2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → HCID 10060389, compound

HRID 1585269Notes

Reaction equation

HRID 1585269 reaction equation
[CH3:1][O:2][C:3]1[C:4]([CH:16]([CH3:18])[CH3:17])=[C:5]2[C:10](=[CH:11][C:12]=1[O:13][CH3:14])[CH:9]=[CH:8][CH:7]([CH3:15])[CH2:6]2.ClC1C(=O)C(C#N)=C(C#N)C(=O)C=1Cl>C1C=CC=CC=1>[CH3:14][O:13][C:12]1[C:3]([O:2][CH3:1])=[C:4]([CH:16]([CH3:17])[CH3:18])[C:5]2[C:10](=[CH:9][CH:8]=[C:7]([CH3:15])[CH:6]=2)[CH:11]=1

Participants

4

Reactant 2

HCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 10014812HCID 10014812, compound

Product 1

HCID 10060389HCID 10060389, compoundYield 95.1%

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

Procedure

Compound 12 (3.00 g, 12.2 mmol) was dissolved in 25 mL of benzene and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (2.80 g, 12.2 mmol) was added slowly with stirring and stirring was continued for 3 h. The reaction mixture was filtered through a short column of alumina which was washed with dichloromethane. The solvent was evaporated from the colorless eluant and the residual product was crystallized from petroleum ether to give 2.83 g (11.6 mmol, 95%) of 18 as colorless microcrystalline plates: mp 62-63° C.; 1H NMR: δ1.51 (d, J=7.2 Hz, 6H), 2.50 (s, 3H), 3.88 (s, 3H), 3.90 (sept, J=7.2 Hz, 1H), 3.94 (s, 3H), 7.01 (s, 1H), 7.20 (d, J=8.3 Hz, 1H), 7.60 (d, J=8.3 Hz, 1H), 7.88 (s, 1H). Anal. (C16H20O2) C, H. 8-Deoxyhemigossypol dimethyl ether (19; 2,3-dimethoxy-6-methyl-4-(1-methylethyl)-1-naphthaldehyde. A reaction mixture consisting of 18 (2.5 g, 10.2 mmol) and dichloromethyl methyl ether (3 g, 2.4 ml, 26.5 mmol) in 20 mL of dichloromethane under nitrogen was cooled in an ice bath. Titanium tetrachloride (1.5 ml, 14 mmol) was added slowly with stirring. The mixture was stirred into 100 g of ice with 10 mL of 6 M HCl and the reaction mixture was extracted with ether. The ether layer was washed with water and brine and dried over magnesium sulfate. Petroleum ether was added, the solution was concentrated and the product was allowed to crystallize to give 2.28 g (8.36 mmol, 82%) of 19 as light yellow crystals: mp 103-104° C.; IR 16865 (aldehyde); 1H NMR δ1.52 (d, J=7.2 Hz, 6H), 2.50 (s, 3H), 3.91 (s, 3H), 3.99 (sept, J=7.2 Hz, 1H), 4.02 (s, 3H), 7.38 (d, J=8.7 Hz, 1H), 7.93 (br s, 1H), 9.16 (d, J=8.7 Hz, 1H), 10.75 (s, 1H). Anal. (C17H20O3) C, H.

Workup

  1. stirringstirring
  2. filtrationThe reaction mixture was filtered through a short column of alumina which
  3. washwas washed with dichloromethane
  4. customThe solvent was evaporated from the colorless eluant
  5. customthe residual product was crystallized from petroleum ether

Sources & evidence

ORD record
ord-336d555422dc4b359afdf760a6036808
Source dataset
uspto-grants-1999_08
Patent number
US05936120

Reaction notes

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