Anilines ethylated

Wolfbeis investigated the reactions of amines and orthoesters with different CH-acid molecules (81CB3471). When the reactions of aniline, ethyl orthoformate, and dialkyl malonates (2 mol) were carried out at 130-140°C for 4 hr, phenylaminomethylenemalonamates (245) were obtained (81CB3471). Similar reactions with aliphatic amines were unsuccessful. Phenylaminomethylenemalonic acid could not be prepared in the reactions of aniline, methyl orthoformate or orthoacetate, and malonic acid. When these reactions were carried out in 2-propanol, only amidines (246) were obtained. 

The uncatalyzed reactions between anilines, ethyl orthoformate, and diethyl malonate afforded ethyl arylaminomethylenemalonamates (252) in 67-85% yields (87SC549). However, if the malonate was first reacted with ethyl orthoformate and acetic anhydride in the presence of a catalytic amount of ZnCl2 at boiling temperature for 5 hr and aniline was then added to the reaction mixture, reflux being maintained for 0.5 hr, arylaminomethylenemalonates (253) were obtained in 52-85% yields. 

Phenylaminomethylenemalonates (444) were prepared in 92-95% yields in the reactions of aniline, ethyl orthoformate, and the appropriate cyclic ester of malonic acid [441, R = R1 = Me, —(CH2)5—] at reflux temperature or 15 min (80CB2630). 

N-Ethyl-N-nitro-3,5-dimethyl-2,4,6-trinitro-aniline [Ethyl-(trinitrodimethyIphenyl)tiitramine], (CH3)2Cfl(N02)8.N(N02).C2H6 mw 329 24,... 

For mare information on this subject see individual explosives, eg, tri- and tetra-nitro aniline, ethyl enedi amine dinitrate, tetryl, etc... 

Finally, when methyl metaphosphate is generated in the presence of ethyl acetate and aniline, ethyl N-phenylbenzamidate is produced. Presumably, the reaction follows the course shown in Equation 12. 

N-Ethyl-N-nitro-3,6-di methyl-2,4-dinitro-aniline [Ethyl-(dinitrodimethylphenyl)nitramine], (CH8)2CaH(N02)2.N(N02).C2HB mw 284.23,... 

Properties Lemon to orange oily liq., faint char, odor, biller taste sol. in water, alcohol, aniline, ethyl acetate, toluene insol. in min. and veg. oils m.w. 1311.90 HLB 14.9 acid no. 2 max. sapon. no. 45-55 hyd. no. 81-96 nonionic... 

Dimethyl aniline Diethylamine Aniline Ethyl iodide Toluidine... 

A mixture of aniline, ethyl orthoformate, and cyanamide refluxed 5-30 min. 

Reddy et al. synthesized 5-hydroxyindole derivatives via the Nenitzescu reaction by coupling of aniline, ethyl acetoacetate, and p-benzoquinone, in 1,2-dichloroethane, using montmorillonite KSF clay as catalyst (Scheme 18) [87]. The reaction was also performed using acyclic and cyclic 1,3-diketones and with aryl and alkyl amines. Among several catalysts tested in this reaction, montmorillonite KSF clay proved to be the best catalyst leading to the highest yields in a shorter reaction time. 

Similar substituted quinolines can be efficiently obtained starting from N-alltylaniline (including glycine) derivatives by reaction with alkenes in the presence of FeCls (10 mol%) and TEMPO oxoammonium tetrafluoroborate salt (2 equiv.) as the oxidant in dichloromethane (DCM) at 60 °C. Interestingly, the same quinolines can be obtained starting from anilines, ethyl glyoxalate and alkenes, in a one-pot multi-component reaction, under similar conditions. ... 

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