Benzylamine → 1-Benzyl-4-methyl-4-phenyl-[1,4]azasilinane

HRID 40552Notes

Reaction equation

HRID 40552 reaction equation
O[CH2:2][CH2:3][Si:4]([CH3:14])([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[CH2:5][CH2:6]O.C(N(CC)CC)C.S(Cl)(C)(=O)=O.[CH2:27]([NH2:34])[C:28]1[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1>ClCCl.O>[CH2:27]([N:34]1[CH2:6][CH2:5][Si:4]([CH3:14])([C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)[CH2:3][CH2:2]1)[C:28]1[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1

Participants

7

Reactant 4

HCID 7504BenzylamineHCID 8471Triethylamine2×HCID 31297Methanesulfonyl chlorideHCID 676060772-[(2-Hydroxy-ethyl)-methyl-phenyl-silanyl]-ethyl alcohol

Product 1

HCID 669259441-Benzyl-4-methyl-4-phenyl-[1,4]azasilinane

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

8.5 g of 2-[(2-hydroxy-ethyl)-methyl-phenyl-silanyl]-ethyl alcohol is put in 80 ml of anhydrous dichloromethane under nitrogen. 14.2 ml of triethylamine is added, and then, at 0° C., 6.9 ml of mesyl chloride is added dropwise using a dropping funnel. The mixture is stirred for 2 h at 0° C. and gradually turns orange with appearance of a precipitate. Once conversion is complete, 14.2 ml of triethylamine is added and then 4.7 ml of benzylamine at 0° C. The reaction mixture is brought back to room temperature and then refluxed for 6 h. After hydrolysis with H2O at room temperature, the reaction mixture is extracted with ethyl acetate three times. The organic phases are combined, washed with a saturated aqueous solution of sodium chloride, dried over magnesium sulfate and concentrated under vacuum. The raw product obtained is chromatographed on silica gel, eluting with a gradient of ethyl acetate and heptane containing 3% of triethylamine varying from 0/10 to 3/7. 3.6 g of 1-benzyl-4-methyl-4-phenyl-[1,4]azasilinane is obtained in the form of a clear yellow oil.

Workup

  1. customat 0° C
  2. customis brought back to room temperature
  3. temperaturerefluxed for 6 h
  4. extractionthe reaction mixture is extracted with ethyl acetate three times
  5. washwashed with a saturated aqueous solution of sodium chloride
  6. dry with materialdried over magnesium sulfate
  7. concentrationconcentrated under vacuum
  8. customThe raw product obtained
  9. customis chromatographed on silica gel
  10. washeluting with a gradient of ethyl acetate and heptane containing 3% of triethylamine varying from 0/10 to 3/7

Sources & evidence

ORD record
ord-a5b0b803f8a343b28db39de98504b53f
Source dataset
uspto-grants-2013_09
Patent number
US08530473B2

Reaction notes

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