58696-54-1Relevant academic research and scientific papers
Reaction of Aromatic and Unsaturated Compounds with the Potassium Permanganate/HCI (HBr) Acetonitrile Reagent
Liu, Lilian Kao,Lin, Ching-Shan
, p. 61 - 66 (2007/10/03)
Addition of hydrochloric or hydrobromic acid to a solution of potassium permanganate in acetonitrile produced a homogeneous mixture, which is suitable for laboratory chlorination or bromination, respectively. Aromatic compounds more reactive than alkylbenzenes can be chlorinated or brominated without additional catalyst. Alkenes and alkynes give the corresponding vicinal dihaloalkanes and vinyl halides. All reactions complete within two hours under mild condition (25-60 °C) with excellent to moderate yields.
Energy Barrier for 1,2-Chlorine Migration in α-Methyl-α-chlorobenzyl(chloro)carbene
Liu, Michael T. H.,Murray, Shawn K.,Zhu, Jianhuan
, p. 1650 - 1652 (2007/10/02)
An activation energy of 3.4 kcal mol-1 (1 cal = 4.184 J) was obtained for the 1,2-chlorine migration in α-methyl-α-chlorobenzyl(chloro)carbene.
ROLE OF THE POLYMER BACKBONE ON THE REACTIVITY OF POLYMER-SUPPORTED (DICHLOROIODO)BENZENE
Sket, Boris,Zupan, Marko,Zupet, Pavle
, p. 1603 - 1606 (2007/10/02)
Chlorination of iodinated crosslinked polystyrene with Cl2 gave polyaryliododichloride containing 1.1 mmol of active chlorine per gram of resin, while fluorination of the same iodinated resin with XeF2 gave polyaryliododifluoride, co
Halogen Epoxides, 3. Reactions of 2-Chloro- and 2,3-Dichlorooxiranes with Silver Tetrafluoroborate: Synthesis of α-Fluorinated Carbonyl Compounds
Griesbaum, Karl,Keul, Helmut,Kibar, Riza,Pfeffer, Bernd,Spraul, Manfred
, p. 1858 - 1870 (2007/10/02)
Reactions of chlorinated oxiranes with silver tetrafluoroborate in ether have been investigated.Substituted-2-chlorooxiranes (4a - e) afforded the corresponding α-fluorocarbonyl compounds (7a - e) as major products and the isomeric α-chlorocarbonyl compounds (8a - e) as minor products.Substituted 2,3-dichlorooxiranes (10, 14, 20, 24) yielded the isomeric α,α-dichloroketones (13, 19, 22, 26b, 29b) as well as the corresponding α-chloro-α-fluoroketones (12, 17, 21, 26a, 29a) and α,β-unsaturated α-chloroketones (18, 23, 27, 30).The course of the reaction was rationalized.Similar reaction with α-chloroketones and with α,α-dichloroketones succeeded only at substrates (8b, 35) in which the chlorine substituents were in benzylic positions.
Vinyl Cation Intermediates in Electrophilic Additions to Triple Bonds. 1. Chlorination of Arylacetylenes
Yates, Keith,Go, T. Andrew
, p. 2377 - 2384 (2007/10/02)
The products of ionic addition of chlorine to phenylacetylene, β-methylphenylacetylene, 4-methylphenylacetylene, β-ethylphenylacetylene, and tolan have been investigated in anhydrous acetic acid.The major products are the α,β-dichlorostyrenes arising from simple 1,2-addition, but significant yields of solvent-incorporated products are also found.In some cases significant yields of β-chlorophenylacetylenes are found, presumably arising from an addition-elimination process.No products arising from addition of 2 mol of Cl2 were observed.The reactions are clearlynonstereospecific and show only weak stereoselectivity varying from predominant syn to predominant anti addition.However, the reactions are all completely regiospecific in the Markovnikov sense.In the presence of low concentrations of added salts such as lithium chloride, acetate, and perchlorate, the product distribution and stereochemistry are hardly affected.Only at high concentrations of these salts is there any significant change in product distribution.The second-order rates of addition have been measured for five additional phenyl-substituted compounds.The seven ring-substituted phenylacetylenes show an excellent correlation with ?+, giving a large negative ρ value (-4.19).The effects of β-substitution on the rate of chlorination are very small.The results are interpreted in terms of a simple Ad-E2 process, in which the rate-determining transition state is an open vinyl-cation-like species, with most of the positive charge being developed at Cα.The subsequent product-determining intermediate is considered to be a tight ion pair between an open α-phenylvinyl cation and a chloride counterion.This ion pair can react by ion-pair collapse, solvent attack, or internal proton elimination.Activation parameters determined for three of the above compounds show that the higher rates of chlorination (over bromination) of the acetylene system are due almost entirely to lower Δ H(excit.) values.
