7005-72-3

Usage

Uses

Used in Environmental Testing and Research:
4-Chlorodiphenyl ether is used as a standard for environmental testing and research, particularly in the assessment of biodegradability studies with organic priority pollutant compounds. Its stability and solubility properties make it suitable for such applications.
Used in Chemical Synthesis:
4-Chlorodiphenyl ether is used in the preparation of 4′-chloro-2,2′,3,3′,4,5,5′,6,6′-nonabromodiphenyl ether (Cl-BDE-208), which serves as an internal standard in the analysis of highly brominated diphenyl ethers. This application is crucial for accurate quantification and monitoring of these compounds in various environmental and industrial samples.

Synthesis Reference(s)

The Journal of Organic Chemistry, 57, p. 391, 1992 DOI: 10.1021/jo00027a071

Air & Water Reactions

Insoluble or slightly soluble in water.

Reactivity Profile

4-Chlorodiphenyl ether oxidizes readily in air to form unstable peroxides that may explode spontaneously [Bretherick, 1979 p.151-154, 164].

Fire Hazard

Combustible.

Environmental fate

Biological. 4-Chlorophenyl phenyl ether (5 and 10 mg/L) did not significantly biodegrade following incubation in settled domestic wastewater inoculum at 25 °C. Percent losses reached a maximum after 2–3 wk but decreased thereafter suggesting a deadaptive process was occurring (Tabak et al., 1981). In activated sludge, a half-life of 4.0 h was measured (Branson, 1978). Photolytic. In a methanolic solution irradiated with UV light (λ >290 nm), dechlorination of 4- chlorophenyl phenyl ether resulted in the formation of diphenyl ether (Choudhry et al., 1977). Photolysis of an aqueous solution containing 10% acetonitrile with UV light (λ = 230–400 nm) yielded 4-hydroxybiphenyl ether and chloride ion (Dulin et al., 1986). At influent concentrations of 1.0, 0.1, 0.01, and 0.001 mg/L, the GAC adsorption capacities were 111, 61, 33, and 18 mg/g, respectively (Dobbs and Cohen, 1980).

InChI:InChI=1/C12H9Cl.C4H10O/c13-12-8-6-11(7-9-12)10-4-2-1-3-5-10;1-3-5-4-2/h1-9H;3-4H2,1-2H3

Upstream product

• 101-84-8 diphenylether 
• 108-86-1 bromobenzene 
• 1193-00-6 sodium 4-chlorophenolate 
• 106-46-7 para-dichlorobenzene 
• 100-67-4 potassium phenolate 
• 2444-89-5 4,4'-dichlorodiphenyl ether 
• 56-23-5 tetrachloromethane 
• 7553-56-2 iodine 
• 7782-50-5 chlorine 
• 64-19-7 acetic acid 
• 1121-74-0 potassium 4-chlorophenoxide 
• 106-48-9 4-chloro-phenol 
• 108-95-2 phenol 
• 591-50-4 iodobenzene 

Downstream Products

• 69199-63-9 5-chloro-2-phenoxy-benzoic acid 
• 5753-33-3 RB₂₀₂ 
• 10230-34-9 2-Chlor-phenoxathiin 
• 2444-89-5 4,4'-dichlorodiphenyl ether 
• 1836-74-4 4-(4-chlorophenoxy)nitrobenzene 
• 10265-98-2 (4-chloro-3-nitro-phenyl)-phenyl ether 
• 6842-61-1 3-(4-chlorophenoxy)phenyl bromide 
• 30427-95-3 1-bromo-4-(4-chlorophenoxy)benzene 
• 854259-78-2 (3-bromo-4-chloro-phenyl)-phenyl ether 
• 854257-01-5 1-chloro-4-(4-iodophenoxy)benzene 
• 57148-29-5 3-<4-(4-chlorophenoxy)benzoyl>propionic acid 
• 57148-40-0 4-<4-(4-chlorophenoxy)benzoyl>butyric acid 
• 101973-95-9 2-methylene-3-<4-(4-chlorophenoxy)benzoyl>propionic acid 
• 13221-80-2 2-chloro-1-[4-(4-chlorophenoxy)phenyl]ethanone 

Relevant academic research and scientific papers

Magnetization of graphene oxide nanosheets using nickel magnetic nanoparticles as a novel support for the fabrication of copper as a practical, selective, and reusable nanocatalyst in C-C and C-O coupling reactions

Catalyst species are an important class of materials in chemistry, industry, medicine, and biotechnology. Moreover, waste recycling is an important process in green chemistry and is economically efficient. Herein, magnetic graphene oxide was synthesized using nickel magnetic nanoparticles and further applied as a novel support for the fabrication of a copper catalyst. The catalytic activity of supported copper on magnetic graphene oxide (Cu-ninhydrin@GO-Ni MNPs) was investigated as a selective, practical, and reusable nanocatalyst in the synthesis of diaryl ethers and biphenyls. Some of the obtained products were identified by NMR spectroscopy. This nanocatalyst has been characterized by atomic absorption spectroscopy (AAS), scanning electron microscopy (SEM), wavelength dispersive X-ray spectroscopy (WDX), energy-dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FT-IR), and vibrating sample magnetometer (VSM) techniques. The results obtained from SEM shown that this catalyst has a nanosheet structure. Also, XRD and FT-IR analysis show that the structure of graphene oxide and nickel magnetic nanoparticles is stable during the modification of the nanoparticles and synthesis of the catalyst. The VSM curve of the catalyst shows that this catalyst can be recovered using an external magnet; therefore, it can be reused several times without a significant loss of its catalytic efficiency. The heterogeneity and stability of this nanocatalyst during organic reactions was confirmed by the hot filtration test and AAS technique.

Copper nanoparticle anchored biguanidine-modified Zr-UiO-66 MOFs: a competent heterogeneous and reusable nanocatalyst in Buchwald-Hartwig and Ullmann type coupling reactions

We have designed a functionalized metal-organic framework (MOF) of UiO topology as a support, with an extremely high surface area, adjustable pore sizes and stable crystalline coordination polymeric structure and implanted copper (Cu) nanoparticles thereon. The core three dimensional Zr-derived MOF (UiO-66-NH2) was modified with a biguanidine moiety following a covalent post-functionalization approach. The morphological and physicochemical features of the material were determined using analytical methods such as FT-IR, SEM, TEM, EDX, atomic mapping, XRD and ICP-OES. The SEM and XRD results justified the unaffected morphology of Zr-MOF after structural modifications. The as-synthesized UiO-66-biguanidine/Cu nanocomposite was catalytically explored in the aryl and heteroaryl Buchwald-Hartwig C-N and Ullmann type C-O cross coupling reactions with excellent yields. A library of biaryl amine and biaryl ethers was synthesized over the catalyst under mild and green conditions. Furthermore, the catalyst was isolated by centrifugation and recycled 11 times with no significant copper leaching or change in its activity.

Synergistic effect of copper nanocrystals-nanoparticles incorporated in a porous organic polymer for the Ullmann C-O coupling r–eaction

A quinoxaline-based porous organic polymer (Q-POP) as a mesoporous organic copolymer was developed as a new platform for the immobilization of CuNPs and copper nanocrystals. The prepared materials were characterized by FT-IR, XRD, N2 adsorption-desorption isotherms, ICP, TGA, SEM, HR-TEM, EDX, and single-crystal X-ray crystallography. The obtained catalyst presented extraordinary catalytic activity towards Ullmann C–O coupling reactions with high surface area, hierarchical porosity, and excellent thermal and chemical stability. Due to its high porosity, and synergistic effect of copper nanocrystals incorporated in the polymer composite, the as-synthesized catalyst was successfully utilized for the Ullmann C–O coupling reaction of phenols and different aryl halides to prepare various diaryl ether derivatives. All types of aryl halides (except aryl fluorides) were screened in the Ullmann C–O coupling reaction with phenols to produce diaryl ethers in good to excellent yields (70–97 %), and it was found that aryl iodides have the best results. Besides, due to the strong interactions between CuNPs, N, and O-atoms of quinoxaline moiety existing in the polymeric framework, the copper leaching from the support was not observed. Furthermore, the catalyst was recycled and reused for five consecutive runs without significant activity loss.

Oxidative Photochlorination of Electron-Rich Arenes via in situ Bromination

Electron-rich arenes are oxidatively photochlorinated in the presence of catalytic amounts of bromide ions, visible light, and 4CzIPN as organic photoredox catalyst. The substrates are brominated in situ in a first photoredox-catalyzed oxidation step, followed by a photocatalyzed ipso-chlorination, yielding the target compounds in high ortho/para regioselectivity. Dioxygen serves as a green and convenient terminal oxidant. The use of aqueous hydrochloric acid as the chloride source reduces the amount of saline by-products.

Palladium complexes of chalcogenoethanamine (S/Se) bidentate ligands: Applications in catalytic arylation of C[sbnd]H and O[sbnd]H bonds

This report describes the syntheses of N,E (E = S, Se) coordinated bidentate palladium complexes, by the reaction of N-(2-bromobenzyl)-2-(phenylthio/selanyl)ethanamine (3, 4) with [PdCl2(CH3CN)2]. The new ligands and palladium complexes were characterized by techniques like 1H, 13C{1H} NMR, IR, and elemental analysis. The coordination modes of ligand with palladium precursor in complexes 5 and 6 were authenticated by single crystal X-ray diffraction. The complexes possess distorted square planar geometry around palladium center. Thermally robust and air stable complexes 5 and 6 were used as catalyst for regioselective arylation of imidazole and O-arylation of phenol. In case of regioselective arylation of imidazole, the reaction proceeds smoothly under mild reaction conditions, only 2.0 mol% of catalyst loading is required to achieve high yield (76–92%). This protocol is applicable to a broad substrate scope showing excellent tolerance towards different functional groups. Whereas for O-arylation of phenol also only 2.0 mol% catalyst loading is sufficient to give good yield (71–92%) with excellent tolerance towards a broad range of functional groups. Among sulfur and selenium coordinated ligands, selenium ligand coordinated complex, was found to outperform the catalytic reactions in both cases as compare to sulfur ligand. The mercury and triphenylphosphine poisoning tests suggest homogeneous nature of catalysis.

CoII Immobilized on Aminated Magnetic-Based Metal–Organic Framework: An Efficient Heterogeneous Nanostructured Catalyst for the C–O Cross-Coupling Reaction in Solvent-Free Conditions

Abstract: In this paper, we report the synthesis of Fe3O4?AMCA-MIL53(Al)-NH2-CoII NPs based on the metal–organic framework structures as a magnetically separable and environmentally friendly heterogeneous nanocatalyst. The prepared nanostructured catalyst efficiently promotes the C–O cross-coupling reaction in solvent-free conditions without the need for using toxic solvents and/or expensive palladium catalyst. Graphic Abstract: [Figure not available: see fulltext.].

Trimethoxyphenyl (TMP) as a Useful Auxiliary for in situ Formation and Reaction of Aryl(TMP)iodonium Salts: Synthesis of Diaryl Ethers

Herein, we describe a synthetic approach for arylation that exploits the in situ formation and reaction of an unsymmetrical diaryliodonium salt. In this way, aryl iodides are used as reagents in a metal-free reaction with phenols, and a trimethoxyphenyl (TMP) group is used as a “dummy” group to facilitate transfer of a wide range of aryl moieties. The scope of aryl electrophiles and phenol nucleophiles is broad (>30 examples) and the yields are high (52–95%, 80% avg.). One-pot coupling reactions avoid the synthesis of diaryliodonium salts and provide opportunities for sequential reactions and novel chemoselectivity. (Figure presented.).

Diaza crown-type macromocycle (kryptofix 22) functionalised carbon nanotube for efficient Ni2+ loading; A unique catalyst for cross-coupling reactions

Raising the capability of supporting and suppressing the leaching possibility to a very insignificant level has still remained challenging for some class of transition metals, i.e. Ni2+. Here we present the covalent functionalisation of macrocyclic ligand, 4,13-diaza-18-crown-6 (kryptofix 22), on the surface of carbon nanotube (CNT), leading to a unique adsorptive capability for supporting Ni2+. This material was incorporated as a promising catalyst in coupling reactions including C[sbnd]C, CN, and CO[sbnd][sbnd] cross-coupling reactions. We demonstrate that the kryptofix 22 functionalisation on the surface of CNT has a key role in the enhancement of the adsorption capability Ni2+ and subsequent catalytic activity. We further prove that this ligand causes a significant boost in the recyclability of the reactions due to the extremely trivial Ni2+ leaching from the CNT's surface during the reactions.

Magnetically recyclable nano copper/chitosan in O-arylation of phenols with aryl halides

Interaction of chitosan (CS) with Fe3O4, followed by embedding Cu nanoparticles (NPs) on the magnetic surface through adsorption of Cu2+, and its reduction to Cuo via NaBH4, offers a reusable efficient catalyst (Fe3O4/CS-Cu NPs) that is employed in cross-coupling reactions of aryl halides with phenols, which affords the corresponding diaryl ethers, with good to excellent yields. The catalyst is completely recoverable from the reaction mixture by using an external magnet. It can be reused four times, without significant loss in its catalytic activity.

Cu(I)-PNF, an organic-based nanocatalyst, catalyzed C-O and C-S cross-coupling reactions

Peptide nanofiber has been prepared via a self-assembly protocol and decorated with Cu(I) to prepare a nanostructural catalyst. The catalytic activity of this prepared nanomaterial (Cu(I)-PNF) was examined in C-O and C-S cross-coupling reactions. Compared with conventional copper-ligand catalytic systems, CuNP-PNF has unique advantages such as water solubility, high efficiency, and low cost, which makes it a highly efficient and beneficial catalyst to reuse in cross-coupling reactions.