3,3,3-Trifluoropropyne → HCID 57804176, compound

HRID 2102941Notes

Reaction equation

HRID 2102941 reaction equation
C([Li])CCC.[F:6][C:7]([F:11])([F:10])[C:8]#[CH:9].I[C:13]1[CH:21]=[CH:20][C:16]([C:17]([OH:19])=[O:18])=[CH:15][C:14]=1[CH3:22]>C1COCC1.[Cl-].[Cl-].[Zn+2].C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH3:22][C:14]1[CH:15]=[C:16]([CH:20]=[CH:21][C:13]=1[C:9]#[C:8][C:7]([F:11])([F:10])[F:6])[C:17]([OH:19])=[O:18]

Participants

7

Reactant 3

HCID 695783,3,3-TrifluoropropyneHCID 15173224-Iodo-3-methylbenzoic acidHCID 178418339Butyllithium

Product 1

HCID 57804176HCID 57804176, compound

Reagents, catalysts & solvents 3

HCID 3007855ZincchlorideCatalystHCID 178418397HCID 178418397, compoundCatalystHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

The method is based upon a procedure detailed by Yoneda et al in Bulletin Chemical Society Japan 1990, 63, 2124-2126. A solution of n-butyl lithium (2.5M in hexanes; 1 eq) was added carefully to a solution of 3,3,3-trifluoroprop-1-yne (1 eq) in THF at −78° C. under nitrogen. The mixture was stirred at −78° C. for 30 min then a solution of ZnCl2 (3 eq) in THF was added slowly. The mixture was allowed to warm to room temperature, stirred for 30 min then Pd(Ph3P)4 (5 mol %) was added, followed by 4-iodo-3-methylbenzoic acid (0.5 eq). The mixture was heated to 50° C. and stirred for 15 h, then heated further to 80° C. for 5 h, and finally at 100° C. overnight. After allowing to cool to room temperature the mixture was concentrated under vacuum to a crude residue. The residue was purified by column chromatography on silica gel to give the product as a solid. m/z=227 (M−1).

Workup

  1. temperatureto warm to room temperature
  2. stirringstirred for 30 min
  3. temperatureThe mixture was heated to 50° C.
  4. stirringstirred for 15 h
  5. temperatureheated further to 80° C. for 5 h
  6. customfinally at 100° C.
  7. customovernight
  8. temperatureto cool to room temperature the mixture
  9. concentrationwas concentrated under vacuum to a crude residue
  10. customThe residue was purified by column chromatography on silica gel

Sources & evidence

ORD record
ord-be95da783e744b6e8fbc1ca100a1bdff
Source dataset
uspto-grants-2009_08
Patent number
US07576099B2

Reaction notes

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