344-14-9

Basic information

• Product Name: Dimethyl fluoromalonate
• Synonyms: 2-FLUORO-MALONIC ACID DIMETHYL ESTER;2-FLUORO-4-METHOXYACETOACETIC ACID METHYL ESTER;BUTYRIC ACID, 2-FLUORO-3-OXO-4-METHOXY-, METHYL ESTER;DIMETHYL FLUOROMALONATE;Dimethyl 2-fluoromalonate;METHYL 2-FLUORO-4-METHOXYACETOACETATE;fluoro-malonicaciddimethylester;Dimethyl fluoromalonate 97%
• CAS NO: 344-14-9
• Molecular Formula: C₅H₇FO₄
• Molecular Weight: 150.11
• EINECS: -0
• Product Categories: Small molecule;API intermediates
• Mol File: 344-14-9.mol
• Article Data: 19

Chemical Properties

• Boiling Point: 76 °C
• Flash Point: 111-112°C/45mm
• Appearance: white to light yellow crystal powder
• Density: 1.211 g/cm³
• Vapor Pressure: 6.18mmHg at 25°C
• Refractive Index: 1.4032
• PKA: 10.35±0.46(Predicted)
• BRN: 1768414
• CAS DataBase Reference: Dimethyl fluoromalonate(CAS DataBase Reference)
• NIST Chemistry Reference: Dimethyl fluoromalonate(344-14-9)
• EPA Substance Registry System: Dimethyl fluoromalonate(344-14-9)

Safety Data

• Hazard Codes: T,C
• Statements: 34
• Safety Statements: 26-36/37/39-45-23 2636/37/3945-20
• RIDADR: 3265
• HazardClass: 8
• PackingGroup: II
• Hazardous Substances Data: 344-14-9(Hazardous Substances Data)

Usage

Chemical Properties

white to light yellow crystal powder

Uses

Dimethyl 2-fluoromalonate is used as an intermediate in organic synthesis.

Preparation

synthesis of dimethyl 2-fluoromalonate: Dimethyl malonate (19.8 g, 0.15 mol) and Cu(NO3)2·2.5H2O (3.50 g, 15 mmol) were dissolved in acetonitrile (85 mL), the mixture was cooled to 0–5 °C and stirred at 650 rpm using an overhead stirrer. After purging the system with N2 for 5 minutes, fluorine gas (20% v/v in N2, 50 mL min-1 , 170 mmol) was introduced into the reaction mixture for 7 h. After purging with nitrogen for 20 minutes, the solvent was removed in vacuo and the residue was partitioned between water (30 mL) and ethyl acetate (20 mL). The aqueous phase was extracted with ethyl acetate (2 × 20 mL) and the combined organic layer was washed with saturated brine (20 mL). After drying over sodium sulphate, the solvent was evaporated under reduced pressure to give dimethyl 2-fluoromalonate (21.8 g, 97% yield, 95% purity) as a colourless oil;IR (neat, cm-1 ) 2962, 1748, 1438, 1250, 1206, 1112, 1016; δH (CDCl3, 400 MHz) 3.85 (6H, s, CH3), 5.31 (1H, d, 2 JHF 48.0, CHF); δF (CDCl3, 376 MHz): -195.73 (d, 2 JHF 48.0, CH–F); δC (CDCl3, 100 MHz) 53.48 (CH3), 85.19 (d, 1 JCF 197.2, C–F), 164.39 (d, 2 JCF 24.0, CvO); m/z (EI+ ) 150 (3%, [M]+ ), 119 (42%, [M-OMe]+ ), 91 (73%, [M-COOMe]+ ), 59 (100%, [COOMe]+ ).

InChI:InChI=1/C5H7FO4/c1-9-4(7)3(6)5(8)10-2/h3H,1-2H3

Upstream product

• 67-56-1 methanol 
• 392-41-6 methyl trifluoropropenoate 
• 685-88-1 fluoromalonic acid diethyl ester 
• 453-18-9 methyl fluoroacetate 
• 616-38-6 carbonic acid dimethyl ester 
• 6773-29-1 dimethyl diazomalonate 
• 382-93-4 methyl 2,3,3,3-tetrafluoropropanoate 
• 27931-91-5 hydroxymethylenemalonic acid dimethyl ester 
• 79546-70-6 methyl 3-chlorodifluoropropenoate 
• 108-59-8 malonic acid dimethyl ester 
• 77778-66-6 methyl 2-fluoro-3,3,3-trimethoxypropanoate 
• 78948-09-1 acetyl hypofluorite 
• 18424-76-5 sodiodimethylmalonate 
• 124-41-4 sodium methylate 

Downstream Products

• 133384-81-3 dibenzyl 2-fluoromalonate 
• 101128-09-0 (E)-2-fluoro-4-phenyl-2-pentenoic acid methyl ester 
• 101128-10-3 Z-fluoro-2 phenyl-4 pentene-2 oate de methyle 
• 453-09-8 2-fluoropropane-1,3-diol 
• 1137669-98-7 C₂₀H₁₉FO₄ 
• 1201676-77-8 C₁₃H₁₃FN₂O₈ 

Relevant articles and documents

FACILE SYNTHESIS OF DIALKYL FLUOROMALONATES AND THEIR DERIVATIVES

Dimethyl and diethyl fluoromalonates were prepared by the stepwise basic alcoholysis of hexafluoropropene in a total yield of 50 - 55 percent.These dialkyl fluoromalonates were alkylated with alkyl halides, and the resulting dialkyl α-fluoroalkylmalonates were cyclized with urea affording 5-fluorobarbituric acid derivatives.

Electrochemical Intermolecular Monofluoroalkylation of α,β-Unsaturated Carboxylic Acids and Heteroaromatics with 2-Fluoromalonate Esters

An electrochemical approach for the preparation of monofluorides from α,β-unsaturated carboxylic acids and heteroaromatics with readily available 2-fluoromalonate esters as monofluoroalkyl radical precursors has been developed. The electrosynthesis employs ferrocene (Cp2Fe) as a catalyst in a simple undivided cell with a broad substrate scope, which obviates the need for sacrificial oxidizing reagents.

Continuous synthesis method for 2-fluoroethyl malonate compound

The invention discloses a continuous synthesis method for a 2-fluoroethyl malonate compound. The continuous synthesis method comprises the following steps: taking a formula shown in the description asa raw material, and carrying out a continuous decarbonylation reaction in continuous reaction equipment, thereby obtaining the 2-fluoroethyl malonate compound represented by a formula shown in the description, wherein R and R' separately represent straight-chain or branched alkyl, substituted or unsubstituted aryl or substituted or unsubstituted heterocycle or cyclic alkyl and are the same or different. According to the method, the high-temperature decarbonylation reaction of 2-fluoro-3-oxo-disuccinate is achieved by adopting the continuous reaction equipment. Compared with the traditional pot type reaction, the amount of materials participating in reaction in unit time is reduced greatly, so that a high-temperature hazardous area is reduced, and the security risk is greatly lowered.

Preparation method for fluoromalonic acid diester

The invention especially relates to a preparation method for fluoromalonic acid diester, belonging to the field of organic synthesis. The preparation method comprises a step of subjecting fluoroacetate and dialkyl carbonate to a condensation reaction in the presence of alkali so as to prepare fluoromalonic acid diester. The preparation method provided by the invention is mild in reaction process;the preparation method has low toxicity and corrosivity due to elimination of conventional chlorination and fluorination steps; and the preparation method does not produce difluoromalonic acid diesterimpurities, has low requirements on factory equipment and is simple and safe to operate.