10-Undecenoic acid, derivs

Scheme 8 CM of 10-undecenoic acid-derived platform chemicals with acrylonitrile [70]...

Cross-linked PUs with shape memory properties were prepared by Galia, Meier et al. using linear polyols synthesized by ADMET [140]. In this work, ADMET of a 10-undecenoic acid-derived a,co-diene containing a hydroxyl group was performed in the presence of 0.1 mol% of C4. 10-Undecenol was used as chain stopper, and the mixture of oligomers and diols (from 10-undecenol SM) obtained was cross-linked with MDI. The PUs obtained displayed outstanding values of strain fixity and recovery. 

Ricinoleic acid (Figure 3.8) is the major fatty acid found in castor oil from seeds of the castor oil plant (Ricinus communis Euphorbiaceae), and is the 12-hydroxy derivative of oleic acid. It is formed by direct hydroxylation of oleic acid (usually esterified as part of a phospholipid) by the action of an 02- and NADPH-dependent mixed function oxidase, but this is not of the cytochrome P-450 type. Castor oil has a long history of use as a domestic purgative, but it is now mainly employed as a cream base. Undecenoic acid (A9-undecenoic acid) can be obtained from ricinoleic acid by thermal degradation, and as the zinc salt or in ester form is used in fungistatic preparations. 

The CM of fatty acids and derived compounds also has been used for the production of fine chemicals that are difficult to obtain by other synthetic approaches. Some examples include the synthesis of a plant growth stimulant, an insect pheromone precursor, the sex pheromone of the peach twig borer moth, and others [28]. Furthermore, the conjugation of fatty acid derivatives, sugars, and amino acids via CM was shown by Vemall and Abell [41]. C4 with a catalyst loading of 20 mol% was used to perform the CM of either Ai-Boc-L-ly sine or N-Boc-L-cysteine bearing a 10-undecenoic chain with methyl 10-undecenoate or a sugar olefin. 

Monomers derived from 10-undecenoic acid with amide functional groups have been polymerized via ADMET as well [133]. However, the low tolerance of... 

Undecenoic acid and its derivatives are thought to be suitable for mild forms of athlete s foot characterised by dry scaling of tissue, but are less effective where the skin is macerated and moist. Undecenoic acid and tolnaftate have been found to be about equally effective. 

Other modifications of vegetable oils in polymer chemistry include the introduction of alkenyl functions, the study of novel polyesters and polyethers and the synthesis of semi-interpenetrating networks based on castor oil (the triglyceride of ricinoleic acid) [42], and also the production of sebacic acid and 10-undecenoic acid from castor oil [44]. Additionally, the recent application of metathesis reactions to unsaturated fatty acids has opened a novel avenue of exploitation leading to a variety of interesting monomers and polymers, including aliphatic polyesters and polyamides previously derived from petrochemical sources [42, 45]. 

Allylic aeetates or carbonates can undergo nucleophilic substitutions via palla-dium(0)-catalysis (11). In this paper, we report on the extension of this reaction to unsaturated fatty aeids by the preparation of allyl carbonates and acetates of oleic, linoleic, and 10-undecenoic acid and their substitution with carbon- and heteroatom-nucleophiles by palladium(0)-catalysis. In this way, different substituents can be in-trodueed into the alkyl chain of fatty acids. This leads to fatty acid derivatives in which the properties of biologically active compounds may possibly be combined with the amphiphilic property of the fatty acid. 

Conjugated fatty acids derived from 10-undecenoate... 

The Lewis acid-induced acylation of unsaturated fatty compounds combined with the following reactions allows the synthesis of natural products derived from fats. Acylation of 10-undecenoic acid [2a] with heptanoyl chloride gave 12-oxo-9-octadecenoic acid reduction with NaBHq afforded the racemate of ricinelaidic acid [6], a natural product (Fig. 2). 

Dicarboxylic acid derivatives were reacted as well. Additions of dimethyl 2-alkyl-3-bromosuceinates [9] to methyl 10-undecenoate [2b] gave new derivatives of tetradecandioic acid with an additional y-lactone moiety [10] (Scheme 3). 

The fact that castor oil is a well-established industrial commodity because of the importance of some of its derivatives and macromolecular materials explains why so many studies on polymers derived from vegetable oils have focused on the use of ricinoleic acid, 10-undecenoic acid, and several other molecules based on their structures. Chapter 3 considered the context of direct polymerisation of this oil and its main fatty acid. This section is devoted to reviewing the most salient recent aspects of the vast realm of monomers and polymers based on their second-generation derivatives. Its treatment begins after the exhaustive review that Mutlu and Meier published in 2010 [124]. The impressive number of contributions since 2010 testifies to the relevance that this area has acquired. Some general notions are, however, needed to set the stage . 

Most of the studies in the last decade have concentrated on the ADMET polymerisation of fatty acids and its derivatives to obtain polyesters as the final materials. In 2008, Meier and Rybak [39] described the synthesis of an a,(0-diene by transesterification of 10-undecenoic acid with the corresponding alcohol (10-undecenol). ADMET polymerisation of this monomer was conducted to achieve a C20 unsaturated polyester. 

Recently, renewable PU were synthesised from vegetable oil derivatives by the research team of Cramail [46] in a new and very interesting approach to obtain an a,oo-diene urethane monomer by converting 10-undecenoic acid into the corresponding acyl azide, followed by urethanisation with 10-undecenol (Scheme 5.11). 

The first publication on the thiol-ene reaction of a vegetable-oil derivative dates to 1957, when Koenig and Swern published the free-radical addition of mercaptoacetic acid to oleic acid, methyl oleate, methyl ricinoleate and 10-undecenoic acid. That is, the synthesis of derivatives of a,(0-dicarboxylic oleic acid through thiol-ene addition [6]. 

Another recent study on polyester synthesis through thiol-ene reactions for preparation of monomers from fatty-acid derivatives was described by Pang and co-workers [16]. Authors adopted the same approach for preparing aliphatic diols and diester from 10-undecen-l-ol, methyl 10-undecenoate and thiols. In parallel, they prepared aromatic diesters from methyl vanillate and a series of thermoplastic polyesters were synthesised by polycondensation of the diols and diesters using conventional transesterification methods. These materials were obtained with Mn values of 12-27 kDa and T values of -13 to 13 °C. 

The mechanism of this type of polymerisation reaction follows typical step-growth polymerisation rules, and the diene dithiol (AA BB) ratio is therefore a very important parameter [19]. This observation implies that, in contrast to some of the grafting reactions mentioned above, the dithiol compound cannot be used in excess to compensate for the lower reaction rates with internal alkenes. Hence, these polymerisations are limited to the use of structures bearing terminal double bonds [19]. If this rule is applied to vegetable oils, 10-undecenoic acid and its derivatives are the only species that fulfill this criterion. 

An interesting study on the synthesis of polyethylene (PE) mimics derived from fatty-acid derivatives and thiol-ene polymerisation [39] involved preparation of two different diene monomers from a commercially available derivative of undecenoic acid, 11-bromo-l-undecene, and 10-undecenol for the synthesis of a series of non-biodegradable polymers (Scheme 6.13). The authors considered these non-biodegradable polymers to be renewable plant oil-derived substitutes for PE. 

Cadiz and co-workers [50] demonstrated use of the thiol-yne reaction for the synthesis of polyols for application in partially renewable PU (Scheme 6.18). The starting materials were 10-undecynoic acid and 9-octadecynoic acid, which were prepared by dehydrobromination of the corresponding derivatives of 10-undecenoic acid and 9-octadecenoic acid. 

In our studies, functional long-chain alkene comonomers with different electronic and steric environments were selected for copolymerization experiments. Most of these comonomers can be considered derivatives of 10-undecenoic acid. 

There have been several reports on the copolymerization of functionalized olefins with carbon monoxide. Catalysts consisting of Pd and DPPP were found to catalyze the copolymerization of CO with various functionalized olefins such as methyl 10-undecenoate, 10-undecenoic acid, 10-undecenyl alcohol, 3-butenol, and allylbenzene derivatives, as well as terpolymeriza-tions of these functionalized olefins, nonpolar olefins, and CO 12,74,75 fhnctionalized olefins bearing benzo-... 

Another divergent approach was demonstrated by the use of castor oil-derived platform chemicals. Here, 10-undecenal, 10-undecenoic acid, and 10-isocyanodec-1-ene served as components for the formation of the core unit via Passerini-3CR [59]. The resulting product, having three terminal olefins, was subsequently reacted with an excess of ferf-butyl acrylate in a cross-metathesis reaction, followed by hydrogenation of the newly formed double bonds. The introduced tert-hvXy esters were cleaved with trifiuoroacetic acid thus, three carboxylic acid groups were... 

Hayes, D.G., Mannam, V.K., Ye, R., Zhao, H., Ortega, S., Montiel, M.C., 2012. Modification of oligo-ricinoleic acid and its derivatives with 10-undecenoic acid via lipase-catalyzed esterification. Polymers (Basel, Switz.) 4,1037-1055. 

Kolb and Meier [43] prepared a malonate derivative of methyl 10-undecenoate, which was polymerised further with 1,6-hexanediol using titanium (IV) isopropoxide as a catalyst. This polymalonate, bearing a C9 aliphatic side chain with terminal double bonds, was then subjected to grafting by ruthenium-catalysed cross-metathesis reactions with acrylates or thiol-ene addition reactions. This functionalisation enabled a subsequent Passerini multi-component reaction [44] using the pendant carboxylic-acid moiety of the modified polymers that resulted from the thiol-ene addition of 3-mercaptopropionic acid into the initial double bonds of the polymer. 

---