602-09-5Relevant articles and documents
ortho-Selective phenol-coupling reaction by anodic treatment on boron-doped diamond electrode using fluorinated alcohols
Kirste, Axel,Nieger, Martin,Malkowsky, Itamar M.,Stecker, Florian,Fischer, Andreas,Waldvogel, Siegfried R.
, p. 2273 - 2277 (2009)
A study was conducted to demonstrate ortho-selective phenol-coupling reaction by anodic treatment on boron-doped diamond electrode using fluorinated alcohols. A protocol for the conversion of neat phenol on boron-doped diamond (BDD) electrodes was also developed for the study. Partial conversion of 30% was carried out to prevent electrochemical incineration and to avoid by-products. It was observed that the free path length of oxyl radicals generated on BDD electrodes were found in the nanometer range. Methanol and other simple alcohols were used in the study on the anodic phenol coupling reaction. It was also found that some amount of methanol disappeared from the electrolysis cell despite cooling the electrolyte. Hexafluoroisopopanol with supporting electrolytes produced a powerful electrolyte system for the anodic coupling reaction of phenols.
Visible Light-Promoted C-C Bond Formation from Hydroxyaryls in Water
Saporito, Dafne,Rodriguez, Sergio A.,Baumgartner, Maria T.
, p. 978 - 982 (2019)
An eco-friendly and direct arylation of hydroxyaryls in water using photoinduced reactions with different substrates (1-bromo-2-naphthol, 1-iodo-2-naphthol, N-(2-iodophenyl)acetamide, 5-bromouracil, 2-iodo-N-methylbenzamide, and 2-iodobenzamide) was studied. For example, π-expanded coumarins, compounds with potential optical applications, were synthesized in very high yield, without the use of toxic reagents, in a one-pot reaction. In addition, we demonstrate that the irradiation source (halogen lamp) can be efficiently replaced by an LED without altering the reaction yield.
Resolution of Racemic 1,1'-Bi-2-naphthol Using (S)-Proline via a Cyclic Borate Ester
Shan, Zixing,Xiong, Ying,Zhao, Dejie
, p. 3893 - 3896 (1999)
1,1'-Bi-2-naphtholborane generated from racemic 1,1'-bi-2-naphthol and borane dimethyl sulfide complex reacted with (S)-proline in tetrahydrofuran to form a spirocyclic 1,1'-bi-2-naphtholboric proline anhydride. Its two diastereoisomers could be separated efficiently under the experimental conditions, from which enantiomerically pure (R)-(+)- and (S)-(-)-1,1'-bi-2-naphthol were obtained in ca. 80 percent overall yield, respectively. - Keywords: resolution; 1,1'-bi-2-naphthol; (S)-proline; cyclic borate ester.
Oxidation of 2-naphthol in the presence of catalysts based on modified β-cyclodextrins
Karakhanov,Kardahseva,Maksimov,Egazar'Yants,Karapetyan,Zatolochnaya
, p. 402 - 408 (2007)
The oxidation of 2-naphthol to 1,1'-bi-2-naphthol in a biphasic system in the presence of β-cyclodextrins was studied. It was found that the use of macrocyclic receptors leads to substantial enhancement of the activity of catalytic systems. It was shown that the product yield and the reaction rate substantially increase when ligands obtained via molecular imprinting in the presence of 1,1'-bi-2-naphthol as a template are added.
Supramolecular Ammine-Copper rac-BINOLAT Salts through in-situ R- or S-BINOL Racemization
Wisser, Barbara,Labahn, Andreas,N?ther, Christian,Janiak, Christoph
, p. 734 - 739 (2020)
The molecule rac-1,1'-binaphthalene-2,2'-diol (rac-1,1'-bi-2-naphthol, rac-BINOL) shows a propensity for supramolecular, charge-assisted O–H···O– hydrogen-bonded strand formation when crystallized with its deprotonated form BINOLAT2– and Cu2+ in conc. ammonia. The naphthyl-paneled cavities in the {(rac-BINOLAT2–)(rac-BINOL)2} strands host the [Cu(NH3)5]2+-guest cation through second-sphere N–H···O hydrogen bonding in the structure of [Cu(NH3)5]2+(rac-BINOLAT2–)(rac-BINOL)2. Decreasing the copper(II) and ammonia concentrations in the crystallization leads to {(rac-BINOLAT2–)(rac-BINOL)} strands, in which rac-BINOLAT2– coordinates to two copper(II) atoms in the structure of [Cu(NH3)2(μ-rac-BINOLAT2–-κ2O,O':κO)]2(rac-BINOL)2. In the {Cu2+(NH3)2} moiety two BINOLAT-oxide atoms act as bridging ligands. Both copper structures could be obtained by using the racemic rac-BINOL or the enantiomeric R- or S-BINOL, through an in-situ racemization of the latter.
A practical procedure for the solid-phase synthesis of racemic 2,2'-dihydroxy-1,1'-binaphthyl
Rasmussen,Axelsson,Tanner
, p. 4027 - 4030 (1997)
A high yielding solid-phase dimerisation of 2-naphthol by means of a ball-milling procedure is described.
A simple, convenient preparation for enantiomerically pure 1,1'-bi-2- naphthols
Shan, Zixing,Xiong, Ying,Li, Weizhong,Zhao, Dejie
, p. 3985 - 3989 (1998)
A new preparative method for enantiomerically pure 1,1'-bi-2-naphthols is described. 1,1'-Bi-2-naphtholboric anhydride generated from the reaction of racemic 1,1'-bi-2-naphthol and boric acid in toluene is reacted with (S)- proline to produce 1,1'-bi-2-naphtholboric proline anhydride. Its two diastereomers were efficiently separated in THF. After treating successively with NaOH, HCl, and recrystallizing from benzene, enantiomerically pure (S)- and (R)-1,1'-bi-2-naphthol were obtained in 71-79% yield and in 62-74% yield, respectively.
Selective removal of isoquinoline and quinoline from simulated fuel using 1,1′-binaphthyl-2,2′-diol (BINOL): Crystal structure and evaluation of the adduct electronic properties
Ogunlaja, Adeniyi S.,Hosten, Eric,Betz, Richard,Tshentu, Zenixole R.
, p. 39024 - 39038 (2016)
1,1′-Binaphthyl-2,2′-diol/quinoline (BINOL/QUN) and 1,1′-binaphthyl-2,2′-diol/isoquinoline (BINOL/ISOQUN) adducts were successfully synthesized. X-ray single crystals of BINOL/QUN and BINOL/ISOQUN were grown and analysed. The crystal packing of the molecules in both adducts confirmed that they are held in aggregates by strong hydrogen bonds (O2-H2?O3), (O3-H3?N1), (O2-H2?O1), (O1-H1?N1), (O2-H2?O1) and weak hydrogen C-H?π bonds. The patterns of the hydrogen bonding network as well as the conformation of BINOL contribute to the formation of the shape of the voids that entrap quinoline and isoquinoline. Molecular modelling which was employed to investigate the electronic properties of BINOL/QUN and BINOL/ISOQUN shows that the HOMO positions of the adducts are localized around the 1,1′-binaphthyl-2,2′-diol (BINOL), while the LUMO is positioned on isoquinoline and quinoline. Thermodynamic parameters obtained from isothermal titration calorimetry (ITC) revealed a stronger isoquinoline/BINOL interaction compared to quinoline/BINOL. 6-Vinyl-1,1′-binaphthyl-2,2′-diol was co-polymerized with styrene to form [DBN-co-STY]. Electrospun [DBN-co-STY] exhibited selectivity for quinoline and isoquinoline in a model simulated fuel presenting an adsorption capacity of 2.2 and 2.4 mg g-1 respectively. The adsorption study showed a higher adsorption capacity for isoquinoline compared to quinoline. This may be attributed to the more favourable electronic properties (HOMO-LUMO properties) of isoquinoline. This concept demonstrates the possibility of extracting/separating isoquinoline and quinoline from fuel.
A new family of bis-tetrazole (BIZOL) BINOL-type ligands
Dabbagh, Hossein A.,Najafi-Chermahini, Alireza,Banibairami, Soodabeh
, p. 3929 - 3932 (2006)
The synthesis and characterization of 5-(1-(2-(1H-tetrazole-5-yloxy)naphthalen-1-yl)naphthalen-2-yloxy)-1H-tetrazole (BIZOL) as the first bis-tetrazole BINOL-type ligands is described.
A facile large scale preparation of racemic 2,2′-dihydroxy-1,1′-binaphthyl
Deussen,Frederiksen,Bjornholm,Bechgaard
, p. 484 - 486 (1996)
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C-C coupling reaction of 1,5-dibromo-2,6-dihydroxynaphthalene with alakli 2-naphthoxide. Opposite effects of counterion coordination and hydrogen bonding on stereoselectivity in the formation of cis- and trans-1,1':5',1''-ternaphthyls
Belohradsky, Martin,Budesinsky, Milos,Guenterova, Jana,Hodacova, Jana,Holy, Petr,Zavada, Jiri,Cisarova, Ivana,Podlaha, Jaroslav
, p. 11013 - 11024 (1996)
The title reaction yields cis- and trans-2,2',6',2''-tetrahydroxy-1,1':5',1''-ternaphthyls as the main products. In contrast to non-selective distribution of the stereoisomers in the thermodynamic equilibrium, very high selectivity can be attained under conditions of kinetic control. The observed values of cis-/trans- ratios range between the extremes 94:6 and 6:94, depending on the solvent and counterion employed. The coordination of the metal counterion plays a key role in the reaction performed in toluene, supporting formation of the cis-stereoisomer. When the coordination ability of the counterion is suppressed by 18-crown-6, intramolecular hydrogen bonding of the departing bromide group prevails in the stereocontrol, providing support for the trans-stereoisomer formation.
A simple convenient method for the resolution of racemic 2,2'-dihydroxy-1,1'-binaphthyl using (S)-proline
Periasamy,Bhanu Prasad,Bhaskar Kanth,Kishan Reddy
, p. 341 - 344 (1995)
The racemic mixture of 2,2'-dihydroxy-1,1'-binaphthyl has been resolved to obtain the R(+) and S(-) enantiomers in essentially pure forms by refluxing with (S)-proline (1eq.) in benzene in three successive operations.
Visible-Light-Driven di-t-Butyl Peroxide-Promoted the Oxidative Homo- and Cross-Coupling of Phenols
Jia, Hanqiang,He, Min,Yang, Shilei,Yu, Xiaoqiang,Bao, Ming
, (2022/03/01)
The visible-light-induced oxidative homo- and cross-coupling of phenols by di-t-butyl peroxide (DTBP) are described. These reactions occur with metal-free process and feature high chemo- and regioselectivity under mild reaction conditions. DTBP is an inexpensive, benign, stable at room temperature, and commercially available oxidizer. It can be irradiated by blue LEDs to generate tert-butoxyl radical (tBuO?), which induces the oxidative homo-coupling of phenols and the cross-coupling of phenols with naphthols, respectively.
Fe(III) superoxide radicals in halloysite nanotubes for visible-light-assisted benzyl alcohol oxidation and oxidative C[sbnd]C coupling of 2-naphthol
Baruah, Manash J.,Bora, Tonmoy J.,Dutta, Rupjyoti,Roy, Subhasish,Guha, Ankur Kanti,Bania, Kusum K.
, (2021/09/20)
Selective oxidation of benzyl alcohols to aldehydes and 2-naphthol to BINOL was achieved by activation of molecular oxygen (O2) and hydrogen peroxide (H2O2) over an iron-oxide catalyst embedded in halloysite nanotube. Electron spin resonance spectroscopy (ESR), Raman and in situ FTIR spectroscopic analysis provided direct evidence for the involvement of superoxide radical bound FeIII species in the oxidation reaction. Both the analysis suggested the end-on binding of superoxide radical with FeIII-centre. The stability of such radical bound FeIII-species in halloysite nanotube was analyzed through density functional theory (DFT) calculations. Results suggested that end-on (η1) binding was favourable by 13.5 kcal/ mol than the side-on (η2) binding mode. The formation of such reactive species was believed to play the crucial role in bringing the high selectivity in the catalytic oxidation of benzyl alcohol and oxidative C[sbnd]C coupling of 2-naphthol. UV–Vis spectroscopic studies on the oxidation of benzyl alcohol suggested for the initial adsorption of substrate molecule on the catalyst surface followed by its interaction with FeIII -superoxide/hydroperoxide species generated upon photoirradiation with visible light in presence of O2. The presence of a suitable band gap ～2.14 eV enabled the catalyst to catalyze the reaction under visible light irradiation. Both the reactions (benzyl alcohol and 2-naphthol oxidation) were tested in presence of both O2 and H2O2 as oxidants at ambient temperature. The influence of different parameters like rate of oxygen flow, amount of peroxide, nature of solvent, and catalyst amount on the conversion and selectivity of the reactions were studied to understand their role in the catalytic reactions. Successful oxidation of 2-naphthol with H2O2 as oxidant was a real success to overcome the limitations associated with this reaction using H2O2 as oxidant.
Method for efficiently preparing 1, 1'-bi-2-naphthol under catalysis assistance of solid ligand
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Paragraph 0033-0044, (2021/03/31)
The invention relates to a method for efficiently preparing 1, 1'-bi-2-naphthol under catalysis assistance of solid ligand; the method comprises the following steps: 1), adding 2-naphthol, solid cuprous chloride, solid phenanthroline and an n-butyl alcohol solvent into a four-neck flask; 2), installing a thermometer, a heating and stirring device and a reflux condensing pipe on the four-neck bottle; 3), starting to stir at normal pressure, performing heating to dissolve, introducing air to oxidize, and performing heating to react to obtain a reaction mixed solution; 4), adding water into the reaction mixed solution, performing stirring, performing heating, performing washing with water, separating liquid, and removing a wastewater layer to obtain an organic layer; 5), cooling, crystallizing, filtering and drying the organic layer to obtain an off-white 1, 1'-bi-2-naphthol crude product, carrying out reduced pressure distillation on the filtrate, and recycling the n-butyl alcohol solvent; and 6), performing recrystallizing and drying to obtain a white crystal 1, 1'-bi-2-naphthol product. The reaction temperature is low, the reaction conditions are mild, the yield of the product obtained by recrystallization after the reaction is greater than 80%, and the purity of the product is higher than 99.3%.
