Bromoacetyl chloride → HCID 70066743, compound

HRID 648829Notes

Reaction equation

HRID 648829 reaction equation
[C:1]1([S:7][C@@H:8]2[CH2:12][NH:11][C@H:10]([C:13]([OH:15])=[O:14])[CH2:9]2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.C[Si](C([Si](C)(C)C)C(N)=O)(C)C.[Br:28][CH2:29][C:30](Cl)=[O:31].C1(SC2CN[C@H](C(O)=O)C2)C=CC=CC=1>C(Cl)Cl>[Br:28][CH2:29][C:30]([N:11]1[CH2:12][C@@H:8]([S:7][C:1]2[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=2)[CH2:9][C@H:10]1[C:13]([OH:15])=[O:14])=[O:31]

Participants

6

Reactant 4

HCID 89602Bromoacetyl chlorideHCID 11379084cis-4-phenylthio-l-prolinHCID 11708267BistrimethylsilylacetamidHCID 54181826HCID 54181826, compound

Product 1

HCID 70066743HCID 70066743, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a suspension of (4S)-4-(phenylthio)-L-proline (2.2 g., 10 mmole) in methylene chloride (50 ml., freshly distilled) is added bis(trimethylsilyl)acetamide (7.35 ml., 30 mmole). The reaction mixture is stirred at room temperature for 2 hours until it becomes almost clear. The reaction mixture is then cooled to -5° and bromoacetyl chloride (1.9 g., 1.0 ml., 12 mmole) is added dropwise keeping the temperature at -5°. After stirring overnight (-5° to room temperature), the reaction mixture is concentrated to about 50% of its volume, partitioned between saturated sodium bicarbonate/ethyl acetate and the layers are separated. The organic layer is extracted once more with saturated sodium bicarbonate. The combined aqueous layers are acidified to pH 2.0 with 10% potassium bisulfate and extracted with ethyl acetate (3×). The ethyl acetate fractions are combined, dried (Na2SO4) and concentrated to give 3.5 g. of (4S)-1-bromoacetyl)-4-(phenylthio)-L-proline as a viscous oil.

Workup

  1. distillation, freshly distilled)
  2. temperatureThe reaction mixture is then cooled to -5°
  3. customat -5°
  4. stirringAfter stirring overnight (-5° to room temperature)
  5. concentrationthe reaction mixture is concentrated to about 50% of its volume
  6. custompartitioned between saturated sodium bicarbonate/ethyl acetate
  7. customthe layers are separated
  8. extractionThe organic layer is extracted once more with saturated sodium bicarbonate
  9. extractionextracted with ethyl acetate (3×)
  10. dry with materialdried (Na2SO4)
  11. concentrationconcentrated
  12. customto give 3.5 g

Sources & evidence

ORD record
ord-d427c185e74f44f1ad912f8b0a9710eb
Source dataset
uspto-grants-1988_04
Patent number
US04736066

Reaction notes

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