Triethylamine → 3-Amino-2-(4-chloro-phenylethynyl)-benzoic acid methyl ester

HRID 33334

反応式

HRID 33334 の反応式
[CH3:1][O:2][C:3](=[O:14])[C:4]1[CH:9]=[CH:8][CH:7]=[C:6]([N+:10]([O-])=O)[C:5]=1I.[Cl:15][C:16]1[CH:21]=[CH:20][C:19]([C:22]#[CH:23])=[CH:18][CH:17]=1.C(N(CC)CC)C>C1(C)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.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Pd].[Cu]I>[CH3:1][O:2][C:3](=[O:14])[C:4]1[CH:9]=[CH:8][CH:7]=[C:6]([NH2:10])[C:5]=1[C:23]#[C:22][C:19]1[CH:20]=[CH:21][C:16]([Cl:15])=[CH:17][CH:18]=1

参加物

7

反応物 3

HCID 8471TriethylamineHCID 70118Benzene, 1-chloro-4-ethynyl-HCID 264093Methyl 2-iodo-3-nitrobenzoate

生成物 1

HCID 183400043-Amino-2-(4-chloro-phenylethynyl)-benzoic acid methyl ester

試薬・触媒・溶媒 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 11979704Tetrakis(triphenylphosphine)palladium触媒HCID 1140Toluene溶媒

反応条件

温度
80 °C

実験手順

2-iodo-3-nitro-benzoic acid methyl ester (0.79 g, 2.84 mmol), 1-chloro-4-ethynylbenzene (0.41 g, 2.99 mmol), palladium tetrakis(triphenylphosphine) (0.16 g, 0.14 mmol), copper (I) iodide (0.03 g, 0.14 mmol), and triethylamine (1.44 g, 14.19 mmol) were dissolved in 15 mL toluene. Argon was bubbled through the resulting solution for 15 min. The reaction was stirred under argon at 80° C. for 2 h and 20 min. The reaction mixture was then washed once with water, dried (MgSO4), and concentrated in vacuo. The orange oil was purified by flash chromatography eluting with 50 to 100% CHCl3/hexanes to yield 3-amino-2-(4-chloro-phenylethynyl)-benzoic acid methyl ester, 0.76 g (94%) as a yellow oil. 1H NMR (300 MHz, d6-DMSO) δ 3.84 (s, 3H), 5.84 (br s, 2H), 6.97 (dd, J=8.1, 1.3 Hz, 1H), 7.05 (dd, J=7.5, 1.2 Hz, 1H), 7.17 (app t, J=7.5 Hz, 1H), 7.49 (d, J=8.7 Hz, 2H), 7.63 (d, J=8.7 Hz, 2H). MS (electrospray, MH+) 286.

後処理

  1. customArgon was bubbled through the resulting solution for 15 min
  2. washThe reaction mixture was then washed once with water
  3. dry with materialdried (MgSO4)
  4. concentrationconcentrated in vacuo
  5. customThe orange oil was purified by flash chromatography
  6. washeluting with 50 to 100% CHCl3/hexanes

出典と根拠

ORDレコード
ord-c91e41adde3e4db7afd98cf266b7aeae
出典データセット
uspto-grants-2008_09
特許番号
US07429578B2

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