Triethylamine → HCID 59475105, compound

HRID 450701Notes

Reaction equation

HRID 450701 reaction equation
Br[C:2]1[S:6][C:5]([CH2:7][CH:8]([NH:10][C:11]([C:13]2[C:14]([CH:19]([F:21])[F:20])=[N:15][N:16]([CH3:18])[CH:17]=2)=[O:12])[CH3:9])=[C:4]([Cl:22])[CH:3]=1.[CH:23]1([C:26]#[CH:27])[CH2:25][CH2:24]1.C(N(CC)CC)C.C(OC(=O)C)C>[Cu]I.O>[Cl:22][C:4]1[CH:3]=[C:2]([C:27]#[C:26][CH:23]2[CH2:25][CH2:24]2)[S:6][C:5]=1[CH2:7][CH:8]([NH:10][C:11]([C:13]1[C:14]([CH:19]([F:21])[F:20])=[N:15][N:16]([CH3:18])[CH:17]=1)=[O:12])[CH3:9]

Participants

7

Reactant 4

HCID 8471TriethylamineHCID 8857Ethyl AcetateHCID 138823Cyclopropylacetylene2×HCID 59475102HCID 59475102, compound

Product 1

HCID 59475105HCID 59475105, compound

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 962WaterSolvent

Conditions

Temperature
60 °C

Procedure

In a sulfonation flask a mixture containing of 240 mg (0.58 mmol) 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid[2-(5-bromo-3-chlorothiophen-2-yl)-1-methylethyl]amide, 80 mg (1.15 mmol) cyclopropyacetylene, 10 mg copper(I)iodide, 36 mg (0.05 mmol) bistriphenylphosphine palladium dichloride and 30 ml triethylamine is stirred at 60° C. for 2 days. Then another 80 mg of cyclopropylacetylene is added and stirring continued for 24 hours. After cooling to ambient temperature ethylacetate and water is added and the organic layer separated and washed again twice with water. After drying (sodium sulphate) and distilling off the solvent in a water jet vacuum, the crude product is obtained. Purification is achieved by column chromatography over silicagel (eluent: ethylacetate/heptane 1:1). Yield: 90 mg (23% of theory) of a slightly brown resin (1H-NMR: 0.8/m/2H, 0.9/m/2H, 1.22/d/3H, 1.45/m/1H, 3.01/d/2H, 3.9/s/3H, 4.40/m/1H, 6.28/s (broad)/1H, 6.88/t/1H—CF2H, 6.89/s/1H, 7.85/s/1H).

Workup

  1. stirringstirring
  2. waitcontinued for 24 hours
  3. additionis added
  4. customthe organic layer separated
  5. washwashed again twice with water
  6. dry with materialAfter drying (sodium sulphate)
  7. distillationdistilling off the solvent in a water jet vacuum

Sources & evidence

ORD record
ord-344c2ad6f5e34f75b9c9884a85f80e43
Source dataset
uspto-grants-2013_07
Patent number
US08486986B2

Reaction notes

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