Acetic Acid → HCID 68855098, compound

HRID 1782732Notes

Reaction equation

HRID 1782732 reaction equation
[NH2:1][C:2]1[C:31]([Br:32])=[CH:30][C:5]([CH2:6][C@H:7]([C:16]([N:18]2[CH2:23][CH2:22][CH:21]([N:24]3[CH2:29][CH2:28][CH2:27][CH2:26][CH2:25]3)[CH2:20][CH2:19]2)=O)[NH:8][C:9]([O:11][C:12]([CH3:15])([CH3:14])[CH3:13])=[O:10])=[CH:4][C:3]=1[Br:33].[BH4-].[Na+].C(O)(=O)C>O1CCOCC1>[NH2:1][C:2]1[C:31]([Br:32])=[CH:30][C:5]([CH2:6][C@@H:7]([NH:8][C:9]([O:11][C:12]([CH3:14])([CH3:13])[CH3:15])=[O:10])[CH2:16][N:18]2[CH2:19][CH2:20][CH:21]([N:24]3[CH2:25][CH2:26][CH2:27][CH2:28][CH2:29]3)[CH2:22][CH2:23]2)=[CH:4][C:3]=1[Br:33]

Participants

5

Reactant 3

HCID 176Acetic AcidHCID 4311764Sodium borohydrideHCID 53910082HCID 53910082, compound

Product 1

HCID 68855098HCID 68855098, compound

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent2×

Conditions

Temperature
5 °C

Procedure

To a solution of 10 g (0.017 mol) of 1-[4-amino-3,5-dibromo-N-[(1,1-dimethylethoxy)carbonyl]-D-phenylalanyl]-4-(1-piperidinyl)-piperidine in 350 ml of dioxane were added 3.1 g (0.082 mol) of sodium borohydride and the reaction mixture was cooled to 5° C. Then a solution of 4.92 g (0.082 mol) of acetic acid in 100 ml of dioxane was added dropwise with stirring. The reaction mixture was stirred for a further hour at room temperature and for 3 hours at 85° C. Then ice water was added, the organic solvent was removed in vacuo and the aqueous residue was repeatedly extracted with methylene chloride. The combined organic phases were dried, evaporated down in vacuo and the residue was purified by column chromatography (MN-silica gel 60, Macherey-Nagel, 70-230 mesh ASTM, eluant: methylene chloride/methanol/cyclohexane/conc. aqueous ammonia=3600/150/150/20 (v/v/v/v). 4.1 g (42% of theory) of a colourless foam were obtained.

Workup

  1. stirringThe reaction mixture was stirred for a further hour at room temperature and for 3 hours at 85° C
  2. customthe organic solvent was removed in vacuo
  3. extractionthe aqueous residue was repeatedly extracted with methylene chloride
  4. customThe combined organic phases were dried
  5. customevaporated down in vacuo
  6. customthe residue was purified by column chromatography (MN-silica gel 60, Macherey-Nagel, 70-230 mesh ASTM, eluant
  7. custom4.1 g (42% of theory) of a colourless foam were obtained

Sources & evidence

ORD record
ord-5bf4cd61999549b1b00eff1a1f4e86b8
Source dataset
uspto-grants-2009_03
Patent number
US07498325B2

Reaction notes

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