Supramolecular amide and thioamide synthons in hydrogen bonding patterns of N-aryl-furamides and N-aryl-thiofuramides

Pavlović, Gordána; Tralić‐Kulenović, Vesna; Vinković, Marijana; Vikić‐Topić, Dražen; Matanović, Ivana; Popović, Zora

doi:10.1007/s11224-006-9029-x

Cited by 8 publications

(3 citation statements)

References 30 publications

(44 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Synthesis and characterisation : A number of synthetic methods are available for converting amides into thioamides 25. We selected P 2 S 5 because of its ease of reaction and accessibility 25d. After optimisation of the reaction conditions, thioBTAs 2 a – c were prepared by treating their amide counterparts 1 a – c with an excess of P 2 S 5 at reflux in toluene (Scheme ).…”

Section: Resultsmentioning

confidence: 99%

Thioamides: Versatile Bonds To Induce Directional and Cooperative Hydrogen Bonding in Supramolecular Polymers

Mes

Cantekin

Balkenende

et al. 2013

Chemistry A European J

View full text Add to dashboard Cite

The amide bond is a versatile functional group and its directional hydrogen-bonding capabilities are widely applied in, for example, supramolecular chemistry. The potential of the thioamide bond, in contrast, is virtually unexplored as a structuring moiety in hydrogen-bonding-based self-assembling systems. We report herein the synthesis and characterisation of a new self-assembling motif comprising thioamides to induce directional hydrogen bonding. N,N',N''-Trialkylbenzene-1,3,5-tris(carbothioamide)s (thioBTAs) with either achiral or chiral side-chains have been readily obtained by treating their amide-based precursors with P2S5. The thioBTAs showed thermotropic liquid crystalline behaviour and a columnar mesophase was assigned. IR spectroscopy revealed that strong, three-fold, intermolecular hydrogen-bonding interactions stabilise the columnar structures. In apolar alkane solutions, thioBTAs self-assemble into one-dimensional, helical supramolecular polymers stabilised by three-fold hydrogen bonding. Concentration- and temperature-dependent self-assembly studies performed by using a combination of UV and CD spectroscopy demonstrated a cooperative supramolecular polymerisation mechanism and a strong amplification of supramolecular chirality. The high dipole moment of the thioamide bond in combination with the anisotropic shape of the resulting cylindrical aggregate gives rise to sufficiently strong depolarised light scattering to enable depolarised dynamic light scattering (DDLS) experiments in dilute alkane solution. The rotational and translational diffusion coefficients, D(trans) and D(rot), were obtained from the DDLS measurements, and the average length, L, and diameter, d, of the thioBTA aggregates were derived (L = 490 nm and d = 3.6 nm). These measured values are in good agreement with the value L(w) = 755 nm obtained from fitting the temperature-dependent CD data by using a recently developed equilibrium model. This experimental verification validates our common practice for determining the length of BTA-based supramolecular polymers from model fits to experimental CD data. The ability of thioamides to induce cooperative supramolecular polymerisation makes them effective and broadly applicable in supramolecular chemistry.

show abstract

Section: Resultsmentioning

confidence: 99%

Thioamides: Versatile Bonds To Induce Directional and Cooperative Hydrogen Bonding in Supramolecular Polymers

Mes

Cantekin

Balkenende

et al. 2013

Chemistry A European J

View full text Add to dashboard Cite

show abstract

“…The amide N-H group in 1 is double proton donor and participate also in the formation of the intermolecular hydrogen bonds of the N-H · · · O type forming characteristic supramolecular synthons N-H · · · O=C for amide group (N1 · · · O1 2.980(3) Å) [17][18][19][20][21][22][23][24]. In this way, molecules are connected through the formation of C(4) infinite chains spreading along c-axis.…”

Section: Crystal Structure Descriptionmentioning

confidence: 99%

Potentially biologically active new substituted anilides of benzo[2,3-b]thiophene series

2007

View full text Add to dashboard Cite

New substituted anilides of the heterocyclic series 2, 4, 5, 6, 7 together with the earlier described compounds 1 and 3 J Med Chem 48:2346), were synthesized from the corresponding heterocyclic carbonyl chlorides, methoxycarbonyl-and cyano-substituted anilines. Compounds 2 and 7 were prepared by methylation with methyl-iodide on the amide and the pyridine nitrogen. The Pinner reaction was used in the preparations of amidinosubstituted compounds. It seems that all the prepared compounds could be biologically interesting, especially amidinosubstituted anilides prepared in the form of water-soluble hydrochlorides or hydroiodides.Molecular and crystal structures of the three compounds, namely, 4 -methoxycarbonyl-N-phenyl-3-chloro benzo[b]thiophene-2-carboxamide (1), N-(4 -amidinophe nyl)-3-chlorobenzo[b]thiophene-2-carboxamide hydrochloride monohydrate (4) and 1-methyl-N-(4-amidinophenyl)-3-pyridine carboxamide iodide hydroiodide (7) have been determined by X-ray single-crystal diffractometry in the solid state. Compounds 1, 4 and 7 are not planar and the amide group (C=O in relation to NH group) is in trans position in all three compounds. The 3-chlorobenzo[b]thiophene moiety in 1 and 4 is oriented with the chloro substituent in cis position in relation to amide NH group. The conformational charac-

show abstract

“…In order to establish supramolecular amide and thioamide synthons of hydrogen-bonding patterns in the class of N-aryl-furamides N-(4-bromophenyl)-5-bromo-2-furancarboxamide and N-(4-chlorophenyl)-5-bromo-2-furancarboxamide) and in the class of N-aryl-thiofuramides, N-(4-methoxyphenyl)-2-furanthiocarboxamide were synthesized and characterized by Pavlović et al [161] and compared to already published data [162,163]. In addition the possibility of formation of different types of hydrogen bonds in these compounds was investigated.…”

Section: Issuementioning

confidence: 99%

Interplay of thermochemistry and Structural Chemistry, the journal (volume 17, 2006) and the discipline

Ponikvar‐Svet

Liebman

2009

Struct Chem

View full text Add to dashboard Cite

show abstract

Supramolecular amide and thioamide synthons in hydrogen bonding patterns of N-aryl-furamides and N-aryl-thiofuramides

Cited by 8 publications

References 30 publications

Thioamides: Versatile Bonds To Induce Directional and Cooperative Hydrogen Bonding in Supramolecular Polymers

Thioamides: Versatile Bonds To Induce Directional and Cooperative Hydrogen Bonding in Supramolecular Polymers

Potentially biologically active new substituted anilides of benzo[2,3-b]thiophene series

Interplay of thermochemistry and Structural Chemistry, the journal (volume 17, 2006) and the discipline

Contact Info

Product

Resources

About