74283-75-3

Upstream product

• 6397-31-5 di-morpholin-4-yl-acetic acid ethyl ester 
• 121-69-7 N,N-dimethyl-aniline 
• 924-44-7 glyoxylic acid ethyl ester 
• 586-77-6 4-bromo-N,N-dimethylaniline 
• 141-78-6 ethyl acetate 
• 401-55-8 ethyl bromofluoroacetate 
• 21911-66-0 N-(3-methylphenyl)glycine ethyl ester 
• 69825-49-6 N-(2-methylphenyl)glycine ethyl ester 
• 2216-92-4 N-phenylglycine ethyl ester 

Relevant academic research and scientific papers

Friedel-Crafts reactions catalyzed by samarium diiodide

Samarium diiodide is an efficient precatalyst for the Friedel-Crafts reaction involving various aromatic substrates and chelating electrophiles. Alkyl 3,3,3-trifluoropyruvates are transformed into α-hydroxyesters in good yields with total regioselectivity

Visible Light Mediated Organocatalytic Activation of Ethyl Bromofluoroacetate: Coupling with Indoles and Anilines

The activation of ethyl bromofluoroacetate employing a visible light mediated, Eosin Y catalyzed photoredox transformation is reported. Using indoles and anilines as nucleophiles, the reaction leads to the formation of two C sp2-C sp3 bonds resulting in an efficient synthesis of bisindolyl and bisanilinoyl acetate derivatives. Application of this method to the direct synthesis of unsymmetrical diarylacetates featuring indoles and N-substituted anilines was also demonstrated.

K2S2O8-HFIP synergistically promoted: Para -selective sp3 C-H bond diarylation of glycine esters

A metal-free K2S2O8-HFIP synergistically promoted double Friedel-Crafts alkylation between a glycine derivative and N-substituted aniline was developed to efficiently synthesize diarylmethane derivatives with high para-selectivity. The reaction proceeded smoothly in the absence of any metal and ligand, and exhibited a good tolerance of functional groups.

Reductive amination of tertiary anilines and aldehydes

An unprecedented oxidant-mediated reductive amination of tertiary anilines and aldehydes without external reducing agents was developed via the nucleophilic attack of the oxygen atom of the carbonyl group to in situ generated iminium ions, in which tertiary anilines were used as both nitrogen source and reducing agent for the first time. The Royal Society of Chemistry 2013.

Palladium/copper-catalyzed Di-α-arylation of acetic acid esters

A bimetallic palladium/copper catalyst system was found to effectively promote the diarylation of alkyl acetates with aryl halides under unprecedentedly mild conditions. The phenanthroline-copper-phosphine catalyst stabilizes the enolate intermediate to the extent that the deprotonation of esters can be achieved even with the mild base potassium phosphate. The palladium tri-tert-butylphosphine co-catalyst mediates the coupling of the resulting copper enolate with a wide variety of aryl halides with selective formation of the corresponding diarylacetic acid esters. Copyright

Combination of lithium chloride and hexafluoroisopropanol for friedel-crafts reactions

A combination of weak Lewis acid (LiCl) and weak Br?nsted acid (hexafluoroisopropanol, HFIP) promotes efficiently the Friedel-Crafts reaction of electron-rich aromatic compounds with ethyl glyoxylate. Georg Thieme Verlag Stuttgart.

Friedel-Crafts reaction catalyzed by perfluorinated rare earth metals

The Friedel-Crafts reaction of anisole with acetic anhydride can be carried out in the presence of perfluorinated rare earth metal catalyst without organic solvent. Perfluorodecalin (C10F18, cis- and trans-mixture) can be used as a fluorous phase solvent for this reaction. Whereas, the reaction of N,N-dimethylaniline with acetic anhydride did not give the corresponding Friedel-Crafts reaction product. On the other hand, the Friedel-Crafts reaction of N,N-dimethylaniline with ethyl glyoxylate was also examined in the presence of perfluorinated Lewis acids. Three products were in fact formed at the same time.

Etudes sur les composes gem-diamines-V-Reactions d'anilines sur des composes gem-dimorpholines.

A systematic study of gem-dimorpholino compounds, which produce aldehydes by hydrolysis, has shown that such compounds do indeed have aldehydic character and can be used in synthesis in place of the corresponding aldehydes.As part of this study we have examined the behaviour of such gem-dimorpholino compounds towards some nucleophilic reagents such as mercaptans, amides and anilines under acid conditions.We have found experimental conditions under which symmetrical geminal compounds are produced: dithioacetals, gem-bis(acylamino), gem-diamino and gem-diaryl compounds.We have thus developed several new synthetic methods which compare favourably with existing methods.In most cases we have been able to show that the reaction proceeds by an intermediate in which only one of the morpholino groups has been replaced by the nucleophile.In this paper we report on the condensation of some anilines with gem-dimorpholino compounds.N,N-dimethylaniline condenses with gem-dimorpholino compounds as with the corresponding aldehydes to give gem-diaryl compounds.The case of primary arylamines is remarkable for the different results obtained.As could be expected from our most recent results, most of the condensation products are complex mixtures which are either non-distillable and non-crystallisable oils or glassy solids with indistinct melting points.It is often impossible to isolate any pure chemical substance from these mixtures.We shall thus only describe certain cases: the behaviour of 2,6-xylidine is particularly interesting.Under certain conditions this aniline derivative can condense on the aromatic ring similarly to N,N-dimethylaniline.The initial product of the reaction is an aldimine or "anil".Benzaldimines which are stabilised by conjugation do not react further while phenylglyoxaldimines are transformed into gem-diaryl compounds by heating in acetic acid. 2,5-dimethoxyaniline also condenses by way of the aromatic ring to give a gem-diaryl compound but the corresponding aldimine could not be shown to be an intermediate. 2-nitro and 3-nitroaniline, in which the aromatic ring is deactivated, can only condense by the nitrogen atom to give gem-diamino compounds.In summary, we think that primary arylamines in acetic acid condense with gem-dimorpholino compounds preferentially on the nitrogen atom of the amino group.These compounds can subsequently, according to their stability, rearrange provided that the aromatic ring is activated by electron-donating substituents.It still remains to be determined if there is a definite point at which a primary aniline starts to act as an ambifunctional nucleophile.