Oxidation of Cyclododecane

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. 

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A similar procedure has been developed by Chemische Werke Hulls for the oxidation of cyclododecane to a cyclododecanol-one mixture by air in the presence of boric acid with trace amounts of cobalt(II) carboxylate at 160-180 °C and 1-3 atm.556 The ol-one mixture (5 1) is... 

The Bashkirov oxidation (liquid-phase oxidation of n-alkanes or cycloalkanes in the presence of boric acid and hydrolysis) yields the corresponding secondary alcohols [16, 17]. The reaction is used industrially for oxidation of C10 to C18 n-alkanes, providing raw materials for detergents and for oxidation of cyclododecane to cyclo-dodecanol as an intermediate for the production of Nylon 12 (Table 1, entry 8). The process is not of much commercial importance in the western world, however. Oxidation in the absence of boric acids usually leads to mixtures of alcohols, ketones, and carboxylic acids (Table 1, entry 9). 

Cyclododecanol 0.01 0.02 tubular reactor. Oxygen is used as initiator (radical formation) Oxidation of cyclododecane. Air is sometimes... 

Under Gif conditions copper(II) salts show a similar reactivity in the oxidation of saturated hydrocarbons with hydrogen peroxide. In the oxidation of cyclododecane, Geletii et alP obtained only a 0.019 M solution of oxidized products which shows that the activity of the copper catalyst is smaller than that of the corresponding iron(III) catalyst. On the other hand, the GoChAgg system, without addition of picolinic acid, is nearly as rapid as the GoAgg system and the addition of water does not reduce its efficiency. There are further differences between the two systems which prove that the metal itself participates actively in the activation process. " ... 

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... 

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). 

Consider an equilibrium-limited esterification reaction. One way to drive the reaction to completion is to remove the water formed by the reaction selectively through a membrane. This can be an attractive strategy when higher temperatures are undesirable due to factors like colouration of the materials and formation of undesirable products even though these may be present at a low level. As another example, consider the air oxidation of cyclohexane or cyclododecane to cyclohexanone/-ol or cyclododecanone/-ol, where the product can undergo more facile oxidation to unwanted or much lower value products. Consequently, industrial processes operate at a level of less than 5% conversion. If a membrane can selectively remove cyclohexanone as it is formed, the problems mentioned above can be thwarted. However, selective polymeric membranes, which can work at oxidation temperature, have not yet been proved. 

VG Bykovchenko. Kinetics and Mechanism of Cyclododecane Oxidation Directed to Hydroperoxide and Cyclododecanone. Ph.D. thesis, Moscow State University, Moscow, 1962, pp. 3-11 [in Russian]. 

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. 

It is fairly apparent that encapsulation of the RuFiePc complex in NaX dramatically alters the catalytic activity and selectivity, however, that in itself is not evidence for the intrazeolite location of the complex. Therefore, we examined the oxidation of the much larger cyclododecane using the same reaction conditions as for cyclohexane. We found the homogeneous RuFisPc catalyst had virtually no preference for either cycloalkane, showing approximately the same number of turnovers per day. In contrast, the RuFiePc-NaX catalyst exhibited relatively low activity ( 300 tumovers/day) for the larger cyclododecane. The acti dty of the zeolite encapsulated complex was nearly 10 times greater for the smaller cyclohexane. This shape selectivity is consistent with the active sites located inside the zeolite. 

It has been shown that Ti-Beta zeolite Is a useful catalyst for the selective oxidation of olefins in the presence of HjOj. This large pore Ti-zeolite takes advantage over the TS-1 when bulkier organic molecules are to be oxidized, as was shown for cyclododecane (14) and now for cyciic olefins. It has also been seen that the presence of Al in Ti-Beta affects negatively the red-ox properties of the catalyst by reducing the reaction rate. 

The Gif system, which consists of triplet oxygen, acetic acid, pyridine, zinc and an iron catalyst, oxidizes saturated hydrocarbons mainly to ketones and gives minor amounts of aldehydes. Tertiary hydrogen is only substituted in exceptional cases. With the Gif-Orsay II system in which zinc is replaced by the cathode [divided cell, cpe at — 0.6 to —0.7 V vs see, trifluoroacetic acid, pyridine, Fe30(0Ac)6Pyr3.5], adamantane is converted in 3.8% coulombic yield the ratio of attack at a secondary tertiary CH bond (C /C ratio) is 15.0. Comparable conversions were carried out with cyclododecane to afford 21% oxidation with a ratio of alcohol ketone = 1 14. TranS decalin yielded 22% product, consisting of 0.6% 9-ol, 0.9% l-ol, 9.0% 1-on 0.65% 2-ol and 11% 2-one. A radical mechanism for this conversion can be excluded since for the cobalt-catalyzed radical oxidation of trans-decalin the C /C ratio is 0.13, which is far removed from 36 found with the Gif system. 

At BASF, cyclododecyl carbinol is formed by an oxo synthesis addition reaction of CDT with CO and H2, and this, through fusion with potash, is further oxidized to cyclododecan monocarboxylic acid, which is then transformed into a lactam with nitrosyl hydrogen sulfate. 

Many oxidation reactions have been carried out using hydrogen peroxide and the titanosilicate, TS-1. However, this catalyst has relatively small pores and is therefore not an efficient catalyst for the oxidation of large molecules. This problem has been solved by the successful generation of a medium-pore titanium zeolite Beta-Ti [136]. Cyclododecane and cyclohexane are both oxidised selectively by H2O2 in the presence of the new titanium zeolite, favouring the ketone product. 

CoHMA Four-coordinated framework Co + on A1 sites UV-vis Presence of Br0nsted and Lewis sites no leaching of Co with calcination Oxidation of cycloalkanes (cyclohexane, cyclooctane, cyclododecane), mild conditions (296- 298)... 

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. ... 

Oxidation of cis- and trans-cyclododecane-l,2-diols with 1-phenylbut-l-en-3-one and tris(triphenylphosphine)ruthenium dichloride gives good yields of cyclododecane-1,2-dione. ... 

The by-product of this process, pelargonic acid [112-05-0] is also an item of commerce. The usual source of sebacic acid [111-20-6] for nylon-6,10 [9008-66-6] is also from a natural product, ticinoleic acid [141-22-0] (12-hydroxyoleic acid), isolated from castor oil [8001-79-4]. The acid reacts with excess sodium or potassium hydroxide at high temperatures (250—275°C) to produce sebacic acid and 2-octanol [123-96-6] (166) by cleavage at the 9,10-unsaturated position. The manufacture of dodecanedioic acid [693-23-2] for nylon-6,12 begins with the catalytic trimerization of butadiene to make cyclododecatriene [4904-61-4] followed by reduction to cyclododecane [294-62-2] (see Butadiene). The cyclododecane is oxidatively cleaved to dodecanedioic acid in a process similar to that used in adipic acid production. 

Cyclooctadiene is reacted with bromine to make fire-retardants. Cyclododecane is oxidized with air and then nitric acid to make a diacid containing 12 carbons. This acid is used to prepare some types of nylon, and its esters are used in synthetic lubricating oils. 

In the linear versus cyclic case, n-hexane oxidizes 18.9 times as fast as cyclohexane (see Fig. 6-6) however, under slightly different conditions (same temperature and pressure, acetone solvent) and a slightly different preparation of TS-1, n-hexane oxidizes only 4.8 times as fast as cyclohexane.45 These differences in TOFs between the linear and cyclic isomers are also attributed to the size restrictions of the zeolite. When the channel diameter is increased, as in the Ti-(1 catalyst (-6.5 A), larger cycloalkanes, such as cyclododecane, can be oxidized.45... 

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