A-Tocopherol vitamin

X5lenol is an important starting material for insecticides, xylenol—formaldehyde resins, disinfectants, wood preservatives, and for synthesis of a-tocopherol (vitamin E) (258) and i7/-a-tocopherol acetate (USP 34-50/kg, October 1994). The Bayer insecticide Methiocarb is manufactured by reaction of 3,5-x5lenol with methylsulfenyl chloride to yield 4-methylmercapto-3,5-xylenol, followed by reaction with methyl isocyanate (257). Disinfectants and preservatives are produced by chlorination to 4-chloro- and 2,4-dich1oro-3,5-dimethylpheno1 (251). 

Woodward-Eschenmoser method, 4, 431-440 neo-Vitamin B,2, 4, 421 Vitamin C — see Ascorbic acid Vitamin E — see a-Tocopherol Vitamin K epoxide, 7, 119 synthesis, 1, 439 Vitamins heterocyclic... 

Thus, it is uncertain to what extent the apparent protective effects of fruit and vegetable consumption on risk of stomach cancer can be attributable to their phytoestrogen content. This appears not to have been studied directly, and other constituents such as ascorbic acid (vitamin C), a-tocopherol (vitamin E) and /1-carotene may be potentially protective. 

Encouraged by the short synthesis of K vitamins, the chromium-mediated benzannulation was extended to the synthesis of vitamin E 68 [59]. The problem of imperfect regioselectivity of alkyne incorporation - which did not hamper the approach to vitamin K due to the final oxidation to the quinone - was tackled by demethylation of both regioisomeric hydroquinone monomethyl ethers 67 to give the unprotected hydroquinone. Subsequent ring closure yielded a-tocopherol (vitamin E) 68 (Scheme 39). 

Naturally occurring oxaarenes based on polycyclic pyrans encompass a plethora of structures including the plant polyphenols such as anthocyanins and a-tocopherol (vitamin E). Halogenated dibenzo-p-dioxins and dibenzofurans are formed both as by-products during the manufacture of chlorophenols, and from the incineration of organic matter in the presence of inorganic halides. 

Addition of such a-lithiosulfinyl carbanions to aldehydes could proceed with asymmetric induction at the newly formed carbinol functionality. One study of this process, including variation of solvent, reaction temperature, base used for deprotonation, structure of aldehyde, and various metal salts additives (e.g., MgBrj, AlMej, ZnClj, Cul), has shown only about 20-25% asymmetric induction (equation 22) . Another study, however, has been much more successful Solladie and Moine obtain the highly diastereocontrolled aldol-type condensation as shown in equation 23, in which dias-tereomer 24 is the only observed product, isolated in 75% yield This intermediate is then transformed stereospecifically via a sulfoxide-assisted intramolecular 8, 2 process into formylchromene 25, which is a valuable chiron precursor to enantiomerically pure a-Tocopherol (Vitamin E, 26). 

The major lipid-soluble antioxidant primarily associated with lipid membranes is a-tocopherol (vitamin E). Circulating a-tocopherol is carried by chylomicrons, LDL and HDL and also has extracellular antioxidant capacities. As a chain-breaking antioxidant, it short circuits the propagation phase of lipid peroxidation because the peroxyl radical will react with a-tocopherol more rapidly than a polyunsaturated ffitty acid (Burton and Traber, 1990). The resulting a-tocopheryl radical reacts with a second peroxyl radical to form an inactive, nonradical complex. In vitro, ascorbate regenerates the tocopheryl radical into its native non-radical form (Burton and Traber, 1990). 

Examples of the use of dimethylsulfonium methylide and dimethylsulfoxonium methylide are listed in Scheme 2.21. Entries 1 to 5 are conversions of carbonyl compounds to epoxides. Entry 6 is an example of cyclopropanation with dimethyl sulfoxonium methylide. Entry 7 compares the stereochemistry of addition of dimethylsulfonium methylide to dimethylsulfoxonium methylide for nornborn-5-en-2-one. The product in Entry 8 was used in a synthesis of a-tocopherol (vitamin E). 

An enantioselective hydrogenation of this type is also of interest in the production of a-tocopherol (vitamin E). Totally synthetic a-tocopherol can be made in racemic form from 2,3,5-trimethylhydroquinone and racemic isophytol. The product made in this way is a mixture of all eight possible stereoisomers. 

S )-3-nydroxy-2-mcthylpropanoic acid, 13-A, can be obtained in enantiomeri-cally pure form from isobutyric acid by a microbiological oxidation. The aldehyde 13-B is available from a natural product, pulegone, also in enantiomerically pure form. Devise a synthesis of enantiomerically pure 13-C, a compound of interest as a starting material for the synthesis of a-tocopherol (vitamin E). 

The best known and undoubtedly most important natural antioxidants are a-tocopherol (vitamin E) and ascorbic acid (vitamin C), which are major biological antioxidants in lipid... 

Basically, the Rf value of a solute is determined by its distribution ratio which in turn is dependent on relative solubilities for partition systems or relative polarities for adsorption systems. For example, if adsorption TLC is used to separate a mixture of squalene (a hydrocarbon), methyl oleate, cholesterol and a-tocopherol (vitamin E), then squalene, being the least polar, will move furthest and the cholesterol, being the most polar, will remain close to the origin. Methyl oleate is less polar than a-tocopherol and will therefore be found between it and the squalene. The role of polarity is discussed more fully on p. 82. 

Quinols and ends a-Tocopherol (vitamin E) Ubiquinol (coenzyme Q) Ascorbic acid (vitamin C)... 

This first example of a Bi(OTf)3-catalyzed Friedel-Crafts alkylation originated in the following procedures, including benzylations of 2,4-pentanediones or hydroarylation and hydroalkylation reactions. A related procedure was simultaneously developed by Bonrath et al. [39]. The authors utilized Bi(OTf)3 in the synthesis of (all-rac)-a-tocopherol (Vitamin E) [39], Besides rare earth metal triflates, such as Ga(OTf)3, Hf(OTf)3, Sc(OTf)3 and Gd(OTf)3, Bi(OTf)3 was shown to be the most efficient catalyst for the Friedel-Crafts-type reaction between trimethylhydroquinone acetate 10b and isophytols 11a, b. With only 0.02 mol% Bi(OTf)3 (substrate to catalyst ratio 5,000 1) the desired a-tocopherols 12a and 12b were isolated in excellent yields (Scheme 10). 

Superoxide dismutases together with catalase (EC 1.11.1.6) and glutathione peroxidase (EC 1,11.1.9) are important enzymes for the protection against oxygen toxicity 1.197-199) Protection is also provided by substances like a-tocopherol (vitamin E)... 

Figure 6.20 The role of a-tocopherol (vitamin E) in removing damaging lipid peroxides from membranes. The a-tocopherol is regenerated by ascorbate (vitamin C).

Tobacco mosaic virus 247, 334s, 336s Tocopherols 392,815 — 822,818 as antioxidants 822 a-Tocopherol (vitamin E) 819s Tocopherolquinone 818, 819, 819s Tocotrienols 818 Togavirus 247... 

Oxidation of chromans has been extensively studied, especially of those which resemble the tocopherols which act as antioxidants in nature and in food. The behaviour of a-tocopherol (vitamin E, 547) and many simpler model compounds under oxidizing conditions varies with the oxidizing agent. Among the many products formed are the o- and p-quinones (609) and (610), the spiran (611) and dimer (612). A detailed account is available (81HC(36)59). 

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