Tin tetrachloride → (2-Benzyl-benzo[b]thiophen-3-yl)-(3,5-diisopropyl-4-methoxy-phenyl)-methanone

HRID 1873125Notes

Reaction equation

HRID 1873125 reaction equation
C(Cl)(=O)C(Cl)=O.[CH:7]([C:10]1[CH:11]=[C:12]([CH:16]=[C:17]([CH:21]([CH3:23])[CH3:22])[C:18]=1[O:19][CH3:20])[C:13]([OH:15])=O)([CH3:9])[CH3:8].[CH2:24]([C:31]1[S:35][C:34]2[CH:36]=[CH:37][CH:38]=[CH:39][C:33]=2[CH:32]=1)[C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1.[Sn](Cl)(Cl)(Cl)Cl>ClCCl.O.CN(C=O)C>[CH2:24]([C:31]1[S:35][C:34]2[CH:36]=[CH:37][CH:38]=[CH:39][C:33]=2[C:32]=1[C:13]([C:12]1[CH:16]=[C:17]([CH:21]([CH3:23])[CH3:22])[C:18]([O:19][CH3:20])=[C:10]([CH:7]([CH3:8])[CH3:9])[CH:11]=1)=[O:15])[C:25]1[CH:26]=[CH:27][CH:28]=[CH:29][CH:30]=1

Participants

8

Reactant 4

HCID 24287Tin tetrachlorideHCID 65578Oxalyl chlorideHCID 127581572-Benzyl-1-benzothiopheneHCID 15895030HCID 15895030, compound

Product 1

HCID 15481276(2-Benzyl-benzo[b]thiophen-3-yl)-(3,5-diisopropyl-4-methoxy-phenyl)-methanone

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 6344DichloromethaneSolvent2×

Conditions

Temperature
-78 °C

Procedure

A drop of DMF was added to a solution of oxalyl chloride (1.4 mL, 16.2 mmmol), 3,5-diisopropyl-4-methoxybenzoic acid (4.0 g, 14.7 mmol) in dichloromethane under a dry nitrogen atmosphere. After 4 h the solvent was removed and the resulting solid was triturated with petroleum ether and dried in vacuo. To this solid was added 2-benzyl-benzo[b]thiophene (3.32 g, 13.4 mmol) and dichloromethane (75 mL). The resulting solution was stirred under a dry nitrogen atmospher and cooled to -78° C. Tin tetrachloride (3.44 mL, 29.48 mmol) was added dropwise over a 20 minute period. The reaction mixture was warmed to room temperature and stirred overnight. The reaction mixture was added to water and extracted with ether. The ether extract was washed with water and brine. Silica gel was added and the solvent was removed. The adsorbate was flash chromatographed (gradient, petroleum ether to 95:5 petroleum ether:ethyl acetate). The solvent was removed and the solid was triturated with ether to give the title compound as a a white solid (3.68 g, 62%): mp 124-125° C.; NMR (CDCl3); δ 7.75 (ddd, J=8, 2, 1 Hz, 1H), 7.64 (s, 2H), 7.48 (ddd, J=8, 2, 1, 1H), 7.30-7.19 (m, 7H), 4.22 (s, 2H), 3.80 (s, 3H) 3.35 (septuplet, J=7 Hz, 2H), 1.19 (d, J=7 Hz, 12H); MS (+FAB): 443 (100%, M+H); Anal. Calc. for C29H30O2S: C, 78.69, H, 6.83, N, 0.00. Found: C, 78.57, H, 6.88, N, 0.14.

Workup

  1. customAfter 4 h the solvent was removed
  2. customthe resulting solid was triturated with petroleum ether
  3. customdried in vacuo
  4. temperatureThe reaction mixture was warmed to room temperature
  5. stirringstirred overnight
  6. extractionextracted with ether
  7. extractionThe ether extract
  8. washwas washed with water and brine
  9. additionSilica gel was added
  10. customthe solvent was removed
  11. customchromatographed (gradient, petroleum ether to 95:5 petroleum ether:ethyl acetate)
  12. customThe solvent was removed
  13. customthe solid was triturated with ether

Sources & evidence

ORD record
ord-8dd26752813b4058934f62f72d2b866d
Source dataset
uspto-grants-2000_08
Patent number
US06110962

Reaction notes

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