Short chain primary alcohols

The nickel oxide electrode is generally useful for the oxidation of alkanols in a basic electrolyte (Tables 8.3 and 8.4). Reactions are generally carrried out in an undivided cell at constant current and with a stainless steel cathode. Water-soluble primary alcohols give the carboxylic acid in good yields. Water insoluble alcohols are oxidised to the carboxylic acid as an emulsion. Short chain primary alcohols are effectively oxidised at room temperature whereas around 70 is required for the oxidation of long chain or branched chain primary alcohols. The oxidation of secondary alcohols to ketones is carried out in 50 % tert-butanol as solvent [59], y-Lactones, such as 10, can be oxidised to the ketoacid in aqueous sodium hydroxide [59]. 

Savary, P. (1971). The action of pure pig pancreatic lipase upon esters of long-chain fatty acids and short-chain primary alcohols. Biochim. Biophys. Acta 248,149-155. 

What this really means is that the ternary complex has such a transitory existence that it never makes up a significant fraction of the total amount of enzyme. Steady-state kinetics concerns itself only with those complexes which, by their existence, detectably alter the pattern of dependence of reaction rate on substrate concentration. The Theorell-Chance mechanism may be seen perhaps as a manifestation of highly effective catalysis. Certainly, in the case of the enzyme for which it was first described, horse liver alcohol dehydrogenase, the mechanism is obeyed for good substrates i.e. short-chain primary alcohols with secondary alcohols, which are poor substrates, the ternary complex becomes kinetically significant - because it works less well [44]. 

Short chain primary alcohols such as methanol, ethanol, and butanol are widely employed in FAAE production. Secondary alcohols include isopropanol and 2-butanol for industrial production. Methanol and ethanol are used because of their availability and low cost. Ethanol is less toxic but yields a lower conversion efficiency than methanol. Alcohol requirements are based on the type of lipase or chemical catalyst and reactor used for the process. Glycerol obtained... 

Short-chain primary -C-C-C- 1 C isobutyl or isoamyl alcohol C4-C5p... 

Deamination of short-chain primary alkylamines with nitrous acid has long been known to give not only an enhanced (25-30%) yield of olefin compared with the analogous 5i,l reactions of halides, but also rearranged products absent from the latter. The proportion of rearranged alcohols falls with increasing homology (Table 1) and... 

Short-chain unbranched primary alcohols M—(H20 + CH3) from hydroxy steroids... 

Fungal cutinase catalyzes hydrolysis of model substrates and in particular p-nitrophenyl esters of short chain fatty acids, providing a convenient spectro-photometric assay for this enzyme activity [101,102,116]. Hydrolysis of model esters by this cutinase showed the high degree of preference of this enzyme for primary alcohol ester hydrolysis. Wax esters and methyl esters of fatty acids were hydrolyzed at low rates. Alkane-2-ol esters were hydrolyzed much more slowly than wax esters and esters of mid-chain secondary alcohols were not... 

Photochemical transformations of cyclic and short chain polysilane oligomers have been intensively investigated (39). Irradiation of these materials in the presence of trapping reagents, such as silanes or alcohols, has suggested that substituted silylenes and silyl radicals are primary reactive intermediates. The former have been... 

The next phase focused on the goal of elaboration of the side chain in the desired sense. The primary alcohol function at C7 was unveiled by hydrogenolysis (Pd(OH)2/EtOAc-MeOH). Oxidation of the resultant compound 13 with chromic oxide pyridine afforded aldehyde 14, which was now to be elongated through some variation of a Homer-Emmons type of reaction. Shortly before tiiese investigations were launched. Still had demonstrated the use of phosphonate 15 as a device to achieve the two-carbon extension of an aldehyde to a Z-enoate (12). Happily, application of the Still method to compound 14 afforded the desired 16, mp 120-121° C, in 80% yield as a 20 1 mixture of Z E enoates. 

The crystal structure of 5-chloro-2-deoxyuridine [CLDOUR] has a very simple pattern with two infinite chains (Fig. 17.21). One is through the O -H groups, and the other through the minor component of a three-center bond formed by 0(30-H. It strongly resembles a carbohydrate hydrogen-bonding pattern. A very simple scheme is also formed by 2-chloro-2 -deoxyuridine [CDURID] with a short finite chain and a separate link from the primary alcohol (Fig. 17.22). 

Most single-chain surfactants do not lower the oil-water interfacial tension sufficiently to form microemulsions nor are they of the correct molecular structure, and short- to medium-chain length alcohols are necessary as cosurfactants. The cosurfactant also ensures that the interfacial film is flexible enough to deform readily around each droplet as their intercalation between the primary surfactant molecules decreases both the polar head group interactions and the hydrocarbon chain interactions. Medium-chain alcohols such as pentanol and hexanol have been used by many investigators as they are particularly effective... 

The aliphatic alcohol oxidase, a FAD-dependent enzyme, catalyzes the oxidation of primary short-chain alcohols to the corresponding aldehydes. Dioxygen can be replaced by synthetic acceptors such as dichlorophenolindophenol or phenazine methosulfate [147l... 

Transformation of different polyoxyalkylene diols and triols with ammonia to the corresponding primary amines is of great practical importance. The results have been disclosed almost exclusively in the patent literature a summary can be found in a previous review [26], The catalyst of choice is Raney Ni or supported Ni, modified with selectivity and stability promoters such as Fe, Co, Cr, or Mo. The use of a non-porous or mesoporous support is essential to enable access of the bulky reactants to the active sites. Scientific evaluation of these processes is, unfortunately, difficult on the basis of the information available. At best, the conversion is estimated from the amount of water formed and the ratio of primary to secondary amines is determined. On the basis of these data the yields of primary amines are excellent, reaching 85-90%. It seems that selectivity is barely affected by the conversion, in contrast with general observation in the amination of short-chain alcohols and diols [3,4,14]. 

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