Chlorotrimethylsilane → HCID 66760563, compound

HRID 889203Notes

Reaction equation

HRID 889203 reaction equation
C[Si](Cl)(C)C.[CH2:6]([O:8][C:9](=[O:14])[C:10](Br)([F:12])[F:11])[CH3:7].[C:15]([O:19][C:20]([N:22]1[CH2:27][CH2:26][N:25]([CH2:28]C2C3N=NNC=3C=CC=2)[CH2:24][CH2:23]1)=[O:21])([CH3:18])([CH3:17])[CH3:16].C([O-])(O)=O.[Na+]>C1COCC1.[Zn]>[C:15]([O:19][C:20]([N:22]1[CH2:27][CH2:26][N:25]([CH2:28][C:10]([C:9]([O:8][CH2:6][CH3:7])=[O:14])([F:12])[F:11])[CH2:24][CH2:23]1)=[O:21])([CH3:18])([CH3:17])[CH3:16]

Participants

7

Reactant 4

HCID 6397ChlorotrimethylsilaneHCID 69585Ethyl bromodifluoroacetateHCID 516892Sodium BicarbonateHCID 178452300HCID 178452300, compound

Product 1

HCID 66760563HCID 66760563, compoundYield 22%

Reagents, catalysts & solvents 2

HCID 23994ZincCatalystHCID 8028TetrahydrofuranSolvent

Procedure

To a suspension of zinc dust (1.93 g, 29.5 mmol) in dry THF (30 mL), under nitrogen, was added TMS-Cl (trimethylsilyl chloride) (1.28 g, 11.8 mmol). The reaction mixture was stirred for 15 min, and then ethylbromodifluoroacetate (4.49 g, 22.1 mmol) was slowly added, followed 15 min later by a solution 4-benzotriazol-ylmethylpiperazine-1-carboxylic acid tert-butyl ester (4.68 g, 14.8 mmol). After, 3 h stirring at room temperature, the mixture was poured onto 5% aqueous NaHCO3 (40 mL) and filtered on celite. The filtrate was diluted with ethyl acetate and organic layer was separated, dried (MgSO4) and concentrated to give an oil which was purified by flash chromatography (Hexane-Ethyl acetate (8:2) to give 1.05 g of 4-(2-ethoxycarbonyl-2,2-difluoro-ethyl)-piperazine-1-carboxylic acid tert-butyl ester as an oil.

Workup

  1. stirringAfter, 3 h stirring at room temperature
  2. filtrationfiltered on celite
  3. additionThe filtrate was diluted with ethyl acetate and organic layer
  4. customwas separated
  5. dry with materialdried (MgSO4)
  6. concentrationconcentrated
  7. customto give an oil which
  8. customwas purified by flash chromatography (Hexane-Ethyl acetate (8:2)

Sources & evidence

ORD record
ord-80a05ec192104a869a739efa39ef0370
Source dataset
uspto-grants-2012_08
Patent number
US08252793B2

Reaction notes

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