Diisopropylamine → Ethyl 1-benzyl-4-(N,N'-di-tert-butyloxycarbonylhydrazino)piperidin-4-ylcarboxylate

HRID 1602325Notes

Reaction equation

HRID 1602325 reaction equation
C(NC(C)C)(C)C.C([Li])CCC.CCCCCC.[CH2:19]([N:26]1[CH2:31][CH2:30][CH:29]([C:32]([O:34][CH2:35][CH3:36])=[O:33])[CH2:28][CH2:27]1)[C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1.[CH3:37][C:38]([O:41][C:42](/[N:44]=[N:45]/[C:46]([O:48][C:49]([CH3:52])([CH3:51])[CH3:50])=[O:47])=[O:43])([CH3:40])[CH3:39].C(=O)([O-])[O-].[K+].[K+]>CCOCC>[CH2:19]([N:26]1[CH2:31][CH2:30][C:29]([C:32]([O:34][CH2:35][CH3:36])=[O:33])([N:44]([C:42]([O:41][C:38]([CH3:40])([CH3:39])[CH3:37])=[O:43])[NH:45][C:46]([O:48][C:49]([CH3:50])([CH3:51])[CH3:52])=[O:47])[CH2:28][CH2:27]1)[C:20]1[CH:21]=[CH:22][CH:23]=[CH:24][CH:25]=1

Participants

8

Reactant 6

HCID 7912DiisopropylamineHCID 8058HexaneHCID 11430Potassium CarbonateHCID 90423Ethyl 1-benzylpiperidine-4-carboxylateHCID 6034084Di-tert-butyl diazene-1,2-dicarboxylateHCID 178418339Butyllithium

Product 1

HCID 15663644Ethyl 1-benzyl-4-(N,N'-di-tert-butyloxycarbonylhydrazino)piperidin-4-ylcarboxylateYield 54.1%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent3×

Procedure

A solution of diisopropylamine (8.8 ml, 0.063 mol) in ether (400 ml) at -70° C. under nitrogen was treated with 1.6M n-butyllithium in hexane (37.5 ml, 0.060 mol) and stirred for 10 minutes. A solution of ethyl 1-benzylpiperidin-4-ylcarboxylate (13.6 g, 0.055 mol) in ether (70 ml) was added over 5 minutes and the resulting mixture then stirred at -70° C. for 40 minutes, before adding a solution of di-tert-butylazodicarboxylate (13.5 g, 0.058 mol) in ether (80 ml). The reaction mixture was allowed to warm to room temperature over 0.5 h, then stirred for a further 2 h before adding dilute potassium carbonate solution (150 ml). The ether layer was separated, dried (Na2SO4) and concentrated in vacuo to leave an orange oil. This was chromatographed on silica gel eluting initially with 20% ether/60-80 petrol, then with neat ether to afford the title compound (D26) (14.2 g, 54%) as a yellow oil.

Workup

  1. stirringthe resulting mixture then stirred at -70° C. for 40 minutes
  2. stirringstirred for a further 2 h
  3. customThe ether layer was separated
  4. dry with materialdried (Na2SO4)
  5. concentrationconcentrated in vacuo
  6. customto leave an orange oil
  7. customThis was chromatographed on silica gel eluting initially with 20% ether/60-80 petrol

Sources & evidence

ORD record
ord-4d15d8c812124afbbaea4c6dc2d4082c
Source dataset
uspto-grants-1999_11
Patent number
US05981545

Reaction notes

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