Methanol → HCID 66869528, compound

HRID 1992630Notes

Reaction equation

HRID 1992630 reaction equation
[CH2:1]([O:3][C:4](=[O:19])[CH2:5][C:6]1[C:15]2[C:10](=[CH:11][CH:12]=[C:13]([O:16][CH3:17])[CH:14]=2)[CH2:9][CH2:8][C:7]=1[Cl:18])[CH3:2].ClC1C(=O)C(C#N)=C(C#N)C(=O)C=1Cl.CO>O1CCOCC1>[CH2:1]([O:3][C:4](=[O:19])[CH2:5][C:6]1[C:15]2[C:10](=[CH:11][CH:12]=[C:13]([O:16][CH3:17])[CH:14]=2)[CH:9]=[CH:8][C:7]=1[Cl:18])[CH3:2]

Participants

5

Reactant 3

HCID 887MethanolHCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 66869542HCID 66869542, compound

Product 1

HCID 66869528HCID 66869528, compound

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Procedure

A mixture of [2-Chloro-7-methoxy-3,4-dihydro-2H-naphthalen-(1E/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-2f4d405dac32413b980d7cd0fe95a092
Source dataset
uspto-grants-2010_01
Patent number
US07648989B2

Reaction notes

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