- 19F-MRS/1H-MRI dual-1 of β-galactosidase activity
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Because of the importance of lacZ gene in various applications ranging from molecular biology to clinical trials, the development of non-invasive bimodal techniques for improving precision and accuracy to assay gene expression has attracted much attention. In this paper, we propose a dual-function probe for synergistic combination of 19F-MRS/1H-MRI to simultaneously detect β-gal activity. Based on this strategy, we have designed, synthesized and characterized a series of 19F-MRS/ 1H-MRI reporters, and demonstrated the feasibility of 1-O-(β-d-galactopyranosyl)-3-fluorocatechol MGD-3-FCAT for assessing β-gal activity in solution and in vitro with lacZ transfected tumor cells as well, by the characterization of β-gal responsive 19F- chemical shift changes ΔδF, hydrolytic kinetics, and T1, T2 relaxation mapping.
- Yu, Jian-Xin,Kodibagkar, Vikram D.,Liu, Li,Zhang, Zhongwei,Magnusson, Jennifer,Liu, Yuting
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Read Online
- Method for promoting iron-catalyzed oxidation of aromatic compound carbon - hydrogen bond to synthesize phenol by ligand
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The method comprises the following steps: iron is used as - a catalyst metal; a sulfur-containing amino acid or cystine-derived dipeptide is a ligand; and under the common action of hydrogen peroxide as an oxidizing agent, an aromatic compound is synthesized to prepare a phenol. Under the action of an acid as an accelerant and hydrogen peroxide as an oxidizing agent, the aryl carbon - hydrogen bond is directly hydroxylated to form a phenolic compound, and the method for preparing the phenol by the catalytic oxidation reaction has a plurality of advantages. The reaction raw materials, the oxidant and the promoter are wide in source, low in price, environment-friendly and good in stability. The aromatic compound carbon - hydrogen bonds directly participate in the reaction to react in one step to form phenol. The reaction condition is mild, the functional group compatibility and the application range are wide. The reaction selectivity is good; under the optimized reaction conditions, the target product separation yield can reach 85%.
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Paragraph 0088-0089; 0128
(2021/09/21)
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- Iron-catalyzed arene C-H hydroxylation
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The sustainable, undirected, and selective catalytic hydroxylation of arenes remains an ongoing research challenge because of the relative inertness of aryl carbon-hydrogen bonds, the higher reactivity of the phenolic products leading to over-oxidized by-products, and the frequently insufficient regioselectivity. We report that iron coordinated by a bioinspired L-cystine-derived ligand can catalyze undirected arene carbon-hydrogen hydroxylation with hydrogen peroxide as the terminal oxidant. The reaction is distinguished by its broad substrate scope, excellent selectivity, and good yields, and it showcases compatibility with oxidation-sensitive functional groups, such as alcohols, polyphenols, aldehydes, and even a boronic acid. This method is well suited for the synthesis of polyphenols through multiple carbon-hydrogen hydroxylations, as well as the late-stage functionalization of natural products and drug molecules.
- Cheng, Lu,Wang, Huihui,Cai, Hengrui,Zhang, Jie,Gong, Xu,Han, Wei
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- Isosteres of ester derived glucose uptake inhibitors
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Glucose transporters (GLUTs) facilitate glucose uptake and are overexpressed in most cancer cells. Inhibition of glucose transport has been shown to be an effective method to slow the growth of cancer cells both in vitro and in vivo. We have previously reported on the anticancer activity of an ester derived glucose uptake inhibitor. Due to the hydrolytic instability of the ester linkage we have prepared a series of isosteres of the ester moiety. Of all of the isosteres prepared, the amine linkage showed the most promise. Several additional analogues of the amine-linked compounds were also prepared to improve the overall activity.
- Bergmeier, Stephen C.,Chen, Xiaozhuo,Liu, Yi,Qian, Yanrong,Roberts, Dennis A.,Shriwas, Pratik,Wang, Liyi,Zhang, Weihe
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- Phenol compound ortho-position direct fluorination method
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The invention relates to a phenol compound ortho-position direct fluorination method which comprises the following steps: reacting a phenol compound shown in a formula (1A) with a fluorination reagentin a solvent under the action of a photocatalyst and a light source at room temperature, and separating and purifying a reaction mixture after the reaction to obtain a fluorinated phenol compound shown in a formula (2A). The advantages are as follows: the method for directly fluorinating phenol by organic photocatalysis is simple in operation process; raw materials are commercialized and easy toobtain; the photocatalyst is low in price, easy to obtain and environmentally friendly; the reaction condition is mild; the site selectivity is high; the reaction is efficient; and a fluorinated phenol derivative can be prepared only through one step.
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Paragraph 0064-0066
(2020/04/17)
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- Deuterated optical isomer and medical application thereof
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The invention provides compounds as shown in structural formulae Ia and Ib, non-toxic pharmaceutically-acceptable salts of the compounds and applications of the compounds to preparation of drugs fortreating depression. In a formula I, R1, R2, R3, R4, R5, R6, R7 and R8 are independently H or deuterium (D); and meanwhile, at least one of R1, R2, R3, R4, R5, R6, R7 and R8 is D.
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Paragraph 0010; 0011; 0012
(2019/01/08)
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- List fluoro Radicamine compounds and their use and preparation method
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The invention discloses a mono-fluorinated Radicamine compound which has a structure as shown in a formula (1), and further provides a preparation method for the mono-fluorinated Radicamine compound with the structure as shown in the formula (1) and an application of the mono-fluorinated Radicamine compound or the mono-fluorinated Radicamine compound prepared with the method to preparation of drugs for preventing and/or treating diabetes, drugs for preventing and/or treating Gaucher's diseases, drugs for preventing and/or treating tumors or antiviral drugs. The mono-fluorinated Radicamine compound provided by the invention is good in glycosidase inhibition activity.
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Paragraph 0091-0093
(2017/12/02)
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- Optical isomer and medical use thereof
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The invention relates to optical isomers shown in formula Ia and Ib, i.e. (R)-N-methyl-3-[(benzo[1,3]dioxolane-4-yl)oxo]-3-(thiophene-2-yl)-propylamine and (S)-N-methyl-3-[(benzo[1,3]dioxolane-4-yl)oxo]-3-(thiophene-2-yl)-propylamine, pharmaceutically acceptable salts thereof, pharmaceutical composition containing the optical isomers shown in formula Ia or Ib and pharmaceutically acceptable salts thereof as active ingredients and application of the pharmaceutical composition as antidepressant drug.
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Paragraph 0018-0019
(2017/06/29)
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- Fluorinated Radicamine A and B: Synthesis and Glycosidase Inhibition
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Fluorinated derivatives of radicamine A and radicamine B have been synthesized from D-arabinose-derived cyclic nitrone. Structure-activity relationship studies showed that glycosidase inhibition of these fluorinated derivatives was significantly influenced by the position of the fluorine atom. C-7 or C-11 fluorination of the aromatic ring decreased α-glucosidase inhibition of the derivatives, whereas C-8 or C-10 fluorination preserved glycosidase inhibitory activities. Fluorinated derivatives of radicamine A and B have been synthesized from D-arabinose-derived cyclic nitrone. Structure-activity relationship studies revealed that glycosidase inhibition of these fluorinated derivatives was significantly influenced by the position of the fluorine atom.
- Li, Yi-Xian,Iwaki, Ren,Kato, Atsushi,Jia, Yue-Mei,Fleet, George W. J.,Zhao, Xuan,Xiao, Min,Yu, Chu-Yi
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p. 1429 - 1438
(2016/03/16)
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- Fries rearrangement: Scalable synthesis of key fluoro building blocks 3-fluoro-4-methoxybenzoyl chloride and 1,2-diethoxy-3-fluorobenzene
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Lewis acid catalyzed Fries rearrangement of 2-fluorophenyl acetate (3) was performed on kg scale. The ortho 5 and para 4 isomers obtained were separated in an industrially feasible way. Compound 4 was then converted into fluorinated building block 3-fluoro-4-methoxybenzoyl chloride (1) while compound 5 was converted into 1,2-diethoxy-3-fluorobenzene (2) in high yields.
- Yerande, Swapnil G.,Shendage, Deepak M.,Wakchaure, Prasad B.,Phadtare, Ganesh R.,Bhoite, Madhavrao Y.,Gangopadhyay, Ashok Kumar,Nagarajan, Kuppuswamy,Rupp, Richard Helmut
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p. 2426 - 2429
(2014/05/06)
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- Selective ortho-hydroxylation-defluorination of 2-fluorophenolates with a Bis(μ-oxo)dicopper(III) species
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The bis(μ-oxo)dicopper(III) species [CuIII 2(μ-O)2(m-XYLMeAN)]2+ (1) promotes the electrophilic ortho-hydroxylation-defluorination of 2-fluorophenolates to give the corresponding catechols, a reaction that is not accomplishable with a (η2:η2-O2) dicopper(II) complex. Isotopic labeling studies show that the incoming oxygen atom originates from the bis(μ-oxo) unit. Ortho-hydroxylation-defluorination occurs selectively in intramolecular competition with other ortho-substituents such as chlorine or bromine. O in, F out: [CuIII2(μ-O) 2(m-XYLMeAN)]2+ is a bis(μ-oxo)dicopper(III) species and promotes the electrophilic ortho-hydroxylation-defluorination of 2-fluorophenolates to give the corresponding catechols. Isotopic labeling shows that the incoming oxygen atom originates from the bis(μ-oxo) unit. Ortho-hydroxylation-defluorination occurs selectively in intramolecular competition with other ortho-substituents such as chlorine or bromine.
- Serrano-Plana, Joan,Garcia-Bosch, Isaac,Miyake, Ryosuke,Costas, Miquel,Company, Anna
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supporting information
p. 9608 - 9612
(2014/10/15)
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- An efficient strategy for protecting dihydroxyl groups of catechols
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A novel strategy for protecting dihydroxyl groups of catechols has been developed. Base-mediated cyclizations of catechols with 1,3-dibromopropane provided the corresponding benzo[b]1,4-dioxepans, and herefrom the protecting group was easily cleaved by aluminum chloride. The preparation of the antibacterial and antifungal agent 4-(2-aminothiazol-4-yl)benzene-1,2-diol from catechol reliably verified its availability amenable to various harsh reaction conditions. Georg Thieme Verlag Stuttgart - New York.
- Huang, Wei-Bin,Guo, Ying,Jiang, Jian-An,Pan, Xian-Dao,Liao, Dao-Hua,Ji, Ya-Fei
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supporting information
p. 741 - 746
(2013/05/09)
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- Structure, stereochemistry and synthesis of enantiopure cyclohexenone cis-diol bacterial metabolites derived from phenols
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Biotransformation of 3-substituted and 2,5-disubstituted phenols, using whole cells of P. putida UV4, yielded cyclohexenone cis-diols as single enantiomers; their structures and absolute configurations have been determined by NMR and ECD spectroscopy, X-ray crystallography, and stereochemical correlation involving a four step chemoenzymatic synthesis from the corresponding cis-dihydrodiol metabolites. An active site model has been proposed, to account for the formation of enantiopure cyclohexenone cis-diols with opposite absolute configurations.
- Boyd, Derek R.,Sharma, Narain D.,Malone, John F.,McIntyre, Peter B. A.,Stevenson, Paul J.,Allen, Christopher C. R.,Kwit, Marcin,Gawronski, Jacek
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body text
p. 6217 - 6229
(2012/09/05)
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- PROCESS FOR PRODUCING 1,2-DIALKOXY-3-FLUOROBENZENE
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The present invention relates to a process for producing a 2-fluoro-6-halophenol as an intermediate; a process for producing a 2-alkoxy-3-fluorophenol and further a 1,2-dialkoxy-3-fluorobenzene from the 2-fluoro-6-halophenol; a second process for producing a 1,2-dialkoxy-3-fluorobenzene from the 2-fluoro-6-halophenol; and a 2-alkoxy-3-fluorophenol. The 2-fluoro-6-halophenol can be obtained using a 2-fluorophenol as a starting material and through a sulfonation reaction, a halogenation reaction, and a deprotection reaction. The 2-fluoro-6-halophenol is alkyl-etherified, and subsequently the halogen atom is converted into a hydroxyl group to obtain the 2-alkoxy-3-fluorophenol, which is further alkyl-etherified to thereby obtain the 1,2-dialkoxy-3-fluorobenzene. Alternatively, a 1,2-dialkoxy-3-fluorobenzene is also obtained by converting the halogen atom of the 2-fluoro-6-halophenol into a hydroxyl group to thereby form 3-fluorocatechol and subsequently alkyl-etherifying two hydroxyl groups thereof. The processes of the invention realize low production costs and high process yields, and thus are suitable for industrial production of a 1,2-dialkoxy-3-fluorobenzene.
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Page/Page column 9
(2009/06/27)
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- Process for producing 1,2-dialkoxy-3-fluorobenzene
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The present invention relates to a process for producing a 2-fluoro-6-halophenol as an intermediate; a process for producing a 2-alkoxy-3-fluorophenol and further a 1,2-dialkoxy-3-fluorobenzene from the 2-fluoro-6-halophenol; a second process for producing a 1,2-dialkoxy-3-fluorobenzene from the 2-fluoro-6-halophenol; and a 2-alkoxy-3-fluorophenol. The 2-fluoro-6-halophenol can be obtained using a 2-fluorophenol as a starting material and through a sulfonation reaction, a halogenation reaction, and a deprotection reaction. The 2-fluoro-6-halophenol is alkyl-etherified, and subsequently the halogen atom is converted into a hydroxyl group to obtain the 2-alkoxy-3-fluorophenol, which is further alkyl-etherified to thereby obtain the 1,2-dialkoxy-3-fluorobenzene. Alternatively, a 1,2-dialkoxy-3-fluorobenzene is also obtained by converting the halogen atom of the 2-fluoro-6-halophenol into a hydroxyl group to thereby form 3-fluorocatechol and subsequently alkyl-etherifying two hydroxyl groups thereof. The processes of the invention realize low production costs and high process yields, and thus are suitable for industrial production of a 1,2-dialkoxy-3-fluorobenzene.
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Page/Page column 6
(2009/09/26)
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- A comparative study of the synthesis of 3-substituted catechols using an enzymatic and a chemoenzymatic method
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A series of cis-dihydrodiol metabolites, available from the bacterial dioxygenase-catalysed oxidation of monosubstituted benzene substrates using Pseudomonas putida UV4 , have been converted to the corresponding catechols using both a heterogeneous catalyst (Pd/c) and a naphthalene cis-diol dehydrogenase enzyme present in whole cells of the recombinant strain Escherichia coli DH5α(pUC129: nar B). A comparative study of the merits of both routes to 3-substituted catechols has been carried out and the two methods have been found to be complementary. A similarity in mechanism for catechol formation under both enzymatic and chemoenzymatic conditions, involving regioselective oxidation of the hydroxyl group at C-1, has been found using deuterium labelled toluene cis-dihydrodiols. The potential, of combining a biocatalytic step (dioxygenase-catalysed cis-dihydroxylation) with a chemocatalytic step (Pd/C-catalysed dehydrogenation), into a one-pot route to catechols, from the parent substituted benzene substrates, has been realised.
- Berberian,Allen,Sharma,Boyd,Hardacre
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p. 727 - 739
(2008/02/09)
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- One-pot synthesis of substituted catechols from the corresponding phenols
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Phenols are converted to salicylaldehydes with paraformaldehyde, MgCl 2-Et3N in THF, and when subsequently treated with aqueous NaOH and H2O2 afford the corresponding catechols. The sequence is conveniently carried out as a one-pot procedure.
- Hansen, Trond Vidar,Skatteb?l, Lars
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p. 3357 - 3358
(2007/10/03)
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- Kinetics and mechanisms of the photolytic and OH° radical induced oxidation of fluorinated aromatic compounds in aqueous solutions
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Laboratory experiments with H2O2/UV oxidation processes and photolysis at 253.7 nm wavelength have been carried out on dilute aqueous solutions (C0 = 0.1 to 3.0 mM) of trifluorobenzene derivatives (1,3,5-trifluorobenzene, 1,2,3 and 1,2,4-trifluorobenzene) and of α,α,α-trifluorotoluene in the presence and in the absence of dissolved oxygen. The analyses of fluoride ions content during the oxidation experiments showed that the first steps lead to the production of about 2 mol of F-/mol of trifluorobenzene decomposed and of 1 mol of F-/mol of trifluorotoluene decomposed. Kinetic studies lead to the determination of the quantum yield for the photolysis of 1,3,5-trifluorobenzene, 1,2,3 and 1,2,4-trifluorobenzene (Φ = 0.011, 0.010 and 0.015 respectively), and of trifluorotoluene (Φ = 0.015). The rate constants for the reaction of hydroxyl radicals with these molecules, determined under specific experimental conditions, were found to range from 3.7 109 to 4.9 109 M-1.s-1). GC/MS analyses carried out on extracts at different irradiation time (UV, H2O2/UV) lead to the identification of numerous by-products from trifluorobenzene and trifluorotoluene. They consist mostly in hydroxylated and dehalogenated compounds. Dimers have also been observed during photolysis. Moreover, experiments carried out under oxygen limiting conditions revealed the formation of other compounds. For each case studied, a detailed mechanism involving radical intermediates and the different reaction sequences is proposed.
- Karpel vel Leitner,Gombert,Ben Abdessalem,Dore
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p. 893 - 906
(2007/10/03)
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- Syntheses of Fluorinated 2-Benzylimidazolines
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Perturbation of the electronic properties of the phenyl ring of 2-benzylimidazoline without appreciable steric modification can be achieved by fluorine substitution on the phenyl ring.The effects of such perturbation on biological activity can be evaluated.Syntheses of several fluorinated synthetic intermediates and 2-benzylimidazolines are described.Fluorine coupling of ortho benzylic protons and ortho methoxy protons were found to be 0-1.3 Hz.
- Adejare, Adeboye,Miller, Duane D.
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p. 171 - 193
(2007/10/02)
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