Aluminum(III) Chloride → 4,4-Dimethyl-6-bromo-2-oxo-thiochroman

HRID 1449666Notes

Reaction equation

HRID 1449666 reaction equation
[Cl-].[Al+3].[Cl-].[Cl-].[CH3:5][C:6]([CH3:18])=[CH:7][C:8]([S:10][C:11]1[CH:16]=[CH:15][C:14]([Br:17])=[CH:13][CH:12]=1)=[O:9]>C(Cl)Cl.[Cl-].[Na+].O>[CH3:5][C:6]1([CH3:18])[C:12]2[C:11](=[CH:16][CH:15]=[C:14]([Br:17])[CH:13]=2)[S:10][C:8](=[O:9])[CH2:7]1

Participants

5

Reactant 2

HCID 6451240Aluminum(III) ChlorideHCID 15661118S-(4-bromophenyl) 3,3-dimethylthioacrylate2×

Product 1

HCID 156611194,4-Dimethyl-6-bromo-2-oxo-thiochroman

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolvent2×HCID 57417360Sodium chloride; waterSolvent

Procedure

To a stirred, ice-cooled suspension of 15.9 g (119 mmol) of aluminum chloride in 140 ml of methylene chloride was added under nitrogen a solution of 21.64 g (79.9 mmol) of S-(4-bromophenyl) 3,3-dimethyl-thioacrylate (Compound 30) in 100 ml of methylene chloride. The mixture was then stirred at room temperature for 72 h and then poured into 250 g of an ice and brine mixture. The mixture was extracted with methylene chloride and the combined organic extracts were washed with saturated NaCl solution and then dried (MgSO4). The solvent was removed in vacuo and the residue recrystaliized from hexanes to give the title compound as white crystals. PMR (CDCl3): & 1.40 (6H, s), 2.67 (2H, s), 7.31-7.4.0 (3H, m). MS exact mass, m/e 269.9714 (calcd. for C11H11SOBr, 269.9714).

Workup

  1. temperatureTo a stirred, ice-cooled
  2. extractionThe mixture was extracted with methylene chloride
  3. washthe combined organic extracts were washed with saturated NaCl solution
  4. dry with materialdried (MgSO4)
  5. customThe solvent was removed in vacuo

Sources & evidence

ORD record
ord-f497673d9cc8493fb62f41e1b9f3b92a
Source dataset
uspto-grants-1997_02
Patent number
US05599819

Reaction notes

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