5334-40-7

Basic information

• Product Name: 4-Nitropyrazole-3-carboxylic acid
• Synonyms: 4-Nitro-3-pyrazolecarboxylic acid,95%;4-nitro-1H-pyrazole-5-carboxylic acid;4-nitro-1H-pyrazole-3-carboxylic acid(SALTDATA: FREE);NSC 1411;Pyrazole-3(or 5)-carboxylic acid, 4-nitro- (6CI);Pyrazole-3-carboxylic acid, 4-nitro- (8CI);4 - nitro pyrazole - 3 - forMic acid;4-Nitro-1H-pyrazole-3-carboxylicacid,98%
• CAS NO: 5334-40-7
• Molecular Formula: C₄H₃N₃O₄
• Molecular Weight: 157.08
• Product Categories: Building Blocks;C3 to C5;Chemical Synthesis;Heterocyclic Building Blocks;Building Blocks;Heterocyclic Building Blocks;Pyrazoles
• Mol File: 5334-40-7.mol
• Article Data: 2

Chemical Properties

• Melting Point: 195°C
• Boiling Point: 509.596 °C at 760 mmHg
• Flash Point: 261.995 °C
• Appearance: White to off-white crystalline powder
• Density: 1.84 g/cm³
• Vapor Pressure: 3.3E-11mmHg at 25°C
• Refractive Index: 1.679
• Storage Temp.: Keep in dark place,Sealed in dry,Room Temperature
• PKA: 1.41±0.35(Predicted)
• CAS DataBase Reference: 4-Nitropyrazole-3-carboxylic acid(CAS DataBase Reference)
• NIST Chemistry Reference: 4-Nitropyrazole-3-carboxylic acid(5334-40-7)
• EPA Substance Registry System: 4-Nitropyrazole-3-carboxylic acid(5334-40-7)

Safety Data

• Hazard Codes: Xi
• Statements: 20/21/22-36/37/38
• Safety Statements: 22-36/37/39-37/39-26
• WGK Germany: 3
• HazardClass: IRRITANT
• Hazardous Substances Data: 5334-40-7(Hazardous Substances Data)

Usage

Chemical Properties

White to off-white crystalline powder

Uses

Different sources of media describe the Uses of 5334-40-7 differently. You can refer to the following data:
1. 4-Nitro-1H-pyrazole-3-carboxylic Acid, is a building block used for the synthesis of biologically active compounds. It is an intermediate for the synthesis of pyrazole-benzimidazole derivatives as potent Aurora A/B kinase inhibitors.
2. 4-Nitro-3-pyrazolecarboxylic acid may be used as a starting reagent for the synthesis of library of pyrazole derivatives, potential A3 adenosine receptor (A3AR) antagonists.

General Description

4-Nitro-3-pyrazolecarboxylic acid is a pyrazole derivative. Catalytic activity of bimetallic colloids, composed of silver nanoparticles partially coated with Pd clusters, adsorbed on 4-nitro-3-pyrazolecarboxylic acid, has been investigated by Surface-enhanced Raman scattering (SERS) spectroscopy. Effects of this pyrrazole on blood flow and its palladium hydrogenation has been studied.

InChI:InChI=1/C4H3N3O4/c8-4(9)3-2(7(10)11)1-5-6-3/h1H,(H,5,6)(H,8,9)

Synthetic route

3-Methylpyrazole (1453-58-3) → 4-nitro-1H-pyrazole-3-carboxylic acid (5334-40-7)

Conditions	Yield
With sodium dichromate; sulfuric acid; nitric acid 1.) 100 deg C, 4 h, 2.) 60 deg C, 10 h; Yield given. Multistep reaction;

methanol (67-56-1) + 4-nitro-1H-pyrazole-3-carboxylic acid (5334-40-7) → methyl 4-nitro-1H-pyrazole-3-carboxylate (138786-86-4)

Conditions	Yield
Stage #1: methanol; 4-nitro-1H-pyrazole-3-carboxylic acid With acetyl chloride at 20℃; for 16h; Stage #2: With water; sodium hydrogencarbonate In methanol; ethyl acetate pH=8 - 9; Product distribution / selectivity;	100%
Stage #1: methanol; 4-nitro-1H-pyrazole-3-carboxylic acid With acetyl chloride Stage #2: With sodium hydrogencarbonate In methanol; water; ethyl acetate pH=8 - 9;	100%
With thionyl chloride at 0 - 20℃;	100%

methanol (67-56-1) + thionyl chloride (7719-09-7) + 4-nitro-1H-pyrazole-3-carboxylic acid (5334-40-7) → methyl 4-nitro-1H-pyrazole-3-carboxylate (138786-86-4)

Conditions	Yield
at 0 - 25℃; for 16 - 48h; Product distribution / selectivity;	99.5%

methanol (67-56-1) + 4-nitro-1H-pyrazole-3-carboxylic acid (5334-40-7) → 4-nitro-2H-pyrazole-3-carboxylic acid methyl ester (138786-86-4)

Conditions	Yield
With thionyl chloride at 0 - 20℃; for 16.5h;	99%
With thionyl chloride at 0 - 20℃;	82%
With thionyl chloride at 0 - 35℃;	82%

4-nitro-1H-pyrazole-3-carboxylic acid (5334-40-7) → methyl 4-nitro-1H-pyrazole-3-carboxylate (138786-86-4)

Conditions	Yield
With thionyl chloride In methanol at 70℃; for 5h;	99%
With thionyl chloride In methanol; toluene
With thionyl chloride In methanol
With thionyl chloride In methanol; toluene
In methanol; toluene

ethanol (64-17-5) + 4-nitro-1H-pyrazole-3-carboxylic acid (5334-40-7) → 4-nitro-1H-pyrazole-3-carboxylic acid ethyl ester (55864-87-4)

Conditions	Yield
With hydrogenchloride Reflux;	98%
With hydrogenchloride Reflux; Inert atmosphere;	98%
With thionyl chloride at 20℃; for 2h; Cooling with ice;	98%

4-fluoroaniline (371-40-4) + 4-nitro-1H-pyrazole-3-carboxylic acid (5334-40-7) → 4-nitro-1H-pyrazole-3-carboxylic acid (4-fluorophenyl)amide (844443-71-6)

Conditions	Yield
With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In N,N-dimethyl-formamide at 20℃; for 16h;	97%
With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In N,N-dimethyl-formamide at 20℃; for 2h;	82%
With benzotriazol-1-ol; N-(3-dimethylaminopropyl)-N-ethylcarbodiimide In N,N-dimethyl-formamide at 20℃;
With benzotriazol-1-ol; N-(3-dimethylaminopropyl)-N-ethylcarbodiimide In N,N-dimethyl-formamide at 20℃;
With benzotriazol-1-ol; N-(3-dimethylaminopropyl)-N-ethylcarbodiimide In DMF (N,N-dimethyl-formamide) at 20℃;

4-nitro-1H-pyrazole-3-carboxylic acid (5334-40-7) → 4-nitro-1H-pyrazole-3-carboxylic acid ethyl ester (55864-87-4)

Conditions	Yield
With thionyl chloride In ethanol at 20℃; for 48h;	96%
Stage #1: ethanol With acetyl chloride at 0 - 20℃; for 0.5h; Stage #2: 4-nitro-1H-pyrazole-3-carboxylic acid at 20℃; for 48h;

4-nitro-1H-pyrazole-3-carboxylic acid (5334-40-7) → 4-nitro-1H-pyrazole-3-carboxamide (65190-36-5)

Conditions	Yield
Stage #1: 4-nitro-1H-pyrazole-3-carboxylic acid With oxalyl dichloride In tetrahydrofuran at 25℃; for 0.5h; Stage #2: With ammonium hydroxide In tetrahydrofuran at 25℃; for 3h; Cooling with ice;	96%
Stage #1: 4-nitro-1H-pyrazole-3-carboxylic acid With thionyl chloride; N,N-dimethyl-formamide Stage #2: With ammonium hydroxide at 20℃;	57%

3,4-dihydro-2H-pyran (110-87-2) + 4-nitro-1H-pyrazole-3-carboxylic acid (5334-40-7) → 4-nitro-1-(tetrahydro-2H-pyran-2-yl)-1H-pyrazole-3-carboxylic acid (906087-80-7)

Conditions	Yield
With p-toluenesulfonic acid monohydrate In tetrahydrofuran at 20℃; for 16h;	95%
With toluene-4-sulfonic acid In tetrahydrofuran at 20℃;	95%
With toluene-4-sulfonic acid In tetrahydrofuran Inert atmosphere; Reflux;	93.2%

methanol (67-56-1) + 4-nitro-1H-pyrazole-3-carboxylic acid (5334-40-7) → methyl 4-nitro-1H-pyrazole-3-carboxylate hydrochloride (1166981-47-0)

Conditions	Yield
With acetyl chloride	90%
With acetyl chloride at 0 - 20℃; for 24h;
With thionyl chloride at 20℃; Cooling with ice;

4-[(4-methyl-1-piperazinyl)methyl]aniline (70261-82-4) + 4-nitro-1H-pyrazole-3-carboxylic acid (5334-40-7) → N-(4-((4-methylpiperazin-1-yl)methyl))phenyl-4-nitro-1H-pyrazole-3-carboxamide (1308400-19-2)

Conditions	Yield
With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In N,N-dimethyl-formamide at 20℃; for 24h;	88.2%
With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In N,N-dimethyl-formamide at 20℃; for 24h;
With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In N,N-dimethyl-formamide at 20℃; for 24h;	11.1 g

1,2-diamino-benzene (95-54-5) + 4-nitro-1H-pyrazole-3-carboxylic acid (5334-40-7) → 2-(4-nitro-1H-pyrazol-3-yl)-1H-benzoimidazole (825615-90-5)

Conditions	Yield
With 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphinane-2,4,6-trioxide; N-ethyl-N,N-diisopropylamine for 5h; Reflux; Inert atmosphere;	85%
With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In N,N-dimethyl-formamide at 20℃; for 27h; Reflux;	69%
Stage #1: 1,2-diamino-benzene; 4-nitro-1H-pyrazole-3-carboxylic acid With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In N,N-dimethyl-formamide at 20℃; Stage #2: With acetic acid Reflux;

1-(tert-butoxycarbonyl)-4-aminopiperidine (87120-72-7) + 4-nitro-1H-pyrazole-3-carboxylic acid (5334-40-7) → 4-[(4-nitro-1H-pyrazole-3-carbonyl)amino]piperidine-1-carboxylic acid tert-butyl ester (844443-80-7)

Conditions	Yield
With 1-hydroxy-7-aza-benzotriazole; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In N,N-dimethyl-formamide at 20℃; for 16h;	84%
With 1-hydroxy-7-aza-benzotriazole; N-(3-dimethylaminopropyl)-N-ethylcarbodiimide In N,N-dimethyl-formamide at 20℃;
With 1-hydroxy-7-aza-benzotriazole; N-(3-dimethylaminopropyl)-N-ethylcarbodiimide In N,N-dimethyl-formamide at 20℃;

1-adamanthanol (768-95-6) + 4-nitro-1H-pyrazole-3-carboxylic acid (5334-40-7) → 1-(1-adamantyl)-3-carboxy-4-nitropyrazole

Conditions	Yield
With phosphoric acid In acetic acid at 60℃; for 3h;	82%

1,3-diazido 2-propanol (57011-48-0) + 4-nitro-1H-pyrazole-3-carboxylic acid (5334-40-7) → 1,3-diazidopropan-2-yl 4-nitro-1H-pyrazole-3-carboxylate

Conditions	Yield
With dmap; dicyclohexyl-carbodiimide In dichloromethane at 20℃; Green chemistry;	78%

3-Methylpyrazole (1453-58-3) → 4-nitro-1H-pyrazole-3-carboxylic acid (5334-40-7)

Conditions	Yield
With sodium dichromate; sulfuric acid; nitric acid 1.) 100 deg C, 4 h, 2.) 60 deg C, 10 h; Yield given. Multistep reaction;

methanol (67-56-1) + 4-nitro-1H-pyrazole-3-carboxylic acid (5334-40-7) → methyl 4-nitro-1H-pyrazole-3-carboxylate (138786-86-4)

Conditions	Yield
Stage #1: methanol; 4-nitro-1H-pyrazole-3-carboxylic acid With acetyl chloride at 20℃; for 16h; Stage #2: With water; sodium hydrogencarbonate In methanol; ethyl acetate pH=8 - 9; Product distribution / selectivity;	100%
Stage #1: methanol; 4-nitro-1H-pyrazole-3-carboxylic acid With acetyl chloride Stage #2: With sodium hydrogencarbonate In methanol; water; ethyl acetate pH=8 - 9;	100%
With thionyl chloride at 0 - 20℃;	100%

methanol (67-56-1) + thionyl chloride (7719-09-7) + 4-nitro-1H-pyrazole-3-carboxylic acid (5334-40-7) → methyl 4-nitro-1H-pyrazole-3-carboxylate (138786-86-4)

Conditions	Yield
at 0 - 25℃; for 16 - 48h; Product distribution / selectivity;	99.5%

methanol (67-56-1) + 4-nitro-1H-pyrazole-3-carboxylic acid (5334-40-7) → 4-nitro-2H-pyrazole-3-carboxylic acid methyl ester (138786-86-4)

Conditions	Yield
With thionyl chloride at 0 - 20℃; for 16.5h;	99%
With thionyl chloride at 0 - 20℃;	82%
With thionyl chloride at 0 - 35℃;	82%

4-nitro-1H-pyrazole-3-carboxylic acid (5334-40-7) → methyl 4-nitro-1H-pyrazole-3-carboxylate (138786-86-4)

Conditions	Yield
With thionyl chloride In methanol at 70℃; for 5h;	99%
With thionyl chloride In methanol; toluene
With thionyl chloride In methanol
With thionyl chloride In methanol; toluene
In methanol; toluene

ethanol (64-17-5) + 4-nitro-1H-pyrazole-3-carboxylic acid (5334-40-7) → 4-nitro-1H-pyrazole-3-carboxylic acid ethyl ester (55864-87-4)

Conditions	Yield
With hydrogenchloride Reflux;	98%
With hydrogenchloride Reflux; Inert atmosphere;	98%
With thionyl chloride at 20℃; for 2h; Cooling with ice;	98%

4-fluoroaniline (371-40-4) + 4-nitro-1H-pyrazole-3-carboxylic acid (5334-40-7) → 4-nitro-1H-pyrazole-3-carboxylic acid (4-fluorophenyl)amide (844443-71-6)

Conditions	Yield
With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In N,N-dimethyl-formamide at 20℃; for 16h;	97%
With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In N,N-dimethyl-formamide at 20℃; for 2h;	82%
With benzotriazol-1-ol; N-(3-dimethylaminopropyl)-N-ethylcarbodiimide In N,N-dimethyl-formamide at 20℃;
With benzotriazol-1-ol; N-(3-dimethylaminopropyl)-N-ethylcarbodiimide In N,N-dimethyl-formamide at 20℃;
With benzotriazol-1-ol; N-(3-dimethylaminopropyl)-N-ethylcarbodiimide In DMF (N,N-dimethyl-formamide) at 20℃;

4-nitro-1H-pyrazole-3-carboxylic acid (5334-40-7) → 4-nitro-1H-pyrazole-3-carboxylic acid ethyl ester (55864-87-4)

Conditions	Yield
With thionyl chloride In ethanol at 20℃; for 48h;	96%
Stage #1: ethanol With acetyl chloride at 0 - 20℃; for 0.5h; Stage #2: 4-nitro-1H-pyrazole-3-carboxylic acid at 20℃; for 48h;

4-nitro-1H-pyrazole-3-carboxylic acid (5334-40-7) → 4-nitro-1H-pyrazole-3-carboxamide (65190-36-5)

Conditions	Yield
Stage #1: 4-nitro-1H-pyrazole-3-carboxylic acid With oxalyl dichloride In tetrahydrofuran at 25℃; for 0.5h; Stage #2: With ammonium hydroxide In tetrahydrofuran at 25℃; for 3h; Cooling with ice;	96%
Stage #1: 4-nitro-1H-pyrazole-3-carboxylic acid With thionyl chloride; N,N-dimethyl-formamide Stage #2: With ammonium hydroxide at 20℃;	57%

3,4-dihydro-2H-pyran (110-87-2) + 4-nitro-1H-pyrazole-3-carboxylic acid (5334-40-7) → 4-nitro-1-(tetrahydro-2H-pyran-2-yl)-1H-pyrazole-3-carboxylic acid (906087-80-7)

Conditions	Yield
With p-toluenesulfonic acid monohydrate In tetrahydrofuran at 20℃; for 16h;	95%
With toluene-4-sulfonic acid In tetrahydrofuran at 20℃;	95%
With toluene-4-sulfonic acid In tetrahydrofuran Inert atmosphere; Reflux;	93.2%

methanol (67-56-1) + 4-nitro-1H-pyrazole-3-carboxylic acid (5334-40-7) → methyl 4-nitro-1H-pyrazole-3-carboxylate hydrochloride (1166981-47-0)

Conditions	Yield
With acetyl chloride	90%
With acetyl chloride at 0 - 20℃; for 24h;
With thionyl chloride at 20℃; Cooling with ice;

4-[(4-methyl-1-piperazinyl)methyl]aniline (70261-82-4) + 4-nitro-1H-pyrazole-3-carboxylic acid (5334-40-7) → N-(4-((4-methylpiperazin-1-yl)methyl))phenyl-4-nitro-1H-pyrazole-3-carboxamide (1308400-19-2)

Conditions	Yield
With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In N,N-dimethyl-formamide at 20℃; for 24h;	88.2%
With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In N,N-dimethyl-formamide at 20℃; for 24h;
With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In N,N-dimethyl-formamide at 20℃; for 24h;	11.1 g

1,2-diamino-benzene (95-54-5) + 4-nitro-1H-pyrazole-3-carboxylic acid (5334-40-7) → 2-(4-nitro-1H-pyrazol-3-yl)-1H-benzoimidazole (825615-90-5)

Conditions	Yield
With 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphinane-2,4,6-trioxide; N-ethyl-N,N-diisopropylamine for 5h; Reflux; Inert atmosphere;	85%
With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In N,N-dimethyl-formamide at 20℃; for 27h; Reflux;	69%
Stage #1: 1,2-diamino-benzene; 4-nitro-1H-pyrazole-3-carboxylic acid With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In N,N-dimethyl-formamide at 20℃; Stage #2: With acetic acid Reflux;

1-(tert-butoxycarbonyl)-4-aminopiperidine (87120-72-7) + 4-nitro-1H-pyrazole-3-carboxylic acid (5334-40-7) → 4-[(4-nitro-1H-pyrazole-3-carbonyl)amino]piperidine-1-carboxylic acid tert-butyl ester (844443-80-7)

Conditions	Yield
With 1-hydroxy-7-aza-benzotriazole; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In N,N-dimethyl-formamide at 20℃; for 16h;	84%
With 1-hydroxy-7-aza-benzotriazole; N-(3-dimethylaminopropyl)-N-ethylcarbodiimide In N,N-dimethyl-formamide at 20℃;
With 1-hydroxy-7-aza-benzotriazole; N-(3-dimethylaminopropyl)-N-ethylcarbodiimide In N,N-dimethyl-formamide at 20℃;

1-adamanthanol (768-95-6) + 4-nitro-1H-pyrazole-3-carboxylic acid (5334-40-7) → 1-(1-adamantyl)-3-carboxy-4-nitropyrazole

Conditions	Yield
With phosphoric acid In acetic acid at 60℃; for 3h;	82%

1,3-diazido 2-propanol (57011-48-0) + 4-nitro-1H-pyrazole-3-carboxylic acid (5334-40-7) → 1,3-diazidopropan-2-yl 4-nitro-1H-pyrazole-3-carboxylate

Conditions	Yield
With dmap; dicyclohexyl-carbodiimide In dichloromethane at 20℃; Green chemistry;	78%

4-nitro-1H-pyrazole-3-carboxylic acid (5334-40-7) + 4-(4-tert-butoxycarbonyl-piperazino-methyl)-aniline (304897-49-2) → C20H26N6O5

Conditions	Yield
With N-ethyl-N,N-diisopropylamine; N-[(dimethylamino)-3-oxo-1H-1,2,3-triazolo[4,5-b]pyridin-1-yl-methylene]-N-methylmethanaminium hexafluorophosphate In N,N-dimethyl-formamide at 20℃; for 12h;	76%
With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In N,N-dimethyl-formamide at 20℃; for 24h;

methanol (67-56-1) + 4-nitro-1H-pyrazole-3-carboxylic acid (5334-40-7) + methyl iodide (74-88-4) → 1-methyl-4-nitro-1H-pyrazole-3-carboxylic acid methyl ester (400877-57-8)

Conditions	Yield
Stage #1: methanol; 4-nitro-1H-pyrazole-3-carboxylic acid With thionyl chloride at 0 - 20℃; Stage #2: methyl iodide With sodium hydride In N,N-dimethyl-formamide at 0 - 20℃;	75%

4-nitro-1H-pyrazole-3-carboxylic acid (5334-40-7) → 4-amino-1H-pyrazole-3-carboxylic acid (116008-52-7)

Conditions	Yield
With iron(III) chloride hexahydrate; pyrographite; hydrazine hydrate In water for 30h; Reflux;	75%

isopropylamine (75-31-0) + 4-nitro-1H-pyrazole-3-carboxylic acid (5334-40-7) → N-isopropyl-4-nitro-1H-pyrazole-3-carboxamide (906087-45-4)

Conditions	Yield
With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In N,N-dimethyl-formamide at 20℃; for 16h;	70%
With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In N,N-dimethyl-formamide at 20℃; for 16h;	70%

methyl 4-(aminomethyl)benzoate hydrochloride (6232-11-7) + 4-nitro-1H-pyrazole-3-carboxylic acid (5334-40-7) → methyl 4-((4-nitro-1H-pyrazole-3-carboxamido)methyl)benzoate

Conditions	Yield
With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; N-ethyl-N,N-diisopropylamine In N,N-dimethyl-formamide at 20℃; for 12h;	65%

C12H17N3O + 4-nitro-1H-pyrazole-3-carboxylic acid (5334-40-7) → C16H16N6O3

Conditions	Yield
With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In N,N-dimethyl-formamide at 20℃;	63%

4-nitro-1H-pyrazole-3-carboxylic acid (5334-40-7) + N,N-dimethylformamide di-tert-butyl acetal (36805-97-7) → tert-butyl 4-nitro-1H-pyrazole-3-carboxylate

Conditions	Yield
at 100℃; for 12h; Inert atmosphere;	63%

methoxycyclohexanamine hydrochloride (121588-79-2) + 4-nitro-1H-pyrazole-3-carboxylic acid (5334-40-7) → N-((1r,4r)-4-methoxycyclohexyl)-4-nitro-1H-pyrazole-3-carboxamide

Conditions	Yield
With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In N,N-dimethyl-formamide at 20℃; for 16h; Inert atmosphere;	62%

4-morpholin-4-ylmethylbenzene-1,2-diamine (825619-02-1) + 4-nitro-1H-pyrazole-3-carboxylic acid (5334-40-7) → 4-((2-(4-nitro-1H-pyrazol-3-yl)-1H-benzo[d]imidazole-5-yl)methyl)morpholine (825619-29-2)

Conditions	Yield
Stage #1: 4-morpholin-4-ylmethylbenzene-1,2-diamine; 4-nitro-1H-pyrazole-3-carboxylic acid With benzotriazol-1-ol; N-(3-dimethylaminopropyl)-N-ethylcarbodiimide In N,N-dimethyl-formamide at 20℃; for 24h; Stage #2: With acetic acid for 3h; Product distribution / selectivity; Heating / reflux;	61%
Stage #1: 4-morpholin-4-ylmethylbenzene-1,2-diamine; 4-nitro-1H-pyrazole-3-carboxylic acid With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In N,N-dimethyl-formamide at 20℃; for 24h; Stage #2: With acetic acid for 3h; Reflux;	61%
Stage #1: 4-morpholin-4-ylmethylbenzene-1,2-diamine; 4-nitro-1H-pyrazole-3-carboxylic acid With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In N,N-dimethyl-formamide at 20℃; for 24h; Stage #2: With acetic acid for 3h; Product distribution / selectivity; Heating / reflux;	61%

2-amino-benzenethiol (137-07-5) + 4-nitro-1H-pyrazole-3-carboxylic acid (5334-40-7) → 2-(4-nitro-1H-pyrazol-3-yl)-benzothiazole (1607441-38-2)

Conditions	Yield
Stage #1: 4-nitro-1H-pyrazole-3-carboxylic acid With oxalyl dichloride In tetrahydrofuran; N,N-dimethyl-formamide at 20℃; for 1h; Stage #2: 2-amino-benzenethiol In tetrahydrofuran; N,N-dimethyl-formamide at 100℃; for 1h;	61%
With 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphinane-2,4,6-trioxide; N-ethyl-N,N-diisopropylamine for 5h; Reflux; Inert atmosphere;

4-[(diethylamino)methyl]benzene-1,2-diamine (1254229-47-4) + 4-nitro-1H-pyrazole-3-carboxylic acid (5334-40-7) → N-ethyl-N-{[2-(4-nitro-1H-pyrazol-3-yl)-1H-benzo[d]imidazol-5-yl]methyl}ethanamine (1254229-50-9)

Conditions	Yield
Stage #1: 4-[(diethylamino)methyl]benzene-1,2-diamine; 4-nitro-1H-pyrazole-3-carboxylic acid With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In N,N-dimethyl-formamide at 20℃; for 24h; Stage #2: With acetic acid for 3h; Reflux;	57.8%

4-methyl-1,2-diaminobenzene (496-72-0) + 4-nitro-1H-pyrazole-3-carboxylic acid (5334-40-7) → 5-methyl-2-(4-nitro-1H-pyrazol-3-yl)-1H-benzo[d]imidazole (1254229-49-6)

Conditions	Yield
Stage #1: 4-methyl-1,2-diaminobenzene; 4-nitro-1H-pyrazole-3-carboxylic acid With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In N,N-dimethyl-formamide at 20℃; for 24h; Stage #2: With acetic acid for 3h; Reflux;	57.3%

methanol (67-56-1) + p-methoxybenzyl chloride (824-94-2) + 4-nitro-1H-pyrazole-3-carboxylic acid (5334-40-7) → methyl 1-(4-methoxybenzyl)-4-nitro-1H-pyrazole-3-carboxylate (896467-74-6)

Conditions	Yield
Stage #1: methanol; 4-nitro-1H-pyrazole-3-carboxylic acid With thionyl chloride Stage #2: p-methoxybenzyl chloride With potassium carbonate In acetonitrile	56%

4-(((4aR,7aR)-tetrahydro-2H-[1,4]dioxino[2,3-c]pyrrol-6(3H)-yl)methyl)benzene-1,2-diamine + 4-nitro-1H-pyrazole-3-carboxylic acid (5334-40-7) → (4aR,7aR)-6-((2-(4-nitro-1H-pyrazol-3-yl)-1H-benzo[d]imidazol-5-yl)methyl)hexahydro-2H-[1,4] dioxino[2,3-c]pyrrole

Conditions	Yield
With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride at 20℃;	54%
With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride at 20℃;

benzyl bromide (100-39-0) + 4-nitro-1H-pyrazole-3-carboxylic acid (5334-40-7) → benzyl 1-benzyl-4-nitro-1H-pyrazole-3-carboxylate (1355011-61-8)

Conditions	Yield
With caesium carbonate In N,N-dimethyl-formamide at 20℃; for 1.5h;	51%

Upstream product

• 5334-39-4 3-methyl-4-nitro-1H-pyrazole 
• 116008-52-7 4-amino-1H-pyrazole-5-carboxylic acid 
• 1453-58-3 3-Methylpyrazole 

Downstream Products

• 444010-34-8 1-(1-adamantyl)-3-carboxy-4-nitropyrazole 
• 844443-71-6 4-nitro-1H-pyrazole-3-carboxylic acid (4-fluorophenyl)amide 
• 844443-75-0 4-nitro-1H-pyrazole-3-carboxylic acid 4-hydroxy-cyclohexylamide 
• 896466-65-2 4-nitro-1H-pyrazole-3-carboxylic acid (2-amino-4,5-dimethoxy-phenyl)-amide 
• 825619-29-2 4-((2-(4-nitro-1H-pyrazol-3-yl)-1H-benzo[d]imidazole-5-yl)methyl)morpholine 
• 55864-87-4 4-nitro-1H-pyrazole-3-carboxylic acid ethyl ester 
• 902152-82-3 4-nitro-1H-pyrazole-3-carboxylic acid 4-hydroxy-cyclohexylamide 
• 309740-93-0 4-nitro-1H-pyrazole-3-carboxylic acid phenylamide 
• 518990-55-1 4-nitro-1H-pyrazole-5-carbonyl chloride 
• 138786-86-4 methyl 4-nitro-1H-pyrazole-3-carboxylate 
• 518990-55-1 4-nitro-1H-pyrazole-3-carboxylic acid 
• 309740-49-6 methyl 1-methyl-4-nitro-1H-pyrazole-5-carboxylate 
• 923283-86-7 methyl 1-isopropyl-4-nitro-1H-pyrazole-5-carboxylate 
• 400877-57-8 1-methyl-4-nitro-1H-pyrazole-3-carboxylic acid methyl ester 

Relevant articles and documents

A green and facile approach for synthesis of nitro heteroaromatics in water

A convenient and green method for the oxidation of nitrogen-rich heterocyclic amines to nitro-substituted heteroaromatics using potassium peroxymonosulfate (2KHSO5·KHSO4·K 2SO4, Oxone) in water was developed. This method has several advantages over previous methods: operational simplicity, safety, inexpensive reagents, the use of H2O as the sole solvent, and mild conditions. The utility of the present oxidative system was demonstrated by the synthesis of the important energetic compounds 3,4,5-trinitro-1H-pyrazole (TNP) and 5-amino-3-nitro-1H-1,2,4-triazole (ANTA).