Hydrochloric Acid → HCID 54267559, compound

HRID 1378568Notes

Reaction equation

HRID 1378568 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[C:8](=[CH:12][C:13]1[CH:18]=[CH:17][C:16]([S:19][CH3:20])=[CH:15][CH:14]=1)C(O)=O.C(N(CC)CC)C.C1(P(N=[N+]=[N-])(C2C=CC=CC=2)=[O:35])C=CC=CC=1.C(O)(C)(C)C.Cl>C1(C)C=CC=CC=1.O>[Cl:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[C:8](=[O:35])[CH2:12][C:13]1[CH:18]=[CH:17][C:16]([S:19][CH3:20])=[CH:15][CH:14]=1

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 6386tert-ButanolHCID 8471TriethylamineHCID 199401P,P-Diphenylphosphinic azideHCID 53753124HCID 53753124, compound

Product 1

HCID 54267559HCID 54267559, compoundYield 90%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 1140TolueneSolvent

Conditions

Temperature
0 °C

Procedure

A solution of the acid from Step 1 (17.88 g, 58.7 mmol) and triethylamine (9.53 g, 94.2 mmol) was dissolved in 50 mL of anhydrous toluene, cooled to 0° C. and treated with diphenylphosphoryl azide (16.46 g, 59.8 mmol). The solution was maintained at 0° C. for 36 minutes and warmed to room temperature for 4 hours. The reaction was poured into water, extracted with ether, dried over magnesium sulfate, and concentrated in vacuo to remove the ether. The remaining toluene solution was heated to 110° C. for 1 hour. Tert-Butyl alcohol (7 mL, 74 mmol) was added to the reaction mixture. After an additional twenty minutes, concentrated hydrochloric acid (5 mL) was cautiously added and the reaction maintained at 90° C. for 16 hours. The solution was concentrated in vacuo and the residue taken up in ethyl acetate, washed with water, sat. aq. NaHCO3, and brine, dried over anhydrous MgSO4, filtered and concentrated in vacuo to provide the ketone as an orange oil (14.62 g, 90%) that was used in the next step without further purification: 1H NMR (CDCl3) 300 MHz 7.40-7.10 (m,8H), 4.20 (s, 2H), 2.46 (s, 3H).

Workup

  1. temperatureThe solution was maintained at 0° C. for 36 minutes
  2. temperaturewarmed to room temperature for 4 hours
  3. extractionextracted with ether
  4. dry with materialdried over magnesium sulfate
  5. concentrationconcentrated in vacuo
  6. customto remove the ether
  7. temperatureThe remaining toluene solution was heated to 110° C. for 1 hour
  8. waitAfter an additional twenty minutes
  9. temperaturethe reaction maintained at 90° C. for 16 hours
  10. concentrationThe solution was concentrated in vacuo
  11. washwashed with water, sat. aq. NaHCO3, and brine
  12. dry with materialdried over anhydrous MgSO4
  13. filtrationfiltered
  14. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-dccd886a848540de84d5a1998a298e47
Source dataset
uspto-grants-1997_09
Patent number
US05668161

Reaction notes

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