Phosphorous acid amide imide

Phosphorous acid, 4 55 Phosphorous acid amide imide, formation of, from phosphoryl triamide, 6 111... 

Aoids (709) 69. Imidodiphosphoric or Imidopyropbosphoric Aoid (712) 70. Amides and Imides of the Higher Phosphoric Acids (714) 71. The Meta-phosphimic Acids and their Salts (716) 72. Phosphorus Chloronitrides or Phosphonitrilic Chlorides (721) 73. Ammonia Derivatives of Thiophosphoric Acid (725). 

Figure 7.2 illustrates the phosphorus pentoxide-mediated dehydration of a primary amide to a nitrile, using the transformation of nicotine amide (A) into nicotine nitrile (B) as an example. The reaction of phosphorus pentoxide at the carboxyl oxygen furnishes the partially ring-opened iminium ion E (simplified as F) via the polycyclic iminium ion C. E is deprotonated to give the mixed anhydride G from imidic acid and phosphoric acid. Imidic acids are characterized by the functional group R-C(=NH)-OH. This anhydride is transformed into the nitrile B by an El elimination via the intermediate nitrilium salt D. Nitrilium salts are iV-pro-tonated or V-alkylated nitriles. 

Amido-derivatives of Phosphorous and Orthopbosphoric Acids—Amido- and Imido-derivatives of Metaphosphoric Acid.—Amides and Imides of Condensed Phosphoric Acids—Nitrilophosphoric Acids—Amido-, Imido- and Nitrilo-thiophosphoric Acids—Phosphorus Halonitrides or Amidohalides— Phosphorus Nitride. 

Non-acidic functional replacement analogues are named by replacing the word acid with the appropriate class name occurring earliest in the following list hydrazide, halide, azide, amide, cyanide, nitride, imide. Other replacing groups are denoted by infixes, as described earlier for acidic functional replacement analogues. The examples below are derived from phosphoric acid. 

A new peptide synthesis with adducts of phosphorous compounds and tetrahalomethanes has been reported N-(Chlorophosphoryl)pyri-dinium betaines are remarkably reactive acylating agents for the preparation of esters, amides, and peptides. They can easily be prepared from phosphorous acid or its esters, pyridine, and mercuric chloride Peptides have also been prepared through polymeric N-acoxydicar-boxylic acid imides with markedly reduced coupling times at elevated temperature (70°). The solid-phase method, first used in the synthesis of peptides, gains wider application. Recently a solid-phase Wit-tig synthesis of olefins has been published . 

A poly(inude-urea) can be synthesized in a two-stage procedure including the condensation reaction between 2-anunophenol, 2-amino thiophenol, or m-phenylenedianune and 3,5-diaminobenzoic acid in the presence of poly(phosphoric acid). Then this product is refluxed in glacial acetic acid with trimellitic anhydride to get an aromatic poly(amide-imide) with ben-zazole hetero rings. From these products, poly(imide-urea)s can be obtained by the direct polycondensation with aromatic diamines [15]. 

The neutral and acid-catalyzed hydrolyses of a series of phosphoric carboxylic imides X2P(0)NRC(0)R (28) (X = EtO, MeO, Et R = H, Me R = Me, Ph) have been compared with the behavior of related carboxylic acid and phosphoric amides, particularly in acidic conditions where the latter two systems differ greatly. In acid the carboxylic amides react slowly by attack of solvent on the oxygen-protonated form of the substrate and the phosphoric amide reacts rapidly by direct Sjv2(P) displacement via an N-protonated substrate. The acid hydrolysis of (28) lies between these two extremes with the protonation of carbonyl oxygen stabilizing the resonance structure which renders the phosphorus atom more electrophilic and the P-N bond less labile with the consequence that the reactivity of the P-N and C-N linkages become comparable. ... 

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