N-methyl-o-phenylenediamine

Benzazinotropones 118a-c (Scheme 28) are synthesized by the reactions of certain 2-methoxy-3-bromotropones (116) with o-aminophenol (117a 91BCJ2131), o-aminothiophenol (117b 61BCJ146), and N-methyl-o-phenylenediamine [117c 89H(29)1459], respectively. 

Mono-N-methyl-o-phenylenediamine reacts with acetylacetone to provide 1,2,4-trimethylbenzodiazepinium salts, but the yield is low, and it was not possible to isolate the base. This has also been ascribed to destabiliza-... 

Similarly to 3,3 -diaminobenzidine, other aromatic o-diamines also react with selenium(rV) in HCl medium. The o-phenylenediamine method [30,31] is more sensitive than the DAB method. The following reagents have been proposed for selenium N-methyl-o--phenylenediamine (e = 1.9-10 at 346 nm) [32], 2-aminodiphenylenediamine [33], 4-nitro-1,2-diaminobenzene [34], 4,5-diamino-2,6-dimercaptopyrimidine [35], l,2-diamino-4-chlorobenzene [36], 4,5,6-triaminopyrimidine [37], 3,4-diaminobenzoic acid [38], and 2,3-diaminonaphthalene [39,40]. 

The use of unsymmetrical o-phenylenediamines in these reactions clearly leads to products of ambiguous structure however the condensation reactions of N-substituted o-phenylenediamines (e.g., N-methyl-o-phenylenediamines) yields quinoxalinones of known structme (4). Since... 

Although the condensation of mesoxalic acid with o-phenylenediamine and N-methyl-o-phenylenediamine hydrochloride proceeds in an analogous manner, when sodium mesoxalate is reacted with o-phenylenediamine and the reaction mixture is acidified, the reduced acid 3 and benzimidazole-2-carboxylic acid (4) are formed. The primary products of reaction are thought to be the expected quinoxalinonecarboxylic acid (1) and the dihydrobenzimidazoledicarboxylic acid (2). Reduction of the quinoxalinonecarboxylic acid is thought to involve the dihydro-... 

New developments in this area include uric acid sensors based on the mediation of urate oxidase by a novel redox polymer, poly(N-methyl-o-phenylenediamine) [145], and by the freely diffusing mediator 1-methoxy-5-methylphenazinium [146], continued research on the direct amperometric detection of NADH [147] and the use of redox mediators [148] for dehydrogenase enzymes, to allow practical sensors that exploit this large class of enzymes, and the use of cytochrome P450-modified glassy carbon electrodes as drug metabolism biosensors [149]. 

By ( clization of N-(l-adamantoyl)-N -methyl-o-phenylenediamine in absolute chloroform and alcohol environment, in the presence of polyphosphoric aeid ester (ppe), l-methyl-2-(adamantyl)benzimidazole (79) is obtained with 35% yield. 6-nitrobenzimidazole-2-earboxylic acid-(l-adamantylamide)-l-oxyde (80) was obtained with 3% yield by treatment of l-(N-2,4-dinitro-phenylgli( lamino)adamantane in pH 8.5 phosphate buffer, at 90 C during 136 hours. 

Benzothiadiazolium salts and their seleno-analogues (187) have been produced by the condensation of N-methyl-o-phenylenediamines with thionyl chloride or selenious acid (HaSeOa) 6-(2-aminophenylthio)-4-methyl-2,l,3-benzoselenadiazole has been similarly prepared. ... 

N-Substituted quinoxalines are obtained from N-substituted o-phenylenediamines. Thus methyl 2,3-dibromopropionate condenses with (V,A -bis(/7-toluenesulfonyl)-o-phenylenediamine to give l,4-bis(p-tolu-enesulfonyl)-2-methoxycarbonyl-1,2,3,4-tetrahydroquinoxaline (20).25 AVV -Disubstituted cyclohexane-1,2-diamines with suitable a/7-dihalides yield decahydroquinoxalines.26 Condensation of cyclohexane- 1,2-diones with glycine amide gives 2-oxo-5,6,7,8-tetrahydroquinoxalines.27... 

Hydroxylamine hydrochloride in water treated portionwise with an equimolar amount of NaHCOg, then mixed with an ethanolic soln. of 0.5 mole N-cyano-methyl-o-phenylenediamine, and refluxed on a water bath until NH -evolution ceases after 16 hrs. 2-oximino-l,2,3,4-tetrahydroquinoxaline (Y 78%) (B.105, 805) refluxed 0.5 hr. in acetic anhydride -> 2-acetaminoquinoxaline (Y 75%) (B. 105, 813). K. Harsanyi et al., B. 105, 805, 813 (1972). 

The intramolecular 1,3-dipolar cycloadditions of homochiral nitrilimines derived from methyl esters of glycine, L-alanine, L-phenylalanine, and (S)-2-phenylglycine produced enantiopure 2,3,3a,4,5,6-hexahydropyrrolo[3,4-c]pyrazoles in fair to good overall product yields.50 The thermal reaction of diphenylnitrilimine with N-substituted benzimidazoles (47) produced lV,AP-disubstituted o-phenylenediamines (51). The reaction involved two 1,3-dipolar cycloadditions with two nitrilimine moieties yielding adducts (48-50), followed by a ring opening of the azolic ring of (50) (Scheme 13).51... 

Manninotriose (0.8 g.) was heated with 1.44 g. of phenylhydrazine hydrochloride, 0.22 g. of o-phenylenediamine, and 0.5 g. of glacial acetic acid in 20 ml. of water at 100° in a stoppered tube. After 3 hours, the reaction mixture was cooled and neutralized with 40 ml. of 0.5 N sodium hydroxide. The trisaccharide flavazole was isolated by fractional extraction of the solution with ether (to remove organic bases and colored impurities), ethyl methyl ketone (to remove traces of monosaccharide and disaccharide flavazoles, as well as other colored impurities), and butanol (which extracted the trisaccharide flavazole). Each step in the fractionation process was followed by... 

Heterocycles Acetylacetone. N-Aminophthalimide. Boron trichloride. Dichloro-formoxime. Oicyanodiamide. Dicyclohexylcarbodiimide. Dietboxymethyl acetate. Diethyl oxalate. Diketene. Dimethylformaniide diethylacetal. Diphenyldiazomethene. Ethyl ethoxy-methylenecyanoacetate. Formaldehyde. Formamide. Formamidine acetate. Formic acid. Glyoxal. Hydrazine. Hydrazoic acid. Hydroxylamine. Hydroxylamine-O-sulfonic acid. Methyl vinyl ketone. o-Phenylenediamine. Phenylhydrazine. Phosphorus pentasullide. Piperidine. Folyphosphoric acid. Potassium diazomethanedisulfonate. Sodium ethoxide. Sodium nitrite. Sodium thiocyanate. Tetracyanoethylene. Thiosemicarbozide. Thiourea. Triethyl orthoformate. Tris-formaminomethane. Trityl perchlorate. Urea. Vinyl triphenyl-phosphonium bromide. 

Ethyl-3-methyl- and 2-n-butyl-3-n-propylbenzodiazepines have been prepared by condensation reactions involving /3-ketoaldehydes and o-phenylenediamine,17 and a series of 2,3-cycloalkenobenzodiazepines was... 

Quinoxalinones have been prepared by reaction of the dichloroacetyl derivative of o-phenylenediamine with either morpholine or N-methyl-piperazine in the presence of sulfur (Scheme 6). Treatment of 0-phenylenediamine with l,2-dichloro-l,2-diethoxyethane gives a small... 

When o-phenylenediamine is allowed to react with alloxan in aqueous solution, the quinoxaline ureide 19 is produced.The structure of the product formed in this reaction has been the subject of controversy. It was at first suggested to be the anil 20 since a superficially similar product, now known to be the spiro compound 22, is obtained by reaction of o-aminodimethylaniline and alloxan in aqueous ethanol. Compound 22 is believed to be formed via the intermediate anil 21, which undergoes a unique cyclization in which an N-methyl group is involved. 

Parbendazole, (S-Butyl-lH-benzimidazoi-2-yi)-carbamic acid methyl ester methyl 5 -butyl -2-benzimidazole-carbamate 5-butyl -2-(carbomethoxyamino)benzimidazole SKF 29044 Hdmatac Verminum Worm Guard. C,H17-NjO, mol wt 247,29. C 63.14%, H 6.93%. N 16.99%, O 12.94%. Prepd from 4-butyl -o-phenylenediamine and car-bomethoxycyanamide Actor el aL. Nature 215, 321... 

An alternative pathway started with N-hydroxyalkyl-o-nitro-anilines (VIII), which were successively chlorinated with thionyl-choride and coupled with l-(a, a -diarylmethyl)-piperazine (II) to give the intermediates XV. Catalytic hydrogenation of the nitro group afforded o-phenylenediamines XVI, which could be used to synthesize either III or XIII. Cyclisation of XVI with CS2 in ethanol gave the 2-mercaptoimidazole (XVII) (10). which was methylated to XVIII with methylsulphate. On the other hand, ring closure, with methyl (a-imino-a-methoxymethyl)carbamate, gave the 2-methoxy carbonylamino derivative XIX (11). which was further hydrolyzed and then reacylated affording 2-amino (XX) and 2-acetylamino (XXI) derivatives (Scheme 5). These compounds are also summarized in Table II. 

Cl 37100. See 2-Methyl-4-nitroaniline Cl 37105. See 2-Methyl-5-nitroaniline Cl 37107. See p-Toluidine Cl 37110. See 3-Nitro-p-toluidine Cl 37115. See o-Anisidine hydrochloride Cl 37130. See 2-Methoxy-5-nitroaniline Cl 37225. See Benzidine Cl 37230. See o-Tolidine Cl 37235. See Dianisidine Cl 37240. See N-Phenyl-p-phenylenediamine Cl 37500. See P-Naphthol Cl 40000. See Direct yellow 11 Cl 40002 Cl 40003. See 4,4 -Diaminostilbene-2,2 -disulfonic acid Cl 40645. See Sodium-2-(4-styrvl-3-sulfophenyl)-2H-naphtho-(1,2-d)-triazole Cl 40800... 

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