Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
  • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides

Definitions

• 5-chloro-2-nitro-anilines can be used with thiophenols e.g. implement in such a way that you first with a
• Oil emulsion of sodium hydride in dimethylformamide from the thiophene pole forms the corresponding sodium thiophenolate and converts this to the product by adding a 5-chloro-2-nitroaniline, which is then precipitated with water (see DE-A 2 406 584).
• Potassium carbonate is also used in accordance with EP-A 61 1 10.
• 2-methyl-6-nitro-3-phenylthio-aniline was produced in dimethyl sulfoxide at 110 ° C. with a yield of 92%.
• a disadvantage of all these processes is that the product mixtures which contain dipolar reaction mixtures containing aprotic solvents have to be worked up in aqueous form. This creates a wastewater heavily contaminated with organic solvents, that has to be disposed of. In addition, the yield and / or the purity of the product obtained is often unsatisfactory.
• R 1 is hydrogen, C r C 8 alkyl, C 3 -C 8 cycloalkyl, C r C 8 alkoxy or halogen and
• R 2 is hydrogen, C, -C 8 alkyl, C 3 -C 8 cycloalkyl, C r C 8 -alkoxy, halogen or optionally substituted with C ⁇ -C 8 -alkyl, C 8 -alkoxy or halogen-substituted C 6 -C ⁇ 0 aryl stand,
• R 1 has the meaning given for formula (I),
• R 2 has the meaning given for formula (I),
• R 1 preferably represents hydrogen, C r C 4 alkyl or chlorine, particularly preferably hydrogen, methyl or chlorine.
• 5-Chloro-2-nitroanilines of the formula (II) and thiophenols of the formula (III) which can be used in the process according to the invention can, if they are not commercially available, be obtained in a known manner or analogously thereto.
• the respective 5-chloro-2-nitroaniline is prepared by chlorine-amine exchange from the corresponding 2,4-dichloronitrobenzene with ammonia (see, for example, J. Med. Chem. 35, 4455 (1992) and DE-A 3 431 827)) and then carries out the process according to the invention without intermediate isolation of the 5-chloro-2-nitroaniline formed by adding the thiophenol and optionally metering in ammonia in the same reaction vessel.
• the order in which the reactants are put together is not critical in the process according to the invention.
• the 5-chloro-2-nitroaniline of the formula (II) is preferably dissolved in a solvent with ammonia and then a thiophenol of the formula (III) is added.
• the reactants can also be combined in any other order. They can also be metered into the reaction mixture simultaneously.
• R 2 preferably represents hydrogen or C1-C 4 -alkyl, particularly preferably hydrogen.
• solvents for the process according to the invention for example inorganic solvents such as water or anhydrous ammonia and organic solvents such as alcohols, ethers, hydrocarbons, aromatics, chloroaromatics and dipolar aprotic solvents.
• inorganic solvents such as water or anhydrous ammonia
• organic solvents such as alcohols, ethers, hydrocarbons, aromatics, chloroaromatics and dipolar aprotic solvents.
• organic solvents are: methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, tert-butanol, glycol, diethyl ether, methyl tert-butyl ether, tetrahydrofuran, Dimethylformamide, N-methylpyrrolidone, toluene and chlorobenzene.
• Nonpolar and slightly polar solvents such as alcohols, ethers, hydrocarbons, aromatics and chloroaromatics are preferred, in particular methanol, isopropanol, isobutanol, toluene and chlorobenzene.
• phase transfer catalysts is not necessary.
• the ammonia can be used in technical qualities.
• the method according to the invention can e.g. at temperatures in the range of 20 to 140 ° C. It is preferred to work at 40 to 100 ° C.
• Implementation of the method according to the invention can e.g. There are pressures in the range from 1 to 20 bar.
• the process is preferably carried out at 3 to 12 bar, in particular under the pressure which sets itself in a closed reaction vessel under the reaction conditions used. It is advantageous, especially towards the end of the reaction, to keep the temperature below 80 ° C. and the pressure below 10 bar.
• the method according to the invention can e.g. carry out in such a way that the 5-chloro-2-nitroaniline of the formula (II) is initially introduced together with the solvent in an autoclave, then heated to the desired reaction temperature, then added ammonia and then the thiophenol of the formula (III) is metered in , e.g. in the course of 0.5 to 5 hours. It is advantageous to replenish ammonia during the addition of the thiophenol, e.g. so that the pressure that prevailed before the thiophenol was metered in is maintained within a range of deviation of + 20%. After the end of the thiophenol dosing, you can still for some time, e.g. 1 to 20 hours under the above Stir the pressure and temperature conditions, especially at temperatures below 80 ° C.

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

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• 1998
  • 1998-07-01 DE DE19829357A patent/DE19829357A1/de not_active Withdrawn
• 1999
  • 1999-06-21 DE DE59909246T patent/DE59909246D1/de not_active Expired - Fee Related
  • 1999-06-21 US US09/720,011 patent/US6552230B1/en not_active Expired - Fee Related
  • 1999-06-21 HU HU0102237A patent/HUP0102237A3/hu unknown
  • 1999-06-21 CN CNB998082104A patent/CN1178908C/zh not_active Expired - Fee Related
  • 1999-06-21 AT AT99929294T patent/ATE264838T1/de not_active IP Right Cessation
  • 1999-06-21 JP JP2000558074A patent/JP2002519409A/ja not_active Withdrawn
  • 1999-06-21 AU AU46143/99A patent/AU4614399A/en not_active Abandoned
  • 1999-06-21 WO PCT/EP1999/004296 patent/WO2000001669A2/de not_active Ceased
  • 1999-06-21 EP EP99929294A patent/EP1091935B1/de not_active Expired - Lifetime
  • 1999-06-21 IL IL13994799A patent/IL139947A0/xx unknown
  • 1999-06-21 BR BR9911763-0A patent/BR9911763A/pt not_active IP Right Cessation

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