614-45-9Relevant articles and documents
Immobilization of (l)-valine and (l)-valinol on SBA-15 nanoporous silica and their application as chiral heterogeneous ligands in the Cu-catalyzed asymmetric allylic oxidation of alkenes
Ashouri, Akram,Mahramasrar, Mahsa,Majidian, Shiva,Rashid, Hersh I,Samadi, Saadi
supporting information, p. 17630 - 17641 (2021/10/04)
SBA-15 nanoporous silica was synthesized by hydrothermal method using P123 surfactant and tetraethoxyortosilicate in acidic condition and then functionalized by 3-chloropropyltrimethoxysilane. Next, by immobilization of chiral amino acid (S)-2-amino-3-methyl butanoic acid (l-valine) and chiral amino alcohol (S)-2-amino-3-methylbutane-1-ol (l-valinol), preparedviathe reduction ofl-valine by NaBH4/I2in THF, on functionalized-SBA-15, chiral heterogeneous ligands AL*-i-Pr-SBA-15 and AA*-i-Pr-SBA-15 were prepared and characterized by FT-IR, XRD, TGA, EDX, SEM, BET-BJH techniques. The asymmetric allylic oxidation of alkenes was done using copper-complexes of these ligands and the as-synthesized peresters. The reactions were optimized by varying various parameters such as temperature, solvent, amount of chiral heterogeneous ligand, as well as the type and amount of copper salt. Under optimized conditions, 6 mg of AL*-i-Pr-SBA-15 and 3.2 mol% of Cu(CH3CN)4PF6in acetonitrile at 50 °C, the chiral allylic ester was obtained with 80% yield and 39% enantiomeric excess in 24 h. The recyclability of the chiral heterogeneous catalysts was also evaluated without significant reduction in the reaction results up to three runs.
Sunlight assisted solvent free synthesis of tert-butylperesters
Shit, Prasenjit,Singha, Raju
supporting information, p. 1 - 6 (2020/07/15)
A green and efficient methodology has been developed for the direct conversion of aryl aldehydes to the corresponding tert-butyl peresters. The reaction has been carried out in absence of any solvent and the sunlight is used as the green source of energy. In this reaction tetrabutylammonium iodide (TBAI) acts as the mild organo catalyst and tert-butyl hydroperoxide (TBHP) serve as the source of tert-butyl group.
2-Aminopyrazine-functionalized MCM-41 nanoporous silica as a new efficient heterogeneous ligand for Cu-catalyzed allylic C–H bonds oxidation of olefins
Samadi, Saadi,Ashouri, Akram,Kamangar, Shadi,Pourakbari, Fatemeh
, p. 557 - 569 (2019/11/03)
In spite of the importance of the application of allylic C–H bond oxidation of olefins in organic synthesis and existence of the numerous reports, lots of limitations such as large excess of the olefin respect to the oxidant, low chemical yield, long time of reaction and a large amount of the catalyst were reminded. We introduced a novel catalytic system using functionalized MCM-41 as catalyst support to promote efficiency of this reaction. The heterogeneous ligand Pyr-MCM-41 was prepared by substituted 2-aminopyrazine ligand on functionalized MCM-41 with 3-chloropropyltrimthoxysilane and characterized by FT-IR, XRD, SEM, EDX, BET, TGA, CHN techniques. In situ immobilized Pyr-MCM-41 by copper (I) trifluoromethanesulfonate (CuOTf) was applied in direct catalytic esterification of inert C–H bonds in olefins using various peresters at room temperature.
Preparation method of tert-butyl peroxybenzoate
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Paragraph 0027-0036, (2020/11/05)
The invention discloses a preparation method of tert-butyl peroxybenzoate, specifically comprising the following steps of: salifying tert-butyl hydroperoxide and caustic soda liquid; then dropwise adding benzoyl chloride into sodium tert-butoxide peroxide for coupling, and washing a coupling product twice after liquid separation; and adding a stabilizer into the product, drying, dewatering and carrying out suction filtration to obtain the tert-butyl peroxybenzoate product. The preparation method comprises the following steps of: dropwise adding benzoyl chloride into sodium tert-butoxide peroxide; and after liquid separation, washing with water twice, adding a stabilizer into the upper product phase, adding anhydrous magnesium sulfate for drying, and carrying out suction filtration to obtain tert-butyl peroxybenzoate with the yield of not less than 95% and the content of not less than 99%, so that the product can be stored in a dark place and transported for a long distance.
A Woven Supramolecular Metal-Organic Framework Comprising a Ruthenium Bis(terpyridine) Complex and Cucurbit[8]uril: Enhanced Catalytic Activity toward Alcohol Oxidation
Li, Zhan-Ting,Liu, Yi,Wang, Hui,Wang, Ze-Kun,Xu, Zi-Yue,Zhang, Dan-Wei,Zhang, Yun-Chang
, p. 1498 - 1503 (2020/08/05)
The self-assembly of a diamondoid woven supramolecular metal–organic framework wSMOF-1 has been achieved from intertwined [Ru(tpy)2]2+ (tpy=2,2′,6′,2′′-terpyridine) complex M1 and cucurbit[8]uril (CB[8]) in water, where the intermolecular dimers formed by the appended aromatic arms of M1 are encapsulated in CB[8]. wSMOF-1 exhibits ordered pore periodicity in both water and the solid state, as confirmed by a combination of 1H NMR spectroscopy, UV-vis absorption, isothermal titration calorimetry, dynamic light scattering, small angle X-ray scattering and selected area electron diffraction experiments. The woven framework has a pore aperture of 2.1 nm, which allows for the free access of both secondary and primary alcohols and tert-butyl hydroperoxide (TBHP). Compared with the control molecule [Ru(tpy)2]Cl2, the [Ru(tpy)2]2+ unit of wSMOF-1 exhibits a remarkably higher heterogeneous catalysis activity for the oxidation of alcohols by TBHP in n-hexane. For the oxidation of 1-phenylethan-1-ol, the yield of acetophenone was increased from 10 percent to 95 percent.
Decarboxylative Borylation of mCPBA-Activated Aliphatic Acids
Wei, Dian,Liu, Tu-Ming,Zhou, Bo,Han, Bing
supporting information, p. 234 - 238 (2020/01/02)
A decarboxylative borylation of aliphatic acids for the synthesis of a variety of alkylboronates has been developed by mixing m-chloroperoxybenzoic acid (mCPBA)-activated fatty acids with bis(catecholato)diboron in N,N-dimethylformamide (DMF) at room temperature. A radical chain process is involved in the reaction which initiates from the B-B bond homolysis followed by the radical transfer from the boron atom to the carbon atom with subsequent decarboxylation and borylation.
DECOMPOSITION OF ORGANIC PEROXIDES AND HYDROGEN PEROXIDE BY THE IRON THIOLATES AND RELATED COMPLEXES
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Paragraph 0725; 0733; 0746-0747, (2020/07/04)
Disclosed herein is a method of reducing or disproportionating peroxide, comprising combining an organic chalcogenide, an iron salt, and the peroxide in the presence of an additional reductant, which can be the organic chalcogenide. The method can be used to, e.g., prepare alcohols from peroxides and to disproportionate hydrogen peroxide into water and oxygen.
Microfluidic Synthesis of tert-Butyl Peresters via KI-Catalyzed Oxidative Coupling of Methyl Arenes and tert-Butyl Hydroperoxide
Hua, Jiawei,Guo, Shiyu,Yang, Zhao,Fang, Zheng,Guo, Kai
supporting information, p. 1633 - 1637 (2017/10/25)
A green and efficient organic-aqueous two-phase reaction route for the synthesis of tert-butyl peresters by KI-catalyzed C-H oxidation of methyl arenes in a microfluidic chip reactor has been developed. Moreover, a series of tert-butyl perester products were obtained in moderate to good yields under metal-free conditions. A scale-up continuous flow system was constructed to verify the application of this method.
Dirhodium(II)-Catalyzed Carbonylation Peroxidation of α,β-Unsaturated Esters: Mechanistic Insight into the Role of Aryl Aldehydes
Zhao, Lili,Wang, Yi,Ma, Ziling,Wang, Yuanhua
, p. 8166 - 8174 (2017/07/22)
Peroxidation has received considerable attention as a synthetically useful method used to prepare organic peroxides, which are useful synthetic building blocks in synthetic chemistry. The difunctionalization of alkenes to introduce a peroxide and another functional group has become a useful tool for quickly increasing molecular complexity in synthesis. In this work, a three-component oxidative coupling of aryl aldehydes with α,β-unsaturated esters and tert-butyl hydroperoxide catalyzed by dirhodium(II) catalyst Rh2(esp)2 (esp = α,α,α′,α′-tetramethyl-1,3-benzenedipropanoate) under mild conditions is developed. The synthesized carbonylation peroxidation products (β-peroxyketones) are stable enough to be isolated by silica gel column and characterized. The β-peroxyketones used as reactants have been applied to the synthesis of the epoxides, polysubstituted furans, carbazole alkaloids, and biologically important natural products. Interestingly, besides being a reactant, aryl aldehydes also play an important role in avoiding the catalyst deactivation during the reaction as shown by ultraviolet/visible analysis. The excess amount of aldehydes was used to ensure the stability of the Rh2(esp)2 catalyst in the reaction by forming the monoaldehyde ligated dirhodium(II) complex. It is important to note that the aldehydes were also found to reduce the inactive Rh2(esp)2Cl species generated in the reaction.
Temperature-controlled solvent-free selective synthesis of tert-butyl peresters or acids from benzyl cyanides in the presence of the TBHP/Cu(OAc)2 system
Hashemi,Saberi,Poorsadeghi,Niknam
, p. 7619 - 7622 (2017/02/05)
Solvent-free room temperature synthesis of tert-butyl peresters was achieved via copper-catalyzed oxidative-coupling of benzyl cyanides with tert-butyl hydroperoxide in short reaction times. Various derivatives of tert-butyl peresters were synthesized by this pathway in good to excellent yields. Further investigation revealed that the above-mentioned protocol is effective for the synthesis of benzoic acid derivatives when the reaction is conducted at 80?°C, under the same reaction conditions.
