3-Amino-4-pyrazolecarbonitrile
- Iupac Name：5-amino-1H-pyrazole-4-carbonitrile
- CAS No.: 16617-46-2
- Molecular Weight：108.10100
- Modify Date.: 2022-11-25 01:16
- Introduction: 3-Amino-4-pyrazolecarbonitrile has been a useful synthetic intermediate. 3-Amino-4-pyrazolecarbonitrile Preparation Products And Raw materials Preparation Products
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1. Names and Identifiers
- 1.1 Name
- 3-Amino-4-pyrazolecarbonitrile
- 1.2 Synonyms
1H-Pyrazole-4-carbonitrile, 3-amino- 3-Amino-1H-pyrazole-4-carbonitrile 3-Amino-4-Ccyanopyrazole 3-amino-4-cyano-1H-pyrazole 3-Amino-4-cyanopyrazole 3-Amino-4-Cyanopyrozale 3-Amino-4-cyanopyrozole (intermediate of zaleplon) 3-Amino-4-cyanopyrrole 3-AMINO-4-PYRAZOLOCARBONITRILE 3-Aminopyrazole-4-Carbonitrile 3-aminopyrazolo-4-carbonitrile 4-cyano-5-aminopyrazole 5-amino-1H-pyrazole-4-carbonitrile 5-AMINO-4-CYANOPYRAZOLE 5-amino-4-pyrazolecarbonitrile 5-aminopyrazole-4-carbonitrile Allopurinol Impurity 7 Allopurinol Nitrile IMpurity Amino-1H-Pyrazole-4-Carbonitrile EINECS 240-665-6 MFCD00005237 pyrazolecarbonitrile Zaleplon intermediate
- 1.3 CAS No.
- 16617-46-2
- 1.4 CID
- 85515
- 1.5 EINECS(EC#)
- 240-665-6
- 1.6 Molecular Formula
- C4H4N4 (isomer)
- 1.7 Inchi
- InChI=1S/C4H4N4/c5-1-3-2-7-8-4(3)6/h2H,(H3,6,7,8)
- 1.8 InChkey
- FFNKBQRKZRMYCL-UHFFFAOYSA-N
- 1.9 Canonical Smiles
- C1=NNC(=C1C#N)N
- 1.10 Isomers Smiles
- C1=NNC(=C1C#N)N
2. Properties
- 2.1 Density
- 1.42g/cm3
- 2.1 Melting point
- 172-174°C(lit.)
- 2.1 Boiling point
- 476.37ºC at 760 mmHg
- 2.1 Refractive index
- 1.621
- 2.1 Flash Point
- 476.37 °C at 760 mmHg
- 2.1 Precise Quality
- 108.04400
- 2.1 PSA
- 78.49000
- 2.1 logP
- 0.44478
- 2.1 Appearance
- Crystalline Solid
- 2.2 Storage
- Ambient temperatures.
- 2.3 Chemical Properties
- Tan Crystalline Solid
- 2.4 Color/Form
- Light yellow to brown-orange
- 2.5 pKa
- 11.58±0.50(Predicted)
- 2.6 Stability
- Stable at room temperature in closed containers under normal storage and handling conditions.
- 2.7 StorageTemp
- Store in a tightly closed container. Store in a cool, dry, well-ventilated area away from incompatible substances.
3. Use and Manufacturing
- 3.1 Methods of Manufacturing
- Hydrazine (5 g, 0.156 mol) was carefully added into 2-(ethoxymethylene)malononitrile (8.64 g, 0.070 mol) in ethanol and heated on the steam-bath for 30 min. After completion of the reaction, white precipitate was gradually appeared that kept in a refrigerator overnight. The product was then filtered and washed with a small amount of cold ethanol to afford the desired product 5-amino-1H-pyrazole-4-carbonitrile (1) as white solid; (3.05 g, 86percent); mp 168-170 °C (Lit. mp 169-170 °C) [33].Ethoxy methylene malonic eye 15.0g (0.12 μM) is slowly added at room temperature to 85percent hydrazine hydrate 12 ml (0.25 μM) in, the water bath heating reflux reaction 1h, in the reaction system by adding 10 ml of water. Placed in the refrigerator overnight, filtered, washing the filter cake, washing the yellow solid 10.6g, yield 81.7percent. The resulting spectrogram consistent with literature reports.Ν2Η42Ο (33 g, 640 mmol) was added to a solution of 2- (ethoxymethylene)malononitrile (20 g, 163.77 mmol) in acetic acid (200 mL) and the reaction was stirred overnight at 85°C. The resulting mixture was concentrated in vacuo and the residue was diluted with HTo 2-(ethoxymethylene)propanedinitrile (20 g, 163.80 mmol) was added hydrazine hydrate (15.9 mL, 327.60 mmol) dropwise at 0 °C and the resultant reaction mixture was heated at 100 °C in a closed reagent bottle for 1 h. The reaction was monitored by TLC. After completion of reaction, the mixture was cooled to RT and water (50 mL) was added to the reaction mixture. The product was extracted using EtOAc (3x200 mL). The combined organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure to obtain 15 g of 5-amino-1H-pyrazole-4-carbonitrile as a light brown solid.To 2-(ethoxymethylene)propanedinitrile (20 g, 163.80 mmol) was added hydrazine hydrate (15.9 mL, 327.60 mmol) dropwise at 0 °C and the resultant reaction mixture was heated at 100 °C in a closed reagent bottle for 1h. The reaction was monitored by TLC. After completion, the reaction mixture was cooled to RT and water (50 mL) was added. The product was extracted using EtOAc (3x200 mL). The combined organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure to obtain 15 g of 5- amino-1H-pyrazole-4-carbonitrile as a light brown solid.Add malononitrile (16.5 g, 0.25 mol), triethyl orthoformate (38 g, 0.29 mol) and acetic anhydride (55 g, 0.54 mol) to a 1 L three-necked flask, slowly heat to 115 °C, reflux reaction for 2 h .The temperature of the mixture was lowered to 20 °C, hydrazine hydrate (15.5 g, 0.31 mol) was added dropwiseover 40minutes, and the temperature was maintained at 18-22 °C.The reaction was then carried out at 20-30 ° C for 18 h.Thereaction wasmonitoredbyTLC, neutralized with a sodium hydroxide aqueous solution (36 g of sodium hydroxide in 72 ml of water) at 25 °C to obtain a prize mixture, and the mixture washeated and azeotropically distilled to collect 45 ml fractions.This fraction was cooled at 0 to 5 ° C for 1.5 h, and a pale brown solid was collected, rinsedwithcold water and dried to give product (19.2 g, 72percent yield).
- 3.2 Usage
- 3-Amino-4-pyrazolecarbonitrile has been a useful synthetic intermediate. 3-Amino-4-pyrazolecarbonitrile Preparation Products And Raw materials Preparation Products
4. Safety and Handling
- 4.1 Hazard Codes
- Xn
- 4.1 Risk Statements
- R20/21
- 4.1 Safety Statements
- S22-S24/25-S23
- 4.1 Packing Group
- III
- 4.1 Hazard Class
- 6.1
- 4.1 Hazard Declaration
- H301+H311+H331
- 4.1 RIDADR
- 3439
- 4.1 Caution Statement
- P261, P264, P270, P271, P280, P301+P310, P301+P312, P302+P352, P304+P312, P304+P340, P305+P351+P338, P311, P312, P321, P322, P330, P332+P313, P337+P313, P361, P362, P363, P403+P233, P405, P501
- 4.1 WGK Germany
- 3
- 4.1 Safety
-
Hazard Codes:?
Xn,
T
Risk Statements: 20/21/22-20/21-36/37/38
R20/21/22:Harmful by inhalation, in contact with skin and if swallowed.?
R20/21:Harmful by inhalation and in contact with skin.?
R36/37/38:Irritating to eyes, respiratory system and skin.
Safety Statements: 22-24/25-23-36-26
S22:Do not breathe dust.?
S24/25:Avoid contact with skin and eyes.?
S23:Do not breathe vapour.?
S36:Wear suitable protective clothing.?
S26: In case of contact with eyes, rinse immediately with plenty of water and seek medical advice.
RIDADR: 3439
WGK Germany: 3
F: 10
HazardClass: 6.1
PackingGroup: III
HS Code: 29331990
- 4.2 Specification
-
? 3-Amino-4-pyrazolecarbonitrile , with CAS number of 16617-46-2, can be called 1H-pyrazole-4-carbonitrile, 3-amino- ; 5-Amino-1H-pyrazole-4-carbonitrile ; 3-Amino-1H-pyrazole-4-carbonitrile . It is a?crystalline solid and be?a useful synthetic intermediate.
5. MSDS
2.Hazard identification
2.1 Classification of the substance or mixture
Not classified.
2.2 GHS label elements, including precautionary statements
| Pictogram(s) |  |
| Signal word | Warning |
| Hazard statement(s) | H302 Harmful if swallowed H315 Causes skin irritation H319 Causes serious eye irritation H335 May cause respiratory irritation |
| Precautionary statement(s) | |
| Prevention | none |
| Response | none |
| Storage | none |
| Disposal | none |
2.3 Other hazards which do not result in classification
none
7. Synthesis Route
16617-46-2Total: 6 Synthesis Route
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|
|
 |
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Literatures:
Xu, Jingli; Liu, Hang; Li, Guixia; He, Yong; Ding, Rui; Wang, Xiao; Feng, Man; Zhang, Shuting; Chen, Yurong; Li, Shilei; Zhao, Mingxia; Qi, Chuanmin; Dang, Yonghong
Bioorganic and Medicinal Chemistry Letters, 2011 , vol. 21, # 16 p. 4736 - 4741
Yield: ~78%
|
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9. Other Information
- 9.0 Storage Conditions
- Hydrazine (5 g, 0.156 mol) was carefully added into 2-(ethoxymethylene)malononitrile (8.64 g, 0.070 mol) in ethanol and heated on the steam-bath for 30 min. After completion of the reaction, white precipitate was gradually appeared that kept in a refrigerator overnight. The product was then filtered and washed with a small amount of cold ethanol to afford the desired product 5-amino-1H-pyrazole-4-carbonitrile (1) as white solid; (3.05 g, 86percent); mp 168-170 °C (Lit. mp 169-170 °C) [33].Ethoxy methylene malonic eye 15.0g (0.12 μM) is slowly added at room temperature to 85percent hydrazine hydrate 12 ml (0.25 μM) in, the water bath heating reflux reaction 1h, in the reaction system by adding 10 ml of water. Placed in the refrigerator overnight, filtered, washing the filter cake, washing the yellow solid 10.6g, yield 81.7percent. The resulting spectrogram consistent with literature reports.Ν2Η42Ο (33 g, 640 mmol) was added to a solution of 2- (ethoxymethylene)malononitrile (20 g, 163.77 mmol) in acetic acid (200 mL) and the reaction was stirred overnight at 85°C. The resulting mixture was concentrated in vacuo and the residue was diluted with HTo 2-(ethoxymethylene)propanedinitrile (20 g, 163.80 mmol) was added hydrazine hydrate (15.9 mL, 327.60 mmol) dropwise at 0 °C and the resultant reaction mixture was heated at 100 °C in a closed reagent bottle for 1 h. The reaction was monitored by TLC. After completion of reaction, the mixture was cooled to RT and water (50 mL) was added to the reaction mixture. The product was extracted using EtOAc (3x200 mL). The combined organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure to obtain 15 g of 5-amino-1H-pyrazole-4-carbonitrile as a light brown solid.To 2-(ethoxymethylene)propanedinitrile (20 g, 163.80 mmol) was added hydrazine hydrate (15.9 mL, 327.60 mmol) dropwise at 0 °C and the resultant reaction mixture was heated at 100 °C in a closed reagent bottle for 1h. The reaction was monitored by TLC. After completion, the reaction mixture was cooled to RT and water (50 mL) was added. The product was extracted using EtOAc (3x200 mL). The combined organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure to obtain 15 g of 5- amino-1H-pyrazole-4-carbonitrile as a light brown solid.Add malononitrile (16.5 g, 0.25 mol), triethyl orthoformate (38 g, 0.29 mol) and acetic anhydride (55 g, 0.54 mol) to a 1 L three-necked flask, slowly heat to 115 °C, reflux reaction for 2 h .The temperature of the mixture was lowered to 20 °C, hydrazine hydrate (15.5 g, 0.31 mol) was added dropwiseover 40minutes, and the temperature was maintained at 18-22 °C.The reaction was then carried out at 20-30 ° C for 18 h.Thereaction wasmonitoredbyTLC, neutralized with a sodium hydroxide aqueous solution (36 g of sodium hydroxide in 72 ml of water) at 25 °C to obtain a prize mixture, and the mixture washeated and azeotropically distilled to collect 45 ml fractions.This fraction was cooled at 0 to 5 ° C for 1.5 h, and a pale brown solid was collected, rinsedwithcold water and dried to give product (19.2 g, 72percent yield).
- 9.1 Mesh Entry Terms
- 5-amino-4-cyanopyrazole
- 9.2 Manufacturing Info
- 1H-Pyrazole-4-carbonitrile, 3-amino-: INACTIVE
- 9.3 BRN
- 2647
- 9.4 Chemical Properties
- Tan Crystalline Solid
- 9.5 Uses
- A useful synthetic intermediate
10. Computational chemical data
- Molecular Weight: 108.10100g/mol
- Molecular Formula: C4H4N4
- Compound Is Canonicalized: True
- XLogP3-AA: 0.1
- Exact Mass: 108.043596145
- Monoisotopic Mass: 108.043596145
- Complexity: 123
- Rotatable Bond Count: 0
- Hydrogen Bond Donor Count: 2
- Hydrogen Bond Acceptor Count: 3
- Topological Polar Surface Area: 78.5
- Heavy Atom Count: 8
- Defined Atom Stereocenter Count: 0
- Undefined Atom Stereocenter Count: 0
- Defined Bond Stereocenter Count: 0
- Undefined Bond Stereocenter Count: 0
- Isotope Atom Count: 0
- Covalently-Bonded Unit Count: 1
- CACTVS Substructure Key Fingerprint: AAADcYBjgAAAAAAAAAAAAAAAAAAAAWAAAAAAAAAAAAAAAAABgAAAHAAYAAAADADBGgQtsJBjAACyBhJnYACwBAKAgAAUMSAgRBAAgIAAQEAAhAAQCAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAA==
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