Triphenylphosphine → 1-(Bromomethyl)adamantane

HRID 866546Notes

Reaction equation

HRID 866546 reaction equation
O[CH2:2][C:3]12[CH2:12][CH:7]3[CH2:8][CH:9]([CH2:11][CH:5]([CH2:6]3)[CH2:4]1)[CH2:10]2.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Br:32]Br>CN(C)C=O>[Br:32][CH2:2][C:3]12[CH2:12][CH:7]3[CH2:8][CH:9]([CH2:11][CH:5]([CH2:6]3)[CH2:4]1)[CH2:10]2

Participants

5

Reactant 3

HCID 11776TriphenylphosphineHCID 24408BromineHCID 64556Tricyclo(3.3.1.1'3,7)dec-1-ylmethanol

Product 1

HCID 14163041-(Bromomethyl)adamantane

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Procedure

To 1-Hydroxymethyladamantane (366 gm.) and triphenylphosphine (598 gm.) in 1600 ml. dimethylformamide was added a solution of 366 gm. bromine in 800 ml. dimethylformamide over a 5 hour period. The mixtue was left overnight at room temperature and then distilled (under aspirator) to remove solvent and product. The distillate was poured into 8 liters of water and filtered. The solid was dissolved in petroleum ether (30°-60°), washed with K2CO3 solution, then with water, dried, and concentrated to dryness. The residue recrystallized from 2.5 liters methanol gave 426.6 gm., m.p. 43°-4°. (1st crop plus additional crops obtained on concentration of the mother liquors.)

Workup

  1. distillationdistilled (under aspirator)
  2. customto remove solvent and product
  3. additionThe distillate was poured into 8 liters of water
  4. filtrationfiltered
  5. dissolutionThe solid was dissolved in petroleum ether (30°-60°)
  6. washwashed with K2CO3 solution
  7. dry with materialwith water, dried
  8. concentrationconcentrated to dryness
  9. customThe residue recrystallized from 2.5 liters methanol
  10. customgave 426.6 gm
  11. custom(1st crop plus additional crops obtained on concentration of the mother liquors

Sources & evidence

ORD record
ord-64b0b6bcbf104e7fae646bf53a3ffc8d
Source dataset
uspto-grants-1978_07
Patent number
US04100170

Reaction notes

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