N-Methyl dicyclohexylamine → HCID 89923050, compound

HRID 921928Notes

Reaction equation

HRID 921928 reaction equation
[NH2:1][C:2]1[C:3]([Cl:11])=[CH:4][C:5](Br)=[C:6]([CH:9]=1)[C:7]#[N:8].[CH3:12][C:13](=[O:17])/[CH:14]=[CH:15]/[CH3:16].C(P(C(C)(C)C)C1C=CC=CC=1C1C=CC=CC=1C)(C)(C)C.C1(N(C)C2CCCCC2)CCCCC1>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].CC#N>[NH2:1][C:2]1[C:3]([Cl:11])=[CH:4][C:5](/[C:15](=[CH:14]/[C:13](=[O:17])[CH3:12])/[CH3:16])=[C:6]([CH:9]=1)[C:7]#[N:8]

Participants

7

Reactant 4

HCID 24210N-Methyl dicyclohexylamineHCID 637920(3E)-3-Penten-2-oneHCID 27349372-(Di-tert-butylphosphino)-2'-methyl-1,1'-biphenylHCID 532162295-Amino-2-bromo-4-chlorobenzonitrile

Product 1

HCID 89923050HCID 89923050, compoundYield 23.7%

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 6342AcetonitrileSolvent

Conditions

Temperature
90 °C

Procedure

5-amino-2-bromo-4-chlorobenzonitrile (0.5 g, 2.16 mmol), (E)-pent-3-en-2-one (0.273 g, 3.24 mmol), Pd2(dba)3 (0.020 g, 0.022 mmol), di-tert-butyl(2′-methyl-[1,1′-biphenyl]-2-yl)phosphine (0.020 g, 0.065 mmol), and N-cyclohexyl-N-methylcyclohexanamine (0.633 g, 3.24 mmol) were combined in a 20 dram vial and CH3CN (4 mL) was added. The vial was evacuated and backfilled with N2, and the reaction was heated at 90° C. for 3 h. The reaction was cooled to room temperature and diluted with water, extracting 3× with EtOAc. The organic layers were dried over Na2SO4, filtered, and concentrated in vacuo. The material was purified by flash column chromatography (0-100% EtOAc/Hex). (E)-5-amino-4-chloro-2-(4-oxopent-2-en-2-yl)benzonitrile (120 mg) was obtained as a yellow solid.

Workup

  1. customThe vial was evacuated
  2. temperatureThe reaction was cooled to room temperature
  3. additiondiluted with water
  4. extractionextracting 3× with EtOAc
  5. dry with materialThe organic layers were dried over Na2SO4
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. customThe material was purified by flash column chromatography (0-100% EtOAc/Hex)

Sources & evidence

ORD record
ord-849b0fb46c5448729e8d242c2a7fa4c3
Source dataset
uspto-grants-2016_03
Patent number
US09273057B2

Reaction notes

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