Water → 1,1-Dimethylethyl 4-azido-1-piperidinecarboxylate

HRID 369113Notes

Reaction equation

HRID 369113 reaction equation
Br[CH:2]1[CH2:7][CH2:6][N:5]([C:8]([O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[O:9])[CH2:4][CH2:3]1.[N-:15]=[N+:16]=[N-:17].[Na+].O.C(=O)(O)[O-].[Na+]>CN(C=O)C.[I-].[Na+]>[N:15]([CH:2]1[CH2:7][CH2:6][N:5]([C:8]([O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[O:9])[CH2:4][CH2:3]1)=[N+:16]=[N-:17]

Participants

7

Reactant 4

HCID 962WaterHCID 33557Sodium AzideHCID 516892Sodium BicarbonateHCID 15541517tert-Butyl 4-bromopiperidine-1-carboxylate

Product 1

HCID 114587941,1-Dimethylethyl 4-azido-1-piperidinecarboxylateYield 100.2%

Reagents, catalysts & solvents 2

HCID 5238Sodium IodideCatalystHCID 6228DimethylformamideSolvent

Procedure

To a solution of 45.3 g (172 mmol) of 4-bromo-1-t-butoxycarbonylpiperidine in 750 mL of DMF was added 22.3 g (343 mmol) of sodium azide and 2.5 g (17 mmol) of sodium iodide. The reaction was stirred at rt for 24 h and then at 60° C. for 4 h. The mixture was poured into water containing 20 mL of sodium bicarbonate and extracted twice with 1:1 ether:hexanes. The organic layers were each washed with a portion of water and brine, dried over sodium sulfate, combined and concentrated. The residue was purified by FCC eluting with 5 -10% ethyl acetate/hexanes to afford 39 g of title compound having a trace of elimination biproduct. 1H NMR (400 MHz, CDCl3): δ 1.43 (s,9H), 1.52 (m, 2H), 1.85 (m, 2H), 3.07 (m, 2H), 3.55 (m, 1H), 3.78 (m, 2H).

Workup

  1. waitat 60° C. for 4 h
  2. extractionextracted twice with 1:1 ether
  3. washeach washed with a portion of water and brine
  4. dry with materialdried over sodium sulfate
  5. concentrationconcentrated
  6. customThe residue was purified by FCC
  7. washeluting with 5 -10% ethyl acetate/hexanes

Sources & evidence

ORD record
ord-46647a34bbee455cae7a7ed789f493eb
Source dataset
uspto-grants-2000_10
Patent number
US06136827

Reaction notes

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