Hydroquinone diacetate → 10-(2,5-Dihydroxy-phenyl)-10-oxo-decanoic acid

HRID 576007

Reaction equation

HRID 576007 reaction equation
[O:1]1[C:11](=[O:12])[CH2:10][CH2:9][CH2:8][CH2:7][CH2:6][CH2:5][CH2:4][CH2:3][C:2]1=[O:13].C([O:17][C:18]1[CH:23]=[CH:22][C:21]([O:24]C(=O)C)=[CH:20][CH:19]=1)(=O)C.[Cl-].[Cl-].[Cl-].[Al+3]>C(=S)=S>[OH:17][C:18]1[CH:23]=[CH:22][C:21]([OH:24])=[CH:20][C:19]=1[C:2](=[O:13])[CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][C:11]([OH:1])=[O:12]

Participants

5

Reactant 3

HCID 71006Hydroquinone diacetateHCID 75712Oxacycloundecane-2,11-dioneHCID 6451240Aluminum(III) Chloride

Product 1

HCID 31185710-(2,5-Dihydroxy-phenyl)-10-oxo-decanoic acidYield 3%

Reagents, catalysts & solvents 1

HCID 6348Carbon DisulfideSolvent

Procedure

To a 500 mL flask, equipped with mechanical stirrer and under inert atmosphere, was added the previously made Oxacycloundecane-2,11-dione (37.95 g, 206 mmol), 1,4-diacetoxy-benzene (20 g, 103 mmol), and 200 mL carbon disulfide. Aluminum (III) trichloride (68.7 g, 515 mmol) was added and the reaction stirred for 72 hours. Carbon disulfide was decanted away, and ice was carefully added until most of mixture was dissolved. The insoluble material was collected by suction filtration and washed with 2×100 mL of water. The solid was then dissolved in 50 mL of 1 M aqueous sodium hydroxide and stirred for 1 hour. The solution was acidified with 1 M aqueous hydrochloric acid until pH=2. The crude product precipitate was collected by filtration and was re dissolved in acetonitrile (50 mL) and methylene chloride (15 mL) and allowed to precipitate slowly over a week. The resulting brown powder was collected by filtration and recrystallized from 10:3 acetic acid:water. The product (0.8 g, 3%) was isolated by filtration. Found: C, 65.55, H, 7.69%; C16H22O5 requires C, 65.29; H, 7.53% 1H NMR (d6-DMSO): δ 12.0, s, 1H (COOH); δ 11.4, s, 1H (aryl-hydroxyl); δ 9.2, s, 1H (aryl-hydroxyl); δ 7.2 d, 1H (aryl H); δ 7.0, dd, 1H, (arylH); δ 6.8, d, 1H (aryl H's), 3.0, t, 2H(CH2 α to carbonyl); δ 2.2, t, 2H (CH2 β to COOH); δ 1.6, multiplet, 2H (CH2 β to carbonyl), δ 1.5, multiplet, 2H (CH2 β to COOH), δ 1.3, multiplet, 8H (rest of CH2's).

Workup

  1. customTo a 500 mL flask, equipped with mechanical stirrer and under inert atmosphere
  2. customCarbon disulfide was decanted away
  3. additionice was carefully added until most of mixture
  4. dissolutionwas dissolved
  5. filtrationThe insoluble material was collected by suction filtration
  6. washwashed with 2×100 mL of water
  7. dissolutionThe solid was then dissolved in 50 mL of 1 M aqueous sodium hydroxide
  8. stirringstirred for 1 hour
  9. filtrationThe crude product precipitate was collected by filtration
  10. dissolutionwas re dissolved in acetonitrile (50 mL)
  11. customto precipitate slowly over a week
  12. filtrationThe resulting brown powder was collected by filtration
  13. customrecrystallized from 10:3 acetic acid

Sources & evidence

ORD record
ord-4299433710254fb19e893b6541d3be3f
Source dataset
uspto-grants-2015_05
Patent number
US09035085B2

Linked notes

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