,-Unsaturated carboxylic esters have been obtained using this procedure (eq 9).Homologated ethyl esters have also been prepared by insertion of ethoxycarbonylcarbene generated by catalytic decomposition of EDA in C-H,, C-O and C-S, or Si-H bonds. Ethyl 2-alkoxyacetates have been obtained in good yield by RhII-catalyzed decomposition of EDA in the presence of various alcohols.This reagent, which is stable only below -50 °C, can be prepared by treating EDA with in THF at -115 to -78 °C. Reaction of with alkyl-, acyl-, and trialkylsilyl halides results in the formation of 2-substituted ethyl diazoesters (eq 10).,,This reagent also reacts with carbonyl compounds, forming 2-diazo-3-hydroxy esters (eq 11).,Transmetalation of ethyl lithiodiazoacetate gives access to silver, mercury, and tin derivatives of EDA.,Thermal or photochemical decomposition of EDA in benzene and its derivatives leads to the formation of cycloheptatriene esters in moderate yields., has been recently reported to be a very effective catalyst for this reaction and increased the yields of cycloheptatrienes (eq 12).In addition to methods of -keto ester synthesis described above, these compounds can be prepared by the addition of EDA to aldehydes in the presence of (eq 13).Catalytic decomposition of EDA in the presence of sulfides, tertiary amines, or iodides leads to formation of intermediate ylides which undergo Stevens rearrangement (eq 14).,, Ylides bearing an allylic double bond give the products of a [2,3]-sigmatropic rearrangement (eq 15)., has been shown to be the most useful catalyst for this transformation.
17,17-Ethylenedioxy-1,3,5(10)-estratrien-3β-ol () was converted into ethyl ester by reaction with ethyl chloroacetate in the presence of potassium. The ethyl ester on reaction with hydrazine gave hydrazide , which on condensation with aromatic aldehydes gave Schiff bases -. The reaction of Schiff bases - with chloroacetyl chloride in the presence of triethylamine afforded β-lactams -.
Rotundic acid (RA, 1) () is one of the pentacyclictriterpenoids, mainly found in , and other plants (–).RA can also be isolated from , and (–). RA and its derivatives inhibit cellgrowth. Due to its unstable nature during the metabolic processes,RA induces serious gastrointestinal adverse effects. A considerablenumber of patents on RA and its derivatives have been applied byour research group in the recent years. Our studies explored thesenovel compounds extensively and focused on reducing these adverseeffects (–). In our previous study, eight aminoacid derivatives of RA at the 28-COOH position were synthesized,and their cytotoxic properties were evaluated onthree tumor cell lines, A375 (human malignant melanoma cells),HepG2 (human hepatoma cells), and NCI-H446 (human small cell lungcancer cells) ().
Based on the natural structure of RA, six newderivatives 4a–4f were designed and synthesized in this study toimprove its bioactivity. Their structures were elucidated on thebasis of spectroscopic assays such as IR, MS, H NMR andC NMR. The cytotoxicity and antitumor effects of RAderivatives were assayed by MTT colorimetric assay with the HeLa,HepG2 and SGC-7901 cell lines. Cell cycle distribution andmeasurement of the percentage of apoptotic cells were performed byflow cytometry, following staining with propidium iodide (PI) andAnnexin V-FITC.
3-Oxo-2-arylhydrazononitriles 1a-c react readily with chloroacetonitrile, ethyl chloroacetate, and with phenacyl chloride to give 4-aminopyrazoles 4a-e. The pyrazolo[4,3-d]pyrimidine derivatives 7 and 10 are synthesized via reaction of the aminopyrazole 4b with phenylisothiocyanate and DMFDMA/NH4OAc respectively.
Ethyl chloroacetate is a reagent used in the preparation of 5 member heterocycles. It is used as pharmaceutical and organic intermediate. It is used as a solvent for organic synthesis.
Andrew J Moad; Lee J Klein; Dennis G Peters; Jonathan A Karty; James P Reilly. Catalytic reduction of ethyl chloroacetate by cobalt(I) salophen electrogenerated at vitreous carbon cathodes. Journal of Electroanalytical Chemistry. 2002, 531, (2), 163-169.