Anisoles peroxide

Methyl phenyl sulfoxide has also been prepared from thio-anisole by the action of hydrogen peroxide,2,3 lead tetraacetate,4 and dinitrogen tetroxide,5,6 and from methanesulfinyl chloride and benzene with anhydrous aluminum chloride.7... 

The reaction course of hydrogenation and the composition of hydrogenated products strongly depend on polarity and donor strength of the used solvent. No hydrogenation reaction was observed in nonpolar or less polar solvents, such as hydrocarbons and aromatics. In these solvents the reaction starts by the addition of radical initiators, e.g., AIBN or dibenzoyl peroxide. The radical initiated reactions result in the formation of SiHCl3. A similar course was observed in less polar ethereal solvents, such as 1,4-dioxane, anisole, and dibenzyl ether. Radical steps seem to play an important role for the hydrogenation in these solvents. 

Phenol was hydroxylated with TS-1 and hydrogen peroxide to give a 1 1 mixture of catechol (4) and hydroquinone (5) (Eqn. 21.6).26>29 Anisole and other substituted benzenes gave similar results. Secondary and tertiary aliphatic C-H bonds were oxidized to give alcohols and ketones, but primary C-H bonds were... 

Spices and herbs have been used for centuries to mask unpleasant tastes and odors and to slow down spoilage. It has been found that sage, cloves, oregano, rosemary, and thyme prevent peroxide formation. Food chemists have found that they can synthesize compounds that work more effectively, cost less, are of known purity, and are free of insect contamination. Those compounds used most often are butylated hydroxy anisole (BHA), butylated hydroxy toluene (BHT), and propylgallate shown below. 

ANISOLE (100-66-3) Forms explosive mixture with air (flash point 125°F/51°C oc). Forms unstable peroxides, unless inhibited. Violent reaction with oxidizers, strong acids. Flow or agitation of substance may generate electrostatic charges due to low conductivity. 

Complexes of metal + ligand + protein or DNA can also catalyze the Diels Alder cycloaddition or oxidations with hydrogen peroxide. Copper complexes bound to DNA catalyzed the Diels-Alder cycloaddition with up to 99% ee [15, 16], Cu(phthalocyanine) complexed to serum albumin also catalyzed the enantioselective (98% ee) Diels-Alder reaction, but only with very high catalyst loading (10 mol%) and only with pyridine-bearing dienophiles (presumably to complex the copper) [17]. Achiral Cr(III) complexes or Mn(Schiff-base) complexes inserted into the active site of apomyoglobin variants catalyzed the sulfoxidation of thio-anisole with up to 13 and 51% ee, respectively [18, 19]. A copper phenanthroline complex attached to the adipocyte lipid-binding protein catalyzed the enantioselective hydrolysis of esters and amides [20]. 

Another radical reaction shown by the same cation is the addition across an oxygen molecule to yield the peroxide Not all aromatic oxidations in organic solvents proceed through the initial ionisation of the substrate molecule. In particular, several methoxylations appear to occur by primary oxidation of the solvent, methanol, to form a radical. Parker showed the methoxylation of anisole, in methanol containing 1 % H2SO4, to proceed at electrode potentials less positive than those required for the ionisation of anisole. ° The proposed mechanism is ... 

Meanwhile, Nicholas succeeded in the development of catalytic variants of work by Yu and Chatani in Eqs. (1) and (2). The key to the success is a careful choice of the solvent an anisole/DMSO cosolvent system is essential for the good conversion (Eq. 27) [52]. Li and coworkers also reported the catalytic system with tert-butyl peroxide (TBP) as an oxidant (Eq. 28) [53]. In the latter case, an aminyl radical species might be involved in the C-N forming step [54], although the details are not clear. Additionally, the sulfoximine is also a promising coupling partner for 2-phenylpyridine, albeit with a stoichiometric amount of Cu(OAc)2 (Eq. 29) [55]. 

Phenol, anisole, and phenolic ethers are readily hydroxylated by hydrogen peroxide in the presence of microcrystalline ZrP and acetic acid (151). The selectivity for catechol formation was greater than 29% at 47% conversion, and hydroqui-... 

Study of the interaction of toluene, nitrobenzene, dimethylaniline, phenol, anisole, and chlorobenzene with pernitrous acid (HOONO) at 8-98 C enabled formulation of the reaction mechanism [22]. HOONO is an important intermediate in the interconversion of nitrogen-containing species [23]. It forms upon reaction between hydrogen peroxide and nitrous acid. HOONO undergoes homolytic detachment ... 

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