Potassium Carbonate → [3,5-dimethyl-1-(2-chloro-4-nitrobenzyl)-1H-pyrazol-4-yl]acetic acid tert-butyl ester

HRID 409391

反応式

HRID 409391 の反応式
[C:1]([O:5][C:6](=[O:15])[CH2:7][C:8]1[C:9]([CH3:14])=[N:10][NH:11][C:12]=1[CH3:13])([CH3:4])([CH3:3])[CH3:2].CC(=O)CC(=O)C.[Cl:23][C:24]1[CH:31]=[C:30]([N+:32]([O-:34])=[O:33])[CH:29]=[CH:28][C:25]=1[CH2:26]Br.C([O-])([O-])=O.[K+].[K+]>C(#N)C>[C:1]([O:5][C:6](=[O:15])[CH2:7][C:8]1[C:12]([CH3:13])=[N:11][N:10]([CH2:26][C:25]2[CH:28]=[CH:29][C:30]([N+:32]([O-:34])=[O:33])=[CH:31][C:24]=2[Cl:23])[C:9]=1[CH3:14])([CH3:4])([CH3:3])[CH3:2]

参加物

6

反応物 4

HCID 11430Potassium CarbonateHCID 31261AcetylacetoneHCID 30163681-(Bromomethyl)-2-chloro-4-nitrobenzeneHCID 66707418tert-butyl 2-(3,5-dimethyl-1H-pyrazol-4-yl)acetate

生成物 1

HCID 68276418[3,5-dimethyl-1-(2-chloro-4-nitrobenzyl)-1H-pyrazol-4-yl]acetic acid tert-butyl ester

試薬・触媒・溶媒 1

HCID 6342Acetonitrile溶媒

反応条件

温度
60 °C

実験手順

To a solution of (3,5-dimethyl-1H-pyrazol-4-yl)-acetic acid tert-butyl ester (2.6 g, 12.4 mmol, preparation according to WO2007/141267 by using 2,4-pentanedione instead of 3,5-heptanedione) and 2-chloro-4-nitrobenzyl bromide (3.11 g, 12.4 mmol) in acetonitrile (30 mL) is added K2CO3 (2.575 g, 18.6 mmol) and the mixture is stirred for 48 hours at room temperature and after that 2 hours at 60° C. The solid is filtered off and the solvent is removed by evaporation. The residue is dissolved in dichloromethane/water. After extraction with dichloromethane the organic layer is dried over MgSO4 and evaporated under reduced pressure to yield 4.4 g of [3,5-dimethyl-1-(2-chloro-4-nitrobenzyl)-1H-pyrazol-4-yl]acetic acid tert-butyl ester (ESI mass spectrum: [M+H]+=380). b) To a solution of [3,5-dimethyl-1-(2-chloro-4-nitrobenzyl)-1H-pyrazol-4-yl]acetic acid tert-butyl ester (4.40 g, 11.6 mmol) in methanol (80 mL) is added Raney nickel (440 mg) and the mixture is hydrogenated at 50 psi and room temperature for 12 hours. The catalyst is filtered off and the filtrate is concentrated under reduced pressure to yield 2.4 g of the title compound (ESI mass spectrum: [M+H]+=350; Retention time HPLC: 0.76 min (method D)).

後処理

  1. filtrationThe solid is filtered off
  2. customthe solvent is removed by evaporation
  3. dissolutionThe residue is dissolved in dichloromethane/water
  4. extractionAfter extraction with dichloromethane the organic layer
  5. dry with materialis dried over MgSO4
  6. customevaporated under reduced pressure

出典と根拠

ORDレコード
ord-64f7a0f4b75a4a099a6e1399a62bc141
出典データセット
uspto-grants-2014_06
特許番号
US08759386B2

関連ノート

読み込み中…