Aluminium lithium hydride → 2-[(3,5-Bis[1,1-dimethylethyl]-4-hydroxyphenyl)amino]benzaldehyde

HRID 1885231Notes

Reaction equation

HRID 1885231 reaction equation
C[O:2][C:3](=O)[C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][C:5]=1[NH:10][C:11]1[CH:16]=[C:15]([C:17]([CH3:20])([CH3:19])[CH3:18])[C:14]([OH:21])=[C:13]([C:22]([CH3:25])([CH3:24])[CH3:23])[CH:12]=1.[H-].[Al+3].[Li+].[H-].[H-].[H-].[Cr](Cl)([O-])(=O)=O.[NH+]1C=CC=CC=1>C(OCC)C.C(Cl)Cl>[CH3:25][C:22]([C:13]1[CH:12]=[C:11]([NH:10][C:5]2[CH:6]=[CH:7][CH:8]=[CH:9][C:4]=2[CH:3]=[O:2])[CH:16]=[C:15]([C:17]([CH3:18])([CH3:19])[CH3:20])[C:14]=1[OH:21])([CH3:23])[CH3:24]

Participants

6

Reactant 3

HCID 21226445Aluminium lithium hydrideHCID 53640968HCID 53640968, compoundHCID 178418287HCID 178418287, compound

Product 1

HCID 198803512-[(3,5-Bis[1,1-dimethylethyl]-4-hydroxyphenyl)amino]benzaldehydeYield 100%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolvent2×HCID 6344DichloromethaneSolvent

Procedure

2-[(3,5-Bis[1,1 -dimethylethyl]-4-hydroxyphenyl)amino]-benzoic acid methyl ester (1.1 g, 3.1 mmols) is dissolved in 100 mL of diethyl, ether and added to a suspension of lithium aluminum hydride (0.46 g, 12.4 mmols) in 20 mL of diethyl ether at room temperature under an argon atmosphere. After 30 minutes the reaction is quenched with 0.46 mL of water, followed by 0.46 mL of 15% (w/v) aqueous sodium hydroxide and then 1.38 mL of water. The solids are removed by filtration of the reaction mixture into a flask containing sodium dithionite (15 g) and 300 mL of 50% aqueous tetrahydrofuran. The filtrate is concentrated in vacuo and the organics are extracted into two 100 mL portions of methylene chloride. The methylene chloride extracts are washed with 100 mL of brine, dried over magnesium sulfate, and filtered. The filtrate is added to a suspension of pyridinium chlorochromate (2.0 g, 9.3 mmols) and alumina (7.0 g) in 100 mL of methylene chloride. The reaction is stirred at room temperature for 12 hours, then filtered through a silica gel pad which is washed with 100 mL of diethyl ether. The filtrate is concentrated in vacuo and the residue is taken up in 100 mL of tetrahydrofuran. Sodium dithionite (15 g) is dissolved in 100 mL of water and added to the tetrahydrofuran solution. After 15 minutes the mixture is concentrated in vacuo and then extracted with three 50 mL portions of diethyl ether. The ether extract is washed with 50 mL of brine and dried over magnesium sulfate. Evaporation gives 1.0 g (100%) of 2-[(3,5-bis[1,1-dimethylethyl]-4-hydroxyphenyl)amino]benzaldehyde, mp 105°-107° C. An analytical sample is obtained by recrystallization from water/methanol.

Workup

  1. customAfter 30 minutes the reaction is quenched with 0.46 mL of water
  2. customThe solids are removed by filtration of the reaction mixture into a flask
  3. additioncontaining sodium dithionite (15 g) and 300 mL of 50% aqueous tetrahydrofuran
  4. concentrationThe filtrate is concentrated in vacuo
  5. extractionthe organics are extracted into two 100 mL portions of methylene chloride
  6. washThe methylene chloride extracts are washed with 100 mL of brine
  7. dry with materialdried over magnesium sulfate
  8. filtrationfiltered
  9. filtrationfiltered through a silica gel pad which
  10. washis washed with 100 mL of diethyl ether
  11. concentrationThe filtrate is concentrated in vacuo
  12. dissolutionSodium dithionite (15 g) is dissolved in 100 mL of water
  13. additionadded to the tetrahydrofuran solution
  14. concentrationAfter 15 minutes the mixture is concentrated in vacuo
  15. extractionextracted with three 50 mL portions of diethyl ether
  16. extractionThe ether extract
  17. washis washed with 50 mL of brine
  18. dry with materialdried over magnesium sulfate
  19. customEvaporation

Sources & evidence

ORD record
ord-55555552cbbb4d12b61f811000a69a99
Source dataset
uspto-grants-1992_09
Patent number
US05143929

Reaction notes

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