Water → HCID 53721501, compound

HRID 1378570Notes

Reaction equation

HRID 1378570 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C:8](=[CH:12][C:13]2[CH:18]=[CH:17][C:16]([S:19][CH3:20])=[CH:15][CH:14]=2)C(O)=O)=[CH:4][CH:3]=1.C(N(CC)CC)C.C1(P(N=[N+]=[N-])(C2C=CC=CC=2)=[O:35])C=CC=CC=1.O>C1(C)C=CC=CC=1>[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C:8](=[O:35])[CH2:12][C:13]2[CH:18]=[CH:17][C:16]([S:19][CH3:20])=[CH:15][CH:14]=2)=[CH:4][CH:3]=1

Participants

6

Reactant 4

HCID 962WaterHCID 8471TriethylamineHCID 199401P,P-Diphenylphosphinic azideHCID 54006809HCID 54006809, compound

Product 1

HCID 53721501HCID 53721501, compoundYield 30%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
0 °C

Procedure

The acid from Step 1 (9.01 g, 29.6 mmol) and triethylamine (3.03 g, 29.9 mmol) were dissolved in 45 mL of anhydrous toluene, cooled to 0° C. and treated with diphenylphosphoryl azide (8.22 g, 29.9 mmol). The solution was maintained at 0° C. for 10 minutes and warmed to room temperature for 2 hours. The reaction was poured into water, extracted with ether, dried over anhydrous MgSO4, and concentrated in vacuo to remove the ether. The remaining toluene solution was heated to 90° C. for 15 minutes. Tert-Butyl alcohol (10 mL) was added to the reaction mixture. After an additional twenty minutes, concentrated hydrochloric acid (8 mL) was cautiously added and the reaction maintained at 90° C. for 15 minutes. The solution was cooled to room temperature and a precipitate formed that was isolated by filtration, washed with ether and air dried to provide the desired ketone as a white solid (2.43 g, 30%): mp 143°-147.5° C. 1H NMR (CDCl3) 300 MHz 8.08 (d, J=8.8 Hz, 2H), 7.55 (d, J=8.5 Hz, 2H), 7.24 (m, 4H), 4.35 (s, 2H), 2.05 (s, 3H). Mass spectrum: M+H=277.

Workup

  1. temperatureThe solution was maintained at 0° C. for 10 minutes
  2. temperaturewarmed to room temperature for 2 hours
  3. extractionextracted with ether
  4. dry with materialdried over anhydrous MgSO4
  5. concentrationconcentrated in vacuo
  6. customto remove the ether
  7. temperatureThe remaining toluene solution was heated to 90° C. for 15 minutes
  8. additionTert-Butyl alcohol (10 mL) was added to the reaction mixture
  9. waitAfter an additional twenty minutes
  10. additionconcentrated hydrochloric acid (8 mL) was cautiously added
  11. temperaturethe reaction maintained at 90° C. for 15 minutes
  12. temperatureThe solution was cooled to room temperature
  13. customa precipitate formed
  14. customthat was isolated by filtration
  15. washwashed with ether and air
  16. customdried

Sources & evidence

ORD record
ord-874363dde44f45939002602200194b7e
Source dataset
uspto-grants-1997_09
Patent number
US05668161

Reaction notes

Loading…