1-Piperazinecarboxylic acid, ethyl ester → HCID 19921653, compound

HRID 1647805Notes

Reaction equation

HRID 1647805 reaction equation
Cl[C:2]1[CH:7]=[CH:6][N:5]=[CH:4][C:3]=1[N+:8]([O-:10])=[O:9].C(=O)([O-])[O-].[K+].[K+].[N:17]1([C:23]([O:25][CH2:26][CH3:27])=[O:24])[CH2:22][CH2:21][NH:20][CH2:19][CH2:18]1>CC#N>[N+:8]([C:3]1[CH:4]=[N:5][CH:6]=[CH:7][C:2]=1[N:20]1[CH2:19][CH2:18][N:17]([C:23]([O:25][CH2:26][CH3:27])=[O:24])[CH2:22][CH2:21]1)([O-:10])=[O:9]

Participants

5

Reactant 3

HCID 84311-Piperazinecarboxylic acid, ethyl esterHCID 11430Potassium CarbonateHCID 27357814-Chloro-3-nitropyridine

Product 1

HCID 19921653HCID 19921653, compoundYield 73.6%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Conditions

Temperature
23 °C

Procedure

A solution of technical grade 3-nitropyridone (25 g, 177 mmol) (contains about 20% 3,5-dinitropyridone by weight) in 150 mL of phosphorous oxychloride was heated at 90° C. for 2 h. The excess phosphorous oxychloride was removed by distillation and the remaining oil poured into ice/water. The aqueous solution was extracted with five 300 mL portions of CH2Cl2. The CH2Cl2 extracts were dried (MgSO4), filtered and concentrated in vacuo to yield 26.7 g of crude 4-chloro-3-nitropyridine. To a solution of the crude 4-chloro-3-nitropyridine (26.7 g) in 200 mL of MeCN was added potassium carbonate (25.7 g, 186 mmol) and ethyl 1-piperazinecarboxylate (27.2 mL, 186 mmol). The reaction mixture was stirred at 23° C. for 16 h and then concentrated in vacuo. The mixture was diluted with ethyl acetate (1 L), and the organic solution was washed with water, dried (brine, MgSO4), filtered and concentrated in vacuo to a solid mass. Silica gel chromatography of the mixture gave ethyl 4-(3-nitro-4-pyridinyl)-1-piperazinecarboxylate (34.73 g, 73%): mp 101°-103° C., and ethyl 4-(3,5-dinitro-4-pyridinyl)-1-piperazinecarboxylate (7.07 g, 22%): mp 165°-167° C. Anal. Calcd for C12H16N4O4 : C, 51.42; H, 5.75; N, 19.99. Found: C, 51.26; H, 5.69; N, 19.91. Anal. Calcd for C12H15N5O6 : C, 44.31; H, 4.65; N, 21.53. Found: C, 44.51; H, 4.65; N, 21.36.

Workup

  1. concentrationconcentrated in vacuo
  2. additionThe mixture was diluted with ethyl acetate (1 L)
  3. washthe organic solution was washed with water
  4. dry with materialdried (brine, MgSO4)
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo to a solid mass

Sources & evidence

ORD record
ord-9286f412fa4d49efb7c4401d69302655
Source dataset
uspto-grants-1995_07
Patent number
US05434154

Reaction notes

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