Phosphinic chloride, diphenyl

By Arbusov and Related Reactions.—Details have been presented of the formation of phosphine oxides from alkyl benzoates and diphenyl-phosphinous chloride (16), although this route is not likely to be of preparative significance [see Chapter 3, Section 1, p. 52]. The sulphides (17) have been prepared from alkyl chloroacetates. Further syntheses of benzoylphosphine oxides (18) have appeared, and their dipole moments... 

The main method for obtaining these heterocycles is the interaction of amines with oxymethylphosphines. Frank and Drake (72JOC2752 77JOC4040) isolated 5-aminomethyl-l,3-diphenyl-l,3,5-diazaphosphori-nane (39) by treating tris(oxymethyl) phosphine (40) or tetrakis(oxy-methyl)phosphonium chloride (38) with aniline. The reaction with p-toluidine proceeds in a similar manner [Eq. (24)] (83IZV1379). 

Diacylphosphines may be prepared by treatment of bis(trimethylsilyl)phenyl-phosphine (65) with acid chlorides.60 A diphosphine derivative (66) is formed with benzoyl chloride.60 A series of complex reactions occurs between nitrobenzenes and diphenyl(trimethylsilyl)phosphine (67).61 The oxides noted below were the only isolable products, and the yields were not high.61... 

If the assumption of this reaction sequence is correct, the photolysis of tetraphenylphosphonium chloride must then only lead to biphenyl, diphenylphosphine, ethyl diphenyl-phosphinate and triphenylphosphine and its oxidation products. After 2 h of irradiation, biphenyl, diphenylphosphine and its oxidation products, triphenylphosphine and triphenylphosphine oxide, in a ratio of 3 1 5, along with raw material, are obtained. Ethyl diphenylphosphinate was detected in trace amounts7. These results support the postulate of the reversibility of phosphoranyl radical formation in such systems and indicate one-electron transfer processes15 in the formation and decomposition of the tetraarylphosphonium cation. This reaction is comparable to the observation of an electron transfer from halide ions to hydroxyl radicals or hydrogen atoms in aqueous solutions16,... 

Arene(tricarbonyl)chromium complexes, 19 Nickel boride, 197 to trans-alkenes Chromium(II) sulfate, 84 of anhydrides to lactones Tetrachlorotris[bis(l,4-diphenyl-phosphine)butane]diruthenium, 288 of aromatic rings Palladium catalysts, 230 Raney nickel, 265 Sodium borohydride-1,3-Dicyano-benzene, 279 of aryl halides to arenes Palladium on carbon, 230 of benzyl ethers to alcohols Palladium catalysts, 230 of carboxylic acids to aldehydes Vilsmeier reagent, 341 of epoxides to alcohols Samarium(II) iodide, 270 Sodium hydride-Sodium /-amyloxide-Nickel(II) chloride, 281 Sodium hydride-Sodium /-amyloxide-Zinc chloride, 281 of esters to alcohols Sodium borohydride, 278 of imines and related compounds Arene(tricarbonyl)chromium complexes, 19... 

Manganese(III) acetate, 171 4-Methoxy-2,2,6,6-tetramethyl-l -oxopiperidinium chloride, 183 Palladium(II) chloride-Copper(II) chloride, 235 Samarium(II) iodide, 270 Tetrachlorotris[bis(l,4-diphenyl-phosphine)butane]diruthenium, 288... 

In 1971 it was shown (1) that the interaction of diphenyl-amine and phosphorus trichloride at 210° (followed by treatment of the reaction mixture with water) yields not only the previously described phosphine oxide 1 but also the spirophospho-nium chloride 2. 

A previous description of the synthesis of (CH3)3SiP(C6H5)2 in Inorganic Syntheses1 involves the initial preparation of sodium diphenylphosphide from diphenylphosphinous chloride. This method of preparation of the diphenylphosphide anion requires rigorous conditions and long reaction times. At least two other easier methods of preparation of the diphenylphosphide anion (lithium counterion) are known. One synthesis uses diphenyl-phosphine and n-butyllithium2 as reactants, whereas the second uses triphenylphosphine and elemental lithium.3,4 The second method is described here. 

Selenolates prepared from diphenyl or dimethyl diselenide by reduction with NaBH4 smoothly transform various benzylic alcohols 24 into the corresponding selenides 25 in the presence of aluminum chloride (Scheme 30 a) [41]. AICI3 is considered to activate the alcohol substrate by coordinating to the oxygen. Similar transformations are possible by the reaction of alcohols with phenyl selenocyanate in the presence of tributyl phosphine [52]. When the selenolate is reacted with aromatic aldehydes or ketones 26 in the presence of AICI3, the corresponding benzylic selenides 27 are obtained in moderate yields (Scheme 30b) [41]. 

A new one-pot method has been developed by Kraszewski for the synthesis of aryl nucleoside phosphate (3a-p) and phosphorothioate (4a-p) diesters. This method, based on H-phosphonate chemistry, employed diphenyl phosphoroch-loridate and a series of phenols. Depending on the substituents present on the phenols, oxidation conditions were optimized to avoid competing hydrolysis. A versatile procedure that permits easy access to H-phosphonoselenoate monoesters (5) has been developed by Stawinski. These monoesters, obtained by selenisation of a phosphinate using triphenylphosphine selenide in combination with trimethylsilyl chloride, reacted with a suitable nucleoside in pyridine/acetonitrile in the presence of diphenyl phosphorochloridate to yield... 

Several reports have appeared of the application of unusual organometallic reagents in phosphine synthesis. Treatment of 2-lithiopyridine with anhydrous zinc chloride results in the formation of a 2-pyridylzinc reagent which can be used to introduce the 2-pyridyl group at phosphorus in a controlled manner. Thus, e.g., in its reaction with phenyldichlorophosphine, the 2-pyridyl-(phenyl)chlorophosphine (15) is formed. This has then been converted via the phosphide route into a new class of binucleating ligands (16). The sterically crowded dichlorophosphine (17) (accessible from the reaction of phosphorus trichloride with lithium diphenyl(2-pyridyl)methanide) is converted into the thermally stable phosphirane (18) on treatment with calcium, strontium or barium cyclooctatetraenide.The reaction of phenyldichlorophosphine with the readily accessible titanacycle (19) affords a convenient route to the phosphetene (20). ... 

FeBgCigHso, [l,l-commo-bis(2,3-dicarba-l-ferra-c/oio-heptaborane)](12),2,2, 3,3 -tetraethyI-l,l-dihydro-, 22 215 FeBrMg02PC29H4s, Magnesium, bromo(Ti -cyclopentadienyI)[l, 2-ethanediyl-bis(diphenylphosphine)]bis-(tet ahy-d ofu an)i on-, (Fe-Mg), 24 172 FeBrP2C3iH29, Iron, bromo(Ti -cyclopenta-dienyl)[l,2-ethanediylbis(diphenyl-phosphine)]-, 24 170 FeQO, Iron chloride oxide intercalate with 4-aminopyridine (4 1),22 86... 

Pd2Cl2P4C5,H44, Palladium(I), (x-carbonyl-dichlorobis[methylenebis(diphenyl-phosphine)]di-, 21 49 PrCL, Praseodymium chloride, 22 39 PrFi8Ns06Pi2C72H72, Praseodymium(III), hexakis(diphenylphosphinic amide)-, tris(hexafluorophosphate), 23 180 PrN30,3C8H,6, Praseodymium(III), trini-trato( 1,4,7,10-tetraoxacy clododecane)-, 23 151... 

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