Dimethylformamide → 3-[4,4-Dimethylthiochroman-6-yl]-3-chloro-2-propene-1-al

HRID 2219797Notes

Reaction equation

HRID 2219797 reaction equation
[C:1]([C:4]1[CH:5]=[C:6]2[C:11](=[CH:12][CH:13]=1)[S:10][CH2:9][CH2:8][C:7]2([CH3:15])[CH3:14])(=O)[CH3:2].CN(C)[CH:18]=[O:19].P(Cl)(Cl)([Cl:23])=O.C([O-])(=O)C.[Na+]>O>[CH3:14][C:7]1([CH3:15])[C:6]2[C:11](=[CH:12][CH:13]=[C:4]([C:1]([Cl:23])=[CH:2][CH:18]=[O:19])[CH:5]=2)[S:10][CH2:9][CH2:8]1

Participants

6

Reactant 4

HCID 6228DimethylformamideHCID 24813Phosphorus oxychloride2×HCID 517045Sodium AcetateHCID 117083551-(4,4-Dimethylthiochroman-6-yl)ethanone

Product 1

HCID 729909543-[4,4-Dimethylthiochroman-6-yl]-3-chloro-2-propene-1-al

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

In a 500 ml 4-necked round bottom flask fitted with a mechanical stirrer and a reflux condenser, 6-acetyl-4,4-dimethylthio-chroman (22 g) and dimethylformamide (38 ml) are added at a temperature in the range of from about 35° C. to about 95° C. under stirring. The reaction mixture is then cooled to a temperature in the range of from about −5° C. to about 0° C. Phosphorus oxychloride (17.2 g) is added to the reaction mixture dropwise over about 30 minutes. Following the addition of the phosphorous oxychloride, the reaction mixture is maintained at a temperature in the range of from about 10° C. to about 15° C. for about 8 hours to about 10 hours. After completion of the reaction as determined by TLC, the reaction mixture is added to cold water (100 ml) at a temperature of from about 0° C. to about 5° C. containing sodium acetate (25 g). The aqueous layer is extracted with dichloromethane (200 ml×3). The organic layer is washed with demineralized water (100 ml×3) until it becomes neutral.

Workup

  1. customIn a 500 ml 4-necked round bottom flask fitted with a mechanical stirrer and a reflux condenser
  2. temperatureThe reaction mixture is then cooled to a temperature in the range of from about −5° C. to about 0° C
  3. temperaturethe reaction mixture is maintained at a temperature in the range of from about 10° C. to about 15° C. for about 8 hours to about 10 hours
  4. customAfter completion of the reaction
  5. extractionThe aqueous layer is extracted with dichloromethane (200 ml×3)
  6. washThe organic layer is washed with demineralized water (100 ml×3) until it

Sources & evidence

ORD record
ord-1f69f88c18544b9aaaecacaa5b44a8e1
Source dataset
uspto-grants-2008_08
Patent number
US07414143B2

Reaction notes

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