- The synthesis and herbicidal evaluation of fluorine-containing phenoxyacetoxyalkylphosphonate derivatives
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To investigate the influence of a fluorine moiety on the biological activity of phenoxyacetoxyalkylphosphonates, a series of fluorine-containing phenoxyacetoxyalkylphosphonates were synthesized and screened for herbicidal activity in a greenhouse. The majority of the title compounds showed better preemergence activity than postemergence activity against the test plants, especially on monocotyledon. Compound 5l exhibited notable activity. Results showed that by introducing a fluorine moiety to the parent structure of phenoxyacetoxyalkylphosphonates, a series of new compounds with satisfactory herbicidal activity could be synthesized. A reasonable combination of a fluorine moiety and other substituents on the benzene ring had a great influence on the herbicidal activity. Copyright Taylor & Francis Group, LLC.
- Chen, Ting,Shen, Ping,Li, Yanjun,He, Hongwu
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- An efficient route to chiral α- and β-hydroxyalkanephosphonates
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Enzymatic kinetic resolution of α- and β-hydroxyphosphonates in combination with ruthenium-catalyzed alcohol isomerization led to a successful dynamic kinetic resolution. A variety of racemic hydroxyphosphonates were efficiently transformed to the corresponding enantiomerically pure acetates (ee up to 99% and yield up to 87%).
- Pamies, Oscar,Baeckvall, Jan-E.
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- Enzymes in Organic Chemistry, Part 1: Enantioselective Hydrolysis of α-(Acyloxy)phosphonates by Esterolytic Enzymes
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α-Hydroxyphosphonates (+/-)-3 were prepared and transformed into esters (+/-)-5.Eight lipases as well as pig liver esterase were tested as catalysts for enantioselective hydrolyses of α-(acyloxy)phosphonates in a biphasic system.Two of them proved to be useful.The highest enantioselectivity was obtained with lipase F-AP 15 and α-(acetyloxy)phenylmethylphosphonates (+/-)-5a and (+/-)-5b as substrates.The (S)-enantiomers were exclusively hydrolyzed to give optically pure alcohols (S)-(-)-3a and (S)-(-)-3b.Lipases AP 6 and F-AP 15 were used to prepare phosphonates(S)-(-)-3b, (S)-(+)-3d and (S)-(-)-3e on a preparative scale with an enantiomeric excess of 81percent, 87percent, and 89percent, respectively.The absolute configurations of the α-hydroxyphosphonates were assigned by Horeau's method and 1H NMR spectroscopy of Mosher's derivatives.
- Li, Yong-Fu,Hammerschmidt, Friedrich
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- Synthesis and herbicidal activity of α-[(substituted phenoxybutyryloxy or valeryoxy)]alkylphosphonates and 2-(substituted phenoxybutyryloxy)alkyl-5,5-dimethyl-1,3,2-dioxaphosphinan-2-one containing fluorine
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Based on our previous work on the structural modification of the lead compound I, three series of novel fluorine-containing phosphonates derivatives (II, III and IV) were designed and synthesized. Their post-emergence herbicidal activities against some species of weeds were evaluated in a green house. The compounds II were synthesized by introducing of two methylene into the structure I. Compared with the commercial herbicidal clacyfos, compounds II showed moderate herbicidal activity with 60–85% inhibition effect against chingma abutilon (Abutilon theophrasti), common amaranth (Amaranthus retroflexus) and white eclipta (Eclipta prostrate) at a rate of 150 g ai/ha. The compounds III were designed by introducing open-chain phosphonates, which displayed notable herbicidal activity. Especially, the compounds III-1–III-4, III-6, III-8, III-11 and III-12 exhibited significant herbicidal activity (80–100%) comparing to the clacyfos against all tested broadleaf weeds, while compounds IV with five carbon atoms in the carboxylic acid chain were inactive against all of the tested weeds. Structure-activity relationship analyses indicated that the length of the carbon chain had a great effect on the herbicidal activity. Furthermore, a broad spectrum test confirmed that compounds III-4 and III-8 were comparable with glyphosate against all of the tested weeds at a rate of 75 g ai/ha.
- Wang, Wei,Zhou, Yuan,Peng, Hao,He, Hong-Wu,Lu, Xing-Tao
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- Synthesis and Herbicidal Activity of α-(Substituted Phenoxybutyryloxy or Valeryloxy)alkylphosphonates and 2-(Substituted Phenoxybutyryloxy)alkyl-5,5-dimethyl-1,3,2-dioxaphosphinan-2-one
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On the basis of our work on the modification of alkylphosphonates 1, a series of α-(substituted phenoxybutyryloxy or valeryloxy)alkylphosphonates (4-5) and 2-(substituted phenoxybutyryloxy)alkyl-5,5-dimethyl-1,3,2-dioxaphosphinan-2-one (6) were designed and synthesized. The bioassay results indicated that 14 of title compounds 4 exhibited significant postemergence herbicidal activity against velvetleaf, common amaranth, and false daisy at 150 g ai/ha. Compounds 5 were inactive against all tested weeds. Compounds 6 exhibited moderate to good inhibitory effect against the tested dicotyledonous weeds. Structure-activity relationship (SAR) analyses showed that the length of the carbon chain as linking bridge had a great effect on the herbicidal activity. Broad-spectrum tests of compounds 4-1, 4-2, 4-9, 4-30, and 4-36 were carried out at 75 g ai/ha. Especially, 4-1 exhibited 100% inhibition activity against the tested dicotyledonous weeds, which was higher than that of glyphosate.
- Wang, Wei,Zhang, Sha-Sha,Zhou, Yuan,Peng, Hao,He, Hong-Wu,Lu, Xing-Tao
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p. 6911 - 6915
(2016/10/03)
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- Potent inhibition of mandelate racemase by a fluorinated substrate-product analogue with a novel binding mode
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Mandelate racemase (MR) from Pseudomonas putida catalyzes the Mg 2+-dependent 1,1-proton transfer that interconverts the enantiomers of mandelate. Because trifluorolactate is also a substrate of MR, we anticipated that replacing the phenyl rings of the competitive, substrate-product analogue inhibitor benzilate (Ki = 0.7 mM) with trifluoromethyl groups might furnish an inhibitor. Surprisingly, the substrate-product analogue 3,3,3-trifluoro-2-hydroxy-2-(trifluoromethyl)propanoate (TFHTP) was a potent competitive inhibitor [Ki = 27 ± 4 μM; cf. Km = 1.2 mM for both (R)-mandelate and (R)-trifluorolactate]. To understand the origins of this high binding affinity, we determined the X-ray crystal structure of the MR-TFHTP complex to 1.68 A resolution. Rather than chelating the active site Mg2+ with its glycolate moiety, like other ground state analogues, TFHTP exhibited a novel binding mode with the two trifluoromethyl groups closely packed against the 20s loop and the carboxylate bridging the two active site Bronsted acid-base catalysts Lys 166 and His 297. Recognizing that positioning a carboxylate between the Bronsted acid-base catalysts could yield an inhibitor, we showed that tartronate was a competitive inhibitor of MR (Ki = 1.8 ± 0.1 mM). The X-ray crystal structure of the MR-tartronate complex (1.80 A resolution) revealed that the glycolate moiety of tartronate chelated the Mg2+ and that the carboxylate bridged Lys 166 and His 297. Models of tartronate in monomers A and B of the crystal structure mimicked the binding orientations of (S)-mandelate and that anticipated for (R)-mandelate, respectively. For the latter monomer, the 20s loop appeared to be disordered, as it also did in the X-ray structure of the MR triple mutant (C92S/C264S/K166C) complexed with benzilate, which was determined to 1.89 A resolution. These observations indicate that the 20s loop likely undergoes a significant conformational change upon binding (R)-mandelate. In general, our observations suggest that inhibitors of other enolase superfamily enzymes may be designed to capitalize on the recognition of the active site Bronsted acid-base catalysts as binding determinants.
- Nagar, Mitesh,Lietzan, Adam D.,St. Maurice, Martin,Bearne, Stephen L.
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p. 1169 - 1178
(2014/03/21)
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- Synthesis and biological activities of O, O-dialkyl 1-((4,6- Dichloropyrimidin-2-yl)carbamyloxy) alkylphosphonates
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(Equation present) A series of new 1-((4,6-dichloropyrimidin-2-yl) carbamyloxy) alkylphosphonates were designed and synthesized. The structures of all the title compounds were confirmed by IR, 1H-NMR, 31P-NMR and elemental analysis. The results of the bioassay showed that all of title compounds exhibited weak herbicidal activities against monocotyledons and dicotyledons; however, some of them showed potential plant growth regulatory activities. 2014 Copyright Taylor & Francis Group, LLC.
- Xu, Liang,You, Geyun,Peng, Hao,He, Hongwu
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p. 812 - 818
(2014/07/08)
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- Synthesis and herbicidal activities of sodium hydrogen 1-(substituted phenoxyacetoxy)alkylphosphonates
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A series of sodium hydrogen 1-(substituted phenoxyacetoxy) alkylphosphonates was designed and synthesized. The test for herbicidal activity indicated that most of the phosphonates (8) possessed excellent postemergence herbicidal activities against broadleaf weeds. Especially, 8f and 8g showed the best herbicidal activity against rape and amaranth with more than 95% inhibitory rate. Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.
- Long, Qingwu,Deng, Xiaoyan,Gao, Yujiao,Xie, Huayong,He, Hongwu,Peng, Hao
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p. 819 - 825
(2013/08/23)
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- Synthesis and herbicidal activities of 2-methylpropan-2-aminium methyl 1-(substituted phenoxyacetoxy) alkylphosphonates
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A series of 2-methylpropan-2-aminium methyl 1-(substituted phenoxyacetoxy) alkylphosphonates were selectively synthesized by reacting the corresponding dimethyl 1-(substitutedphenoxyacetoxy)alkylphosphonates with an excess of 2-methylpropan-2-amine. All the title compounds were identified by IR, 1H NMR, and 31P NMR, some of them were further analyzed by 19F NMR and 13C NMR. Their herbicidal activity was investigated and the results showed that most of the demethylated aminium salts exhibited notable herbicidal activities against Brassica napus L. and Echinochloa crusgalli. Supplementary materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfer, and Silicon and the Related Elements for the following free supplemental files: Additional text, figures and tables.
- Gao, Ling,Deng, Xiaoyan,Tan, Xiaosong,Long, Qingwu,Peng, Hao,He, Hongwu
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p. 989 - 994
(2013/09/02)
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- Synthesis and herbicidal activities of lithium or potassium hydrogen 1-(substituted phenoxyacetoxy)alkylphosphonates
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A series of lithium or potassium hydrogen 1-(substituted phenoxyacetoxy)alkylphosphonates were designed and synthesized. All the title compounds were identified by IR, 1H NMR, and 31P NMR, some of them were further analyzed by MS and elemental analyses. The test for herbicidal activity indicated that most of the phosphonates (8) possessed excellent postemergence herbicidal activities against broadleaf weeds. Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.
- Peng, Hao,Long, Qingwu,Deng, Xiaoyan,He, Hongwu
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p. 1868 - 1874
(2013/11/06)
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- Synthesis and herbicidal activity of O,O-dimethyl-(3-phenacryloyloxy) alkyl phosphonates
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In an attempt to discover novel compounds with high biological activity and low toxicity, a series of new O,O-dimethyl-(3-phenacryloyloxy) alkyl phosphonates 4a-m have been designed and synthesized by the reaction of 3-phenacryloyl chloride with α-hydroxyalkyl phosphonate. All new compounds were characterized by elemental analysis, IR, and 1H NMR spectroscopy as well as by mass spectrometry. The results of preliminary bioassay indicate that some of the target compounds have excellent inhibitory activities on Triticum aestivum (wheat) and Brassica napus L. (rape). Copyright Taylor and Francis Group, LLC.
- Wang, Tao,Huang, Hai Jin,Luo, Jin,Yu, Dan Hong
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p. 135 - 141
(2012/05/04)
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- Studies of O,O-Dimethyl α-(2,4-Dichlorophenoxyacetoxy) ethylphosphonate (HW02) as a new herbicide. 1. Synthesis and herbicidal activity of HW02 and analogues as novel inhibitors of pyruvate dehydrogenase complex
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On the basis of the previous work for optimization of O,O-diethyl α-(substituted phenoxyacetoxy)alkylphosphonates, further extensive syntheticmodifications were made to the substituents in alkylphosphonate and phenoxymoieties of the title compounds. New O,O-dimethyl α-(substituted phenoxyacetoxy)alkylphosphonates were synthesized as potential inhibitors of pyruvate dehydorogenase complex (PDHc). Their herbicidal activity and efficacy in vitro against PDHc were examined. Some of these compounds exhibited significant herbicidal activity and were demonstrated to be effective inhibitors of PDHc from three different plants. The structure-activity relationships of these compounds including previously reported analogous compoundswere studied by examining their herbicidal activities. Both inhibitory potency against PDHc and herbicidal activity of title compounds could be increased greatly by optimizing substituent groups of the title compounds. O,O-Dimethyl α-(2,4- dichlorophenoxyacetoxy)ethylphosphonate (I-5), which acted as a competitive inhibitor of PDHc with much higher inhibitory potency against PDHc from Pisum sativum and Phaseolus radiatus than from Oryza sativa, was found to be themost effective compound against broadleaf weeds and showed potential utility as herbicide.
- He, Hong-Wu,Yuan, Jun-Lin,Peng, Hao,Chen, Ting,Shen, Ping,Wan, Shu-Qing,Lee, Yanjun,Tan, Hong-Liang,He, Ya-Hui,He, Jun-Bo,Li, Yan
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p. 4801 - 4813
(2011/12/04)
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- Synthesis and biological activity of O,O-Dimethyl-2,6-Pyridinyl diformyloxy alkyl phosphonates
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In an attempt to discover novel compounds with high activity and low toxicity, a series of new O,O-dimethyl-2,6-pyridinyl diformyloxy alkyl phosphonates 4a-4p has been designed and synthesized by the reaction of 2,6-pyridinyl diformyloxy chloride with α-hydroxyalkyl phosphonate. The structures of all new compounds were characterized by elementary analysis, IR, 1H NMR, and MS spectroscopies. The results of a preliminary bioassay indicate that some of the target compounds have obviously promotive action for plant growth against the stalk of barnyard grass.
- Wang, Tao,Lei, Da You,Huang, Ying,Ao, Li Hua
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p. 2777 - 2785
(2010/04/03)
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- Synthesis and herbicidal activity of α-[2-(fluoro-substituted phenoxy)propionyloxy] alkyl phosphonates
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Eight of novel fluoro-substituted phosphonate derivatives were synthesized and the preliminary bioassay indicated that these compounds exhibited herbicidal activities. Copyright Taylor & Francis Group, LLC.
- Li, Yan-Jun,He, Hong-Wu
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p. 712 - 713
(2009/04/05)
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- 5-Fluorouracil derivatives containing α-hydroxy phosphonates
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In order to find high acitivity and low toxicity antitumor drug-lead compounds, 13 novel N1-(2-furanidyl)-N3-(O,O- dialkylphosphonyl aryl (alkyl)methoxy-carbonylmethyl)-5-fluorouracils were synthesized via phase-transferred catalytic reactions of chloroacetyloxyalkyl phosphonates 2 with N1-(2-furanidyl)-5-fluorouracil. The structures of the products were confirmed by 1H NMR, 31P NMR, IR, and MS spectra and elemental analyses. The results of preliminary bioassay showed that the new compounds possess some extent of inhibitory effect against HCT-8 and Bel-7402 cell lines and good fungicidal activities. Copyright Taylor & Francis Group, LLC.
- Shi, De-Qing,Li, Xiao-Ju,Wei, Jia
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p. 405 - 412
(2007/10/03)
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- Synthesis and herbicidal activity of O,O-dialkyl phenoxyacetoxyalkylphosphonates containing fluorine
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A series of substituted phenoxyacetoxyalkylphosphonates bearing fluorine were designed and synthesized. All the new compounds were identified by elemental analysis, IR, 1H NMR and MS and were tested for herbicidal activity in greenhouse at a rate of 1.5 kg/ha. The results of preliminary bioassay showed that fluorine moiety introduced to the core structure could help to improve the herbicidal activity, and compounds with a 3-trifluoromethyl in benzene ring exhibited higher inhibitory activity.
- Chen, Ting,Shen, Ping,Li, Yanjun,He, Hongwu
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p. 291 - 295
(2007/10/03)
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- Synthesis and dealkylation of 1 -(dichloro-phenoxyacetoxy) alkyl phosphonates
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Using the silylation procedure with chlorotrimethylsilane/sodium iodide followed by alcoholysis, 1-(dichlorophenoxy acetoxy)alkyl phosphonic acid dimethyl esters can be transformed into the parent phosphonic acids without influence on carboxylate ester group.
- He, Hongwu,Liu, Xufeng,Hu, Liming,Wang, Siquan,Liu, Zhaojie
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p. 633 - 636
(2007/10/03)
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