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Ethyl 2-methyl-2-(6-methyl-5-phenyl-2,3-dihydro-4-oxo-4H-1,3-oxazin-3-yl)-propionate → 2-(2,3-dihydro-6-methyl-4-oxo-5-phenyl-4H-1,3-oxazin-3-yl)-2-methylpropionaldehyde

HRID 1274876
Notes
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Reaction equation

HRID 1274876 reaction equation
[CH3:1][C:2]1[O:7][CH2:6][N:5]([C:8]([CH3:15])([CH3:14])[C:9](OCC)=[O:10])[C:4](=[O:16])[C:3]=1[C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1.[H-].[Al+3].[Li+].[H-].[H-].[H-]>O1CCCC1.CCOCC.[Cl-].[Na+].O>[CH3:1][C:2]1[O:7][CH2:6][N:5]([C:8]([CH3:14])([CH3:15])[CH:9]=[O:10])[C:4](=[O:16])[C:3]=1[C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

6

Reactant 2

HCID 10968683Ethyl 2-methyl-2-(6-methyl-5-phenyl-2,3-dihydro-4-oxo-4H-1,3-oxazin-3-yl)-propionateHCID 21226445Aluminium lithium hydride

Product 1

HCID 221182842-(2,3-dihydro-6-methyl-4-oxo-5-phenyl-4H-1,3-oxazin-3-yl)-2-methylpropionaldehydeYield 61.2%

Reagents, catalysts & solvents 3

HCID 3283Diethyl EtherSolvent2×
HCID 8028
Tetrahydrofuran
Solvent
HCID 57417360Sodium chloride; waterSolvent

Conditions

Temperature
-40 °C

Procedure

A solution of ethyl 2-(2,3-dihydro-6-methyl-4-oxo-5-phenyl-4H-1,3-oxazin-3-yl)-2-methylpropanoate (43 g) in tetrahydrofuran was added to lithium aluminium hydride (220 ml of a 1M solution in ether) with stirring at -40° C. After 1 hour the solution was cooled to -70° C., diluted with ether, and treated with brine via dropwise addition, initially at -70° C. and then at -30° C. After warning to room temperature the organic layer was dried (magnesium sulphate), evaporated and the residue purified by dry column chromatography on silica gel eluting with dichloromethane to give 2-(2,3-dihydro-6-methyl-4-oxo-5-phenyl-4H-1,3-oxazin-3-yl)-2-methylpropionaldehyde as a cream solid (22.5 g), NMR 1.35(s,6H), 1.95(s,3H), 5.25(s,2H), 7.22-7.38(m,5H), 9.42(s,1H).

Workup

  1. temperatureAfter 1 hour the solution was cooled to -70° C.
  2. customat -30° C
  3. customAfter warning to room temperature
  4. dry with materialwas dried (magnesium sulphate)
  5. customevaporated
  6. customthe residue purified
  7. dry with materialby dry column chromatography on silica gel eluting with dichloromethane

Sources & evidence

ORD record
ord-45e166af6d364581ad0e1ed6a164f470
Source dataset
uspto-grants-2000_12
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US06159902

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes