Diisopropylamine → 5-benzyloxy-2-[3-(4-cyanophenoxy)-3-methyl-2-oxobutyl]pyridine N-oxide

HRID 1073940Notes

Reaction equation

HRID 1073940 reaction equation
C([Li])CCC.C(NC(C)C)(C)C.[CH2:13]([O:20][C:21]1[CH:22]=[CH:23][C:24]([CH3:28])=[N+:25]([O-:27])[CH:26]=1)[C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1.[C:29]([C:31]1[CH:45]=[CH:44][C:34]([O:35][C:36]([CH3:43])([CH3:42])[C:37](OCC)=[O:38])=[CH:33][CH:32]=1)#[N:30]>CCCCCC.O1CCCC1.C(OCC)(=O)C>[CH2:13]([O:20][C:21]1[CH:22]=[CH:23][C:24]([CH2:28][C:37](=[O:38])[C:36]([O:35][C:34]2[CH:44]=[CH:45][C:31]([C:29]#[N:30])=[CH:32][CH:33]=2)([CH3:43])[CH3:42])=[N+:25]([O-:27])[CH:26]=1)[C:14]1[CH:15]=[CH:16][CH:17]=[CH:18][CH:19]=1

Participants

8

Reactant 4

HCID 7912DiisopropylamineHCID 205808Propanoic acid, 2-(4-cyanophenoxy)-2-methyl-, ethyl esterHCID 123972525-Benzyloxy-2-methylpyridine 1-oxideHCID 178418339Butyllithium

Product 1

HCID 543932385-benzyloxy-2-[3-(4-cyanophenoxy)-3-methyl-2-oxobutyl]pyridine N-oxideYield 23%

Reagents, catalysts & solvents 3

HCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
-78 °C

Procedure

5 ml of a 1.2M solution of butyllithium in n-hexane were added to a solution of 0.6 g of diisopropylamine in 10 ml of tetrahydrofuran while stirring at -78° C. under a nitrogen atmosphere. The solution was stirred for a further 15 minutes and then 1.07 g of 5-benzyloxy-2-methylpyridine N-oxide in 10 ml of tetrahydrofuran were added. The mixture was allowed to warm to 20° C. stirred for 30 minutes and then cooled to -78° C. 1.16 g of ethyl (4-cyanophenoxy)-2-methylpropionate were added and the mixture was then allowed to warm to 20° C. and was stirred for 16 hours. The mixture was diluted with 50 ml of ethyl acetate and washed in succession with water and sodium chloride solution The organic phase was evaporated and the residue was chromatographed on silica gel using dichloromethane/methanol (94:4) for the elution to give 0.46 g of 5-benzyloxy-2-[3-(4-cyanophenoxy)-3-methyl-2oxobutyl]pyridine N-oxide in the form of a pale yellow

Workup

  1. stirringThe solution was stirred for a further 15 minutes
  2. temperatureto warm to 20° C.
  3. stirringstirred for 30 minutes
  4. temperaturecooled to -78° C
  5. temperatureto warm to 20° C.
  6. stirringwas stirred for 16 hours
  7. washwashed in succession with water and sodium chloride solution The organic phase
  8. customwas evaporated
  9. customthe residue was chromatographed on silica gel
  10. washfor the elution

Sources & evidence

ORD record
ord-a10de9ef5adc4211b38c9594e868a507
Source dataset
uspto-grants-1990_11
Patent number
US04971982

Reaction notes

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