Trimethyl phosphite → HCID 54009753, compound

HRID 2379031Notes

Reaction equation

HRID 2379031 reaction equation
Br[CH2:2][C:3]1[C:12]2[C:7](=[CH:8][CH:9]=[CH:10][CH:11]=2)[C:6]([CH2:13]Br)=[CH:5][CH:4]=1.C[O:16][P:17]([O:20][CH3:21])[O:18][CH3:19]>C1(C)C=CC=CC=1>[CH3:19][O:18][P:17]([CH2:2][C:3]1[C:12]2[C:7](=[CH:8][CH:9]=[CH:10][CH:11]=2)[C:6]([CH2:13][P:17](=[O:16])([O:20][CH3:21])[O:18][CH3:19])=[CH:5][CH:4]=1)(=[O:16])[O:20][CH3:21]

Participants

4

Reactant 2

HCID 8472Trimethyl phosphiteHCID 5930171,4-Bis(bromomethyl)naphthalene

Product 1

HCID 54009753HCID 54009753, compoundYield 82.1%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

A 200 mL round bottom flask is charged with 1,4-bis(bromomethyl)naphthalene (Example 26(b), 2.07 g, 6.6 mmol) and toluene (75 mL). The flask is equipped with a Dean-Stark trap, condenser, and nitrogen inlet. The mixture is heated to reflux temperature to dry the toluene and starting material. A total of 25 mL of toluene is collected in the Dean-Stark trap and then discarded. The mixture is cooled to room temperature and then trimethyl-phosphite (4 mL, 34 mmol) is added and the reaction is heated at a gentle reflux overnight. The reaction is checked by TLC after 24 hours and found to be complete. The toluene and excess trimethylphosphite are removed at a reduced pressure to yield an oil. The product is chromatographed on 400 g of 40-63 μm silica gel. The sample is applied in ethyl acetate and elution is with 10% methanol-ethyl acetate. Fractions which contained 50 mL each are collected. The desired product (2.01 g, 0.00542 mole, 81%) is eluted in fractions 60-80 and is a viscous oil.

Workup

  1. customThe flask is equipped with a Dean-Stark trap, condenser, and nitrogen inlet
  2. temperatureThe mixture is heated
  3. temperatureto reflux temperature
  4. dry with materialto dry the toluene
  5. customA total of 25 mL of toluene is collected in the Dean-Stark trap
  6. temperaturethe reaction is heated at
  7. temperaturea gentle reflux overnight
  8. customThe toluene and excess trimethylphosphite are removed at a reduced pressure
  9. customto yield an oil
  10. customThe product is chromatographed on 400 g of 40-63 μm silica gel
  11. washelution
  12. customare collected

Sources & evidence

ORD record
ord-9a082a5a7beb47e5986a4caef0260ff6
Source dataset
uspto-grants-1994_11
Patent number
US05360797

Reaction notes

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