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

HRID 1259174Notes

Reaction equation

HRID 1259174 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 vaccuo 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 vaccuo
  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-4e8c4b6ac7574210a1e3352ff59719cb
Source dataset
uspto-grants-2013_06
Patent number
US08466167B2

Reaction notes

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