Methyl 4-bromocrotonate Chemical Properties

Boiling point:

83-85 °C13 mm Hg(lit.)

Density 

1.522 g/mL at 25 °C(lit.)

refractive index 

n20/D 1.501

Flash point:

197 °F

storage temp. 

2-8°C

form 

Liquid

Specific Gravity

1.52

color 

Clear yellow

Water Solubility 

Slightly soluble in water.

BRN 

1745755

InChI

InChI=1S/C5H7BrO2/c1-8-5(7)3-2-4-6/h2-3H,4H2,1H3/b3-2+

InChIKey

RWIKCBHOVNDESJ-NSCUHMNNSA-N

SMILES

C(=O)(OC)/C=C/CBr

CAS DataBase Reference

1117-71-1(CAS DataBase Reference)

NIST Chemistry Reference

2-Butenoic acid, 4-bromo-, methyl ester(1117-71-1)

EPA Substance Registry System

2-Butenoic acid, 4-bromo-, methyl ester (1117-71-1)

Safety Information

Hazard Codes 

Xi,C

Risk Statements 

37/38-41-34-20/21/22

Safety Statements 

26-39-45-36/37/39

RIDADR 

3265

WGK Germany 

3

RTECS 

GQ3120000

F 

8-9

Hazard Note 

Corrosive

TSCA 

Yes

HazardClass 

8

PackingGroup 

III

HS Code 

29161900

MSDS

• Language:English Provider:Methyl 4-bromocrotonate
• Language:English Provider:SigmaAldrich
• Language:English Provider:ACROS
• Language:English Provider:ALFA

Methyl 4-bromocrotonate Usage And Synthesis

Chemical Properties

clear yellow liquid

Uses

It is a useful synthetic intermediate. It was used in the synthesis of irreversible inhibitors of EGFR and HER-2 tyrosine kinases with enhanced antitumor activities.

Preparation

ethyl or methyl crotonate is treated with N-Bromosuccinimide/CCl4 and Dibenzoyl Peroxide.

Synthesis

General procedure for the synthesis of methyl 4-bromobut-2-enoate from methanol and (E)-4-bromobut-2-enoic acid: (E)-4-bromobut-2-enoic acid (1.525 g, 9.24 mmol) and anhydrous methanol (10 ml) were added to a 50 ml three-necked flask, and stirred at 0 °C until complete dissolution. Subsequently, sulfoxide chloride (5.49 g, 46.19 mmol, 5 ml) was added slowly dropwise, taking care to control the rate of titration to avoid violent outgassing. After dropwise addition, the reaction mixture was gradually warmed up to room temperature and the reaction was continued with stirring for 15 h. The reaction progress was monitored by thin layer chromatography (TLC). After completion of the reaction, the reaction mixture was concentrated to dryness under reduced pressure. The residue was extracted with ethyl acetate and water to separate the organic and aqueous phases. The organic phase was collected and dried with anhydrous sodium sulfate. The dried organic phase was concentrated under reduced pressure to remove the solvent to give the crude product. The crude product was purified by column chromatography with petroleum ether:ethyl acetate=8:1 (v/v) as eluent, resulting in 1.54 g of a red oily liquid of methyl 4-bromobut-2-enoate (compound 26) in 93.1% yield.

storage

handle under nitrogen and in a fume hood. Store refrigerated and tightly closed.

References

[1] Patent: CN107556289, 2018, A. Location in patent: Paragraph 0112; 0117; 0118; 0119
[2] Tetrahedron Asymmetry, 2009, vol. 20, # 10, p. 1164 - 1167

Methyl 4-bromocrotonate (1117-71-1)Related Product Information

• Tribenuron methyl
• Pirimiphos-methyl
• Methyl formate
• 4-BROMOCROTONIC ACID
• Methyl 2-bromobenzoate
• Methyl acrylate
• Methyl salicylate
• Methyl 3-aminocrotonate
• Methyl acetate
• Methyl 4-bromobutyrate
• Crotonic acid
• METHYL JASMONATE
• Methyl 4-(bromomethyl)benzoate
• METSULFURON METHYL
• FATTY ACID METHYL ESTER MIX C8-C22
• Kresoxim-methyl
• POLY(METHYL ACRYLATE)
• Methyl 2-bromo-2-methylpropionate