4-Nitrobenzyl hydrogen malonate Chemical Properties

Melting point:

109 °C

Boiling point:

455.8±30.0 °C(Predicted)

Density 

1.447±0.06 g/cm3(Predicted)

storage temp. 

Sealed in dry,Room Temperature

solubility 

soluble in Methanol

form 

powder to crystal

pka

2.49±0.32(Predicted)

color 

White to Almost white

InChI

InChI=1S/C10H9NO6/c12-9(13)5-10(14)17-6-7-1-3-8(4-2-7)11(15)16/h1-4H,5-6H2,(H,12,13)

InChIKey

RIGFMUNSTCPGNP-UHFFFAOYSA-N

SMILES

C(OCC1=CC=C([N+]([O-])=O)C=C1)(=O)CC(O)=O

CAS DataBase Reference

77359-11-6(CAS DataBase Reference)

Safety Information

HS Code 

2917399590

4-Nitrobenzyl hydrogen malonate Usage And Synthesis

Uses

4-Nitrobenzyl hydrogen malonate is a reagent used in the synthesis of (±)-thienamycin, a β-Lactam antibiotics. Also, it is useful for chiral key intermediate of carbapenem syntheses.

Preparation

Preparation of mono-4-nitrobenzyl malonate:
In a flame-dried 150 mL pressure tube under argon, add 5.00 g (34.7 mmol) of Meldrum's acid and 40 mL of anhydrous MeCN.
Add 5.58 g (36.4 mmol) of p-nitrobenzyl alcohol to the resulting solution.
Cap the tube tightly and reflux the reaction overnight.
Concentrate the reaction mixture under reduced pressure.
Purify the residue using column chromatography with a 55/45 hexane/EtOAc mixture.
The resulting product is mono-4-nitrobenzyl malonate with a yield of 87%.

Synthesis

Meldrum acid (5.00 g, 34.7 mmol) and anhydrous acetonitrile (40 mL) were added to a flame-dried 150 mL pressure tube under argon protection. To this solution was added p-nitrobenzyl alcohol (5.58 g, 36.4 mmol), the pressure tube was sealed and the reaction was carried out overnight under reflux conditions. Upon completion of the reaction, the solvent was removed by concentration under reduced pressure and the crude product was purified using column chromatography (eluent ratio 55:45 hexane/ethyl acetate) to afford mono-p-nitrobenzyl malonate (16a, 6.86 g, 27.1 mmol) as an off-white solid in 83% yield. A small amount of the product (1.00 g) was recrystallized by tert-butanol/hexane mixed solvent to give purified mono-p-nitrobenzyl malonate (16a, 225 mg, 0.889 mmol) as a white solid.

References

[1] Bioorganic and Medicinal Chemistry Letters, 2015, vol. 25, # 21, p. 4933 - 4936
[2] Tetrahedron, 2001, vol. 57, # 9, p. 1837 - 1847
[3] Tetrahedron Letters, 2003, vol. 44, # 40, p. 7499 - 7502

4-Nitrobenzyl hydrogen malonate(77359-11-6)Related Product Information

• Diethyl methylmalonate
• Ethyl hydrogen malonate
• (4-Nitrophenyl)methyl 3-oxobutanoate
• 4-Nitrobenzyl chloroformate
• Dimethyl malonate
• Hydrogen
• Malonic acid
• 4-Nitrobenzyl alcohol
• Diethyl malonate
• 2-([(BENZYLOXY)CARBONYL]AMINO)-2-HYDROXYACETIC ACID
• 4-(Benzyloxycarbonyl)-2-azetidinone
• Propanoic acid, 2,2-diMethyl-3-oxo-, Methyl ester
• Malonyl chloride
• Methyl malonyl chloride
• BPMO
• MALONIC ACID MONO-4-NITROBENZYL ESTER MAGNESIUM SALT
• 4-Nitrobenzyl chloride
• Hydrogen peroxide