Aliphatic primary alcohols

Aromatic primary alcohols diflfer from aliphatic primary alcohols in that they react with concentrated hydrochloric acid in the cold to yield the corresponding chlorides, for example ... 

Lower aliphatic primary alcohols including octanol, halogeno alcohols, and benzylic alcohols yield only alkyl fluorides [81, 82 The reaction of higher primary alcohols gives a mixture of fluorides and alkyl 2,3,3,3-tetrafluoropropionates [S3] and 2-nitro alcohols, alcohols branched at C-2 [82, 84 and unsaturated alcohols [55] give 2,3,3,3-tetrafluoropropionates exclusively... 

N-bromosuccinimide is a selective oxidising agent and oxidises OH groups without disturbing other oxidisable groups. Thus while it does not oxidise aliphatic primary alcohols in presence of water it is highly selective for the oxidation of secondary alcohols to ketones. 

The aliphatic primary alcohols are oxidised by N-Chlorosuccinimide, but the mechanism is not clear. 

Varieties of primary and secondary alcohols are selectively oxidized to aldehyde or carbonyl compounds in moderate to excellent yields as summarized in Table 3. As can be seen, /(-substituted benzyl alcohols (e.g., -Cl, -CH3, -OCH3, and -NO2) yielded > 90% of product conversion in 3-4 h of reaction time with TOP in the range of 84-155 h (entries 2-5, Table 3), Heterocyclic alcohols with sulfur- and nitrogen-containing compoimds are found to show the best catalytic yield with TOP of 1517 and 902 h for (pyrindin-2-yl)methanol and (thiophene-2-yl) methanol, respectively (entries 9 and 10, Table 3). Some of aliphatic primary alcohols (long chain alcohols) and secondary alcohols (cyclohexanol, its methyl substituted derivatives and norboman-2-ol) are also selectively oxidized by the membrane catalyst (entries 11-14 and 15-17, Table 3) with TOP values in the window of 8-... 

Zinc and copper nitrates on silica gel are able to oxidize benzylic and saturated secondary alcohols but not aliphatic primary alcohols.157 On the other hand, ZrO(OAc)2 is able to catalyze, under the action of f-BuOOH, the oxidation of benzylic alcohols—both primary and secondary—and primary saturated alcohols to aldehydes and ketones, while secondary saturated alcohols are very unreactive.158... 

Benzyl and allyl alcohols are oxidized with iodosylbenzene 18 in refluxing dioxane to aldehydes [67]. Further oxidation of aldehydes to carboxylic acids does not take place. Aliphatic primary alcohols are not oxidized under the conditions. Ligand exchange of 18 with alcohols produces alkoxy-A3-iodanes, which result in reductive /3-elimination to give aldehydes [Eq. (33)]. 

Studies performed on the anaerobic version of this catalytic system revealed that aliphatic primary alcohols were oxidized with the same efficiency as all the other classes of alcohols, thus ruling out complexes A, B, and E as the culprit for the decomposition pathway. Whilst we could not experimentally disgard complex D, coordination of an alcohol to D should involve the participation of a pentacoordi-nated copper species. Whilst these are not uncommon, their formation requires a higher activation energy than the coordination to C. 

Selenoxides undergo elimination at temperatures even lower than room temperature. The Grieco elimination is an organic reaction describing the elimination reaction of an aliphatic primary alcohol through a selenide to a terminal alkene. 

The use of ethoxycarbonyl-protected amino acids as well as methoxycarbonyl derivatives for peptide synthesis was reported in 1903 by Fischer, although the protecting groups in related peptide derivatives could not be cleaved without affecting the peptide bonds,f since urethanes derived from aliphatic primary alcohols are about as stable as the amide bond. Thus, this type of carbamate can only be used for reversible protection of amino groups, at least in... 

Character and Types.— Aromatic acids bear exactly the same relationship to aromatic primary alcohols and aldehydes that the aliphatic acids do to the aliphatic primary alcohols and aldehydes, i.e. the acids are the final oxidation products of the other two groups. In the aliphatic series we showed how the alcohols may be considered as the first oxidation products of the hydrocarbons. The entire series of oxidation relationships being illustrated as follows ... 

Used only for aliphatic primary alcohols and phenols having no branch chains. 

This is a black, hydrous mixture of higher oxides of nickel made by treating nickel sulfate in alkaline solution with sodium hypochlorite. In alkaline solution, saturated aliphatic primary alcohols of adequate water-solubility are oxidized to the carboxylic acids (30°, 3-5 hrs.). Benzyl alcohol is oxidized by the alkaline reagent to benzoic acid, but with benzene as solvent and a slight excess of nickel peroxide it is oxidized to benzaldehyde. Allylic alcohols also can be oxidized to aldehydes by this method. 

Dytol [Rohm Haas], TM for aliphatic primary alcohols derived from natural fats and oils (C10 to C18). 

By his efficient, mild, rapid eco-friendly method, Das et al. [44] treated different per-O-acetylglycals (49a,b and i-rhamnal, 49c, and L-arabinal, 49d) with aliphatic primary alcohols, in the presence of indium(III) chloride in acetonitrile solution in an open vessel, to afford the corresponding 2,3-unsaturated products 53 in good to excellent yields in a few seconds (Scheme 12.24). 

An efficient and mild procedure has been described for the oxidation of different types of alcohols to carbonyl compounds using TEMPO as the catalyst and (dichloroiodo)benzene as a stoichiometric oxidant at 50 °C in chloroform solution in the presence of pyridine [157]. Under these conditions, 1,2-diols are oxidized to p-hydroxyketones or p-diketones depending upon the amount of PhICh used. Interestingly, a competitive study has shown that this system preferentially oxidizes aliphatic secondary alcohols over aliphatic primary alcohols [157], while the PhI(OAc)2-TEMPO system selectively converts primary alcohols into the corresponding aldehydes in the presence of secondary alcohols. 

The structure of the organic molecules should also be considered in interpreting the catalytic effects caused by the modifiers. This can be deduced from the comparative studies (performed in acid solutions) of the UPD effect on the oxidation of two different series of organic compounds with the same functional group, such as aliphatic primary alcohols [85] and monosaccharides [103]. The lack of uniform catalytic behavior (based on current densities) leads to the conclusion that besides the third-body effect of the ad-atoms that is physical in nature the specific interacting forces of the reaction intermediates with the modified electrode surface must also play a significant role in the electro-catalytic process. 

Infrared Analysis. The conversion of a branched-chain aliphatic primary alcohol to an acetate ester results in significant changes in the infrared spectrum of the molecule. These changes are similar to those observed in straight-chain systems. The two macro group frequency trains in the present example are... 

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