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Chemical Structure| 20055-00-9

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Product Details of [ 20055-00-9 ]

CAS No. :20055-00-9
Formula : C4H6N4O2
M.W : 142.12
SMILES Code : CN1N=C(N)C(N(=O)=O)=C1
MDL No. :MFCD00463971

Safety of [ 20055-00-9 ]

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H302-H315-H319
Precautionary Statements:P501-P270-P264-P280-P302+P352-P337+P313-P305+P351+P338-P362+P364-P332+P313-P301+P312+P330

Application In Synthesis of [ 20055-00-9 ]

* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

  • Downstream synthetic route of [ 20055-00-9 ]

[ 20055-00-9 ] Synthesis Path-Downstream   1~2

  • 1
  • [ 20055-00-9 ]
  • [ 89607-15-8 ]
YieldReaction ConditionsOperation in experiment
With tert.-butylnitrite; copper(ll) bromide; In acetonitrile; at 0 - 25℃; for 2h; Step 4: Into a 250 mL round bottom flask containing a solution of copper(II) bromide (3.0 g, 14 mmol) and tert-butyl nitrite (1.7 mL, 14 mmol) in acetonitrile (150 mL) was added 1-methyl-4- nitro-1H-pyrazol-3-amine (2 g, 14 mmol) in acetonitrile (20 mL) at 0 C and the reaction was stirred at room temperature for 2 h. The reaction mixture was concentrated under reduced pressure. The residue was dissolved in ethyl acetate (120 mL), washed with water and brine,dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. Theresidue was purified by column chromatography eluting with ethyl acetate in petroleum ether(20-30%) to afford 3-bromo-1-methyl-4-nitro-1H-pyrazole as a solid. ?H NMR (CDC13, 300MHz): 5 8.25 (s, 1H), 3.89 (s, 3H).
With tert.-butylnitrite; copper(ll) bromide; In acetonitrile; at 0 - 25℃; for 2.08333h; Step 3: A mixture of copper(II) bromide (5.5 g, 25 mmol) and tert-butyl nitrite (2.5 g, 25 mmol) in acetonitrile (100 mL) was taken into a 250 mL round bottom flask and cooled to 0 C. Asolution of 1-methyl-4-nitro-1H-pyrazol-3-amine (3.5 g, 25 mmol) in acetonitrile (20 mL) was added dropwise over a period of 5 mm. The reaction mixture was slowly warmed to room temperature and stirred for 2 h. The reaction mixture was diluted with ethyl acetate, washed with water and brine, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The residue was purified by flash chromatography eluting with ethyl acetate in petroleum ether (15-20%) to afford 3-bromo-1-methyl-4-nitro-1H-pyrazole as a solid. ?H NMR (DM50-cl6, 400 MHz): 8.94 (s, 1H), 3.89 (s, 3H).
With tert.-butylnitrite; copper(ll) bromide; In acetonitrile; at 0 - 20℃; for 2h; Stpe 4: Into a 250 mL round bottom flask containing a solution of copper(II) bromide (3.0 g, 14 mmol) and fert-butyl nitrite (1.7 mL, 14 mmol) in acetonitrile (150 mL) was added l-methyl-4- nitro-lH-pyrazol-3-amine (2 g, 14 mmol) in acetonitrile (20 mL) at 0 C and the reaction was stirred at room temperature for 2 h. The reaction mixture was concentrated under reduced pressure. The residue was dissolved in ethyl acetate (120 mL), washed with water and brine, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The residue was purified by column chromatography eluting with ethyl acetate in petroleum ether (20-30%) to afford 3-bromo-l-methyl-4-nitro-lH-pyrazole as a solid. NMR (CDC13, 300 MHz): delta 8.25 (s, 1H), 3.89 (s, 3H).
With tert.-butylnitrite; copper(ll) bromide; In acetonitrile; at 0 - 20℃; for 2h; Step 4: Into a 250 mL round bottom flask containing a solution of copper(II) bromide (3.0 g, 14 mmol) and tert-butyl nitrite (1.7 mL, 14 mmol) in acetonitrile (150 mL) was added 1-methyl-4- nitro-1H-pyrazol-3-amine (2 g, 14 mmol) in acetonitrile (20 mL) at 0 oC and the reaction was stirred at room temperature for 2 h. The reaction mixture was concentrated under reduced pressure. The residue was dissolved in ethyl acetate (120 mL), washed with water and brine, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The residue was purified by column chromatography eluting with ethyl acetate in petroleum ether (20-30%) to afford 3-bromo-1-methyl-4-nitro-1H-pyrazole as a solid. 1H NMR (CDCl3, 300 MHz): delta 8.25 (s, 1H), 3.89 (s, 3H).

  • 2
  • [ 20055-00-9 ]
  • [ 299930-70-4 ]
YieldReaction ConditionsOperation in experiment
With hydrogenchloride; sodium nitrite; In water; acetonitrile; at 0 - 25℃; for 16.0h; Step 1: Into a 250 mL round bottom flask containing a solution of 1-methyl-4-nitro-1H-pyrazol-3-amine (4.0 g, 28 mmol) in acetonitrile (100 mL) was added concentrated hydrochloric acid (8mL) dropwise at 0 C. To this reaction mixture was added sodium nitrite (8.0 g, 116 mmol) inportions and the reaction mixture was gradually brought to room temperature and stirred for 16h. The reaction mixture was cooled to 0 C, treated with water (30 mL) and extracted with ethyl acetate (2x50 mL). The combined organics were washed with saturated sodium bicarbonate solution, water and brine, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The residue was purified by column chromatography eluting with ethylacetate in petroleum ether (20-30%) to furnish 3-chloro-1-methyl-4-nitro-1H-pyrazole as a solid.‘H NMR (CDC13, 300 MHz): 5 8.25 (s, 1H), 3.98 (s, 3H).
With hydrogenchloride; sodium nitrite; In water; acetonitrile; at 0 - 25℃; for 16.0h; Step 1: Into a 250 mL round bottom flask containing a solution of 1-methyl-4-nitro-1H-pyrazol- 3-amine (4.0 g, 28 mmol) in acetonitrile (100 mL) was added concentrated hydrochloric acid (8 mL) dropwise at 0 C. To this reaction mixture was added sodium nitrite (8.0 g, 116 mmol) in portions and the reaction mixture was gradually brought to room temperature and stirred for 16h. The reaction mixture was cooled to 0 C, treated with water (30 mL) and extracted with ethyl acetate (2x50 mL). The combined organics were washed with saturated sodium bicarbonate solution, water and brine, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The residue was purified by column chromatography eluting with ethyl acetate in petroleum ether (20-30%) to furnish 3-chloro-1-methyl-4-nitro-1H-pyrazole as a solid.‘H NMR (CDC13, 300 MHz): 5 8.25 (s, 1H), 3.98 (s, 3H).
With hydrogenchloride; sodium nitrite; In water; acetonitrile; at 0 - 20℃; for 16.0h; Step 1: Into a 250 mL round bottom flask containing a solution of l-methyl-4-nitro-lH-pyrazol- 3-amine (4.0 g, 28 mmol) in acetonitrile (100 mL) was added concentrated hydrochloric acid (8 mL) dropwise at 0 C. To this reaction mixture was added sodium nitrite (8.0 g, 116 mmol) in portions and the reaction mixture was gradually brought to room temperature and stirred for 16 h. The reaction mixture was cooled to 0 C, treated with water (30 mL) and extracted with ethyl acetate (2x50 mL). The combined organics were washed with saturated sodium bicarbonate solution, water and brine, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The residue was purified by column chromatography eluting with ethyl acetate in petroleum ether (20-30%) to fumish 3-chloro-l-methyl-4-nitro-lH-pyrazole as a solid. 1H NMR (CDC13, 300 MHz): δ 8.25 (s, 1H), 3.98 (s, 3H).
With hydrogenchloride; sodium nitrite; In acetonitrile; at 0 - 20℃; for 16.0h; Step 1: Into a 250 mL round bottom flask containing a solution of 1-methyl-4-nitro-1H-pyrazol- 3-amine (4.0 g, 28 mmol) in acetonitrile (100 mL) was added concentrated hydrochloric acid (8 mL) dropwise at 0 oC. To this reaction mixture was added sodium nitrite (8.0 g, 116 mmol) in portions and the reaction mixture was gradually brought to room temperature and stirred for 16 h. The reaction mixture was cooled to 0 oC, treated with water (30 mL) and extracted with ethyl acetate (2x50 mL). The combined organics were washed with saturated sodium bicarbonate solution, water and brine, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The residue was purified by column chromatography eluting with ethyl acetate in petroleum ether (20-30%) to furnish 3-chloro-1-methyl-4-nitro-1H-pyrazole as a solid. 1H NMR (CDCl3, 300 MHz): δ 8.25 (s, 1H), 3.98 (s, 3H).

 

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