Sulfuric Acid → 2,5-Bishydroxymethyl-2',5'-dimethylbiphenyl

HRID 1635759Notes

Reaction equation

HRID 1635759 reaction equation
[H-].[H-].[H-].[H-].[Li+].[Al+3].[CH3:7][C:8]1[CH:13]=[CH:12][C:11]([CH3:14])=[CH:10][C:9]=1[C:15]1[CH:25]=[C:24]([C:26](OCC)=[O:27])[CH:23]=[CH:22][C:16]=1[C:17](OCC)=[O:18].S(=O)(=O)(O)O>C1COCC1>[OH:18][CH2:17][C:16]1[CH:22]=[CH:23][C:24]([CH2:26][OH:27])=[CH:25][C:15]=1[C:9]1[CH:10]=[C:11]([CH3:14])[CH:12]=[CH:13][C:8]=1[CH3:7]

Participants

5

Reactant 3

HCID 1118Sulfuric AcidHCID 18676609Diethyl 2-(2',5'dimethylphenyl)terephthalateHCID 21226445Aluminium lithium hydride

Product 1

HCID 184199172,5-Bishydroxymethyl-2',5'-dimethylbiphenyl

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
67 °C

Procedure

LiAlH4 (7.9 g, 208 mmol) together with about 250 ml of THF were placed in a reaction vessel under a blanket of argon. Diethyl 2-(2′,5′-dimethylphenyl)terephthalate (48.6 g, 149 mmol) (cf. C3) was diluted in a dropping funnel with about 60 ml of THF and slowly added dropwise. The reaction mixture was stirred vigorously during this addition. The mixture was diluted with another 100 ml of THF and then refluxed at 67° C. After 2 hours, it was cooled to RT. While cooling on a water bath and blanketing with argon, ice water was added dropwise until gas evolution had ceased. Dilute (10% strength) sulfuric acid was subsequently added dropwise until the turbid gray mixture became clear. The phase mixture was separated by addition of a generous amount of chloroform and the aqueous phase was subsequently shaken twice with chloroform. The organic phases were shaken once with H2O and evaporated. The crude product was recrystallized from chloroform/hexane: 24.7 g (68%) of colorless, microcrystalline powder; melting point: 145-148° C. (purity>95%).

Workup

  1. additionslowly added dropwise
  2. temperatureit was cooled to RT
  3. temperatureWhile cooling on a water bath
  4. additionwas added dropwise until gas evolution
  5. additionwas subsequently added dropwise until the turbid gray mixture
  6. customThe phase mixture was separated by addition of a generous amount of chloroform
  7. stirringthe aqueous phase was subsequently shaken twice with chloroform
  8. stirringThe organic phases were shaken once with H2O
  9. customevaporated
  10. customThe crude product was recrystallized from chloroform/hexane

Sources & evidence

ORD record
ord-18d97c1bd4ed4ee68f75c12dac3a1027
Source dataset
uspto-grants-2003_01
Patent number
US06509507B2

Reaction notes

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