Benzenamine, 2-bromo-4-nitro- → 2-(Cyclopropylethynyl)-4-nitroaniline

HRID 1847398

反応式

HRID 1847398 の反応式
Br[C:2]1[CH:8]=[C:7]([N+:9]([O-:11])=[O:10])[CH:6]=[CH:5][C:3]=1[NH2:4].[C:12]([CH:14]1[CH2:16][CH2:15]1)#[CH:13]>C(N(CC)CC)C.[Cu]I.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[CH:14]1([C:12]#[C:13][C:2]2[CH:8]=[C:7]([N+:9]([O-:11])=[O:10])[CH:6]=[CH:5][C:3]=2[NH2:4])[CH2:16][CH2:15]1

参加物

6

反応物 2

HCID 25840Benzenamine, 2-bromo-4-nitro-HCID 138823Cyclopropylacetylene

生成物 1

HCID 591292622-(Cyclopropylethynyl)-4-nitroaniline収率 23,243.199%

試薬・触媒・溶媒 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 178418476HCID 178418476、化合物触媒HCID 8471Triethylamine溶媒

反応条件

温度
70 °C

実験手順

To a deoxygenated solution of 2-bromo-4-nitroaniline (2.17 g, 0.01 mmol), ethynylcyclopropane (1 g, 15 mmol) and CuI (10 mg, 0.05 mmol) in triethylamine (20 mL) was added Pd(PPh3)2Cl2 (210 mg, 0.3 mmol) under N2. The mixture was heated at 70° C. and stirred for 24 hours. The solid was filtered off and washed with EtOAc (50 mL×3). The filtrate was evaporated under reduced pressure, and the residue was purified by column chromatography on silica gel (petroleum ether/ethyl acetate=10/1) to give 2-(cyclopropylethynyl)-4-nitroaniline (470 mg, 23%). 1H NMR (300 MHz, CDCl3) δ 8.14 (d, J=2.7 Hz, 1H), 7.97 (dd, J=2.7, 9.0 Hz, 1H), 6.63 (d, J=9.0 Hz, 1H), 4.81 (brs, 2H), 1.55-1.46 (m, 1H), 0.98-0.90 (m, 2H), 0.89-0.84 (m, 2H).

後処理

  1. filtrationThe solid was filtered off
  2. washwashed with EtOAc (50 mL×3)
  3. customThe filtrate was evaporated under reduced pressure
  4. customthe residue was purified by column chromatography on silica gel (petroleum ether/ethyl acetate=10/1)

出典と根拠

ORDレコード
ord-f447044cdfad4da5938f209789e3f71d
出典データセット
uspto-grants-2015_02
特許番号
US08952050B2

関連ノート

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