Ammonium Chloride → HCID 67995940, compound

HRID 1615136Notes

Reaction equation

HRID 1615136 reaction equation
[CH2:1]([Mg]Cl)[CH:2]=[CH2:3].C(OC(=O)[C:10]([C:24]#[N:25])=[C:11]1[CH2:23][CH2:22][C:14]2([O:19][CH2:18][C:17]([CH3:21])([CH3:20])[CH2:16][O:15]2)[CH2:13][CH2:12]1)C.[NH4+].[Cl-]>O1CCCC1.[Cu]I>[CH2:16]([O:15][C:14](=[O:19])[CH2:13][CH:10]([C:11]1([CH2:1][CH:2]=[CH2:3])[CH2:12][CH2:13][C:14]2([O:19][CH2:18][C:17]([CH3:20])([CH3:21])[CH2:16][O:15]2)[CH2:22][CH2:23]1)[C:24]#[N:25])[CH3:17]

Participants

6

Reactant 3

HCID 25517Ammonium ChlorideHCID 67995728HCID 67995728, compoundHCID 178418473HCID 178418473, compound

Product 1

HCID 67995940HCID 67995940, compound

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 8028TetrahydrofuranSolvent

Procedure

Allylmagnesium chloride (2 mol/L in tetrahydrofuran, 56 ml) is added to a solution of cyano-(3,3-dimethyl-1,5-dioxa-spiro[5.5]undec-9-ylidene)-acetic acid ethyl ester (13.7 g) and CuI (2.7 g) in tetrahydrofuran (100 mL) under argon atmosphere and chilled in an ice bath. The mixture is warmed in the cooling bath to room temperature and stirred overnight. Aqueous NH4Cl solution is then added and the resulting mixture is extracted with tert-butyl methyl ether. The combined extracts are washed with brine, dried (Na2SO4), and concentrated. The residue is chromatographed on silica gel (cyclohexane/ethyl acetate 1:02:3) to give the title compound. Yield: 5.0 g (31% of theory); Mass spectrum (ESI+): m/z=336 [M+H]+.

Workup

  1. temperaturechilled in an ice bath
  2. extractionthe resulting mixture is extracted with tert-butyl methyl ether
  3. washThe combined extracts are washed with brine
  4. dry with materialdried (Na2SO4)
  5. concentrationconcentrated
  6. customThe residue is chromatographed on silica gel (cyclohexane/ethyl acetate 1:02:3)

Sources & evidence

ORD record
ord-2cc8543f490f4959a5a1566dc2e7ca9e
Source dataset
uspto-grants-2014_07
Patent number
US08765744B2

Reaction notes

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