Sodium amide → 1,3,5-Tris[3-(3-tert-butyl-2-hydroxy-5-methylphenyl)propoxycarbonyl]benzene

HRID 1249650Notes

Reaction equation

HRID 1249650 reaction equation
[C:1]1([C:15]([O:17][CH3:18])=[O:16])[CH:6]=[C:5]([C:7]([O:9][CH3:10])=[O:8])[CH:4]=[C:3]([C:11]([O:13][CH3:14])=[O:12])[CH:2]=1.[C:19]([C:23]1[C:24]([OH:34])=[C:25]([CH2:30][CH2:31]CO)[CH:26]=[C:27]([CH3:29])[CH:28]=1)([CH3:22])([CH3:21])[CH3:20].[NH2-].[Na+]>CN(C)C=O>[C:19]([C:23]1[C:24]([OH:34])=[C:25]([CH2:30][CH2:31][CH2:18][O:17][C:15]([C:1]2[CH:6]=[C:5]([C:7]([O:9][CH2:10][CH2:31][CH2:30][C:25]3[CH:26]=[C:27]([CH3:29])[CH:28]=[C:23]([C:19]([CH3:22])([CH3:21])[CH3:20])[C:24]=3[OH:34])=[O:8])[CH:4]=[C:3]([C:11]([O:13][CH2:14][CH2:31][CH2:30][C:25]3[CH:26]=[C:27]([CH3:29])[CH:28]=[C:23]([C:19]([CH3:20])([CH3:21])[CH3:22])[C:24]=3[OH:34])=[O:12])[CH:2]=2)=[O:16])[CH:26]=[C:27]([CH3:29])[CH:28]=1)([CH3:22])([CH3:21])[CH3:20]

Participants

5

Reactant 3

HCID 24533Sodium amideHCID 75881Trimethyl benzene-1,3,5-tricarboxylateHCID 139809533-(3-Tert-butyl-2-hydroxy-5-methylphenyl)-1-propanol

Product 1

HCID 139809661,3,5-Tris[3-(3-tert-butyl-2-hydroxy-5-methylphenyl)propoxycarbonyl]benzeneYield 53%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Procedure

Into a 100 ml reactor equipped with a condenser, thermometer and nitrogen introducing thin tube were charged 1.54 g (6.00 mmol) of trimethyl 1,3,5-benzenetricarboxylate, 4.00 g (18.00 mmol) of 3-(3-tert-butyl-2-hydroxy-5-methylphenyl)-1-propanol and 20 ml of N,N-dimethylformamide. The pressure of the reaction system was reduced to 20 mmHg and 75 vol% (15 ml) of N,N-dimethylformamide was distilled away to dry the reactants, solvent and apparatus. The reaction system was cooled to room temperature, and the vacuum was broken by introducing dry nitrogen. 0.07 g (1.8 mmol) of sodium amide was immediately added to initiate the ester exchange reaction. The reaction system was heated at 50° to 60° C. under 20 mmHg for 2 to 3 hours, and then heated at 60° to 80° C. under 20 mmHg for 2 to 3 hours while distilling N,N-dimethylformamide. Thereafter, the reaction mixture was further heated at 100° to 120° C. under 5 mmHg for 2 to 3 hours. When the reaction was completed, the reaction product was neutralized with dilute hydrochloric acid and then chloroform was added. After liquid separation and dehydration with anhydrous sodium sulfate, the organic solvent was removed under reduced pressure. After separation by silica gel chromatography (solvent: chloroform), 2.60 g (3.16 mmol) of the desired product was obtained. The yield was 53%. The physical properties of the product are shown below.

Workup

  1. customInto a 100 ml reactor equipped with a condenser
  2. distillationwas distilled away
  3. customto dry the reactants, solvent and apparatus
  4. additionby introducing dry nitrogen
  5. temperatureThe reaction system was heated at 50° to 60° C. under 20 mmHg for 2 to 3 hours
  6. temperatureheated at 60° to 80° C. under 20 mmHg for 2 to 3 hours
  7. distillationwhile distilling N,N-dimethylformamide
  8. temperatureThereafter, the reaction mixture was further heated at 100° to 120° C. under 5 mmHg for 2 to 3 hours
  9. additionchloroform was added
  10. customAfter liquid separation and dehydration with anhydrous sodium sulfate
  11. customthe organic solvent was removed under reduced pressure
  12. customAfter separation by silica gel chromatography (solvent: chloroform)

Sources & evidence

ORD record
ord-c0616542655844d7b374f6ce8a6fabd7
Source dataset
uspto-grants-1986_12
Patent number
US04633008

Reaction notes

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