822-87-7Relevant articles and documents
The room temperature formation of gold nanoparticles from the reaction of cyclohexanone and auric acid; A transition from dendritic particles to compact shapes and nanoplates
Uppal, Madeeha A.,Kafizas, Andreas,Ewing, Michael B.,Parkin, Ivan P.
, p. 7351 - 7359 (2013)
A new straightforward method for the synthesis of gold nanoparticles from addition of cyclohexanone to aqueous solutions of auric acid at room temperature is presented. By understanding this process we have discovered a new organic chemistry transformation reaction for converting cyclic ketones to α-chloro ketones and a mechanism for the nanoparticle formation. Contrary to conventional gold nanoparticle syntheses, the reaction self- initiates at room temperature and forms an increasingly red solution over ≈60 minutes. By studying the gold colloid's formation using transmission electron microscopy it was observed that large dendritic (63 ± 21 nm diameter) structures made of clustered particles (6 ± 1 nm) were initially formed. These dendritic particles then compacted into an array of denser shapes that slowly increase in size until the reaction is complete. The most prominent shapes observed were spheres (43 ± 7 nm); other shapes included dodecahedra (39 ± 10 nm) triangular (≈50 nm in height) and hexagonal (≈70 nm wide) nanoplates. The solution was stable to precipitation for over 3 months. During this period the nanoplate structures substantially increased in size (triangular ≈ 250 nm, hexagonal ≈ 320 nm) whereas other structures showed no further growth. X-ray diffraction studies demonstrated that the gold nanoparticles were crystalline. The formation of the 2-chlorocyclohexanone by-product was observed in solution phase 1H & 13C NMR, gas phase chromatography and IR spectroscopy. A mechanism is presented to account for this by-product and the reduction of auric acid to gold. The Royal Society of Chemistry 2013.
Synthesis of Ti-Al binary oxides and their catalytic application for C-H halogenation of phenols, aldehydes and ketones
Su, Peigen,Fan, Chao,Yu, Heng,Wang, Wanqin,Jia, Xin,Rao, Qifan,Fu, Chenxi,Zhang, Donghua,Huang, Benhua,Pan, Cheng,Zheng, Aqun,Sun, Yang
, (2019/06/13)
Traditional C–H halogenation of organic compounds often requires corrosive agent or harsh condition, and current researches are focused on the use of noble metals as catalyst. In order to give an efficient, benign, activity-adjustable and cost-effective system for halogenation, a series of Ti-Al mixed oxides are prepared as catalyst through sol-gel in this work. Characterizations reveal all catalysts contain more aluminum than titanium, but preparative conditions affect their composition and crystallinity. Monitoring of particle size, zeta potential and UV–vis of preparative solution reveals that formation of catalyst colloids undergoes chemical reaction, affecting catalyst morphology. In halogenation, all catalysts show moderate to high activities, copper chloride proves to be an effective halogen source rather than sodium chloride. The chlorination and bromination are better than iodization, phenol and ketone appear to be more appropriate substrates than aldehyde. Additionally, oxide backbone of catalyst is more durable than its organic components during recycling. This study may provide new catalytic materials for progress of C–H activation.
Method for preparing o-chlorocyclohexanone by using cyclohexanone by-product lightweight oil
-
Paragraph 0016; 0017; 0018; 0019; 0020, (2018/04/01)
The invention discloses a method for preparing o-chlorocyclohexanone through lightweight oil, wherein the lightweight oil is the by-product obtained from cyclohexanone preparation through oxidation ofcyclohexane, and the o-chlorocyclohexanone is prepared in the presence of an auxiliary agent and a catalyst by completely utilizing the cyclohexene oxide in the lightweight oil through ring opening,oxidation and other reactions. According to the present invention, with the method, the disadvantages of more impurities, harsh reaction condition or complex product purification and the like in the prior art are solved. The method comprises: in the presence of an auxiliary agent, carrying out a reaction on lightweight oil containing 1 mole of cyclohexene oxide and 1-2 moles of a hydrogen chloridesolution for 1-4 h at a temperature of 10-60 DEG C to generate 2-chlorocyclohexanol, distilling to remove the relatively low boiling point components to obtain high-purity 2-chlorocyclohexanol, carrying out a reaction on the high-purity 2-chlorocyclohexanol as a raw material and a certain amount of an oxidizing agent, washing, separating, rectifying, and collecting the distillate at a temperatureof 203-204 DEG C to obtain the o-chlorocyclohexanone with the purity of more than 99%, wherein the yield of the o-chlorocyclohexanone is more than 90%.
Ammonium Tungstate as an Effective Catalyst for Selective Oxidation of Alcohols to Aldehydes or Ketones with Hydrogen Peroxide under Water - A Synergy of Graphene Oxide
Fu, Huihui,Hu, Chuanfeng,Huang, Zhida,Zhou, Jianhao,Peng, Xinhua
supporting information, p. 447 - 451 (2017/11/27)
Ammonium tungstate was found to be a facile and efficient catalyst for selective oxidation of alcohols to the corresponding carbonyl compounds with hydrogen peroxide as oxidant. Heterogeneous graphene oxide as acid effectively intensified the transformations and resulted in excellent yields. The use of water as solvent rendered the reactions promising both economically and environmentally.
Efficient α-chlorination of carbonyl containing compounds under basic conditions using methyl chlorosulfate
Silva, Saúl,Maycock, Christopher D.
supporting information, p. 1233 - 1238 (2018/02/27)
An efficient method for the α-chlorination of ketones under basic conditions is described using methyl chlorosulfate. Its applicability for the chlorination of other functional groups has also been studied and it is equally useful for the synthesis of α-chloroesters and amides. Methyl chlorosulfate is described for the first time as a positive chlorine source. Some aldol reactions which occur during the chlorination of some substrates are also reported.
Rearrangement Reaction Based on the Structure of N-Fluoro- N-alkyl Benzenesulfonamide
Wang, Han-Ying,Pu, Xiao-Qiu,Yang, Xian-Jin
, p. 13103 - 13110 (2018/10/20)
A novel rearrangement reaction based on the structure of N-fluoro-N-alkyl benzenesulfonamide was developed. The reaction proceeded readily at 50 °C in formic acid and generated a variety of benzenesulfonamides and aldehydes or ketones simultaneously. The reaction mechanism is believed to be a concerted mechanism that consist of 1,2-aryl migration with the departure of fluorine anion via an SN2 mechanism. This rearrangement reaction features an interesting reaction mechanism, mild reaction conditions, simple operations, and a broad substrate scope.
Trichloromethanesulfonyl chloride: A chlorinating reagent for aldehydes
Jimeno, Ciril,Cao, Lidong,Renaud, Philippe
, p. 1251 - 1255 (2016/02/19)
Trichloromethanesulfonyl chloride (CCl3SO2Cl), a commercially available reagent, has been found to perform efficiently in the α-chlorination of aldehydes, including its catalytic asymmetric version, under very mild reaction conditions. Under our reaction conditions, this compound outperforms typical chlorinating reagents for organic synthesis, facilitates workup and purification of the product, and minimizes the formation of toxic, chlorinated organic waste.
Direct conversion of alcohols to α-chloro aldehydes and α-chloro ketones
Jing, Yuanyuan,Daniliuc, Constantin G.,Studer, Armido
supporting information, p. 4932 - 4935 (2015/04/27)
Direct conversion of primary and secondary alcohols into the corresponding α-chloro aldehydes and α-chloro ketones using trichloroisocyanuric acid, serving both as stoichiometric oxidant and α-halogenating reagent, is reported. For primary alcohols, TEMPO has to be added as an oxidation catalyst, and for the transformation of secondary alcohols (TEMPO-free protocol), MeOH as an additive is essential to promote chlorination of the intermediary ketones.
Development of a generic activation mode: Nucleophilic α-substitution of ketones via oxy-allyl cations
Vander Wal, Mark N.,Dilger, Andrew K.,Macmillan, David W. C.
, p. 3075 - 3079 (2013/07/26)
Oxy-allyl cations have been known as transient electrophilic species since they were first proposed as intermediates in the Favorskii rearrangement in 1894. Since that time, they also have been used as a mode of activation for [4 + 3] cycloadditions in a variety of natural product syntheses. In this manuscript, we describe a method for the interception of oxy-allyl cations with a diverse range of common nucleophiles, thereby demonstrating the value of this intermediate as a generic mode of activation. This simple, mild, room temperature protocol allows for the formation of a variety of high value carbon-carbon and carbon-heteroatom bonds that are readily incorporated within a series of cyclic and acyclic ketone systems. Initial efforts into the development of an enantioselective catalytic variant are also described.
