Malonic acid, monoethyl ester

The synthesis of the moxifloxacin core (de Souza, 2006 Martel et al., 1997 Seidel et al., 2000) proceeds from a Grohe-Heitzer sequence as described earlier in the chapter. Unlike the traditional Grohe-Heitzer sequence, however, the opening step involved the reaction between acid chloride 101 with the mono potassium salt of malonic acid monoethyl ester (102) in the presence of triethylamine to deliver ketoester 103 (Scheme 4.18). Treatment of 103 with ethyl orthoformate furnished acrylate 104, which reacted with cyclopropyl amine to afford 105. Cyclization of 105 in the presence of sodium fluoride in DMF gave the moxifloxicin core 106. 

Keywords aromatic aldehyde, primary amine, malonic acid monoethyl ester, Rodionov reaction, microwave irradiation, / -aryl-/ -amino acid ester, ethyl cinna-mate... 

Monoethyl malonate Malonic acid, monoethyl ester (8) Propanedioic acid, monoethyl ester (9) (1071-46-1)... 

Isobutyryl chloride (8) Propanoyl chloride, 2-methyl (9) (79-30-1) Potassium monoethylmalonate Malonic acid, monoethyl ester, potassium salt (8) Propanedioic acid, monoethyl ester, potassium salt (9) (6148-64-7)... 

In order to find amphiphilic, less hydrophilic derivatives we used various kinds of organic acids as the source of counter anions of LUC derivatives. Strong acids such as 2-bromoethanesulfonic acid and tetracyanohydroquinone readily formed LUC derivatives, BES and TCHQ in route a. On the other hand, LUC derivatives from rather weak acids such as malonic acid monoethyl ester and benzoic acid could not be purified by conventional methods. Therefore we developed a new synthetic method, route b to afford pure LUC derivatives, MA, MAE, BA, SAL, BrBA, CBA, MMT, FBA, 3,5-DABA. All of them showed characteristic absorption, fluorescence and chemiluminescence spectra of bicridinium di-cation as LUC itself. These features indicate that these derivatives are as useful chemiluminescent probes as LUC. The specific reactivity of MMT toward superoxide among ROS (02, H2O2, HCIO, OH, 02) was examined by using chemically produced ROS. It is confirmed that MMT has the specific reactivity as well as LUC. 

In their synthesis of the pyrimidine segment of the potent antitumor antibiotic bleomycin, Umezawa, Ohno and coworkers have described the reaction of highly functionalized imine (96) with malonic acid monoethyl ester to afford 3-amino ester (97 equation 16)." The low yield of (97) is largely due to elimination of the amino side chain, giving the corresponding acrylate derivative. A subsequent modification of this reaction using a boron enolate overcomes this problem and will be discussed in Section 4.1.3.2.2.ii. 

Oleic acid and Malonic acid monoethyl ester + Methanol Amberlyst-15 Petrini (1988)... 

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