Ethyl a-cyanoacrylate

Among Michael acceptors that have been shown to react with ketone and ester enolates under kinetic conditions are methyl a-trimethylsilylvinyl ketone,295 methyl a-methylthioacrylate,296 methyl methylthiovinyl sulfoxide,297 and ethyl a-cyanoacrylate.298 Each of these acceptors benefits from a second anion-stabilizing substituent. The latter class of acceptors has been found to be capable of generating contiguous quaternary carbon centers. 

Surprisingly, a-cyanoacrylic acid is reported to react spontaneously with triethylsilane in the absence of any additional acid to give a quantitative yield of the triethylsilyl ester of a-cyanopropionic acid.236 Ethyl a-cyanoacrylate requires the presence of trifluoroacetic acid to undergo reduction to ethyl 2-cyanopropionate.236 Many of these reductions are highly stereoselective. For example, treatment of... 

POLY (ETHYL a - CYANOACRYLATE -CO-ETHYL a -CARBOXAMIDO ACRYLATE) (9 1) (FMR-E101 (FUJI CHEMICAL)) CN CONH- I I CH c-CH.-C-2 I I COOC2H5 COOC2H5 2 X 1 05 1.5 54... 

CYANON 5MSP CYANON S DA 737S 910EM ETHYL a-CYANOACRYLATE ETHYL 2-CYANO-ACRYLATE ETHYL 2-CYANO-2-PROPENOATE N 135 2-PROPENOIC ACID, 2-CYANO-, ETHYL ESTER PTR-E 3 PTR-E 40 SICOMET 8400 SUPER 3-1000 SUPER GLUE TK 200 TK 201... 

The latest vinylferrocene monomer / -C5H4CH202CC(CH3) = CH2 rj -C5H4CH = C(CN)C02Et Fe 15 that undergoes radical polymerization has been prepared as shown in Scheme 10-3 [17] Copolymerization of the monomer with methyl methacrylate produced copolymer 16, via radical initiation using AIBN in benzene. The ethyl a-cyanoacrylate moiety on the ferrocene remained intact through the polymerization process. The thermal behavior of 16 was similar to that of polymethyl methacrylate glass transition temperature, 7 120 °C, melt transition... 

Cyclopropanation via the 3-halo-l,4-zwitterion 394 is observed when l,l-diethoxy-2-bromoethylene (392) reacts with ethyl a-cyanoacrylate (393) to form diethyl l-cyano-1,2-cyclopropanedicarboxylate (395). The initially formed zwitterion 394 undergoes intramolecular displacement of the bromide ion to form the dialkoxycarbenium ion, which in turn undergoes dealkylation to yield the cyclopropane 395 (equation 131) ... 

Finally, a unusual MIRC reaction should also be discussed, where 2-bromo-l,l-diethoxyethene reacts with ethyl a-cyanoacrylate at 0 °C over one hour to form diethyl 1 -cyanocyclopropane-1,2-dicarboxylate 12. The reaction proceeds via the initially formed 3-halo-l,4-zwitterion. 

Recent work has shown that a similar strategy, using a ferrocene —> ethyl a-cyanoacrylate CTTS excitation, can be... 

It was argued that the MLCT excited state has a change in hapticity (from if to rf), and this facilitates solvent attack on the Fe center, leading to loss of a CpR ligand. The anion thus produced efficiently initiates the anionic polymerization of ethyl a-cyanoacrylate. It was likewise shown that cationic polymerizations could be initiated by LF excitation of CpFe( 7 -arene) complexes. 

Ethyl a-cyanoacrylate Ethyl 2-cyano-2-propenoate 2-Propenoic acid, 2-cyano-, ethyl ester... 

Kutal et reviewed the chemistry of several iron (II) metallocenes that are effective photoinitiators for ionic polymerization reactions. Photoexcitation of ferrocene and 1,1-dibenzoyl -ferrocenes in solutions of ethyl-a-cyanoacrylate produces anionic species that initiate the polymerization of electrophilic monomers. Irradiation of CsHs-Fe (t] - arene) in epoxide containing media generates several cationic species capable of initiating ringopening polymerizations. It was concluded that iron(II) metallocenes exhibit a diversity of photoinitiation mechanisms. 

Alvoddinov,.A. (1982) Study of the kinetics of polymerisation of Ethyl-a-cyanoacrylate. Dokl. Akad. Nauk. Uzb. SSJl 7, 41-43. 

YAM 07], For example, they have reported the implementation of the Pt(acac)2 complex toward the photoinitiated anionic polymerization of ethyl-a-cyanoacrylate (ECA) [PAL 95], It is understood that the initiating species were free acetylacetonate anions freed by UV excitation of the complex (Diagram 3.14). 

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