Chlorotrimethylsilane → HCID 18403070, compound

HRID 1017201Notes

Reaction equation

HRID 1017201 reaction equation
[CH2:1]([PH:5](=[O:7])[OH:6])[CH2:2][CH2:3][CH3:4].C(N(CC)CC)C.C[Si](Cl)(C)C.[CH2:20]=[C:21]([CH2:32][CH2:33][C:34]([O:36][CH2:37][C:38]1[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=1)=[O:35])[C:22]([O:24][CH2:25][C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1)=[O:23]>ClCCl>[CH2:1]([P:5]([CH2:20][CH:21]([C:22]([O:24][CH2:25][C:26]1[CH:27]=[CH:28][CH:29]=[CH:30][CH:31]=1)=[O:23])[CH2:32][CH2:33][C:34]([O:36][CH2:37][C:38]1[CH:39]=[CH:40][CH:41]=[CH:42][CH:43]=1)=[O:35])(=[O:6])[OH:7])[CH2:2][CH2:3][CH3:4]

Participants

6

Reactant 4

HCID 6397ChlorotrimethylsilaneHCID 8471TriethylamineHCID 10947302Dibenzyl 2-methylenepentanedioateHCID 178454911HCID 178454911, compound

Product 1

HCID 18403070HCID 18403070, compoundYield 40.6%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

Butylphosphinic acid (2.0 g, 16 mmol) in 80 mL of dry dichloromethane was cooled to 0° C. under an atmosphere of nitrogen. Triethylamine (6.7 g, 66 mmol) was added followed by trimethylsilyl chloride (58 mL, 58 mmol, 1.0 M in dichloromethane). The mixture was stirred at 0° C. for 10 minutes and dibenzyl 2-methylenepentanedioate (2) (6.4 g, 20 mmol) in 20 mL of dichloroemthane was added. The cold bath was removed and the reaction warmed to room temperature and stirred overnight. The mixture was then cooled to 0° C. and quenched by the slow addition of 5% hydrochloric acid. The dichloromethane layer was then removed and washed with 5% hydrochloric acid and with brine. The organic layer was dried (MgSO4) and evaporated to give a clear light golden liquid. The liquid was purified by flash chromatography and eluted with 3:1 hexane/ethyl acetate containing 5% acetic acid. The desired fractions were combined and evaporated to give butyl[2,4-di(benzyloxycarbonyl)butyl]phosphinic acid (3,R=-butyl, R1=H) (2.9 g, 40%) as a clear and colorless oil. Rf 0.12 (3:1, Hex./EtOAc 5% AcOH).

Workup

  1. customThe cold bath was removed
  2. temperaturethe reaction warmed to room temperature
  3. stirringstirred overnight
  4. temperatureThe mixture was then cooled to 0° C.
  5. customquenched by the slow addition of 5% hydrochloric acid
  6. customThe dichloromethane layer was then removed
  7. washwashed with 5% hydrochloric acid and with brine
  8. dry with materialThe organic layer was dried (MgSO4)
  9. customevaporated
  10. customto give a clear light golden liquid
  11. customThe liquid was purified by flash chromatography
  12. washeluted with 3:1 hexane/ethyl acetate containing 5% acetic acid
  13. customevaporated

Sources & evidence

ORD record
ord-993a6dabf0aa4743b28ff05eb46ac5bc
Source dataset
uspto-grants-2002_11
Patent number
US06479471B1

Reaction notes

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