Alcohols phosphonic acid ester

Sodium alcohol Phosphonic acid esters from dialkyl phosphites and ethylene derivs. 

Mixed phosphonate acid esters can also be prepared from alkylphosphonate monoesters, although here the activation is believed occur at the alcohol.57... 

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 ". ... 

There have been further applications of MesSil and MesSiBr as dealkylating agents for ethers, esters, phosphonic acid esters, and alcohols, the last reaction using McsSil being a useful alkyl iodide synthesis. MesSil also converts acetals into ketones or sulphoxides into sulphides, whilst a mixture of PhSiMes and I2 is capable of dealkylating esters at ca. 110°C. ... 

Sodium iodide Phosphonic acid esters from phosphites and alcohols... 

Excluding consideration of a multitude of representatives of solvent extraction classes (water-insoluble alcohols, ethers, acids, esters, ketones and diketones) that have been examined and found to be inadequate in some respect or another, it is the intent here to focus upon only a few representatives of just three classes of extractants (1) neutral phosphorous agents (2) monoacidic orthophosphate and phosphonate esters and (3) primary, secondary, tertiary and quaternary ammonium ion species. 

Addition of the alcohol 42 to a solution of BF3 Et20/TMSCN in DCM provided the nitrile 43 in 83% yield. Hydrolysis of nitrile 43 then furnished amide 44 in 85% yield. Demethylation of the methoxyindole 44 with BBra in DCM provided the hydroxyindole 45 in 80% yield. This was followed by alkylation of 45 with the bromide 46 under phase transfer conditions to provide the phosphonate ester 47 and subsequent cleavage of the methyl ester by TMS-I furnished trimethylsilyl phosphonic acid 48, which upon alcoholic workup afforded LY311727. 

The reaction is performed most simply by the addition of the propargylic alcohol to a solution of the phosphorus halide. Rearrangement of the phosphorus ester proceeds at ambient temperature or with mild heating. When phosphorus trihalides are used, the product can be isolated as the phosphonic dichloride.168169 Aqueous workup provides the phosphonic acid.162 In most instances, however, a dialkyl phosphorochloridite with only a single halogen on phosphorus available for reaction with alcohol has been used.165 170 174... 

A new thiol auxiliary (45, R = COEt) participates in boron-mediated anti-aldol reactions with aldehydes with high yield and de.124 Reaction of the product with (g> nucleophiles displaces it (in the form of the thiol, 45 R = H), converting the aldol product under mild conditions into esters, thiolates, phosphonates, alcohols, or acids. 

Seven-, eight-, and nine-membered heterocycles containing nitrogen, oxygen, and phosphorus atoms 288 were prepared by the reaction of phosphonic dichlorides with corresponding amino alcohols 287. Obtained esters 288 were converted into hydroxamic acids 289 upon treatment with NaOMe and 0-(trimethylsilyl)hydroxylamine <2003BMC5461>. 

Several new routes involve formation of one carbon-carbon bond in pre-formed substrates. Palladium-catalyzed cyclization of /3-hydroxyenamine derivatives has been employed in a route to substituted pyrroles and 4,5,6,7-tetrahy-droindoles with multiple substituents by formation of the C-3-C-4 bond as the key feature, as illustrated by construction of the molecule 534 (Equation 146) <2006T8533>. Zinc perchlorate-catalyzed addition of alcohols to the nitrile functionality of a-cyanomethyl-/3-ketoesters, followed by annulation gave access to a series of substituted ethyl 5-alkoxypyrrole-3-carboxylates <2007T461>. Similar chemistry has also been used for synthesis of a related set of pyrrole-3-phosphonates <2007T4156>. A study on preparation of 3,5,7-functionalized indoles by Heck cyclization of suitable A-allyl substituted 2-haloanilines has also appeared <2006S3467>. In addition, indole-3-acetic acid derivatives have been prepared by base induced annulation of 2-aminocinnamic acid esters (available for instance from 2-iodoani-lines) <2006OL4473>. 

The principally practicable route to allyl vinyl ethers by alkenation of allyl formates, has not yet been exploited in this context. In another approach, the nucleophilic addition of allylic alcohols to alkynic esters, one observes the exclusive formation of franr-enol ethers 2 the stereochemical information is lost, however, after the rearrangement, due to enolization of the formed formylacetic acid derivatives. On the other hand the nucleophilic addition of allyl alcohols to acceptor-substituted allenes like allenic sul-fones or phosphonates offers a novel route with fascinating potential. " Such systems that are readily... 

Reports of examples of arylphosphonates include those of water-soluble phosphinic-polyphosphonic acids, e.g. 132, and the phosphonate 133 which when coupled to alcohols, to give e.g. 134, act as linkers to proteins in experiments intended to generate antibodies to catalyse cationic cyclisation reactions.Novel water-soluble phosphonate-substituted phthalocyanines have been prepared.The phosphonate esters 135 are insoluble in water but can be hydrolysed by hydrochloric acid to give the water-soluble phosphonic acids 136. Aromatic phosphonate-phosphines 137, and their air-stable complexes, have been obtained from the reaction of 4-halogeno-substituted phenylphosphonates with lithium diphenylphosphide. ... 

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. ... 

The prototypical representatives of the group are the carboxylic acids. However, a huge number of bioisosteres such as sulfonic or phosphonic acids, tetrazoles or 3-hydrox-yisoxazoles are available (see Chapter 15). In addition functions like esters, amides, peptides, aldehydes, primary alcohols and related functions can work as prodrugs or bioprecursors (see Chapter 36). 

Optically active phosphorus(iii) acid esters PhR P (OR ) have recently been prepared for the first time by the reaction of a chiral phosphorus chloride and an alcohol or thiol in the presence of an optically active amine, in this case (-)-NN-dimethyl-(l-phenylethyl)amine. (See also Refs. 449 and 450). A kinetic investigation shows that phosphorous acid and chloral react to give 2,2,2-trichloro-l-hydroxyethyl phosphonate at a much lower rate than the corresponding reaction with dimethyl hydrogen phosphite. Phosphorus trichloride and dialkyl phosphites (R0)2P(0)H have been shown to react at low temperature in the presence of pyridine, producing tris(dialkoxyphosphoryl)phosphines [(RO)2P(0)]3P. ... 

Beilstein Handbook Reference) BRN 1099706 Butyl alcohol, hydrogen phosphite Butyl phosphonate ((BuO)aHPO) Di-n-butyi hydrogen phos-phite Dibutoxyphosphine oxide Dibutyl hydrogen phosphite Dibutyl hydrogen phosphonate Dibu l phosphite Dibutyl phosphonate Dibutylfosfit EINECS 217-316-1 HSDB 2597 Mobil DBHP NSC 2668 Phosphonic acid, dibutyl ester Phosphorous acid, dibutyl ester Syn-O-M P-316. Used as amine salts in mineral and synthetic base stocks as load-carrying additives with secondary activity as low-temperature stabilizers and metal deactivators. Liquid bpii = 118-119" d = 0.9950. Akzo Chemie. 

General method for preparation of diphenyl esters of Gong-chain alkyl)phosphonic acids Equivalent amounts of the alcohol and triphenyl phosphite, together with 10 moles-% of sodium iodide, are placed in a flaskfitted with a thermometer, gas-inlet tube, stirrer, and distillation head water at about 50° is circulated through the attached condenser to prevent crystallization of the phenol. Nitrogen is led into the flask while the mixture is heated at the required temperature by a radiant heater until no more phenol distils (about 20 h). The remaining material is distilled at < 0.05 mm and the distillate is taken up in ether. The ethereal solution is washed with 2N-sodium hydroxide solution, dried and evaporated, and the residue is redistilled. 

Further esterification of monobenzyl benzylphosphonate may be carried through the Mitsunobu procedure, the best yields being achieved using the potassium salt of the substrate. Monoesters of iV-protected (1-aminoalkyl)phosphonic acids are further esterified by alcohols in the presence of BOP-type reagents [(l-aminoalkyl)alkylj- and [(l-aminoalkyl)aryl]-phosphinic acids, again as their potassium salts, have been converted into esters by reactive alkyl halides in the presence of 18-crown-6 ether (see also reference The... 

Other Studies. - The P NMR chemical shifts of alcohols, carboxylic acids and phenols phosphitylated with 2-chloro-4,4,5,5-tetramethyl-dioxaphospholane have been correlated with substituent effects of phenols. P NMR spectroscopy has also been used to study activation pathways of aryl H-phosphonate ester condensation reactions, the conversion of allenyl and divinyl phosphines to 1- and 2-phosphadienes, the reaction of tetraphosphorus decasulfide with dialkyl disulfides, the reaction of phosphine with cyclic olefins, the chemical shift tensors of powder samples of phosphole derivatives, the reactions of alcohols and mercaptans with tetraphosphorus trichalcogen diiodides, the structure of aminomethanebisphosphonic acids, and reactions of 00-di-(2-ethylhexyl)dithiophosphoric acids. ... 

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