Diphenyl nitrogen

N 18.42% crysts, dec on crystn from ethyl acet forming 4,4 -Dinitro-diphenylamine was prepd by action of NO on 4,4 7Dinitro-diphenyl nitrogen oxide, (02NC6H4)2N0, in cold chlf (Refs I 2)... 

Atom transfer to form a stable radical which does not reinitiate polymerization, as in the reaction of poly(vinyl acetate) radical and diphenylamine to yield a diphenyl nitrogen radical which will not add vinyl acetate but may terminate a macroradical. 

Diarylamines are compounds that have two aromatic groups and one hydrogen atom attached to nitrogen. Diphenyl amine (DPA), or... 

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. 

Amination at an azole ring nitrogen is known for Af-unsubstituted azoles. Thus 4,5-diphenyl-1,2,3-triazole with hydroxylamine-O-sulfonic acid gives approximately equal amounts of the 1- (104) and 2-amino derivatives (105) (74AHC(16)33). Pyrazole affords (106) and indazole gives comparable amounts of the 1- and 2-amino derivatives. 

The present preparation illustrates a general and convenient irethod for ring contraction of cyclic ketones. The first step is the usual procedure for the preparation of enamines. The second step involves 1,3-dipolar cycloaddition of diphenyl phosphorazidate to an enamine followed by ring contraction with evolution of nitrogen. Ethyl acetate and tetrahydrofuran can be used as a solvent in place of toluene. Pyrrolidine enamines from various cyclic ketones smoothly undergo the reaction under similar reaction conditions. Diphenyl (cycloalkyl-1-pyrrolidinylmethylene)phosphoramidates with 5,6,7, and 15 members in the ring have been prepared in yields of 68-76%. 

Diphenyl disulfide (phenyl disulfide) [882-33-7] M 218.3, m 60.5 . Crystd from MeOH. [Alberti et al. J Am Chem Soc 108 3024 1986]. Crystd repeatedly from hot diethyl ether, then vac dried at 30° over P2O5, fused under nitrogen and re-dried, the whole procedure being repeated, with a final drying under vac for 24h. Also recrystd from hexane/EtOH soln. [Burkey and Griller 7 Am Chem Soc 107 246 1985.]... 

Biphenylyl diphenyl phosphate [132-29-6] M 302.4, n l.5925. Vacuum distd, then percolated through an alumina column. Passed through a packed column maintained at 150° to remove residual traces of volatile materials by a counter-current stream of nitrogen at reduced pressure. [Dobry and Keller J Phys Chem 61 1448 1957.]... 

Enby 6 is an example of a stereospecific elimination reaction of an alkyl halide in which the transition state requires die proton and bromide ion that are lost to be in an anti orientation with respect to each odier. The diastereomeric threo- and e/ytAra-l-bromo-1,2-diphenyl-propanes undergo )3-elimination to produce stereoisomeric products. Enby 7 is an example of a pyrolytic elimination requiring a syn orientation of die proton that is removed and the nitrogen atom of the amine oxide group. The elimination proceeds through a cyclic transition state in which the proton is transferred to die oxygen of die amine oxide group. 

Most N-phenyl quaternary salts are not prepared by direct quater-nization but rather by introducing the nitrogen substituent before ring closure. It has recently been found that diphenyl iodonium boro-fluoride reacts smoothly with pyridine the phenyl carbonium ions formed give the 1-phenylpyridinium ion good yield. ... 

Tlie smallest compounds among the azafulvalenes described to date are the azacalicenes, which are formed by combining a cyclopropenylidene moiety with a nitrogen-containing cyclopentadienylidene. Tlius, heating di-or triphenylpyrroles with diphenyl-methylsulfanyl-cyclopropenylium perchlorate in acetic acid gives the aza-triafulvalenium salts 33 and 34... 

Among the variety of nitrogen-containing fulvalenes emerging from types 7-14, X-ray structural determinations have been performed on about 20 representative examples. Tire first crystal structure determination was carried out by application of the folding-molecule method on 3,3 -diphenyl-l,l -bi-isoindolylidene 64 (R = FI) (71CB3108). Tire dimeric isoindolenine system... 

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). ... 

To make the hydrochloride salt, the bisacetamide or, by another name, 1,11-diphenyl-2,2,3,9,10,10-hexamethyl-4 3hydroxy ethyl )-3,6,9-triazaundecane is dissolved In n-butanol. The solution is chilled and then dry hydrogen chloride gas is passed into the solution causing an oil to separate. To the heavy oil ether is added and then stirred causing crystallization to occur. MP146°Cto 147°C. Analysis for nitrogen calc. 8.3%, found 8.2%. 

In a 250-ml. round-bottomed flask equipped with a gas-inlet tube and reflux condenser 20 g. (0.094 mole) of N.N -diphenyl-ethylenediamine (1,2-dianilinoethane) (Note 1) and 100 ml. of purified triethyl orthoformate (Note 2) are heated by an oil bath under nitrogen (Note 3) for 5 hours. The oil bath is maintained between 190° and 200°, and water is allowed to stand in the condenser. The water in the condenser begins to boil slowly, and the alcohol which is produced is allowed to escape (Note 4). The reaction product which crystallizes during the reaction is filtered after cooling and washed with ether. There is obtained 19-20 g. (91 95%) of product, m.p. 285° (dec.) (Note 5). 

Likewise, thermolysis of 4-azidophenyl methyl ketone in methanol yields 5-acetyl-2-methoxy-3//-azepine (60%), compared to only an 8% yield from the photolytic reaction.78 119 The thermolysis of phenyl azide in refluxing cyclohexanol yields no 3H-azepine, only diphenyl-diazene (10%) and aniline (30%).74 In contrast, thermolysis of methyl 2-azidobenzoate in cyclohexanol furnishes a mixture of methyl 2-(cyclohexyloxy)-3//-azepine-3-carboxylate (20 % bp 127°C/0.1 Torr) and methyl 2-aminobenzoate (60%). Thermolysis of the azido ester in methanol under nitrogen in an autoclave at 150 C yields a 7 10 mixture (by 1HNMR spectroscopy) of the amino ester and methyl 2-methoxy-3//-azepine-3-carboxylate, which proved to be difficult to separate, and much tar.74 The acidic medium179 is probably responsible for the failure of methyl 2-azidoberjzoate to yield a 3//-azepine when thermolyzed in 3-methoxyphenol aniline (40%) is the major product.74... 

When heated, the benzotrithiadiazepines undergo a rearrangement with loss of nitrogen to give 1,2,3-benzotrithioles, e.g. the reaction of 6,9-dimethyl-7,8-diphenyl-1,3A4,5,2,4-benzotri-thiadiazepine.393... 

Example 12. PA-6,1 from diphenyl isophthalate.65 To a well-dried 50-mL straight-wall three-necked flask with nitrogen inlet/outlet, condenser unit, and magnetic stirrer in a heating block (Fig. 3.18b), 15.1 g of diphenyl isophthalate and 6.15 g of 1,6-hexamethylene diamine are added. The mixture is heated to 190° C over a 1-h period and to 253° C over a further 40 min, a vacuum is then... 

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