58696-38-1

Upstream product

• 536-74-3 phenylacetylene 
• 71955-87-8 trichloro[(Z)-2-chloro-2-phenylethenyl]-λ⁴-tellane 
• 64-19-7 acetic acid 
• 2889-74-9 perchlorate d'acetyle 
• 1483-82-5 phenylethynyl chloride 

Relevant academic research and scientific papers

Chlorination of Acetylenes with Sulfuryl Chloride

The reactions of some acetylenes with sulfuryl chloride in benzene and carbon tetrachloride at the reflux temperature afford the corresponding (E)- and (Z)-dichloroalkenes in good to moderate yields via homolytic pathway.The kinetically controlled isomer ratios (E/Z) depended very much on the kind of acetylenes employed; i.e., 93/7 for 1-octyne to 14/86 for 3,3-dimethyl-1-phenyl-1-butyne in benzene.

Hydrogen-Bonding-Assisted Br?nsted Acid and Gold Catalysis: Access to Both (E)- and (Z)-1,2-Haloalkenes via Hydrochlorination of Haloalkynes

We have developed an efficient synthesis of both (Z)- and (E)-chlorohaloalkenes via hydrochlorination of haloalkynes, based on two distinct hydrogen-bond-network-assisted catalytic systems: Br?nsted acid catalysis and gold catalysis. Both systems offer high stereoselectivity, good chemical yields, and diverse functional group tolerance.

Selective 1,2-dihalogenation and oxy-1,1-dihalogenation of alkynes by N-halosuccinimides

1,2-Dihalogenation and oxy-1,1-dihalogenation of alkynes by N-halosuccinimides can be selectively realized through using different reaction conditions. α,β-Dihalo alkenes were obtained exclusively using THF as solvent without using any catalyst, while α,α

Quaternary ammonium polychlorides as efficient reagents for chlorination of unsaturated compounds

Chlorination of unsaturated compounds by benzyltributylammonium polychlorides results in higher yields of addition products compared to those obtained with molecular chlorine.

Reaction of Aromatic and Unsaturated Compounds with the Potassium Permanganate/HCI (HBr) Acetonitrile Reagent

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.

INFLUENCE OF APROTIC SOLVENTS AND CHLORIDE ANIONS ON THE STEREOSELECTIVITY OF CHLORINATION OF PHENYLACETYLENE

Chlorination of phenylacetylene in aprotic solvents was studied.The stereoselectivity of chlorine addition to a triple bond was found to depend on the chlorination mechanism.In aprotic solvents (CCl4, hexane, Freon-113) a significant contribution of radical process is observed, which gives rise to trans-addition of chlorine.Passing to the less polar (CHCl3) or aromatic (benzene, toluene, chlorobenzene) solvents and lowering the temperature to -60 deg C increase the contribution of molecular process and hence the yield of the cis-product.Additions of pyridinium chlorides result in selective formation of trans-product due to synchronous reaction of chlorine and chloride anion with the triple bond of phenylacetylene (donor-molecule-acceptor trimolecular principle).

ROLE OF THE POLYMER BACKBONE ON THE REACTIVITY OF POLYMER-SUPPORTED (DICHLOROIODO)BENZENE

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

Vinyl Cation Intermediates in Electrophilic Additions to Triple Bonds. 1. Chlorination of Arylacetylenes

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.

Peroxide-induced α-Elimination of Organic Halides from Organotellurium(IV) Halides

Treatment of organotellurium(IV) halides with t-butyl hydroperoxide in 1,4-dioxan, acetic acid, or acetonitrile affords the corresponding organic halides in good to moderate yields presumably as the result of a 1,2-halogen shift.