Sodium Acetate → HCID 86713145, compound

HRID 713623Notes

Reaction equation

HRID 713623 reaction equation
[OH:1][C:2]1([C:12]#[C:13]/[C:14](/[C:21]([F:24])([F:23])[F:22])=[CH:15]\[C:16]([O:18][CH2:19][CH3:20])=[O:17])[C:7]([CH3:9])([CH3:8])[CH2:6][C:5](=O)[CH:4]=[C:3]1[CH3:11].Cl.[CH3:26][O:27][NH2:28].C([O-])(=O)C.[Na+]>C(O)C.O>[OH:1][C:2]1([C:12]#[C:13]/[C:14](/[C:21]([F:24])([F:22])[F:23])=[CH:15]\[C:16]([O:18][CH2:19][CH3:20])=[O:17])[C:7]([CH3:8])([CH3:9])[CH2:6][C:5](=[N:28][O:27][CH3:26])[CH:4]=[C:3]1[CH3:11]

Participants

6

Reactant 3

HCID 517045Sodium AcetateHCID 521874O-Methylhydroxylamine hydrochlorideHCID 86713140HCID 86713140, compound

Product 1

HCID 86713145HCID 86713145, compoundYield 63%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 962WaterSolvent

Conditions

Temperature
60 °C

Procedure

Ethyl (2E)-5-(1-hydroxy-2,6,6-trimethyl-4-oxocyclohex-2-en-1-yl)-3-(trifluoromethyl)pent-2-en-4-ynoate (60 mg, 0.17 mmol), O-methylhydroxylamine hydrochloride (17 mg, 0.21 mmol) and sodium acetate (30 mg, 0.37 mmol) were dissolved in a 1:1 mixture of ethanol and water (4 ml) and then stirred at a temperature of 60° C. for 4 h. After cooling to room temperature, ethanol was removed under reduced pressure and the aqueous phase was extracted repeatedly with dichloromethane. The combined organic phases were dried over magnesium sulfate, filtered and concentrated under reduced pressure. By column chromatography purification of the resulting crude product (ethyl acetate/heptane gradient), ethyl (2E)-5-[1-hydroxy-4-(methoxyimino)-2,6,6-trimethylcyclohex-2-en-1-yl]-3-(trifluoromethyl)pent-2-en-4-ynoate (40 mg, 58% of theory) was obtained in the form of a colorless solid. 1H-NMR (400 MHz, CDCl3 δ, ppm) 6.65/6.63 (s, 1H), 6.00/5.94 (s, 1H), 4.27 (q, 2H), 3.89/3.86 (s, 3H), 2.62/2.56 (br. s, 1H, OH), 2.46 (d, 1H), 2.39 (m, 1H), 2.08/2.05 (s, 3H), 1.31 (t, 3H), 1.18 (s, 3H), 1.11 (s, 3H).

Workup

  1. temperatureAfter cooling to room temperature
  2. customethanol was removed under reduced pressure
  3. extractionthe aqueous phase was extracted repeatedly with dichloromethane
  4. dry with materialThe combined organic phases were dried over magnesium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure
  7. customBy column chromatography purification of the resulting crude product (ethyl acetate/heptane gradient)

Sources & evidence

ORD record
ord-35679f346148419aa09c69b9b57202c1
Source dataset
uspto-grants-2015_11
Patent number
US09185914B2

Reaction notes

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