Bathophenanthroline

Preparative Methods the reagent is prepared in three steps from o-nitroaniline. 

Handling, Storage, and Precautions hazardous in case of eye contact or ingestion. Slightly hazardous in case of skin contact or inhalation. 

Preparation. o-Nitroaniline generates 4-phenyl-8-nitroquinoline through an SeAt cyclization mechanism when treated with arsenic acid, concentrated sulfuric acid, and (/ -chloropropiophenone. Crystallization from a benzene-petroleum ether system leads to 4-phenyl-8-nitroquinoline (eq 1).  

4-Phenyl-8-nitroquinoline is then reduced to 4-phenyl-8-aminoquinoline upon treatment with acetic acid and powdered iron (eq 2)  

10- phenanthroline using arsenic acid and 85% phosphoric acid with a gradual addition of ( 8-chloropropiophenone. 4,7-diphenyl- 

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Saito described a quantitative spectrophotometric procedure for iron based on a solid-phase extraction using bathophenanthroline in a poly(vinyl chloride) membrane. ... 

In the absence of Fe +, the membrane is colorless, but when immersed in a solution of Fe + and C, the membrane develops a red color as a result of the formation of a Fe +-bathophenanthroline complex. A calibration curve determined using a set of external standards with known molar concentrations of Fe + gave a standardization relationship of... 

Diphenyl-l,10-phenanthrolinedisulfonic acid, di-Na salt 3H2O (bathophenanthroline-disulfonic acid di-Na salt) [52746-49-3] M 590.6, m 300 , pKesj-O (for free acid). Dissolve crude sample in the minimum volume of water and add EtOH to ppte the contaminants. Carefully evaporate the filtrate to obtain pure material. 

Ten Brink et al. (2000) have shown how biphasic systems, sometimes with the sparingly soluble alcohols as one phase and an aqueous phase as the other phase, benefit from the strategy for air oxidation to aldehydes/ketones by using water soluble Pd complex of bathophenanthroline disulphonate. This is a nice example of green technology. 

In the mechanism of an interfacial catalysis, the structure and reactivity of the interfacial complex is very important, as well as those of the ligand itself. Recently, a powerful technique to measure the dynamic property of the interfacial complex was developed time resolved total reflection fluorometry. This technique was applied for the detection of the interfacial complex of Eu(lII), which was formed at the evanescent region of the interface when bathophenanthroline sulfate (bps) was added to the Eu(lII) with 2-thenoyl-trifuluoroacetone (Htta) extraction system [11]. The experimental observation of the double component luminescence decay profile showed the presence of dinuclear complex at the interface as illustrated in Scheme 5. The lifetime (31 /as) of the dinuclear complex was much shorter than the lifetime (98 /as) for an aqua-Eu(III) ion which has nine co-ordinating water molecules, because of a charge transfer deactivation. 

Recently, great advancement has been made in the use of air and oxygen as the oxidant for the oxidation of alcohols in aqueous media. Both transition-metal catalysts and organocatalysts have been developed. Complexes of various transition-metals such as cobalt,31 copper [Cu(I) and Cu(II)],32 Fe(III),33 Co/Mn/Br-system,34 Ru(III and IV),35 and V0P04 2H20,36 have been used to catalyze aerobic oxidations of alcohols. Cu(I) complex-based catalytic aerobic oxidations provide a model of copper(I)-containing oxidase in nature.37 Palladium complexes such as water-soluble Pd-bathophenanthroline are selective catalysts for aerobic oxidation of a wide range of alcohols to aldehydes, ketones, and carboxylic acids in a biphasic... 

Shriadah and Ohzeki [350] determined iron in seawater by densitometry after enrichment as a bathophenanthroline disulfonate complex on a thin layer of anion exchange resin. Seawater samples (50 ml) containing iron (II) and iron (III) were diluted to 150 ml with water, followed by sequential addition of 20% hydrochloric acid (100 xl), 10% hydroxyl-ammonium chloride (2 ml), 5 M ammonium solution (to pH 3.0 for iron (III) reduction), bathophenanthroline disulfonate solution (1.0 ml), and 10% sodium acetate solution (2.0 ml) to give a mixture with a final pH of 4.5. A macroreticular anion exchange resin in the... 

Radioisotope dilution using the chelating agent bathophenanthroline has been used to determine down to 5 xg/l iron in seawater [357]. 

Iron Conversion to bathophenanthroline complex adsorption om anion exchange resin (Amberlite A27) Densitometric scanning of resin at 550 nm [350]... 

Early determinations of iron and hemoglobin in blood were described by Herrmann et al53) and Bohmer et al 54). Zettner and co-workers ss) determinent serum iron by extracting the bathophenanthroline complex into MIBK. The serum could be diluted with water and aspirated only if the iron level was above 2 ppm. Rodgerson and Heifer S6) tried aspirating undiluted serum but obtained irreproduc-... 

A broad range of metal centers have been used for the complexation of functional ligands, including beryllium [37], zinc, transition metals such as iridium [38], and the lanthanide metals introduced by Kido [39], especially europium and terbium. Common ligands are phenanthroline (phen), bathophenanthrolin (bath), 2-phenylpyridine (ppy), acetylacetonate (acac), dibenzoylmethanate (dbm), and 11 thenoyltrifluoroacetonate (TTFA). A frequently used complex is the volatile Eu(TTFA)3(phen), 66 [40]. 

The electron mobility of oxadiazoles have been measured in a polymer matrix, values of 10 7 up to 10 3 cm2/Vs have been obtained [262, 263], These values are exceeded by starburst phenylquinoxalines (30) that approach 10-4 cm2/Vs at 106 V/cm [264]. Other material classes that are very interesting candidates for electron-transport layers comprise naphtalene-, 60, and perylenetetracarboxylic diimides, 59 [265], as well as bathophenanthroline [266] with reported electron mobilities of 10 3 and 4.2 x 10 4cm2/Vs, respectively. 

A prime advantage of such biphasic systems is that the catalyst resides in one phase and the starting materials and products are in the second phase, thus providing for easy recovery and recycling of the catalyst by simple phase separation. A pertinent example is the aerobic oxidation of alcohols catalyzed by a water-soluble Pd-bathophenanthroline complex (Figure 9.5). The only solvent used is water, the oxidant is air, and the catalyst is recycled by phase separation. 

Figure 9.5 Aerobic oxidation of alcohols catalyzed by Pd(II)/bathophenanthroline in...

Along with palladium, several metal-based catalysts have been used for the Suzuki-Miyaura reaction. Zhou and Fu have reported on the use of Ni(COD)2 and bathophenanthroline for the coupling of unactivated secondary bromides... 

H. Diehl and G. F. Smith, The Iron Reagents — Bathophenanthroline, Batho-phenanthroline Sulphonic Acid, 2,4,6-Tripyridyl-s-triazine, Phenyl-2-pyridyl Ketox-ime. Smith Chem. Co., Columbus, Ohio, 1965. 

The removal of metals from sensitive sites by chelation can serve to suppress HO degradation of tissue. Whereas EDTA reacts with 02 and H20273, both diethylene-triaminepentaacetic add (DTPA) and bathophenanthroline induce a diminuition in iron-dependent production of HO however DFOA has proved to be the most effective76. (The structure of DFOA is given in Sect. 3.3.2.)... 

Hazemoto et al (1+0) developed an ion-selective electrode sensitive to saccharin, by establishing an ion association between Fe2+-bathophenanthroline chelate and saccharin in nitrobenzene. The electrode developed could measure saccharin ion in presence of other sweetening agents e.g., sucrose, glucose, sodium cyclamate and sorbitol in the concentration range of 10 - - to 10 M. 

Pd(II) catalysts have been widely used for aerobic oxidation of alcohols. The catalytic systems Pd(OAc)2-(CH3)2SO [14] and Pd(OAc)2-pyridine [15] oxidize allylic and benzylic alcohols to the corresponding aldehydes and ketones. Secondary aliphatic alcohols, with relatively high water solubility, have been oxidized to the corresponding ketones by air at high pressure, at 100 °C in water, by using a water-soluble bathophenanthroline disulfonate palladium complex [PhenS Pd(OAc)2] [5d]. The Pd catalyst has also been successfully used for aerobic oxidative kinetic resolution of secondary alcohols, using (-)-sparteine [16]. 

TABLE 6.3. Silver-Bathophenanthroline Catalysis of a Mild Intermolecular C-H Amination... 

Figure 6.3. X-ray crystallographic structure of silver-bathophenanthroline catalyst system AglA is coordinated with two triflate molecules, while Ag2A is coordinated with a water molecule.

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