Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C315/00—Preparation of sulfones; Preparation of sulfoxides
  • C07C315/04—Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/50—Improvements relating to the production of bulk chemicals
  • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

• the present invention relates to the production of sulphonyl benzoic acids by oxidation of sulphonyl alkyl benzene derivatives.
• Sulphonyl benzoic acids are useful as intermediates in the preparation of agrochemicals in particular herbicides as described for example in US 4,695,673 and US 4,780,127.
• R is C00H, and R and R are independently selected from hydrogen, halo, haloalkyl, nitro, hydroxy, alkoxy, haloalkoxy or alkoxyalkoxy; which process comprises oxidising a compound of formula (II), where R , R and R are as defined in relation to formula (I) and R is
• alkyl refers to straight or branched chains having for example up to 20 carbon atoms.
• haloalkyl refers to an alkyl group substituted by at least one halogen such as fluorine and chlorine.
• haloalkoxy refers to an alkoxy group substituted by at least one halogen such as fluorine and chlorine.
• halo refers to fluoro, chloro, bromo and iodo.
• Suitable optional substituents for the alkyl and phenyl groups R include halogen such as fluorine and chlorine.
• R is a C, g alkyl group such as methyl or ethyl; trifluoromethyl or phenyl. Most preferably R is methyl.
• R 3 and R4 are selected from hydrogen, chloro, nitro, hydroxy, trifluoromethyl or C, alkoxy.
• R 3 is H.
• the group R4 is preferably ortho to the group R 2.
• a preferred group R4 is chloro.
• the 5 group R is preferably H or C, * alkyl, most preferably H.
• the oxidation may be suitably performed at moderate temperatures of from 0 to 50°C, usually at less than 25°C.
• the reaction may be continued for extended periods of from 1 to 72 hours until a reasonable yield of desired product is achieved. This will generally be dependent upon the nature of the reactants and catalysts employed.
• the reaction is carried out at a pH in the range 7-11, preferably 8-10, even more preferably at a constantly maintained pH of 9 - 9.5 and most preferably at a constant pH of 9.
• Suitable organic solvents include halogenated alkanes and arenes such as dichloro ethane, chloroform, ethylene dichloride, chlorobenzene, dichlorobenzene; alkanes and cyloalkanes such as hexane and cyclohexane or esters such as ethyl acetate and isopropyl acetate.
• phase transfer catalyst The selection of a suitable phase transfer catalyst can be determined by routine procedures well known to the skilled chemist.
• Known phase transfer catalysts include tetralkyl ammonium halides and phosphonium salts.
• Preferred catalysts are tetralkyl ammonium halides, especially tetrabutyl ammonium chloride.
• the phase transfer catalyst is generally used at 1-10 mol%.
• the oxidation catalyst comprising a ruthenium or palladium compound may be for example ruthenium chloride, RuCl 2 (PPh-j) 3l ruthenium dioxide supported on an inert carrier such as silica or titania or palladium on carbon.
• a preferred oxidation catalyst is ruthenium chloride.
• the amount of ruthenium or palladium catalyst should be sufficient to catalyse the reaction in a reasonable ti escale. This will depend upon many factors including the catalyst selected, the nature of the compounds of formula (II) and other reaction conditions. In general 0.01 mol% to 5 mol% of ruthenium or palladium catalyst is suitable.
• the reaction may be performed as a batch process or as a continuous process.
• Unreacted starting materials may be re-cycled, optionally with the addition of further oxidation catalyst and phase transfer catalyst. Further starting material may be added to the recycled liquors.
• Sodium hypochlorite (119.12g, 1.6 moles) was pumped into the reaction flask over a 1 hour period (pH adjusted automatically to pH 9 using 20% sulphuric acid 2 minutes into addition) then maintained at pH 9 automatically using 10% sodium hydroxide for a further hour.
• the reaction was agitated at 570 r.p.m. and the temperature controlled at ⁇ 25°C throughout.
• the reaction mass was diluted with water to dissolve any precipitated sodium salt of the product, the phases separated and the aqueous phase filtered through a bed of clarcel flo filter aid to remove the ruthenium catalyst.
• the aqueous phase was acidified with 20% sulphuric acid and the precipitated product filtered off, washed with water and dried to yield 2-chloro-4-methylsulphonylbenzoic acid, (15.27g, yield 51.5%), .p. 189°C.
• More sodium hypochlorite (184g) was then charged slowly to the reactor the pH being maintained at 9 to 9.5 by the addition of sodium hydroxide as required, the temperature was allowed to rise to 25 to 28°C during this time, controlled if necessary with water on the reactor jacket.
• the reaction mass was left stirring for 6 hours at room temperature, the reactor was tested with starch iodide to ensure some hypochlorite was present and if necessary a drop or two of hypochlorite was added. The agitation was stopped and the lower aqueous phase was separated off.
• the lower aqueous phase was then agitated and heated to 50°C then acidified to pH 2 with hydrochloric acid to precipitate the 2-chloro-4-methylsulphonylbenzoic acid product.
• the reaction mixture was cooled to room temperature and the product was filtered off and washed with water.
• the organic phase was re-cycled and an additional ethyl acetate and ruthenium trichloride charge (10% of the amounts used in the first reaction) introduced into the reaction vessel.
• Example 2 The procedure of Example 2 was repeated using dichloroethane as solvent in place of ethyl acetate. The yield of 2-chloro-4-methylsulphonylbenzoic acid was 88.6%.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Catalysts (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
• Physical Or Chemical Processes And Apparatus (AREA)

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• 1993
  • 1993-05-24 GB GB939310699A patent/GB9310699D0/en active Pending
• 1994
  • 1994-04-28 GB GB9408387A patent/GB9408387D0/en active Pending
  • 1994-04-29 WO PCT/GB1994/000934 patent/WO1994027959A1/en not_active Ceased
  • 1994-04-29 ES ES94913748T patent/ES2110745T3/es not_active Expired - Lifetime
  • 1994-04-29 EP EP94913748A patent/EP0700379B1/en not_active Expired - Lifetime
  • 1994-04-29 CA CA002161219A patent/CA2161219C/en not_active Expired - Fee Related
  • 1994-04-29 KR KR1019950704968A patent/KR100344013B1/ko not_active Expired - Fee Related
  • 1994-04-29 AU AU65782/94A patent/AU6578294A/en not_active Abandoned
  • 1994-04-29 AT AT94913748T patent/ATE161827T1/de active
  • 1994-04-29 HU HU9503229A patent/HU218710B/hu not_active IP Right Cessation
  • 1994-04-29 CN CN94192182A patent/CN1037265C/zh not_active Expired - Fee Related
  • 1994-04-29 JP JP52583494A patent/JP3556222B2/ja not_active Expired - Fee Related
  • 1994-04-29 DE DE69407783T patent/DE69407783T2/de not_active Expired - Lifetime
  • 1994-05-04 IL IL10956094A patent/IL109560A/en not_active IP Right Cessation
  • 1994-05-10 TW TW083104213A patent/TW275061B/zh not_active IP Right Cessation
• 1996
  • 1996-11-18 US US08/751,272 patent/US5783729A/en not_active Expired - Lifetime

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