Formaldehyde → 1-(Tributylstannyl)methanol

HRID 642951Notes

Reaction equation

HRID 642951 reaction equation
C(NC(C)C)(C)C.C([Li])CCC.[CH2:13]([SnH:17]([CH2:22][CH2:23][CH2:24][CH3:25])[CH2:18][CH2:19][CH2:20][CH3:21])[CH2:14][CH2:15][CH3:16].[CH2:26]=[O:27]>O.O1CCCC1>[CH2:22]([Sn:17]([CH2:26][OH:27])([CH2:13][CH2:14][CH2:15][CH3:16])[CH2:18][CH2:19][CH2:20][CH3:21])[CH2:23][CH2:24][CH3:25]

Participants

7

Reactant 4

HCID 712FormaldehydeHCID 5948TributylstannaneHCID 7912DiisopropylamineHCID 178418339Butyllithium2×

Product 1

HCID 41935931-(Tributylstannyl)methanolYield 200%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a mixture of diisopropylamine (62 ml, 0.44 mol) and tetrahydrofuran (1000 ml) were added dropwise n-butyllithium (2.6M n-hexane solution, 100 ml, 0.26 mol) and n-butyllithium (1.6M n-hexane solution, 95 ml, 0.15 mol) at −78° C. (external temperature). Then, the reaction mixture was stirred for 30 minutes. To the mixture was added dropwise tributyltin hydride (100 ml, 0.37 mol) at −78° C. (external temperature). Then, the reaction mixture was stirred at 0° C. (external temperature) for 60 minutes. After the reaction mixture was cooled at −78° C. (external temperature) and paraformaldehyde (13 g, 0.15 mol) was added to the reaction mixture. The reaction mixture was gradually raised to room temperature, and then, the reaction mixture was stirred at room temperature overnight. To the reaction mixture were added water, an aqueous ammonium chloride solution and diethyl ether, and the organic layer was separated. The organic layer was sequentially washed with an aqueous saturated sodium bicarbonate solution and an aqueous saturated sodium chloride solution. The organic layer was separated, and the solvent was distilled off under reduced pressure. The residue was purified by neutral silica gel column chromatography (heptane:diethyl ether=4:1) to obtain the title compound (95 g, 0.30 mol, 80%).

Workup

  1. stirringThen, the reaction mixture was stirred at 0° C. (external temperature) for 60 minutes
  2. additionwas added to the reaction mixture
  3. stirringthe reaction mixture was stirred at room temperature overnight
  4. customan aqueous ammonium chloride solution and diethyl ether, and the organic layer was separated
  5. washThe organic layer was sequentially washed with an aqueous saturated sodium bicarbonate solution
  6. customThe organic layer was separated
  7. distillationthe solvent was distilled off under reduced pressure
  8. customThe residue was purified by neutral silica gel column chromatography (heptane:diethyl ether=4:1)

Sources & evidence

ORD record
ord-4635697e9d1e4028a15ed65e212d4f48
Source dataset
uspto-grants-2010_04
Patent number
US07696347B2

Reaction notes

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