Triethylamine → Isopropyl 3-nitro-4-(3-(1-piperidinyl)anilino)benzoate

HRID 49822

反応式

HRID 49822 の反応式
Cl[C:2]1[CH:13]=[CH:12][C:5]([C:6]([O:8][CH:9]([CH3:11])[CH3:10])=[O:7])=[CH:4][C:3]=1[N+:14]([O-:16])=[O:15].[N:17]1([C:23]2[CH:24]=[C:25]([CH:27]=[CH:28][CH:29]=2)[NH2:26])[CH2:22][CH2:21][CH2:20][CH2:19][CH2:18]1.C(N(CC)CC)C>CN1C(=O)CCC1>[N+:14]([C:3]1[CH:4]=[C:5]([CH:12]=[CH:13][C:2]=1[NH:26][C:25]1[CH:27]=[CH:28][CH:29]=[C:23]([N:17]2[CH2:22][CH2:21][CH2:20][CH2:19][CH2:18]2)[CH:24]=1)[C:6]([O:8][CH:9]([CH3:11])[CH3:10])=[O:7])([O-:16])=[O:15]

参加物

5

反応物 3

HCID 8471TriethylamineHCID 693119Isopropyl 4-chloro-3-nitrobenzoateHCID 71278063-(Piperidin-1-yl)aniline

生成物 1

HCID 22741931Isopropyl 3-nitro-4-(3-(1-piperidinyl)anilino)benzoate収率 54.1%

試薬・触媒・溶媒 1

HCID 13387N-methyl-2-pyrrolidone溶媒

反応条件

温度
80 °C

実験手順

To a mixture of isopropyl 4-chloro-3-nitrobenzoate (3.0 g, 12.3 mmol) and 2a (2.16 g, 12.3 mmol) in anhydrous NMP (5 ml) was added triethylamine (1.71 ml, 12.3 mmol) and the mixture was stirred at 80° C. under a stream of nitrogen overnight. The cooled mixture was partitioned between ethyl acetate and water. The organic phase was extracted with diluted hydrochloric acid (4M). The aqueous extract was rendered alkaline by addition of aqueous sodium hydroxide (12M) and extracted with ethyl acetate. This organic extract was dried over sodium sulfate and concentrated under reduced pressure. The residue was chromatographied on silica gel using a mixture of ethyl acetate and petroleum ether (1:1 v/v) as the eluent to yield isopropyl 3-nitro-4-(3-(1-piperidinyl)anilino)benzoate (2.55 g, 54%) as a red oil. This intermediate product was dissolved in ethanol (50 ml) hydrogenated at ambient pressure. The resulting diamine was treated with formic acid (25 ml) at 80° C. for 1 hour. The reaction mixture was poured into water (100 ml) and rendered alkaline by addition of aqueous sodium hydroxide (10M). The crude product was filtered off, washed with water and dried. Purification was achieved by treatment with activated carbon in refluxing 2-propanol followed by trituration with diethyl ether. Yield of 4e1: 1.27 g (53%). M.p. 160-161° C.

後処理

  1. customThe cooled mixture was partitioned between ethyl acetate and water
  2. extractionThe organic phase was extracted with diluted hydrochloric acid (4M)
  3. extractionThe aqueous extract
  4. additionby addition of aqueous sodium hydroxide (12M)
  5. extractionextracted with ethyl acetate
  6. extractionThis organic extract
  7. dry with materialwas dried over sodium sulfate
  8. concentrationconcentrated under reduced pressure
  9. additiona mixture of ethyl acetate and petroleum ether (1:1 v/v) as the eluent

出典と根拠

ORDレコード
ord-a1e0d3c3ea1b49c9854b79cc5a70b30a
出典データセット
uspto-grants-2004_03
特許番号
US06710044B2

関連ノート

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