Diethyl chlorophosphate → HCID 10520788, compound

HRID 1378763Notes

Reaction equation

HRID 1378763 reaction equation
CC(C)([O-])C.[K+].[C:7]([N:11]1[C:20]2[CH:15]([CH2:16][CH2:17][CH2:18][CH:19]=2)[NH:14][C:13](=O)[C:12]1=[O:22])([CH3:10])([CH3:9])[CH3:8].P(Cl)(OCC)(OCC)=O.[F:32][C:33]1[CH:41]=[CH:40][C:36]([CH2:37][N+:38]#[C-:39])=[CH:35][CH:34]=1>C1COCC1>[C:7]([N:11]1[C:20]2[C:15](=[CH:16][CH:17]=[CH:18][CH:19]=2)[N:14]2[CH:39]=[N:38][C:37]([C:36]3[CH:40]=[CH:41][C:33]([F:32])=[CH:34][CH:35]=3)=[C:13]2[C:12]1=[O:22])([CH3:10])([CH3:9])[CH3:8]

Participants

6

Reactant 4

HCID 13139Diethyl chlorophosphateHCID 27589644-FluorobenzylisocyanideHCID 23665647Potassium tert-butoxide2×HCID 86749675HCID 86749675, compound

Product 1

HCID 10520788HCID 10520788, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

Potassium tert-butoxide (1.0M in THF, 24.1 ml) is added to a mixture of 1-(tert-butyl)tetrahydroquinoxalin-2,3-dione (XXXI, 5.00 g) and THF (54.0 ml) at -20°. The mixture is allowed to warm to 0° over 30 min. After cooling to -40°, diethyl chlorophosphate (3.53 ml) is added and the solution is allowed to warm to 20°-25° over 40 min. After cooling to -78°, a solution of 4-fluorobenzyl isocyanide (3.62 g) and THF (5.0 ml) is added. Potassium tert-butoxide (24.1 ml) is then added dropwise over several min. The mixture is stirred at -78° for 30 min and is allowed to warm slowly to 20°-25° over 2 hr. Aqueous workup (ethyl acetate, magnesium sulfate) and purification by flash chromatography eluting with ethyl acetate/hexane (1/2), pooling the appropriate fractions and concentration gives the title compound, mp 135°-137°; IR (mineral oil) 2953, 2925, 2855, 1668, 1498, 1299 and 751 cm-1 ; NMR (CDCl3) 8.31, 8.22, 7.63, 7.55, 7.05-7.35 and 1.76 δ; MS (m/z) 335, 279.

Workup

  1. temperatureto warm to 0° over 30 min
  2. temperatureAfter cooling to -40°
  3. temperatureto warm to 20°-25° over 40 min
  4. temperatureAfter cooling to -78°
  5. temperatureto warm slowly to 20°-25° over 2 hr
  6. customAqueous workup (ethyl acetate, magnesium sulfate) and purification by flash chromatography
  7. washeluting with ethyl acetate/hexane (1/2)
  8. concentrationthe appropriate fractions and concentration

Sources & evidence

ORD record
ord-10cafa66a99a4fcfb97f9d57267777e6
Source dataset
uspto-grants-1997_09
Patent number
US05668282

Reaction notes

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