Ethylenediamine → N-(6-Methoxy-2-methyl-3-pyridyl)ethane-1,2-diamine

HRID 631797Notes

Reaction equation

HRID 631797 reaction equation
Br[C:2]1[C:3]([CH3:10])=[N:4][C:5]([O:8][CH3:9])=[CH:6][CH:7]=1.[CH2:11]([NH2:14])[CH2:12][NH2:13].CC(C)([O-])C.[Na+]>O1CCOCC1.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].C1(P(C2CCCCC2)C2C(OC)=CC=C(OC)C=2C2C(C(C)C)=CC(C(C)C)=CC=2C(C)C)CCCCC1>[CH3:9][O:8][C:5]1[N:4]=[C:3]([CH3:10])[C:2]([NH:13][CH2:12][CH2:11][NH2:14])=[CH:7][CH:6]=1

Participants

7

Reactant 3

HCID 3301EthylenediamineHCID 107981463-Bromo-6-methoxy-2-methylpyridineHCID 23676156Sodium t-butoxide

Product 1

HCID 89825702N-(6-Methoxy-2-methyl-3-pyridyl)ethane-1,2-diamineYield 78.1%

Reagents, catalysts & solvents 3

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 25112535BrettphosCatalystHCID 312751,4-DioxaneSolvent

Procedure

3-Bromo-6-methoxy-2-methylpyridine (50 mg, 0.247 mmol), ethane-1,2-diamine (0.083 ml, 1.237 mmol), sodium tert-butoxide (47.6 mg, 0.495 mmol) and dicyclohexyl-[3,6-dimethoxy-2-(2,4,6-thisopropylphenyl)phenyl]phosphane (6.64 mg, 0.012 mmol) were dissolved under argon in anhydrous 1,4-dioxane (2.5 ml). Next, Pd2(DBA)3 (11.33 mg, 0.012 mmol) was added and the mixture was heated in a sealed flask to 70 C overnight. The reaction mixture was filtered over kieselguhr, rinsed with EtOAc and the combined filtrates were concentrated under reduced pressure. The residue was purified by flash column chromatography (silica, gradient of 0.5% to 10% of [7N NH3 in MeOH] in DCM to yield 35 mg (0.193 mmol, 78%) of a yellow oil. MS(ESI) m/z=182.2 [M+1]+.

Workup

  1. temperaturethe mixture was heated in a sealed flask to 70 C overnight
  2. filtrationThe reaction mixture was filtered over kieselguhr
  3. washrinsed with EtOAc
  4. concentrationthe combined filtrates were concentrated under reduced pressure
  5. customThe residue was purified by flash column chromatography (silica, gradient of 0.5% to 10% of [7N NH3 in MeOH] in DCM

Sources & evidence

ORD record
ord-d5e22886585b46a39544a71a49e0a03f
Source dataset
uspto-grants-2016_04
Patent number
US09321724B2

Reaction notes

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