Imide-azides

Azidoformamidine or Guanylazide (Triazo-formamidin, Carbamid-imid-azid or Kohlen-saure-amidin-azid, in Ger), N3C(=NH)NH2 mw 85.07, N 82.33%, OB -65.9% Prepd... 

Azidoformomidine or Guanylazide (Triazo-fotmamidin, Carbamid-imid-azid or Kohlen-saure-amidin-azid, in Ger), N3C(=NH)NH2 mw 85.0 7, N 82.33%, OB -65.9%- Prepd from the nitrate salt (which was prepd from aminoguanidine nitrate and nitrous acid) by treatment with NaOEt in ale, but quickly rearranged to the Tetrazole. Consequently, it is known only as its salts Ref l) Beil 3, 130, (60) 2391... 

More typically, activated amines in the form of amides or sulfonamides are employed as coupling partners in the Mitsunobu reaction. Amides, sulfonamides, lactams, imides, azides, and more esoteric acidic amine derivatives work well in this context. The figures below list a significant number of amine derivatives that have been used in the Mitsunobu reaction. Phthalimide, originally employed by Mitsunobu s group many years ago, remains one of the most important amine surrogates for use... 

Amines are suitable nucleophiles in the Tsuji-Trost reaction, with the use of simple amines, imides, azides, sulfonamides and heterocyclic amines having been reported." In fact, one of the first examples of the catalytic version of the Tsuji-Trost reaction involved the use of aliphatic amine nucleophiles. Subsequently these important nucleophiles have been used extensively in synthesis. 

The reaction of anhydrides with aryl azides, in the presence of McaSiCl and Nal, gives N-aryl imides. 

Besides addition reactions, azides or hydrazoic acid can also yield tetrazoles through displacement reactions. Thus, halide displacement in imide chloride (78) yields 1,5-disubstituted tetrazoles (79), and in 2-chloro-pyridine (80), yields tetrazolopyridine (81) (Eq. 16a,b).141 143 Vinylogous... 

Die bei den unter Umlagerung verlaufenden Azidzerfallen gebildeten Produkte enthalten eine Imid-Gruppierung -NX. Beim Zerfall organischer Azide sind diese Produkte in monomerer Form meist isolierbar,... 

Complex 165 reacts with CO at room temperature to give />-tolyl isocyanate and the golden dicarbonyl compound 166. The latter can also be generated by reaction of 164 with excess of CO and converted back to imide 165 by the addition of 2 equiv of /> toly 1 azide (2003JA322). Reaction of cobalt(m) imide 167 analogous to 165, available from [PhB(CH2PPh2)3]CoI 156 by the same procedure as for 165, with CO proceeds similarly <2002JA11238>. 

Oxidation of 158 and 159 with sodium amalgam as well as of 170 and 171 with ferrocenium (Cp2Fe+) leads to dinuclear N2-bridged products 173, converted to iron(m) and cobalt(m) imides 174 under action of adamantyl and p-tolyl azides (Scheme 66) <2003JA10782>. 

The reaction of S2C12 with gaseous ammonia in DMF at ca. -10 °C, followed by hydrolysis with cold dilute hydrochloric acid, is a standard preparation of these cyclic sulfur imides.199 The reaction of sodium azide with elemental sulfur in (Me2N)3PO is an excellent source of S7NH. The tetraimide 69 is prepared by reduction of S4N4 with methanolic SnCl2.2H20. 

OpticaUy active iV-tosylsulfoximides produced in the copper-catalyzed reaction of chiral sulfoxides with tosyl azide may be hydrolyzed with strong acid (H2SO4) to optically active free sulfoximides. However, this procedure often fails and/or results in decomposition. It is interesting to note in this connection that a simple one-step method for the preparation of optically active unsubstituted sulfoximides has been reported recently by Johnson and co-workers (180). It involves the reaction between optically active sulfoxides and 0-mesi-tylsulfonylhydroxylamine and results in sulfoximides 60 of high optical purity. As expected, this imidation process occurs with retention of configuration at sulfur. 

Thus, it is of interest to generate oligosaccharides of the type C-B-A in 56, all of which are linked inter-glycosidically by a-(1->4)-bonds. We have previously synthesized various derivatives of the terminal C-B disaccharides employing the Perrier glycosylation approach (59. 60). At that same time we could combine the azide functionalization of glycals (61) with the N-iodosuccin-imide method (1 ) and develop a general approach to 3-... 

The cyclic sulfur imides S NH and 1,3-, 1,4-, and l,5-S(j(NH)2 are obtained by acid hydrolysis of the deep blue intermediate formed from the reaction of SjClj with ammonia in polar solvents, e.g. DMF or by the reaction of sodium azide with elemental sulfur in HMPA The blue chromophore formed in both these reactions is S4N and it has therefore been suggested that this anion is involved in equilibria with cyclic sulfur-nitrogen anions which are the precursors of the imides... 

Propioloyl chloride, 1065 t Propionyl chloride, 1163 Sebacoyl chloride, 3341 Sulflnyl chloride, 4096 Sulfonyl chloride, 4099 Sulfm oxide-(iV-fluorosulfonyl)imide, 4305 Sulfuryl azide chloride, 4031 Terephthaloyl chloride, 2880... 

Closely related to the already mentioned electrocyclizations of N-acyl thione S-imide (see Section 4.14.9.2) are some intermolecular cycloadditions involving this unusual class of 1,3-dipoles. Thus, the thione-S-imide intermediate (233) is probably involved in the formation of spirodithiazoline derivative (234) from the thione (235) and aryl azides <93HCA2147>. Also fluorenone-S-/ -tosylimide affords with carbonyl or thiocarbonyl compounds (R H) the corresponding oxathia- or dithia-zolidine derivatives (236) (Y = O or S) <80BCJ1023> (Scheme 44) (see also Section 4.14.6.1). 

Substituted anhydro-5-hydroxy-l,2,3,4-oxatriazolium hydroxides (4) decompose on heating in strong acids <320912,56JA5124>. The 3-alkyl substituted compounds produce carbon dioxide, azo-imide (HN3), and the alcohol corresponding to the 3-substituent. The 3-aryl substituted analogues produce carbon dioxide and aryl azide. In some cases the initially formed aryl azide decomposes further to anilines under the conditions of the reaction <82JCS(P2)70l>. Kinetic studies indicate that 3-methyl-anhydro-5-hydroxy-l,2,3,4-oxatriazolium hydroxide (24) reacts via a bimolecular A-2... 

Phenyl azide reacts with 2//-l,2,3-diazaphospholes with loss of nitrogen to give a cyclic trimer (85) of the diazaphosphole P-imide which is suggested as an intermediate (Scheme 27) <81IZV1600, 90ZOB35>. 

Reaction of dichorobenzaldoxazine with sodium azide followed by 1-propa-nethiol-triethylamine gave the tetrazine imide 367 as the major product. Its formation is thought to involve the reaction sequence shown which includes an unprecedented electrocyclization of the nitrile imine 366 as the final step (210). 

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