F-Phosphoramidate

The high reactivity of N-H bonds has also been exploited to produce N-F denvatives without significant substitution on neighbonng C-H bonds, Diethyl-phosphoramidates of ammonia, alkylammes, and a,polar solvents to produce difluoroamine [57], N,N-difluoroalkylamines, and a,to-bis(At,7V-difluoroamino)alkanes [52] Acetamide undergoes fluonnation to give modest yields of N,N difluoroacetatnide and acetyl fluonde when fluorinated... 

Boulm F., Freund F., Moreau S., Nielsen P.E., Gryaznov S., Toulme J.J., Litvak S. Modified (PNA, 2-O-methyl and phosphoramidate) anti-TAR anti-sense oligonucleotides as strong and specific inhibitors of in vitro HI.V.-l reverse transcription. Nucleic Acids Res. 1998 26 5492-5500. 

Several approaches to the 1,2,3-triazole core have been published in 2000. Iodobenzene diacetate-mediated oxidation of hydrazones 152 led to fused 1,2,3-triazoloheterocycles 153 <00SC417>. Treatment of oxazolone 154 with iso-pentyl nitrite in the presence of acetic acid gave 1,2,3-triazole 155, a precursor to 3-(W-l,2,3-triazolyl)-substituted a,P-unsaturated a amino acid derivatives <00SC2863>. Aroyl-substituted ketene aminals 156 reacted with aryl azides to provide polysubstituted 1,23-triazoles 157 <00HC387>. 2-Aryl-2T/,4/f-imidazo[43-d][l,2,3]triazoles 159 were prepared from the reaction of triethyl AM-ethyl-2-methyl-4-nitro-l//-imidazol-5-yl phosphoramidate (158) with aryl isocyanates <00TL9889>. 

When the phosphoramidic difluoride (116) reacts with diols, alkanolamines, or diamines, the manner of ring closure is dependent on n in a way which is both novel, and, from the synthetic viewpoint, potentially useful, although for compounds for which n = 2 a mixture of products (117 R = F or MeaN) may result.88... 

Savignac, P. Leroux, F. Normant, H. Carb-anions-a phosphoramides. II. Formation, stabilite et utilisation en synfhese des carb-anions derivant de N-methyl N-benzylphos-phoramides. Tetrahedron 1975, 31, 877-884. 

In the palladium-catalyzed allylic amination reaction, primary and secondary amines can be used as nucleophiles, whereas ammonia does not react. Therefore, many ammonia synthons have been developed, and a variety of protected primary allyl amines can now be prepared using azide, sulphonamide, phthalimide, di-f-butyl iminocarbonate ((Boc)2NLi), and dialkyl A-(rerr-butoxycarbonyl)phosphoramide anions as the nucleophile [20], An example of the use of ((Boc)2NLi) 30 as the amine nucleophile in the palladium-catalyzed allylic amination reaction is shown in Eq. (9). This reaction also illustrates the problem with the regioselectivity in the reaction as a mixture of the products 31-33 are obtained [21]. 

The X-ray structure of [Zn2(8-H)F is shown in Pig. 2. The p for the doubly coordinated pendant alcohol is below 4, in accord with corresponding measurements made on water molecules coordinated to a pair of Zn(II) ions in a cyclic octaamine (<7) 22), or in a cyclic tetraamine with four pendant amines (<5.3) 23). On reaction with 4-nitrophenyl phosphate, 4-nitrophenol is released and a complexed phosphoramide is produced, [Zn2(9)] +, resulting from attack of a secondary amine at phosphorus. 

Crufomate. (0-methyl-0-(4-rm-butyl-2-chloro-phenyl)methylphosphoramidate 4-f-butyl-2-chlo-rophenylmethyl methyl phosphoramidate ruel-ene). 

C-F bonds are normally difficult to reduce, but it has now been shown that such bonds a to the carbonyl group of alkyl perfluoroesters can be photoreduced in hexamethylphosphorotriamide in a reaction which involves electron transfer from excited phosphoramide (Portella and Iznaden). Several reports of the photoreduction of carbon dioxide have appeared for photoreduction to methane see Yamase and Sugeta, and Diirr et al. for reduction to formate see Lehn and Ziessel, and Matsuoka et al. Gollnick and Held have reported that mercurochrome is an efficient sensitizer for type II singlet oxygen photo-oxygenations. 

PHENOL, 4-tert-BUTYL-2-CHLORO-, ESTER WITH METHYL METHYL-PHOSPHORAMIDATE (299-86-5) Incompatible with antimony(V) pentafluoride, lead diacetate, magnesium, silver nitrate. Alkalis, strong acids, and elevated temperatures cause decomposition, forming fumes of chlorine, nitrogen oxides, and phosphorus oxides. Unstable over long periods of time in water and at temperatures above 140°F/60°C. 

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