1,2-Dibromoethane → Methyl 1-(4-(4,4,4-trifluorobutoxy)benzoyl)cyclopropanecarboxylate

HRID 1629779Notes

Reaction equation

HRID 1629779 reaction equation
[O:1]=[C:2]([C:8]1[CH:13]=[CH:12][C:11]([O:14][CH2:15][CH2:16][CH2:17][C:18]([F:21])([F:20])[F:19])=[CH:10][CH:9]=1)[CH2:3][C:4]([O:6][CH3:7])=[O:5].C([O-])([O-])=O.[K+].[K+].Br[CH2:29][CH2:30]Br>CN(C=O)C.CCOC(C)=O>[F:21][C:18]([F:19])([F:20])[CH2:17][CH2:16][CH2:15][O:14][C:11]1[CH:12]=[CH:13][C:8]([C:2]([C:3]2([C:4]([O:6][CH3:7])=[O:5])[CH2:30][CH2:29]2)=[O:1])=[CH:9][CH:10]=1

Participants

6

Reactant 3

HCID 78391,2-DibromoethaneHCID 11430Potassium CarbonateHCID 86685868Methyl 3-oxo-3-(4-(4,4,4-trifluorobutoxy)phenyl)propanoate

Product 1

HCID 86685869Methyl 1-(4-(4,4,4-trifluorobutoxy)benzoyl)cyclopropanecarboxylateYield 64.5%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of Intermediate 14A (6.0 g, 19.7 mmol) in DMF (197 mL) was added K2CO3 (8.18 g, 59.2 mmol) followed by 1,2-dibromoethane (2.6 mL, 30 mmol). The reaction mixture was stirred at rt for 2 days. The reaction was reduced in volume in vacuo, then diluted with EtOAc, washed with a 1:1 solution of sat'd aq NaCl and water, dried over anhydrous MgSO4, filtered and concentrated. The product was isolated by silica gel chromatography (220 g silica gel, eluted with EtOAc in hexanes) to provide Intermediate 14B (4.2 g, 61%) as a colorless oil. 1H NMR (500 MHz, CDCl3) δ 1.45-1.49 (m, 2H), 1.56-1.61 (m, 2H), 2.03-2.14 (m, 2H), 2.26-2.39 (m, 2H), 3.60 (s, 3H), 4.09 (t, J=6.05 Hz, 2H), 6.90-6.94 (m, 2H), 7.86-7.93 (m, 2H).

Workup

  1. washwashed with a 1:1 solution of sat'd aq NaCl and water
  2. dry with materialdried over anhydrous MgSO4
  3. filtrationfiltered
  4. concentrationconcentrated
  5. customThe product was isolated by silica gel chromatography (220 g silica gel, eluted with EtOAc in hexanes)

Sources & evidence

ORD record
ord-17bd775beea24986b7a6dac6463a252f
Source dataset
uspto-grants-2014_07
Patent number
US08791091B2

Reaction notes

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