23229-37-0

Usage

Synthesis Reference(s)

Tetrahedron Letters, 25, p. 1023, 1984 DOI: 10.1016/S0040-4039(01)80090-3

InChI:InChI=1/C11H16N2/c1-12-8-9-13(2)11(12)10-6-4-3-5-7-10/h3-7,11H,8-9H2,1-2H3

Upstream product

• 100-52-7 benzaldehyde 
• 138767-63-2 Dimethyl-[2-(1,2,3-trimethyl-[1,3,2]diazasilolidin-2-yl)-benzyl]-amine 
• 110-70-3 N,N`-dimethylethylenediamine 
• 4222-25-7 3-bromo-3-phenyl-3H-diazirine 
• 100-51-6 benzyl alcohol 
• 24374-10-5 α-bromo-4'-nitro-chalcone 
• 5443-49-2 α-bromocinnamaldehyde 
• 6935-75-7 2-bromo-1,3-diphenyl-2-propen-1-one 
• 31207-17-7 3-bromo-4-phenyl-but-3-en-2-one 
• 104-55-2 3-phenyl-propenal 
• 122-57-6 1-Phenylbut-1-en-3-one 
• 20432-02-4 1-(4-nitro-phenyl)-3-phenyl-propenone 
• 66894-04-0 2,3-dibromo-3-phenyl propanal 
• 6310-44-7 3,4-dibromo-4-phenylbutan-2-one 

Downstream Products

• 113924-89-3 1,3-dimethyl-2-<2-(dimethylarsino)phenyl>imidazolidine 
• 7022-45-9 2-(methylsulfanyl)benzaldehyde 
• 217791-52-1 2-(1,3-dimethylimidazolidine-2-yl)phenyltrimethoxysilane 
• 61372-53-0 1,3-Dimethyl-2-phenyl-imidazolinium iodid 
• 102-11-4 N-benzyl-N-methyl-N'-methylethylenediamine 
• 65838-45-1 N,N'-(cyclohexane-1,2-diyl)bis(1-phenylmethanimine) 
• 1043893-48-6 cis-(1R,2S)-N,N'-dibenzylcyclohexane-1,2-diamine 
• 1271736-28-7 C₂₅H₂₈N₂O 
• 1043893-52-2 1,3-dibenzyl-2-phenyloctahydro-1H-benzoimidazole 

Relevant academic research and scientific papers

π-Face Promoted Catalysis in Water: From Electron-deficient Molecular Cages to Single Aromatic Slides

Exploiting noncovalent π-interactions particularly emerging anion-π interactions to drive efficient catalysis is fascinating. Even with exciting progresses, can anion-π activation operate in water remains elusive. Here we report the design, synthesis and catalytic studies of a class of water-soluble electron-deficient molecular cages and relevant aromatic slide compounds. The prism-like cages contain three divided, long, cationic aromatic walls which constitute three highly electron-deficient V-shape cavities. They were efficiently synthesized in two steps from a parent triformyl cage in gram-scale. Crystal structure showed the π-walls bind to the counter bromide through strong anion-π interactions. Just 5 mol% of cages were effective in catalyzing decarboxylative Aldol reactions of aldehydes and malonic acid half thioesters in water but not in organic solvents, showing a pronounced hydrophobic amplification effect. Meantime, a series of single π-slides resembling the π-wall of the cage performed equally well, while those lacking an extended π-surface were ineffective, highlighting the essential role of electron-deficient π-face on promoting the conversion.

Rediscovering aminal chemistry: Copper(ii) catalysed formation under mild conditions

Aminals, the N,N analogues of acetals, have been thoroughly explored in organic chemistry, with a particular focus on heteroaromatic aldehyde lithiation. Nevertheless, the existing methodologies for their formation typically employ harsh conditions limiting their usefulness. In this work, we present an efficient and mild methodology for the preparation of aminals from aromatic aldehydes, including furanic platforms. These mild conditions allowed ease of access to a plethora of aminals and as such we set out to explore previously unaccessible potential applications. By studying the stability of various aminals, we were able to develop a simple aldehyde protecting group based on a commercial diamine which is deprotected under mind conditions. We developed a protocol for the scavenging of genotoxic aldehydes by taking advantage of our methodology and a diamine resin, as well as early studies on the development of a stimuli-responsive release system using a salycil aldehyde derived aminal. This journal is

Experimental and Theoretical Study of an Intramolecular CF3-Group Shift in the Reactions of α-Bromoenones with 1,2-Diamines

The reactions of trifluoromethylated 2-bromoenones and N,N′-dialkyl-1,2-diamines have been studied. Depending on the structures of the starting compounds, the formation of 2-trifluoroacetylpiperazine or 3-trifluoromethylpiperazine-2-ones was observed. The mechanism of the reaction is discussed in terms of multistep processes involving sequential substitution of bromine in the starting α-bromoenones and intramolecular cyclization of the captodative aminoenones as key intermediates to form the target heterocycles. The results of theoretical calculations are in perfect agreement with the experimental data. The unique role of the trifluoromethyl group in this reaction is demonstrated.

Reversible aminal formation: Controlling the evaporation of bioactive volatiles by dynamic combinatorial/covalent chemistry

Dynamic mixtures generated by reversible aminal formation efficiently prolong the duration of evaporation of bioactive volatile aldehydes. Secondary diamines used for the generation of dynamic mixtures are obtained by treatment of primary diamines with carbonyl compounds and reduction of the diimines with NaBH4. The reversibilities of the reactions were demonstrated by NMR measurements in buffered aqueous solutions. Kinetic rate constants and equilibrium constants for the formation and hydrolysis of aminals were determined. The performance of dynamic mixtures as delivery systems for perfumery ingredients was tested after deposition onto cotton, and the long-lastingness of fragrance evaporation was investigated by dynamic headspace analysis against a reference sample. The simplicity of the concept together with its excellent performance makes this delivery system highly interesting for applied perfumery. Reversible aminal formation might also be successfully applicable to dynamic combinatorial/covalent chemistry for screening of pharmaceutically or catalytically active ligands and receptors. The evaporation of bioactive volatiles that are emitted from flowers to attract insects and that are used as fragrances in our everyday life is limited in time. Dynamic mixtures obtained by reversible aminal formation of suitably designed diamines with volatile aldehydes prolong the perception of these compounds in functional perfumery.

The unexpected role of pyridine-2-carboxylic acid in manganese based oxidation catalysis with pyridin-2-yl based ligands

A number of manganese-based catalysts employing ligands whose structures incorporate pyridyl groups have been reported previously to achieve both high turnover numbers and selectivity in the oxidation of alkenes and alcohols, using H2O2 as terminal oxidant. Here we report our recent finding that these ligands decompose in situ to pyridine-2-carboxylic acid and its derivatives, in the presence of a manganese source, H2O 2 and a base. Importantly, the decomposition occurs prior to the onset of catalysed oxidation of organic substrates. It is found that the pyridine-2-carboxylic acid formed, together with a manganese source, provides for the observed catalytic activity. The degradation of this series of pyridyl ligands to pyridine-2-carboxylic acid under reaction conditions is demonstrated by 1H NMR spectroscopy. In all cases the activity and selectivity of the manganese/pyridyl containing ligand systems are identical to that observed with the corresponding number of equivalents of pyridine-2-carboxylic acid; except that, when pyridine-2-carboxylic acid is used directly, a lag phase is not observed and the efficiency in terms of the number of equivalents of H 2O2 required decreases from 6-8 equiv. with the pyridin-2-yl based ligands to 1-1.5 equiv. with pyridine-2-carboxylic acid.

Reversible formation of aminals: A new strategy to control the release of bioactive volatiles from dynamic mixtures

Dynamic mixtures generated by reversible aminal formation of fragrance aldehydes with N,N′-dibenzyl alkyldiamines in aqueous systems were found to be suitable delivery systems for the controlled release of bioactive volatiles. The Royal Society of Chemistry 2010.

CONTROLLED RELEASE OF ACTIVE ALDEHYDES AND KETONES FROM EQUILIBRATED DYNAMIC MIXTURES

The present invention concerns a dynamic mixture obtained by combining, in the presence of water, at least one diamine derivative, comprising at least one benzylamine moiety, with at least one active aldehyde or ketone. The invention's mixture is capable of releasing in a controlled and prolonged manner said active compound, in particular perfuming ingredients, in the surrounding environment.

Reductive lithiation of 1,3-dimethyl-2-arylimidazolidines

Naphthalene catalyzed lithiation of 1,3-dimethyl-2-phenylimidazolidine led to cleavage of the benzylic carbon-nitrogen bond, with formation of an intermediate dianion. Under similar conditions, 1,3-dimethyl-2-(4-chlorophenyl) imidazolidine underwent regioselective cleavage of the aromatic carbon-chlorine bond, leading to a 4-formylphenyllithium equivalent, whilst 1,3-dimethyl-2-(4- methoxymethylphenyl)imidazolidine underwent regioselective cleavage of the benzylic carbon-oxygen bond, leading to a 4-formylbenzyllithium equivalent.

Preparation of aminals in water

Aminals, which are used as protecting groups in syntheses and are part of many biologically active compounds, are normally prepared from aldehydes and diamines under conditions that remove water in order to shift the equilibrium to the side of the aminal.

Synthesis of substituted 1H-4,5-dihydroimidazolium salts by dehydrogenation of imidazolidines

A study is presented on the scope of the method to obtain 1H-4,5-dihydroimidazolium salts 3 by dehydrogenation of 1,3-di and 1,2,3-trisubstituted imidazolidines 2. Of the dehydrogenating agents used, N-bromoacetamide leads to the best results, providing a