1.5.9- Cyclododecatriene

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. 

Whether butadiene reacts with itself to give linear polymers or 8- or 12-carbon rings is a function of the catalyst and conditions used. Development of catalysts needed to give the desired products is the job of catalyst research chemists. Although catalysis is critically important in the chemical industry and much work has been done on it in research laboratories for many years, catalyst development remains more of an art than a predictable science, and the chemists involved in this type of research use methods they have learned experimentally, not from books or in classrooms. 

Properties Clear, colorless, flammable liquid that boils at 80°C (176°F) and freezes at 5.5°C (42°F). It has a very characteristic odor. Recently it has been found to be toxic and is suspected of being a human carcinogen. Fxposure to it should be very limited or, preferably, avoided. 

Commercial grades Available in three grades refined-535, refined-485 (nitration grade), and industrial. The numbers following the grade refer to the freezing point specification times 100. It is shipped in steel drums, tank trucks, and tank cars under heavily regulated conditions. 

Uses It is used as a chemical raw material for a myriad of everyday products such as plastics, detergents, textile fibers, drugs, dyes, and insecticides. It is also found in gasoline with other aromatic hydrocarbons. 

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The reaction of a mixture of 1,5,9-cyclododecatriene (CDT), nickel acetylacetonate [3264-82-2], and diethylethoxyalurninum in ether gives red, air-sensitive, needle crystals of (CDT)Ni [12126-69-1] (66). Crystallographic studies indicate that the nickel atom is located in the center of the 12-membered ring of (CDT)Ni (104). The latter reacts readily with 1,5-cyclooctadiene (COD) to yield bis(COD) nickel [1295-35-8] which has yellow crystals and is fairly air stable, mp 142°C (dec) (20). Bis(COD)nickel also can be prepared by the reaction of 1,5-COD, triethylaluminum, and nickel acetylacetonate. 

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). 

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. 

Fluorination of perhydroacenaphihene gives a 45% yield of perfluoroper-hydroacenaphthene. The same compound is also obtained from cis,irons,trans-1,5,9-cyclododecatriene in 50% yield [7[Pg.124]

Fluorination of cis,rran.t,trani-l,5,9-cyclododecatriene with cobalt trifluoride gives a 50% yield of perfluoroperhydroacenaphthene [2[Pg.128]

The 1,2-azaphosphole i7 (P)-coordinated complexes 83 and 84 follow from the corresponding ligand and [(i -allyl)NiCl]2 and [(1,5,9-cyclododecatriene)Ni], respectively (98ICA(270)273). 

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 ... 

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. 

Cyclododecane from cyclododecatriene may also he converted to the Ci2 lactam, which is polymerized to nylon 12. 

Cyclic dienes and polyenes, monocyclic as well as bicyclic, can be metathesized in the same way as cyclic monoenes. As expected, cyclobutene 27), 1,5-cyclooctadiene, and 1,5,9-cyclododecatriene 28) yield the same polyalkenamer, in this case polybutenamer (1,4-polybutadiene), since these reactants consist of the same base units, i.e.—(CH2)2CH==CH— ... 

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... 

Hexabromocyclododecane (HBCD) is prepared by the bromination of lZ,5E,9E-cyclododecatriene (CDT). The term "HBCD" will be used here to denote the commercial product containing various isomer compositions. Bromination of CDT leads to three isomers, HBCD-1 (y), HBCD-2 (P) and HBCD-3(a). All three isomers (Fig. 1) were isolated and fully identified (refs. 1,2). 

BH3 itself. One example is the formation of 9-BBN, shown above. Another is conversion of 1,5,9-cyclododecatriene to perhydro-9(i -boraphenalene ... 

Conjugated dienes can be dimerized or trimerized at their 1,4 positions (formally, [4 4- 4] and [4 4-4 4-4] cycloadditions) by treatment with certain complexes or other transition metal compounds. " Thus butadiene gives 1,5-cyclooctadiene and 1,5,9-cyclododecatriene. " The relative amount of each product can be controlled by use of the proper catalyst. For example, Ni P(OC6H4—o-Ph)3 gives predominant dimerization, while Ni(cyclooctadiene)2 gives mostly trimerization. The products arise, not by direct 1,4 to 1,4 attack, but by stepwise mechanisms involving metal-alkene complexes. " ... 

The Ni sandwich is also obtained when excess ligand is treated with Ni(CDT) (CDT = all-trans-cyclododecatriene) at 70-80 C. The yield of the orange-red sandwich is 78%. 

With ttt-l,5,9-cyclododecatriene-nickel a novel bimetallic nickel sandwich is formed ... 

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

GP15][R4] Theselectivehydrogenationofl,5-cyclooctadiene(COD)ataPdcata-lystismorefacilethanfor c,t,t-l,5,9-cyclododecatriene,sincenodeactivationdur-ingacatalyticmnis found [130],... 

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

Nickel(O) reacts with the olefin to form a nickel(0)-olefin complex, which can also coordinate the alkyl aluminum compound via a multicenter bond between the nickel, the aluminum and the a carbon atom of the trialkylaluminum. In a concerted reaction the aluminum and the hydride are transferred to the olefin. In this mechanistic hypothesis the nickel thus mostly serves as a template to bring the olefin and the aluminum compound into close proximity. No free Al-H or Ni-H species is ever formed in the course of the reaction. The adduct of an amine-stabihzed dimethylaluminum hydride and (cyclododecatriene)nickel, whose structure was determined by X-ray crystallography, was considered to serve as a model for this type of mechanism since it shows the hydride bridging the aluminum and alkene-coordinated nickel center [31]. 

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