Allyltributylstannane → 5-Allyl-6-ethyl-pyridin-3-yl-acetonitrile

HRID 900973Notes

Reaction equation

HRID 900973 reaction equation
Cl[C:2]1[CH:3]=[C:4]([CH2:10][C:11]#[N:12])[CH:5]=[N:6][C:7]=1[CH2:8][CH3:9].[CH2:13]([Sn](CCCC)(CCCC)CCCC)[CH:14]=[CH2:15]>C(#N)C.CS(C)=O.[F-].[K+].C(OCC)(=O)C.C1(P(C2C=CC=CC=2)[C-]2C=CC=C2)C=CC=CC=1.[C-]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C1.[Fe+2].Cl[Ni]Cl>[CH2:15]([C:2]1[CH:3]=[C:4]([CH2:10][C:11]#[N:12])[CH:5]=[N:6][C:7]=1[CH2:8][CH3:9])[CH:14]=[CH2:13]

Participants

8

Reactant 2

HCID 90628AllyltributylstannaneHCID 596987915-Chloro-6-ethyl-pyridin-3-yl-acetonitrile

Product 1

HCID 596988125-Allyl-6-ethyl-pyridin-3-yl-acetonitrileYield 79%

Reagents, catalysts & solvents 5

HCID 178479585HCID 178479585, compoundCatalystHCID 679Dimethyl SulfoxideSolventHCID 6342AcetonitrileSolventHCID 8857Ethyl AcetateSolventHCID 522689Potassium FluorideSolvent

Conditions

Temperature
85 °C

Procedure

A solution of 5-chloro-6-ethyl-pyridin-3-yl-acetonitrile (3.00 g, 16.6 mmol) and allyl-tri-n-butyltin (5.4 mL, 17.4 mmol) in acetonitrile (30 mL, 0.5 M) and dimethylsulfoxide (2 mL), is degassed and treated with 1,1′-bis(diphenylphosphino)ferrocene-dicloronickel(II) (Ni(dppf)Cl2) (0.38 g, 0.55 mmol). The mixture is warmed to 85° C. for 2 h. After cooling to room temperature the solution is diluted with 10% aq potassium fluoride (30 mL) and ethyl acetate (30 mL). The solids are filtered and rinsed with ethyl acetate (30 mL). The organic layer is washed with saturated aq NaCl (80 mL) and dried over Na2SO4. The product is purified by MPLC (25-90% ethyl acetate in n-heptane) to provide 5-allyl-6-ethyl-pyridin-3-yl-acetonitrile as a yellow oil (2.43 g, 79%): Rf 0.28 (50% ethyl acetate in n-heptane), 1H NMR (CDCl3, 300 MHz) δ 8.36 (s, 1 H), 7.44 (s, 1 H), 6.00-5.84 (m, 1 H), 5.15 (d, J=10.3 Hz, 1 H), 5.03 (d, J=17.2 Hz, 1 H), 3.71 (s, 2 H), 3.42 (d, J=6.0 Hz, 2 H), 2.83 (q, J=7.6 Hz, 2 H), 1.28 (t, J=7.6 Hz, 3 H). ESI-LCMS m/z calcd for C12H14N2: 186.1; found 187.0 (M+1)+.

Workup

  1. temperatureAfter cooling to room temperature the solution
  2. filtrationThe solids are filtered
  3. washrinsed with ethyl acetate (30 mL)
  4. washThe organic layer is washed with saturated aq NaCl (80 mL)
  5. dry with materialdried over Na2SO4
  6. customThe product is purified by MPLC (25-90% ethyl acetate in n-heptane)

Sources & evidence

ORD record
ord-1e1b442603c44a99b566874c0ff6ea8c
Source dataset
uspto-grants-2008_04
Patent number
US07361671B2

Reaction notes

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