Formaldehyde → 2,2-Adamantane dimethanol

HRID 555202Notes

Reaction equation

HRID 555202 reaction equation
[CH:1]12[CH2:10][CH:5]3[CH2:6][CH:7]([CH2:9][CH:3]([CH2:4]3)[CH:2]1[CH:11]=[O:12])[CH2:8]2.C12CC3CC(CC(C3)[C:14]1=[O:23])C2.ClCC([O-])=O.C=O.[OH-].[Na+]>CO.O1CCCC1>[CH:1]12[CH2:10][CH:5]3[CH2:6][CH:7]([CH2:9][CH:3]([CH2:4]3)[C:2]1([CH2:14][OH:23])[CH2:11][OH:12])[CH2:8]2

Participants

8

Reactant 5

HCID 712FormaldehydeHCID 14798Sodium HydroxideHCID 64151AdamantanoneHCID 518964ChloroacetateHCID 12470455Adamantane-2-carbaldehyde

Product 1

HCID 578740082,2-Adamantane dimethanol

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a mixture of 283 g of 2-adamantane carbaldehyde (which had been synthesized by Darzen reaction of adamantanone with chloroacetate, hydrolysis of the resulting glycidyl ester, and subsequent heating for decarbonation), 300 g of tetrahydrofuran, and 500 ml of methanol under ice cooling, 380 g of a 37% formaldehyde aqueous solution was added and then 350 g of a 25% sodium hydroxide aqueous solution was added dropwise over 30 minutes. After the completion of dropwise addition, the ice bath was removed, and the reaction mixture was stirred for 18 hours at room temperature. The reaction mixture was poured into a saturated sodium chloride aqueous solution, which was extracted with a 1:1 tetrahydrofuran/ethyl acetate mixture. The crude product obtained by concentrating the organic layer was recrystallized from n-hexane/diethyl ether, collecting 288 g (yield 85%) of the target compound.

Workup

  1. additionAfter the completion of dropwise addition
  2. customthe ice bath was removed
  3. additionThe reaction mixture was poured into a saturated sodium chloride aqueous solution, which
  4. extractionwas extracted with a 1:1 tetrahydrofuran/ethyl acetate mixture

Sources & evidence

ORD record
ord-f366247e4fda4f1d8b51566fcf81c06a
Source dataset
uspto-grants-2011_11
Patent number
US08053165B2

Reaction notes

Loading…