Oxygenation catechol

Molecular oxygen is activated in basic solutions and oxygenates catechol to give ring-opened products. Grinstead reported in 1964 that the dioxygenated product (2, lactonic... 

METHOD 4 [110, 111] - guaiacol and cupric perchlorate (Cu(CI04)2)-ascorbic acid (that s vitamin C, bubba ) are mixed in an appropriate solvent under oxygen atmosphere in a flask to give about 30% catechol. 

Several oxygen- and sulfur-substituted boranes have been reported (125—130). 1,3,2-Benzodioxaborole [274-07-7] (catecholborane, CB) (15) is the one best studied. It is commercially available or can be prepared by the reaction of catechol with borane-THF (57,131), or by other procedures (132). The product is a Hquid existing as a monomer, remarkably stable to disproportionation. No... 

Conversion of Aromatic Rings to Nonaromatic Cyclic Structures. On treatment with oxidants such as chlorine, hypochlorite anion, chlorine dioxide, oxygen, hydrogen peroxide, and peroxy acids, the aromatic nuclei in lignin typically ate converted to o- and -quinoid stmctures and oxinane derivatives of quinols. Because of thein relatively high reactivity, these stmctures often appear as transient intermediates rather than as end products. Further reactions of the intermediates lead to the formation of catechol, hydroquinone, and mono- and dicarboxyhc acids. 

Step 2. Find common low energy confonnations for all of the compounds. The commonality was assessed by comparing the distances between each of the hydroxyl oxygens and the nitrogen and the angle between the planes of the catechol ring and the accessory ring. 

Chemical Reactivity - Reactivity with Water No reaction Reactivity with Common Materials No reactions Stability During Transport Stable Neutralizing Agents for Acids and Caustics Not pertinent Polymerization Polymerization is accelerated by heat and exposure to oxygen, as well as the presence of contamination such as iron rust. Iron surfaces should be treated with an appropriate reducing agent such as sodium nitrate, before being placed into isoprene service Inhibitor of Polymerization Tertiary butyl catechol (0.06 %). Di-n-butylamine, phenyl-beta-naphthylamine andphenyl-alpha-naphthylamine are also recommended. 

As with the crowns, the situation becomes more complicated when there are other heteroatoms or substituents in one of the cryptand bridges. The symbol B is used to designate a benzo- or catechol unit in the bridge and subscripts are used to designate heteroatoms when non-oxygen heteroatoms are present. Examples of this are shown in structures 12 and 13 above. 

The main product of the Elbs reaction is the 1,4-dihydroxybenzene (hydro-quinone). If the para position is already occupied by a substituent, the reaction occurs at an ortho position, leading to a catechol derivative although the yields are not as good as for a hydroquinone. Better yields of catechols 7 can be obtained by a copper-catalyzed oxidation of phenols with molecular oxygen ... 

An anti-oxygen such as catechol or hydroquinone is used to prevent polymerization. Hydroquinone should be added in the ratio of one part per thousand unless the phenylethylene is to be used immediately.1... 

An interesting combination of enzymatic with non-enzymatic transformation in a one-pot three-step multiple sequence was reported by Waldmann and coworkers [82]. Phenols 125 in the presence of oxygen and enzyme tyrosinase are hydroxylated to catechols 126 which are then oxidized in situ to ortho quinones 127. These intermediates subsequently undergo a Diels-Alder reaction with inverse electron demand by reaction with different dienophiles (Table 4.19) to give endo bicyclic 1,2-diketones 128 and 129 in good yields. 

When catechol was oxidized with Mn04 under aprotic conditions, a semiquinone radical ion intermediate was involved. For autoxidations (i.e., with atmospheric oxygen) a free-radical mechanism is known to operate. 

The piperonal synthesis (p T 9) is an example where the two ortho oxygen substituents would be very difficult to set up. We therefore (guideline 7) start with available catechol ( o-dihydroxybenzene),... 

As strong metal ion chelators due to their catechol structure, tea flavonoids are able to bind and thus decrease the level of free cellular ferric and ferrous ions, which are required for the generation of reactive oxygen radicals via the Fenton reaction (Yang and Wang, 1993). 

Krooneman J, EBA Wieringa, ERB Moore, J Gerritse, RA Prins, JC Gottschal (1996) Isolation of Alcalig-enes sp. strain L6 at low oxygen concentrations and degradation of 3-chlorobenzoate via a pathway not involving (chloro)catechols. Appl Environ Microbiol 62 2427-2434. 

Kukor JJ, RH Olsen (1996) Catechol 2,3-dioxygenases functional in oxygen-limited hypoxic environments. Appl Environ Microbiol 62 1728-1740. 

In a classical study, it was shown that during bacterial oxidation of benzene to catechol both atoms of oxygen came from 62 (Gibson et al. 1970). This initiated the appreciation of the role of dioxygenases in the degradation of aromatic xenobiotics, and many examples are given in Chapter 8, Parts 1 and 2. 

Benzaldehyde is easily oxidised by atmospheric oxygen giving, ultimately, benzoic acid. This auto-oxIdation is considerably influenced by catalysts tiicse are considered to react with the unstable peroxide complexes which are the initial products of the oxidation. Catalysts which inhibit or retard auto-oxidation are termed anti-oxidants, and those that accelerate auto-oxidation are called pro-oxidants. Anti-oxidants find important applications in preserving many organic compounds, e.g., acrolein. For benzaldehyde, hydroquinone or catechol (considerably loss than 0-1 per cent, is sufficient) are excellent anti-oxidants. 

In addition to the QM structure of the natural terpene QMs, the reactive oxygen species (ROS) may also play a significant role in the observed biological activities. In the synthesis of taxodione and taxodone, QMs were formed from the catechol precursors through the spontaneous oxidation in the presence of silica gel.7, 8,49-51... 

---