Triethyl phosphite → Diethyl 4-(4-methoxybenzoyl)benzylphosphonate

HRID 1525312Notes

Reaction equation

HRID 1525312 reaction equation
Br[CH2:2][C:3]1[CH:8]=[CH:7][C:6]([C:9]([C:11]2[CH:16]=[CH:15][C:14]([O:17][CH3:18])=[CH:13][CH:12]=2)=[O:10])=[CH:5][CH:4]=1.[P:19]([O:26]CC)([O:23][CH2:24][CH3:25])[O:20][CH2:21][CH3:22]>CN(C=O)C.O>[CH3:18][O:17][C:14]1[CH:15]=[CH:16][C:11]([C:9]([C:6]2[CH:7]=[CH:8][C:3]([CH2:2][P:19](=[O:26])([O:23][CH2:24][CH3:25])[O:20][CH2:21][CH3:22])=[CH:4][CH:5]=2)=[O:10])=[CH:12][CH:13]=1

Participants

5

Reactant 2

HCID 31215Triethyl phosphiteHCID 131506704-(4-Methoxybenzoyl)benzyl bromide2×

Product 1

HCID 89462655Diethyl 4-(4-methoxybenzoyl)benzylphosphonateYield 72%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent

Conditions

Temperature
150 °C

Procedure

(4-(bromomethyl)phenyl)(4-methoxyphenyl)methanone, 32-c, (3 g, 10 mmol) and triethyl phosphite (2 g, 11.9 mmol) was dissolved in DMF (20 ml), and then stirred for 10 h at 150° C. The resulting mixture was cooled to ambient temperature, diluted with water (50 ml) and extracted with ethyl acetate (3×50 ml). The organic layer was combined, washed with brine (2×100 ml), dried over Na2SO4 anhydrous, purified by chromatography on silica gel (petroleum ether/ethyl acetate=1:1.5). The pure product, 32-d, was obtained as a colorless oil (2.6 g, 72% yield). 1H NMR (300 MHz, CDCl3) δ 1.20-1.27 (m, 6H), 2.80-2.88 (d, J=22.8, 2H) 3.81 (s, 3H), 3.93-4.07 (m, 4H), 6.86-6.90 (m, 2H), 7.31-7.35 (m, 2H), 7.62-7.93 (m, 4H). LC-MS 363 [MH]+.

Workup

  1. temperatureThe resulting mixture was cooled to ambient temperature
  2. extractionextracted with ethyl acetate (3×50 ml)
  3. washwashed with brine (2×100 ml)
  4. dry with materialdried over Na2SO4 anhydrous
  5. custompurified by chromatography on silica gel (petroleum ether/ethyl acetate=1:1.5)

Sources & evidence

ORD record
ord-17276aeb6b5542bf8bbbcebcf41e85bf
Source dataset
uspto-grants-2015_07
Patent number
US09079930B2

Reaction notes

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