4381-01-5

Upstream product

• 51229-53-9 Phenyl-(3-cyan-benzyl)-sulfid 
• 73900-19-3 3-Diazomethyl-benzonitrile 
• 109-89-7 diethylamine 
• 28188-41-2 m-(bromomethyl)benzonitrile 
• 691-38-3 (Z)-4-methyl-2-pentene 
• 110-82-7 cyclohexane 
• 117269-72-4 (3-cyano-benzyl)zinc(II) bromide 
• 64407-07-4 3-(chloromethyl)benzonitrile 
• 823-78-9 meta-bromobenzyl bromide 
• 591-17-3 meta-bromotoluene 
• 82732-03-4 1,1'-(1,2-ethanediyl)bis-3-bromobenzene 
• 544-92-3 copper(I) cyanide 

Downstream Products

• 4380-99-8 1,2-bis(3-carboxyphenyl)ethane 
• 108843-01-2 3,3'-bis(hydroxymethyl)diphenylethane 
• 121262-86-0 1,2-Bis<3-(brommethyl)phenyl>ethan 
• 96841-94-0 1,2-bis(m-methoxycarbonylphenyl)ethane 

Relevant academic research and scientific papers

Reversed electron apportionment in mesolytic cleavage: The reduction of benzyl halides by SmI2

The paradigm that the cleavage of the radical anion of benzyl halides occurs in such a way that the negative charge ends up on the departing halide leaving behind a benzyl radical is well rooted in chemistry. By studying the kinetics of the reaction of substituted benzylbromides and chlorides with SmI2 in THF it was found that substrates para-substituted with electron-withdrawing groups (CN and CO2Me), which are capable of forming hydrogen bonds with a proton donor and coordinating to samarium cation, react in a reversed electron apportionment mode. Namely, the halide departs as a radical. This conclusion is based on the found convex Hammett plots, element effects, proton donor effects, and the effect of tosylate (OTs) as a leaving group. The latter does not tend to tolerate radical character on the oxygen atom. In the presence of a proton donor, the tolyl derivatives were the sole product, whereas in its absence, the coupling dimer was obtained by a SN2 reaction of the benzyl anion on the neutral substrate. The data also suggest that for the para-CN and CO2Me derivatives in the presence of a proton donor, the first electron transfer is coupled with the proton transfer. Reverse breakup: In the mesolytic cleavage of the radical anions of benzyl halides that are para-substituted by CN or CO2Me groups, the halogen departs, counterintuitively, as a radical and the benzyl system carries the negative charge (see figure).

Iron nanoparticle-promoted Cu (I)-catalysed homocoupling of arylmethyl halides for the synthesis of 1,2-diarylethanes

Carbon-carbon bond formation is important in organic synthesis for the preparation of natural products, organic materials and polymers and so on. An efficient and mild reductive homocoupling of arylmethyl halides is now described. Treatment of various benzylic halides in the presence of zero valent iron nanoparticles (nZVI) and a catalytic amount of CuBr in air and water at room temperature afforded 1,2-diarylethanes in excellent yields.

Direct preparation of benzylic manganese reagents from benzyl halides, sulfonates, and phosphates and their reactions: Applications in organic synthesis

The use of highly active manganese (Mn)*, prepared by the Rieke method, was investigated for the direct preparation of benzylic manganese reagents. The oxidative addition of the highly active manganese to benzylic halides was easily completed under mild conditions. Moreover, benzylic manganese sulfonates and phosphates were prepared by direct oxidative addition of Mn* to the carbon-oxygen bonds of benzylic sulfonates and phosphates. The resulting benzylic manganese reagents were found to undergo cross-coupling reactions with a variety of electrophiles. Most of these reactions were carried out in the absence of any transition metal catalyst under mild conditions. In addition, the use of highly active manganese was also studied for preparation of homo-coupled products of functionalized benzyl halides without transition metal catalysts. These useful approaches provided not only a facile synthetic route to the preparation of resoricinolic lipids but a facile synthesis of functionalized 4-benzylpyridines by regioselective and chemo selective γ-addition of benzylic group to N-alkoxycarbonylpyridinum salts.

Palladium-catalyzed homocoupling reactions between two Csp3-Csp3 centers

(Matrix Presented) A novel palladium-catalyzed coupling reaction between two Csp3-Csp3 centers has been investigated. This protocol is initiated by the oxidative addition of an α-halo carbonyl compound to a palladium(0) species, followed by the double transmetalation. The key dialkyl palladium intermediate undergoes reductive elimination to form the desired coupling product.

Benzylic Manganese Halides, Sulfonates, and Phosphates: Preparation, Coupling Reactions, and Applications in Organic Synthesis

The use of highly active manganese, prepared by the Rieke method, for the direct preparation of benzylic manganese reagents was investigated. The oxidative addition of the highly active manganese (Mn*) to benzylic halides was easily completed under mild conditions. More importantly, benzylic manganese sulfonates and phosphates were prepared by direct oxidative addition of Mn* to the carbon-oxygen bonds of benzylic sulfonates and phosphates. The resulting benzylic manganese reagents were found to undergo cross-coupling reactions with a variety of electrophiles. The majority of these reactions were carried out in the absence of any transition metal catalyst under mild conditions. This approach also provided a facile synthetic route to the preparation of resorcinolic lipids.

Substituent effects on the photocleavage of benzyl-sulfur bonds. Observation of the "Meta effect"

Benzyl phenyl sulfide has been used to investigate the photocleavage mechanism for benzyl-sulfur bonds. Four experiments have shown that the reaction goes through a radical intermediate. First, the photoproducts observed can all be justified by radical mechanisms. Second, the radical intermediate was trapped with a five hexenyl tether. Third, UV analysis of analogs for the 4-NO2 derivative indicate no exciplex or electron transfer pathway. Fourth, no strong correlation is observed between a values and the quatum yields for loss of substituted benzyl phenyl sulide. The effect of oxygen on quantum yields is best observed after samples are thoroughly outgassed with consecutive freeze-pump-thaw cycles. It is shown that oxygen diminishes the substituent effect. Upon photolysis of the outgassed samples, the meta-substituted derivatives showed more significant variances than the para derivatives. The meta derivatives are most efficiently cleaved in the following order: 3-CN > 3-NO2 > 3-CF3 > 3-CH3 > 3-OCH3. These findings are justified by an increase in electron density of the radical ipso to the forming benzyl radical for the 3-OCH3 derivative and a decrease in the electron density of the radical ipso to the forming benzyl radical for the 3-CN derivative.

Photocleavage of Benzyl-Sulfide Bonds

The nucleoside transport inhibitor 6--9-(β-D-ribofuranosyl)purine, NBMPR, has been used successfully in photoaffinity labeling.We have studied the mechanism for photocleavage of the benzyl-sulfur bond by using substituted benzyl phenyl sulfides as analogues of NBMPR.This has enabled us to enhance the photoreactivity of the benzyl-sulfur bond.We have also performed "radical clock" studies with a hexenyl side chain to trap reactive intermediates.The mechanistic interpretation from the substituent and side chain studies is that the benzyl-sulfur moiety is photocleaved via a homolytic pathway.

THE EFFECT OF ARYL SUBSTITUENTS ON ARYLCARBENE REACTIVITY

Substituted (p-MeO, p-Me, H, p-Cl, p-Br, m-Br, m-MeO, 3,4-Cl2, p-CO2Me, m-CN and p-CN) monophenylcarbenes are generated in a binary mixture of substrates (methanol, cis-4-methyl-2-pentene and cyclohexane) and the relative rate of O - H insertion into methanol to stereospecific cyclopropanation of the olefin to C - H insertion into cyclohexane are calculated from the ratios of products and substrates.It is found (i) that the reactivities of the substrates decrease in the order of methanol, olefin and cyclohexane and (ii) that electron-donating substituents generally lead to reaction with the more reactive substrates while the reaction with the less reactive substrates is favoured in the case of electron-withdrawing substituents.These results are interpreted in terms of the change in the electrophilicity of the singlet arylcarbene by the substituents rather than the change in the singlet-triplet equilibrium.

REDUCTIVE COUPLING OF BENZYL HALIDES USING NICKEL(0)-COMPLEX GENERATED IN SITU IN THE PRESENCE OF TETRAETHYLAMMONIUM IODIDE, A SIMPLE AND CONVENIENT SYNTHESIS OF BIBENZYLS

Zerovalent nickel complex generated in situ by reduction of NiBr2(PPh3)2 with zinc powder in the presence of Et4NI was found to be an effective catalyst for homo-coupling of benzyl halides.The catalytic reactions proceeded smoothly in various solvents under mild conditions to afford dehalogenative-coupling products in good to high yields.

Electron Transfer in Competition with Loss of Nitrogen in Photochemical Reactions of Aryldiazomethane with Diethylamine

The photolysis of aryldiazomethanes was studied as a function of aryl substituents and the p-nitro group was found to exert a special effect of product distribution.