18684-82-7

Upstream product

• 563-79-1 2,3-Dimethyl-2-butene 
• 91309-66-9 3-chloro-3-(p-chlorobenzyl)diazirine 
• 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 
• 1073-67-2 4-vinylbenzyl chloride 
• 64-17-5 ethanol 
• 691-38-3 (Z)-4-methyl-2-pentene 
• 1615-02-7 3-(4-chlorophenyl)prop-2-enoic acid 
• 88211-10-3 p-chlorobenzyl(chloro)carbene 
• 5676-62-0 (Z)-3-(4-chlorophenyl)acrylic acid 
• 107-21-1 ethylene glycol 

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 

Relevant academic research and scientific papers

Synthesis of 3-Substituted Indolizines from the Reaction of Chlorocarbenes with 2-Vinylpyridine

3-Substituted indolizines have been obtained in a one-step procedure from the reaction of chlorocarbenes with 2-vinylpyridine.

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.

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.

Microwave induced halodecarboxylation of α,β-unsaturated carboxylic acids

Halodecarboxylations of α,β-unsaturated carboxylic acids 1a-g, 4 by N-cholorobenzotriazole under 5-10 minutes of microwave irradiation gave the corresponding β-arylvinyl halides 3a-g, 5 in yields of 70-90%.

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.

Oxidative Halo-Decarboxylation of α,β-Unsaturated Carboxylic Acids

A procedure for oxidative halo-decarboxylation of α,β-unsaturated carboxylic acids using iodosylbenzene, or iodosylbenzene diacetate, and N-chloro-, N-bromo-, or N-iodosuccinimide is presented.Good yields of the corresponding bromoalkenes are obtained when the α,β-unsaturated carboxylic acids are substituted with an aromatic substituent in the β-position and N-bromosuccinimide is used as the halogenation reagent.The scope of mainly the oxidative bromo-decarboxylation reaction is presented, and a tentative mechanism is proposed.

Laser flash photolysis study of substituent effects on the rate of 1,2-H migration in a series of benzylchlorocarbenes

Laser flash photolysis of para-substituted 3-chloro-3-benzyldiazirines in isooctane produces the corresponding carbenes, which react with pyridine to form ylides or undergo 1,2-H migration to form the (Z)- and (E)-β-chlorostyrenes. The rate for the 1,2-H migration is determined by plotting the pseudo-first-order rate constants for the growth of the ylide vs [pyridine] and extrapolating to zero pyridine concentration. In the case of (p-chlorobenzyl)chlorocarbene, the carbene decay can be monitored directly at 310 nm, whereas in [p-(trifluoromethyl)benzyl]chlorocarbene, the 285-nm trace may be analyzed as the sum of the absorption of the carbene and of the product β-chlorostyrenes. A Hammett plot of the logarithms of the rate constants for 1,2-H migration vs σp values gave a ρ value of -1.0, consistent with a hydride-like 1,2-H shift to the carbene center. The rate constants for the cyclopropanation of carbenes with tetramethylethylene (TME) were determined. In particular, the cyclopropanation of (p-chlorobenzyl)chlorocarbene with TME gave a negative activation energy of -4.7 kcal mol-1.

Thermolysis and Photolysis of 3-Chloro-3-benzyldiazirines in Alkenes: Evidence for a Carbene-Alkene Complex

Photolysis and thermolysis of substituted 3-chloro-3-benzyldiazirines in alkenes yielded cyclopropanes and chlorostyrenes as products.The results suggest that the cyclopropanation of benzylchlorocarbenes is independent of substituents.However, 1,2-hydrogen migration is accelerated by OCH3 or CH3 substituents, and is decelerated by a Cl substituent on the phenyl ring.These results support the existence of an energy barrier to 1,2-H migration.Evidence is provided for carbene-alkene complexation.

Substituent and Temperature Effects on the Reactions of Benzylchlorocarbene with Alcohol

The insertion reaction of the para-substituted benzylchlorocarbenes with methanol shows a second-order dependence in methanol, but only a first-order dependence in ethylene glycol.The results are consistent with a mechanism whereby the carbene inserts into the O-H bond of the alcohol dimer or oligomer by electrophilic attack of the carbene on the oxigenone pair to produce a reversibly formed ylide intermediate.The effects of the substituents indicate that electron-releasing group favours rearrangement while electron-withdrawing group facilitates insertion.Photolysis of halogenodiazirines in methanol at low temperatures give rise to V-shaped Arrhenius behaviour and the importance of N2 in influencing the reactivity of the singlet halogenocarbene in the matrix is demonstrated.