Chlorotrimethylsilane → HCID 18403062, compound

HRID 1003170Notes

Reaction equation

HRID 1003170 reaction equation
C(P(=O)O)C1C=CC=CC=1.[CH2:11]([P:18]([CH2:21][CH:22]([C:35]([O:37][CH2:38][C:39]1[CH:44]=[CH:43][CH:42]=[CH:41][CH:40]=1)=[O:36])[CH2:23][CH2:24][C:25]([O:27][CH2:28][C:29]1[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=1)=[O:26])(=[O:20])[OH:19])[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.C(N(CC)CC)C.C[Si](Cl)(C)C.C=C(CCC(OCC1C=CC=CC=1)=O)C(OCC1C=CC=CC=1)=O>ClCCl>[CH2:11]([P:18]([CH2:21][CH:22]([C:35]([O:37][CH2:38][C:39]1[CH:40]=[CH:41][CH:42]=[CH:43][CH:44]=1)=[O:36])[CH2:23][CH2:24][C:25]([O:27][CH2:28][C:29]1[CH:30]=[CH:31][CH:32]=[CH:33][CH:34]=1)=[O:26])(=[O:19])[OH:20])[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1

Participants

6

Reactant 4

HCID 6397ChlorotrimethylsilaneHCID 8471TriethylamineHCID 10947302Dibenzyl 2-methylenepentanedioateHCID 178520629HCID 178520629, compound

Product 1

HCID 18403062HCID 18403062, compoundYield 28%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
0 °C

Procedure

Benzyl[2,4-di(benzyloxycarbonyl)butyl]phosphinic acid Benzylphosphinic acid (2.3 g, 15 mmol) in 150 mL of dry dichloromethane was cooled to 0° C. under a nitrogen atmosphere. Triethylamine (6.5 g, 65 mmol) was added followed by trimethylsilyl chloride (5.8 g, 54 mmol) while the reaction temperature was maintained at 0° C. After 30 minutes dibenzyl 2-methylenepentanediote (2) in 20 mL of dichloromethane was added over 5 minutes. The reaction mixture was left to warm to room temperature and stirred overnight. The clear solution was cooled to 0° C. and quenched with 5% hydrochloric acid and with brine, dried (MgSO4) and evaporated to give a clear yellow liquid. Purification by flash chromatography and elution with 1:1 hexane/ethyl acetate containing 10% acetic acid yielded 2.0 g (28%) of benzyl[2,4-di(benzyloxycarbonyl)butyl]phosphinic acid (3, R=CH2Ph, R1+H) as a clear light yellow oil. Rf 0.37 (1:1 Hex./EtOAc, 10% AcOH). 1H NMR (d6-DMSO): 7.2 ppm(m,15H), 5.0 ppm(s,4H),3.0 (d,2H),2.8 ppm(m,lH),2.3 ppm(t,2H), 1.9 ppm(m,2H), 1.7 ppm(t,1H)

Workup

  1. waitThe reaction mixture was left
  2. temperatureto warm to room temperature
  3. temperatureThe clear solution was cooled to 0° C.
  4. customquenched with 5% hydrochloric acid and with brine
  5. dry with materialdried (MgSO4)
  6. customevaporated
  7. customto give a clear yellow liquid
  8. customPurification
  9. washby flash chromatography and elution with 1:1 hexane/ethyl acetate containing 10% acetic acid

Sources & evidence

ORD record
ord-691fe26bb7674a24a9cb1c4db00ecc15
Source dataset
uspto-grants-2000_04
Patent number
US06046180

Reaction notes

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