Water → HCID 12168230, compound

HRID 505865Notes

Reaction equation

HRID 505865 reaction equation
C1(C)C=CC(S(O[C:11]2[C:12](Br)=[CH:13][CH:14]=[C:15]3[C:20]=2[N:19]=[CH:18][CH:17]=[CH:16]3)(=O)=O)=CC=1.[O:23]1[CH:27]=[CH:26][CH:25]=[CH:24]1.C([Li])CCC.O>C1COCC1>[O:23]1[CH:27]2[C:11]3[C:12](=[CH:13][CH:14]=[C:15]4[C:20]=3[N:19]=[CH:18][CH:17]=[CH:16]4)[CH:24]1[CH:25]=[CH:26]2

Participants

6

Reactant 4

HCID 962WaterHCID 8029FuranHCID 11211130HCID 11211130, compoundHCID 178418339Butyllithium

Product 1

HCID 12168230HCID 12168230, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

A stirred solution of the tosyl ester (4a) (5.00 g, 13.2 mmol) in dry THF (150 mL) and freshly distilled furan (24.3 mL, 22.6 g, 0.33 mol, 25 equiv.) cooled at −78° C. under nitrogen was treated dropwise with n-butyllithium in hexanes (2.5 M, 5.55 mL, 13.8 mmol, 1.05 equiv.). The reaction was stirred for 1 hr at −78° C. and then allowed to warm to room temperature over 3 hours. The reaction mixture was treated with water (5 mL) and then heated under reduced pressure to remove most of the THF. This mixture was then diluted with water (150 mL), extracted with dichloromethane (3×100 mL). The organic layers were combined, dried (MgSO4) and concentrated to give a crude brown solid (2.31 g). This material was dissolved in the minimum amount of dichloromethane/petroleum and absorbed onto a pad of neutral alumina. Gradient elution with ethyl acetate/petroleum ether afforded the product, which was recrystallized from dichloromethane/ether/petroleum ether to afford the endoxide (7,10-epoxy-7,10-dihydrobenzo[h]quinoline (6) as cream colored crystals (1.07 g, 42%). 1H NMR (CDCl3, 300 MHz) δ ppm 8.88 (dd, 1H, J=4.1, 1.7 Hz); 8.14 (dd, 1H, J=8.4, 1.7 Hz); 7.60 and 7.57 (ABq, 2H, J=7.8 Hz); 7.27-7.33 (m, 2H); 7.21 (dd, 1H, J=5.5, 1.8 Hz); 6.54 (bs, 1H); 5.95 (m, 1H).

Workup

  1. temperatureto warm to room temperature over 3 hours
  2. temperatureheated under reduced pressure
  3. customto remove most of the THF
  4. additionThis mixture was then diluted with water (150 mL)
  5. extractionextracted with dichloromethane (3×100 mL)
  6. dry with materialdried (MgSO4)
  7. concentrationconcentrated
  8. customto give a crude brown solid (2.31 g)
  9. customabsorbed onto a pad of neutral alumina
  10. washGradient elution with ethyl acetate/petroleum ether
  11. customafforded the product, which
  12. customwas recrystallized from dichloromethane/ether/petroleum ether

Sources & evidence

ORD record
ord-d5ade5f45e91478cbfe048ecfb019043
Source dataset
uspto-grants-2010_08
Patent number
US07781589B2

Reaction notes

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