Phosphorous acid amides ethers

I Aliphatic ethers, nethvl t-butyl ether, tetramethylguanidine, hexamethyl phosphoric acid amide (trialkyleuaines)... 

A solution of 7.5 g (0.1 mol) of 1,3-propanolamine and 20.2 g of triethylamine in 100 cc of absolute dioxane is added dropwise at 25°C to 30°C while stirring well to a solution of 25.9 g (0.1 mol) of N,N-bis-(p-chloroethyl)-phosphoric acid amide dichloride in 100 cc of absolute dioxane. After the reaction is complete, the product is separated from the precipitated triethylamine hydrochloride and the filtrate is concentrated by evaporation in waterjet vacuum at 35°C. The residue is dissolved in a large amount of ether and mixed to saturation with water. The N,N-bis-(p-chloroethyl)-N,O-propylene phosphoric acid diamide crystallizes out of the ethereal solution, after it has stood for some time in a refrigerator, in the form of colorless water-soluble crystals. MP 48°C to 49°C. Yield 65% to 70% of the theoretical. 

CI3OP Noncombustible liquid. Fumes in moist air. Contact with water, steam, or alcohols produces hydrochloric acid, phosphoric acid, and phosphine gas, which is pyrophoric, with possible ignition or explosion (may be a delayed reaction). Contact with air produces corrosive fumes. Violent reaction with acetone and possibly other ketones carbon disulfide, 2,6-dimethylpyridine-A-oxide, dimethyl sulfoxide, ethers (especially when metal salts are present) ferrocene-l,l -dicarboxylie acid, pyridine, zinc powder or dust. Reacts, possibly violently, with acids, bases, amines, amides, inorganic hydroxides alkali metals, alkalis, combustible materials, dimethyl... 

In the absence of free water, pure sulfuric and phosphoric acids undergo self-ionization. Addition of water, as a proton receptor, promotes the dissociation of the acids. Polymers bearing basic sites, such as ether, alcohol, imine, amide, or... 

A synthetic route to ( )-0,f>-dimethyltubocurarine iodide (CXXV), via the racemate of 0,0-dimethylbebeerine (CXXIII), was announced in 1959 by Tolkachev and his collaborators (94). It started by the condensation of 3-methoxy-4-hydroxyphenethylamine with 4-benzyloxy-phenylacetic acid to give the amide CXXVI. Reaction of the potassium salt of the latter with the methyl ester of 3-bromo-4-methoxyphenyl-acetic acid in the presence of copper powder gave compound CXXVII. This on condensation with 3-methoxy-4-hydroxy-5-bromophenethyl-amine afforded compound CXXVIII, which was methylated to CXXIX. The latter compound was cyclized with phosphorous oxychloride to the dihydroisoquinoline derivative CXXX. Debenzylation of CXXX followed by intramolecular Ullmann condensation yielded compound CXXXI. The latter was converted to racemic dimethylbebeerine (CXXIII) by reduction with zinc dust in acetic acid followed by methyla-tion. Finally, treatment of ( + )-CXXIII with methyl iodide furnished the dimethyl ether of ( + )-tubocurarine iodide, identified by comparison of its UV-spectrum with that of the dimethyl ether of natural tubo-curarine iodide and by melting-point determination of a mixture of the two specimens. 

Phosphorylation. Chambers et al. found the reagent useful for the preparation of nucleoside diphosphoric acids (3, R —adenine, uracil, etc.). A nucleotide (I) is converted into the 5 -phosphoramidate (2) by reaction with ammonia and dicyclo-hexylcarbodiimide (DCC), and the amidate (2) is treated with dioxane diphosphate in o-chlorophenol (3 hrs..0 ). The diphosphoric acid (3) is precipitated with petroleum ether and purified as the ammonium salt. Yields are around 90%, whereas when 8.5% phosphoric add was used yields were in the order of 50-60%. However, anhydrous... 

White powder, dec 250. Sol in aqneous alkali, foimic acid. Slightly sol in hot water, DMSO. Insol in cold water, alcohol, ether, chloroform, pyridine, hexameth yl phosphor -amide. Stable against sulfuric and hydrochloric acids. [o] J + 13.5-14.5 On 2% NaOH) +19.5-21.5 On 10% NaOH). 

Surfactant alkylbenzene sulfonate, paraffin sulfonate, alkyl sulfate, ethoxylated alcohol sulfate, ethoxylated alcohol, alkanol amide fatty acid, carbamates, amine oxide, ethoxylated alcohols, betaines Builder carbonates, citrates (Tielator EDTA Alkalinity sodium hydroxide, alkanolamines, sodium carbonate Acid phosphoric, dicarboxylic (like glutaric), citric, sulfamic, acetic Solvent alcohols, glycol ether Disinfectant quaternary ammonium surfactants... 

Several chapters describe ROP of major classes of monomers such as cyclic ethers, acetals, esters, sulfides, amines, amides, oxazolines, and less common ones, like N-carboxyanhydrides (NCAs) of a-amino acids, leading to polypeptides or ROP of cyclic esters of phosphoric add allowing synthesis of the backbones of DNA. 

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