N-(TERT-BUTOXYCARBONYL)-2-BROMOANILINE Chemical Properties

Boiling point:

110 °C0.3 mm Hg(lit.)

Density 

1.342 g/mL at 25 °C(lit.)

refractive index 

n20/D 1.54(lit.)

Flash point:

>230 °F

storage temp. 

Sealed in dry,Room Temperature

pka

12.93±0.70(Predicted)

Appearance

Light yellow to light brown Liquid

Safety Information

Hazard Codes 

Xi

Risk Statements 

36/37/38

Safety Statements 

26-36

WGK Germany 

3

N-(TERT-BUTOXYCARBONYL)-2-BROMOANILINE Usage And Synthesis

Uses

N-(tert-Butoxycarbonyl)-2-bromoaniline may be used in the synthesis of N-boc-protected o-aryl anilines, which undergoes coupling reaction with bromoacetylenes to form the corresponding arene?ynamides.

General Description

N-(tert-Butoxycarbonyl)-2-bromoaniline, also known as tert-butyl-N-(2-bromophenyl)carbamate, is an N-Boc-protected o-bromoaniline.1 It reacts with ethyl perfluorooctanoate in the presence of tert-butyllithium to form the corresponding 1-hydroxy-1H-perfluorooctyl compound.

Synthesis

The general procedure for the synthesis of N-(tert-butoxycarbonyl)-2-bromoaniline from di-tert-butyl dicarbonate and o-bromoaniline: di-tert-butyl dicarbonate (10.90 g, 50 mmol) was added to a solution of 2-bromoaniline (3.43 g, 20 mmol) in tetrahydrofuran (THF, 40 mL), followed by stirring of the reaction mixture for 3 days under reflux conditions. Upon completion of the reaction, the mixture was diluted by adding ether (50 mL), and the organic phase was washed sequentially with saturated sodium chloride solution (50 mL x 3) and dried with anhydrous magnesium sulfate (MgSO?). The solvent was removed by concentration under reduced pressure to obtain the crude product. The crude product was purified by silica gel column chromatography with the eluent of petroleum ether/ethyl acetate (20:1, v/v), and tert-butyl N-(2-bromophenyl)carbamate (4.73 g, 87% yield) was finally obtained.

References

[1] Organic Letters, 2009, vol. 11, # 22, p. 5130 - 5133
[2] Bioorganic and Medicinal Chemistry, 2004, vol. 12, # 8, p. 1867 - 1880
[3] Journal of Organic Chemistry, 2008, vol. 73, # 14, p. 5658 - 5661
[4] Heterocycles, 1996, vol. 43, # 12, p. 2741 - 2746
[5] Tetrahedron Letters, 2007, vol. 48, # 47, p. 8318 - 8322