Water → HCID 135973978, compound

HRID 703357Notes

Reaction equation

HRID 703357 reaction equation
[C:1]([C:5]1[C:6](=[O:29])[CH2:7][CH:8]([C:12]2[CH:17]=[CH:16][CH:15]=[C:14]([O:18][C:19]3[CH:24]=[CH:23][C:22]([S:25]([CH3:28])(=[O:27])=[O:26])=[CH:21][N:20]=3)[CH:13]=2)[CH2:9][C:10]=1[OH:11])(=O)[CH2:2][CH3:3].Cl.[CH2:31]([O:33][NH2:34])[CH3:32].C([O-])(=O)C.[Na+].O>C(Cl)Cl.C(O)C.C(OCC)C>[CH2:31]([O:33][N:34]=[C:1]([C:5]1[C:6](=[O:29])[CH2:7][CH:8]([C:12]2[CH:17]=[CH:16][CH:15]=[C:14]([O:18][C:19]3[CH:24]=[CH:23][C:22]([S:25]([CH3:28])(=[O:27])=[O:26])=[CH:21][N:20]=3)[CH:13]=2)[CH2:9][C:10]=1[OH:11])[CH2:2][CH3:3])[CH3:32]

Participants

8

Reactant 4

HCID 962WaterHCID 76850O-ethylhydroxylamine hydrochlorideHCID 517045Sodium AcetateHCID 178458860HCID 178458860, compound

Product 1

HCID 135973978HCID 135973978, compound

Reagents, catalysts & solvents 3

HCID 702EthanolSolventHCID 3283Diethyl EtherSolventHCID 6344DichloromethaneSolvent

Procedure

A partially dissolved mixture of 64.5 g (0.155 mol) of 2-propionyl-3-hydroxy-5-(3-(5-(methylsulfonyl)-2-pyridyloxy)phenyl)cyclohex-2-en-1-one in 200 mL of CH2Cl2 and 700 mL of absolute ethanol was treated with 17.7 g (0.186 mol) of ethoxyamine hydrochloride and 15.3 g (0.186 mol) of sodium acetate. The resulting slurry was stirred for 20 hours at room temperature. The slurry was poured into 3 liters (L) of water and the CH2Cl2 layer was thoroughly removed. The CH2Cl2 layer was dried over MgSO4, filtered and the CH2Cl2 evaporated off to yield a pale oily residue. The residue was passed through a short column of silica gel (about 300 g), eluting with CH2Cl2. Evaporation of the initial 2 L of eluent afforded a pale oil. This oil was dissolved in 400 mL of diethyl ether which briefly formed a clear solution before precipitating the product as a white solid. The product was filtered and dried in vacuo to afford 63.5 g (89 percent of theoretical) of the above indicated product as a white crystalline solid. The product melted at 125.5°-128° C.; 1H NMR (CDCl3): δ1.17 (t, 3H, --N=CCH2CH3), 1.32 (t, 3H, --OCH2CH3), 2.68-3.62 (m includes s at 3.10, 10H, --N=CCH2 --, ring CH2CHCH2 --, CH3SO2 --), 4.18 (q, 2H, --OCH2 --), 7.05-7.58 (m, 5H, ArH's), 8.22 (dd, 1H, ArH), 8.78 (d, 1H, ArH), 15.1 (br s, 1H, enol H) (Compound 3).

Workup

  1. customthe CH2Cl2 layer was thoroughly removed
  2. dry with materialThe CH2Cl2 layer was dried over MgSO4
  3. filtrationfiltered
  4. customthe CH2Cl2 evaporated off
  5. customto yield a pale oily residue
  6. washeluting with CH2Cl2
  7. customEvaporation of the initial 2 L of eluent
  8. customafforded a pale oil
  9. custombriefly formed a clear solution
  10. custombefore precipitating the product as a white solid
  11. filtrationThe product was filtered
  12. customdried in vacuo

Sources & evidence

ORD record
ord-ae80bf85342848c980baca0f221385f3
Source dataset
uspto-grants-1991_01
Patent number
US04983211

Reaction notes

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