Diethyl chlorophosphate → HCID 44572352, compound

HRID 1111632Notes

Reaction equation

HRID 1111632 reaction equation
[I:1][C:2]1[CH:3]=[CH:4][C:5]2[NH:11][C:10](=O)[CH2:9][N:8]=[C:7]([C:13]3[CH:18]=[CH:17][CH:16]=[CH:15][C:14]=3[F:19])[C:6]=2[CH:20]=1.CC(C)([O-])C.[K+].P(Cl)(OCC)(OCC)=O.[N+:36]([CH2:38][C:39]([O:41][CH2:42][CH3:43])=[O:40])#[C-:37]>CN(C)C=O>[I:1][C:2]1[CH:3]=[CH:4][C:5]2[N:11]3[CH:37]=[N:36][C:38]([C:39]([O:41][CH2:42][CH3:43])=[O:40])=[C:10]3[CH2:9][N:8]=[C:7]([C:13]3[CH:18]=[CH:17][CH:16]=[CH:15][C:14]=3[F:19])[C:6]=2[CH:20]=1

Participants

6

Reactant 4

HCID 13139Diethyl chlorophosphateHCID 533707Ethyl isocyanoacetateHCID 3082318Ro 7-9749HCID 23665647Potassium tert-butoxide2×

Product 1

HCID 44572352HCID 44572352, compound

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Procedure

A stirred solution of 3.8 g (0.01 mol) of 7-iodo-1,3-dihydro-5-(2-fluorophenyl)-2H-1,4-benzodiazepine-2-one in 50 ml of dimethyl formamide was cooled in an ice bath under an atmosphere of nitrogen. Potassium t-butoxide, 1.29 g (0.0115 mol) was added and after stirring for 5 minutes, 2.59 g (0.015 mol) of diethyl chlorophosphate was added and the stirring was continued for 5 minutes. A mixture of 2.26 g (0.02 mol) of ethyl isocyanoacetate in 50 ml of dimethylformamide that had been treated with 2.24 g (0.02 mol) of potassium t-butoxide just prior to the addition, was then added. After 5 minutes the ice bath was removed and the stirring was continued for 3 hours. The mixture was acidified with 2 ml of glacial acetic acid, diluted with 200 ml of saturated sodium bicarbonate solution and extracted with two 125 ml portions of toluene which were dried and evaporated. The residue was crystallized from ethyl acetate. For analysis, the crude product was chromatographed over silica gel using methylene chloride/ethyl acetate 1:1 (v/v) and then crystallized from ethyl acetate/hexane to give pure product with mp 200°-202°.

Workup

  1. waitthe stirring was continued for 5 minutes
  2. additionto the addition
  3. additionwas then added
  4. customAfter 5 minutes the ice bath was removed
  5. waitthe stirring was continued for 3 hours
  6. additiondiluted with 200 ml of saturated sodium bicarbonate solution
  7. extractionextracted with two 125 ml portions of toluene which
  8. customwere dried
  9. customevaporated
  10. customThe residue was crystallized from ethyl acetate
  11. customFor analysis, the crude product was chromatographed over silica gel
  12. customcrystallized from ethyl acetate/hexane
  13. customto give pure product with mp 200°-202°

Sources & evidence

ORD record
ord-af4f57c53ebf47a2ba77bbea8a9d81e1
Source dataset
uspto-grants-1978_10
Patent number
US04118386

Reaction notes

Loading…