69673-92-3Relevant articles and documents
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.
Synthesis and reactivity of α-sulfenyl-β-chloroenones, including oxidation and Stille cross-coupling to form chalcone derivatives
Kearney, Aoife M.,Murphy, Linda,Murphy, Chloe C.,Eccles, Kevin S.,Lawrence, Simon E.,Collins, Stuart G.,Maguire, Anita R.
supporting information, (2021/05/04)
The synthesis of a range of novel α-sulfenyl-β-chloroenones from the corresponding α-sulfenylketones, via a NCS mediated chlorination cascade, is described. The scope of the reaction has been investigated and compounds bearing alkyl- and arylthio substituents have been synthesised. In most instances, the Z α-sulfenyl-β-chloroenones were formed as the major products, while variation of the substituent at the β-carbon position led to an alteration in stereoselectivity. Stille cross-coupling with the Z α-sulfenyl-β-chloroenones led to selective formation of Z sulfenyl chalcones, while the E α-sulfenyl-β-chloroenones did not react under the same conditions. Oxidation of the Z α-sulfenyl-β-chloroenones was followed by isomerisation, leading to the E α-sulfinyl-β-chloroenones. Stille cross-coupling with the E α-sulfinyl-β-chloroenones produced the E sulfinyl chalcones. Either the E or Z sulfinyl chalcones can be obtained by altering the sequence of oxidation and Stille cross-coupling.
Production method of 2-(4-bromomethyl phenyl)propionic acid
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Paragraph 0016; 0022; 0025, (2020/03/06)
The invention discloses a production method of 2-(4-bromomethyl phenyl)propionic acid. An adopted ionic liquid catalyst can be recycled and used, no molten aluminum trichloride is generated, a material does not need to be washed for multiple times, only layered extraction needs to be conducted, then a required product can be obtained, aluminum trichloride and triethanolamine salt ionic liquid is used, thus environmentally friendliness is achieved, the cost is also saved, and that is, an original cumbersome process is simplified. An original bromination reaction in a glass kettle is changed toa cooling glass pipeline circulation-type bromination reaction in the kettle, through the glass pipeline type reaction, the contact area of the material and light is increased, through circulation, the situation that the material is gathered on the illumination surface, and consequently light illumination is affected is avoided, thus the reaction efficiency is higher, the reaction time is shortened, the occurrence of a side reaction is controlled, and the product purity is higher.
Phase I metabolites of mephedrone display biological activity as substrates at monoamine transporters
Mayer,Wimmer,Dillon-Carter,Partilla,Burchardt,Mihovilovic,Baumann,Sitte
, p. 2657 - 2668 (2016/10/19)
Background and Purpose: 4-Methyl-N-methylcathinone (mephedrone) is a synthetic stimulant that acts as a substrate-type releaser at transporters for dopamine (DAT), noradrenaline (NET) and 5-HT (SERT). Upon systemic administration, mephedrone is metabolized to several phase I compounds: the N-demethylated metabolite, 4-methylcathinone (nor-mephedrone); the ring-hydroxylated metabolite, 4-hydroxytolylmephedrone (4-OH-mephedrone); and the reduced keto-metabolite, dihydromephedrone. Experimental Approach: We used in vitro assays to compare the effects of mephedrone and synthetically prepared metabolites on transporter-mediated uptake and release in HEK293 cells expressing human monoamine transporters and in rat brain synaptosomes. In vivo microdialysis was employed to examine the effects of i.v. metabolite injection (1 and 3?mg·kg?1) on extracellular dopamine and 5-HT levels in rat nucleus accumbens. Key Results: In cells expressing transporters, mephedrone and its metabolites inhibited uptake, although dihydromephedrone was weak overall. In cells and synaptosomes, nor-mephedrone and 4-OH-mephedrone served as transportable substrates, inducing release via monoamine transporters. When administered to rats, mephedrone and nor-mephedrone produced elevations in extracellular dopamine and 5-HT, whereas 4-OH-mephedrone did not. Mephedrone and nor-mephedrone, but not 4-OH-mephedrone, induced locomotor activity. Conclusions and Implications: Our results demonstrate that phase I metabolites of mephedrone are transporter substrates (i.e. releasers) at DAT, NET and SERT, but dihydromephedrone is weak in this regard. When administered in vivo, nor-mephedrone increases extracellular dopamine and 5-HT in the brain whereas 4-OH-mephedrone does not, suggesting the latter metabolite does not penetrate the blood–brain barrier. Future studies should examine the pharmacokinetics of nor-mephedrone to determine its possible contribution to the in vivo effects produced by mephedrone.
Method for synthesizing loxoprofen sodium medicine intermediate 1-p-methylphenyl-2-chloro-acetone
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Paragraph 0015; 0016, (2016/11/14)
The invention relates to a method for synthesizing a Loxoprofen sodium medicine intermediate 1-p-methylphenyl-2-chloro-acetone. The method comprises the following steps: (i) adding 2.4 to 2.43 mol of stannous chloride and 1.2L of methylbenzene to a reaction vessel provided with a stirrer, a thermometer, a reflux condenser and a dropping funnel, reducing the temperature of the solution to 2 to 5 DEG C, and dropwise adding 2.1 mol of 2-chloride propionamide, wherein the dropwise adding time is controlled within 3h to 4h; maintaining the stirring speed to be 180rpm to 210 rpm for 9h to 10h, pouring the reactant to 2L of sodium chloride solution, reducing the temperature of the solution to 2 to 4 DEG C, separating an organic layer out, extracting a water layer with methylbenzene for 3 to 6 times, merging the organic layers, washing with a sodium carbonate solution and a salt solution in sequence, carrying out reduced-pressure distillation, recovering a solvent to obtain an oily matter, reducing the temperature of the solution to 12 to 15 DEG C and separating solid out, adding a cyclohexane solution, maintaining the stirring speed to be 200rpm to 230rpm, carrying out suction filtering, and dehydrating with a dehydrating agent to obtain white solid 1-p-methylphenyl-2-chloro-acetone.
Iodine(III)-Mediated Oxidative Hydrolysis of Haloalkenes: Access to α-Halo Ketones by a Release-and-Catch Mechanism
Jobin-Des Lauriers, Antoine,Legault, Claude Y.
supporting information, p. 108 - 111 (2016/01/15)
An unprecedented iodine(III)-mediated oxidative transposition of vinyl halides has been accomplished. The products obtained, α-halo ketones, are useful and polyvalent synthetic precursors. There are only a handful of reported examples of the direct conversion of vinyl halides to their corresponding α-halo carbonyl compounds. Insights into the mechanism and demonstration that this synthetic transformation can be done under enantioselective conditions are reported.
Efficient α-chlorination and α-bromination of carbonyl compounds using N-halosuccinimides/UHP in ionic liquid
Lee, Jong Chan,Park, Hyun Jung
, p. 87 - 90 (2007/10/03)
A facile and efficient method for the α-halogenation of carbonyl compounds utilizing N-halosuccinimides (NXS) in the presence of urea-hydrogen peroxide (UHP) in [bmim]BF4 has been newly developed. Copyright Taylor & Francis Group, LLC.
Efficient α-chlorination of aryl ketones using aluminum chloride/urea-hydrogen peroxide in ionic liquid
Jong, Chan Lee,Hyun, Jung Park
, p. 777 - 780 (2007/10/03)
Effective α-chlorination reactions of aryl ketones into the corresponding α-chloroketones have been accomplished with aluminum chloride hexahydrate and urea-hydrogen peroxide in [bmim]BF4 ionic liquid. Copyright Taylor & Francis Group, LLC.
Photochemical Rearrangement of α-Chloro-Propiophenones to α-Arylpropanoic Acids: Studies on Chirality Transfer and Synthesis of (S)-(+)-Ibuprofen and (S)-(+)-Ketoprofen
Sonawane, Harikisan,Bellur, Nanjundiah S.,Kulkarni, Dilip G.,Ayyangar, Nagaraj R.
, p. 1243 - 1260 (2007/10/02)
A new single-step efficient photochemical approach for α-arylpropanoic acids (4) from α-chloro-propiophenones (5) is described.It involves carbonyl triplet excited state directed 1,2-aryl migration of the aryl group which has been found to be highly dependent upon the nature of the aryl substituent.The mode of the rearrangement is probed by the study of the photobehaviour of a set of optically active α-chloro-propiophenones.The results suggest that the nature of the carbonyl triplets (n, ?*/ ?, ?*) plays an important role in the chirality transfer.This method finds application in the synthesis of optically active ibuprofen (4e) and ketoprofen (26), though in moderate optical yields.
One-Pot Synthesis of α-Chloro Ketones from Secondary Alcohols Using N,N-Dichloro-p-toluenesulfonamide
Kim, Yong Hae,Lee, In Sang,Lim, Sang Chul
, p. 1125 - 1128 (2007/10/02)
Various alkyl aryl secondary alcohols reacted with N,N-dichloro-p-toluenesulfonamide (N,N-dichloroamine-T) in CH3CN at 35 deg C to give the corresponding α-chloro ketones in excellent yields under mild and neutral conditions.
