2648-61-5Relevant academic research and scientific papers
Reactions of α-chloro β-oxo aldehydes with CH-acid anions
Guseinov, F. I.
, p. 743 - 745 (1999)
The reactions of α-chloro and α,α-dichloro β-oxo aldehydes with carbanions are accompanied by the cleavage of the carbon-carbon bond in the chloro aldehydes and result in formylation of CH-acids. These electrophiles react with carbanions, which are generated in situ from CH-acids in the presence of AcONa in aprotic solvents, to form polyfunctional hydroxy compounds.
Access to α,α-dihaloacetophenones through anodic C[dbnd]C bond cleavage in enaminones
Zhang, Zhenlei,Yang, Jiusi,Wu, Kairui,Yu, Renjie,Bu, Jiping,Huang, Zijun,Li, Shaoke,Ma, Xiantao
supporting information, (2021/12/20)
We have developed a method to synthesize α,α-dihaloketones under electrochemical conditions. In this reaction, the Cl- or Br- is oxidized to Cl2 or Br2 at the anode, which undergoes two-step addition reactions with the N,N-dimethyl enaminone, and finally breaks C[dbnd]C of the N,N-dimethyl enaminone to generate α,α-dihaloketones. The electrosynthesis reaction can be conveniently carried out in an undivided electrolytic cell at room temperature. In addition, various functional groups are compatible with this green protocol which can be applied simultaneously to the gram scale without significantly lower yield.
Method for preparing alpha,alpha-dichloroketone under solvent-free condition
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Page/Page column 4-5, (2021/06/21)
The invention provides a method for synthesizing an alpha,alpha-dichloroketone compound by taking methyl ketone and sulfonyl chloride as raw materials. The method comprises the following steps: heating a reaction mixture of methyl ketone and sulfonyl chloride to 80 DEG C under a dry air condition, stirring for 4-8 hours, after the reaction is finished, removing sulfonyl chloride from the obtained mixture, and carrying out silica gel column chromatography separation by taking ethyl acetate-hexane as an eluent to obtain the alpha,alpha-dichloroketone compound. The synthesis method provided by the invention has the advantages of extremely high chemical reactivity and selectivity, simple and easily available raw materials, low price, simple operation, no need of any catalyst and solvent, reduction of the synthesis cost and the pollution of organic solvents to the environment, greenness, economy and the like.
Solvent-free preparation of α,α-dichloroketones with sulfuryl chloride
Tu, Dewei,Luo, Juan,Jiang, Wengao,Tang, Qiang
supporting information, (2021/09/15)
An efficient and facile method is reported for the synthesis of a series of α,α-dichloroketones. The direct dichlorination of methyl ketones and 1,3-dicarbonyls using an excess amount of sulfuryl chloride affords the corresponding gem-dichloro compounds in moderate to excellent yields. Moreover, the protocol features high yields, broad substrate scope, and simple reaction conditions without using any catalysts and solvents.
Method for synthesizing mandelic acid
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Paragraph 0032-0033; 0035-0036; 0038-0039; 0041-0042, (2021/02/06)
The invention relates to the technical field of compound preparation, and provides a method for synthesizing mandelic acid, which comprises the following steps: by using styrene as a basic raw material, trichloroisocyanuric acid as a chlorinating agent an
Modular and Chemoselective Strategy for Accessing (Distinct) α,α-Dihaloketones from Weinreb Amides and Dihalomethyllithiums
Malik, Monika,Pace, Vittorio,Senatore, Raffaele,Touqeer, Saad,Urban, Ernst
supporting information, p. 5056 - 5061 (2020/10/21)
The selective transfer of diversely functionalized dihalomethyllithiums (LiCHBrCl, LiCHClI, LiCHBrI, LiCHCl2, LiCHBr2, LiCHFI) to Weinreb amides for preparing gem-dihaloketones in one synthetic operation is reported. The capability of these amides as acylating agents and, the wide availability of dihalomethanes as pronucleophiles, enable a straightforward route to the title compounds under full chemocontrol. No racemization phenomena were evidenced in the case of optically active materials. Additionally, tolerance to sensitive functional groups (esters, amides, halogens, olefins etc.) was uniformly noticed, thus making this conceptually intuitive strategy flexible and tunable by the operator. (Figure presented.).
Dichloroacetophenone Derivatives: A Class of Bioconjugation Reagents for Disulfide Bridging
Wu, Liu-Hai,Zhou, Shuguang,Luo, Qun-Feng,Tian, Jie-Sheng,Loh, Teck-Peng
supporting information, p. 8193 - 8197 (2020/11/18)
A mild and biocompatible method for the construction of disulfide bridging in peptides using dichloroacetophenone derivatives is developed. This method is highly selective (chemo, diastereo, regio, etc.) and atom economic and works under biocompatible reaction conditions (metal-free, water, pH 7, rt, etc.).
Electrochemical synthesis of α,α-dihaloacetophenones from terminal alkyne derivatives
Li, Zhibin,Sun, Qi,Qian, Peng,Hu, Kangfei,Zha, Zhenggen,Wang, Zhiyong
supporting information, p. 1855 - 1858 (2020/03/10)
By virtue of electrochemistry, a series of α,α-dihaloacetophenones were easily obtained with good to excellent yields. This electrochemical procedure was taken in a divided cell with constant current in aqueous media. The reaction can be carried out smoothly at room temperature under metal and oxidant free condition, which provides an eco-friendly synthesis for the α,α-dihaloacetophenone derivatives.
Oxidative Photochlorination of Electron-Rich Arenes via in situ Bromination
Düsel, Simon Josef Siegfried,K?nig, Burkhard
supporting information, p. 1491 - 1495 (2019/04/30)
Electron-rich arenes are oxidatively photochlorinated in the presence of catalytic amounts of bromide ions, visible light, and 4CzIPN as organic photoredox catalyst. The substrates are brominated in situ in a first photoredox-catalyzed oxidation step, followed by a photocatalyzed ipso-chlorination, yielding the target compounds in high ortho/para regioselectivity. Dioxygen serves as a green and convenient terminal oxidant. The use of aqueous hydrochloric acid as the chloride source reduces the amount of saline by-products.
Electrochemical Oxidative Oxydihalogenation of Alkynes for the Synthesis of α,α-Dihaloketones
Meng, Xiangtai,Zhang, Yu,Luo, Jinyue,Wang, Fei,Cao, Xiaoji,Huang, Shenlin
supporting information, p. 1169 - 1174 (2020/02/04)
An electrochemical oxydihalogenation of alkynes has been developed for the first time. Using this sustainable protocol, a variety of α,α-dihaloketones can be prepared with readily available CHCl3, CH2Cl2, ClCH2CH2Cl, and CH2Br2 as the halogen source under electrochemical conditions at room temperature.
