Diisopropylamine → 4-Chloro-1,5-dimethyl-6-oxo-2-trimethylsilanylethynyl-1,6-dihydropyridine-3-carboxylic acid ethyl ester

HRID 2111104Notes

Reaction equation

HRID 2111104 reaction equation
[CH2:1]([O:3][C:4]([C:6]1[C:11]([Cl:12])=[C:10]([CH3:13])[C:9](=[O:14])[N:8]([CH3:15])[C:7]=1Br)=[O:5])[CH3:2].[CH3:17][Si:18]([C:21]#[CH:22])([CH3:20])[CH3:19].N(C(C)C)C(C)C>C1COCC1.C(OCC)(=O)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>[CH2:1]([O:3][C:4]([C:6]1[C:11]([Cl:12])=[C:10]([CH3:13])[C:9](=[O:14])[N:8]([CH3:15])[C:7]=1[C:22]#[C:21][Si:18]([CH3:20])([CH3:19])[CH3:17])=[O:5])[CH3:2]

Participants

8

Reactant 3

HCID 7912DiisopropylamineHCID 66111TrimethylsilylacetyleneHCID 666741602-Bromo-4-chloro-1,5-dimethyl-6-oxo-1,6-dihydropyridine-3-carboxylic acid ethyl ester

Product 1

HCID 666748954-Chloro-1,5-dimethyl-6-oxo-2-trimethylsilanylethynyl-1,6-dihydropyridine-3-carboxylic acid ethyl ester

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a mixture of 2-bromo-4-chloro-1,5-dimethyl-6-oxo-1,6-dihydropyridine-3-carboxylic acid ethyl ester (1.00 equivalent), trimethylsilylacetylene (1.20 equivalents) and iPr2NH (2.00 equivalents) in THF is added CuI (0.10 equivalents) followed by Pd(PPh3)2Cl2 (0.10 equivalents). After stirring the reaction mixture at reflux for 16 hours, it is cooled to room temperature and diluted with ethyl acetate. The organic layer is washed with saturated NH4Cl solution and brine, dried (MgSO4) and concentrated under reduced pressure. The desired product is obtained by flash column chromatography as necessary.

Workup

  1. temperatureat reflux for 16 hours
  2. washThe organic layer is washed with saturated NH4Cl solution and brine
  3. dry with materialdried (MgSO4)
  4. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-41f10d609a324da39db2d4901b617c08
Source dataset
uspto-grants-2009_04
Patent number
US07517994B2

Reaction notes

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