Bromo Groups Research Articles

Palladium-Catalyzed Cascade Distal C-H Methylation and Cyclization for the Construction of Spirooxindole Skeletons.

Transition metal-catalyzed C-H methylation represents a straightforward approach for introducing methyl groups into organic molecules. Herein, we report a palladium-catalyzed alkene-relayed remote C-H methylation reaction that utilizes dimethyl carbonate as the methylation reagent. The aryl groups distal to a bromo group were dimethylated via C-H activation, leading to the formation of spirooxindoles as the final products through C(sp3)-H activation and C(sp3)-C(sp3) coupling. This cascade process involves the formation of four C-C bonds and the activation of three C-H bonds. The reaction not only provides a new approach to C-H methylation but also offers a novel method for constructing spirooxindole skeletons by merging skeleton construction and methylation into a single step.

In Vivo Optogenetics Based on Heavy Metal‐Free Photon Upconversion Nanoparticles

AbstractPhoton upconversion (UC) from red or near‐infrared (NIR) light to blue light is promising for in vivo optogenetics. However, the examples of in vivo optogenetics have been limited to lanthanide inorganic UC nanoparticles, and there have been no examples of optogenetics without using heavy metals. Here the first example of in vivo optogenetics using biocompatible heavy metal‐free TTA‐UC nanoemulsions is shown. A new organic TADF sensitizer, a boron difluoride curcuminoid derivative modified with a bromo group, can promote intersystem crossing to the excited triplet state, significantly improving TTA‐UC efficiency. The TTA‐UC nanoparticles formed from biocompatible surfactants and methyl oleate acquire water dispersibility and remarkable oxygen tolerance. By combining with genome engineering technology using the blue light‐responding photoactivatable Cre‐recombinase (PA‐Cre), TTA‐UC nanoparticles promote Cre‐reporter EGFP expression in neurons in vitro and in vivo. The results open new opportunities toward deep‐tissue control of neural activities based on heavy metal‐free fully organic UC systems.

Aerobic Copper-Catalyzed Oxysulfonylation of Vinylarenes with Sodium Sulfinates under Mild Conditions: A Modular Synthesis of β-Ketosulfones.

An aerobic copper-catalyzed oxysulfonylation of vinylarenes with sodium sulfinates is described. This protocol features mild reaction conditions, convenient operation, and broad substrate scope with respect to vinylarenes and sodium sulfinates. Notably, the protocol demonstrates excellent tolerance of functional groups such as chloro, bromo, ester, cyano, and nitro groups. Mechanistic investigations indicated that the reaction should undergo radical cascades involving a sulfonyl radical generated from sodium sulfinate with air as the terminal oxidant, addition across alkene to deliver a benzylic radical, and subsequent cross-coupling with air.

Synthesis of pyrazole and pyrazoline derivatives of β-ionone: Exploring anti-inflammatory potential, cytotoxicity, and molecular docking insights

In the present paper, pyrazole and pyrazoline derivatives of β-ionone were synthesized. The protocol involved intramolecular oxidative C–H amination of hydrazone to yield corresponding pyrazole in moderate to good yields. Another methodology comprising of condensation of hydrazine hydrochloride with β-ionone in methanol leading to pyrazoline and its oxidative dehydrogenation using hypervalent iodine reagent to synthesize pyrazole is also achieved. One pot methodology for synthesis of pyrazole is also developed by refluxing the hydrazine hydrochloride with β-ionone in acetic acid. The structures of the synthesized compounds were elucidated using 1H NMR, 13C NMR, FTIR and mass spectrometry. All the pyrazole and pyrazoline derivatives were subjected to bovine serum albumin assay for in-vitro anti-inflammatory activity and all the compounds exhibited good to excellent activity. Compounds containing bromo and sulfonamide group exhibited inhibition rates of 87.36 % and 85.82 %, respectively, at a concentration of 0.5 mg/mL, surpassing the efficacy of the standard drug celecoxib (81.67 %). Further, cytotoxicity of the compounds was also evaluated against VERO cell line and all the compounds exhibited the cytotoxic values almost similar to the standard. Molecular docking was performed to study binding affinity of the potent compounds i. e bromo bearing pyrazole and sulfonamide bearing pyrazoline into the crystal structure of COX-II enzyme (PDB ID: 3LN1) at celecoxib binding site to determine the binding energy and interactions.

Transition‐Metal‐Free (Hetero)arylsulfonylation of 1‐Iodopyrrolo[1,2‐a]quinoxalines

AbstractWe describe herein a method for transition‐metal‐free (hetero)arylsulfonylation of 1‐iodopyrrolo[1,2‐a]quinoxalines with sodium arylsulfinates. The corresponding aryl iodides were in situ prepared from eletrophilic iodination of C1−H bonds in pyrrolo[1,2‐a]quinoxalines with N‐iodosuccinimide. The ensuing sulfonylation only required DMSO as solvent and completed after 15 min. Many arylsulfinates bearing chloro, bromo, methylsufonyl, acetamide, and nitro groups were competent substrates. Heteroarylsulfonylation of pyrrolo[1,2‐a]quinoxalines were also feasible.

Controllable Supramolecular Aggregation of Hydroazaheptacene Tetraimides and Derivatives in Nonpolar and Polar Solvents.

Rational control of the supramolecular aggregation of π-conjugated molecules plays an important role in determining their optoelectronic properties and applications. Here, we report a systematic study of the factors, including solvent polarity, concentration, and surfactants, that affect the aggregation behavior of a brominated hydroazaheptacene tetraimide (HATI) and its thiophene-substituted derivative, Th-HATI, as near-infrared fluorophores, in both nonpolar and polar solvents. The thermal stability of the aggregates is also studied by monitoring their optical absorption against temperature change. Our results indicate that the aggregation of HATI is highly sensitive to the solvent polarity. Moreover, the average aggregation number of HATI inside the colloidal nanoparticles formed in aqueous media can be controlled by surfactants. The substitution of the bromo groups in HATI by thiophene units induces a slight blue shift of the optical absorption, enhanced crystallinity, distinct aggregation behavior in both nonpolar and polar solvents, and improved thermal stability. The multifacet understanding of the supramolecular aggregation of these systems may offer insight for other π-conjugated molecular chromophores with various optoelectronic properties and applications.

Unsymmetrization of 1,8-Dibromonaphthalenes by Acid-Induced Halogen Dance Reaction.

A simple and powerful tool for preparing uncommon bromoarenes via the unsymmetrization of a naphthalene ring was developed. The steric repulsion between the peri-bromo groups of 1,8-dibromonaphthalene distorts the naphthalene ring, allowing for nonelectronical activation. Ring distortion facilitates the 1,2-rearrangement of the bromo group, affording 1,7-dibromonaphthalene upon treatment with trifluoromethanesulfonic acid (halogen dance reaction). For 1,4,5,8-tetrabromonaphthalene, stepwise 1,2-rearrangements proceeded successively to furnish 1,3,5,7-tetrabromonaphthalene. Density functional theory calculations suggest that this reaction is initiated by ipso-protonation, with a subsequent 1,2-rearrangement occurring via the bromonium transition state. Utilizing 1,7-dibromonaphthalene, which is characterized by two C-Br bonds arranged at a 60° angle, a unique metal-organic framework comprising a 52-membered ring network was synthesized.

Characteristics of pyroclastic deposits and evolution of Maar Bethok Lamongan Volcano Tiris Probolinggo East Java Indonesia

The Lamongan Volcano Complex has a very different character from the Bromo and Argopuro Volcano groups. Lamongan Volcano has 37 volcanic cones and 27 maars (ranu). This volcano is quarter-old and occupies part of East Java Province. Maar Bethok is composed of lava and intercalation between pyroclastic deposits from phreatomagmatic and magmatic falls that still need to be firmly consolidated. These pyroclastic deposits characterize a strombolian eruption with more lava dome or crater wall material ejected. The rocks that make up the Bethok maar include olivine-pyroxene basalt lava and pyroclastic fall deposits with fragments of olivine basalt and basalt composition. The evolution of the Bethok maar eruption started from magma with an alkaline composition and ended with a more acidic composition. The magmatism of Bethok maar has an island arc calc-alkaline affinity.

AgSCF3 Radical Addition Based on an Oxidant-Free α,β-Amide (Trifluoromethyl)sulfanylation Reaction

Abstract(Trifluoromethyl)sulfanylamides are an important class of organic compounds that are common among natural products and drug molecules. Here, we report a (trifluoromethyl)sulfanylation reaction using silver(I) (trifluoromethyl)sulfide as a free-radical (trifluoromethyl)sulfanylation reagent for β-amide compounds. This reaction does not require stoichiometric oxidants or additional transition-metal catalysts, and can be achieved by adding common organic acids. This method has excellent applicability and can accommodate several functional groups, including ester groups, acyl groups, and even bromo or iodo groups. Heterocyclic α,β-amides can also be readily converted into the corresponding products. This reaction also provides a new method for the synthesis of deuterated (trifluoromethyl)sulfanylamides.

Pincer Nickel-Catalyzed Olefination of Alcohols with Benzylphosphine Oxides.

N,N,P-Pincer nickel complexes effectively catalyze reaction of alcohols with benzylphosphine oxides to form alkenes in good yields. The protocol suits for a wide scope of substrates and generates only E-configurated alkenes. The method also shows good compatibility of functional groups. Methoxy, methylthio, trifluoromethyl, ketal, fluoro, chloro, bromo, thienyl, and furyl groups are tolerated. The mechanism studies support that the reaction proceeds through catalytic dehydrogenation of alcohols to aldehydes or ketones followed by condensation with benzyldiphenylphosphine oxides in the presence of KOtBu.

Ultrafast Halogen Dance Reactions of Bromoarenes Enabled by Catalytic Potassium Hexamethyldisilazide.

Lochmann-Schlosser base, a stoichiometric combination of nBuLi and KOtBu, is commonly used as a superbase for deprotonating a wide range of organic compounds. In the present study, we report that catalytic potassium hexamethyldisilazide (KHMDS) exhibits higher catalytic activity than KOtBu for successive bromine-metal exchanges. Accordingly, 1-10 mol% of KHMDS dramatically enhances halogen dance reactions to introduce various electrophiles to bromopyridine, bromoimidazole, bromothiophene, bromofuran, and bromobenzene derivatives with the bromo group translocated from the original position. A dual catalytic cycle is proposed to explain the ultrafast bromine transfer.

Influence of Steric Effects on the Emission Behavior of Pyrene-Based Blue Luminogens.

Pyrene-based derivatives have been widely deployed in organic luminescent materials because of their bright fluorescence, high charge carrier mobility, and facile modification. Nevertheless, the fluorescence output of conventional pyrenes is prone to quenching upon aggregation due to extensive intermolecular π-π stacking interactions. To address this issue, a set of new Y-shaped pyrene-containing luminogens are synthesized from a new bromopyrene chemical precursor, 2-hydroxyl-7-tert-butyl-1,3-bromopyrene, where the bromo and hydroxyl groups at the pyrene core can be readily modified to obtain the target products and provide great flexibility in tuning the photophysical performances. When the hydroxy group at the 2-position of pyrene was replaced by a benzyl group, the steric hindrance of the benzyl group not only efficiently inhibits the detrimental intermolecular π-π stacking interactions but also rigidifies the molecular conformation, resulting in a narrow-band blue emission. Moreover, the TPE-containing compounds 2c and 3c possessed characteristic aggregation-induced emission (AIE) properties with fluorescence quantum yields of up to 66% and 38% in the solid state, respectively. Thus, this article has methodically investigated the factors influencing the optical behavior, such as intermolecular interactions, and the steric effects of the substituent group, thereby opening up the potential to develop narrow-band pyrene-based blue emitters for OLED device applications.

Developments and applications of α-bromonitrostyrenes in organic syntheses.

The presence of the bromo and nitro groups in the structure of α-bromonitrostyrene makes them highly reactive and versatile reagents in organic syntheses. α-Bromonitrostyrenes act as an effective dielectrophile in the reaction with various nucleophiles. In these reactions, the bromo and nitro groups behave as good leaving groups for the assembly of a diverse range of heterocyclic compounds, such as dihydrofurans, dihydropyranes, furans, pyrroles, pyrazoles, isooxazolines, spiropyrrolidines, etc. In the current review, we have focused on the transformations of α-bromonitrostyrenes under organocatalysis, metal catalysis, and base-catalysis systems as well as catalyst-free conditions, since 2010.

BODNs as biocompatible brominating reagents: visible-light photocatalytic tyrosine modification under physiologically favorable conditions.

The photochemical reactivity of 1-bromo-2-oxo-1,2-dihydronaphthalene-1-carboxylates (BODNs) was demonstrated. They are inert in the dark under physiological conditions but become active as brominating reagents for tyrosine modification under visible light irradiation in the presence of a photocatalyst. The BODNs can be applied to protein labeling with bromo groups as sensitive mass tags.

A chemoselective hydroxycarbonylation and 13C-labeling of aryl diazonium salts using formic acid as the C-1 source.

We report a one-pot synthesis of aryl carboxylic acids utilizing HCOOH as a CO surrogate with low Pd-catalyst loading. This operationally simple and scalable method does not require use of a high-pressure reactor, two-chamber reaction vessel, phosphine ligand, or base and proceeds in a relatively short amount of time at ambient temperature. Notably, halides, including iodo and bromo groups, and nitro groups remain intact under these mild reaction conditions. This methodology has been successfully applied to synthesizing 13C-labeled aryl carboxylic acids with satisfactory yields.

Facile synthesis of dibenzothiophene S-oxides from sulfinate esters.

An efficient method to prepare dibenzothiophene S-oxides is disclosed. Suzuki-Miyaura cross-coupling of 2-bromoaryl sulfinate esters with arylboronic acids selectively at the bromo group followed by electrophilic cyclization of the resulting sulfinate ester moiety provides diverse dibenzothiophene S-oxides. Further transformations including Pummerer-type C-H propargylation and aryne reactions realize to synthesize highly functionalized dibenzothiophene derivatives.

Third-order nonlinear optical properties of highly electron deficient, nonplanar push-pull porphyrins: β-nitro-hexa-substituted porphyrins bearing bromo, phenyl, and phenylethynyl groups.

β-Heptasubstituted porphyrins [MTPP(NO2)X6; M = 2H, NiII, CuII, and ZnII; X = Br, Ph, and PE] were synthesized and their third-order nonlinear optical (NLO) properties explored using the single-beam Z-scan technique with femtosecond, MHz pulses in the visible range. The three-photon absorption (γ), third-order nonlinear optical susceptibility (χ3), three-photon absorption cross-section (σ3), and nonlinear refractive index (n2) have been determined from theoretical fits with experimental results. The sign and magnitude of the nonlinear refractive index (n2) have been obtained from the closed-aperture experiment while the three-photon absorption coefficient and three-photon absorption cross-section were determined from the open-aperture experiment. The magnitudes of the 3PA and σ3 extended in the range of (2.7-3.4) × 10-23 cm3 W-2 and (5.5-7.0) × 10-78 cm6 s2, respectively. The higher magnitude of the NLO coefficients ensures their utility in optical and photonic applications.

Synthesis of N-β-brominated alkenyl isothiocyanates via dehydrogenation of alkyl isothiocyanates.

This study presents a new dehydrogenative synthesis of alkenyl isothiocyanates, providing compounds with bromo and isothiocyanate groups. These reactive functionalities offer versatility for further transformations. Application in an amine sensor utilizing a coumarin-attached product demonstrates practical utility. This streamlined approach facilitates access to alkenyl isothiocyanates, valuable tools for biological studies.

Synthesis of quinoxalines and assessment of their inhibitory effects against human non-small-cell lung cancer cells.

Twenty-six quinoxalin derivatives were synthesized to assess their biological activities against human non-small-cell lung cancer cells (A549 cells). Compound 4b (IC50 = 11.98 ± 2.59 μM) and compound 4m (IC50 = 9.32 ± 1.56 μM) possess anticancer activity comparable to 5-fluorouracil (clinical anticancer drug) (IC50 = 4.89 ± 0.20 μM). Western blot tests further confirmed that compound 4m effectively induced apoptosis of A549 cells through mitochondrial- and caspase-3-dependent pathways. The introduction of bromo groups instead of nitro groups into the quinoxaline skeleton has been shown to provide better inhibition against lung cancer cells in this article. This modification in the molecular structure could enhance the biological activity and effectiveness of quinoxaline derivatives in the design and synthesis of anticancer drugs, making bromo-substituted quinoxalines a promising avenue for further research and development in anticancer therapeutics.

Synthesis and properties of bay-functionalized 9,9′-bifluorenylidene derivatives

Abstract Here, we disclose the effect of substitution at the bay-region of 9,9′-bifluorenylidene on its optical and electrochemical properties. Bay-brominated 9,9′-bifluorenylidene was synthesized by the reductive dimerization of 4,5-dibromofluorenone with triethyl phosphite. The subsequent Suzuki–Miyaura cross-coupling afforded arylated derivatives. X-ray diffraction analysis revealed that the bulky bay-substituents twist the overall structure through the relay of the steric repulsion from the bay-region to the fjord-region. The π-extension at the bay-region with tolyl and 4-dimethylaminophenyl groups increases the electron-donating ability, while the introduction of bromo groups enhances the electron-accepting ability.