Diisopropylamine → HCID 12638302, compound

HRID 1903362Notes

Reaction equation

HRID 1903362 reaction equation
C(NC(C)C)(C)C.C([Li])CCC.[O:13]=[C:14]1[NH:19][CH2:18][CH2:17][N:16]([C:20]([O:22][C:23]([CH3:26])([CH3:25])[CH3:24])=[O:21])[CH2:15]1.[CH2:27]([O:34][C:35]1[CH:42]=[CH:41][C:38]([CH2:39]Cl)=[CH:37][CH:36]=1)[C:28]1[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1>C1COCC1.CCCCCC>[O:13]=[C:14]1[NH:19][CH2:18][CH2:17][N:16]([C:20]([O:22][C:23]([CH3:26])([CH3:25])[CH3:24])=[O:21])[CH:15]1[CH2:39][C:38]1[CH:41]=[CH:42][C:35]([O:34][CH2:27][C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=2)=[CH:36][CH:37]=1

Participants

7

Reactant 4

HCID 7912DiisopropylamineHCID 700424-Benzyloxybenzyl chlorideHCID 3157178Tert-butyl 3-oxopiperazine-1-carboxylateHCID 178418339Butyllithium

Product 1

HCID 12638302HCID 12638302, compound

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent3×HCID 8058HexaneSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of dry diisopropylamine (7.7 ml, 5.5 ×10-2 mol) and dry THF (25 ml) under argon at 0° C. is added dropwise a hexane solution of n-butyl-lithium (21.1 ml, 5.5 ×10-2 mol). After stirring 1/2 hour at 0° C. a solution of t-boc-piperazinone (2) (5.0 g, 2.5 ×10-2 mol) and dry THF (125 ml) is added dropwise. The resultant mixture is stirred at 0° C. for 3 hours before a solution of p-benzyloxybenzyl chloride (6.40 g, 0.75 ×10-2 mol) and dry THF (20 ml) is added dropwise via syringe. This mixture is stirred an additional hour at 0° C. before the cooling bath is removed and the reaction allowed to warm to room temperature. After stirring overnight the mixture is quenched into saturated aqueous NH4Cl. The aqueous phase is extracted with Et2O (3 times) and CH2Cl2 (2 times). The ethereal extracts are combined and subsequently washed with saturated aqueous NaCl as are the CH2Cl2 extracts. The ethereal and CH2Cl2 extracts are then combined and dried over Na2SO4. Filtration of the drying agent and evaporation of the filtrate gives 3a as an almost colorless solid which crystallizes from ethyl acetate as colorless prisms 5.2 g (53%), m.p. 145°-147° C.

Workup

  1. additionis added dropwise
  2. additionis added dropwise via syringe
  3. customis removed
  4. temperatureto warm to room temperature
  5. stirringAfter stirring overnight the mixture
  6. customis quenched into saturated aqueous NH4Cl
  7. extractionThe aqueous phase is extracted with Et2O (3 times) and CH2Cl2 (2 times)
  8. washsubsequently washed with saturated aqueous NaCl
  9. dry with materialdried over Na2SO4
  10. filtrationFiltration of the drying agent and evaporation of the filtrate

Sources & evidence

ORD record
ord-610aa20c520c4c51b111dc0faeb7d354
Source dataset
uspto-grants-1984_03
Patent number
US04435571

Reaction notes

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