Carbon tetrabromide → 2,6-dichloro-3-[N-[4-(methylcarbamoyl)cinnamoylglycyl]-N-methylamino]benzyl bromide

HRID 1604526Notes

Reaction equation

HRID 1604526 reaction equation
[Cl:1][C:2]1[C:7]([N:8]([CH3:27])[C:9](=[O:26])[CH2:10][NH:11][C:12](=[O:25])[CH:13]=[CH:14][C:15]2[CH:20]=[CH:19][C:18]([C:21](=[O:24])[NH:22][CH3:23])=[CH:17][CH:16]=2)=[CH:6][CH:5]=[C:4]([Cl:28])[C:3]=1[CH2:29]O.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(Br)(Br)(Br)[Br:51]>ClCCl>[Cl:1][C:2]1[C:7]([N:8]([CH3:27])[C:9](=[O:26])[CH2:10][NH:11][C:12](=[O:25])[CH:13]=[CH:14][C:15]2[CH:20]=[CH:19][C:18]([C:21](=[O:24])[NH:22][CH3:23])=[CH:17][CH:16]=2)=[CH:6][CH:5]=[C:4]([Cl:28])[C:3]=1[CH2:29][Br:51]

Participants

5

Reactant 3

HCID 11205Carbon tetrabromide2×HCID 11776Triphenylphosphine2×HCID 540364432,6-dichloro-1-hydroxymethyl-3-[N-methyl-N-[4-(methylcarbamoyl)cinnamoylglycyl]amino]-benzene

Product 1

HCID 538052362,6-dichloro-3-[N-[4-(methylcarbamoyl)cinnamoylglycyl]-N-methylamino]benzyl bromideYield 69.3%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a mixture of 2,6-dichloro-1-hydroxymethyl-3-[N-methyl-N-[4-(methylcarbamoyl)cinnamoylglycyl]amino]benzene (8.10 g) in dichloromethane (81 ml) was added triphenylphosphine (5.66 g) and carbon tetrabromide (8.95 g) at 0° C. After 15 minutes the reaction mixture was stirred at ambient temperature for 3 hours. To the mixture was added triphenylphosphine (1.42 g) and carbon tetrabromide (2.39 g) and stirred for another 2 hours. The reaction mixture was washed with saturated sodium hydrogen carbonate, water and brine. After dried over anhydrous magnesium sulfate, the mixture was filtered and evaporated in vacuo. The residue was purified by flash column chromatography eluting with dichloromethane:ethyl acetate (1:1, V/V) followed by crystallizing from ethyl acetate to give 2,6-dichloro-3-[N-methyl-N-[4-(methylcarbamoyl)cinnamoylglycyl]amino]benzyl bromide (6.40 g) as pale yellow crystals.

Workup

  1. stirringstirred for another 2 hours
  2. washThe reaction mixture was washed with saturated sodium hydrogen carbonate, water and brine
  3. dry with materialAfter dried over anhydrous magnesium sulfate
  4. filtrationthe mixture was filtered
  5. customevaporated in vacuo
  6. customThe residue was purified by flash column chromatography
  7. washeluting with dichloromethane:ethyl acetate (1:1, V/V)
  8. customby crystallizing from ethyl acetate

Sources & evidence

ORD record
ord-90dbc3af21cb4b2490f49eabfbe4a0fe
Source dataset
uspto-grants-1999_11
Patent number
US05994368

Reaction notes

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