Ethylenediaminetetraacetic Acid → 4,5-Diaminophthalonitrile
Reaction equation
[NH2:1][C:2]1[CH:7]=[C:6](I)[C:5](I)=[CH:4][C:3]=1[NH2:10].[C:11]([Cu])#[N:12].C(N(CC(O)=O)CC(O)=O)[CH2:15][N:16](CC(O)=O)CC(O)=O>>[NH2:1][C:2]1[CH:7]=[C:6]([C:15]#[N:16])[C:5]([C:11]#[N:12])=[CH:4][C:3]=1[NH2:10]Participants
Conditions
- Temperature
- 120 °C
Procedure
A 50 mL round-bottom flask was charged with 2 (6.94 g, 19.3 mmol), and CuCN (6.91 g, 77.2 mmol, 4 eq), and a magnetic stirring bar. The vessel was capped with a septum and flushed with Ar for 10 min, and NMP (20 mL) was added. The vessel was heated to 120° C. for 3 h, then diluted with DMF (20 mL) and added to a hot aqueous solution of EDTA (88 g, 232 mmol, in 500 mL H2O) in a 1 L conical flask. Oxygen was bubbled through the mixture as it was stirred and heated for 2 h. After 2 h of this treatment, the dark heterogeneous mixture turned to a homogeneous green solution. The hot green solution was extracted twice with ethyl acetate, and the extracts were washed with water, followed by brine, dried over Na2SO4, filtered, and concentrated to dryness. The residue was recrystallized (EtOH/water), giving tiny tan needles (1.66 g, 55%): mp 262-264° C.; NMR (d6-acetone) δ 5.40 (br s, 4H), 7.04 (s, 2H); 13C NMR (d6-acetone) δ 103.8, 117.1, 117.4, 139.4; FAB-MS obsd 158.0591, calcd 158.0592 (C6H6N4).
Workup
- customThe vessel was capped with a septum
- customflushed with Ar for 10 min
- additionNMP (20 mL) was added
- additiondiluted with DMF (20 mL)
- customOxygen was bubbled through the mixture as it
- temperatureheated for 2 h
- extractionThe hot green solution was extracted twice with ethyl acetate
- washthe extracts were washed with water
- dry with materialdried over Na2SO4
- filtrationfiltered
- concentrationconcentrated to dryness
- customThe residue was recrystallized (EtOH/water)
Sources & evidence
- ORD record
- ord-8b44dffc1a4c4ca68927d3732a4669a5
- Source dataset
- uspto-grants-2011_04
- Patent number
- US07919770B2
Reaction notes
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