Phosphines, tris amides

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

Chemical Designations - Synonyms-. APO Phosphoric acid triethileneimide Triethylenephosphor-amide Tris (1-aziridinyl) phosphin oxide Chemical Formula-. (CH2CHiN)3PO or C HjjNjPO. Observable Characteristics - Physical State (as normally shipped)-. Solid Color. > ite Odor. Data not available. 

This chapter will also deal with compounds containing two or three phosphinous amide units, which, for simpUcity, will be named here as bis(amino-phosphanes) or tris(aminophosphanes) but not with phosphinous amides containing other additional organophosphorus functionaUties as, for instance, the so-called aminophosphine phosphinites (AMMP), which have been the subject of increasing attention in the Uterature dealing with catalytic asymmetric transformations and have been treated in other reviews [2,3]. 

An alternative method for preparing phosphinous amides makes a profit on the high affinity between silicon and halogen atoms. This is the driving force of the reactions between halophosphanes and Ar-(trimethylsilyl)anilines, AT-(tri-methylsilyl)amides or AT-(trimethylsilyl)ureas and thioureas, as represented in the Scheme 6. In these processes the desired P-N bond and an halosilane are simultaneously formed [53,58-60]. 

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. ... 

The alcoholysis and transamination of various aminophosphines have been studied as functions of the basicity of the attacking nucleophile and the substituents on phosphorus. As might be expected the reaction is facilitated by electron-withdrawing groups on phosphorus. The hydrolysis of tris(dimethylamino)phosphine (90) to phosphorous acid has been investigated using thin-layer chromatography and the amides (91) and (92) have been identified as intermediates. 

A method for the preparation of 1,3,2-diazaphospholidine heterocydes has been described by Deng and Chen (Scheme 6.225) [402], The authors found that treating hindered 1,2-diamino substrates such as a-amino acid amides with tris(diethylami-no)phosphine as reagent/solvent under open-vessel microwave conditions at 250 °C for 1 min furnished a trivalent phosphorus intermediate. Subsequent thiation of this intermediate with elemental sulfur in refluxing benzene provided the target l,3,2-diazaphospholidin-4-ones in good overall yields. The yields were much improved compared to those achieved by standard thermal methods. 

Trimethylsilylimino) (trimethylsilyl) [tris(dimethylamino)phosphoranylidene] methyl phosphine (64), produced by the reaction of [(dichlorophosphanyl)methyl]tris (dimethylamino)phosphonium tetraphenylborate with sodium bis(trimethylsilyl)amide,... 

Introducing a chiral center in the amide functionality renders all 32 potential isomers diastereomeric and thus discernable (in principle) by NMR spectroscopy. In practice, the lanthanide complexes formed (Eu, Gd and Tb) with macrocyclic monoamide tris(phosphinate) ligands bearing a chiral center on the amide group exist as only two non-interconverting diastereomers in a ratio of 2 1 and 4 1 for the a-phenylethyl and a-l-napthylethyl derivatives, respectively (DOTMP-MPMeA and DOTMP-MNaphMeA) [114]. The configuration at... 

The following order of stability can be proposed amide (diglycolamides < malona-mides < monoamides (183, 199, 216)) = CMPO < HDEHP = TBP (10, 42, 77) < tri-alkylphosphonate < trialkyl phosphine oxide (308). 

When dibromodifluoromethane and tris(dimethylamino)phosphine (hexa-methylphosphorous amide) react with fluorinated ketones, the oxygen-free product Q is obtained. What is it, and how is it formed ... 

First, dibromodifluoromethane and hexamethylphosporous amide form a phosphonium salt. The intermediate thus formed reacts with tris(dimethyl-amino)phosphine to give dibromotris(dimethylamino)phosphorane and an ylide with difluoromethylene group attached to phosphorus, difluoro-methylenetris(dimethylamino)phosphorane. 

AMIDES Catecholborane. o-Nitrophenyl thiocyanate. Nitiosonium hexafluoro-phosphate. Sodium superoxide. Tri-ethoxydiiodophosphorane. Triphenyl-phosphine-Carbon tetrachloride. 

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... 

Acid amide-triphenylphosphine dihalide adducts (4) have found wide application in organic synthesis. - Synthetic equivalents are adducts (5) from acid amides and triphenylphosphine/CCU, which are prepared in situ from the educts. - With these reagents the following transformations have been performed dehydration of amides or aldoximes to nitriles, preparation of isonitriles from secondary form-amides, preparation of imidoyl halides from amides or acylhydrazines and preparation of ketene imines from amides. Using polymer-supported triphenylphosphine the work-up procedure is much easier to achieve. Triphenylphosphine can be replaced by tris(dialkylamino)phosphines. - Instead of CCI4 hexa-chloroethane, hexabromoethane or l,l,2,2-tetrabromo-l,2-dichloroethane can be used " the adducts thus formed are assumed to be more effective than those from the triphenylphosphine/CCU system. 

---