Cyclododecane oxide

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]. 

Cyclododecadiyne, 356 Cyclododecane oxide, cis- and trans-, 247 Cyclododecanone, 212, 213, 327, 350, 420 rrans-Cyclododecene, 269 trans-2-Cyclododecenol, 247... 

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. 

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). 

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. 

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. 

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... 

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. 

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). 

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. 

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

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. 

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

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