Water → 5-Methyl-3-(3-nitro-4-pyridinyl)-2-cyclohexen-1-one

HRID 1920212Notes

Reaction equation

HRID 1920212 reaction equation
[CH3:1][CH:2]1[CH2:7][C:6](=[O:8])[CH:5]=[C:4](B2OC(C)(C)C(C)(C)O2)[CH2:3]1.Cl[C:19]1[CH:24]=[CH:23][N:22]=[CH:21][C:20]=1[N+:25]([O-:27])=[O:26].O>O1CCOCC1.C([O-])([O-])=O.[Na+].[Na+].CCOC(C)=O.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH3:1][CH:2]1[CH2:7][C:6](=[O:8])[CH:5]=[C:4]([C:19]2[CH:24]=[CH:23][N:22]=[CH:21][C:20]=2[N+:25]([O-:27])=[O:26])[CH2:3]1

Participants

8

Reactant 3

HCID 962WaterHCID 27357814-Chloro-3-nitropyridineHCID 592265515-Methyl-2-cyclohexene-1-one-3-boronic acid pinacol ester

Product 1

HCID 592265435-Methyl-3-(3-nitro-4-pyridinyl)-2-cyclohexen-1-one

Reagents, catalysts & solvents 4

HCID 178418397HCID 178418397, compoundCatalystHCID 8857Ethyl AcetateSolventHCID 10340Sodium CarbonateSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
120 °C

Procedure

To a solution of 5-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)cyclohex-2-enone (1.0 equiv.) in degassed dioxane and 2M Na2CO3 was added 4-chloro-3-nitropyridine (1.2 equiv.) and Pd(PPh3)4 (0.05 equiv.). The reaction was heated in an oil bath to 120° C. for 2 h. (reaction can also be carried out in the microwave for 10 min at 120° C.). Cooled to room temperature, then diluted with EtOAc, added H2O—dark solution, lots of emulsions. Filtered to get rid of the solids, then extracted the organic phase, dried with Na2SO4, and concentrated. The crude was purified via silica gel chromatography to yield 5-methyl-3-(3-nitropyridin-4-yl)cyclohex-2-enone. LC/MS=233.2 (M+H); Rt=0.69 min, LC=2.70 min.

Workup

  1. customreaction
  2. temperatureCooled to room temperature
  3. filtrationFiltered
  4. customto get rid of the solids
  5. extractionextracted the organic phase
  6. dry with materialdried with Na2SO4
  7. concentrationconcentrated
  8. customThe crude was purified via silica gel chromatography

Sources & evidence

ORD record
ord-3e5f450b49984f94a5a70eb87682a0bb
Source dataset
uspto-grants-2012_05
Patent number
US08168794B2

Reaction notes

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