Oxidation imides

The phosphorus oxides, imides, their derivatives and their analogs usually have the adamantane-type structure shown in scheme 1. 

As previously described in Scheme 2 in Section 4.20.6, Suslova et al. investigated the oxidation, imidation, and A-methylation reactions of five-membered 1,3-thiasilacycloalkanes <2003JOM73>. 

Dinitrogen complexes of molybdenum and tungsten with mono-, di - and tii - tertiary phosphine co -ligands are electrosynthesised from molecular nitrogen andMo or precursors vw cleavage of halide or thiolate bonds and from Mo or oxide, imide or hydrazide complexes by... 

Intramolecular oxidative imidation of aromatic C-H bonds of A-arylamidines with DAIB leads to the formation of 2-substituted benzimidazoles in high yields. A reaction mechanism involving radical intermediates has been proposed (Scheme 15). ... 

Wang, H., Ugomori, T., and Wang, Y. 2000. Sorption and pervaporation properties of cross-linked membranes of poly(ethylene oxide imide) segmented copolymer to aromatic/ nonaromatic hydrocarbon mixtures. J. Polym. Sci. B Polym. Phys. 38 1800-1811. 

Isocyanates are derivatives of isocyanic acid, HN=C=0, ia which alkyl or aryl groups, as weU as a host of other substrates, are direcdy linked to the NCO moiety via the nitrogen atom. StmcturaHy, isocyanates (imides of carbonic acid) are isomeric to cyanates, ROCMSI (nitriles of carbonic acid), and nitrile oxides, RCMSI—>0 (derivatives of carboxyUc acid). 

Polyimides have been synthesized by Diels-Alder cycloaddition of bismaleimides and substituted biscydopentadienones (81,82). The iatermediate tricychc ketone stmcture spontaneously expeU carbon monoxide to form dihydrophthalimide rings, which are readily oxidized to imides ia the presence of nitrobenzene. 

To minimize the formation of fuhninating silver, these complexes should not be prepared from strongly basic suspensions of silver oxide. Highly explosive fuhninating silver, beheved to consist of either silver nitride or silver imide, may detonate spontaneously when silver oxide is heated with ammonia or when alkaline solutions of a silver—amine complex are stored. Addition of appropriate amounts of HCl to a solution of fuhninating silver renders it harmless. Stable silver complexes are also formed from many ahphatic and aromatic amines, eg, ethylamine, aniline, and pyridine. 

Virtually all of the organo derivatives of CA are produced by reactions characteristic of a cycHc imide, wherein isocyanurate nitrogen (frequendy as the anion) nucleophilically attacks a positively polarized carbon of the second reactant. Cyanuric acid and ethylene oxide react neady quantitatively at 100°C to form tris(2-hydroxyethyl)isocyanurate [839-90-7] (THEIC) (48—52). Substitution of propylene oxide yields the hydroxypropyl analogue (48,49). At elevated temperatures (- 200° C). CA and alkylene oxides react in inert solvent to give A/-hydroxyalkyloxazohdones in approximately 70% yield (53). Alternatively, THEIC can be prepared by reaction of CA and 2-chloroethanol in aqueous caustic (52). THEIC can react further via its hydroxyl fiinctionahty to form esters, ethers, urethanes, phosphites, etc (54). Reaction of CA with epichlorohydrin in alkaline dioxane solution gives... 

These materials also have high thermal and oxidative stabiHty. Flexible segments such as amide siloxane can be incorporated into the imide-based stmcture for hot melt or injection appHcations. General Electric (GE) and Hoechst-Celanese are suppHers of these high performance plastics. 

There are various photochemical transformations of pyridazines, their corresponding benzo analogs, N-oxides and N-imides. Gas-phase photolysis of pyridazine affords nitrogen and vinylacetylene as the main products. Perfluoropyridazine gives first perfluoropyrazine, which isomerizes slowly into perfluoropyrimidine. 

Azolinones, azolinethiones, azolinimines N-Oxides, N-imides, N-ylides of azoles Thermal and Photochemical Reactions Formally Involving No Other Species 2.1 Thermal fragmentation... 

Azole iV-oxides, iV-imides and iV-ylides are formally betaines derived from iV-hydroxy-, iV-amino- and iV-alkyl-azolium compounds. Whereas iV-oxides (Section 4.02.3.12.6) are usually stable as such, in most cases theiV-imides (Section 4.02.3.12.5) andiV-ylides (Section 4.02.3.12.3) are found as salts which deprotonate readily only if the exocyclic nitrogen or carbon atom carries strongly electron-withdrawing groups. 

The oxygen is ehemisorbed on the eatalyst. This then reaets with ammonia to produee a ehemisorbed imide radieal. The imide reaets with a moleeular oxygen to yield nitrie oxide. 

Cyclic chalcogen imides in which sulfur is in the formal -f2 oxidation state (or lower) can, in the case of sulfur, act as a source of binary S-N... 

It will be convenient to describe first the binary. sulfur nitrides SjN,. and then the related cationic and anionic species, S,Nv. The sulfur imides and other cyclic S-N compounds will then be discus.sed and this will be followed by sections on S-N-halogen and S-N-O compounds. Several compounds which feature i.solated S<—N, S-N, S = N and S=N bonds have already been mentioned in the. section on SF4 e.g. F4S NC,H, F5S-NF2. F2S = NCF3, and FiS=N (p. 687). Flowever. many SN compounds do not lend themselves to simple bond diagrams, - and formal oxidation states are often unhelpful or even misleading. 

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