Phthalic Anhydride → 1,2-Benzenedimethanol

HRID 1284264Notes

Reaction equation

HRID 1284264 reaction equation
[BH4-].[Na+].B(F)(F)F.CCOCC.[C:12]1(=O)[O:17][C:15](=[O:16])[C:14]2=[CH:18][CH:19]=[CH:20][CH:21]=[C:13]12.[BH4-].[Na+].B(F)(F)F.C(=O)([O-])[O-].[K+].[K+]>C(OCC)C.O.O1CCCC1>[C:13]1([CH2:12][OH:17])[C:14]([CH2:15][OH:16])=[CH:18][CH:19]=[CH:20][CH:21]=1

Participants

9

Reactant 5

HCID 6811Phthalic AnhydrideHCID 8000Boron trifluoride etherateHCID 11430Potassium CarbonateHCID 4311764Sodium borohydrideHCID 131710444HCID 131710444, compound

Product 1

HCID 691531,2-BenzenedimethanolYield 95%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
20 °C

Procedure

A 2-liter, 4-necked glass reaction vessel equipped as described in Example 1 was charged with 44.6 grams (1.12 moles plus 5% excess) of sodium borohydride, 0.75 liter of tetrahydrofuran, and 0.185 liter (1.5 moles) of boron trifluoride diethyl etherate at 0°-5°C using the procedure described in Example 1. In a separate 3-liter, 4-necked glass reaction vessel equipped as described in Example 1 was placed 148 grams (1.0 mole) of phthalic anhydride and 0.25 liter of tetrahydrofuran. The resulting slurry was cooled to 0°-5°C using an external ice/water bath. The sodium borohydride-boron trifluoride reaction mixture was then transferred under nitrogen pressure to the anhydride/tetrahydrofuran slurry over a 1.5 hour period while maintaining a temperature of 5°-10°C. After stirring the reaction mixture for 12 hours at 20°C, 0.25 liter of water was added dropwise over a one hour period followed by one liter of diethyl ether. The aqueous layer was saturated with anhydrous potassium carbonate and the organic layer was removed. The aqueous layer was extracted with diethyl ether (2 × 0.25 liter) and the combined organic extracts were dried over anhydrous potassium carbonate, filtered, and concentrated on a rotary evaporator giving 131 grams (95% yield) of 1,2-benzene dimethanol as a crystalline solid, mp 58°-60°C.

Workup

  1. customA 2-liter, 4-necked glass reaction vessel
  2. customequipped
  3. customIn a separate 3-liter, 4-necked glass reaction vessel
  4. customequipped
  5. temperatureThe resulting slurry was cooled to 0°-5°C
  6. customover a 1.5 hour
  7. temperaturewhile maintaining a temperature of 5°-10°C
  8. customthe organic layer was removed
  9. extractionThe aqueous layer was extracted with diethyl ether (2 × 0.25 liter)
  10. dry with materialthe combined organic extracts were dried over anhydrous potassium carbonate
  11. filtrationfiltered
  12. concentrationconcentrated on a rotary evaporator

Sources & evidence

ORD record
ord-50e7f16e33f1415e8680dc93435aab29
Source dataset
uspto-grants-1976_08
Patent number
US03978140

Reaction notes

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