2-Iodoxybenzoic acid → HCID 59456512, compound

HRID 1922637Notes

Reaction equation

HRID 1922637 reaction equation
I(C1C=CC=CC=1C(O)=O)(=O)=O.[Br:13]/[CH:14]=[C:15]1\[CH2:16][CH2:17][CH2:18][C@@:19]2([CH3:26])[C@H:24]\1[CH2:23][C:22](=[O:25])[CH2:21][CH2:20]2.C(=O)([O-])O.[Na+]>CS(C)=O>[Br:13]/[CH:14]=[C:15]1\[CH2:16][CH2:17][CH2:18][C@@:19]2([CH3:26])[C@H:24]\1[CH2:23][C:22](=[O:25])[CH:21]=[CH:20]2

Participants

5

Reactant 3

HCID 1087942-Iodoxybenzoic acidHCID 516892Sodium BicarbonateHCID 59456522HCID 59456522, compound2×

Product 1

HCID 59456512HCID 59456512, compoundYield 46.8%

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent

Conditions

Temperature
80 °C

Procedure

To a solution of ortho-iodoxybenzoic acid (1.56 g, 5.57 mmol) in dimethyl sulfoxide (17 ml), (E,4aR,8aR)-8-(bromomethylene)-octahydro-4a-methylnaphthalene-2(1H)-one (Compound 25: 955 mg, 3.71 mmol) was added, and the resulting mixture was stirred at 80° C. for 18 hours. The resulting mixture was cooled to room temperature, and 5% aqueous sodium hydrogen carbonate solution was added thereto. The resulting mixture was extracted with diethyl ether, and the organic layer was washed with water and saturated brine. Further, the combined aqueous layer was extracted with ethyl acetate which was then washed with water and saturated brine. The combined organic layer was dried over sodium sulfate and evaporated under reduced pressure. The obtained crude product (976 mg) was purified by flash column chromatography to obtain (4aR,8E,8aR)-8-(bromomethylene)-4a,5,6,7,8,8a-hexahydro-4a-methylnaphthalene-2(1H)-one (443 mg, 46.8%). 1H NMR (CDCl3) δ: 6.76 (d, J=9.9 Hz, 1H), 5.88 (d, J=9.9 Hz, 1H), 5.74 (t, J=1.5 Hz, 1H), 2.95-3.10 (m, 1H), 2.66 (ddd, J=11.7 Hz, 5.7 Hz, 1.5 Hz, 1H), 2.45 (d, J=12.0 Hz, 1H), 2.43 (d, J=6 Hz, 1H), 1.50-1.90 (m, 5H), 0.98 (s, 3H)

Workup

  1. temperatureThe resulting mixture was cooled to room temperature
  2. extractionThe resulting mixture was extracted with diethyl ether
  3. washthe organic layer was washed with water and saturated brine
  4. extractionFurther, the combined aqueous layer was extracted with ethyl acetate which
  5. washwas then washed with water and saturated brine
  6. dry with materialThe combined organic layer was dried over sodium sulfate
  7. customevaporated under reduced pressure
  8. customThe obtained crude product (976 mg)
  9. customwas purified by flash column chromatography

Sources & evidence

ORD record
ord-82dce271a1fd4c308a075f5d1ad6e5c7
Source dataset
uspto-grants-2012_05
Patent number
US08173824B2

Reaction notes

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