Benzo(B)Thiophene → HCID 67593962, compound

HRID 611734Notes

Reaction equation

HRID 611734 reaction equation
[CH2:1]([Li])[CH2:2][CH2:3][CH3:4].[CH:6]1[CH:7]=[CH:8][C:9]2[S:14]C=[CH:12][C:10]=2[CH:11]=1.C(Br)C=C.[NH4+].[Cl-]>C1COCC1>[CH3:4][CH:3]=[CH:2][C:1]1[S:14][C:9]2[CH:8]=[CH:7][CH:6]=[CH:11][C:10]=2[CH:12]=1

Participants

6

Reactant 4

HCID 7221Benzo(B)ThiopheneHCID 7841Allyl bromideHCID 25517Ammonium ChlorideHCID 178418339Butyllithium

Product 1

HCID 67593962HCID 67593962, compoundYield 58%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

n-Butyl lithium (16.7 ml, 2.5 N in hexanes) was added dropwise to a stirred solution of thianaphthene (5.0 g, 37.3 mmol) in THF (80 mL) at -78° C. under a dry N2 atmosphere. After the addition wascompleted, the mixture was warmed up and stirred at 0° C. for 30 min. Allylbromide (16.1 mL, 186.5 mmol ) was added. After an additional 3.5 h., sat. aq. NH4Cl was added and the reaction mixture was partitioned between water and ether. The ether phase was washed with brine and dried. Silica gel (120 mL) was added. Solvents were removed and the silica adsorbate was flash chromatographed (eluent petroleum ether) to provide the title compound as an oil (3.74 g, 58%): NMR (CDCl3); δ 7.76 (d, J=9 Hz, 1H), 7.66 (d, J=9 Hz, 1H), 7.36-7.20 (m, 2H), 7.02 (s, 1H), 6.14-5.96 (m, 1H), 5.22 (dd, J=2, 17 Hz, 1H), 5.16 (dd, J=2, 17 Hz, 1H), 3.66 (d, J=8 Hz, 2H); MS (EI): [M+] 174 (100%); Anal. Calc. for C11H10S: C, 75.82, H, 5.78, N, 0.00. Found: C, 72.88, H, 5.56, N, 0.13.

Workup

  1. additionAfter the addition
  2. temperaturethe mixture was warmed up
  3. waitAfter an additional 3.5 h.
  4. customthe reaction mixture was partitioned between water and ether
  5. washThe ether phase was washed with brine
  6. customdried
  7. additionSilica gel (120 mL) was added
  8. customSolvents were removed
  9. customchromatographed (eluent petroleum ether)

Sources & evidence

ORD record
ord-7a01ea31049240f8bbfb40bcc8231783
Source dataset
uspto-grants-1999_12
Patent number
US06001867

Reaction notes

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