Hydrochloric Acid → 1-(4,4-Dimethylthiochroman-6-yl)ethanone

HRID 1193614Notes

Reaction equation

HRID 1193614 reaction equation
[CH3:1][C:2]1([CH3:12])[C:11]2[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=2)[S:5][CH2:4][CH2:3]1.[C:13](Cl)(=[O:15])[CH3:14].O.Cl>C1C=CC=CC=1>[CH3:1][C:2]1([CH3:12])[C:11]2[C:6](=[CH:7][CH:8]=[C:9]([C:13](=[O:15])[CH3:14])[CH:10]=2)[S:5][CH2:4][CH2:3]1

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 962WaterHCID 6367Acetyl chlorideHCID 110194304,4-Dimethylthiochroman

Product 1

HCID 117083551-(4,4-Dimethylthiochroman-6-yl)ethanone

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

Procedure

A solution of 14.3 g (80.21 mmol) of 4,4-dimethylthiochroman (from Example 2) and 6.76 g (86.12 mmol) of acetyl chloride in 65 ml benzene was cooled in an ice bath and treated dropwise with 26.712 g (102.54 mmol) of stannic chloride. The mixture was stirred at room temperature for 12 hours, then treated with 65 ml water and 33 ml conc. hydrogen chloride and heated at reflux for 0.5 hours. After being cooled to room temperature, the organic layer was separated and the aqueous layer extracted with 5×50 ml benzene. The recovered organic fractions were combined and washed with 5% sodium carbonate, water, saturated NaCl and then dried (MgSO4). The solvent was removed in vacuo and the residue purified by flash chromatography (silica; 5% ethyl acetate in hexanes) followed by kugelrohr distillation (150° C., 0.7 mm) to give the title compound as a pale yellow oil. PMR (CDCl): δ 1.35 (6H, s), 1.92-1.98 (2H, m) 2.54 (3H, s), 3.02-3.08 (2H, m), 7.13 (1H, d, J~8.6 Hz), 7.58 (1H, dd, J~8.6 Hz, 2 Hz), 7.99 (1H, d, J~2 Hz).

Workup

  1. temperatureheated
  2. temperatureat reflux for 0.5 hours
  3. temperatureAfter being cooled to room temperature
  4. customthe organic layer was separated
  5. extractionthe aqueous layer extracted with 5×50 ml benzene
  6. washwashed with 5% sodium carbonate, water, saturated NaCl
  7. dry with materialdried (MgSO4)
  8. customThe solvent was removed in vacuo
  9. customthe residue purified by flash chromatography (silica; 5% ethyl acetate in hexanes)
  10. distillationfollowed by kugelrohr distillation (150° C., 0.7 mm)

Sources & evidence

ORD record
ord-6abde0552def4bf7b826c56a996f701d
Source dataset
uspto-grants-1989_03
Patent number
US04810804

Reaction notes

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