10-Methyl undecenoate

Methyl-lO-undecenoate has been described as a raw material for the synthesis of renewable semicrystalline polyesters and poly(ester amide)s (1). Diester, ester-amide, monoamide and diamide linkages have been s mthesized from methyl-10-imdecenoate. 

The S5mthesis runs via transesterification, amidation and thiol-ene reactions to get aliphatic diols containing ester, these diols are then reacted with a biobased methyl diester. Most of these polyesters display a good thermal stability with temperature at 5% weight loss in the range 330-350°C. 

The incorporation of amide functions in the polyester backbones result in semicrystalline materials with melting points of 22-127°C and a complex melting behavior due to pol5mciorphism and melting crystallization processes (1). 

Monomers containing the 1,4-cyclohexylene unit are interesting because they are potentially biobased and rigid enough to improve the glass transition temperature as well as the melting temperature (2). The preparation of poly(l,4-cyclohexylenedimethylene adipate) has been described. 

The material has been compared to similar polymers, e.g., poly-(butylene adipate), poly(butylene-l,4-cyclohexanedicarboxylate), 

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Methoxytrimethylsilane, 123 Methyl acetoacetate, 92 Methyl bromoacetate, 107 Methyl 11-hydroxyundecanoate, 58 Methyl lithium, 27,28 Methyl 10-undecenoate, 58 2-Methyl-l, 3-dithiane, 81 (fl/ ,5 )-Methyl-3-phenyldiniethyl-silyl-3-phenylpropionic acid, 53-4 2-Methyl-3-Phenylprop-2-cnal, 111 2-Methyl 2-lrimethylsilyl-1,3-dithiane, 81 2-Methyl-l-(trimcthylsilyloxy)cyclo-hex-l-ene, 100,109 2-Melhyl-l-lrimethylsilyloxy)cyclo-hcx-6-enc, 100 2-Methyl-2-trimethylsilyloxy-pentan-3-one, 132 2-Methylacetophenone, 42-3 2-Methylbutyraldehyde, 85 2-Methylcyclohexanone, 99,100 2-Methylcyclohexanone, 131 4-Methyldec-4-ene, 67-8 Methylenation, 63 2-Methylpropen-l-ol, 131 Methyltriphenylphosphonium bromide, 27 Michael addition, 85 Monohydridosilanes, 128 Monohydroalumination, 29... 

In summary, the order of reactivity for the most commonly used ruthenium-based metathesis catalysts was found to be 56d>56c>9=7. This order of reactivity is based on IR thermography [39], determination of relative rate constants for the test reaction 58—>59 (Eq. 8) [40], and determination of turnover numbers for the self metathesis of methyl-10-undecenoate [43]. 

Scheme 2. Copper-initiated radical addition of methyl 2-iodopropionate to methyl 10-undecenoate [15].

The performance of C3-C5, and the Zhan catalyst (structure in Scheme 6) in the SM of methyl 10-undecenoate was compared by Meier et al. [45]. Loadings between 0.1 and 1 mol% were tested at 50 and 70°C, observing higher conversions (over 96%) for the second-generation catalysts, if compared to C3 (67-87%). However, also higher degree of double-bond isomerization was observed in the case of second-generation catalysts (55-90%), if compared to C3 (below 17%). Furthermore, 1,4-benzoquinone was used to suppress olefin isomerization side... 

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. 

The production of a,m-diesters from fatty esters can be realized via their SM as already explained, but it can also be performed by CM with methyl acrylate. The bulk CM of several unsaturated fatty acid methyl esters containing double bonds in different positions with methyl acrylate was studied by Rybak and Meier (Scheme 6) [43], C4 and C5 displayed very good activities with high conversions and CM selectivities. Among them, C5 showed the best performance for both methyl oleate (97% conversion, 92% selectivity, with 0.2 mol%) and methyl 10-undecenoate (99% conversion, 99% selectivity, with 0.1 mol%). The same conditions were successfully applied to methyl erucate and methyl petroselinate. The reaction conditions were further optimized, also considering the effect of 1,4-benzoquinone as additive for the reduction of double-bond isomerization [39], The CM of methyl 10-undecenoate and methyl acrylate worked with full conversions and high selectivity if five- to tenfold excess of methyl acrylate is used. Furthermore, using a 1 1 ratio between both reactants led, after optimization of the reaction... 

Apart from methyl acrylate, allyl chloride was used to synthesize a,co-difunctional monomers via bulk CM of methyl oleate and methyl 10-undecenoate (Scheme 6) [68]. While C4 failed with yields below 20%, C5 and the Zhan catalyst were able to catalyze the reaction with good results. Using C5, the best yield (90%) for the CM of methyl oleate was obtained at 50°C and 1 mol% catalyst using a fourfold excess of allyl chloride. The Zhan catalyst performed similarly, but gave... 

A similar study described the CM of methyl 10-undecenoate with diethyl maleate [70]. The performance of six ruthenium-based catalysts was tested for this reaction, and as in the previous study, all reaction parameters were screened for... 

Fell et al. presented a micellar two-phase system in which fatty acid esters can be hydroformylated [30]. Short fatty acids react in a mixture of water and the substrate without adding any surfactants. The rhodium/NaTPPTS catalyst system was able to conduct the reaction of methyl 10-undecenoate at 100°C with 30-bar synthesis gas pressure with a conversion of 99% without any surfactant. The reaction of linolenic acid ester was hindered by phase transfer problems which could be overcome by employing surfactants. The addition decreased the reaction time, so the same rhodium catalyst could achieve a conversion for linolenic methyl ester of 100%. The authors... 

SYNS METHYL 9-UNDECENOATE METHYL 10-UNDECENOATE METHYL UNDECYLENATE... 

The hydrosilylation of methyl 10-undecenoate with triethoxysilane catalyzed by anhydrous H2PtClg was studied in the thermomorphic solvent system propene carbonate (sl)/cyclohexane (s2)/toluene (s3) [Eq. (9)] [18]. 

Metzger, J.O., and F. Bangert, Ane Additions to Unsaturated Fatty Compoimds Thermally Initiated Additions of Alkanes to Methyl 10-Undecenoate, Fat Sci. Technol. 97 7-9(1995). 

For the allylic oxidation of alkenes, a large variety of methods have been reported in the literature (17-20). However, after a fair number of those oxidants were applied to methyl 10-undecenoate [1], only the substoichiometric oxidation with selenium dioxide (17) was found to work satisfactorily. Methyl 10-undecenoate [1] in dichloromethane was stirred with 0.5 equivalents of selenium dioxide and i-butylhy-droperoxide for 48 h at room temperature to yield 55% allylalcohol [2] and 7%... 

Addition of Carbon-Nucieophiies to the Allyl Carbonates [10a,b] and [11a,b] of Methyl 10-Undecenoate and Methyl Oleate... 

Another possibility for substituting flie hydroxyl group by a nucleophile is the Mitsunobu reaction (31,32). In this case, the alcohol is linked to the nucleophile using diethyl azodicarboxylate (DEAD) and Iriphenylphosphine. This reaction was applied to the allylic alcohols [5a,b] (from mefliyl oleate) (Eq. 13, Table 3) and [2] (from methyl 10-undecenoate) (Eq. 14, Table 4). 

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