Ethyl bromodifluoroacetate → HCID 86724272, compound

HRID 594875Notes

Reaction equation

HRID 594875 reaction equation
Br[C:2]([F:9])([F:8])[C:3]([O:5][CH2:6][CH3:7])=[O:4].[Br:10][C:11]1[CH:12]=[C:13]2[C:20](=[CH:21][CH:22]=1)[O:19][CH2:18][C:15]1([CH2:17][CH2:16]1)[C:14]2=[N:23][S:24]([C:26]([CH3:29])([CH3:28])[CH3:27])=[O:25]>CCOCC.C1COCC1.[Zn]>[Br:10][C:11]1[CH:12]=[C:13]2[C:20](=[CH:21][CH:22]=1)[O:19][CH2:18][C:15]1([CH2:17][CH2:16]1)[C:14]2([C:2]([F:9])([F:8])[C:3]([O:5][CH2:6][CH3:7])=[O:4])[NH:23][S:24]([C:26]([CH3:29])([CH3:28])[CH3:27])=[O:25]

Participants

5

Reactant 2

HCID 69585Ethyl bromodifluoroacetateHCID 86724254HCID 86724254, compound

Product 1

HCID 86724272HCID 86724272, compoundYield 96.6%

Reagents, catalysts & solvents 2

HCID 23994ZincCatalystHCID 21868444Ether tetrahydrofuranSolvent2×

Procedure

To a suspension of activated zinc (3.44 g, 52.5 mmol) in Et2O-THF (50% v/v, 80 ml) under reflux was slowly added a solution of ethyl bromodifluoroacetate (8.00 g, 39.4 mmol) and N-(6-bromo-4H-spiro[chromene-3,1′-cyclopropan]-4-ylidene)-2-methylpropane-2-sulfinamide (4.68 g, 13.1 mmol) in Et2O-THF (50% v/v, 80 ml) over 40 minutes, and the mixture was stirred for 4 hours at the same temperature. After cooling, the mixture was filtrated through celite pad and washed with EtOAc. To the filtrate were added saturated aqueous NH4Cl and EtOAc. After separation, the water layer was extracted with EtOAc. The combined organic layer was dried over MgSO4 and concentrated. The residue was purified by silica gel chromatography (EtOAc:hexane=20:80-100:0) to give ethyl {6-bromo-4-[(tert-butylsulfinyl)amino]-4H-spiro[chromene-3,1′-cyclopropan]-4-yl}(difluoro)acetate (6.08 g).

Workup

  1. temperatureunder reflux
  2. temperatureAfter cooling
  3. filtrationthe mixture was filtrated through celite pad
  4. washwashed with EtOAc
  5. additionTo the filtrate were added saturated aqueous NH4Cl and EtOAc
  6. customAfter separation
  7. extractionthe water layer was extracted with EtOAc
  8. dry with materialThe combined organic layer was dried over MgSO4
  9. concentrationconcentrated
  10. customThe residue was purified by silica gel chromatography (EtOAc:hexane=20:80-100:0)

Sources & evidence

ORD record
ord-8413a7853cc442e2b456c38b8d1522b7
Source dataset
uspto-grants-2016_01
Patent number
US09242973B2

Reaction notes

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