METHYL 3-OXOTETRAHYDROTHIOPHENE-2-CARBOXYLATE Chemical Properties

Melting point:

38 °C (lit.)

Boiling point:

232-254 °C/0.1 mmHg (lit.)

Density 

1.281 g/mL at 1.281 °C (lit.)

refractive index 

n20/D 1.511(lit.)

Flash point:

>230 °F

storage temp. 

2-8°C

form 

Liquid

pka

11.11±0.20(Predicted)

Appearance

Off-white to light yellow <38°C Solid,>38°C Liquid

Water Solubility 

Slightly soluble in water.

EPA Substance Registry System

2-Thiophenecarboxylic acid, tetrahydro-3-oxo-, methyl ester (2689-69-2)

Safety Information

Hazard Codes 

Xn

Risk Statements 

22-36

Safety Statements 

26-36/37

WGK Germany 

3

HS Code 

2934999090

MSDS

• Language:English Provider:SigmaAldrich
• Language:English Provider:ALFA

METHYL 3-OXOTETRAHYDROTHIOPHENE-2-CARBOXYLATE Usage And Synthesis

Uses

Methyl 3-oxotetrahydrothiophene-2-carboxylate is used in the production of dihydro-thiophen-3-one.

Synthesis Reference(s)

Journal of the American Chemical Society, 68, p. 2229, 1946 DOI: 10.1021/ja01215a034

Synthesis

Step 1: Under vigorous stirring, 1.1 g of sodium metal pre-sliced into thin slices was slowly added to 11 ml of methanol. The resulting solution was heated to reflux followed by the slow addition of 3.0 g of methyl 3-[(2-methoxy-2-oxoethyl)thio]propionate (completed in about 10 minutes). After maintaining the reflux state for 30 minutes, the solution was allowed to cool to room temperature. The reaction mixture was poured into about 100 ml of ice water under continuous stirring, continued for 30-40 min and acidified with concentrated hydrochloric acid to pH 2. The aqueous phase was extracted five times with dichloromethane, the organic phases were combined and concentrated by rotary evaporation after drying to afford 1.7 g of the crude product in the form of an oil.GC-MS analysis showed that the crude product contained about 3% of the isomer (tetrahydro-3-oxa-2- methyl thiophenecarboxylate) (HPLC retention time = 2.53 min). The crude product was purified using a Flash Master Personal system and a STRATA column pre-filled with Phenomenex silica (20 g). The crude product was dissolved in a dichloromethane:hexane (1:1) solvent mixture, dried, upsampled and eluted with the same ratio of solvent mixture. Finally 1.12 g of white solid product was obtained in 54% yield.

References

[1] Patent: US2008/275023, 2008, A1. Location in patent: Page/Page column 9
[2] Patent: WO2006/97449, 2006, A1. Location in patent: Page/Page column 24-25
[3] Tetrahedron, 1991, vol. 47, # 27, p. 4847 - 4860
[4] Patent: WO2013/50508, 2013, A1. Location in patent: Page/Page column 42; 55
[5] Organic Process Research and Development, 2016, vol. 20, # 5, p. 982 - 988

METHYL 3-OXOTETRAHYDROTHIOPHENE-2-CARBOXYLATE(2689-69-2)Related Product Information

• METHYL THIOPHENE-2-CARBOXYLATE
• Tetrahydrothiophene
• Methyl 4-oxotetrahydrothiophene-3-carboxylate
• 3-METHYLTHIO-2-BUTANONE
• 3-Oxo-tetrahydro-thiophene-2-carboxylic acid ethyl ester
• Tetrahydrothiophen-3-one
• 2-(ethylthio)propanoic acid
• METHYL 2-(METHYLTHIO)BUTYRATE
• METHYL 2-(METHYLTHIO)PROPIONATE
• 3-Mercapto-2-butanone
• Dihydro-2-methyl-3(2H)-thiophenone
• METHYL 3-OXOTETRAHYDROTHIOPHENE-2-CARBOXYLATE