1,2-Dibromoethane → HCID 86590140, compound

HRID 1840529Notes

Reaction equation

HRID 1840529 reaction equation
BrCCBr.I[CH2:6][CH2:7][C@H:8]([NH:19][C:20]([O:22][CH2:23][C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1)=[O:21])[C:9]([O:11][CH2:12][C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1)=[O:10].C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.Br[C:53]1[CH:58]=[CH:57][C:56]([N+:59]([O-:61])=[O:60])=[CH:55][N:54]=1>CN(C)C=O.C(OCC)(=O)C.[Zn].C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C[Si](Cl)(C)C>[N+:59]([C:56]1[CH:57]=[CH:58][C:53]([CH2:6][CH2:7][C@H:8]([NH:19][C:20]([O:22][CH2:23][C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=2)=[O:21])[C:9]([O:11][CH2:12][C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)=[O:10])=[N:54][CH:55]=1)([O-:61])=[O:60]

Participants

10

Reactant 4

HCID 78391,2-DibromoethaneHCID 782402-Bromo-5-nitropyridineHCID 80271Tri-o-tolylphosphineHCID 10863357HCID 10863357, compound

Product 1

HCID 86590140HCID 86590140, compoundYield 74.5%

Reagents, catalysts & solvents 5

HCID 6397ChlorotrimethylsilaneCatalystHCID 23994ZincCatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 6228DimethylformamideSolvent3×HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
60 °C

Procedure

A suspension of 6 g (92 mmol) of zinc powder and 0.4 ml (4.7 mmol) of 1,2-dibromoethane in 7 ml of anhydrous N,N-dimethylformamide is heated at 60° C. with stirring and under argon for 45 min. 0.126 ml (1 mmol) of trimethylsilyl chloride is then added and the mixture is stirred vigorously at room temperature for 30 min. A solution of 7 g (15.4 mmol) of phenylmethyl (S)-4-iodo-2-[[(phenylmethoxy)carbonyl]amino]butanoate in 1 ml of anhydrous N,N-dimethylformamide is then added. After 30 min at room temperature, 0.28 g (0.31 mmol) of tris(dibenzylideneacetone)dipalladium (0), 0.38 g (1.24 mmol) of tri-ortho-tolylphosphine, 3.78 g (18.5 mmol) of 2-bromo-5-nitropyridine and 1 ml of anhydrous N,N-dimethylformamide are added at room temperature and the mixture is stirred for 3 h at room temperature. The reaction medium is taken up in 200 ml of ethyl acetate and 5 g of active charcoal and then filtered through a cake of Celite. The cake is rinsed with 2×100 ml of ethyl acetate and the organic phases are combined, washed with 5×100 ml of water, dried over sodium sulphate and concentrated under reduced pressure. The residue is purified by filtration on a column of silica gel, eluting with a cyclohexane/ethyl acetate gradient of from 0 to 20% ethyl acetate. 5.16 g of phenylmethyl (S)-5-nitro-α-[[(phenylmethoxy)carbonyl]amino]-2-pyridinebutanoate are thus obtained in the form of a yellow foam.

Workup

  1. stirringthe mixture is stirred vigorously at room temperature for 30 min
  2. waitAfter 30 min at room temperature
  3. stirringthe mixture is stirred for 3 h at room temperature
  4. filtration5 g of active charcoal and then filtered through a cake of Celite
  5. washThe cake is rinsed with 2×100 ml of ethyl acetate
  6. washwashed with 5×100 ml of water
  7. dry with materialdried over sodium sulphate
  8. concentrationconcentrated under reduced pressure
  9. filtrationThe residue is purified by filtration on a column of silica gel
  10. washeluting with a cyclohexane/ethyl acetate gradient of from 0 to 20% ethyl acetate

Sources & evidence

ORD record
ord-411d20c3be564d678a2a217adb3fd596
Source dataset
uspto-grants-2004_01
Patent number
US06680329B2

Reaction notes

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