Diisopropylamine → Ammonia

HRID 355430Notes

Reaction equation

HRID 355430 reaction equation
C([Li])CCC.C([NH:9]C(C)C)(C)C.C([N-]C(C)C)(C)C.[Li+].[C:21]([C:24]1[CH:37]=[CH:36][C:35]2[S:34][C:33]3[C:28](=[CH:29][CH:30]=[CH:31][CH:32]=3)[NH:27][C:26]=2[CH:25]=1)(=[O:23])[CH3:22].[N:38]12[CH2:45][CH2:44][CH:41]([CH2:42][CH2:43]1)[C:40](=[O:46])[CH2:39]2>C(Cl)(Cl)Cl.CO.O.C1COCC1.CCCCCC>[NH3:9].[CH:25]1[C:26]2[NH:27][C:28]3[C:33](=[CH:32][CH:31]=[CH:30][CH:29]=3)[S:34][C:35]=2[CH:36]=[CH:37][C:24]=1[C:21]([CH2:22][C:40]1([OH:46])[CH:41]2[CH2:44][CH2:45][N:38]([CH2:43][CH2:42]2)[CH2:39]1)=[O:23]

Participants

12

Reactant 5

HCID 7912DiisopropylamineHCID 195073-QuinuclidinoneHCID 81131Methyl phenothiazin-2-yl ketoneHCID 2724682Lithium diisopropylamideHCID 178418339Butyllithium

Product 2

HCID 222AmmoniaYield 29%HCID 18942260HCID 18942260, compoundYield 7%

Reagents, catalysts & solvents 5

HCID 887MethanolSolventHCID 962WaterSolventHCID 6212ChloroformSolventHCID 8028TetrahydrofuranSolvent3×HCID 8058HexaneSolvent

Procedure

In an atmosphere of argon, a hexane solution of n-butyl lithium (1.71M, 6.1 ml, 10.5 mmol) was added at -78° C. to a THF (10 ml) solution of diisopropylamine (1.54 ml, 11 mmol), and the mixture was stirred for 40 minutes. To the resulting solution of lithium diisopropylamide was added a THF (8 ml) solution of 2-acetylphenothiazine (1.21 g, 5.0 mmol). The mixture was stirred for 30 minutes, a THF (3 ml) solution of 3-quinuclidinone (626 mg, 5.0 mmol) was added, and the mixture was stirred for 30 minutes. Water was added to the reaction mixture and the reaction product was extracted with chloroform. The extract was washed with saturated sodium chloride aqueous solution, dried over anhydrous magnesium sulfate, and then concentrated under a reduced pressure. The resulting residue was purified by silica gel column chromatography (eluent; 29% aqueous ammonia:methanol:chloroform=0.8:8:92 then 2:20:80), to give the title compound (127 mg, 0.35 mmol, 7%) as yellow foam.

Workup

  1. stirringThe mixture was stirred for 30 minutes
  2. stirringthe mixture was stirred for 30 minutes
  3. extractionthe reaction product was extracted with chloroform
  4. washThe extract was washed with saturated sodium chloride aqueous solution
  5. dry with materialdried over anhydrous magnesium sulfate
  6. concentrationconcentrated under a reduced pressure
  7. customThe resulting residue was purified by silica gel column chromatography (eluent

Sources & evidence

ORD record
ord-5d45b6d7cd664394bae14a95d81d6963
Source dataset
uspto-grants-1998_11
Patent number
US05830902

Reaction notes

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