1,5,9-Cyclododecatriene hydrogenation

Butadiene when trimerised over Ziegler-Natta catalyst to yields 1, 5, 9-cyclododecatriene. Hydrogenation form cyclododecane which yields dodecyl lactam. 

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). 

Other methods have been described to produce dodecanedioic acid. Cyclododecene is prepared from cyclododecatriene by partial hydrogenation. Ozonolysis of the cyclododecene followed by oxidation of the intermediate ozonides gives dodecanedioic acid (72). Hydrogenation of riciaoleic acid gives 12-hydroxystearic acid, which upon treatment with caustic at high temperatures, 325—330°C, gives a mixture of undecanedioic and dodecanedioic acids. 

Cyclododecatriene is a precursor for dodecane-dioic acid through a hydrogenation step followed hy oxidation. The diacid is a monomer for the production of nylon 6/12. 

Crotonaldehyde, hydrogenation of, 43-48 Cubane, isomerization of, 148 Cyclic dienes, metathesis of, 135 Cyclic polyenes, metathesis of, 135 Cycloalkenes, metathesis of, 134-136 kinetic model, 164 ring-opening polymerization, 143 stereoselectivity, 158-160 transalkylation, 142-144 transalkylidenation, 142-144 Cyclobutane configuration, 147 geometry of, 145, 146 Cyclobutene, metathesis of, 135 1,5,9-Cyclododecatriene, metathesis of, 135... 

WiESSMEiER, G., Honigke, D., Heterogeneously catalyzed gas-phase hydrogenation of cis,trans,trans-1,5,9-cyclododecatriene on palladium catalysts having regular pore systems,... 

DietzschE.HonickeJD.Eichtner, M.SchubertK WiessmeierG-, The formationofcycloalkenesinthepartialgas phase hydrogenation of c, t,t-1,5,9-cyclododecatriene, 1,5-cyclooctadieneand... 

A m-RuCl2(CO)2(PPh3)2 complex, which catalyzes hydrogenation of dienes and monoenes, becomes useful in the presence of added phosphine for selective hydrogenation of 1,5,9-cyclododecatriene to cyclododecene the catalyst is a HRuCl(CO)2(PPh3)2 hydride that operates via steps analogous to those of reactions (9)-(11) (144, 145). 

The very unusual selective hydrogenation of ,/3-unsaturated aldehydes to the unsaturated alcohols, Eq. (30), has been accomplished using [RhCl(CO)2]2 in the presence of tertiary amines under oxo conditions (162). RhCl(PPh3)3 systems under similar conditions reduce the olefinic bond (162), as do Co2(CO)8 systems in the presence of amines or phosphites (163). Further details on the versatile Rh(BH4)(amide)py2Cl2 systems (/, p. 280) have appeared (164, 165) ketones are also slowly hydrogenated (166), and 1,5,9-cyclododecatriene has been selectively reduced to cyclododecene (167). 

Use of molten salts as solvent allows easy separation of organic products by distillation (376), and in this way PtCl2 with tetraalkylammonium salts of SnCl3 and GeCl3 has been used to selectively hydrogenate 1,5,9-cyclododecatriene to cyclododecene the salts in this case act as both solvent and ligand (377). A molten salt medium has been used in a homogeneously catalyzed Fischer-Tropsch synthesis (see Section VI,B). 

Cyclododecene may be prepared from 1,5,9-cyclododecatriene by the catalytic reduction with Raney nickel and hydrogen diluted with nitrogen, with nickel sulfide on alumina, with cobalt, iron, or nickel in the presence of thiophene, with palladium on charcoal, with palladimn chloride in the presence of water, with palladium on barium sulfate, with cobalt acetate in the presence of cobalt carbonyl, and with cobalt carbonyl and tri- -butyl phosphine. It may also be obtained from the triene by reduction with lithium and ethylamine, by disproportionation, - by epoxidation followed by isomerization to a ketone and WoliT-Kishner reduction, and from cyclododecanone by the reaction of its hydrazone with sodium hydride. ... 

The behavior of dienes and polyenes - both open chain and cyclic - toward reduction depends especially on the respective positions of the double bonds. Carbon-carbon double bonds separated by at least one carbon atom behave as independent units and can be partly or completely reduced by catalytic hydrogenation or by diimide. cis, trans, /rani-l,5,9-Cyclododecatriene treated with hydrazine and air in the presence of copper sulfate (diimide in situ) gave cij-cyclododecene in 51-76% yield [269]. It appears as if the trans double bonds were reduced preferentially. 

Of interest, 1,5,9-cyclododecatriene prepared by trimerization of 1,3-butadiene undergoes only hydrogenation to cyclododecene. This reaction has potential since cyclododecene is a precursor to 1,12-dodecanedioic acid, a commercial polyamide intermediate. [RuCl2(CO)2(PPh3)2] gives 98-99% yield of cyclododecene under mild conditions (125-160°C, 6-12 atm, in benzene with added PPh3 or in N,N-dimethylformamide).143... 

The hydrogenation of 1,5,9-cyclododecatriene (1,5,9-CDT) to cyclododecadienes (CDD) and cyclododecene (CDE) proceeds much less selectively than in the case of 1,5-COD. This may be due to the fact that the three double bonds in 1,5,9-CDT cannot assist each other on adsorption to catalyst, as may be deduced from the inspection of its molecular model. Thus, it is expected that the difference in strength of adsorption or reactivity between 1,5,9-CDT and CDD or CDE would be considerably smaller than that between 1,5-COD and COE. Hanika et al. studied the hydrogenation of 1,5,9-... 

Scheme 3.11 Hydrogenation of 1,5,9-cyclododecatriene (CDT) via cyclododecadiene (CDD) and cyclododecene (CDE) as intermediates.

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