3-Butyn-1-OL → HCID 23374723, compound

HRID 377203Notes

Reaction equation

C([Li])C[CH2:3][CH3:4].[CH2:6]([OH:10])[CH2:7][C:8]#[CH:9].[CH2:11]([Si:13](Cl)([CH2:16][CH3:17])[CH2:14][CH3:15])[CH3:12]>CCCCCC.C1COCC1.C([O-])([O-])=O.[Na+].[Na+]>[CH2:11]([Si:13]([C:8]([Si:13]([CH2:3][CH3:4])([CH2:14][CH3:15])[CH2:11][CH3:12])([CH3:9])[C:7]#[C:6][OH:10])([CH2:16][CH3:17])[CH2:14][CH3:15])[CH3:12]

Participants

Conditions

Temperature: -30 °C

Procedure

n-Butyl lithium (776 ml of a 2.5M solution in hexane, 1.94 mol) was added over a 2 h period to a stirred solution of 3-butyn-1-ol (68 g, 0.97 mol), in anhydrous THF (1.16 l), at -30° C. The mixture was stirred at -30° C. for 1 h (dianion precipitates out) and triethylsilyl chloride (300 g, 1.99 mol) was then added dropwise, ensuring that the temperature remained below -20° C. The solution was stirred at -10° C. for 1 h and then at room temperature for 1 h. Hexane (1.36 l) and Na2CO3 solution (7.0 g in 700 ml of H2O) were added to the reaction mixture, at -10° C., and the layers separated. The aqueous layer was extracted with hexane and the combined extracts were washed with water, dried (Na2SO4) and evaporated to give the title-bis triethylsilyl butynol (289 g, 100%), δ (250 MHz, CDCl3) 0.80-0.94 (12H, m, 6 of SiCH2CH3), 1.22-1.32 (18H, m, 6 of SiCH2CH3), 2.76 (2H, t, J=7.3Hz, CH2), 4.00 (2H, t, J=7.3Hz, CH2).

Workup

additionwas then added dropwise
customremained below -20° C
stirringThe solution was stirred at -10° C. for 1 h
waitat room temperature for 1 h
customthe layers separated
extractionThe aqueous layer was extracted with hexane
washthe combined extracts were washed with water
dry with materialdried (Na2SO4)
customevaporated

Sources & evidence

ORD record: ord-93b3d4c9af64431382ad445263699fa5
Source dataset: uspto-grants-2000_02
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US06025374

Reaction notes

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