56180-49-5

Upstream product

• 104-93-8 p-methylanizole 
• 106-44-5 p-cresol 

Downstream Products

• 38064-90-3 2,4-dimethoxytoluene 
• 615-62-3 3-chloro-4-methylphenol 
• 85033-97-2 2,3,4-trichloro-4-methylcyclohexa-5-enone 
• 54788-38-4 2-chloro-4-methoxy-1-methylbenzene 
• 100777-46-6 1-chloro-5-methoxy-2-methyl-4-nitrobenzene 
• 100278-74-8 5-chloro-4-methyl-2-nitrophenol 
• 112251-93-1 3-chloro-4-methyl-2-nitro-phenol 
• 112251-96-4 3-chloro-4-methyl-4-nitrocyclohexa-2,5-dienone 
• 112251-95-3 3-chloro-1-methoxy-4-methyl-2-nitro-benzene 

Relevant academic research and scientific papers

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.

Ipso-chlorination of para-alkylphenols ethers with SbF5-CH2Cl2 (CHCl3, CCl4): a novel route to 4-chlorocyclohexa-2,5-dienones

Chlorination of mono or polycyclic para-alkylphenols ethers with SbF5-CH2Cl2 (CHCl3, CCl4) gives the corresponding 4-chlorocyclohexa-2,5-dienones in a better yield than reaction with SbCl5-CH2Cl2(SO2).The postulated mechanism implies electrophilic chlorin

Ipso-Chlorination of 4-Alkylphenols Ethers. A Novel Route to 4-Chlorocyclohexa-2,5-dienones.

Selective chlorination of 4-alkylphenols ethers with SbF5/CH2Cl2 (CHCl3, CCl4) yields 4-chlorocyclohexa-2,5-dienones; no α-chlorination to a carbonyl group is observed in the reaction conditions.

Highly Selective Aromatic Chlorinations. Part 2. The Chlorination of Substituted Phenols, Anisoles, Anilines, and Related Compounds with N-Chloroamines in Acidic Solution

Phenols, anisoles, anilines, and related compounds are chlorinated in trifluoroacetic acid at room temperature by N-chlorodialkylamines and N-chlorotrialkylammonium salts.With monsubstituted compounds and their 2- and 3-substituted derivatives the reaction occurs efficiently and selectively at the 4-position.The reactivity of these substrates and the selectivity of their chlorinations are determined by electronic rather than steric effects of the substituent.Blocking the reaction with a substituent at the 4-position generally leads to only poor or moderate yields of the 2-chlorinated product.Evidence for radical and cation radical intermediates has been obtained in the reactions of some of the 4-substituted reactants and the mechanism of chlorination is discussed in the light of these findings.The reactions of selected substrates have been scaled up to give laboratory syntheses.

Phenol-Dienone Rearrangement in the Chlorination of p-Cresol with t-Butyl Hypochlorite

From the chlorination of p-cresol with t-butyl hypochloride (3 mol) in acetic acid five non-phenolic compounds have been isolated and identified as substituted 2,5-cyclohexadienones (I-V).The formation of these compounds has been explained in terms of phenol-dienone and dienone-phenol rearrangements. 2,6-Dichloro-4-(2-chloro-4-methylphenoxy)-4-methyl-2,5-cyclohexadienone is a condensation product of the intermediate chlorocresols and its mechanistic details have been discussed.

Electrophilic Chlorination of 4-Methylphenols with Molecular Chlorine. Synthesis of Dimethoxy Aromatics by Methanolysis of 4-Chloro-4-methylcyclcohexa-2,5-dienones

The chlorination of p-cresol (1a), 2,4-dimethylphenol (1b), 3,4-dimethylphenol (1c), 2,4,5-trimethylphenol (1d), 2,4,6-trimethylphenol (1e) and the various possible mono- and dichloro derivatives of these phenols (3a-d, 6a and 6 c) with molecular chlorine was investigated in dichloromethane or dimethyl formamide solution.The 2,6-substituted p-cresol derivatives all give quantitative yields of 4-chloro-4-methylcyclohexa-2,5-dienones (5b, 5d, 7a, 7c and 2e), whereas the less substituted p-cresol derivatives give a 20-25percent yield of corresponding 4-chloro-4-methylcyclohexa-2,5-dienones (2a-d, 5a and 5c), the other products being chlorinated phenols.Treatment of 4-chloro-4-methylcyclohexa-2,5-dienones with at least one of the double bonds of the ring unsubstituted (2a-c and 4a) with methanol gave a quantitative yield of a 1,3-dimethoxybenzene derivative (9a-c and 10), whereas similar treatment of 4-chloro-2,4,5-trimethylcyclohexa-2,5-dienone (2d) gave 5-methoxy-2,3-dimethylbenzyl methyl ether (11).Treatment of the other 4-chlorodienones with methanol gave the corresponding 4-methoxydienones.Electrophilic chlorination of certain p-cresol derivatives followed by methanolysis hence is a facile although low-yield method for 3-methoxylation or selective side chain oxidation of these p-cresol derivatives.