Cope cyanoacetate

The above procedure is essentially that described by Cope et al.2 Ethyl (1-phenylethylidene) cyanoacetate has been prepared also by condensing acetophenone with ethyl cyanoacetate in the presence of zinc chloride and aniline.3... 

Problem 26.4 (a) Cyclohexanone reacts with cyanoacetic ester (ethyl cyanoace-tate, N CCH2C00C2H5) in the presence of ammonium acetate to yield a product of formula CnHt502N. What is this compound, and how is it formed (This is an example of the Cope reaction. Check your answer in Problem 21.22 (g), p. 714.)... 

Cope rearrangements typically have entropies of activation of about — 10 eii. (see Table 5) and isomerization of ethyl allyl(l-ethyl-propenyl)cyanoacetate at 119°C has volumes of activation of about —7 cm. mole" in a variety of solvents. The negative entropies and volumes of activation are consistent with rate-limiting formation of a cyclic transition state which has fewer rotational degrees of freedom than the ground state. ... 

Chromic anhydride-pyridine, 70 Chromium hexacarbonyl, 71 Chromones, 423 Chromous chloride, 73 Chrysanthemic acid, 49, 50, 207-208 Chrysanthemic esters, 183-184 Cinnamic esters, 362 CitroneUol, 5, 308, 309 Claisen rearrangement, 2, 372 Clemmensen reduction, 426 Cocaine, 384 Codeine, 236, 347, 348 Conjugate addition, 86, 102, 119-120, 133, 226-227, 253, 353, 400 Cope rearrangement, 66, 397 Copper, 73-74 Copper(I) acetate, 80 Copper(II) acetate, 39, 117, 126, 186 Copper(I) bromide-Lithium trimethoxy-aluminum hydride, 80 Copper(I) bromide, 79-80 Copper(I) chloride, 50, 80-81 Copper(II) chloride, 126, 79 Copper(l) cyanoacetate, 74 Copper halide nitrosyls, 73 CopperO) iodide, 81-82 Copper(I) methyltrialkylborates, 4,75 CopperGD perchlorate. 79 COpper(I) phenylacetylide, 237 Copper(II) sulfate, 117 CopperO) trifluoiomethanesulfonate, 75-76... 

Later, the same research group [101, have reported on synthesis of two 5-bromo substituted 2-aminothiophenes 35 (Table 10) via a two-step Gewald synthesis. In a reaction of 3-trifluoromethylacetophenone (30) with either benzoylacetonitrile or ethyl cyanoacetate (31) in the presence titanium(IV) chloride [102] afforded Knoevenagel-Cope product 32. In subsequent treatment of 32 with sulfur the 2-aminothiophene core 33 is formed under basic conditions. The free C-5 position of derivative 33 is substituted with bromine in two following steps - first the free amino group is being Boc protected and then C-5 position brominated with A-bromosuccinimide (Scheme 16) [101]. 

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