1,2-Dichloroethane → HCID 22628569, compound

HRID 278515Notes

Reaction equation

HRID 278515 reaction equation
[C:1]([C:5]1[CH:10]=[C:9]([C:11]([CH3:14])([CH3:13])[CH3:12])[CH:8]=[CH:7][C:6]=1[OH:15])([CH3:4])([CH3:3])[CH3:2].[C:16]([OH:20])(=O)[CH:17]=O.ClCCCl.[CH:25]1[C:37]2[CH2:36][C:35]3[C:30](=[CH:31][CH:32]=[CH:33][CH:34]=3)[C:29]=2[CH:28]=[CH:27][CH:26]=1>O.C1(C)C=CC(S(O)(=O)=O)=CC=1.O>[C:11]([C:9]1[CH:10]=[C:5]([C:1]([CH3:4])([CH3:3])[CH3:2])[C:6]2[O:15][C:16](=[O:20])[CH:17]([C:32]3[CH:33]=[CH:34][C:35]4[CH2:36][C:37]5[C:29]([C:30]=4[CH:31]=3)=[CH:28][CH:27]=[CH:26][CH:25]=5)[C:7]=2[CH:8]=1)([CH3:14])([CH3:13])[CH3:12]

Participants

7

Reactant 4

HCID 111,2-DichloroethaneHCID 760Glyoxylic AcidHCID 6853FluoreneHCID 73112,4-Di-tert-butylphenol

Product 1

HCID 22628569HCID 22628569, compoundYield 17.1%

Reagents, catalysts & solvents 2

HCID 521998p-Toluenesulfonic acid monohydrateCatalystHCID 962WaterSolvent2×

Procedure

A mixture of 15.9 g (75 mmol) of 2,4di-tert-butylphenol (97%), 12.2 g (82 mmol) of 50% aqueous glyoxylic acid, 40 mg (0.20 mmol) of p-toluenesulfonic acid monohydrate and 25 ml of 1,2-dichloroethane is refluxed for 3.5 hours under nitrogen on a water separator. The reaction mixture is thereafter concentrated on a vacuum rotary evaporator. The residue is dissolved in 30 ml of n-octane and 12.5 g (75 mmol) of fluorene and 3 g of Fulcat 22B are added to the solution. This reaction mixture is refluxed for 3.5 hours under nitrogen on a water separator, then cooled and filtered. The filtrate is concentrated on a vacuum rotary evaporator. Chromatography of the residue on silica gel with the solvent system dichloromethane/hexane=2:1 and subsequent crystallisation of the pure fractions from methanol yields 5.28 g (17%) of 5,7-di-tert-butyl-3-(9H-fluoren-3-yl)-3H-benzofuran-2-one, m.p. 140-153° C. (compound (121), Table 1). The product may additionally contain minor amounts of other structural isomers in accordance with the substitution at the fluorene ring.

Workup

  1. concentrationThe reaction mixture is thereafter concentrated on a vacuum rotary evaporator
  2. dissolutionThe residue is dissolved in 30 ml of n-octane
  3. temperaturecooled
  4. filtrationfiltered
  5. concentrationThe filtrate is concentrated on a vacuum rotary evaporator
  6. customChromatography of the residue on silica gel with the solvent system dichloromethane/hexane=2:1 and subsequent crystallisation of the pure fractions from methanol

Sources & evidence

ORD record
ord-40e1324555ac4647a5746643b2382efc
Source dataset
uspto-grants-2002_03
Patent number
US06359148B1

Reaction notes

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