18225-90-6

Basic information

• Product Name: 5-FLUORO-1H-BENZOTRIAZOLE
• Synonyms: 5-FLUORO-1H-BENZOTRIAZOLE;1H-Benzotriazole, 6-fluoro-;5-Fluoro-1H-1,2,3-benzotriazole;5-fluoro-1H-benzo[d][1,2,3]triazole;5-fluoro-2H-benzotriazole;5-Fluorobenzo(4,5)-1,2,3-triazole;6-Fluoro-1H-1,2,3-benzotriazole;Benzotriazole, 5-fluoro-
• CAS NO: 18225-90-6
• Molecular Formula: C₆H₄FN₃
• Molecular Weight: 137.11
• Mol File: 18225-90-6.mol
• Article Data: 7

Chemical Properties

• Boiling Point: 280.881 °C at 760 mmHg
• Flash Point: 123.672 °C
• Appearance: /
• Density: 1.482 g/cm³
• Vapor Pressure: 0.00368mmHg at 25°C
• Refractive Index: 1.673
• PKA: 7.78±0.40(Predicted)
• CAS DataBase Reference: 5-FLUORO-1H-BENZOTRIAZOLE(CAS DataBase Reference)
• NIST Chemistry Reference: 5-FLUORO-1H-BENZOTRIAZOLE(18225-90-6)
• EPA Substance Registry System: 5-FLUORO-1H-BENZOTRIAZOLE(18225-90-6)

Safety Data

• Hazard Codes: Xn
• Statements: 22
• HazardClass: IRRITANT
• Hazardous Substances Data: 18225-90-6(Hazardous Substances Data)

Usage

General Description

5-FLUORO-1H-BENZOTRIAZOLE is an organic compound with the chemical formula C6H4N3F. It is a benzotriazole derivative and is commonly used as a corrosion inhibitor in various industrial applications, particularly in the protection of metals such as copper, aluminum, and steel. It is also used as an additive in lubricants, greases, and hydraulic fluids to prevent rust and corrosion. Additionally, 5-FLUORO-1H-BENZOTRIAZOLE is employed in the synthesis of pharmaceuticals, agrochemicals, and other specialty chemicals. It is considered to be relatively safe for use, with low toxicity and minimal environmental impact.

InChI:InChI=1/C6H4FN3/c7-4-1-2-5-6(3-4)9-10-8-5/h1-3H,(H,8,9,10)

Synthetic route

4-fluoro-1,2-phenylenediamine (367-31-7) → 5-fluoro-1H-benzo[d][1,2,3]triazole (18225-90-6)

Conditions	Yield
With tert.-butylnitrite In acetonitrile at 27 - 29℃; for 0.25h;	95%
With acetic acid; sodium nitrite In water at 0 - 20℃;	85%
With acetic acid; sodium nitrite In water at 20℃; Cooling with ice;	85%
With acetic acid; sodium nitrite In water at 4 - 50℃;	60%

1-azido-2-bromo-4-fluorobenzene (85862-81-3) → 5-fluoro-1H-benzo[d][1,2,3]triazole (18225-90-6)

Conditions	Yield
With n-butyllithium In tetrahydrofuran; hexane at -85 - 20℃;	92%

4-fluoro-2-(trimethylsilyl)phenyl trifluoromethanesulfonate → 5-fluoro-1H-benzo[d][1,2,3]triazole (18225-90-6)

Conditions	Yield
With sodium azide; 18-crown-6 ether; cesium fluoride In acetonitrile at 70℃; for 12h; Inert atmosphere;	50%

4-fluoro-1,2-phenylenediamine (367-31-7) → 6-fluoro-1H-benzotriazole + 5-fluoro-1H-benzo[d][1,2,3]triazole (18225-90-6)

Conditions	Yield
With acetic acid; sodium nitrite In water at 4 - 70℃; stereoselective reaction;

4-fluoroaniline (371-40-4) → 5-fluoro-1H-benzo[d][1,2,3]triazole (18225-90-6)

Conditions	Yield
Multi-step reaction with 3 steps 1.1: N-Bromosuccinimide / dichloromethane / 0 - 5 °C / Schlenk technique; Inert atmosphere 2.1: sulfuric acid / water / Heating 2.2: 1 h / 0 - 5 °C 2.3: 4 h / 10 - 20 °C 3.1: n-butyllithium / tetrahydrofuran; hexane / -85 - 20 °C View Scheme

2-bromo-4-fluoroaniline (1003-98-1) → 5-fluoro-1H-benzo[d][1,2,3]triazole (18225-90-6)

Conditions	Yield
Multi-step reaction with 2 steps 1.1: sulfuric acid / water / Heating 1.2: 1 h / 0 - 5 °C 1.3: 4 h / 10 - 20 °C 2.1: n-butyllithium / tetrahydrofuran; hexane / -85 - 20 °C View Scheme

Methyl phenyldiazoacetate (22979-35-7) + 5-fluoro-1H-benzo[d][1,2,3]triazole (18225-90-6) → methyl 2-(5-fluoro-1H-benzo[d][1,2,3]triazol-1-yl)-2-phenylacetate

Conditions	Yield
With tert.-butylnitrite; p-benzoquinone In dichloromethane at 20℃; for 48h; Irradiation;	86%

4-tert-Butylstyrene (1746-23-2) + 5-fluoro-1H-benzo[d][1,2,3]triazole (18225-90-6) → 2-(1-(4-tert-butylphenyl)vinyl)-5-fluoro-2H-benzo[d][1,2,3]triazole + 1-(1-(4-tert-butylphenyl)vinyl)-5-fluorobenzo[d][1,2,3]triazole

Conditions	Yield
Stage #1: 4-tert-Butylstyrene; 5-fluoro-1H-benzo[d][1,2,3]triazole With N-iodo-succinimide In chloroform at 30℃; for 0.0833333h; Stage #2: With potassium carbonate In methanol for 12h; Reflux; Overall yield = 80 %; regioselective reaction;	A 75% B n/a

5-fluoro-1H-benzo[d][1,2,3]triazole (18225-90-6) + 1,3-chlorobromopropane (109-70-6) → 1-(3-chloropropyl)-5-fuloro-1H-benzo[d]-[1,2,3]triazole

Conditions	Yield
With potassium carbonate In MeCN at 20℃; for 72h;	65%

1-[2-(2,4-difluorophenyl)-2,3-epoxypropyl]-1H-1,2,4-triazole (86386-76-7, 123632-22-4, 141113-42-0, 150024-48-9) + 5-fluoro-1H-benzo[d][1,2,3]triazole (18225-90-6) → 2-(2,4-difluorophenyl)-1-(6-fluoro-1H-benzo[d][1,2,3]-triazol-1-yl)-3-(1H-1,2,4-triazol-1-yl)propan-2-ol (1228885-19-5) + 2-(2,4-difluorophenyl)-1-(5-fluoro-1H-benzo[d][1,2,3]-triazol-1-yl)-3-(1H-1,2,4-triazol-1-yl)propan-2-ol (1228885-18-4)

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide at 40 - 80℃;	A 14.9% B 35.7%

C23H37BrO3 + 5-fluoro-1H-benzo[d][1,2,3]triazole (18225-90-6) → C29H40FN3O3 + C29H40FN3O3 + C29H40FN3O3

Conditions	Yield
With potassium carbonate In tetrahydrofuran at 20℃; for 16h; Inert atmosphere;	A 33% B 22% C 18%

5-fluoro-1H-benzo[d][1,2,3]triazole (18225-90-6) → 5-fluoro-4,6,7-tribromo-1H-benzotriazole (1240784-77-3)

Conditions	Yield
With bromine; nitric acid In water at 130℃; for 15h;	22%

5-fluoro-1H-benzo[d][1,2,3]triazole (18225-90-6) + (2R)-3-bromo-N-[4-cyano-3-(trifluoromethyl)phenyl]-2-hydroxy-2-methylpropanamide (206193-17-1) → (S)-N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-2-methyl-3-(5-fluoro-1H-benzo[d][1,2,3]triazol-1-yl)propanamide

Conditions	Yield
Stage #1: 5-fluoro-1H-benzo[d][1,2,3]triazole With sodium hydride In tetrahydrofuran; mineral oil for 3h; Inert atmosphere; Cooling with ice; Stage #2: (2R)-3-bromo-N-[4-cyano-3-(trifluoromethyl)phenyl]-2-hydroxy-2-methylpropanamide In tetrahydrofuran; mineral oil at 20℃; Inert atmosphere;	12.6%

5-fluoro-1H-benzo[d][1,2,3]triazole (18225-90-6) → 3-(5-fluoro-1H-benzo[d][1,2,3]triazol-1-yl)-N,N,N-trimethylpropan-1-aminium iodide

Conditions	Yield
Multi-step reaction with 2 steps 1.1: potassium carbonate / MeCN / 72 h / 20 °C 2.1: potassium iodide / acetone / 2 h 2.2: 72 h / 60 °C View Scheme

1-methylindole (603-76-9) + 5-fluoro-1H-benzo[d][1,2,3]triazole (18225-90-6) → 5-fluoro-1-(3-iodo-1-methyl-1H-indol-2-yl)-1H-benzo[d][1,2,3]triazole + C15H10FIN4 + C15H10FIN4

Conditions	Yield
With ammonium iodide In dimethyl sulfoxide; acetonitrile at 20℃; Electrochemical reaction; Green chemistry; Overall yield = 35 percent; Overall yield = 27.3 mg;

Upstream product

• 367-31-7 4-fluoro-1,2-phenylenediamine 
• 1003-98-1 2-bromo-4-fluoroaniline 
• 371-40-4 4-fluoroaniline 
• 85862-81-3 1-azido-2-bromo-4-fluorobenzene 

Downstream Products

• 1228885-19-5 2-(2,4-difluorophenyl)-1-(6-fluoro-1H-benzo[d][1,2,3]-triazol-1-yl)-3-(1H-1,2,4-triazol-1-yl)propan-2-ol 
• 1228885-18-4 2-(2,4-difluorophenyl)-1-(5-fluoro-1H-benzo[d][1,2,3]-triazol-1-yl)-3-(1H-1,2,4-triazol-1-yl)propan-2-ol 

Relevant articles and documents

Blending Ionic and Coordinate Bonds in Hybrid Semiconductor Materials: A General Approach toward Robust and Solution-Processable Covalent/Coordinate Network Structures

Inorganic semiconductor materials are best known for their superior physical properties, as well as their structural rigidity and stability. However, the poor solubility and solution-processability of these covalently bonded network structures has long be

Making endo-cyclizations favorable again: A conceptually new synthetic approach to benzotriazoles via azide group directed lithiation/cyclization of 2-azidoaryl bromides

Although benzotriazoles are important and ubiquitous, currently there is only one conceptual approach to their synthesis: bridging the two ortho-amino groups with an electrophilic nitrogen atom. Herein, we disclose a new practical alternative-the endo-cyclization of 2-azidoaryl lithiums obtained in situ from 2-azido-aryl bromides. The scope of the reaction is illustrated using twenty-four examples with a variety of alkyl, alkoxy, perfluoroalkyl, and halogen substituents. We found that the directing effect of the azide group allows selective metal-halogen exchange in aryl azides containing several bromine atoms. Furthermore, (2-bromophenyl)diazomethane undergoes similar cyclization to give an indazole. Thus, cyclizations of aryl lithiums containing an ortho-X = Y = Z group emerge as a new general approach for the synthesis of aromatic heterocycles. DFT computations suggested that the observed endo-selectivity applies to the anionic cyclizations of other functionalities that undergo "1,1-additions" (i.e., azides, diazo compounds, and isonitriles). In contrast, cyclizations with the heteroatomic functionalities that follow the "1,2-addition" pattern (cyanates, thiocyanates, isocyanates, isothiocyanates, and nitriles) prefer the exo-cyclization path. Hence, such reactions expand the current understanding of stereoelectronic factors in anionic cyclizations.

Rhodium-catalyzed intermolecular hydroarylation of internal alkynes with N-1-phenylbenzotriazoles

A rhodium-catalyzed intermolecular hydroarylation of internal alkynes with N-1-phenylbenzotriazoles via C-H bond activation is described. This transformation offers an alternative method for the hydroarylation of internal alkynes with high stereoselectivity. The reaction mechanism was discussed according to the deuterium-labeling experiments.