Pyridine Derivatives as Insecticides: Part 6. Design, Synthesis, Molecular Docking, and Insecticidal Activity of 3-(Substituted)methylthio-5,6,7,8-tetrahydroisoquinoline-4-carbonitriles Toward Aphis gossypii (Glover, 1887).

Three new series of 3-(substituted)methylthio-4-cyano-5,6,7,8-tetrahydroisoquinolines were designed and synthesized starting from readily available materials, 7-acetyl-4-cyano-1,6-dimethyl-6-hydroxy-8-(4-pyridyl, 3-pyridyl, phenyl, 4-methoxyphenyl, or 4-chlorophenyl)-5,6,7,8-tetrahydrosoquinoline-3(2H)-thiones 2a-e in high yields and very pure states. Thus, compounds 2a-e were reacted with some chloro reagents, namely, N-aryl-2-chloroacetamides 3a-f and N-(naphthalen-2-yl)-2-chloroacetamide (3g) under mild basic conditions to give the first two series of the target compounds, 3-(N-aryl)carbamoylmethylthio-5,6,7,8-tetrahydroisoquinoline-4-carbonitriles 4a-l and 5a-e, respectively. Reaction of compounds 2d,e with ethyl chloroacetate under the same conditions gave the other series, 3-ethoxycarbonyl-methylthio-5,6,7,8-tetrahydroisoquinoline-4-carbonitriles 6d,e. Structural formulas of all of the new compounds were elucidated and confirmed by elemental and spectral analyses. The insecticidal activity of all synthesized 5,6,7,8-tetrahydrosoquinolines toward the nymphs and adults of Aphis gossypii were screened. The results revealed the promising insecticidal activity of some tested compounds. Moreover, the structure-activity relationships as well as molecular docking of some representative compounds were evaluated.

New Water-Soluble Poly(propylene imine) Dendrimer Modified with 4-Sulfo-1,8-naphthalimide Units: Sensing Properties and Logic Gates Mimicking.

A new water-soluble poly(propylene imine) dendrimer (PPI) modified with 4-sulfo-1,8-naphthalimid units (SNID) and its related structure monomer analog (SNIM) has been prepared by a simple synthesis. The aqueous solution of the monomer exhibited aggregation-induced emission (AIE) at 395 nm, while the dendrimer emitted at 470 nm due to an excimer formation beside the AIE at 395 nm. Fluorescence emission of the aqueous solution of either SNIM or SNID was significantly affected by traces of different miscible organic solvents, and the limits of detection were found to be less than 0.05% (v/v). Moreover, SNID exhibited the function to execute molecular size-based logic gates where it mimics XNOR and INHIBIT logic gates using water and ethanol as inputs and the AIE/excimer emissions as outputs. Hence, the concomitant execution of both XNOR and INHIBIT enables SNID to mimic digital comparators.

Angular Regioselective Synthesis of Varied Functionalized Hexahydro-1,2,4-triazolo[4,3-a]quinazolin-9-ones and Their Antiproliferative Action.

New 2-thioxopyrimidin-4-ones capable of participating in regioselective reactions with functionally diverse hydrazonoyl chlorides towards angular regioisomers, rather than linear ones, were designed and synthesized to form stereoisomeric cis- and trans-hexahydro [1,2,4]triazolo[4,3-a]quinazolin-9-ones to be tested as antitumor candidates. The angular regiochemistry of the products was verified through crystallographic experiments and NMR studies. In addition, the regioselectivity of the reaction was found to be independent of the stereochemistry of the used 2-thioxopyrimidin-4-one. Only compound 4c demonstrated satisfactory growth inhibition against all the cancer cells used among all the produced drugs.

Enhanced Photodynamic Efficacy Using 1,8-Naphthalimides: Potential Application in Antibacterial Photodynamic Therapy.

This study addresses the need for antibacterial medication that can overcome the current problems of antibiotics. It does so by suggesting two 1,8-naphthalimides (NI1 and NI2) containing a pyridinium nucleus become attached to the imide-nitrogen atom via a methylene spacer. Those fluorescent derivatives are covalently bonded to the surface of a chloroacetyl-chloride-modified cotton fabric. The iodometric method was used to study the generation of singlet oxygen (1O2) by irradiation of KI in the presence of monomeric 1,8-naphthalimides and the dyed textile material. Both compounds generated reactive singlet oxygen, and their activity was preserved even after they were deposited onto the cotton fabric. The antibacterial activity of NI1 and NI2 in solution and after their covalent bonding to the cotton fabric was investigated. In vitro tests were performed against the model gram-positive bacteria B. cereus and gram-negative P. aeruginosa bacteria in dark and under light iradiation. Compound NI2 showed higher antibacterial activity than compound NI1. The light irradiation enhanced the antimicrobial activity of the compounds, with a better effect achieved against B. cereus.

Low Molecular Weight Probe for Selective Sensing of PH and Cu2+ Working as Three INHIBIT Based Digital Comparator.

A novel simple molecular chemosensor 2 was synthesized and examined for pH, cations and anions detection. At pH values higher than 10, probe 2 switches on a green emission where the excited state intramolecular proton transfer (ESIPT) is ceased. Also, the probe absorption spectrum shows a clear pH dependence, and the probe aqueous solution (ethanol/water = 1:2, borate buffer) responds selectively and sensitively through its fluorescence spectrum to the presence of Cu2+. Job's plot gave a 2:1 stoichiometry of Probe-2/Cu2+ complex, which responds to the presence of S2- and H2PO4- in aqueous solution (ethanol/water = 1:2, borate buffer) by its absorption and fluorescence spectra. In addition, probe 2 mimics a digital comparator based on three INHIBIT logic gates by different outputs using HO- and H+ as inputs. Moreover, probe 2 also executes AND and NOT TRANSFER logic gates using Cu2+ and S2- as inputs.

Self-Associated 1,8-Naphthalimide as a Selective Fluorescent Chemosensor for Detection of High pH in Aqueous Solutions and Their Hg2+ Contamination.

A novel diamino triazine based 1,8-naphthalimide (NI-DAT) has been designed and synthesized. Its photophysical properties have been investigated in different solvents and its sensory capability evaluated. The fluorescence emission of NI-DAT is significantly impacted by the solvent polarity due to its inherent intramolecular charge transfer character. Moreover, the fluorescence emission quenched at higher pH as a result of photo-induced electron transfer (PET) from triazine moiety to 1,8-naphthalimide after cleaving hydrogen bonds in the self-associated dimers. Furthermore, the new chemosensor exhibited a good selectivity and sensitivity towards Hg2+ among all the used various cations and anions in the aqueous solution of ethanol (5:1, v/v, pH = 7.2, Tampon buffer). NI-DAT emission at 540 nm was quenched remarkably only by Hg2+, even in the presence of other cations or anions as interfering analytes. Job's plot revealed a 2:1 stoichiometric ratio for NI-DAT/Hg2+ complex, respectively.

Crystal structure and Hirshfeld surface analysis of N-[(Z)-(2-hy-droxy-phen-yl)methyl-idene]aniline N-oxide.

The conformation of the title compound, C13H11NO2, is partially determined by a strong, intra-molecular O-H⋯O hydrogen bond. The crystal packing consists of strongly corrugated layers parallel to the ac plane and associated through C-H⋯π(ring) inter-actions. A Hirshfeld surface analysis of the crystal structure indicates that the most significant contributions to the crystal packing are from H⋯H (44.1%), C⋯H/H⋯C (29.4%) and O⋯H/H⋯O (17.3%) contacts.

Crystal structure and Hirshfeld surface analysis of (3S,3aR,6aS)-3-(1,3-diphenyl-1H-pyrazol-4-yl)-5-(4-meth-oxy-phen-yl)-2-phenyl-3,3a,4,5,6,6a-hexa-hydro-2H-pyrrolo-[3,4-d][1,2]oxazole-4,6-dione.

In the title compound, C33H26N4O4, the two fused five-membered rings and their N-bound aromatic substituents form a pincer-like motif. The relative conformations about the three chiral carbon atoms are established. In the crystal, a combination of C-H⋯O and C-H⋯N hydrogen bonds and C-H⋯π(ring) inter-actions leads to the formation of layers parallel to the bc plane. A Hirshfeld surface analysis indicates that the most significant contributions to the crystal packing are from H⋯H (44.3%), C⋯H/H⋯C (29.8%) and O⋯H/H⋯O (15.0%) contacts.

Angular Regioselectivity in the Reactions of 2-Thioxopyrimidin-4-ones and Hydrazonoyl Chlorides: Synthesis of Novel Stereoisomeric Octahydro[1,2,4]triazolo[4,3-a]quinazolin-5-ones.

The regioselective synthesis of cis and trans stereoisomers of variously functionalized octahydro[1,2,4]triazolo[4,3-a]quinazolin-5-ones was performed. The 2-thioxopyrimidin-4-ones used in the synthesis reacted with hydrazonoyl chlorides in a regioselective manner to produce the angular regioisomers [1,2,4]triazolo[4,3-a]quinazolin-5-ones rather than the linear isomers [1,2,4]triazolo[4,3-a]quinazolin-5-ones. The synthesis process took place with electronic control. The angular regiochemistry of the products was confirmed by X-ray experiments and two-dimensional NMR studies.

Diastereoselective synthesis of atropisomeric pyrazolyl pyrrolo[3,4-d]isoxazolidines via pyrazolyl nitrone cycloaddition to facially divergent maleimides: intensive NMR and DFT studies.

A pyrazolyl nitrone (2) underwent 1,3-dipolar cycloadditions to afford some N-substituted maleimides (3a-o). An atropisomeric character was introduced into the formed cycloadducts by using maleimides that have a restricted rotation around the C-N bond. Also, facial selectivity of both endo and exo cycloaddition was observed where the major atropisomer was one that is formed by attacking the nitrone from the less hindered face of the dipolarophile. On the other hand, maleimides with free rotation around the C-N bond led to endo and exo cycloadducts without atropisomerism. The presence of atropisomerism in the formed cycloadducts was confirmed by extensive NMR studies and DFT calculations.

Retro Diels Alder protocol for regioselective synthesis of novel [1,2,4]triazolo[4,3-a]pyrimidin-7(1H)-ones.

Reactions of diastereochemically varied norbornene-condensed 2-thioxopyrimidin-4-ones 6 and 10 with variously functionalized hydrazonoyl chlorides 2a-h gave regioselectively angular norbornene-based [1,2,4]triazolo[4,3-a]pyrimidin-7(1H)-ones 7a-h and 11a,c-e, respectively. Thermal retro Diels-Alder (RDA) reaction of 7a-h and 11a,c-e resulted in the target compounds 4a-h as single products. On the other hand, reactions of thiouracil 1 and hydrozonoyl chlorides 2a-e gave regioselectively [1,2,4]triazolo[4,3-a]pyrimidinone-5(1H)-ones 3a-e. The opposite regioselectivity of thiouracil 1 and norbornene-condensed 2-thioxopyrimidin-4-ones 6 and 10 was attributed to electronic factors according to DFT calculations. The angular structure of norbornene based [1,2,4]triazolo[4,3-a]pyrimidin-7(1H)-ones was confirmed by single crystal X-ray crystallography.

A chemosensoring molecular lab for various analytes and its ability to execute a molecular logical digital comparator.

We reported here the unique ability of a Rhodamine 6G-based probe (3) to detect discriminately several targets, including H+, HO-, Cu2+, Hg2+, Fe3+, Co2+, Cd2+, Zn2+, Sn2+, Ni2+, Al3+, Pb2+, Ce3+and Ag+, by unambiguously colorimetric and fluorimetric outcomes. In aqueous solutions, the presence of proton induced the ring-opening of rhodamine moiety but the presence of hydroxide induced the conversion of 2-hydroxyphenyl hydrazone moiety from the non-fluorescent benzenoid form into the fluorescent quinoid form. The probe could to distinguish between different cations in DMF and to work like an artificial tongue at molecular level. Several logic gates including OR, INHIBIT and TRANSFER, were performed by the probe. Moreover, the probe is able to execute three INHIBIT logic gates by two inputs, which was exploited to execute a digital molecular comparator.

A smart chemosensor: Discriminative multidetection and various logic operations in aqueous solution at biological pH.

A novel rhodamine-pyrazole based molecular probe was designed and easily synthesized. The probe could to detect several analytes in aqueous solution at biological pH (HEPES, pH = 7.2). Several heavy metal cations, including Cu2+, Fe3+, Al3+, Hg2+ and Ni2+ were detected discriminately by the probe. Also, the novel compound exhibited a good sensory selectivity towards S2O52- by both absorption and emission spectra. Moreover, probe/Cu2+ complex could to detect several anions, including F-, CN-, S2-, CH3COO-, CO32- and NO2-. Furthermore, the probe exhibited a high potential to work as a molecular system able to perform a number of logical operations such as AND, NAND, NOR and INHIBIT logic gates.

Synthesis of a single 1,8-naphthalimide fluorophore as a molecular logic lab for simultaneously detecting of Fe3+, Hg2+ and Cu2.

A novel fluorescence sensing 1,8-naphthalimide fluorophore is synthesized and investigated. The novel probe comprising two different binding moieties is capable to detect selectively Fe3+ over the other representative metal ions as well as a combination of biologically important cations such as Fe3+, Cu2+ and Hg2+ in the physiological range without an interfering effect of the pHs. Due to the remarkable fluorescence changes in the presence of Fe3+, Hg2+ and Cu2+ ions, INH and AND logic gates are executed and the system is able to act as a single output combinatorial logic circuit with three chemical inputs.