Tetrahydrofuran → HCID 178467710, compound

HRID 1789282Notes

Reaction equation

HRID 1789282 reaction equation
[NH2:1][C:2]1[N:7]=[C:6](Cl)[CH:5]=[C:4]([CH3:9])[N:3]=1.[CH3:10][C:11]([OH:15])([C:13]#[CH:14])C.O1CCCC1>[Cu]I.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.Cl[Pd]Cl.C(N(CC)CC)C>[NH2:1][C:2]1[NH:3][C:4]([C:14]#[C:13][CH:11]([OH:15])[CH3:10])([CH3:9])[CH:5]=[CH:6][N:7]=1

Participants

7

Reactant 3

HCID 8028TetrahydrofuranHCID 82582-Methyl-3-butyn-2-olHCID 218102-Amino-4-chloro-6-methylpyrimidine

Product 1

HCID 178467710HCID 178467710, compound

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 6102075Dichlorobis(triphenylphosphine)palladiumCatalystHCID 8471TriethylamineSolvent

Procedure

A mixture of 10.0 g of 2-amino-4-chloro-6-methylpyrimidine, 8.8 ml of 2-methyl-3-butyn-2-ol, 400 ml of tetrahydrofuran (THF), 0.06 g of copper (I) iodide, 0.5 g of bis(triphenylphosphine)palladium (II) chloride and 20.4 ml of triethylamine was heated overnight at reflux under a nitrogen atmosphere. The reaction mixture was allowed to cool. It was then partitioned between 200 ml of ethyl acetate and 100 ml of sodium bicarbonate. The organic layer was washed successively with 100 ml of water and 100 ml of brine. The organic layer was dried (MgSO4), filtered and concentrated under reduced pressure. The residue was placed on a silica gel dry column and eluted with dichloromethane/ethyl acetate/THF (10:90:0.1). The product band was extracted with THF. The organic extract was concentrated. Trituration of the residue (butyl chloride) gave 4.44 g of the title compound as a solid, m.p. 155°; PMR (90 MHz, CDCl3) δ1.65(s, 6H, CH3), 2.3(s, CH3, 3H), 2.8(s, OH, 1H), 5.2(bs, 2H, NH2), 6.6(s, Het-H, 1H); IR(nujol) 2221(w, C≡C) cm-1.

Workup

  1. temperaturewas heated overnight
  2. temperatureat reflux under a nitrogen atmosphere
  3. temperatureto cool
  4. customIt was then partitioned between 200 ml of ethyl acetate and 100 ml of sodium bicarbonate
  5. washThe organic layer was washed successively with 100 ml of water and 100 ml of brine
  6. dry with materialThe organic layer was dried (MgSO4)
  7. filtrationfiltered
  8. concentrationconcentrated under reduced pressure
  9. customdry column
  10. washeluted with dichloromethane/ethyl acetate/THF (10:90:0.1)
  11. extractionThe product band was extracted with THF
  12. extractionThe organic extract
  13. concentrationwas concentrated

Sources & evidence

ORD record
ord-696211169c204a97a942d3f05a95269f
Source dataset
uspto-grants-1987_08
Patent number
US04689069

Reaction notes

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