Hydroxyamine hydrochloride → HCID 58388227, compound

HRID 1879101Notes

Reaction equation

HRID 1879101 reaction equation
[CH2:1]([C:8]1([C:17]#[C:18][Si:19]([CH3:22])([CH3:21])[CH3:20])[CH2:13][C:12](=[CH:14]O)[C:11](=[O:16])[CH:10]=[CH:9]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.Cl.[NH2:24]O>C(O)C.O>[CH2:1]([C:8]1([C:17]#[C:18][Si:19]([CH3:22])([CH3:21])[CH3:20])[CH2:13][C:12]2[CH:14]=[N:24][O:16][C:11]=2[CH:10]=[CH:9]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

5

Reactant 2

HCID 443297Hydroxyamine hydrochlorideHCID 67113927HCID 67113927, compound

Product 1

HCID 58388227HCID 58388227, compoundYield 22.4%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 962WaterSolvent2×

Conditions

Temperature
120 °C

Procedure

Under a nitrogen atmosphere a solution of 4-benzyl-6-hydroxymethylene-4-((trimethylsilyl)ethynyl)cyclohex-2-enone (76 mg, 0.245 mmol) in ethanol (6.13 mL) was added to a stirred solution of hydroxylamine hydrochloride (177.6 mg, 2.53 mmol, 10.3 eq) in water (256 μL) at room temperature. The mixture was heated to 120° C. and stirred at reflux for 1 hour. After heating, the reaction mixture was diluted with water (10 mL) and the aqueous layer was extracted with dichloromethane/ethyl ether (1:2, 3×10 mL). The organic layers were then combined and washed with saturated aqueous sodium bicarbonate solution (1×10 mL) and brine (2×10 mL), dried over magnesium sulfate, filtered, and concentrated in vacuo to give the crude product as a yellow-brown oil (76.4 mg). The crude was purified first by dissolving the product in petroleum ether/ethyl ether (5:1) and decanting the soluble portion from the insoluble solid. The insoluble material was washed with petroleum ether/ethyl ether (5:1) several times and the resulting mother liquor was found by thin layer chromatography (TLC) to contain the desired compound. The mother liquor was purified by flash column chromatography [petroleum ether-ethyl ether (5:1)] to give 32 (17.1 mg, 0.055 mmol, 22%) as a colorless oil: 1H NMR (CDCl3) δ 8.09 (1H, s), 7.32-7.22 (5H, m), 6.56 (1H, dd, J=1, 10 Hz), 6.0 (1H, d, J=10 Hz), 2.96 (1H, d? J=16 Hz), 2.94 (1H, d, J=13 Hz), 2.83 (1H, d, J=16 Hz), 2.73 (1H, d, J=13 Hz), 0.16 (9H, s); 13C NMR (CDCl3) δ 164.4, 148.7, 139.3, 135.0, 131.0, 128.0, 127.1, 114.4, 109.1, 88.4, 44.2, 39.2, 30.3, 0.13. MS (ESI+) m/z 308.1 [M+H]+, HRMS (ESI+) calcd for C19H21NOSi+H 308.1471. found 308.1467.

Workup

  1. temperatureat reflux for 1 hour
  2. temperatureAfter heating
  3. extractionthe aqueous layer was extracted with dichloromethane/ethyl ether (1:2, 3×10 mL)
  4. washwashed with saturated aqueous sodium bicarbonate solution (1×10 mL) and brine (2×10 mL)
  5. dry with materialdried over magnesium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. customto give the crude product as a yellow-brown oil (76.4 mg)
  9. customThe crude was purified first
  10. dissolutionby dissolving the product in petroleum ether/ethyl ether (5:1)
  11. customdecanting the soluble portion from the insoluble solid
  12. washThe insoluble material was washed with petroleum ether/ethyl ether (5:1) several times
  13. customThe mother liquor was purified by flash column chromatography [petroleum ether-ethyl ether (5:1)]

Sources & evidence

ORD record
ord-6c16d29ee28e47a8a2af47874620ee76
Source dataset
uspto-grants-2012_11
Patent number
US08314137B2

Reaction notes

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