IV-Phenyl

Among the less widely exploited interconversion processes are those involving thermal reactions with ethyl azidoformate, which convert furan into A-ethoxycarbonyl-A -pyrrolin-2-one, and thiophenes into A-ethoxycarbonylpyrroles (Scheme 96a) (64TL2185). The boron trifluoride catalyzed reaction of l,3-diphenylbenzo[c]furan with A-sulfinylaniline results in the replacement of the oxygen by an iV-phenyl group (Scheme 96b) 63JOC2464). 

Clearly, the proportion of substitution occurring adjacent to the pyridinic nitrogen atom is increased by protonation. Also noteworthy are the high proportion of ortho substitution product and the selective attack at C-3 in the iV-phenyl derivative. 

Pioneering studies have shown that the yield of iV-phenyl-3//-azepin-2-amine (32, R = Ph) from the thermolysis of phenyl azide in aniline increases as the ratio of azide to aniline decreases, and in dilute solution with an azide to aniline ratio of 1 200 a 54% yield of the 3//-azepine can be achieved.34 The reaction is successful with other arylamines, but the procedure is of limited preparative value as large volumes of amine are required and only moderate yields of 3H-azepines are obtained. 

The yield of 3//-azepine appears to be influenced by substituents on the azide ring although no in-depth study has been reported. 4-Halophenyl azides, in most cases, give rise to complex mixtures of products.177 4-Tolyl azide, on thermolysis in aniline, yields 5-methyl-iV-phenyl-3//-azepin-2-amine (18% mp 157-158°C), whereas the thermolyses of 4-methoxy-, 4-methyl-, 4-chloro-, and 4-nitrophenyl azides in a range of arylamines (4-chloro-, 4-methoxy-, and pen-tafluoroaniline) yield only azo compounds and uncharacterized tarry products.178... 

Z-Gly Gly Gly-OEtfGlyeine, A7-[A -[iV-[(phenyl-methoxy)earbonyl]glycyl]g]ycyl]-, ethyl ester] A 91%... 

Diffusion Coefficients for iV-lsopropyl-A/ -Phenyl-p-Phenylenediamine (IPPD), A/-(1,3-Dimethylbutyl)-iV -Phenyl-p-Phenylenediamine (6PPD), and A/-(1 -Phenylethyl)-A/ -Phenyl-p-Phenylenediamine (SPPD) (See Figure 15.14), in Different Rubbers and at Different Temperatures... 

A -( 1,3-dimethylbutyl)-iV -phenyl-para-phenylenediamine. Tetrahydro-l,3,5-tri-(n)-butyl-(S)-triazinethione. 

An interesting switch in enantioselectivity is observed with variation of the A-snbstituent of the NHC nsed to catalyse the [4+2] addition of ketenes and A-aryl-A-benzoyldiazenes. For example, A-phenyl-snbstituted NHC 212 (Ar = Ph) gave (R)-215 in 84% ee in the reaction with ethylphenyUcetene and iV-phenyl-iV-benzoyldiazene 213, while A-mesityl-substituted NHC 214 (Ar = Mes) gave (S)-211 in 76% yield and 96% ee (Scheme 12.45) [81],... 

No stereoselectivity was observed in the formation of a 1 1 diastereomeric mixture of 2-hydroxy-2-phenylethyl p-tolyl sulfoxide 145 from treatment of (R)-methyl p-tolyl sulfoxide 144 with lithium diethylamide . However, a considerable stereoselectivity was observed in the reaction of this carbanion with unsymmetrical, especially aromatic, ketones The carbanion derived from (R)-144 was found to add to N-benzylideneaniline stereoselectivity, affording only one diastereomer, i.e. (Rs,SJ-( + )-iV-phenyl-2-amino-2-phenyl p-tolyl sulfoxide, which upon treatment with Raney Ni afforded the corresponding optically pure amine . The reaction of the lithio-derivative of (-t-)-(S)-p-tolyl p-tolylthiomethyl sulfoxide 146 with benzaldehyde gave a mixture of 3 out of 4 possible isomers, i.e. (IS, 2S, 3R)-, (IS, 2R, 3R)- and (IS, 2S, 3S)-147 in a ratio of 55 30 15. Methylation of the diastereomeric mixture, reduction of the sulfinyl group and further hydrolysis gave (—)-(R)-2-methoxy-2-phenylacetaldehyde 148 in 70% e.e. This addition is considered to proceed through a six-membered cyclic transition state, formed by chelation with lithium, as shown below . ... 

Seven different copper(II) complexes [181] of 2-acetylpyridine iV-phenyl-thiosemicarbazone, 14, all having the general formula, [Cu(14-H)A] have been prepared and characterized. Their spectral data are included in Table 2 and g is similar to other copper(II) complexes of 2-acetylpyridine thiosemicarbazones. However, the d-d spectra all show two bands, suggesting planar stereochemistry these bands are of higher energy than the analogous complexes of the bicyclononyl derivative, 4 [128, 175]. 

Copperfll) complexes of 4,5-dimethyl-3-formylpyrazole IV-phenyl-thiosemicarbazone, 41, have been prepared by refluxing in ethanol [191]. [Cu(41-H)A], where A = Cl, Br, NO3, NCS and N3, were shown to involve bonding by Al(ring), azomethine nitrogen, and thiol sulfur atoms and all have magnetic moments in the range 1.8-1.9 B.M. The electronic and ESR spectral data for these complexes are comparable to that found for 2-acetylpyridine " iV-phenylthiosemicarbazone, 14 [181],... 

Recently mononuclear ruthenium(II) and binuclear ruthenium(III) complexes of 5 and its iV-phenyl derivative have been isolated [214], Although many of the complexes were not soluble in the culture medium, both ruthenium(II) and ruthenium(III) complexes showed considerably more activity against E. coli than the uncomplexed thiosemicarbazones. Similar results were found for the oxovanadium(IV) complexes of the same ligands [VO(L)2Br]Br, where L is the deprotonated 2-formylpyridine N-phenylthiosemicarbazone, was the most potent inhibitory activity [215]. 

Benzenesulfonyloxy-1 //-pyrrolo[3,4-Z> quinoxaline-1,3(2//)-dione (591) gave iV-phenyl-3-(/V -phenylureido)-2-quinoxalinecarboxamide (592) (PhNH2, PhH, 20°C, 6 h 82% the mechanism probably involved Lossen rearrangement at an intermediate stage but remains unprove) 623 (V-p-tolyl-3-(iV -p-tolyl-ureido)-2-quinoxalinecarboxamide (87%) was made similarly using p-toluidine.623... 

Accordingly, iV-phenyl-substituted isothiazolium salts bearing a benzo crown ether substituent were employed in this synthetic protocol and led to the synthesis of various crown ether-substituted 6aA4-thia-l,6-diazapentalenes 201... 

A suspension of 414 in aquoeus dioxane was treated with proline 433a and iV-phenyl isatin 432a and the reaction mixture was heated at 80-90 °C overnight. The resin-containing cycloaddition product was reduced in aqueous tetrahydrofuran with lithium borohydride for 12 h at room temperature to afford a mixture of mainly 437 and a trace of 438 unlike in solution phase where in equal amount of 437 and 438 were produced (Scheme 99). 

The reaction of imines with thiohydrazides gives 1,3,4-thiadiazole via a thioacylimidohydrazine intermediate. The imidoyl chloride 148 when treated with the IV-phenyl thiosemicarbazide 149 gave the 1,3,4-thiadiazole hydrochloride 150 (Equation 53) <2002MI1241>. 

Benzenediamine, iV-phenyl-iV -(1-methylethyl)-, (p-Phenylendiamine, iV-phenyl-iV -isopropyl-)... 

We observed a more complicated behavior in the study of retarding action of amines (IV-benzyl-IV -phenyl-l,4-benzenediamine and 4-hydroxyphenyl-2-naphtalenamine) on fuel T-6 oxidation catalyzed by the copper powder [13]. Both antioxidants appeared to retard the autoxidation of T-6 very effectively. They stop chain oxidation during the induction period in concentrations equal to 5 x 10 5mol L 1 and higher. The induction period was found to be the longer, the higher the concentration of the antioxidant and lower the amount of the copper powder introduced in T-6. 

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