1-Hexyne → 3,5-Diethyl-1-(3-hex-1-ynyl-phenyl)-1H-pyrazole-4-carboxylic acid methyl ester

HRID 1011866

Reaktionsgleichung

Reaktionsgleichung von HRID 1011866
[CH3:1][O:2][C:3]([C:5]1[C:6]([CH2:19][CH3:20])=[N:7][N:8]([C:12]2[CH:17]=[CH:16][CH:15]=[C:14](Br)[CH:13]=2)[C:9]=1[CH2:10][CH3:11])=[O:4].[CH:21]#[C:22][CH2:23][CH2:24][CH2:25][CH3:26]>N1CCCCC1.[Cu]I.[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[CH3:1][O:2][C:3]([C:5]1[C:6]([CH2:19][CH3:20])=[N:7][N:8]([C:12]2[CH:17]=[CH:16][CH:15]=[C:14]([C:21]#[C:22][CH2:23][CH2:24][CH2:25][CH3:26])[CH:13]=2)[C:9]=1[CH2:10][CH3:11])=[O:4]

Komponenten

6

Edukt 2

HCID 127321-HexyneHCID 673139921-(3-Bromo-phenyl)-3,5-diethyl-1H-pyrazole-4-carboxylic acid methyl ester2×

Produkt 1

HCID 673141873,5-Diethyl-1-(3-hex-1-ynyl-phenyl)-1H-pyrazole-4-carboxylic acid methyl ester

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)KatalysatorHCID 11979704Tetrakis(triphenylphosphine)palladiumKatalysatorHCID 8082PiperidineLösungsmittel2×

Reaktionsbedingungen

Temperatur
60 °C

Versuchsvorschrift

A solution of 4.20 g (10.0 mmol) of 1-(3-bromo-phenyl)-3,5-diethyl-1H-pyrazole-4-carboxylic acid methyl ester (intermediate 1C) in 35 ml of piperidine was treated with 0.19 g (1.0 mmol) of copper(I)iodide and 1.16 g (1.0 mmol) of tetrakis-(triphenylphosphine)-palladium. The reaction mixture was warmed up to 60° C. and after 15 min, a solution of 0.82 g=1.00 ml (10.0 mmol) of hex-1-yne in 15 ml of piperidine was added drop by drop during 1 hour. After 30 min, the oil bath temperature was steadily increased to 80° C. The reaction mixture was then stirred at 80° C. for 4 hours, and subsequently cooled down to RT. The solvent was evaporated and the residue poured into crashed ice, acidified with HCl (37%) to pH 1-2 and extracted twice with EtOAc; the organic phases were washed with water, dried over magnesium sulfate, filtered and evaporated. The residue was purified by flash column chromatography (n-heptane:EtOAc 1:0-9:1) to afford the title compound as light yellow oil. MS: 339.0 (MH+).

Aufarbeitung

  1. temperaturethe oil bath temperature was steadily increased to 80° C
  2. temperaturesubsequently cooled down to RT
  3. customThe solvent was evaporated
  4. additionthe residue poured
  5. extractionextracted twice with EtOAc
  6. washthe organic phases were washed with water
  7. dry with materialdried over magnesium sulfate
  8. filtrationfiltered
  9. customevaporated
  10. customThe residue was purified by flash column chromatography (n-heptane:EtOAc 1:0-9:1)

Quellen und Nachweise

ORD-Eintrag
ord-136b20bce9594ee99e6b6b12daba7ba8
Quelldatensatz
uspto-grants-2011_07
Patentnummer
US07977358B2

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