Methyltriphenylphosphonium iodide → 8-Vinylbenzo[f][1,7]naphthyridin-5-amine

HRID 340306

Reaction equation

HRID 340306 reaction equation
[I-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Li][CH2:23][CH2:24][CH2:25][CH3:26].[NH2:27][C:28]1[C:37]2[N:36]=[CH:35][CH:34]=[CH:33][C:32]=2[C:31]2[CH:38]=CC(C=O)=[CH:41][C:30]=2[N:29]=1>C1COCC1>[CH:25]([C:24]1[CH:23]=[CH:38][C:31]2=[C:32]3[C:37](=[C:28]([NH2:27])[N:29]=[C:30]2[CH:41]=1)[N:36]=[CH:35][CH:34]=[CH:33]3)=[CH2:26]

Participants

5

Reactant 3

HCID 638159Methyltriphenylphosphonium iodideHCID 866523555-Aminobenzo[f][1,7]naphthyridine-8-carbaldehydeHCID 178418339Butyllithium

Product 1

HCID 582136728-Vinylbenzo[f][1,7]naphthyridin-5-amine

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of methyl triphenyl phosphonium iodide (6.0 eq.) was added nBuLi (7.0 eq.) at −78° C. The reaction mixture was allowed to warm to 0° C. and stirred for 30 minutes (deep orange color). The reaction was again cooled down to −78° C. and 5-aminobenzo[f][1,7]naphthyridine-8-carbaldehyde (from Example 87) (1.0 eq.) in THF was introduced dropwised to the reaction. The reaction was allowed to warm to ambient temperature overnight. The reaction was quenched by saturated NH4Cl and extracted with EtOAc. The combined organic layer was washed with brine, dried over MgSO4 and concentrated en vacuo to obtain a crude residue. The crude material was purified by flash chromatography on a COMBIFLASH® system (ISCO) using 0-50% EtOAc/Hexanes to give 8-vinylbenzo[f][1,7]naphthyridin-5-amine as a white solid: 1H NMR (acetone-d6): 1H NMR (acetone-d6): δ 9.00 (dd, 1H), 8.90 (dd, 1H), 8.41 (d, 1H), 7.84 (dd, 1H), 7.65 (d, 1H), 7.52 (dd, 1H), 6.91 (dd, 1H), 6.77 (br s, 2H), 5.97 (dd, 1H), 5.34 (dd, 1H). LRMS [M+H]=222.1.

Workup

  1. additionwas introduced
  2. customdropwised to the reaction
  3. temperatureto warm to ambient temperature overnight
  4. customThe reaction was quenched by saturated NH4Cl
  5. extractionextracted with EtOAc
  6. washThe combined organic layer was washed with brine
  7. dry with materialdried over MgSO4
  8. concentrationconcentrated en vacuo
  9. customto obtain a crude residue
  10. customThe crude material was purified by flash chromatography on a COMBIFLASH® system (ISCO)

Sources & evidence

ORD record
ord-7f32d600e93c41d09de350dfe99e1854
Source dataset
uspto-grants-2014_11
Patent number
US08895577B2

Linked notes

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