5963-49-5Relevant academic research and scientific papers
Visible-Light-Induced Vicinal Dichlorination of Alkenes through LMCT Excitation of CuCl2
Li, Jingjing,Lian, Pengcheng,Long, Wenhao,Wan, Xiaobing,Zheng, Yonggao
supporting information, p. 23603 - 23608 (2020/10/29)
This work demonstrates photoredox vicinal dichlorination of alkenes, based on the homolysis of CuCl2 in response to irradiation with visible light. This catalysis proceeds via a ligand to metal charge transfer process and provides an exciting opportunity for the synthesis of 1,2-dichloride compounds using an inexpensive, low-molecular-weight chlorine source. This new process exhibits a wide substrate scope, excellent functional group tolerance, extraordinarily mild conditions and does not require external ligands. Mechanistic studies show that the ready formation of chlorine atom radicals is responsible for the facile formation of C?Cl bonds in this synthetic process.
Vicinal dichlorination of olefins using NH4Cl and oxone
Swamy, Peraka,Reddy, Marri Mahender,Kumar, Macharla Arun,Naresh, Mameda,Narender, Nama
, p. 251 - 257 (2014/03/21)
A mild and efficient protocol for the preparation of 1,2-dichloroalkane derivatives from olefins using NH4Cl and Oxone at room temperature is described. A variety of terminal, internal, and cyclic alkenes reacted smoothly to give the corresponding dichlorinated products in good to excellent yields. Moreover, 1,2-disubstituted symmetrical and unsymmetrical olefins dichlorinated with moderate to excellent diastereoselectivity. This method precludes the use of acidic additives and transition metals in the synthesis of vicinal dichlorides.
Bis- N -heterocyclic carbene palladium(IV) tetrachloride complexes: Synthesis, reactivity, and mechanisms of direct chlorinations and oxidations of organic substrates
McCall, A. Scott,Wang, Hongwang,Desper, John M.,Kraft, Stefan
scheme or table, p. 1832 - 1848 (2011/04/15)
This Article describes the preparation and isolation of novel octahedral CH2-bridged bis-(N-heterocyclic carbene)palladium(IV) tetrachlorides of the general formula LPdIVCl4 [L = (NHC)CH 2(NHC)] from LPdIICl2 and Cl2. In intermolecular, nonchelation-controlled transformations LPdIVCl 4 reacted with alkenes and alkynes to 1,2-dichlorination adducts. Aromatic, benzylic, and aliphatic C-H bonds were converted into C-Cl bonds. Detailed mechanistic investigations in the dichlorinations of alkenes were conducted on the 18VE PdIV complex. Positive solvent effects as well as kinetic measurements probing the impact of cyclohexene and chloride concentrations on the rate of alkene chlorination support a PdIV-Cl ionization in the first step. Product stereochemistry and product distributions from various alkenes also support Cl+-transfer from the pentacoordinated PdIV-intermediate LPdIVCl 3+ to olefins. 1-Hexene/3-hexene competition experiments rule out both the formation of π-complexes along the reaction coordinate as well as in situ generated Cl2 from a reductive elimination process. Instead, a ligand-mediated direct Cl+-transfer from LPd IVCl3+ to the π-system is likely to occur. Similarly, C-H bond chlorinations proceed via an electrophilic process with in situ formed LPdIVCl3+. The presence of a large excess of added Cl- slows cyclohexene chlorination while the presence of stoichiometric amounts of chloride accelerates both PdIV-Cl ionization and Cl+-transfer from LPdIVCl3 +. 1H NMR titrations, T1 relaxation time measurements, binding isotherms, and Job plot analysis point to the formation of a trifurcated Cl-...H-C bond in the NHC-ligand periphery as a supramolecular cause for the accelerated chemical events involving the metal center.
Insights into the reaction of trans-diarylethenes with thionyl chloride: A practical synthesis of chlorobenzo[b]thiophenes
Han, Jie,Wang, Qiong,Chang, Xiaoyong,Liu, Yuxin,Wang, Yanmei,Meng, Jiben
experimental part, p. 8865 - 8872 (2011/12/02)
The reactivity of a variety of trans-1,2-diarylethenes with thionyl chloride has been investigated. All the substrates could readily afford 3-chlorobenzo[b]thiophenes in moderate yields and a pair of threo- and erythro-1,2-dichloro-1,2-diarylethanes as th
Synthesis of chloroalkoxypyridinium salts by conjugate chlorination of unsaturated compounds in the presence of pyridine N-oxides
Britsun,Serguchev
, p. 789 - 793 (2007/10/03)
Conjugate chlorination of terminal alkenes in the presence of pyridine N-oxides yields mixtures of regioisomeric chloroalkoxypyridinium chlorides. The same reaction with internal arylalkenes is regioselective, but the resulting quaternary salt is a mixture of erythro and threo stereoisomers.
A Structurally Characterized Dichloro-manganese(IV) Complex Capable of Halogenating Alkenes
Law, Neil A.,Machonkin, Timothy E.,McGorman, Joel P.,Larson, Erlund J.,Kampf, Jeff W.,Pecoraro, Vincent L.
, p. 2015 - 2016 (2007/10/02)
MnIV(salpn)Cl2 regioselectively trans-halogenates alkenes in a reaction for which the Mn-containing product is also identified; this is the first Mn-based halogenating system for which the reactive and final Mn-containing products are structurally characterized.
PHOSPHORUS PENTACHLORIDE REACTIONS WITH CONJUGATED CARBONYL COMPOUNDS AND CONJUGATED OLEFINS
Duty, Robert C.,Farley, Thomas H.
, p. 271 - 280 (2007/10/02)
Phosphorus pentachloride was reacted with conjugated aromatic and carbonyl compounds.The conjugated aromatic compounds were cis and trans stilbene, and the carbonyl compounds were diphenylketene and 2,3,4,5-tetraphenylcyclopentadienone.Two solvents used for these reactions were 1,1,2,2-tetrachlorethane and methylene chloride.Phosphorus pentachloride can dissociate into phosphorus trichloride and chlorine and our results indicated this was the reaction mechanism for phosphorus pentachloride reacting with 2,3,4,5-tetraphenylcyclopentadienone.With stilbene, cis andtrans, the mechanism with phosphorus pentachloride was the sp3d2 octahedral complex mechanism.With diphenylketene the mechanism was the dissociation of phosphorus pentachloride into the phosphorus tetrachloro action and the phosphorus hexachloro anion.Key words: Phosphorus pentachloride, stilbene, diphenylketene, and 2,3,4,5-tetraphenylcyclopentadienone.
