Synthetic Route of 51122-91-9, 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. 51122-91-9, name is Dimethyl Isopropylmalonate belongs to esters-buliding-blocks compound, it is a common compound, a new synthetic route is introduced below.
Synthetic Route of 51122-91-9, 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. 51122-91-9, name is Dimethyl Isopropylmalonate belongs to esters-buliding-blocks compound, it is a common compound, a new synthetic route is introduced below.
Example 1; 382g (406ml) of DMF were initially charged in a Schmizzo and 137g (141 ml) of 1.0 eq. NaOMe (30% solution in methanol) were added. This mixture was then heated to 600C (+ 3C) and 131g (0.753mol) of dimethyl isopropylmalonate were metered in within one hour. Subsequently, a methanol/DMF mixture (201 g) was distilled off under pressure (300 mbar to 60 mbar) and a temperature of 600C. Thereafter, at 800C (+ 30C), 86 g (79 ml, 0.779 mol, 1.03 eq.) of 1 ,3-dichloropropene were metered in within one hour and the reaction mixture was then heated at 800C (+ 3C) for two hours.The reaction mixture was heated to 1400C and a 25% solution of LiCI (0.6 eq.) in methanol (19 g of LiCI in 58 g of methanol) was metered in within two hours, and the reaction mixture was heated at 140-1420C for a further 6 hours, in the course of which a portion of the methanol was distilled off and approx. 1.5 mol of gas (mainly CH3CI and CO2) formed. The maximum amount of gas in the first half hour was approx. 6 liters.On completion of reaction, the solvent (DMF) and the excess methanol were distilled off substantially fully under reduced pressure. The remainder was admixed with 200 g of water, 89 g of 34% HCI and 200 g of MTBE, and the phases were separated. The organic phase was washed 1x with 50 g of water and the solvent was removed under reduced pressure. Approx. 140 g of product were obtained, of which approx. 125 g were ester and 13 g the corresponding acid.To prepare the corresponding acid, the above product was processed further. 140 g of crude product were suspended in 15O g of water and 70 g of 50% NaOH (1.15 eq.) were added. The reaction mixture was initially charged in an autoclave and heated at max. 3 bar and a temperature of 100-1100C for two hours. On completion of reaction, the methanol formed was distilled off via the top. Thereafter, the mixture EPO was adjusted to pH 1.5 with H2SO4 (76%) and extracted 2x with 100 g of IPAT each time, and the solvent was removed under reduced pressure. 125-127 g of acid (96% of theory) were obtained as a colorless liquid; Example 2; A reaction vessel was charged with dimethylformamide (406 ml, 382 g) and sodium methoxide (140 ml, 136 g, 753 mmol, a 30% solution in methanol). The reaction mixture was heated to 600C. Dimethyl isopropylmalonate (127 ml, 131 g, 753 mmol) was metered in within thirty minutes, and methanol was distilled off at a temperature of 69-74C and a pressure of 330-50 mbar. frans-1 ,3-Dichloropropene (70 ml, 84 g, 753 mmol) was metered in at 800C within one hour and the reaction solution was stirred at 8O0C for ninety minutes.CaCb (83.5 g, 753 mmol) was added and the mixture was heated to 140-1450C. Methanol was metered in continuously (a total of 30 ml, 24 g, 742 mmol), in the course of which the reaction temperature was kept at approx. 140-1450C. The suspension is stirred at this temperature for 12 hours, in the course of which gas (mainly CH3CI and CO2) formed. The maximum amount of gas in the first half hour was approx. 6 liters.Dimethylformamide (260 ml, 247 g) was distilled off at 70-800C and a pressure of (150 – 25 mbar). The resulting suspension was cooled to 55C, and admixed with 250 g of water, 90 g of HCI (a 34% aqueous solution) and 190 g of MTBE. The phases were separated and the organic phase was washed with 100 g of water. The organic phase thus obtained was worked up as follows: EPO The organic MTBE phase was concentrated under reduced pressure. The remainder of MTBE was removed by adding 50 g of water and distilling off an MTBE/water mixture.Water (135 g) and sodium hydroxide solution (75 g, 49 ml, a 50% aqueous solution) were added, and the reaction solution was heated at a pressure of max. 3 bar and 105-1100C for two hours. On completion of reaction, approx. 60 ml of an MeOH/water mixture were distilled off. Thereafter, water (135 g) was added and adjusted to pH 3.0-4.0 with H2SO4 (76% aqueous solution). The solution was admixed with isopropyl acetate at 25C and the phases were separated. The organic phase was washed with 30 g of water and the solvent was removed under reduced pressure. 191 g of racemic acid were obtained as brownish liquid (92% of theory).The organic MTBE phase was extracted with water (25 g) and sodium hydroxide solution (10 g, 50% aqueous solution), and then washed with water (25 g). The combined aqueous phases contained 17 g of rac. acid (13% of theory) which can be esterified with MeOH and catalytic amounts of H2SO4.The organic phase was concentrated under reduced pressure and the residue was distilled at 170-1710C and standard pressure. 113 g of rac. ester were obtained as a colorless liquid (79% of theory).
The synthetic route of Dimethyl Isopropylmalonate has been constantly updated, and we look forward to future research findings.
Reference:
Patent; DSM FINE CHEMICALS AUSTRIA NFG GMBH & CO KG; WO2007/17018; (2007); A1;,
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