Phosphonous acid derivs esters

Some new bactericidal and fungicidal derivatives of purine and pyrazolo[l,2,4]triazine have been synthesized by the reaction of 4-arylidene-2-phenyl-S-oxazolones with different nucleophilic reagents <99IJC(B)445>. A variety of pyrazolo[3,2-c][l,2,4]-triazin-3-yl 55, 59 and l,2,4-triazolo[33-c][l,2,4]-triazin-3-yl-phosphonic acid dialkyl esters 56, 60 have been synthesized from diazobetaines of pyrazoles 57 and ttiazoles 58 and monocarbanions of certain phosphonates, respectively <99H513>. 

Reaction of 4-aryl-7-iodoperhydropyrido]2,l-c][l,4]oxazin-6-ones (07USA2007/0117839, 08WOP2008/013213) and 7-iodo-6-oxo-4-(3,4,5-tri-fluorophenyl)perhydropyrido[2,l-a]pyrazine-2-carboxylate (07USA2007/ 0117839) with P(OEt)3 at 120 °C for 2 h afforded 7-phosphonic acid diethyl esters. 3-Hydroxy-6-arylperhydropyrido[2,l-c][l,4]oxazin-4-ones first were reacted with triphenylphosphonium bromide in refluxing MeCN, then with 3-methoxy-4-(4-methyl-lH-imidazol-l-yl)benzaldehyde at ambient temperature in the presence of NEt3 to provide (Z)-3- l-[3-methoxy-4-(4-methyl-lH-imidazol-l-yl)phenyl]methylidene] derivatives (07USA2007/ 0117798, 08USA2008 /0207900). 

By the alkylation of N-benzoyl uracil with the chiral 2-trityloxy-oxirane was obtained glycoside-like derivative N-[l-(2-hydroxy-3-trityloxy-propyl)-2-oxo-l,2-dihydroxypyrimidin-4-yl]-N-methylbenzamide as a single isomer. From N-[1-(2-hydroxy-3-trityloxy-propyl)-2-oxo-l,2-dihydroxypyrimidin-4-yl]-N-methylbenzamide and toluene-(4-sulfomethyl)phosphonic acid diethyl ester was prepared [2-[(benzoylmethylamino)-2-oxo-2H-pyrimidin-l-yl]-l-trityloxymethylethoxymethyljphosphonic acid diethyl ester. As a result of... 

Several guanine-based phosphonic acid derivatives have been synthesized from the phosphonic acid esters (208 a-e) and suitably... 

Diaryl methyl- and benzyl-phosphonates are conveniently prepared in high yields by heating mixtures of triaryl phosphites, methanol or benzyl alcohol, and a trace of methyl or benzyl halide. In a reaction that is usefully complementary to the previously reported formation of pyridine-2-phosphonic acid derivatives from sodium dialkyl phosphonates and //-methoxypyridinium compounds ( Organophosphorus Chemistry , Vol. 7, p. 111), N-triphenylmethylpyridinium tetrafluoroborate affords the pyridine-4-phosphonic dialkyl ester when heated with sodium dialkyl phosphonates. ... 

T.l.c.— The separation of phosphonic acid derivatives has been studied. Reports on the application of t.l.c. to the analysis and separation of nucleotides and other biologically important phosphates abound. Enzymatic reagents have been used to develop chromatograms of phosphate esters which inhibit cholinesterase. Clean, sharp-edged spots against a dark background are obtained. ... 

Moskva, V.V., Maikova, A.I., and Razumov, A.I., Phosphonic and phosphonous acid derivatives. Part 64. Reaction of phosphites and arylphosphonates with orthoacetic ester, Zh. Obshch. Khim., 39, 2451, 1969 J. Gen. Chem. (Engl. Transl.), 39, 2391, 1969. 

Scheme 18). Phosphonic acid derivatives, e.g. (149), of prostaglandins Fia and p2a have been prepared by Arbusov reactions of the corresponding prostaglandin terminal iodides. The familiar difficulty of removing both phosphorus ester groups was encountered. 

The syntheses of carbocyclic analogs of phosphononucleosides (29) and (30a-c) have been reported. Phosphonic acid (29) was obtained by introduction of the benzoylated thymine on the 2(4-hydroxycyclopent-2-enyl)ethyl phosphonic acid diisopropyl ester under Mitsunobu conditions while (30a-c) were prepared by building-up the base around a phosphono-cyclopentylamine moi-ety. The vinylphosphonate derivatives of uridine, cytidine and cytosine ara-binoside (31a-c) have been prepared by Wittig condensation of [(diethoxyphos-phinyl)methylidene]triphenylphosphorane with the appropriately protected 5-aldehydic nucleoside derivatives. Dihydroxylation of the novel vinyl phosphon-ates offered the dihydroxylated phosphonate derivatives (32a-c). Each of these novel compounds was evaluated as substrates for the enzyme nucleotide monophosphate kinase, and their toxicity to K562 cells. All analogues were found to be poorly phosphorylated by the kinase and exhibited poor in vivo toxicity. ... 

Some features of the prototropic isomerization of (1-alkenyl)phosphonic acids and their derivatives have been investigated for basic conditions. By using (halogenoalkenyl)-phosphonic esters, together with CD OD + CD O , it was shown that the speed of isomerization of (1-alkenyi)phosphonic acid derivatives e.g., (308), to the 2-alkenyl)phosphonic isomers, here (309), was faster than H/D exchange at position 3 isotope exchange occurs at position 1 in (309). The 1-alkenyl structure... 

Hydroxy-l,2,4-thiadiazoles readily form esters with phosphoric acid and its various analogs. Because of the pesticidal properties of these organo-phosphorus compounds, and their reported relatively low toxicity to warmblooded animals, a large volume of preparative work has been undertaken. The patent literature exemplifies almost the full range of possible phosphoric and phosphonic acid derivatives, and their thio analogs. For their production, a hydroxy-1,2,4-thiadiazole is condensed with the phosphoro- or phosphono-chloridic ester (426 or 429), in the presence of a base.332-336 Alternatively, a halogeno-1,2,4-thiadiazole is allowed to react with the appropriate free acid (424 or 427).337-341 The use of mercapto-l,2,4-thiadiazoles, or of the... 

As for all reactions which generate chlorophosphonium cations, in addition to furnishing phosphonic dichlorides by hydrolysis, the work-up can be modified to give other phosphonic acid derivatives and, for example, alcoholysis yields first the chloride esters, RP(0)(0R )C1, and then the diesters, RP(0)(0R )2 " -... 

The enantiomeric composition of the free (l-hydroxyalkyl)phosphonic acids, or derived diesters, may be conveniently ascertained by means of P NMR spectroscopy, through an examination of the derived and optically active a-methoxy-a-(trifluoromethyl)phenylac-etates (Mosher esters). The P chemical shift differences may be used to assign absolute configurations to the phosphonic acids or esters . 

The synthesis of phosphonic acid derivatives by the direct oxidation of those of the corresponding phosphonous acid has been afforded very little interest (Chapter 2, Section VI.c), unlike the more controllable synthesis of derivatives of the thio- or seleno-phos-phonic acid derivatives (Chapter 5, Section II.B.4). In the present instance, the oxidation of A -protected (fmoc) (l-aminoalkyl)phosphinic esters has been carried out with NaI04 with high yields. Quantitative yields of (aminoalkyl)phosphonic acids were obtained in oxidation reactions with bromine water and with HgCl2-H20. In an alternative approach (Scheme 59), the A -protected (cbz) ethyl(l-aminoalkyl)phosphinate is initially converted into a (l-aminoalkyl)phosphonous acid diester, which is then subjected to the Atherton procedure to achieve change in valence at phosphorus. ... 

The bromination of (buta-l,3-dienyl)phosphonic acid derivatives (dichloride or diethyl ester) and those of diethyl (Z)- and (. -(2-methylbuta-l,3-dienyl)phosphonates occurs across the double bond remote from phosphorus the products may subsequently be dehydrobrominated with The chlorination (with CI2 or SO2CI2) of dialkyl (2-... 

Amongst several other transformations of the alka-l,2-dienyl moiety in derived phosphonic acid derivatives, is that of the chromyl chloride-assisted conversion of the 1-ethenyl substituted esters into cyclopentenylphosphonic derivatives (equation 33) and the oxidative cyclization (using 3-chloroperoxyl nzoic acid) of the free acids to 1,2-oxaphosph(V)olan-4-ones (equation 34) ... 

Shi et al. [161-164] studied a different reaction of an array of triphenylmethane and triarylmethane derivatives such as alkanes, alkenes, alkynes, phosphonates, phosphonic acids and esters, dialkylamines, triaryl acetic acid, triaryl acetonitriles, triaryl acetates, and tetraarylmethanes and published a review of their work [65]. Mainly from product studies they proposed the special case of di-Jt-methane and oxa-di-7u-methane reactions [165], viz. a,a-elimination gives a biaryl and the corresponding carbenes and operates in polar and nonpolar sol-... 

R = H), derived from (+)-oxopinic acid, and (aminomethyl)phosphonic acid diethyl ester, was alkylated in the usual way and the products hydrolysed to give the (S)-( 1-aminoalkyl)phosphonic diesters with 15. 62, 93, and 92% e.e. for R = Me, Et. Bn. and allyl. The reaction between (347 R = Li) and diethyl vinylphosphonate gave the (lS)-(347 R = CH2CH2P02Et2) which was acidolysed ( aqueous acetic acid) to... 

Phosphorus-containing compounds provide useful substrates for ozonolysis reactions as well and can provide several products depending on the reaction workup. Several biological uses exist for -amino-a-hydroxy phosphonic acid derivatives and they can be readily prepared by ozonolysis of Al-(ethoxycarbonyl)-/3-amino-Q -methylene phosphonic esters after reductive workup with sodium borohydride (eq 54). When the reaction mixture is treated with sodium hydroxide in MeOH, an anomalous ozonolysis reaction occurs and cleavage of the methylene as well as the carbon-phosphorus bond occurs to yield (V-(ethoxycarbonyl)-a-amino methyl carboxylic esters. 

These polar phosphonic acid-derived Ru-BINAP systems were also used to catalyze the asymmetric hydrogenation of / -keto esters in ILs with complete conversions and ee values higher than those obtained from homogeneous... 

CAS 42595-45-9 EINECS/ELINCS 255-902-9 Synonyms Phosphonic acid, methyl-, bis [(5-ethyl-2-methyl-1,3,2-dioxaphosphorinan-5-yl) methyl ester, p,p -dioxide Phosphonic acid, methyl-, bis [(5-ethyl-2-methyl-2-oxido-1,3,2-dioxaphosphorinan-5-yl) methyl ester Phosphonic acid, methyl-, bis [(5-ethyl-2-methyl-2-oxido-1,3,2-dioxaphosphorinan-5-yl) methyl ester, p,p -dioxide Phosphonic acid, methyl (5-methyl-2-methyl-1,3,2-dioxaphosphorinan-5-y) ester,P,P -dioxide Classification 1,3,2-Dioxaphosphorinane, phosphonic acid deriv. 

Phosphonate esters can be readily prepared from alcohols and phosphonic acid derivatives. The selective phosphorylation of the 5 -hydroxy groups of thymidine and uridine was originally reported Mitsunobu s group in 1969. More recent examples include the modified derivative of the antitumor C-nucleoside tiazofurin (240) and an AZT triphosphate analog (241) shown... 

Similarly, l,2-phenylenebis(phosphonic acid dimethyl ester) derivatives have been obtained from differently substituted 2-pyrones and l,2-bis(phosphonic acid dimethyl ester)acetylene as the reaction partners (Scheme 16.35) [38]. 

In the following year (2012), Rao Kolia and Lee extended the reaction for the synthesis of such biologically relevant 2-amino-4//-chromen-4-ylphosphonate derivatives (35) from the one-pot three-component condensation of substituted salicylaldehydes, malononitrile (or ethylcyanoacetate) and triethylphosphite in the presence of ethyle-nediamine diacetate (EDDA) as a catalyst in alcohol under room temperature conditions (Scheme 15). Recently, Brahmachari and Laskar (2014) have also developed an energy-efficient multicomponent one-pot procedure for the facile synthesis of a wide range of diverse (2-amino-3-cyano-4/f-chromen-4-yl)phosphonic acid diethyl esters at room temperature from the reaction of salicylaldehydes, malononitrile (or ethyl cyanoacetate) and triethylphosphite on the surface of a reusable heterogeneous MgO-nanocatalyst in aqueous ethanolic... 

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