5334-41-8

Basic information

• Product Name: 1-Methyl-4-cyano-5-amino-1,2-pyrazole
• Synonyms: TIMTEC-BB SBB007110;AKOS B020561;5-AMINO-1-METHYL-1H-PYRAZOLE-4-CARBONITRILE;5-AMINO-4-CYANO-1-METHYLPYRAZOLE;ART-CHEM-BB B020561;BUTTPARK 52\04-84;5-Amino-4-cyano-1-methyl-1,2-pyrazole;1-Methyl-4-cyano-5-amino-1,2-pyrazole
• CAS NO: 5334-41-8
• Molecular Formula: C₅H₆N₄
• Molecular Weight: 122.13
• EINECS: 1806241-263-5
• Product Categories: Pyrazole series;Aromatic Nitriles;Nucleotides and Nucleosides;Heterocyclic;Nucleotide;Amines
• Mol File: 5334-41-8.mol
• Article Data: 18

Chemical Properties

• Melting Point: 221-223°C
• Boiling Point: 342.376 °C at 760 mmHg
• Flash Point: 160.864 °C
• Appearance: Off-White Crystalline Solid
• Density: 1.321 g/cm³
• Vapor Pressure: 1.36E-08mmHg at 25°C
• Refractive Index: 1.559
• Storage Temp.: -20?C Freezer
• Solubility: DMSO, Methanol
• PKA: 0.50±0.10(Predicted)
• CAS DataBase Reference: 1-Methyl-4-cyano-5-amino-1,2-pyrazole(CAS DataBase Reference)
• NIST Chemistry Reference: 1-Methyl-4-cyano-5-amino-1,2-pyrazole(5334-41-8)
• EPA Substance Registry System: 1-Methyl-4-cyano-5-amino-1,2-pyrazole(5334-41-8)

Safety Data

• Hazard Codes: Xi
• HazardClass: IRRITANT
• Hazardous Substances Data: 5334-41-8(Hazardous Substances Data)

Usage

Chemical Properties

Off-White Crystalline Solid

InChI:InChI=1/C12H16N2O2/c1-8(2)13-12(16)10-4-6-11(7-5-10)14-9(3)15/h4-8H,1-3H3,(H,13,16)(H,14,15)

Synthetic route

2-(methoxymethylene)malononitrile (672-81-1) + methylhydrazine (60-34-4) → 5-amino-4-cyano-1-methylpyrazole (5334-41-8)

Conditions	Yield
With sulfuric acid; sodium carbonate In ethanol Solvent; Reflux;	81.6%
In ethanol Reflux;

methylhydrazine (60-34-4) + Ethoxymethylenemalononitrile (123-06-8) → 5-amino-4-cyano-1-methylpyrazole (5334-41-8)

Conditions	Yield
In ethanol for 1h; Heating;	78%
In ethanol for 1h; Heating;	70%
In ethanol for 1h; Reflux;	50%

acetonitrile (75-05-8) + Ethoxymethylenemalononitrile (123-06-8) → 5-amino-4-cyano-1-methylpyrazole (5334-41-8)

Conditions	Yield
In ethanol for 2h; Reflux;	78%

methylhydrazine sulfuric acid (302-15-8) + Ethoxymethylenemalononitrile (123-06-8) → 5-amino-4-cyano-1-methylpyrazole (5334-41-8)

Conditions	Yield
With triethylamine In methanol Reflux;	77%
With triethylamine In methanol Reflux;	77%
With triethylamine In methanol Reflux;	77%

N-methyl hydrazine sulfate + Ethoxymethylenemalononitrile (123-06-8) → 5-amino-4-cyano-1-methylpyrazole (5334-41-8)

Conditions	Yield
With triethylamine In methanol Reflux;	77%

3-Amino-4-cyanopyrazole (16617-46-2) + methyl iodide (74-88-4) → 3-amino-1-methyl-1H-pyrazole-4-carbonitrile (21230-50-2) + 5-amino-4-cyano-1-methylpyrazole (5334-41-8)

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide at 100 - 120℃;	A 67.3% B n/a

methylhydrazine (60-34-4) + Ethoxymethylenemalononitrile (123-06-8) → 3-amino-1-methyl-1H-pyrazole-4-carbonitrile (21230-50-2) + 5-amino-4-cyano-1-methylpyrazole (5334-41-8)

Conditions	Yield
In ethanol at 0 - 70℃; for 17.5h; Inert atmosphere; regioselective reaction;	A 15 %Chromat. B 49%

N-amino-N-methyl-N'-(1-methyl-4-cyanopyrazol-5-yl)-formamidine (111267-92-6) → 5-amino-4-cyano-1-methylpyrazole (5334-41-8) + 3-(5-amino-1-methylpyrazol-4yl)-1methyl-1,2,4-triazole (111267-93-7)

Conditions	Yield
With trifluoroacetic acid In methanol; toluene for 72h; Heating;	A 48% B 43%
With trifluoroacetic acid In methanol; toluene Heating;	A 48% B 43%

orthoformic acid triethyl ester (122-51-0) + methylhydrazine (60-34-4) + malononitrile (109-77-3) → 5-amino-4-cyano-1-methylpyrazole (5334-41-8)

Conditions	Yield
In ethanol for 2h; Heating;	17%
In ethanol Heating;

4-cyano-5-<(methoxymethylene)amino>-1-methylpyrazole (111267-91-5) → 5-amino-4-cyano-1-methylpyrazole (5334-41-8)

Conditions	Yield
Multi-step reaction with 2 steps 1: 89 percent / acetonitrile / Ambient temperature 2: 48 percent / trifluoroacetic acid / toluene; methanol / 72 h / Heating View Scheme

cis,trans-2,5-dimethoxytetrahydrofuran (696-59-3) + 5-amino-4-cyano-1-methylpyrazole (5334-41-8) → 4-cyano-1-methyl-5-(1H-pyrrol-1-yl)-1H-pyrazole (146885-48-5)

Conditions	Yield
With acetic acid for 0.5h; Heating;	100%
In acetic acid for 0.5h; Heating;	95%

5-amino-4-cyano-1-methylpyrazole (5334-41-8) → 5-amino-1-methyl-1H-pyrazole-4-carboxylic acid amide (18213-75-7)

Conditions	Yield
Stage #1: 5-amino-4-cyano-1-methylpyrazole With sulfuric acid at 20℃; for 1h; Stage #2: With ammonia; water pH=8; Product distribution / selectivity; Cooling with ice;	91%
With sodium hydroxide; water; dihydrogen peroxide In methanol at 20℃; Product distribution / selectivity;	87%

5-amino-4-cyano-1-methylpyrazole (5334-41-8) + N,N-dimethyl acetamide (127-19-5) → 5-<1-(dimethylamino)ethylideneamino>-1-methylpyrazole-4-carbonitrile (144945-01-7)

Conditions	Yield
With trichlorophosphate In acetonitrile for 0.0833333h; Ambient temperature;	90%

5-amino-4-cyano-1-methylpyrazole (5334-41-8) → 5-Amino-1-methylpyrazole (1192-21-8)

Conditions	Yield
With phosphoric acid at 170 - 180℃; for 20h;	90%

5-amino-4-cyano-1-methylpyrazole (5334-41-8) + orthoformic acid triethyl ester (122-51-0) → 4-cyano-5-<(ethoxymethylene)amino>-1-methylpyrazole

Conditions	Yield
for 8h; Heating;	90%

5-amino-4-cyano-1-methylpyrazole (5334-41-8) + trimethyl orthoformate (149-73-5) → 4-cyano-5-<(methoxymethylene)amino>-1-methylpyrazole (111267-91-5)

Conditions	Yield
With trifluoroacetic acid for 1h; Heating;	86%
trifluoroacetic acid for 1h; Heating;	86%

5-amino-4-cyano-1-methylpyrazole (5334-41-8) → 1-methyl-5-amino-4-(tetrazol-5-yl)pyrazole

Conditions	Yield
Stage #1: 5-amino-4-cyano-1-methylpyrazole With sodium azide In toluene Reflux; Stage #2: With hydrogenchloride In methanol; toluene at 20℃; Solvent;	86%
With manganese(II) bromide; sodium azide In 2-methoxy-ethanol at 65℃; for 18h; Reagent/catalyst; Solvent; Temperature;	60%

5-amino-4-cyano-1-methylpyrazole (5334-41-8) + orthoformic acid triethyl ester (122-51-0) → N-(4-cyano-2-methyl-2H-pyrazol-3-yl)-formimidic acid ethyl ester (62564-58-3)

Conditions	Yield
for 6h; Reflux;	84%

5-amino-4-cyano-1-methylpyrazole (5334-41-8) → 5-chloro-1-methyl-1H-pyrazole-4-carbonitrile (111493-52-8)

Conditions	Yield
Stage #1: 5-amino-4-cyano-1-methylpyrazole With hydrogenchloride; sodium nitrite In water at 0 - 5℃; Stage #2: With urea; copper(l) chloride In water at 0 - 20℃;	84%
Stage #1: 5-amino-4-cyano-1-methylpyrazole With hydrogenchloride In water at 20℃; Stage #2: With sodium nitrite In water at 0 - 5℃; Stage #3: With urea; copper(l) chloride In water at 0 - 20℃;
Stage #1: 5-amino-4-cyano-1-methylpyrazole With hydrogenchloride; sodium nitrite In water at 0 - 5℃; Stage #2: With urea; copper(l) chloride In water at 0 - 20℃;

5-amino-4-cyano-1-methylpyrazole (5334-41-8) + N,N-dimethylacetamide dimethyl acetal (18871-66-4) → 5-<1-(dimethylamino)ethylideneamino>-1-methylpyrazole-4-carbonitrile (144945-01-7)

Conditions	Yield
In acetonitrile	77%

carbon disulfide (75-15-0) + 5-amino-4-cyano-1-methylpyrazole (5334-41-8) → 1-methylpyrazolo[3,4-d]pyrimidin-4,6(5H,7H)-dithione (30682-70-3)

Conditions	Yield
With pyridine for 10h; Heating;	75.9%

5-amino-4-cyano-1-methylpyrazole (5334-41-8) → 5-amino-1-methylpyrazole-4-carboxaldehyde

Conditions	Yield
With hydrogen; T-1 Raney Nickel In acetic acid under 760 Torr; for 72h; Ambient temperature;	73%

5-amino-4-cyano-1-methylpyrazole (5334-41-8) + methyl isocyanate (624-83-9) → 4-Amino-1,5-dimethyl-1,5-dihydro-pyrazolo[3,4-d]pyrimidin-6-one (135108-63-3)

Conditions	Yield
With sodium methylate In N,N-dimethyl-formamide at 60℃; for 12h;	72%

5-amino-4-cyano-1-methylpyrazole (5334-41-8) → 5-bromo-1-methyl-1H-pyrazole-4-carbonitrile

Conditions	Yield
With hydrogen bromide; copper(I) bromide; sodium nitrite In water at 0 - 20℃;	72%
With hydrogen bromide; copper(I) bromide; sodium nitrite In water at 0 - 20℃;	72%
With hydrogen bromide; copper(I) bromide; sodium nitrite In water at 0 - 20℃;	69%
Stage #1: 5-amino-4-cyano-1-methylpyrazole With hydrogen bromide In water at 0 - 5℃; Stage #2: With copper(I) bromide; sodium nitrite In water at 0 - 20℃;	69%

5-amino-4-cyano-1-methylpyrazole (5334-41-8) → 7-Methyl-4-oxo-3,4-dihydro-7H-pyrazolo<3,4-d>-1,2,3-triazin-N2-oxid (89403-96-3)

Conditions	Yield
With sulfuric acid; nitric acid at 0 - 5℃; for 2h;	70%

5-amino-4-cyano-1-methylpyrazole (5334-41-8) + 6-(3,5-dimethylpyrazol-1-yl)-1,2,4-triazolo<4,3-b><1,2,4,5>tetrazine (220696-97-9) → 5-([1,2,4]triazolo[4,3-b][1,2,4,5]tetrazin-6-ylamino)-1-methyl-1H-pyrazole-4-carbonitrile (1527497-93-3)

Conditions	Yield
With potassium carbonate In acetonitrile at 80℃; for 4h; Reflux; Inert atmosphere; chemoselective reaction;	69%

ammonium thiocyanate + 5-amino-4-cyano-1-methylpyrazole (5334-41-8) + 4-chloro-benzoyl chloride (122-01-0) → 4-Cyano-1-methyl-5-(p-chlorobenzoylthioureido)-pyrazole

Conditions	Yield
In water; acetone	65%

5-amino-4-cyano-1-methylpyrazole (5334-41-8) + carbon dioxide (124-38-9) → 1-Methyl-1H-pyrazolo<3,4-d>pyrimidine-4,6(5H,7H)-dione (5401-15-0)

Conditions	Yield
With 1,5-diazabicyclo[4.3.0]non-5-ene 2,2,2-trifluoroethanol at 90℃; for 72h;	65%
With 1,5-diazabicyclo[4.3.0]non-5-ene 2,2,2-trifluoroethanol at 90℃; under 760.051 Torr; for 72h; Green chemistry;	65%

5-amino-4-cyano-1-methylpyrazole (5334-41-8) + ethyl trifluoroacetate, (383-63-1) → 1-methyl-6-trifluoromethyl-1H-pyrazolo[3,4-d]pyrimidin-4-ol

Conditions	Yield
Stage #1: 5-amino-4-cyano-1-methylpyrazole With sodium hydride In ethanol at 10℃; for 0.5h; Stage #2: ethyl trifluoroacetate, In ethanol at 80℃; for 8h;	64%

5-amino-4-cyano-1-methylpyrazole (5334-41-8) + phenyl isothiocyanate (103-72-0) → 4-imino-1-methyl-5-phenyl-4,5,6,7-tetrahydro-1H-pyrazolo[3,4-d]pyrimidine-6-thione (501919-89-7)

Conditions	Yield
Stage #1: 5-amino-4-cyano-1-methylpyrazole; phenyl isothiocyanate With potassium hydroxide In N,N-dimethyl-formamide for 2.5h; Heating; Stage #2: With acetic acid In water; N,N-dimethyl-formamide	55%

5-amino-4-cyano-1-methylpyrazole (5334-41-8) + cyclopentanone (120-92-3) → 4-methyl-2,4,5-triazatricyclo[7.3.0.03,7]dodeca-1,3(7),5,8-tetraen-8-amine

Conditions	Yield
With aluminum (III) chloride In tetrahydrofuran; 1,2-dichloro-ethane at 85℃; for 2h;	52%

5-amino-4-cyano-1-methylpyrazole (5334-41-8) + methylmagnesium bromide (75-16-1) → 1-(5-amino-1-methyl-1H-pyrazol-4-yl)-ethanone

Conditions	Yield
With tetrahydrofuran at 0 - 70℃; for 2h;	52%

5-amino-4-cyano-1-methylpyrazole (5334-41-8) + 4,5-dichloro-1,2,3-dithiazolium chloride (75318-43-3) → (4-chloro-[1,2,3]dithiazol-5-ylidene)(1-methyl-4-cyanopyrazol-5-yl)amine

Conditions	Yield
With pyridine In dichloromethane at 20℃; for 7h;	50%

Upstream product

• 60-34-4 methylhydrazine 
• 123-06-8 Ethoxymethylenemalononitrile 
• 111267-92-6 N-amino-N-methyl-N'-(1-methyl-4-cyanopyrazol-5-yl)-formamidine 
• 122-51-0 orthoformic acid triethyl ester 
• 109-77-3 malononitrile 
• 111267-91-5 4-cyano-5-<(methoxymethylene)amino>-1-methylpyrazole 
• 672-81-1 2-(methoxymethylene)malononitrile 
• 16617-46-2 3-Amino-4-cyanopyrazole 
• 74-88-4 methyl iodide 
• 302-15-8 methylhydrazine sulfuric acid 
• 75-05-8 acetonitrile 

Downstream Products

• 139308-39-7 1-methyl-4-cyano-5-<(triphenylphosphoranylidene)amino>pyrazole 
• 89403-96-3 7-Methyl-4-oxo-3,4-dihydro-7H-pyrazolo<3,4-d>-1,2,3-triazin-N²-oxid 
• 1192-21-8 5-Amino-1-methylpyrazole 
• 111493-52-8 5-chloro-1-methyl-1H-pyrazole-4-carbonitrile 
• 66121-71-9 1-methyl-1H-pyrazole-4-carbonitrile 
• 62564-90-3 5-amino-1-methyl-1H-pyrazole-4-carbaldehyde 
• 30682-70-3 1-methylpyrazolo[3,4-d]pyrimidin-4,6(5H,7H)-dithione 
• 5334-54-3 1,5-dimethylallopurinol 
• 62564-58-3 N-(4-cyano-2-methyl-2H-pyrazol-3-yl)-formimidic acid ethyl ester 
• 4058-91-7 5-amino-1-methyl-1H-pyrazole-4-carboxylic acid 
• 18213-77-9 1-methyl-5-nitro-1H-pyrazole-4-carboxylic acid 
• 1428733-96-3 C₂₄H₂₆N₄O₄ 
• 1269293-80-2 5-bromo-1-methyl-1H-pyrazole-4-carbonitrile 
• 120162-55-2 azimsulfuron 

Relevant articles and documents

Preparation method and applications of azimsulfuron key intermediate

The present invention provides a preparation method of 1-methyl-4-(2-methyl-2H-tetrazole-5-yl)1H-pyrazole-5-sulfamide. The preparation method comprises that trimethyl orthoformate and malononitrile are adopted as starting raw materials, a three-step reaction is performed to obtain 1-methyl-5-amino-4-(tetrazole-5-yl)pyrazole, the 1-methyl-5-amino-4-(tetrazole-5-yl)pyrazole reacts with dimethylsulfate in the presence of an acid-binding agent to obtain 2-methyl-5-(1-methyl-5-amino-1H-pyrazole-4-yl)-2H-tetrazole, the 2-methyl-5-(1-methyl-5-amino-1H-pyrazole-4-yl)-2H-tetrazole is subjected to a sodium nitrite diazo-reaction under an acid condition, the obtained material reacts with a sodium sulfite-copper chloride-acetic acid mixture, and finally hydrolysis with ammonia is performed to obtain the target product. The present invention further provides a preparation method of azimsulfuron prepared from the 1-methyl-4-(2-methyl-2H-tetrazole-5-yl)1H-pyrazole-5-sulfamide. The preparation method of the present invention has characteristics of short reaction route, environmental protection raw materials, and high yield.

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