Alkyl- diphenylphosphine oxides

In the next part, the recent results on the addition of >P(0)H species to unsaturated substrates are summarized. The photoinduced hydropho-sphinylation of alkenes with diphenylphosphine oxide afforded substituted alkyl-diphenylphosphine oxides (Scheme 21). ... 

Zirconocene-alkene complexes reacted with chlorodiphenylphosphine to form zircono-ethylphosphine derivatives with high regioselectivity, subsequently giving p-functionalized alkyl-diphenylphosphine oxides by reaction with a variety of halides (Scheme 13) ... 

The Horner modification244,246-249 of the Wittig reaction uses substituted lithio-(dialkylaminomethyl)diphenylphosphine oxide (49, R1 = H, alkyl, aryl R2 = Me, Et, Ph NR2 = morpholino). 

The Keglevich group has continued to deal with environmentally friendly and P-heterocyclic chemistry. The solid liquid phase alkylation of P=0-functionalised CH acidic compounds was accomplished under phase transfer catalytic and microwave (MW) conditions." a-Hydroxy-benzylphosphine oxides were synthesized by the addition of diphenylphosphine oxide to the carbonyl group of substituted benzaldehydes under MW conditions." The double Kabachnik-Fields (phospha-Mannich) reaction was utilized in the preparation of bis(phosphinoxidomethyl)amines. The Diels Alder cycloadditions of 1,2-dihydrophosphinine oxides and subsequent... 

Boiling a solution of (2,2-dimethylhydrazino)diphenyl-phosphine in benzene overnight in contact with dry air causes precipitation of the oxide, (C8H5)2P(0)NHN(CH3)2 (m.p. 167 to 168°). Addition of a stoichiometric amount of sulfur to a boiling benzene solution of (2,2-dimethylhydrazino) diphenylphosphine yields, on cooling, the sulfide, (C H5)2P(S)NHN(CH3)2 (m.p. 95.5 to 97.0°). Alkylation to [(C6H5)2(CH3)PNHN(CH3)2]I (m.p. 156 to 158°) occurs upon reaction with methyl iodide in ether. Reaction with chloramine in ether yields the aminophosphonivun salt, [(C,H,)2P(NH2)NHN(CH,)2]C1 (m.p. 195°). All of the above-described derivatives are colorless solids. 

Cyclohexene oxide and its 3-hydroxy derivatives have been opened regio- and stereospecifically with phosphodiesters. The mechanism of the reaction of oxiranes with sodium dialkyl phosphite and diphenylphosphines has been studied. Cyclopropanecarboxylic acid derivatives have been obtained from substituted oxiranes with triethylphosphonoacetate anion.The mechanism of formation of isomeric alkoxyalkylacetates from oxiranes with alkyl halides and mercuric acetate has been discussed. ... 

The reactions of a number of phospholes with alkali metals have been investigated. If the temperature of the reaction is kept low, C—P bond cleavage does not occur and radical anions (identified by e.s.r. spectroscopy) are formed. Increasing the reaction temperature leads to C—P bond cleavage and the formation of metal phosphacyclopentadienides. Various alkylation reactions were carried out with these compounds. Alkali metals reduce phosphole oxides to their radical anions. The radical anions formed by electrochemical reduction of a number of 4-nitrophenyl diphenylphosphinates have been examined by e.s.r. spectroscopy and hyperconjugation invoked to explain the observed coupling of phosphorus... 

The mode of reaction of alkyl- or arylphosphonic halides with Grignard reagents in ether is most often unpredictable. Bis(p-tolyl)phenyl-phosphine oxide is reported as the major product from phenylphos-phonic dichloride and the required quantity of Grignard reagent (148). Attempted synthesis of diallylphenylphosphine oxide under similar circumstances gave only undistillable black oils and tars (13). Equimolar quantities of reactants furnished diphenylphosphinic acid in good yield plus a small quantity of triphenylphosphine oxide (45). 

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