DIMETHYL 2-(2-NITROPHENYL)MALONATE synthesis
- Product Name:DIMETHYL 2-(2-NITROPHENYL)MALONATE
- CAS Number:26465-37-2
- Molecular formula:C11H11NO6
- Molecular Weight:253.21
Yield:26465-37-2 88%
Reaction Conditions:
with sodium hydride in tetrahydrofuran; for 16 h;Reflux;
Steps:
Dimethyl 2-(2-nitrophenyl)malonate
General procedure: A solution of dimethyl malonate (24.8mL, 0.21mol) in anhyd·THF (150mL) was cooled to 0°C and treated with NaH (8.51g, 0.21mol). The resulting suspension was then stirred at 0°C for 15min and subsequently treated with a solution of 18 (7.55mL, 0.07mol) in anhyd·THF (50mL). The reaction mixture was then heated to reflux for 16h. Upon completion, the crude reaction mixture was poured into acetic acid (100mL, 10% aq. soln. v/v) then extracted with EtOAc (3×25mL). The organic phase was subsequently washed with sat. NaHCO3 solution (2×25mL), dried (MgSO4), filtered and concentrated invacuo. Column chromatography (7% EtOAc in hexane) gave 20 (15.86g, 88%) as a pale yellow solid; Rf 0.77 (50% EtOAc in hexane); mp=59.7-63.9°C; IR (neat) υmax 3012, 2958, 2866, 1751, 1613, 1578, 1518, 1431, 1341, 1270, 1199, 1031, 794, 718cm-1; 1H NMR (CDCl3, 400MHz) δ 8.07, (dd, 1H, J=8.2, 0.9Hz, ArH), 7.66 (ddd, 1H, J=7.6, 7.6, 0.9Hz, ArH), 7.56-7.51 (m, 2H, ArH), 5.34 (s, 1H, CH), 3.81 (s, 6H, OCH3); 13C NMR (CDCl3, 100MHz) δ 167.6 (2C, C=O), 148.8 (ArCNO2), 133.6 (ArCH), 131.4 (ArCH), 129.3 (ArCH), 127.9 (ArC), 125.3 (ArCH), 54.1 (CH), 53.1 (2C, OCH3); MS (ES+) m/z calcd for C11H11NO6 [M] 253.1. Found [M+Na]+ 276.0; Anal. calcd for C11H11NO6: C, 52.18; H, 4.38; N, 5.53. Found: C, 52.03; H, 4.46; N, 5.58.
References:
Ortuzar, Natalia;Karu, Kersti;Presa, Daniela;Morais, Goreti R.;Sheldrake, Helen M.;Shnyder, Steve D.;Barnieh, Francis M.;Loadman, Paul M.;Patterson, Laurence H.;Pors, Klaus;Searcey, Mark [Bioorganic and Medicinal Chemistry,2021,vol. 40,art. no. 116167]
