Sodium borohydride → [1-(6-Tert-butylpyridin-3-yl)ethyl]amine

HRID 1919834Notes

Reaction equation

HRID 1919834 reaction equation
C[Mg+].[Br-].[C:4]1(C)C=CC=CC=1.C1COCC1.[C:16]([C:20]1[CH:27]=[CH:26][C:23]([C:24]#[N:25])=[CH:22][N:21]=1)([CH3:19])([CH3:18])[CH3:17].[BH4-].[Na+]>C1COCC1.C(Cl)Cl.O.CO>[C:16]([C:20]1[N:21]=[CH:22][C:23]([CH:24]([NH2:25])[CH3:4])=[CH:26][CH:27]=1)([CH3:19])([CH3:17])[CH3:18]

Participants

9

Reactant 4

HCID 4311764Sodium borohydrideHCID 194251856-Tert-butylpyridine-3-carbonitrile2×HCID 22635083Tetrahydrofuran tolueneHCID 178418689HCID 178418689, compound

Product 1

HCID 67500288[1-(6-Tert-butylpyridin-3-yl)ethyl]amine

Reagents, catalysts & solvents 4

HCID 887MethanolSolventHCID 962WaterSolventHCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent

Procedure

A solution of MeMgBr 1.4 M 75/25 toluene/THF (8.9 ml, 12.48 mmol) is added dropwise over 5 min to an ice cooled solution of 6-tert-butylnicotinonitrile (intermediate 21) (1 g, 6.24 mmol) in 15 mL of THF. The reaction is stirred for 6 hr and cooled with a dry ice bath. MeOH is then added dropwise followed by the incremental addition of NaBH4 (0.59 g, 15.9 mmol). The reaction is stirred over night, water and CH2Cl2 are then added and the resulting paste is filtered through celite and rinsed with CH2Cl2. The reaction is concentrated to remove the organics and extracted 3 times with ethyl acetate. The combined organic layers are extracted with 1 H HCl. The aqueous layer is basified with 28% NH4OH and extracted 3 times with ethyl acetate. The combined organic layers are washed with brine, dried over Na2SO4, filtered and concentrated. (Yield: 488 mg, 49%). 1H NMR (400 MHz, CDCl3) δ ppm 1.36 (s, 9 H) 1.40 (d, J=6.60 Hz, 3 H) 4.15 (q, J=6.60 Hz, 1H) 7.31 (d, J=8.20 Hz, 1 H) 7.63 (dd, J=8.20, 2.34 Hz, 1 H) 8.52 (d, J=2.34 Hz, 1 H).

Workup

  1. temperaturecooled with a dry ice bath
  2. stirringThe reaction is stirred over night
  3. filtrationthe resulting paste is filtered through celite
  4. washrinsed with CH2Cl2
  5. concentrationThe reaction is concentrated
  6. customto remove the organics and
  7. extractionextracted 3 times with ethyl acetate
  8. extractionThe combined organic layers are extracted with 1 H HCl
  9. extractionextracted 3 times with ethyl acetate
  10. washThe combined organic layers are washed with brine
  11. dry with materialdried over Na2SO4
  12. filtrationfiltered
  13. concentrationconcentrated

Sources & evidence

ORD record
ord-3c5c0022bc0d4c1b868cef5c47f14131
Source dataset
uspto-grants-2012_05
Patent number
US08168668B2

Reaction notes

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