Ethyl Acetate → (Z)-3-Tributylstannanyl-but-2-en-1-ol

HRID 918753Notes

Reaction equation

HRID 918753 reaction equation
[Al].[Li].[H-].[CH2:4]([OH:8])[C:5]#[C:6][CH3:7].C(OCC)(=O)C.[CH2:15]([Sn:19](C[O-])([CH2:24][CH2:25][CH2:26][CH3:27])[CH2:20][CH2:21][CH2:22][CH3:23])[CH2:16][CH2:17][CH3:18]>C1COCC1.O.CO>[CH2:24]([Sn:19]([CH2:15][CH2:16][CH2:17][CH3:18])([CH2:20][CH2:21][CH2:22][CH3:23])/[C:6](/[CH3:7])=[CH:5]\[CH2:4][OH:8])[CH2:25][CH2:26][CH3:27]

Participants

8

Reactant 4

HCID 8857Ethyl AcetateHCID 129912-Butyn-1-olHCID 19822445Tri(n-butyl)stannyl-methanolateHCID 57419139CID 57419139

Product 1

HCID 11405747(Z)-3-Tributylstannanyl-but-2-en-1-ol

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

To 156.9 ml (156.9 mmol) of a 1 molar solution of lithium-aluminum-hydride in THF 0.77 g (14.3 mmol) sodium methylate have been added and the temperature has been lowered to 0° C. afterwards. Then a solution of 10.0 g (142.7 mmol) 2-butin-1-ol in 108 ml THF has been added dropwise with stirring at this temperature. Stirring was continued for 36 h at 4° C. Thereafter, at about 0° C., 28.6 ml (292.5 mmol) ethyl acetate was-added slowly while stirring. A strongly exothermic reaction was observed. Stirring was continued for 10 min without cooling. After cooling to about 0° C., 45.8 g (142.7 mmol) tri(n-butyl)stannyl-methanolate have been added dropwise while stirring. Stirring was continued for 2 d at 4° C. After addition of 112.9 g methanol stirring was continued for 1 h at ambient temperature. The reaction mixture was poured into 250 ml of water, extracted thrice with 150 ml diethyl ether each, the combined extracts were washed twice with 80 ml of water each, then once with 40 ml saturated aqueous sodium chloride solution, dried with sodium sulfate and concentrated in vacuo. Yield 48.6 g oil, which have been purified by chromatography on 300 g silica gel with hexane/MTBE (10:1). Final yield 34.6 g (67%) oil. δ=0.90 (m); 1.30 (m); 1.50 m); 1.97 (s); 4.02 (t); 6.27 (t).

Workup

  1. customhas been lowered to 0° C.
  2. stirringStirring
  3. stirringwhile stirring
  4. customA strongly exothermic reaction
  5. stirringStirring
  6. waitwas continued for 10 min
  7. temperaturewithout cooling
  8. stirringwhile stirring
  9. stirringStirring
  10. waitwas continued for 2 d at 4° C
  11. waitwas continued for 1 h at ambient temperature
  12. extractionextracted thrice with 150 ml diethyl ether each, the combined extracts
  13. washwere washed twice with 80 ml of water each, then once with 40 ml saturated aqueous sodium chloride solution
  14. dry with materialdried with sodium sulfate
  15. concentrationconcentrated in vacuo
  16. customYield 48.6 g oil, which have been purified by chromatography on 300 g silica gel with hexane/MTBE (10:1)

Sources & evidence

ORD record
ord-8af60de8b2a3497a8e63739b1e4a231b
Source dataset
uspto-grants-2016_03
Patent number
US09271501B2

Reaction notes

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