Dibromodifluoromethane → 2-[2-(3-Chlorophenyl)ethynyl]-8-(difluoromethylene)-4-oxa-3-azaspiro[4.5]dec-2-ene

HRID 2040905Notes

Reaction equation

HRID 2040905 reaction equation
CN(P(N(C)C)N(C)C)C.Br[C:12](Br)([F:14])[F:13].[Cl:16][C:17]1[CH:18]=[C:19]([C:23]#[C:24][C:25]2[CH2:29][C:28]3([CH2:34][CH2:33][C:32](=O)[CH2:31][CH2:30]3)[O:27][N:26]=2)[CH:20]=[CH:21][CH:22]=1>C1COCC1>[Cl:16][C:17]1[CH:18]=[C:19]([C:23]#[C:24][C:25]2[CH2:29][C:28]3([CH2:34][CH2:33][C:32](=[C:12]([F:14])[F:13])[CH2:31][CH2:30]3)[O:27][N:26]=2)[CH:20]=[CH:21][CH:22]=1

Participants

5

Reactant 3

HCID 6382DibromodifluoromethaneHCID 15355Hexamethylphosphorous triamideHCID 566464673-[(3-Chlorophenyl)ethynyl]-1-oxa-2-azaspiro[4.5]dec-2-en-8-one

Product 1

HCID 574937912-[2-(3-Chlorophenyl)ethynyl]-8-(difluoromethylene)-4-oxa-3-azaspiro[4.5]dec-2-eneYield 13.7%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A solution of tris-dimethylaminophosphine in 2.6 mL of anhydrous THF was added under a nitrogen atmosphere to a solution of dibromodifluoromethane in 3.9 mL of anhydrous THF at 0° C. over 15 min. The reaction mixture was stirred at r.t. for 30 min. Afterwards, a solution of the Compound of Example 32 (0.275 g, 0.956 mmol) was added dropwise. After overnight resting, the solution was evaporated and taken up with EtOAc. Washing with water, drying the organic layer with Na2SO4 and evaporating to dryness in vacuo afforded a crude which was purified by means of automated flash chromatography (Isolera®TM-Biotage; gradient Petroleum Ether-EtOAc from 95:5 to 8:2) giving 42 mg of the title compound. Yield: 13.7%.

Workup

  1. waitAfter overnight resting
  2. customthe solution was evaporated
  3. washWashing with water
  4. dry with materialdrying the organic layer with Na2SO4
  5. customevaporating to dryness in vacuo
  6. customafforded a crude which
  7. customwas purified by means of automated flash chromatography (Isolera®TM-Biotage; gradient Petroleum Ether-EtOAc from 95:5 to 8:2)

Sources & evidence

ORD record
ord-e56a6de3407a4d31b4db61aaa68199e9
Source dataset
uspto-grants-2013_11
Patent number
US08580962B2

Reaction notes

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