- Method for preparing boric acid derivative (by machine translation)
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The invention provides a preparation method of p-hydroxyphenylboronic acid. The method is characterized by comprising the following -0.1 mpa steps: at 0 - 10 °C vacuum conditions and temperature, heating the alkoxyl phenylboronic acid and acid first chloride compound in organic solvent, then heating the aqueous layer minutes every interval until 10 °C 15 the temperature is raised to, and then 30 - 100 °C carrying out 1 - 2h constant temperature reaction to obtain the intermediate pH. The aqueous layer 9-11 is further recrystallized by organic solvent 3-4 to obtain intermediate compound and second alkali adjusting system pH. 3rd. The p-hydroxyphenylboronic acid is obtained. The method has the advantages that the reaction temperature is relatively mild, the reaction time can be obviously shortened, the consumption of the catalyst is reduced, and the method has higher yield and purity. (by machine translation)
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Paragraph 0044-0045
(2020/12/29)
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- Preparation method of hydroxyphenylboronic acid
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The invention discloses a preparation method of hydroxyphenylboronic acid, which belongs to the technical field of boric acid synthesis in medical intermediates. The method comprises the following steps: starting from bromophenol, carrying out BOC, trimethylsilyl or benzyl protection, forming a Grignard reagent, reacting with borate, or carrying out one-pot reaction with borate and n-butyllithium,and hydrolyzing to obtain hydroxyphenylboronic acid. According to the invention, cheap and easily available protecting groups are adopted, so that the protecting groups are easy to remove during boronation reaction hydrolysis, industrial amplification is easy to realize, batch production is carried out on the scale of dozens of kilograms, and the process stability is good.
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Paragraph 0042-0043; 0045
(2020/05/08)
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- Virtues of Volatility: A Facile Transesterification Approach to Boronic Acids
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Boronic acids are an increasingly important compound class for many applications, including C-C bond formation reactions, medicinal chemistry, and diagnostics. The deprotection of boronic ester intermediates is frequently a problematic and inefficient step in boronic acid syntheses. We describe an approach that highly facilitates this transformation by leveraging the volatility of methylboronic acid and its diol esters. The method is performed under mild conditions, provides high yields, and eliminates cumbersome and problematic purification steps.
- Hinkes, Stefan P.A.,Klein, Christian D.P.
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supporting information
p. 3048 - 3052
(2019/05/10)
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- Rhodium(II)-Catalyzed Aryl C?H Carboxylation of 2-Pyridylphenols with CO2
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A protocol for C?H carboxylation of electron-deficient 2-pyridylphenols with CO2 through a Rh(II)-catalyzed C?H bond activation under redox-neutral conditions has been developed. A suitable phosphine ligand was crucial for this reaction. This m
- Cai, Zhihua,Li, Shangda,Gao, Yuzhen,Li, Gang
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supporting information
p. 4005 - 4011
(2018/09/20)
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- Bedford-type palladacycle-catalyzed miyaura borylation of aryl halides with tetrahydroxydiboron in water
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A mild aqueous protocol for palladium catalyzed Miyaura borylation of aryl iodides, aryl bromides and aryl chlorides with tetrahydroxydiboron (BBA) as a borylating agent is developed. The developed methodology requires low catalyst loading of Bedford-type palladacycle catalyst (0.05 mol %) and works best under mild reaction conditions at 40 °C in short time of 6 h in water. In addition, our studies show that for Miyaura borylation using BBA in aqueous condition, maintaining a neutral reaction pH is very important for reproducibility and higher yields of corresponding borylated products. Moreover, our protocol is applicable for a broad range of aryl halides, corresponding borylated products are obtained in excellent yields up to 93% with 29 examples demonstrating its broad utility and functional group tolerance.
- Zernickel, Anna,Du, Weiyuan,Ghorpade, Seema A.,Sawant, Dinesh N.,Makki, Arwa A.,Sekar, Nagaiyan,Eppinger, J?rg
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p. 1842 - 1851
(2018/02/23)
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- Metal complex and OLED (Organic Light Emitting Device) thereof
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The invention discloses a metal complex and an OLED (Organic Light Emitting Device) thereof, and relates to the technical field of organic photoelectric materials. The metal complex has a structure asshown in a formula (I), wherein an electron-rich dinitrogen coordination structure in the structure of the metal complex is beneficial for stabilizing central trivalent metal cations, and meanwhile,electron cloud distribution on metal iridium can also be affected, so that great influence to the photoelectric properties of a whole complex molecule can be generated; a quaternary ring formed by a ligand of the dinitrogen coordination structure and metal has stronger rigidity and is beneficial for reducing unnecessary vibration energy loss and realizing high-efficiency luminescence property. Byregulating substituent groups, the metal complex has better thermal stability and chemical property; by preparing the metal complex into a device and particularly using the metal complex as a doping material, the device has the advantages of low driving voltage and high luminous efficiency and is superior to a commonly used OLED.
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Paragraph 0072; 0073; 0074; 0075
(2018/10/19)
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- A process for preparing between neighbour para-substituted hydroxy, thio boric acid
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A method of preparing phenylboronic acid ortho- meta- and para-substituted with hydroxy and mercapto is disclosed. The method includes adding a compound of a formula I into an organic solvent, adding 1.2-2.0 eq of acetyl chloride, lowering the temperature of the solution to a temperature between -10 DEG C and 0 DEG C, adding 0.1-0.3 eq of anhydrous aluminium chloride, heating to 20-120 DEG C, stirring for 2-10 h to obtain a compound of a formula II, adding an alkali to adjust pH to be 11-12 after TLC detection proves that the reaction is finished, layering, removing the organic layer, adding hydrochloric acid into the water layer to adjust pH to be 2-3, extracting with ethyl acetate, subjecting the organic layer to rotary drying, and beating the obtained crude product with a mixture of acetone or dichloromethane and n-heptane to obtain a solid product of a formula III, wherein R in the formula I is methyl or tert-butyl, and M in the formula I, M in the formula II and M in the formula III are oxygen simultaneously or sulfur simultaneously. The product produced by the method is high in purity and high in yield.
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- 2 - hydroxybenzene boric acid method
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The invention discloses a method for preparing a 2-hydroxyphenylboronic acid. The method comprises the following steps: S1, adding a hydroxyl protecting agent to a mixed solution of phenol/organic solvent, and forming a mixed solution containing phenol intermediates after reaction; S2, controlling the mixed solution containing the phenol intermediates to be at a first temperature, adding n-butyllithium to the mixed solution containing the phenol intermediates with the first temperature, and forming a pre-reaction solution after reaction; S3, controlling the pre-reaction solution to be at a second temperature, adding borate to the pre-reaction solution with the second temperature and forming a to-be-hydrolyzed solution after reaction; S4, carrying out hydrolysis reaction on the to-be-hydrolyzed solution, extracting and then concentrating the extracting solution to obtain a 2-hydroxyphenylboronic acid crude product, wherein the first temperature is smaller than or equal to 0 DEG C and the second temperature and the second temperature are the same or different. The hydroxyl protecting agent is adopted in the method and the reaction temperatures are controlled, so that the yield of the 2-hydroxyphenylboronic acid is improved. Meanwhile, the phenol is taken as the raw material, so that the production cost of the 2-hydroxyphenylboronic acid is reduced.
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Paragraph 0051; 0052; 0053; 0054; 0055; 0056; 0057-0206
(2017/09/16)
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- A process for preparing 2-hydroxybenzene boric acid method
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The invention provides a method for preparing 2-hydroxybenzeneboronic acid, which relates to the technical field of industrial production for 2-hydroxybenzeneboronic acid. The method is characterized by comprising the following steps of: selecting raw material phenol which is already commercialized in the market as an initial raw material, in a normal-temperature condition, protecting hydroxyl at first, and then directly dripping n-butyllithium in the mixture of protected hydroxyl intermediate and borate compounds without separating crude products, and after the reaction is finished, hydrolyzing to prepare 2-hydroxybenzeneboronic acid. The method is easily-available in raw materials, high in both the purity and yield of the reaction product, stable in process conditions, simple to operate and suitable for large-scale production, and provides novel thinking and method for preparing 2-hydroxybenzeneboronic acid.
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Paragraph 0026; 0027
(2017/02/09)
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- Structural analogues of the natural products magnolol and honokiol as potent allosteric potentiators of GABAA receptors
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Biphenylic compounds related to the natural products magnolol and 4′-O-methylhonokiol were synthesized, evaluated and optimized as positive allosteric modulators (PAMs) of GABAA receptors. The most efficacious compounds were the magnolol analog 5-ethyl-5′-hexylbiphenyl-2,2′-diol (45) and the honokiol analogs 4′-methoxy-5-propylbiphenyl-2-ol (61), 5-butyl-4′-methoxybiphenyl-2-ol (62) and 5-hexyl-4′-methoxybiphenyl-2-ol (64), which showed a most powerful potentiation of GABA-induced currents (up to 20-fold at a GABA concentration of 3 μM). They were found not to interfere with the allosteric sites occupied by known allosteric modulators, such as benzodiazepines and N-arachidonoylglycerol. These new PAMs will be useful as pharmacological tools and may have therapeutic potential for mono-therapy, or in combination, for example, with GABAA receptor agonists.
- Fuchs, Alexander,Baur, Roland,Schoeder, Clara,Sigel, Erwin,Müller, Christa E.
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p. 6908 - 6917
(2015/02/02)
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- Phenolate substituent effects on ring-opening polymerization of ε-caprolactone by aluminum complexes bearing 2-(phenyl-2-olate)-6-(1- amidoalkyl)pyridine pincers
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Interaction of the 2-(phenyl-2-ol)-6-ketiminopyridines 2-(4′-R 1-C6H3-2′-OH)-6-{CMe=N(2″,6″- i-Pr2C6H3)}C5H3N (R 1 = H (L1a-H), But (L
- Alkarekshi, Wafaa,Armitage, Andrew P.,Boyron, Olivier,Davies, Christopher J.,Govere, Matifadza,Gregory, Andrew,Singh, Kuldip,Solan, Gregory A.
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p. 249 - 259
(2013/02/25)
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- New 5-aryl-1H-imidazoles display in vitro antitumor activity against apoptosis-resistant cancer models, including melanomas, through mitochondrial targeting
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We designed and synthesized 48 aryl-1H-imidazole derivatives and investigated their in vitro growth inhibitory activity in cancer cell lines known to present various levels of resistance to proapoptotic stimuli. The IC50 in vitro growth inhibitory concentration of these compounds ranged from >100 μM to single digit μM. Among the most active compounds, 2i displayed similar in vitro growth inhibition in cancer cells independent of the cells' levels of resistance to proapoptotic stimuli and was found to be cytostatic in melanoma cell lines. Compound 2i was then tested by the National Cancer Institute Human Tumor Cell Line Anti-Cancer Drug Screen, and the NCI COMPARE algorithm did not reveal any correlation between its growth inhibition profiles with the NCI database compound profiles. The use of transcriptomically characterized melanoma models then enabled us to highlight mitochondrial targeting by 2i. This hypothesis was further confirmed by reactive oxygen production measurement and oxygen consumption analysis.
- Mathieu, Véronique,Van Den Berge, Emilie,Ceusters, Justine,Konopka, Tomasz,Cops, Antonin,Bruyère, Céline,Pirker, Christine,Berger, Walter,Trieu-Van, Tran,Serteyn, Didier,Kiss, Robert,Robiette, Rapha?l
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p. 6626 - 6637
(2013/10/01)
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- Scope of the palladium-catalyzed aryl borylation utilizing bis-boronic acid
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The Suzuki-Miyaura reaction has become one of the more useful tools for synthetic organic chemists. Until recently, there did not exist a direct way to make the most important component in the coupling reaction, namely the boronic acid. Current methods to make boronic acids often employ harsh or wasteful reagents to prepare boronic acid derivatives and require additional steps to afford the desired boronic acid. The scope of the previously reported palladium-catalyzed, direct boronic acid synthesis is unveiled, which includes a wide array of synthetically useful aryl electrophiles. It makes use of the newly available second generation Buchwald XPhos preformed palladium catalyst and bis-boronic acid. For ease of isolation and to preserve the often sensitive C-B bond, all boronic acids were readily converted to their more stable trifluoroborate counterparts.
- Molander, Gary A.,Trice, Sarah L. J.,Kennedy, Steven M.,Dreher, Spencer D.,Tudge, Matthew T.
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supporting information; experimental part
p. 11667 - 11673
(2012/09/05)
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- An expedient synthesis of ellipticine via Suzuki-Miyaura coupling
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A simple and efficient total synthesis of ellipticine was developed via the Suzuki-Miyaura coupling of sterically sensitive 2-hydroxybenzeneboronic acid with a multifunctional aryl halide using Pd(OAc)2 as a catalyst and Cu(OAc)2·H2O as an additive in DMSO/H2O as a key step followed by double N-arylation and cyclization.
- Konakahara, Takeo,Kiran,Okuno, Yuri,Ikeda, Reiko,Sakai, Norio
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supporting information; experimental part
p. 2335 - 2338
(2010/06/13)
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- Deprotection of pinacolyl boronate esters via hydrolysis of intermediate potassium trifluoroborates
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An efficient two-step procedure for the deprotection of pinacolyl organoboronate esters is described. Reaction with excess potassium hydrogen fluoride produces the corresponding stable, crystalline potassium organotrifluoroborate salts. Treatment of the trifluoroborates with either inorganic base or trimethylsilyl chloride and water affords the corresponding organoboronic acid in high yield.
- Yuen, Alexander K.L.,Hutton, Craig A.
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p. 7899 - 7903
(2007/10/03)
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- Bridged bi-aromatic ligands, catalysts, processes for polymerizing and polymers therefrom
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New ligands and compositions with bridged bis-aromatic ligands are disclosed that catalyze the polymerization of monomers into polymers. These catalysts with metal centers have high performance characteristics, including higher comonomer incorporation int
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- Deprotection of pinacolyl boronate esters by transesterification with polystyrene-boronic acid
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A mild, efficient method for the deprotection of pinacolyl organoboronate esters is described. Treatment of the organoboronate ester with excess polystyrene-boronic acid followed by filtration and evaporation of the solvent provides the corresponding organoboronic acid. Mild deprotection of pinacolyl boronate esters to the corresponding boronic acids was achieved in the presence of excess polystyrene-boronic acid via a transesterification process. The procedure allows for the cleavage of pinacolyl boronate esters in the presence of sensitive functional groups. Crown Copyright
- Pennington, Thomas E.,Kardiman, Cynantya,Hutton, Craig A.
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p. 6657 - 6660
(2007/10/03)
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- Compositions and methods of inhibiting the binding of E-selectin or P-selectin or sialyl-Lewisx or sialyl-Lewisa
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This invention relates to compounds that inhibit the binding of E-selectin or P-selectin to sialyl-Lewisx or sialyl-Lewisa presented on a cell surface having the general structure: STR1 This invention also relates to methods of inhibiting the binding of E-selectin or P-selectin to sialyl-Lewisx or sialyl-Lewisa presented on a cell surface using said compounds and to pharmaceutically active compositions comprising compounds that inhibit the binding of E-selectin to sialyl-Lewisx and to methods of treatment of septic shock, ARDS, Crohn's disease, chronic inflammatory diseases, such as psoriasis and rheumatoid arthritis, and reperfusion injuries that occurs following heart attacks, strokes and organ transplants and to the treatment of cancer.
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