m-Bromobenzenethiol → 8-Bromo-2,3,4,5-tetrahydro-5-methyl-1-benzothiepine

HRID 373559Notes

Reaction equation

HRID 373559 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([SH:8])[CH:5]=[CH:6][CH:7]=1.Br[C:10]1[CH:21]=[CH:20]C2C(=O)CCCS[C:12]=2[CH:11]=1.C[Mg]I>CCOCC>[Br:1][C:2]1[CH:7]=[CH:6][C:5]2[CH:11]([CH3:12])[CH2:10][CH2:21][CH2:20][S:8][C:4]=2[CH:3]=1

Participants

5

Reactant 3

HCID 80597m-BromobenzenethiolHCID 223374568-bromo-3,4-dihydro-2H-benzo[b]thiepin-5-oneHCID 178418373HCID 178418373, compound

Product 1

HCID 184061098-Bromo-2,3,4,5-tetrahydro-5-methyl-1-benzothiepine

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

First, m-bromothiophenol was converted into 8-bromo-3,4-dihydro-1-benzothiepin-5(2H)-one. This ketone was methylated with MeMgI in ether and the resulting tertiary alcohol was deoxygenated as follows: 22.85 g were placed in 250 ml of hexane under argon and treated in succession with 75.1 g of sodium iodide (NaI), 26.4 ml of acetonitrile and 63.5 ml of Me3SiCl. The mixture was stirred at room temperature overnight, poured on to ice, extracted with ether, washed with bisulfite solution and water, dried and evaporated. Chromatography on silica gel with petroleum ether gave 18.1 g of 8-bromo-2,3,4,5-tetrahydro-5-methyl-1-benzothiepine as a pale yellow oil.

Workup

  1. customthe resulting tertiary alcohol was deoxygenated
  2. additiontreated in succession with 75.1 g of sodium iodide (NaI), 26.4 ml of acetonitrile and 63.5 ml of Me3SiCl
  3. additionpoured on to ice
  4. extractionextracted with ether
  5. washwashed with bisulfite solution and water
  6. customdried
  7. customevaporated

Sources & evidence

ORD record
ord-8dc06c14ed644393bd04fca9e08db30f
Source dataset
uspto-grants-1992_11
Patent number
US05164387

Reaction notes

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