58-27-5Relevant articles and documents
A new metal-free access to vitamin K3
Bohle, Anne,Schubert, Anett,Sun, Yu,Thiel, Werner R.
, p. 1011 - 1015 (2006)
2-Methylnaphthalene is oxidized in about 80% yield with 7-9/1 regioselectivity to 2-methyl-1,4-naphthoquinone by hydrogen peroxide with a strong mineral acid as the catalyst. No (transition) metal catalyst is required for this transformation.
Catalytic synthesis of 2-methyl-1,4-naphthoquinone (vitamin K3) over silica-supported aminomethyl phosphine-Ru(II), Pd(II), and Co(II) complexes
Urus, Serhan,Keles, Mustafa,Serindag, Osman
, p. 1416 - 1424 (2010)
Ru(II), Pd(II), and Co(II) complexes of the free ditertiary aminomethylphosphine ligand, N,N-bis(diphenylphosphinomethyl) aminopropyltriethoxysilane [(EtO)3Si(CH2)3 N(CH2PPh2)2] (DIPAPTES), and its SiO2-DIPAPES have been synthesized under a nitrogen atmosphere using Schlenk techniques. All the complexes were used as catalysts for the oxidation of 2-methyl naphthalene (2MN) to give 2-methyl-1,4-naphthoquinone (vitamin K3, menadione, 2MNQ) in the presence of hydrogen peroxide as a clean and cheap oxidant. The catalytic synthesis of vitamin K3 was investigated using both homogeneous catalysis with free complexes and heterogeneous catalysis with silica-supported complexes. [(DIPAPTES)PdCl2] and its silica-supported form showed the best catalytic activity for the selective oxidation of 2-methyl naphthalene to 2-methyl-1,4-naphtoquinone compared to the other metal complexes. 2MNQ yield reached 52.26% with the 2MN conversion of 90.52% using complex [(DIPAPTES)PdCl2] and 58.59% with the 2MN conversion of 99.56% using the silica supported [SiO2(DIPAPES)PdCl2] complex for 1 h. Recycling was investigated for the silica-supported Pd(II) complex and compared with the classical production of vitamin K3. Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file. Copyright Taylor & Francis Group, LLC.
An Experimental Test of the Competition Correction for Charge Capture from the Matrix in Intermolecular Electron Tunnelling Reactions
Huddleston, R. Kurt,Miller, John R.
, p. 4867 - 4872 (1983)
Further experimental tests have been made of a previously presented method to correct for competition for charge capture from the matrix in intermolecular electron transfer (ET) reactions in rigid media.The method is based on a two-step tunnelling model which takes into account the correlation between matrix charge capture and intermolecular electron transfer.The goal is to obtain reliable intermolecular ET rates as a function of distance from measurements on rigid solutions containing two randomly distributed solutes.The method should yield the same rate vs. distance function for different donor solute concentrations.Good agreement was obtained by applying the competition correction to pulse radiolysis data for the reaction of the biphenyl anion with 2-methyl-1,4-naphthoquinone in 2-methyltetrahydrofuran (MTHF) at 77 K for donor:acceptor solute concentration ratios of 20:1 to 2:1.Worse agreement was obtained for the reaction of biphenyl anion with phenanthrene in MTHF, in which case the reaction is slow, and its energetics are substantially influenced by solvation.For such slow reactions, accurate measurements of intermolecular ET rates require donor:acceptor solute concentration ratios such that the donor solute captures most of the matrix charges.It was observed that some biphenyl cations are produced by direct ionizations and are stable in frozen MTHF.
Selective synthesis of vitamin K3 over mesoporous NbSBA-15 catalysts synthesized by an efficient hydrothermal method
Selvaraj,Park,Kim,Kawi,Ha
, p. 9633 - 9638 (2012)
Well hexagonally ordered NbSBA-15 catalysts synthesized by an efficient hydrothermal method were used, for the first time, for the selective synthesis of vitamin K3 by liquid-phase oxidation of 2-methyl-1-naphthol (2MN1-OH) under various reaction conditions. The recyclable NbSBA-15 catalysts were also reused to find their catalytic activities. To investigate the leaching of non-framework niobium species on the surface of silica networks, the results of original and recyclable NbSBA-15 catalysts were correlated and compared. To find an optimum condition for the selective synthesis of vitamin K3, the washed NbSBA-15(2.2pH) was extensively used in this reaction with various reaction parameters such as temperature, time and ratios of reactant (2M1N-OH to H2O2), and the obtained results were also demonstrated. Additionally, the liquid-phase oxidation of 2M1N-OH was carried out with different solvents to find the best solvent with a good catalytic activity. Based on the all catalytic studies, the vitamin K3 selectivity (97.3%) is higher in NbSBA-15(2.2pH) than that of other NbSBA-15 catalysts, and the NbSBA-15(2.2pH) is found to be a highly active and eco-friendly heterogeneous catalyst for the selective synthesis of vitamin K3.
Manganese(II) naphthenate as effective catalyst for the clean oxidation of 2-methylnaphthalene by hydrogen peroxide
Yan, Tingfeng,Hong, Mei,Niu, Lei,Jiang, Feng,Xiao, Guomin
, p. 1839 - 1846 (2012)
Oxidation of 2-methylnaphthalene (2-MN) with aqueous hydrogen peroxide was conducted in acetic acid. The epoxidation pathway was investigated by increasing the CH3CO3H content and adding manganese(II) naphthenate (MnPc) as catalyst. 2-Methyl-1,4-naphthoquinone was obtained in 75.6% conversion and with 80.0% selectivity under the latter conditions. A probable mechanism in which MnPc catalyzes the oxidation of 2-MN by hydrogen peroxide in acetic acid is proposed. Springer Science+Business Media B.V. 2012.
Synthesis of crab type Aminomethyldiphosphine-Oxovanadium(IV) complexes supported on magnetic Nano particles: Selective and recoverable catalysts in vitamin K3 synthesis
Uru?, Serhan,?aylar, Mahmut,Ko?er, Ferudun
, (2018)
Nano Fe3O4 particles were obtained in microvawe oven using closed system. Oxovanadium(IV) complexes of Fe3O4@SiO2@(aminomethylphosphine) type ligands were synthesized and characterized using SEM, EDX, TEM, UV-Visible, XRD, FT-IR and TG/DTA techniques. Catalytic properties of the synthesized pincer type oxovanadium(IV)-aminomethylphosphine complexes supported on magnetic nano structure were investigated in the synthesis of 2-methyl-1, 4-naphthoquinone (Vitamin K3, menadione, 2MNQ) from 2-methyl naphthalene (2MN) in hydrogen peroxide, acetic acid and sulfuric acid. Magnetic-nano particle supported oxovanadium(IV)-aminomethylphosphine type complexes were very efficient catalysts with the 51.36-55.20 % selectivities in conversions of 89.78-95.01 %. Besides, the hetergeneous complexes were very active in five cycling tests on avarage evaluated in the reusability.
OXIDATION OF 2-METHYLNAPHTHALENE TO 2-METHYL-1,4-NAPHTHOQUINONE WITH HYDROGEN PEROXIDE IN THE PRESENCE OF Pd(II)-POLYSTYRENE SULFONIC ACID RESIN
Yamaguchi, Satoru,Inoue, Masami,Enomoto, Saburo
, p. 827 - 828 (1985)
The oxidation of 2-methylnaphthalene was carried out in acetic acid with aqueous(60percent) hydrogen peroxide in the presence of Pd(II)-polystyrene sulfonic acid resin. 2-Methyl-1,4-naphthoquinone was obtained in a yield of 50 to 60percent at 50 deg C for 8 h.The catalysts recovered by the filtration were reusable.
Preparation of Vitamin K3 in Mo–V–P Heteropoly Acid Solutions by Diene Synthesis
Gogin, L. L.,Zhizhina, E. G.
, p. 276 - 282 (2020)
Abstract: The possibility of obtaining vitamin K3 (2-methyl-1,4-naphthoquinone, menadione) by diene synthesis from accessible substrates such as 2-methylphenol (o-cresol) and 2-methylaniline (o-toluidine) was shown. The bifunctional catalysts of these processes are the aqueous solutions of Mo–V–P heteropoly acids, which allow the oxidation and diene synthesis to be performed as a one-pot process.
Oxidation of 1,2,4-trimethylbenzene (TMB), 2,3,6-trimethylphenol (TMP) and 2-methylnaphthalene to 2,3,5-trimethylbenzoquinone (TMBQ) and menadione (vitamin K3)
M?ller, Konstanze,Wienh?fer, Gerrit,Westerhaus, Felix,Junge, Kathrin,Beller, Matthias
, p. 68 - 75 (2011)
The synthesis of industrially important quinones as intermediates for vitamin syntheses is reviewed with special emphasis on recent developments in our own group.
Liquid phase oxidation of 2-methylnaphthalene to 2-methyl-1,4- naphthoquinone over lanthanum doped MCM-41
Zi, Guoli,Chen, Daomei,Li, Bin,Li, Zhiqiang,Luo, Xia,Zhang, Jinping,Li, Lin,Wang, Jiaqiang
, p. 10 - 14 (2014)
Liquid phase oxidation of 2-methylnaphthalene was carried out under mild reaction conditions over lanthanum doped MCM-41 using aqueous hydrogen peroxide (30%) as oxidant and acetic acid as solvent without adding any initiator. The catalyst exhibited very high substrate conversion (95.8%) and reasonable product (2-methyl-1,4-naphthoquinone) selectivity (69.3%) under mild condition. Fast hot catalyst filtration experiment proved that the catalyst acted as a heterogeneous one and it can be reused two times without losing its activity to a greater extent. A possible mechanism was proposed.
