2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → 3-Ethyl 5-methyl 2-amino-6-methyl-4-(p-tolyl)pyridine-3,5-dicarboxylate

HRID 1912528Notes

Reaction equation

HRID 1912528 reaction equation
[NH2:1][C:2]1[NH:3][C:4]([CH3:24])=[C:5]([C:20]([O:22][CH3:23])=[O:21])[CH:6]([C:13]2[CH:18]=[CH:17][C:16]([CH3:19])=[CH:15][CH:14]=2)[C:7]=1[C:8]([O:10][CH2:11][CH3:12])=[O:9].C(C1C(=O)C(Cl)=C(Cl)C(=O)C=1C#N)#N>ClCCl>[NH2:1][C:2]1[C:7]([C:8]([O:10][CH2:11][CH3:12])=[O:9])=[C:6]([C:13]2[CH:18]=[CH:17][C:16]([CH3:19])=[CH:15][CH:14]=2)[C:5]([C:20]([O:22][CH3:23])=[O:21])=[C:4]([CH3:24])[N:3]=1

Participants

4

Reactant 2

HCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 712091963-Ethyl 5-methyl 2-amino-6-methyl-4-(p-tolyl)-1,4-dihydropyridine-3,5-dicarboxylate

Product 1

HCID 712089973-Ethyl 5-methyl 2-amino-6-methyl-4-(p-tolyl)pyridine-3,5-dicarboxylateYield 96.4%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

A solution of 3-ethyl 5-methyl 2-amino-6-methyl-4-(p-tolyl)-1,4-dihydropyridine-3,5-dicarboxylate (2 g, 6.05 mmol) in dichloromethane (DCM) (30 ml) was treated with DDQ (1.374 g, 6.05 mmol) and stirred at rt for 1.5 hours. The reaction was filtered through a pad of celite and washed with DCM. The filtrate was diluted with sat. NaHCO3, extracted with DCM, washed with brine, dried with Na2SO4, filtered, and concentrated to afford 3-ethyl 5-methyl 2-amino-6-methyl-4-(p-tolyl)pyridine-3,5-dicarboxylate (1.9145 g, 5.83 mmol, 96% yield) as brown solid: 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 7.14 (d, J=7.8 Hz, 2 H), 7.08-7.00 (m, 2 H), 6.05 (br. s., 2 H), 3.86 (q, J=7.2 Hz, 2 H), 3.45 (s, 3 H), 2.43 (s, 3 H), 2.37 (s, 3 H), 0.69 (t, J=7.2 Hz, 3 H); LCMS (m/z) ES+=329 (M+1).

Workup

  1. filtrationThe reaction was filtered through a pad of celite
  2. washwashed with DCM
  3. additionThe filtrate was diluted with sat. NaHCO3
  4. extractionextracted with DCM
  5. washwashed with brine
  6. dry with materialdried with Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated

Sources & evidence

ORD record
ord-7fdfe7bc3bd146b494d7bc2025e80087
Source dataset
uspto-grants-2013_12
Patent number
US08609653B2

Reaction notes

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