Hydrochloric Acid → 3-Thiatricyclo(5.2.1.0,2,6)deca-2(6),4-diene-4-carboxylic acid

HRID 1968584Notes

Reaction equation

HRID 1968584 reaction equation
[S:1]1[C:5]([C:6]([O:8]CC)=[O:7])=[CH:4][C:3]2[CH:11]3[CH2:15][CH:14]([C:2]1=2)[CH2:13][CH2:12]3.C(O)C.[OH-].[Li+].Cl>O.C1COCC1>[S:1]1[C:5]([C:6]([OH:8])=[O:7])=[CH:4][C:3]2[CH:11]3[CH2:15][CH:14]([C:2]1=2)[CH2:13][CH2:12]3

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 702EthanolHCID 3939Lithium HydroxideHCID 58266997Ethyl 4,5,6,7-Tetrahydro-4,7-methanobenzo[b]thiophene-2-carboxylate

Product 1

HCID 582669813-Thiatricyclo(5.2.1.0,2,6)deca-2(6),4-diene-4-carboxylic acidYield 94.4%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
50 °C

Procedure

A 100-mL single-neck round bottomed flask equipped with a magnetic stirrer and reflux condenser was purged with nitrogen and charged with 1d (930 mg, 4.19 mmol), ethanol (7 mL), THF (7 mL), water (7 mL) and lithium hydroxide (301 mg, 12.6 mmol) and the mixture heated at 50° C. for 4 h. After this time, the reaction was cooled to room temperature and acidified to pH 1.5 with 2N hydrochloric acid. The resulting precipitate was collected by vacuum filtration, washed with water (2×10 mL) and dried overnight under vacuum to afford a 94% yield (768 mg) of 1e as a white solid: mp 183-184° C.; 1H NMR (500 MHz, DMSO-d6) δ 12.66 (br s, 1H), 7.48 (s, 1H), 3.59 (m, 1H), 3.41 (m, 1H), 1.97-1.83 (m, 3H), 1.61 (dt, 1H, J=9.0, 2.5 Hz), 0.96 (dd, 2H, J=12.5, 3.5 Hz); MS (APCI−) m/z 193.2 (M−H).

Workup

  1. customA 100-mL single-neck round bottomed flask equipped with a magnetic stirrer
  2. temperaturereflux condenser
  3. customwas purged with nitrogen
  4. temperatureAfter this time, the reaction was cooled to room temperature
  5. filtrationThe resulting precipitate was collected by vacuum filtration
  6. washwashed with water (2×10 mL)
  7. customdried overnight under vacuum

Sources & evidence

ORD record
ord-142eecfd79e44b3e9a87773bf2c5bea0
Source dataset
uspto-grants-2013_04
Patent number
US08426424B2

Reaction notes

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