- Method for synthesizing 1, 3-dicarbonyl compound based on terminal alkyne and acyl halide by one-pot process
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The invention belongs to the technical field of catalytic synthesis, and discloses a method for synthesizing a 1, 3-dicarbonyl compound by a one-pot process, and the method comprises the following steps: by using simple palladium and copper salts as catalysts, reacting terminal alkyne with acyl halide at 0-80 DEG C for 0.5-12 hours under the action of trifluoromethanesulfonic acid to obtain the 1,3-dicarbonyl compound, wherein the molar ratio of the terminal alkyne to the acyl halide to the palladium salt to the copper salt to the trifluoromethanesulfonic acid is 1 to (1 to 2) to (0.00001 to0.10) to (0.00001 to 0.10) to (0.00004 to 0.40); the catalysts used in the method are common the commercialized palladium salt and copper salt, reagents used in the reaction are commercialized reagents, in addition, the raw materials are cheap and easy to obtain, functional group tolerance is good, reaction conditions are mild, operation is easy and convenient, and atom economy is high.
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Paragraph 0069-0074; 0084-0086
(2020/07/21)
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- 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 0060-0063
(2020/02/19)
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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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- Method of preparing 1,3-diketone compound by acetyenic ketone
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The invention relates to a preparation method of preparing a 1,3-diketone compound by acetyenic ketone. The preparation method comprises the following steps: S1, putting alpha-alkynyl ketone compound,water, gold salt and silver salt in a reaction solvent to obtain a precursor mixture, wherein the molar ratio of the alpha-alkynyl ketone compound, water, gold salt and silver salt is 1: (1-50): (0.001-0.10): (0.002-0.15); and S2, putting the precursor mixture obtained in the S1 to react at a reaction temperature of 0-50 DEG C to obtain the 1,3-diketone compound, wherein the reaction time is 5 min to 48 h. The method is simple in reaction condition, free of acid or alkaline additives and high in yield, and can be applied to modern production on a large scale.
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Paragraph 0174-0180
(2019/06/12)
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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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- 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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- 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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- Solid-phase synthesis of traceless 1,3-diketones
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A traceless synthesis of 1,3-diketones has been achieved through enamine methodology from solid-phase organic synthesis. Thus, piperazine served as a linker for this traceless cleavage of β-diketones from solid support.
- Park, Kyung-Ho,Cox, Linda J.
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p. 1067 - 1069
(2007/10/03)
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- Synthesis of some β-diketone complexes of lanthanides and study of their shift reagent effects
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A series of complexes of ortho, meta and para substituted dibenzoylmethane(DBM) with lanthanides(Ln) have been synthesized and the induced shifts in 1H NMR spectra on n-pentanol have been studied. The studies of the shift behaviour of trivalent
- Salar Amoli,Aziz,Mohanazadeh
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p. 1004 - 1005
(2007/10/03)
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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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- Extraction of Nickel(II), Copper(II), and Zinc(II) in Carbon Tetrachloride with Monothiodibenzoylmethane and Derivatives
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The overall stability constants of nickel(II), copper(II), and zinc(II) chelates with SDBM (monothiodibenzoylmethane) and SDBM derivatives such as F-SDBM ((p-fluorobenzoyl)(thiobenzoyl)methane) and C2H5-SDBM ((p-ethylthiobenzoyl)benzoylmethane) in aqueous
- Honjo, Takaharu,Freiser, Henry
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p. 1258 - 1265
(2007/10/02)
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