Dimethyl fluoromalonate

white to light yellow crystal powder

General procedure: PhIO (550 mg, 2.5 mmol), Et3N·5HF (800 mg, 4 mmol), and DCE (1 mL)were placed in a Teflon test tube. After stirring at r.t. for 15 min, the appropriate malonic ester 1 (1 mmol) and DCE (1 mL) were added. The test tube was sealed with a septum rubber and heated at 70 °C for 24 h with stirring. The reaction mixture was neutralized with aq NaHCO3 and the product was extracted with CH2Cl2 (3 × 10 mL). The combined organic layers were washed with brine (20 mL), dried (Na2SO4), and concentrated under reduced pressure. The product was purified by column chromatography on silica gel with hexane–CH2Cl2 as eluent.General procedure: Anhydrous liquid hydrogen fluoride (5 mL, 0.25 mmol) was placed into polypropylene flask at 0 °C under nitrogen atmosphere. Diazomalonate (0.5 mmol) was added dropwise into the stirred reaction mixture at 0 °C. The reaction mixture was stirred at 0 °C for 5 h. Then, reaction mixture was poured into ice-water (100 mL). The obtained mixture was neutralized with solid NaHCO3, and extracted with dichloromethane (3x25 mL). The combined organic layers were washed with water (25 mL), dried over Na2SO4, and concentrated under reduced pressure. Crude material was purified by column chromatography (silica gel; hexane/EtOAc; linear gradient: 0-2percent EtOAc).Into a 250 ml round bottom flask, add 80.0g of dimethyl carbonate and 7.0g of sodium methoxide, heat to reflux, add 9.0g of methyl fluoroacetate drop-wise, and react for 2h. With 30percent hydrochloric acid quench the reaction, liquid separation, organic phase distillation, obtained 9.1g of dimethyl fluoromalonate (content: 98.5percent), yield 60.8percent.To a stirred solution of 2-methyl-2-thiopseudourea sulfate (4.17 g, 15 mmol) and First, put a stir bar in a 35 mL sealed tube, and then add phenylacetylene (38 muL, 0.33 mmol), 0.9 mL tetrahydrofuran (0.9 mL), and 2-chloroacetamidoquinoline (66.2 mg, 0.3 mmol).Dimethyl 2-fluoromalonate (70.4 mg, 0.45 mmol). To the mixed solution, CuI (5.7 mg, 0.03 mmol) and Cs2CO3 (117.3 mg, 0.36 mmol) were added accordingly. The tube was filled with N2 for 3 minutes, the air was fully expelled, the nozzle was sealed with a cock, and the reaction was stirred at 80 C for 1.5 hours. After the reaction, the system was cooled to room temperature, 2 ml of distilled water was added to the reaction system, and extracted with ethyl acetate The organic phases were combined, the solvent of the organic phase was distilled off under reduced pressure, and 123.1 mg of the product 4a was separated by silica gel column chromatography with a yield of 94%.First, put a stirrer in a 35 mL sealed tube, and then add 2-methyl-1-butene-3-yne (32 muL, 0.33 mmol), 0.9 mL tetrahydrofuran (0.9 mL), and 2-chloroacetamido Quinoline (66.2mg, 0.3mmol), First, put a stir bar in a 35 mL sealed tube, and then add methyl propargyl ether (28 muL, 0.33 mmol), 0.9 mL tetrahydrofuran (0.9 mL), and 2-chloroacetamidoquinoline (66.2 mg, 0.3 mmol), First, put a stirrer in a 35 mL sealed tube, and then add 2-ethynylpyridine (34 muL, 0.33 mmol), 0.9 mL of tetrahydrofuran (0.9 mL), and 2-chloroacetamidoquinoline (66.2 mg, 0.3 mmol). ), Dimethyl 2-fluoromalonate (70.4 mg, 0.45 mmol), and CuI (5.7 mg, 0.03 mmol) and Cs2CO3 (117.3 mg, 0.36 mmol) were added to the uniformly mixed solution in this manner. The glass tube was filled with N2 for 3 minutes, the air was fully expelled, the nozzle was sealed with a cock, and the reaction was stirred at 800C for 1.5 hours. After the reaction was completed, the system was cooled to room temperature, 2 ml of distilled water was added to the reaction system, and extracted with ethyl acetate. The organic phases were combined, the solvent of the organic phase was distilled off under reduced pressure, and 103.6 mg of product 4c was separated by silica gel column chromatography with a yield of 79%.First, put a stir bar in a 35 mL sealed tube, and then add 4-ethynylbiphenyl (60.6 mg, 0.33 mmol), 0.9 mL of tetrahydrofuran (0.9 mL), and 2-chloroacetamidoquinoline (66.2 mg , 0.3 mmol),

Molecular Weight:150.10
XLogP3:0.6
Hydrogen Bond Acceptor Count:5
Rotatable Bond Count:4
Exact Mass:150.03283686
Monoisotopic Mass:150.03283686
Topological Polar Surface Area:52.6
Heavy Atom Count:10
Complexity:129
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes