Diethylenetriamine → [2-(4-Bromo-2-methyl-phenyl)-4-hydroxy-butyl]-carbamic acid tert-butyl ester

HRID 503909Notes

Reaction equation

HRID 503909 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([CH:8]([CH2:11][CH2:12][OH:13])[C:9]#[N:10])=[C:4]([CH3:14])[CH:3]=1.[O:15](C(OC(C)(C)C)=O)[C:16]([O:18][C:19]([CH3:22])([CH3:21])[CH3:20])=O.[BH4-].[Na+].NCCNCCN>CO>[C:19]([O:18][C:16](=[O:15])[NH:10][CH2:9][CH:8]([C:5]1[CH:6]=[CH:7][C:2]([Br:1])=[CH:3][C:4]=1[CH3:14])[CH2:11][CH2:12][OH:13])([CH3:22])([CH3:21])[CH3:20]

Participants

6

Reactant 4

HCID 8111DiethylenetriamineHCID 90495Di-tert-butyl dicarbonateHCID 4311764Sodium borohydrideHCID 594283342-(4-Bromo-2-methyl-phenyl)-4-hydroxy-butyronitrile

Product 1

HCID 66877268[2-(4-Bromo-2-methyl-phenyl)-4-hydroxy-butyl]-carbamic acid tert-butyl esterYield 79%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

To a solution of 2-(4-bromo-2-methyl-phenyl)-4-hydroxy-butyronitrile (27.3 g, 0.1074 mol) in MeOH (750 mL) at 0° C. was added (BOC)2O (46.9 g, 0.2149 mol), followed by NiCl2.6H2O (2.55 g, 0.01074 mol) and sodium borohydride (27.83 g, 0.7359 mol). The mixture was stirred at room temperature for 24 hours, and diethylenetriamine (12 mL, 0.1074 mol) was added. The reaction mixture was stirred for 30 minutes, then solvent was evaporated under reduced pressure. The resulting crude material was partitioned between NaHCO3 (10% aqueous solution) and EtOAc. The organic phase was washed with water and brine; dried over Na2SO4, filtered, and evaporated under reduced pressure. The residue was purified via flash chromatography (hexane/EtOAc, 6/4) to give 30.3 g (79% yield) of [2-(4-bromo-2-methyl-phenyl)-4-hydroxy-butyl]-carbamic acid tert-butyl ester.

Workup

  1. stirringThe reaction mixture was stirred for 30 minutes
  2. customsolvent was evaporated under reduced pressure
  3. customThe resulting crude material was partitioned between NaHCO3 (10% aqueous solution) and EtOAc
  4. washThe organic phase was washed with water and brine
  5. dry with materialdried over Na2SO4
  6. filtrationfiltered
  7. customevaporated under reduced pressure
  8. customThe residue was purified via flash chromatography (hexane/EtOAc, 6/4)

Sources & evidence

ORD record
ord-39332c3eba7f4c8f96fc2c290a455d07
Source dataset
uspto-grants-2010_08
Patent number
US07776910B2

Reaction notes

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