Triethylamine → 2-(3-Oxo-2-phenyl-2,3-dihydropyridazine-4-carbonyl)-cyclohexane-1,3-dione

HRID 575517Notes

Reaction equation

HRID 575517 reaction equation
[O:1]=[C:2]1[C:7]([C:8]([OH:10])=O)=[CH:6][CH:5]=[N:4][N:3]1[C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1.[C:17](Cl)(=[O:21])[C:18](Cl)=O.C(N(CC)CC)C.[C:30]1(=O)[CH2:35][CH2:34]CC[C:31]1=[O:36]>ClCCl.CN(C)C=O.CC(C)(O)C#N>[O:1]=[C:2]1[C:7]([C:8]([CH:18]2[C:17](=[O:21])[CH2:34][CH2:35][CH2:30][C:31]2=[O:36])=[O:10])=[CH:6][CH:5]=[N:4][N:3]1[C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1

Participants

8

Reactant 4

HCID 8471Triethylamine3×HCID 130061,2-CyclohexanedioneHCID 65578Oxalyl chlorideHCID 46380363-Oxo-2-phenyl-2,3-dihydropyridazine-4-carboxylic acid

Product 1

HCID 627050522-(3-Oxo-2-phenyl-2,3-dihydropyridazine-4-carbonyl)-cyclohexane-1,3-dione

Reagents, catalysts & solvents 3

HCID 6228DimethylformamideCatalystHCID 6406Acetone CyanohydrinCatalystHCID 6344DichloromethaneSolvent2×

Procedure

3-Oxo-2-phenyl-2,3-dihydropyridazine-4-carboxylic acid (0.52 g, 2.42 mmol) was stirred in anhydrous dichloromethane (13 ml) and 1 drop of anhydrous dimethylformamide was added. Oxalyl chloride (0.25 mL, 2.90 mmol) was added dropwise to the suspension resulting in a brown solution. After 1.5 h the reaction was concentrated in vacuo. The residue obtained was dissolved in dichloromethane (20 ml). To the brown solution anhydrous triethylamine (1 ml), then cyclohexanedione (0.33 g, 2.90 mmol) was added, producing a reddish coloured solution. A further 0.33 ml of anhydrous triethylamine was added. The reaction mixture was stirred at room temperature for 2 h (reaction monitored by LCMS), then acetone cyanohydrin (1 drop) and anhydrous triethylamine (0.67 ml) was added and the reaction mixture was stirred overnight. LCMS indicated the desired product had been formed. The reaction mixture was concentrated in vacuo. The residue obtained was purified using column chromatography (SiO2, Toluene/Triethylamine/Dioxane/EtOH/Water 100:40:20:20:5 by volume), and then further purified by column chromatography (SiO2, hexane/ethyl acetate/acetic acid 2:1:0.02 to 0:100:2) to afford the title compound as an orange oil (25 mg, 3% yield). 1H NMR (CDCl3) 2.04 (m, 2H), 2.61 (br s, 4H), 7.18 (d, 1H) 7.46 (m, 2H), 7.59 (m, 3H) 7.96 (d, 1H) ppm.

Workup

  1. customresulting in a brown solution
  2. concentrationAfter 1.5 h the reaction was concentrated in vacuo
  3. customThe residue obtained
  4. customproducing a reddish coloured solution
  5. custom(reaction monitored by LCMS)
  6. stirringthe reaction mixture was stirred overnight

Sources & evidence

ORD record
ord-d434ea8519fc48d2b836289ba21021d1
Source dataset
uspto-grants-2015_05
Patent number
US09035049B2

Reaction notes

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