- Design and Synthesis of Novel 4-Hydroxyl-3-(2-phenoxyacetyl)-pyran-2-one Derivatives for Use as Herbicides and Evaluation of Their Mode of Action
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In order to develop a novel herbicide containing the β-triketone motif, a series of 4-hydroxyl-3-(2-phenoxyacetyl)-pyran-2-one derivatives were designed and synthesized. The bioassay results showed that compound II15 had good pre-emergent herbicidal activity even at a dosage of 187.5 g ha-1. Moreover, compound II15 showed a broader spectrum of weed control when compared with a commercial herbicide 2,4-dichlorophenoxyacetic acid (2,4-D), and displayed good crop safety to Triticum aestivum L. and Zea mays Linn. when applied at 375 g ha-1 under pre-emergence conditions, which indicated its great potential as a herbicide. More importantly, studying the molecular mode of action of compound II15 revealed that the novel triketone structure is a proherbicide of its corresponding phenoxyacetic acid auxin herbicide, which has a herbicidal mechanism similar to that of 2,4-D. The present work indicates that the 4-hydroxyl-3-(2-phenoxyacetyl)-pyran-2-one motif may be a potential lead structure for further development of novel auxin-type herbicides.
- Lei, Kang,Li, Pan,Yang, Xue-Fang,Wang, Shi-Ben,Wang, Xue-Kun,Hua, Xue-Wen,Sun, Bin,Ji, Lu-Sha,Xu, Xiao-Hua
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p. 10489 - 10497
(2019/10/02)
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- Click Chemistry-Assisted Synthesis of a β- D -Galactose-Targeted SiO2@RC Shell-Core Structure as a Nanoplatform for Metal-Based Complex Delivery
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A facile reversed-phase microemulsion method was used to synthesize shell-core nanospheres of SiO2@RCs (SiO2-encapsuled rare-earth metal complexes). β-d-Galactose was then grafted onto the surfaces of the nanospheres through the copper(I)-catalyzed azide-alkyne cycloaddition click reaction for targeted delivery. The chemical characteristics and surface profiles of the nanocarriers were investigated by Fourier transform infrared spectroscopy, dynamic light scattering, transmission electron microscopy, and scanning electron microscopy. A high-efficiency microwave synthesis method was applied to prepare five complex cores by the reaction of different rare-earth metal salts with two isomeric ligands, o-CPA (2-chlorophenoxyacetic acid) and m-CPA (3-chlorophenoxyacetic acid). The crystal structures of the five synthesized RC cores were confirmed through X-ray diffraction, which revealed the formulas of five RCs, [Dy(o-CPA)3(H2O)]·H2O RC1, [Ho(o-CPA)3(H2O)]·H2O RC2, 2[Er(m-CPA)3(H2O)]·3H2O RC3, 2[Gd(m-CPA)3(H2O)]·3H2O RC4, and [Ce2(m-CPA)6(H2O)3]·2H2O RC5. An in vitro cell study revealed that all RCs exhibited certain anticancer activities. RC2, in particular, showed the strongest cytotoxicity against HepG2 cells. The enhanced cell permeability and drug retention considerably improved the cytotoxicity of all SiO2@RC2-gal relative to that of RC2. The selective uptake of the β-d-galactose-conjugated nanospheres by HepG2 cells through mechanisms mediated by cell surface receptors resulted in fewer side effects on extrahepatic tissues. Our contribution provides a novel design concept of a target SiO2@RCs-gal nanocarrier for delivering affordable antitumor complexes in cancer therapy.
- Xu, Xiuling,Hu, Fan,Shuai, Qi
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supporting information
p. 10694 - 10701
(2018/09/13)
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- Facile microwave synthesis, structural diversity and herbicidal activity of six novel alkaline-earth metal complexes (AECs) based on skeletal isomerization chlorophenoxyacetic acids
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Six novel AECs of [Sr(o-CPA)2(H2O)4]·(o-CPA) 1, [Ba(o-CPA)2(H2O)]·H2O 2, [Sr(m-CPA)2(H2O)4]·(m-CPA) 3, [Ba(m-CPA)2(H2O)4]2·2(m-CPA)·H2O 4, [Sr(p-CPA)2(H2O)] 5 and [Ba(p-CPA)2(H2O)] 6 (o-CPA = 2-chlorophenoxyacetic acid, m-CPA = 3-chlorophenoxyacetic acid and p-CPA = 4-chlorophenoxyacetic acid) were synthesized by a facile microwave-assistant reaction. The solid-state structures were well established by X-ray crystallography and routine analyses of Fourier transform infrared, elemental analysis, field emission scanning electron microscope (FESEM) and thermogravimetric analysis. The structure data reveal that complexes of 1, 3 and 4 are one-dimensional chains with a zigzag arrangement, while 2, 5 and 6 are (4, 4) rhomboid two-dimensional grid structures. It is noticed that the carboxyl group in these complexes displays multiple coordination modes of μ2-η1:η1 (1, 2, 3, 4, 5 and 6), μ3-η1:η2 (1, 2, 3 and 4), μ2-η1:η2 (2), μ3-η2:η2 (5 and 6). Interestingly, the oxygen atoms of flexible -OCH2- in phenoxy groups take part in coordination behavior with metal centers through the rotation of the C-O and C-C bonds in complexes 2, 5 and 6, while only carboxyl group coordination can be found in complexes 1, 3 and 4. FESEM images indicate that the surface appearances of complexes are totally different from ligands after coordination. All ligands and complexes were evaluated for activity as plant-growth inhibitors against Amaranth (Amaranthus spp.) and barnyard grass. Compared with ligands, complexes 1, 3 and 4 exhibited better response index (RI) values of Shoot elongation against barnyard grass. Moreover, complexes 1, 3 and 4 demonstrated a higher inhibitory activity than 2, 5 and 6. It is significant to develop a new kind of environmentally-friendly herbicide based on these kinds of complexes for their low toxicity and high efficiency.
- Xu, Xiuling,Hu, Fan,Ma, Yuwei,Gao, Jinming,Shuai, Qi
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p. 4155 - 4166
(2018/03/21)
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- Calcium coordination compounds based on phenoxyacetic acids: Microwave synthesis, thermostability and influences on the crystal structures of chlorine substituent group on ligands
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Three calcium coordination compounds, [Ca(CPA)(H2O)4]·(CPA), 1, [Ca(MCPA)2(H2O)2]·H2O, 2, and [Ca(TCPA)2(H2O)3]·2H2O, 3 [HCPA = 3-chlorophenoxyacetic acid, HMCPA = 2-methyl-4-chlorophenoxyacetic acid, and HTCPA = 2,4,6-trichlorophenoxyacetic acid], have been synthesized by the microwave method with advantages that include shorter reaction times, lower energy consumption, and higher product yield. The structures have been characterized by IR, elemental analysis, and single-crystal X-ray diffraction. Influences on the crystal structures by changing the number and position of chlorine substituent group in phenoxyacetic acid are discussed. Steric hindrance effects involving the Cl and an ability to form the O-HCl hydrogen bonds enrich the structure diversity. TG analysis reveals that the thermostability for the three compounds is 3 > 1 > 2, which could be influenced by the existence of hydrogen bonds (O-HCl and O-HO).
- Xu, Xiuling,Yan, Saisai,Hu, Fan,Zhao, Wei,Shuai, Qi
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p. 541 - 550
(2016/02/26)
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- The optically pure sodium alcoholate dextrorotary chlorine forefront of the method for the preparation of
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The invention relates to a preparation method of optically pure dextro cloprostenol sodium. The method comprises the following steps: using the combination of ketonic acid and S-phenylethylamine resolving agent, and carrying out chiral resolution to obtain S-propenylphosphonate with the structural formula of R-ketonic acid; then separating to obtain R-chlorone and preparing to obtain R-cloprostenol sodium. The preparation method has the benefits that the optically pure dextro cloprostenol sodium in the invention is called D-cloprostenol sodium for short, the using amount only needs one third of cloprostenol sodium being a racemic modification in current market, and the pesticide effect is obviously better than cloprostenol sodium with three times of using amount.
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Paragraph 0129 - 0131
(2018/02/04)
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- An Efficient One-Pot Synthesis of 2-(Aryloxyacetyl)cyclohexane-1,3-diones as Herbicidal 4-Hydroxyphenylpyruvate Dioxygenase Inhibitors
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4-Hydroxyphenylpyruvate dioxygenase (EC 1.13.11.27, HPPD) is an important target for new bleaching herbicides discovery. As a continuous work to discover novel crop selective HPPD inhibitor, a series of 2-(aryloxyacetyl)cyclohexane-1,3-diones were rationally designed and synthesized by an efficient one-pot procedure using N,N′-carbonyldiimidazole (CDI), triethylamine, and acetone cyanohydrin in CH2Cl2. A total of 58 triketone compounds were synthesized in good to excellent yields. Some of the triketones displayed potent in vitro Arabidopsis thaliana HPPD (AtHPPD) inhibitory activity. 2-(2-((1-Bromonaphthalen-2-yl)oxy)acetyl)-3-hydroxycyclohex-2-en-1-one, II-13, displayed high, broad-spectrum, and postemergent herbicidal activity at the dosage of 37.5-150 g ai/ha, nearly as potent as mesotrione against some weeds. Furthermore, II-13 showed good crop safety against maize and canola at the rate of 150 g ai/ha, indicating that II-13 might have potential as a herbicide for weed control in maize and canola fields. II-13 is the first HPPD inhibitor showing good crop safety toward canola.
- Wang, Da-Wei,Lin, Hong-Yan,He, Bo,Wu, Feng-Xu,Chen, Tao,Chen, Qiong,Yang, Wen-Chao,Yang, Guang-Fu
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p. 8986 - 8993
(2016/12/09)
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- Finding new elicitors that induce resistance in rice to the white-backed planthopper Sogatella furcifera
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Herein we report a new way to identify chemical elicitors that induce resistance in rice to herbivores. Using this method, by quantifying the induction of chemicals for GUS activity in a specific screening system that we established previously, 5 candidate elicitors were selected from the 29 designed and synthesized phenoxyalkanoic acid derivatives. Bioassays confirmed that these candidate elicitors could induce plant defense and then repel feeding of white-backed planthopper Sogatella furcifera.
- He, Xingrui,Yu, Zhaonan,Jiang, Shaojie,Zhang, Peizhi,Shang, Zhicai,Lou, Yonggen,Wu, Jun
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p. 5601 - 5603
(2015/11/17)
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- Synthesis, evaluation and in silico molecular modeling of pyrroyl-1,3,4-thiadiazole inhibitors of InhA
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Enoyl acyl carrier protein reductase (ENR) is an essential type II fatty acid synthase (FAS-II) pathway enzyme that is an attractive target for designing novel antitubercular agents. Herein, we report sixty-eight novel pyrrolyl substituted aryloxy-1,3,4-thiadiazoles synthesized by three-step optimization processes. Three-dimensional quantitative structure-activity relationships (3D-QSAR) were established for pyrrolyl substituted aryloxy-1,3,4-thiadiazole series of InhA inhibitors using the comparative molecular field analysis (CoMFA). Docking analysis of the crystal structure of ENR performed by using Surflex-Dock in Sybyl-X 2.0 software indicates the occupation of pyrrolyl substituted aryloxy 1,3,4-thiadiazole into hydrophobic pocket of InhA enzyme. Based on docking and database alignment rules, two computational models were established to compare their statistical results. The analysis of 3D contour plots allowed us to investigate the effect of different substituent groups at different positions of the common scaffold. In vitro testing of ligands using biological assays substantiated the efficacy of ligands that were screened through in silico methods.
- Joshi, Shrinivas D.,More, Uttam A.,Koli, Deepshikha,Kulkarni, Manoj S.,Nadagouda, Mallikarjuna N.,Aminabhavi, Tejraj M.
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p. 151 - 167
(2015/03/30)
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- Copper(II)-catalyzed hydroxylation of aryl halides using glycolic acid as a ligand
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Copper(II)-catalyzed hydroxylation of aryl halides has been developed to afford functionalized phenols. The protocol utilizes the reagent combination of Cu(OH)2, glycolic acid, and NaOH in aqueous DMSO, all of which are cheap, readily available, and easily removable after the reaction. A broad range of aryl iodides and activated aryl bromides were transformed into the corresponding phenols in excellent yields. Moreover, it has been shown that C-O(alkyl)-coupled product, instead of phenol, can be predominantly formed under similar reaction conditions.
- Xiao, Yan,Xu, Yongnan,Cheon, Hwan-Sung,Chae, Junghyun
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p. 5804 - 5809
(2013/07/25)
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- 1,2-asymmetric induction in diastereoselective zwitterionic aza-Claisen rearrangements: Key steps in optically active alkaloid synthesis
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The zwitterionic aza-Claisen rearrangement of optically active N-allylpyrrolidines and α-phenoxyacetyl fluorides proceeds with complete simple diastereoselectivity (internal asymmetric induction) and complete 1,2-asymmetric induction to generate a new C-C bond adjacent to a chiral C-N-Boc functionality. The resulting γ,δ-unsaturated amides were cyclised to give the corresponding pyrrolizidinones, which enabled the determination of the relative configuration of the stereotriads. Vinyl group degradation and a final lactam reduction gave an optically active analogue of (+)-petasinine (a pyrrolizidine alkaloid). Furthermore, the stereotriad-containing amides should be useful key intermediates for the total synthesis of optically active elaeocarpin (an indolizidine alkaloid). Copyright
- Heescher, Carolin,Schollmeyer, Dieter,Nubbemeyer, Udo
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supporting information
p. 4399 - 4404
(2013/07/26)
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- The synthesis of ethacrynic acid thiazole derivatives as glutathione S-transferase pi inhibitors
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Glutathione S-transferase pi (GSTpi) is a phase II enzyme which protects cells from death and detoxifies chemotherapeutic agents in cancer cells. Ethacrynic acid (EA) is a weak GSTpi inhibitor. Structure modifications were done to improve the ability of EA to inhibit GSTpi activity. Eighteen EA thiazole derivatives were designed and synthesized. Compounds 9a, 9b and 9c with a replacement of carboxyl group of EA by a heterocyclic thiazole exhibited improvement over EA to inhibit GSTpi activity.
- Li, Ting,Liu, Guyue,Li, Hongcai,Yang, Xinmei,Jing, Yongkui,Zhao, Guisen
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scheme or table
p. 2316 - 2322
(2012/05/07)
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- Inhibition of monoamine oxidase by 8-phenoxymethylcaffeine derivatives
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A recent study has reported that a series of 8-benzyloxycaffeines are potent and reversible inhibitors of both human monoamine oxidase (MAO) isoforms, MAO-A and -B. In an attempt to discover additional caffeine derivatives with potent MAO inhibitory activities, and to contribute to the known structure-activity relationships of MAO inhibition by caffeine derived compounds, the present study investigates the MAO inhibitory potencies of series of 8-phenoxymethylcaffeine and 8-[(phenylsulfanyl)methyl]caffeine derivatives. The results document that the 8-phenoxymethylcaffeine derivatives act as potent reversible inhibitors of MAO-B, with IC50 values ranging from 0.148 to 5.78 μM. In contrast, the 8-[(phenylsulfanyl)methyl]caffeine derivatives were found to be weak inhibitors of MAO-B, with IC50 values ranging from 4.05 to 124 μM. Neither the 8-phenoxymethylcaffeine nor the 8-[(phenylsulfanyl)methyl]caffeine derivatives exhibited high binding affinities for MAO-A. While less potent than the 8-benzyloxycaffeines as MAO-B inhibitors, this study concludes that 8-phenoxymethylcaffeines may act as useful leads for the design of MAO-B selective inhibitors. Such compounds may find application in the therapy of neurodegenerative disorders such as Parkinson's disease. Using molecular docking experiments, this study also proposes possible binding orientations of selected caffeine derivatives in the active sites of MAO-A and -B.
- Okaecwe, Thokozile,Swanepoel, Abraham J.,Petzer, Anél,Bergh, Jacobus J.,Petzer, Jacobus P.
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experimental part
p. 4336 - 4347
(2012/08/28)
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- The synthesis of α,β-unsaturated carbonyl derivatives with the ability to inhibit both glutathione S-transferase P1-1 activity and the proliferation of leukemia cells
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Ethacrynic acid (EA), an α,β-unsaturated carbonyl compound, is a glutathione S-transferase P1-1 (GSTP1-1) inhibitor. Twenty-one novel EA derivatives have been synthesized. The effects of these compounds on GSTP1-1 activity and on the proliferation of human leukemia HL-60 cells have been determined. Compounds with a halogen substitution at the 3′-position of the aromatic ring have greater inhibitory effects on GSTP1-1 activity than those of compounds with a methyl substitution there. Compounds with substitutions at both the 2′- and 3′-positions of the aromatic ring have more antiproliferative ability than those with one substitution at 3′-position. Esterification of the carboxyl group appears to increase the antiproliferative ability.
- Zhao, Guisen,Liu, Chuan,Wang, Rui,Song, Dandan,Wang, Xiaobing,Lou, Hongxiang,Jing, Yongkui
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p. 2701 - 2707
(2008/02/07)
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- Synthesis of 1,1,1-trichloro-2,2-bis-(carboxymethoxyaryl)ethanes as potential antimicrobial and insecticidal agents
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Some new 1,1,1-trichloro-2,2-bis-(carboxymethoxyaryl)-ethanes 2a-t have been synthesised by the treating aryloxyacetic acid (two moles) with chloral hydrate (1 mole) in the presence of catalytic amount of conc. sulphuric acid. The aryloxyacetic acid are prepared by the reaction of substituted phenols with chloroacetic acid in the presence of aq. sodium hydroxide. The antimicrobial activity of these compounds have been assayed against various Gram+ve, Gram-ve bacteria and fungi. The constitution of the products have been elucidated by IR, 1H NMR and mass spectral data and elemental analyses.
- Purohit,Shah
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p. 618 - 622
(2007/10/03)
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