Sodium hydride → 12-(tert-Butoxycarbonyl)-6,12-bis(benzyloxy)-7-oxo-6,12-diazadodecanenitrile

HRID 1109843Notes

Reaction equation

HRID 1109843 reaction equation
[C:1]([O:5][C:6]([NH:8][O:9][CH2:10][C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1)=[O:7])([CH3:4])([CH3:3])[CH3:2].[H-].[Na+].[CH2:19]([O:26][N:27]([CH2:35][CH2:36][CH2:37][CH2:38][C:39]#[N:40])[C:28](=[O:34])[CH2:29][CH2:30][CH2:31][CH2:32]Cl)[C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1>CN(C=O)C>[C:1]([O:5][C:6]([N:8]([O:9][CH2:10][C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1)[CH2:32][CH2:31][CH2:30][CH2:29][C:28](=[O:34])[N:27]([O:26][CH2:19][C:20]1[CH:21]=[CH:22][CH:23]=[CH:24][CH:25]=1)[CH2:35][CH2:36][CH2:37][CH2:38][C:39]#[N:40])=[O:7])([CH3:4])([CH3:2])[CH3:3]

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 736159Tert-butyl N-(benzyloxy)carbamateHCID 10087530N-(Benzyloxy)-N-(4-cyanobutyl)-5-chloropentanamide

Product 1

HCID 1032403412-(tert-Butoxycarbonyl)-6,12-bis(benzyloxy)-7-oxo-6,12-diazadodecanenitrileYield 77%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Conditions

Temperature
0 °C

Procedure

N-(tert-Butoxycarbonyl)-O-benzylhydroxylamine (4.2 g, 18.8 mmol) was dissolved in DMF (120 mL) and cooled to 0° C. Sodium hydride (80%, 0.564 g, 18.8 mmol) was added, and the mixture was stirred at 0° C. for 30 minutes. A solution of (3) (6.0 g, 18.6 mmol) in DMF (30 mL) was slowly added to the cold solution which was then allowed to stir at room temperature for 20 minutes and at 80° C. overnight. The DMF was removed under high vacuum, and the reside was quenched with H2O (50 mL) and extracted with CH2Cl2 (3×70 mL). Organic extracts were washed with saturated sodium chloride, and the solvent was removed by rotary evaporation. Silica gel column chromatography, eluting with 2:1 hexane/EtOAc produced 7.29 g (77%) of (4) as an oil: NMR δ 1.50 (s, 9 H), 1.40-1.90 (m, 8 H), 2.30 (t, 2 H, J=6), 2.40 (t, 2 H, J=6), 3.40 (t, 2 H, J=6), 3.63 (t, 2 H, J=6), 4.77 (s, 2 H), 4.80 (s, 2 H), 7.33 (s, 10 H) . Anal. (C29H39N3O5), C, H, N.

Workup

  1. stirringto stir at room temperature for 20 minutes and at 80° C. overnight
  2. customThe DMF was removed under high vacuum
  3. customthe reside was quenched with H2O (50 mL)
  4. extractionextracted with CH2Cl2 (3×70 mL)
  5. washOrganic extracts were washed with saturated sodium chloride
  6. customthe solvent was removed by rotary evaporation
  7. washSilica gel column chromatography, eluting with 2:1 hexane/EtOAc

Sources & evidence

ORD record
ord-050b8b9542394a5ca208230978a6d71a
Source dataset
uspto-grants-1994_06
Patent number
US05322961

Reaction notes

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