2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → HCID 21706781, compound

HRID 1594771Notes

Reaction equation

HRID 1594771 reaction equation
[C:1]([O:4][C:5]1[CH:6]=[C:7]2[C:12](=[CH:13][C:14]=1[O:15][CH3:16])[CH2:11][CH2:10][CH2:9][CH2:8]2)(=[O:3])[CH3:2].C(C1C(=O)C(Cl)=C(Cl)C(=[O:22])C=1C#N)#N>O1CCOCC1>[C:1]([O:4][C:5]1[CH:6]=[C:7]2[C:12]([CH2:11][CH2:10][CH2:9][C:8]2=[O:22])=[CH:13][C:14]=1[O:15][CH3:16])(=[O:3])[CH3:2].[C:1]([O:4][C:5]1[C:14]([O:15][CH3:16])=[CH:13][C:12]2[C:7](=[CH:8][CH:9]=[CH:10][CH:11]=2)[CH:6]=1)(=[O:3])[CH3:2]

Participants

5

Reactant 2

HCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinone2×HCID 13197843HCID 13197843, compound2×

Product 2

HCID 15364255HCID 15364255, compoundYield 23%HCID 21706781HCID 21706781, compoundYield 62%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent2×

Conditions

Temperature
25 °C

Procedure

A 220 mg (1 mmol) quantity of 6-acetoxy-7-methoxytetralin was dissolved in 1 mL, of dioxane containing 5% water. DDQ (454 mg, 2 mmol) was dissolved in 4 mL of dioxane containing less than 0.01% water. The solution of DDQ was added dropwise over a period of 5 minutes to the stirred solution of 6-acetoxy-7-methoxytetralin at 25° C., under nitrogen. The reaction solution was stirred at 25° C. under nitrogen for 20 hours, after which time the reaction mixture was filtered through a sintered glass funnel and the precipitate (DDHQ) washed with 2 mL dioxane. The residue on evaporation of the filtrate was portioned between 10 mL 5% NaHCO3 (aq) and 80 mL of EtOAc. The EtOAc layer was separated and washed with 5% NaHCO3 (aq)(1×5 mL), water (1×5 mL), and brine (2×5 ml). The organic layer was dried over MgSO4 and evaporated to dryness. The residue was purified by flash chromatography (hexane: EtOAc, 2.5:1.5) to give two products, 146 mg (62% yield) of 7-acetoxy-6-methoxytetralin-1-one (87) and 50 mg (23% yield) of 2-acetoxy-3-methoxy naphthalene (88). 7-acetoxy-6-methoxytetralin-1-one: mp 118.5-119.5° C.; IR 1769 (C═O str.), 1674, 1613, 1506, 1272, 1210, 1186, 1031 cm−1; 1H NMR (CDCl3) δ7.69 (1H, s, H-8), 6.74 (1H, s, H-5), 3.86 (3H, s, —OCH3), 2.91 (2H, t, J=6.08 Hz, H-2), 2.57 (2H, t, J=6.53 Hz, H-4), 2.28 (3H, s, OCOCH3), 2.11 (2H, qn, J=6.35 Hz, H-3); 13C NMR (CDCl3) δ196.2 (C-1), 168.8, 155.2, 144.5, 138.7, 126.1, 121.5, 111.3, 56.0, 38.4, 29.7, 23.2, 20.4; LRMS EI m/z 234 [M+], 164 [base peak]. 2-acetoxy-3-methoxy naphthalene: mp 114-116° C.; IR 1764 (C═O str.), 1633, 1508, 1483, 1371, 1261, 1201, 1108, 1015 cm−1; 1H NMR (CDCl3) δ7.75 (1H, dd, J=8.13, 1 Hz, H-5 or H-8), 7.73 (1H, dd, J=7.43, 1.1 Hz, H-5 or H-8), 7.50 (1H, s, H-1), 7.44 1H, ddd, J=8.23, 7.55, 1.34 Hz, H-6 or H-7), 7.36 1H, ddd, J=8.14, 7.51, 1.24 Hz, H-6 or H.7), 7.22 (1H, s, H-4), 3.95 (3H, s, —OCH3), 2.38 (3H, s, —OCOCH3); 13C NMR(CDCl3)d 169.2, 150.2, 140.3, 132.5, 128.3, 127.2, 126.5. 124.2, 120.3, 107.3, 55.8, 20.6; LRMS EI m/z 216 [M+], 174 [base peak].

Workup

  1. filtrationafter which time the reaction mixture was filtered through a sintered glass funnel
  2. washthe precipitate (DDHQ) washed with 2 mL dioxane
  3. customThe residue on evaporation of the filtrate
  4. customThe EtOAc layer was separated
  5. washwashed with 5% NaHCO3 (aq)(1×5 mL), water (1×5 mL), and brine (2×5 ml)
  6. dry with materialThe organic layer was dried over MgSO4
  7. customevaporated to dryness
  8. customThe residue was purified by flash chromatography (hexane: EtOAc, 2.5:1.5)

Sources & evidence

ORD record
ord-e9ddf3f645604847b006b1562a4891ba
Source dataset
uspto-grants-2001_09
Patent number
US06284789B1

Reaction notes

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