Chlorotrimethylsilane → HCID 178476819, compound

HRID 1938777Notes

Reaction equation

HRID 1938777 reaction equation
[PH2](O)=O.ClC([O:7][CH2:8][CH3:9])=O.[PH2:10]([O:12][CH2:13][CH3:14])=[O:11].[CH3:15][Si](Cl)(C)C.[PH2](=O)O[Si](C)(C)CCC>C1COCC1.CC(C)=O.C(N(CC)CC)C>[OH:7][C:8]([PH:10](=[O:11])[O:12][CH2:13][CH3:14])([CH3:9])[CH3:15]

Participants

9

Reactant 5

HCID 6397ChlorotrimethylsilaneHCID 10928Ethyl chloroformateHCID 4124402Phosphinic AcidHCID 178460913HCID 178460913, compoundHCID 178476775HCID 178476775, compound

Product 1

HCID 178476819HCID 178476819, compound

Reagents, catalysts & solvents 3

HCID 180AcetoneSolventHCID 8028TetrahydrofuranSolventHCID 8471TriethylamineSolvent2×

Procedure

Hypophosphorous acid (100%, 2.0 g, 0.03M) and ethyl chloroformate (3.3 g, 0.03M) are stirred under nitrogen at room temperature in THF (40 ml). Triethylamine (3.03 g, 0.03M) is carefully added with cooling over 1 hour. 31P nmr shows that there is 85% conversion to ethyl hypophosphite (31P nmrδ=16 ppm). Trimethylsilyl chloride (3.3 g, 0.3M) is added followed by triethylamine (3.03 g, 0.03M). The mixture is stirred for 1 hour, when conversion to ethyltrimethylsilyl phosphinate (31P nmrδ=149 ppm) is complete. Acetone (5 ml) is added and the mixture is stirred for 1 hour at 60° C. The mixture is then cooled, quenched with water and washed with methylene chloride. The aqueous phase is evaporated and the residual gum is stirred with ether. Evaporation of the ether gives ethyl (1-hydroxy-1-methylethyl)phosphinate after distillation.

Workup

  1. temperaturewith cooling over 1 hour
  2. stirringthe mixture is stirred for 1 hour at 60° C
  3. temperatureThe mixture is then cooled
  4. customquenched with water
  5. washwashed with methylene chloride
  6. customThe aqueous phase is evaporated
  7. stirringthe residual gum is stirred with ether
  8. customEvaporation of the ether

Sources & evidence

ORD record
ord-b127ead543984c4694ffe270299b5f27
Source dataset
uspto-grants-1997_12
Patent number
US05693799

Reaction notes

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