Acid chlorides phosphine, tris

Carbon-phosphorus double bonds are also formed in addition reactions of tris(trimethylsilyl)phosphine 1692 (which can be readily prepared from white phosphorus, sodium, and TCS 14 [13a,b,c]) to give oxazohum fluorides 1691 which then give the azaphospholes 1694, via 1693 [3, 14]. On addition of 1692 to 1695, the diazaphosphole 1696 [3, 15] is prepared, whereas l,3-azaphospholo[l,2a]pyridines 1698 [16] are formed from 1692 and 1697, and 1,3-thiaphospholes 1700 are formed from the dithiohum fluorides 1699 [17]. l,3-Benzodiphospholyl anions 1703 are generated by reaction of acid chlorides with the dihthium salts 1701, via 1702 [18] (Scheme 11.3). 

Mach isolated a crystalline stericaUy uniform substance, m.p. 77-78,5 °C, identified as 4-chloro-phosphinic acid chloride 94. 1.1.1.4-Tetra-chloro-2.4.6-tri-tert-butyl-X -phosphorin 93 is assumed to be the primary chlorination product. 

Tris(trimethylsilyl)phosphine and its more reactive derivative lithium bis-(trimethylsilyl)phosphide-2tetrahydrofuran are very useful reagents for the preparation of compounds with a single or a multiple element phosphorus bond. They react readily with various element halides, with carboxylic acid chlorides, and with carboxylic esters, as well as with other organic electrophiles via a substitution of lithium and/or a cleavage of the weak polar Si-P bonds. 

Isopropyl titanium triisostearate Methacrylic acid 2-Methylacrylic acid 2-(2-oxo-imidazolidin-1-yl) ethyl ester Methyltrimethoxysilane Oleic aminoethylimidazoline PEG-3 dimethacrylate PEG-6 trimethylolpropane Pentaerythrityl-tris-(B-(N-aziridinyl) propionate Polyethylenimine Propylene/MA copolymer PVPA/A copolymer Rosin, polymerized Styrene/allyl alcohol copolymer Styrene/MA copolymer Tallowaminopropylamine Tetraisopropyl di (dioctylphosphito) titanate Triallylcyanurate Tricaprylyl methyl ammonium chloride Trimethylolpropane tris-(B-(N-aziridinyl) propionate) Tris [1-(2-methyl-aziridinyl) phosphine oxide] adhesion promoter, acrylic resins... 

Phosphonitrilic chloride Phosphoric acid amides Phosphonic acid amides Phosphinic acid amides Tris(aziridinyl) phosphine oxide... 

Geranyl chloride can be prepared from geraniol by the careful use of triphenylphosphine in carbon tetrachloride. Tris(dimethylamino)phosphine reacts with carbon tetrachloride to form the complex (42) which can be used to form the enol esters (43) from acid anhydrides. Similarly, aldehydes form the alkenes (44), and esters or amides of trichloroacetic acid are converted to glycidic esters. ... 

Methods (i) and (ii) require palladium(II) salts as reactants. Either palladium acetate, palladium chloride or lithium tetrachloropalladate(II) usually are used. These salts may also be used as catalysts in method (iii) but need to be reduced in situ to become active. The reduction usually occurs spontaneously in reactions carried out at 100 °C but may be slow or inefficient at lower temperatures. In these cases, zero valent complexes such as bis(dibenzylideneacetone)palladium(0) or tetrakis(triphenylphos-phine)palladium(O) may be used, or a reducing agent such as sodium borohydride, formic acid or hydrazine may be added to reaction mixtures containing palladium(II) salts to initiate the reactions. Triarylphosphines are usually added to the palladium catalysts in method (iii), but not in methods (i) or (ii). Normally, 2 equiv. of triphenylphosphine, or better, tri-o-tolylphosphine, are added per mol of the palladium compound. Larger amounts may be necessary in reactions where palladium metal tends to precipitate prematurely from the reaction mixtures. Large concentrations of phosphines are to be avoided, however, since they usually inhibit the reactions. 

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