- Non-metal catalytic method for preparing 1,3-diketone compounds based on acetyenic ketone
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The invention discloses a non-metal catalytic method for preparing 1,3-diketone compounds based on acetyenic ketone. The preparation method is a stepwise method or a one-pot method. The stepwise method comprises the following steps: mixing an acetyenic ketone compound I, a nitrogen-containing aromatic compound II and a No.1 base for a reaction, performing separation and purification to obtain an intermediate product, mixing the intermediate product and a No.2 base for a reaction, and performing separation and purification to obtain the product; and the one-pot method comprises the following steps: firstly mixing an acetyenic ketone compound I and a nitrogen-containing aromatic compound II, adding a No.1 base, performing a reaction for a period of time, adding a No.2 base, continuing a reaction for a period of time, and finally performing separation and purification to obtain the product. The method provided by the invention has mild reaction conditions, simple operation and a higher yield, wherein the yield is generally 80% or more, and the method has greater practical application value in drug synthesis.
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Paragraph 0104-0107
(2020/02/19)
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- Analyzing the Relation between Structure and Aggregation Induced Emission (AIE) Properties of Iridium(III) Complexes through Modification of Non-Chromophoric Ancillary Ligands
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Unconventionally modified dibenzoylmethane (dbm) ligands have been synthesized and successfully utilized as ancillary ligands for neutral iridium(III) complexes of the formula [Ir(dFppy)2(LX)], where dFppyH is 2-(2,4-difluorophenyl)pyridine and LX is tribenzoylmethane (tbm) or 1-phenyl-3-(4-(pyridin-2-yl)phenyl)propane-1,3-dione (pydbm). The modification of the ligands aims to prevent or enhance possible intermolecular interactions between the dFppy and/or the LX moiety in comparison with the previously reported [Ir(dFppy)2(dbm)] complex. The aggregation induced emission (AIE) properties of these complexes are significantly modulated, as a consequence of the different π–π interactions revealed by X-ray crystallography.
- Galán, Laura Abad,Cordes, David B.,Slawin, Alexandra M. Z.,Jacquemin, Denis,Ogden, Mark I.,Massi, Massimiliano,Zysman-Colman, Eli
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p. 152 - 163
(2018/11/23)
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- Novel Bifunctionalization of Activated Methylene: Base-Promoted Trifluoromethylthiolation of β-Diketones with Trifluoromethanesulfinyl Chloride
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A novel bifunctionalization of activated methylene was achieved successfully through the base-promoted trifluoromethylthiolation of β-diketones or β-ketoesters with trifluoromethanesulfinyl chloride. A series of α-trifluoromethylthiolated α-chloro-β-diketones and α-chloro-β-ketoesters were obtained in moderate to good yields under mild conditions. When β-diketones containing a phenyl group with a hydroxyl or amino substituent at the ortho position were used as substrates, intramolecular trifluoromethylthiolation/cyclization reaction took place to give the corresponding cyclic products. Furthermore, the protocol could be extended to perfluoroalkylthiolation with the sodium perfluoroalkanesulfinate/POCl3 system. On the basis of experimental results, plausible mechanisms are proposed.
- Sun, Dong-Wei,Jiang, Min,Liu, Jin-Tao
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supporting information
p. 10797 - 10802
(2019/07/03)
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- An effective preparation of both 1,3-diketones and nitriles from alkynones with oximes as hydroxide sources
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An effective phosphine-catalyzed protocol has been established for the syntheses of 1,3-diketones and nitriles from alkynones with oximes as hydroxide surrogates. This method features the use of a phosphine catalyst, compatibility with various functional groups and ambient temperature, which makes this approach very practical. A plausible mechanism was proposed.
- Chen, Pei,Zhang, Qian-Qian,Guo, Jia,Chen, Lu-Lu,Wang, Yan-Bo,Zhang, Xiao
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p. 6958 - 6966
(2018/10/02)
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- Triphenylamine-modified difluoroboron dibenzoylmethane derivatives: Synthesis, photophysical and electrochemical properties
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Two new triphenylamine functionalized difluoroboron (BF2) β-diketonate complexes, one asymmetrical 2 and the other symmetrical 3, were synthesized and fully characterized. The effects of the triphenylamine substituent on the photoluminescence,
- Zhang, Hao,Liu, Chun,Xiu, Jinghai,Qiu, Jieshan
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p. 798 - 806
(2016/09/28)
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- Synthesis and photophysical properties of halogenated derivatives of (dibenzoylmethanato)boron difluoride
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A series of (dibenzoylmethanato)boron difluoride (BF2DBM) derivatives with a halogen atom in one of the phenyl rings at the para-position were synthesized and used to elucidate the effects of changing the attached halogen atom on the photophysi
- Kononevich, Yuriy N.,Surin, Nikolay M.,Sazhnikov, Viacheslav A.,Svidchenko, Evgeniya A.,Aristarkhov, Vladimir M.,Safonov, Andrei A.,Bagaturyants, Alexander A.,Alfimov, Mikhail V.,Muzafarov, Aziz M.
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p. 177 - 184
(2017/01/03)
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- Room-Temperature Coupling/Decarboxylation Reaction of α-Oxocarboxylates with α-Bromoketones: Solvent-Controlled Regioselectivity for 1,2- and 1,3-Diketones
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A transition-metal-free and room-temperature coupling/decarboxylation reaction between α-oxocarboxylates and α-bromoketones is reported herein. It represents the first mild and regioselective synthesis of either 1,2- or 1,3-diketones from the same starting materials. Notably, the regioselectivity is simply controlled by solvents. The preliminary experimental data and DFT calculations suggest sequential Darzens-type coupling, alkaline hydrolysis, KOH-promoted oxirane opening and decarboxylation in one pot. This method is efficient for the synthesis of α,β-epoxy-γ-butyrolactone and curcuminoids.
- He, Zhen,Qi, Xiaotian,She, Zhijie,Zhao, Yinsong,Li, Shiqing,Tang, Junbin,Gao, Ge,Lan, Yu,You, Jingsong
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supporting information
p. 1403 - 1411
(2017/02/10)
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- 2-Hydroxylation of 1,3-Diketones with Atmospheric Oxygen
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An efficient method for the 2-hydroxylation of 1,3-diketones by using atmospheric oxygen as an oxidant under transition-metal-free condition is described. The protocol has the advantages of using an inexpensive and stable oxidant, producing high yields, and requiring ecofriendly conditions.
- Li, Zheng,Li, Tianpeng,Li, Jiasheng,He, Lili,Jia, Xianggui,Yang, Jingya
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supporting information
p. 2863 - 2865
(2015/12/18)
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- Transition-metal-free formal decarboxylative coupling of ?±-oxocarboxylates with ?±-bromoketones under neutral conditions: A simple access to 1,3-diketones
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A transition-metal-free formal decarboxylative coupling reaction between ?±-oxocarboxylates and ?±-bromoketones to synthesize 1,3-diketone derivatives is presented. In this reaction, a broad scope of substrates can be employed, and neither a metal-based reagent nor an additional base is required. DFT calculations reveal that this reaction proceeds through a coupling followed by decarboxylation mechanism and the ?±-bromoketone unprecedentedly serves as a nucleophile under neutral conditions. The rate-determining step is an unusual hydrogen-bond-assisted enolate formation by thermolysis.
- He, Zhen,Qi, Xiaotian,Li, Shiqing,Zhao, Yinsong,Gao, Ge,Lan, Yu,Wu, Yiwei,Lan, Jingbo,You, Jingsong
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p. 855 - 859
(2015/02/05)
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- Asymmetric transfer hydrogenation of unsymmetrical benzils
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In this paper, the asymmetric transfer hydrogenation of unsymmetrical benzils with m, p-substituents was conducted with a substrate/catalyst molar ratio of 100 at 40°C for 24 h to produce (S,S)-hydrobenzoins in good yields (76.2% to 97.1%) with high diastereomeric (syn/anti = 10.8 to 29.7/1) and enantiomeric purities (86.1%ee syn to 98.9%ee syn). Unfortunately, the unsymmetrical benzils with the o-substituents such as electron-donating (R = CH3, OCH3) and electron-withdrawing groups (R = F, Cl, CF3) resulted in poor yields (0% to 31.2%), even at 40°C for 72 h. These products had inefficient diastereoselectivities (syn/anti = 1.5 to 5.0/1) caused by steric effects. Furthermore, the results of a dynamic-kinetic study were used to propose a plausible reaction pathway of unsymmetrical benzil using 3-methoxy-1,2-diphenyl ethanedione as an example.
- Zhang, Hao,Feng, Dandan,Sheng, Haibo,Ma, Xuebing,Wan, Jinwei,Tang, Qian
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p. 6417 - 6423
(2014/02/14)
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- Chemo- and regioselective preparation and reaction of a kinetic zinc enolate formed from a thiol ester and bis(iodozincio)methane
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(Chemical Equation Presented) Reactive functionalized enolates that are otherwise difficult to obtain can be prepared in a simple procedure by the treatment of a thiol ester with bis(iodozincio)methane in the presence of a palladium catalyst (see scheme). The terminal zinc enolates thus formed are kinetically controlled and react with a variety of electrophiles, such as aldehydes, ketones, and acyl cyanides. FG = functional group.
- Ikeda, Zenichi,Hirayama, Takaharu,Matsubara, Seijiro
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p. 8200 - 8203
(2007/10/03)
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- Synthesis of vinyl-substituted β-diketones for polymerizable metal complexes
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Polymerizable β-diketones for application to metal ion coordination have been prepared and characterized. Bromine-substituted β-diketones were synthesized under Claisen-Schmidt-type condensation conditions. Vinyl groups were substituted for the halide by
- Southard, Glen E.,Murray, George M.
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p. 9036 - 9039
(2007/10/03)
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- Synthesis of 1,3-diketones by reaction of α-haloketones with acyl cynides promoted by samarium diiodide
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α-Haloketones reacted with acyl cyanides to form 1,3-diketones in the presence of samarium diiodide. The reaction was assumed to proceed via a mechanism involving samarium enolates in situ from α-haloketones.
- Baek, Heung Soo,Yoo, Byung Woo,Keum, Sam Rok,Yoon, Cheol Min,Kim, Sung Hoon,Kim, Joong Hyup
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- A practical synthesis of dibenzoylmethanes
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Dibenzoylmethanes are easily prepared in two steps starting from acetophenones, phenol and benzoyl chlorides. The phenyl benzoate is obtained by condensation of benzoyl chloride with phenol in a classical way. Stirring of the phenyl benzoate and acetophenone in DMSO with powdered sodium hydroxide during a few minutes gave the dibenzoylmethanes in yields depending on substituents on the phenyl rings.
- Wallet, Jean-Claude,Gaydou, Emile M.
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p. 4097 - 4103
(2007/10/03)
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- Imidazo[2,1-b]thiazole derivatives XII. Synthesis and immunoactivity in vitro on human T lymphocyte of several 3-aroylmethyl and 2-aroyl-3-methyl(aryl)-5,6-dihydroimidazo[2,1-b]thiazoles
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To estimate the influence of aryl group position on the immunostimulant properties of imidazo[2,1-b]thiazole derivatives, several compounds were obtained and tested, versus tetramisole hydrochloride, on the mobilisation of CD2 receptor by human T lymphocyte. The synthesis use the action of monobrominated β-diketones on the 2-mercaptoimidazoline. So, 1-aryl-4-bromobutane-1,3-diones lead to 3-aroylmethyl-5,6-dihydroimidazo[2,1-b]thiazoles 4. Same, 1-aryl-2-bromobutane-1,3-diones and 1,3-diaryl-2-bromopentane-1,3-diones give respectively 3-aroyl-2-methyl-5,6-dihydroimidazo[2,1-b]thiazoles 5 and 3-aroyl-2-aryl-5,6-dihydroimidazo[2,1-b]thiazoles 6. Better yields are obtained when the reaction presents two steps. The first one, realized in acetone at room temperature, leads to an intermediate S-substituted 4,5-dihydroimidazole which, in second step, is cyclized in imidazo[2,1-b]thiazole compound via an unisolated carbinolamine. This one explains the univocal formation of 5 derivatives and the feasible blending in case of 6. The immunoactivity of several imidazothiazoles 4, 5 and 6 is lower that them of 6-aryl substituted compounds and particularly that the levamisole which is the reference product in this series.
- Robert,Hassanine,Harraga,Seilles
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p. 261 - 271
(2007/10/02)
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