- Synthesis and chiral purification of 14C-labeled novel neonicotinoids, paichongding
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Paichongding, a novel neonicotinoids pesticide with excellent insecticidal activity against imidacloprid-resistant brown planthopper, has been sold in the Chinese market as new pesticide. [14C]Paichongding was proposed as a tracer to support the further study to elucidate the metabolism of the commercialized pesticide. This paper describes an efficient synthesis of [ 14C]paichongding in five radiochemical steps from [ 14C]nitromethane (1). Then the four diastereoisomers (a, b, c, and d) were separated by preparative chiral HPLC and characterized by HPLC and HPLC-LSC. This methodology could be utilized in the syntheses of other 14C-labeled nitromethylene neonicotinoids derivatives.
- Li, Chao,Xu, Xiao-Yong,Li, Ju-Ying,Ye, Qing-Fu,Li, Zhong
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Read Online
- Novel nicotinoid structures for covalent modification of wood: An environmentally friendly way for its protection against insects
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Timber is constantly exposed to environmental influences under outdoor conditions which limits its lifetime and usability. In order to counteract the damaging processes caused by insects, we have developed a novel and more environmentally friendly method to protect wood materials via covalent modification by organic insecticides. Starting with an important class of synthetic insecticides which are derived from the natural insecticide nicotine, various new carboxylic acid derivatives of imidacloprid were made accessible. These activated neonicotinoids were utilized for the chemical modification of wood hydroxy groups. In contrast to conventional wood preservation methods in which biocides are only physically bound to the surface for a limited time, the covalent fixation of the preservative guarantees a permanent effect against wood pests, demonstrated in standardized biological tests. Additionally, the environmental interaction caused by non-bound neonicotinoids is significantly reduced, since both, a smaller application rate is required and leaching of the active ingredient is prevented. By minimizing the pest infestation, the lifetime of the material increases while preserving the natural appearance of the material.
- Acker, Sophie,Kaufmann, Dieter E.,Namyslo, Jan C.,Plarre, Rudy,S?ftje, Martin
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Read Online
- Synthesis, insecticidal activity, and QSAR of novel nitromethylene neonicotinoids with tetrahydropyridine fixed cis configuration and exo-ring ether modification
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To keep the nitro group in the cis position, a series of nitromethylene neonicotinoids containing a tetrahydropyridine ring with exo-ring ether modifications were designed and synthesized. All of the compounds were characterized and confirmed by 1/s
- Tian, Zhongzhen,Shao, Xusheng,Li, Zhong,Qian, Xuhong,Huang, Qingchun
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Read Online
- Synthetic method of imidacloprid
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The invention provides a synthetic method of imidacloprid, which comprises the following steps: by using 2-chloro-5-chloromethylpyridine, ethylenediamine and guanidine nitrate as raw materials, carrying out aminating, cyclizing, dehydrating and the like to synthesize imidacloprid. According to the method, the safety problem caused by generation of unstable nitroguanidine in the reaction process isavoided, the production process is high in safety, the product purity is good, the yield is high, and industrialization is easy to realize.
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Paragraph 0017-0018; 0021-0023
(2020/03/02)
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- Method for synthesizing imidacloprid at high yield
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The invention provides a method for synthesizing imidacloprid at a high yield. 2-chloro-5-chloromethylpyridine, ethylenediamine and cyanogen halide, which are used as raw materials, are aminated, cyclized and nitrified to synthesize the imidacloprid. The method has the advantages of high safety in the production process, good purity and high yield of the product, and easiness in industrializationrealization.
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Paragraph 0018; 0019; 0022-0024
(2020/02/20)
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- One-pot process for preparing 2 - chloro -5 - ((2 - (nitro-methylene) imidazoline -1 - yl) methyl) pyridine (by machine translation)
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The present invention discloses a one-pot process for preparing 2 - chloro - 5 - ((2 - (nitro-methylene) imidazoline - 1 - yl) methyl) pyridine method, in order to 2 - chloro - 5 - chloromethyl pyridine as the starting material, directly with ethylenediamine to generate condensation reaction, the system results in the chlorine [...] ethylenediamine; chloro [...] ethylene diamine and 1, 1, 1 - trichloro - 2 - nitroethane in the presence of acid, cyclization to obtain the target product. The method avoid the use of expensive reagent such as phase transfer catalyst, the use of ethylenediamine is easy to be recycled, this craft is friendly to the environment; the method of the reaction raw material, mild reaction conditions, the reaction step is simple, easy to operate, the total yield is relatively high, in particular, the intermediate does not need of separation and purification, therefore the equipment utilization is high; according to the method the production of target product purity up to 98% or more. In short, the one-pot process for preparing 2 - chloro - 5 - ((2 - (nitro-methylene) imidazoline - 1 - yl) methyl) pyridine method is very suitable for large-scale industrial production. (by machine translation)
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Page/Page column 6-8
(2019/03/06)
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- Synthesis and insecticidal evaluation of tetrahydroimidazo[1,2-a]pyridin-5(1H)-one derivatives
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A series of novel tetrahydroimidazo[1,2-a]pyridine-5(1H)-one derivatives containing a electronegative pharmacophore (=CNO2) were synthesized via practical aza-ene reaction and characterized by 1H NMR, 13C NMR, 19F NMR and HRMS. Preliminary bioassays showed that some of the target compounds exhibited good insecticidal activity against brown planthopper (Nilaparvata lugens) and cowpea aphids (Aphis craccivora) at 500 mg L-1. Among them, compound 11h was active against brown planthopper at 100 mg L-1. The insecticidal activities varied significantly depending on the types and patterns of the substituents, which provided guidance for further investigation on structure modifications.
- Liu, Xuan-Qi,Liu, Ya-Qin,Shao, Xu-Sheng,Xu, Zhi-Ping,Xu, Xiao-Yong,Li, Zhong
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- Synthetic method of 2-chlorine-5-((2-(nitromethylene)imidazoline-1-yl)methyl)pyridine
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The invention provides a synthetic method of 2-chlorine-5-((2-(nitromethylene)imidazoline-1-yl)methyl)pyridine. The method comprises the steps of taking 2-chlorine-5-nitrapyrin as a starting material, enabling the starting material to be subjected to a substitution reaction with ethylenediamine in the presence of a phase transfer catalyst and alkali to generate chloropyridine ethylenediamine, adding 1,1-dimethoxy-2-nitroethylene into the same reaction vessel, performing a reflux reaction, performing after-treatment to prepare a target product, i.e., the 2-chlorine-5-((2-(nitromethylene)imidazoline-1-yl)methyl)pyridine is synthesized by a one-pot method. By adopting the synthetic method, the target product of high content can be obtained, an intermediate of the first-step reaction does not need separation and purification, the two-step synthesis unit operation is completed in the same reaction vessel, the equipment utilization rate is high, the after-treatment is simple in process, the operation conditions are mild, thus a prospect of industrial production is achieved.
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Paragraph 0040; 0041
(2016/10/09)
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- Oxidation strategy for the synthesis of regioisomeric spiroisobenzofuranopyrroles: Facile entries to spiro[isobenzofuran-1,2′-pyrrole] and Spiro[isobenzofuran-1,3′-pyrrole] derivatives
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Two practical and efficient approaches have been developed to synthesize two kinds of racemic spiroisobenzofuranopyrrole analogues as regioisomers. In the presence of sodium periodate, cis-indeno[1,2-b]pyrrol-4(1H)-ones were converted into spiro[isobenzofuran-1,2′-pyrrole] derivatives by a two-step process. In addition, oxidative reactions promoted by lead tetraacetate were demonstrated using cis-indeno[2,1-b]pyrrol-8(1H)-ones as substrates, affording spiro[isobenzofuran-1,3′-pyrrole] derivatives. The remarkable features of two approaches included mild and convenient reaction conditions, a broad substrate scope, and moderate to excellent yields. Possible mechanisms were proposed based on the comparison of the intermediates and products.
- Fan, Yefeng,Liu, Song,Chen, Nanyang,Shao, Xusheng,Xu, Xiaoyong,Li, Zhong
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supporting information
p. 393 - 403
(2015/02/19)
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- Synthesis and insecticidal activities of tetrahydroimidazo[1,2-a] pyridinones: Further exploration on cis-neonicotinoids
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cis-Neonicotinoid, in which the nitro and cyano pharmacophore point to the same position relative to the heteroaromatic moiety, is a further extension of the neonicotinoid library. While seeking new cis-neonicotinoid candidates, a series of tetrahydroimidazo[1,2-a]pyridinone derivatives were synthesized by reactions of nitromethylene analogs with itaconic anhydride. All the compounds were confirmed by 1H NMR, 13C NMR, and high-resolution mass spectroscopy. The target compounds had excellent insecticidal activities against cowpea aphids (Aphis craccivora) and brown planthopper (Nilaparvata lugens). Against armyworm, most of the compounds showed moderate activities. Interestingly, compound 12p was active against Tetranychus cinnabarinus. The synthesized compounds displayed good insecticidal activities against different insect species, which might provide useful guidance for further design of cis-neonicotinoid candidates. [Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications for the following free supplemental resource(s): Full experimental and spectral details.]
- Ren, Liping,Lou, Yanpeng,Chen, Nanyang,Xia, Shanshan,Shao, Xusheng,Xu, Xiaoyong,Li, Zhong
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p. 858 - 867
(2014/03/21)
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- PEST CONTROL AGENT
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Specific amine derivatives have been found to possess excellent activities as pest control agents.
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Paragraph 0458
(2013/06/27)
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- Nitrogen-containing hetercyclic derivate having 2-imino group and pest control agent including the same
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Provided is a nitrogen-containing heterocyclic derivative having a 2-imino group, which is represented by the following Formula (I). [in the formula, Ar represents a phenyl group which may be substituted, a 5- to 6-membered heterocycle which may be substituted, or a 4- to 10-membered heterocycloalkyl group, A represents a heterocycle having a 5- to 10-membered unsaturated bond including one or more nitrogen atoms, and has an imino group substituted with an R group at a position adj acent to the nitrogen atom present on the cycle, Y represents a hydrogen atom, a halogen atom, a hydroxyl group, a C1 to C6 alkyl group which may be substituted with a halogen atom, a C1 to C6 alkyloxy group which may be substituted with a halogen atom, a cyano group, or a nitro group, and R represents any one of groups represented by the following Formulae (a) to (e), (y) or (z).]
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Paragraph 0301
(2013/09/12)
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- Design and synthesis of heterocyclic enamine derivatives based on skeleton of neonicotinoids
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Novel heterocyclic enamine derivatives based on skeleton of neonicotinoids were designed and prepar ed by the substitution reaction between heterocyclic enamines with intermediates of neonicotinoids, which provides readily accessible neonicotinoid analogs
- Liu, Chuanxiang,Yi, Fengping,Zou, Jianzhong
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p. 113 - 116
(2013/01/16)
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- Synthesis and insecticidal activities of novel neonicotinoid analogs bearing an amide moiety
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Figure represented. A series of novel neonicotinoid analogs containing an amide moiety were synthesized, characterized, and subsequently evaluated for their insecticidal activity. According to the preliminary bioassay, the compounds 6c, 6e, 6f, 6j, 6n, and 6r exhibited > 50% activity against Nilaparvata lugens at 100 mg/L. Amongst the active compounds, 6f and 6r revealed insecticidal activities similar to that displayed by standard buprofezin. J. Heterocyclic Chem., (2011)
- Wu, Jian,Yang, Song,Song, Bao-An,Bhadury, Pinaki S.,Hu, De-Yu,Zeng, Song,Xie, Hua-Peng
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scheme or table
p. 901 - 906
(2011/10/02)
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- Designing tetrahydroimidazo[1,2- a ]pyridine derivatives via catalyst-free Aza-Diels-Alder Reaction (ADAR) and their insecticidal evaluation
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A series of tetrahydroimidazo[1,2-a]pyridine derivatives were synthesized by the reaction of 2-vinyl-4,5-dihydroimidazole derivatives with substituted benzylidenemalononitrile via a catalyst-free aza-Diels-Alder reaction. Insecticidal activities of target
- Zhang, Wenwen,Chen, Yinbo,Chen, Weidong,Liu, Zewen,Li, Zhong
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scheme or table
p. 6296 - 6299
(2011/08/05)
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- Design, synthesis, and bioactivity of cyanonitrovinyl neonicotinoids as potential insecticides
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A series of cyanonitrovinyl neonicotinoids were designed and synthesized via five steps in about 35% overall yields. All compounds were structurally characterized by 1H nuclear magnetic resonance (NMR), 13C NMR, infrared (IR), and high-resolution mass spectrometry (HRMS), and single-crystal X-ray diffraction analysis of 2-[1-[(6-chloropyridin-3-yl)methyl] -2-imidazolidinylidene]-2-nitroacetonitrile revealed that the double bond is (E)-configured. The preliminary agriculture bioassay indicated that one compound exhibited moderate insecticidal activity against pea aphid. Springer-Verlag 2010.
- Wang, Kewei,Qian, Xuhong,Cui, Jingnan
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scheme or table
p. 1117 - 1122
(2012/06/18)
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- One step from nitro to oxime: a convenient preparation of unsaturated oximes by the reduction of the corresponding vinylnitro compounds
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A series of novel unsaturated oximes were conveniently prepared from the corresponding vinylnitro compounds by reduction with SnCl2·2H2O. The structures of the oximes were characterized by 1H and 13C NMR, IR and HRMS, and X-ray crystallography analysis of 1-(6-chloro-pyridin-3-ylmethyl)-4,5-dihydro-1H-imidazole-2-carbaldehyde oxime 2a reveals that, the hydroxyl group is arranged in a trans configuration. Some evidences from a brief investigation suggest that these oximes seem to be formed by reduction of the aci form of nitro aliphatic compounds.
- Wang, Kewei,Qian, Xuhong,Cui, Jingnan
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experimental part
p. 10377 - 10382
(2010/02/27)
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- Design, synthesis, and evaluation of unsymmetrical difluoro-boron complexes with imidazoline as potential fungicides
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A series of unsymmetrical difluoroboron (BF2) complexes with pyridine and imidazoline were synthesized by reaction of new chelating ligands (arylmethyl-imidazolidinylidene)-pyridin-2-yl-amine with boron trifluoride diethyl etherate. All the ligands and BF2 complexes were structurally characterized by IR, HRMS, 1H, 13C, 11B, and 19F NMR,indicating the bidentate complexation of imidazoline nitrogen and the pyridine nitrogen to the boron center. Evaluation of agricultural bioactivities showed that some of the BF2 complexes exhibited moderate fungicidal activities, and most of the BF2 complexes exhibited higher activities than the none-BF2 complexed substrates.
- Wang, Kewei,Cui, Jingnan,Xie, Lijuan,Qian, Xuhong
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experimental part
p. 418 - 424
(2010/08/05)
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- PREPARATION METHOD AND USE OF COMPOUNDS HAVING HIGH INSECTICIDAL ACTIVITIES
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The present invention discloses a kind of nitromethylene derivatives as well as their preparation method and their uses. The insecticidal activity tests show that the nitromethylene derivatives of the present invention not only show high insecticidal activities against insects with piercing-sucking type or scratching type mouthparts, such as aphid, leafhopper, plant hopper, thrips and white fly and their resistant strains, but also show high insecticidal activities against Lissorhoptrus oryzophilus, carmine spider mite, and they can also be used to prevent sanitary pest, and white ant.
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(2009/05/28)
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- Design, synthesis, and insecticidal activities of novel analogues of neonicotinoids: Replacement of nitromethylene with nitroconjugated system
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To replace nitromethylene pharmacophore with a nitroconjugated system, a series of novel neonicotinoid analogues bearing five-membered aromatic heterocycles were designed and synthesized. Bioassays indicated that some of the synthesized compounds exhibited higher insecticidal activities than imidacloprid against cowpea aphids (Aphis craccivora), armyworm (Pseudaletia separate Walker), Nephotettix bipunctatus (Fabricius), and small brown rice planthopper (Laodelphasx striatellus). Exhilaratingly, the activity levels of derivatives 13a and 13j rivaled that of imidacloprid.
- Shao, Xusheng,Li, Zhong,Qian, Xuhong,Xu, Xiaoyong
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scheme or table
p. 951 - 957
(2010/04/05)
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- cis-Nitromethylene neonicotinoids as new nicotinic family: Synthesis, structural diversity, and insecticidal evaluation of hexahydroimidazo[1,2-α]pyridine
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A series of neonicotinoids analogues of hexahydroimidazo[1,2-α]pyridine were modified at 5-, 6-, and 7-positions, and their insecticidal activities were evaluated. Introducing a methyl or ethyl at 7-position increased the insecticidal activities, while ot
- Shao, Xusheng,Zhang, Wenwen,Peng, Yanqing,Li, Zhong,Tian, Zhongzhen,Qian, Xuhong
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scheme or table
p. 6513 - 6516
(2009/09/30)
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- PREPARATION METHOD AND USE OF COMPOUNDS HAVING HIGH BIOCIDAL ACTIVITIES
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The present invention discloses a kind of nitromethylene derivatives as well as their preparation method and their uses. The insecticidal activity tests show that the nitromethylene derivatives of the present invention not only show high insecticidal activities against insects with piercing-sucking type or scratching type mouthparts, such as aphid, leafhoppei, plant hopper, thrips and white fly and their resistant strains, but also show high insecticidal activities against Lissorhoptrus oryzophilus, carmine spider mite, and they can also be used to prevent sanitary pest, and white ant.
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(2009/01/20)
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- NITROMETHYLENE DERIVATIVES AND THEIR USE
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The present invention discloses nitromethylene derivatives and the uses thereof. These derivatives are obtained by adding ring structure onto the known nitromethylene compounds, by which both their stability for light and their liposolubility are increased. Furthermore, by using the substituents linked to ether bond, the steric orientation of the nitro group and the liposolubility of the compounds are controlled. The insecticidal activity tests show that the compounds and their derivatives of the invention display high efficiency on killing various destructive insects with piercing-sucking type or scratching type mouthparts, such as aphid, leafhopper, plant hpooer, thrips and white fly.
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Page/Page column 6
(2008/06/13)
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- [6-chloro-3-pyridylmethyl-3H]neonicotinoids as high-affinity radioligands for the nicotinic acetylcholine receptor: Preparation using NaB3H4 and LiB3H4
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NaB3H4, and LiB3H4 at 78% and 97% isotopic enrichments, respectively, were used in the synthesis of 3H-labeled 1-(6-chloro-3-pyridyl)-methyl-2-nitromethyleneimidazolidine (CH-IMI) and N'-[(6-chloro-3-pyridyl)methyl]-N''-cyano-N'-methylacetamide (acetamiprid) (two very potent insecticides) and of 1-(6-chloro-3-pyridyl)methyl-2-iminoimidazolidine (desnitro-IMI) (a metabolite of the commercial insecticide imidacloprid). 6-Chloronicotinoyl chloride was treated with either NaB3H4 in methanol or LiB3H4 in tetrahydrofuran and the resulting alcohol transformed to 2-chloro-5-chloromethylpyridine, which was then coupled to N-cyano-N'-methylacetamidine to give [3H]acetamiprid (45 Ci/mmol). 2-Chloro-5-chloro [3H]methylpyridine was also reacted with ethylenediamine and the product was either refluxed in absolute ethanol with 1,1-bis(methylthio)-2-nitroethylene to provide [3H]CH-IMI or reacted in toluene with a solution of cyanogen bromide to produce [3H]desnitro-IMI (each 55 Ci/mmol).
- Latli, Bachir,Than, Chit,Morimoto, Hiromi,Williams, Philip G.,Casida, John E.
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p. 971 - 978
(2007/10/03)
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- Process for preparing a 2-chloro-5-aminomethyl-pyridine
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A 2-Chloro-5-aminomethylpyridine is prepared in one step by reacting 2-chloro-5-trichloromethylpyridine with an amine and hydrogen in the presence of a hydrogenation catalyst.
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- Process for the preparation of N-(2-chloro-pyridin-5-yl-methyl)-ethylenediamine
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The present invention relates to a new process for the preparation of N-(2-chloro-pyridin-5-yl-methyl)-ethylene-diamine of the formula (I) STR1 in a technically simple manner in high yield and in very good quality. The new process is characterized in that N-(2-chloro-pyridin-5-yl-methyl)-aminoacetonitrile of the formula (II) STR2 is reacted with hydrogen in the presence of ammonia and in the presence of a catalyst and also in the presence of a diluent, at temperatures between 0° C. and 100° C. and a pressure between 1 bar and 100 bar. N-(2-Chloro-pyridin-5-yl-methyl)-ethylenediamine (I) can be used as an intermediate for the preparation of insecticides.
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- 1-pyridylmethyl-2-nitromethylene-1,3-diazacycloalkane insecticides
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Novel insecticides of the formula STR1 in which R is a hydrogen atom or a lower alkyl group, X is a halogen atom, a lower alkyl group, a lower alkoxy group, a lower alkylthio-group, a lower alkylsulfinyl group, a lower alkylsulfonyl group, a lower alkenyl group, a lower alkynyl group, an aryl group, an aryloxy group which may be optionally substituted by a halogen atom, an arylthio group which may be optionally substituted by a halogen atom, or an aralkyl group, l is 1, 2, 3 or 4, m is 2, 3, or 4, and n is 0, 1, 2 or 3, or salts thereof. Intermediates therefor of the formula STR2 are also new.
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