3 -phenothiazinyl

DETERMINATION OF l-[2-OXO-2-(TRIFLUOROMETHYL-10-PHENOTHIAZINYL)-ETHYL]-4-HYDROXYIMINOMETHYL-PYRIDINIUM CHLORIDE BY DERIVATIVE UV-SPECTROPHOTOMETRY... 

The sodium derivative of the 2-trifluoromethylphenothiazine was prepared from 26.7 g (0.1 mol) of 2-trifluoromethylphenothiazine and 2.3 g (0.1 g atom) of sodium in 500 ml of liquid ammonia. After the reaction was completed, the ammonia was driven off and 500 ml of dry toluene were added. A solution of 25 g (0.09 mol) of N-(3-chloropropyl)-N -[2-(1,3-dioxanyl)-ethyl] -piperazine In 200 ml of toluene was added drop by drop to this solution which was then refluxed with stirring for 1B hours. After cooling, the precipitate which had formed was filtered and the filtrate was washed with water, dried and concentrated in vacuo. 33 g of brown oil, the N-3-(2-trifluoromethyl-10-phenothiazinyl)-propyl-N -2-[2-(1,3-dioxanyl)] -ethyl-piperazine, were obtained. 

Mixtures of 4- and 7-azaphthalides carrying a wide variety of heterocycles such as carbozolyl, pyrrolyl, acridinyl, phenothiazinyl, thianaph-thenyl, and thienyl as well as indolyl of the general formulas 19 and 20 have also been described.86 Table 1 illustrates the variety of hues available with such compounds. 

Since superoxide reduces readily quinoid structures (e.g. B) (14), product C (7-hydroxy-3H-phenothiazine-3 one) may have a similar genesis, and 7-(10-phenothiazinyl)-3H-phenothiazine-3-one (D) represents one of the many possible recombination products starting from PT . 

Chemical Name N-3-(2-Trifluoromethyl-10-phenothiazinyl)-propyl-N -2-[2-(l,3-dioxanyl)]ethyl-piperazine disuccinate... 

Molecular Recognition and Chemistry in Restricted Reaction Spaces. Photophysics and Photoinduced Electron Transfer on the Surfaces of Micelles, Dendrimers and DNA [N. J. Turro, J. K. Barton, D. A. Tomalia, Acc. Chem. Res. 1991, 24, 332], Self-Assembly in Synthetic Routes to Molecular Devices. Biological Principles and Chemical Perspectives A Review [J. S. Lindsey, New J. Chem. 1991,15, 153], Amorphous molecular materials synthesis and properties of a novel starburst molecule, 4,4, 4 -tri(N-phenothiazinyl)triphenylamine [A. Higuchi, H. Inada, T. Kobata, Y. Shirota, Adv. Mat. (Weinheim, Ger.) 1991, 3(11), 549-550],... 

Phenacyl ethers, to protect phenols, 153 Phenacylsulfonamides, to prote ct amines, 385 Phenols, protection of, 143-170 as esters, 162-170 as ethers, 145-162 Reactivity Chart 4, 425-428 Phenothiazinyl-(10)-carbonyl derivatives, to protect amines, 346... 

Fig. 5. Dependence of g values upon the spin-orbit coupling parameter A of the halogen, in halogenated phenothiazinyls.

E. Formation of Phenothiazinyl Radicals through Homolytic Cleavages... 

A third type of homolytic cleavage leading to phenothiazinyl radicals is represented by the dissociation of 10,10 -biphenothiazines, which may be considered as tetraarylhydrazines. Although 10,10 -biphenothiazines were prepared long ago by oxidation with bivalent... 

G. Reactions Involving Phenothiazinyl Radicals and Phenazathionium Cations... 

Dimerization of the Phenothiazinyl Free Radicals It was pointed out in Section IV, B, 3 that the greatest spin density in the molecule of the phenothiazinyl free radicals is located on the nitrogen, sulfur, C-3 and C-7 atoms. Since the sulfur atom of pheno-thiazines is involved in a sulfide bridge, and has, consequently, no tendency to form a third covalence, there are only three kinds of... 

When lithiated phenothiazine is treated with methyl sulfate, acetyl chloride, and ethylene oxide 10-substituted derivatives are obtained. Lithium salts of carboxylic acids, however, lead to 1-phenothiazinyl ketones Scheme 14 presents the evidence for the structures assigned to these substances. 

Most of the reactions of the phenothiazinyl ketones discussed here were carried out on compounds of the 2 series readily available by Friedel-Crafts acylation (See Section V,A,4,c) many products derived from these ketones are of pharmacological importance. 

The Leuckhardt reaction has been applied to 2-acetylphenothiazine, giving 1 -(2-phenothiazinyl )ethylamine. ... 

Burger and Clements converted 2-acetylphenothiazine into a-(2-phenothiazinyl)thioacetomorpholide (160) with sulfur and morpholine in a Willgerodt reaction hydrolysis of the latter to a-(2-phenothiazinyl)acetic acid, which on decarboxylation gave 2-methyl-phenothiazine (113), was reported by Massie et al. The same reaction sequence has been performed recently starting from 2-chloro-8-acetylphenothiazine. ... 

Reactions at the active a-methyl or a-methylene group have also been investigated. Under Mannich reaction conditions 10-methyl-phenothiazinyl 2- and 3-ketones yielded the expected products. ... 

Fujimoto chlorinated 2-acetylphenothiazine and obtained a product to which structure 162 was assigned. One of the chlorine atoms is very labile, in agreement with the observation of Massie et that in 2-chloroacetylphenothiazine the chlorine may easily be replaced by Br, I, CN, and thiourea the latter yields 2-amino-4-(2-phenothiazinyl)thiazole (163). 

HYDROXYETHYL)-4-(3-(2-CHLORO-10-PHENOTHIAZINYL)PROPYL)PIPERAZINE see CJM250... 

Other Romanian workers have studied solid-state properties of octachloro-phenothiazinyl (257). ° The ENDOR spectrum of 2-chlorophenothia-zine has been measured. ... 

Hanson and co-workers have studied substituent effects on the distribution of spin in cation, neutral, and nitroxyl radicals of phenothiazine. The substituent effects were described quantitatively using Taft s (Tj and various ctr values, and are understandable in terms of a redistribution of spin population principally between N and S in the cation-radicals and phenothiazinyls, and between N and O in the nitroxyls. 

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