Dimethyl 4,4'-biphenyldicarboxylate → 4,4'-Bis(hydroxymethyl)biphenyl

HRID 374234

Reaction equation

HRID 374234 reaction equation
[H-].[H-].[H-].[H-].[Li+].[Al+3].C[O:8][C:9]([C:11]1[CH:16]=[CH:15][C:14]([C:17]2[CH:22]=[CH:21][C:20]([C:23](OC)=[O:24])=[CH:19][CH:18]=2)=[CH:13][CH:12]=1)=O>O1CCCC1>[OH:8][CH2:9][C:11]1[CH:12]=[CH:13][C:14]([C:17]2[CH:22]=[CH:21][C:20]([CH2:23][OH:24])=[CH:19][CH:18]=2)=[CH:15][CH:16]=1

Participants

4

Reactant 2

HCID 13099Dimethyl 4,4'-biphenyldicarboxylateHCID 21226445Aluminium lithium hydride

Product 1

HCID 6117864,4'-Bis(hydroxymethyl)biphenylYield 96.7%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
50 °C

Procedure

789 mg (20.8 mmoles) of LiAlH4 in 150 ml of anhydrous THF (tetrahydrofuran) are placed in a 2-liter flask which has a mechanical agitator, cooler, filler funnel and heating bath. A solution, heated to 50° C., of 7.5 g (27.7 mmoles) of 4,4'-bis (methoxycarbonyl)biphenyl in 500 ml of anhydrous THF is added dropwise, over a period of 1 hour, to the mixture, heated in an inert atmosphere to 50° C. under agitation. After a further 30 minutes of agitation in a heating bath, the mixture is cooled to ambient temperature and the excess LiAlH4 is destroyed by the careful addition of 15 ml of a THF/H2O (80:20) mixture. The reaction mixture is filtered on Septum G2, washing the precipitate with anydrous ethanol (3×100 ml). The combined filtrate and washings are evaporated to dryness under vacuum with the heating bath at 40° C. The residue is then redissolved with 100 ml of hot acetone (50° C.), eliminating the insoluble residue by filtration, dried on anhydrous Na2SO4 and evaporated to dryness. 5.74 g of 4,4'-bis (hydroxymethyl) biphenyl are obtained with a molar yield of 96.6%.

Workup

  1. temperatureheating bath
  2. additionis added dropwise, over a period of 1 hour, to the mixture
  3. temperaturethe mixture is cooled to ambient temperature
  4. customthe excess LiAlH4 is destroyed by the careful addition of 15 ml of a THF/H2O (80:20) mixture
  5. filtrationThe reaction mixture is filtered on Septum G2
  6. washwashing the precipitate with anydrous ethanol (3×100 ml)
  7. customThe combined filtrate and washings are evaporated to dryness under vacuum with the heating bath at 40° C
  8. dissolutionThe residue is then redissolved with 100 ml of hot acetone (50° C.)
  9. filtrationby filtration
  10. dry with materialdried on anhydrous Na2SO4
  11. customevaporated to dryness

Sources & evidence

ORD record
ord-dc1cc74ee0e64fada48665083944095b
Source dataset
uspto-grants-1992_11
Patent number
US05166380

Linked notes

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