4-Bromo-1,8-naphthalic anhydride

4-Bromo-1,8-naphthalic anhydride Property

Melting point:

217-219 °C (lit.)

Boiling point:

467.2±28.0 °C(Predicted)

Density 

1.812±0.06 g/cm3(Predicted)

storage temp. 

Inert atmosphere,Room Temperature

solubility 

DMSO (Slightly), Methanol (Slightly)

form 

Solid

color 

Off-White to Pale Yellow

InChI

InChI=1S/C12H5BrO3/c13-9-5-4-8-10-6(9)2-1-3-7(10)11(14)16-12(8)15/h1-5H

InChIKey

DTUOTSLAFJCQHN-UHFFFAOYSA-N

SMILES

C1(=O)OC(=O)C2=CC=C(Br)C3=C2C1=CC=C3

CAS DataBase Reference

81-86-7(CAS DataBase Reference)

EPA Substance Registry System

1H,3H-Naphtho[1,8-cd]pyran-1,3-dione, 6-bromo- (81-86-7)

Safety

Hazard Codes 

Xi

Risk Statements 

36/37/38

Safety Statements 

26-37/39

WGK Germany 

3

HS Code 

29173990

Hazard and Precautionary Statements (GHS)

Symbol(GHS)

Signal word

Warning

Hazard statements

H315Causes skin irritation

H319Causes serious eye irritation

H335May cause respiratory irritation

Precautionary statements

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

P264Wash hands thoroughly after handling.

P264Wash skin thouroughly after handling.

P271Use only outdoors or in a well-ventilated area.

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

P302+P352IF ON SKIN: wash with plenty of soap and water.

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

4-Bromo-1,8-naphthalic anhydride Chemical Properties,Usage,Production

Uses

4-Bromo-1,8-naphthalic Anhydride is used as a starting material in the synthesis of a fluorescent probe for the detection of copper ions in living human LO-2 cell lines.

Synthesis

1. Oxidation: 1,8-Naphthalenedicarboxylic anhydride (2.31 g, 15.0 mmol) was dissolved in acetic acid (60 mL) and sodium dichromate (11.17 g, 40.0 mmol) was added under stirring conditions at room temperature. The suspension was heated to 75 °C and the reaction was carried out for 8 hours. After the reaction was completed, cold water was added to precipitate the product, which was filtered and washed with water to obtain white 1,8-naphthalenedicarboxylic anhydride (2.6 g, 80%, melting point 266-268 °C). 2. Bromination: 1,8-naphthalenedicarboxylic anhydride (1.98 g, 10.0 mmol) was dissolved in aqueous KOH (2.8 g KOH in 12 mL of water), cooled, and bromine was added dropwise. The reaction mixture was heated to 60 °C and kept for 6 h, then acidified with HCl solution. The crude product was obtained by filtration, the solid was dissolved by heating with 5% NaOH solution, filtered and neutralized with HCl solution, filtered again and washed with cold water, and dried to obtain yellow 4-bromo-1,8-naphthalenedicarboxylic anhydride (2.05 g, 82%, melting point 117-119 °C). 3. Condensation: 4-bromo-1,8-naphthalenedicarboxylic anhydride (2.00 g, 5.0 mmol) was refluxed with o-phenylenediamine (0.618 g, 5.0 mmol) in THF for 6 hours. After completion of the reaction (monitored by TLC), the reaction mixture was cooled, filtered and washed with THF to afford brown 3-bromo-benzo[de]benzo[4,5]imidazo[2,1-a]isoquinolin-7-one (2.51 g, 63%, melting point 190-192 °C). Product characterization: 1H NMR (CDCl3 + TFA) δ 8.90 (dd, J=8.48, 0.68 Hz, 1H, ArH), 8.79 (dd, J=7.36, 0.84 Hz, 1H, ArH), 8.53 (d, J=7.92 Hz, 1H, ArH), 8.24 (d, J=7.92 Hz, 1H, ArH), 8.04 (dd, J=7.92 Hz, 1H, ArH), 8.04 (dd, J=7.92 Hz, 1H, ArH), 8.05 (dd, J=7.92 Hz, 1H, ArH). 8.04 (dd, J=8.48, 7.48 Hz, 1H, ArH), 7.74 (m, 3H, ArH), 7.56 (m, 1H, ArH); 13C NMR (CDCl3 + TFA) δ 165.76, 136.55, 134.50, 134.42, 133.44, 131.92, 131.75, 131.68, 131.15, 130.90, 129.30, 128.64, 128.20, 127.26, 124.97, 121.02, 119.98; EIMS m/z: 350 (M+ + 1). Calculated elemental analysis (C18H9BrN2O): C, 61.91; H, 2.60; N, 8.08. Measured values: C, 61.76; H, 2.81; N, 8.45.

References

[1] Chemistry - A European Journal, 2011, vol. 17, # 44, p. 12257 - 12261
[2] European Journal of Medicinal Chemistry, 2013, vol. 68, p. 352 - 360
[3] RSC Advances, 2015, vol. 5, # 52, p. 41803 - 41813
[4] New Journal of Chemistry, 2011, vol. 35, # 8, p. 1690 - 1700
[5] Dyes and Pigments, 2018, vol. 158, p. 353 - 361