Triethylamine → 4-(Diethylphosphono)phenylmethyl acetate

HRID 866082Notes

Reaction equation

HRID 866082 reaction equation
C(N(CC)CC)C.[P:8]([O-:15])([O:12][CH2:13][CH3:14])[O:9][CH2:10][CH3:11].[C:16]([O:19][CH2:20][C:21]1[CH:26]=[CH:25][C:24](Br)=[CH:23][CH:22]=1)(=[O:18])[CH3:17]>C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C(OCC)(=O)C>[C:16]([O:19][CH2:20][C:21]1[CH:26]=[CH:25][C:24]([P:8]([O:12][CH2:13][CH3:14])([O:9][CH2:10][CH3:11])=[O:15])=[CH:23][CH:22]=1)(=[O:18])[CH3:17]

Participants

6

Reactant 3

HCID 8471TriethylamineHCID 3780918DiethylphosphiteHCID 111071264-Bromobenzyl acetate

Product 1

HCID 190409274-(Diethylphosphono)phenylmethyl acetateYield 68%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
100 °C

Procedure

A mixture of 9.7 mL (0.057 mole) of triethylamine and 2.4 grams (0.002 mole) of tetrakis(triphenylphosphine)palladium(0) was stirred, and 7.3 mL (0.057 mole) of diethyl phosphite was added. To this was added 13.2 grams (0.057 mole) of 4-bromophenylmethyl acetate. The reaction mixture was warmed to about 100° C., where it stirred for 30 minutes. The reaction mixture was cooled, and 200 mL of ethyl acetate was added. The resultant solid was collected by filtration, and washed with 50 mL of ethyl acetate. The combined wash and filtrate were concentrated under reduced pressure to a residual oil, which was subjected to column chromatography on silica gel, with 3:7 heptane:ethyl acetate as eluant. The product-containing fractions were combined and concentrated under reduced pressure, yielding 11.1 grams of 4-(diethylphosphono)phenylmethyl acetate. The NMR spectrum was consistent with the proposed structure.

Workup

  1. stirringwhere it stirred for 30 minutes
  2. temperatureThe reaction mixture was cooled
  3. filtrationThe resultant solid was collected by filtration
  4. washwashed with 50 mL of ethyl acetate
  5. washThe combined wash
  6. concentrationfiltrate were concentrated under reduced pressure to a residual oil, which
  7. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-9513029817104f8daebcc40b7becb0f3
Source dataset
uspto-grants-1996_10
Patent number
US05569664

Reaction notes

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