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

HRID 1493791ノート

反応式

HRID 1493791 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 9s) 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 lash chromatography (silica; 5% ethyl acetate in hexanes) to give the title compound as a yellow oil. PMR (CDCl3): & 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 (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 mass, 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 lash chromatography (silica; 5% ethyl acetate in hexanes)

出典と根拠

ORDレコード
ord-472b39675d3740b6bb73b11ab77a2c22
出典データセット
uspto-grants-1991_06
特許番号
US05023341

反応ノート

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