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WO1997033875A1 - 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
WO1997033875A1
WO1997033875A1 PCT/EP1997/001062 EP9701062W WO9733875A1 WO 1997033875 A1 WO1997033875 A1 WO 1997033875A1 EP 9701062 W EP9701062 W EP 9701062W WO 9733875 A1 WO9733875 A1 WO 9733875A1
Authority
WO
WIPO (PCT)
Prior art keywords
alkyl
optionally substituted
diyl
chlorine
fluorine
Prior art date
Application number
PCT/EP1997/001062
Other languages
German (de)
English (en)
Inventor
Heinz-Jürgen Wroblowsky
Roland Andree
Mark Wilhelm Drewes
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 EP97908163A priority Critical patent/EP0888312A1/fr
Priority to BR9708315A priority patent/BR9708315A/pt
Priority to JP9532244A priority patent/JP2000506178A/ja
Priority to IL12607797A priority patent/IL126077A0/xx
Priority to AU20236/97A priority patent/AU2023697A/en
Publication of WO1997033875A1 publication Critical patent/WO1997033875A1/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
    • C07D239/545—Two oxygen atoms as doubly bound oxygen atoms or as unsubstituted hydroxy radicals with other 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
    • C07D239/557—Two oxygen atoms as doubly bound oxygen atoms or as unsubstituted hydroxy radicals with other 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 with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms, e.g. orotic acid
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links

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 increased pressure (cf. Justus Liebigs Ann. Chem. 431 (1923), 201-205).
  • the disadvantage of this synthesis method for implementation on an industrial scale is the increased pressure required.
  • 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. 82 (1960), 2656-2657). With this method, however, the need to use gaseous hydrogen chloride is unfavorable for the technical feasibility.
  • gaseous hydrogen chloride hydrogen chloride
  • substituted aromatic thiocarboxamides can be prepared by reacting corresponding substituted aromatic nitriles with hydrogen sulfide (hydrogen sulfide, H 2 S) or with thioacetamide (cf. WO 95/30661). For working up, 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. Here too, the problem of recovering the organic reaction components remains unsolved. It has now been found that substituted aromatic thiocarboxamides of the general formula (I)
  • R 1 represents hydrogen or halogen
  • R 2 represents the grouping below
  • a 1 represents a single bond, represents oxygen, sulfur, -SO-, -SO 2 -, -CO- or the grouping -NA 4 -, wherein A 4 represents hydrogen, hydroxy, alkyl, alkoxy, aryl, alkylsulfonyl or Arylsulfonyl, or (A 1 ) stands for optionally substituted alkanediyl, alkenediyl, alkindiyl, cycloalkanediyl, cycloalkenediyl or arendiyl,
  • a 4 represents hydrogen, hydroxy, alkyl, aryl, alkoxy, alkylsulfonyl or arylsulfonyl, or (A 2 ) represents in each case optionally substituted alkanediyl, alkenediyl, alkynediyl, Cycloalkanediyl, Cycloalkendiyl or Arendiyl stands, 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,
  • hydrogen sulfide hydrogen sulfide
  • H 2 S hydrogen sulfide
  • aromatic thioamides of the general formula (I) which have been substituted by the process according to the invention can be obtained in considerably higher yields than previously described and can be obtained in very good quality
  • pyridine as a solvent can be dispensed with and the work-up and isolation of the reaction products is possible in a very simple manner - in general by simple suctioning off.
  • 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 2 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 hydrogen, hydroxy, C, -C 4 alkyl, C r C 4 alkoxy, phenyl, C, -C 4 alkylsulfonyl or phenylsulfonyl, or (A 1 ) for C, -C 6 -alkanediyl, C 2 -C 6 substituted by fluorine or chlorine in each case Alkenediyl, C 2 -C 6 alkynediyl, C 3 -C 6 cycloalkanediyl, C 3 -C 6 cycloalkenediyl 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 -alkyl- sulfonyl, or phenylsulfonyl, or (A 2) for respectively optionally substituted by fluorine or chlorine-substituted C ⁇ C 8 alkanediyl, C 2 -C 6 - Alkenediyl, C 2 -C 6 . Alkindiyl, C 3 -C 6 -cycloalkanediyl, C 3 -C 6 -cycloalkenediyl or phenylene,
  • Alkynyloxycarbonyl each having 2 to 6 carbon atoms in the alkenyl, alkylidene or alkynyl groups, for cycloalkyl optionally substituted by halogen, cyano, carboxy, C, -C 4 -alkyl and / or C, -C 4 - alkoxy-carbonyl , Cycloalkyloxy, cycloalkylalkyl, cycloalkylalkoxy, cycloalkylidenamino, cycloalkyloxycarbonyl or cycloalkylalkoxycarbonyl each having 3 to 6 carbon atoms in the cycloalkyl groups and optionally 1 to 4 carbon atoms in the alkyl groups, or, if appropriate, by nitro, cyano, carboxy, Halogen, C r C 4 alkyl, C, -C 4 haloalkyl, C, -C 4 alkyloxy, C j -C 4 haloalky
  • R 3 stands for hydrogen, fluorine, chlorine or bromine or together with R 2 stands for an alkanediyl or alkenediyl grouping 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 1 -C 4 alkyl group, a carbonyl group and / or a thiocarbonyl group, and
  • R 1 represents hydrogen, fluorine or chlorine
  • R 2 represents the grouping below
  • a 4 represents hydrogen, hydroxy, methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methylsulfonyl or ethylsulfonyl, or (A 1 ) for methylene, ethane-l, l-diyl, ethane-l, 2-diyl, propane-l, l-diyl, propane-l, 2-diyl, propane-l, 3-diyl, ethene-l , 2-diyl, propene-1,2-diyl,
  • a 2 represents a single bond, represents oxygen, sulfur, -SO-, -SO 2 -, -CO- or the grouping -NA 4 -, wherein A 4 represents hydrogen, hydroxy, methyl, ethyl, n- or i Propyl, methoxy, ethoxy, n- or i-propoxy, methyl sulfonyl, ethylsulfonyl, n- or i-propylsulfonyl or phenylsulfonyl, or (A 2 ) represents methylene, ethane
  • R 3 stands for hydrogen, fluorine or chlorine or together with R 2 stands for an alkanediyl or alkenediyl grouping with 1 to 3 carbon atoms in each case, which optionally contains an oxygen atom, a sulfur atom at the beginning (or end) or within the hydrocarbon chain, a
  • 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 series -CO-, -CS-, -SO- and / or SO 2 -, and which is optionally substituted by one or more Groupings from the series nitro, hydroxy, amino, cyano, carboxy, carbamoyl, thiocarbamoyl,
  • Methyl, ethyl, n- or i-propyl are substituted), phenyl, phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl or phenylamino (each of which may be nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, methoxycarbonyl or ethoxycarbonyl) are substituted).
  • 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 as preferred or as particularly preferred in connection with the description of the compounds of the formula (I) for R 1 , R 2 , R 3 and Z have been specified.
  • 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;
  • Basic organic African nitrogen compounds into consideration. These include, in particular, dialkylamines, trialkylamines, dialkylcycloalkylamines, dicycloalkylamines and alkyldicycloalkylamines, such as, for example, diisopropylamine, diisobutylamine, disecbutylamine, dicyclopentylamine, dicyclohexylamine, trimethylamine, triethylamine, tripropylamine, naphthylamine, ethyldihylamine, tributylamine, ethyldihylamine, tributylamine, ethiutylamine, tributylamine, ethynylaminodiaminodiaminodiaminodiaminodiamin, cyclohexylamine, N, N-dialkyl-
  • Trialkylamines e.g. Trimethylamine, triethylamine, tripropylamine and tributylamine, and N, N-dialkylarylalkylamines, such as e.g. N, N-dimethylbenzylamine are particularly preferably used as basic organic nitrogen compounds in the process according to the invention.
  • a non-polar or moderately polar organic solvent 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 isobutyl ketone; Nitriles, such as acetonitrile, propionitrile or n- or
  • Toluene is particularly preferably used as the solvent in the process according to the invention.
  • 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 at temperatures between 20 ° C and 120 ° C, in particular at temperatures between 40 ° C and
  • the process according to the invention is generally carried out under normal pressure. However, it is also possible to work under increased or reduced pressure - generally between 0.1 bar and 10 bar.
  • the substituted aromatic nitrile is introduced together with a suitable basic organic compound in a suitable solvent and, after heating to the suitable reaction temperature, hydrogen sulfide is introduced. The mixture is then stirred until the reaction has ended.
  • 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).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Plural Heterocyclic Compounds (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 indiquée dans la description. Selon ce procédé, on fait réagir des nitriles aromatiques substitués de formule (II) avec de l'acide sulfhydrique en présence d'un composé organique basique et d'un solvant organique non polaire ou faiblement polaire.
PCT/EP1997/001062 1996-03-14 1997-03-03 Procede de fabrication d'amides aromatiques substitues de l'acide thiocarboxylique WO1997033875A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP97908163A EP0888312A1 (fr) 1996-03-14 1997-03-03 Procede de fabrication d'amides aromatiques substitues de l'acide thiocarboxylique
BR9708315A BR9708315A (pt) 1996-03-14 1997-03-03 Processo para preparação de tiocarboamidas aromática substituídas
JP9532244A JP2000506178A (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
IL12607797A IL126077A0 (en) 1996-03-14 1997-03-03 Process for preparing substituted aromatic thiocarboxamides
AU20236/97A AU2023697A (en) 1996-03-14 1997-03-03 Process for producing substituted aromatic thiocarboxylic acid amides

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19610785A DE19610785A1 (de) 1996-03-14 1996-03-14 Verfahren zur Herstellung von substituierten aromatischen Thiocarbonsäureamiden
DE19610785.7 1996-03-14

Publications (1)

Publication Number Publication Date
WO1997033875A1 true WO1997033875A1 (fr) 1997-09-18

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ID=7788756

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1997/001062 WO1997033875A1 (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) EP0888312A1 (fr)
JP (1) JP2000506178A (fr)
AU (1) AU2023697A (fr)
BR (1) BR9708315A (fr)
CZ (1) CZ292998A3 (fr)
DE (1) DE19610785A1 (fr)
HU (1) HUP9902110A2 (fr)
IL (1) IL126077A0 (fr)
WO (1) WO1997033875A1 (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

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 (1)

* Cited by examiner, † Cited by third party
Title
FAIRFULL ET AL.: "A convenient reagent for the preparation of thioamides, and the thiohydrolysis of S-alkylisothiourea derivatives", JOURNAL OF THE CHEMICAL SOCIETY, 1952, pages 742 - 744, XP000654983 *

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
JP2000506178A (ja) 2000-05-23
HUP9902110A2 (hu) 1999-11-29
CZ292998A3 (cs) 1999-01-13
DE19610785A1 (de) 1997-09-18
BR9708315A (pt) 1999-08-03
IL126077A0 (en) 1999-05-09
EP0888312A1 (fr) 1999-01-07
AU2023697A (en) 1997-10-01

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