Dimethyl 1,3-acetonedicarboxylate

Dimethyl 1,3-acetonedicarboxylate Property

Melting point:

16-17°C

Boiling point:

237-241 °C/760 mmHg (lit.)

Density 

1.206 g/mL at 20 °C (lit.)

refractive index 

n20/D 1.444(lit.)

Flash point:

>230 °F

storage temp. 

2-8°C

solubility 

Chloroform (Sparingly), Ethyl Acetate (Slightly), Methanol (Slightly)

form 

Liquid

pka

9.06±0.50(Predicted)

color 

Clear colorless to light yellow

Water Solubility 

approx. 120 g/L (20 ºC)

BRN 

1366042

CAS DataBase Reference

1830-54-2(CAS DataBase Reference)

NIST Chemistry Reference

Pentanedioic acid, 3-oxo-, dimethyl ester(1830-54-2)

EPA Substance Registry System

Pentanedioic acid, 3-oxo-, dimethyl ester (1830-54-2)

Safety

Hazard Codes 

Xi

Risk Statements 

43

Safety Statements 

36/37

WGK Germany 

1

Hazard Note 

Irritant

TSCA 

Yes

HS Code 

29183000

Hazard and Precautionary Statements (GHS)

Symbol(GHS)

Signal word

Warning

Hazard statements

H317May cause an allergic skin reaction

Precautionary statements

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

P272Contaminated work clothing should not be allowed out of the workplace.

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

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

P333+P313IF SKIN irritation or rash occurs: Get medical advice/attention.

Dimethyl 1,3-acetonedicarboxylate Chemical Properties,Usage,Production

Chemical Properties

colorless to yellowish

Uses

Dimethyl 1,3-acetonedicarboxylate is used as intermediate for the syntheses of organic chemicals. Product Data Sheet

Uses

Dimethyl-1,3-acetonedicarboxylate is used in the preparation of optically active lycorane. It has also been substituted into bispidone derivatives for their use as ligands in PET imaging.

Definition

ChEBI: 4(R),8-dimethyl-trans-2-nonenoyl-CoA is an oxo carboxylic acid.

Synthesis

1. 490 kg (370 L) of anhydrous dichloromethane and 1320 kg (753 L) of chlorosulfonic acid were added to a reactor, ensuring that the ratio of dichloromethane to chlorosulfonic acid was 0.5:1 by volume. 2. The temperature of the mixture was adjusted to 10-15 °C and 665.0 kg of citric acid monohydrate was added at a rate of 1.25 kg/min, maintaining the reaction temperature between 10-15 °C. 3. after the addition is complete, continue to stir the reaction mixture at 10-15 °C until no gas is released (at least 6 hours). 4. Cool the reaction mixture to 3-5°C and slowly add 640 kg (800 L) of anhydrous methanol, controlling the internal temperature to no more than 25°C. 5. Warm the reaction mixture to 30-35 °C and stir for 2 hours to complete the esterification reaction. 6. Cool the reaction mixture to 10-12 °C. Slowly add 1300 L of water, controlling the temperature to no more than 15 °C. 7. 800 mL of dichloromethane was added, stirred for 15 minutes and then allowed to stand for 30 minutes to separate the organic phase. 8. The aqueous phase was extracted three times with 400 mL of dichloromethane and the organic phases were combined. 9. The organic phase was washed sequentially with 1000 L of water and 75 kg of sodium bicarbonate in 1000 L of aqueous solution, adjusting the pH to about 7. 10. The organic phase was separated, washed twice with 750 mL of water and evaporated under vacuum. Evaporation conditions: 3-5 kPa, internal temperature not exceeding 75°C. 11. 535 kg of dimethyl 3-oxoglutarate was obtained and used in subsequent reactions without further purification. 12. Gas chromatography analysis conditions: HP-6850 gas chromatograph, HP-1.25 m x 0.32 mm column, film thickness 0.17 μm, carrier gas is hydrogen, programmed temperature increase: 80 ℃ held for 5 minutes, 10 ℃/min to 200 ℃ and held for 8 minutes, detector FID 280 ℃, injector 200 ℃. 13. Expected retention times: 1.18 min for methyl acetoacetate, 5.77 min for dimethyl 3-oxoglutarate, 8.15 min for enol ethers, 10.00 min for trimethyl aconite, 10.42 min for trimethyl citrate, 18.76 min for isosorbic acid derivatives. 14. Area normalization results: methyl acetoacetate 0.31%, dimethyl 3-oxoglutarate 98.33%, enol ether 0.81%, trimethylaconate 0.28%, trimethyl citrate 0.19%, isosorbic acid derivatives not detected, and other contaminants (>0.2%) not detected.

References

[1] Patent: WO2004/89867, 2004, A2. Location in patent: Page 20-26