2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → HCID 68733124, compound

HRID 1910656Notes

Reaction equation

HRID 1910656 reaction equation
[CH2:1]([O:8][C@@H:9]1[C@@H:21]([O:22]CC2C=CC(OC)=CC=2)[C@:20]([CH3:33])([OH:32])[C@@H:19]([CH2:34][O:35][Si:36]([C:39]([CH3:42])([CH3:41])[CH3:40])([CH3:38])[CH3:37])[O:18][C@H:10]1[O:11][CH2:12][CH2:13][Si:14]([CH3:17])([CH3:16])[CH3:15])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.ClC1C(=O)C(C#N)=C(C#N)C(=O)C=1Cl>C(Cl)Cl.O>[CH2:1]([O:8][C@@H:9]1[C@@H:21]([OH:22])[C@:20]([CH3:33])([OH:32])[C@@H:19]([CH2:34][O:35][Si:36]([C:39]([CH3:42])([CH3:41])[CH3:40])([CH3:38])[CH3:37])[O:18][C@H:10]1[O:11][CH2:12][CH2:13][Si:14]([CH3:15])([CH3:17])[CH3:16])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

5

Reactant 2

HCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 131731072HCID 131731072, compound

Product 1

HCID 68733124HCID 68733124, compoundYield 78%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent2×

Procedure

To a stirred solution of 5.08 (7.2 g, 11.6 mmol) in CH2Cl2 (137 mL) and H2O (8 mL) at 0° C. was added 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (3.4 g, 15.0 mmol). The reaction mixture was stirred for 1 h then diluted with CH2Cl2 and sequentially washed with saturated aqueous NaHCO3, H2O, and brine. After concentration of the organic phase in vacuo, the crude residue was purified by silica gel chromatography (25% EtOAc/petroleum ether) to afford the title compound (4.5 g, 9.0 mmol, 78%). 1H NMR (500 MHz, CDCl3): δ ppm 7.39-7.32 (m, 4H, PhH), 7.29 (t, J=6.8 Hz, 1H, PhH), 4.95, 4.68 (ABq, J=11.2 Hz, 1H each, OCH2Ph), 4.42 (d, J=7.8 Hz, 1H, H-1), 4.01-3.94 (m, 1H, OCHHCH2SiMe3), 3.90-3.80 (m, 2H, H-6), 3.60 (d, J=9.8 Hz, 1H, H-3), 3.60-3.54 (m, 1H, OCHHCH2SiMe3), 3.51 (br s, 1H, OH), 3.41 (t, J=6.8 Hz, 1H, H-5), 3.16 (dd, J=9.8, 7.8 Hz, 1H, H-3), 2.48 (br s, 1H, OH), 1.25 (s, 3H, Me), 1.05-0.99 (m, 2H, OCH2CH2SiMe3), 0.90 (s, 9H, SiCMe3), 0.11, 0.11 (s, 3H each, SiME2), 0.02 (s, 9H, SiMe3); 13C NMR (125 MHz, CDCl3): δ ppm 138.73, 128.56, 128.03, 127.86, 103.70, 80.62, 78.29, 75.77, 74.63, 73.80, 67.81, 62.57, 25.91, 18.68, 18.21, 15.31, −1.31, −5.39, −5.52; HRMS calcd for C25HSONO6Si2 [M+NH4]+: 516.3177. found 516.3165.

Workup

  1. washsequentially washed with saturated aqueous NaHCO3, H2O, and brine
  2. customAfter concentration of the organic phase in vacuo, the crude residue was purified by silica gel chromatography (25% EtOAc/petroleum ether)

Sources & evidence

ORD record
ord-df2c0d06aff94cca88e0ca3431f71182
Source dataset
uspto-grants-2013_12
Patent number
US08604004B2

Reaction notes

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