1,5,9-Cyclododecatriene 1,3-butadiene

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). 

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 ... 

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. " ... 

Among transition metal complexes used as catalysts for reactions of the above-mentioned types b and c, the most versatile are nickel complexes. The characteristic reactions of butadiene catalyzed by nickel complexes are cyclizations. Formations of 1,5-cyclooctadiene (COD) (1) and 1,5,9-cyclododecatriene (CDT) (2) are typical reactions (2-9). In addition, other cyclic compounds (3-6) shown below are formed by nickel catalysts. Considerable selectivity to form one of these cyclic oligomers as a main product by modification of the catalytic species with different phosphine or phosphite as ligands has been observed (3, 4). 

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

Type [55] complexes are obtained from cyclooctadienes (74), too, but also from cy-clododecatrienes (59, 117), hexadienes (765), and butadienes (755). Some of these reactions also lead to tetraruthenium olefm clusters. Of these, the complex [7 ] has been mentioned already, and is obtained from cyclooctadiene (74, 75, 283), whereas the complex [59] results from cyclododecatriene (56, 59). 

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... 

Homogeneous nickel complexes proved to be versatile catalysts in dimerization and trimerization of dienes to yield different oligomeric products.46-55 Depending on the actual catalyst structure, nickel catalyzes the dimerization of 1,3-butadiene to yield isomeric octatrienes, and the cyclodimerization and cyclotrimerization to give 1,5-cyclooctadiene and all-trans-l,5,9-cyclododecatriene, respectively46 56 [Eq. (13.13)]. Ziegler-type complexes may be used to form cis,trans,trans-1,5,9-cyclododecatriene37,57 58 [Eq. (13.14)], which is an industrial intermediate ... 

The titanium trichloride-diethylaluminum chloride catalyst converted butadiene to the cis-, trans,-trans-cyclododecatriene. Professor Wilke and co-workers found that the particular structure is influenced by coordination during cyclization between the transition metal and the growing diene molecules. Analysis of the influence of the ionicity of the catalyst shows effects on the oxidation and reduction of the alkyls and on the steric control in the polymerization. The lower valence of titanium is oxidized by one butadiene molecule to produce only a cis-butadienyl-titanium. Then the cationic chain propagation adds two trans-butadienyl units until the stereochemistry of the cis, trans, trans structure facilitates coupling on the dialkyl of the titanium and regeneration of the reduced state of titanium (Equation 14). 

With more 1,3-butadiene, 21 is converted first to 22, which after rearrangement reacts with 1,3-butadiene to give back 21 with liberation of trans,trans,trans-1,5,9-cyclododecatriene ... 

The starting point of this development was the discovery by Wilke (18) of the synthesis of cyclododecatriene-1,5,9 from butadiene using typical organometallic mixed catalysts. 

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... 

Nickel-triarylphosphite complexes catalyze the dimerisation of butadiene to cyclooctadiene. Cyclododecatriene is an unwanted by-product, which results from trimerization catalyzed by the same catalyst. Table 3.2 shows the product yields using various ligand-metal complexes (the remainder in each case is a tarry polymeric material). 

The reduction of nickel(II) in the presence of butadiene as the only available ligand (i.e., naked-nickel3) (69) produces a catalyst which is able to trimerize butadiene to a mixture of all-trans- trans,trans,cis- and trans,cis,cis-i, 5,9-cyclododecatriene in which the all-trans form predominates. 

Poly-l,4-trans-isopren (mit der Struktur der Guttapercha). Bemerkenswert sind auch Oligomerisationsreaktionen des 1,3-Bu-tadiens zu 1,5-Cydooctadienund 1,5,9-Cyclododecatrien, femerdie Misch-oligomerisation aus zwei Molen 1,3-Butadien und einem Mol Athylen zu Cyclodecadien mit tlbergangsmctall-ir-Komplexen als Katalysatoren. 

Wilke and his co-workers have shown that zera-valent complexes, especially of nickel, obtained by reduction with aluminium alkyls can be used in a wide variety of polymerisations such as trimerisation of butadiene to trans, tran, trans-cyclododecatriene. 

Butadiene could also be trimerized to give cyclododecatriene. The trimer is again used by Hulls to manufacture nylon 12 and Vestamid . The codimerization of butadiene and ethylene is used by DuPont to manufacture 1,4-hexadiene, one of the monomers of EPDM (ethylene, propylene, diene, monomers) rubber. The role of the diene monomer in EPDM rubber is to provide with two double bonds of different reactivities. The more reactive, terminal double bond takes part in the polymerization with ethylene and propylene. The less reactive internal one is used later on for cross-linking. These important catalytic reactions are shown in Fig. 7.6. 

In the absence of added phosphine the main product is the cyclic trimer of butadiene—cyclododecatriene. The presence of three double bonds in this molecule means other geometric isomers apart from the one shown in Fig. 7.6 exist. Identification of the species 7.31 by NMR is evidence for the involvement of rf-allyl intermediates. The complex 7.31 reductively eliminates cyclododecatriene. 

It has been known for many years that the key intermediate in the cy-clotrimerization of butadiene to 1,5,9-cyclododecatriene is an Tj3,i73-do-decatrienediyl nickel species (73). We have recently reinvestigated this complex in the hope of obtaining further structural information, and the 13C-NMR spectrum is shown in Fig. 9. The spectra in THF-dg and toluene-t(8 are practically identical, indicating that THF is not here functioning as a ligand. The spectrum shown in Fig. 9 was run in THF-dg and... 

Cyclooctadiene (COD) is an intermediate for the manufacture of poly-octenamers, while 1,5,9-cyclododecatriene (CDT) is the starting material for the manufacture of dodecanoic acid and lauryl lactam. The latter is converted to the polyamide fiber Vestamide (DuPont). Both COD and CDT are made from butadiene (Equations 21 and 22). 

Interestingly a Ziegler Natta catalyst (Chapter 7) consisting of TiCU associated with an aluminium alkyl co-catalyst in a 1 1 molar ratio, polymerizes butadiene, but it is also able to afford cyclododecatriene provided that the TiCU/co-catalyst molar ratio is kept approximately to 0.1 instead of 1 [M. Rapoport and D. L. Sullivan, Can. Patent 1 055 052 (1979), to DuPont]. Although the mechanism is unclear, this is a good example of how delicate can be the modulation of a catalytic system for a selective synthesis. 

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