| Identification | More | [Name]
Dimethyl fluoromalonate | [CAS]
344-14-9 | [Synonyms]
2-FLUORO-4-METHOXYACETOACETIC ACID METHYL ESTER
2-FLUORO-MALONIC ACID DIMETHYL ESTER
BUTYRIC ACID, 2-FLUORO-3-OXO-4-METHOXY-, METHYL ESTER
Dimethyl 2-fluoromalonate
DIMETHYL FLUOROMALONATE
METHYL 2-FLUORO-4-METHOXYACETOACETATE
fluoro-malonicaciddimethylester
Dimethyl fluoromalonate 97%
Dimethylfluoromalonate97%
Dimethyl 2-fluoropropanedioate | [EINECS(EC#)]
670-542-6 | [Molecular Formula]
C5H7FO4 | [MDL Number]
MFCD00054680 | [Molecular Weight]
150.11 | [MOL File]
344-14-9.mol |
| Chemical Properties | Back Directory | [Appearance]
white to light yellow crystal powder | [Boiling point ]
76 °C | [density ]
1.4g/ml | [refractive index ]
1.4032 | [Fp ]
111-112°C/45mm | [storage temp. ]
Store at room temperature | [form ]
solid | [pka]
10.35±0.46(Predicted) | [color ]
Colourless to off-white / liquid | [BRN ]
1768414 | [InChI]
InChI=1S/C5H7FO4/c1-9-4(7)3(6)5(8)10-2/h3H,1-2H3 | [InChIKey]
ZVXHZSXYHFBIEW-UHFFFAOYSA-N | [SMILES]
C(OC)(=O)C(F)C(OC)=O | [CAS DataBase Reference]
344-14-9(CAS DataBase Reference) |
| Safety Data | Back Directory | [Hazard Codes ]
T,C | [Risk Statements ]
R34:Causes burns. | [Safety Statements ]
S26:In case of contact with eyes, rinse immediately with plenty of water and seek medical advice .
S36/37/39:Wear suitable protective clothing, gloves and eye/face protection .
S45:In case of accident or if you feel unwell, seek medical advice immediately (show label where possible) . | [RIDADR ]
3265 | [Hazard Note ]
Toxic | [HazardClass ]
8 | [PackingGroup ]
II | [HS Code ]
29171900 |
| Hazard Information | Back Directory | [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]+ ). | [Synthesis]
GENERAL PROCEDURE: PhIO (550 mg, 2.5 mmol), Et3N-5HF (800 mg, 4 mmol) and DCE (1 mL) were placed in a PTFE test tube. After stirring for 15 min at room temperature, appropriate amounts of dimethyl malonate (1 mmol) and DCE (1 mL) were added. The test tube was sealed with septum rubber and heated with stirring at 70°C for 24 hours. After completion of the reaction, the reaction mixture was neutralized with aqueous NaHCO3 and the product was extracted with CH2Cl2 (3 x 10 mL). The organic layers were combined, washed with brine (20 mL), dried over anhydrous Na2SO4 and concentrated under reduced pressure. Finally, the product was purified by silica gel column chromatography with hexane-CH2Cl2 mixed solvent as eluent. | [References]
[1] Green Chemistry, 2015, vol. 17, # 5, p. 3000 - 3009
[2] Journal of Fluorine Chemistry, 1992, vol. 58, # 1, p. 71 - 79
[3] Synthesis (Germany), 2015, vol. 47, # 20, p. 3241 - 3245
[4] Journal of Fluorine Chemistry, 2014, vol. 167, p. 74 - 78
[5] Journal of the Chemical Society, Chemical Communications, 1991, # 3, p. 179 - 181 |
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