- Promoting charge separation in donor-acceptor conjugated microporous polymers: Via cyanation for the photocatalytic reductive dehalogenation of chlorides
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Conjugated microporous polymers (CMPs) have emerged as promising heterogeneous photocatalysts for organic transformations owing to their structural designability and functional versatility. However, limited by the insufficient separation of the photo-generated excitons, their photocatalytic efficiency falls far short of expectations. Herein, we demonstrate a cyanation strategy to promote charge carrier separation in CMPs by selectively incorporating carbazole and cyano groups as electron-donating and electron-withdrawing units, respectively. The resulting CMPs feature π-extended donor (D)-acceptor (A) conjugation structures endowing them with distinct semiconducting properties, in which the efficient charge separation and transfer and wide visible-light absorption are facilitated. Compared to the cyano-free counterpart, the cyano-functionalized CMPs showed superior photocatalytic efficiency as exemplified by photocatalytic reductive dehalogenation of chlorides. More prominently, full recyclability of the designed CMPs as well as catalytic activity for at least ten runs without the loss of catalytic performance in photocatalytic reductive dehalogenation of chlorides demonstrated their robustness and sustainability. This journal is
- Deng, Jiyong,Fang, Zhengjun,Lan, Donghui,Liao, Yunfeng,Liu, Qingquan,Zhang, Weijie,Zhou, Xiang
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p. 7151 - 7159
(2021/11/17)
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- The dehydrogenative oxidation of aryl methanols using an oxygen bridged [Cu-O-Se] bimetallic catalyst
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Herein, we report a new protocol for the dehydrogenative oxidation of aryl methanols using the cheap and commercially available catalyst CuSeO3·2H2O. Oxygen-bridged [Cu-O-Se] bimetallic catalysts are not only less expensive than other catalysts used for the dehydrogenative oxidation of aryl alcohols, but they are also effective under mild conditions and at low concentrations. The title reaction proceeds with a variety of aromatic and heteroaromatic methanol examples, obtaining the corresponding carbonyls in high yields. This is the first example using an oxygen-bridged copper-based bimetallic catalyst [Cu-O-Se] for dehydrogenative benzylic oxidation. Computational DFT studies reveal simultaneous H-transfer and Cu-O bond breaking, with a transition-state barrier height of 29.3 kcal mol?1
- Choudhury, Prabhupada,Behera, Pradyota Kumar,Bisoyi, Tanmayee,Sahu, Santosh Kumar,Sahu, Rashmi Ranjan,Prusty, Smruti Ranjita,Stitgen, Abigail,Scanlon, Joseph,Kar, Manoranjan,Rout, Laxmidhar
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supporting information
p. 5775 - 5779
(2021/04/12)
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- Oxidative Cleavage of Alkenes by O2with a Non-Heme Manganese Catalyst
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The oxidative cleavage of C═C double bonds with molecular oxygen to produce carbonyl compounds is an important transformation in chemical and pharmaceutical synthesis. In nature, enzymes containing the first-row transition metals, particularly heme and non-heme iron-dependent enzymes, readily activate O2 and oxidatively cleave C═C bonds with exquisite precision under ambient conditions. The reaction remains challenging for synthetic chemists, however. There are only a small number of known synthetic metal catalysts that allow for the oxidative cleavage of alkenes at an atmospheric pressure of O2, with very few known to catalyze the cleavage of nonactivated alkenes. In this work, we describe a light-driven, Mn-catalyzed protocol for the selective oxidation of alkenes to carbonyls under 1 atm of O2. For the first time, aromatic as well as various nonactivated aliphatic alkenes could be oxidized to afford ketones and aldehydes under clean, mild conditions with a first row, biorelevant metal catalyst. Moreover, the protocol shows a very good functional group tolerance. Mechanistic investigation suggests that Mn-oxo species, including an asymmetric, mixed-valent bis(μ-oxo)-Mn(III,IV) complex, are involved in the oxidation, and the solvent methanol participates in O2 activation that leads to the formation of the oxo species.
- Bennett, Elliot L.,Brookfield, Adam,Guan, Renpeng,Huang, Zhiliang,Mcinnes, Eric J. L.,Robertson, Craig M.,Shanmugam, Muralidharan,Xiao, Jianliang
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supporting information
p. 10005 - 10013
(2021/07/19)
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- MnO2as a terminal oxidant in Wacker oxidation of homoallyl alcohols and terminal olefins
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Efficient and mild reaction conditions for Wacker-type oxidation of terminal olefins of less explored homoallyl alcohols to β-hydroxy-methyl ketones have been developed by using a Pd(ii) catalyst and MnO2 as a co-oxidant. The method involves mild reaction conditions and shows good functional group compatibility along with high regio- and chemoselectivity. While our earlier system of PdCl2/CrO3/HCl produced α,β-unsaturated ketones from homoallyl alcohols, the present method provided orthogonally the β-hydroxy-methyl ketones. No overoxidation or elimination of benzylic and/or β-hydroxy groups was observed. The method could be extended to the oxidation of simple terminal olefins as well, to methyl ketones, displaying its versatility. An application to the regioselective synthesis of gingerol is demonstrated.
- Fernandes, Rodney A.,Ramakrishna, Gujjula V.,Bethi, Venkati
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p. 6115 - 6125
(2020/10/27)
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- Synthesis method of 2, 4-dichloroacetophenone
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The invention discloses a synthesis method of 2, 4-dichloroacetophenone. The method comprises the following steps: carrying out electrophilic substitution reaction on m-dichlorobenzene and acetyl chloride in an ionic liquid (Bmin)Cl-FeCl3 medium to synthesize the 2, 4-dichloroacetophenone; adding m-dichlorobenzene and acetyl chloride into the (Bmin)Cl-FeCl3 ionic liquid according to a molar ratioof 1:(1.1-1.2), carrying out a stirring reaction for 4h at a temperature of 40-60 DEG C, extracting 2, 4-dichloroacetophenone with cyclohexane, and carrying out reduced pressure distillation to removethe solvent so as to obtain 2, 4-dichloroacetophenone. The weight ratio of the feeding amount of the ionic liquid (Bmim)Cl-FeCl3 to the total feeding amount of m-dichlorobenzene and acetyl chloride is 1:(1-0.8). The method has the advantages that the use of anhydrous aluminum chloride is avoided, the conversion rate of raw materials is improved, byproducts are reduced, and green and environment-friendly production is realized.
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Paragraph 0011-0014
(2020/05/30)
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- Clean production method for improving reaction yield of 2, 4-dichloroacetophenone
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The invention relates to a clean production method for improving the reaction yield of 2, 4-dichloroacetophenone, which comprises the following steps: S1, separating and extracting m-dichlorobenzene by using chlorinated aromatic hydrocarbon waste; S2, preparing crude 2, 4-dichloroacetophenone; and S3, separating and purifying the crude 2, 4-dichloroacetophenone to obtain a dichloroacetophenone product. The method has the advantages that the optimal reaction conditions are found through the influence of the feeding ratio, the reaction temperature, the reaction time, different Lewis acids and the AlCl3 dosage on the product yield, the purity and the yield of the product are guaranteed, the purity of the product can reach 99.5% or above, and the yield of the product can reach 65% or above.
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Paragraph 0011-0022
(2020/04/06)
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- Efficient Palladium(0) supported on reduced graphene oxide for selective oxidation of olefins using graphene oxide as a ‘solid weak acid’
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Selective oxidation of olefin derivatives to ketones has made innovative development over palladium(0) supported on reduced graphene oxide. Compared to traditional Wacker oxidation, the novel method offers an economical and environment-friendly option by using graphene oxide (GO) as a ‘solid weak acid’ instead of classical homogeneous catalysts like H2SO4 and CF3COOH. X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscope and transmission electron microscopy images of Pd0/RGO showed that the nanoscaled Pd particles generated at the flake structure of reduced graphene oxide. Under optimized condition, up to 44 kinds of ketones with different structures can be prepared with excellent yields.
- Gao, Xi,Zhou, Jianhao,Peng, Xinhua
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- Synthetic process of difenoconazole
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The invention discloses a synthetic process of difenoconazole, comprising the steps of synthesizing 2,4-dichloroacetophenone through ionic liquid acylation using m-dichlorobenzene as a raw material; then synthesizing alpha-bromo-2,4-dichloroacetophenone through a green bromination method; subjecting the alpha-bromo-2,4-dichloroacetophenone and 1,2-propanediol to cyclization to generate a ketal compound that is 2-(2,4-dichlorophenyl)-2-bromomethyl-4-methyl-1,3-dioxolane; subjecting the ketal compound and 1,2,4-triazole potassium to condensation to generate 1-[[2-(2,4-dichlorophenyl)-4-methyl-1,3-dioxolan-2-yl]methyl]-1H-1,2,4-triazole; and finally subjecting the 1-[[2-(2,4-dichlorophenyl)-4-methyl-1,3-dioxolan-2-yl]methyl]-1H-1,2,4-triazole and parachlorophenol to etherification to obtain the difenoconazole. The process has advantages of easily available raw materials, a high reaction conversion ratio, few byproducts, capability of being friendly to production environment and a low cost.
- -
-
Paragraph 0013; 0018; 0023
(2019/07/16)
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- Method for synthesizing pesticide intermediate 2,4-dichloroacetophenone by recycling epoxypropane coproduct
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The invention belongs to the technical field of organic chemical industry, relates to a preparation method of a halogen-containing aromatic ketone organic compound 2,4-dichloroacetophenone, and concretely relates to a method for synthesizing an important pesticide intermediate 2,4-dichloroacetophenone, for an efficient bactericide propiconazole, a pesticide chlorfenvinphos and a herbicide difenzoquat, from alpha-methylbenzyl alcohol, co-produced through an ethylbenzene co-oxidation technology (PO/SM technology), by halogenation, chlorination, alkaline hydrolysis and oxidation reactions. The total yield is 85% or above, and the purity of the product is 99.7% or above. The method has the advantages of clean process, low raw material cost, high product purity, and easiness in industrialization realization.
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Paragraph 0040; 0041; 0042; 0043; 0044
(2019/01/21)
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- Synthetic method of 2,4-dichloroacetophenone
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The invention discloses a synthetic method of 2,4-dichloroacetophenone, and the 2,4-dichloroacetophenone is prepared by carrying out electrophilic substitution reaction on m-dichlorobenzene and aceticanhydride as raw materials. According to the method, the electrophilic substitution reaction is carried out by adopting a reaction rectification mode, and the vacuum degree of a reaction rectifying tower is adjusted, and the temperature of the reaction rectifying tower is controlled at optimal temperature for reaction rectification. The single consumption of a catalyst is reduced, the single consumption of the acetic anhydride is reduced, and the production process is simplified.
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Paragraph 0032; 0033; 0034-0037
(2019/02/04)
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- Synthetic method for 2,4-dichloroacetophenone
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The invention discloses a synthetic method for 2,4-dichloroacetophenone. The method comprises the step of performing an electrophilic substitution reaction by using m-dichlorobenzene and acetic anhydride as raw materials to synthesize the 2,4-dichloroacetophenone. According to the method provided by the invention, the electrophilic substitution reaction is performed by adopting a reactive rectification manner, a vacuum degree of a reaction rectification column is adjusted, temperature of the reaction rectification column is controlled, reactive rectification is performed under the optimal temperature condition, so that the catalyst unit consumption and the acetic anhydride unit consumption are reduced, and the production process is simplified.
- -
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Paragraph 0033-0038
(2019/05/16)
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- Design, synthesis and structure-based optimization of novel isoxazole-containing benzamide derivatives as FtsZ modulators
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Antibiotic resistance among clinically significant bacterial pathogens is becoming a prevalent threat to public health, and new antibacterial agents with novel mechanisms of action hence are in an urgent need. Utilizing computational docking method and structure-based optimization strategy, we rationally designed and synthesized two series of isoxazol-3-yl- and isoxazol-5-yl-containing benzamide derivatives that targeted the bacterial cell division protein FtsZ. Evaluation of their activity against a panel of Gram-positive and -negative pathogens revealed that compounds B14 and B16 that possessed the isoxazol-5-yl group showed strong antibacterial activity against various testing strains, including methicillin-resistant Staphylococcus aureus and penicillin-resistant S. aureus. Further molecular biological studies and docking analyses proved that the compound functioned as an effective inhibitor to alter the dynamics of FtsZ self-polymerization via a stimulatory mechanism, which finally terminated the cell division and caused cell death. Taken together, these results could suggest a promising chemotype for development of new FtsZ-targeting bactericidal agent.
- Bi, Fangchao,Song, Di,Zhang, Nan,Liu, Zhiyang,Gu, Xinjie,Hu, Chaoyu,Cai, Xiaokang,Venter, Henrietta,Ma, Shutao
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- Method for synthesizing azaconazole through 4-amino-4H-1,2,4-triazole alkylation
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The invention discloses a method for synthesizing azaconazole through 4-amino-4H-1,2,4-triazole alkylation. The method comprises step 1, preparing a raw material which is shown in a following image; step 2, synthesizing 1-(2,4-dichlorophenyl)-2-(1H-1,2,4-triazole-1-yl) ethanone; step 3, synthesizing azaconazole. The method disclosed by the invention has the advantages that development of a novel azaconazole bactericide successfully fills the blank in China, synthesis researches of similar derivatives based on the azaconazole bactericide will be in the ascendant, and successful development andindustrial implementation of varieties of novel bactericides have a far-reaching influence on national economy development. The method disclosed by the invention is an azaconazole synthesizing method.
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Paragraph 0035
(2018/11/03)
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- Synthesis method of azaconazole intermediate
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The invention discloses a synthesis method of an azaconazole intermediate. The synthesis method mainly comprises a synthesis method of 2,4-dichloroacetophenone, a synthesis method of 2-bromo-1-(2,4-dichlorophenyl) ethyl ketone, and a synthesis method of ketal. The preparation method has the advantages that the development of the novel azaconazole bactericide fills up a domestic blank in the field,similar derivative synthesis research based on the synthesis method is in the ascendant, and successful development and industrial implementation of various novel bactericides can be realized. The invention provides a novel azaconazole synthesis method.
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Paragraph 0036
(2019/01/04)
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- Fe(NO3)3·9H2O-catalyzed aerobic oxidative deoximation of ketoximes and aldoximes under mild conditions
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A mild, simple process for the effective aerobic oxidative deoximation of a wide range of ketoximes and aldoximes has been developed that utilizes Fe(NO3)3·9H2O as the single catalyst and molecular oxygen as the green oxidant. The environmentally benign protocol provides moderate to excellent yield and broad functional groups tolerance and is a valuable synthetic method for practical applications. According the relevant verification experiment, a plausible mechanism has been proposed.
- Li, Yongshu,Xu, Nizhou,Mei, Guangyao,Zhao, Yun,Zhao, Yiyong,Lyu, Jinghui,Zhang, Guofu,Ding, Chengrong
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supporting information
p. 810 - 814
(2018/08/09)
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- A TEMPO-like nitroxide combined with an alkyl-substituted pyridine: An efficient catalytic system for the selective oxidation of alcohols with iodine
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An efficient method for the oxidation of alcohols to aldehydes or ketones in a two-phase CH2Cl2/NaHCO3 (aq.) system, using iodine and catalytic amounts of 4-acetylamino-2,2,6,6-tetramethylpiperidine-1-oxyl and 2,4,6-trimethylpyridine, was developed. The performance of the method was demonstrated by the selective oxidation of 37 variously substituted alcohols in ≥90% yield, including the gram-scale synthesis of the important chemical 2,5-diformylfuran from biomass-derived 5-hydroxylmethylfurfural.
- Kashparova, Vera P.,Klushin, Victor A.,Zhukova, Irina Yu.,Kashparov, Igor S.,Chernysheva, Daria V.,Il'chibaeva, Irina B.,Smirnova, Nina V.,Kagan, Efim Sh.,Chernyshev, Victor M.
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supporting information
p. 3517 - 3521
(2017/10/05)
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- A Rapid, efficient method for deprotection of oximes to carbonyl compounds with naclo2 in water
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A rapid, efficient method for deprotection of oximes to carbonyl compounds is demonstrated by using sodium chlorite (NaClO2) in water. The protocol has been found to be applicable to a wide range of aldoximes and ketoximes with good to excellent yields of the corresponding carbonyl compounds.
- Yao, Yuan-Yuan,Zhao, Xian-Liang
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- Palladium catalyzed decarboxylative acylation of arylboronic acid with ethyl cyanoacetate as a new acylating agent: Synthesis of alkyl aryl ketones
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Palladium catalyzed acylation of arylboronic acid containing various functional groups was performed efficiently by ethyl cyanoacetate/substituted ethyl cyanoacetate as the acylating agent in aqueous triflic acid medium. The alkyl aryl ketones were obtained in good to excellent yields, first by addition of arylboronic acid to the nitrile group of ethyl cyanoacetate and their derivatives, followed by in situ decarboxylation of the resulting β-ketoester.
- Yousuf, Md,Das, Tuluma,Adhikari, Susanta
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p. 8763 - 8770
(2015/11/10)
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- γ-halo-enones: A method for their synthesis from arylacyl halides and their application to the preparation of five-membered ring heterocycles
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A simple method has been developed for synthesis of γ-halo-enones. The approach employs a sequence involving initial indium-mediated allenylation reactions of phenacyl halides with propargyl bromide. This process is followed by acid-promoted rearrangement reactions of the formed homoallenic halohydrins. The new method can be incorporated into routes for the efficient synthesis of various five-membered heterocyclic compounds.
- Lin, Mei-Huey,Huang, Yen-Chih,Kuo, Chung-Kai,Tsai, Chang-Hsien,Li, Yi-Syuan,Hu, Ting-Chia,Chuang, Tsung-Hsun
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p. 2751 - 2757
(2014/04/17)
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- Practical metal- and additive-free methods for radical-mediated reduction and cyclization reactions
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Two facile, metal- and additive-free protocols for radical dehalogenation, deoxygenation and cyclization reactions are reported. Irradiation by household fluorescent light bulbs or the presence of an air atmosphere is shown to initiate the desired reactions, thus providing highly practical reaction setups for radical-mediated reductions and cyclizations.
- Jiang, Hao,Bak, Jesper R.,Lopez-Delgado, Francisco Javier,Jorgensen, Karl Anker
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supporting information
p. 3355 - 3359
(2013/12/04)
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- Highly selective Wacker reaction of styrene derivatives: A green and efficient aerobic oxidative process promoted by benzoquinone/NaNO 2/HClO4 under mild conditions
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A green and efficient catalytic redox system for the aerobic oxidative Wacker oxidation of styrene derivatives at room temperature using molecular oxygen as the terminal oxidant without copper chloride has been developed. The newly developed system exhibited excellent catalytic activity for the smooth transformation of terminal styrene derivatives to the desired methyl ketones with up to 96% yield and >99% selectivity. The Royal Society of Chemistry 2013.
- Zhang, Guofu,Xie, Xiaoqiang,Wang, Yong,Wen, Xin,Zhao, Yun,Ding, Chengrong
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supporting information
p. 2947 - 2950
(2013/07/25)
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- L-Proline: An efficient N,O-bidentate ligand for copper-catalyzed aerobic oxidation of primary and secondary benzylic alcohols at room temperature
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A novel and highly practical copper-catalyzed aerobic alcohol oxidation system with l-proline as the ligand at room temperature has been developed. A wide range of primary and secondary benzylic alcohols tested have been smoothly transformed into corresponding aldehydes and ketones with high yields and selectivities.
- Zhang, Guofu,Han, Xingwang,Luan, Yuxin,Wang, Yong,Wen, Xin,Ding, Chengrong
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supporting information
p. 7908 - 7910
(2013/09/02)
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- Candida tenuis xylose reductase catalyzed reduction of aryl ketones for enantioselective synthesis of active oxetine derivatives
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Candida tenuis xylose reductase shows high catalytic efficiencies in carbonyl reduction of acetophenone and 1-phenyl-1-propanone derivatives. The quite low substrate solubility in aqueous buffer systems is circumvented by addition of methanol or by two-phase solvent systems. In the latter, methanol improves the substrate phase transfer as solvent mediator and leads to reasonable space/time yields. Resulting enantiomerically pure chiral alcohols are key intermediates for synthesis of active pharmaceutical ingredients. (R)-Atomoxetine is exemplarily synthesized in four steps, and the further use for generation of other oxetine derivatives and a polo-like kinase 1 inhibitor are discussed. Copyright
- Vogl, Michael,Brecker, Lothar,Kratzer, Regina,Nidetzky, Bernd
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p. 847 - 853,7
(2020/07/31)
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- Stereoselective oxidation and reduction by immobilized Geotrichum candidum in an organic solvent
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Cells of the fungus, Geotrichwn candidum, were immobilized on a water-absorbing polymer and used for stereoselective oxidation and reduction in an organic solvent using cyclohexanone, cyclopentanol or alkan-2-ols as additive. Enantiomerically pure (.β)-1-arylethanols were obtained by the stereoselective oxidation of racemic 1-arylethanols, whereas enantiomerically pure (S)- 1-arylethanols were obtained by the reduction of the corresponding ketones, in contrast to reduction in water by the free cells in which (R)- or (S)- 1-arylethanols were produced in low ee. The reaction mechanism was investigated by measuring the partition of the substrates and products between the organic phase and aqueous phase in the polymer around which the cells were immobilized. Deuterated compounds were used to determine the role of the additives.
- Nakamura, Kaoru,Inoue, Yuko,Matsuda, Tomoko,Misawa, Ibuki
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p. 2397 - 2402
(2007/10/03)
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- N-(α-alkylbenzylidene)-α-phenylalkylamine, its use and process for producing the same and process for producing intermediate therefor
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There is disclosed an N-(α-alkylbenzylidene)-α-phenylalkylamine represented by the general formula (1): STR1 wherein R1 represents a lower alkyl group, R2 represents a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkoxy group and X represents a halogen atom or a lower alkoxy group, its use and a process for producing the same and processes for producing intermediates therefor.
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- Preparation of carbon-14 labeled organophosphate pesticides: Chlorfenvinphos
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Synthesis of [vinyl-14C]chlorfenvinphos, utilizing [14C]iodomethane as the source of the label, was accomplished in 28% radiochemical yield by the methylation of 2,4-dichlorobenzoyl chloride, chlorination of the resulting [14C]-2,4-dichloroacetophenone, and condensation of the product with triethylphosphite. The product, isolated as a mixture of E and Z isomere (3.6 and 96.3%, respectively), was obtained in >99% purity and had specific activity 20 mCl/mmol.
- Fudala, Louise,Lewin, Anita H.
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p. 261 - 266
(2007/10/03)
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- CYANO-CARBONATES (I) - EFFICIENT LATENT ACYL CARBANIONS
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Cyano-carbonates, conveniently prepared in excellent yields by in situ trapping of cyanohydrin anions with chloroformates under PTC conditions, have been found to be efficient ketone precursors.
- Au, Andrew T.
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p. 743 - 748
(2007/10/02)
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- REACTIONS OF 2,4- AND 2,6-DICHLOROPHENACYLIDENE HALIDES WITH TRIALKYLPHOSPHITES IN PROTIC SOLVENTS. DIRECT EVIDENCE FOR THE "ENOLATE ANION" PATHWAY
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The reactions of 2,6-dichlorophenacyl and 2,6-dichlorophenacylidene chlorides and bromides with trimethyl and triethyl phosphites have been investigated.The reactivity of 2,6-dichlorophenacylidene chloride and bromide towards trialkyl phosphites was compared with that of 2,4-dichlorophenacylidene chloride and bromide.The influence of methanol, acting as a model protic solvent, on the above mentioned processes has also benn investigated.The mechanism of Perkow reaction of sterically hindered α-haloketones with bulky substituents around the carbonyl center is discussed.
- Mlotkowska, Barbara,Majewski, Piotr,Koziara, Anna,Zwierzak, Andrzej,Sledzinski, Bohdan
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p. 631 - 642
(2007/10/02)
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