25951-54-6Relevant academic research and scientific papers
An integrated process for partial oxidation of alkanes
Zhou, Xiao-Ping,Yilmaz, Aysen,Yilmaz, Gurkan A.,Lorkovic, Ivan M.,Laverman, Leroy E.,Weiss, Michael,Sherman, Jeffrey H.,McFarland, Eric W.,Stucky, Galen D.,Ford, Peter C.
, p. 2294 - 2295 (2003)
The partial oxidation of alkanes via bromination followed by the reaction with solid metal oxide mixtures (MO) is shown to give an array of products that can be tuned by varying the MO and the reaction conditions.
Electrophilic bromination of ethylene and ethylene-d4. A combined experimental and theoretical study
Koerner, Terry,Brown,Gainsforth,Klobukowski
, p. 5628 - 5636 (1998)
The deuterium kinetic isotope effect (dkie) for the electrophilic bromination of ethylene-h4 and ethylene-d4 in methanol and dichloroethane (DCE) at 25 °C has been determined using mass spectrometry. The dkie's are inverse, that in methanol being k(H)/k(D) = 0.664 ± 0.050 and that in DCE being k(H)/k(D) = 0.572 ± 0.048. A product study of the bromination of trans-ethylene-d2 in dichloroethane indicates that the addition is trans. Computations of the expected equilibrium deuterium isotope effect (EIE) for the process C2H4 + Br+ ? C2H4-Br+ using density functional theory indicate that the EIE is also inverse at K(H)/K(D) = 0.63. Detailed analyses of the molar partition functions and the zero-point energies for the various vibrational modes in the ground and ion states indicate that the major contributor to the EIE is the creation of a new mode in the ion, termed the CH2-symmetric twist, that arises from the loss of the rotational freedom about the C-C axis in ethylene. In the absence of this new mode, the computed EIE is normal, K(H)/K(D) = 1.12. The computations also indicate that the ion state undergoes very little rehybridization of the carbons, the sum of the H- C-H and H-C-C angles at each carbon being 357.3°. A discussion is presented concerning the detailed sequence of events contributing to the reaction mechanism in both solvents and how each of these might contribute to the dkie.
Catalytic reaction of methane with CBrF3
Li, Kai,Kennedy, Eric,Dlugogorski, Bogdan,Howe, Russell
, p. 709 - 710 (1999)
The catalytic reaction of CH4 with CBrF3 over Co, Cu and Mn ZSM-5 zeolites is described; major products (at low temperatures) are those expected for simple hydrodebromination: CH3Br and CHF3.
Radical Carbonyl Propargylation by Dual Catalysis
Huang, Huan-Ming,Bellotti, Peter,Daniliuc, Constantin G.,Glorius, Frank
supporting information, p. 2464 - 2471 (2020/12/07)
Carbonyl propargylation has been established as a valuable tool in the realm of carbon–carbon bond forming reactions. The 1,3-enyne moiety has been recognized as an alternative pronucleophile in the above transformation through an ionic mechanism. Herein, we report for the first time, the radical carbonyl propargylation through dual chromium/photoredox catalysis. A library of valuable homopropargylic alcohols bearing all-carbon quaternary centers could be obtained by a catalytic radical three-component coupling of 1,3-enynes, aldehydes and suitable radical precursors (41 examples). This redox-neutral multi-component reaction occurs under very mild conditions and shows high functional group tolerance. Remarkably, bench-stable, non-toxic, and inexpensive CrCl3 could be employed as a chromium source. Preliminary mechanistic investigations suggest a radical-polar crossover mechanism, which offers a complementary and novel approach towards the preparation of valuable synthetic architectures from simple chemicals.
PROCESS FOR THE PRODUCTION OF FERROPORTIN INHIBITORS
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Page/Page column 33-34; 43-46, (2021/10/02)
The invention relates to a new process for preparing compounds of the formula (I) and pharmaceutically acceptable salts thereof, which act as ferroportin inhibitors being suitable for the use as medicaments in the prophylaxis and/or treatment of diseases caused by a lack of hepcidin or of iron metabolism disorders leading to increased iron levels or increased iron absorption, including iron overload, thalassemia, sickle cell disease and hemochromatosis.
Compounds and methods for the reduction of halogenated hydrocarbons
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Page/Page column 19, (2017/12/27)
The present application relates to methods for the reduction of halogenated hydrocarbons using compounds of Formula (I): wherein the reduction of the halogenated compounds is carried out, for example, under ambient conditions without the need for a transition metal containing co-factor. The present application also relates to methods of recovering precious metals using compounds of Formula (I) that are absorbed onto a support material.
Ultrasonically Assisted Decarboxylative Bromination of α,β-Unsaturated Carboxylic Acids under Vilsmeier-Haack Conditions
Kumar, M. Satish,Rajanna,Venkanna,Venkateswarlu,Sudhakar Chary
, p. 642 - 646 (2015/12/26)
An efficient method for decarboxylative bromination of cinnamic acids (α,β-unsaturated carboxylic acids or 3-arylpropenoic acids) was achieved under relatively mild conditions using Vilsmeier-Haack reagent and KBr in acetonitrile media. Vilsmeier-Haack reagent is prepared by using 1:1 ratio of oxychloride (SOCl2 or POCl3) and DMF under chilled condition. Ultrasonically assisted reactions underwent smoothly with highly significant rate enhancements and afforded bromostyrenes as products in very good yields even though the reactions were too sluggish.
Synthetic methods and intermediates for the preparation of xenicanes
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Page/Page column, (2014/09/03)
The invention provides novel synthetic intermediates and synthetic methods that are useful for preparing compounds of the xenicane family. Certain compounds of the invention may also possess anti-cancer properties.
Total synthesis and biological evaluation of (-)-9-deoxy-englerin a
Ushakov, Dmitry B.,Navickas, Vaidotas,Strobele, Markus,Maichle-Moessmer, Caecilia,Sasse, Florenz,Maier, Martin E.
supporting information; experimental part, p. 2090 - 2093 (2011/06/22)
An effective total synthesis of (-)-9-deoxy-englerin (4), an analogue of the natural guaiane sesquiterpene englerin A (1), has been achieved. The synthesis features a transannular epoxide opening to construct the 5,7-fused ring system followed by transannular ether formation with mercury(II) trifluoroacetate.
Unimolecular reactions of CH2BrCH2Br, CH 2BrCH2Cl, and CH2BrCD2Cl: Identification of the Cl-Br interchange reaction
Friederich, Laura,Duncan, Juliana R.,Heard, George L.,Setser,Holmes, Bert E.
experimental part, p. 4138 - 4147 (2010/09/04)
The recombination reactions of CH2Br and CH2Cl radicals have been used to generate vibrationally excited CH 2BrCH2Br and CH2BrCH2Cl molecules with 91 kcal mol-1 of energy in a room-temperature bath gas. The experimental unimolecular rate constants for elimination of HBr and HCl were compared to calculated statistical rate constants to assign threshold energies of 58 kcal mol-1 for HBr elimination from C2H 4Br2 and 58 and 60 kcal mol-1, respectively, for HBr and HCl elimination from C2H4BrCl. The Br-Cl interchange reaction was demonstrated and characterized by studying the CH 2BrCD2Cl system generated by the recombination of CH 2Br and CD2Cl radicals. The interchange reaction was identified from the elimination of HBr and DCl from CH2ClCD 2Br. The interchange reaction rate is much faster than the rates of either DBr or HCl elimination from CH2BrCD2Cl, and a threshold energy of ?43 kcal mol-1 was assigned to the interchange reaction. The statistical rate constants were calculated from models of the transition states that were obtained from density functional theory using the B3PW91 method with the 6-31G(d′,p′) basis set. The model for HBr elimination was tested versus published thermal and chemical activation data for C2H5Br. A comparison of Br-Cl interchange with the Cl-F and Br-F interchange reactions in 1,2-haloalkanes is presented.
