15910-49-3

Upstream product

• 67-56-1 methanol 
• 732-26-3 2,4,6-tri-tert-butylphenoxol 
• 1988-75-6 4-bromo-2,4,6-tri-tert-butyl-2,5-cyclohexadiene-1-one 
• 3315-32-0 2,4,6-tri-tert-butylphenoxyl 
• 7732-18-5 water 
• 5457-60-3 4-chloro-2,4,6-tri-tert-butylcyclohexa-2,5-dienone 

Downstream Products

• 489-01-0 2,6-Di-t-butyl-4-methoxyphenol 
• 15910-86-8 3,6-Di-tert.-butyl-guajacol 
• 15910-85-7 3-Methoxy-2,4,6-tri-tert-butyl-cyclohexa-2,5-dien-1-on 
• 110678-05-2 (4S,5S)-2,5-Di-tert-butyl-4-(2,2-dimethyl-propionyl)-4-methoxy-cyclopent-2-enone 
• 150-76-5 4-methoxy-phenol 
• 2444-28-2 2,6-di-tert-butyl-4-hydroxyphenol 
• 20137-67-1 2,6-di-tert-butyl-4-methoxyphenoxyl radical 
• 719-22-2 2,6-Di-tert-butyl-1,4-benzoquinone 
• 1975-15-1 2,6,2',6'-tetra-tert-butyl-4,4'-dimethoxy-4,4'-peroxy-bis-cyclohexa-2,5-dienone 
• 20031-57-6 2,6-Di-tert-butyl-4-phenylazo-phenol 

Relevant academic research and scientific papers

Monitoring Electrochemical Reactions by 13C NMR Spectroscopy

The anodic conevrsion of 2,4,6-tri-tert-butylphenol in methanol, leading to 2,4,6-tris(1,1-dimethylethyl)-4-methoxy-2,5-cyclohexadien-1-one, has been followed by two types of 13C NMR experiments: (a) a static procedure, inserting the electrodes directly i

Solvolysis of 4-halogeno-4-alkyl-2,6-di-tert-butylcyclohexa-2,5-dienones induced by positive halogen donors as electrophiles

Positive halogen donors such as N-iodosuccinimide (NIS) induce solvolysis of dienones 1, as model 4-halogenocyclohexa-2,5-dienones, in different hydroxylic solvents (ROH), yielding the 4-RO-cyclohexa-2,5-dienones (2). The rate of the solvolysis with NIS is highly dependent on the structure of ROH. The problem of such dependency is overcome by running the reaction in ROH diluted with MeCN, a polar aprotic solvent, in place of pure ROH; the rate of the reaction in the ROH-MeCN solvent mixture is almost independent of the structure (or the polarity) of ROH, and the reaction is completed faster or markedly faster than in neat ROH. The results suggest that the solvolysis rate is controlled by the polarity of the solvent system, although the hydrogen-bond acceptability of MeCN for dilution also accelerates the reaction. A mechanism for the solvolysis is proposed, involving electrophilic attack of a positive halogen donor at the halogen atom of 1, generating the 4-oxocyclohexa-2,5-dienyl cation intermediates (8) via the rate-limiting polar transition states. CSIRO 2013.

P-quinols and p-quinol Ethers from 2,4,6-trialkylphenols

The oxidation of 2,4,6-trialkylphenols with lead(IV) oxide and 70% perchloric acid in water-acetone or in alcohols gives p-quinols or p-quinol ethers, respectively. Some nonmetallic oxidants serve the same purpose. Georg Thieme Verlag Stuttgart.

Electron transfer between protonated and unprotonated phenoxyl radicals

(Chemical Equation Presented) The reaction of phenoxyl radicals with acids is investigated. 2,4,6-Tri-tert-butylphenoxyl radical (13), a persistent radical, deteriorates in MeOH/PhH in the presence of an acid yielding 4-methoxycyclohexa-2,5-dienone 18a and the parent phenol (14). The reaction is facilitated by a strong acid. Treatment of 2,6-di-tert-butyl-4-methylphenoxyl radical (2), a short-lived radical, generated by dissociation of its dimer, with an acid in MeOH provides 4-methoxycyclohexa-2,5-dienone 4 and the products from disproportionation of 2 including the parent phenol (3). A strong acid in a high concentration favors the formation of 4 while the yield of 3 is always kept high. Oxidation of the parent phenol (33) with PbO2 to generate transient 2,6-di-tert-butylphenoxyl radical (35) in AcOH/H2O containing an added acid provides eventually p-benzoquinone 39 and 4,4′-diphenoquinone 42, the product from dimerization of 35. A strong acid in a high concentration favors the formation of 39. These results suggest that a phenoxyl radical is protonated by an acid and electron transfer takes place from another phenoxyl radical to the protonated phenoxyl radical, thus generating the phenoxyl cation, which can add an oxygen nucleophile, and the phenol (eq 5). The electron transfer is a fast reaction.

Development of a novel environmentally friendly electrolytic system by using recyclable solid-supported bases for in situ generation of a supporting electrolyte from methanol as a solvent: Application for Anodic methoxylation of organic compounds

We have successfully developed a novel environmentally friendly electrolytic system using recyclable solid-supported bases for in situ generation of a supporting electrolyte from methanol as a solvent. It was found that solid-supported bases are electrochemically inactive at an electrode surface. It was also found that solid-supported bases dissociate methanol into methoxide anions and protons. Therefore, in the presence of solid-supported bases, it was clarified that methanol serves as both a solvent and a supporting electrolyte generated in situ. Anodic methoxylation of various compounds with solid-supported bases was carried out to provide the corresponding methoxylated products in good to excellent yields with a few exceptions. The methoxylated products and the solid-supported bases were easily separated by only filtration, and the desired pure methoxylated products were readily isolated simply by concentration of the filtrates. The separated and recovered solid-supported bases were recyclable for several times.

Bromide-assisted oxidation of substituted phenols with hydrogen peroxide to the corresponding p-quinol and p-quinol ethers over WO4 2--exchanged layered double hydroxides

A simple and efficient one-pot synthesis of p-quinols and their ethers occurs over tungstate-exchanged layered double hydroxides (WO4 2--LDHs), which catalyze the bromide-assisted oxidation of substituted phenols to the corresponding 4-alkoxy- and 4-hydroxycyclohexa-2,5- dienones in high yields (see scheme).

Reactivity and selectivity of aryloxylium ions

The reactivity and selectivity of aryloxylium ions in acetonitrile-water mixtures are described. The 4-bromo-2,4,6-trialkylcyclohexa-2,5-dienones used as substrates were synthesised by electrophilic bromination in yields of 60% (3 R = Me) and 52% (7 R = B

Phenolic Oxidations with Phenyliodonium Diacetate

Phenyliodonium diacetate (PIDA) in methanol interacts smoothly with phenols to yield p-quinones, o-quinones, 4,4-dialkoxycyclohexa-2,5-dienones or 4-alkyl-4-alkoxycyclohexa-2,5-dienones, dependant on the constitution of the phenolic substrate.The reactions proceed in mild conditions and good yields and are synthetically useful.

PHENOLIC OXIDATION WITH (DIACETOXYIODO)BENZENE

(Diacetoxyiodo)benzene oxidises quinols and extended quinols to the corresponding quinones smoothly and in high yield.Excess of the reagent in methanol with monohydric phenols directly yields p-quinone ketals, also in good yields. 4-Alkyl and 4-alkoxyphenols give the corresponding 4-alkyl-4-methoxycyclohexadienones and 4-alkoxy-4-methoxycyclohexadienones.

Formation of Quinol Ethers using (Diacetoxyiodo)benzene

The use of (diacetoxyiodo)benzene for the oxidative coupling of a hindered phenol with aliphatic alcohols or other phenols has been investigated.