MINO COMPOUNDS

It is interesting to compare the biphenylamine substituted compounds with the corresponding carbazoles, phenoxazines, and phenothiazines. For the triaryla-mino-based structures, the carbazole 24 has the highest oxidation potential (0.69 V vs. Ag/0.01 Ag+) [102], followed by the phenoxazine 25a (0.46 V vs. Ag/0.01 Ag+) [166]. A similar observation was made for the corresponding derivatives of 36a the phenothiazine (0.27 V vs. Fc/Fc+) and the phenoxazine (0.29 V vs. Fc/Fc+) have higher oxidation potentials than the parent compound. The carbazole 37 has an even higher oxidation potential, but in this case the oxidation is not reversible [234]. The redox properties of carbazoles are not fully understood yet. In some devices, a carbazole such as CBP (10) was used as an interface layer on the cathode side, suggesting a lower barrier for electron injection [50]. 

So far, not much literature on the biological activity of iminophosphor-anes has appeared. Compounds possessing triorganylphosphoranylidenea-mino structural elements such as mitomycin (41) have proved to be interesting anti-tumor reagents the cancerostatic activity seems to be localized in the aziridine units of 40 (Scheme 19) [87PS(30)845]. 

Nomenclature.—A definite system of nomenclature has been adopted for metal-ammines, and the old names derived from the colour of the compounds have, in the main, been abandoned, as they lead to confusion. The system adopted is that suggested by Werner. Ammonia molecules present in the complex are indicated by the terms monam-mino, diammino, triammino, tetrammino, pentammino, hexammino, the word ammino, written with a double m, having been adopted to show the relationship with ammonia and to distinguish from the ammonium salts and the substituted ammonia compounds, namely, the amines. 

Ammino-lithium Halides.—Lithium halides absorb gaseous ammonia in the dry state. The chloride forms four compounds depending on the temperature at which absorption takes place. Below 13° C. tetrammino-lithium chloride, [Li(NH3)4]Cl, is produced. Triam-mino-lithium chloride, [Li(NH3)3]Cl, is formed between 20° and 60° C. diammino-lithium chloride, [Li(NH3)2]Cl, between 60° and 85° C. and at 85° C. the monmnmine, [Li(NH3)]Cl, is produced. These are white unstable substances.1... 

Ammines of Cadmium Halides.—Cadmium chloride unites with ammonia with formation of the following compounds Mon-ammino-cadmium chloride, [Cd(NH3)]Cl2 diammino-cadmium chloride, [Cd(NH3)a]Cl2 triammino-cadmium chloride, [Cd(NH3)3]Cl2 letram-mino-cadmium chloride, [Cd(NH3)4]Cl2 hexammino-cadmium chloride, [Cd(NH3)6]Cl2A... 

Tetrammino-salts arc also known in which a divalent acidic radicle takes the place of two monovalent acidic radicles in the diacido-tetram-mino-series, giving rise to efs-compounds such as the earbonato-tetram-mino- and the oxalato-tctrammino-cobaltic salts. 

The diol-compounds are readily decomposed by concentrated hydrochloric and hydrobromic acids, yielding a mixture of m-diaquo-tetram-mino-cobaltic and cis-diacido-tetrammino-cobaltic salts, a reaction which has proved useful in determining the configuration of stereo-isomeric cobalt-ammines. 

Palladous salts on treatment with excess of ammonia yield tetram-mino-palladous salts, from which on the addition of acid the corresponding diacido-diammino-compounds are precipitated. This method may be employed for the preparation of the chloro-, bromo-, and iodo-compounds, which are sparingly soluble in water, and the other members of the series are prepared from these by double decomposition. Ammonia transforms the compounds info tetrammino-palladous salts. 

These substances are obtained by heating the corresponding tetrani-mino-platinous salts. They dissolve in aqueous ammonia until reformation of the tetrammino-salts, and they can take up two atoms of chlorine yielding the corresponding platinic compound thus ... 

Metzger S, Mihalopoulos N, Lelieveld J (2006) Importance of mineral cations and organics in gas-aerosol partitioning of reactive nitrogen compounds case study based on MINOS results. Atmos Chem Phys 6 2549-2567... 

The success achieved with the Rh(II)-catalyzed transformations of E-oxi-mino diazo carbonyl compounds prompted our group to study some additional systems where the C-N n-bond was configurationally locked so that azo-methine ylide formation would readily occur. To this end, we investigated the Rh(II)-catalyzed behavior of isoxazoline 128 in the presence of DMAD. This reaction afforded the azomethine-derived cycloadduct 129 as a 4 1-mixture of diastereomers in 65% yield. A similar transformation occurred using the a-diazoacetophenone derivative 130 which produced isoxazolo[3,2-a]isoqui-noline 131 as a 2 1-mixture of diastereomers in 82% yield. 

Under alkaline conditions, alkyl nitrites nitrosate imidazoles that possess a free NH group, at the 4-position. Nitrosation of 3,5-dimethylpyrazoles gives the 4-diazonium salt by further reaction of the nitroso compound with more NO+. 4-Nitrosopyrazoles 188 can be used as spin traps. 5-Pyrazolinones are nitrosated readily at the 4-position. Imidazo[l,2-tf] benzimidazoles are nitrosated with NaN02 in acetic acid giving 3-nitrosoderivatives 189. Nitrosation of 2-(dimethyla-mino)thiazoles under acid conditions gives 5-nitroso-derivatives 190. 3-Alkyl-5-acetamidoisothiazoles undergo 4-nitrosation. 

The compounds of Type II will be discussed first (Section II), and the similarity of some of their properties to those of piperidine will be noted. Following this, the compounds of Type III, having an acyli-mino group in the ring, will be described (Section III), and in particular, their nuclear magnetic resonance spectra will be discussed. In the last Section (IV), the compounds of Type I, containing sulfiir in the hemiacetal ring, will be treated. 

Steric eifects can also be caused by other types of strain. 1,8-Bis(diethyla-mino)-2,7-dimethoxynaphthalene (8) is an extremely strong base for a tertiary amine (pZa of the conjugate acid = 16.3 compare 7/,7/-dimethylaniline, pA a = 5.1), but proton transfers to and from the nitrogen are exceptionally slow slow enough to be followed by a UV spectrophotometer. Compound 8 is severely strained because the two nitrogen lone pairs are forced to be near each other. Protonation reheves the strain one lone pair is now connected to a hydrogen, which forms a hydrogen bond to the other lone pair (shown in 9). 

A-Alkylisoxazolium compounds may be reduced in neutral solution to 3-alkyla-mino-2-butenones (Eq. (30)] [277, 279] and A-alkyl-4,5-dihydroisoxazolium salts to 4-hydroxy-2-butanones [277]. 

A novel example of this type of SnR2 Lewis acid compound is the product obtained from the transmetallation reaction of bis[3-(dimethyla-mino)propyl]zinc with bis(dibenzoylmethanato)tin(II). 

These compounds include the following type of C,N-chelating ligands 2-[(dimethylamino)methyl]phenyl 40a-45 (54.114-117) [2-(dimethyla-mino)phenyl]methyl 46a-c, 47a-c (80) 8-dimethylamino-l-naphthyl 48 -50 (110) 2-[(dimethylamino)methyl]phenyl methyl 51,52 (118), 8-(dimethylamino)methyl-l-naphthyl, 53,54 (118), 2-(4,4-dimethyl-2-oxa-zoline)-5-(methyl)phenyl 55,56 (119) and 2-(phenylazo)phenyl 57a,57b (120,121). For some representative examples, the structure was unambiguously proven by an X-ray crystal structure determination 40c (115), 41b (114), 44b (116), 47b (80), 49 (96), 54 (118), 56 (119), 57a (121), and 57b (122). The last compound was obtained as an unexpected by-product from the reaction of 2,4-dinitrophenyldiazonium cation with (3-methoxy-phenyl)trimethyltin (120) ... 

Sodium salts of 1-aroylamino-u-triazoles (124) are acylated at low temperature at the oxygen atom, affording isoimides 122. The latter compounds, as already noted, are isomerized on heating to l-(A,A-diaroyla-mino)-u-triazoles (78JHC1255 84JHC1653). 

Bismuth tris(2-amino-l-cyclopentene-l-dithiocarboxylate) 1 and 2-(ethyla-mino)cyclopentene-l-dithiocar-boxylate 2 are obtained as red crystals by treating BiCl3 or BiOCl with the corresponding dithiocarboxylic acids in EtOH. Compound 1 is insoluble in common organic solvents except for DMF and DMSO, in which it is sparingly soluble. Compound 2 is moderately soluble in common organic solvents [87IC1453]. 

Even if no nitrenes are produced as intermediates, the isocyanates formed in Curtius-type rearrangements are of value for the synthesis of heterocyclic compounds. For example, transient isocyanates cyclize unto azine rings, giving imidazoazines (Scheme 21).161 N,N-Diphenylcarbamoyl azide rearranges thermally to 1-phenylindazolone (Eq. 35) via the elusive diphenyla-mino isocyanate.162 Further examples have been summarized by Reichen.163... 

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