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

HRID 6561ノート

反応式

HRID 6561 の反応式
[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

参加物

5

反応物 2

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

生成物 1

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

試薬・触媒・溶媒 2

HCID 6102075Dichlorobis(triphenylphosphine)palladium触媒HCID 8471Triethylamine溶媒

反応条件

温度
55 °C

実験手順

A solution of 233 mg (1.09 mmol) of 2,2,4,4-tetramethyl-6-ethynylchroman (Compound 5) and 209 mg (1.09 mmol) of ethyl 6-chloronicotinate (Compound 98) 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): δ 1.36 (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 (1 H, dd, J~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).

後処理

  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)

出典と根拠

ORDレコード
ord-63143f8bc47845178483dc51a00282c1
出典データセット
uspto-grants-1993_09
特許番号
US05248777

反応ノート

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