Of m-phenylenediamine

Another short protocol for preparation of 3 was recently presented by Knolker and Reddy, who devised a short sequence involving a double iron-mediated arylamine cyclization as the key step (Scheme 19). Thus, the reaction of m-phenylenediamine (140) with the tricarbonyliron-complexed cyclohexadienyl cation 141 yielded the complex 142, which was eventually transformed into indolo-[2,3-()]carbazole (3) via cyclization and dehydrogenation (98TL4007 00T4733). 

A range of products was obtained from aniline including those from oxidative coupling (azozybenzene, azobenzene, and benzidine), and phenazine by dimerization (Chan and Larson 1991). Oxidation of m-phenylenediamine was initiated by the oxidation of two molecules to produce an A-phenyl-2-aminoquinone-imine that reacted with m-phenylenediamine to produce 2-amino-5-phenylaminoquinone-imine after further oxidation (Kami et al. 2000). 

Kami H, T Watanabe, S Takemura, Y Kameda, T Hirayama (2000) isolation and chemical-structural identification of a novel aromatic amine mutagen in an ozonized solution of m-phenylenediamine. Chem Res Toxicol 13 165-169. 

The antiseptic acriflavine (6.203) is obtained by condensation of m-phenylenediamine with glycerol and oxalic acid, followed by methylation of the product. 

In general, the acid-sorbing resins may be classified as high molecular weight polyamines or polyimines. Thus, the original Adams and Holmes material was a polymer of m-phenylenediamine. Cation Exchange materials include synthetic resins, such as sulfonated phenol-formaldehyde or polystyrene types, and sulfonated coal. Some manufacturers have a variety of sub-types which are considered superior for particular applications. 

The thermal cyclization of m-phenylenediamine derivatives (799) by heating in diphenyl ether afforded angular l,7-phenanthroline-3,9-dicarboxylate (800), if a substituent was not present at position 2 of the phenyl ring of 799 (R = H), but the linear pyrido[3,2-g]quinolinecarbox-ylate (801, R = Me, R1 = R2 = H) was prepared from the 2-methyl-substituted derivative (799, R = Me, R1 = R2 = H) (72GEP2220294). 

The double iron-mediated arylamine cyclization provides a highly convergent route to indolo[2,3-fc]carbazole (Scheme 16). Double electrophilic substitution of m-phenylenediamine 34 by reaction with the complex salt 6a affords the diiron complex 35, which on oxidative cyclization using iodine in pyridine leads to indolo[2,3-b]carbazole 36 [98].Thus,ithasbeen demonstrated that the bidirectional annulation of two indole rings can be applied to the synthesis of indolocarbazoles. 

A related entry to the 1,7-phenanthroline ring system involves reaction of m-phenylenediamine with dimethyl acetylenedicarboxylate in methanol at ambient temperature.177 This affords the intermediate bis-fumarate which cyclizes in diphenyl ether at 250° giving, in 95% yield, 2,8-dicarbomethoxy-4,10-dihydroxy-1,7-phenanthroline. The angular... 

The polyamide-hydrazide 7 was prepared by solution polymerization in anhydrous dimethylacetamide from terephthaloyl chloride and p-amino-benzhydrazide at ca. 10 °C. The polyamide 8 resulted from the polycondensation of m-phenylenediamine with isophthaloyl chloride at —20 °C, whereas 9 was prepared by the reaction of terephthaloyl chloride with the complex diamine l,3-bis(3-aminobenzamide)benzene at —20 °C. The water flux and salt rejection through these membranes were summarized in Table 5. The polyamide-hydrazide (7) membranes were prepared from polymer solutions containing 6 7% polymer (Mv 3 34,000) by casting on glass plates. The material was placed in an oven for 30 60 min and coagulated in deionized... 

If m-tolylenediamine is used in place of m-phenylenediamine, the dyestuff formed is Chrysoidine R. 

NH-CgH2(N02)s. Red crysts(from acet), mp 206-7°, expl on rapid heating easily sol in acet, diff sol in ale AcOH. Can be prepd by a 2-hr heating of picryl chloride with equivalent quantities of m-phenylenediamine-hydroch loride and Na acetate in ale... 

This reagent is used here for the diazotisation of 4-amino-3,5-diiodobenzoic acid in the preparation of 3,4,5-triiodobenzoic acid (cognate preparation in Expt 6.70). It is also used for the bis-diazotisation of m-phenylenediamine (the... 

C. I. Direct Black 19, 35255 [6428-31-5] (19) is also an important dye. It is obtained by coupling two equivalents of j9-nitraniline to H acid, sulfhydrate reduction of the two nitro groups, and coupling of the bis-diazotized intermediate compound with two equivalents of m -phenylenediamine. 

The excess used is about 24 per cent in the case of m-phenylenediamine, and about 20 per cent in the case of toluylenediamine. The diamine is then completely used in the dye formation as can be shown by salting out a test portion. 

If m-toluylenediamine is used in place of m-phenylenediamine, deep black V is formed. This dye gives somewhat more reddish shades. In this case also, it is necessary to add some soda after warming the reaction mixture in order to obtain a filterable product. 

Technical Observations. If 1,2,4-toIuyIenediamine is used in place of m-phenylenediamine, an analogous dye is formed which is somewhat more fast to acids. In this case, one of the positions para to the amino group is occupied, and hence the formula given above for the m-phenylenediamine dye must be correct, i.c., the second azo group must enter the position between the two amino groups, and not the position para to the —NHa. ... 

The tetrazotization of m-phenylenediamine has been described also, under special conditions (nitrosylsulfuric acid in glacial acetic acid) a similar conversion of the ortho isomer has been accomplished. This procedure has been adaf>ted to the tetrazotization of certain naphthalene diamines. The simultaneous diazotization of two amino groups in the biphenyl series is illustrated by the synthesis of 4,4 -biphenylene-fejs-diazonium chloride and its 3,3 "dimethyl analog. ... 

Their biosensor consisted in a Pt wire on which GOD was immobilized by the electropolymerization of m-phenylenediamine. The advantage of this type of immobilization consists in creating an effective barrier against electrochemical interference due to the polymer formed onto the electrode. Moreover, an extended linearity for the glucose sensor was also obtained, and this was a requisite for the direct measurement of the subcutaneous glucose at diabetic levels, since in practice an extremely low dilution of the subcutaneous fluid was realized. 

Also, the mixture of m-phenylenediamine dihydrochloride and hydrochloric acid used later has not gained acceptance. The solution turns purple upon light absorption because of a slow dimerization of the amine and, thus, has only a limited stability. 

In composite RO membranes, the selective top layer and the porous support layer are usually made of different polymeric materials. The selective top layer is formed on the porous support in a second step, typically by an interfacial polymerization reaction. For example, a commercially available thin film composite RO membrane is made by coating a porous polysulfone support with a polyamide thin film formed by the interfacial reaction of m-phenylenediamine and 1,3,5-benzenetricarbonyl trichloride. Details regarding membrane structures can be found elsewhere in the... 

For cation chromatography there are basically two eluent systems used. In the case of monovalent cations, the normal eluent is 0.005M HC1. However, the concentrations of hydrogen ion required for divalent cations are such that hydrogen ion is impractical eluent for divalent cations. Instead, the preferred cation for divalent cations like the alkaline earth cations is m-phenylenediamine dihydrochloride. The divalent nature of m-phenylenediamine makes it an efficient eluent for other divalent cations, while its weakly basic character results in very little conductivity when it is converted to the free base form in the suppressor. 

Results obtained so far show that the levels of conversion and selectivity of the rearrangement of aniline to a-picoline and of toluidine to lutidine or collidine are limited only the rearrangement of m-toluidine shows promise for further studies. Results from rearrangements of m-phenylenediamine and naphthylamine give hope that further work (with flow instead of batch reactors, and with Fe- and Ga-ZSM-5 catalysts) might lead to efficient syntheses of aminopicolines and methyl-isoquinolines. 

A similar reaction, the rearrangement of m-phenylenediamine was patented by Bayer (Figure 1) [6]. In this patent, a much higher conversion and a better selectivity than obtainable with aniline was reported. Two reaction mechanisms were proposed for the aniline rearrangement reaction [3,7]. In this contribution, we will discuss this interesting reaction and report on some studies on process variables and on the reaction mechanism. As a model compound, we used m-phenylenediamine because of the higher conversion and relatively milder reaction conditions required for its conversion into 2-amino-6-methylpyridine (a-amino-a -picoline). 

The optimal conditions for conversion and selectivity in the rearrangement of m-phenylenediamine were 593 K and 10000 kPa. Results obtained with various zeolites are given in Table 2. 

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