- Silver-Catalyzed Olefination of Acetals and Ketals with Diazoesters to β-Alkoxyacrylates
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The first silver-catalyzed reaction of acetals or ketals with diazoesters leading to trisubstituted or tetrasubstituted β-alkoxyacrylates is now reported. A broad range of acetals and ketals bearing different substituents is compatible with this protocol and thus provides an attractive approach for the synthesis of complex β-alkoxyacrylates. The power of this method was further demonstrated by the successful synthesis of picoxystrobin, which is one of the most popular agricultural fungicides commercialized by Dupont.
- Li, Jiawen,Qian, Bo,Huang, Hanmin
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supporting information
p. 7090 - 7094
(2018/11/23)
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- Method for preparing alkoxy acrylate
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The invention discloses a method for preparing an alkoxy acrylate. The method comprises that diazo ester and substituted acetal or ketal as raw materials undergo an alkenylation reaction in the presence of Lewis acid as a catalyst at 50-120 DEG C for 1-24h, then the solvent is drained through pumping and the product is subjected to column chromatography separation so that the alkoxy acrylate compound is obtained. The reaction raw materials and the catalyst are easily available and cheap, the synthesis process is simple, the synthesis cost is greatly reduced, the reaction conditions are mild, the yield is high, the industrialization is easy, the reaction raw materials and the catalyst are clean and non-toxic, and the environmental pollution is small.
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Paragraph 0048
(2018/11/27)
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- Synthesis and evaluation of essential oil-derived β-methoxyacrylate derivatives as high potential fungicides
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Essential oils (EOs) are plant-derived aroma compounds with a wide range of biological activity, but their actions are slow, and they are typically unstable to light or heat, difficult to extract and so on. To find highly potential fungicides derived from natural EOs, a series of essential oil-based β-methoxyacrylate derivatives have been designed and synthesized. The target compounds have been screened for their potential fungicidal activity against eleven species of plant pathogen fungi, including Alternaria alternata, Phomopsis adianticola, Pestalotiopsis theae, Sclerotinia sclerotiorum, etc. Compared with intermediates I, the parent essential oils and azoxystrobin, almost all of essential oil-based β-methoxyacrylate derivatives exhibited significantly better fungicidal activity. Further investigation revealed that some compounds showed remarkable inhibitory activities against Pestalotiopsis theae, Phomopsis adianticola, Sclerotinia sclerotiorum and Magnapothe grisea at different concentrations in contrast to the commercial product azoxystrobin. Compound II-8 exhibited particularly significant fungicidal activity.
- Su, Haihuan,Wang, Wenda,Bao, Longzhu,Wang, Shuangshuang,Cao, Xiufang
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- Synthesis and antifungal potential of 1,2,3-triazole and 1,2,4-triazole thiol substituted strobilurin derivatives
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β-Methoxyacrylate group is an important pharmacophore of commercially used strobilurin fungicides. In the present study, a total of seventeen 1,2,4-triazole thiols 8a-h and 1,2,3-triazole substituted 10a-i strobilurin derivatives have been synthesized. 1,2,4-Triazole thiol substituted strobilurin derivatives 8a-h have been found to inhibit the growth of plant pathogens such as Fusarium oxysporum, Magnaporthe grisea, Drechslera oryzae and human pathogens Aspergillus fumigatus and different strains of Cryptococcus neoformans, with MIC in the range of 16-256 μg/mL. In case of Candida albicans tested strain, the MIC is > 256 μg/mL. p-Chlorophenyl substituted 1,2,4-triazole thiol strobiulrin derivative 8e is the most potent inhibitor with MIC of 16-64 μg/mL against most of the tested pathogens. Antifungal action of the compounds is due to inhibition of mitochondrial respiration. In the resazurin reduction assay, EC50 for inhibition of RZ reduction in D. oryzae by azoxystrobin and 8e are 3.42±0.03 μg/mL and 3.63±0.21 μg/mL, respectively; while in case of C. neoformans, EC50 of azoxystrobin and 8e are between 0.65-0.85 μg/mL. In a non-pathogenic model Benjaminiella poitrasii, though the MIC for all the synthesized compounds 8a-h and 10a-i are > 256 μg/ml, yeast to hypha transition is inhibited in the range of 21-75% at 4 μg/mL concentration while EC50 for inhibition of RZ reduction by azoxystrobin and 8e are 31.5±0.4 μg/mL and 17.95 ± 0.7 μg/mL, respectively. The 50% germ tube formation inhibition in case of C. albicans is observed at 108.49 μg/mL. 1,2,4-Triazole thiol substituted strobilurin derivatives hold promise for the control of pathogenic fungi in agriculture and health care.
- Chaudhary, Preeti M.,Tupe, Santosh G.,Jorwekar, Shweta U.,Sant, Duhita G.,Deshpande, Sunita R.,Maybhate, Shailaja P.,Likhite, Anjali P.,Deshpande, Mukund V.
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p. 908 - 917
(2015/08/18)
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- Synthesis and bioactivity of novel strobilurin derivatives containing the pyrrolidine-2,4-dione moiety
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(E)-Methyl-2-(2-(bromomethyl)phenyl)-3-methoxyacrylate was reacted with substituted 1-acetylpyrrolidine-2,4-diones and 3-(1-(hydroxylamino)ethylidene) pyrrolidine-2,4-diones respectively to synthesize two series of β-methoxyacrylate derivatives containing
- Lu, Gui-Hua,Chu, Hai-Bin,Chen, Min,Yang, Chun-Long
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- Synthesis and biological activity of novel phenyltriazolinone derivatives
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Phenyltriazolinones are one of the most important classes of herbicides targeting the protoporphyrinogen oxidase enzyme. A series of triazolinone derivatives containing a strobilurin pharmacophore were designed and synthesized with the aim of discovering new phenyltriazolinone analogues with high activity. The herbicidal activity of the synthesized compounds was assayed and some of the test compounds displayed moderate herbicidal activity at 150 g ai/ha.
- Wu, Qiongyou,Wang, Guodong,Huang, Shaowei,Lin, Long,Yang, Guangfu
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p. 9024 - 9034
(2011/03/20)
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- Synthesis and fungicidal evaluation of novel chalcone-based strobilurin analogues
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Strobilurin derivatives have become one of the most important classes of agricultural fungicide due to a novel action mode, wide fungicidal spectrum, lower toxicity toward mammalian cells, and environmentally benign characteristics. To discover new strobilurin analogues with high activity against resistant pathogens, a series of new chalcone-based strobilurin derivatives are designed and synthesized by integrating a chalcone scaffold with a strobilurin pharmacophore. The preliminary bioassay showed that some of the chalcone analogues exhibited good in vivo fungicidal activities against Pseudoperoniospora cubensis and Sphaerotheca fuliginea at the dosage of 200 μg mL-1. Two compounds, (£)-methyl 2-[2-({3-[(£)-3-(2- chlorophenyl)acryloyl]phenoxy}methyl)phenyl]-3-meth-oxyacrylate (1e) and (E)-methyl 2-[2-({3-[(E)-3-(3-bromophenyl)acryloyl]phenoxy}methyl)phenyl]-3- methoxyacrylate (11), were found to display higher fungicidal activities against P. cubensis (EC90 = 118.52 μg ml-1 for 1e and EC 90 = 113.64 μg mL-1 for 11) than Kresoxim-methyl (EC90 = 154.92 μg mL-1) and were identified as the most promising candidates for further study. The present work demonstrated that strobilurin analogues containing chalcone as a side chain could be used as a lead structure for further developing novel fungicides. To our knowledge, this is the first report about the syntheses and fungicidal activities of chalcone-based strobilurin derivatives.
- Zhao, Pei-Liang,Liu, Chang-Ling,Huang, Wei,Wang, Ya-Zhou,Yang, Guang-Fu
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p. 5697 - 5700
(2008/03/14)
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- Fungicidal compounds having a fluorovinyl-or fluoropropenyl-oxyphenyloxime moiety and process for the preparation thereof
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A fungicidal compound of formula (I) having a fluorovinye- or fluoropropenyl-oxyphenyloxime moiety and stereoisomers thereof are useful for protecting crops from fungal diseases: wherein, X is CH or N; Y is O or NH; R1is hydrogen, C1-4alkyl, or halogen-substituted C1-4alkyl, R2is a phenyl group optionally carrying one or more substituents selected from the group consisting of C1-4alkyl, C1-4alkoxy, methylenedioxy and halogen; or a naphthyl group; and R3is hydrogen or CF3.
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- Fungicidial compounds having a fluorovinyloxphyenyl moiety and process for the preparation thereof
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A fungicidal compound of formula (I) having a fluorovinyloxyphenyl moiety and stereoisomers thereof are useful for protecting crops from fungal diseases: wherein: X is CH or N; Y is O or S; Z is O or NH; R1is hydrogen or CF3; and R2is hydrogen, a C1-10alkyl, naphthyl, thiophenyl or a phenyl group optionally carrying one or more substituents selected from the group consisting of C1-6alkyl, halogen-substituted C1-6alkyl, C1-6alkoxy, phenoxy, halogen, and methylenedioxy radicals.
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- PROCESSES FOR PRODUCING ACRYLIC ACID DERIVATIVE
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Processes for producing a compound (1) represented by formula (1), which includes an acrylic acid derivative and is useful as an agricultural chemical or medicine. One of the processes comprises the step of formylating a compound (3) (step (1)) and the step of converting the OH of the resultant compound (2) into OR" (step (2)). The step (1) comprises reacting a formic or orthoformic ester in the presence of a Lewis acid and a base. The step (2) comprises [1] reacting the compound (2) with R" OH or with R" OH and CH(OR")3under acidic conditions or [2] using a phase-transfer catalyst in a two-phase system and regulating the base and the concentration thereof to stereoselectively synthesize the target compound. In another process, the compound (1) is efficiently produced without isolating the compound (2). In still another process, the compound (1) is directly produced without via the compound (2).
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- Chemical process
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Process for preparing the (E)-isomer of a compound (II) by contacting the (E) or (Z) isomer of the 2-methylphenyl precursor, or a mixture of both, with bromine in an organic solvent, in the presence of a polymeric base and light. STR1
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- Acrylate fungicides
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Compounds of formula I STR1 wherein X is oxygen or sulphur, W is CH or N, m is 0 or 1, and either a) n is 1 and Q is a non-aromatic heterocyclic ring of 3 to 10 ring atoms, containing one to three hetero atoms selected from oxygen, sulphur and nitrogen, which may be substituted and may be fused to another ring, with the proviso a) that if Q is thiazol-2-in-2-yl, it is substituted but not by methylene, and b) Q is not a six membered ring containing only two nitrogen atoms, or b) n is 0 or 1 and STR2 where R1 is alkyl, alkoxy or alkylthio, and R2 is heteroaryl, non aromatic heterocyclyl, optionally substituted cycloalkyl or optionally substituted alkyl containing at least 5 carbon atoms, phenyl substituted by one or more groups selected from halogen, optionally substituted alkyl, alkoxy, haloalkoxy, aryloxy, alkylthio and alkoxycarbonyl, and when R1 is alkyl or alkoxy, or, when W is nitrogen, R2 can also be unsubstituted phenyl, have pesticidal especially fungicidal activity.
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- Acrylate fungicides
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The invention provides compounds of formula I STR1 wherein W, D, R1, R2, R3, x, m, n and p are as defined in the description. The compound have valuable pesticidal activity especially against fungi, insects, nematodes, aca
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- Process for preparation of thiazolylalkoxy acrylates
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A process for the preparation of a compound of the formula STR1 wherein R1 and R2 are individually selected from the group consisting of hydrogen, halogen, --CF3, alkyl, alkoxy and alkylthio of 1 to 8 carbon atoms, alkenyl and alkynyl of 2 to 8 carbon atoms, --SO2 alk and alk is alkyl of 1 to 8 carbon atoms, optionally substituted aryl, aryloxy and arylthio of 6 to 18 carbon atoms and optionally substituted heteroaryl, heteroaryloxy and heterocyclic of 5 to 6 ring members, R3 is selected from the group consisting of alkyl of 1 to 8 carbon atoms, alkenyl and alkynyl of 2 to 8 carbon atoms, aryl of 6 to 18 carbon atoms and alkoxyalkoxyalkyl of 3 to 14 carbon atoms, X is selected from the group consisting of --O--, --S-- and --NR4 --, R4 is selected from the group consisting of hydrogen, alkyl, alkenyl and alkynyl of up to 8 carbon atoms, --SO2 alkyl, --SO2 alkenyl and --SO2 alkynyl of up to 8 carbon atoms and optionally substituted aryl and --SO2 aryl of 6 to 18 carbon atoms, the double bond between the heterocycle of 5 member ring and the aromatic nucleus is of E and/or Z geometry comprising reacting a halide of the formula STR2 wherein R3 is as defined above and Hal is hydrogen with a compound of the formula STR3 wherein X, R1 and R2 have the above definitions in the presence of a base to obtain the corresponding product of formula I in the form of a mixture of isomers and optionally separating the isomers and novel intermediates of formula II.
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- Fungicides
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Fungicidal compounds of the formula (I): STR1 and stereoisomers thereof, wherein R1 is optionally substituted aryl or optionally substituted heteroaryl; Y is oxygen, sulphur or NR4 ; R2, R3 and R4, which may be the same or different, are hydrogen, C1-4 alkyl or C2-4 alkenyl; X is halogen, C1-4 alkyl, C2-4 alkenyl, C1-4 alkoxy, nitro or cyano; and n is 0 or an integer of 1 to 4; provided that when Y is oxygen, n is O and R1 is unsubstituted phenyl at least one of R2 and R3 is other than hydrogen or methyl.
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