3,3-Dimethyl-1-butyne → HCID 68871827, compound

HRID 2105875Notes

Reaction equation

HRID 2105875 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([CH:8]2[CH:12]([C:13]3[CH:18]=[CH:17][C:16]([Cl:19])=[CH:15][CH:14]=3)[NH:11][C:10]([C:20]3[CH:25]=[CH:24][C:23](I)=[CH:22][C:21]=3[O:27][CH2:28][CH3:29])=[N:9]2)=[CH:4][CH:3]=1.[CH3:30][C:31]([CH3:35])([CH3:34])[C:32]#[CH:33]>C(N(CC)CC)C.CN(C)C=O.[Cu]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>[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([CH:8]2[CH:12]([C:13]3[CH:18]=[CH:17][C:16]([Cl:19])=[CH:15][CH:14]=3)[NH:11][C:10]([C:20]3[CH:25]=[CH:24][C:23]([C:33]#[C:32][C:31]([CH3:35])([CH3:34])[CH3:30])=[CH:22][C:21]=3[O:27][CH2:28][CH3:29])=[N:9]2)=[CH:4][CH:3]=1

Participants

7

Reactant 2

HCID 135123,3-Dimethyl-1-butyneHCID 68872121HCID 68872121, compound

Product 1

HCID 68871827HCID 68871827, compoundYield 83.7%

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 6228DimethylformamideSolventHCID 8471TriethylamineSolvent

Conditions

Temperature
50 °C

Procedure

4,5-Bis-(4-chlorophenyl)-2-(2-ethoxy-4-iodophenyl)-4,5-dihydro-1H-imidazole (566 mg, 1.05 mmol, example 27), copper(I) iodide (9.5 mg, 0.11 mmol), dichlorobis(triphenylphosphine)-palladium(II) (148 mg, 0.211 mmol) and 3,3-dimethyl-1-butyne (0.182 mL, 1.48 mmol) were dissolved under nitrogen in a flame-dried Schlenk tube in a mixture of triethylamine (1.7 mL) and dimethylformamide (1.7 mL). The reaction mixture was warmed in a 50° C. oil bath for 20 h, allowed to cool to room temperature and then partitioned between 2% sodium carbonate solution (70 mL) and diethyl ether (2×100 mL). The combined organic phases were washed with water (2×50 mL) and brine (50 mL), then dried over sodium sulfate and evaporated. The residue was purified by flash column chromatography (silica gel, eluting with 1% methanol in methylene chloride) to give 4,5-bis-(4-chlorophenyl)-2-[4-(3,3-dimethylbut-1-ynyl)-2-ethoxyphenyl]-4,5-dihydro-1H-imidazole as an off-white foam (0.432 g, 83%). LC-MS: 491.3 [(M+H)+].

Workup

  1. temperatureto cool to room temperature
  2. custompartitioned between 2% sodium carbonate solution (70 mL) and diethyl ether (2×100 mL)
  3. washThe combined organic phases were washed with water (2×50 mL) and brine (50 mL)
  4. dry with materialdried over sodium sulfate
  5. customevaporated
  6. customThe residue was purified by flash column chromatography (silica gel, eluting with 1% methanol in methylene chloride)

Sources & evidence

ORD record
ord-0d738e6d28a34c39bca99e7ce7e02733
Source dataset
uspto-grants-2009_08
Patent number
US07579368B2

Reaction notes

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