Azides phosphonate

Nucleophiles like alcohols [2, S], hydrogen sulfide [2], thiols [2,10], ammonia, amines, hydrazines, hydroxylamines [2 11, 12, 13, 14, 75], azides [2], other pseudohalides [2], phosphonates [2,16,17,18,19, 20], and phosphanes [2,19] add rapidly across the CO or CN double bond to yield stable adducts The phosphonate adduets undergo a subsequent aleohol—lester rearrangement [19, 20] (equation 2)... 

A series of amides, hydrazides, and azides of phosphoric, phosphonic, and phosphinic acids were synthesized via the corresponding pyrazolides. 

The reduction of an azide group with triphenylphosphine in tetrahydrofuran by microwave heating at 130 °C for 5 min has been described by Kihlberg and colleagues (Scheme 6.152) [297]. The use of diethyl 4-(hydrazinosulfonyl)benzyl phosphonate as an in situ diazene precursor for the reduction of trisubstituted gem-diiodoalkenes to terminal geminal diodides under microwave conditions has also been reported [298],... 

Arsonic acids are easily detected on paper electrophoresis and chromatography by the fact that they bind Fe3+ tightly. Hence, they show up in the test of Wade and Morgan (130) for phosphates, in which the paper is sprayed with a solution of FeCl3 (1%) and sulfosalicylic acid (1%). Phosphonates and arsonates show up like phosphates as white spots on a purple background, because they remove the Fe3+ from its purple complex with the acid. For following column effluent, a test with a similar principle may be used. The sample is mixed with a buffered, acidic solution of Fe3+ and azide, and the absorbance at 450 nm is diminished by phosphates and phosphonates (52) we have since used this method successfully with arsonates. 

AMIDES Bis(o-nitrophenyl)phenyl-phosphonate. N,N-Bis(2-oxo-3-oxazoli-dinyl)phosphordiainidic chloride. 2-Chloro-2-oxo-l,3,2-bcnzodioxa-ph05-phole. Iodine azide. N-Methyl-N-phenyl-benzohydrazonyl bromide. Phase-transfer catalysts. N-Phenylseleno-phthalimidc. (SEProlinol. 

The assignment of a A4-triazoline structure277 for the product obtained from the reaction of acrylonitrile and phenyl azide appears highly unlikely, because later work indicates this adduct to have an unambiguous l-aryl-4-cyano-A2-l,2,3-triazoline structure (Scheme 72).32 Likewise, vinyl phos-phonates react with phenyl azide, leading to triazoline-4-phosphonates.278... 

In the reaction of nitrile compounds with aryl azides bearing a carboxyl424 or nitrile423 function in the ortho position, fused triazoles are formed by further reaction of the 5-amino group with the ortho substituent on the 1-phenyl ring. Whereas a-cyanomethylene phosphonate gives the expected... 

Phosphonium iodide, 4510 Phosphonium perchlorate, 4000 Phosphorous acid, see Phosphonic acid, 4499 Phosphorus azide difluoride—borane, 4310 Phosphorus azide difluoride, 4309 Phosphorus chloride difluoride, 3973 f Phosphorus, 4868... 

Depending on the nature of X, the (CH3)4SbX products were found to be either covalent molecular species (OH, OR, SR, F) or saltlike materials (azide, thiocyanide, chloride, dimethylphosphinate). The state of bonding may be different in solution from the solid state, and it may vary with the nature of the solvent (carboxylates). Only the stronger acids, if employed in excess, will afford the R3SbX2 species. This is true with the halogen hydrides, halosulfuric or -phosphonic acids, etc. 

Although some reactions of electrophilic animation of phosphorus-stabilized anions had already been reported in the literature [5a,d], the first example of such a stereoselective reaction opening access to optically active a-amino phosphonic acids was described in 1992 by Denmark and co-workers [45] and by Jommi and co-workers [46]. Both of these groups used chiral amino alcohols as auxiliaries for diastereo-selective induction in the animating process. Denmark and co-workers chose trisyl azide (2,4,6-triisopropylbenzenesulfonyl azide) as equivalent of NHJ , whereas Jommi and co-workers performed the reaction with DTBAD. 

Not surprisingly, thiols can be oxidized cleanly to disulfides [138], as in the CdS-photocatalyzed conversion of cysteine to cystine, where the uptake of oxygen was pH dependent. The reaction rate was not increased in deuterium oxide nor decreased by added azide, suggesting that singlet oxygen is not involved. Superoxide dismutase did inhibit the conversion. Phosphines and phosphonic acids undergo similar oxidative transformations [139]. 

The Rh" acetate catalysed decomposition of dimethyl a-diazobenzylpl-ospho-nate (204) in the presence of primary amines and amides offers a simple route to the corresponding a-aminophosphonates. 1-Aminocycloalkylphosphonates 205 have been synthesised from the corresponding cycloalkylphosphonate via electrophilic azidation of the phosphonate carbanion followed by catalytic hydrogenation. ... 

Several addition reactions of unsaturated phosphonic and phosphinic esters have been reported during the course of the year. Dithiophosphoric acids add to 2-alkoxy-vinylphosphine esters in the expected manner, and in the addition of phenyl azide to vinylphosphonates, the initial triazole (95) may be thermolysed to a C-phosphory-lated aziridine, but in the presence of triethylamine the final products are 2-anilino-vinylphosphonates. ... 

Allspach, T., Gtimbel, H., and Regitz, M., Studies on diazo compounds and azides. Part 63. Silylation of a-diazo phosphonates and carboxylates with silyl triflates, J. Organomet. Chem., 290, 33, 1985. 

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