Acetate, vitamin

Valentinite, see Antimony(III) oxide Verdigris, see Copper acetate hydrate Vermillion, see Mercury(II) sulflde Villiaumite, see Sodium fluoride Vitamin B3, see Calcium (+)pantothenate Washing soda, see Sodium carbonate 10-water Whitlockite, see Calcium phosphate Willemite, see Zinc silicate(4—)... 

Vitamin E acetate [58-95-7] serves primarily as an antioxidant and is closely associated with selenium. Vitamin E usually is present in... 

Ethanol, acetaldehyde, acetic acid, acetone, glycerol, n - butanol, n - butyric acid, amyl alcohols, oxalic acid, lactic acid, citric acid, amino acids, antibiotics, vitamins... 

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). 

There are numerous reports of the effects of antioxidant vitamins on transformation. Vitamin C suppresses x-ray-induced transformation when CSHlOTy cells are treated daily for one week following irradiation (97), suppresses transformation by y-rays or neutrons, and prevents the promotion of radiation-induced transformation by 12-0-tetradecanoylphorbol 13-acetate (TPA), but has no effect on cell survival (98). In these studies, the continuous presence of vitamin C for a critical period appears to be necessary for suppression of transformation. Vitamin C may act on the promotion stage of... 

Rearrangement of dehydrolinalool (4) using vanadate catalysts produces citral (5), an intermediate for Vitamin A synthesis as well as an important flavor and fragrance material (37). Isomerization of the dehydrolinalyl acetate (6) in the presence of copper salts in acetic acid followed by saponification of the acetate also gives citral (38,39). Further improvement in the catalyst system has greatly improved the yield to 85—90% (40,41). 

Petrochemical-based methods of citral manufacture are very important for the large-scale manufacture of Vitamin A and carotenoids. Dehydrolinalool and its acetate are both made from the important intermediate, P-methyUieptenone. 

Fig. 1. Vitamin A and derivatives retinol (1), retinyl acetate [127-47-9] (2), retinyl palmitate [79-81-2] (3), and retinyl propionate [7069-42-3] (4).

Vitamin A acetate [11098-51-4] (2) is the commercially significant form of the vitamin and is mainly produced by Hoffmann-La Roche, BASF, and Rhc ne-Poulenc (Fig. 4). AH of these processes have P ionone (18) as their key intermediate and in this regard are based on work performed in the 1940s... 

Vitamin A palmitate [79-81-2] (3), a commercially important form of the vitamin, is produced from vitamin A acetate (2) via a transesterification reaction with methyl palmitate. En2ymatic preparation of the palmitate from the acetate has also been described (22). 

In other work, sulfone chemistry plays an integral part of the syntheses of both -carotene and vitamin A by workers at Kuraray. In this approach, the anion of C q P-cyclogeranyl sulfone (36) is condensed with the C q aldehyde (37). The resulting P-hydroxy sulfone (38) is treated with dihydropyran followed by a double elimination to yield vitamin A acetate. Alternatively, the P-hydroxy sulfone (38) can be converted to the 5-halo sulfone (39) and a similar double elimination scheme is employed (23,24) (Fig. 8). 

Hoffmaim-La Roche has produced -carotene since the 1950s and has rehed on core knowledge of vitamin A chemistry for the synthesis of this target. In this approach, a five-carbon homologation of vitamin A aldehyde (19) is accompHshed by successive acetalizations and enol ether condensations to prepare the aldehyde (46). Metal acetyUde coupling with two molecules of aldehyde (46) completes constmction of the C q carbon framework. Selective reduction of the internal triple bond of (47) is followed by dehydration and thermal isomerization to yield -carotene (21) (Fig. 10). 

Spectroscopic methods such as uv and fluorescence have rehed on the polyene chromophore of vitamin A as a basis for analysis. Indirectly, the classical Carr-Price colorimetric test also exploits this feature and measures the amount of a transient blue complex at 620 nm which is formed when vitamin A is dehydrated in the presence of Lewis acids. For uv measurements of retinol, retinyl acetate, and retinyl palmitate, analysis is done at 325 nm. More sensitive measurements can be obtained by fluorescence. Excitation is done at 325 nm and emission at 470 nm. Although useful, all of these methods suffer from the fact that the method is not specific and any compound which has spectral characteristics similar to vitamin A will assay like the vitamin... 

One development involves the use of vitamin B 2 to cataly2e chemical, in addition to biochemical processes. Vitamin B 2 derivatives and B 2 model compounds (41,42) cataly2e the electrochemical reduction of alkyl haUdes and formation of C—C bonds (43,44), as well as the 2inc—acetic acid-promoted reduction of nitriles (45), alpha, beta-unsaturated nitriles (46), alpha, beta-unsaturated carbonyl derivatives and esters (47,48), and olefins (49). It is assumed that these reactions proceed through intermediates containing a Co—C bond which is then reductively cleaved. 

TorteUi-JaffH reaction acetic acid + 2 wt% Br2 in CHCl green sterols with ditertiary double bonds vitamin D and compounds that give similar bonds upon isomerization or... 

The biological activity of various vitamin E forms was estabUshed by the fetal resorption assay ia tats and is assumed to be appHcable to humans. The results of some human studies may iadicate that the ratio of 1.36 underestimates the biological activity of the RRR form relative to the all-rac form of a-tocopheryl acetate (10—12). 

The recommended daily allowance for vitamin E ranges from 10 international units (1 lU = 1 mg all-rac-prevent vitamin E deficiency in humans. High levels enhance immune responses in both animals and humans. Requirements for animals vary from 3 USP units /kg diet for hamsters to 70 lU /kg diet for cats (13). The complete metaboHsm of vitamin E in animals or humans is not known. The primary excreted breakdown products of a-tocopherol in the body are gluconurides of tocopheronic acid (27) (Eig. 6). These are derived from the primary metaboUte a-tocopheryl quinone (9) (see Eig. 2) (44,45). 

Dye-Sensitized Photoisomerization. One technological appHcation of photoisomerization is in the synthesis of vitamin A. In a mixture of vitamin A acetate (all-trans stmcture) and the 11-cis isomer (23), sensitized photoisomerization of the 11-cis to the all-trans molecule occurs using zinc tetraphenylporphyrin, chlorophyU, hematoporphyrin, rose bengal, or erythrosin as sensitizers (73). Another photoisomerization is reported to be responsible for dye laser mode-locking (74). In this example, one metastable isomer of an oxadicarbocyanine dye was formed during flashlamp excitation, and it was the isomer that exhibited mode-locking characteristics. 

The following polyvitamin prepai ations were analyzed Kal tsid (OAO Comfort Plus , Russia), Asvitol (OAO INC Marbiofarm , Russia), Pikovit (KRKA, d.d. The New Place, Slovenia), Yeast with vitamin C (000 EKKO Plus , Russia). Chromatographic experiment has been carried out using Silufol UV-254 (Kavalier, Czech Republic) and acetone - ethyl acetate - acetic acid - ethanol (3 5 1 1) - CTAB (2T0 M) as a mobile phase mixture. The linearity calibration plot, built in coordinate S = f (IgqAC), is valid in the interval 5-25 p.g. Correctness of the determination has been checked by photometry. The obtained results for the ascorbic acid determination are presented below. 

Retinyl acetate [127-47-9] M 328.5, m 57". Separated from retinol by column chromatography, then crystd from MeOH. See Kofler and Rubin [Vitamins and Hormones (NY) 18 315 1960] for review of purification methods. Stored in the dark, under N2 or Ar, at 0°. See Vitamin A acetate p. 574 in Chapter 6. 

Retinal (Vitamin A aldehyde). Retinoic acid (Vitamin A acid), Retinyl acetate, Retinyl palmitate see entries in Chapter 4. 

Allylic bromination of pregnenolone acetate with dibromodi-methylhydantoin affords the 7-bromo compound (155) of undefined stereochemistry. Dehydrobromination by means of collidine followed by saponification affords the 5,7 endocyclic cis,cis-diene, 156. This compound contains the same chromophore as ergosterol, a steroid used as a vitamin D precursor. The latter displays a complex series of photochemical reactions among the known products is lumisterol, in which the stereochemistry at both C9 and Cio is inverted. Indeed, irradiation of 156 proceeds to give just such a product (158). This reaction can be rationalized by... 

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