Diethyl Ether → HCID 22630145, compound

HRID 1636461Notes

Reaction equation

HRID 1636461 reaction equation
[CH3:1][C:2]1([CH3:18])[CH2:7][C:6]([CH3:9])([CH3:8])[CH2:5][C:4](=[C:10]([C:16]#[N:17])[C:11]([O:13][CH2:14][CH3:15])=[O:12])[CH2:3]1.[NH4+].[Cl-].[CH3:21]COCC>[Cu]Cl>[CH3:21][C:4]1([CH:10]([C:16]#[N:17])[C:11]([O:13][CH2:14][CH3:15])=[O:12])[CH2:3][C:2]([CH3:1])([CH3:18])[CH2:7][C:6]([CH3:8])([CH3:9])[CH2:5]1

Participants

5

Reactant 3

HCID 3283Diethyl Ether2×HCID 25517Ammonium ChlorideHCID 10610637HCID 10610637, compound

Product 1

HCID 22630145HCID 22630145, compoundYield 47%

Reagents, catalysts & solvents 1

HCID 62652Cuprous chlorideCatalyst

Procedure

Anhydrous copper (I) chloride (0.8 g, 8 mmol) was added to a cooled solution of alkylmagnesium iodide (prepared from magnesium (0.46 g, 19.2 mmol) and iodomethane (2.84 g, 20 mmol)) in ether (12 ml). The mixture was stirred in an inert atmosphere for 5 min and a solution of ethyl (3,3,5,5-tetramethylcyclohexylidene)cyanoacetate (16) (2 g, 8 mmol) in ether (10 ml), was added dropwise keeping the temperature below -15° C. After the addition of ketone was completed, the reaction mixture was stirred for 3 h and carefully neutralised with saturated aqueous NH4Cl solution. Traditional workup for Grignard reactions gave crude material which was separated on a silica gel column, eluting with a petroleum ether--ethyl acetate mixture (20:1) to give 1.0 g (47%) of 17 as an oil. 1H NMR (CDCl3, TMS) δ: 0.98 (9H, s, 3,5-CH3eq and 1-CH3); 1.06 (6H, s, 3,5-CH3ax); 1.31 (3H, t, J=7 Hz, ethyl-CH3); 1.2-1.5 (6H, m, ring protons); 3.41 (1H, s, α-CH) and 4.25 ppm (2H, q, J=7 Hz, CH2O).

Workup

  1. customthe temperature below -15° C
  2. stirringthe reaction mixture was stirred for 3 h
  3. customTraditional workup for Grignard reactions gave crude material which
  4. customwas separated on a silica gel column
  5. washeluting with a petroleum ether

Sources & evidence

ORD record
ord-33aedc9e76404e04a96769c46b6c64b3
Source dataset
uspto-grants-2000_03
Patent number
US06034134

Reaction notes

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