Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
  • C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
  • C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
  • C07C303/22—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof from sulfonic acids, by reactions not involving the formation of sulfo or halosulfonyl groups; from sulfonic halides by reactions not involving the formation of halosulfonyl groups

Definitions

• the present invention relates to a process for the preparation of compounds of the general formula (I)
• n 1 to 18,
• R 1, R2 independently of one another are H, F, Cl, Br, (-CC 8 ) -alkyl, (C 1 -C 8 ) -alkoxy, (C 2 -C 8 ) -alkoxyalkyl, (C 3 -C 8 ) - cycloalkyl, (C 6 -C 18 ) aryl, (C 7 -C 19 ) aralkyl,
• R 1 and R2 can each represent different substituents
• R 3 means H, Cl, Br, I, R 1 ,
• n, R, R, R and shark can assume the meaning given above, and sulfite salts with subsequent halogenation.
• the invention also relates to the use of the compounds of the general formula (I).
• the compounds of general formula (I) are important substrates for the synthesis of bioactive substances, such as the fungicide Methasulfocarb ® (CAS No .:
• the object of the invention was therefore to provide a process which makes it possible to provide sulfonic acid halides with improved yields and bypassing the intermediate isolation and drying of the sulfonic acid salt stage.
• n 1 to 18,
• R 1, R2 independently of one another denote H, F, Cl, Br, (-C-Cg) -alkyl, (C ⁇ -C 8 ) -alkoxy, (C 2 -C 8 ) -alkoxyalkyl, (C 3 -C 8 )
• R 3 means H, Cl, Br, I, R 1 ,
• R and shark can assume the meaning given above, in water as a solvent.
• water-miscible organic solvents such as alcohols such as methanol or ethanol etc. or ethers such as THF or dioxane or ketones such as acetone can also be added to the water.
• Phase transfer catalysis as described in DE 2545644, also lends itself here.
• Halogenation reaction are in principle all indifferent fully or partially water-miscible organic solvents familiar to the person skilled in the art, which allow the water to be removed from the reaction mixture. Ternary mixtures with water as a component are also suitable for this. However, preference is given to using ethers in the subsequent halogenation. Particularly preferred ethers are diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether,
• T ⁇ ethylenglykoldiethylether or tetraethylene glycol diethyl ether T ⁇ ethylenglykoldiethylether or tetraethylene glycol diethyl ether.
• halogenating agents that can be used are described in Houben-Weyl (Methods of Organic Chemistry Eil, p. 1071ff or VIII p. 347ff). The following can preferably be used: thionyl chloride, phosphorus pentachloride, phosphorochloride, phosphorus oxychloride, oxalyl chloride. However, the use of phosgene as halogenating agent is particularly preferred.
• the sulfonic acid salt is preferably prepared in aqueous media.
• the temperature in the reaction can vary between 20 ° and 200 ° C., preferably 40 ° and 150 ° C.
• the reaction is preferably carried out in a closed vessel.
• the pressure which can be established in the reaction is generally between 1 to 100, preferably 3 to 15, bar.
• the subsequent halogenation can be carried out at a temperature of 0 ° to 150 ° C., preferably 50 ° to 100 ° C.
• a catalyst is preferably added to the halogenation with phosgene.
• Such catalysts are u. a. N-alkyl lactams, such as N-methylpyrrolidone, and also mentioned in DE 2743542 and the literature cited therein
• the invention also relates to the use of the compounds of the general formula (I) prepared by the process of claim 1 m syntheses for the production of bioactive active substances.
• reaction of sulfite salts with organic halides is particularly preferably carried out in water as the solvent.
• water e.g. Sodium sulfide water dissolved, if necessary with an alcohol or acetone
• phase mediator and e.g. a haloalkane, such as methylene chloride.
• phase mediators e.g. a haloalkane, such as methylene chloride.
• the use of phase mediators in the reaction is not absolutely necessary. The reaction proceeds without problems with a yield of 88 to 91%.
• the subsequent halogenation for example chlorination
• chlorination must be carried out under anhydrous conditions.
• the Tachmann stands for this a number of options are available. Among others it was possible to azeotropically dewater the concentrated aqueous product phase with a water-immiscible solvent.
• the salt formed in the preliminary stage precipitates and leads to caking and incrustation on the reactor and the Ruhrwerk, which prevents this variant from being used industrially.
• the disadvantage of extreme drying of a salt mixture has already been reported above.
• the aqueous product phase of sulfonate formation is therefore converted into an organic solvent by adding a partially or fully water-miscible organic solvent, with the aid of which water can be easily removed from the reaction mixture by distillation.
• diethylene glycol dimethyl ether was examined for its suitability.
• the sulfonate solution is greatly concentrated, diethylene glycol dimethyl ether is added and the water is separated off by distillation. With this method there is always only one liquid phase in which the solid (salt) is homogeneously distributed. There is therefore no tendency for solid to settle on the reactor wall.
• reaction mixture has been separated, which is technically much easier than concentrating a salt mixture to dryness, the halogenation can take place.
• phosgene is preferably used as the agent of choice.
• the reaction can e.g. B. by
• N, N-dialkylformamides preferably N, N-dimethylformamide
• the optimum amount of catalyst is 0.1-20 mol%, preferably 0.2-5 mol%. In this special case the reaction starts at a temperature of 40 ° C, but higher temperatures are cheaper.
• the phosgene preferably reacts within a short time at 80 ° C., so that only small phosgene concentrations in the reaction mass are achieved with continuous metering.
• Chloromethanesulfonic acid chloride production the product is worked up by distillation, the product being distilled off at 72 ° C./20 mbar and the high-boiling ether remaining as a solvent in the sump.
• the product obtained in this way has an excellent purity of> 98% after removal of the solvent.
• the product can be distilled off from the reaction mixture after the halogenation step, as described above, and then the salts can be filtered.
• the solvent used in the present form can be used again in the subsequent reaction, or it is preferably purified beforehand by distillation.
• a (-CC 8 ) -alkyl radical is understood to mean a radical with 1 to 8 saturated C atoms, which can have any branching.
• the groups methyl, ethyl, n-propyl, isopropyl, N-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl etc. can be subsumed under this group.
• a (-CC 8 ) alkoxy radical is understood to mean a radical having 1 to 8 saturated C atoms, which can have any branching and is bonded to the intended molecule via an oxygen atom.
• a (C 2 -C 6) -alkoxyalkyl radical is understood to mean a radical with 2 to 8 saturated C atoms, which can have any branching and in which a CH 2 group in the radical is replaced by an oxygen atom.
• the shape of the alkyl parts in this residue can take the same form as the alkyl residues specified above.
• a (C 3 -Cs) cycloalkyl radical denotes a radical from the group of cyclic alkyl radicals having 3 to 8 C atoms and optionally any branch.
• the radicals cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl are to be subsumed under this group. One or more double bonds may be present in this remainder.
• a (C 6 -C 8 ) aryl radical is understood to mean an aromatic radical having 6 to 18 carbon atoms. In particular, these include compounds such as phenyl, naphthyl, anthryl, phenanthryl, biphenyl radicals.
• a (C7-C1 9 ) aralkyl radical is a (C 6 -C 18 ) aryl radical bonded to the molecule via a (Ci-Cs) alkyl radical.
• a (C 3 -C18) heteroaryl radical denotes a five-, six- or seven-membered aromatic ring system composed of 3 to 18 carbon atoms, which has heteroatoms such as nitrogen, oxygen or sulfur in the ring.
• heteroaromatics are in particular radicals, such as 1-, 2-, 3-furyl, such as 1-, 2-, 3-pyrrolyl, 1-, 2-, 3-thienyl, 2-, 3-, 4-pyridyl, 2-, 3-, 4-, 5-, 6-, 7-indolyl, 3-, 4-, 5-pyrazole, 2-, 4-, 5-imidazole, acridinyl, quinolinyl, phenanthridinyl, 2-, 4- , 5-, 6-pyrimidinyl.
• radicals such as 1-, 2-, 3-furyl, such as 1-, 2-, 3-pyrrolyl, 1-, 2-, 3-thienyl, 2-, 3-, 4-pyridyl, 2-, 3-, 4-, 5-, 6-, 7-indolyl, 3-, 4-, 5-pyrazole, 2-, 4-, 5-imidazole, acridinyl, quinolinyl, phenanthridinyl, 2-, 4- , 5-, 6-pyrimidinyl.
• a (C 4 -C 19 ) heteroaralkyl is understood to mean a heteroaromatic system corresponding to the (C 7 -C 19 ) aralkyl radical.
• phosgene 128.5 g (1.3 mol) phosgene
• the aqueous solution from 1) is first concentrated to a concentration of 70-80%, a bottom temperature of 120 to 124 ° C. being established. After cooling to about 100 ° C, the glycol ether is added. The water in the suspension is removed by distillation.
• N, N-dimethylformamide is added as a catalyst and phosgene is introduced into the suspension in liquid form within one hour.
• phosgene is introduced into the suspension in liquid form within one hour.
• the suspension is cooled and the sodium chloride is filtered off.
• the product solution is distilled under vacuum.

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• Chemical Kinetics & Catalysis (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Plural Heterocyclic Compounds (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

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• 1998
  • 1998-08-25 DE DE19838516A patent/DE19838516A1/de not_active Withdrawn
• 1999
  • 1999-07-08 JP JP2000566240A patent/JP2002523394A/ja active Pending
  • 1999-07-08 WO PCT/EP1999/004809 patent/WO2000010966A1/de not_active Application Discontinuation
  • 1999-07-08 EP EP99939995A patent/EP1107950A1/de not_active Withdrawn
  • 1999-07-08 IL IL14058299A patent/IL140582A0/xx unknown
  • 1999-07-08 AU AU54102/99A patent/AU5410299A/en not_active Abandoned
  • 1999-08-23 AR ARP990104217A patent/AR020248A1/es not_active Application Discontinuation
  • 1999-08-25 US US09/382,781 patent/US6291710B1/en not_active Expired - Fee Related

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