Methanol → HCID 21480579, compound

HRID 1490202Notes

Reaction equation

HRID 1490202 reaction equation
[Cl:1][C:2]1[CH:15]=[CH:14][C:13]2[CH:12]3[CH2:16][C:5]([C:17]([OH:19])=[O:18])([C:6]4[C:11]3=[CH:10][CH:9]=[CH:8][CH:7]=4)[C:4]=2[CH:3]=1.S(Cl)(Cl)=O.[CH3:24]O.[OH-].[Na+]>C1(C)C=CC=CC=1>[Cl:1][C:2]1[CH:15]=[CH:14][C:13]2[CH:12]3[CH2:16][C:5]([C:17]([O:19][CH3:24])=[O:18])([C:6]4[C:11]3=[CH:10][CH:9]=[CH:8][CH:7]=4)[C:4]=2[CH:3]=1

Participants

6

Reactant 4

HCID 887MethanolHCID 14798Sodium HydroxideHCID 24386Thionyl ChlorideHCID 196986472-Chloro-9,10-dihydro-9,10-methano-9-anthracenecarboxylic acid

Product 1

HCID 21480579HCID 21480579, compoundYield 97%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

To a solution of 2-chloro-9,10-dihydro-9,10-methano-9-anthracenecarboxylic acid (described in example 1j) (10.03 g, 37.1 mmol) in toluene (100 mL) was added thionyl chloride (4.05 mL, 55.7 mmol, 1.5 eq). The reaction was heated to reflux monitoring gas evolution with a bubbler of mineral oil. Gas evolution ceased after 30 min at which time the reaction was cooled slightly under nitrogen and a large excess of methanol (10 mL) was added. The solution was again heated to reflux for 1 h, cooled to room temperature under nitrogen, and stirred for 18 h. Aqueous NaOH (2.5N, 60 mL) was added and the aqueous phase was extracted with ethyl acetate (2×70 mL). Combined organic extracts were dried over anhydrous magnesium sulfate, filtered, and reduced to a solid. The reaction product was purified by flash chromatography over silica gel (250 mL, eluent: 15% ethyl acetate in hexane) to yield 10.2 g (97%) of the title compound as a highly crystalline white solid. TLC (Rf 0.45, 10% ethyl acetate in hexane). MS (CI, CH4) m/z 285 (M+1,100), 287 (31), 313 (M+29,11), 253 (14), 225 (14), 205 (8)

Workup

  1. temperatureThe reaction was heated
  2. temperatureto reflux monitoring gas evolution with a bubbler of mineral oil
  3. temperaturethe reaction was cooled slightly under nitrogen
  4. temperatureThe solution was again heated
  5. temperatureto reflux for 1 h
  6. extractionthe aqueous phase was extracted with ethyl acetate (2×70 mL)
  7. dry with materialCombined organic extracts were dried over anhydrous magnesium sulfate
  8. filtrationfiltered
  9. customThe reaction product was purified by flash chromatography over silica gel (250 mL, eluent: 15% ethyl acetate in hexane)

Sources & evidence

ORD record
ord-f57107414aea47a78ea70796f33aa8b1
Source dataset
uspto-grants-1997_10
Patent number
US05681840

Reaction notes

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