Diphenylphosphinous acid synthesis

Phenyllead(IV) azides, synthesis 15 Tetraphosphorus hexamethylhexaimide, synthesis 16 Diphenyl phosphorochloridite, synthesis 17 Diphenylphosphinic acid, synthesis 18 (2,2-Dimethylhydrazino)diphenylphosphine, synthesis 19 Alkoxy- and aryloxycyclophosphazenes, synthesis 20 Mercapto derivatives of chlorocyclophosphazencs, synthesis 21 Dialkylsulfamoyl chlorides, synthesis 27 N- and J T,A1 -Substituted sulfamides, synthesis 28 Dialkylamides of (trichlorophosphoranylidene)sulfamic acid, synthesis 29... 

The initial 2-iodopropyolanilides are rather inaccessible compounds. Their preparation requires a three-stage synthesis with diphenylphosphinic acid azide as the starting material. 

Peptides. A new amide or peptide synthesis is based on the formation of iminophosphoranes, R N=PR3, from the reaction of azides with a tertiary phosphine. These phosphoranes react with carboxylic acids to form amides.1 Ethyl diphenylphosphinite is more useful than a triarylphosphine because the by-product is hydrolyzed to diphenylphosphinic acid, which can be readily removed. The iminophosphorane 2, derived from 1 and ethyl azidoacetate, reacts with CboGly-L-Phe-OH to give optically pure 3 in 70% yield.2... 

Several publications have been devoted to the synthesis of phosphorylated derivatives of pyrrole by cyclization and condensation reactions. Diphenylphosphinylaminopyrroles 176 were obtained [193] by the cyclization of dicarbonyl compounds in the presence of diphenylphosphinous acid hydrazide ... 

Bernasconi, S. Comini, A. Corbella, A. Gariboldi, M. S., Activation of 2-Alkenoic Acids as Mixed Anhydrides with Diphenylphosphinic Acid for the Formation of Carboxamides. Synthesis 1980, 385. 

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). 

Diphenyl-(a-naphthylmethyl) phosphine oxide and K-ferf-butoxide in toluene stirred 1 hr. with exclusion of air and moisture, heated to 70°, styrene oxide in toluene added dropwise, refluxed 12 hrs., and treated with water l-phenyl-2-a-naphthylcyclopropane (Y 62.5%) and diphenylphosphinic acid (Y 90%). F. e. and method, also synthesis of the intermediate y-hydroxy-phosphine oxides with phenyllithium in high yields, s. L. Horner, H. Hoffmann, and V. G. Toscano, B. 95, 536 (1962). 

In the multi-step total synthesis of Herboxidiene methyl ester, one step involved an Arhuzov reaction of an allyl bromide with the ethyl ester of diphenylphosphinous acid (Scheme 6)7... 

Han L-B, Zhao Ch-Q, Tanaka M (2001) Rhodium-catalyzed regio- and stereoselective addition of diphenylphosphine oxide to alkynes. J Org Chem 66 5929-5932 Hua R, Tanaka M (1998) Ruthenium-catalyzed addition reaction of diphenylphosphinic acid to terminal alkynes regioselective synthesis of alkenyl diphenylphosphinates. Chem Lett 27 431-432... 

The application of / -(diphenylphosphinyl)benzenesulphonic acid (58) to the synthesis of esters of amino-acids has made the work-up much simpler, since the resultant oxide is water-soluble. Diphenylphosphinyl isocyanate (59) can be prepared from diphenylphosphinic amide. 

The previous extension of solvent mixtures involved solvent interfaces. This organic-water interfacial technique has been successfully extended to the synthesis of phenylacetic and phenylenediacetic acids based on the use of surface-active palla-dium-(4-dimethylaminophenyl)diphenylphosphine complex in conjunction with dode-cyl sodium sulfate to effect the carbonylation of benzyl chloride and dichloro-p-xylene in a toluene-aqueous sodium hydroxide mixture. The product yields at 60°C and 1 atm are essentially quantitative based on the substrate conversions, although carbon monoxide also undergoes a slow hydrolysis reaction along with the carbonylation reactions. The side reaction produces formic acid and is catalyzed by aqueous base but not by palladium. The phosphine ligand is stable to the carbonylation reactions and the palladium can be recovered quantitatively as a compact emulsion between the organic and aqueous phases after the reaction, but the catalytic activity of the recovered palladium is about a third of its initial activity due to product inhibition (Zhong et al., 1996). 

A new acyl anion equivalent derived from an aldehyde, a secondary amine and diphenylalkylphos-phine oxide, e.g. (N-morpholinomethyl)diphenylphosphine oxide, reacts with aldehydes or ketones to form enamines, which on acid hydrolysis afford aldehydes or ketones (Scheme 32). The usefulness of this acyl anion equivalent is demonstrated by the synthesis of dihydrojasmone and (Z)-6-henicosen-11-one. ... 

Uses of Phosphonic and Phosphinic Acid Derivatives -Analogues of Lawesson s reagent have been employed in the preparation of thiopeptides and the diphenylphosphinothioyl group protects tryptophane during peptide synthesis.Diphenylphosphinic chloride assists in the formation of 3-lactams from 249... 

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