Water → HCID 22630117, compound

HRID 2307095Notes

Reaction equation

HRID 2307095 reaction equation
[C:1]([CH:3]([C:9]1([CH3:19])[CH2:14][C:13]([CH3:16])([CH3:15])[CH2:12][C:11]([CH3:18])([CH3:17])[CH2:10]1)[C:4]([O:6][CH2:7][CH3:8])=[O:5])#[N:2].[H-].[Na+].[CH2:22](Br)[CH:23]=[CH2:24].O>CS(C)=O>[C:1]([C:3]([C:9]1([CH3:19])[CH2:14][C:13]([CH3:16])([CH3:15])[CH2:12][C:11]([CH3:18])([CH3:17])[CH2:10]1)([CH2:24][CH:23]=[CH2:22])[C:4]([O:6][CH2:7][CH3:8])=[O:5])#[N:2]

Participants

6

Reactant 4

HCID 962WaterHCID 7841Allyl bromideHCID 24758Sodium hydrideHCID 22630145HCID 22630145, compound

Product 1

HCID 22630117HCID 22630117, compoundYield 63.9%

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent

Conditions

Temperature
50 °C

Procedure

To a solution of cyanoacetate 47 (1.25 g, 4.71 mmol) in anhydrous DMSO (10 ml) was added sodium hydride (0.284 g, 7.09 mmol; 60% mineral oil dispersion). The mixture was stirred for 30 min at 50° C., and cooled to 20° C. To this was added allylbromide (0.86 g, 7.1 mmol) and the mixture was stirred for 3 h at room temperature, then for 30 min at 50° C. The mixture was cooled, treated with water and extracted with diethyl ether. The extract was washed with water and with brine, dried over anhydrous MgSO4, filtered and evaporated. The residue was purified by flash chromatography on silica gel (light petroleum ether-ethyl acetate, 20:1) to give 48 (0.92 g, 63.7%) as a colorless oil. 1H NMR (CDCl3, TMS): 0.98 (6H, s, 3′,5′-CH3eq); 1.11 (6H, s, 3′,5′-CH3ax); 1.00-1.85 (6H, m, ring CH); 1.31 (3H, t, 7 Hz, CH3-ethyl); 1.33 (3H, s, 1′-CH3); 2.42 and 2.86 (total 2H, both dd, 13 and 7 Hz, 3-CH2); 4.02 (2H, q, 7 Hz, OCH2); 5.05-5.37 (2H, m, ═CH2) and 5.55-6.05 ppm (1H, m, ═CH).

Workup

  1. temperaturecooled to 20° C
  2. stirringthe mixture was stirred for 3 h at room temperature
  3. waitfor 30 min at 50° C
  4. temperatureThe mixture was cooled
  5. extractionextracted with diethyl ether
  6. washThe extract was washed with water and with brine
  7. dry with materialdried over anhydrous MgSO4
  8. filtrationfiltered
  9. customevaporated
  10. customThe residue was purified by flash chromatography on silica gel (light petroleum ether-ethyl acetate, 20:1)

Sources & evidence

ORD record
ord-05ee0906f71e4c3ba4852f03cbb5a6e3
Source dataset
uspto-grants-2004_12
Patent number
US06828462B2

Reaction notes

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