Ethyl acetoacetate cyanoacetate

The Michael Addition Reaction consists in the addition of the sodio-derivative of ethyl acetoacetate, ethyl malonate or ethyl cyanoacetate to an olefine group... 

The most convenient synthesis of 6-hydroxy-2-pyridones is by the condensation of a P-ketoester, eg, ethyl acetoacetate, with an active methylene compound, eg, malonic ester, cyanoacetic ester, and an amine. The amine can be omitted if an acetamide is used and in some cases this modification results in a higher yield. 

Ethanol, 2-(cyclohexyloxy)-, 47, 37 Ether, l butyl phenyl, 46, 89 fi-Ethoxyphenyl isothiocyanate, 46, 21 Ethyl acetoacetate, 46, 82 Ethyl benzoyloxy cyanoacetates, 46, 38 Ethyl y-bromobutyrate, 46, 42 Ethyl 2-bromocyclopentane acetate, 46, 44... 

The pyridone coupling components (4-8), which came into use in the 1960s chiefly for the preparation of greenish yellow disperse and reactive dyes, are made by the condensation of an alkylamine with ethyl acetoacetate and ethyl cyanoacetate. Coupling occurs at the position indicated by the arrow in Scheme 4-13. 

P-keto esters with a,p-unsaturated aldehydes liquidrliquid two-phase conditions [20] but, in contrast, under analogous conditions a-cyanoacetic esters produce aldol adducts with a,p-unsaturated aldehydes [20], Ethyl acetoacetate undergoes a catalysed Michael reaction addition with trans but-2-en-l,4-diones the products are generally insufficiently stable for isolation, but can be converted into furans [21 ]. 

Thiadiazolines were also obtained by a 1,5-dipolar ring reconstruction of mesoionic ylides. The bromine adduct of 2,3-diphenyltetrazolium-5-thiolate (181) reacts with the sodium salt of diethyl malonate to yield as the only product 5,5-bis(ethoxycarbonyl)-4-phenyl-2-phenylazo-2,3-dihydro-1,3,4-thiadiazole (182) (Scheme 33). The same type of product was obtained from reactions with ethyl cyanoacetate and ethyl acetoacetate <88BCJ2979>. 

The condensation of benzaldehyde with ethyl cyanoacetate, ethyl malonate and ethyl acetoacetate were carried out with high rates and selectivity promoted by lithium-, sodium, potassium-, and caesium-exchanged X and Y zeolites and on sodium-Germanium substituted faujasite. 

The results in Table 2 show that the pyridine is less active than any of the X zeolites and Ge faujasite except the lithium form which shows slightly lower activity, whereas all Y zeolites show lower activity than pyridine. Piperidine, however, is more active than any of the zeolite samples studied here. From this comparison, it appears that, most of the basic sites of the zeolites must have pK<10.3. However, the fact that zeolites are also active for catalyzing the condensation of benzaldehyde with ethyl malonate, indicate that these samples have some basic sites with pK< 13.3. On a quantitative bases, and comparing the activity of zeolites for condensation with ethyl cyanoacetate, ethyl acetoacetate and ethyl malonate (Fig. 2), we can conclude that most of the basic sites of the zeolite have pK<9.0 with a sensible amount with 9.0basic strength of different solid base catalysts. 

Ethyl acetoacetate, ethyl ethoxymethylenemalonate, ethyl acetoacetate, and ethyl cyanoacetate afford 2-(ethoxycarbonylvinylamino)-l,8-naph-thyridines (84). Some of these compounds have been successfully cyclized to pyrimido [ 1,2-u]-1,8-naphthyridines (85).4 5... 

Ethyl acetoacetate (EtOH, CH3CN/KI) Ethyl cyanoacetate Ethyl phenylacetate (EtOH, CH3CN/KI)... 

The procedure described here for compound 1 is a scaleup of a published method.6 Phase-transfer catalysis7 and concentrated alkali are used to effect a one-pot conversion of diethyl malonate to the cyclopropane diacid, which is easily obtained by crystallization. Apparently alkylation of the malonate system occurs either at the diester or monocarboxylate, monoester stage since the method fails when malonic acid itself is used as the starting material. This method of synthesizing doubly activated cyclopropanes has been extended to the preparation of 1-cyanocyclopropanecar-boxylic acid (86%) by the use of ethyl cyanoacetate and 1-acetyl-cyclopropanecarboxylic acid (69%) by use of ethyl acetoacetate.6... 

Carbon-carbon bond formation via the Michael addition of a,P-unsaturated ketone and 1,3-diketone is achieved in high yields and short times to give (61) by employing catalytic amounts of EUCI3 in dry media under microwave irradiation (Soriente et al, 1997). Ranu et al. (1997) reported the Michael addition of ethyl acetoacetate, acetyl acetone, and ethyl cyanoacetate to cycloalkenones, P-substituted enones and enal. The reaction accomplished efficiently on the surface of alumina under microwave irradiation in dry media. Baruah et al. (1997a,b) also demonstrated the BiClj and Cdl2 catalyzed solvent-free Michael addition of 1,3-dicarbonyl compounds under microwave irradiations with good yields. 

Fused thiazolopyridazinones such as 96 and 97 were obtained from anilines which were converted to phenyl diazonium salts and reacted with ethyl acetoacetate to prepare phenyl hydrazones 98 (Scheme 23). These compounds participated in a Knoevenagel-type condensation with ethyl cyanoacetate to provide pyridazinones... 

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