2-三氟甲基丙二酸二甲酯

反应条件: temp:70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A mixture of dimethyl(trifluoromethyl)malonate (4.0 g, 20 mmol), methyl vinyl ketone (1.54 g, 22 mmol), triethylamine (0.30 g, 3 mmol), and pyridine (20 ml) was heated for 4 h at 70° C. The reaction mixture was poured into water and worked up as usual. The adduct, dimethyl 1,1,1-trifluoro-5-oxo-2,2-hexanedicarboxylate (3.97 g), b.p. 88°-89° C./0.2 mmHg, was obtained and identified in a similar way.

反应条件: temp:70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A mixture of dimethyl(trifluoromethyl)malonate (4.0 g, 20 mmol), methyl vinyl ketone (1.54 g, 22 mmol), triethylamine (0.30 g, 3 mmol), and pyridine (20 ml) was heated for 4 h at 70° C. The reaction mixture was poured into water and worked up as usual. The adduct, dimethyl 1,1,1-trifluoro-5-oxo-2,2-hexanedicarboxylate (3.97 g), b.p. 88°-89° C./0.2 mmHg, was obtained and identified in a similar way.

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Into a mixture of sodium hydride (0.36 g, 15 mmol) and N,N-dimethylformamide (5 ml), a solution of dimethyl(trifluoromethyl)malonate (2.00 g, 10 mmol) in N,N-dimethylformamide (5 ml) was added dropwise with cooling the vessel in an ice-bath. After being stirred for 2 h at room temperature, the reaction mixture was poured into dilute aqueous HCl, and worked up as usual. Distillation under vacuum gave tetramethyl 2,4,4,4-tetrafluoro-1-butene-1,1,3,3-tetra-carboxylate (1.27 g, 70%), b.p. 122°-124° C./0.3 mmHg. Found: C: 40.74; H: 3.53%. Calcd.for C8H12O8F4 : C: 40.01; H: 3.36%. 19F NMR: δ--15.1 (d. CF3), +10.7 (q, =CF--). 1H NMR: δ 3.77 (s, CH3), 3.87 (s, CH3), 3.90 (COCH3)). IR: 1665 (C=C), 1750 (C=O) cm-1 with cooling the vessel in an ice-bath Distillation under vacuum

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A mixture of dried CsF (9.11 g, 60 mmol), diglyme (41 ml), dimethyl(trifluoromethyl)malonate (4 g, 20 mmol), and methyl iodide (3.12 g, 22 mmol) was stirred overnight at room temperature. The reaction mixture was poured into water and the resultant oily layer and the ether-extract from the aqueous layer were combined and washed with water to remove diglyme. After drying over MgSO4, the ether was evaporated and the residue was subjected to distillation, giving dimethyl methyl(trifluoromethyl)malonate (2.56 g, 60%), b.p. 63°-65° C./10 mmHg. This product showed the following analytical properties: 19F NMR: δ--7.5 (s, CF3); 1H NMR: δ 3.81 (s, 6H, CO2CH3), 1.66 (s, CH3). the resultant oily layer and the ether-extract from the aqueous layer washed with water to remove diglyme After drying over MgSO4 the ether was evaporated the residue was subjected to distillation

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A mixture of dried CsF (9.11 g, 60 mmol), diglyme (41 ml), dimethyl(trifluoromethyl)malonate (4 g, 20 mmol), and methyl iodide (3.12 g, 22 mmol) was stirred overnight at room temperature. The reaction mixture was poured into water and the resultant oily layer and the ether-extract from the aqueous layer were combined and washed with water to remove diglyme. After drying over MgSO4, the ether was evaporated and the residue was subjected to distillation, giving dimethyl methyl(trifluoromethyl)malonate (2.56 g, 60%), b.p. 63°-65° C./10 mmHg. This product showed the following analytical properties: 19F NMR: δ--7.5 (s, CF3); 1H NMR: δ 3.81 (s, 6H, CO2CH3), 1.66 (s, CH3). the resultant oily layer and the ether-extract from the aqueous layer washed with water to remove diglyme After drying over MgSO4 the ether was evaporated the residue was subjected to distillation

反应条件: temp:70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A mixture of dimethyl(trifluoromethyl)malonate (4.0 g, 20 mmol), methyl vinyl ketone (1.54 g, 22 mmol), triethylamine (0.30 g, 3 mmol), and pyridine (20 ml) was heated for 4 h at 70° C. The reaction mixture was poured into water and worked up as usual. The adduct, dimethyl 1,1,1-trifluoro-5-oxo-2,2-hexanedicarboxylate (3.97 g), b.p. 88°-89° C./0.2 mmHg, was obtained and identified in a similar way.

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Into a mixture of sodium hydride (0.36 g, 15 mmol) and N,N-dimethylformamide (5 ml), a solution of dimethyl(trifluoromethyl)malonate (2.00 g, 10 mmol) in N,N-dimethylformamide (5 ml) was added dropwise with cooling the vessel in an ice-bath. After being stirred for 2 h at room temperature, the reaction mixture was poured into dilute aqueous HCl, and worked up as usual. Distillation under vacuum gave tetramethyl 2,4,4,4-tetrafluoro-1-butene-1,1,3,3-tetra-carboxylate (1.27 g, 70%), b.p. 122°-124° C./0.3 mmHg. Found: C: 40.74; H: 3.53%. Calcd.for C8H12O8F4 : C: 40.01; H: 3.36%. 19F NMR: δ--15.1 (d. CF3), +10.7 (q, =CF--). 1H NMR: δ 3.77 (s, CH3), 3.87 (s, CH3), 3.90 (COCH3)). IR: 1665 (C=C), 1750 (C=O) cm-1 with cooling the vessel in an ice-bath Distillation under vacuum

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A mixture of dried CsF (9.11 g, 60 mmol), diglyme (41 ml), dimethyl(trifluoromethyl)malonate (4 g, 20 mmol), and methyl iodide (3.12 g, 22 mmol) was stirred overnight at room temperature. The reaction mixture was poured into water and the resultant oily layer and the ether-extract from the aqueous layer were combined and washed with water to remove diglyme. After drying over MgSO4, the ether was evaporated and the residue was subjected to distillation, giving dimethyl methyl(trifluoromethyl)malonate (2.56 g, 60%), b.p. 63°-65° C./10 mmHg. This product showed the following analytical properties: 19F NMR: δ--7.5 (s, CF3); 1H NMR: δ 3.81 (s, 6H, CO2CH3), 1.66 (s, CH3). the resultant oily layer and the ether-extract from the aqueous layer washed with water to remove diglyme After drying over MgSO4 the ether was evaporated the residue was subjected to distillation