ホームMCPワークベンチSkills
ホームワークベンチ通知マイページ
llms.txt · MCPガイドプライバシーポリシー · 利用規約 · サポートv1.8.0
  1. ホーム
  2. /反応

Diethyl Ether → 3-Nitro-4-(3-(4-methylpiperazin-1-yl)phenylamino)-phenylacetic acid

HRID 1633608
ノート
印刷プレビュー

反応式

HRID 1633608 の反応式
F[C:2]1[CH:7]=[CH:6][C:5]([CH2:8][C:9]([OH:11])=[O:10])=[CH:4][C:3]=1[N+:12]([O-:14])=[O:13].[CH3:15][N:16]1[CH2:21][CH2:20][N:19]([C:22]2[CH:23]=[C:24]([CH:26]=[CH:27][CH:28]=2)[NH2:25])[CH2:18][CH2:17]1.C(N(CC)CC)C.C(OCC)C>CN1C(=O)CCC1>[N+:12]([C:3]1[CH:4]=[C:5]([CH2:8][C:9]([OH:11])=[O:10])[CH:6]=[CH:7][C:2]=1[NH:25][C:24]1[CH:26]=[CH:27][CH:28]=[C:22]([N:19]2[CH2:18][CH2:17][N:16]([CH3:15])[CH2:21][CH2:20]2)[CH:23]=1)([O-:14])=[O:13]
参加物反応条件実験手順後処理出典と根拠反応ノート

参加物

6

反応物 4

HCID 3283Diethyl EtherHCID 8471TriethylamineHCID 111272614-Fluoro-3-nitrophenylacetic acidHCID 115646133-(4-Methylpiperazin-1-yl)aniline

生成物 1

HCID 227418433-Nitro-4-(3-(4-methylpiperazin-1-yl)phenylamino)-phenylacetic acid収率 29.1%

試薬・触媒・溶媒 1

HCID 13387
N-methyl-2-pyrrolidone
溶媒

反応条件

温度
80 °C

実験手順

To a suspension of 1i (3.0 g, 15.1 mmol) in anhydrous NMP (2 ml) was added 2c (2.88 g, 15.1 mmol) and triethylamine (2.1 ml, 30.2 mmol). The mixture was stirred at 80° C. under a stream of nitrogen overnight. The cooled mixture was poured into a mixture of diethyl ether and petroleum ether (100 ml, 1:1 v/v) resulting in separation of an oily lower phase. The mixture was decanted and the oil was dissolved in dichloromethane and eluted through silica gel with a mixture of dichloromethane and methanol (4:1 v/v) to yield 3-nitro-4-(3-(4-methylpiperazin-1-yl)phenylamino)-phenylacetic acid (1.63 g, 29%). This acid (0.64 g, 1.73 mmol) was dissolved in methanol and concentrated hydrochloric acid (0.2 ml) was added. The mixture was heated to reflux for 4 days. The solvent was removed under reduced pressure and the residue was purified by column-chromatography on silica gel using a mixture of dichloromethane, methanol and aqueous ammonia (90:10:1 v/v/v) as the eluent to leave the ester (0.47 g, 71%) as a red oil. This oil was hydrogenated in methanol at ambient pressure using Pd (5% on activated carbon) as the catalyst to yield the corresponding diamine (0.38 g). This diamine was treated with triethyl orthoformate (0.35 ml, 2.14 mmol) and a catalytic amount of pTSA in THF (5 ml) at 80° C. for 30 min. The solvent was evaporated and the residue was partitioned between aqueous sodium hydroxide (1M) and ethyl acetate. The organic phase was dried over sodium sulfate, concentrated and eluted through a silica gel column with a mixture of dichloromethane, methanol and aqueous ammonia (90:10:1 v/v/v). The product precipitated as the hydrochloride by addition of a solution of anhydrous hydrogen chloride in diethyl ether to the eluate. Yield of 4l1: 0.2 g (41%). M.p. 140-142° C.

後処理

  1. customresulting in separation of an oily lower phase
  2. customThe mixture was decanted
  3. dissolutionthe oil was dissolved in dichloromethane
  4. washeluted through silica gel with a mixture of dichloromethane and methanol (4:1 v/v)

出典と根拠

ORDレコード
ord-d56030d7feda4a9e917019413e3e13d5
出典データセット
uspto-grants-2003_01
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US06503925B1

反応ノート

読み込み中…

このページの内容参加物反応条件実験手順後処理出典と根拠反応ノート