Lithium Chloride → 3-Bromo-7-[2-ethoxyvinyl]-1,5-naphthyridine

HRID 273241

Reaction equation

HRID 273241 reaction equation
Br[C:2]1[CH:3]=[N:4][C:5]2[C:10]([CH:11]=1)=[N:9][CH:8]=[C:7]([Br:12])[CH:6]=2.C([Sn](CCCC)(CCCC)[CH:18]=[CH:19][O:20][CH2:21][CH3:22])CCC.[Li+].[Cl-].[F-].[K+]>C1(C)C=CC=CC=1.C(Cl)Cl.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[Br:12][C:7]1[CH:8]=[N:9][C:10]2[C:5]([CH:6]=1)=[N:4][CH:3]=[C:2]([CH:18]=[CH:19][O:20][CH2:21][CH3:22])[CH:11]=2

Participants

8

Reactant 4

HCID 433294Lithium ChlorideHCID 522689Potassium FluorideHCID 12366583,7-Dibromo-1,5-naphthyridineHCID 2763294(Z)-1-Ethoxy-2-(tributylstannyl)ethene

Product 1

HCID 670823433-Bromo-7-[2-ethoxyvinyl]-1,5-naphthyridineYield 55%

Reagents, catalysts & solvents 3

HCID 178418476HCID 178418476, compoundCatalystHCID 1140TolueneSolventHCID 6344DichloromethaneSolvent

Procedure

A solution of 3,7-dibromo-1,5-naphthyridine (0.5 g, 1.74 mmol), tributyl-2-ethoxy-vinylstannane (1.91 mmol, 0.69 g), LiCl (8.7 mmol, 0.37 g) and 0.085 g of PdCl2(PPh3)2 in 50 mL of toluene was heated at 95° C. for 16 hr. After cooling off, 20 mL of a 2 M solution of KF was added to the mixture and stirring was continued for 0.5 hr. The mixture was diluted with 100 mL of CH2Cl2 and washed successively with a saturated solution of sodium bicarbonate, brine and water. The organic layer was dried over sodium sulfate, filtered and evaporated under reduced pressure. The residue was chromatographed using 5% MeOH in CH2Cl2 to give the desired material in 55% yield. 1H NMR (CDCl3, 300 MHz) δ 1.40 (m, 3H), 4.05 (m, 2H), 5.85 (s, 1H), 7.25 (s, 1H), 8.15 (m, 1H), 8.55 (m, 1H), 8.85 (m, 2H). MS (ESI) [M+H]+ at 280.

Workup

  1. temperatureAfter cooling off
  2. washwashed successively with a saturated solution of sodium bicarbonate, brine and water
  3. dry with materialThe organic layer was dried over sodium sulfate
  4. filtrationfiltered
  5. customevaporated under reduced pressure
  6. customThe residue was chromatographed

Sources & evidence

ORD record
ord-8d80b49db92246b7aecd4cc2c5ec4b31
Source dataset
uspto-grants-2008_11
Patent number
US07456196B2

Linked notes

Loading…