Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
  • C07D495/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains three hetero rings
  • C07D495/14—Ortho-condensed systems

Definitions

• the present invention relates to a novel process for the preparation of dithiine-tetracarboxy-diimides.
• Dithiine-tetracarboxy-diimides as such are already known. It is also known that these dithiine tetracarboxiimides can be used as anthelminthics against internal parasites of animals, in particular nematodes, and have insecticidal activity (cf US Pat. No. 3,364,229). In addition, it is known that certain dithiine-tetracarboxy-diimides have antibacterial activity and have some activity against human mycoses (see II Farmaco 2005, 60, 944-947). It is also known that dithiine-tetracarboxy-diimides can be used as fungicides against phytopathogenic fungi in crop protection (compare WO 2010/043319).
• dithiine-tetracarboxy-diimides can be used as pigments in electrophotographic photoreceptors or as dyes in paints and polymers (compare JP-A 10-251265, PL-B 143804).
• R 1 and R 2 are the same or different and are hydrogen, for optionally mono- or polysubstituted by halogen, -OR 3 , -COR 4 -substituted Ci-Cg-alkyl, optionally mono- or polysubstituted by halogen, Ci-C / i-alkyl or Ci-C / i-haloalkyl substituted C3-C 7 -cycloalkyl, in each case optionally mono- or polysubstituted (by halogen, Ci-C / i-alkyl, Ci-C / i-haloalkyl, -COR 4 or sulfonylamino substituted aryl or aryl Ci-C 4 alkyl),
• R 3 is hydrogen, C 1 -C 1 -alkyl, C 1 -C 4 -alkylcarbonyl or aryl which is optionally monosubstituted or polysubstituted by halogen, C 1 -C 6 -alkyl or C 1 -C 6 -haloalkyl,
• R 4 is hydroxy, C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy
• succinic anhydride is reacted in a first stage with an amine of formula (II) optionally in the presence of a diluent.
• the succinic acid amides of the formula (III) thus obtained are then reacted with a large excess of thionyl chloride in the presence of dioxane as diluent at room temperature, the dithiine-tetracarboxiimides of the formula (I) finally being obtained in a series of reaction steps ,
• the dithiine-tetracarboxydiimides are optionally isolated directly from the reaction mixture or after addition of water by filtration.
• dithiine diisoimides of the formula (IV) it is possible under certain circumstances for the dithiine diisoimides of the formula (IV) to be isolated before they are converted into the dithiine-tetracarboximides of the formula (I):
• a disadvantage of this process is the long reaction time and the result that either the yields obtained usually do not exceed about 30-40% of theory or the purities of the isolated products are insufficient.
• in an aqueous workup of the reaction mixture is disadvantageous that thereby large amounts of thionyl chloride are destroyed; The resulting gases (SO 2 and HCl) must be disposed of.
• Another disadvantage is the fact that experience has shown that the product is not obtained in one portion. Rather, it is often the case that after a first product isolation by filtration from the filtrate after prolonged standing (for example, overnight), further product precipitates, which must be isolated again by filtration. Sometimes this process needs to be done again. This way of working is very cumbersome and time consuming.
• R is R 1 or R 2 ,
• the dichloromaleimides used as starting materials in carrying out the process according to the invention are generally defined by the formula (VI).
• R stands for the meanings of R or R.
• R 1 and R 2 are preferably identical or different and preferably represent hydrogen, represent optionally mono- or polysubstituted by fluorine, chlorine, bromine, -OR 3, -COR 4 substituted C ö alkyl optionally mono- or polysubstituted by chlorine, Methyl or trifluoromethyl-substituted C 3 -C 7 -cycloalkyl, each optionally mono- or polysubstituted by fluorine, chlorine, bromine, methyl, trifluoromethyl, -COR 4 , sulfonylamino-substituted phenyl or phenyl- (C 1 -C 4 -alkyl).
• R 1 and R 2 are particularly preferably identical or different and are particularly preferably hydrogen, optionally substituted once or more by fluorine, chlorine, hydroxyl, methoxy, ethoxy, methylcarbonyloxy, carboxyl-substituted Ci-C i-alkyl, optionally mono- or polysubstituted by Chlorine, methyl or trifluoromethyl-substituted C 3 -C 7 -cycloalkyl, in each case optionally monosubstituted to trisubstituted by fluorine, chlorine, bromine, methyl, trifluoromethyl, -COR 4 , sulfonylamino, phenyl, benzyl, 1-phenethyl, 2-phenethyl or 2- methyl-2-phenethyl.
• R 1 and R 2 are very particularly preferably identical or different and are very particularly preferably hydrogen, methyl, ethyl, n-propyl, isopropyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, in each case optionally by chlorine, methyl or trifluoromethyl substituted cyclopropyl or cyclohexyl.
• R 1 and R 2 are insJbesondere ⁇ beyorzugt simultaneously methyl.
• R 3 is preferably hydrogen, methyl, ethyl, methylcarbonyl, ethylcarbonyl or optionally mono- or polysubstituted by fluorine, chlorine, methyl, ethyl, n-propyl, isopropyl or trifluoromethyl-substituted phenyl.
• R 3 particularly preferably represents hydrogen, methyl, methylcarbonyl or phenyl.
• R is preferably hydroxy, methyl, ethyl, methoxy or ethoxy. is particularly preferably hydroxy or methoxy.
• N-methyldichloromaleimide (VI-1), R Me, as starting material, to give, as the end product, the compound (1-1) 2,6-dimethyl-1H, 5H- [1,4-dithiino [ 2,3-c: 5,6-c '] dipyrrolyl, 3,5,7 (2H, 6H) -tetrone.
• the process according to the invention requires no organic solvent which has to be disposed of or recovered after the end of the reaction, and achieves higher yields.
• the thiourea is used in amounts between 0.8 and 2 moles per mole of dichloromaleimide of the formula (VI). Preferably, amounts between 0.9 and 1.7 moles of thiourea, more preferably between 1.0 and 1.3 moles of thiourea per mole of dichloromaleimide of the formula (VI).
• the thiourea may be added to the reaction mixture in solid form or as a solution / suspension in water. Preference is given to the thiourea in water before.
• the reaction temperature of the process according to the invention can be varied within wide limits and is between 40 ° C and 150 ° C. To achieve satisfactory space-time yields, it is preferred to work at temperatures between 50 ° C and 120 ° C; more preferably between 60 ° C and 100 ° C.
• the Dichlormaleinklareimid of formula (VI) is preferably added at temperatures of 60 ° C to 90 ° C to the aqueous solution.
• phase transfer catalyst In the reaction in water, if necessary, a phase transfer catalyst (PTC) may be added.
• PTC phase transfer catalyst
• Such compounds may, for example, be phase transfer catalysts from the series of quaternary ammonium salts or quaternary phosphonium salts.
• This phase transfer catalyst preferably has the general formula (VII)
• A is N or P
• R 5 , R 6 , R 7 and R 8 are the same or different and are independently branched or unbranched ci
• X for halogen, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate or
• phase transfer catalysts of formula (VII) include: Benzyltributylammonium- bromide, benzyltributylammonium chloride, benzyltriethylammonium bromide, Benzyltriethylammoniumchlo- chloride, benzyltrimethylammonium chloride, cetyltrimethylammonium bromide, Didecyldimethylammoniumchlo- chloride, Dimethyldistearylammoniumbisulfat, Dimethyldistearylammonium methosulfate, Dodecyltrimethylam- ammonium bromide, dodecyltrimethylammonium chloride, Methyltributyl ammonium chloride, moniumhydrogensulfat Methyltributylam-, methyltricaprylyl
• phase transfer catalysts such as 4-dialkylamino-pyridinium salts or hexaalkyl-guanidiniumsalze can be used.
• the phase transfer catalyst can be used in the range from 0.1 to 20 mol% based on the dichloromaleic acid amide of the formula (VI).
• the reaction time of the inventive method is between 15 minutes and 24 hours. Preference is given to working between 30 minutes and 12 hours, more preferably between 1 and 6 hours.
• the work-up of the product is carried out by filtration.
• the comparative example is carried out according to Chemische Berichte 1967. 100, 1559-1570 (page 1566, method B).

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Indole Compounds (AREA)

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• 2011
  • 2011-05-02 RU RU2012152237/04A patent/RU2012152237A/ru not_active Application Discontinuation
  • 2011-05-02 CN CN201180033469XA patent/CN103270041A/zh active Pending
  • 2011-05-02 WO PCT/EP2011/056967 patent/WO2011138281A2/de active Application Filing
  • 2011-05-02 JP JP2013508457A patent/JP2013534904A/ja active Pending
  • 2011-05-02 BR BR112012028395A patent/BR112012028395A2/pt not_active Application Discontinuation
  • 2011-05-02 EP EP11716588A patent/EP2566871A2/de not_active Withdrawn
  • 2011-05-02 KR KR1020127031586A patent/KR20130065663A/ko not_active Application Discontinuation
  • 2011-05-02 MX MX2012012872A patent/MX2012012872A/es not_active Application Discontinuation
  • 2011-05-05 US US13/101,739 patent/US8609868B2/en not_active Expired - Fee Related

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