Phosphonic acid anhydrides esters

Metal ions have been shown to catalyze the hydrolysis of phosphate esters, phosphoric and phosphonic acid halides, and various phosphoric acid anhydrides including acyl phosphates, pyrophosphate derivatives, and ATP. 

Coppola, G.M., Hardtmann, G.E., and Pfister, O.R., Chemistry of 2//-3,l-bcn/.oxazinc-2,4(l//)-dione (isatoic anhydride). Part 2. Reactions with thiopseudoureas and carbanions, J. Org. Chem., 41, 825,1976. Kabachnik, M.L, Rossiiskaya, P.A., and Shepeleva, E.S., Esters of a-keto phosphonic acids. Part 3. Two types of carboxylic acid derivatives, Izv. Akad. Nauk SSSR, Ser. Khim., 163, 1947 Chem. Abstr, 42, 4132i, 1948. 

Zhang, J., and Xu, X., Total synthesis of 6-ep/-sarsolilide A, Tetrahedron Lett., 41, 941, 2000. Boehm, H.M.. I landa, S., Pattenden, G., Roberts. L.. Blake, A.J., and Li, W.-S., Cascade radical cyclizations leading lo steroid ring constructions. Regio- and stereo-chemical studies using ester- and fluoroalkene substituted polyene acyl radical intermediates.,/. Chem. Soc., Perkin Trans. 1, 3522, 2000. Hampton, A.. Sasaki, T, and Paul, B., Synthesis of 6 -cyano-6 -deoxyhomoadenosine-6 -phosphonic acid and its phosphoryl and pyrophosphoryl anhydrides and studies of their interactions with adenine nucleotide utilizing enzymes, J. Am. Chem. Soc.. 95. 4404, 1973. 

Simple derivatives of (a-hydroxyalkyl)phosphonic and analogous acids have been obtained directly by procedures analogous to those adopted for the parent compounds. Thus, O-acetates of (2,2,2-trichloro-l-hydroxyethyl)phosphonic acid esters have been prepared through the interaction of the appropriate halogenated acetaldehyde and phosphorous-acetic acid anhydrides An aromatic aldehyde and dialkyl phospho-roisocyanatidite in the presence of water or an alcohol yields analogous 0-carbamoyl derivatives of (a-hydroxybenzyl)phosphonic diesters, probably through cyclic intermedi-ates ". ... 

The Michaelis-Arbuzov reaction is unable to provide the simplest of the acylphospho-nic acids, namely (oxomethyl)phosphonic acid, the diethyl ester of which, 493, has been obtained from triethyl phosphite and formic-acetic anhydride at -10 °C at a higher temperature, decomposition sets in with the liberation of CO and formation of diethyl hydrogenphosphonate. Ensuing reactions lead ultimately to 494 ... 

The monoaminomonophosphonic acids, either in the free state or, very often, as their diethyl esters, have been resolved by the usual techniques of repeated crystallization of appropriate salts those of L-(+)-tartaric acid (2,3-dihydroxybutanedioic acid) or its mono-or di-benzoyl derivativesor of D-(-)-mandelic acid, have been widely employed the use of di-O-benzoylated L-tartaric anhydride, which is based on the separation of diastereoisomeric amides (111), has also been employed to a limited extent. In selected cases, such as the monoaminomonophosphonocarboxylic acids or A -acylated (aminoalkyl)phosphonic acids, resolution following salt formation with organic bases has also been carried out ephedrine, quinine and both enantiomers of l-phenylethylamine have all been used. In many cases, only one enantiomer of the (aminoalkyl)phosphonic acid (or diester) has been isolated in optically pure form. Sometimes, the acidity of the substrate, and hence choice of base for resolution, can be modified by using a mono- (as opposed to di-) ester or (or even in addition to) protection of the amino group as, for example, the phthalimido, benzyloxycarbonyl (cbz) or r r -butyloxycarbonyl (boc) derivative. Resolved di- and mono-esters can be hydrolysed to the free acids under acidic conditions, and A -protection can also be removed through the customary procedures. 

Another approach employs treatment of H-phosphonic acid or its monoalkyl ester with a carboxylic acid anhydride and an alcohol at 20-50 C. Dimethyl H-phosphonate is obtained according to this procedure in quantitative yield based on the starting phospho-nic acid (See Appendix) [38]. 

Amino-l-cyclohexylmethylphosphonic acid diethyl ester was utilized for the preparation of hapten 1, recently employed to induce the first monoclonal catalytic antibodies capable of catalyzing peptide bond formation[97]. The key steps of the synthesis of 1 include (a) preparation of scalemic a-aminophosphonate, (b) generation of the p-nitrobenzyl ester, (c) installation of a suitable second phosphonate ester linkage, (d) M-acylation with glutaric anhydride. 

Bis phosphonates (phosphonic anhydrides) (6.745b) can be obtained by the action of heat on some phosphonic acids (6.746), while methylene bis (phosphonates) (6.745f) with central carbon chains result from the condensation of a trialkyl phosphite with a halogenated hydrocarbon chain (6.747). Phosphorus pentachloride will convert some esters of this type into the corresponding chlorides (6.748). 

MixedPhosphona.te Esters. Unsaturated, mixed phosphonate esters have been prepared from monoesters of 1,4-cyclohexanedimethanol and unsaturated dicarboxyhc acids. Eor example, maleic anhydride reacts with this diol to form the maleate, which is treated with benzenephosphonic acid to yield an unsaturated product. These esters have been used as flame-retardant additives for thermoplastic and thermosetting resias (97). 

Synthesis of isomeric chiral protected (63 )-6-amino-hexahydro-2,7-dioxopyrazolo[l,2- ]pyrazole-l-carboxylic acid 280 is shown in Scheme 36. Crude vinyl phosphonate 275, obtained by treatment of diethyl allyloxycarbonylmethyl-phosphonate with acetic anhydride and tetramethyl diaminomethane as a formaldehyde equivalent, was used in the Michael addition to chiral 4-(f-butoxycarbonylamino)pyrazolidin-3-one 272. The Michael addition is run in dichloro-methane followed by addition of f-butyl oxalyl chloride and 2 equiv of Huning s base in the same pot to provide 276 in 58% yield. The allyl ester is deprotected using palladium catalysis to give the corresponding acid 277, which is... 

C-Acylations of C,H-acidic compounds have also been realized on insoluble supports. The few examples that have been reported include the C-acylation of support-bound ester enolates with acyl halides [9], Claisen condensations of polystyrene-bound ketones with benzoic acid esters, the C-acylation of nitriles with acyl nitriles or anhydrides, and the C-acylation of phosphonates with acyl halides (Entries 5-9, Table... 

Chlorinated paraffins, which contain up to 60-70% chlorine, are low in cost and are used as secondary plasticizer in PVC wire and cable insulations. Perchlorobicyclopentadiene has little plasticizing action and is used in polyethylene. Some of the more expensive bromine-containing fire retardants which have been used in the ratio of 5 p.p.h. in polystyrene foam, may be reduced to 0.5 p.p.h. by adding synergists such as peroxides or nitroso compounds. The reaction-type retardants, such as chlorendic acid and anhydride, hydroxy-terminated phosphonated esters, and specific brominated aliphatic esters, are admixed to rigid and flexible polyurethane foams, reinforced polyesters, phenolics, and epoxy resins. 

A different approach toward preparation of phosphinous and phosphonous iodides uses the reaction of iodoalkanes with either PI3 or PI5. This reaction is specific for iodoalkanes and phosphorus iodides and is not applicable to other halides. From the resultant highly reactive phosphinous and phosphonous iodides, the full range of the parent acid derivatives may be prepared (esters, other acid halides, anhydrides, amides). We will not be concerned here with these preparations of derivatives of the parent acids, topics that are considered in other reports. ... 

A-Phosphorylated imidazoles and benzimidazoles can be made by direct phosphorylation by halides, esters, amides, amidoesters, isocyanates, and thiocyanates of phosphorus-containing acids, or from reaction of phosphonic or phosphinic imidazolides with a sulfonic acid or anhydride <82CB1636>. Stable charge transfer complexes are produced when a 1 1 or 1 2 ratio of imidazole (or benzimidazole) and sulfur trioxide are refluxed in ether, dioxane, THE, or 1,2-dichloroethane. These complexes are stable on storage in the absence of water and have sharp melting points. Indeed, the benzimidazole SO3 complex must be boiled for five hours in water to decompose it. On fusion, the complexes form the C-sulfonic acids (see Section 3.02.5.3.3) <87CHE1084>. Sulfonyl chlorides readily A-sulfonate imidazoles <94JMC332>. 

The same phosphonate with the anhydride (138) gave the phosphonate (139 X = CN), existing as the acid (139) in the solid and as an equilibrium between (139) and the lactone (140) in solution. The corresponding product from the ester phosphonate is the lactone (140 X = C02Et) both in the solid and in solution. 

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