Formic Acid → HCID 66589180, compound

HRID 1092214Notes

Reaction equation

HRID 1092214 reaction equation
Cl[C:2]1[N:7]=[C:6]([NH:8][C:9]2[CH:13]=[C:12]([CH:14]3[CH2:16][CH2:15]3)[NH:11][N:10]=2)[C:5]([N+:17]([O-])=O)=[CH:4][CH:3]=1.[CH2:20]([NH2:30])[C:21]1[CH:29]=[CH:28][C:27]2[O:26][CH2:25][O:24][C:23]=2[CH:22]=1.[C:31]([O-])(O)=O.[Na+].C(O)=O.C([O-])([O-])=O.[Na+].[Na+]>[Zn].C(Cl)Cl.CO.O1CCOCC1>[O:26]1[C:27]2[CH:28]=[CH:29][C:21]([CH2:20][NH:30][C:2]3[N:7]=[C:6]4[N:8]([C:9]5[CH:13]=[C:12]([CH:14]6[CH2:16][CH2:15]6)[NH:11][N:10]=5)[CH:31]=[N:17][C:5]4=[CH:4][CH:3]=3)=[CH:22][C:23]=2[O:24][CH2:25]1

Participants

10

Reactant 5

HCID 284Formic AcidHCID 10340Sodium CarbonateHCID 75799Benzo-1,3-dioxole-5-methylamineHCID 516892Sodium BicarbonateHCID 589359036-Chloro-N-(5-cyclopropyl-1H-pyrazol-3-yl)-3-nitropyridin-2-amine

Product 1

HCID 66589180HCID 66589180, compound

Reagents, catalysts & solvents 4

HCID 23994ZincCatalystHCID 887MethanolSolventHCID 6344DichloromethaneSolventHCID 312751,4-DioxaneSolvent2×

Conditions

Temperature
100 °C

Procedure

A mixture of 6-chloro-N-(5-cyclopropyl-1H-pyrazol-3-yl)-3-nitropyridin-2-amine (Method 77, 70 mg, 0.25 mmol), piperonylamine (54 mg, 0.36 mmol), saturated NaHCO3 (0.5 ml), and anhydrous 1,4-dioxane (0.5 ml) was heated at 100° C. for 3 hours. The reaction was allowed to cool to room temperature, and the solvents were evaporated in a Genevac. The resulting residue was treated with zinc dust (195 mg, 2.98 mmol), formic acid (140 μL, 3.71 mmol), and 1,4-dioxane (0.5 ml), and the resulting mixture was reheated to 100° C. After 4 hours of heating, the reaction was allowed to cool and the volatile components were evaporated using a Genevac. The concentrated reaction mixture was treated with MeOH (1 ml), DCM (1 ml), and Na2CO3 (125 mg). This mixture was allowed to stir at room temperature for 45 minutes, at which point the entire mixture was loaded on top of a short column of silica gel (˜3 cm long×1.5 cm diameter). The column was flushed with MeOH (˜15 ml), and the eluent was concentrated in a Genevac. The title compound was obtained from the residue by crystallization from CHCl3/MeOH (7.2 mg). 1H NMR (400 MHz) 0.65-0.76 (m, 2H), 0.99 (m, 2H), 1.96 (m, 1H), 4.41 (m, 2H), 5.94 (s, 2H), 6.45 (s, 1H), 6.52 (m, 1H), 6.75 (m, 1H), 6.83 (m, 1H), 6.92 (m, 1H), 7.35 (m, 1H), 7.71 (m, 2H), 8.27 (s, 1H), 12.60 (s, 1H). MS: Calcd.: 374; Found: [M+H]+ 375.

Workup

  1. temperatureto cool to room temperature
  2. customthe solvents were evaporated in a Genevac
  3. customwas reheated to 100° C
  4. temperatureAfter 4 hours of heating
  5. temperatureto cool
  6. customthe volatile components were evaporated
  7. customThe concentrated reaction mixture
  8. customThe column was flushed with MeOH (˜15 ml)
  9. concentrationthe eluent was concentrated in a Genevac

Sources & evidence

ORD record
ord-8435905d87994b6b846d9557dba76d7b
Source dataset
uspto-grants-2012_03
Patent number
US08129403B2

Reaction notes

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