Ethylene derivs., sulfur-activated

The six-membered ring 85 is obtained from the allylamine 84 [31]. The sulfur-containing ring 87 was obtained from 86 using the Mo catalyst. The Ru catalyst is not active for this reaction [32]. The (S, f )-chromene derivative 89 was obtained in 97% yield by the Mo-catalysed intramolecular metathesis of (S,f )-cycloheptenyl styrenyl ether 88 under an atmosphere of ethylene. In the absence of ethylene, 89 and its dimer were obtained. The enantioselective total synthesis of (.S, / ,/ , / )-ncbivoIoI (90) has been carried out from 89 [33]. No cyclization of the cyclopentene 91 was observed, because the highly strained cyclobutane intermediate 92 is difficult to form. 

Styrenes are available by dehydration of either a-arylethyl or /S-aryl-ethyl alcohols. The procedures were reviewed in 1S>49. /S-Phenylethyl alcohol loses water at 140° over a roixture of molten sodium and potassium hydroxides to give styrene, C,H5CH=CH2, in 57% yield. The 2,4-dimethyI derivative has been prepared in a similar manner from the primary alcohol. " Many substituted styrenes have been made by dehydration of methylarylcarbinols with potassium hydrogen sulfate, phosphorus pentoxide, or activated alumina. 1,1-Diphenyl-ethylene and 2-phenyl-2-butene are easily obtained by boiling the corresponding tertiary alcohols with dilute sulfuric acid. 

In commercial polyethylene operations, poisons may enter the process as trace (ppm) contaminants in ethylene, comonomer, hydrogen (CTA), nitrogen (used as inert gas), solvents and other raw materials. These poisons reduce catalyst activity. Most damaging are oxygen and water. However, CO, CO, alcohols, acetylenics, dienes, sulfur-containing compounds and other protic and polar contaminants can also lower catalyst performance. With the exception of CO, aluminum alkyls react with contaminants converting them to alkylaluminum derivatives that are less harmful to catalyst performance. Illustrative reactions of contaminants with triethylaluminum are provided in eq 4.9-4.11 ... 

A review has appeared on the synthesis and reactivity of (sUylamino) and (silyl-anilino)phosphines. The S5mthesis, derivatisation and coordination behaviour of the morpholine (69) and piperazine (70) derivatives have been described. They are formed from the appropriate amine with diphenylchlorophosphine, and both react with sulfur or selenium to give the chalcogenide, whilst reaction of (69) with paraformaldehyde leads to insertion of methylene into the P N bond to give the phosphine oxide. The reaction between ethylenediamine and diphenylchlorophosphine can lead to the bis-, tris- and tetrakis(diphenylphosphino)ethylene-diamines, depending upon the stoichiometry. The first two are oxidised in situ whist the latter, (71), is stable. A nickel complex of (71) has been shown to be active as a catalyst for ethylene pol5nnerisation. ... 

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