Triethylamine → 4-Chloro-5-(phenylethynyl)pyrimidine

HRID 1271029Notes

Reaction equation

HRID 1271029 reaction equation
[Cl:1][C:2]1[C:7](I)=[CH:6][N:5]=[CH:4][N:3]=1.C(N(CC)CC)C.[C:16]1([C:22]#[CH:23])[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>ClCCl.[Cu](I)I>[Cl:1][C:2]1[C:7]([C:23]#[C:22][C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=2)=[CH:6][N:5]=[CH:4][N:3]=1

Participants

7

Reactant 4

HCID 8471TriethylamineHCID 10821PhenylacetyleneHCID 11776TriphenylphosphineHCID 112302044-Chloro-5-iodopyrimidine

Product 1

HCID 713507934-Chloro-5-(phenylethynyl)pyrimidine

Reagents, catalysts & solvents 2

HCID 83717Copper iodideCatalystHCID 6344DichloromethaneSolvent

Procedure

A mixture of 2.1 g of 4-chloro-5-iodopyrimidine, 10 mL of triethylamine, 1.2 mL phenylacetylene, 80 mg copper iodide and 160 mg of dichlorobis(triphenylphosphine was stirred at room temperature for 18 hours. The mixture was diluted with dichloromethane and evaporated in vacuo. The residue was redissolved in a few mL of dichloromethane, 10 mL of triethylamine added and the mixture heated at reflux for one hour. The heterogeneous mixture was evaporated in vacuo and the residue obtained was partitioned between water and dichloromethane. A gelatinous precipitate which formed on shaking the two layers was filtered off, enabling separation of the two layers. The organic extracts were dried over sodium sulfate, filtrated and evaporated in vacuo to yield 2.5 g of a dark brown syrup. The syrup was purified by column chromatography on silica gel, twice, eluting with hexanes, 1:1 hexanes/dichloromethane, dichloromethane and finally ethyl acetate. Like fractions from dichloromethane elution were pooled, obtaining 350 mg of the product, 5-phenylethynyl-4-chloropyrimidine as an oil which solidified to white rosettes.

Workup

  1. customevaporated in vacuo
  2. dissolutionThe residue was redissolved in a few mL of dichloromethane, 10 mL of triethylamine
  3. additionadded
  4. temperaturethe mixture heated
  5. temperatureat reflux for one hour
  6. customThe heterogeneous mixture was evaporated in vacuo
  7. customthe residue obtained
  8. customwas partitioned between water and dichloromethane
  9. customA gelatinous precipitate which formed
  10. stirringon shaking the two layers
  11. filtrationwas filtered off
  12. customseparation of the two layers
  13. dry with materialThe organic extracts were dried over sodium sulfate
  14. filtrationfiltrated
  15. customevaporated in vacuo

Sources & evidence

ORD record
ord-958c05f0255441f9bb036111c7c70630
Source dataset
uspto-grants-2007_04
Patent number
US07205297B2

Reaction notes

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