Propyne → HCID 11084950, compound

HRID 2168827Notes

Reaction equation

HRID 2168827 reaction equation
[CH:1]#[C:2][CH3:3].C([Li])CCC.[Cl-].C([Al+]CC)C.[CH2:15]([O:22][CH2:23][C@H:24]1[CH2:26][O:25]1)[C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1>C1(C)C=CC=CC=1>[CH2:15]([O:22][CH2:23][C@H:24]([OH:25])[CH2:26][C:1]#[C:2][CH3:3])[C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1

Participants

6

Reactant 4

HCID 6335PropyneHCID 159746(-)-Benzyl (R)-glycidyl etherHCID 16686102Diethyl aluminum chlorideHCID 178418339Butyllithium

Product 1

HCID 11084950HCID 11084950, compound

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

Prop-1-yne was bubbled through a solution of n-butyllithium (2.5 M in hexanes, 1.06 L, 2.65 mol) in toluene (5 L) at 0° C. for 1.5 hours, until a thin suspension was obtained. Diethylaluminum chloride (1 M in hexanes, 2.44 L, 2.44 mol) was added, and the reaction mixture was stirred at 0° C. for 2 hours, whereupon (2R)-2-[(benzyloxy)methyl]oxirane (200 g, 1.22 mol) was added. After 10 minutes, the reaction was quenched with water (100 mL) and then with aqueous hydrochloric acid (2 M, 2 L). The mixture was extracted with ethyl acetate (2 L), and the combined organic layers were dried over sodium sulfate, concentrated, and purified by chromatography on silica gel (Gradient: 2% to 17% ethyl acetate in petroleum ether) to afford the product as a pale brown oil. Yield: 250 g, 1.22 mol, 100%. 1H NMR (400 MHz, CDCl3) δ 7.28-7.41 (m, 5H), 4.58 (s, 2H), 3.89-3.97 (s, 1H), 3.60 (dd, half of ABX pattern, J=9.5, 3.9 Hz, 1H), 3.50 (dd, half of ABX pattern, J=9.5, 6.7 Hz, 1H), 2.50 (br s, 1H), 2.38-2.43 (m, 2H), 1.79 (t, J=2.6 Hz, 3H).

Workup

  1. customwas obtained
  2. additionwas added
  3. customthe reaction was quenched with water (100 mL)
  4. extractionThe mixture was extracted with ethyl acetate (2 L)
  5. dry with materialthe combined organic layers were dried over sodium sulfate
  6. concentrationconcentrated
  7. custompurified by chromatography on silica gel (Gradient: 2% to 17% ethyl acetate in petroleum ether)

Sources & evidence

ORD record
ord-08c7c3af549041d9a0b8285d8b8e18a7
Source dataset
uspto-grants-2015_06
Patent number
US09045499B2

Reaction notes

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