Dibenzyl aniline

Reductive alkylation of aromatic nitro compounds is possible. The reaction of nitrobenzene with allylic or benzyl hahdes in the presence of an excess of tin metal in methanol, leads to the A,A -diaUyl or dibenzyl aniline. A similar reaction occurs with nitrobenzene, allyl bromide, and indium metal in aq. acetonitrile. 

A,A-Dibenzyl-2-(ethoxycarbonylmethyl)amino-4-(trifluoromethyl)aniline (27) underwent reductive debenzylation and spontaneous cyclization to 6-trifluoro-methyl-3,4-dihydro-2(17/)-quinoxalinone (28) [Pd(OH)2/C, EtOH, H2 (3 atm), 3 days 97%]. " °... 

When (3-substituted phenyl)aminomethylenemaIonate (1163, 3-R = H) was applied, a mixture of 5-substituted and 7-substituted 4-hydroxyquino-lines (1164, 5-R + H and 7-R + H) was obtained. For example, the thermal cyclization of (3-nitrophenyl)aminomethylenemalonate in dibenzyl ether at 250°C afforded a 3 1 mixture of 7-nitro- and 5-nitro-4-hydroxy-quinolines (1164, R = 7-N02 and 5-NO ). 4-Hydroxyquinolines (1164) could also be prepared when a mixture of anilines, triethyl orthoformate, and isopropylidene malonate was slowly heated to 100°C in Dowtherm A, stirred over a period of 30 minutes, and then raised to a temperature of... 

Others 1,4-dioxane, 1,3,5-trioxane, terahydrofuran, 2-butyl tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, epsilon-caprolactam, benzothiazole, biphenyl, pyrazine, 2-butanone oxime, l-methyl-2-pyrrolidone, N,N-dimethyl-aniline, N,N-dimethyl-p-toluidine, l-methyl-7-isopropyl phenanthrene, dibenzyl-amine, hexamethylenetetramine, squalene, 2-ethylanthraquinone... 

The yields obtained on dominating the following amines further illustrate the wide utilitybf hypophosphorous acid 2,4-diethyl-6-bromoaniliae (70%),89 3-nitro-4-aminophenylarsonic acid (45%),90 3-amino-6-bromo-benzoic acid (75%),13 3,3 -dimethylbenzidine (76-82%),80-81 4-amino-7-chlorohydrindone-1 (85%),91 5-methyl-8-aminoquinoline (72%) 84 o-(/3-phenylethyl)-aniline (XXII) (47%).86 In the last case, when ethanol is used dibenzyl is not obtained instead the products are 9,10-dihydro-phenanthrene (co. 50%) and o-(j8-phenylethyl)-phenol (23%).66... 

The benzyl protection group can be applied to primary amines. In the Romero et al. synthesis of HIV-1 (human immunodeficiency virus) protease inhibitors, the aniline unit in 128 was treated with excess benzyl bromide to give the V,V-dibenzyl derivative 129 in 89% yield.The alkyl fragment was elaborated in six steps to give 130. Catalytic hydrogenation with a palladium on carbon catalyst removed both benzyl groups to give aniline derivative 131 in 90% yield. 

N-Cyclohexyl-2-benzothiazolesulfenamide 1,3-Dibutylthiourea Dicyclohexylbenzothiazyl-2-sulfenamide Dimethyl diphenyl thiuram disulfide 2,6-Dimethylmorpholine Diphenylamine 4,4 -Dithiodimorpholine 2-Ethylbutyraldehyde Ethyl morpholine Formaldehyde aniline 2,6-Lutidine N-Nitrosodimethylamine Paraldehyde p-Quinone dioxime Selenium Selenium dimethyidithiocarbamate Sodium diethyidithiocarbamate Sodium dimethyidithiocarbamate Sodium nitrite N,N,N, N -Tetrabenzylthiuram disulfide Tetraisobutylthiuram disulfide Tetramethylthiuram disulfide Thiocarbamyl sulfenamide Thiophenol Thiourea Triethanolamine Triethylamine Triethylenetetramine n-Valeraldehyde Zinc dialkyl dithiophosphate Zinc diamyidithiocarbamate Zinc dibenzyl dithiocarbamate Zinc diisobutyidithiocarbamate Zinc isopropyl xanthate Zinc 2-mercaptobenzothiazole Zinc oxide Zinc-N-pentamethylene dithiocarbamate Zinc peroxide accelerator, rubber articles for repeated use food-contact... 

Chapter 2 covers recent advances in the Synthesis of Quinoxalines involving the methods based on the (a) condensation of 1,2-diaminobenzenes and derivatives with various two-carbon unit suppliers, (b) condensation of o-benzoquinone diimines and diimides with various two-carbon unit suppliers, (c) condensation of A,A-dimethyl(dibenzyl)ethylenediamine with 1,2- and 1,4-dihydroxybenzenes, (d) synthesis of quinoxalines from aniline and its derivatives, (e) synthesis of quinoxalines from heterocyclic systems and (f) synthesis of quinoxalines based on the carbocyclic system. 

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