Introducing chirality in halogenated 3-arylsydnones and their corresponding 1-arylpyrazoles obtained by 1,3-dipolar cycloaddition

Popa, Marcel Mirel; Shova, Sergiu; Hrubaru, Madalina; Barbu, Loredana; Drăghici, Constantin; Dumitraşcu, Florea; Dumitrescu, Dan

doi:10.1039/d0ra02368j

Cited by 12 publications

(15 citation statements)

References 54 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The structures of 3-bromocarprofen and 3-iodocarprofen obtained by regioselective halogenation of carprofen were assigned by NMR spectroscopy and X-ray analysis. Another motivation for investigating the crystal structures of the carprofen derivatives was to establish the extent of possible halogen bonding that might prevail, given our ongoing interest in this phenomenon in the context of halogenated N-heterocycles [26][27][28]. In the H-NMR spectra of the acids 2 and 3, the hydrogen atoms H-1 and H-4 (see numbering of the atoms in Figure 2) appear in both compounds as sharp singlets (δC-1 = 7.48 ppm for The structures of 3-bromocarprofen and 3-iodocarprofen obtained by regioselective halogenation of carprofen were assigned by NMR spectroscopy and X-ray analysis.…”

Section: Scheme 1 Chemical Transformations Of Carprofenmentioning

confidence: 99%

In Silico and Experimental Investigation of the Biological Potential of Some Recently Developed Carprofen Derivatives

et al. 2022

Self Cite

View full text Add to dashboard Cite

The efficient regioselective bromination and iodination of the nonsteroidal anti-inflammatory drug (NSAID) carprofen were achieved by using bromine and iodine monochloride in glacial acetic acid. The novel halogenated carprofen derivatives were functionalized at the carboxylic group by esterification. The regioselectivity of the halogenation reaction was evidenced by NMR spectroscopy and confirmed by X-ray analysis. The compounds were screened for their in vitro antibacterial activity against planktonic cells and also for their anti-biofilm effect, using Gram-positive bacteria (Staphylococcus aureus ATCC 29213, Enterococcus faecalis ATCC 29212) and Gram-negative bacteria (Escherichia coli ATCC 25922 and Pseudomonas aeruginosa ATCC 27853). The cytotoxic activity of the novel compounds was tested against HeLa cells. The pharmacokinetic and pharmacodynamic profiles of carprofen derivatives, as well as their toxicity, were established by in silico analyses.

show abstract

Section: Scheme 1 Chemical Transformations Of Carprofenmentioning

confidence: 99%

In Silico and Experimental Investigation of the Biological Potential of Some Recently Developed Carprofen Derivatives

et al. 2022

Self Cite

View full text Add to dashboard Cite

show abstract

“…In a recent study [46], we investigated the propensity for 5-iodopyrazoles (Figure 2) to form halogen bonds. We observed the tendencies of 5-iodopyrazoles and 4-iodosydnones [44][45][46] to form halogen bond interactions with several Lewis bases by 13 C-NMR spectroscopy in solution and this subsequently prompted us to focus on solid-state interactions in such compounds. Interestingly, the iodine atom in the proposed 5-iodo-1-arylpyrazoles was found to be involved in C-I⋯N, C-I⋯O and C-I⋯π type interactions, and this was consistent with interactions observed in other similar structures from the CSD [46,57].…”

Section: Resultsmentioning

confidence: 99%

“…The 5-iodopyrazoles under investigation (Table 1) were synthesized by 1,3-dipolar cycloaddition of the corresponding 4-iodosydnones with dimethyl acetylenedicarboxylate via a previously described procedure [45,[47][48][49][50].…”

Section: Synthesis and Crystal Growthmentioning

confidence: 99%

“…More particularly, halogen-oxygen, halogen-nitrogen or halogen-π (Figure 1c) interactions were reported both in liquid and solid state. We recently discovered that halogenated sydnones [44,45] and pyrazoles [46] are molecules with high potential for investigating the propensity of halogen bonding and its contribution among the other intermolecular interactions. We reported three types of halogen bonding in our investigations, all involving the iodine atom: I⋯N, I⋯O and I⋯π [46].…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

5-Iodo-1-Arylpyrazoles as Potential Benchmarks for Investigating the Tuning of the Halogen Bonding

et al. 2020

Self Cite

View full text Add to dashboard Cite

5-Iodo-1-arylpyrazoles are interesting templates for investigating the halogen bond propensity in small molecules other than the already well-known halogenated molecules such as tetrafluorodiiodobenzene. Herein, we present six compounds with different substitution on the aryl ring attached at position 1 of the pyrazoles and investigate them in the solid state in order to elucidate the halogen bonding significance to the crystallographic landscape of such molecules. The substituents on the aryl ring are generally combinations of halogen atoms (Br, Cl) and various alkyl groups. Observed halogen bonding types spanned by these six 5-iodopyrazoles included a wide variety, namely, C–I⋯O, C–I⋯π, C–I⋯Br, C–I⋯N and C–Br⋯O interactions. By single crystal X-ray diffraction analysis combined with the descriptive Hirshfeld analysis, we discuss the role and influence of the halogen bonds among the intermolecular interactions.

show abstract

“…Later on, the same group showed that by introducing an additional Br‐atom in the phenyl ring, other variety of XBs such as C−I⋅⋅⋅O, C−I⋅⋅⋅π, C−I⋅⋅⋅Br, C−Br⋅⋅⋅O, other than C−I⋅⋅⋅N were involved in dictating the supramolecular polymerization [103] . In another instance, two new di‐bromo halogenated systems were reported, namely 3‐(2‐isopropylphenyl) sydnones and 1‐(2‐isopropylphenyl) pyrazoles that produced 1D chains by Br⋅⋅⋅Br Type II halogen bonding and concomitant C−H⋅⋅⋅O hydrogen bonding [104] . Similarly, multiple halogen‐halogen interactions were reported in the solid‐state supramolecular polymers of aromatic dichlorodiazadienes, which by DFT calculations and Hirshfield analysis were found to dictate the molecular packing.…”

Section: Halogen Bonded Supramolecular Polymers and Materialsmentioning

confidence: 99%

Recent Developments in Polymeric Assemblies and Functional Materials by Halogen Bonding

Biswas

Das

2021

ChemNanoMat

View full text Add to dashboard Cite

Polymers have long been known to us for their versatile utility in our daily lives. With many years of successful advancement in controlled polymer synthesis and supramolecular chemistry, currently an amalgamation of these two fields is becoming increasingly important for generating modern‐day emerging polymeric materials. Hydrogen bonding and other noncovalent interactions like π‐stacking, host‐guest interaction, electrostatic interaction, metal‐ligand coordination have been explored much to this context, unlike the recently emerged halogen bonding, which indeed shows advantageous features like superior hydrophobicity, directionality and polar solvent resistance compared to ubiquitous hydrogen bonding. Hence, rendering these properties of halogen bonding into polymeric domain for generating functional materials for application in advance nanotechnologies is highly desirable. In the recent years, substantial progress has been made in fulfilling this challenging goal. This is evident from the escalating number of scientific publications in this research area every year. In this minireview, we have summarized the most recent developments in the field of halogen bonded polymeric assemblies and supramolecular polymers and discussed them in the context of their emerging materials properties and functions. Emphasis is given on highlighting various design criteria adopted in crystal engineering, covalent and supramolecular polymers in the past five years for constructing diverse organic functional materials, viz. liquid crystals, photoresponsive and photochromic materials, biomaterials and gels, self‐healing materials and many others by virtue of this highly directional supramolecular tool. In conclusion, a brief perspective on the advantages, challenges and future prospects in this rapidly growing field of research is discussed.

show abstract

Introducing chirality in halogenated 3-arylsydnones and their corresponding 1-arylpyrazoles obtained by 1,3-dipolar cycloaddition

Abstract: New 1-arylpyrazoles substituted with halogen atoms (Br, I) were synthesized from the corresponding sydnones by 1,3-dipolar cycloaddition.

Cited by 12 publications

References 54 publications

In Silico and Experimental Investigation of the Biological Potential of Some Recently Developed Carprofen Derivatives

In Silico and Experimental Investigation of the Biological Potential of Some Recently Developed Carprofen Derivatives

5-Iodo-1-Arylpyrazoles as Potential Benchmarks for Investigating the Tuning of the Halogen Bonding

Recent Developments in Polymeric Assemblies and Functional Materials by Halogen Bonding

Contact Info

Product

Resources

About