Diethyl bis(hydroxymethyl)malonate Chemical Properties

Melting point:

49-51 °C (lit.)

Boiling point:

281.15°C (rough estimate)

Density 

1.2286 (rough estimate)

refractive index 

1.4390 (estimate)

Flash point:

>230 °F

storage temp. 

Sealed in dry,Room Temperature

pka

12.59±0.10(Predicted)

form 

Crystalline Solid

color 

White to almost white

Water Solubility 

Slightly soluble in water.

BRN 

1788515

InChI

InChI=1S/C9H16O6/c1-3-14-7(12)9(5-10,6-11)8(13)15-4-2/h10-11H,3-6H2,1-2H3

InChIKey

WIOHBOKEUIHYIC-UHFFFAOYSA-N

SMILES

C(OCC)(=O)C(CO)(CO)C(OCC)=O

CAS DataBase Reference

20605-01-0(CAS DataBase Reference)

NIST Chemistry Reference

Diethyl bis(hydroxymethyl)malonate(20605-01-0)

EPA Substance Registry System

Propanedioic acid, bis(hydroxymethyl)-, diethyl ester (20605-01-0)

Safety Information

Hazard Codes 

Xi

Risk Statements 

36/37/38

Safety Statements 

23-24/25-36-26

WGK Germany 

3

TSCA 

Yes

HazardClass 

IRRITANT

HS Code 

29181998

MSDS

• Language:English Provider:Diethyl bis(hydroxymethyl)malonate
• Language:English Provider:SigmaAldrich
• Language:English Provider:ACROS
• Language:English Provider:ALFA

Diethyl bis(hydroxymethyl)malonate Usage And Synthesis

Chemical Properties

white to almost white crystalline solid

Uses

Diethyl bis(hydroxymethyl)malonate is used as a reagent for preparing 1,3-dioxanes from acetals, aldehydes and ketones. It is also used as an intermediate for the preparation of substituted malonic, acrylic and isobutyric esters, for conversion to the useful dienophiles, ?-bromomethylacrylic acid and its ethyl ester and to bis(bromomethyl)acetic acid and its methyl ester.

Synthesis

A 35% aqueous formaldehyde solution (16.07 mL, 187.3 mmol, 3.0 eq.) was mixed with potassium bicarbonate (0.53 g, 5.27 mmol, 0.08 eq.) in a 20 °C water bath. Diethyl malonate (10.00 g, 62.43 mmol, 1.0 eq.) was added slowly and the reaction mixture was stirred overnight. After completion of the reaction, saturated sodium sulfate solution was added and the product was extracted with ether. The organic layers were combined, dried with anhydrous sodium sulfate, filtered and concentrated under reduced pressure to give the crude product diethyl 2,2-bis(hydroxymethyl)malonate (13.79 g, 100%) as a clear colorless oil. The product could be used in the next reaction without further purification. Thin layer chromatography (TLC) Rf value was 0.31 (unfolding agent: 50% ethyl acetate/hexane). IR spectrum (neat, cm-1): 3433 (O-H), 2982 (C-H), 1790 (C=O), 1209, 1028. 1H NMR (300 MHz, CDCl3): δ 4.22 (q, 4H, J = 6.7 Hz, 2 × OCH2CH3), 4.09-4.04 (m, 4H, 2 × CH2OH), and 2.99 (s, 2H, 2 × OH), 1.25 (t, 3H, J = 7.1 Hz, OCH2CH3), 1.24 (t, 3H, J = 7.1 Hz, OCH2CH3).13C NMR (75 MHz, CDCl3): δ 169.58, 63.54, 61.97, 61.21, 14.04.

References

[1] European Journal of Medicinal Chemistry, 2017, vol. 127, p. 671 - 690
[2] Synthesis, 1997, # 11, p. 1281 - 1284
[3] Patent: WO2014/110388, 2014, A1. Location in patent: Page/Page column 21; 22
[4] Tetrahedron, 1991, vol. 47, # 6, p. 1001 - 1012
[5] Journal of Medicinal Chemistry, 1991, vol. 34, # 5, p. 1675 - 1692

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