0888314 A1 EP 0888314A1 EP 97906156 A EP97906156 A EP 97906156A EP 97906156 A EP97906156 A EP 97906156A EP 0888314 A1 EP0888314 A1 EP 0888314A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
diyl
chlorine
fluorine
optionally substituted
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Withdrawn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
EP97906156A
Other languages
German (de)
English (en)
Inventor
Heinz-Jürgen Wroblowsky
Rudolf Thomas
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 EP0888314A1 publication Critical patent/EP0888314A1/fr
Withdrawn legal-status Critical Current

Links

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.
EP97906156A 1996-03-14 1997-03-03 Procede de fabrication d'amides aromatiques substitues de l'acide thiocarboxylique Withdrawn EP0888314A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19610786A DE19610786A1 (de) 1996-03-14 1996-03-14 Verfahren zur Herstellung von substituierten aromatischen Thiocarbonsäureamiden
DE19610786 1996-03-14
PCT/EP1997/001061 WO1997033876A1 (fr) 1996-03-14 1997-03-03 Procede de fabrication d'amides aromatiques substitues de l'acide thiocarboxylique

Publications (1)

Publication Number Publication Date
EP0888314A1 true EP0888314A1 (fr) 1999-01-07

Family

ID=7788757

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97906156A Withdrawn EP0888314A1 (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)

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
WO2001022819A1 (fr) * 1999-09-30 2001-04-05 Bayer Aktiengesellschaft Herbicides selectifs a base de n-aryle-triazoline(thi)ones
IL141034A0 (en) 2000-02-04 2002-02-10 Sumitomo Chemical Co Uracil compounds and use thereof
SI1226127T1 (sl) * 2000-05-04 2009-10-31 Basf Se Substituirani fenilsulfamoil karboksamidi
CN100368392C (zh) * 2002-10-30 2008-02-13 巴斯福股份公司 双官能异(硫)氰酸苯酯、其制备方法和中间体

Family Cites Families (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 (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9733876A1 *

Also Published As

Publication number Publication date
DE19610786A1 (de) 1997-09-18
CZ293098A3 (cs) 1999-01-13
AU2094997A (en) 1997-10-01
IL126098A0 (en) 1999-05-09
BR9708186A (pt) 1999-07-27
WO1997033876A1 (fr) 1997-09-18
JP2000506177A (ja) 2000-05-23
HUP9902109A2 (hu) 1999-11-29

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