Acetic Acid → HCID 58425604, compound

HRID 1966475Notes

Reaction equation

HRID 1966475 reaction equation
[NH2:1][C:2]1[CH:3]=[C:4]([N:9]2[CH2:14][CH2:13][N:12]([C:15]([C:17]3[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=3)=[O:16])[CH2:11][CH2:10]2)[CH:5]=[CH:6][C:7]=1[NH2:8].[C:23](O)(=O)[CH3:24].C(=O)C=O>C(#N)C>[C:17]1([C:15]([N:12]2[CH2:11][CH2:10][N:9]([C:4]3[CH:3]=[C:2]4[C:7](=[CH:6][CH:5]=3)[N:8]=[CH:24][CH:23]=[N:1]4)[CH2:14][CH2:13]2)=[O:16])[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=1

Participants

5

Reactant 3

HCID 176Acetic AcidHCID 7860GlyoxalHCID 13511176HCID 13511176, compound

Product 1

HCID 58425604HCID 58425604, compoundYield 28.1%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Conditions

Temperature
50 °C

Procedure

A suspension of (4-(3-amino-4-nitrophenyl)piperazin-1-yl)(phenyl)methanone (2.0 g, 9.0 mmol), 5 ml acetic acid and palladium on carbon (100 mg, 5%) in 50 ml ethanol was stirred at room temperature under hydrogen atmosphere overnight. The mixture was filtered with the aid of celite. Crude (4-(3,4-diaminophenyl)piperazin-1-yl)(phenyl)methanone (1.2 g, 41%) was obtained after removing of solvents. A suspension of (4-(3,4-diaminophenyl)piperazin-1-yl)(phenyl)methanone (0.2 g, 0.67 mmol), acetic acid (0.23 ml, 4.0 mmol) and 40% oxalaldehyde (0.14 ml, 1.0 mmol) in 40 ml acetonitrile was stirred at 50° C. under argon atmosphere overnight. The reaction was quenched with the 5 ml water and extracted with ethyl acetate (3×40 ml). The extraction was concentrated after drying over anhydrous sodium sulfate. Phenyl(4-(quinoxalin-6-yl)piperazin-1-yl)methanone (0.060 g, 28%) was obtained by flash column chromatograph (10% acetone in ethyl acetate). 1H NMR (500 MHz, CDCl3) δ (ppm) 3.37 (d, br, 4H), 3.69 (s, br, 2H), 4.01 (s, br, 2H), 7.30 (d, J=2.7 Hz, 1H), 7.48 (m, 5H), 7.50 (dd, J=9.3, 2.7 Hz, 1H), 7.56 (d, J=9.3 Hz, 1H), 8.65 (d, J=1.9 Hz, 1H), 8.73 (d, J=1.9 Hz, 1H). 13C NMR (125 MHz, CDCl3): δ (ppm) 49.1, 49.3, 110.8, 123.0, 127.6, 29.0, 130.4, 130.5, 1135.7, 139.0, 142.6, 144.9, 151.9, 145.6, 170.9.

Workup

  1. customafter removing of solvents
  2. customThe reaction was quenched with the 5 ml water
  3. extractionextracted with ethyl acetate (3×40 ml)
  4. extractionThe extraction
  5. concentrationwas concentrated
  6. dry with materialafter drying over anhydrous sodium sulfate

Sources & evidence

ORD record
ord-ccdab3c94e7143879820796cbadf4902
Source dataset
uspto-grants-2013_04
Patent number
US08420640B2

Reaction notes

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