2762-20-1

Upstream product

• 2100-25-6 2,3,5,6-tetramethyliodobenzene 
• 95-93-2 1,2,4,5-tetramethylbenzene 
• 7647-01-0 hydrogenchloride 
• 59457-26-0 1-chloro-1λ³-benzo[d][1,2]iodaoxol-3(1H)-one 
• 64-19-7 acetic acid 

Downstream Products

• 5153-39-9 6-chloro-1,2,3,4,5-pentamethylbenzene 
• 856070-12-7 3-chloro-2,4,5-trimethyl-benzenesulfonic acid 
• 23069-28-5 Tetramethyl-3-chlor-1,2,4,5-benzol-tetracarboxylat 
• 6590-41-6 4-Chlor-2,3,5,6-tetramethyl-benzotrichlorid 
• 1746-27-6 2,3,5,6-Tetramethyl-4-chlorbenzylchlorid 
• 52415-09-5 chloronitrodurene 
• 856070-14-9 chloronitrodurene 
• 95-93-2 1,2,4,5-tetramethylbenzene 
• 79128-50-0 6-chloro-3-chloroacetyl-durene 
• 6590-37-0 3,7,7-Trichlor-2,4,5-trimethyl-bicyclo<4,2,0>octa-1,3,5-trien 
• 6590-40-5 3-Chlor-2,4,5-trimethyl-bicyclo<4,2,0>octa-1,3,5-trien-7-on 
• 110614-67-0 bis(chloroduryl)mercury 
• 27021-25-6 4-Chlor-2,3,5,6-tetramethylbenzylnitrat 
• 72649-76-4 2,3,5,6-Tetramethyl-4-chlor-benzylcyanid 

Relevant academic research and scientific papers

C-H borylation by platinum catalysis

Herein, we describe the platinum-catalyzed borylation of aromatic C-H bonds. N-Heterocyclic carbene-ligated platinum catalysts are found to be efficient catalysts for the borylation of aromatic C(sp2)-H bonds when bis(pinacolato)diboron is used as the boron source. The most remarkable feature of these Pt catalysts is their lack of sensitivity towards the degree of steric hindrance around the C-H bonds undergoing the borylation reaction. These Pt catalysts allow for the synthesis of sterically congested 2,6-disubstituted phenylboronic esters, which are otherwise difficult to synthesize using existing C-H borylation methods. Furthermore, platinum catalysis allows for the site-selective borylation of the C-H bonds ortho to fluorine substituents in fluoroarene systems. Preliminary mechanistic studies and work towards the synthetic application of this platinum catalyzed C-H borylation process are described.

An efficient monochlorination of electron-rich aromatic compounds catalysed by ammonium iodide

An efficient monochlorination of electron-rich aromatic compounds is developed, with which a series of regioselective monochlorinated products are obtained in good yields. In the reaction, ammonium iodide is used as catalyst and m-chloroperbenzoic acid is used as the terminal oxidant. Ammonium iodide is first oxidised to hypoiodous acid by m-chloroperbenzoic acid. The in situ generated active iodine species then reacts with the aromatic compound to form the active hypervalent iodine intermediate in two steps and this reacts with lithium chloride to afford eventually the chlorinated compounds.

An efficient chlorination of aromatic compounds using a catalytic amount of iodobenzene

An efficient method was developed for chlorination of aromatic compounds with electron-donating groups using iodobenzene as the catalyst and m-chloroperbenzoic acid as the terminal oxidant in the presence of 4-methylbenzenesulfonic acid in THF at room temperature for 24 h, and a series of the monochlorinated compounds was obtained in good yields. In this protocol, the catalyst iodobenzene was first oxidized into the hypervalent iodine intermediate, which then treated with lithium chloride and finally reacted with aromatic compounds to form the chlorinated compounds.

Bis- N -heterocyclic carbene palladium(IV) tetrachloride complexes: Synthesis, reactivity, and mechanisms of direct chlorinations and oxidations of organic substrates

This Article describes the preparation and isolation of novel octahedral CH2-bridged bis-(N-heterocyclic carbene)palladium(IV) tetrachlorides of the general formula LPdIVCl4 [L = (NHC)CH 2(NHC)] from LPdIICl2 and Cl2. In intermolecular, nonchelation-controlled transformations LPdIVCl 4 reacted with alkenes and alkynes to 1,2-dichlorination adducts. Aromatic, benzylic, and aliphatic C-H bonds were converted into C-Cl bonds. Detailed mechanistic investigations in the dichlorinations of alkenes were conducted on the 18VE PdIV complex. Positive solvent effects as well as kinetic measurements probing the impact of cyclohexene and chloride concentrations on the rate of alkene chlorination support a PdIV-Cl ionization in the first step. Product stereochemistry and product distributions from various alkenes also support Cl+-transfer from the pentacoordinated PdIV-intermediate LPdIVCl 3+ to olefins. 1-Hexene/3-hexene competition experiments rule out both the formation of π-complexes along the reaction coordinate as well as in situ generated Cl2 from a reductive elimination process. Instead, a ligand-mediated direct Cl+-transfer from LPd IVCl3+ to the π-system is likely to occur. Similarly, C-H bond chlorinations proceed via an electrophilic process with in situ formed LPdIVCl3+. The presence of a large excess of added Cl- slows cyclohexene chlorination while the presence of stoichiometric amounts of chloride accelerates both PdIV-Cl ionization and Cl+-transfer from LPdIVCl3 +. 1H NMR titrations, T1 relaxation time measurements, binding isotherms, and Job plot analysis point to the formation of a trifurcated Cl-...H-C bond in the NHC-ligand periphery as a supramolecular cause for the accelerated chemical events involving the metal center.

Chlorination of aromatics with trichloroisocyanuric acid (TCICA) in bronsted-acidic imidazolium ionic liquid [BMIM(SO3H)][OTf]: An economical, green protocol for the synthesis of chloroarenes

A survey study on electrophilic chlorination of aromatics with trichloroisocyanuric acid (TCICA) in Bronsted-acidic imidazolium ionic liquid [BMIM(SO3H)][OTf] is reported. The reactions are performed under very mild conditions (at ～50°C) and give good to excellent yields, depending on the substrates. Chemoselectivity for mono- v. dichlorination can be tuned by changing the arene-to-TCICA ratio and the reaction time. The survey study and competitive experiments suggest that triprotonated/protosolvated TCICA is a selective/moderately reactive transfer-chlorination electrophile. Density functional theory was used as guide to obtain further insight into the nature of the chlorination electrophile and the transfer-chlorination step. CSIRO 2007.

Oxidative halogenation of aromatic compounds with metal halides and sodium bismuthate

A new mild and efficient method for aromatic halogenation with a wide variety of halides in the presence of sodium bismuthate NaBO3 in AcOH is reported. Metal halides of groups Ia, IIa, IIIa, IVa, Va, and the first row of transition elements are suitable for this method.

Aromatic iodination: A new investigation on the nature of the mechanism

Following a suggestion by the late Lennart Eberson, we have employed the ICl-HFP (HFP being hexafluoropropan-2-ol) system in iodination reactions, and found unambiguous evidence for the occurrence of an ET-mechanism of halogenation. The evidence is based on the use of 'intelligent' substrates, which make it possible to fix the boundaries between the occurrence of an ET-mechanism and of a conventional polar mechanism. In an 'intelligent' substrate, in fact, the nature of the product(s) changes significantly depending on the operating mechanism. The ICl-HFP combination is instrumental to the onset of a one-electron oxidation with electron-rich substrates, followed by halogenation. The most prominent example is that of the electron-rich substrate durene (1,2,4,5-tetramethylbenzene, DUR), when compared to mesitylene (1,3,5-trimethylbenzene, MES): with a 'conventional' iodination system (i.e., I2/ Ag+) and in common solvents, where the polar mechanism holds, durene is less reactive (kMES/kDUR = 46 ± 3), but becomes more reactive (kMES/kDUR = 0.23) in HFP with ICl, where the ET-mechanism takes over. Other substrates also support the onset of ET-pathways in HFP. Finally, a preliminary survey of a biohalogenation reaction induced by laccase indicates the modest occurrence of a polar process of iodination with a few substrates.

Mild chlorination of aromatic compounds with tin(IV) chloride and lead tetraacetate

SnCl4/Pb(OAc)4 acts as a safe source of Cl2 for the chlorination of aromatic compounds. A variety of aromatic compounds are effectively chlorinated with SnCl4/Pb(OAc)4 under mild conditions. The mixture is a selective chlorinating agent, particularly with polyalkylbenzenes, polycyclic aromatic compounds and anisoles.

Ring Halogenations of Polyalkylbenzenes by Ionic Halides and Koser's Reagent

Ring chlorinations of polyalkylbenzenes such as mesitylene have been carried out at room temperature with LiCl or NaCl and stoichiometric amounts of Koser's reagent.Solvent range from water to methylene chloride.The procedures were extended to bromination and iodination.