Diethyl Ether → HCID 571501, compound

HRID 496560Notes

Reaction equation

HRID 496560 reaction equation
[Mg].Br[CH:3]1[CH2:5][CH2:4]1.[C:6]([C:8]1[CH:13]=[CH:12][N:11]=[CH:10][CH:9]=1)#N.C([O:16]CC)C>II>[CH:3]1([C:6]([C:8]2[CH:13]=[CH:12][N:11]=[CH:10][CH:9]=2)=[O:16])[CH2:5][CH2:4]1

Participants

6

Reactant 4

HCID 3283Diethyl EtherHCID 75064-CyanopyridineHCID 78037BromocyclopropaneHCID 5462224Magnesium2×

Product 1

HCID 571501HCID 571501, compoundYield 43%

Reagents, catalysts & solvents 1

HCID 807IodineCatalyst

Procedure

Dry magnesium powder (0.760 g, 31.2 mmol), which had been previously crushed in a mortar with a pestle, was charged into a dry round bottom flask under a nitrogen atmosphere. To this was added diethyl ether (20 mL), followed by bromocyclopropane (3.77 g, 2.49 mL, 31.2 mmol). A small amount of iodine (0.002 g) was added to initiate formation of the Grignard reagent. The reaction was heated to a gentle reflux for a short period of time (˜1 hour) until all of the magnesium metal had reacted. The flask was then cooled in an ice bath and to this was added 4-cyanopyridine (1.62 g, 15.6 mmol). The mixture was stirred for 3 hours, and then carefully quenched with sat. ammonium chloride (3 mL). The reaction was then acidified with 15% aq. hydrochloric acid (3 ML). The mixture was stirred for 20 minutes, and then made basic by the addition of 10 N sodium hydroxide until the pH was approximately 9. To this solution was added ethyl acetate (300 mL), and the aqueous layer was extracted with water (30 mL). The organic layer was washed with brine, dried over Na2SO4 and evaporated to dryness giving the title compound as a yellow oil (1.0 g, 43%). 1H NMR (300 MHz, DMSO-d6): δ 1.15 (m, 4H); 2.93 (s, 1H); 7.91 (d, 1H; J=6.0 Hz); 8.83 (d, 1H, J=6.0 Hz).

Workup

  1. additionwas charged into a dry round bottom flask under a nitrogen atmosphere
  2. temperatureThe reaction was heated to
  3. customhad reacted
  4. temperatureThe flask was then cooled in an ice bath
  5. customcarefully quenched with sat. ammonium chloride (3 mL)
  6. stirringThe mixture was stirred for 20 minutes
  7. additionmade basic by the addition of 10 N sodium hydroxide until the pH was approximately 9
  8. additionTo this solution was added ethyl acetate (300 mL)
  9. extractionthe aqueous layer was extracted with water (30 mL)
  10. washThe organic layer was washed with brine
  11. dry with materialdried over Na2SO4
  12. customevaporated to dryness

Sources & evidence

ORD record
ord-c1bdab5a14b2485aae0d624d24fe1619
Source dataset
uspto-grants-2005_09
Patent number
US06946463B2

Reaction notes

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