Benzoyl phosphonate

Arbusov reactions have been observed with many different types of reactive halogeno compounds, e.g. with polyhalogeno-alkanes,1 esters of halogenocarboxylic acids,2 alkylaryl halides3 and certain heterocyclic halides.4 5 Acetyl chloride and benzoyl chloride react at room temperature to give esters of the corresponding acetyl and benzoyl phosphonic esters. ... 

Diethylbarbituric acid, A002 Diethyl benzoyl phosphonate, AT83 Diethyl ci s-bromobutenedioate. 

An insight into the mechanistic details of this transformation has been gained from the extensive studies of Takamizawa and co-workers. Initially, the reaction of thiamine hydrochloride (96) with diethyl benzoyl-phosphonate in the presence of sodium hydroxide was shown to give the dihydrothiazinone 97. When the reaction was carried out in AT,JV-dimethyl-formamide containing triethylamine, compound 84 (R = H) was obtained ... 

Certain 1,2,4-thiadiazoles undergo ring expansion on treatment with dialkyl acylphosphonates. Thus, the action of diethyl acetyl(or benzoyl)-phosphonates (383, R = Me, Ph) on 4-benzyl-3-methyl-l,2,4-thiadiazolium bromide (382) produces substituted 1,2,4-thiadiazines (384), albeit in low yield. The pyrimidyl analog (385, formally comparable with thiamin) behaves similarly, but a cyclization (to 387) competes with the ring expansion (to 386). The structure of these and other complex products, and the mechanism of their formation, were discussed in detail.286... 

A (l-oxoalkyl)phosphonic diester (9 R = R O), generally available through a Michaelis-Arbuzov reaction using the acyl chloride R COCl and the phosphorus(III) ester (R 0)3P, is converted into its / -toluenesulphonylhydrazone (Scheme 2), and the latter is then decomposed by the action of a base, very often simply aqueous KOH or Na2C03. The method was originally applied to esters from acetyl- and benzoyl-phosphonic acids and has since been applied to a wide range of dimethyl (l-oxoalkyl)phosphonates and also to analogous phosphinic esters (10 R = Ph or substituted phenyl)to (l-oxoalk-2-enyl) phosphonic diesters and to (3-oxoalk-l-enyl)phosphonic diesters An exception... 

Thus, clean formation of the solvate complex [Rh(L)2(S)2]" (150) where L = f-BuP((S)-binaphthoxo) existing in equilibrium with its dimer 150a (Scheme 1.36) was reported. Only very weak binding with MAC (4) or benzoyl phosphonate (73) was detected at -100°C. Nevertheless, using C... 

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... 

The 7t-extended 1,3-dithiole 237 containing a cycloproparene moiety was synthesized in the Horner-Wittig reaction involving the phosphonate carbanion derived from 235 and the benzoyl-substituted cycloproparene 236 (Equation 16) <2004EJ0138>. 

The most systematically investigated acyl anion equivalents have been the IMS ethers of aromatic and heteroaromatic aldehyde cyanohydrins, TBDMS-protected cyanohydrins, - benzoyl-protected cyanohydrins, alkoxycaibonyl-protected cyanohydrins, THP-protected cyanohydrins, ethoxyethyl-protect cyanohydrins, a-(dialkylamino)nitriles, cyanophosphates, diethyl l-(trimethylsiloxy)-phenyimethyl phosphonate and dithioacetals. Deprotonation di these masked acyl anions under the action of strong basie, usually LDA, followed by treatment with a wide varies of electrophiles is of great synthetic value. If the electrophUe is another aldehyde, a-hydroxy ketones or benzoins are formed. More recently, the acyl caibanion equivalents formed by electroreduction of oxazolium salts were found to be useful for the formation of ketones, aldehydes or a-hydroxy ketones (Scheme 4). a-Methoxyvinyl-lithium also can act as an acyl anion equivalent and can be used for the formation of a-hydroxy ketones, a-diketones, ketones, y-diketones and silyl ketones. - - ... 

Organophosphorus extractants such as di(2-ethyl-hexyl) phosphoric acid (DEHPA), 2-ethylhexyl-phosphonic acid mono-2-ethylhexyl ester (EHPA), N-benzoyl-A-phenylhydroxylamine (BPHA), and tetra-octylethylenediamine (TOEDA) are often used due to their solubility properties in the stationary organic phase [1-3]. 

A study has been made of the kinetics of epoxidation of allylphosphinates and of the addition of C-benzoyl-iV-phenylnitrone to vinyl- and allyl-phosphonates. Boron trifluoride stabilizes phosphorus(v) thiocyanates, preventing their isomerization to isothiocyanates. Cleavage of the phosphinothioic methanesulphonic anhydride (97) with aluminium halides yields the phosphinic halide with retained chirality. ... 

It has not proved possible to obtain C-alkylated products from diethyl 1-(ethoxycarbonyl )meth-ylphosphonate by the action of acetyl chloride on the alkali metal salts. However, when the ethoxymagnesium salt of diethyl l-(ethoxycarbonyl)methylphosphonate is employed, diethyl 1-ethoxycarbonyl-l-acetyhnethylphosphonate is isolated in a good yield (73%, Scheme 8.20). Similarly, diethyl 1-ethoxycarbonyl-l-benzoyhnethylphosphonate has been prepared in 56% yield from diethyl l-(ethoxycarbonyl)methylphosphonate and benzoyl chloride. The diethyl 1-lithio-1-fluoro-l-(ethoxycarbonyl)methylphosphonate generated with n-BuLi in THF reacts with acid chlorides, fluorine-substituted acid chlorides, and oxalylchloride to form the corresponding acylated phosphonates. By contrast, phosphorylation of the sodium diethyl l-(ethoxycarbonyl)meth-ylphosphonate leads to the O-phosphory lation product. The synthetically useful potassium enolate of diethyl 1,2-/ .v(ethoxycarbonyl)-2-oxocthylphosphonatc is prepared by reaction of the potassium salt of diethyl l-(ethoxycarbonyl)methylphosphonate with diethyl oxalate. ... 

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. ... 

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