4-Bromo-2-nitrobenzoic acid Chemical Properties

Melting point:

165-169 °C

Boiling point:

368.6±32.0 °C(Predicted)

Density 

1.892±0.06 g/cm3(Predicted)

storage temp. 

Sealed in dry,Room Temperature

solubility 

soluble in Methanol

form 

powder to crystal

pka

1.97±0.25(Predicted)

color 

White to Gray to Brown

CAS DataBase Reference

99277-71-1(CAS DataBase Reference)

Safety Information

Hazard Codes 

Xn,N,Xi

Risk Statements 

22-36/37/38-43-50

Safety Statements 

26-36/37-61

RIDADR 

UN 3077 9/PG 3

WGK Germany 

2

HazardClass 

IRRITANT

PackingGroup 

III

HS Code 

29163990

MSDS

• Language:English Provider:SigmaAldrich

4-Bromo-2-nitrobenzoic acid Usage And Synthesis

Chemical Properties

Solid

Uses

Undergoes Negishi-type coupling with dimethylzinc in the presence of palladium-phosphine catalysis.

Uses

4-Bromo-2-nitrobenzoic acid is an intermediate in the synthesis of Lonafarnib (L469445), a potential anticancer agent.

Synthesis

Step 1: Synthesis of 4-bromo-2-nitrobenzoic acid The reference method was modified as follows (Boojamra, C.G.; Burow, K.M.; Thompson, L.A.; Ellman, J.A. J. Org. Chem., 1997, 62, 1240-1256): 1. An aqueous solution (65 mL) of NaNO2 (1.9 g, 27.4 mmol) was slowly added to a stirring solution of 4-amino-2-nitrobenzoic acid (1) (5 g, 27.4 mmol) dissolved in 48% aqueous HBr (40 mL) at 0 °C. After about 15 minutes, the turbid reaction mixture transformed into a clarified orange-yellow solution. 2. After continued stirring for 25 minutes, the solution was added dropwise to a solution of CuBr (5.2 g, 36.3 mmol) dissolved in 48% aqueous HBr (90 mL) at 0°C. Yellow foam generation and gas release from the purple-brown mixture were observed during the reaction. 3. After stirring at 0 °C for 1 h, the reaction mixture was concentrated under reduced pressure. 4. The aqueous layer was extracted with EtOAc (4 x 300 mL), the organic phases were combined, dried over Na2SO4 and concentrated to dryness to give a dark solid crude product. 5. The crude product was filtered through a column of Florisilica clay (~20 g) and washed with EtOAc. 6. The combined organic fractions were evaporated to about 50 mL, 200 mL of water was added, washed sequentially with 1 M HCl (2 x 50 mL), brine (50 mL), then dried with Na2SO4, filtered and concentrated to dryness to give 6.1 g of light yellow solid product (2) in 91% yield and >90% HPLC purity.

References

[1] Patent: US2005/256157, 2005, A1
[2] Patent: US2005/261307, 2005, A1

4-Bromo-2-nitrobenzoic acid(99277-71-1)Related Product Information

• 4-Nitrobenzoic acid
• Sodium 3-nitrobenzoate
• 4-Bromo-2-methylbenzoic acid
• 4-Nitrophenyl chloroformate
• 4-Bromo-2-nitrophenol
• 2-Nitrobenzoic acid
• Methyl 2-bromobenzoate
• 3-Bromoanisole
• 4-Bromobenzoic acid
• 3-Bromonitrobenzene
• tert-Butyl 4-bromo-2-nitrobenzoate
• 2-amino-5-bromo-3-nitrobenzoic acid
• 3-BROMO-5-NITROBENZOIC ACID
• 2-BROMO-3-NITROBENZOIC ACID, TECH., 90%,2-Bromo-3-nitrobenzoic acid 95%,2-BROMO-3-NITROBENZOIC ACID (KG LEVEL),2-BROMO-3-NITROBENZOIC ACID
• Ethyl 2-bromo-3-nitrobenzoate
• Methyl 4-bromo-3-nitrobenzoate
• Bromine
• METHYL 4-BROMO-2-NITROBENZOATE