Cyclododecanol, oxidation cyclododecanone

Dodecanedioic Acid. Dodecanedioic acid (DDDA) is produced commercially by Du Pont ia Victoria, Texas, and by Chemische Werke Hbls ia Germany. The starting material is butadiene which is converted to cyclododecatriene usiag a nickel catalyst. Hydrogenation of the triene gives cyclododecane, which is air oxidized to give cyclododecanone and cyclododecanol. Oxidation of this mixture with nitric acid gives dodecanedioic acid (71). 

Nylon 12 first beeame available on a semieommercial scale in 1963. The monomer, dodecanelactam, is prepared from butadiene by a multistaged reaction. In one proeess butadiene is treated with a Ziegler-type eatalyst system to yield the cyclic trimer, cyclododeca-1, 5, 9-triene. This may then be hydrogenated to give cyelododeeane, which is then subjeeted to direct air oxidation to give a mixture of cyclododecanol and cyclododecanone. Treatment of the mixture with... 

Thioanisolc. A system utilizing thio-anisole as an organic mediator was developed for the oxidation of secondary alcohols to ketones (Fig. 5 2-octanol to 2-octanone 99%, menthol to menthone 92%, cyclododecanol to cyclododecanone 75%) [43]. The use of 2,2,2-trifluoroethanol as a solvent in the mediatory system improved the yields [44]. 

Oxidation of Cyclododecane. 1,12-Cyclododecanedioic acid used in the production of polymers is synthesized in a two-step process864,866 similar to the manufacture of adipic acid. Cyclododecane is first oxidized to a mixture of cyclododecanol and cyclododecanone. Both the cobalt-catalyzed and the borate processes (Huels) are used. Further oxidation of the product mixture leads to 1,12-cyclododecanedioic acid. 

The CDT is then hydrogenated and further oxidized at 150°C to cyclododecanol and cyclododecanone with oxygen from the air. In this reaction, up to 5% ketone hydroperoxide occurs, which can be decomposed to form cyclododecanol, cyclododecanone, and dicarboxylic acid. These undesired reactions can be prevented by adding boric acid, which is present as polyboric acid at this temperature. The peroxide probably forms an adduct with the polyboric acid, and the course of this reaction is not yet fully understood. The cyclododecanone is changed to lauryl lactam via the oxime in the usual way (cf. nylon 6). 

Dodecanedioic acid is prepared from cyclododecene (obtained from butadiene) by methods which are entirely analogous to those used to prepare adipic acid from benzene (section 10.2.2(a)). The cyclododecene is reduced to cyclododecane, which is oxidized firstly to a mixture of cyclododecanol and cyclododecanone and then to dodecanedioic acid. Dodecanedioic acid is a colourless crystalline solid, m.p. 129°C. 

More reactive hydroperoxides can be converted selectively to alcohols via the method of Bashkirov (Fig. 4.44), where a boric acid ester protects the product from further oxidation and thus increases the selectivity [121]. The method is used to convert C10-C20 paraffins to alcohols which are used as detergents and surfactants, for the oxidation of cyclohexane (see elsewhere) and cyclododecane to cyclododecanol (cyclododecanone) for the manufacture of nylon-12. 

Consider the oxidation of cyclododecanol (1) to cyclododecanone (2) using hypochlorous acid to answer the following questions. 

The homogeneous catalytic oxidation of cyclododecane (3) was performed using iron-substituted Keggin-type POMs as catalysts, cyclododecanone (3.1) and cyclododecanol (3.2) being the main products obtained [44, 46]. However, cyciododecyl hydroperoxide (3.3) and dodecanal may also be obtained, depending on the reaction conditions. The best results were found for a molar ratio S/C = 667 and H202/sub = 6 (Table 5.1). All the catalysts studied in the oxidation of 3 had identical... 

Di-t-butyl chromate and its pyridine adduct are suitable for large-scale oxidations of alcohols to ketones, thus cyclododecanol was converted into cyclododecanone (97 Alcohols are easily separated from non-hydroxylic compounds via their calcium chloride complexes. This method was used to separate cyclododecanone and cyclododecanol and is suitable for the separation of large quantities of material." All-cis-cyclododecane-l,5,9-triol was converted into the all-cis-tri-amine by tosylation, azide substitution, and reduction, and the amine acylated with 2,3-dimethoxybenzoyl chloride to give the tri-amide, an analogue of enterochelin. ... 

Sodium bromate in presence of CAN or CAS is an effective reagent for the oxidation of secondary alcohols into the corresponding ketones (Tomioka et al., 1982 Kanemoto et al., 1986). For instance cyclododecanol is oxidized in 98% yield to cyclododecanone, and bor-neol is oxidized in 77% yield into camphor. Primary alcohols are not affected, so that this is a useful methodology for the oxidation of secondary alcohols in presence of primary ones. The presence of a double bond in the substrate, even at a position far way from the sec-... 

---