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
  • C07C319/18—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by addition of thiols to unsaturated compounds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
  • C07C319/26—Separation; Purification; Stabilisation; Use of additives
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
  • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
  • C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
  • C07C323/52—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated

Definitions

• the present invention concerns a process for the preparation of 3-((3,3,3-trifluoro- propyl)thio)propionic acid and esters thereof. More particularly, the present invention concerns a process for the preparation of 3-((3,3,3-trifluoropropyl)thio)-propionic acid and esters thereof by the free radical coupling of 3-mercaptopropionic acid and esters thereof with 3,3,3- trifluoropropene .
• 3-((3,3,3-Trifluoropropyl)thio)propionic acid and methyl 3-((3,3,3-trifluoropropyl)- thio)propionate are useful to produce pesticidal thioether and pesticidal sulfoxides such as N-(3- chloro- l-(pyridin-3-yl)- lH- razol-4-yl)-N-ethyl-3-((3,3,3-trifluoro ropyl)thio)-propanamide.
• Methyl 3-((3,3,3-trifluoropropyl)thio)propionate has typically been produced by the free radical addition of methyl 3-mercaptopropionate to 3,3,3-trifluoropropene in the presence of a free radical initiator such as a-azobisisobutyronitrile (AIBN) at high temperatures.
• a free radical initiator such as a-azobisisobutyronitrile (AIBN) at high temperatures.
• AIBN a-azobisisobutyronitrile
• the present invention concerns a process for the preparation of 3-((3,3,3-trifluoro- propyl)thio)propionic acid or esters thereof by the low temperature free radical initiated coupling of 3-mercaptopropionic acid or esters thereof with 3,3,3-trifluoropropene. More particularly, the present invention concerns a process for the preparation of 3-((3,3,3- trifluoropropyl)thio)propionic acid or esters thereof (Formula I)
• R represents H or (C C 4 ) alkyl
• V-70 2,2'-azobis(4-methoxy-2,4-dimethyl) valeronitrile
• alkyl denotes branched or unbranched hydrocarbon chains.
• the low temperature free radical initiated coupling of the present invention more selectively prepares 3-((3,3,3-trifluoropropyl)thio)propionic acid or esters thereof.
• the ratio of linear to branched isomer is enhanced from about 10: 1 to about 40: 1 or greater for the acid and is enhanced from about 10: 1 to about 20: 1 or greater for the esters.
• V-70 From about 1 to about 10 mole percent initiator, V-70, is typically used, with about 5 mole percent being preferred.
• the low temperature free radical initiated coupling is conducted in an inert organic solvent.
• Typical inert organic solvents must remain liquid to -50 °C, must remain relatively inert to the free radical conditions and must dissolve the reactants at reaction temperatures.
• Preferred inert organic solvents are solvents such as toluene, ethyl acetate, and methanol.
• the temperature at which the reaction is conducted is from about 0 °C to about 40 °C.
• the 3-mercaptopropionic acid or esters thereof and V-70 are added to an inert organic solvent.
• the solution is cooled to less than about -50 °C and the 3,3,3- trifluoropropene is transferred into the reaction mixture.
• the reaction mixture is heated to about 50 °C for about 1 hour to decompose any remaining V-70 initiator followed by cooling and solvent removal.
• octanophenone 526.2 mg as an internal standard and was purged and pressure checked with nitrogen.
• the reactor was cooled with dry ice and the 3,3,3-trifluoropropene (3.10 g, 32.3 mmol) was condensed into the reactor.
• the ice bath was removed and the reactor heated to 60 °C and stirred for 27 hours.
• the internal yield of the reaction was determined to be 80% by use of the octanophenone internal standard (12.2: 1 lineanbranched isomer by GC).
• the pressure was released and the crude mixture removed from the reactor.
• the mixture was concentrated by rotary evaporation and sodium hydroxide (10 wt%, 50 mL) was added.
• a 2 L autoclave reactor was charged with toluene (716.45 g), methyl 3-mercapto- propionate (187.78 g, 1562.6 mmol), and a-azobisisobutyronitrile (12.890 g, 78.500 mmol).
• the reactor was sealed and pressurized with nitrogen (-100 psig) three times to purge the system of air.
• 3,3,3-Trifluoropropene (153.20 g, 1595.0 mmol) was added via transfer cylinder at 12 °C (cold water bath). The reaction was heated to 80 °C and stirred for 21 hours. The reaction was allowed to cool to room temperature and vacuum transferred out of the reactor.

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

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Citations (2)

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• 2014
  • 2014-10-17 CA CA2957164A patent/CA2957164A1/en not_active Abandoned
  • 2014-10-17 CN CN201480082356.2A patent/CN107074756A/zh active Pending
  • 2014-10-17 EP EP14899236.5A patent/EP3177590A4/en not_active Withdrawn
  • 2014-10-17 AR ARP140103917A patent/AR098111A1/es unknown
  • 2014-10-17 KR KR1020177005869A patent/KR20170039268A/ko not_active Application Discontinuation
  • 2014-10-17 WO PCT/US2014/061022 patent/WO2016022162A1/en active Application Filing
  • 2014-10-17 JP JP2017506866A patent/JP2017524001A/ja active Pending
  • 2014-10-17 BR BR112017001996A patent/BR112017001996A2/pt not_active Application Discontinuation
• 2015
  • 2015-08-06 TW TW104125646A patent/TW201612155A/zh unknown
• 2017
  • 2017-01-30 IL IL250361A patent/IL250361A0/en unknown

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Non-Patent Citations (2)

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