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Effect of phenoxazine derivatives (actinomycin D, l,8-dimethyl-3-aminophenoxazone-2, 3-aminophenoxazone-2, sodium resazurate, gallocyanine, fluorescent blue and capri blue) on amino acid transport in rat small intestine was investigated using tissue accumulation method. Capri blue (CI–51015) inhibited the accumulation of l-leucine, l-alanine and l-valine, and scarcely inhibited that of D-glucose. Kinetic analysis showed that the inhibition of amino acid accumulation by this pigment was non-competitive. Actinomycin D had no effect on amino acids and d-glucose accumulation in vitro at the high and low concentrations of these substances. High concentration of actinomycin D and long period of incubation had no effect, too. Accumulation of amino acids into the intestinal tissue was not significantly decreased or increased by the presence of other phenoxazine derivatives.

The ENDOR spectra of solutions of the neutral free radicals of the biologically interesting compounds phenoxazine, phenothiazine and chlorophenothiazine are reported. The combined use of ENDOR and computer simulation of EPR spectra has enabled us to determine the small (75 mG) hyperfine coupling of chlorine nuclei in chlorophenothiazine. This technique is likely to be important for the determination of halogen hyperfine couplings in radicals of biologically interesting molecules in solution.

Die Photoelektron-Spektren der Titelverbindungen 1–4 wurden gemessen. Eine Zuordnung der Ionisationspotentiale wird aufgrund eines LCMO-Modells und CNDO/2-Rechnungen vorgenommen. Aus dem Anstieg der Bande der ersten Ionisation wird eine Diskussion der Molekulgeometrien abgeleitet. Electronic Structure of Aromatic Amines: Photoelectron Spectra of 5,10-Dimethyl-5,10-dihydrophenazine, 5-Methyl-10-phenyl-5,10-dihydrophenazine, Phenoxazine and Phenothiazine The photoelectron spectra of the title compounds 1–4 have been measured, and the lower ionization potentials have been assigned on the basis of a CNDO calculation. The slope of the onset of the first band in the spectra is related to the geometry of the molecule.

Nous avons effectue les spectres de masse de phenoxazines et d'azaphenoxazines substituees. Ces composes sont caracterises par la presence d' un hydrogene sur l'azote heterocyclique et la position de substituants NO2 et Cl sur les cycles aromatiques. A l'aide de mecanismes classiques, nous avons rationalise les processus de fragmentation et explique les pics principaux de ces specters. La presence de substituants Cl et NO2 perturbent totalement la fragmentation observee dans le cas de la molecule de phenoxazine. Ils favorisent la localisation de la charge suivant leur position sur le cycle, soit sur l'azote, soit sur l'oxygene heterocycliques. Quant au gropement NO2 par isomerisation (forme nitroso), il donne lieu ea une fragmentation specifique. Mass spectra of substituted phenoxazines and azaphenoxazines have been determined and are discussed here. These compounds are characterised by hydrogen on the heterocyclic nitrogen and aromatic rings with nitro groups and chlorine as substituents. The fragmentation patterns are explained by known mechanisms. An interpretation of almost all the peaks is offered. The presence of the substituents causes a complete change in the fragmentation patterns compared with the unsubstituted phenoxazine. This is due to changes in charge localisation, caused by the substituents. Isomerisation of the nitro group to the nitroso group gives rise to a particular fragmentation route.

The high resolution proton magnetic resonance spectra of acridine, phenazine, phenoxazine and phenothiazine have been measured at 220 MHz in various solvents and at several temperatures. Spectra for all four molecules were analyzed iteratively and good agreement was obtained between observed and calculated spectra. Significant differences are noted between the coupling constants and chemical shifts of acridine and phenazine on the one hand and phenoxazine and phenothiazine on the other. These differences are attributed to a nonplanar heterocyclic ring conformation for phenoxazine and phenothiazine in solution. Moreover, it is concluded from the temperature measurements that the heterocyclic rings of phenoxazine and phenothiazine are conformationally flexible in the range covered. Possible mechanisms are suggested for the chemical shift and coupling constant changes.

The electrical resistivities and Seebeck coefficients of the 2 : 3 iodine complexes of phenoxazine, phenoselenazine, and benzophenothiazines were measured as a function of the temperature. They have resistivity values at 20°C ranging from 10 ohm·cm for the phenoxazine complex to 34 ohm·cm for the benzo[a]phenothiazine complex. Employing the equation of Johnson and Lark-Horowitz for the Seebeck coefficient of an intrinsic semiconductor, the ratio of the electron-to-hole mobility in the phenoselenazine complex was found to be 1.07 and the electron mobility was estimated as 0.26 cm2/V sec. By an examination of the vibrational spectra, the expected cation-radical character was confirmed for the complexes of phenoselenazine and benzophenothiazines. The presence of a broad electronic absorption band in the rock-salt region characteristic of low-resistivity organic semiconductors was noted in every case.

Systematic studies were made on thianthrene, phenoxathiin, diphenylene dioxide, phenothiazine, and phenoxazine for the correlation between the folded structure and electronic spectra in terms of the semiempirical SCF–MO–CI method. The calculated results are in good agreement with the experimental results, the folded structure being prominent in the sulfur-containing molecules. The dihedral angle dependency of the all valenceelectronic energy and ionization potential was also studied by the extended Huckel method.

Paramagnetic resonance of the phosphorescent triplet state was carried out for phenoxazine molecules in rigid glasses at 77°K. The line shapes, in Δm=2 and Δm=1 regions, depend upon the incident light polarization. With complementary results from mixed crystals of diphenylphenoxazine, it was possible to relate the principal‐axis system of the tensor describing the zero‐field splitting to the molecular‐axis system. The zero‐field energy levels of the triplet state are of the same order of magnitude as those of aromatic molecules.Selective excitation of the families of molecules corresponding to stationary values of the resonance field showed that:(1) the resonant triplet state is mainly populated via one singlet—singlet transition S1←S0,(2) the dipolar electric transition moment of this excitation is approximately parallel to the nitrogen—oxygen axis of the phenoxazine molecule.Different aspects of photoselection of magnetoselected phosphorescent molecules are discussed.

The reaction of benzo[a]phenoxazin-9-one and its 5-sulfides with ethylenimine has given 11-ethyleneamino derivatives. It has been shown that in contrast to the arylamines, which enter position 5 of benzo[a]-phenoxazin-9-one, ethylenimine reacts at the quinoid nucleus of the phenoxazine system. Absorption spectra in the visible region for phenoxazinones substituted in the quinoid nucleus have been recorded.

The 13 C chemical shifts of six heterocycles related to 9,10-dihydroanthracene have been measured. Resonance assignments of 9,10-dihydroanthracene, acridan, xanthene, and thioxanthene were based on comparison to similar compounds with assigned chemical shifts and off resonance proton decoupling techniques. The 13 C resonances of phenoxazine, phenothiazene, and phenoxathiin were predicted from a simple set of additive relationships based upon the assigned shifts of 9,10-dihydroanthracene, acridan, xanthene, and thioxanthene. Comparison of the predicted to the observed resonances is quite good, with the lone exception of the bridgehead carbons in phenoxazine.

1. The previously unknown 10-[(O,O-dialkylphosphonothio)acetyl]phenothiazines (alkyl: ethyl, propyl, i-propyl, butyl, i-butyl), 10-methyl(ethyl)-3-[(O,O-diethylthionophosphonothlo)acetamido]phenothiazines, [(O,O-diethyldithiophosphono)acetyl]phenothiazine, 10-(O,O-diethylphosphonothioacetyl)phenoxazine, 10-[(O,O-dialkyldithiophosphono) acetyl]phenoxazines (alkyl: ethyl, propyl, i-butyl) and 2,10-bis-[(O,O-diethyl-dithiophosphono) acetyl phenothiazine were obtained. 2. The preliminary biological testing of the compounds for larvicidal and antifungal activity gave negative results.

The purpose of this paper is to assign some specific vibrational bands at 1700-1000 cm −1 to molecular vibrations of the basic benzo(α)phenoxazine skeleton, and to describe the position of the vibrational bands of some substituents attached to this skeleton. In addition, the effect of the electronic behaviour of the substituents on the frequency of the carbonyl vibrations of benzo(α)phenoxazones was determined and the possible electronic interactions in the individual molecules were discussed. The compounds investigated are of the types I, II, and III, where R 1 –R 4 are the individual substituents. All the substances were synthesized for use as acid—base indicators for aqueous and anhydrous media and as oxidation reduction indicators.

A new method for the production of cation radicals is described. The method which consists of a mixture of sulfuric acid and nitromethane has been used to obtain well resolved esr spectra from the cation radicals of phenothiazine, 10-methylphenothiazine and phenoxazine. These results together with some previous results on some related compounds have been compared with Molecular Orbital Calculations of the electron spin densities to evaluate a consistent set of molecular orbital parameters for the nitrogen, sulfur and oxygen atoms.

Chemical and spectroscopic evidence leads to the conclusion that all common α-aminoacids, with the exception of proline and hydroxyproline, undergo oxidative deamination by the action of the model aminochrome, 4-methyl-5-(1′-pyrrolidyl)-1,2-benzoquinone(2), to give the same intensely greenish-blue phenoxazine dye 3. This new colour-forming reaction may form the basis for a new method for the detection, specifically, of α-aminoacids. Unlike ninhydrin, 2 is not capable to bring about the oxidative deamination of β-amino-acids and amines. As expected, the SH-containing aminoacid cysteine reacts differently with 2, giving a yellow condensation product, identified as 3-carboxy-5-hydroxy-8-methyl-7-(1′-pyrrolidyl)-2H-1,4-ben (7).

In the cyclization of 2-chloroaryl 2′-arenesulfamidoaryl ethers to N-arylsulfonylphenoxazines rearrangement of the latter to C-arylsulfonyl-substituted phenoxazines is observed.

1. A number of new 10-(O,O-dialkyldithiophosphonoacyl)phenoxazines was synthesed. 2. 10-(α-Bromobutyryl)phenoxazine, 10-(β-bromopropionyl)phenoxazine, and 10-(γ-chlorobutyryl)-phenoxazine were obtained and characterized.

Phenox azine, 10-ethyl-, and 10-phenylphenoxazine are metalated by n- butyllithium to give what probably are 4-substituted carboxylic acids. Attempts to prove the structures by interconversion of the acids were not successful. 10- Ethylphenoxazine-8-carboxylic acid and 10-(4-carboxyphenyl)-phenoxnzine were prepared by a halogen-metal interconversion reaction, which established these structures. (auth)

Bei der Acetylierung von 3-Amino-4.5-dimethyl-phenoxazon-(2) mit Acetanhydrid/Natriumacetat wird 4.5-Dimethyl-phenoxazon-3-isocyanat als Nebenprodukt isoliert. Seine Bildung kann durch Abspaltung von Aceton aus der 3-Acetoacetylamino-Verbindung erklart werden.

Die Photoelektron-Spektren der Titelverbindungen 1–4 wurden gemessen. Eine Zuordnung der Ionisationspotentiale wird aufgrund eines LCMO-Modells und CNDO/2-Rechnungen vorgenommen. Aus dem Anstieg der Bande der ersten Ionisation wird eine Diskussion der Molekulgeometrien abgeleitet. Electronic Structure of Aromatic Amines: Photoelectron Spectra of 5,10-Dimethyl-5,10-dihydrophenazine, 5-Methyl-10-phenyl-5,10-dihydrophenazine, Phenoxazine and Phenothiazine The photoelectron spectra of the title compounds 1–4 have been measured, and the lower ionization potentials have been assigned on the basis of a CNDO calculation. The slope of the onset of the first band in the spectra is related to the geometry of the molecule.

A proton-magnetic-resonance study of the complex formed between actinomycin D and 10,11-dihydro-3H-naphth[1,2-g]indazol-7-ol strongly suggests that the indazole lies above the phenoxazine ring of actinomycin D. The complex can be destroyed by addition of dimethyl sulphoxide or dimethylformamide. The actinomycin D–indazole complex inhibits growth of Pseudomonas fluorescens and raises the thermal denaturation response of DNA. These data support the hypothesis that a molecular complex is formed which readily inhibits cell growth and interacts with DNA.

This chapter discusses the nomenclature, general methods of synthesis, properties, typical reactions and stereochemical aspects of the oxazines, benzoxazines, phenoxazines, thiazines, benzothiazines, and phenothiazines and their derivatives. Oxazines are studied as 1,2-Oxazines, 1,3-Oxazines, 1,4-Oxazines and related compounds, such as morpholines and morpholones. Nominally there are nine possible benzoxazines; some are readily interconverted by tautomerism. These include 1,2-Benzoxazines, 1,3-Benzoxazines, 1,4-Benzoxazines and their hydro derivatives. The study of phenoxazine is important because some of its derivatives are highly colored and are used as dyes and also because certain phenoxazines show pharmacological activity. The simple derivatives of phenoxazines include the nitrophenoxazines, aminophenoxazines, 3-methoxyphenoxazines, phenoxazinecarboxylic acids, halogenophenoxazines, N-alkylphenoxazines and N-arylphenoxazines, acylphenoxazines, phenoxazinones and phenoxazonium salts, naturally occurring phenoxazine derivatives, such as actinomycins, cinnabarine and so on, benzophenoxazines and benzophenoxazinones. The isomeric forms of thiazines, having one sulfur and one nitrogen atom in a six-membered ring, and their hydro- and benzo- derivatives correspond with structures in the oxazine series, and are named and numbered in the same way. They include 1,2-thiazines and their hydro derivatives, 1,3-thiazines and related compounds, 1,4-thiazines, and their hydro derivatives. Phenothiazines represent an important class of drug substances, which show activity against numerous disorders. Some examples include phenothiazine homologs, halogenophenothiazines, nitrophenothiazines, aminophenothiazines and so on.

Publisher Summary This chapter presents the properties of the azine dyes such as phenazine, oxazine, thiazine, and sulfur dyes, and also their applications. Cyclocondensation of an o -aminophenol with an o -chloronitrobenzene leads to the formation of oxazine derivatives. Substituted 5 H -benzo[a]phenoxazin-5-ones are formed when o -aminophenol is condensed with 2,3-dichloro-1,4-naphthoquinones. The ratio of the isomers formed varies with the nature of R but the 4-substituted derivatives tend to predominate. Oxazine dyes are applied as indicators in bromatometry, for the titrimetric determination of ascorbic acid, redox indicators in inorganic analysis, and in the photometric determination of nitrates and nitrites in water. Some of the oxazine dyes discussed are triphenodioxazines and spirooxazines. The electrical oxidation converts bromide ion into bromine which in turn oxidizes the leuco compound to a dye itself. The reaction of 3,7-bis(diethylamino)phenoxazine with phosgene gives the 10-chlorocarbonyl derivative which is converted into an ester on treatment with potassium t -butoxide. Basic dyes for use in dye diffusion thermal transfer include the phenoxazine derivative.

Summary(1) S-phenylamino-9-dialkyl-aminobenzo[a]phenoxazine dyes stained fat in vivo when administered to mice in their food. (2) The fat staining properties of the dyes were not materially altered by substituents on the phenyl nucleus other than those of highly acidic nature, or by substitutions of the naphthyl group and certain nitrogen heterocyclic rings for the phenyl group. The 5-phenylamino-9-morpholinyl derivatives also stained fat in vivo. (3) S-benzylamino-9-di-methylamino- and diethylaminobenzo[a]phenoxazine dyes did not stain fat in vivo, al-though they did stain tumor tissue. The corresponding dyes in which the alkyl group on the 9-nitrogen contained more than 2 carbon atoms stained fat in vivo. These dyes also stained tumor tissue in vivo.

1. 1. The object of the present investigation has been to show that the optical absorption(s) produced by mixing phenothiazine, or related compounds, with certain electron-acceptor species is the result of an intermolecular charge-transfer transition in an electron-donor-acceptor complex. Observation of a new absorption in a single mixture is not in itself a strong criterion for such complex formation. However, it has previously been shown that linear correlations of frequencies of charge-transfer bands often exist for related groups of complexes. 2. 2. Such correlations are observed between many of the systems: phenothiazine, 3,7-dimethylphenothiazine, 10-methylphenothiazine, chlorpromazine, phenoxazine and thianthrene with various electron acceptors compared with the corresponding complexes of hexamethylbenzene. 3. 3. With certain very strong electron acceptors, the new optical absorptions observed on mixing cannot be assigned to intermolecular charge-transfer transitions. It appears that, in these cases, ionisation to the corresponding radical cation of the donor by single electron transfer occurs. These radicals are unstable in neutral solution, though stable at low pH. 4. 4. In the further reaction which occurs in the case of phenothiazine, it is suggested that a dimer is formed.

Publisher Summary In azine, oxazine, and thiazine dyes, described in this chapter, the basic onium chromophore is normally substituted in position 3 or in positions 3 and 7 by auxochromic groups capable of donating electrons via mesomerism, for example, amino, substituted amino and hydroxyl. The positive ions of dyes so substituted exist as resonance hybrids, and their deep and intense colors are due to electronic transitions within the charged form. Methods of synthesis and commercial uses of phenazine, oxazine, thiazine and sulfur dyes are examined along with examples of individual members of these groups. Phenazine dyes include eurhodines and eurhodols, aposafranines, safranines, fluorindines, indulines and nigrosines, and aniline black. Phenoxazine dyes include basic type, gallocyanines, and triphendioxazines. The bright blue fiber-reactive triphendioxazine dyestuffs for cotton— for example, PROCION Blue H-EGN (C.I. Reactive Blue 198)—have gained considerable commercial importance at the expense of the more traditional anthraquinonoid products. Phenothiazine dyes are mostly salts of the oxidized form of 3,7-diaminophenothiazine with substituents on the amino groups, for example, Methylene Blue, Brilliant Alizarin Blue G, and Leuco-Methylene Blue. The sulfur dyes constitute a wide range of coloring matters cheaply produced by the introduction of sulfur into a variety of organic substances, for example, Immedial Black, Immedial Pure Blue, Hydron Blue R.

Phenoxazine (I), phenothiazine (II), and phenoselenazine (III) form solid iodine complexes of a 2:3 mole ratio when the components dissolved in benzene are mixed (1,2). They are all black polycrystalline powder.