18684-97-4

Upstream product

• 100-69-6 2-vinylpyridine 
• 91309-66-9 3-chloro-3-(p-chlorobenzyl)diazirine 
• 563-79-1 2,3-Dimethyl-2-butene 
• 623-91-6 diethyl Fumarate 
• 4412-41-3 1-Chloro-4-(2,2-dichloro-ethyl)-benzene 
• 124-48-1 chlorodibromomethane 
• 52372-80-2 (4-chlorobenzylidene)hydrazine 
• 75-25-2 Bromoform 
• 75-27-4 bromodichloromethane 
• 1615-02-7 p-chlorocinnamic acid 
• 104-88-1 4-chlorobenzaldehyde 
• 68089-86-1 chloromethyl(triphenyl)phosphonium iodide 
• 67-56-1 methanol 
• 88211-10-3 p-chlorobenzyl(chloro)carbene 

Downstream Products

• 104-51-8 1-butylbenzene 
• 1083-56-3 1,4-diphenylbutane 
• 824-90-8 1-phenylbut-1-ene 
• 886-65-7 1,4-diphenyl-1,3-butadiene 
• 27486-17-5 (E)-1-(4-chlorostyryl)-2-methylbenzene 
• 1657-50-7 (E)-1-(4-chlorophenyl)-2-phenylethene 
• 3041-83-6 (E)-4-chloro-4'-methylstilbene 

Relevant academic research and scientific papers

Continuous Flow Chlorination of Alkenyl Iodides Promoted by Copper Tubing

A simple continuous flow synthesis of alkenyl chlorides from the corresponding readily available alkenyl iodides in copper reactor tubing is described. A variety of alkenyl chlorides were obtained in good to excellent yields with full retention of the dou

Transition metal free large-scale synthesis of aromatic vinyl chlorides from aromatic vinyl carboxylic acids using bleach

While continuing our research on Hunsdiecker reaction, we came across an interesting application of bleach, sodium hypochlorite (NaOCl) for decarboxylative chlorination reaction. The reaction is easily scaled up to 10 mmol. The reaction has good tolerance towards wide variety of functional groups. The reaction has mild conditions and gave relatively high chemical yield of the desired product.

A General Copper-Catalyzed Vinylic Halogen Exchange Reaction

An efficient and general system for the halogen exchange reaction in alkenyl halides has been developed. Upon reaction with catalytic amounts of copper iodide and trans-N,N′-dimethylcyclohexane-1,2-diamine in the presence of tetramethylammonium chloride or bromide, a wide range of easily accessible alkenyl iodides can be smoothly transformed to their far less available chlorinated and brominated derivatives in excellent yields and with full retention of the double bond geometry. This reaction also enables the chlorination of bromoalkenes and could be extended to the use of gem-dibromoalkenes.

Development of a general copper-catalyzed vinylic Finkelstein reaction—application to the synthesis of the C1–C9 fragment of laingolide B

An efficient and broadly applicable procedure for the copper-catalyzed vinylic Finkelstein reaction is reported. Using a simple, readily available and cheap catalytic system, a broad range of alkenyl iodides and bromides can be smoothly converted to their lower homologues with high yields and full retention of the double bond geometry. Key features of this vinylic Finkelstein reaction are its broad applicability, enabling the conversion of readily available alkenyl iodides to their less available brominated and chlorinated counterparts, and the mild reaction conditions compatible with a range of highly functionalized substrates. The potential of this vinylic halogen exchange reaction in total synthesis and medicinal chemistry was demonstrated by its successful use for the synthesis of the C1–C9 fragment of laingolide B and for the late-stage modification of drug-like molecules. The extension of this halogen exchange to the acetylenic and allenic Finkelstein reactions is also reported.

Kinetically controlled E-selective catalytic olefin metathesis

A major shortcoming in olefin metathesis, a chemical process that is central to research in several branches of chemistry, is the lack of efficient methods that kinetically favor E isomers in the product distribution. Here we show that kinetically E-selective cross-metathesis reactions may be designed to generate thermodynamically disfavored alkenyl chlorides and fluorides in high yield and with exceptional stereoselectivity.With 1.0 to 5.0 mole % of a molybdenum-based catalyst, which may be delivered in the form of air- and moisture-stable paraffin pellets, reactions typically proceed to completion within 4 hours at ambient temperature. Many isomerically pure E-alkenyl chlorides, applicable to catalytic cross-coupling transformations and found in biologically active entities, thus become easily and directly accessible. Similarly, E-alkenyl fluorides can be synthesized from simpler compounds or more complex molecules.

METATHESIS CATALYSTS AND METHODS THEREOF

The present application provides, among other things, compounds and methods for metathesis reactions. In some embodiments, the present disclosure provides methods for preparing alkenyl halide with regioselectivity and/or stereoselectivity. In some embodim

A green hunsdiecker reaction of cinnamic acids

Tribromo- and trichloroisocyanuric acids react with cinnamic acids in NaOH/H2O/Et2O at room temperature to produce (E)-2-halostyrenes regioselectively in 25-95percent yield. Mechanism studies using Hammett correlations and DFT (density functional theory) calculations have shown that this reaction has as rate determining step the electrophilic addition of chlorine atom to the double bond.

Catalytic olefination. Estimation of the reactivity of polyhaloalkanes

Global electrophilicity indices and carbon-halogen bond energies of a wide series of halogen derivatives were calculated in terms of the density functional theory (DFT). The calculated values were used to estimate the reactivity of halogen derivatives under conditions of catalytic olefination. Reactions of N-unsubstituted hydrazones with polyhaloalkanes in the presence of CuCl afforded substituted alkenes. The relation between the structure of polyhaloalkanes and their reactivity was studied using the reaction with 4-chlorobenzaldehyde hydrazone as an example. It was found that increase in the global electrophilicity index and decrease in the C-Hlg bond energy are accompanied by increase in the olefinating power of halogen derivatives.

Catalytic olefination reaction of carbonyl compounds. A study on stereoselectivity of alkene formation

The mechanism of formation of alkene stereoisomers in the catalytic olefination reaction of carbonyl compounds was studied. 4-Chlorobenzaldehyde hydrazone 1 stereoselectively reacts with a number of F-, Cl-, Br-, and I-containing polyhaloalkanes in the presence of catalytic amounts of CuCl to give ω-substituted styrenes 2 with the more thermodynamically stable alkene isomer being the major product. A model for the formation of the stereoisomers of alkenes 2 in the olefination reaction is proposed. Stereoselectivity of the reaction is determined by elimination of copper(II) halides from the lowest-lying conformers of organocopper intermediates II. According to quantum-chemical calculations, the elimination should involve the staggered conformations with antiperiplanar arrangement of C-Hal and C-Cu bonds and proceed by the E2 anti-elimination mechanism. The results of quantum-chemical calculations are in good agreement with the experimental E/Z alkene isomer ratios.

Reaction of Catalytic Olefination of Hydrazones with Polyhaloalkanes. Investigation of Alkene Formation Chemoselectivity

Hydrazones of carbonyl compounds at treatment with polyhaloalkanes in the presence of CuCl as catalyst are converted into substituted alkenes with formation of a new C=C bond.