Hexanol, from hexanal

In liver microsomes, the formation of 1-, 2-, and 3-hexanol from -hexane was best described kinetically by a 2-enzyme system, while for lung microsomes, single-enzyme kinetics were indicated for each metabolite. For conversion to 1-hexanol, apparent Km values were 0.4 and 300 M, and Vmax values were 0.09 and 1.2 nmol/mg protein/min, respectively. For conversion to 2-hexanol, apparent Km values were 6 and 1,100 M, and Vmax values were 1 and 4.6 nmol/mg protein/min respectively. Insufficient information was available to estimate the high-affinity activity for 3-hexanol, the low-affinity activity had an apparent Km of 290 M and a Vmax of 0.5 nmol/mg protein/min. In the lung, Km values were 9,... 

Pyrolysis of 1.0 ml. of high boiling product afforded 0.8 ml. of condensate which from gas chromatography was shown to consist of hexanal, 28.6% (from hexan-1, 2-diol-2-acetate), hexanone-2, 16.0% (from hexan-1, 2-diol-l-acetate), and hexenyl acetates 55.4% (from hexan-l-2-diol diacetate). These hexenyl acetates upon reduction gave only hexanol-l-acetate. 

Photolysis of solutions of C6o(OH)ig at low solute concentration leads to [C6o(OH)i8] by electron transfer from Me2C(OH) radicals or from hydrated electrons, and this has enabled the reduction potential of the C6o(OH)ig/ [C6o(OH)ig] couple to be estimated. The kinetics of the photoreduction of hexanal using RhCl(PMe3)2CO as catalyst have been measured and the feasibility of a photocatalytic synthesis of hexanol from pentane, CO, and H2 in the presence of rhodium complexes has been demonstrated. Irradiation of a chiral bimolecular crystal of acridine and R-(-)- or S-(+)-2-phenylpropionic acid induces photodecarboxylation followed by stereoselective condensation to give a mixture of three optically active products, and the 3-0-S-methyl dithiocarbo-nate derivatives of oleanolic and ursolic methyl esters have been used as models for the photodeoxygenation of alcohols. ... 

Guava flavor G.f., resembling pear and quince flavor, contains )8- caryophyllene, numerous fruit esters, e.g., ethyl butanoate and ethyl hexanoate, cinna-myl acetate (see cassia oil) and the green notes from hexanal, ( )-2- hexenal, and (Z)-3- hexen-l-ol. Important trace components are C -C,g-dienals, Fura-neol, some pyrazines and thiazoles, as well as 6-mercapto-I-hexanol(CiHnOS, Mr 134.24,CAS [1633-78-9]) ... 

The existence of an interfacial minimum in dA h(z) indicates that the alcohols are interfacially active. The free energy of transferring a solute molecule from the gas phase to the interface decreases with the chain length and is equal to —6.0, —6.9, —8.2 and —9.6 kcal/mol for methanol, ethanol, butanol and hexanol, respectively. The free energy of transferring the four alcohols from hexane to the interface, however, is almost eonstant, and equals to 4.5 + 0.3 keal/mol. This, in turn, implies that when the alcohols are in the minimum free energy positions, their hydroearbon portions are buried in hexane. 

Figure 1 Peak profile for extract from roasted peanuts (a) mild conditions 145°C. 3 minutes, and (b) severe conditions 170°C, 17 minutes. Peak notation 1, methylpyrrole 2, hexanol 3, hexanal 4, methylpyrazine 5, 2,6-dimethylpyrazine 6, furancarboxalde-hyde 7, 2,3,5-trimethylpyrazine 8, 2-ethyl-5-methylpyrazine and 2-ethyl-6-methylpyra-zine 9, 3-ethyl-2,5-dimethylpyrazine. (From Ref. 14.)...

No information is available as to whether metabolism of -hexane in children differs from that of adults. No studies were located comparing metabolism in young and adult animals. The toxicity of -hexane results from biotransformations yielding the active metabolite, 2,5-hexanedione. The initial step is an oxidation to 2-hexanol catalyzed by a cytochrome P-450 enzyme. Some P-450 enzymes are develop-mentally regulated (Leeder and Keams 1997). As the above discussion indicates, it is not completely clear which P-450 enzymes are involved in -hexane metabolism. 

The findings from the evacuation experiment confirmed the interpretation that the observed slight deactivation over time was not due to catalyst decomposition, as an accompanying decrease in activity and selectivity otherwise would have been observed. Instead, we expected the formation of aldol products 2-ethyl-hexanal and 2-ethyl-hexanol to be of relevance, as traces of these high boiling side products were observed at particular high conversions. 

Only hexanoic acid liberates CO, from aqueous Na,CO,. Na reacts with hexanol to liberate H,. Hexane is... 

When considering bipolar solutes (e.g., aniline, 1-hexanol, phenol, hexanoic acid), we can see that depending on the relative magnitudes of the solvent s at and /3, values, solute solvent interactions may become quite attractive. For example, for aniline, for which j6 trichloromethane is still the most favorable solvent, whereas for phenol (a, > j6,), diethylether wins over the others. Finally, due to the lack of polar interactions in hexane, bipolar solutes partition rather poorly from water into such apolar solvents (Table 7.1). 

IOB alone can oxidize some alcohols, but catalysed oxidations are much more efficient. Thus, in the presence of RuCl2(PPh3)2 primary aliphatic alcohols were oxidized cleanly to aldehydes, at room temperature the use of m-iodosylbenzoic acid instead of IOB considerably increased the yields for example, hexanal was formed from hexanol quantitatively (by GC) [19], Another catalytic system involved the use of simple lanthanide salts such as ytterbium triacetate [20]. Cyclic y-stannyl alcohols, readily available from cyclic vinyl ketones and Bu3SnLi, underwent oxidation accompanied by carbon-carbon bond cleavage (Grab fragmentation), when treated with IOB.BF3 and DCC. The products were unsaturated aldehydes or ketones. 

By y-ray irradiation at room temperature, ZnS nanowires were grown, in which the crystal growth was in situ templated by an inverted hexagonal liquid crystal formed from oligo(ethylene oxide)oleyl ether amphiphiles, n-hexane, n-hexanol/ isopropanol (2/1) and water [151]. Nanocrystalline jS-ZnS (sphalerite) was prepared in aqueous isopropanol solution [152]. The TEM images (Figure 7.36) indicate that the product from mercaptoethanol is most well dispersed, and that from thiourea... 

---