tert-Butanol → 3-Amino-3-(4-chlorophenyl)-2-methyl-2-propenenitrile

HRID 2422699Notes

Reaction equation

HRID 2422699 reaction equation
[Cl:1][C:2]1[CH:9]=[CH:8][C:5]([C:6]#[N:7])=[CH:4][CH:3]=1.[C:10](#[N:13])[CH2:11][CH3:12].CC(C)([O-])C.[K+].C(O)(C)(C)C>O1CCCC1>[NH2:7][C:6]([C:5]1[CH:8]=[CH:9][C:2]([Cl:1])=[CH:3][CH:4]=1)=[C:11]([CH3:12])[C:10]#[N:13]

Participants

6

Reactant 4

HCID 6386tert-ButanolHCID 7854PropionitrileHCID 121634-ChlorobenzonitrileHCID 23665647Potassium tert-butoxide

Product 1

HCID 671823103-Amino-3-(4-chlorophenyl)-2-methyl-2-propenenitrileYield 49.5%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

In a 2 L round bottom flask (fitted with rubber septum, nitrogen blanket and stir bar) combine 4-chlorobenzonitrile (60.0 g, 1.00 equiv, 432 mmol), propionitrile (61.2 mL, 2.00 equiv, 864 mmol), tetrahydrofuran (43.2 mL) and 1.0 M potassium t-butoxide in t-butanol (tert-butyl alcohol, potassium derivative, 475 mL, 1.10 equiv; 475 mmol); and stir for 24 h. Quench with aqueous NaHCO3 and extract with ethyl acetate. Wash the organic phase 2 times with brine, dry (K2CO3), filter, and concentrate to dryness. Purify by flash chromatography on silica, eluting with 15:85 to 50:50 ethyl acetate/hexane, to afford 3-amino-3-(4-chlorophenyl)-2-methylacrylonitrile (as an uncharacterized E-/Z-mixture). Yield: 49.5%. LCMS: 193.0 (m+1).

Workup

  1. customIn a 2 L round bottom flask (fitted with rubber septum, nitrogen blanket and stir bar)
  2. customQuench with aqueous NaHCO3
  3. extractionextract with ethyl acetate
  4. washWash the organic phase 2 times with brine
  5. dry with materialdry (K2CO3)
  6. filtrationfilter
  7. concentrationconcentrate to dryness
  8. customPurify by flash chromatography on silica
  9. washeluting with 15:85 to 50:50 ethyl acetate/hexane

Sources & evidence

ORD record
ord-9bb6b7bda7a74c68bfc96b7f61ba20e8
Source dataset
uspto-grants-2011_06
Patent number
US07960419B2

Reaction notes

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