Benzene, 1-chloro-4-ethynyl- → 4-Chloro-5-(4-chlorophenylethynyl)-2-diisopropylaminomethyleneaminopyrimidine

HRID 1271031Notes

Reaction equation

HRID 1271031 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.[Cl:18][C:19]1[CH:24]=[CH:23][C:22]([C:25]#[CH:26])=[CH:21][CH:20]=1>[Cu](I)I.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.C(N(CC)CC)C>[Cl:1][C:2]1[C:7]([C:26]#[C:25][C:22]2[CH:23]=[CH:24][C:19]([Cl:18])=[CH:20][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 70118Benzene, 1-chloro-4-ethynyl-HCID 734464514-Chloro-2-diisopropylaminomethyleneamino-5-iodopyrimidine

Product 1

HCID 734464494-Chloro-5-(4-chlorophenylethynyl)-2-diisopropylaminomethyleneaminopyrimidineYield 94.7%

Reagents, catalysts & solvents 3

HCID 83717Copper iodideCatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8471TriethylamineSolvent

Procedure

A mixture of 0.722 g 4-chloro-2-diisopropylaminomethyleneamino-5-iodopyrimidine, 3.5 mL triethylamine, 0.025 g copper iodide, 0.037 g dichlorobis(triphenyl)phosphine palladium II and 0.289 g 1-chloro-4-ethynylbenzene was stirred under nitrogen at room temperature for 18 hours. The dark brown mixture was evaporated in vacuo at a bath temperature of 30–35° C. The beige residue was partitioned between dichloromethane and water. The organic phase was washed twice with water, dried over sodium sulfate, filtered and evaporated to yield 1.0 g of a caramel colored film. The residue was dissolved in 1:1 dichloromethane/hexanes and purified by column chromatography on silica gel, eluting successively with 1:1 dichloromethane/hexanes, dichloromethane and ethyl acetate. The product was recovered from the latter two eluates by evaporation to yield 0.7 g of 4-chloro-5-(4-chlorophenylethynyl)-2-diisopropylaminomethyleneaminopyrimidine.

Workup

  1. customThe dark brown mixture was evaporated in vacuo at a bath temperature of 30–35° C
  2. customThe beige residue was partitioned between dichloromethane and water
  3. washThe organic phase was washed twice with water
  4. dry with materialdried over sodium sulfate
  5. filtrationfiltered
  6. customevaporated
  7. customto yield 1.0 g of a caramel colored film
  8. custompurified by column chromatography on silica gel
  9. washeluting successively with 1:1 dichloromethane/hexanes, dichloromethane and ethyl acetate
  10. customThe product was recovered from the latter two eluates by evaporation

Sources & evidence

ORD record
ord-5f70233f91a747e5ae1790c09c11c6e5
Source dataset
uspto-grants-2007_04
Patent number
US07205297B2

Reaction notes

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