Thionyl Chloride → HCID 57816477, compound

HRID 1684862Notes

Reaction equation

HRID 1684862 reaction equation
S(Cl)(Cl)=O.[Br:5][C:6]1[CH:7]=[C:8]([CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][C:17]([OH:19])=O)[CH:9]=[CH:10][CH:11]=1.[Cl-].[Cl-].[Cl-].[Al+3]>C(=S)=S>[Br:5][C:6]1[CH:11]=[CH:10][C:9]2[C:17](=[O:19])[CH2:16][CH2:15][CH2:14][CH2:13][CH2:12][C:8]=2[CH:7]=1

Participants

5

Reactant 3

HCID 24386Thionyl ChlorideHCID 6451240Aluminum(III) ChlorideHCID 57816641HCID 57816641, compound

Product 1

HCID 57816477HCID 57816477, compoundYield 67.4%

Reagents, catalysts & solvents 1

HCID 6348Carbon DisulfideSolvent

Conditions

Temperature
60 °C

Procedure

Thionyl chloride (13.2 mL, 181 mmol) was added (neat) to Example 2a, 6-(3-bromophenyl)hexanoic acid (16 g, 59.2 mmol) in a 1 L round-bottomed flask under a nitrogen atmosphere. The mixture was warmed to 60° C. for 2 h, excess reagent was removed in vacuo, and the residue was subjected to azeotropic conditions (benzene 3×). The acid chloride was dissolved in carbon disulfide (550 mL) and cannulated into a solution of aluminum trichloride (26.3 g, 198 mmol) in carbon disulfide (1315 mL) heated at reflux. The reaction was stirred 20 h, cooled, decanted, concentrated, and the resultant solids were stirred in diethyl ether/THF (1:1, 1 L), and 1N HCl (500 mL) for 1.5 hours. The organic layer was filtered, washed with water, and brine to give Example 3c, 2-bromo-7,8,9,10-tetrahydrobenzo[8]annulen-5(6H)-one 10.1 g (66%) as a colorless oil. 1H NMR (300 MHz, CDCl3) δ 7.55 (d, J=8.4 Hz, 1H), 7.38 (dd, J=8.4 Hz, 1.8 Hz, 1H), 7.33 (d, J=1.8 Hz, 1H), 2.99 (t, J=6.6 Hz, 2H), 2.89 (t, J=6.6 Hz, 2H), 1.85-1.73 (m, 4H), 1.52-1.44 (m, 2H). RT=2.8 minutes (condition 2); LRMS: Anal. Calcd. for C12H13BrO: 253.02. found: 253.15 (M+H).

Workup

  1. customexcess reagent was removed in vacuo
  2. dissolutionThe acid chloride was dissolved in carbon disulfide (550 mL)
  3. temperatureheated
  4. temperatureat reflux
  5. temperaturecooled
  6. customdecanted
  7. concentrationconcentrated
  8. stirringthe resultant solids were stirred in diethyl ether/THF (1:1, 1 L)
  9. wait1N HCl (500 mL) for 1.5 hours
  10. filtrationThe organic layer was filtered
  11. washwashed with water, and brine

Sources & evidence

ORD record
ord-a51f87140c98494db29a41846820382b
Source dataset
uspto-grants-2012_04
Patent number
US08147818B2

Reaction notes

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