Trimethyl phosphite → (9-Anthracenylmethyl)phosphonic acid dimethyl ester

HRID 1440665Notes

Reaction equation

HRID 1440665 reaction equation
Cl[CH2:2][C:3]1[C:4]2[C:9]([CH:10]=[C:11]3[C:16]=1[CH:15]=[CH:14][CH:13]=[CH:12]3)=[CH:8][CH:7]=[CH:6][CH:5]=2.[CH3:17][O:18][P:19]([O:22]C)[O:20][CH3:21]>>[CH3:17][O:18][P:19]([CH2:2][C:3]1[C:4]2[C:9]([CH:10]=[C:11]3[C:16]=1[CH:15]=[CH:14][CH:13]=[CH:12]3)=[CH:8][CH:7]=[CH:6][CH:5]=2)(=[O:22])[O:20][CH3:21]

Participants

3

Reactant 2

HCID 8472Trimethyl phosphiteHCID 323859-(Chloromethyl)anthracene

Product 1

HCID 54194150(9-Anthracenylmethyl)phosphonic acid dimethyl esterYield 40.5%

Procedure

A solution of 9-(chloromethyl)anthracene (2.5 g, 0.011 M) in trimethylphosphite (5 mL, 5.26 g, 0.042 M) is heated at reflux temperature for 72 hours. Excess trimethylphosphite is removed under reduced pressure and the residue is chromatographed over silica gel (400 g, 40-63 μm, CH2Cl2, 50 mL fractions) using CH2Cl2 (60 fractions) and 2% CH3OH in CH2Cl2 for the remaining fractions. Fractions 86-93 (2.99 g) are found to contain desired material and an impurity and are rechromatographed (400 g silica gel, 40-63 μm, CH2Cl2, 50 mL fractions) using 2.5% acetone-CH2Cl2 to elute the column. Fractions 100-160 contains compound (1.495 g, 0.00498 M, 45%) as a yellow solid. Crystallization from ethyl acetate gives the title compound (1.34 g) as yellow needles, mp 152°-153° C.

Workup

  1. temperatureat reflux temperature for 72 hours
  2. customExcess trimethylphosphite is removed under reduced pressure
  3. customthe residue is chromatographed over silica gel (400 g, 40-63 μm, CH2Cl2, 50 mL fractions)
  4. customan impurity and are rechromatographed (400 g silica gel, 40-63 μm, CH2Cl2, 50 mL fractions)
  5. washto elute the column
  6. customCrystallization from ethyl acetate

Sources & evidence

ORD record
ord-c4a24b2cd2c645fb99c69982f88c52ab
Source dataset
uspto-grants-1996_03
Patent number
US05500417

Reaction notes

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