- Lewis acidic strength controlled highly selective synthesis of oxime via liquid-phase ammoximation over titanosilicates
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The Lewis acidity of titanosilicates determines the selectivity of the oxime in ammoximation. Higher Lewis acidic strength of Ti active sites could promote free H2O2 to participate in the highly efficient formation of NH2OH by lowering the reaction activation energy for the formation of Ti-OOH species, and thus fundamentally suppress the side reactions of deep oxidation.
- Zhuo, Zuoxi,Wu, Lizhi,Wang, Lei,Ding, Yichun,Zhang, Xiaoqian,Liu, Yueming,He, Mingyuan
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Read Online
- Access to multi-functionalized oxazolines via silver-catalyzed heteroannulation of enamides with sulfoxonium ylides
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Disclosed herein is an efficient Ag-catalyzed [4 + 1] heteroannulation reaction of enamides with α-carbonyl sulfoxonium ylides. The diastereoselective transformation provides a practical access to a diverse range of multi-functionalized oxazoline derivatives. The synthetic utility of the resultant tetra-substituted oxazolines is further demonstrated by a series of useful manipulations into valuable building blocks of pharmaceutical relevance.
- Liu, Rui-Hua,Shan, Qi-Chao,Gao, Ya,Loh, Teck-Peng,Hu, Xu-Hong
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Read Online
- Discovery and preclinical development of AR453588 as an anti-diabetic glucokinase activator
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Glucose flux through glucokinase (GK) controls insulin release from the pancreas in response to high levels of glucose. Flux through GK is also responsible for reducing hepatic glucose output. Since many individuals with type 2 diabetes appear to have an inadequacy or defect in one or both of these processes, identifying compounds that can activate GK could provide a therapeutic benefit. Herein we report the further structure activity studies of a novel series of glucokinase activators (GKA). These studies led to the identification of pyridine 72 as a potent GKA that lowered post-prandial glucose in normal C57BL/6J mice, and after 14d dosing in ob/ob mice.
- Aicher, Thomas D.,Baer, Brian R.,Boyd, Steven A.,Chicarelli, Mark D.,Condroski, Kevin R.,DeWolf, Walter E.,Fischer, John,Frank, Michele,Hingorani, Gary P.,Hinklin, Ronald J.,Lee, Patrice A.,Neitzel, Nickolas A.,Pratt, Scott A.,Singh, Ajay,Sullivan, Francis X.,Turner, Timothy,Voegtli, Walter C.,Wallace, Eli M.,Williams, Lance
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- Separation and purification method for acetaldehyde oxime
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The invention discloses a separation and purification method for acetaldehyde oxime, and relates to the technical field of separation and purification of oxime. The method comprises the following steps: 1) performing an oxime exchange reaction on cyclohexanone oxime and acetaldehyde to obtain an acetaldehyde oxime reaction solution, performing neutralization by using a base, and after the neutralization is completed, controlling the pH of the acetaldehyde oxime reaction solution to 7; 2) adding toluene into the acetaldehyde oxime reaction solution, performing distillation under reduced pressure to separate acetaldehyde oxime and cyclohexanone to obtain an acetaldehyde oxime and toluene mixed liquid and the cyclohexanone; 3) adding extractant water into the obtained acetaldehyde oxime and toluene mixed liquid, and separating the toluene and the acetaldehyde oxime by using a continuous extraction process to obtain an acetaldehyde oxime aqueous solution and the toluene, respectively; and4) performing reduced-pressure rectification on the acetaldehyde oxime aqueous solution to obtain the acetaldehyde oxime product. The method provided by the invention has simple operation and high purity and yield of the acetaldehyde oxime, does not generate waste liquid, and is an environment-friendly green process route for production separation and purification of the acetaldehyde oxime.
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Paragraph 0031-0065
(2020/02/19)
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- A preparation method of acetaldoxime
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The present invention relates to organic chemical synthesis technology field, in particular to a acetaldoxime preparation method. The invention acetaldoxime preparation method, comprises the following steps: 1) the hydroxylamine and distilled water and stirring to dissolve, then dropping in the ice water bath under the conditions of the acetaldehyde, acetic acid catalyst, after the completion of the dropping 0 - 10 °C stirring reaction for 10 - 30 minutes, make acetaldoxime solution; 2) in the step 1) in dichloromethane is used for extraction of acetaldoxime solution, extraction solution after drying with anhydrous sodium sulfate, the solvent first atmospheric distillation, distillation under reduced pressure, collecting the fraction, transparent liquid is acetaldoxime. The invention acetaldoxime preparation method to acetic acid as catalyst, hydroxylamine and acetaldehyde as raw material to make the acetaldoxime solution, after extraction, drying, atmospheric fractionation, distilling and getting the colorless transparent liquid is acetaldoxime, acetaldoxime made without water, purity ≥ 99%, yield ≥ 92%.
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Paragraph 0017-0036
(2019/03/24)
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- Method for preparing oxime
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The invention discloses a method for preparing oxime. The method is characterized in that catalytic reaction for oxime synthesis is performed by using a titanium silicate molecular sieve of a MSE topological structure as a catalyst and using ketone or aldehyde, ammonia and hydrogen peroxide as a reaction system, wherein in the reaction system, the weight ratio of ketone or aldehyde to the catalystto a solvent is 1:(0.03 to 0.15):(1 to 15); the molar ratio of the ketone or aldehyde to the ammonia is 1:(1 to 4); the catalyst is Ti-MSE or a combination body of Ti-MSE and silicon dioxide or a titanium-containing molecular sieve. Compared with the prior art, the method has the advantages that the selectivity is high; the catalytic activity is high; the aftertreatment is simple and convenient;the conversion rate of reactants of ketone or aldehyde reaches up to 99 percent; the product oxime selectivity reaches up to 99 percent, so that the molecular sieve shows excellent catalytic activityin the specific catalysis field; the application field of the molecular sieve is expanded; a novel and environment-friendly ammoxidation oxime preparation path is provided; certain industrial popularization and application prospects and prominent economic values are realized.
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Paragraph 0034; 0035; 0036
(2018/09/08)
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- Chemically synthesized heterocyclic insecticide intermediate and preparation method thereof
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The invention discloses a chemically synthesized heterocyclic insecticide intermediate and a preparation method thereof. The chemically synthesized heterocyclic insecticide intermediate is prepared from the following raw materials in parts by weight: 100 to 150 parts of distilled water, 65 to 90 parts of hydroxylamine sulphate, 80 to 100 parts of ammonia water, 20 to 30 parts of acetaldehyde, 30 to 40 parts of sodium hydroxide, 35 to 50 parts of potassium permanganate, 45 to 60 parts of concentrated hydrochloric acid and 15 to 20 parts of saturated salt water. According to the chemically synthesized heterocyclic insecticide intermediate, the preparation method is relatively mature and a technology is relatively simple; a production progress, and the dosage ratio of each index are convenient to control and the raw materials for synthesizing are materials which are common in the market and are cheap and easy to obtain; the yield of the prepared intermediate methylthioacetaldoxime reaches 75 percent to 80 percent and is much higher than the average yield of an existing market; the medicinal effect is improved; the intermediate methylthioacetaldoxime has stable chemical properties and does not have viscous decomposition or deterioration problems and the like at room temperature, and the economic benefits are improved.
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Paragraph 0042
(2017/11/29)
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- An efficient protocol for the synthesis of six-membered N, O-heterocycles via a 1,3-dipolar (3+3) cycloaddition between nitrile oxide and α-diazo esters
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In this manuscript, we are reporting an efficient protocol for the construction of highly functionalized N, O-heterocyclic derivatives such as 1,2,4-oxadiazine and 1,4,2-dioxazine-6-carboxylate derivatives via a 1,3-dipolar (3 + 3) cycloaddition between nitrile oxide and unprotected α-diazo esters in the presence of 2 mol% Cu(OTf)2 catalyst. The expected N, O-heterocycles were obtained in excellent yields. These N, O-heterocycles are known to exhibit insecticidal and acaricidal properties.
- Kuruba, Bharath Kumar,Vasanthkumar, Samuel
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p. 3860 - 3865
(2017/06/14)
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- Investigations of the Thermal Responsiveness of 1,4,2-Oxathiazoles
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The first systematic study of the thermal rearrangement/fragmentation of 5,5-disubstituted 1,4,2-oxathiazoles into isothiocyanates is reported. Structure-activity relationships reveal that the choice of substituent at the 5-position of the 1,4,2-oxathiazoles is the predominant factor to influence the ease of fragmentation.
- Hewitt, Russell J.,Ong, Michelle Jui Hsien,Lim, Yi Wee,Burkett, Brendan A.
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p. 6687 - 6700
(2015/10/29)
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- Synthesis and evaluation of 4,5-dihydro-5-methylisoxazolin-5-carboxamide derivatives as VLA-4 antagonists
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A novel set of compounds containing a 4,5-dihydro-5-methylisoxazoline have been successfully designed as VLA-4 receptor antagonists. Compound (14p) had a high receptor binding affinity of 4 nM and also found to be metabolically stable in vitro.
- Soni, Ajay,Rehman, Abdul,Naik, Keshav,Dastidar, Sunanda,Alam,Ray, Abhijit,Chaira, Tridib,Shah, Vanya,Palle, Venkata P.,Cliffe, Ian A.,Sattigeri, Viswajanani J.
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p. 1482 - 1485
(2013/03/14)
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- Direct spectrophotometric determination of nickel (II) with o-chlorophenylazo-bis-acetoxime
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A new reagent o-chlorophenylazo-bis-acetoxime has been used for spectrophotometric determination of Ni (II). Nickel forms a 1:2 (Ni: R) ethanol soluble greenish yellow complex with the reagent. The working wavelength was taken at 370 nm (ε-2451) in the pH range 7.3-7.9. Beer's law obeyed between 0.117 - 0.939 ppm and Sandell's sensitivity is 23.09 ng/cm2. The values of log β found from the two different methods were 8.95 and 8.76, respectively. Interference of 24 diverse ions has been examined.
- Khanam, Rehana,Khan, Saba,Dashora, Rekha
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p. 603 - 608
(2013/11/06)
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- Synthesis and antibacterial activity of oxime ester derivatives containing 16-isopropyl-5,9-dimethyl tetracyclo [10.2.2.01,10.04,9] hexadec-15-ene-5,14- dicarboxyl group
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Acrylpimaric acid (16-isopropyl-5,9- dimethyltetracyclo [10. 2. 2. 0 1,10.04,9]hexadec- 15-ene-5,14-dicarboxylic acid) was prepared by rosin through Diels-Alder addition reaction, then a series of oxime ester derivatives containing acrylpimaryl (16-isopropyl-5,9-dimethyltetracyclo [10.2.2.01,10.04,9]hexadec-15-ene-5,14-dicarboxyl) group were synthesized. Their structures were characterized by IR, 1HNMR, MS, and elemental analysis. The antibacterial activity of these newly synthesized oxime ester derivatives against Gram-negative bacteria and Gram-positive bacteria were also investigated. The results indicate that compounds display extensive anti-bacterial activity against Gram-negative bacteria and Gram-positive bacteria. Especially compounds (4c, 4d, 4f, 4h and 4k) exhibit excellent anti-bacterial activity against Escherichia coli (Gram-negative bacteria). Compared with the diameter of inhibition zone is 9.66mm of the standard compound bromogeramine, which the diameter of inhibition zone is 12.17mm, 10.00mm, 10.33mm, 9.67mm and 9.67mm respectively.
- Li, Jian,Rao, Xiaoping,Shang, Shibin,Gao, Yanqing,Song, Binglei
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experimental part
p. 217 - 222
(2012/04/23)
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- Ruthenium-catalyzed rearrangement of aldoximes to primary amides in water
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The rearrangement of aldoximes to primary amides has been studied using the readily available arene-ruthenium(II) complex [RuCl2(η 6-C6Me6){P(NMe2)3}] (5 mol %) as catalyst. Reactions proceeded cleanly in pure water at 100 °C without the assistance of any cocatalyst, affording the desired amides in high yields (70-90%) after short reaction times (1-7 h). The process was operative with both aromatic, heteroaromatic, α,β-unsaturated, and aliphatic aldoximes and tolerated several functional groups. Reaction profiles and experiments using 18O-labeled water indicate that two different mechanisms are implicated in these transformations. In both of them, nitrile intermediates are initially formed by dehydration of the aldoximes. These intermediates are then hydrated to the corresponding amides by the action of a second molecule of aldoxime or water. A kinetic analysis of the rearrangement of benzaldoxime to benzamide is also discussed.
- Garcia-Alvarez, Rocio,Diaz-Alvarez, Alba E.,Borge, Javier,Crochet, Pascale,Cadierno, Victorio
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p. 6482 - 6490
(2012/10/30)
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- METHOD FOR OBTAINING PROPYLENE OXIDE
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An object the present invention is to provide a method for obtaining propylene oxide in which the content of acetaldehyde is reduced by enabling the removal of acetaldehyde. More specifically, the present invention provides a method for obtaining propylene oxide, which includes steps of: mixing a hydroxylamine compound in a reaction mass which is obtained by reacting both raw materials of (a) hydrogen peroxide, or hydrogen and oxygen, and (b) propylene in an acetonitrile-containing solvent in the presence of a catalyst, thereby entirely or partially converting acetaldehyde contained in the reaction mass into acetaldoxime, and then separating or removing the acetaldoxime from the reaction mass; and recovering the reaction mass obtained by the former step or propylene oxide existing in the reaction mass.
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Page/Page column 64-66
(2012/10/18)
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- Synthesis and antiproliferative evaluation of 3,5-disubstituted 1,2,4-triazoles containing flurophenyl and trifluoromethanephenyl moieties
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An efficient 1,3-dipolar cycloaddition method was performed for the synthesis of a series of monofluoro- and trifluoromethane-3,5-disubstituted 1,2,4-triazoles. This efficient cycloaddition method was to react hydrazonoyl hydrochlorides with a series of aldehydes in the presence of NEt3 as catalytic basic agent to provide the corresponding product in 28-94%. Their growth inhibitory results against cancer cells indicated that some of the fluorine- and trifluoromethane-containing compounds could effectively inhibit the growth of NCI-H226 and T-cell leukemia (Jurkat) cells. Among the compounds, trifluoromethane-containing 1,2,4-triazoles possessed the five-membered ring groups on the C-5 position of the triazolic ring, including cyclopentyl, 3-furyl, 3-thienyl, and 2-pyrrolyl, possessed the significant inhibitory activity for NCI-H226 cancer cells.
- Wang, Li-Ya,Tseng, Wen-Che,Wu, Tian-Shung,Kaneko, Kimiyoshi,Takayama, Hiroyuki,Kimura, Masayuki,Yang, Wen-Chin,Wu, Jin Bin,Juang, Shin-Hun,Wong, Fung Fuh
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supporting information; experimental part
p. 5358 - 5362
(2011/10/03)
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- Facile method for conversion of 2-(Chloroseleno)benzoyl chloride into 2-substituted 3-hydroxybenzo[b]selenophenes
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The easily accessible 2-(chloroseleno)benzoyl chloride has broad application in the synthesis of benzizoselenazol-3(2H)-ones and benzo[b]selenophen-3(2H)-ones. Treatment of 2-acylbenzo[b]selenophen-3(2H)-ones with nitrogen nucleophiles such as hydrazines
- Lisiak, Rafal,Mochowski, Jacek
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experimental part
p. 4271 - 4281
(2009/12/31)
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- Synthesis of 5-isoxazol-5-yl-2′-deoxyuridines exhibiting antiviral activity against HSV and several RNA viruses
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This paper describes a simple method for synthesizing a small library of 5-isoxazol-5-yl-2′-deoxyuridines from 5-iodo-2′-deoxyuridine. Nitrile oxides were generated in situ from oximes using a commercial bleaching agent; their cycloaddition with 5-ethynyl-2′-deoxyuridine yielded isoxazoles possessing activity against herpes simplex viruses 1 and 2, Encephalomyocarditis virus, Coxsackie B3, and vesicular stomatitis virus; these isoxazoles were, however, inactive against corona virus, influenza virus, and HIV.
- Lee, Yoon-Suk,Park, Sun Min,Kim, Byeang Hyean
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scheme or table
p. 1126 - 1128
(2009/08/07)
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- Discovery and optimization of substituted piperidines as potent, selective, CNS-penetrant α4β2 nicotinic acetylcholine receptor potentiators
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The discovery of a series of small molecule α4β2 nAChR potentiators is reported. The structure-activity relationship leads to potent compounds selective against nAChRs including α3β2 and α3β4 and optimized for CNS penetrance. Compounds increased currents through recombinant α4β2 nAChRs, yet did not compete for binding with the orthosteric ligand cytisine. High potency and efficacy on the rat channel combined with good PK properties will allow testing of the α4β2 potentiator mechanism in animal models of disease.
- Albrecht, Brian K.,Berry, Virginia,Boezio, Alessandro A.,Cao, Lei,Clarkin, Kristie,Guo, Wenhong,Harmange, Jean-Christophe,Hierl, Markus,Huang, Liyue,Janosky, Brett,Knop, Johannes,Malmberg, Annika,McDermott, Jeff S.,Nguyen, Hung Q.,Springer, Stephanie K.,Waldon, Daniel,Woodin, Katrina,McDonough, Stefan I.
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scheme or table
p. 5209 - 5212
(2009/05/07)
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- Chemistry of the diazeniumdiolates. 3. Photoreactivity
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We have found O2-substituted diazeniumdiolates, compounds of structure R2N - N(O)=NOR′ that are under development for various possible pharmaceutical uses, to be rather photosensitive. With R = ethyl and R′ = methyl, benzyl, or 2-nit
- Srinivasan,Kebede,Saavedra,Nikolaitchik,Brady,Yourd,Davies,Keefer,Toscano
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p. 5465 - 5472
(2007/10/03)
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- REACTION OF THE OXIMES OF ALIPHATIC ALDEHYDES AND KETONES WITH ALKOXYETHENES
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In the reaction of acetone oxime with alkyl vinyl ethers in the presence of zinc chloride variable amounts of acetone O,O'-(2-propylidene)dioxime, acetaldehyde dialkyl acetal, acetaldehyde O-(1-alkoxyethyl)oxide, and acetone O-(1-alkoxy-1-methylethyl)oxime, depending on the reaction conditions, are formed in addition to acetone O-(1-alkoxyethyl)oxime (the initial addition product).In the reaction of acetaldehyde oxime with alkyl vinyl ethers in the presence of zinc chloride acetaldehyde dialkyl acetal was isolated in addition to acetaldehyde O-(1-alkoxyethyl)oxime.A mechanism for the formation of the obtained compounds is proposed.
- Voronkov, M. G.,Keiko, N. A.,Shuvashev, Yu. A.,Kalikhman, I. D.,Keiko, V. V.
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- SUBSTITUENT AND COORDINATION EFFECTS IN SINGLET REACTIONS OF 3-DIAZO-3H-1,2,4-TRIAZOLES WITH SUBSTITUTED BENZENES AND NITRO COMPOUNDS
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3-Diazo-3H-1,2,4-triazoles convert to singlet 3H-1,2,4-triazol-3-ylidenes which (1) effect directed electrophilic substitutions of benzenes and (2) coordinate with benzenoid substituents and nitro compounds to give decomposition or rearrangement products.
- Glinka, J.,Fiscus, D.,Rao, C. B.,Shechter, H.
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p. 3221 - 3224
(2007/10/02)
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- Oxidation of Hydroxylamine Derivatives. VI. Anodic Oxidation of N-Alkyl-β-hydroxyhydroxylamines in Aqueous Buffer Solution
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Anodic oxidation of N-alkylhydroxylamines with and without a β-hydroxy group was studied by cyclic voltammetry and controlled potential electrolysis in aqueous buffer solution of pH 8.8.The hydroxylamines with a β-hydroxy group were oxidized initially to the corresponding nitroxides and gave the final products via two routes; i) cleavage of the (α)C-(β)C bond to give aldehydes and oximes, and ii) disproportionation of the nitroxides to form the nitroso compounds.The hydroxylamines without a β-hydroxy group did not undergo cleavage of the (α)C-(β)C bond and gave nitroso compounds.Substituents on the α and β carbons affected the product distribution.When a phenyl group or two methyl groups were present on the (β)C, or one methyl group was present on both (α)C and (β)C, (α)C-(β)C bond cleavage was predominant. Keywords - N-alkyl-β-hydroxyhydroxylamine; anodic oxidation; C-C bond fission; C-nitroso compound; aldehyde; oxime; azoxy compound
- Ozaki, Shigeko,Nishiguchi, Susumu,Masui, Masaichiro
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p. 2609 - 2616
(2007/10/02)
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- DIVINYL SULFIDE X. REACTION WITH MERCURIC CHLORIDE AND ACID HYDROLYSIS
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In a 20percent ethanol solution of mercuric chloride divinyl sulfide undergoes quantitative decomposition with the formation of acetaldehyde diethyl acetal, hydrochloric acid, and a complex salt of mercury.The hydrolysis of divinyl sulfide by hydrochloric acid in a water-dioxane medium leads to the production of hydrogen sulfide, acetaldehyde, 2,4,6-trimethyl-1,3,5-trithiane, and a small amount of acetaldehyde and thioacetaldehyde oligomers.The same products are formed during the hydrolysis of divinyl sulfide and an acidified solution of hydroxylamine hydrochloride; the acetaldehyde relased here is oximated.
- Gavrilova, G. M.,Gostevskaya, V. I.,Trofimov, B. A.,Amosova, S. V.
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p. 1613 - 1615
(2007/10/02)
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