1561-86-0Relevant academic research and scientific papers
Formation of iron(III) meso-chloro-isoporphyrin as a reactive chlorinating agent from oxoiron(IV) porphyrin π-cation radical
Cong, Zhiqi,Kurahashi, Takuya,Fujii, Hiroshi
, p. 4469 - 4472 (2012)
Iron(III) isoporphyrin, a tautomer of porphyrin with a saturated meso carbon, is one of the isoelectronic forms of oxoiron(IV) porphyrin π-cation radical, which is known as an important reactive intermediate of various heme enzymes. The isoporphyrin has been believed to be incapable of catalyzing oxygenation and oxidation reactions. Here, we report that an oxoiron(IV) porphyrin π-cation radical can be converted to iron(III) meso-chloro- isoporphyrin in the presence of trifluoroacetic acid and chloride ion. More importantly, this study shows the first evidence that iron(III) meso-chloro-isoporphyrin is an excellent reactive agent for chlorinating aromatic compounds and olefins. The results of this study suggest that the mechanism involves electrophilic chlorination of substrate with iron(III) meso-chloro-isoporphyrin.
Lipase catalysed oxidations in a sugar-derived natural deep eutectic solvent
Vagnoni, Martina,Samorì, Chiara,Pirini, Daniele,Vasquez De Paz, Maria Katrina,Gidey, Dawit Gebremichael,Galletti, Paola
, (2021/05/06)
Chemoenzymatic oxidations involving the CAL-B/H2O2 system was developed in a sugar derived Natural Deep Eutectic Solvent (NaDES) composed by a mixture of glucose, fructose and sucrose. Good to excellent conversions of substrates like cyclooctene, limonene, oleic acid and stilbene to their corresponding epoxides, cyclohexanone to its corresponding lactone and 2-phenylacetophenone to its corresponding ester, demonstrate the viability of the sugar NaDES as a reaction medium for epoxidation and Baeyer-Villiger oxidation.
Method for preparing o-chlorocyclohexanone by using cyclohexanone by-product lightweight oil
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Paragraph 0016; 0017; 0018; 0019; 0020, (2018/04/01)
The invention discloses a method for preparing o-chlorocyclohexanone through lightweight oil, wherein the lightweight oil is the by-product obtained from cyclohexanone preparation through oxidation ofcyclohexane, and the o-chlorocyclohexanone is prepared in the presence of an auxiliary agent and a catalyst by completely utilizing the cyclohexene oxide in the lightweight oil through ring opening,oxidation and other reactions. According to the present invention, with the method, the disadvantages of more impurities, harsh reaction condition or complex product purification and the like in the prior art are solved. The method comprises: in the presence of an auxiliary agent, carrying out a reaction on lightweight oil containing 1 mole of cyclohexene oxide and 1-2 moles of a hydrogen chloridesolution for 1-4 h at a temperature of 10-60 DEG C to generate 2-chlorocyclohexanol, distilling to remove the relatively low boiling point components to obtain high-purity 2-chlorocyclohexanol, carrying out a reaction on the high-purity 2-chlorocyclohexanol as a raw material and a certain amount of an oxidizing agent, washing, separating, rectifying, and collecting the distillate at a temperatureof 203-204 DEG C to obtain the o-chlorocyclohexanone with the purity of more than 99%, wherein the yield of the o-chlorocyclohexanone is more than 90%.
Photoreduction of Thioether Gold(III) Complexes: Mechanistic Insight and Homogeneous Catalysis
Cao, Zhen,Bassani, Dario M.,Bibal, Brigitte
supporting information, p. 18779 - 18787 (2018/11/23)
Complexes formed between AuCl3 and thioether ligands underwent a photoinduced reductive elimination under homogeneous conditions in dichloromethane and toluene solutions to afford the corresponding AuI complexes. All the gold(III) complexes were rapidly reduced to the gold(I) chloride complexes under 365 nm irradiation or ambient light while being thermally stable below 55 °C. The mechanism of photoreduction through Cl2 elimination is discussed based on a kinetic study and the chemical trapping of chlorine species: Cl2, radical Cl., and possibly Cl+. The catalytic activities of the gold(III) chloride complexes and the corresponding gold(I) complexes obtained by in situ reduction were evaluated in the cyclization of N-propargylic amides to oxazoles. The merits of such photoreducible complexes in homogeneous gold catalysis are illustrated by a cascade reaction catalyzed by thioether gold complexes that affords a 4H-quinolizin-4-one in high yields.
Highly selective halogenation of unactivated C(sp3)-H with NaX under co-catalysis of visible light and Ag@AgX
Liu, Shouxin,Zhang, Qi,Tian, Xia,Fan, Shiming,Huang, Jing,Whiting, Andrew
, p. 4729 - 4737 (2018/10/23)
The direct selective halogenation of unactivated C(sp3)-H bonds into C-halogen bonds was achieved using a nano Ag/AgCl catalyst at RT under visible light or LED irradiation in the presence of an aqueous solution of NaX/HX as a halide source, in air. The halogenation of hydrocarbons provided mono-halide substituted products with 95% selectivity and yields higher than 90%, with the chlorination of toluene being 81%, far higher than the 40% conversion using dichlorine. Mechanistic studies demonstrated that the reaction is a free radical process using blue light (450-500 nm), with visible light being the most effective light source. Irradiation is proposed to cause AgCl bonding electrons to become excited and electron transfer from chloride ions induces chlorine radical formation which drives the substitution reaction. The reaction provides a potentially valuable method for the direct chlorination of saturated hydrocarbons.
Chlorohydrination of allyl chloride with HCl and H2O2 catalyzed by hollow titanium silicate zeolite to produce dichloropropanol
Peng, Xinxin,Xia, Changjiu,Lin, Min,Yuan, Hui,Zhu, Bin,Zhang, Yao,Wang, Baorong,Shu, Xingtian
supporting information, p. 1221 - 1225 (2017/08/15)
Overall, over 95% of epichlorohydrin is industrially manufactured via the chlorohydrination route with hazardous Cl2 as a reagent, which brings serious operation and pollution problems. Herein, we describe a novel Cl2-free process for the synthesis of dichloropropanols from allyl chloride with H2O2 and HCl catalyzed by hollow titanium silicate zeolite under mild conditions. A high conversion and overall dichloropropanol selectivity exceeding 95% are simultaneously achieved, and the heterogeneous catalyst is highly stable and amenable for reuse. Comprehensive experimental and spectroscopic data suggest that the Lewis acidity of the framework Ti species has a synergistic effect with the Br?nsted acidity of HCl that promotes the epoxidation of allyl chloride and the ring opening of the epoxy groups.
Visible light induced oxygenation of alkenes with water sensitized by silicon-porphyrins with the second most earth-abundant element
Remello, Sebastian Nybin,Hirano, Takehiro,Kuttassery, Fazalurahman,Nabetani, Yu,Yamamoto, Daisuke,Onuki, Satomi,Tachibana, Hiroshi,Inoue, Haruo
, p. 176 - 183 (2015/10/28)
Silicon as the second most abundant element on Earth was effectively utilized as the central atom in the porphyrin to induce photochemical oxygenation of alkenes as the first example of photocatalytic reaction through activation of water molecule in the presence of K2PtCl6 as an electron acceptor. Oxygen atom of water was confirmed to be incorporated in the oxygenated product by the photoreaction with H218O. The excited triplet state of silicon porphyrin was revealed to be responsible for the photochemical oxygenation. The one-electron oxidized silicon porphyrin was predicted by DFT calculation to have its spin population mostly on the axially ligated hydroxyl oxygen atom. The oxyl radical character of the axial ligand could rationalize the oxygenation reaction.
Photochemical oxygenation of cyclohexene with water sensitized by aluminium(III) porphyrins with visible light
Mathew, Siby,Kuttassery, Fazalurahman,Gomi, Yuki,Yamamoto, Daisuke,Kiyooka, Ryuichi,Onuki, Satomi,Nabetani, Yu,Tachibana, Hiroshi,Inoue, Haruo
, p. 137 - 142 (2015/10/28)
Aluminium(III)-tetramesitylporphyrin, with the Earth's the most abundant metal and the third most abundant element as the Al(III) ion, induces the photochemical oxygenation of cyclohexene in deaerated aqueous acetonitrile to form the corresponding epoxide and alcohol with water as both electron and oxygen atom donor upon visible light irradiation. The Al(III) should be the most available and meaningful element to be utilized in the artificial photosynthetic unit. The excited triplet state of the water-coordinated porphyrin is responsible for the photochemical oxygenation.
Enzymatic preparation of (1S,2R)- and (1R,2S)-stereoisomers of 2-halocycloalkanols
Kolodiazhna, Olga O.,Kolodiazhna, Anastasy O.,Kolodiazhnyi, Oleg I.
, p. 37 - 42 (2013/02/25)
The stereoisomers of cis-2-halocycloalkanols were resolved by a kinetically controlled transesterification with vinyl acetate in the presence of lipases in organic media. High enantioselectivities (ee >98%) and good isolated yields were obtained for all substrates using the appropriate lipase. Burkholderia cepacia lipase was the most efficient enzyme for the resolution of these substrates. The enantiomeric purities of the compounds were defined by derivatization with Mosher's acid and the absolute configurations were determined by chemical correlation.
Preparation of ionic liquid-based vilsmier reagent from novel multi-purpose dimethyl formamide-like ionic liquid and its application
Hullio, Ahmed Ali,Mastoi
scheme or table, p. 1647 - 1657 (2012/09/21)
In continuation of research to explore the applied potential of DMF-like ionic liquid, the ionic liquid version of N,N-dimethyliminiumchloride (Vilsmier reagent) has been synthesized from DMF-like ionic liquid and tested effectively for its capacity to achieve more useful organic transformations. The results show that DMF-like ionic liquid is world's first task specific ionic liquid which has catalyzed numerous diverse type of reaction and is multipurpose in its application. Thus a new term for this DMF-like ionic liquid has been coined that is DMF-like "multipurpose" ionic liquid. Copyright
