Synthesis of <i>N</i>-[Tris(hydroxymethyl)methyl]benzene- carboxamides:  A Convenient Route to Polyhydroxylated Dendritic Cores

Hernandez, Bernadette A.; Chang, Virginia; Villanueva, Ignacio; Heagy, Michael D.

doi:10.1021/jo990560k

Cited by 6 publications

(3 citation statements)

References 9 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…1 . Cyanuric chloride [ 1 – 17 ], 1,3,5-tris(bromomethyl)benzene [ 37 ] and trimesic acid trichloride [ 38 ] are commercial chemicals, classically known as reactive m -trivalent (hetero)aryl halo compounds, that are easily convertible into dendritic cores in reactions with various dendrons as N - and O -nucleophiles.…”

Section: Resultsmentioning

confidence: 99%

Design, synthesis and structure of novel G-2 melamine-based dendrimers incorporating 4-(n-octyloxy)aniline as a peripheral unit

Morar¹,

Lameiras²,

Bende³

et al. 2018

Beilstein J. Org. Chem.

View full text Add to dashboard Cite

Background: 4-(n-Octyloxy)aniline is a known component in the elaboration of organic materials with mesogenic properties such as N-substituted Schiff bases, perylene bisimide assemblies with a number of 2-amino-4,6-bis[4-(n-octyloxy)phenylamino]-s-triazines, amphiphilic azobenzene-containing linear-dendritic block copolymers and G-0 monomeric or dimeric dendritic liquid crystals with photochromic azobenzene mesogens. The present ab initio study explores a previously unknown use of 4-(n-octyloxy)aniline in the synthesis, structure and supramolecular behaviour of new dendritic melamines. Results: Starting from 4-(n-octyloxy)aniline, seven G-2 melamine-based dendrimers were obtained in 29–79% overall yields. Their iterative convergent- and chemoselective synthesis consisted of SN2-Ar aminations of cyanuric chloride and final triple N-acylations and Williamson etherifications (→ G-2 covalent trimers) or stoichiometric carboxyl/amino 1:3 neutralisations (→ G-2 ionic trimers). These transformations connected G-1 chloro- and amino-termini dendrons to m-trivalent cores (triazin-2,4,6-triyl and benzene-1,3,5-triyl units) or tripodands (central building blocks), such as N-substituted melamines with 4-hydroxyphenyl or phenyl-4-oxyalkanoic motifs. Owing to the diversity of cores and central building blocks, the structural assortment of the dendritic series was disclosed by solvation effects (affecting reactivity), rotational stereodynamism and self-organisation phenomena (determining a vaulted and/or propeller macromolecular shape in solution). DFT calculations (in solution), (VT) NMR and IR (KBr) spectroscopy supported these assignments. TEM analysis revealed the ability of the title compounds towards self-assembling into homogeneously packed spherical nano-aggregates. Conclusions: The (non)covalent synthesis and step-by-step structural elucidation of novel G-2 melamine dendrimers based on 4-(n-octyloxy)aniline are reported. Our study demonstrates the crucial influence of the nature (covalent vs ionic) of the dendritic construction in tandem with that of its central building blocks on the aptitude of dendrimers to self-organise in solution and to self-assembly in the solid state.

show abstract

Section: Resultsmentioning

confidence: 99%

Design, synthesis and structure of novel G-2 melamine-based dendrimers incorporating 4-(n-octyloxy)aniline as a peripheral unit

Morar¹,

Lameiras²,

Bende³

et al. 2018

Beilstein J. Org. Chem.

View full text Add to dashboard Cite

show abstract

“…The simplest 1 f 3 branched monomer TRIS has been used for simple amidation in which it readily transforms esters to the corresponding amide by a facile two-step procedure, transesterification followed by rearrangement. 214 This ester triol transformation (K 2 CO 3 , DMSO, TRIS) has been demonstrated in the conversion of numerous initially nondendritic hydrophobic materials into more hydrophilic compounds: e.g., a neutral, cyclophanedodecaalcohol, 320 diverse (cyclo)alkyl 321 and benzene cores, 321,322 and lower rim polyhydroxylated calix [4]arenes. 323 Other nonionic TRISbased polyols, useful as sugar macronutrient substrates in low-calorie food formulations, have been reported by Yalpani et al 324 Alvarez and Strumia 325 studied two protocols for obtaining hydrophilic acrylic acid-ethylene glycol dimethylacrylate matrices.…”

Section: F 3 C-branched Amide (Tris) Connectivitymentioning

confidence: 99%

Dendrimers Derived from 1 → 3 Branching Motifs

2010

View full text Add to dashboard Cite

“…5 Since this amine is of current interest for TRIS connectivity in the generation of dendritic cores, as well as our project that utilizes the TRIS moiety for the production of polydentate ligands 6 , we wish to report a convenient route towards the synthesis of such N-tris(hydroxymethyl)methylcarboxamides. 7 The selective conversion of either aliphatic or aromatic carboxylic acids to their corresponding TRIS carboxamides has been achieved in one step using the acyl-transfer reagent N-ethoxycarbonyl-2-ethoxy-1,2dihydroquinoline, (EEDQ) 8 (Scheme).…”

mentioning

confidence: 99%

One-Step Coupling of Tris(hydroxymethyl)aminomethane to Aliphatic and Aromatic Carboxylic Acids

Villanueva¹,

Hernandez²,

Chang³

et al. 2000

Synthesis

Self Cite

View full text Add to dashboard Cite

A convenient and general method was established to append tri-, hexa-, and nonadentate ligands about an aromatic or aliphatic core. This approach allows a variety of commercially available carboxylic acids to be transformed to their N-tris(hydroxymethyl)methylcarboxamides in one step. The selective activation of the acid functionality to form the polyhydroxylated dendritic cores has been achieved using the acyl transfer agent N-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline (EEDQ).

show abstract

Synthesis of N-[Tris(hydroxymethyl)methyl]benzene- carboxamides: A Convenient Route to Polyhydroxylated Dendritic Cores

Cited by 6 publications

References 9 publications

Design, synthesis and structure of novel G-2 melamine-based dendrimers incorporating 4-(n-octyloxy)aniline as a peripheral unit

Design, synthesis and structure of novel G-2 melamine-based dendrimers incorporating 4-(n-octyloxy)aniline as a peripheral unit

Dendrimers Derived from 1 → 3 Branching Motifs

One-Step Coupling of Tris(hydroxymethyl)aminomethane to Aliphatic and Aromatic Carboxylic Acids

Contact Info

Product

Resources

About