Trimerization of 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. 

The procedure described is based on the selective reduction with diimide described by Ohno and Okamoto and by Nozaki and Noyori. It illustrates the generation of diimide from the air oxidation of hydrazine and the use of diimide for the selective reduction of the trans double bond in cis,trans,trans-, S,9-cyc o-dodecatriene, the product of trimerization of butadiene. ... 

Nylon-12,12. Nylon-12,12 [36497-34-4], [36348-71-7] was introduced into the marketplace by Du Pont in the late 1980s (174). This polymer possesses very low moisture absorption, high dimensional stability, and excellent chemical resistance, with a moderately high melt point (Tm = 185° C) (175). Its manufacture begins with the formation of dodecanedioic acid produced from the trimerization of butadiene in a process identical to that used in the manufacture of nylon-6,12. The other starting material, 1,12-dodecanediamine, is prepared in a two-step process that first converts the dodecanedioic acid to a diamide, and then continues to dehydrate the diamide to the dinitrile. In the second step, the dinitrile is then hydrogenated to the diamine with hydrogen in the presence of a suitable catalyst. 

Examples of both oxidation and reduction have been found. Breil, Heimbach, Kroner, Muller and Wilke (130) have studied the cyclization of butadiene. Three different cyclic trimers of butadiene have been obtained depending on the catalyst system. These are summarized in Table 10. 

Both di- and trimerization of butadiene with soluble nickel catalysts are well-established homogeneous catalytic reactions. The precatalyst having nickel in the zero oxidation state may be generated in many ways. Reduction of a Ni2+ salt or a coordination complex such as Ni(acac)2 (acac = acetylacetonate) with alkyl aluminum reagent in the presence of butadiene and a suitable tertiary phosphine is the preferred method. The nature of the phosphine ligand plays an important role in determining both the activity and selectivity of the catalytic... 

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. 

Figure 11 Representation of di- and trimerization of butadiene on nickel(0) to give bis-allylic intermediates and cyclic olefins.

When butadiene is treated with RuCls in 2-methoxyethanol at 100°C, yellow-brown crystals of composition (C4H8)3RuCl2 are obtained 381). Crystal structural analysis has identified 381, 382] the complex as (2,6,10-dodecatriene-l,12-diyl)dichlororuthenium (146), analogous to the nickel complex (194) suggested 608) as the catalytic intermediate in the nickel-catalyzed cyclic trimerization of butadiene. In this complex, the ruthenium atom has a trigonal-bipyramidal configuration with the... 

Diene Cyclization. In 1952 Reed (157) discovered the catalytic dimerization of butadiene with Reppe catalyst in the presence of acetylene. Important results were obtained by Wilke (200) in the cyclization of butadiene with a nickel(0) catalyst. With bis-7r-allylnickel, biscyclo-i,5-octadienenickel, or cyclododecatrienenickel, he obtained the trimerization of butadiene to cyclododecatetraene while, with a catalyst of the type Ni(PR3)4, in which perhaps one coordination site cannot be replaced, he obtained the dimerization to cycloocta-l,5-diene. The mechanism of these reactions, in which 7r-allyl systems can be in equilibrium with o--7r-allyl systems (Figure 7), have been proved by Wilke and co-workers who isolated the intermediate compounds. It is worth noting that all these catalysts have ligands of weak -acceptor character which are labile and do not prevent butadiene from coordinating. The presence of weak t acceptors on the nickel tends to favor the structure of the diene, as was emphasized by Mason (112). 

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... 

W, Keim/SHELL (1977) SHOP W, S, Knowles / MONSANTO (1971) L-DOPA R, L, Pruett (1970) Rh/PRs-oat, for 0x0 synth. F. E. Paulik, J. F. Roth / MONSANTO (1968) carbonylation of CH3OH T. Alderson / DuPONT (1961) RhCi3-catalyzed butadiene/ethylene coupling G. Wilke (1959) Ni-catalyzed trimerization of butadiene... 

The C12H18 ligand is formed from trimerization of butadiene and is composed of two allyl functions and one olefin moiety. These functionalities coordinate to... 

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

Selective reduction. Use of reagent, generated by cupric ion-catalyzed air oxidation of hydrazine, for the preparation of m-cyclododecene by the selective reduction of cis.trans.trans-1,5,9-cyclododccatriene, the product of trimerization of butadiene,7-8 is described by Ohno and Okamoto9 (see also 1,258, ref. 10). 

The titanium(IV) chloride adducts of (75) and (79), after reduction with diethylaluminum chloride, catalyzed the dimerization of isoprene and the trimerization of butadiene as effectively as other rf-cyclopentadienyl-based tertiary arsine ligands <84TLl97l). 

Hexamethylene diamine can be produced by various processes (see also Chapter 24), and is industrially mostly produced from adipic acid, butadiene, or acrylonitrile. Sebacic acid is obtained from castor oil. Because of the uncertain supply situation, the sebacic acid for such polyamides is being increasingly replaced by dodecane diacid, which is obtained by the oxidation of cyclododecatriene, the cyclic trimer of butadiene. The monomers for polyamide 13,13 are derived from erucic acid (see also Chapter 24). 

In addition to the described allyl complexes which are formed by dimerization of butadiene, allyl compounds consisting of trimers of butadiene may be obtained see equation (13.81). 

If phosphines or phosphites are not present, Ni(0) compounds cause trimerization of butadiene [scheme (13.84)]. In addition to the isomer trans,trans,trans-... 

Organlco management was interested in the development of a high carbon number nylon that wouldn t be dependent on a vegetable oil and hence vulnerable to crop failures or excessive dependency on imported supply from a very few tropical nations. Genas noticed the publication by G. Wilke describing trimerization of butadiene to cyclododecatriene. 

These nickel compounds have high reactivities and high selectivities to substrates and are easily handled in experimental operations. Then, these compounds are widely available as reagents and catalysts for organic syntheses [61-72]. In particular, the production of acrylic acid by Reppe reactions, the production of butene by the dimerization of ethylene, and the synthesis of 1,5-cyclooctadiene or 1,5,9-cyclododecatriene by the dimerization or trimerization of butadiene, are well known as reactions using nickel catalysts, shown in eqs. (19.35)-(i9-38) [61,65,72-77]. 

What metal 7c-complexes are active for a /./.. -cyclododecatriene synthesis by trimerization of butadiene ... 

Dimerization or trimerization of butadiene produces 1,5-cyclooctadiene (COD) or 1,5,9-cyclododecatriene (CDDT), respectively. Each of these monomers undergoes efficient... 

The trimerization of butadiene and relatad raactions catalyzed by some n-allyl complexes... 

PA-12 is obtained by polymerization of the corresponding lactam, which itself is obtained from the trimerization of butadiene. 

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