Hydrochloric Acid → HCID 14883920, compound

HRID 2373019Notes

Reaction equation

HRID 2373019 reaction equation
C(OC)(=O)[CH2:2][C:3]([CH3:5])=[O:4].[OH-].[Na+].Cl.C([O-])=O.[Na+].[CH3:16][C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][C:18]=1[S:23][CH:24]([CH3:28])[CH2:25][CH:26]=[O:27]>O.[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.C1(C)C=CC=CC=1>[OH:27][CH:26]([CH2:25][CH:24]([S:23][C:18]1[CH:19]=[CH:20][CH:21]=[CH:22][C:17]=1[CH3:16])[CH3:28])[CH2:2][C:3](=[O:4])[CH3:5]

Participants

9

Reactant 5

HCID 313Hydrochloric Acid2×HCID 7757Methyl acetoacetateHCID 14798Sodium HydroxideHCID 2723810Sodium FormateHCID 19902773HCID 19902773, compound

Product 1

HCID 14883920HCID 14883920, compoundYield 85.3%

Reagents, catalysts & solvents 3

HCID 74236Tetrabutylammonium BromideCatalystHCID 962WaterSolventHCID 1140TolueneSolvent

Procedure

9.86 Grams of methyl acetoacetate was dissolved in 15 ml of water, and 12.67 g of a 30% aqueous sodium hydroxide solution was added thereto by drops while cooling the mixture to 25° C. or less. After having been stirred at 30°-35° C. for 3 hours, the mixture was adjusted to pH 7.0 with a concentrated aqueous hydrochloric acid solution. Thereafter, 0.68 g of sodium formate and 2.42 g of tetrabutylammonium bromide were added thereto. Thereafter a concentrated aqueous hydrochloric acid solution was added to the resulting mixture so that the mixture had a pH of 6.8. Further, 27.2 g of a toluene solution containing 35.1% of 3-(2-methylphenylthio)butanal was added thereto and stirred at 45°-50° C. for 9 hours. The organic layer separated from the mixture was washed with a 5% aqueous acetic acid solution and then with a saturated aqueous sodium chloride solution. Thereafter the layer was dried over anhydrous magnesium sulfate. Removing the solvent from the layer under reduced pressure gave 12.44 g of crude 4-hydroxy-6-(2-methylphenylthio)-2-heptanone (purity: 85.1%, yield: 85.3%). A purified product was obtained by column chromatography. The purified product had an nD21 of 1.5477.

Workup

  1. temperatureby drops while cooling the mixture to 25° C. or less
  2. additionwas added
  3. stirringstirred at 45°-50° C. for 9 hours
  4. customThe organic layer separated from the mixture
  5. washwas washed with a 5% aqueous acetic acid solution
  6. dry with materialThereafter the layer was dried over anhydrous magnesium sulfate
  7. customRemoving the solvent from the layer under reduced pressure

Sources & evidence

ORD record
ord-e0b2af4e52514e439a030dd56d398e0e
Source dataset
uspto-grants-1992_03
Patent number
US05101076

Reaction notes

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