Phosphoramidates hydrocarbons

From phosphorus trichloride, benzyl alcohol and 2 mol. of a tertiary base, dibenzyl hydrogen phosphite (XIV), is obtained which on treatment with chlorine or a chlorinating agent (e.g. sulphuryl chloride)4 gives the phosphorochloridate (XV). Although not isolated, (XV) is almost certainly obtained by treatment of (XIV) with a polyhalogen hydrocarbon because reaction in the presence of an alcohol or of a primary or secondary amine gives a triester (XVI) or a phosphoramidate. 

Closely related to supported PTC are the so-called polymer-supported dipolar aprotic solvents [99]. These are polymers carrying strongly dipolar species which are able to solvate alkali metal cations in hydrocarbon solvents and hence function like solvents. This then activates the attendant anion so the effect overall is very similar to that of PTC. Bound phosphoramides were reported some time ago [103] and more recently bound formamides were shown to be effective [104]. Perhaps somewhat surprisingly phosphine oxide groups have now also proved to form the basis of useful polymer cosolvents [105]. This could prove to be a significant advance because the triphenylphosphine oxide residue is particularly stable and the polymeric cosolvent has been readily re-used with good retention of activity. 

The preparation of wholly aromatic sterns in halogenated hydrocarbon-salt mixtures, poly(l,4-benzamide) synthesis by thermal and suspension methods and extended chain systems, and their liquid crystal solutions have similarly been reviewed. The polycondensation of poIy(p-benzamide) chain ends has been shown to occur in the solid and liquid-crystalline state and the reactivity in the former exceeds that in the latter. Poly(l,4-phenyleneterephthalamide) and poly(chloro-l, 4-phenyleneterephthalamide) have been synthesized in hexamethyl-phosphoramide-iV-methyl-2-pyrollidooe and conditions established for the formation of liquid crystalline solutions. ... 

Benzyl alcohol at 155.4°C Tetrahydrofuran, acetone-carbon disulfide mixtures, methyl ethyl ketone Toluene, xylene, methylene chloride, ethylene chloride, perchloroethylene-acetone mixtures, 1,2-dichlorobenzene, tetrahydrofurfuryl alcohol, dioxane, acetone-oarbon disulfide mixtures, cyclopentanone, diisopropyl ketone, mesityl oxide, isophorone, dimethyl-formamide, nitrobenzene, hexamethyl-phosphoramide, tricresyl phosphate Aliphatic and aromatic hydrocarbons, vinyl chloride monomer, alcohols, glycols, aniline, acetone, carboxylic acids, acetic anhydride, esters, nitroparaffins, carbon disulfide, nonoxidizing mineral acids, concentrated alkalies... 

The first low-temperature solution processable PAs from acid chlorides were carried out in halogenated hydrocarbons. Piperazines and aliphatic or aromatic diacid based polymers were the first attempted pol)rmers. Now this is not a preferred route to synthesize wholly aromatic PAs [16]. The solvents used are polar aprotic solvents like N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), hexamethyl phosphoramide... 

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