Benzyl alcohol, a-

An unusual by-product was obtained in small yield in palladium-catalyzed reduction of 2-amino-4,5-dimethoxyindanone hydrochloride, The reduction was done in two stages first, a rapid absorption of 1 mol of hydrogen at 38 C to give the amino alcohol, and then a much slower reduction in the presence of HCIO4 at 70 "C. The rearranged by-product was shown to arise from attack of acid on the amino alcohol (50), Resistance to hydrogenolysis is characteristic of / -amino aromatic alcohols (56), a fact that makes reduction of aromatic oximino ketones to amino benzyl alcohols a useful synthetic reaction. 

Benzyl alcohol, a-vinyl- [Benzene-methanol, a-ethenyl-), 106 Bcnzylamine-polystyrene [Benzene, di-ethenyl-, polymer with ethenyl-benzene, aminomethylated), 95 Benzyl bromide [Benzene, (bromo-methyl)-, 78... 

Other examples of conversion using a nickel oxide electrode are the oxidation of benzyl alcohols. A nickel foam electrode was used for oxidation [18] in this case and the mechanism was studied by... 

Benzyl alcohol Benzyl alcohol, a preservative contained in the diluent supplied, has been associated with a fatal gasping syndrome in premature infants. 

Benzyl alcohol,a-vinyl-, 56, 106 Benzylamme-polystyrene, 56, 95 Benzyl bromide, 56, 78 Benzyl bromide methylisopropylamine, 58, 118... 

FIGURE 3.14. Benzyl alcohol. A. O—H stretch intermolecular hydrogen bonded,... 

The Mitsunobu reaction is usually only suitable for the alkylation of negatively charged nucleophiles rather than for the alkylation of amines, and only a few examples of such reactions (mainly intramolecular N-alkylations or N-benzylations) have been reported (Entry 15, Table 10.2). Halides, however, are very efficiently alkylated under Mitsunobu conditions, and it has been found that the treatment of resin-bound ammonium iodides with benzylic alcohols, a phosphine, and an azodicarboxylate leads to clean benzylation of the amine (Entry 9, Table 10.3). Unfortunately, alkylations with aliphatic alcohols do not proceed under these conditions. The latter can, however, also be used to alkylate resin-bound aliphatic amines when (cyanomethyl)-phosphonium iodides [R3P-CH2CN+][r] are used as coupling reagents [62]. These reagents convert aliphatic alcohols into alkyl iodides, which then alkylate the amine (Entry 10, Table 10.3). 

IUPAC name (-)-3,4-dihydroxy-OC- [(methylamino)methyf benzyl alcohol (-)-a(aminomethyl)-3,4- dihydroxybenzyl alcohol... 

When aldehyde 11 was reacted with z -Pr2Zn in the presence of chiral (S)-benzyl alcohol-a-d, (fi)-alkanol 12 with 96% ee was obtained with a yield of 95%. On the other hand, in the presence of (fi)-deuterated alcohol (> 95% ee), (S)-12 with 95% ee was obtained in 98% yield. Thus, (S)- and (fi)-benzyl alcohol-a-d acted as chiral inducers to give (R)- and (S)-pyrimidyl alkanols with high ee after consecutive asymmetric autocatalysis, respectively. 

Figure 3. CD curves for testosterone phenylpropionate injections with various concentrations of benzyl alcohol a 1.0 ml injection was diluted to 25.0 ml with cyclohexane, (a) 50pl, (b) 200 pi, (c) 600pi benzyl alcohol per 1 ml oily solution. The descending ordinate represents increasing negative ellipticity and the scale divisions are 0.01°. (From Ref. 22).

Tlie use of aqueous NaOH results in the isolation of a 0-hydroxy ketone provided the alcohol is not a substituted benzyl alcohol. The alcohol can be heated with add or I3 to yield the o -unsaturated carbonyl molecule. In cases wliere the initially formed alcohol is a derivative of benzyl alcohol, a molecule of H,C is lost spontaneously. 

The transformation was called an homologation reaction because essentially it consisted in going from one alcohol to an alcohol containing one carbon atom more than the starting material (Wender, Levine, and Orchin, 14). Tertiary alcohols reacted most rapidly, secondary alcohols less rapidly and primary alcohols only very slowly. It was of considerable importance to ascertain whether the olefin intermediate was essential and for this purpose, methanol and benzyl alcohol, neither of which can dehydrate to an olefin, were used in the reaction. Both compounds, contrary to other primary alcohols, reacted quite rapidly and gave the homologous alcohol of the methanol converted, about 40 mole per cent went to ethanol and with benzyl alcohol, a 30% yield of 2-phenylethanol was secured. In both examples, however, reduction products were also present of the methanol converted, 8 mole per cent went to methane and from benzyl alcohol, a 50 to 60% yield of toluene was secured. The conversion of methanol to methane appears to be the only case in which an appreciable quantity of hydrocarbon is secured from a purely aliphatic alcohol. The behavior of benzyl alcohol and its derivatives will be discussed later. 

In summary, we have developed a recyclable heterogeneous catalyst for the bleach oxidation of alcohols and polyols. In contrast to previously reported systems, neither a chlorinated hydrocarbon solvent nor a bromide cocatalyst is necessary to achieve good activity. Besides bleach-oxidation, PIPO is also effective in the CuCl/nitroxyl catalysed aerobic oxidation of benzyl alcohol. A further advantage of our system is that PIPO is readily prepared from inexpensive and commercially available raw materials. We believe that it will find wide application in organic synthesis. 

In contrast to benzyl alcohol, a-substituted benzyl alcohols, benzyl ethers, and aryl ketones may be successfully hydrogenated over rhodium and rhodium-platinum catalysts to give the corresponding saturated products in high yields, as shown in eqs. 11.38-11.41. In the hydrogenations shown in eqs. 11.38 and 11.39, no racemization took place D-mandelic acid afforded D-hexahydromandelic acid in 94% yield and meso- and dl-2,3-dicyclohexyl-2,3-butanediol were obtained in 93 and 94% yields, respectively, by hydrogenation of the corresponding diphenyl compounds. 

FIGURE 17 Left TEM images of the yttria nanocomposite synthesized in 4-tert-butyl benzyl alcohol (A) and its Fourier transform (B). Scale bar = 50 nm. Reprinted with permission from Pinna et al. (2005). Copyright 2005 Wiley-VCH. Right Structures of a unit cell of the biphenolate and benzoate based hybrid materials. Reprinted with permission from Pinna (2007). Copyright 2007 the Royal Chemical Society. 

Direct toxicity effects related to use of preservatives also has been documented. For example, severe metabolic acidosis and death in infants was attributed to the presence of benzyl alcohol, a preservative used in bacterostatic normal saline that was used to flush catheters.f ... 

Figure 2.4 Experimental and calculated band profiles of benzyl alcohol (a) and phenylethanol (b). Sample volume 0.5 mL, Co = 25 g/1. Column, Symmetry-Cig mobile phase, methanol and water (1 1, v/v) flow rate, 1 ml/min. Experimental profiles (circles), profiles calculated with a rectangular injection (dashed line) and with the experimental injection profiles (solid line). Reproduced with permission from 1. Quinones et ah, Anal. Chem., 72 (2000) 1495 (Fig. 6). 2000, American Chemical Society.

Benzyl alcohol, a-methyl 30-4° 0-017m HCIO4 1-05 Grunwald et al. (1957)... 

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