Reference of 344-14-9, In the next few decades, the world population will flourish. As the population grows rapidly and people all over the world use more and more resources, all industries must consider their environmental impact. 344-14-9, name is Dimethyl 2-fluoromalonate belongs to esters-buliding-blocks compound, it is a common compound, a new synthetic route is introduced below.
Reference Example 1Mixture of dimethyl fluoro[(1R,5R)-5-hydroxycyclopent-2-en-1-yl]propanedioate (8a) and dimethyl fluoro[(1S,5S)-5-hydroxycyclopent-2-en-1-yl]propanedioate (8b) 23.81 g (110.2 mmol) of a 25 w/w % methanol solution of sodium methoxide (NaOMe) was added to a methanol (90.4 mL) solution of 18.19 g (121.2 mmol) of dimethyl fluoropropanedioate (7) over 3 minutes while keeping the internal temperature between 25 C. and 38 C. After stirring the solution thus obtained for 15 minutes, 4.52 g (55.1 mmol) of 6-oxabicyclo [3.1.0] hex-2-ene (6) was added thereto over 2 minutes while keeping the internal temperature between 25 C. and 38 C. After stirring at room temperature for 1 hour, 45 mL of a saturated ammonium chloride aqueous solution was added over 10 minutes while keeping the internal temperature between 26 C. and 35 C. The reaction mixture was concentrated under reduced pressure, most of the methanol was removed by evaporation, and 108 g of a brown solution containing solids was obtained. After extraction with 136 mL of ethyl acetate was carried out twice, washing with 45 mL of water was carried out. After the organic layer was concentrated under reduced pressure, 100 mL of toluene was added, and concentration under reduced pressure was carried out again. The concentrated residue was purified by flash silica gel column chromatography (eluent:toluene/ethyl acetate), thus giving 7.21 g of a mixture of the compound of the formula 8a and the compound of the formula 8b as a yellow oily substance.1H NMR (500 MHz, DMSO-d6): delta (ppm) 2.13-2.17 (m, 1H), 2.56 (dddd, J=2.2, 4.3, 7.1, 17.2 Hz, 1H), 3.32-3.40 (m, 1H), 3.77 (s, 3H), 3.79 (s, 3H), 4.20 (m, 1H), 5.04 (d, J=6.1 Hz, 1H), 5.47 (ddd, J=2.1, 4.3, 6.1 Hz, 1H), 5.85 (ddd, J=2.2, 4.4, 6.1 Hz, 1H). 13C NMR (125 MHz, DMSO-d6): delta (ppm) 41.93, 53.39 (d, J=19.5 Hz), 58.70 (d, J=20.8 Hz), 70.43 (d, J=2.6 Hz), 93.55, 95.14, 125.59, 133.32, 165.42 (d, J=15.6 Hz), 165.62 (d, J=14.3 Hz). 19F NMR (470 MHz, DMSO-d6): delta (ppm) -172.43, -172.36. HRMS(ES)m/z: [M+Na]+ calcd for CHH13O5FNa; 255.0645, found 255.0635. IR (neat) 3528, 3408, 2960, 1755, 1438, 1284, 1253, 1173, 1111, 1068, 1031, 936, 838, 787, 722, 668, 415 cm-1.
In the field of chemistry, the synthetic routes of compounds are constantly being developed and updated. I will also mention this compound in other articles, Dimethyl 2-fluoromalonate, other downstream synthetic routes, hurry up and to see.
Reference:
Patent; TAISHO PHARMACEUTICAL CO., LTD; US2012/232304; (2012); A1;,
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