Triethylamine → HCID 54268063, compound

HRID 1535031Notes

Reaction equation

HRID 1535031 reaction equation
[C:1]([C:5]1[CH:6]=[C:7]([CH2:16][C:17]([OH:19])=[S:18])[CH:8]=[C:9]([C:12]([CH3:15])([CH3:14])[CH3:13])[C:10]=1[OH:11])([CH3:4])([CH3:3])[CH3:2].C(N(CC)CC)C.C(Cl)(=O)O[CH2:29][CH:30]([CH3:32])[CH3:31].Cl.CNO>ClCCl>[C:12]([C:9]1[CH:8]=[C:7]([CH2:16][C:17]([O:19][CH2:29][CH:30]([CH3:32])[CH3:31])=[S:18])[CH:6]=[C:5]([C:1]([CH3:4])([CH3:2])[CH3:3])[C:10]=1[OH:11])([CH3:13])([CH3:15])[CH3:14]

Participants

6

Reactant 4

HCID 8471Triethylamine2×HCID 62365Isobutyl chloroformateHCID 77906N-methylhydroxylamine hydrochlorideHCID 178440977HCID 178440977, compound

Product 1

HCID 54268063HCID 54268063, compoundYield 55%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent3×

Procedure

To 20 ml of a solution of 1.48 g (5 mmol) of 2-(3,5-di-tert-butyl-4-hydroxyphenyl)thioacetic acid (II1) in dichloromethane was added 555 mg (5.5 mmol) of triethylamine and 5 ml of a solution of 750 mg (5.5 mmol) of isobutyl chlorocarbonate in dichloromethane was added dropwise to the resulting mixture over an about 5 minutes period under cooling at -45° C.±5° C. and stirring. The mixture was stirred for 1 hour at the same temperature. To the reaction mixture was added 450 mg (5.5 mmol) of N-methyl hydroxylamine hydrochloride and then added dropwise 5 ml of a solution of 1.21 g (12 mmol) of triethylamine in dichloromethane. The mixture was stirred at the same temperature for 30 minutes and then additional 2 hours after removal of the cooling bath. The reaction mixture was poured into 50 ml of a cold 5% aqueous solution of hydrochloric acid and extracted with 50 ml of dichloromethane. The extract was washed twice with 50 ml of water, dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was chromatographed on silica gel. The fractions eluted with a mixture of ethyl acetate-n-hexane (2:1) were collected. From the first fraction, 892 mg of isobutyl 2-(3,5-di-tert-butyl-4-hydroxyphenyl)thioacetate was obtained as colorless oil in 55% yield and the aimed compound (I1) obtained from the second fraction was recrystallized from a mixture of ether-n-hexane (1:1) to give 350 mg of colorless prismatic crystals in 21.5% yield. Mp. 84°-85° C.

Workup

  1. additionwas added dropwise to the resulting mixture over an about 5 minutes period
  2. temperatureunder cooling at -45° C.±5° C.
  3. stirringThe mixture was stirred for 1 hour at the same temperature
  4. stirringThe mixture was stirred at the same temperature for 30 minutes
  5. customadditional 2 hours after removal of the cooling bath
  6. additionThe reaction mixture was poured into 50 ml of a cold 5% aqueous solution of hydrochloric acid
  7. extractionextracted with 50 ml of dichloromethane
  8. washThe extract was washed twice with 50 ml of water
  9. dry with materialdried over anhydrous sodium sulfate
  10. concentrationconcentrated under reduced pressure
  11. customThe residue was chromatographed on silica gel
  12. washThe fractions eluted with a mixture of ethyl acetate-n-hexane (2:1)
  13. customwere collected

Sources & evidence

ORD record
ord-11398a00c8be4a00a8468e1d4f5f67d1
Source dataset
uspto-grants-1992_02
Patent number
US05091569

Reaction notes

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