Diethyl Ether → HCID 22630151, compound

HRID 2307077Notes

Reaction equation

HRID 2307077 reaction equation
[CH3:1][C:2]1([CH3:13])[CH2:7][C:6]([CH3:9])([CH3:8])[CH2:5][C:4](=[CH:10][CH2:11]O)[CH2:3]1.[Cl:14][C:15]([Cl:19])([Cl:18])[C:16]#[N:17].C([O:22]CC)C>>[Cl:14][C:15]([Cl:19])([Cl:18])[C:16]([NH:17][C:4]1([CH:10]=[CH2:11])[CH2:3][C:2]([CH3:13])([CH3:1])[CH2:7][C:6]([CH3:9])([CH3:8])[CH2:5]1)=[O:22]

Participants

4

Reactant 3

HCID 3283Diethyl Ether2×HCID 11011TrichloroacetonitrileHCID 22630144HCID 22630144, compound

Product 1

HCID 22630151HCID 22630151, compoundYield 66%

Conditions

Temperature
-10 °C

Procedure

To a solution of alcohol 3 (0.8 g, 4.7 mmol) in diethyl ether (5 ml) NaH (0.22 g of a 55% dispersion in mineral oil (0.22 mmol)) was added. The reaction mixture was cooled to −10° C. and a solution of trichloroacetonitrile (0.68 g, 4.7 mmol) in diethyl ether (3 ml) was added dropwise. The solution was allowed to warm to room temperature and the solvent evaporated. Pentane (8 ml) containing methanol (0.018 ml) was added to the residue. The resulting mixture was filtered through a pad of celite and evaporated. The residual oil was dissolved in xylene (10 ml) and refluxed for 10 h. Main amount of xylene was distilled off at reduced pressure (11 mm Hg) and the residue purified by flash chromatography on silica gel (hexane, hexane-ethyl acetate, 10:1) to give 4 (0.98 g, 66%) as an oil. 1H NMR (CDCl3, TMS): 0.95 (6H, s, 3,5-CH3); 1.18 (6H, s, 3,5-CH3); 1.1-1.5 (2H, m, 4-CH2); 1.32 (2H, d, 15 Hz, 2,6-CH2); 2.15 (2H, d, 15 Hz, 2,6-CH2); 5.08 (1H, d, 11 Hz, ═CH2); 5.13 (1H, d, 18 Hz, ═CH2); 5.85 (1H, dd, 18 and 11 Hz, —HC═) and 6.7 ppm (1H, br s, NH).

Workup

  1. temperatureto warm to room temperature
  2. customthe solvent evaporated
  3. additionPentane (8 ml) containing methanol (0.018 ml)
  4. additionwas added to the residue
  5. filtrationThe resulting mixture was filtered through a pad of celite
  6. customevaporated
  7. dissolutionThe residual oil was dissolved in xylene (10 ml)
  8. temperaturerefluxed for 10 h
  9. distillationMain amount of xylene was distilled off at reduced pressure (11 mm Hg)
  10. customthe residue purified by flash chromatography on silica gel (hexane, hexane-ethyl acetate, 10:1)

Sources & evidence

ORD record
ord-892c6bb6819a4c8b8bd2d4ccd890d348
Source dataset
uspto-grants-2004_12
Patent number
US06828462B2

Reaction notes

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