105-45-3Relevant articles and documents
Synthesis of methyl acetoacetate from acetone and dimethyl carbonate with alkali-promoted MgO catalysts
Wu, Dudu,Chen, Zhi
, p. 758 - 766 (2010)
The synthesis of methyl acetoacetate (MAA) by methoxycarbonylation of acetone with dimethyl carbonate (DMC) was carried out in the presence of MgO and alkali-promoted MgO catalysts. From among Li, Na, K, and Cs, potassium was found to be the most effective promoter to improve the activity of MgO. The effect of K/MgO with variable content of K was also investigated, and the individual catalysts were characterised by the XRD, BET, SEM, CO2-TPD, and in situ CO2 IR techniques. The results showed that the addition of a small amount of K (1.97 mass %) could promote MAA formation, but a higher K loading caused a decrease in the yield of MAA, which might result from particle agglomeration and the presence of stable potassium carbonates. In situ FTIR experiments of co-adsorbed reactants indicated that the reaction probably proceeded via abstraction of Hα from acetone by base sites.
Catalytic Dimerization of Ketene. A Simple and Convenient Method for the Preparation of Diketene and Esters of Acetoacetic Acid
Jarowicki, Krzysztof,Kwitakowski, Stefan
, p. 141 - 144 (1985)
A new method for the preparation of diketene is described.The main feature of the procedure is the dimerization of ketene in the presence of tetramethylethylenediamine (TMEDA) and the direct use of crude diketene in the syntheses of acetoacetic esters.Keywords: Dimerization of ketene; Tetramethylethylenediamine, catalytic action of
Asymmetric Aerobic Epoxidation of Unfunctionalized Olefins Catalyzed by Optically Active α-Alkoxycarbonyl-β-ketoiminato Manganese(III) Complexes
Mukaiyama, Teruaki,Yamada, Tohru,Nagata, Takushi,Imagawa, Kiyomi
, p. 327 - 330 (1993)
Optically active N,N'-ethylenebis(α-alkoxycarbonyl-β-ketoimine) was found to be a new class of effective ligand of manganese(III) complex catalyst for the asymmetric aerobic epoxidation of simple olefins, such as 1,2-dihydronaphthalene derivatives, to afford the corresponding optically active epoxides with good to high enantioselectivities.
Synthesis of β-keto esters by carbonylation of halomethylketones
Lapidus,Eliseev,Bondarenko,Sizan,Ostapenko,Beletskaya
, p. 317 - 319 (2002)
A number of β-keto esters were synthesized by Pd-catalyzed carbonylation of halomethylketones in the presence of tributylamine in 68-86percent yields. The reaction is completed in 2 hours at 110°C and 10 bar CO pressure. Chloromethylketones are carbonylated selectively while 2-bromoacetophenone is partly reduced to acetophenone as a byproduct. The reaction can be carried out at atmospheric pressure though the rate stays low. The reaction mechanism is discussed.
New method of zinc activation by electrochemistry: synthetic applications to the Blaise reaction
Zylber, N.,Zylber, J.,Rollin, Y.,Dunach, E.,Perichon, J.
, p. 1 - 4 (1993)
A new electrochemical zinc metal activation method based on the cathodic reduction of a catalytic amount of zinc bromide in the presence of a zinc anode is described.This procedure is applied to the coupling of α-bromoesters with nitriles, and affords β-ketoesters in good yield.
Inversion of cpADH5 Enantiopreference and Altered Chain Length Specificity for Methyl 3-Hydroxyalkanoates
Ensari, Yunus,Dhoke, Gaurao V.,Davari, Mehdi D.,Bocola, Marco,Ruff, Anna Jo?lle,Schwaneberg, Ulrich
, p. 12636 - 12645 (2017)
Expanding the substrate scope of enzymes opens up new routes for synthesis of valuable chemicals. Ketone-functionalized fatty acid derivatives and corresponding chiral alcohols are valuable building blocks for the synthesis of a variety of chemicals including pharmaceuticals. The alcohol dehydrogenase from Candida parapsilosis (cpADH5) catalyzes the reversible oxidations of chiral alcohols and has a broad substrate range; a challenge for cpADH5 is to convert alcohols with small substituents (methyl or ethyl) next to the oxidized alcohol moiety. Molecular docking studies revealed that W286 is located in the small binding pocket and limits the access to substrates that contain aliphatic chains longer than ethyl substituent. In the current manuscript, we report that positions L119 and W286 are key residues to boost oxidation of medium chain methyl 3-hydroxy fatty acids; interestingly the enantiopreference toward methyl 3-hydroxybutyrate was inverted. Kinetic characterization of W286A showed a 5.5 fold increase of Vmax and a 9.6 fold decrease of Km values toward methyl 3-hydroxyhexanoate (Vmax: 2.48 U mg? and Km: 4.76 mm). Simultaneous saturation at positions 119 and 286 library yielded a double mutant (L119M/W286S) with more than 30-fold improved activity toward methyl 3-hydroxyoctanoate (WT: no conversion; L119M/W286S: 30 %) and inverted enantiopreference (S-enantiomer ≥99 % activity decrease and R-enantiomer >20-fold activity improvement) toward methyl 3-hydroxybutyrate.
Carbonylation of chloroacetone to methyl acetoacetate
Lapidus,Eliseev,Bondarenko,Sizan,Ostapeako
, p. 2239 - 2241 (2001)
Methyl acetoacetate was prepared by the selective carbonylation of chloroacetone in the presence of a homogeneous palladium catalyst at 100 °C and under a CO pressure of 1.5 MPa.
A NEW PREPARATIVE METHOD FOR 1,3-DICARBONYL COMPOUNDS BY THE REGIOSELECTIVE OXIDATION OF α,β-UNSATURATED CARBONYL COMPOUNDS, CATALYZED BY PdCl2 USING HYDROGENPEROXIDES AS THE REOXIDANT OF Pd0
Tsuji, Jiro,Nagashima, Hideo,Hori, Kimihiko
, p. 257 - 260 (1980)
α,β-Unsaturated esters and ketones are oxidized regioselectively to give β-keto esters and 1,3-diketones in good yields in aqueous acetic acid using Na2PdCl4 as the catalyst and t-butyl hydroperoxide or hydrogen peroxide as the reoxidant of Pd0.
Versatile PdTe/C catalyst for liquid-phase oxidations of 1,3-butadiene
Kuznetsova,Zudin,Kuznetsova,Zaikovskii,Kajitani,Utsunomiya,Takahashi
, p. 30 - 38 (2016)
A commercial Pd catalyst based on Sibunit carbon support was treated with H6TeO6 in a reducing media to obtain a Te coating on the surface of Pd particles. The PdTe/C catalyst prepared in this way showed the ability to control the radical chain oxidation of 1,3-butadiene by promoting the selective formation of 2-butene-1,4-diol, 4-hydroxybut-2-enal and furan in DMA (total selectivity of 61% and yield of 7%). At the same time, the catalyst induced oxidation of 1,3-butadiene by a non-radical heterolytic mechanism involving the formation of two groups of primary products: (1) crotonaldehyde and methyl vinyl ketone and (2) the products of oxygenation at the 1,4-positions. The compounds of the second group including 1,4-dimethoxy-2-butene and maleic acid dimethyl ester were formed on PdTe centers in MeOH. Increasing the Te concentration in the PdTe/C catalyst forced the conversion of 1,3-butadiene toward 1,4-oxygenation and simultaneously decreased the intensity of secondary oxidation, resulting in the selective formation of derivatives of the 1,4-oxygenation - 1,4-dimethoxy-2-butene and allenic alcohol methyl ether (total selectivity of 84% and yield of 48%).
Revisiting ageless antiques; synthesis, biological evaluation, docking simulation and mechanistic insights of 1,4-Dihydropyridines as anticancer agents
Sidhom, Peter A.,El-Bastawissy, Eman,Salama, Abeer A.,El-Moselhy, Tarek F.
supporting information, (2021/06/21)
The historic DHP nucleus was serendipitously discovered by Arthur Hantzsch about 130 years ago and is still considered a hidden treasure for various pharmacological activities. Twenty-one DHP analogues were synthesized using the expedient one pot Hantzsch synthesis for screening as anticancer agents. Initially, the in vitro anti-proliferative single dose against a panel of 18 cancer cell lines showed that compounds 11b and 8f were the superlative candidates regarding their antitumor effect (GI% mean = 66.40% and 50.42%, correspondingly) compared to cisplatin (GI% mean = 65.58%) and doxorubicin (GI% mean = 74.56%). Remarkably, compound 11b showed a remarkable MDA-MB-468 anticancer activity (GI%=80.81%), higher than cisplatin (64.44%) and doxorubicin (76.72%), as well as strong antitumor activity against lung cancer A549 (GI%= 83.02%), more powerful than both cisplatin and doxorubicin. Compound 11b exhibited an exceptional anticancer activity against lung cancer cell line (A549) as its GI50 in nanomolar was (540 nM) with a 9-fold increase greater than cisplatin (GI50 = 4.93 μM) and with a selectivity index = 131 to cancer cells over normal cells. Further mechanistic investigations proved that DHPs anticipate simultaneously TOPI and RTKs (VEGFR-2, HER-2 and BTK) which can stimulate BAX/BAK and the executioner caspases via rtPCR studies.
