O-Phenylenedi amines

Preparative applications have been found with the anhydrous bis-hy-drochlorides of various o-phenylenediamines 46. These were produced at the 50-g scale and all of these were required for enabling gas-solid condensation reactions with acetone [5]. If the monohydrochlorides of the o-phenylenedi-amines are required, the dihydrochlorides 47 are simply milled with a stoichiometric amount of the corresponding free solid diamine 46 in order to get... 

N-Phenyl-N,-(2,4,6-trinitropheny Q-o-phenylene-diamine or N-Phenyl-N -picryl-o-phenylene-diamine, C6H5.NH.C6H4.NH.C6H2(N02)3, garnet-red pltlts (from ale), mp — decomp on heating to 120° or by heating with ale NaOH at 100°. It was prepd from reaction of pi cry 1-chloride St N-phenyl-o phenylenedi amine (Refs 1 3)... 

Several examples of oxidative ring closures by attack on an azomethine group by an amine have been reported78 thus arylidene-o-phenylenedi-amines (32) have been oxidized to 2-arylbenzimidazoles (33) [Eq. (35)]. 

In a similar way indole isomerizes to benzyl cyanide, pyridine to cyano-butadiene and quinoline to cinnamic acid nitrile. Aniline and o-phenylenedi-amine also form large amounts of unsaturated nitriles in glow discharges. 

An alternative procedure starts from a metal complex of o-phenylenedi-amine. For example, the bis(o-phenylenediamine) complex of nickel(II) chloride reacts with acetylacetone to give a mixture of a nickel complex of the diamine and diketone together with 2,4-dimethylbenzodiazepinium chloride (76CPB1934 91JPR327). Chromium complexes have been used in the same way [91JCS(D)2045]. 

Vinamidines are examples of push-pull alkenes, and other push-pull alkenes R1COCR2=CR3X (X = SR, OR) also react with o-phenylenedi-amine to give benzodiazepines, e.g., Scheme 15 (85JHC405 96TL9155). 

Another case in which the thermal stability of the coordination polymer is reported to be lower than that of the monomeric coordination compound is worth mentioning. Marvel and Tarkoy (18) examined the thermal stability of the nonpolymeric Zn-salicylaldehyde-o-phenylenedi-amine compound (X), which they reported was stable when heated in air at 250°C., losing less than 5% by weight after 24 hours. The related Schiff base coordination polymer (XI) was less stable and decreased in weight by 12% after only 3 hours in air at 250°C. 

Prepare daily EPO substrate solution Dissolve a 20 mg tablet of o-phenylenedi-amine dihydrochloride (OPD, Sigma) in 12.8 mL Tris/HCl buffer (see Note 3). Prepare fresh and keep dark. Just before addition to the samples, add 43 pL of 3% H202. 

Also included in Expt 8.44, is the preparation of 2,3-diphenylquinoxaline (114) and 3-benzyl-2-oxo-l,2-dihydroquinoxaline (115) from o-phenylenedi-amine and benzil or phenylpyruvic acid respectively. 

Biphenylyl isothiocyanate, 36, 57 l-(2-Biphenylyl)urea, 31,10 l-(4-Biphenylyl)urea, 31,10 Bischloromethyl ether, 36,1 N,N -Bis-2-cyanoethyl-o-phenylenedi-amine, 36, 7... 

By condensing the sodium salt of rhodizonic acid with o-phenylenedi-amine a quinone was obtained as early as 1888, but the originally proposed structure as a 2,3-dione (1888CB1227) was shown to be incorrect, the compound being in fact 295 (62LA131). 

A nonisotopic ELISA method in which serum specimens are added to microtiter wells coated with human Tg is also available. In this method, antibody binding is assessed using a peroxidase-conjugated anti-IgG/o-phenylenedi-amine system. An automated two-step fluorescent enzyme immunoassay has been reported. In this assay, Tg is immobilized on magnetic beads, and anti-human IgG mouse monoclonal antibody is labeled with alkafine phosphatase 4-methyiumbelliferyl phosphate is used as the substrate. IRMA and ELISA both have similar detection limits (approximately 3 to 5 U/mL). A considerably more sensitive radioassay has been reported in which diluted serum is incubated with T-labeled Tg to allow formation of antigen-antibody complexes these complexes are then precipitated by adding solid-phase protein A. Its detection limit is reported to be approximately 0.2 U/mL. 

An alternative approach to the synthesis of benzodiazepines involves the reaction of /3-chlorovinyl carbonyl compounds with o-phenylenedi-amine. In the first example methyl /3-chlorovinyl ketone was used to obtain 5-methylbenzodiazepinium chloride.31 An extensive investigation has been made of the use of /3-chlorovinylaldehydes for the preparation of 2,3-substituted benzodiazepines.3233 The preferred conditions for reaction were in alcoholic hydrogen chloride. By this means a variety of 2-aryl-, 2,3-cycloalkeno-, and 2,3-diarylbenzodiazepines was prepared. If no acid is present an uncyclized anil results, formed by condensation of one amino group with the aldehyde. Since the /3-chlorovinylaldehydes are themselves readily obtained by reaction of a-methylene ketones with phosphoryl chloride and N, JV-dimethylformamide or jV-methylformani-lide,34 this provides an attractive route to 2,3-disubstituted benzodiazepines. 

A number of reports concern the attack of nucleophiles on perfluoro-olefins to give cumulenes or heterocumulenes, which in turn imdergo nucleophilic attack to give heterocyclic compounds with perfluoroalkyi substituents. o-Phenylenedi-amine reacts with hexafluoropropene to give 2-(o j8j8>tetrafluoroethyl)benzimidazole (301) ketenimine intermediates have also been utilized in the formation of quinolines (302) (see p. lll) 89.59o j,y intramolecular cyclization, and (303) (see p. 112) by intermolecular cyclization, naphthyridines (304), pyridopyrimidines (305), and isoquinolines (306). The pyran derivative (307) is formed via isomerization of an allene intermediate (see p. 100). 3-Fluoro-2-isopropyl-l,2,4-thiadiazolin-... 

Template reaction of bis(acetylacetone)nickel(II) with molten o-phenylenedi-amine results in formation of the dibenzotetraaza[14]annulene eomplex [Ni(L263)] in low yield (Eq. 2.158) [308]. 

Whilst there are no reports in the literature of crystalline products having been obtained from the interactions of adrenochrome with o-phenylenedi-amine. Auterhoff and Hamacher have prepared a phenazine derivative (103) by the interaction of o-phenylenediamine with rubreserine (66) (a compound structurally similar to the aminochromes) [193]. In the same paper, the authors describe the reaction of rubreserine with ammonia in alcohol at reflux temperatures. A complex mixture of products including the phenoxazone derivative, eserine blue was obtained [193]. 

Methoxy-1,2-benzenedi-amine 4-Methoxy-o-phenylenedi- amine C7H, N20 102-51-2 138.166 grn pi 51 200" vs eth... 

Scheme 38 Substituted-1 l/-/-indeno[l,2-5]quinoxaline-l 1-ones from o-phenylenedi-amine and 3.

A facile synthesis of 4-phenyl-1/f-1,5-benzodiazepines from o-phenylenedi-amines and 1,3-diketones in the presence of a catalytic amount of acetic acid has been achieved, in excellent yields (62-97%) in 2-10 min, under microwave irradiation (Tsoleridis et al, 2008). This method is very simple and the reaction conditions are mild, environmentally friendly and quick. 

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