26524-38-9Relevant academic research and scientific papers
FIRST DETERMINATION OF AN ABSOLUTE RATE CONSTANT FOR A 1,2-PHENYL MIGRATION TO A CARBENE
Liu, Michael T. H.
, p. 696 - 698 (1993)
The first determination of a 1,2-phenyl shift in α,α-dimethylbenzylchlorocarbene was achieved by nanosecond laser flash photolysis, τ = 50 ns.
Palladium-Catalyzed Synthesis of Deuterated Alkenes through Deuterodechlorination of Alkenyl Chlorides
Kuriyama, Masami,Yano, Gemba,Kiba, Hirotoshi,Morimoto, Tetsuro,Yamamoto, Kosuke,Demizu, Yosuke,Onomura, Osamu
supporting information, p. 1552 - 1557 (2019/08/08)
The palladium-catalyzed deuterodechlorination of alkenyl chlorides has been developed, and a variety of deuterated alkenes were synthesized with precise control of the deuterium incorporation. This catalytic process tolerates heterocyclic moieties and frameworks derived from bioactive agents. In addition to the double incorporation of deuterium, the gram-scale synthesis of a deuterated iminostilbene unit including a core substructure of carbamazepine was achieved in a high yield with an excellent degree of deuteration.
Iodine(III)-Mediated Oxidative Hydrolysis of Haloalkenes: Access to α-Halo Ketones by a Release-and-Catch Mechanism
Jobin-Des Lauriers, Antoine,Legault, Claude Y.
supporting information, p. 108 - 111 (2016/01/15)
An unprecedented iodine(III)-mediated oxidative transposition of vinyl halides has been accomplished. The products obtained, α-halo ketones, are useful and polyvalent synthetic precursors. There are only a handful of reported examples of the direct conversion of vinyl halides to their corresponding α-halo carbonyl compounds. Insights into the mechanism and demonstration that this synthetic transformation can be done under enantioselective conditions are reported.
Mechanistic study of the reaction of 1,1-dihalo-2-methyl-2-phenylpropanes with LDA. Evidence for radical and carbene pathways
Ashby, E. C.,Mehdizadeh, Ali,Deshpande, Abhay K.
, p. 1322 - 1330 (2007/10/03)
An attempt was made to determine the mechanisms involved in the reactions of the model systems 1,1-dichloro-2-methyl-2-phenylpropane (1) and 1,1-diiodo-2-methyl-2-phenylpropane (2) with LDA.These systems were chosen as ones capable of providing evidence for the formation of radical as well as carbene products.The techniques employed in investigating the mechanistic features of these reactions involved studying the effect of the leaving group, the effect of radical and carbene trapping agents on the product distribution, and isotopic tracer experiments using labeled solvent (THF-d8) and nucleophile (LDA-d2).The major product of the reaction of the geminal dichloride (1) is thought to be derived from a chlorocarbene, whereas the geminal diiodide (2) appears to form products derived from both carbene and radical intermediates.On the basis of the results of radical trapping experiments and those of deuterium-labeling experiments, evidence is presented to support the notion that products A, E, and H are derived from a radical precursor.In addition, products A and H are also believed to be formed from the vinilyc halide D (or B) and the monoiodide E, respectively.Reasonable mechanisms for the formation of the other products formed in these reactions have been proposed on the basis of the available data.
Novel reaction: Decarboxylative Bamberg-Backlung rearrangement in some α-isopropyl sulfonyl carboxylic esters
Wladislaw,Marzorati,Torres Russo,Zaim,Di Vitta
, p. 8367 - 8370 (2007/10/02)
The reaction of some isopropylsulfonyl α-mono and disubstituted esters with KOH/t-BuOH/CCl4 is reported. For the α,α-dialkyl and α-monoaryl substituted derivatives the key step of this reaction is proposed to be the decarboxylative 1,3-displacement in the chlorinated intermediates.
An Efficient Synthesis of Some Substituted Vinylic Chloroformates: Reaction Scope and Limitations
Bowman, Mark P.,Senet, Jean-Pierre G.,Malfroot, Thierry,Olofson, R. A.
, p. 5982 - 5986 (2007/10/02)
2,2-Dichlorovinyl chloroformate is isolated in 50percent distilled yield when chloral is treated with phosgene and zinc dust in 2:1 methyl acetate/ether.The reaction has been extended to other α-chloro and α-bromo aldehydes and ketones in which both other α-positions are occupied by either halo and/or alkyl groups.The reaction fails with hydrogen in an α-position.Examples include the synthesis of Cl2C=C(Me)OC(=O)Cl in 23percent yield, MeC(Cl)=CHOC(=O)Cl (56percent, E:Z=1:1.1), Cl2C=C(C6H5)OC(=O)Cl (66percent), and 2-methyl-1-cyclohexenyl chloroformate (68percent).Similar treatment of α-halo esters gives only the C-acylated products expected from a Reformatsky type reaction, while ketenes are the well known products from α-halo acid chlorides.However, acyl cyanides and acyl phosphonates, with leaving groups intermediate between fluoride and alkoxide, are converted to chloroformates; e.g., Me2C=C(CN)OC(=O)Cl in 67percent yield and Me2C=COC(=O)Cl in 83percent yield.Carbonates and urethans from these chloroformates are of interest as monomers, pesticides, and chemical intermediates.
Chlorinations with Carbon Tetrachloride under Conditions of Phase Transfer Catalysis
Lauritzen, Stein Erik,Roemming, Christian,Skatteboel, Lars
, p. 263 - 268 (2007/10/02)
Anion of ketones, sulfones and esters were α-chlorinated by carbon tetrachloride under conditions of phase transfer catalysis (PTC).Alcohols were unreactive.The observed products show that secondary reactions took place in many cases.The chlorination of the sulfone cis-2,5-diphenyltetrahydrothiophene-1,1-dioxide (1) occurred with inversion to give trans-2,5-dichloro-2,5-diphenyltetrahydrothiophene-1,1-dioxide (2).The structures of cis-1 and trans-2 were determined by X-ray diffraction.The reaction conditions are also applicable to brominations using bromotrichloromethane.
