Dimethyl Sulfide → HCID 58197886, compound

HRID 1503397Notes

Reaction equation

HRID 1503397 reaction equation
CN(CCN(C)C)C.[Li][CH:10]([CH2:12]C)[CH3:11].[F:14][C:15]1[CH:16]=[C:17]([CH:21]=[CH:22][C:23]=1[F:24])[C:18]([OH:20])=[O:19].CSC.BrCC=C>C1COCC1>[CH2:12]([C:16]1[C:15]([F:14])=[C:23]([F:24])[CH:22]=[CH:21][C:17]=1[C:18]([OH:20])=[O:19])[CH:10]=[CH2:11]

Participants

7

Reactant 5

HCID 1068Dimethyl SulfideHCID 7841Allyl bromideHCID 8037N,N,N',N'-TetramethylethylenediamineHCID 991663,4-Difluorobenzoic acidHCID 178418400CID 53628100

Product 1

HCID 58197886HCID 58197886, compoundYield 87.4%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Procedure

To a solution of TMEDA (32.2 g, 0.278 mol) in dry THF (150 mL) was added s-BuLi (1.3 M, 0.278 mol, 214 mL) at −78° C. The mixture was stirred at this temperature for 0.5 hour, and then a solution of 3,4-difluorobenzoic acid (20 g, 0.127 mol) in THF (100 mL) was added dropwise. After stirring for 1 hour, CuBr.DMS (3.9 g, 0.019 mol, 15% mol) was added, followed by 3-bromoprop-1-ene (46 g, 0.38 mol) in 50 mL of THF. The reaction mixture was allowed to warm to room temperature and was quenched with water. The aqueous layer was washed with Et2O, and acidified with 4 N HCl. The mixture was extracted with Et2O. The organic layer was washed with brine, dried over Na2SO4, filtered and concentrated to give 2-allyl-3,4-difluorobenzoic acid (22 g, 55%). 1H NMR (CDCl3): 3.91 (d, 2H), 5.06 (m, 2H), 6.01 (m, 1H), 7.12 (m, 1H), 7.90 (m, 1H).

Workup

  1. stirringAfter stirring for 1 hour
  2. customwas quenched with water
  3. washThe aqueous layer was washed with Et2O
  4. extractionThe mixture was extracted with Et2O
  5. washThe organic layer was washed with brine
  6. dry with materialdried over Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated

Sources & evidence

ORD record
ord-4ef05eb1c92b47eaacfcf4a3b87f5b33
Source dataset
uspto-grants-2015_12
Patent number
US09212153B2

Reaction notes

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