Phosphoryl azide, reaction with

Berlin, K. D., and L. A. Wilson Reaction of Phosphoryl Azides with Norbornene. Formation of a Novel Phosphorylated Triazoline. Chem. Comm. 1965, 280. 

Pyridine A-oxides were converted to tetrazolo[l,5-a]pyridines 172 by heating in the presence sulfonyl or phosphoryl azides and pyridine in the absence of solvent <06JOC9540>. 3-R-5-Trinitromethyltetrazolo[l,5-a]-l,3,5-triazin-7-ones 173 have been prepared from the alkylation of 5-trinitromethyltetrazolo[l,5-a]-l,3,5-triazin-7-one silver salt with different alkylation agents <06CHE417>. The use of 2-fluorophenylisocyanide in the combinatorial Ugi-tetrazole reaction followed by a nucleophilic aromatic substitution afforded tricylic tetrazolo[l,5-a]quinoxaline 174 in good yields and with high diversity <06TL2041>. 

Formation of P=N-P-Bridges. A simple reliable synthesis of N-phosphorylated phosphazenes which avoid the handling of the dangerous phosphoryl azides consists in a direct reaction of di- and trialkyl-phosphites and carbon tetrachloride with sodium azide in a single step procedure (eq. 11). The phosphoryl azides formed intermediately instantly react with the trialkylphosphites present. Therefore, their... 

When 3,4-disubstituted 4-aminoisoxazolin-5(4Af)-ones (9) are hydrogenated, and then subsequently recyclized, high yields of imidazoles (10) are obtained (Scheme 6.1.4). The starting materials can be readily made from isoxazolin-5(4Af)-ones by sequential bromination, reaction with sodium azide and conversion of azide into amino by reaction with hydrobromic acid in acetic acid. The amines are then converted into formamidine or acetamidine derivatives with DMF or dimethylacetamide under reflux in phosphoryl chloride-chloroform. Yields at this stage are 50-93%. Catalytic... 

The highly reactive nitrenes derived from phosphoryl azides do not readily undergo rearrangement. They also appear to have a low selectivity with respect to —H insertion reactions. Thus, irradiation of diethylphosphoryl azide (143 R = Et) in cyclohexane, for example, led to formation of diethyl cyclohexyl-phosphoramidate (144 R = Et) in 88% yield.83 A lower yield (67%) of insertion product, diphenyl cyclophosphoramidate (144 R = Ph), was obtained on... 

In this procedure, the C-phosphorylated active methylene compound is first converted into its anion, through its reaction with KOBu BuLi, PhLi, NaH or even Et3N, and the anion is then acted upon by a sulphonyl azide the latter has been / -toluenesulphonyl azide in most recorded examples of the reaction. The first example of the adoption of this procedure to the synthesis of a phosphonic acid derivative appears to have been the conversion of triethyl phosphonoacetate into the diazo derivative (2). Since then, the procedure has been used to obtain A-substituted derivatives of the phosphonoacetamide corresponding to structure 2, but the primary amide itself undergoes further reaction to afford the C-phosphorylated 1,2,3-triazole (3)". Tetraethyl methylenebisphosphonate yields tetraethyl... 

Evans et al. [50] examined the DBU (l)-mediated azidation of a-hydroxy ester with phosphoryl azides and found that the amount of DBU (1) is critical for asymmetric induction (Table 3.3). In the reaction with bis(p-nitrophenyl)phosphoryl azide in DME, the use of 1.2 equiv. of 1 resulted in the production of azide with 80% ee (run 5), while product was obtained with less than 2% racemization and in good yield when 0.95 equiv. of 1 was used. 

Diarylphosphinic and diarylphosphoric azides are rapidly hydrolysed by water to diarylphosphinic and diarylphosphoric acids, respectively. Monophosphazenes are obtained by reaction with phosphines (7.225). Methyl phosphonic diazide (7.223c) can be obtained by reacting methylphosphonic dichloride with sodium azide in pyridine (7.226), while phosphoryl triazide is obtainable with... 

The resulting 2-benzylthioethylamine could be debenzylated by treatment with sodium in liquid ammonia. However, when 2-benzylthioethylamine was treated with carbobenzyloxy-P-alanine azide (prepared from carbobenzyloxy-P-alanylhydrazide by nitrosation), 2-benzylthio-7V-(carbobenzyloxy-P-alanyl)ethyl-amine formed. Reduction with sodium in liquid ammonia was sufficient to remove both the benzyl and carbobenzyloxy protecting groups and, as noted above, reaction with pantolactone yielded pantetheine. Phosphorylation to the mono- and diphosphates of pantetheine has been effected with the corresponding dibenzylphospho-nates (vide supra, ATP). 

The types of reaction open to a nitrene are broadly similar to those undergone by carbenes, but the reactivity of nitrenes is considerably lower. Nitrenes are less indiscriminate than carbenes in their reactions with primary, secondary, and tertiary carbon-hydrogen bonds, for instance, and nitrenes are also somewhat electrophilic, preferring an 0-H over a C-H bond. By far the most frequently used nitrene source is an aryl azide (see Table IV). The derived aryl nitrenes are much less reactive than a-keto, a-sulfonyl, or a-phosphoryl nitrenes, but the use of these acyl nitrenes is ruled out by the high chemical reactivity of the precursor species acyl azides, sulfonyl azides, and phosphoryl azides. 

Diphenyl phosphoryl azide triethylaniine Reactions with diphenyl phosphoryl azide Peptide synthesis by fragment coupling... 

Arylalkyl ketones rearrange on treatment with phosphoryl azides to give the phosphorylated amide of fenvaleric acid (Reaction scheme 191) [526]. 

The scope of the cobalt-catalyzed C-H amination was extended to phosphoryl azide derivatives (Scheme 10.20) [49]. Amination of the benzylic C-H bond of an alkyl group ortho to the phosphoryl azide is efficiently promoted by a cobalt(II) complex [Co(Pl)j with a D2 -symmetric tetraarylporphyrin ligand, which features proximal amide functionalities, thus affording a six-membered cyclic product. The amide functionalities of the catalyst appear to play critical roles in the amination reaction presumably by facihtating catalyst-substrate... 

Recently, it was demonstrated that the CuAAC reaction of sulfonyl or phosphoryl azides with terminal alkynes could form reactive ketenimine species 85, which could... 

Later, it was also claimed that 3-(tetrazolyl)-4//-pyrido[ 1,2-u]pyrimidin-4-ones 159 were obtained in an one-step procedure by heating the appropriate 2-aminopyridine, ethyl (l//-tetrazol-5-yl)acetate, and triethyl orthoformate in dimethylformamide at 90°C for 1 hour, or in boiling tetra-hydrofuran for 6 hours followed by treatment with 1N potassium hydroxide at 50°C for 1 hour, or with anhydrous aluminum chloride under reflux for 6 hours (91EUP462834). 9-Methyl-3-( 1 //-tetrazolyl)-4//-pyrido[ 1,2-a]-pyrimidin-4-one 159 (R = 9-Me) could be prepared when 2-amino-3-meth-ylpyridine hydrochloride and sodium azide were suspended and stirred in dimethylformamide for 1 hour at room temperature, followed by the addition of ethyl ethoxymethylenecyanoacetate, ethoxymethylenemalo-nonitrile, ethyl cyanoacetate and triethyl orthoformate, or malononitrile and triethyl orthoformate and stirring at 90°C for 6-12 hours. Then the reaction mixture was treated with 1 N potassium hydroxide at 50°C for 1 hour, phosphoryl chloride at 90°C for 5 hours, or with concentrated hydrochloric acid at 110°C for 4 hours to give 26-62% yields. 

Earlier we have studied the reactions of fullerene Cgo with the isocyanurato-, phosphoryl-, pyrimidino-, nitropyrimidino-, quinoxalin-, benzopyrazine substituted azides [18-24]. As a result, both 6,6-, 5,6-closed and 5,6-open organofullerens were synthesized, and the series of them were reduced electrochemically easier than the pristine fullerene C6o- Now the reactions of fullerene C6o with isocyanurato- and nitropyrimidine substituted azides were used for the search of the answer to delivered question. For solving the problem the substituents in positions 1 and 3 of the isocyanurate ring and the number of methylene units between ring and azide group in isocyanurate containing azides were varied. 

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