Hydrochloric Acid → 2-(3-Hydroxypropyl)-4,6,7-trimethyl-2H-1,3-benzoxathiol-5-ol

HRID 2350988Notes

Reaction equation

HRID 2350988 reaction equation
[H-].[Al+3].[Li+].[H-].[H-].[H-].COC(CCC([O:15][C:16]1[C:17]([CH3:33])=[C:18]([CH3:32])[C:19]2[O:23][CH:22]([CH2:24][CH2:25][C:26](OC)=[O:27])[S:21][C:20]=2[C:30]=1[CH3:31])=O)=O.C(OCC)(=O)C.Cl>O1CCCC1>[OH:15][C:16]1[C:17]([CH3:33])=[C:18]([CH3:32])[C:19]2[O:23][CH:22]([CH2:24][CH2:25][CH2:26][OH:27])[S:21][C:20]=2[C:30]=1[CH3:31]

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 8857Ethyl AcetateHCID 14802162Methyl 3-[5-(3-methoxycarbonylpropionyloxy)-4,6,7-trimethyl-1,3-benzoxathiole-2-yl]propionateHCID 21226445Aluminium lithium hydride

Product 1

HCID 1275772-(3-Hydroxypropyl)-4,6,7-trimethyl-2H-1,3-benzoxathiol-5-ol

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent4×

Procedure

10 g of lithium aluminum hydride were suspended in 500 ml of dried tetrahydrofuran, and then a solution of 32.0 g of methyl 3-[5-(3-methoxycarbonylpropionyloxy)-4,6,7-trimethyl-1,3-benzoxathiole-2-yl)propionate (prepared as described in Example 31) in 160 ml of tetrahydrofuran was added dropwise with stirring and ice-cooling and under a nitrogen stream to the suspension. After the dropwise addition, the reaction mixture was stirred for 1 hour at room temperature and then refluxed for 4 hours. The reaction mixture was then cooled with ice-water, after which a mixture of 10 g of ethyl acetate and 50 ml of tetrahydrofuran was added dropwise, and the mixture was stirred for 1 hour at room temperature, after which aqueous tetrahydrofuran was added dropwise. The reaction mixture was then poured into ice-water. The pH of the mixture was adjusted to an acid value by the addition of a 10% w/v aqueous solution of hydrochloric acid, and the precipitating product was extracted with ethyl acetate. The extract was washed with water and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure. The resulting crude product was subjected to silica gel column chromatography and the title compound, melting at 116.5°-117° C., was obtained from the fraction eluted with a 9:1 by volume mixture of benzene and ethyl acetate.

Workup

  1. temperatureice-cooling and under a nitrogen stream to the suspension
  2. additionAfter the dropwise addition
  3. stirringthe reaction mixture was stirred for 1 hour at room temperature
  4. temperaturerefluxed for 4 hours
  5. additionwas added dropwise
  6. stirringthe mixture was stirred for 1 hour at room temperature
  7. extractionthe precipitating product was extracted with ethyl acetate
  8. washThe extract was washed with water
  9. dry with materialdried over anhydrous sodium sulfate
  10. distillationThe solvent was distilled off under reduced pressure

Sources & evidence

ORD record
ord-08af5d1e1d104a74a099bb5cdaab5d4a
Source dataset
uspto-grants-1989_10
Patent number
US04871762

Reaction notes

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