Hydrochloric Acid → 7,7'-Di-tert-butyl-5,5'-dimethyl-[3,3']bibenzofuranylidene-2,2'-dione

HRID 430725Notes

Reaction equation

HRID 430725 reaction equation
[C:1]([C:5]1[C:13]2[O:12][C:11](=[O:14])[CH:10](O)[C:9]=2[CH:8]=[C:7]([CH3:16])[CH:6]=1)([CH3:4])([CH3:3])[CH3:2].S(Cl)(Cl)=O.Cl>C1(C)C=CC=CC=1.CN(C=O)C>[C:1]([C:5]1[C:13]2[O:12][C:11](=[O:14])[C:10](=[C:10]3[C:9]4[CH:8]=[C:7]([CH3:16])[CH:6]=[C:5]([C:1]([CH3:2])([CH3:3])[CH3:4])[C:13]=4[O:12][C:11]3=[O:14])[C:9]=2[CH:8]=[C:7]([CH3:16])[CH:6]=1)([CH3:4])([CH3:3])[CH3:2]

Participants

6

Reactant 3

HCID 313Hydrochloric AcidHCID 24386Thionyl ChlorideHCID 186202687-tert-butyl-3-hydroxy-5-methyl-3H-benzofuran-2-one

Product 1

HCID 4358387,7'-Di-tert-butyl-5,5'-dimethyl-[3,3']bibenzofuranylidene-2,2'-dioneYield 57.4%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideCatalystHCID 1140TolueneSolvent

Conditions

Temperature
100 °C

Procedure

22 g of 7-tert-butyl-3-hydroxy-5-methyl-3H-benzofuran-2-one (prepared as described in Example 2 of U.S. Pat. No. 5,614,572) are introduced in 50 ml of toluene as initial charge and admixed with 3 drops of DMF and 15 ml of thionyl chloride. The solution is then gradually heated to 100° C. so that the evolution of HCl and SO2 remains lively but still controllable. Thereafter the reaction mixture is stirred at 100° C. for a further 1 h. About 50 ml of liquid are subsequently distilled off to remove excess thionyl chloride. The residue is diluted with 160 ml of toluene and admixed at room temperature with 14 ml of triethylamine added dropwise. The thick red reaction mixture is then refluxed for 30 min. The precipitated triethylamine hydrochloride is filtered off after cooling to room temperature and the residue is concentrated in a rotary evaporator to an oily consistency. The isoxindigo is crystallized out by addition of 200 ml of acetonitrile, filtered off, washed with acetonitrile and dried to leave 11.6 g (57% of theory) of 7,7′-di-tert-butyl-5,5′-dimethyl[3,3′]bibenzofuranylidene-2,2′-dione of the formula:

Workup

  1. distillationAbout 50 ml of liquid are subsequently distilled off
  2. customto remove excess thionyl chloride
  3. additionThe residue is diluted with 160 ml of toluene
  4. customadmixed at room temperature with 14 ml of triethylamine
  5. additionadded dropwise
  6. customThe thick red reaction mixture
  7. temperatureis then refluxed for 30 min
  8. filtrationThe precipitated triethylamine hydrochloride is filtered off
  9. temperatureafter cooling to room temperature
  10. concentrationthe residue is concentrated in a rotary evaporator to an oily consistency
  11. customThe isoxindigo is crystallized out by addition of 200 ml of acetonitrile
  12. filtrationfiltered off
  13. washwashed with acetonitrile
  14. customdried

Sources & evidence

ORD record
ord-f31598657b104895b2907d5184403ae7
Source dataset
uspto-grants-2001_11
Patent number
US06323267B1

Reaction notes

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