Hydroquinone → HCID 13443680, compound

HRID 2260367Notes

Reaction equation

HRID 2260367 reaction equation
C[CH2:2][O:3]C(C)=O.C1(C)C=CC=CC=1.[C:14]1([CH:21]=[CH:20][C:18]([OH:19])=[CH:17][CH:16]=1)[OH:15].[CH3:22][C:23]([C:25]([CH3:27])=[CH2:26])=[CH2:24]>CO>[CH3:24][C:23]1[CH2:22][CH:20]2[CH:21]([CH2:26][C:25]=1[CH3:27])[C:14](=[O:15])[C:16]([O:3][CH3:2])=[CH:17][C:18]2=[O:19]

Participants

6

Reactant 4

HCID 785HydroquinoneHCID 1140TolueneHCID 8857Ethyl Acetate2×HCID 105662,3-Dimethyl-1,3-butadiene

Product 1

HCID 13443680HCID 13443680, compound

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Conditions

Temperature
65 °C

Procedure

To a vigorously stirred solution of NaIO4 (33.5 g, 157 mmol, Baker) in H2O (1500 mL), there was added solid 2-methoxyhydroquinone (11.00 g, 50.0 mmol) in portions. The reaction immediately became dark orange. The reaction was allowed to stir for 1 h at rt and was extracted with CH2Cl2 (3×150 mL). The extract was washed with half saturated brine (1×150 mL), filtered through cotton and the solvent removed in vacuo to yield 2-methoxybenzoquinone as an orange solid (10.5 g) which was of sufficient purity (TLC analysis, 10% EtOAc/90% CHCl3) for further reaction. The crude quinone was combined with toluene (150 mL) and hydroquinone (1.0 g, Mallinkrodt). Neat 2,3-dimethyl-1,3-butadiene (8.3 g, 101 mmol, Aldrich) was added. The reaction was allowed to stir overnight at 65° C. under N2. TLC (10% EtOAc/90% CHCl3) indicated total consumption of the dienophile. The solvent was removed in vacuo to yield a dark solid. This was triturated with MeOH (100 mL) at rt to give a beige solid. Crystallization from MeOH (dissolved in 140 mL, allowed to cool to rt) yielded a fluffy colorless solid (10.2 g, 64%, >95% pure by 1H NMR analysis); mp 133°-134° C. (MeOH); 1H NMR (CDCl3) δ1.62 (s, 6H), 2.12 (m, 2H), 2.42 (m, 2H), 3.09 (m, 1H), 3.20 (m, 1H), 3.78 (s, 3H), 5.88 (s, 1H).

Workup

  1. customconsumption of the dienophile
  2. customThe solvent was removed in vacuo
  3. customto yield a dark solid
  4. customThis was triturated with MeOH (100 mL) at rt
  5. customto give a beige solid
  6. customCrystallization from MeOH (dissolved in 140 mL, allowed to cool to rt)
  7. customyielded a fluffy colorless solid (10.2 g, 64%, >95% pure by 1H NMR analysis)

Sources & evidence

ORD record
ord-a4961943816945a8bb96063332aa5741
Source dataset
uspto-grants-1995_12
Patent number
US05476933

Reaction notes

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