Diisopropyl malonate

Carbon Monoxide Process. This process involves the insertion of carbon monoxide [630-08-0] into a chloroacetate. According to the hterature (34) in the first step ethyl chloroacetate [105-39-5] reacts with carbon monoxide in ethanol [64-17-5] in the presence of dicobalt octacarbonyl [15226-74-1], Co2(CO)g, at typical temperature of 100°C under a pressure of 1800 kPa (18 bars) and at pH 5.7. Upon completion of the reaction the sodium chloride formed is separated along with the catalyst. The ethanol, as well as the low boiling point components, is distilled and the nonconverted ethyl chloroacetate recovered through distillation in a further column. The cmde diethyl malonate obtained is further purified by redistillation. This process also apphes for dimethyl malonate and diisopropyl malonate. 

Diisopropyl Malonate. This dialkyl malonate has gained industrial importance for the synthesis of the fungicide dialkyl malonate... 

Lithium tetrahydroaluminate, Tetrahydrofuran, 0075 Peroxyacetic acid, Ether solvents, 0837 f 2-Propen-l-ol, Sulfuric acid 1.42/53, 1223 Sulfinyl chloride, Diisopropyl malonate, 4096... 

Diisopropyl Malonate. This dialkyl malonate has gained industrial importance lor the synthesis of the fungicide isoprolhiolnne through condensation with carbon disulfide and ethylene dichloride. Diisopropyl malonate is produced b> Miisuhishi Chemical (Japan) using the carbon monoxide process. 

Sulfinyl chloride, Diisopropyl malonate, 4090 See PEROXIDES IN SOLVENTS, PEROXIDISABLE COMPOUNDS See related UNIT PROCESS OR UNIT OPERATION INCIDENTS... 

A catalytic enantioselective Michael addition of diisopropyl malonate to a,p-unsaturated ketones and aldehydes has been achieved using 5 mol% of the... 

Under an argon atmosphere, a mixture of 1.30 mL diisopropyl malonate (6.72 mmol), 0.50 mL 2-cycloheptenone (4.48 mmol), and 46 mg L-proline rubidium salt (0.22 mmol) in 5 mL chloroform was stirred for 59 h at 25°C. The reaction was quenched with 2 M HCl, and organic materials were extracted twice with EtOAc. The combined extracts were washed with brine, dried over Na2S04, filtered, concentrated, and flash chromatographed over silica gel to give 1.21 g diisopropyl (7 )-(+)-(3-oxocycloheptyl)malonate, in a yield of 91%, and 59% e.e. 

Scheme 2.3 Asymmetric oxidative Mannich-type reaction of diisopropyl malonate reported by Sodeoka.

Yamaguchi and co-workers reported on an important breakthrough in the asymmetric Michael addition of malonate to enone catalyzed by proline lithium salt in 1993. They found that diisopropyl malonate reacted with a series of enones affording the Michael adducts in 51-91% yield with 35-77% ee. The level of asymmetric induction was effected obviously by both enone and malonate partners. 

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