3-Bromo-4-fluoroaniline

3-Bromo-4-fluoroaniline Property

Melting point:

34-36°C

Boiling point:

235°C

Density 

1.694±0.06 g/cm3(Predicted)

Flash point:

235°C

storage temp. 

Keep in dark place,Inert atmosphere,Room temperature

form 

powder to lump

pka

3.58±0.10(Predicted)

color 

White to Orange to Green

Water Solubility 

Insoluble in water.

Sensitive 

Air Sensitive

InChI

InChI=1S/C6H5BrFN/c7-5-3-4(9)1-2-6(5)8/h1-3H,9H2

InChIKey

KOWPUNQBGWIERF-UHFFFAOYSA-N

SMILES

C1(N)=CC=C(F)C(Br)=C1

CAS DataBase Reference

656-64-4(CAS DataBase Reference)

Safety

Hazard Codes 

T,Xi

Risk Statements 

36/37/38-36-36/38-20/21/22

Safety Statements 

26-36/37/39-36/37

RIDADR 

UN2811

Hazard Note 

Toxic

HazardClass 

6.1

PackingGroup 

III

HS Code 

29214200

Hazard and Precautionary Statements (GHS)

Symbol(GHS)

Signal word

Warning

Hazard statements

H302Harmful if swallowed

H312Harmful in contact with skin

H315Causes skin irritation

H319Causes serious eye irritation

H331Toxic if inhaled

Precautionary statements

P261Avoid breathing dust/fume/gas/mist/vapours/spray.

P264Wash hands thoroughly after handling.

P264Wash skin thouroughly after handling.

P270Do not eat, drink or smoke when using this product.

P271Use only outdoors or in a well-ventilated area.

P280Wear protective gloves/protective clothing/eye protection/face protection.

P304+P340IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing.

P305+P351+P338IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continuerinsing.

P405Store locked up.

P501Dispose of contents/container to..…

3-Bromo-4-fluoroaniline Chemical Properties,Usage,Production

Chemical Properties

light yellow crystal

Uses

3-Bromo-4-fluoroaniline is used in organic synthesis as an intermediate of agrochemicals and active pharmaceutical ingredient.

Synthesis

In a 2L four-necked round-bottomed flask equipped with a stirrer, an Erlenmeyer condenser, a 1L dropping funnel, and a thermometer, 466.9 g (2.07 mol) of tin chloride dihydrate and 760 mL of ethanol were added and the mixture was stirred to room temperature. After the tin chloride was completely dissolved, 102.7 g (0.466 mol) of THF solution of 3-bromo-4-fluoronitrobenzene (760 mL) was slowly added dropwise, followed by continuous stirring for 2 hours at 60 °C. Upon completion of the reaction, the reaction solution was cooled to room temperature and the solvent was removed by distillation under reduced pressure. To the residue, 440 g of ice was added and adjusted to alkaline with 1580 mL of aqueous 7% sodium hydroxide. The slurry formed was separated by filtration and the solid residue was washed with 600 mL of dichloromethane (DCM). The filtrates were combined, the organic layer was separated and the aqueous layer was extracted with 600mL DCM. All DCM layers were combined, washed with 600mL of water and subsequently dried with potassium carbonate. After drying, potassium carbonate was removed by filtration and solvent was removed by distillation under reduced pressure. Finally, the crude product was purified by silica gel column chromatography using toluene as the unfolding agent to give 54.7 g (61.7% yield) of 3-bromo-4-fluoroaniline.

References

[1] Journal of Organic Chemistry, 1981, vol. 46, # 11, p. 2280 - 2286
[2] Patent: JP2018/90561, 2018, A. Location in patent: Paragraph 0088
[3] Patent: US2004/122237, 2004, A1. Location in patent: Page 369-370
[4] Journal of Medicinal Chemistry, 2012, vol. 55, # 6, p. 2538 - 2548