Diethyl chlorophosphate → HCID 86603461, compound

HRID 1171007Notes

Reaction equation

HRID 1171007 reaction equation
[CH3:1][C:2]1[CH:18]=[C:17]([S:19]([CH3:22])(=[O:21])=[O:20])[CH:16]=[C:15]([CH3:23])[C:3]=1[O:4][Si:5]([CH:12]([CH3:14])[CH3:13])([CH:9]([CH3:11])[CH3:10])[CH:6]([CH3:8])[CH3:7].[Li]CCCC.[P:29](Cl)(=[O:36])([O:33][CH2:34][CH3:35])[O:30][CH2:31][CH3:32]>C1COCC1>[CH3:23][C:15]1[CH:16]=[C:17]([S:19]([CH2:22][P:29](=[O:36])([O:33][CH2:34][CH3:35])[O:30][CH2:31][CH3:32])(=[O:21])=[O:20])[CH:18]=[C:2]([CH3:1])[C:3]=1[O:4][Si:5]([CH:6]([CH3:7])[CH3:8])([CH:9]([CH3:10])[CH3:11])[CH:12]([CH3:14])[CH3:13]

Participants

5

Reactant 3

HCID 13139Diethyl chlorophosphateHCID 66643156HCID 66643156, compoundHCID 178418339Butyllithium

Product 1

HCID 86603461HCID 86603461, compoundYield 15.4%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

To a stirring solution of (2,6-dimethyl-4-methanesulfonylphenoxy)triisopropylsilane (0.47 g, 1.32 mmol) in THF (15 mL) at −78° C. was added n-BuLi (2.5 M in hexanes, 0.58 mL), the reaction mixture was stirred at −78° C. for 1 hr, then diethyl phosphorochloridate (0.25 mL, 1.72 mmol) was added at −78° C. The reaction mixture was stirred at room temperature for 16 hrs. The reaction mixture was quenched with saturated NH4Cl and diluted with diethyl ether. The organic layer was dried over Na2SO4, filtered and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel, eluting with ethyl acetate-hexanes (1:1) to afford diethyl (3,5-dimethyl-4-triisopropylsilanyloxy-benzenesulfonyl)methylphosphonate as a colorless oil (0.1 g, 15%): 1H NMR (200 MHz, CDCl3-d6): δ 7.57 (s, 2 H), 4.17 (m, 4 H), 3.71 (d, J=17.2 Hz, 2 H), 2.29 (s, 6 H), 1.33 (m, 9 H), 1.10 (d, J=7.2 Hz, 18 H). TLC conditions: Uniplate silica gel, 250 microns; Mobile phase=ethyl acetate-hexanes (1:1); Rf=0.45.

Workup

  1. stirringThe reaction mixture was stirred at room temperature for 16 hrs
  2. customThe reaction mixture was quenched with saturated NH4Cl
  3. additiondiluted with diethyl ether
  4. dry with materialThe organic layer was dried over Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure
  7. customThe residue was purified by column chromatography on silica gel
  8. washeluting with ethyl acetate-hexanes (1:1)

Sources & evidence

ORD record
ord-f194b6583efc4a88a710a7a7fbe1f541
Source dataset
uspto-grants-2010_11
Patent number
US07829552B2

Reaction notes

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