Phosphorus-containing phosphoryl

Chlorination at the position of the side chain is probably the result of phosphorylation of the intermediate vinyl chlorides followed by degradation of the phosphorus-containing products (72ZOB802). 

These phosphorus-containing PAN derivatives are unstable under hydrolytic conditions, and the phosphoryl groups are easily split off under the action of boiling water. If, however, the modified PAN is treated with dimethyl phosphite solution in toluene in the presence of dimethylamine, a modified PAN, stable towards hydrolysis, is obtained. Its composition seems to be the following ... 

The following sections deal with a variety of rather complex syntheses using different versions of phosphorylations by azolides. The syntheses described here are selected primarily not for their specific practical applications but to show the versatility of the azolide method in synthesizing very complicated phosphorus-containing structures. 

In the phosphoryl fullerenyl radical the unpaired electron is - similar to the alkylfullerenyl radical - delocalized over two six-membered rings adjacent to the C-P bond [10]. The rotation barrier for the radical C5oP(0)(0 Pr)2 was determined to be 4.8 kcal mol Another phosphorus-containing radical fullerenyl adduct, determined via ESR spectroscopy, is PFjjO BujCgQ. It can be obtained by photolytic reaction of Cgo with HPF4 and tert-butylperoxide in tert-butylbenzene [43]. 

Analogues of (751) react with derivatives of phosphorus-containing acids to form 1-phosphoryl-imidazoles (90CHE599). The same compound also silylates ketones to give enol silyl ethers and/or siloxyalkylimidazoles (Scheme 107) (87JC271). 

Phosphorus-containing macrocycles, 990, 996, 998 macrocychc effect, 1002 ring size, 1003 stereochemistry, 1003 Phosphorus heterocycles transition metal complexes, 1041 Phosphorus ligands, 989-1061 ir-acid series, 1033 bonding, 1030-1041 cone angle concept, 1012 trigonal bipyramidal complexes, 1036 Phosphorus oxychloride metal complexes, 500 Phosphorus ylides transition metal complexes, 1056 Phosphorylation biological, 978 Phosvitin, 975 Photochromism... 

In 1978 Cohn and Hu (1) demonstrated the isotopic effect by 180 on the Ip-nmr spectrum of inorganic phosphate. For each that replaces an 1 0, an upfield shift of 0.021 ppm results. Thus the chemical shift for HP O 58 is 0.084 ppm downfield from Hpl 04=. Based on this observation it is obvious that any chemical event that potentially involves substitution or exchange of an 0 for 16() in phosphorus containing compounds can be followed by monitoring the Ip-nmr spectrum throughout the course of the reaction. This article describes experiments from my laboratory on two enzymes that catalyze phosphoryl transfer reactions and our use of the [1 0/1 0] lp-nmr methodology to detect intermediates in the enzymic reactions. 

The synthesis of indoles by the Fischer method has been the subject of a review, where phosphorus trichloride and polyphosphoric acid were used as cyclizing agents [6], Although the first publication on the synthesis of phosphorus-containing indoles appeared in 1930 [7], reviews on this subject are few. The treatment of the subject in [8] was fragmentary, while the review [9] covered the literature up to 1975. It is also possible to mention [10], which was devoted to the phosphorylation of pyrrole and its carbonyl derivatives. 

In the search for biologically active compounds a method was proposed [143] for the synthesis of phosphorus-containing hydrazones of 3-formylindole 147. Here hydrazides of diphenylphosphorylcarboxylic acids, which possess high biological activity [144], were used as phosphorylating agents. 

The cyclization of the phosphorylated arylhydrazones, leading to compounds 168, presumably takes place through the initial formation of 3-phosphorylated indoles 69, which isomerize to compounds 168 in the course of the reaction. Such 3—>2 rearrangements are well-known [30, 180-182, 231]. The transposition of the phosphorus-containing substituent in indoles was first observed in [178, 179]. In the review [8] the data on the formation of 2-phosphorylindoles from the arylhydrazones of phosphorylpropionic aldehyde were considered proved, but the results on the cyclization of hydrazones of phosphorylacetaldehyde to the 2-isomers were placed under some doubt. 

However, two other areas are of interest (Fig. 9) namely, a) derivatisation of phenols or amines to phosphorus-containing compounds and b) on-column methylation. In the former, phosphorylation of 7 alcohols and 12 phenols with diethyl chlorophosphate in the presence of triethylamine at 60-70 C in benzene has been reported (35). Aliphatic alcohols, such as methanol, butanol or isoamyl alcohol react instantaneously while phenol and cresols require ca 1-1 1/2 hrs. and xylenols 3-4 hrs. for best results. 

Studies of the synthesis of phosphorus-containing derivatives of cellulose fall into two groups phosphorylation of cellulose with derivatives of phosphoric acids and phosphorous acids, respectively. Until recently, most studies have been of derivatives of cellulose and phosphoric compounds. There are a few publications reporting the synthesis of esters of phosphorous acids and cellulose, but the properties of these compounds have not been studied at all. However, esters ctf phosphorous adds and cellulose can be used for the preparation ctf ters of phosphoric adds and cellulose, which cannot be obtained by direct synttesis (or only with difficulty) by the reaction of the hydroxyl groups of the cellulose macromolecule with phosphorus-containing reagents. 

The phosphorylation of the previously activated cellulose was carried out at 50-60° C with an excess of a mixed phosphorus-containing anhydride, and also with a solution of the same anhydride in an organic solvent. 

A-Phosphorylated imidazoles and benzimidazoles can be made by direct phosphorylation by halides, esters, amides, amidoesters, isocyanates, and thiocyanates of phosphorus-containing acids, or from reaction of phosphonic or phosphinic imidazolides with a sulfonic acid or anhydride <82CB1636>. Stable charge transfer complexes are produced when a 1 1 or 1 2 ratio of imidazole (or benzimidazole) and sulfur trioxide are refluxed in ether, dioxane, THE, or 1,2-dichloroethane. These complexes are stable on storage in the absence of water and have sharp melting points. Indeed, the benzimidazole SO3 complex must be boiled for five hours in water to decompose it. On fusion, the complexes form the C-sulfonic acids (see Section 3.02.5.3.3) <87CHE1084>. Sulfonyl chlorides readily A-sulfonate imidazoles <94JMC332>. 

Phosphorus-containing enamines have been prepared by phosphorylation of N-vinyl substituted tertiary amides, lactams and cyclic imides with phosphorus pentachloride ". Addition of amines to diphosphoryl alkynes has been described. Addition of RR NH [R = H, Ri = Me, cyclohexyl, PhCH2 RR = (CHj) to (Et0)2P(0)C=CP(0K0Et2)2 in CH2CI2 at 25 °C gave 93-100% of (Et0)2P(0)C(NRRi)=CHP(0)(0Et2)2 . Speziale and coworkers have studied the reactions of phosphorus compounds with trichloroacetamides. 

In spite of its high bond strength, phosphoryl oxygen in many phosphorus-containing heterocyclic systems may be replaced without any great difficulty the 3-phospholenes (43 Z = O), 1,2-oxaphospholanes (44 Z = 1,2-oxa-3-phospholenes (45 Z =... 

Polycondensation of Diamine and Diacid via Phosphorylation or with Phosphorus-Containing Activating Agents... 

Several steps are required to convert D-mannose (244) into compound (245) from which, by phosphorylation with diphenyl phosphorochloridate and triethylamine, followed by hydrogenolysis, (246) may be obtained. Attempts to modify this latter substance at C(l) so as to introduce a further phosphorus-containing function have not been. successful. The bis(isopropylidene) derivative (247) reacted with tetraethyl methylenebisphosphonate to give (248), together with its C(l) epimer and (249). Treatment of the anomers of (248) with p-toluenesulphonic acid in acetone so as to remove the 4,6-isopropylidene group, and further phosphorylation (same reagents). 

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