- Synthesis of m-phenoxybenzaldehyde starting from chlorobenzene and m-cresol: Some aspects of process development
-
m-Phenoxybenzaldehyde (MPB) is an important intermediate for synthetic pyrethroids. In the present paper, an economic process scheme was developed to synthesize MPB starting from cheaper reactants. The process scheme was started with the synthesis of m-phenoxytoluene (MPT). Oxidation of MPT by air gave MPB, but the selectivity was found to be high at low conversions of about 10%, and if the conversion level was increased, then large amounts of the undesired m-phenoxybenzoic acid (MPBA) was formed. To obtain the desired aldehyde, Rosenmund reduction of MPBA was carried out to give high yields of the MPB. The effects of different parameters such as catalyst, substrate concentration, temperature, etc., were studied for all three of the reactions, viz., Ullmann ether synthesis, oxidation, and Rosenmund reduction. MPT was prepared from chlorobenzene, a relatively cheaper starting material, in the presence of polyethylene glycol) as cosolvent and cuprous chloride as the catalyst. A selectivity of 97% was obtained with 86% conversion to the product. Oxidation of MPT was carried out by air in the presence of cobalt acetate as catalyst and sodium bromide as catalyst promoter. The selectivity with respect to the aldehyde and the ester was 37.4 and 30.6%, respectively, at a restricted overall conversion of 24%. The process parameters were controlled to achieve high selectivity towards the aldehyde. The acid, formed as the side product, was reduced to the aldehyde by Rosenmund reduction via the acyl chloride. At a conversion level of 85%, a selectivity of 87% to MPB was obtained using Pd/C.
- Chandnani, Kavita H.,Chandalia, Sampatraj B.
-
-
Read Online
- Supported CuO/γ-Al2O3 as heterogeneous catalyst for synthesis of diaryl ether under ligand-free conditions
-
CuO/γ-Al2O3 was employed as catalyst in the coupling reaction of iodobenzene with m-cresol to give 3-methyldiphenyl ether under ligand-free conditions. It performed more efficiently than other supported CuO catalysts (CuO/SBA-15, CuO/ZrO2, CuO/CeO2, CuO/La2O3). Reaction conditions were investigated and the yield reached 76% under the optimized terms. As a heterogeneous catalyst, CuO/γ-Al2O3 could be reused for three cycles with moderate to good yields. According to the results of XRD, TPR and XPS, the catalytic activities of supported CuO catalysts were due to the highly dispersed Cu(II) species and independent of the electronic state of these copper species.
- Ling, Pengxiang,Li, Dao,Wang, Xingyi
-
-
Read Online
- L-Proline N-oxide dihydrazides as an efficient ligand for cross-coupling reactions of aryl iodides and bromides with amines and phenols
-
A novel catalytic system based on L-proline N-oxide/CuI was developed and applied to the cross-coupling reactions of various N- and O- nucleophilic reagents with aryl iodides and bromides. This strategy featured in the employment of an-proline derived dihydrazides N-oxide compound as the superior supporting ligand. By using this protocol, a variety of products, including N-arylimidazoles, N-arylpyrazoles, N-arylpyrroles, N-arylamines, and aryl ethers, were synthesized with up to 99% yield.
- Ding, Zhiqiang,Nie, Nan,Chen, Tian,Meng, Lingxin,Wang, Gongshu,Chen, Zhangpei,Hu, Jianshe
-
supporting information
(2020/12/21)
-
- Preparation method of m-phenoxy benzaldehyde
-
The invention provides a preparation method of m-phenoxy benzaldehyde, and belongs to the technical field of synthesis of medical intermediates. The preparation method comprises the following steps: mixing m-cresol, halogenated benzene, inorganic base and a catalyst for condensation reaction to obtain m-phenoxy toluene; mixing the m-phenoxy toluene with an oxidant, and carrying out an oxidation reaction under acidic conditions to obtain m-phenoxy benzaldehyde. According to the preparation method, m-cresol and halogenated benzene are taken as raw materials, the cost of the raw materials is low, m-phenoxy toluene is firstly prepared through a condensation reaction, then m-phenoxy toluene is oxidized into m-phenoxy benzaldehyde, the yield of the product is high, and the preparation is simple. The result of the embodiment shows that the yield of the m-phenoxybenzaldehyde prepared by the method is 56.8% or above.
- -
-
Paragraph 0056-0057
(2021/04/17)
-
- Preparation method of m-phenoxy benzaldehyde
-
The invention provides a preparation method of m-phenoxy benzaldehyde, and belongs to the technical field of organic synthesis. The preparation method provided by the invention comprises the following steps: condensing m-cresol serving as a raw material with halogenated benzene to obtain m-phenoxytoluene, reacting the m-phenoxytoluene with chlorine to chloridize methyl to obtain a m-phenoxytoluene chloro product, oxidizing the m-phenoxytoluene chloro product through Komblum to obtain an oxide of the m-phenoxytoluene chloro product, and directly hydrolyzing the m-phenoxytoluene chloro product without separation to obtain the product m-phenoxy benzaldehyde. The preparation method provided by the invention has the advantages that the raw materials are cheap and easily available, the yield is high, the product quality meets the market demand, the problems of high raw material price, many side reactions, many impurities, low yield, large wastewater amount and serious environmental pollution in the traditional process are solved, and the production cost of m-phenoxybenzaldehyde is greatly reduced. Data of the embodiment shows that the total yield of m-phenoxybenzaldehyde obtained by the preparation method provided by the invention is 83.5%, and the gas phase content is 99.3%.
- -
-
Paragraph 0075-0076
(2021/04/28)
-
- Preparation and characterization of Cu based on 5,5'-bistetrazole as a recyclable metal-organic framework and application in synthesis of diaryl ether by the Ullmann coupling reaction
-
Cu based on 5,5′-bistetrazole ([Cu2BT · 2H2O] n) as a recyclable metal-organic framework (MOF) heterogeneous catalyst was characterized by FT-IR, 13C NMR, XRD, SEM, EDX, BET, BJH, and ICP-AES analysis. The catalytic activity of the catalyst was probed through the Ullmann reaction for synthesis of diaryl ether derivatives from two component reactions of aromatic arylhalides and phenol derivatives in DMSO. Simple procedure, high yields, short reaction time, and environmentally benign methods are advantages of this protocol. The catalyst was readily separated by simple filtration and reusable without significant loss of its catalytic efficiency.
- Noorpoor, Zeinab,Tavangar, Saeed
-
p. 1651 - 1662
(2021/05/10)
-
- 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.).
- Gallagher, Rory T.,Basu, Souradeep,Stuart, David R.
-
p. 320 - 325
(2019/12/11)
-
- Pd based on 2-Aminopyrimidine and 1H-benzo[d]imidazol-2-amine functionalizedFe3O4 nanoparticles as novel recyclable magnetic nanocatalysts for Ullmann coupling reaction
-
In this study, Pd based on 2-Aminopyrimidine and 1H-benzo[d]imidazol-2-amine functionalized Fe3O4 magnetic nanoparticles [(Pd-APM-PSi-Fe3O4) and (Pd-BIA-PSi-Fe3O4)] was designed and used for the synthesis of di aryl ether by Ulmann cross-coupling reactions. Ulmann reaction performed with mixing of the arylhalides and phenol derivatives in DMF solvent. The prepared catalysts were characterized with various analytical techniques such as FT-IR, XRD, TGA, SEM, TEM, EDX, ICP and VSM. Pd-APM-PSi-Fe3O4 and Pd-BIA-PSi-Fe3O4 catalysts demonstrated good to excellent yields catalytic efficiency for Ulmann reactions in comparison with to commercial palladium catalysts. The catalyst is easily recycled and reused without loss of the catalytic activity. The combined merits of reusable catalyst conditions make the condensation with safe operation, no leaching of pd into environment, low pollution, rapid access to products and simple workup. Also, these novel magnetic nanocatalysts are superior to the industry standard Pd in every relevant aspect. They feature a way higher initial activity, a much more convenient separation, better recycling, and less contamination of the products. Last but not least, they can be very easily prepared from commercially available Fe3O4 nanoparticles using standard laboratory equipment.
- Chen, Jin,Dai, Linfang,Li, Jiayu,Mohammadnia, Majid
-
-
- Preparation and characterization of isatin complexed with Cu supported on 4-(aminomethyl) benzoic acid-functionalized Fe3O4 nanoparticles as a novel magnetic catalyst for the Ullmann coupling reaction
-
Isatin complexed with Cu supported on 4-(aminomethyl) benzoic acid-functionalized Fe3O4 nanoparticles (Cu-IS-AMBA-MNPs) as a new catalyst was designed, prepared and characterized by appropriate analyses. The heterogeneous reusable catalyst was successfully used for the efficient and widespread syntheses of diaryl ethers and diarylamines via the Ullmann coupling reaction. This green catalyst was easily removed, reused several times with no significant loss of its activity, and provided a clean synthesis with excellent yield and reduced time.
- Khodaei, Mohammad Mehdi,Alizadeh, Abdolhamid,Haghipour, Maryam
-
p. 2727 - 2747
(2019/02/13)
-
- 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.
- Mousavi Mashhadi, Seyed Ali,Kassaee, Mohamad Z.,Eidi, Esmaiel
-
-
- Decarbonylative Methylation of Aromatic Esters by a Nickel Catalyst
-
A Ni-catalyzed decarbonylative methylation of aromatic esters was achieved using methylaluminums as methylating agents. Dimethylaluminum chlorides uniquely worked as the methyl source. Because of the Lewis acidity of aluminum reagents, less reactive alkyl esters could also undergo the present methylation. By controlling the Lewis acidity of aluminum reagents, a chemoselective decarbonylative cross-coupling between alkyl esters and phenyl esters was successful.
- Okita, Toshimasa,Muto, Kei,Yamaguchi, Junichiro
-
p. 3132 - 3135
(2018/05/28)
-
- Cu2O/SiC as efficient catalyst for Ullmann coupling of phenols with aryl halides
-
A Cu2O/SiC heterogeneous catalyst was prepared via a two-step liquid-phase method using diethylene glycol as both the solvent and the reducing agent. The catalyst was characterized using X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and H2 temperature-programmed reduction. All the results indicate that Cu is present on the SiC support primarily as Cu2O. The SEM and TEM results show that cubic Cu2O nanoparticles are uniformly dispersed on the β-SiC surface. The reaction conditions, namely the temperature, reaction time, and amounts of base and catalyst used, for the Ullmann-type C–O cross-coupling reaction were optimized. A model reaction was performed using iodobenzene (14.0 mmol) and phenol (14.0 mmol) with Cu2O/SiC (5 wt% Cu) as the catalyst, Cs2CO3 (1.0 equiv.) as the base, and tetrahydrofuran as the solvent at 150 °C for 3 h; a yield of 97% was obtained and the turnover frequency (TOF) was 1136 h?1. The Cu2O/SiC catalyst has a broad substrate scope and can be used in Ullmann-type C–O cross-coupling reactions of aryl halides and phenols bearing a variety of different substituents. The catalyst also showed high activity in the Ullmann-type C–S cross-coupling of thiophenol with iodobenzene and substituted iodobenzenes; a TOF of 1186 h?1 was achieved. The recyclability of the Cu2O/SiC catalyst in the O-arylation of phenol with iodobenzene was investigated under the optimum conditions. The yield decreased from 97% to 64% after five cycles. The main reason for the decrease in the catalyst activity is loss of the active component, i.e., Cu2O.
- Wang, Yibing,Guo, Xiaoning,Lü, Manqian,Zhai, Zhaoyang,Wang, Yingyong,Guo, Xiangyun
-
p. 658 - 664
(2017/04/24)
-
- Cellulose-supported N-heterocyclic carbene silver complex with pendant ferrocenyl group for diaryl ether synthesis
-
A cellulose-supported N-heterocyclic carbene Ag(I) complex has been synthesized by covalent grafting of ferrocenyl ionic liquid in the matrix of cellulose followed by metallation with silver oxide. The complex was employed as a heterogeneous catalyst in the synthesis of diaryl ethers. Reactions of a variety of phenols with aryl halides afford corresponding diaryl ethers in moderate to good yields. Recyclability experiments were executed successfully for five consecutive runs.
- Jagadale, Megha,Salunkhe, Rajashri,Kumbhar, Arjun,Gajare, Shivanand,Rajmane, Mohan,Rashinkar, Gajanan
-
-
- A green approach for arylation of phenols using iron catalysis in water under aerobic conditions
-
The first efficient iron-catalyzed coupling of aryl iodides with phenols was developed exclusively with water as solvent. The reaction is performed with low cost and readily available FeCl3·6H2O and DMEDA catalytic system providing diaryl ethers in good to excellent yields. The effectiveness of this reaction was further revealed by compatibility with a wide range of functional groups. Moreover, the procedure is rendered simple as this transformation is carried out in the presence of air. Thus, the protocol represents a facile, economical and eco-friendly procedure to access diaryl ethers.
- Sindhu, Kallikkakam S.,Ujwaldev, Sankuviruthiyil M.,Keerthi Krishnan,Anilkumar, Gopinathan
-
p. 146 - 150
(2017/03/17)
-
- Synthesis of copper nanoparticles supported on a microporous covalent triazine polymer: An efficient and reusable catalyst for O-arylation reaction
-
Copper nanoparticles were supported on a microporous covalent triazine polymer prepared by the Friedel-Crafts reaction (Cu@MCTP-1). The resulting material was characterized by powder X-ray diffraction, thermogravimetric analysis, N2 adsorption-desorption isotherms at 77 K, transmission electron microscopy, X-ray photoelectron spectroscopy, and inductively coupled plasma optical emission spectroscopy, and Cu particles with an average size of 3.0 nm and a BET total surface area of ca. 1002 m2 g-1 were obtained. Cu@MCTP-1 was evaluated as a heterogeneous catalyst for the Ullmann coupling of O-arylation over a series of aryl halides and phenols without employing expensive ligands or inert atmosphere, which produced an excellent yield of the corresponding diaryl ethers. The catalyst could be recovered by simple centrifugation and was reusable at least five times with only a slight decrease in catalytic activity.
- Puthiaraj, Pillaiyar,Ahn, Wha-Seung
-
p. 1701 - 1709
(2016/04/05)
-
- Evaluation of fluorinated biphenyl ether pro-drug scaffolds employing the chemical-microbial approach
-
Incorporation of fluorine in a drug can dramatically affect its metabolism and methods to assess the effect of fluorine substitution on drug metabolism are required for effective drug design. Employing a previously developed chemical-microbial method the metabolism of a series of fluorinated biphenyl ethers was determined. The substrates were synthesized via Ullmann-type condensation reactions between bromotoluene and fluorophenol. The ethers were incubated with the fungus Cunninghamella elegans, which oxidises xenobiotics in an analogous fashion to mammals, generating a number of hydroxylated biphenyl ethers and acids. The propensity of the fluorinated ring to be hydroxylated depended upon the position of the fluorine atom, and the oxidation of the methyl group was observed when it was meta to the oxygen. The experiments demonstrate the applicability of the method to rapidly determine the effect of fluorine substitution on CYP-catalysed biotransformation of pro-drug molecules.
- Hampton, Alex S.,Mikulski, Lena,Palmer-Brown, William,Murphy, Cormac D.,Sandford, Graham
-
p. 2255 - 2258
(2016/04/20)
-
- Interface Engineering in Two-Dimensional Heterostructures: Towards an Advanced Catalyst for Ullmann Couplings
-
The design of advanced catalysts for organic reactions is of profound significance. During such processes, electrophilicity and nucleophilicity play vital roles in the activation of chemical bonds and ultimately speed up organic reactions. Herein, we demonstrate a new way to regulate the electro- and nucleophilicity of catalysts for organic transformations. Interface engineering in two-dimensional heteronanostructures triggered electron transfer across the interface. The catalyst was thus rendered more electropositive, which led to superior performance in Ullmann reactions. In the presence of the engineered 2D Cu2S/MoS2 heteronanostructure, the coupling of iodobenzene and para-chlorophenol gave the desired product in 92 % yield under mild conditions (100 °C). Furthermore, the catalyst exhibited excellent stability as well as high recyclability with a yield of 89 % after five cycles. We propose that interface engineering could be widely employed for the development of new catalysts for organic reactions.
- Sun, Xu,Deng, Haitao,Zhu, Wenguang,Yu, Zhi,Wu, Changzheng,Xie, Yi
-
supporting information
p. 1704 - 1709
(2016/02/03)
-
- Scope and Mechanistic Analysis for Chemoselective Hydrogenolysis of Carbonyl Compounds Catalyzed by a Cationic Ruthenium Hydride Complex with a Tunable Phenol Ligand
-
A cationic ruthenium hydride complex, [(C6H6)(PCy3)(CO)RuH]+BF4- (1), with a phenol ligand was found to exhibit high catalytic activity for the hydrogenolysis of carbonyl compounds to yield the corresponding aliphatic products. The catalytic method showed exceptionally high chemoselectivity toward the carbonyl reduction over alkene hydrogenation. Kinetic and spectroscopic studies revealed a strong electronic influence of the phenol ligand on the catalyst activity. The Hammett plot of the hydrogenolysis of 4-methoxyacetophenone displayed two opposite linear slopes for the catalytic system 1/p-X-C6H4OH (ρ = -3.3 for X = OMe, t-Bu, Et, and Me; ρ = +1.5 for X = F, Cl, and CF3). A normal deuterium isotope effect was observed for the hydrogenolysis reaction catalyzed by 1/p-X-C6H4OH with an electron-releasing group (kH/kD = 1.7-2.5; X = OMe, Et), whereas an inverse isotope effect was measured for 1/p-X-C6H4OH with an electron-withdrawing group (kH/kD = 0.6-0.7; X = Cl, CF3). The empirical rate law was determined from the hydrogenolysis of 4-methoxyacetophenone: rate = kobsd[Ru][ketone][H2]-1 for the reaction catalyzed by 1/p-OMe-C6H4OH, and rate = kobsd[Ru][ketone][H2]0 for the reaction catalyzed by 1/p-CF3-C6H4OH. Catalytically relevant dinuclear ruthenium hydride and hydroxo complexes were synthesized, and their structures were established by X-ray crystallography. Two distinct mechanistic pathways are presented for the hydrogenolysis reaction on the basis of these kinetic and spectroscopic data. (Chemical Equation Presented).
- Kalutharage, Nishantha,Yi, Chae S.
-
supporting information
p. 11105 - 11114
(2015/09/15)
-
- Anchoring of Pd(ii) complex in functionalized MCM-41 as an efficient and recoverable novel nano catalyst in C-C, C-O and C-N coupling reactions using Ph3SnCl
-
Anchored palladium(ii) in functionalized MCM-41 mesoporous silica was prepared and used as an efficient, recoverable and thermally stable heterogeneous nano catalyst for C-C, C-O and C-N bond formation in cross-coupling reactions in the presence of Ph3SnCl. MCM-41 was prepared trough hydrothermal synthesis using tetraethyl orthosilicate (Si(OC2H5)4) as silica source and cetyltrimethylammonium bromide (CTAB) as a template. The structure of functionalized MCM-41 was studied by FT-IR, XRD, SEM, TEM, TGA, EDS, ICP and BET techniques.
- Ghorbani-Choghamarani, Arash,Nikpour, Farzad,Ghorbani, Farshid,Havasi, Forugh
-
p. 33212 - 33220
(2015/04/27)
-
- Maghemite-Copper Nanocomposites: Applications for Ligand-Free Cross-Coupling (C-O, C-S, and C-N) Reactions
-
A magnetically retrievable, efficient, and benign maghemite-Cu nanocatalyst was synthesized from inexpensive precursors and applied for C-O, C-N, and C-S bond-formation reactions. The obtained maghemite-Cu nanocatalyst was characterized by various techniques such as XRD, X-ray photoelectron spectroscopy, field-emission gun SEM with energy-dispersive spectroscopy, atomic absorption spectroscopy, TEM, high-angle annular dark-field scanning transmission electron microscopy, FTIR spectroscopy, and M?ssbauer spectroscopy. Excellent catalytic activity, ease of recovery, and reusability without a significant loss of yield make the present protocol highly sustainable to deal with industrial and environmental concerns. Magnetic attraction: A magnetically retrievable, efficient, and benign maghemite-Cu nanocatalyst is synthesized from inexpensive precursors and applied for C-O, C-N, and C-S bond-formation reactions. Excellent catalytic activity, ease of recovery, and reusability without significant loss of yield make the present protocol highly sustainable to deal with industrial and environmental concerns.
- Sharma, Rakesh K.,Gaur, Rashmi,Yadav, Manavi,Rathi, Anuj K.,Pechousek, Jiri,Petr, Martin,Zboril, Radek,Gawande, Manoj B.
-
p. 3495 - 3502
(2015/11/10)
-
- Graphene-supported Cu2O nanoparticles: An efficient heterogeneous catalyst for C-O cross-coupling of aryl iodides with phenols
-
Cu2O/graphene as a heterogeneous catalyst can effectively ignite and catalyze the Ullmann C-O cross-coupling of aryl iodides with phenols under mild conditions. The yield of diphenyl ether from the cross-coupling of phenol and iodobenzene can reach up to 96% at 150 °C in 3 h, and the turnover frequency can be as high as 1282 h-1. Meanwhile, the catalyst exhibits activity for varieties of C-O cross-coupling of aryl iodides, bromides and chlorides with phenol derivatives to form the corresponding aryl ethers. This journal is
- Zhai, Zhaoyang,Guo, Xiaoning,Jiao, Zhifeng,Jin, Guoqiang,Guo, Xiang-Yun
-
p. 4196 - 4199
(2015/02/19)
-
- Betti base as an efficient ligand for copper-catalyzed ullmann coupling of phenol with aryl halides
-
GRAPHICAL ABSTRACT A simple, general, and highly efficient Betti base ligand has been developed for copper-catalyzed Ullmann coupling of phenol with aryl halides without the protection of an inert atmosphere. The reaction proceeds smoothly in the presence of K2CO3 as the base and dimethylsulfoxide as the solvent. The catalyst was reused several times with no evident loss of catalytic activity and is environmentally friendly.
- Yang, Li,Yang, Qichao,Shi, Jianxin,Wang, Yufang,Zhang, Mingjie
-
supporting information
p. 2468 - 2477
(2014/08/05)
-
- Carbon nanofiber supported copper nanoparticles catalyzed Ullmann-type coupling reactions under ligand-free conditions
-
A carbon nanofiber supported copper nanoparticle (CuNP/CNF) catalyst was prepared and used for Ullmann-type couplings under ligand-free conditions. The catalyst exhibited high catalytic activity in C-O and C-N bond formation couplings. This journal is
- Li, Hongqiang,Li, Chunping,Bai, Jie,Zhang, Chenglin,Sun, Weiyan
-
p. 48362 - 48367
(2014/12/10)
-
- Impregnated copper on magnetite as catalyst for the O-arylation of phenols with aryl halides
-
Nanoparticle Fe3O4 encapsulated CuO, as a heterogeneous catalyst, is a facile system for the synthesis of diaryl ethers by the cross-coupling reaction of various substituted aryl halides with various substituted phenols, which avoids using any type of expensive ligand and can be recovered from the reaction mixture by using a simple magnet. Moreover, this catalyst can be reused three times with high catalytic activity.
- Zhang, Ying-Peng,Shi, Ai-Hong,Yang, Yun-Shang,Li, Chun-Lei
-
p. 141 - 145
(2014/02/14)
-
- Preparation of carbon nanotube-supported α-Fe2O 3@CuO nanocomposite: A highly efficient and magnetically separable catalyst in cross-coupling of aryl halides with phenols
-
Herein, we introduce the first magnetic CuO nanoparticles based on carbon nanotubes as a highly intriguing magnetic catalyst in Ullmann-type coupling of aryl halides with phenols. Two facile procedures were used for the preparation of this magnetically separable catalytic system. Having been treated with FeSO4 and then H2O2, nanotubes accommodated the resulting iron hydroxides on the walls. The resulting nanocomposite was then exposed to argon atmosphere at 450°C giving rise to a carbon nanotube-supported α-Fe2O3 compound. Ultimately, copper acetate was hydrolysed in the presence of CNT supported α-Fe 2O3 at 100°C and our novel catalyst was gained. Some spectroscopic and microscopic techniques such as Infrared spectroscopy (IR), X-ray diffraction spectroscopy (XRD), Vibrational sample magnetometry (VSM), Brunauer-Emmett-Teller (BET), Barrett-Joyner-Halenda (BJH), Inductively coupled plasma (ICP), Scanning electron microscopy (SEM) and Transmission electron microscopy (TEM) corroborated the structure of the catalyst. The catalyst synthesized showed good activity in C-O cross coupling reactions affording the highest rate of completion. Magnetic feature of the catalyst helped facile separation of it from the reaction medium. The catalyst could also be reused up to six times without any loss of its activity.
- Saberi, Dariush,Sheykhan, Mehdi,Niknam, Khodabakhsh,Heydari, Akbar
-
p. 2025 - 2031
(2013/07/26)
-
- Triphenyltin chloride as a new source of phenyl group for C-heteroatom and C-C bond formation
-
Ph3SnCl is introduced as a very suitable source of phenyl group for coupling with phenols, amines, and thiols in the presence of Cu(OAc)2 in Et3N at room temperature to give aryl ethers, amines, and arylthio ethers in high yields. In addition, the application of Ph3SnCl in the Stille coupling of aryl halides in the presence of Pd(0) catalyst in PEG 400 at 110C is discussed.
- Iranpoor, Nasser,Firouzabadi, Habib,Elham, Etemadi Davan,Rostami, Abed,Nematollahi, Arash
-
p. 123 - 130
(2013/10/01)
-
- Ligand-free catalytic system for the synthesis of diarylethers over Cu 2O/Cu-CNTs as heterogeneous reusable catalyst
-
Various substituted diarylether derivatives were prepared by using heterogeneous reusable Cu2O- and Cu-coated carbon nanotubes (Cu 2O/Cu-CNTs) as catalyst under ligand-free conditions, which provided good to excellent yields. The catalyst was characterized by TEM, XRD, and AAS analysis. The effects of solvent, base, and amount of catalyst for the O-arylation were investigated. The catalyst could be recovered by simple filtration from the reaction mixture without further treatment and reused several times with consistent catalytic activity. In addition, CNTs could also be recovered from the used Cu2O/Cu-CNTs by a simple acid treatment.
- Zhang, Ying-Peng,Jiao, Ya-Cong,Yang, Yun-Shang,Li, Chun-Lei
-
supporting information
p. 6494 - 6497
(2013/11/19)
-
- Potassium tert-butoxide-mediated synthesis of unsymmetrical diaryl ethers, sulfides and selenides from aryl bromides
-
Potassium tert-butoxide mediated carbon-chalcogen C-E (E=O, S and Se) coupling reaction has been studied from aryl bromide and phenol/aryl disulfide/diselenide substrates. A series of unsymmetrical diaryl chalcogenides were accessed from aryl bromide and diaryl dichalcogenide precursors by using 2.5 equiv of potassium tert-butoxide in DMSO at 80 C. Unsymmetrical diaryl ethers were also obtained by using phenol precursors at 40-45 C. Aryl bromides with methyl, trifluoromethyl, methoxy and nitro substituents showed compatibility in the carbon-chalcogen bond forming reaction. 4-Methoxy, methyl, trifluoromethyl substituted bromobenzene substrates gave two regioisomers: 3-substituted and 4-substituted diaryl chalcogenides when reacted with phenols/diaryl disulfides/diselenides. Formation of two regioisomeric diaryl chalcogenides in the reaction mixture suggests that potassium tert-butoxide reacts with bromobenzene to produce benzyne intermediate, which subsequently reacts with diaryl dichalcogenides and finally give a regioisomeric mixture of 4-substituted and 3-substituted diaryl chalcogenides.
- Kumar, Amit,Bhakuni, Bhagat Singh,Prasad, Ch. Durga,Kumar, Shailesh,Kumar, Sangit
-
p. 5383 - 5392
(2013/07/04)
-
- Metal- and ligand-free Ullmann-type C-O and C-N coupling reactions promoted by potassium tert-butoxide
-
A simple, metal- and ligand-free procedure for the Ullmann-type C-O coupling reactions has been achieved by allowing aryl bromides to react with a variety of phenols in the presence of t-BuOK. Moderate to excellent yields of O-arylation products are obtained under mild conditions in a short time. In addition, two examples of C-N coupling reactions are also reported. A benzyne mechanism is proposed according to the experiment data.
- Yang, Shuliang,Wu, Cunqi,Ruan, Mingbo,Yang, Yanqin,Zhao, Yongxia,Niu, Jiajia,Yang, Wei,Xu, Jingwei
-
supporting information; experimental part
p. 4288 - 4292
(2012/09/22)
-
- Ligand free, highly efficient synthesis of diaryl ether over copper fluorapatite as heterogeneous reusable catalyst
-
A novel ligand-free, highly efficient, and an inexpensive method has been developed by using ecofriendly, heterogeneous reusable copper fluorapatite (CuFAP) catalyst for the synthesis of diaryl ethers from the cross coupling reaction of the various substituted aryl halides (fluoride, chloride, bromide, and iodide) with the potassium salts of various substituted phenols in the presence of N-methyl 2-pyrrolidone (NMP) as a solvent at 120 °C. The protocol obtained the corresponding cross coupling products in good to excellent yield. The CuFAP catalyst was recovered by simple filtration from the reaction mixture and reused several times without the loss of catalytic activity.
- Mulla, Shafeek A.R.,Inamdar, Suleman M.,Pathan, Mohsinkhan Y.,Chavan, Santosh S.
-
experimental part
p. 1826 - 1829
(2012/05/04)
-
- Highly efficient copper catalytic system for the O-arylation of phenol with iodoarene
-
An efficient Cu-catalyzed O-arylation was carried out by involving phenols with iodoarenes to afford various substituted diarylether derivatives with tiny loading of Cu2O and 1H-imidazole-4-carboxylic acid as catalytic system under mild conditions, which provided good to excellent yields with good tolerance of functional groups.
- Cheng, An-Yi,Hsieh, Jen-Chieh
-
supporting information; experimental part
p. 71 - 75
(2012/01/31)
-
- Low catalyst loadings for copper-catalyzed O-arylation of phenols with aryl and heteroaryl halides under mild conditions
-
A practical and mild strategy has been developed for the cross-coupling of O-arylation of phenol with differently substituted aryl halides and heteroaryl iodides using low catalyst loading of copper iodide under low operating temperature in DMF with TMHD as the ligand and Cs2CO3 as the base. This method tolerates a variety of functional groups including sterically hindered phenols and heteroaryl iodides to afford products in good to excellent yields (up to 95%). Georg Thieme Verlag Stuttgart. New York.
- Yong, Fui-Fong,Teo, Yong-Chua,Yan, Yaw-Kai,Chua, Guan-Leong
-
supporting information; experimental part
p. 101 - 106
(2012/02/03)
-
- Copper(II) trans-bis-(glycinato): An efficient heterogeneous catalyst for cross coupling of phenols with aryl halides
-
Copper(II) trans-bis-(glycinato) complex, easily prepared by the solid state reaction of copper(II) acetate and glycine (trans-[Cu(glyo) 2·H2O]) was found to be an efficient, recyclable, and high yielding catalyst for the Ullmann type synthesis of diaryl ethers via the cross coupling of phenols with aryl halides without using any additives at relatively low reaction temperature. The catalyst could easily be recovered by simple filtration and was reused for several runs with consistent catalytic activity.
- Verma, Sanny,Kumar, Neeraj,Jain, Suman L.
-
experimental part
p. 4665 - 4668
(2012/09/05)
-
- Chemo-selective copper-catalyzed C-O coupling reactions of phenols with aryl/vinyl halides using enaminone as efficient ligand
-
The copper-catalyzed Ullmann C-O coupling reactions between phenols and aryl/vinyl halides have been efficiently performed by employing (E)-3-(dimethylamino)-1-(2-hydroxyphenyl)prop-2-en-1-one, an easily available enaminone, as ligand. This new ligand is advantageous for its easy availability, broad applicability and good efficiency. Copyright 2012 John Wiley & Sons, Ltd. Copyright
- Wan, Jie-Ping,Wang, Chunping,Liu, Yunyun
-
experimental part
p. 445 - 447
(2012/09/25)
-
- Surfactant-free single-nano-sized colloidal Cu nanoparticles for use as an active catalyst in Ullmann-coupling reaction
-
Surfactant-free, single-nano-sized copper nanoparticles (Cu NPs) (size: about 2 nm) were prepared by the DMF reduction method. The Cu NPs showed high catalytic activity (with a turnover number (TON) of up to 2.2 × 10 4) in Ullmann-type cross-coupling of aryl halides with phenols under ligand-free conditions. The Royal Society of Chemistry 2012.
- Isomura, Yuto,Narushima, Takashi,Kawasaki, Hideya,Yonezawa, Tetsu,Obora, Yasushi
-
supporting information; experimental part
p. 3784 - 3786
(2012/06/16)
-
- Dimethyl sulfoxide/potassium hydroxide: A superbase for the transition metal-free preparation of cross-coupling products
-
Potassium hydroxide (KOH) in dimethyl sulfoxide (DMSO) forms a superbasic medium that allows one to access cross-coupling products from reactions between aryl halides with various sulfur-, oxygen- and nitrogen-based nucleophiles under transition metal-free conditions. Copyright
- Yuan, Yu,Thome, Isabelle,Kim, Seok Hwan,Chen, Duanteng,Beyer, Astrid,Bonnamour, Julien,Zuidema, Erik,Chang, Sukbok,Bolm, Carsten
-
experimental part
p. 2892 - 2898
(2011/01/05)
-
- Cu2O nanocube-catalyzed cross-coupling of aryl halides with phenols via ullmann coupling
-
Thermal and air-stable uniform Cu2O nanocubes were employed in the development of a gram-scale, one-pot polyol synthesis. Herein is reported an efficient cross-coupling reaction of aryl halides and phenols with a catalytic amount (0.1 mol-%) of Cu2O nanocubes as recyclable catalyst and Cs2CO3 as the base in THF at 150 °C. Wiley-VCH Verlag GmbH & Co. KGaA.
- Kim, Jee Young,Park, Ji Chan,Kim, Aram,Young Kim,Lee, Hyun Ju,Song, Hyunjoon,Park, Kang Hyun
-
experimental part
p. 4219 - 4223
(2010/02/16)
-
- CuO nanoparticles catalyzed C-N, C-O, and C-S cross-coupling reactions: Scope and mechanism
-
CuO nanoparticles have been studied for C-N, C-O, and C-S bond formations via cross-coupling reactions of nitrogen, oxygen, and sulfur nucleophiles with aryl halides. Amides, amines, imidazoles, phenols, alcohols and thiols undergo reactions with aryl iodides in the presence of a base such as KOH, Cs 2CO3, and K2CO3 at moderate temperature. The procedure is simple, general, ligand-free, and efficient to afford the cross-coupled products in high yield.
- Jammi, Suribabu,Sakthivel, Sekarpandi,Rout, Laxmidhar,Mukherjee, Tathagata,Mandai, Santu,Mitra, Raja,Saha, Prasenjit,Punniyamurthy, Tharmalingam
-
supporting information; experimental part
p. 1971 - 1976
(2009/07/01)
-
- General, mild, and intermolecular Ullmann-type synthesis of diaryl and alkyl aryl ethers catalyzed by diol-copper(I) complex
-
(Chemical Equation Presented) A wide range of diaryl ethers and alkyl aryl ethers are synthesized through intermolecular C(aryl)-O bond formation from the corresponding aryl iodides/aryl bromides and phenols/alcohols through Ullmann-type coupling reaction in the presence of a catalytic amount of easily available (±)-diol L3-CuI complex under very mild reaction conditions. Less reactive aryl bromides can also be used for O-arylation of phenols under the same reaction conditions without increasing the reaction temperature, catalyst loading, and time. The catalytic system not only is capable of coupling hindered substrate but also tolerates a broad range of a series of functional groups.
- Naidu, Ajay B.,Jaseer,Sekar, Govindasamy
-
supporting information; experimental part
p. 3675 - 3679
(2009/09/26)
-
- Iron-catalyzed C-O cross-couplings of phenols with aryl iodides
-
(Chemical Equation Presented) Low-price coupling: A versatile, practical, and cost-efficient iron-catalyzed O-arylation protocol is applied to the synthesis of a variety of diaryl ethers, which are formed in high yields. Best results were obtained by using FeCl3 and a β-diketo ligand.
- Bistri, Olivia,Correa, Arkaitz,Bolm, Carsten
-
p. 586 - 588
(2008/09/20)
-
- Efficient and versatile sol-gel immobilized copper catalyst for ullmann arylation of phenols
-
A new hybrid silica with urea-based bipyridyl bridging units has been synthesized by a solgel process. The copper-complexed hybrid silica is an efficient heterogeneous catalyst for the Ullmann coupling of aryl halides with phenols. It is easily withdrawn and recovered from the reaction media by filtration. It is also a versatile catalyst for subsequent reactions with several substrates yielding products with the same efficiency even after ten reuses and with minimal leaching. This is the first example of the use of a copper-complexed bridged silsesquioxane for the preparation of a recoverable catalyst in modern Ullmann chemistry. This may represent a promising route to the reduction of waste while maintaining economic viability.
- Benyahya, Sofia,Monnier, Florian,Taillefer, Marc,Man, Michel Wong Chi,Bied, Catherine,Ouazzani, Fouad
-
supporting information; experimental part
p. 2205 - 2208
(2009/10/25)
-
- Nano-CuO-catalyzed ullmann coupling of phenols with aryl halides under ligand-free conditions
-
Nano copper oxide has been found to be a highly efficient and reusable catalyst for the C-O cross-coupling of phenols with aryl halides under ligand-free conditions. With DMSO as solvent, Cs2CO3 and KOH are suitable bases for the cross-coupling reactions with phenyl iodides and bromides, respectively. Diaryl ethers with different substituted groups can be synthesized in moderate-to-good yields. The catalyst can be recycled at least five times without obvious loss in catalytic activity. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.
- Zhang, Jintang,Zhang, Zuhui,Wang, Ye,Zheng, Xiaoqi,Wang, Zhiyong
-
scheme or table
p. 5112 - 5116
(2009/06/06)
-
- Reaction of benzyne with styrene oxide: Insertion of arynes into a C-O bond of epoxides
-
Benzyne inserts into one of the C-O bonds of styrene oxide to form a dihydrobenzofuran as the major product together with five other reaction products. A detailed study of the reaction mixture clarified an intriguing forty-year-old personal communication from Stiles and Haag. Georg Thieme Verlag Stuttgart.
- Beltrán-Rodil, Sandra,Pe?a, Diego,Guitián, Enrique
-
p. 1308 - 1310
(2008/02/07)
-
- Cu-nanoparticle catalyzed O-arylation of phenols with aryl halides via Ullmann coupling
-
Recyclable Cu-nanoparticles provide an efficient, economic, and novel method for the synthesis of diaryl ethers via Ullmann type coupling. This method provides a wide range of substrate applicability and avoids the use of a heavy metal co-catalyst and gives diaryl ethers in satisfactory yields.
- Kidwai, Mazaahir,Mishra, Neeraj Kumar,Bansal, Vikas,Kumar, Ajeet,Mozumdar, Subho
-
p. 8883 - 8887
(2008/03/14)
-
- 1,1,1-Tris(hydroxymethyl)ethane as a new, efficient, and versatile tripod ligand for copper-catalyzed cross-coupling reactions of aryl iodides with amides, thiols, and phenols
-
1,1,1-Tris(hydroxymethyl)ethane was presented as a new, efficient, and versatile tridentate O-donor ligand suitable for the copper-catalyzed formation of C-N, C-S, and C-O bonds. This inexpensive and commercially available tripod ligand has been demonstrated to facilitate the copper-catalyzed cross-coupling reactions of aryl iodides with amides, thiols, and phenols to afford the corresponding desired products in good to excellent yields.
- Chen, Yao-Jung,Chen, Hsin-Hung
-
p. 5609 - 5612
(2007/10/03)
-
- Dimethylaminomethylphosphonic acid derivatives-promoted CuI-catalyzed synthesis of aryl ethers
-
An inexpensive and efficient catalyst system for synthesis of aryl ethers has been developed by using 20 mol% CuI as the catalyst, 30 mol% dimethylaminomethylphosphonic acid derivatives as the new ligands, K 2CO3 as the base and toluene as the solvent. This is the first example using aminophosphonates as the ligands for Ullmann ether coupling reaction. Georg Thieme Verlag Stuttgart.
- Jin, Ying,Liu, Jinyong,Yin, Yingwu,Fu, Hua,Jiang, Yuyang,Zhao, Yufen
-
p. 1564 - 1568
(2007/10/03)
-
- Practical Procedures for the Preparation of N-tert-Butyldimethylsilylhydrazones and Their Use in Modified Wolff-Kishner Reductions and in the Synthesis of Vinyl Halides and gem-Dihalides
-
In this work we develop practical chemistry for the preparation of N-tert-butyldimethylsilylhydrazone (TBSH) derivatives from carbonyl-containing compounds and show that these products serve as superior alternatives to simple hydrazones in Wolff-Kishner-type reduction reactions, in the Barton vinyl iodide preparation, in the synthesis of vinyl bromides, and in the synthesis of gem-diiodides, gem-dibromides, and gem-dichlorides. In our new procedure for silyl hydrazone synthesis, aliphatic and aromatic ketones and aldehydes are shown to undergo highly efficient coupling (typically >95% yield) to form the corresponding TBSH derivatives when combined with equimolar amounts of 1,2-bis(tert-butyldimethylsilyl)-hydrazine (BTBSH) and a catalytic quantity of scandium trifluoromethanesulfonate (typically, 0.01 mol %), neat, or in solvent. Optimized procedures are provided for the use of TBSH derivatives in a Wolff-Kishner-type reduction protocol that proceeds at low temperature (23-100 °C) and in a single reaction flask. Similarly, protocols for the use of TBSH derivatives as precursors to vinyl halides and gem-dihalides are described in detail.
- Furrow, Michael E.,Myers, Andrew G.
-
p. 5436 - 5445
(2007/10/03)
-
- N,N-Dimethyl Glycine-Promoted Ullmann Coupling Reaction of Phenols and Aryl Halides
-
(Matrix presented) Ullmann-type diaryl ether synthesis can be performed at 90°C using either aryl iodides or aryl bromides as the substrates under the assistance of N,N-dimethylglycine.
- Ma, Dawei,Cai, Qian
-
p. 3799 - 3802
(2007/10/03)
-
- Synthesis of diaryl ethers through the copper-catalyzed arylation of phenols with aryl halides using microwave heating
-
The copper-catalyzed arylation of phenols with a variety of aryl halides using microwave heating is described.
- He, Huan,Wu, Yong-Jin
-
p. 3445 - 3446
(2007/10/03)
-
- A Superior Synthesis of Diaryl Ethers by the Use of Ultrasound in the Ullmann Reaction
-
The use of ultrasound in the reactions of phenols with bromoarenes, in the presence of potassium carbonate and copper(I) iodide but without added solvent, gives better yields of diaryl ethers (typically 70-90percent) at lower temperature (140 deg C) than is customary for traditional Ullmann reactions; the role of ultrasound is primarily to break up the particles of the inorganic solids.
- Smith, Keith,Jones, Dennis
-
p. 407 - 408
(2007/10/02)
-