Triene 1,5,9-cyclododecatriene

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). 

Butadiene could be oligomerized to cyclic dienes and trienes using certain transition metal complexes. Commercially, a mixture of TiCU and Al2Cl3(C2H5)3 is used that gives predominantly cis, trans, trans-1,5,9-cyclododecatriene along with approximately 5% of the dimer 1,5-cyclooctadiene ... 

The submitters used material available from Hiils Company in Germany. This material was contaminated with 1-3% of the more easily reduced /raMi,/r(i s,Aldrich Chemical Company, Inc. The gas chromatogram (see Note 6) of this material exhibited no peak corresponding to the all-ira j-triene, an indication that less than 1% of this contaminant was present. 

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. ... 

Many studies of benzene-sensitized isomerizations have been reported. One interesting example is provided by the behavior of cis,trans,trans-1,5,9-cyclododecatriene. With benzene photosensitization it is isomerized to the M-trans and the cis,cis,trans isomers, and a new, probably bicyclic, product is also formed in small yield.274 Another study employed a large number of sensitizers, many of which apparently reacted with the triene, and no particular trend was evident other than that the original isomer remained as the major geometric isomer in the photostationary state, with varying amounts of the all-trans and cis,cis,trans isomers being formed with different sensitizers.275... 

Reaction of excess butadiene with (Ci2Hig)Ni results in displacement of the triene and trimerization of C4H6 (608). At 20°C a new molecule of cyclododecatriene is produced while at —40°C the product, illustrated by structure (194), is considered to involve a C12 chain with a trans double bond and two terminal w-allyl groupings. 

The stoichiometry of the crystalline complex obtained by reaction of cyclic oligoolefins with AuCl in absolute ether at room temperature (0°C for norbornadiene) depends upon the olefin. 1,5-Cyclooctadiene and both cis,cis,trans- and oif-infrared spectra of the trienes indicate the presence of both complexed and free double bonds, the cis,cis,trans-l,5,9-cyc odo-decatriene showing one free cis unsaturation. C is,cyclodeca-diene and dicyclopentadieneform, on the other hand, only 1 1 complexes. The former olefin is complexed only at the trans double bond, whereas the latter is complexed only at the double bond in the norbomene part of the molecule (225). 

Two isomeric 1,5,9-cyclododecatrienes, namely, trans,trans,cis-CijH 18 (XLVI) and trans,trans,trans-CuHis (XLVII), are formed in good yield by the cyclic trimerization of butadiene using certain Ziegler-type catalysts 247, 250, 251, 252). The formation of these 12-membered ring hydrocarbons probably proceeds via metal 7r-complexed intermediates. When the cyclic triene (XLVII) is treated with nickel acetylacetonate and... 

The cyclododecatriene is then converted to lauryllactam by different processes. One of them consists of hydrogenation of the cyclic triene, followed by oxidation to a cyclic ketone, conversion to an oxime, and rearrangement by the Beckmann reaction to the lactam ... 

The progression toward Organlco s commercial production of lactam began in 1958. Initially, cyclododecatriene was epoxidized then hydrogenated to the alcohol. The alcohol was oxidized to the ketone, which was then transformed by reaction with hydroxylamine to the oxime which by Beckmann rearrangement yielded the lactam. They immediately began to work on a method to react nitrosyl chloride directly with dodeca-triene and eliminate some intermediate steps. This program eventually led to the earliest version of the commercial process in 1962. 

Also trienes such as cyclododecatriene-1,5,9 yield mono- and dicarboxylic acid esters [488, 509]. Cyclododecane tricarboxylic acid esters are formed with bis-triphenyl phosphine palladium dichloride as catalyst [448]. The catalyst can be recycled [517]. Nearly quantitative syntheses of monocarboxylic acid esters of cyclododecadiene and of tricarboxylic acid esters of cyclododecane can be achieved with complex Pd-catalysts. 

A review of the uses of cyclododeca-l,5,9-triene has appeared. Stereoselective boron-promoted epoxidation of cis,trans,trans-cyclododecatriene gives l,2-trans-epoxy-cis-5-traws-9-cyclododecadiene, whereas the all-transisomer gives l,2-trans-epoxy-frans,trans-cyclododecadiene. ... 

Cyclododecatriene nickel has also been shown to catalyse the co-cyclization of two molecules of butadiene either with one molecule of ethylene giving cyclodeca-1,5-diene or with one molecule of 2-butyne to give 1,2-dimethyl cyclodeca-1,4,8-triene [72]. 

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