METHYL 3-BROMOTHIOPHENE-2-CARBOXYLATE Chemical Properties

Melting point:

50 °C

Boiling point:

112/4mm

Density 

1.662±0.06 g/cm3(Predicted)

storage temp. 

Keep in dark place,Sealed in dry,Store in freezer, under -20°C

form 

Solid

color 

White

Water Solubility 

Slightly soluble in water.

InChI

InChI=1S/C6H5BrO2S/c1-9-6(8)5-4(7)2-3-10-5/h2-3H,1H3

InChIKey

PEGSJNCGPSIJOX-UHFFFAOYSA-N

SMILES

C1(C(OC)=O)SC=CC=1Br

Safety Information

Hazard Codes 

Xi

Risk Statements 

36/37/38

Safety Statements 

26-37/39

Hazard Note 

Irritant

HS Code 

29349990

METHYL 3-BROMOTHIOPHENE-2-CARBOXYLATE Usage And Synthesis

Chemical Properties

Off-white solid

Uses

Methyl 3-bromothiophene-2-carboxylate is employed as a intermediate for pharmaceutical and chemical research.

Synthesis

The general procedure for the synthesis of methyl 3-bromothiophene-2-carboxylate from methyl 3-amino-2-thiophenecarboxylate was as follows: methyl 3-amino-2-thiophenecarboxylate (100 g, 0.6369 mol) was suspended in hydrobromic acid (220 mL) and stirred at room temperature for 15 min. Subsequently, the mixture was cooled to 0-5 °C and a solution of sodium nitrite (46.0 g, 0.666 mol) in water (100 mL) was slowly added dropwise below 5 °C. After the dropwise addition, stirring was continued for 1 hour. The above mixture was then added to a solution of copper(I) bromide (96.0 g, 0.6692 mol) in hydrobromic acid (260 mL) at room temperature. The reaction system was warmed to 60-65 °C and the reaction was stirred for 2 hours. Upon completion of the reaction, the reaction mixture was diluted with 1200 mL of water at a controlled temperature of 25-30 °C and extracted with two portions of 600 mL of ethyl acetate. The organic phases were combined, washed twice successively with 600 mL of water and dried over anhydrous sodium sulfate. Ethyl acetate was removed by distillation under reduced pressure (60 °C) to give a yellow solid product of 129.0 g in 91.6% yield, melting point 47-48 °C, and HPLC purity of 96%. The structure of the product was confirmed by 1H NMR (400 MHz, CDCl3): δ 3.90 (s, 3H, OCH3), 7.09 (d, 1H), 7.46 (d, 1H); 13C NMR (400 MHz, CDCl3): δ 52.10, 116.96, 127.12, 130.61, 133.63, 161.0; mass spectrum (MS): m/z 222.8 [M+1].

References

[1] Patent: WO2016/92556, 2016, A1. Location in patent: Page/Page column 27; 28
[2] Tetrahedron Letters, 2012, vol. 53, # 52, p. 7135 - 7139
[3] Chemistry - A European Journal, 2018, vol. 24, # 55, p. 14622 - 14626
[4] Patent: CN105164112, 2017, B. Location in patent: Paragraph 0473-0476
[5] Heterocycles, 1985, vol. 23, # 6, p. 1431 - 1435

METHYL 3-BROMOTHIOPHENE-2-CARBOXYLATE(26137-08-6)Related Product Information

• 3-Bromothiophene
• METHYL 3-CHLOROTHIOPHENE-2-CARBOXYLATE
• 4-Bromo-2-thiophenecarboxylic acid
• 3-Chlorothiophene-2-carboxylic acid
• 4-Chlorothiophene-2-carbonitrile
• 3-BROMOTHIOPHENE-2-CARBONITRILE
• 4-CHLOROTHIOPHENE-2-CARBOXYLIC ACID
• 3-Chloro-2-Cyanothiophene
• METHYL THIOPHENE-2-CARBOXYLATE
• METHYL 3-BROMOTHIOPHENE-2-CARBOXYLATE
• Methyl 4-bromothiophene-2-carboxylate
• ETHYL 3-BROMOTHIOPHENE-2-CARBOXYLATE
• SPECS AI-942/25034511
• methyl 3-bromo-5-(nitro)thiophene-2-carboxylate
• BUTTPARK 85\04-56
• AKOS 93625
• SPECS AI-942/25034128
• SPECS AI-942/25034100