Propionic Acid → 2,6-Dimethyl-8-ethyl-1-deazapurine

HRID 728554Notes

Reaction equation

HRID 728554 reaction equation
C(O)(=O)CC.[NH4+:6].[OH-].[CH3:8][C:9]1[C:14](NC(=O)CC)=[C:13]([CH3:20])[N:12]=[C:11]([NH:21][C:22](=O)[CH2:23][CH3:24])[CH:10]=1>>[CH3:20][C:13]1[N:12]=[C:11]2[N:21]=[C:22]([CH2:23][CH3:24])[NH:6][C:10]2=[C:9]([CH3:8])[CH:14]=1

Participants

4

Reactant 3

HCID 1032Propionic AcidHCID 14923Ammonium HydroxideHCID 18983251HCID 18983251, compound

Product 1

HCID 98153742,6-Dimethyl-8-ethyl-1-deazapurine

Conditions

Temperature
90 °C

Procedure

To a mixture of 8.44 g of a 55:45 mixture of 2-Amino-3-nitro-4,6-dimethylpyridine and 2-Amino-4,6-dimethyl-5-nitropyridine in MeOH (1.2 L) was added 10% Pd/C (2.4 g). The reaction vessel was evacuated then purged with H2 at 1 atm. and stirred vigorously for 18 hours. Filtration (celite), and concentration gave 6.65 g of a mixture of 2,3-diamino-4,6-dimethylpyridine and 2,5-diamino-4,6-dimethylpyridine as a dark solid. To 5.4 g (39.4 mmol) of this mixture was added propionic acid (8.8 mL, 118 mmol) followed by polyphosphoric acid (100 mL). This stirred mixture was heated to 90° C. for 3 hours then to 100° C. for 1 hour. After the reaction was complete, the warm mixture was poured onto 300 g of ice and the mixture was made basic with NH4OH. The mixture was extracted (4×50 mL CH2Cl2), dried (K2CO3) and concentrated to give a mixture of the title compound and 4,6-dimethyl-2,5-bis(propionamido)pyridine. Purification (SiO2, 5% MeOH/EtOAc) gave 1.66 g of the title compound as the slower eluting component. 1H NMR (CD3OD, 300 MHz) δ 6.95 (s, 1H), 2.92 (q, 2H, J=7.8 Hz), 2.54 (apparent s, 6H), 1.40 (t, 3H, J=7.8 Hz)

Workup

  1. extractionThe mixture was extracted (4×50 mL CH2Cl2)
  2. dry with materialdried (K2CO3)
  3. concentrationconcentrated
  4. customto give

Sources & evidence

ORD record
ord-dc749c5559e34ae7865e2f8271e3ecbd
Source dataset
uspto-grants-1991_09
Patent number
US05049565

Reaction notes

Loading…