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

HRID 409391

Reaktionsgleichung

Reaktionsgleichung von HRID 409391
[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]

Komponenten

6

Edukt 4

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

Produkt 1

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

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6342AcetonitrileLösungsmittel

Reaktionsbedingungen

Temperatur
60 °C

Versuchsvorschrift

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)).

Aufarbeitung

  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

Quellen und Nachweise

ORD-Eintrag
ord-64f7a0f4b75a4a099a6e1399a62bc141
Quelldatensatz
uspto-grants-2014_06
Patentnummer
US08759386B2

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