Diethyl chlorophosphate → HCID 19896721, compound

HRID 1196860Notes

Reaction equation

HRID 1196860 reaction equation
[C:1]([N:5]1[C:14]2[C:9](=[CH:10][CH:11]=[CH:12][CH:13]=2)[NH:8][C:7](=O)[C:6]1=[O:16])([CH3:4])([CH3:3])[CH3:2].[H-].[Na+].P(Cl)(OCC)(OCC)=O.[N+:28]([CH2:30][C:31]1[O:35][N:34]=[C:33]([CH3:36])[CH:32]=1)#[C-:29].CC(C)([O-])C.[K+]>CN(C)C=O.C(O)(=O)C>[C:1]([N:5]1[C:14]2[C:9](=[CH:10][CH:11]=[CH:12][CH:13]=2)[N:8]2[CH:29]=[N:28][C:30]([C:31]3[O:35][N:34]=[C:33]([CH3:36])[CH:32]=3)=[C:7]2[C:6]1=[O:16])([CH3:4])([CH3:3])[CH3:2]

Participants

8

Reactant 5

HCID 13139Diethyl chlorophosphateHCID 24758Sodium hydrideHCID 106088551-Tert-butyl-1,2,3,4-tetrahydro-2,3-dioxoquinoxalineHCID 19896738HCID 19896738, compoundHCID 23665647Potassium tert-butoxide

Product 1

HCID 19896721HCID 19896721, compound

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 6228DimethylformamideSolvent2×

Conditions

Temperature
-20 °C

Procedure

To a stirred solution of 1-tert-butyl-1,2,3,4-tetrahydro-2,3-dioxoquinoxaline (6.54 g, 30 mmol) in dry dimethylformamide (DMF) (30 ml) under nitrogen was added sodium hydride (80% in oil, 9.6 g, 32 mmol). After stirring for 10 min. the solution was cooled to -20° C. and diethyl chlorophosphate (5.6 ml, 39 mmol) was added. The mixture was allowed to reach room temperature and then cooled to -30° C., whereafter 5-isocyanomethyl-3-methylisoxazole (3.0 g, 25 mmol) and finally a solution of potassium tert-butoxide (3.0 g, 26 mmol) in dry DMF (30 ml) was added keeping the temperature below -20° C. The reaction mixture was warmed to room temperature, acidified with acetic acid (1 ml) and evaporated in vacuo. The residue was triturated with water and ether, and the resulting precipitate was filtered off and partitioned between 0.5 M aqueous sodium hydroxide (50 ml) and dichloromethane (50 ml). The organic layer was filtered through celite, dried, and evaporated to give the title compound, m.p. 395° C. (Compound 17).

Workup

  1. customto reach room temperature
  2. customthe temperature below -20° C
  3. temperatureThe reaction mixture was warmed to room temperature
  4. customevaporated in vacuo
  5. customThe residue was triturated with water and ether
  6. filtrationthe resulting precipitate was filtered off
  7. custompartitioned between 0.5 M aqueous sodium hydroxide (50 ml) and dichloromethane (50 ml)
  8. filtrationThe organic layer was filtered through celite
  9. customdried
  10. customevaporated

Sources & evidence

ORD record
ord-6176151ec8dd45938ad03fa9d82e3ecb
Source dataset
uspto-grants-1992_05
Patent number
US05116841

Reaction notes

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