- Method for synthesizing aryl benzyl ether compound
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The invention discloses a method for synthesizing aryl benzyl ether compounds, which comprises the following steps: by using an iron (III) complex containing 1, 3-di-tert-butyl imidazole cations and having a molecular formula of [(tBuNCH = CHNtBu) CH] [FeBr4] as a catalyst and di-tert-butyl peroxide as an oxidant, carrying out oxidative coupling reaction on phenolic compounds and toluene compounds to synthesize the corresponding aryl benzyl ether compounds. The method is the first example for preparing the aryl benzyl ether compound through the oxidative coupling reaction of the phenolic compound and the toluene compound, which is realized by an iron-based catalyst, and has the advantages of atom economy, environmental friendliness and good substrate applicability.
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Paragraph 0032; 0041
(2021/04/14)
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- Application of iron (III) complex containing 1,3-di-tert-butyl imidazole cations in synthesis of aryl benzyl ether compounds
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The invention discloses an application of an iron (III) complex containing 1,3-di-tert-butyl imidazole cations in synthesis of aryl benzyl ether compounds, and particularly relates to a method for synthesizing corresponding aryl benzyl ether compounds by taking di-tert-butyl peroxide as an oxidizing agent and carrying out oxidative coupling reaction on phenolic compounds and toluene compounds. According to the method, the iron (III) complex is used as the catalyst for the first time, and oxidative coupling of the phenolic compound and the toluene compound is realized. The method is the first oxidative coupling reaction of phenolic compounds and benzyl C(sp3)-H bonds, and a new method is provided for synthesizing aryl benzyl ether compounds. Compared with an existing synthesis method, the method provided by the invention avoids using toxic and polluting halogenated hydrocarbon and strong base, has better atom economy, and conforms to the development concept of green synthetic chemistry.
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Paragraph 0031-0032
(2021/04/26)
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- Transition-Metal-Free and Base-Promoted Carbon-Heteroatom Bond Formation via C-N Cleavage of Benzyl Ammonium Salts
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A facile and general method for constructing carbon-heteroatom (C-P, C-O, C-S, and C-N) bonds via C-N cleavage of benzyl ammonium salts under transition-metal-free conditions was reported. The combination of t-BuOK and 18-crown-6 enabled a wide range of substituted benzyl ammonium salts to couple readily with different kinds of heteroatom nucleophiles, i.e. hydrogen phosphoryl compounds, alcohols, thiols, and amines. Good functional group tolerance was demonstrated. The scale-up reaction and one-pot synthesis were also successfully performed.
- Liu, Long,Tang, Yuanyuan,Wang, Kunyu,Huang, Tianzeng,Chen, Tieqiao
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p. 4159 - 4170
(2021/03/09)
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- Jet Colliding and Mixing Efficiency
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Two experimental methods, the Nile Red dye extraction and the Williamson ether synthesis in biphasic conditions, were used to characterize the mixing performance of a new cheap impinging jet colliding mixer from Gjosa and to compare it to other commercial
- Allemann, Christophe,Eastes, Richard-Emmanuel,Varisco, Massimo,de Lucia, Gianni
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p. 1054 - 1057
(2022/01/15)
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- Towards ortho-selective electrophilic substitution/addition to phenolates in anhydrous solvents
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Alkyl-substituted Li-phenolates with BnBr in water solution lead to a mixture of o- and p-Bn-substituted phenols together with a substantial amount of phenol Bn ether. In CPME, and especially in toluene with 1–2 equivalents of ether or alcohol additives, ortho-selective alkylation is achieved. In the case of o,o,p-tri- and o,o-di-substituted phenols dearomatization occurs affording o-Bn-substituted alkyl cyclohexadienones with yields up to 92% with an o/p ratio up to 90/1.
- Lopu?anskaja, Eleana,Kooli, Anni,Paju, Anne,J?rving, Ivar,Lopp, Margus
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- Metal-Free C-O Bond Functionalization: Catalytic Intramolecular and Intermolecular Benzylation of Arenes
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A catalytic, metal-free intramolecular rearrangement of benzyl phenyl ethers using nitrosonium salt as a catalyst is described. The optimized reaction conditions enabled a catalytic and metal-free Friedel-Crafts alkylation reaction with benzylic alcohols, producing water as the stoichiometric byproduct. A comprehensive scope (>50 examples) for both approaches and application in drug synthesis were demonstrated. Mechanistic studies suggest a Lewis acid-based mechanism for the metal-free Friedel-Crafts reaction.
- Bering, Luis,Jeyakumar, Kirujan,Antonchick, Andrey P.
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supporting information
p. 3911 - 3914
(2018/07/22)
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- Exploring the Reactivity of α-Lithiated Aryl Benzyl Ethers: Inhibition of the [1,2]-Wittig Rearrangement and the Mechanistic Proposal Revisited
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By carefully controlling the reaction temperature, treatment of aryl benzyl ethers with tBuLi selectively leads to α-lithiation, generating stable organolithiums that can be directly trapped with a variety of selected electrophiles, before they can undergo the expected [1,2]-Wittig rearrangement. This rearrangement has been deeply studied, both experimentally and computationally, with aryl α-lithiated benzyl ethers bearing different substituents at the aryl ring. The obtained results support the competence of a concerted anionic intramolecular addition/elimination sequence and a radical dissociation/recombination sequence for explaining the tendency of migration for aryl groups. The more favored rearrangements are found for substrates with electron-poor aryl groups that favor the anionic pathway.
- Velasco, Rocío,Silva López, Carlos,Nieto Faza, Olalla,Sanz, Roberto
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supporting information
p. 15058 - 15068
(2016/10/11)
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- Silica-Supported Oligomeric Benzyl Phosphate (Si-OBP) and Triazole Phosphate (Si-OTP) Alkylating Reagents
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The syntheses of silica-supported oligomeric benzyl phosphates (Si-OBPn) and triazole phosphates (Si-OTPn) using ring-opening metathesis polymerization (ROMP) for use as efficient alkylating reagents is reported. Ease of synthesis and grafting onto the surface of norbornenyl-tagged (Nb-tagged) silica particles has been demonstrated for benzyl phosphate and triazole phosphate monomers. It is shown that these silica polymer hybrid reagents, Si-OBPn and Si-OTPn, can be used to carry out alkylation reactions with an array of different nucleophiles to afford the corresponding benzylated and (triazolyl)methylated products in good yield and high purity.
- Maity, Pradip K.,Faisal, Saqib,Rolfe, Alan,Stoianova, Diana,Hanson, Paul R.
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p. 9942 - 9950
(2015/11/03)
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- Choline chloride based deep eutectic solvent as an efficient solvent for the benzylation of phenols
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Deep eutectic solvents (such as the combination of urea and choline chloride) are found to be promising solvent and phase-transfer-media for benzylation of phenol. These methods avoided the complexity of multiple alkylations giving selectively O-alkylated aromatic products. Good to excellent yields of the corresponding benzyl phenyl ether were obtained. The non-toxic, biodegradable, inexpensive, and recyclable nature of DES make this protocol green and cost-effective.
- Singh, Abhilash S.,Shendage, Suresh S.,Nagarkar, Jayashree M.
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p. 7243 - 7246
(2015/02/02)
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- Tetrabutyl ammonium bromide-mediated benzylation of phenols in water under mild condition
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Benzylation of phenol was successfully achieved in water under room temperature mediated by tetrabutylammonium bromide (TBAB) for only 2 h affording the corresponding benzyl phenyl ether with good to excellent yields. This protocol is very efficient, simple, avoiding catalysts, easy to work-up after reaction, and especially 'green'.
- Wang, Hailei,Ma, Yuping,Tian, Heng,Yu, Ajuan,Chang, Junbiao,Wu, Yangjie
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p. 2669 - 2673
(2014/04/03)
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- Phase-transfer catalysis: Mixing effects in continuous-flow liquid/liquid O-and S-Alkylation processes
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This article describes detailed studies on the importance of mixing effects in the O- and S-alkylation of selected phenol and thiophenol substrates. Direct comparison between various continuous-flow reactors and a batch microwave reactor demonstrates the
- Reichart, Benedikt,Kappe, C.Oliver,Glasnov, Toma N.
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supporting information
p. 2393 - 2396
(2013/11/06)
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- Metal-free synthesis of aryl ethers in water
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The first arylation of allylic and benzylic alcohols with diaryliodonium salts is reported. The reaction yields alkyl aryl ethers under mild and metal-free conditions. Phenols are arylated to diaryl ethers in good to excellent yields. The reaction employs diaryliodonium salts and sodium hydroxide in water at low temperature, and excess amounts of the coupling partners are avoided.
- Lindstedt, Erik,Ghosh, Raju,Olofsson, Berit
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p. 6070 - 6073
(2014/01/06)
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- Liquid ammonia as a dipolar aprotic solvent for aliphatic nucleophilic substitution reactions
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The rate constants for the reactions of a variety of nucleophiles reacting with substituted benzyl chlorides in liquid ammonia (LNH3) have been determined. To fully interpret the associated linear free-energy relationships, the ionization constants of phenols ions in liquid ammonia were obtained using UV spectra. These equilibrium constants are the product of those for ion-pair formation and dissociation to the free ions, which can be separated by evaluating the effect of added ammonium ions. There is a linear relationship between the pKa of phenols in liquid ammonia and those in water of slope 1.68. Aminium ions exist in their unprotonated free base form in liquid ammonia and their ionization constants could not be determined by NMR. The rates of solvolysis of substituted benzyl chlorides in liquid ammonia at 25 °C show a Hammett ρ of zero, having little or no dependence upon ring substituents, which is in stark contrast with the hydrolysis rates of substituted benzyl halides in water, which vary 107 fold. The rate of substitution of benzyl chloride by substituted phenoxide ions is first order in the concentration of the nucleophile indicative of a SN2 process, and the dependence of the rate constants on the pKa of the phenol in liquid ammonia generates a Bronsted βnuc = 0.40. Contrary to the solvolysis reaction, the reaction of phenoxide ion with 4-substituted benzyl chlorides gives a Hammett ρ = 1.1, excluding the 4-methoxy derivative, which shows the normal positive deviation. The second order rate constants for the substitution of benzyl chlorides by neutral and anionic amines show a single Bronsted βnuc = 0.21 (based on the aqueous pKa of amine), but their dependence on the substituent in substituted benzyl chlorides varies with a Hammett ρ of 0 for neutral amines, similar to that seen for solvolysis, whereas that for amine anions is 0.93, similar to that seen for phenoxide ion.(Figure Presented)
- Ji, Pengju,Atherton, John,Page, Michael I.
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scheme or table
p. 1425 - 1435
(2011/04/23)
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- Chemoselectivity in the microwave-assisted solvent-free solid-liquid phase benzylation of phenols: O- versus C-alkylation
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The outcome of the solvent-free benzylation of phenol and 4-substituted phenols (such as 4-cresol and 4-chlorophenol) under MW irradiation was found to depend on the absence or presence of the base (K2CO3) and catalyst (triethylbenzy
- Keglevich, Gy?rgy,Bálint, Erika,Karsai, éva,Grün, Alajos,Bálint, Mária,Greiner, István
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p. 5039 - 5042
(2008/12/22)
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- Williamson reaction in [bmim][BF4]: Clean and facile synthesis of aryl benzyl ethers
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1-Butyl-3-methylimidazolium tetrafluoroborate ([bmin][BF4]) has been demonstrated to be a suitable reaction medium for the synthesis of aryl benzyl ethers by the Williamson reaction. A variety of phenols react with benzyl chloride in [bmim][BF4] to afford the desired ethers in satisfactory yields. The reaction proceeds cleanly and the use of the ionic liquid allows for easy product isolation.
- Wen, Xinmin
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p. 663 - 664
(2007/10/03)
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- Synergism of low energy microwave irradiation and solid-liquid phase transfer catalysis for selective alkylation of phenols to phenolic ethers
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A 100% selectivity with an order of magnitude rate enhancement is obtained in the synthesis of phenolic ethers when synergistic combination of solid-liquid phase transfer catalysis and low energy microwave irradiation (MISL-PTC) is employed. As against conventional microwave heating with 600 W power input, the current work demonstrates that a low input of 40 W leads to remarkable enhancement in rates without any destruction of the catalyst.
- Yadav, Ganapati D.,Bisht, Priyal M.
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p. 2885 - 2892
(2007/10/03)
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- Facile synthesis of alkyl phenyl ethers using cesium carbonate
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A highly efficient alkylation method of phenols using alkyl halide/cesium carbonate/acetonitrile system is described.
- Lee,Yuk,Cho
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p. 1367 - 1370
(2007/10/02)
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- Novel Synthesis of N,N-Diarylarylmethanamines from N-(Arylmethylene)arenamines and (Arylmethoxy)arenes
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Various N,N-diarylarylmethanamines were synthesized by the reaction of N-(arylmethylene)arenamines with (arylmethoxy)arenes in dimethylformamide solution in the presence of a strong base as a catalyst which is obtained in situ by reacting metallic sodium with this solvent.In general, the reaction may be depicted as the reduction of the imine and addition, on the original imino nitrogen atom, of the aryl group (of the aryloxy moiety) of the ether and presumably oxidation of the arylmethoxy group of the ether to its corresponding aldehyde.Side reactions and a proposed reaction mechanism are discussed.
- Paventi, Martino,Hay, Allan S.
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p. 5875 - 5882
(2007/10/02)
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