Ammonium Chloride → HCID 22120417, compound

HRID 1274161Notes

Reaction equation

HRID 1274161 reaction equation
[C:1]([C:3](=[C:9]([CH3:11])[CH3:10])[C:4]([O:6][CH2:7][CH3:8])=[O:5])#[N:2].[CH3:12][O:13][C:14]1[CH:15]=[C:16]([CH:20]=[CH:21][CH:22]=1)[CH2:17][Mg]Cl.COC1C=C(C=CC=1)CCl.[NH4+].[Cl-]>C1COCC1.CCOCC>[C:1]([CH:3]([C:9]([CH3:10])([CH3:11])[CH2:17][C:16]1[CH:20]=[CH:21][CH:22]=[C:14]([O:13][CH3:12])[CH:15]=1)[C:4]([O:6][CH2:7][CH3:8])=[O:5])#[N:2]

Participants

7

Reactant 4

HCID 25517Ammonium ChlorideHCID 699943-Methoxybenzyl chlorideHCID 1365732-Cyano-3-methyl-but-2-enoic acid ethyl esterHCID 178490222HCID 178490222, compound

Product 1

HCID 22120417HCID 22120417, compoundYield 51%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolvent2×HCID 8028TetrahydrofuranSolvent

Procedure

A solution of ethyl 2-cyano-3-methylcrotonate (10.8 g, 0.07 mol) in THF (100 mL) was added dropwise to a stirred ethereal solution of 3-methoxybenzylmagnesium chloride (prepared by adding a solution of 3-methoxybenzyl chloride (9.3 mL, 0.064 mol) in ether (48 mL) to a slurry of Mg (1.7 g, 0.07 mol) in ether (20 mL)). After addition the mixture was stirred at room temperature for a further 2 h then NH4Cl (sat., 50 mL) was added. The solution was partitioned between EtOAc (200 mL) and water (200 mL) and the organic layer separated and dried (MgSO4). The solvent was evaporated and the residue chromatographed on silica gel, eluting with petrol:EtOAc (5:1). The title compound (9.0 g, 51%) was isolated as a colourless oil. 1H NMR (360 MHz, CDCl3) δ 1.10 (3H, s), 1.20 (3H, s), 1.33 (3H, t, J=7.1 Hz), 2.74 (1H, d, J=13.5 Hz), 2.78 (1H, d, J=13.5 Hz), 3.33 (1H, s), 3.81 (3H, s), 4.26 (2H, q, J=7.1 Hz), 6.72-6.82 (3H, m), 7.22 (1H, t, J=7.8 Hz). MS (ES+) 276 (M+1).

Workup

  1. customprepared
  2. additionAfter addition the mixture
  3. customThe solution was partitioned between EtOAc (200 mL) and water (200 mL)
  4. customthe organic layer separated
  5. dry with materialdried (MgSO4)
  6. customThe solvent was evaporated
  7. customthe residue chromatographed on silica gel
  8. washeluting with petrol:EtOAc (5:1)

Sources & evidence

ORD record
ord-35eed30291f64c64883b60c527406f0c
Source dataset
uspto-grants-2000_12
Patent number
US06156761

Reaction notes

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