Methyl polyphosphates

Me0P02 species generated in the gas phase can be trapped by N-methylaniline as the N-methyl N-phenyl phosphoramidate, while in the absence of such a reagent the major non-volatile product is methyl polyphosphate. 

Rates of solvolysis of phenyl and methyl polyphosphates in water and alcohols have been measured and the reasons for the enhanced reactivity of the former relative to the phenyl phosphorochloridate discussed. From studies on a series of substituted aryl sulphatophosphates (19) it was... 

Diaminophenanthrene (DAP) forms 2-substituted phenanthrimidazoles upon direct condensation with a carboxylic acid. The sample (in 10 il of toluene or chloroform) is mixed with 0.5 ml of a solution 2 mg ml ) of DAP in methyl polyphosphate and heated in a sealed tube at 85 °C for 3—6 min. 

Figure 12 Gradient separation of bases, nucleosides and nucleoside mono- and polyphosphates. Column 0.6 x 45 cm. Aminex A-14 (20 3 p) in the chloride form. Eluent 0.1 M 2-methyl-2-amino-l-propanol delivered in a gradient from pH 9.9-100 mM NaCl to pH 10.0-400 mM NaCl. Flow rate 100 ml/hr. Temperature 55°C. Detection UV at 254 nm. Abbreviations (Cyt) cytosine, (Cyd) cytidine, (Ado) adenosine, (Urd) uridine, (Thyd) thymidine, (Ura) uracil, (CMP) cytidine monophosphate, (Gua) guanine, (Guo) guanosine, (Xan) xanthine, (Hyp) hypoxanthine, (Ino) inosine, (Ade) adenosine, (UMP) uridine monophosphate, (CDP) cytidine diphosphate, (AMP) adenosine monophosphate, (GMP) guanosine monophosphate, (IMP) inosine monophosphate, (CTP) cytidine triphosphate, (ADP) adenosine diphosphate, (UDP) uridine monophosphate, (GDP) guanosine diphosphate, (UTP) uridine triphosphate, (ATP) adenosine triphosphate, (GTP), guanosine triphosphate. (Reproduced with permission of Elsevier Science from Floridi, A., Palmerini, C. A., and Fini, C., /. Chromatogr., 138, 203, 1977.)...

The reaction of 151 with methanol to give dimethyl phosphate (154) or with N-methylaniline to form the phosphoramidate 155 and (presumably) the pyrophosphate 156 complies with expectations. The formation of dimethyl phosphate does not constitute, however, reliable evidence for the formation of intermediate 151 since methanol can also react with polymeric metaphosphates to give dimethyl phosphate. On the other hand, reaction of polyphosphates with N-methylaniline to give 156 can be ruled out (control experiments). The formation of 156 might encourage speculations whether the reaction with N,N-diethylaniline might involve initial preferential reaction of monomeric methyl metaphosphate via interaction with the nitrogen lone pair to form a phosphoric ester amide which is cleaved to phosphates or pyrophosphates on subsequent work-up (water, methanol). Such a reaction route would at least explain the low extent of electrophilic aromatic substitution by methyl metaphosphate. 

AOPCP, a, P-methylene-adenosine diphosphate APnA, diadenosine polyphosphate (n=3-6) ARL 67156,6-N,N-diethyl-D- 3,y-dibromomethylene ATP CMTA, 2-(3-cyano-4-isobutoxyphenyl)-4-methyl-5-thiazolecarboxylic acid EHNA, erythro-9-(2-hydroxy-3-nonyl)adenine NBTI, nitrobenzylthioinosine. 

The ethyl 1-methyl-5,7-dimethoxy-4-oxo-l, 4-dihydroquinoline-3-car-boxylate was obtained in 55% yield on the cyclization of diethyl /V-methyl-/V-(3,5-dimethoxyphenyI)aminomethylenemalonate in polyphosphate at 110°C for 1.5 hr (89JMC807). 

Under acidic conditions, the formation of a nearly 1 1 mixture of 5- and 7-substituted quinoline-3-carboxylates, with a slight excess of the former, was observed from the 3-chloro- and 3-methyl derivatives. The cycliza-tions of 3-nitro, 3-trifluoromethyl, and methoxy derivatives were carried out only in polyphosphate to give mainly the 7-substituted isomers. 

V-Methyl-A/-(3-pyrrolyi)aminomethylenemalonates (893, R1 = Me) were cyclized by heating in polyphosphate at 95-100°C for 1.5-2.5 hr to afford pyrrolo[3,2-b]pyridine-6-carboxylates (895) in 50-72% yields (85JHC83). 

Flumequine was prepared when 6-fluoro-2-methyl-1,2,3,4-tertrahydro-quinoline was first reacted with alkylidene malonates and trimethyl orthoformate in THF in the presence of p-toluenesulfonic acid, and then the products, alkylidene (6-fluoro-2-methyl-1,2,3,4-tetrahydroquinolin-1 -yl) methylenemalonates, were cyclized in xylene on the action of polyphos-phoric acid or ethyl polyphosphate at 110-115°C for 1 hr (89EUP310849). 

Fig. 86. Spectrum of a 1 x ltT4 M silver sol before and after the addition of KCN plus methyl-viologen. The sol was prepared by y-irradiation of a 1 x 10 4 M AgCIO solution containing 0.5 M propanol-2,1 x 10" 5 M polyphosphate, and 0.01 M acetone (pH 6.5) [531]...

Naratriptan was also prepared using the Fischer indole reaction (Scheme 15). Thus hydrazine 43 was condensed with Al-methyl-4-piperidineacetaldehyde in aqueous HCl to form hydrazone 44. Fischer indohzation was effected by treating 44 with polyphosphate ester in refluxing CHCI3 to provide naratriptan (3) in low yield. Higher yields may be attainable with the use of milder Fischer cyclization conditions (i.e. acetic acid or aqueous HCl). 

NMO NMP Nu PPA PCC PDC phen Phth PPE PPTS Red-Al SEM Sia2BH TAS TBAF TBDMS TBDMS-C1 TBHP TCE TCNE TES Tf TFA TFAA THF THP TIPBS-C1 TIPS-C1 TMEDA TMS TMS-C1 TMS-CN Tol TosMIC TPP Tr Ts TTFA TTN N-methylmorpholine N-oxide jV-methyl-2-pyrrolidone nucleophile polyphosphoric acid pyridinium chlorochromate pyridinium dichromate 1,10-phenanthroline phthaloyl polyphosphate ester pyridinium p-toluenesulfonate sodium bis(methoxyethoxy)aluminum dihydride (3-trimethylsilylethoxy methyl disiamylborane tris(diethylamino)sulfonium tetra-n-butylammonium fluoride f-butyldimethylsilyl f-butyldimethylsilyl chloride f-butyl hydroperoxide 2,2,2-trichloroethanol tetracyanoethylene triethylsilyl triflyl (trifluoromethanesulfonyl) trifluoroacetic acid trifluoroacetic anhydride tetrahydrofuran tetrahydropyranyl 2,4,6-triisopropylbenzenesulfonyl chloride 1,3-dichloro-1,1,3,3-tetraisopropyldisiloxane tetramethylethylenediamine [ 1,2-bis(dimethylamino)ethane] trimethylsilyl trimethylsilyl chloride trimethylsilyl cyanide tolyl tosylmethyl isocyanide meso-tetraphenylporphyrin trityl (triphenylmethyl) tosyl (p-toluenesulfonyl) thallium trifluoroacetate thallium(III) nitrate... 

If RX is methyl iodide, bromide, or chloride, it may cool the flame and, consequently, reduce combustion. Further, the phosphine can be oxidized readily to the phosphine oxide. The latter reaction may lead to self-extinguishing properties either by absorption of energy to complete the reaction and/or more likely by formation of the polyphosphates and the subsequent shielding of the polymer by this thermally stable glass (19). 

Sodium polyphosphate.—Ignition of the residue left on evaporation of a solution of sodium hydroxide or carbonate with sufficient phosphoric acid gives a vitreous polyphosphate in an impure condition. It dissolves slowly in cold water, but more rapidly on warming. The solution is almost neutral to methyl-orange and to phenolphthalein. It has been found impossible to purify the substance or determine its composition, on account of its energetic action on vessels of glass, porcelain, silica, nickel, and platinum, but it probably has the formula Na4PG017.2... 

H2O and NHs from ammonium polyphosphate methyl methacrylate (major product). CO, CO2. methanol, dimethyl igj ether, hydrocarbons, high boiling chain fragments... 

Cyclodehydration Aluminum chloride see also Methyl fluorene-9-carboxylate). Dowtherm. Fluorosulfonic acid. Hydrogen fluoride. Perchloric add. Phosphorus pentoxide. Phosphoryl chloride. Polyphosphate ester. Polyphosphoric add. Potassium bisulfate. Sodium aluminum chloride. Sulfur trioxide-Dimelhylformamide. />-Toluenesulfonic acid. Trifluoroacetic acid. Trifluoroacetic anhydride. 

Nucleoside Polyphosphates. - The preparation of the phosphonate analogues of IpJ and IpsI (130) and (131) has been described. Various methods for the efficient synthesis of these compounds have been examined. The most convenient method employed tris(imidazolido)phosphate and inosine 5 -methyl-enediphosphonate, which had been prepared from 2, 3 -isopropyledeneinosine and methylenebisphosphonic dichloride. ... 

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