1-Ethyl-4-ethynylbenzene → 4-Chloro-2-diisopropylaminomethyleneamino-5-(4-ethylphenylethynyl)pyrimidine

HRID 1271039Notes

Reaction equation

HRID 1271039 reaction equation
[Cl:1][C:2]1[C:7](I)=[CH:6][N:5]=[C:4]([N:9]=[CH:10][N:11]([CH:15]([CH3:17])[CH3:16])[CH:12]([CH3:14])[CH3:13])[N:3]=1.[CH2:18]([C:20]1[CH:25]=[CH:24][C:23]([C:26]#[CH:27])=[CH:22][CH:21]=1)[CH3:19]>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.[Cu](I)I.C(N(CC)CC)C>[Cl:1][C:2]1[C:7]([C:19]#[C:18][C:20]2[CH:25]=[CH:24][C:23]([CH2:26][CH3:27])=[CH:22][CH:21]=2)=[CH:6][N:5]=[C:4]([N:9]=[CH:10][N:11]([CH:15]([CH3:17])[CH3:16])[CH:12]([CH3:14])[CH3:13])[N:3]=1

Participants

6

Reactant 2

HCID 1424251-Ethyl-4-ethynylbenzeneHCID 734464514-Chloro-2-diisopropylaminomethyleneamino-5-iodopyrimidine

Product 1

HCID 734464504-Chloro-2-diisopropylaminomethyleneamino-5-(4-ethylphenylethynyl)pyrimidineYield 63.7%

Reagents, catalysts & solvents 3

HCID 83717Copper iodideCatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8471TriethylamineSolvent

Procedure

A mixture of 6.3 g of 4-chloro-2-diisopropylaminomethyleneamino-5-iodopyrimidine, 33 mL of triethylamine, 2.43 g of 4-ethyl-1-ethynylbenzene, 0.304 g of dichlorobis(triphenyl)phosphine palladium II and 0.21 g copper iodide was magnetically stirred at reflux temperature for 1.5 hrs. The mixture was filtered and the filtrate evaporated in vacuo. Both the precipitate and the evaporated filtrate were dissolved in dichloromethane and washed with water, dried over sodium sulfate, filtered and evaporated. The residues were dissolved in 1:1 dichloromethane-hexanes and separately purified by column chromatography. After initial elution with 1:1 dichloromethane-hexanes, the product was obtained by elution with dichloromethane and 50% ethyl acetate-dichloromethane. Evaporation of the eluates gave 4.04 g of 4-chloro-2-diisopropylaminomethyleneamino-5-(4-ethylphenylethynyl)pyrimidine as a thick amber syrup.

Workup

  1. temperatureat reflux temperature for 1.5 hrs
  2. filtrationThe mixture was filtered
  3. customthe filtrate evaporated in vacuo
  4. dissolutionBoth the precipitate and the evaporated filtrate were dissolved in dichloromethane
  5. washwashed with water
  6. dry with materialdried over sodium sulfate
  7. filtrationfiltered
  8. customevaporated
  9. dissolutionThe residues were dissolved in 1:1 dichloromethane-hexanes
  10. customseparately purified by column chromatography
  11. washAfter initial elution with 1:1 dichloromethane-hexanes
  12. customthe product was obtained by elution with dichloromethane and 50% ethyl acetate-dichloromethane
  13. customEvaporation of the eluates

Sources & evidence

ORD record
ord-00d218d8dd114839b00fe84d3161ce11
Source dataset
uspto-grants-2007_04
Patent number
US07205297B2

Reaction notes

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