Phosphine oxides ethylene derivatives

Fumigant -calcium cyanide as [CYANIDES] (Vol 7) -ethylene oxide as [ETHYLENE OXIDE] (Vol 9) -methyl bromide as [BROMINE COMPOUNDS] (Vol 4) -phosphine as [PHOSPHINE AND ITS DERIVATIVES] (Vol 18)... 

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. ... 

Synthesis of ethylene derivatives from 0x0 compounds and phosphonic acid esters or phosphine oxides... 

The electron-releasing phosphine promotes oxidative addition of the bromo derivative to Pd(0) and, because of its bulkiness, readily generates free coordination sites by dissociation. Ethylene coordination and insertion then occur, followed by reductive elimination, triethylamine acting as a base to neutralize hydrogen bromide. As in most cases of transition metal-catalyzed reactions the fine details of the mechanism are still under investigation. Thus recent studies by Amatore s group suggest that the palladium(O) species formed by reduction of palladium acetate is an anionic acetato complex. 

The derivatives with triethylphosphine and ethylene, styrene, stilbene, and methylstyrene have been prepared from bispentan-2,4-dionatonickel and alkylaluminum compounds in the presence of the phosphine and the olefin 200). The oxidation number of nickel in these compounds is controversial because the compounds can be considered to be either trico-ordinated nickel(O) derivatives (1) or square planar nickel(II) derivatives (2). 

A number of examples of reactions of chlorophosphines with ethylene oxide have been published. Thus the phosphines (34)—(36) are each converted into P chloroethoxy-derivatives, presumably by nucleophilic attack at phosphorus by the epoxide oxygen. 

Triarylphosphines with formyl or acetyl groups substituted into the aromatic rings can be prepared by a Grignard reaction using ethylene keta derivatives. The resulting phosphines (1) are treated with toluene-p-sulphonic acid. The acetyl derivatives may also be prepared by oxidation of the ethyl derivatives (2) followed by reduction with trichlorosilane. ... 

The catalyst-free and catalyzed addition of >P(0)H species to allenyl-and alkynylphosphine oxide was investigated. The reaction of diphenyl-allenylphosphine oxide with Ph2P(X)H was performed without solvent and catalyst. In this case, the major product was the a-methylene-ethylene(bis-phosphine) derivative, while the methyl-vinyl(bisphosphine derivative) was... 

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