Glyoxylic acid, monohydrate → HCID 18620249, compound

HRID 430729Notes

Reaction equation

HRID 430729 reaction equation
[C:1]([C:5]1[CH:10]=[CH:9][C:8]([OH:11])=[C:7]([CH:12]([CH3:27])[CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH3:26])[CH:6]=1)([CH3:4])([CH3:3])[CH3:2].O.[C:29](O)(=[O:32])[CH:30]=[O:31]>ClCCCl.C1(C)C=CC(S(O)(=O)=O)=CC=1>[C:1]([C:5]1[CH:6]=[C:7]([CH:12]([CH3:27])[CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH3:26])[C:8]2[O:11][C:30](=[O:31])[CH:29]([OH:32])[C:9]=2[CH:10]=1)([CH3:4])([CH3:3])[CH3:2]

Participants

5

Reactant 2

HCID 15620607Glyoxylic acid, monohydrateHCID 18620263HCID 18620263, compound

Product 1

HCID 18620249HCID 18620249, compoundYield 99.6%

Reagents, catalysts & solvents 2

HCID 6101p-Toluenesulfonic acidCatalystHCID 111,2-DichloroethaneSolvent

Procedure

18.7 g of 4-tert-butyl-2-(1 -methylpentadecyl)phenol, 5.06 g of glyoxylic acid monohydrate and 0.05 g of p-toluenesulfonic acid are heated for 7 h under a water separator in 40 ml of 1,2-dichloroethane. The reaction solution is then cooled down, washed 3 times with 80 ml of water each time and freed of solvent in a rotary evaporator to leave 21.4 g of 5-tert-butyl-3-hydroxy-7-(1-methylpentadecyl)-3H-benzofuran-2one as a yellowish oil. This yellowish oil is introduced in 25 ml of toluene as initial charge together with 8 ml of thionyl chloride and 3 drops of DMF and then gradually heated to 100° C. so that the evolution of HCl and SO2 remains lively, but still controllable. The reaction mixture is then stirred at 100° C. for a further 1 h. About 25 ml of liquid are subsequently distilled off to remove excess thionyl chloride. The residue is diluted with 80 ml of toluene and admixed at room temperature with 7 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 down to room temperature, and the filtrate is concentrated to an oily consistency in a rotary evaporator. The residue is chromatographed over silica gel (hexane:ethyl acetate 99:1) to isolate the isoxindigo as a waxy red material, obtaining 4.1 g (20% of theory, based on 4-tert-butyl-2-(1-methylpentadecyl)phenol) of 5,5′-di-tert-butyl-7,7′-bis(1-methylpentadecyl)-[3,3′]bibenzofuranylidene-2,2′-dione of the formula:

Workup

  1. temperatureThe reaction solution is then cooled down
  2. washwashed 3 times with 80 ml of water each time
  3. customfreed of solvent in a rotary evaporator

Sources & evidence

ORD record
ord-24641399566e4ab7928dae1d73b17a57
Source dataset
uspto-grants-2001_11
Patent number
US06323267B1

Reaction notes

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