Toluene → 2-Chloro-5-(2-ethoxy-vinyl)-pyrimidin-4-ylamine

HRID 2426277Notes

Reaction equation

HRID 2426277 reaction equation
Br[C:2]1[C:3]([NH2:9])=[N:4][C:5]([Cl:8])=[N:6][CH:7]=1.C1(C)C=CC=CC=1.C([Sn](CCCC)(CCCC)[CH:22]=[CH:23][O:24][CH2:25][CH3:26])CCC>C(OCC)(=O)C.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[Cl:8][C:5]1[N:4]=[C:3]([NH2:9])[C:2]([CH:22]=[CH:23][O:24][CH2:25][CH3:26])=[CH:7][N:6]=1

Participants

6

Reactant 3

HCID 1140TolueneHCID 27632934-Amino-5-bromo-2-chloropyrimidineHCID 2763294(Z)-1-Ethoxy-2-(tributylstannyl)ethene

Product 1

HCID 573489732-Chloro-5-(2-ethoxy-vinyl)-pyrimidin-4-ylamineYield 46%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
110 °C

Procedure

A 500 mL round bottomed flask is charged with 5-bromo-2-chloropyrimidin-4-ylamine (1) (10 g, 48 mmol), tetrakis(triphenylphosphine)palladium(0) (2.8g, 2.5 mmol), and toluene (200 mL). Tributyl-(2-ethoxyvinyl)-stannane (22 g, 60 mmol) is added and the reaction heated to 110° C. with stirring for approximately 15 hours. After cooling to room temperature, the solution is diluted with 100 mL ethyl acetate and washed with water and brine. The organic extract is dried over Na2SO4, filtered, and concentrated under reduced pressure. Purification by column chromatography (SiO2, Hexane:Ethyl acetate/5:1) provides 2 (4.4 g, 46%) as a yellow solid.

Workup

  1. temperatureAfter cooling to room temperature
  2. washwashed with water and brine
  3. extractionThe organic extract
  4. dry with materialis dried over Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure
  7. customPurification by column chromatography (SiO2, Hexane:Ethyl acetate/5:1)

Sources & evidence

ORD record
ord-fd9622c534054b589b3de758a0ec4964
Source dataset
uspto-grants-2011_06
Patent number
US07968557B2

Reaction notes

Loading…