2-BROMO-2'-METHOXYACETOPHENONE

2-BROMO-2'-METHOXYACETOPHENONE Property

Melting point:

43-45 °C(lit.)

Boiling point:

130 °C1 mm Hg(lit.)

Density 

1.4921 (rough estimate)

refractive index 

1.5500 (estimate)

Flash point:

>230 °F

storage temp. 

2-8°C

form 

Crystalline Powder or Crystals

color 

White to off-white

Water Solubility 

Insoluble in water.

Sensitive 

Lachrymatory

BRN 

1938788

InChI

InChI=1S/C9H9BrO2/c1-12-9-5-3-2-4-7(9)8(11)6-10/h2-5H,6H2,1H3

InChIKey

GKNCPTLOPRDYMH-UHFFFAOYSA-N

SMILES

C(=O)(C1=CC=CC=C1OC)CBr

CAS DataBase Reference

31949-21-0(CAS DataBase Reference)

Safety

Hazard Codes 

C,T

Risk Statements 

34

Safety Statements 

22-26-36/37/39-45

RIDADR 

UN 3261 8/PG 2

WGK Germany 

3

Hazard Note 

Lachrymatory/Toxic/Keep Cold

HazardClass 

8

PackingGroup 

III

HS Code 

29147000

Hazard and Precautionary Statements (GHS)

Symbol(GHS)

Signal word

Danger

Hazard statements

H314Causes severe skin burns and eye damage

Precautionary statements

P260Do not breathe dust/fume/gas/mist/vapours/spray.

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

P303+P361+P353IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower.

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

P363Wash contaminated clothing before reuse.

2-BROMO-2'-METHOXYACETOPHENONE Chemical Properties,Usage,Production

Chemical Properties

White to greyish-green crystalline powder

Uses

2-Bromo-2'-methoxyacetophenone is used as a pharmaceutical intermediate .

Preparation

Also obtained according to the procedure of Buckman (80%).

Synthesis

The general procedure for the synthesis of o-methoxy-2-bromoacetophenone from 2'-methoxyacetophenone was as follows: copper(II) bromide (2.97 g, 6.66 mmol) was added to a two-necked round-bottomed flask equipped with a reflux condenser. Ethyl acetate (10.0 mL) was added to the flask and the mixture was stirred at 70 °C for 5 min under nitrogen protection. A solution of chloroform (10.0 mL) of 1-(2-methoxyphenyl)ethanone (0.50 g, 3.33 mmol) was slowly added, followed by refluxing the reaction mixture for 8 hours. After completion of the reaction, it was cooled to room temperature, filtered through a diatomaceous earth pad and the filter cake was washed with ethyl acetate (20 mL). The filtrate was concentrated under reduced pressure and the crude product obtained was purified by column chromatography (eluent ratio ethyl acetate:hexane = 1:4) to afford the pure o-methoxy-2-bromoacetophenone (0.73 g, 96% yield) as a brown liquid. Thin layer chromatography Rf value was 0.43 (unfolding agent ratio ethyl acetate:hexane = 1:4); 1H NMR (300 MHz, CDCl3) δ: 7.81 (1H, dd, J = 7.8, 1.8 Hz), 7.52 (1H, td, J = 7.8, 1.8 Hz), 7.05-6.96 (2H, m), 4.61 (2H, s). 3.94 (3H, s); 13C NMR (75 MHz, CDCl3) δ: 192.3, 158.8, 134.9, 131.6, 124.9, 121.2, 111.7, 56.0, 38.0.

References

[1] Bulletin of the Korean Chemical Society, 2017, vol. 38, # 12, p. 1481 - 1485
[2] Tetrahedron Letters, 2006, vol. 47, # 27, p. 4707 - 4710
[3] Tetrahedron Letters, 2009, vol. 50, # 6, p. 700 - 703
[4] Chemistry - A European Journal, 2011, vol. 17, # 28, p. 7953 - 7959
[5] Molecules, 2017, vol. 22, # 5,