40000-20-2

Usage

Uses

Used in Organic Synthesis:
5-bromo-1,10-phenanthroline is used as an organic synthesis intermediate for the preparation of various complex organic molecules. Its unique chemical structure allows for selective functionalization and modification, making it a versatile building block in the synthesis of a wide array of compounds.
Used in Pharmaceutical Industry:
5-bromo-1,10-phenanthroline is also used as a pharmaceutical intermediate, playing a crucial role in the development of new drugs and therapeutic agents. Its chemical properties enable it to be incorporated into the structures of potential pharmaceutical compounds, contributing to their overall efficacy and pharmacological properties.
Used in Laboratory Research and Development:
In the context of laboratory research and development, 5-bromo-1,10-phenanthroline is employed as a key compound for exploring new chemical reactions and investigating the properties of novel organic and pharmaceutical compounds. Its unique structure and reactivity make it an essential tool for advancing scientific understanding and driving innovation in the field.
Used in Chemical Production Process:
5-bromo-1,10-phenanthroline is also utilized in the chemical production process, where it serves as an essential intermediate for the large-scale synthesis of various organic and pharmaceutical products. Its role in this context is to facilitate the efficient and cost-effective production of these compounds, ultimately contributing to the overall success and sustainability of the chemical industry.

Synthesis

The compound was synthesized using a modification of the preparation described by Mlochowski.35 The yield of product is quite sensitive to the amount of bromine employed, the temperature, and the reaction time. Higher temperatures result in the formation of varying amounts of 5,6-dibromophenanthroline and 1,10-phenanthroline-5,6-dione. In our hands, the following preparation resulted in the maximum yield of product. A 3.6 g (20 mmol) sample of phenanthroline was placed in a heavy-walled glass reaction tube with a Teflon screw top fitted with a Viton O-ring. The reaction vessel was placed in an ice bath, and 12 mL of oleum (15%) and 0.60 mL (11.6 mmol) of bromine were added. The reaction tube was placed in a silicon oil bath, and the temperature was slowly raised to 135 °C. After 23 h, the reaction mixture was cooled to room temperature, poured over ice, and neutralized with NH4OH. The mixture was extracted with CHCl3. The extracts were stirred with charcoal and then dried over Na2SO4. The crude reaction mixture contained about 5% unreacted phenanthroline as judged by 1H NMR spectroscopy. The solid was recrystallized from hot diethyl ether with a minimum amount of CH2Cl2. Yield 4.67 g (90%).

InChI:InChI=1/C12H7BrN2/c13-10-7-8-3-1-5-14-11(8)12-9(10)4-2-6-15-12/h1-7H

Upstream product

• 53472-18-7 5-bromo-8-aminoquinoline 
• 56-81-5 glycerol 
• 57339-57-8 8-amino-6-bromoquinoline 
• 66-71-7 1,10-Phenanthroline 
• 504-63-2 trimethyleneglycol 
• 41119-20-4 Fe(5-bromophenanthroline)3⁽²⁺⁾ 

Downstream Products

• 312329-53-6 C₅₄H₄₄N₂O₆ 
• 453530-53-5 C₄₆H₅₂N₂O₂ 
• 6153-89-5 5-phenyl-1,10-phenanthroline 
• 1082-21-9 5-cyano-1,10-phenanthroline 

Relevant academic research and scientific papers

Efficient Access to 5-Bromo- and 5,6-Dibromophenanthroline Ligands

Bromo-functionalized precursor molecules are essential for generating desired target compounds through cross-coupling reactions. Herein we show an improved synthetic route, feasible at low temperatures and affording high yields, to the ligands 5-bromo-1,10-phenanthroline (1) and 5,6-dibromo-1,10-phenanthroline (2). The corresponding ruthenium complexes, containing various equivalents of ligand 2, are easily accessible in high yields, including the analogue of tris-homoleptic [Ru(bpy)3]2+ (bpy = 2,2′-bipyridine), [Ru(2)3]2+. X-ray diffraction analyses have provided detailed information on the structures of the ligands and their corresponding metal complexes. An investigation of the electrochemical properties has provided detailed information on the 3MLCT state localized on 2. We show the conversion of heteroleptic ruthenium complexes of these ligands in Suzuki cross-coupling reactions whereas the ligands did not undergo reaction under the same conditions.

Synthesis of poly(1,10-phenanthroline-5,6-diyl)s having a π-stacked, helical conformation

5,6-Dibromo-1,10-phenanthroline and 2,9-di-n-butyl-5,6-dibromo-1,10-phenanthroline were polymerized using a Ni catalyst to afford helical polymers in which the phenanthroline moieties are densely stacked on top of each other. Polymerization of the latter monomer using a chiral catalyst led to a preferred-handed helix. This is the first Ni-catalyzed helix-sense-selective polymerization of aromatic compounds.

Synthesis, Characterization and Photobiological Studies of Ru(II) Dyads Derived from α-Oligothiophene Derivatives of 1,10-Phenanthroline

Three new bis(2,2′-bipyridine)-heteroleptic Ru(II) dyads incorporating thienyl groups (n?=?1–3, compounds 1, 2 and 3, respectively) appended to 1,10-phenanthroline were synthesized and characterized to investigate the impact of n on the photophysical and photobiological properties within the series. All three complexes showed unstructured emission near 618?nm from a triplet metal-to-ligand charge transfer (3MLCT) state with a lifetime (τem) of approximately 1?μs. Transient absorption measurements revealed an additional excited state that was nonemissive and long-lived (τTA?=?43?μs for 2 and 27?μs for 3), assigned as a triplet intraligand (3IL) state that was accessible only in 2 and 3. All three complexes were strong singlet oxygen (1O2) sensitizers, with quantum yields (Φ?) for 2 and 3 being the largest (74–78%), and all three were photocytotoxic to cancer cells with visible light activation in the order: 3?>?2?>?1. Cell-free DNA photodamage followed the same trend, where potency increased with decreasing 3IL energy. Compounds 2 and 3 also showed in?vitro photobiological effects with red light (625?nm), where their molar absorptivities were ?1?cm?1. These findings highlight that Ru(II) dyads derived from α-oligothiophenes directly appended to 1,10-phenanthroline—namely 2 and 3—possess low-lying 3IL states that are highly photosensitizing, and they may therefore be of interest for photobiological applications such as photodynamic therapy (PDT).

Peptide-bridged dinuclear Ru(II) complex for mitochondrial targeted monitoring of dynamic changes to oxygen concentration and ROS generation in live mammalian cells

A novel mitochondrial localizing ruthenium(II) peptide conjugate capable of monitoring dynamic changes in local O2 concentrations within living cells is presented. The complex is comprised of luminescent dinuclear ruthenium(II) polypyridyl complex bridged across a single mitochondrial penetrating peptide, FrFKFrFK-CONH2 (r = d-arginine). The membrane permeability and selective uptake of the peptide conjugate at the mitochondria of mammalian cells was demonstrated using confocal microscopy. Dye co-localization studies confirmed very precise localization and preconcentration of the probe at the mitochondria. This precision permitted collection of luminescent lifetime images of the probe, without the need for co-localizing dye and permitted semiquantitative determination of oxygen concentration at the mitochondria using calibration curves collected at 37 °C for the peptide conjugate in PBS buffer. Using Antimycin A the ability of the probe to respond dynamically to changing O2 concentrations within live HeLa cells was demonstrated. Furthermore, based on lifetime data it was evident that the probe also responds to elevated reactive oxygen species (ROS) levels within the mitochondria, where the greater quenching capacity of these species led to luminescent lifetimes of the probe at longer Antimycin A incubation times which lay outside of the O2 concentration range. Although both the dinuclear complex and a mononuclear analogue conjugated to an octaarginine peptide sequence exhibited some cytotoxicity over 24 h, cells were tolerant of the probes over periods of 4 to 6 h which facilitated imaging. These metal-peptide conjugated probes offer a valuable opportunity for following dynamic changes to mitochondrial function which should be of use across domains in which the metabolic activity of live cells are of interest from molecular biology and drug discovery.

Synthesis of metallo-supramolecular polymers using 5,5′-linked bis(1,10-phenanthroline) ligands

5,5′-Linked bis(1,10-phenanthroline)s were synthesized as new bidentate ligands by a palladium-catalyzed Suzuki-type cross-coupling reaction. Coordination of the ligands to Cu(II), Ni(II), Ag(I), and Zn(II) ions resulted in metallo-supramolecular polymer formation. The 1:1 complexation of the ligands and the metal ions was confirmed by UV-vis titration experiments. The high molecular weights of more than 105 Da, caused by the high complexation constants, were confirmed by the SEC-Viscometry-RALLS method. Georg Thieme Verlag Stuttgart New York.

Novel ruthenium(II) and zinc(II) complexes for two-photon absorption related applications

Two new fluorene derivatized 1,10-phenanthroline ligands and related tris-chelate Ru(ii) or Zn(ii) coordination complexes have been synthesised. The linear and nonlinear (two-photon induced fluorescence) photophysical measurements have contributed to highlight the possibility to tune the absorption spectral range and excited lifetime, depending on ligand substitution and nature of the metal. More significantly, the observation of two-photon absorption (TPA) associated with long-lived metal-to-ligand charge-transfer (MLCT) excited states in the Ru(ii)-based chromophores, opens a wide range of applications in the near infrared. The Royal Society of Chemistry 2007.

Palladium Nanoparticles Encapsulated in [M(C19H11N2O2)2·H2O] (M = Co and Mn) as a Potential Catalyst for the Homocoupling of Aryl Halides

A new ligand, 4-(1,10-phenanthrolin-6-yl)benzoic acid, has been synthesized and employed to prepare new inorganic coordination polymer compounds, [M(C19H11N2O2)2·H2O] (M = Co, Mn). Both the compounds have identical structures formed by the connectivity between octahedral metal centers and the ligand, giving rise to a two-dimensional structure. The 2D structure is interpenetrated by identical units and forms a 2-fold interpenetrated structure. The lattice water molecules can be reversibly removed without altering the gross framework structure. The water removal has been investigated using in situ IR, PXRD, and in situ single-crystal XRD studies. Pd nanoparticles, prepared employing known procedures, were incorporated within the compound. We have successfully encapsulated up to 6.8% of Pd with a particle size of 4.8 ± 0.3 nm in the compound. The Pd@MOF compound was examined for homocoupling of aryl halides, resulting in good yields and recyclability. Magnetic studies indicate antiferromagnetic behavior in both the compounds with good orbital contribution for the cobalt compound.

Confocal fluorescence microscopy studies of a fluorophore-labeled dirhodium compound: Visualizing metal-metal bonded molecules in lung cancer (A549) cells

The new dirhodium compound [Rh2(μ-O2CCH 3)2(η1-O2CCH3) (phenbodipy)(H2O)3][O2CCH3] (1), which incorporates a bodipy fluorescent tag, was prepared and studied by confocal fluorescence microscopy in human lung adenocarcinoma (A549) cells. It was determined that 1 localizes mainly in lysosomes and mitochondria with no apparent nuclear localization in the 1-100 μM range. These results support the conclusion that cellular organelles rather than the nucleus can be targeted by modification of the ligands bound to the Rh24+ core. This is the first study of a fluorophore-labeled metal-metal bonded compound, work that opens up new venues for the study of intracellular distribution of dinuclear transition metal anticancer complexes.

Chemistry on the Complex: Derivatization of TiO4N2-Based Complexes and Application to Multi-Step Synthesis

The chemistry on octahedral TiO4N2-complexes is described. The Ti(IV)-based precursors are composed of two 3,3’-diphenyl-2,2’-biphenolato ligands (1) and one substituted 1,10-phenanthroline ligand (2-5). The application of imine condensation, palladium-catalyzed C?C bond formation or copper-catalysed azide-alkyne cycloaddition allowed the grafting of various new groups onto these species. In particular Sonogashira reactions permitted to observe an excellent conversion of the starting complexes. This systematic study enabled to compile the factors required to preserve the framework of the complexes in the course of a chemical transformation. Thanks to this chemistry realized on the complex, the Ti(1)2 fragment was used as a protecting group to develop a multi-step synthesis of a bis-phenanthroline compound (12), for which the synthesis without this protection failed. Thus, a dinuclear complex [Ti2(1)4(12)] was first prepared starting from complex precursor bearing an acetylenic function via a Hay coupling reaction. This was followed by a deprotection step affording 12. Overall, this work illustrates how the Ti(1)2 fragment could be an useful tool for the preparation of unprecedented diimine compounds.

Turn On of a Ruthenium(II) Photocatalyst by DNA-Templated Ligation

Here, the synthesis of a RuII photocatalyst by light-directed oligonucleotide-templated ligation reaction is described. The photocatalyst was found to have tremendous potential for signal amplification with >15000 turnovers measured in 9 hours. A templated reaction was used to turn on the activity of this ruthenium(II) photocatalyst in response to a specific DNA sequence. The photocatalysis of the ruthenium(II) complex was harnessed to uncage a new precipitating dye that is highly fluorescent and photostable in the solid state. This reaction was used to discriminate between different DNA analytes based on localization of the precipitate as well as for in cellulo miRNA detection. Finally, a bipyridine ligand functionalized with two different peptide nucleic acid (PNA) sequences was shown to enable template-mediated ligation (turn on of the ruthenium(II) photocatalysis) and recruitment of substrate for templated photocatalysis.