F:Flammable;
76-22-2Relevant articles and documents
Rapid, chemoselective and mild oxidation protocol for alcohols and ethers with recyclable N-chloro-N-(phenylsulfonyl)benzenesulfonamide
Badani, Purav,Chaturbhuj, Ganesh,Ganwir, Prerna,Misal, Balu,Palav, Amey
supporting information, (2021/06/03)
Chlorine is the 20th most abundant element on the earth compared to bromine, iodine, and fluorine, a sulfonimide reagent, N-chloro-N-(phenylsulfonyl)benzenesulfonamide (NCBSI) was identified as a mild and selective oxidant. Without activation, the reagent was proved to oxidize primary and secondary alcohols as well as their symmetrical and mixed ethers to corresponding aldehydes and ketones. With recoverable PS-TEMPO catalyst, selective oxidation over chlorination of primary and secondary alcohols and their ethers with electron-donating substituents was achieved. The reagent precursor of NCBSI was recovered quantitatively and can be reused for synthesizing NCBSI.
carba Nicotinamide Adenine Dinucleotide Phosphate: Robust Cofactor for Redox Biocatalysis
D?ring, Manuel,Sieber, Volker,Simon, Robert C.,Tafertshofer, Georg,Zachos, Ioannis
supporting information, p. 14701 - 14706 (2021/05/13)
Here we report a new robust nicotinamide dinucleotide phosphate cofactor analog (carba-NADP+) and its acceptance by many enzymes in the class of oxidoreductases. Replacing one ribose oxygen with a methylene group of the natural NADP+ was found to enhance stability dramatically. Decomposition experiments at moderate and high temperatures with the cofactors showed a drastic increase in half-life time at elevated temperatures since it significantly disfavors hydrolysis of the pyridinium-N?glycoside bond. Overall, more than 27 different oxidoreductases were successfully tested, and a thorough analytical characterization and comparison is given. The cofactor carba-NADP+ opens up the field of redox-biocatalysis under harsh conditions.
Aerobic oxidation of alcohols catalyzed by in situ generated gold nanoparticles inside the channels of periodic mesoporous organosilica with ionic liquid framework
Bigdeli, Akram,Karimi, Babak,Khodadadi Karimvand, Somaiyeh,Khorasani, Mojtaba,Safari, Ali Asghar,Vali, Hojatollah
supporting information, p. 70 - 79 (2020/06/08)
In situ generated gold nanoparticles inside the nanospaces of periodic mesoporous organosilica with an imidazolium framework (Au?PMO-IL) were found to be highly active, selective, and reusable catalysts for the aerobic oxidation of activated and nonactivated alcohols under mild reaction conditions. The catalyst was characterized by nitrogen adsorption-desorption measurement, thermogravimetric analysis (TGA), transmission electron microscopy (TEM), elemental analysis (EA), diffuse reflectance infrared Fourier transform spectroscopy (DRIFT), X-ray photoelectron spectroscopy (XPS), and inductively coupled plasma atomic emission spectroscopy (ICP-AES). The catalyst exhibited excellent catalytic activity in the presence of either Cs2CO3 (35 °C) or K2CO3 (60 °C) as reaction bases in toluene as a reaction solvent. Under both reaction conditions, various types of alcohols (up to 35 examples) including activated benzylic, primary and secondary aliphatic, heterocyclic, and challenging cyclic aliphatic alcohols converted to the expected carbonyl compounds in good to excellent yields and selectivity. The catalyst was also recovered and reused for at least seven reaction cycles. Data from three independent leaching tests indicated that amounts of leached gold particles were negligible (0.2 ppm). It is believed that the combination of bridged imidazolium groups and confined nanospaces of PMO-IL might be a major reason explaining the remarkable stabilization and homogeneous distribution of in situ generated gold nanoparticles, thus resulting in the highly active and recyclable catalyst system.
Method for hydrogenolysis of halides
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Paragraph 0232; 0269-0271, (2021/01/11)
The invention discloses a method for hydrogenolysis of halides. The invention discloses a preparation method of a compound represented by a formula I. The preparation method comprises the following step: in a polar aprotic solvent, zinc, H2O and a compound represented by a formula II are subjected to a reaction as shown in the specification, wherein X is halogen; Y is -CHRR or R; hydrogenin H2O exists in the form of natural abundance or non-natural abundance. According to the preparation method, halide hydrogenolysis can be simply, conveniently and efficiently achieved through a simple and mild reaction system, and good functional group compatibility and substrate universality are achieved.
Dehalogenative Deuteration of Unactivated Alkyl Halides Using D2O as the Deuterium Source
Xia, Aiyou,Xie, Xin,Hu, Xiaoping,Xu, Wei,Liu, Yuanhong
, p. 13841 - 13857 (2019/10/17)
The general dehalogenation of alkyl halides with zinc using D2O or H2O as a deuterium or hydrogen donor has been developed. The method provides an efficient and economic protocol for deuterium-labeled derivatives with a wide substrate scope under mild reaction conditions. Mechanistic studies indicated that a radical process is involved for the formation of organozinc intermediates. The facile hydrolysis of the organozinc intermediates provides the driving force for this transformation.
Method for preparing camphor through continuous dehydrogenation of isoborneol
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Paragraph 0033-0034, (2017/05/20)
The invention relates to a method for preparing camphor through continuous dehydrogenation of isoborneol.In the camphor synthetizing industry at present, the step of preparing camphor through dehydrogenation of isoborneol is critical.The method for preparing camphor through isoborneol overcomes the defects that the conversion rate is low, products are difficultly purified, a catalyst is likely to be inactivated, and hydrogen cannot be recycled due to batch operation.By adopting continuous operation, the camphor yield is high, and obtained hydrogen can be recycled; due to tubular reactors connected in series, the reaction temperature and pressure are controllable, materials are subjected to a reaction on the liquid phase condition, the conversion rate of the reversible reaction is increased, the product purification difficulty is lowered, the catalysis efficiency of the selected catalyst is high on the condition, the service life is long, the product is reproducible, and defects existing in original technologies are overcome to a large extent.
Ultrasmall Platinum Nanoparticles Supported Inside the Nanospaces of Periodic Mesoporous Organosilica with an Imidazolium Network: An Efficient Catalyst for the Aerobic Oxidation of Unactivated Alcohols in Water
Karimi, Babak,Naderi, Zahra,Khorasani, Mojtaba,Mirzaei, Hamid M.,Vali, Hojatollah
, p. 906 - 910 (2016/03/15)
The imidazolium group inside the wall of a periodic mesoporous organosilica provides an excellent environment for the stabilization of ultrasmall Pt nanoparticles ((NP)@PMO-IL) with significant activity and recyclability in the selective aerobic oxidation of various alcohols in water at ambient pressure of oxygen. In particular, the catalyst exhibited high activity in the oxidation of unactivated primary alcohols and sterically encumbered secondary aliphatic alcohols, which remain challenging substrates for many catalytic aerobic protocols.
Nitrite-containing resin as an efficient and recyclable catalyst for aerobic oxidation of oximes to carbonyl compounds
Guo, Shu,Zeng, Renyou,Li, Caiye
supporting information, p. 1446 - 1453 (2016/09/14)
Using novel nitrite-containing resin as an NO source and Amberlyst-15 as cocatalyst, we developed aerobic oxidation of oximes to corresponding carbonyl compounds with molecular oxygen as a clean oxidant reagent. It was distinguished from the previous related reports, and the experimental results indicated that additional water obviously decreased the yield. This process provides a better choice for oxidative deoximation with many advantages, such as high yield, simple procedure, high catalytic performance, and recyclable catalyst.
Reactions of hydroxyl-containing compounds with tert-butyl hydroperoxide in the presence of chromium tetra-tert-butoxide
Stepovik,Zaburdaeva,Fukin,Karaghiosoff
, p. 2547 - 2559 (2015/12/30)
Primary and secondary aliphatic, alkylaromatic, cyclic, and organoelement alcohols are efficiently oxidized by tert-butyl hydroperoxide in the presence of both equimolar and catalytic quantities of chromium tetra-tert-butoxide (C6H6, 20°C). α-Diols containing tertiary hydroxyl groups interact with this system via oxidative splitting of the carbon scaffold. The oxidation includes the stages of formation and decomposition of chromium-containing peroxy compounds. Further transformations of the carbonyl compounds depend on the structure of radicals in the molecules.
A highly efficient palladium(ii)/polyoxometalate catalyst system for aerobic oxidation of alcohols
Dornan, Laura M.,Muldoon, Mark J.
, p. 1428 - 1432 (2015/04/14)
A simple catalyst system composed of Pd(OAc)2, phosphomolybdic acid and tetrabutylammonium acetate oxidises a range of alcohols efficiently, with turnover numbers (TONs) of up to 10000.
