2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → HCID 66869528, compound

HRID 1968713Notes

Reaction equation

HRID 1968713 reaction equation
ClC1CCC2C(=CC(OC)=CC=2)C1.C(OC(=O)C)C.[CH2:20]([O:22][C:23](=[O:38])[CH2:24][C:25]1[C:34]2[C:29](=[CH:30][CH:31]=[C:32]([O:35][CH3:36])[CH:33]=2)[CH2:28][CH2:27][C:26]=1[Cl:37])[CH3:21].ClC1C(=O)C(C#N)=C(C#N)C(=O)C=1Cl>O1CCOCC1.CO>[CH2:20]([O:22][C:23](=[O:38])[CH2:24][C:25]1[C:34]2[C:29](=[CH:30][CH:31]=[C:32]([O:35][CH3:36])[CH:33]=2)[CH:28]=[CH:27][C:26]=1[Cl:37])[CH3:21]

Participants

7

Reactant 4

HCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 8857Ethyl AcetateHCID 66869542HCID 66869542, compoundHCID 86625788HCID 86625788, compound

Product 1

HCID 66869528HCID 66869528, compound

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 312751,4-DioxaneSolvent

Procedure

A mixture of [2-Chloro-7-methoxy-3,4-dihydro-2H-naphthalen-(1 E/Z)-ylidene]-acetic acid ethyl ester and of (2-Chloro-7-methoxy-3,4-dihydro-naphthalen-1-yl)-acetic acid ethyl ester (26.82 g, 95.52 mmol) is dissolved under an atmosphere of argon in dioxane (280 ml). 2,3-Dichloro-5,6-dicyano-p-benzoquinone (DDQ, 47.70 g, 210.16 mmol) is added, and the reaction mixture is refluxed for 2 h. TLC analysis indicates complete conversion of starting material. After cooling to RT, addition of MeOH renders the reaction mixture homogeneous. Silica gel (250 g) is added, and the solvent is removed by rotary evaporation. Purification by FCC (hexane/EtOAc 9:1) yields the title compound. 1H NMR (CDCl3, 400 MHz): δ 1.24 (t, J=8.8 Hz, 3H), 3.95 (s, 3H), 4.19 (q, J=8.8 Hz, 2H), 4.28 (s. 2H), 7.16-7.19 (m, 1H), 7.22 (s, 1H), 7.38 (d, J=10 Hz, 1H), 7.68 (d, J=10 Hz, 1H), 7.75 (d, J=10 Hz, 1H). ES+-MS: 279.2, 281.2 [M+H]+.

Workup

  1. temperaturethe reaction mixture is refluxed for 2 h
  2. additionSilica gel (250 g) is added
  3. customthe solvent is removed by rotary evaporation
  4. customPurification by FCC (hexane/EtOAc 9:1)

Sources & evidence

ORD record
ord-af0a569e7374454ebb3fbbbd544ea1bb
Source dataset
uspto-grants-2013_04
Patent number
US08426440B2

Reaction notes

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