- Mustard Carbonate Analogues as Sustainable Reagents for the Aminoalkylation of Phenols
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N,N-dialkyl ethylamine moiety can be found in numerous scaffolds of macromolecules, catalysts, and especially pharmaceuticals. Common synthetic procedures for its incorporation in a substrate relies on the use of a nitrogen mustard gas or on multistep syntheses featuring chlorine hazardous/toxic chemistry. Reported herein is a one-pot synthetic approach for the easy introduction of aminoalkyl chain into different phenolic substrates through dialkyl carbonate (β-aminocarbonate) chemistry. This new direct alcohol substitution avoids the use of chlorine chemistry, and it is efficient on numerous pharmacophore scaffolds with good to quantitative yield. The cytotoxicity via MTT of the β-aminocarbonate, key intermediate of this synthetic approach, was also evaluated and compared with its alcohol precursor.
- Annatelli, Mattia,Trapasso, Giacomo,Salaris, Claudio,Salata, Cristiano,Castellano, Sabrina,Aricò, Fabio
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supporting information
p. 3459 - 3464
(2021/05/24)
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- Cross-Coupling Reactions of Aryl Halides with Primary and Secondary Aliphatic Alcohols Catalyzed by an O,N,N-Coordinated Nickel Complex
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A synthesis of alkyl aryl ethers was achieved via the cross-coupling of aryl halides with primary and secondary aliphatic alcohols catalyzed by a bench-stable nickel complex supported by a monoanionic O,N,N-tridentate ligand. This nickel-catalyzed reaction proceeds smoothly in the absence of a phosphine ligand, affording alkyl aryl ethers in moderate to good yields. (Figure presented.).
- Hashimoto, Toru,Shiota, Keisuke,Funatsu, Kei,Yamaguchi, Yoshitaka
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supporting information
p. 1625 - 1630
(2021/01/26)
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- Light assisted O-alkylation of phenols to ethers using layered double oxides catalyst under green and mild conditions
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O-alkylation of phenols with dialkyl carbonates to ethers over layered double oxides (LDOs) catalyst under light irradiation is described. A base additive is not required when using the longer-chain diethyl carbonate as an alkylating agent owing to the sufficient basicity provided by LDOs. The synergism of substrate phenols molecules absorbing light to reach the first excited states with acid–base pairs of catalyst enhanced the interaction of reactant molecules with the surface of LDOs, simultaneously accelerating the cleavage of phenolic hydroxyl groups. A variety of phenols are tolerated in this system. This work reports a simple and environmentally benign catalytic process for the dehydrogenation of phenolic hydroxyl groups.
- Wang, Ruiyi,Wang, Xiaoyu,Zheng, Zhanfeng
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- A new alkylation of aryl alcohols by boron trifluoride etherate
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The ethylation of aryl alcohols by an ethyl moiety of boron trifluoride etherate is described. The reaction proceeded cleanly and afforded good yields of the corresponding aryl ethyl ethers. It tolerated the presence of functional groups such as aryl, alkyl, halogens, nitro, nitrile, and amino. However, the presence of amino or nitro groups ortho to a hydroxyl group of an aryl compound drastically reduced the yields of the anticipated products due to the chelation of the aforementioned functional groups with boron trifluoride etherate. A nitrogen atom in the aromatic ring system, as exemplified by hydroxypyridine and 8-hydroxyquinoline, completely inhibited the reaction. Resorcinol, hydroquinone, and aryl alcohols with aldehyde functions decomposed under the reaction conditions.
- Jumbam, Ndze Denis,Maganga, Yamkela,Masamba, Wayiza,Mbunye, Nomthandazo I.,Mgoqi, Esethu,Mtwa, Sphumusa
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- Method for synthesizing alkyl-2-naphthyl ether
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The invention discloses a method for synthesizing alkyl-2-naphthyl ether. 2-naphthol, a catalyst and dialkyl carbonate are heated to 110-120 DEG C, dialkyl carbonate is added dropwise, a mixed solution of dialkyl carbonate and corresponding alcohol is fractionated out during dropwise addition, the temperature is controlled not to exceed 200 DEG C, reaction is stopped when conversion of 2-naphtholreaches 95% or higher, inorganic boric acid and a dehydration solvent are added, unreacted 2-naphthol is removed, and rectification or recrystallization is performed, and a pure product is obtained. The process route has little corrosion to equipment, few 'three wastes' emissions and low environmental pollution.
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Paragraph 0016; 0017
(2019/01/14)
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- Nickel-Catalyzed Deamidative Step-Down Reduction of Amides to Aromatic Hydrocarbons
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To date, cleavage of the C-N bond in aromatic amides has been achieved in molecules with a distorted constitutional framework around the nitrogen atom. In this report, a nickel-catalyzed reduction of planar amides to the corresponding lower hydrocarbon homologue has been reported. This involves a one-pot reductive cleavage of the C-N bond followed by a tandem C-CO bond break in the presence of a hydride source. Substrate scope circumscribes deamidation examples which proceed via oxidative addition of nickel in the amide bonds of nontwisted amides. Mechanistic studies involving isolation and characterization of involved intermediates via different spectroscopic techniques reveal a deeper introspection into the plausible catalytic cycle for the methodology.
- Dey, Aniruddha,Sasmal, Sheuli,Seth, Kapileswar,Lahiri, Goutam Kumar,Maiti, Debabrata
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p. 433 - 437
(2017/06/05)
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- Method for compounding drug intermediate 2-ethoxy naphthalene of sodium nafcillin
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The invention discloses a method for compounding drug intermediate 2-ethoxy naphthalene of sodium nafcillin. The method comprises the following steps: adding 1.2 mol of beta-naphthol and 230 to 260 ml of ethylamine in a reaction vessel which is provided with a stirrer and a reflux condenser, controlling the stirring speed to be 130 to 170 rpm, slowly adding 110 ml of phosphoric acid solution, rising the solution temperature to be 80 to 86 DEG C, carrying out reflux for 15 to 17 hours, pouring the solution into a 1.5-L sodium sulfite solution after cooling, stirring for 90 to 120 minutes, separating crystals out, filtering, washing by a saline solution, washing by acetamide, recrystallizing in ethyl acetate, dissolving the crystals in chlorobenzene, carrying out decompression distillation, collecting a distillate at 120 to 129 DEG C, and obtaining 2-ethoxy naphthalene, wherein the mass percentage of ethylamine in the steps is 90 to 95 percent, the mass percentage of the phosphoric acid solution in the steps is 45 to 50 percent, and the saline solution in the steps is any one of potassium bromide and sodium sulfate.
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Paragraph 0015; 0016
(2016/11/17)
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- Microwave-Assisted solid-liquid phase alkylation of naphthols
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The microwave promoted alkylation of 1- and 2-naphthols with benzyl, butyl, ethyl and isopropyl halides in the presence of an alkali carbonate may result in O- and C-Alkylated products. The alkylations were O-selective in the presence of K2CO3 in acetonitrile as the solvent and in the absence of phase transfer catalyst. The alkylations utilizing butyl and ethyl halides were also O-selective in solventless accomplishment and in the presence of triethylbenzylammonium chloride.
- Balint, Erika,Kovacs, Orsolya,Drahos, Laszlo,Keglevich, Gyoergy
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p. 330 - 336
(2013/07/26)
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- Iridium-catalyzed, intermolecular hydroetherification of unactivated aliphatic alkenes with phenols
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Metal-catalyzed addition of an O-H bond to an alkene is a desirable process because it allows for rapid access to ethers from abundant starting materials without the formation of waste, without rearrangements, and with the possibility to control the stereoselectivity. We report the intermolecular, metal-catalyzed addition of phenols to unactivated α-olefins. Mechanistic studies of this rare catalytic reaction revealed a dynamic mixture of resting states that undergo O-H bond oxidative addition and subsequent olefin insertion to form ether products.
- Sevov, Christo S.,Hartwig, John F.
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supporting information
p. 9303 - 9306
(2013/07/26)
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- O-Alkylation of phenol derivatives via a nucleophilic substitution
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The alkylation of phenol derivatives can be achieved in good yield via Lewis or Bronsted acid. The only by-product of the reaction is water and the catalyst can be recycled when using Bronsted acid.
- Cazorla, Clement,Pfordt, Emilie,Duclos, Marie-Christine,Metay, Estelle,Lemaire, Marc
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experimental part
p. 2482 - 2488
(2011/10/31)
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- An efficient copper-catalyzed etherification of aryl halides
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An efficient and mild copper-catalyzed ether formation from aryl halides and aliphatic alcohols has been developed. The key to the successful coupling is the use of lithium alkoxide, directly or in situ generated by lithium tert-butoxide, and the corresponding alcohol as solvent. Georg Thieme Verlag Stuttgart - New York.
- Huang, Jinkun,Chen, Ying,Chan, Johann,Ronk, Mike L.,Larsen, Robert D.,Faul, Margaret M.
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experimental part
p. 1419 - 1422
(2011/07/30)
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- Synthesis and characterisation of hole transporting materials based on N,N,N-tris-[4-(naphthalen-1-yl-phenylamino)phenyl]-N,N,N-triphenylbenzene-1,3, 5-triamine
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Two derivatives of star shaped compounds based on naphthylamine with symmetric trisubstituted benzene as core, methoxy and ethoxy as end substitutions are synthesized. The synthesized compounds are characterized by UV-visible, FT-IR and NMR spectrometric techniques. The electronic and thermal properties of the compounds are studied using cyclic voltametry (CV) and differential scanning calorimetry (DSC) respectively. The data's obtained have similarity with the arylamines that have been already used in optoelectronic devices. So these compounds are interesting materials for applications in such devices.
- Mathew, Siji,Haridas, Karickal R.
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experimental part
p. 717 - 722
(2011/03/21)
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- Synthesis and characterization of novel starburst phase transfer catalyst
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A new phase transfer catalyst, 3,5-bis[(2-methyl-naphthylene-1 -yl)-phenylamino-phenyl]-butyl-(2methoxy-naphthalene-1 -yl)-phenylammonium bromide (BPBPB) has been synthesized, characterized using spectral analysis and its catalytic activity ascertained. Efficiency of BPBPB is studied using etherification of phenol and compared with tetra butyl ammonium bromide (TBAB). O-Alkylation of naphthol, iV-alkylation of indole and halogen substitution reactions are carried out using BPBPB and its efficiency is compared with reported PTCs. BPBPB gives high yield of product, the time for completion of the reaction is short and is required in a very low concentration. Almost 95% of this catalyst is regenerated and reused.
- Mathew, Siji,Divia,Nair, T.D. Radhakrishnan,Haridas, Karickal R.
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scheme or table
p. 1389 - 1393
(2011/01/13)
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- Synthesis of aryl alkyl ethers by alkylation of phenols with quaternary ammonium salts
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Phenolic compounds can be efficiently O-methylated with tetramethylammonium chloride in diglyme or polyethyleneglycol (PEG) at temperatures of 150-160 °C and in the presence of either K2CO3 or NaOH. When applying benzyl-trimethylammonium chloride as a reagent, the benzylation and methylation of phenols occurs, with the benzylation product always predominating. With allyl-substituted phenols as substrates and using NaOH as a base it was possible to achieve both the alkylation and the double-bond isomerization of the allyl group to obtain (E/Z)-propenyl-substituted methyl and benzyl aryl ethers in a single preparative step.
- Maras, Nenad,Polanc, Slovenko,Kocevar, Marijan
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experimental part
p. 29 - 36
(2010/09/05)
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- Methylation of arenes via Ni-catalyzed aryl C-O/F activation
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Aryl C-O and C-F can be transformed into C-Me via Ni-catalyzed coupling with MeMgBr under mild conditions. The Royal Society of Chemistry.
- Guan, Bing-Tao,Xiang, Shi-Kai,Wu, Tao,Sun, Zuo-Peng,Wang, Bi-Qin,Zhao, Ke-Qing,Shi, Zhang-Jie
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p. 1437 - 1439
(2008/12/21)
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- Solvent-free Williamson synthesis: An efficient, simple, and convenient method for chemoselective etherification of phenols and bisphenols
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Etherification of phenols with dimethyl- and diethylsulfates and benzyl chloride was performed efficiently in the presence of a suitable solid base, NaHCO3 or K2CO3, under solvent-free conditions. The reaction proceeded rapidly at low temperature, and the corresponding ethers were obtained with high purity and excellent yield. Selective etherification of electron-poor phenols in the presence of electron-rich ones and also selective mono-etherification of bisphenols are the noteworthy advantages of this method. This method is environmentally friendly. Copyright Taylor & Francis Group, LLC.
- Massah, Ahmad R.,Mosharafian, Masumeh,Momeni, Ahamad R.,Aliyan, Hamid,Naghash, H. Javaherian,Adibnejad, Mohamad
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p. 1807 - 1815
(2008/02/02)
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- Regioselective alkylation in ionic liquids
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The room temperature ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate, [bmim][PF6], is used as a 'green' recyclable alternative to dipolar aprotic solvents for the regioselective alkylation at the heteroatom of indole and 2-naphthol.
- Earle, Martyn J.,McCormac, Paul B.,Seddon, Kenneth R.
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p. 2245 - 2246
(2007/10/03)
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- Chemoselective O-methylation of phenols under non-aqueous condition
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Chemoselective O-methylation of substituted phenols takes place in dry. tetrahydrofuran (THF) in the presence of LiOH.H2O and dimethylsulfate (DMS). Quantitative methyl transfer from DMS preserves the atom economy.
- Basak, Anindita,Nayak, Mrinal K.,Chakraborti, Asit K.
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p. 4883 - 4886
(2007/10/03)
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- Acylation of 2-Methoxynaphthalene with Acyl Clorides in the Presence of a Catalytic Amount of Lewis Acids
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The regiochemistry of the reaction of 2-methoxynaphthalene 1 with benzoyl chloride 2a using a catalytic amount of Lewis acid is strongly influenced by the identity of the acid catalyst employed as well as by the reaction temperature.By using InCl3, FeCl3, SnCl4 or ZnCl2 and heating at 160 deg C, 2-benzoyl-6-methoxynaphthalene 4a is selectively produced along with 1-benzoyl-7-methoxynaphthalene 5a, while in the case of AlCl3, SbCl5 or TiCl4, 1-benzoyl-2-methoxynaphthalene 3a is the major product. 2-Acyl-6-methoxynaphthalenes 4b-e can be selectively obtained using InCl3 and the corresponding acyl chlorides 2b-e in place of 2a.In the presence of a stoichiometric amount of InCl3, the reaction of 1 with 2a also gives 4a as the predominant product along with 5a even at 50 deg C.This reaction appears to involve isomerisation of 3a to 4a and 5a.
- Pivsa-Art, Sommai,Okuro, Kazumi,Miura, Masahiro,Murata, Satoru,Nomura, Masakatsu
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p. 1703 - 1708
(2007/10/02)
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- Facile Cleavage of Aryl Haloacetates and 2-Chloroethyl Carboxylic Esters with Sodium Telluride. A One-pot Conversion of Aryl Eters into Aryl Esthers under Aprotic Conditions
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Sodium telluride, prepared under aprotic conditions, cleaved aryl haloacetates and 2-chloroethyl carboxylates at room temperature to give phenolic compounds and carboxylic acids, respectively.Based on this cleavage a one-pot conversion of aryl esters into aryl ethers was achieved.
- Suzuki, Hitomi,Padmanabhan, Seetharamaiyer,Ogawa, Takuji
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p. 1017 - 1020
(2007/10/02)
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- Acylation of naphthalenes
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Naphthalene substituted in the 2- or β-position with an electron-donating substituent can be acylated with high regioselectivity in the 6-position by using an acylating agent in substantially anhydrous hydrogen fluoride which functions both as catalyst and solvent.
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- A Simple One-step Synthesis of Phenyl Ethers from Phenyl Acetates
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Phenyl acetates when refluxed with alkyl halides in acetone solution in the presence of a crown ether and anhydrous potassium carbonate undergo alkylation yielding phenyl ethers.
- Banerjee, Sunil K.,Gupta, Bishan D.,Singh, Kuber
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p. 815 - 816
(2007/10/02)
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- Gas-Liquid Phase-transfer Synthesis of Phenyl Ethers and Sulphides with Carbonate as Base and Carbowax as Catalyst
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When a mixture of a phenol (or thiol) and an alkyl halide is passed, in the gaseous state, through a solid bed of potassium carbonate (or sodium hydrogencarbonate) and catalytic amounts of Carbowax 6000, contained in a glass column at 170 deg C, the corresponding ethers (or sulphides) may be collected at the outlet.The Carbowax acts in a similar manner to the crown ethers used in solid-liquid phase-transfer catalysis.The potassium carbonate-Carbowax combination allows the generation of anions up to pKa of ca. 12.The catalysis mechanism is discussed and the synthesis of several ethers and thioethers is reported, some of which are obtained only with difficulty by normal liquid-liquid phase-transfer catalysis.
- Angeletti, Enrico,Tundo, Pietro,Venturello, Paolo
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p. 1137 - 1142
(2007/10/02)
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- Preparation of 2-Alkyl-1-naphthols and 1-Alkyl-2-naphthols
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C-Alkylation of 1-naphthol and 2-naphthol with n-butyllithium and dialkyl sulphate easily afford 2-alkyl-1-naphthols and 1-alkyl-2-naphthols respectively in relatively good yields.
- Saidi, Mohammad R.
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