Ethyl allyl cyanoacetate

Hydrogenolysis of the diallyl alkylmalonate 757 with formic acid in boiling dioxane affords the monocarboxylic acid 758. Allyl ethyl malonates are converted into ethyl carboxylates[471]. The malonic allyl ester TV-allylimide 759 undergoes smooth deallylation in refluxing dioxane to give the simple imide 760(472]. The allyl cyanoacetate 761 undergoes smooth decarboxylation to give... 

The preparation of malonic acid monoesters has been demonstrated using the microbial nitrilase activity of Corynebacterium nitrilophilus ATCC 21 419, Gordona terrae MA-1, or Rhodococcus rhodochrous ATCC 33 025 to hydrolyze methyl cyanoacetate, ethyl cyanoace-tate, M-propyl cyanoacetate, isopropyl cyanoacetate, M-butyl cyanoacetate, tertbutyl cyanoacetate, 2-ethylhexyl cyanoacetate, allyl cyanoacetate, and benzyl cyanoacetate [96]. By maintaining the concentration of nitrile in a reaction mixture at <5 wt%, significant inactivation of the nitrilase activity was avoided for example, a total of 25 g of M-propyl cyanoacetate was added in sequential 5g portions to a lOOmL suspension of Rhodococcus rhodochrous ATCC 33 025 cells (OD630 = 5.6) in 50 mM phosphate buffer (pH 7.0) over 30h at 25 °C to produce mono-M-propyl malonate in 100% yield (Figure 8.17). 

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. ... 

Scheme 2 shows Rapoport s synthesis [15]. The cinnamic acid derivative 3 prepared from m-methoxy benzaldehyde [20] was ethylated by diethyl sulfate to give ethyl cinnamate derivative 4, followed by Michael addition with ethyl cyanoacetate to afford compound 5. Compound 5 was converted to lactam 6 by the reduction of the cyano group and subsequent cyclization. Selective reduction of the lactam moiety of 6 was achieved by treatment with trimethy-loxonium fluorob orate followed by sodium borohydride reduction. Amine 8 was obtained by the reductive methylation of amine 7. Amine 8 was converted to compound 9 by methylene lactam rearrangement [21], followed by selenium dioxide oxidation to provide compound 10. Allylic rearrangement of compound 10 and subsequent hydrolysis gave compound 12. The construction of the decahydroisoquinoline structure began with compound 12,... 

A reaction similar to the Claisen rearrangement but involving the migration of an allyl group from one carbon atom to another has been discovered recently 23 for example, ethyl 1-cyclohexenylallylcyanoacetate (XIII) rearranges quantitatively in ten hours at 170° to ethyl (2-allyl-cydohexylidene)-cyanoacetate (XIV). 

The stereospecific conversion of cyclohexene into the corresponding amido selenide 54 is illustrated in Scheme 8. These amidoselenenylation reactions are commonly employed for the preparation of allylic and saturated amides by oxidative or reductive deselenenylation. Propionitrile, butyronitrile, benzonitrile and ethyl cyanoacetate may be used in place of acetonitrile. Styrene gave poor results and other electron-rich olefins such as 1-methylcyclohexene or 2,3-di-methylbut-2-ene did not give the amidoselenenylation products. The reaction can also be effected starting from the hydroxy- or methoxyselenenylation products of alkenes, in the presence of water and trifluoromethanesulfonic acid in this case the nitriles are used in stoichiometric amounts [48c]. This methodology was employed to prepare the amidoselenenylation products of styrene, 55, and of electron-rich olefins. It was necessary, however, to replace the phenyl-... 

Active methylene compounds such as 1,3-diketones, 1,3-keto carboxylic esters, malononitrile, and ethyl cyanoacetate were alkylated by alkyl halides catalyzed by the ionic liquid [bmim][OH] under microwave irradiation. The alkyl halides included allyl, benzyl, methyl, and butyl bromides/iodides. The open-chain 1,3-ketones produced the monoalkylated products, whereas the cyclic diketones provided the dial-kylated products in one stroke. Malononitrile and ethyl cyanoacetate also furnished the dialkylated products (Fig. 12.24) [17]. 

Grignardization of 1-butynyl magnesium bromide with acetaldehyde and subsequent treatment of the resulting alcohol with PCI5 yields 2-chloro-3-pentyne. Now, ethyl (l-methyl-2-pentynyl)-eyanoaeetate is obtained therefrom by its condensation with ethyl cyanoacetate in the presence of sodium ethylate. Further condensation of the resulting produet with allyl bromide gives rise to ethyl-(l-methyl-2-pentynyl) allylcyanoaeetate. Condensation with N-methyl urea and subsequent neutralization with NaOH produees methohexital sodium. 

In our hands, malonates, malonamide, malononitrile, Meldrum s acid, hexafluoroacetylaceton, 1,3-indanedione, ethyl cyanoacetate also failed to lead to C-glycosyl products. However, collaborating with Pr. Lubineau s team, we succeeded in replacing the 2,4-pentanedione by diketones bearing long allyl chains as described in Scheme 4, but without quantitative yields. 

A quaternary ammonium hydroxide type of anion exchange resin, Amberlite IRA-400 (OH ), is an effective catalyst for the alkylation of ethyl malonate, ethyl cyanoacetate, or cyanoacetamide with various alkyl halides.— E Molar equivalents of 2-ethylcyanoacetamide and allyl bromide stirred 2 hrs. at room temp, with Amberlite IRA-400 (OH ) in ethanol-water 2-allyl-2-ethylcyano-acetamide. Y 82%. F. e. s. K. Shimo and S. Wakamatsu, J. Org. Ghem. 28, 504 (1963). 

In an extension of previous work, it has been found that Pd(0)-catalysed intramolecular cyclization of allylic acetates (21) can be used to prepare the chrysanthemic acid analogues (22). The potentially useful cw-cyclopropane (23) can be simply obtained by base-induced addition of cyanoacetate to ethyl 2-bromo-3,3-dimethylacrylate followed by decarboxylation oddly, a similar reaction using malonate fails to give a cyclopropane. Optically pure dichloro cw-chrysanthemic acid (26) has been obtained by a Favorskii rearrangement of the chiral cyclobutanone (25) prepared from the keten (24) by sequential [2 + 2]cycloaddition, cine-rearrangement, and resolution (Scheme 3). ... 

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