2,2-dimethyl-1,3-dioxane-4,6-dione

• ChemBase ID: 58237
• Molecular Formular: C6H8O4
• Molecular Mass: 144.12532
• Monoisotopic Mass: 144.04225874
• SMILES: C1(=O)OC(OC(=O)C1)(C)C
• Canonical SMILES: O=C1CC(=O)OC(O1)(C)C
• InChI: InChI=1S/C6H8O4/c1-6(2)9-4(7)3-5(8)10-6/h3H2,1-2H3
• InChIKey: GXHFUVWIGNLZSC-UHFFFAOYSA-N

NAMES AND DATABASE IDS

Names

• IUPAC name: 2,2-dimethyl-1,3-dioxane-4,6-dione
• IUPAC Traditional name: meldrum's acid
• Synonyms: 2,2-Dimethyl-1,3-dioxane-4,6-dione; Meldrum’s acid; Malonic acid cyclic isopropylidene ester; cycl-Isopropylidene malonate; 2,2-Dimethyl-1,3-dioxane-4,6-dione; 2,2-Dimethyl-1,3-dioxane-4,6-dione; 2,2-Propanediol Cyclic Malonate; Cyclic Isopropylidene Malonate; Isopropylidene Malonate; Meldrumic Acid; NSC 688343; NSC 71902; Meldrum's acid; Meldrum's Acid; Isopropylidene malonate; 丙二酸亚异丙酯; 丙二酸环亚异丙酯; 米氏酸; 2,2-二甲基-1,3-二噁烷-4,6-二酮; 丙二酸亚异丙酯

Database IDs

• CAS Number: 2033-24-1
• EC Number: 217-992-8
• MDL Number: MFCD00006638
• Beilstein Number: 117310
• Merck Index: 145817
• PubChem SID: 24852618; 162063000
• PubChem CID: 16249
• Chemspider ID: 15418
• Wikipedia Title: Meldrum's_acid

CALCULATED PROPERTIES

• Acid pKa: 10.625212
• H Acceptors: 2
• H Donor: 0
• LogD (pH = 5.5): 0.3768392
• LogD (pH = 7.4): 0.37658447
• Log P: 0.37684244
• Molar Refractivity: 31.2306 cm^3
• Polarizability: 12.73627 Å^3
• Polar Surface Area: 52.6 Å^2
• Rotatable Bonds: 0
• Lipinski's Rule of Five: true

PROPERTIES

Physical Property

• Solubility: Chloroform; Methanol
• Apperance: White Solid
• Melting Point: 89-91°C; 92-96 °C(lit.); 92-96°C; 92-96°C; 94–95 °C (decomposes)
• pKa: 4.97

Safety Information

• Storage Condition: Refrigerator
• Storage Warning: IRRITANT; Irritant/Keep Cold
• RTECS: JH0800000
• European Hazard Symbols: Irritant (Xi)
• German water hazard class: 3
• Risk Statements: 36/37/38
• Safety Statements: 26-37
• TSCA Listed: false; 是
• GHS Pictograms: GHS07
• GHS Hazard statements: H315-H319-H335
• GHS Precautionary statements: P261-P305+P351+P338-P302+P352-P321-P405-P501A
• Personal Protective Equipment: Eyeshields, Gloves, type N95 (US), type P1 (EN143) respirator filter
• Storage Temperature: 2-8°C

Product Information

• Purity: 95+%; 97%; 98%
• Empirical Formula (Hill Notation): C6H8O4

DETAILS

Sigma Aldrich - 210145

Application
Benzyl substituted Meldrum′s acids, available via aldol condensation and reduction with triethylammonium formate,1 were used to form indanones upon hydrolysis, loss of CO2, and Friedel-Crafts cyclization with chlorosulfonic acid.2 Knoevenagel condensations between aldehydes and Meldrum′s acid are accelerated in ionic liquids.3
Used in an efficient synthesis of isofraxidin.
Packaging
10, 25, 100 g in glass bottle

Toronto Research Chemicals - M215250

An antimicrobial agent of deodorant composition. Bactericides, disinfectants, and antiseptics.

REFERENCES

• Nelson, N., et al.: J. Biol. Chem., 245, 143 (1970)
• Kawamura, M., et al.: Plant Cell Physiol., 21, 745 (1970)
• Oettmeier, W., et al.: Biochim. Biophys Acta, 890, 260 (1970)
• See also: Org. Synth., 77, 114 (1999).
• Condensation with lactim ethers, catalyzed by Nickel(II) 2,4-pentanedionate, 18811, with alcoholysis of the resulting enamino Meldrum's acids, gives of cyclic ?-enamino esters, useful as alkaloid precursors: J. Org. Chem., 43, 4662 (1978); for an example, see: Org. Synth. Coll., 8, 263 (1993).
• Malonate ester which is an unusually strong acid (pK_a = 9.97) in comparison with, e.g. Diethyl malonate, A15468: J. Am. Chem. Soc., 70, 3426 (1948). The mild conditions required for alkylation, acylation, etc. and the ease with which the products undergo alcoholysis or hydrolysis-decarboxylation make Meldrum's acid a valuable and versatile synthetic intermediate. Reviews: Chem. Soc. Rev., 7, 345 (1978); Heterocycles, 32, 529 (1991); Synlett, 1649 (2004).
• For phase-transfer alkylation using K₂CO₃ as base, see: Synthesis, 452 (1982); Bull. Soc. Chim. Belg., 104, 643 (1995). Phase-transfer addition to Michael acceptors also occurs: Synthesis, 224 (1984). Mitsunobu dialkylation with an alcohol and DIAD/Ph₃P is also possible: J. Org. Chem., 62, 1617 (1997).
• Knoevenagel condensation with aldehydes gives ylidene derivatives which are solvolyzed by alcohols to give monoesters of alkylidene or arylidene malonic acids: J. Am. Chem. Soc., 74, 5897 (1952). For diastereoselective condensation with citronellal, followed by intramolecular Diels-Alder reaction, see: Org. Synth. Coll., 8, 353 (1993). With formaldehyde in pyridine gives the stable pyridinium methylide which, on treatment with acid, generates the useful reactive Michael acceptor and dienophile, methylene Meldrum's acid: Synthesis, 215 (1996).
• With an aryl aldehyde in the presence of triethylamine and formic acid at ambient temperature, in situ reduction to the arylmethyl Meldrum's acid occurs, whereas at 70-80^oC, the 3-arylpropionic acid is obtained: Synth. Commun., 25, 3067 (1995).
• C-Acylation with acyl chlorides occurs in the presence of 2 equivalents of pyridine in high yield. Alcoholysis of the product provides a good route to ?-keto esters: J. Org. Chem., 43, 2087 (1978); Org. Synth. Coll.,7, 359 (1988), also obtainable by reaction of the Na salt with acid anhydrides in DMF: Synthesis, 451 (1982). Alternatively, mild hydrolysis and decarboxylation of the intermediate acyl Meldrum's acid gives the methyl ketone, providing an alternative to organometallic methods for conversion of acyl chlorides to methyl ketones: Synth. Commun., 10, 221 (1980):