Ethyl lateral group

The reaction of copper(II) acetate with ethyl aminomethylene cyanoacetate of type H2(L22) (55) provides highly stable polymer 1Cu(L22) (56). The supra-molecular 2D geometry of 56 depends basically on the lateral groups of the chelate ligand. The two cyano donors of monomer [Cu(L22)] (57) coordinate differently, with the result that 56 is rather composed of zig-zag-lD-strands, linked among each other to give a 2D-network (Scheme 21) [167]. 

Synthesis This was in fact done by a minor variation on our strategy, the ethyl group being added later ... 

The key here is to recognize that an ethyl substituent can be introduced by Fnedel-Crafts acylation followed by a Clemmensen or Wolff-Kishner reduction step later in the syn thesis If the chlorine is introduced prior to reduction it will be directed meta to the acetyl group giving the correct substitution pattern... 

Naphtho[2,l-6]furo[2,3-c][l,2,4]triazines 198 were prepared (88JHC-1117) by the reaction of 4-5-benzocoumaran-2,3-dione with thiosemicar-bazide to give 195, whose ethylation in the presence of sodium hydroxide gave 197 via 196. Reaction of 197 with aniline gave 198 via the first displacement of the ethylthio group whose product could be isolated with a shorter reaction time. On the other hand, the similar sequence of reactions on coumaran-2,3-diones differs markedly from that of 4,5-benzocoumaran-2,3-diones, where the cyclization of 195 to 198 could not be effected. The behavior of the later dione resembles that of isatin and thianaphthenequinone (Scheme 41). 

Histories . The Na salt was first isolated by the reaction of nitric oxide on acet (Ref 2) later the same worker found that the action of nitric oxide and Na hydroxide on any compd contg the acetyl group would give Na MEDNA [compds treated were mesityl oxide, methylisopropyl ketone, acetophenone, and ethyl dimethyl-... 

One published synthesis follows strategy (b) but adds the ethyl group later by alkylation of enone (32) in the manner of TM (19). 

The combined results of kinetic studies on condensation polymerization reactions and on the degradation of various polymers by reactions which bring about chain scission demonstrate quite clearly that the chemical reactivity of a functional group does not ordinarily depend on the size of the molecule to which it is attached. Exceptions occur only when the chain is so short as to allow the specific effect of one end group on the reactivity of the other to be appreciable. Evidence from a third type of polymer reaction, namely, that in which the lateral substituents of the polymer chain undergo reaction without alteration in the degree of polymerization, also support this conclusion. The velocity of saponification of polyvinyl acetate, for example, is very nearly the same as that for ethyl acetate under the same conditions. ... 

The author also included, for a reason that will be given later, the three alcohols used in the author s laboratory by the students. We excluded ethyl malonate, which caused problems. We will not go into detail concerning calcuiations of S and group determination since these aspect were largeiy covered previously. We will not pass any judgement on the different approaches, ietting the reader be his own judge. 

Three days after Nature published Patterson s article describing industrial lead in snow and seawater, he arrived at work early in the morning as usual. Four men from the lead industry were already waiting for him in his office. Patterson wrote years later that the delegation came from the Ethyl Corporation, but Laurie Patterson remembers that the group also included representatives of the petroleum and chemical industries. In any event, Patterson regarded all four as white shirts and ties, his scornful term for corporate types. 

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