Chlorotrimethylsilane → Trimethylsilyl dibutylphosphinite

HRID 482641Notes

Reaction equation

HRID 482641 reaction equation
[CH2:1]([PH:5](=[O:10])[CH2:6][CH2:7][CH2:8][CH3:9])[CH2:2][CH2:3][CH3:4].C([Mg]Br)CCC.C(OP([O-])OCC)C.[CH3:25][Si:26](Cl)([CH3:28])[CH3:27]>C1(C)C=CC=CC=1.C(N(CC)CC)C>[CH2:1]([P:5]([CH2:6][CH2:7][CH2:8][CH3:9])[O:10][Si:26]([CH3:28])([CH3:27])[CH3:25])[CH2:2][CH2:3][CH3:4]

Participants

7

Reactant 4

HCID 6397ChlorotrimethylsilaneHCID 3780918DiethylphosphiteHCID 178418682HCID 178418682, compoundHCID 178454905HCID 178454905, compound

Product 1

HCID 12651389Trimethylsilyl dibutylphosphiniteYield 86%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolvent2×HCID 8471TriethylamineSolvent

Conditions

Temperature
80 °C

Procedure

The procedure described in Tetrahedron, 1967, 23, 1065 (M. Grayson et al.) was followed. Dibutylphosphine oxide, prepared from butyl magnesium bromide and diethylphosphite, (3.3 g, 20 mmol) and triethylamine (2.02 l g, 20 mml) were dissolved in toluene (20 mL) and treated with a solution of trimethylsilyl chloride (2.17 g, 20 mmol) in toluene (5 mL) at room temperature. The solution got very warm and a precipitate formed immediately. The mixture was heated at 80° C. for two hours, then filtered, washed with toluene, and concentrated. Kugelrohr distillation a 80° C. (1.5 mmHg) afforded 4.1 g (86%) of the desired product. 1H NMR (CDCl3) δ1.8-1.2 (m, 6H), 1.1-0.7 (m, 3H), 0.17 (s, 9H).

Workup

  1. temperatureThe solution got very warm
  2. customa precipitate formed immediately
  3. filtrationfiltered
  4. washwashed with toluene
  5. concentrationconcentrated
  6. distillationKugelrohr distillation a 80° C. (1.5 mmHg)

Sources & evidence

ORD record
ord-9942bdc590ec49c9af7f2405c35bb393
Source dataset
uspto-grants-1986_03
Patent number
US04574060

Reaction notes

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