1-(prop-2-yn-1-yl)-1H-pyrazole → Methyl (e)-[2-methyl-4-[3-[4-[3-(pyrazol-1-yl)propynyl]phenyl]-3-(3-trifluoromethyl phenyl)allyloxy]-phenoxy]acetate

HRID 1810660Notes

Reaction equation

HRID 1810660 reaction equation
I[C:2]1[CH:7]=[CH:6][C:5](/[C:8](/[C:25]2[CH:30]=[CH:29][CH:28]=[C:27]([C:31]([F:34])([F:33])[F:32])[CH:26]=2)=[CH:9]\[CH2:10][O:11][C:12]2[CH:23]=[CH:22][C:15]([O:16][CH2:17][C:18]([O:20][CH3:21])=[O:19])=[C:14]([CH3:24])[CH:13]=2)=[CH:4][CH:3]=1.[CH2:35]([N:38]1[CH:42]=[CH:41][CH:40]=[N:39]1)[C:36]#[CH:37]>O1CCCC1.C(N(CC)CC)C.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Cu]I>[CH3:24][C:14]1[CH:13]=[C:12]([O:11][CH2:10]/[CH:9]=[C:8](\[C:5]2[CH:4]=[CH:3][C:2]([C:37]#[C:36][CH2:35][N:38]3[CH:42]=[CH:41][CH:40]=[N:39]3)=[CH:7][CH:6]=2)/[C:25]2[CH:30]=[CH:29][CH:28]=[C:27]([C:31]([F:34])([F:33])[F:32])[CH:26]=2)[CH:23]=[CH:22][C:15]=1[O:16][CH2:17][C:18]([O:20][CH3:21])=[O:19]

Participants

7

Reactant 2

HCID 117685231-(prop-2-yn-1-yl)-1H-pyrazoleHCID 86629302methyl (E)-[4-[3-(4-iodophenyl)-3-(3-trifluoromethylphenyl)allyloxy]-2-methylphenoxy]acetate

Product 1

HCID 131728885Methyl (e)-[2-methyl-4-[3-[4-[3-(pyrazol-1-yl)propynyl]phenyl]-3-(3-trifluoromethyl phenyl)allyloxy]-phenoxy]acetate

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418397HCID 178418397, compoundCatalystHCID 8028TetrahydrofuranSolventHCID 8471TriethylamineSolvent

Procedure

A solution of the above ester (400 mg, 0.68 mmol) in a mixture of tetrahydrofuran (12 mL) and triethylamine (12 mL) was degassed and 1-propargylpyrazole (144 mg, 1.36 mmol) was added in argon atmosphere. The solution was cooled down; tetrakis(triphenylphosphine)palladium (62 mg, 0.054 mmol) and copper(I) iodide (20 mg, 0.108 mmol) were added and the resulting mixture was stirred at ambient temperature for 30 h. The mixture was evaporated in vacuo; the residue was dissolved in ethyl acetate (20 mL) and the formed solution was washed with water (2×15 mL) and brine (10 mL). The organic solution was dried with anhydrous magnesium sulfate and evaporated in vacuo. The residue was purified by flash column chromatography (silica gel Fluka 60, hexanes/ethyl acetate 7:3) yielding methyl (E)-[2-methyl-4-[3-[4-[3-(pyrazol-1-yl)propynyl]phenyl]-3-(3-trifluoromethylphenyl)-allyloxy]-phenoxy]acetate.

Workup

  1. customwas degassed
  2. temperatureThe solution was cooled down
  3. customThe mixture was evaporated in vacuo
  4. dissolutionthe residue was dissolved in ethyl acetate (20 mL)
  5. washthe formed solution was washed with water (2×15 mL) and brine (10 mL)
  6. dry with materialThe organic solution was dried with anhydrous magnesium sulfate
  7. customevaporated in vacuo
  8. customThe residue was purified by flash column chromatography (silica gel Fluka 60, hexanes/ethyl acetate 7:3)

Sources & evidence

ORD record
ord-c366d6403bbd4988aedf6a29654885f9
Source dataset
uspto-grants-2013_01
Patent number
US08362016B2

Reaction notes

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