Diphenyl amine, substituted

SuIfona.tlon, Sulfonation is a common reaction with dialkyl sulfates, either by slow decomposition on heating with the release of SO or by attack at the sulfur end of the O—S bond (63). Reaction products are usually the dimethyl ether, methanol, sulfonic acid, and methyl sulfonates, corresponding to both routes. Reactive aromatics are commonly those with higher reactivity to electrophilic substitution at temperatures > 100° C. Tn phenylamine, diphenylmethylamine, anisole, and diphenyl ether exhibit ring sulfonation at 150—160°C, 140°C, 155—160°C, and 180—190°C, respectively, but diphenyl ketone and benzyl methyl ether do not react up to 190°C. Diphenyl amine methylates and then sulfonates. Catalysis of sulfonation of anthraquinone by dimethyl sulfate occurs with thaHium(III) oxide or mercury(II) oxide at 170°C. Alkyl interchange also gives sulfation. 

Condensa.tlon, This term covers all processes, not previously iacluded ia other process definitions, where water or hydrogen chloride is eliminated ia a reaction involving the combination of two or more molecules. The important condensation reactions are nitrogen and sulfur heterocycle formation, amide formation from acid chlorides, formation of substituted diphenyl amines, and misceUaneous cyclizations. 

The reaction of substituted chloronitrobenzenes with arylamines to form substituted diphenyl amines is typified by 4-rutrodiphenylamine-2-sulfoiiic acid where 4-chloronitrobenzene-3-sulfonic acid (PN salt) is condensed with aniline ia an aqueous medium at 120°C and 200 kPa (2 atm) ia the presence of alkaline buffer at low pH to avoid the competing hydrolysis of the PN salt. 

Compound parts polymer, 100 Naugard 445 (substituted diphenyl amine), 2 Armeen 18D (octadecyl amine), 0.5 stearic acid, 2 Vanfre VAM (complex organic alkyl acid), 0.5 SRE Carbon Black (N774), 100 DIAK 1 (hexamethylenediamine), 1.25 and di-o-tolylguanidine, 4. 

Nucleophilic aromatic substitution of the anthranilic acid derivatives, 72, on ortho-bromonitrobenzene affords the diphenyl-amine, 73. The ester is then saponified and the nitro group reduced to the amine (74). Cyclization of the resulting amino acid by heat affords the lactam (75). Alkylation on the amide nitrogen with 2-dimethylaminoethyl chloride by means of sodium amide affords dibenzepine (76). ... 

Most of the early applications of palladium to indole chemistry involved oxidative coupling or cyclization using stoichiometric Pd(II). Akermark first reported the efficient oxidative coupling of diphenyl amines to carbazoles 37 with Pd(OAc)2 in refluxing acetic acid [45]. The reaction is applicable to several ring-substituted carbazoles (Br, Cl, OMe, Me, NO2), and 20 years later Akermark and colleagues made this reaction catalytic in the conversion of arylaminoquinones 38 to carbazole-l,4-quinones 39 [46]. This oxidative cyclization is particularly useful for the synthesis of benzocarbazole-6,11-quinones (e.g., 40). 

There appeared to be a good correlation between the mouse toxicity data from an I.P. route and the rat feeding study (Appendix II). With the results from these tests we were able to define the "A" ring substitution requirements required to make the trinitro diphenyl amines toxic to rats. 

Figure 5.33 Chromatograms obtained during the optimization of the composition of a ternary mobile phase for RPLC for the separation of five substituted diphenyl amines (DPAs). Solutes (1) N-nitroso-DPA, (2) 4-nitro-DPA, (3) 2,4 -dinitro-DPA, (4) DPA and (5) 2-nitro-DPA. Stationary phase Hypersil ODS. Figure taken from ref. [576]. Reprinted with permission.

Photocyclization of A -methyl-(p-methoxyphenyl)anilines in the presence of aqueous hydrochloric acid gave a set of carbazolones, as illustrated by the conversion of the diarylamine 241 into the system 242 (Equation 77) <2002CC270>. In addition, it has been reported previously that photocyclization of fluorine-substituted diphenyl-amines leads to formation of carbazoles <1996J(P1)669>. 

Carbazole behaves on substitution like a derivative of diphenyl-amine, i.e., it is attacked first in the positions which are ortho or para to the imino group. Introduction of a substituent in the position meta to the nitrogen can only be accomplished indirectly. Thus, strongly... 

As with the cyclization of A-substituted diphenyl-amines with SOCI2 (Section II, A), the chlorination of A-substituted phenothiazines with thionyl chloride is accompanied by removal of the 10-substituent, 28 ... 

Bisagni and co-workers (113,116) also explored several synthetic routes to the tricyclic y-carbolines (5//-pyrido[4,3-i>]indole ring system). Unfortunately, the attractive one-step Nenitzescu reaction (114) proceeded in only 6% yield to afford 286 (113). The Fischer indolization sequence was far more efficient (Scheme 46) (113). Thus, condensation of phenylhydrazine with 279 in boiling diphenyl ether gave in one step the desired y-carboline 287 in excellent yield. Chlorination of the pyridone functionality gave chloropyridine 288, which was converted to the target amine-substituted y-carbolines 289—291 by heating with the appropriate amines. 

Condensation Reactions. Condensation of substituted benzaldehydes with 2-arninophenol in the presence of a catalyst (aluminum, iron, zinc or phosphoms chlorides) yidds a Schiff base, with the elimination of water, in 52—88% yields (29). In general, substituted diphenyl amines or diphenyl ethers are obtained from arninophenols and suitable reactants by elimination of ammonia or hydrogen chloride. 

The successive introduction of Y-phenyl groups to anihne (diphenyl-amine and triphenylamine), was shown to inhibit ortho substitution, and the bromine tends to occupy one or more of the available para... 

Amine antioxidants are also used. They too are considered to act as radical scavengers. Commonly these are substituted p-phenylenediamines or alkylated diphenyl amines. These are used more in rubber or lubricant formulations and less so in thermoplastics. Often they impart color so they are more likely to be used in formulations that are pigmented with carbon black. 

N-substituted 4-hydroxyphenylthiomethyl amine or urides Octylated diphenyl amines Zn dialkyl dithiophosphates... 

As an example of a relatively simple structural determination, Catellani et al. [415b] took a strong absorption at 920 cm in the spectra of a family of substituted poly(2,5-thienylene vinylene)s to indicate a trans configuration about the vinyl bond. In studies of typical poly(aromatic amines) such as poly(diphenyl amine), poly(4-amino biphenyl) and poly(A/-Phe-2-naphthyl amine), the Dao group [24,46] observed... 

Halogeno-l-methyl-l,2,3-triazoles undergo substitution reactions with amines, but the 4-halogeno analogs do not. 5-Chloro-l,4-diphenyl-l,2,3-triazole with sodium cyanide in DMSO gives the cyano derivative (63JCS2032). 1-Substituted 3-chloro- and 5-chloro-l,2,4-triazoles both react with amines. 

The procedure described is essentially that of Shioiri and Yamada. Diphenyl phosphorazidate is a useful and versatile reagent in organic synthesis. It has been used for racemlzatlon-free peptide syntheses, thiol ester synthesis, a modified Curtius reaction, an esterification of a-substituted carboxylic acld, formation of diketoplperazines, alkyl azide synthesis, phosphorylation of alcohols and amines,and polymerization of amino acids and peptides. - Furthermore, diphenyl phosphorazidate acts as a nitrene source and as a 1,3-dipole.An example in the ring contraction of cyclic ketones to form cycloalkanecarboxylic acids is presented in the next procedure, this volume. 

Because of the ease of ring synthesis, symmetrically trisubstituted s-triazines have been more thoroughly studied, but a few nucleophilic substitutions of derivatives bearing a single leaving group are known. 2-Chloro-4,6-diphenyl- and 2-chloro-4,6-dimethyl-s-triazines (318) undergo facile nucleophilic displacements with ammonia, amines, and hydrazine, with alkoxide, or with hydrosulfide... 

Another approach involves utilization of the amines for addition of a fused pyridine ring to the benzothiadiazole skeleton. The Gould-Jacobs reaction of 4-amino-2,l,3-benzothiadiazole 60 with diethyl ethoxymethylenemalonate gave the substitution product, and, after thermal cyclization in diphenyl ether, afforded the... 

Salts of dithiocarbamic acid can be prepared by the addition of primary or secondary amines to carbon disulfide. This reaction is similar to 16-9. Hydrogen sulfide can be eliminated from the product, directly or indirectly, to give isothiocyanates (RNCS). Isothiocyanates can be obtained directly by the reaction of primary amines and CS2 in pyridine in the presence of DCC. ° In the presence of diphenyl phosphite and pyridine, primary amines add to CO2 and to CS2 to give, respectively, symmetrically substituted ureas and thioureas ... 

Tu found that when aniline was used instead of the secondary amine under otherwise identical conditions 2,4-diphenyl-substituted quinoline was formed in 56% yield. Phenylacetylene and aniline were initially used as model substrates for exploring the aldehyde scope. With aromatic aldehydes the reactions proceeded smoothly to give the corresponding quinolines in moderate to good yields. A heteroaromatic aldehyde is also compatible with this transformation and the expected product was afforded in 83% yield. However, when ahphatic aldehydes were subjected to the reaction, the desired product was obtained in low yield (Scheme 19) [34]. 

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