Propionitrile → HCID 59277590, compound

HRID 1362453Notes

Reaction equation

HRID 1362453 reaction equation
[Br:1][C:2]1[CH:3]=[C:4](I)[C:5]([NH2:8])=[N:6][CH:7]=1.[C:10]([O:14][C:15]([CH3:18])([CH3:17])[CH3:16])(=[O:13])[CH:11]=[CH2:12].C(N(C(C)C)C(C)C)C.C(#N)CC.CC1C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C>CC([O-])=O.CC([O-])=O.[Pd+2].C(OCC)(=O)C.CN(C=O)C>[NH2:8][C:5]1[C:4](/[CH:12]=[CH:11]/[C:10]([O:14][C:15]([CH3:18])([CH3:17])[CH3:16])=[O:13])=[CH:3][C:2]([Br:1])=[CH:7][N:6]=1

Participants

9

Reactant 5

HCID 7854PropionitrileHCID 15458tert-Butyl acrylateHCID 80271Tri-o-tolylphosphineHCID 81531DiisopropylethylamineHCID 15165082-Amino-5-bromo-3-iodopyridine

Product 1

HCID 59277590HCID 59277590, compound

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
90 °C

Procedure

A reaction vessel was charged with 5-bromo-3-iodopyridin-2-amine (1 g, 3.35 mmol), tert-butyl acrylate (0.97 mL, 6.69 mmol), and (i-Pr)2EtN (1.75 mL, 10.01 mmol) followed by propionitrile (20 mL) and then DMF (5 mL). The solution was de-oxygenated with argon for 15 minutes. The mixture was treated with Pd(OAc)2 (75 mg, 0.34 mmol) and P(o-tol)3 (204 mg, 0.67 mmol) then heated to 90° C. for 16 h (overnight) then filtered through a pad of silica gel. The filtrate was concentrated and dried under reduced pressure to give a dark brown residue which was subjected to flash chromatography on silica gel using 20% ethyl acetate:hexanes to 40% ethyl acetate:hexanes. The appropriate fractions were collected and concentrated to give a yellow solid. Yield: 700 mg (70%); 1H NMR (300 MHz, DMSO-d6) δ 8.06 (d, 1H, J=2.3 Hz), 8.03 (d, 1H, J=2.3 Hz), 7.61 (d, 1H, J=15.0 Hz), 6.58 (s, 2H), 6.50 (d, 1H, J=15.0 Hz), 1.50 (s, 9H); ESI MS m/z 299 (100%); 301 (100%)[C12H15N2O2Br+H]+

Workup

  1. filtrationthen filtered through a pad of silica gel
  2. concentrationThe filtrate was concentrated
  3. customdried under reduced pressure
  4. customto give a dark brown residue which
  5. customThe appropriate fractions were collected
  6. concentrationconcentrated
  7. customto give a yellow solid

Sources & evidence

ORD record
ord-0ec2fa7d3f5444d1a581b42716e255a1
Source dataset
uspto-grants-2011_02
Patent number
US07879872B2

Reaction notes

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