Cyclododecatrienes, preparation

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 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. 

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. 

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). 

Several experiments considered as pertinent to the interpretation of the ternary mix data with respect to the possible role of potential species formed in-situ, such as SbBr3f were carried out with HBCD and HBCD mixtures. The organohalogen HBCD is prepared by the bromination of cyclododecatriene and nominally contains bromines at the 1, 2, 5, 6, 9 and 10 positions on the aliphatic ring. 

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. ... 

Significant advances in organonickel chemistry followed the discovery of frtzws,fraws,fraws-(l,5,9-cyclododecatriene)nickel, Ni(cdt), and bis(l,5-cycloocta-diene)nickel Ni(cod)2 by Wilke et. al.1 In these and related compounds, in which only olefinic ligands are bonded to the nickel, the metal is especially reactive both in the synthesis of other compounds and in catalytic behavior. Extension of this chemistry to palladium and to platinum has hitherto been inhibited by the lack of convenient synthetic routes to zero-valent complexes of these metals in which mono- or diolefins are the only ligands. Here we described the synthesis of bis(l,5-cyclooctadiene)platinum, tris(ethylene)-platinum, and bis(ethylene)(tricyclohexylphosphine)platinum. The compound Pt(cod)2 (cod = 1,5-cyclooctadiene) was first reported by Muller and Goser,2 who prepared it by the following reaction sequence ... 

Twelve-membered rings have been obtained using coordination catalysts. The trans,trans,cis-cyclododecatriene has been prepared with a tetrabutyl titanate—diethylaluminum chloride catalyst (48,49) and with a chromium-based system (50). The trans,trans,trans- somer has been prepared with a nickel system. 

Several cyclic oligomers 1-5 are prepared from butadiene using transition metal catalysts. The preparation of 1,5-cyclooctadiene (3 1,5-COD) by a catalyst prepared from Ni(CO)4 and phosphine is the first report on cyclooligomerzation of butadiene [1], However, the activity of this catalyst is low due to strong coordination of CO. Catalyst prepared from TiCU and EtjAl has higher catalytic activity for the formation of 1,5-COD and 1,5,9-cyclododecatriene (1,5,9-CDT 4). Also Ni(0) catalysts are active for the preparation of COD and CDT. In addition to COD and CDT, the cyclic... 

Scheme 7.3 Preparation of (fl//-franj-l,5,9-cyclododecatriene)nickel(0) (12) and its reactions with all-cis-C12H18 to the isomer 13 and with 1,5-cyclooctadiene to the bis(diolefin) nickel(0) complex 14...

Both cis, trans, trans- and aii-iraws-l,5,9-cyclododecatriene yield upon reaction with Zeise s dimer in acetone, the compounds bis(olefin)-yellow-orange plates melting at about 130°C (456). Dissolution of the all-trans product in an organic solvent results in loss of olefin to produce the polymeric species (Ci2Hi8)4(PtCl2)6 (456). An attempted preparation of the platinum(II) complex of cis,[Pg.320]

Haight and co-workers (269) have found that crystalline complexes can be readily obtained by reduction of CuCl2-2H20 or CuBr2 dissolved in ethanol with sulfur dioxide in the presence of the di- or oligoolefin. By this method they have prepared 1 1 complexes with norbomadiene, 1,5-cyclooctadiene, cyclooctatetraene, and dicyclopentadiene, 1 2 complexes with cis,trans,trans- and aW-complex with 1,3-cyclooctadiene. It was noted that rapid addition of SO2 to the system produced 1 2 complexes with norborna-diene and cyclooctatetraene. 

Hexabromocyclododecane (174) prepared by the bromination of cyclododecatriene (173) was treated with a limited amount of sodium ethoxide to give tribromocyclo-dodecatriene (175). The hexabromide 176 was prepared on treatment of 175 with NBS. The dehydrobromination of 176 with four equivalents of sodium ethoxide yielded 5-bromo-l,9-bisdehydro[12]annulene (177) . Treatment of 176 with an... 

The first active catalyst system found was prepared by reaction of nickel ace-tylacetonate with organoaluminum compounds in the presence of phenylacetylene. A dark red solution was obtained which reacted at 80° C. under pressure with butadiene to about 24% cyclo-octadiene, 8% vinylcyclohexene, and 63% all-tmns-cyclododecatriene. The component which stabilizes the reduced nickel was then changed systematically to discover the possibility of directing the synthesis at will in the direction of a trimerization or dimerization. Today we can synthesize cyclo-octadiene in yields of 95% or cyclododecatriene in similarly good yields only by altering the electron-donor molecules used in preparing the catalyst. 

What compounds are the active catalysts in this process By this method of catalyst preparation we do not obtain a mixture of indefinite composition, but TT-complexes which can be isolated and are mostly crystalline. If, for instance, nickel acetylacetonate is reduced in the presence of P(CeH5)3 we obtain a new compound, Ni-(0)-[P(CeH5)3]4. This compound is itself an active catalyst for the cyclo-oligomerization of butadiene, producing about 65 to 70% cyclo-octadiene, 20% vinylcyclohexene, and 10% cyclododecatriene. Instead of P(CeH5)3 we can introduce As(CeH5)3 and isolate Ni-(0)-[As(CeH5)3]4 as an active cata-... 

The intermediate complex mentioned above can be prepared in a very pure state if the centro-nickel compound is treated at —40° C. with an excess of butadiene. Also in this case the cyclododecatriene will be displaced, but no catalytic reaction takes place, and if the excess butadiene is removed at low temperature. 

Finally, the addition of one molecule of P(C2H5)3 induces an electron miration with formation of cyclododecatriene. No displacement occurs and the prodfuct obtained is identical to that prepared from the cyclododecatriene-centro-nickel complex itself ... 

CDE, which is of pivotal importance in many industrial processes, is normally prepared by the selective hydrogenation of 1,5,9-cyclododecatriene (CDT), with metallic Pd being the catalyst of choice. Pd suffers from its lack of selectivity, and a considerable quantity of cyclododecane (CDA) appears as a coproduct of the reaction. 

Catalysts prepared from a Ti(IV) salt and an alkylaluminum compound (Ziegler-Natta type) convert butadiene with high selectivities and yields of 80-90% to 1,5,9-cyclododecatrienes consisting mainly of the trans-trans-cis isomer with small amounts of the all-fra r isomer -. The activity and selectivity of these catalysts systems is improved by adding substances such as NaCl, which can complex with the aluminum chloride. ... 

Unfortunately, this process produces undesired nitrogen oxides at the same time. Some shorter dibasic acids are also formed. Trimerization of 1,3-butadiene is used to prepare 1,5,9-cyclododecatriene, an intermediate for another nylon.212 In the process, 1,5-cyclooctadiene and 4-vinylcyclohexene are formed as by-products (reaction 1.17). 

C15H24O, Mr 220.36, d%j 0.962-0.980, reg° 1.504-1.509, is a colorless to pale yellow liquid with powerful, complex, woody, and amber odor. It does not occur in nature. It is prepared by monoepoxidation of l,5,9-trimethyl-l,5,9-cyclododecatriene with, e.g., peracids. 

In 1953, Karl Ziegler had discovered the polymerisation of ethylene at normal pressure he succeeded in polymerising ethylene to polyethylene in a 5-litre preserving jar with a mixture of titanium tetrachloride and diethyl-aluminium chloride (Fig. 3.43). At the end of the 1950s, Gunther WHke intended to prepare butadiene from acetylene and ethylene with Ziegler catalysts, but preliminary experiments showed that the selected catalysts reacted violently with butadiene, and that the product was not a polymer but cyclododecatriene. Wilke later foimd, by using Ni(0)-com-plexes (which he called naked nickel ), that the isomer ratio was clearly in favour of the zH-trans isomer. 

Some olefin complexes may conveniently be obtained by electrochemical reduction methods. Cyclooctadiene and cyclododecatriene nickel(O) complexes such as Ni(COD)2 and Ni(CDT) may be prepared by electrochemical reduction of nickel acetylacetonate in the presence of butadiene in acetonitrile, dimethoxymethane, or DMF solutions. Complexes [Fe(CO)4 (alkene)] are reduced electrochemically to lie compounds [Fe(CO)3 (alkene)] . In the case of complexes [Fe(CO)3 (f/Miene)] (diene = BD, cyclohexadiene), during reduction, lie anions [Fe(CO)3 (diene)] are formed in which one olefin bond is decomplexed. ... 

Many aliphatic boron heterocyclics can be readily prepared by hydroboration of dienes or polyolefins (30, 45-49). Complete reaction of C=C bonds in polyolefins, such as butadiene, isoprene, 1,5-hexadiene, and cyclododecatrienes, yields colorless liquids which are distillable in many cases under reduced pressure 30, 45-49). 

In addition to the two commercial feedstocks, mixtures of pure hydrocarbons were prepared to simulate the three light oil lumps - Pi(19.5% tridecane, 19.8% pentadecane, 19.9% haexadecane, 20.5 heptadecane,21% octadecane),- H (9.7% tricyclodecane, 38%.5 dicyclohexyl, 13.07% cyclodecane, 38.7% cyclododecatriene),-Ai (17.7% phenylhexane, 23.0% cyclohexylbenzene, 12.2% dimethyl naphth.,22.8% dodecylbenzene, 12.1% Fluorene, 12.1 phenantrene). These mixtures were cracked in the Riser Simulator to reduce the number of data points necessary with just two feedstocks to solve the equations for the 8-lump model. The conditions used were reaction times of 3, 5, 7 and 10 seconds at temperatures of 500 and 550 C using both Octacat and GX-30 catalysts.. 

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