Building block succinic acid

At present succinic acid is a specialty chemical with an annual production volume of about 30 000 tons worldwide. Fossil-based succinic acid is most commonly prepared via hydrogenation of maleic anhydride (by oxidation of n-butane or benzene) [73]. In the field of bio-based chemicals and building blocks succinic acid is considered to be one of the most important platform chemicals [1, 74, 75], and as a result of the introduction of biosuccinic acid the production volume is expected to double or triple within years. Several fermentation processes have been described to produce bio-based succinic acid. Common feedstocks for these processes include glucose, starch and xylose [76]. The commercial potential for bio-succinic acid is illustrated by the numerous initiatives by companies that are working towards, or already... 

Levulinic acid is formed by the treatment of six-carbon sugar carbohydrates from starch or lignocellulosics with acids, or by add treatment plus a reductive step of five-carbon sugars derived from hemicellulose. Levulinic add can serve as a building block for the synthesis of many derivatives of interest may be the selective oxidation to succinic and acrylic add. [i-Acetylacrylic add could be used in the production of new acrylate polymers. 

The strategy for the development of products from biomass needs to be twofold. One approach is to identify those opportunities where we can compete economically with existing petrochemical products. Succinic acid-derived materials fit into this category (Fig. 1). The second approach must include the identification of products with novel functionality that cannot easily or cost effectively be derived from petrochemical building blocks. The challenge with developing new materials is that the market for these products must also be developed and the time and cost can be significant however, the reward may also be substantial. 

Platform chemicals are compounds that serve as building blocks for numerous chemical intermediates and end products. An example is ethylene, which serves as the feedstock for derivatives such as acetaldehyde, ethylene dichloride, ethylene oxide, polyethylene, vinyl acetate, and ethyl acetate. Biobased chemicals such as succinic acid, 3-hydroxypropionic acid (3-HP), and butanol also have the potential to be converted into multiple derivatives, some of which are commodity chemicals and others that are higher-value chemicals. 

Figure 4.4 Succinic acid as a building block for chemical production...

In this section, we seek to identify materials that are the reasonable first structures to arise from biomass deconstruction, and to describe how chemically catalyzed processes are being developed for their production. For that reason, commercially practiced processes that use catalysis, such as the reduction of glucose to sorbitol, are mentioned only briefly or not at all. Chemical catalysis will certainly play an additional role in the further conversion of these initial building blocks into secondary intermediates or final marketplace products (e.g., oxidative conversion of levulinic acid into succinic acid), but such multistep possibilities are outside the scope of this discussion. 

The 3-stage process involves utilisation of plant sugars derived from photosynthetically fixed C02 as carbon sources in the fermentation of organic acids, alcohols and amino acids. These substances are then used as building blocks for the chemical synthesis of polymers. Examples of polymers using the 3-stage process include polylactic acid and polybutylene succinate. 

Ferrioxamines, typical constituents of culture broths of Actinomycetes, occm as both hnear and cychc compounds containing l-amino-5-hydroxyaminopentane (A-hydroxycadaverine) and succinic acid as building blocks (Figure 1(c)). A cyclic trimer of succinyl-(A-hydroxycadaverine), is named ferrioxamine E. In some cases the pentane moiety is replaced by a butane carbon skeleton (putrescine). The most prominent representative of this siderophore family, desferrioxamine B (Figure 1), has become the drug of choice for the treatment of transfusional iron overload (Section 6.2). The crystal structure of ferric ferrioxamine B has been published recently. Certain derivatives of the ferrioxamines display antibiotic activity and therefore have been designated as ferrimycins. ... 

A positive aspect of this combinatorial scheme is typical for approaches with broad practical utility. Special building blocks (i.e., reactants belonging to a distinct chemical class with few commercially available analogues - in this case, mercapto-succinic acid) are used in a crucial role, namely for enabling the insertion of a diversity branch point allowing numerous subsequent derivatizations. 

By retro synthetic analysis collagenase inhibitor RO0319790 (1) can be assembled from two chiral building blocks, (R) -succinate 2 and (S)-tert-leucine N-methyla-mide 13. As the latter can be prepared from commercially available (S)-tert-leucine 8 our work concentrated in particular on the construction of the first building block 2. In order to assemble the carbon skeleton of 2 in the most efficient way, extremely cheap maleic anhydride 4 was converted in a known ene reaction with isobutylene to provide the cyclic anhydride 6. Hydrogenation of the double bond followed by the addition of EtOH/p-TsOH yielded the racemic diethyl ester substrate 9 for the enzyme reaction. The enzymatic monohydrolysis of 9 afforded the monoacid (R)-2a. (R)-2 a was coupled via its acid chloride with leucine amide 13 to ester 14, which finally was converted into the hydroxamic acid 1. 

Both monocyclic building blocks were prepared in a multistep reaction sequence from L-glutamic acid. In another alternative reaction sequence the succinic imide 107 as a common intermediate for rings A an B was synthesized from R-malate. The enantiomerically pure buildings blocks could be transformed along different routes with appropriate D,C pyrroles into the dimers 108 and 109 which on treatment with acid formed the desired bilinimine 110. The outlined total synthesis of porphyrin di established the absolute configuration of natural heme di. 

Step-growth polymerization of different building blocks, such as adipic and succinic acid, in combination with an acetylene-based diol, examples of which are 2-methyl-... 

New product The substitute could be a new product Examples are new polymers based on succinic acid as building block instead of fossil-derived dicar-boxyhc acids. Advantages are new market opportunities and no direct competition from petrochemical routes. Drawbacks Ue in the not-yet-defined market and the requirements of substantial amounts of capital and time to develop it. 

In their follow-up study from 2010, Bozell and Petersen revised this list based on the level of technological development and commercialization [2], Nevertheless, in both studies only three types of bio-based difunctional building blocks were included that is, succinic acid, furan-2,5-dicarboxylic acid (2,5-FDA or FDCA) and 1,4 3,6-dianhydrosorbitol (isosorbide). 

In this chapter we will discuss four types of biomass derived monomers and their application in polyesters three building blocks with a more or less unique structure from the 2004 DoF report (i.e. succinic acid, FDCA, and isosorbide), and one true drop-in replacement (i.e. bio-terephthalic acid). For each type of building block the chemical structure, raw material source, and synthesis will be described. The synthesis and properties of the polyesters will then be discussed and, depending on the type of material, current and future commercial applications will be described. 

So far, the following building blocks can be produced microbially for polymerization purposes hydroxyalkanoic acids with many structural variations, lactic acid, succinic acid, (i )-3-hydroxypropionic acid, bioethylene produced from dehydration of bioethanol, 1,3-propanediol, and c/ s -3,5-cyclohexadiene-I,2-diols from microbial transformation of benzene and other chemicals. They have been successfully used for making various bacterial plastics. 

In 2004, the US Department of Energy elaborated a list of the top 12 most attractive candidates to focus research efforts in future years (Werpy and Petersen, 2004). Succinic acid was shortlisted as one of such top 12 platform chemicals that could be produced from carbohydrates and was still on a revisited list of top platform chemicals in 2010 (Bozell and Petersen, 2010). Over the last decades, the anaerobic fermentation technology for the production of succinic acid from sugars has been the subject of intensive development (Lin et al., 2012). Recently, the commercial production of bio-based succinic acid has been announced by DSM and Roquette (Heerlen, 2011). This makes succinic acid a new bio-derived building-block chemical that could replace the current petrochemical-derived maleic anhydride platform. Therefore, a two-step 1,4-BD production route based on the bio-based succinic acid was proposed (Figure 10.3). In the reported production route to bio-based 1,4-BD, an aqueous-phase hydrogenation of bio-based succinic acid to 1,4-BD over supported bimetallic catalysts was used (Minh et al., 2010 Chen and Patel, 2012). 

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