- Synthesis and Herbicidal Activity of (Z)-Ethoxyethyl 2-Cyano-3-(2-methylthio-5-pyridylmethylamino)acrylates
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2-Methylthio-5-pyridinemethylene amine was prepared from 2-chloro-5-methylpyridine. Ethoxyethyl 2-cyano-3,3-dimethylthioacrylate was prepared from ethoxyethyl cyanoacetate, carbon disulfide, and dimethyl sulfate in 86.2% yield. Its reaction with 2-methylthio-5-pyridinemethylene amine yielded (Z)-ethoxyethyl 2-cyano-3-methylthio-3-(2-methylthio-5-pyridylmethylamino)acrylate. Ethoxyethyl (Z+E)-2-cyano-3-ethoxyacrylate was synthesized from ethoxyethyl 2-cyanoacetate and triethyl orthoacetate in 90.7% yield, and its reaction with 2-methylthio-5-pyridinemethylene amine yielded (Z)-ethoxyethyl 2-cyano-3-methyl-3-(2-methylthio-5-pyridylmethylamino)acrylate. The structures of all of the products were confirmed by 1H NMR, elemental analysis, IR, and mass spectroscopy. The herbicidal activities of the products were evaluated, and the results of bioassay showed that (Z)-ethoxyethyl 2-cyano-3-methyl-3-(2-methylthio-5-pyridylmethylamino) acrylate exhibits good herbicidal activity on rape (Brassica napus) at a dose of 1.5 kg/ha.
- Wang, Qing Min,Sun, Hui Kai,Huang, Run Qiu
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- Method for preparing aldehyde and acid by electrochemical dehydrochlorination of polychloromethylpyridine derivatives
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The invention discloses a method for preparing aldehyde and an acid by electrochemical dechlorination of a polychloromethylpyridine derivative, the method comprises the following steps: dissolving thepolychloromethylpyridine derivative in an acetic acid and acetate- containing buffer solution to obtain an electrolytic reaction solution; taking the electrolytic reaction solution as a cathode liquid, performing electrolytic reduction dechlorination reaction at a cathode, and hydrolyzing in the solution to obtain a polychlorinated pyridylaldehyde or acid derivative. The polychloromethylpyridinederivative is shown in formula (I), and the product polychlorinated pyridylaldehyde or acid derivative is shown in formula (II): in the formula (I), m is 0, 1, 2, 3 or 4, n is 0 or 1, and R' is an easy-to-oxidize or easy-to-hydrolyze substituent. The m and the R' in the formula (II) are same as that in the formula (I), R is H or OH, no waste acid is generated in the preparation process, the easy-to-oxidize or easy-to-hydrolyze substituent contained in the polychloromethylpyridine derivative and carbon-chlorine bonds on pyridine rings are not affected, and the recovery conversion rate is high.
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Paragraph 0035-0037; 0044-0046; 0053-0056
(2020/08/27)
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- Green synthesis method of aromatic acid
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The invention discloses a green synthesis method of aromatic acid. Nickel-catalyzed carbonyl insertion is carried out on aryl iodine in the presence of formate, acid anhydride, a phosphine ligand andan organic solvent by using a nickel catalyst to obtain the aromatic acid. Efficient catalytic conversion is realized by utilizing the cheap nickel catalyst, the reaction conditions are mild, and theoperation is simple.
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Paragraph 0048-0122; 0251-0255; 0271-0272
(2020/05/01)
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- Nickel-catalyzed carboxylation of aryl iodides with lithium formate through catalytic CO recycling
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A protocol for the Ni-catalyzed carboxylation of aryl iodides with formate has been developed with good functional group compatibility for the synthesis of a variety of aromatic carboxylic acids under mild conditions. The reaction tolerates other functionalities for cross-coupling, such as aryl bromide, aryl chloride, aryl tosylate, and aryl pinacol boronate. The reaction proceeds through a carbonylation process with in situ generated carbon monoxide in the presence of a catalytic amount of acetic anhydride and lithium formate, avoiding the use of gaseous CO. The strategy of CO recycling in catalytic amounts is critical for the success of the reaction.
- Fu, Ming-Chen,Fu, Yao,Shang, Rui,Wu, Ya-Nan
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supporting information
p. 4067 - 4069
(2020/04/20)
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- Ultrasounds-mediated 10-seconds synthesis of chalcones as potential farnesyltransferase inhibitors
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A broad range of chalcones and derivatives were easily and rapidly synthesized, following Claisen-Schmidt condensation of (hetero)aryl ketones and (hetero)aryl aldehydes using a ultrasound probe. A comparison was made with classical magnetic stirring experiments, and an optimization study was realized, showing lithium hydroxide to be the best basic catalyst of the studied condensations. By-products of the reactions (β-hydroxy-ketone, diketones, and cyclohexanols) were also isolated. All compounds were evaluated in vitro for their ability to inhibit human farnesyltransferase, a protein implicated in cancer and rare diseases and on the NCI-60 cancer cell lines panel. Molecules showed inhibitory activity on the target protein and cytostatic effect on different cell lines with particular activity against MCF7, breast cancer cells.
- Farce, Amaury,Ghinet, Alina,Homerin, Germain,Nica, Adrian Sorin,Dubois, Jo?lle
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supporting information
(2020/04/10)
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- A 6 - chloro nicotinic acid preparation method and separation and purification method
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The invention discloses a preparation method and a separation and purification method for 6-chloronicotinic acid, belonging to the field of fine chemical engineering. The preparation method comprises the following steps: by taking low-cost DL-malic acid as a raw material, carrying out a cyclization reaction and an ammonification reaction, thereby obtaining 6-hydroxynicotinic acid; by taking 6-hydroxynicotinic acid as a raw material, carrying out a chlorination reaction, thereby obtaining 6-chloronicotinic acid. The reaction conditions are simple, operation is easy, the environmental pollution is slight, and the yield is high. The purification method disclosed by the invention comprises the following step: refining crude 6-chloronicotinic acid by virtue of methanol and activated carbon to finally obtain 6-chloronicotinic acid with the purity of more than 99.5 percent. The requirement of a medical intermediate on the purity is met. The method disclosed by the invention has the advantages of reasonable design, low cost and high economic benefits and has wide application prospects.
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Paragraph 0035; 0039-0092
(2017/08/24)
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- A 6-chloro preparation of nicotinic acid
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The invention discloses a preparation method of 6-chloronicotinic acid. The method comprises the following steps: directly oxidizing 2-choro-5-methylpyridine used as an initial material by virtue of oxygen under the catalysis of cobalt acetate by taking chlorobenzene as a solvent, so as to prepare a 6-chloronicotinic acid crude product; recrystallizing to obtain a 6-chloronicotinic acid product. By adopting the method, a lot of acid or potassium permanganate and the like with large environmental pollution are avoided; the reaction condition is mild; the product quality and the yield achieve a higher level.
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Paragraph 0035; 0036; 0037
(2017/01/12)
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- Electro-catalytic degradation pathway and mechanism of acetamiprid using an Er doped Ti/SnO2-Sb electrode
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Acetamiprid, a type of new neonicotinoid pesticide, shows a high threat to water systems. Electro-catalytic degradation of acetamiprid was evaluated using an Er doped Ti/SnO2-Sb electrode prepared by the Pechini method. The acetamiprid degradation obeys first order reaction kinetics and is controlled by mass transport and oxygen evolution. TOC removal efficiency and UV scan curves revealed that some intermediate products were produced by the Er doped Ti/SnO2-Sb electrode. Through electrospray ionization quadrupole time-of-flight tandem mass spectrometry, the ion mass-to-charge ratio of intermediate products was determined. Combining the experimental results, a degradation pathway was proposed for the electro-catalytic degradation of acetamiprid. Electrodes were mainly characterized by linear sweep voltammetry and cyclic voltammetry. The acetamiprid and TOC concentrations were reduced to 87.45% and 69.31%, respectively, after 180 min of electrolysis at 10 mA cm-2.
- Li, Shanping,Li, Yahui,Zeng, Xueyuan,Wang, Wenran,Shi, Ruoxin,Ma, Lina
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p. 68700 - 68713
(2015/09/01)
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- Amyl nitrite-mediated conversion of aromatic and heteroaromatic primary amides to carboxylic acids
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A series of aromatic and heteroaromatic primary amides were converted directly to carboxylic acids by heating with amyl nitrite in acetic acid. Most conversions proceeded to give reasonable to excellent yields on a range of substrates containing various functional groups. This reagent system is thus applicable for the direct hydrolysis of a range of different primary carboxamides. The reaction with a phenolic aromatic substrate afforded two alternative nitration products as major outcomes, evidencing alternative reaction pathways resulting from the free phenolic OH.
- Potter, Garrett T.,Jayson, Gordon C.,Miller, Gavin J.,Gardiner, John M.
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supporting information
p. 5153 - 5156
(2015/08/19)
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- Photocatalytic degradation of imidacloprid by phosphotungstic acid supported on a mesoporous sieve MCM-41
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Solid catalysts consisting of polyoxometalates (POM) namely phosphotungstic acid H3PW12O40 (HPW) supported on a mesoporous sieve MCM-41 have been prepared and characterized by FT-IR, X-ray diffraction, nitrogen adsorption and high resolution transmission electron microscope (HRTEM). The HPW/MCM-41 with different HPW loadings from 10 to 60 wt% possess large specific surface area and rather uniform mesopores. Keggin structure of HPW retains on the prepared composite catalysts. The photocatalytic performance of HPW/MCM-41 was examined by degradation of a durable pesticide imidacloprid. It is found that the prepared photocatalysts exhibit high activity under irradiation of 365 nm monochromatic light. For 50 mL of imidacloprid (10 mg/L), conversion of imidacloprid using 20 mg of HPW/MCM-41 with 50 wt% loading level and calcined at 300°C reaches 58.0% after 5 h irradiation. Copyright
- Feng, Changgen,Li, Yanzhou,Liu, Xia
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experimental part
p. 127 - 132
(2012/03/09)
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- Second generation 2-pyridyl biphenyl amide inhibitors of the hedgehog pathway
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Potent and efficacious inhibitors of the hedgehog pathway for the treatment of cancer have been prepared using the 2-pyridyl biphenyl amide scaffold common to the clinical lead GDC-0449. Analogs with polar groups in the para-position of the aryl amide ring optimized potency, had minimal CYP inhibition, and possessed good exposure in rats. Compounds 9d and 14f potently inhibited hedgehog signaling as measured by Gli1 mRNA and were found to be equivalent or more potent than GDC-0449, respectively, when studied in a Ptch+/- medulloblastoma allograft model, that is, highly dependent on hedgehog signaling.
- Castanedo, Georgette M.,Wang, Shumei,Robarge, Kirk D.,Blackwood, Elizabeth,Burdick, Daniel,Chang, Christine,Dijkgraaf, Gerrit J.P.,Gould, Stephen,Gunzner, Janet,Guichert, Oivin,Halladay, Jason,Khojasteh, Cyrus,Lee, Leslie,Marsters Jr., James C.,Murray, Lesley,Peterson, David,Plise, Emile,Salphati, Laurent,De Sauvage, Frederic J.,Wong, Susan,Sutherlin, Daniel P.
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scheme or table
p. 6748 - 6753
(2011/01/12)
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- Environmental behaviour and translocation of imidacloprid in eggplant, cabbage and mustard
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The recently registered insecticide, imidacloprid, was applied to three vegetable crops at 20 and 40g AI ha-1. The persistence of the parent insecticide and its translocation, along with the quantification of the metabolites formed on these crops are presented. The parent insecticide dissipated with a half-life of 3-5 days and persisted longest on mustard leaves. The detectable limit of the HPLC method was 0.01 μg g-1. The metabolites 1-(6-chloropyridin-3-yl-methyl)imidazolidin-2-one and 6-chloronicotinic acid were found to be translocated by day 10 in eggplant, cabbage leaves and mustard leaves but not in cabbage curd. The MRL of imidacloprid is not documented by the FAO/WHO on these crops and comparison of the MPI with the TMRG, calculated on the residue data generated in this study, establishes the safety of the schedule. (C) 2000 Society of Chemical Industry.
- Mukherjee, Irani,Gopal, Madhuban
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p. 932 - 936
(2007/10/03)
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- Process for producing chloronicotinic acid compounds
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A chloronicotinic acid compound is prepared by hydrolyzing a 3-trichloromethyl pyridine compound in the presence of sulfuric acid or phosphoric acid. By this process, a highly pure chloronicotinic acid compound is obtainable in good yield. This compound is useful as an intermediate for medicines.
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- Process for the production of 2-halopyridine derivatives
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Process for the production of 2-halopyridine derivatives having the formula: STR1 wherein X is halogen, R is --COOH or a lower alkyl radical and n is a number between 0 and 4. The corresponding 2-pyridine carboxylic acid-N-oxide derivatives having the formula: STR2 are reacted in the presence of an excess of organic anhydrides, tertiary alkylamines and a halogen-producing compound having the formula CHt Xm, wherein t is 1 or 2, m is 2 or 3 and X is halogen, or having the formula C2 Hp Xm, wherein p is 3 or 4, m is 2 or 3 and X is halogen. The reaction mixture is adjusted to a pH value of 12 to 13 and the desired product is isolated from the mixture. Compound comprising (i) a 2-pyridine carboxylic acid-N-oxide derivative, (ii) an organic anhydride, (iii) a tertiary amine and (iv) a halogen-producing compound having the formula CHn Xm. The composition can be used as the starting ingredients for the above process.
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- On derivatives of 4-oxo-3,4-dihydropyrido[2,3-d]pyrimidine (author's transl)
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A typical representative of the hypnotic and anticonvulsive 4-quinazoline group is methaqualone (1). A number of new derivatives of 4-oxo-3,4-dihydropyrido[2,3-d]pyrimidine (10) were synthetized by substituting the benzene ring in the quinazolone molecule by the pyridine ring. The synthesis was achieved by the condensation of 2-acetaminonicotinic acid (9) and a primary amine or by the reaction of 2-aminonicotinic acid (8) with acetic acid and a primary amine. These new compounds were tested on animals for antiphlogistic, analgetic and antipyretic activities and for effects on the central nervous system as well. It was tried to establish, on the basis of the results obtained, relations between the chemical constitution and the pharmacological efficacy. It was found that, depending on the nature of the substituents in the position 3; either the antiphlogistic, analgetic and antipyretic effects or the anticonvulsive action will prevail.
- Kretzschmar
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p. 253 - 256
(2007/10/02)
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- Anti-inflammatory oxazole[4,5-b]pyridines
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The various isomers of oxazolo- and thiazolopyridines having utility as antiinflammatory, antipyretic and analgesic agents are prepared by condensation of an appropriate amino-hydroxypyridine or amino-mercaptopyridine with a carboxylic acid, halide or anhydride.
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