Ethyl 6-chloronicotinate → Ethyl 6-[(2,2,4,4-tetramethylchroman-6-yl)-ethynyl]nicotinate

HRID 1489329Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1489329
[CH3:1][C:2]1([CH3:16])[CH2:11][C:10]([CH3:13])([CH3:12])[C:9]2[C:4](=[CH:5][CH:6]=[C:7]([C:14]#[CH:15])[CH:8]=2)[O:3]1.Cl[C:18]1[CH:28]=[CH:27][C:21]([C:22]([O:24][CH2:25][CH3:26])=[O:23])=[CH:20][N:19]=1>C(N(CC)CC)C.[Pd](Cl)Cl.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][C:2]1([CH3:16])[CH2:11][C:10]([CH3:12])([CH3:13])[C:9]2[C:4](=[CH:5][CH:6]=[C:7]([C:14]#[C:15][C:18]3[CH:28]=[CH:27][C:21]([C:22]([O:24][CH2:25][CH3:26])=[O:23])=[CH:20][N:19]=3)[CH:8]=2)[O:3]1

Komponenten

5

Edukt 2

HCID 2799611Ethyl 6-chloronicotinate2×HCID 156611382,2,4,4-Tetramethyl-6-ethynylchroman2×

Produkt 1

HCID 9820418Ethyl 6-[(2,2,4,4-tetramethylchroman-6-yl)-ethynyl]nicotinate

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 6102075Dichlorobis(triphenylphosphine)palladiumKatalysatorHCID 8471TriethylamineLösungsmittel

Reaktionsbedingungen

Temperatur
55 °C

Versuchsvorschrift

A solution of 233 mg (1.09 mmol) of 2,2,4,4-tetramethyl-6-ethynylchroman (Compound 2) and 209 mg (1.09 mmol) of ethyl 6-chloronicotinate (Compound 29) in 1 ml of triethylamine was degassed and then treated under argon with a powdered mixture of 50 mg (0.26 mmol) of cuprous iodide and 100 mg (0.14 mmol) of bis(triphenylphosphine) palladium (II) chloride. The reaction mixture was heated under argon at 55 degrees C. for 80 h and then cooled to room temperature. The triethylamine was then removed under vacuum and the residue purified by flash chromatography (silica; 5% ethyl acetate in hexanes) to give the title compound as a yellow oil. PMR (CDCl3): δ1.36 (12H, s), 1.42 (3H, t, J-7.2 Hz), 1.85 (2H, s), 4.37 (2H, q, J-7.2 Hz), 6.79 (1H, d, J-.4 Hz), 7.34 (1H, dd, J-8.4 Hz, 2.1 Hz), 7.56 (1H, d, J-8.7 Hz), 7.60 (1H, d, J-2.1 Hz), 8.27 (1H, dd, J-8.7 Hz, 2.4 Hz), 9.19 (1H, d, J-2.4 Hz). MS exact masss, m/e 363.1837 (calcd. for C23H25O3N, 363.1834).

Aufarbeitung

  1. temperaturecooled to room temperature
  2. customThe triethylamine was then removed under vacuum
  3. customthe residue purified by flash chromatography (silica; 5% ethyl acetate in hexanes)

Quellen und Nachweise

ORD-Eintrag
ord-8748e2990fd7483d91087226d4b12ec3
Quelldatensatz
uspto-grants-1997_10
Patentnummer
US05677323

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