Ethyl cyanocinnamate

The catalytic performance of the functionalized MIL-101 was evaluated in the condensation of benzaldehyde and ethyl cyanoacetate in cyclohexane as solvent at 80 °C. A high conversion was obtained with all the ED-, DETA-, and APS-MIL-101 MOF catalysts having a high selectivity for traws-ethyl cyanocinnamate (turnover... 

Another resonance-stabilized intramolecular phosphonium salt (11), the addition product of ethyl 2-cyanocinnamate with triethyl phosphonate, yields after irradiation in cyclohexane solution ethyl 2-cyano-3-diethoxyphosphinyl-3-phenylpropanoate (12) and ethylene (13) (equation 7)35. The structure of 12 was confirmed by IR spectra and an independent synthesis from corresponding reactants. 

Heck Olefination of Aryl Bromides According to Spencer Synthesis of Ethyl 4-Cyanocinnamate[18]... 

Hybrid organic/mineral solid base catalysts bearing primary and tertiary amino functions have been used as catalysts in the Knoevenagel condensation of benzaldehyde and ethyl cyanoacetate at 375 K in the presence of DMSO as solvent. Both catalysts exhibited a selectivity of approximately 100 % in ethyl trans-a-cyanocinnamate and could be recycled several times, after filtration and washing, without decrease in their catalytic performance.11711 The activity was found to be... 

Sometimes, the alkaline condition of the addition reaction is sufficiently strong to cause hydrolysis of the ester group but not of the cyano groups. Decarboxylation rhen occurs to give a dicyanide, as in the preparation of phenylsuccinonitrile from ethyl a-cyanocinnamate. ° ... 

Japanese workers were the first to use the reactive properties of nitrile compounds to synthesize thiazolo[3,2-a]pyridin-3(2//)-ones (77S839). Ethyl a-cyanocinnamate (88, R = Ph, R = CO Et) reacts with ethyl mer-captoacetate in the presence of triethylamine to give 5-amino-2-benzyli-dene-6,8-bis (ethoxycarbonyl )-7-phenyl-7//-thiazolo [3,2-n]pyridin-3(2//)-one (89, R = R- = Ph, R = R = C02Et), which is also obtained from the reaction of 5-benzylidene-2-ethoxycarbonylmethyl-2-thiazolin-4-one (90a) with ehtyl a-cyanocinnamate (77S839). Reaction of 90a,b with ben-zylidenemalononitrile (88, R- = Ph, R" = CN) and of 90c with ethyl a-cyanocinnamate furnish the respective bicyclic compounds 89 [83ZN(B)781] (Scheme 21). Similar results were also obtained from 88 (R = furan-2-yl-or thiophen-2-yl) (86M105). 

C12H10N2O2 4-(4-nitrobenzyl)pyridine 1083-48-3 588.65 52.464 2 23637 C12H11N02 ethyl trans-a-cyanocinnamate 2169-69-9 388.45 33.278 2... 

Chiral ( >2-cyanocinnamates 16 bearing ethyl (.S i-lactate and (7 )-pantolactone as the chiral auxiliary are very efficient dienophiles in the asymmetric Dicls-Alder reaction with cyclopentadiene, opening up a route to the synthesis of cycloaliphatic atnino acids96. 

The catalytic performance of the NCNT was tested via the Knoevenagel condensation of benzaldehyde (BA) with ethylcyanoacetate (ECA) to form ethyl-a-cyanocinnamate (ECC). The NCNT (1 g) were crushed, heated to 423 K under vacuum and maintained under these conditions for 1 h. The reactants, BA (0.01 mol) and ECA (0.01 mol), were dissolved in ethanol (50 mL) and carbondioxide was removed using the freeze-thaw method. The solution was then added to the NCNT and the reaction was performed under reflux conditions. To monitor the progress of the reaction, samples of the reaction mixture were taken regularly for GC analysis. 

Another example of metathesis of olefins bearing functional groups at the a-position is the cross-metathesis of tetracyanoethene with ethyl a-cyanocinnamate to give l,l-dicyano-2-phenylethene and ethyl 2,3,3-tricyanopropenoate, eqn. (23), in the presence of certain rhenium(I)enolate complexes at 20°C (Hirano 1994). 

A microfluidic reaction system has also been used for the production of prodrugs. A multichannel membrane microreactor was fabricated and tested for Knoevenagel condensation of benzaldehyde and ethyl cyanoacetate to produce a-cyanocinnamic acid ethyl ester, a known intermediate for the production of an antihypertensive drug [9]. Knoevenagel condensations of carbonylic coiiqtounds and malonic esters yield several important key products such as nitriles used in anionic polymerization, and the a,p-unsaturated ester intermediates employed in the synthesis of several therapeutic drugs that include niphendip-ine and nitrendipine. Unlike most condensation reactions. 

Cyano-esters. The most common example is cyanoacetic ester (ethyl cyanoacetate). It is a pseudo-acidic liquid substance, insoluble in water but soluble in alkalis. By virtue of its activated methylene group it undergoes the Knoevenagel reaction. Warm 2 ml each of benzaldehyde and the ester with two drops of morpholine (or piperidine) under reflux for 10 minutes. Cool, break up any lumps, wash with a little alcohol and recrystallize the product from alcohol (ethyl a-cyanocinnamate, m.p. 51°). 

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