Homogeneous metal complex catalyzed conjugation of methyl linoleate

Behr, Arno; Witte, Henning; Bayrak, Zeynep

doi:10.1002/ejlt.201200429

Cited by 25 publications

(19 citation statements)

References 15 publications

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“…, CH --CH); 3.69 (s, 6H, 2ÂCHCOOCH 3 ); 3.66 (s, 3H, CH 2 COOCH 3 ); 3.08 (d, 2H, 2 J HH ¼ 6.5 Hz, 2ÂCHCOOCH 3 ) 2.41-2.43 (m, 2H, 2xCHCH 2 ); 2.29 (t, 2H, 3 J HH ¼ 7.4 Hz, CH 2 COOCH 3 ); 1.57-1.63 (qui, 2H, 3 J HH ¼ 7.4 Hz, CH 2 CH 2 COO); 1.26-1.52 (m, 20H, 10ÂCH 2 ); 0.88 (t, 3H, 3 J HH ¼ 6.9 Hz, CH 2 CH 3 ); 13 (17); 378 (6); 346 (94); 328 (22); 318 (22); 296 (4); 287 (29); 279 (55); 269 (12); 247 (100); 233 (17); 215 (13); 203 (14); 189 (42); 175 (10); 145 (61); 119 (11); 113 (37); 105 (34); 91 (31); 79 (14); 69 (15); 55 (28); 43 (21); syn-Trimethyl-3-octyl-(E)-undec-4-ene-1,2,11-tricarboxylate (5a) and syn-Trimethyl-(E)-3-(non-1-ene-1-yl)decane-1,2,10-tricarboxylate(6a) [1,2] : 1 (10); 348 (93); 335 (25); 316 (25); 303 (15); 294 (14); 265 (11); 263 (11); 247 (12); 219 (12); 205 (15); 189 (9); 175 (7); 161 (7); 149 (13); 146 (100); 135 (11); 121 (14); 114 (37); 97 (20); 95 (23); 81 (30); 67 (30); 55 (41); 44 (30); anti-Trimethyl- We have previously reported on the maleinisation of linoleic acid [26], where we found that Rh(OAc) 2 shows a higher activity and leads to higher yields compared to RhCl 3 (H 2 O) 3 . The same tendency was found for 2, which is consistent with the results of Behr and Handwerk [28].…”

Section: Isomerization Of Double Bond Configurationmentioning

confidence: 99%

Maleinisation of monounsaturated fatty acids by Rh‐catalysis

Eschig

Schirp

Salthammer

2014

Euro J Lipid Sci & Tech

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The Rhodium catalyzed maleinisation of monounsaturated fatty acids leads to cyclic 3,6-disubstituted-1,2,3,6-tetrahydro-phthalic acid derivatives and acyclic maleinated byproducts, which are similar to the products formed by Ene-reaction. Two different catalysts, RhCl3(H2O)3 and Rh(OAc)2, were investigated. It was found that Rh(OAc)2 shows a higher selectivity toward the cyclic products as well as higher conversions compared to RhCl3(H2O)3. Furthermore it was observed that the double bond configuration of the fatty acid influences the yields and the product composition of the maleinated products. The Rh(OAc)2-catalysis leads mainly to the cyclic THPAs. If the cis-configurated oleic acid is used, one cyclic main product is formed, whereas the trans-configurated elaidic acid leads to three different isomers. Furthermore a decrease of the overall yield of the maleinated products was observed for elaidic acid, compared to oleic acid. In contrast to that, the RhCl3(H2O)3-catalyst tends to result favorably in the formation of the acyclic products. If oleic acid is used, the formation of two different constitutional syn-isomers was observed. In addition to that the maleinisation of elaidic acid gives also the anti-form, so that four different products could be detected by NMR-experiments. Practical applications: Fatty acid based 3,6-disubstituted-1,2,3,6-tetrahydro-phthalic acid (THPA) derivatives are promising monomers for polycondensation processes. The substructure of the six-membered carbon ring is of great interest for the hardness of the resulting polyesters. The mentioned THPA derivatives are commonly synthesized via Diels-Alder reaction of conjugated fatty acids and maleic anhydride. The main disadvantage of this synthesis route is caused by monounsaturation of many natural fatty acids, e.g., oleic acid, or by the non-conjugation of the most natural fatty acids, e.g., linoleic acid which requires a further step for conjugation. The Rh-catalyzed maleinisation enables the synthesis of such cyclic structures using monounsaturated fatty acids, e.g., oleic acid. The resulting THPAs are considered to be biobased substitutes with good prospects, e.g., for phthalic acid anhydride, trimellitic acid and their di-, tetra-, or hexahydro-derivatives, which are commonly used in polycondensation processes. These fatty acid based THPAs may open the door towards new advanced biobased products, e.g., for lacquers and coatings

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Section: Isomerization Of Double Bond Configurationmentioning

confidence: 99%

Maleinisation of monounsaturated fatty acids by Rh‐catalysis

Eschig

Schirp

Salthammer

2014

Euro J Lipid Sci & Tech

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“…Therefore, this work further exhibited the significant role of Lewis acid properties, rather than the redox properties, of the Cu(II) cation in promoting Pd(II)-catalyzed olefin isomerization. Remarkably, the isomerizations were conducted under air in the present studies, whereas previously reported olefin isomerizations were generally conducted under N 2 or Ar [21][22][23], which highlights the merit of the catalyst system demonstrated here. In 1 H NMR characterizations of ML substrate and CML products, the chemical shift observed at 2.7-2.8 ppm is known as the methylene protons positioned between the two C=C bonds in ML as shown in Fig.…”

Section: Resultsmentioning

confidence: 66%

“…Using methyl linoleate (ML) as a vegetable oil model, a series of non-redox metal ions were tested as Lewis acids to promote simple Pd(OAc) 2 catalyzed olefin isomerization in toluene/t-BuOH at 110 °C, and the results are summarized in Table 1. In the literature, the reported catalysts for efficient vegetable oil isomerization include Ru-and Rhbased metal complexes with phosphine ligands like PPh 3 , while a Pd-based catalyst was not reported [19][20][21][22][23][24][25][26]; even in common olefin isomerization, the reported Pd catalysts were less active than those that were Ru or Rh based [36]. As shown in Table 1, Pd(OAc) 2 alone as a catalyst is also inactive for the transformation of ML to its conjugated methyl linoleates (CML).…”

Section: Resultsmentioning

confidence: 99%

“…Consequently, transition metal ions-based catalytic isomerizations of vegetable oils, for example, methyl linoleate (ML), to the corresponding conjugated oils has recently attracted attention. In the literature, Wilkinson-type catalysts like Ru and Rh complexes having the PPh 3 ligand have demonstrated encouraging catalytic efficiency under low temperature [19][20][21][22][23][24][25][26]. Larock reported that a [RhCl(C 8 H 12 )] 2 catalyst with SnCl 2 and (p-CH 3 C 6 H 4 ) 3 P (TPP) can isomerize soybean oil with 90% yield in absolute ethanol at 60 °C under Ar.…”

Section: Introductionmentioning

confidence: 99%

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Transformation of Methyl Linoleate to its Conjugated Derivatives with Simple Pd(OAc)₂/Lewis Acid Catalyst

Senan

Zhang

Qin

et al. 2017

J Americ Oil Chem Soc

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With the rapid depletion of fossil resources, the exploitation of biomass to partly replace fossil resources as the source of carbon in the chemical industry constitutes a promising alternative for the near future. This work introduces catalytic transformation of vegetable oil, i.e., methyl linoleate, to its conjugated esters by a simple Pd(OAc)2/Sc(OTf)3 catalyst, which has extensive applications in industry. It was found that adding non‐redox metal ions like Sc(III) to a simple Pd(OAc)2 catalyst can effectively improve its isomerization activity in toluene/t‐BuOH solvent, whereas Pd(OAc)2 alone is inactive. Preliminary mechanistic investigations together with previous studies suggested that the in situ‐generated heterobimetallic Pd(II)/Sc(III) dimer serves as the key species for methyl linoleate isomerization, and the reaction proceeds by [1,3]‐hydrogen shift mechanism involving a formal Pd(II)/Pd(IV) cycle.

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“…Another option for the large scale production of CLAs starts from ricinoleic acid [13][14][15]. Besides, there are also investigations on the transition-metal catalysed isomerisation of fatty acids which can be carried out homogeneous [16,17] or heterogeneous [18,19]. Another alternative is the use of microorganism [20][21][22][23].…”

Section: Introductionmentioning

confidence: 99%

Rhodium‐catalysed cyclisation by addition of unsaturated 1,4‐dicarbonyl compounds to oleic acid methyl ester

Eschig

Schirp

2015

Euro J Lipid Sci & Tech

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The Rh-catalysis allows the one-step synthesis of Diels–Alder-like cycloadducts from mono-unsaturated fatty acid and 1,4-dicarbonyl components. In this article we report on the addition of maleic acid-, fumaric acid- and acetylene dicarboxylic acid dimethyl ester to oleic acid methyl ester. In previous studies, Rh(OAc)2 showed the highest selectivity of the investigated catalysts towards the 3,6-disubstituted-1,2,3,6-tetrahydro-phthalic acid derivatives (THPA) for the addition of maleic anhydride to oleic acid. Thus, it was also used in this study. The relative configurations of the final products were identified by comparison with the Diels–Alder products, resulting from conjugated linoleic acid methylester (CLAMe) and the mentioned 1,4-dicarbonyl compounds

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Homogeneous metal complex catalyzed conjugation of methyl linoleate

Cited by 25 publications

References 15 publications

Maleinisation of monounsaturated fatty acids by Rh‐catalysis

Maleinisation of monounsaturated fatty acids by Rh‐catalysis

Transformation of Methyl Linoleate to its Conjugated Derivatives with Simple Pd(OAc)₂/Lewis Acid Catalyst

Rhodium‐catalysed cyclisation by addition of unsaturated 1,4‐dicarbonyl compounds to oleic acid methyl ester

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Homogeneous metal complex catalyzed conjugation of methyl linoleate

Cited by 25 publications

References 15 publications

Maleinisation of monounsaturated fatty acids by Rh‐catalysis

Maleinisation of monounsaturated fatty acids by Rh‐catalysis

Transformation of Methyl Linoleate to its Conjugated Derivatives with Simple Pd(OAc)2/Lewis Acid Catalyst

Rhodium‐catalysed cyclisation by addition of unsaturated 1,4‐dicarbonyl compounds to oleic acid methyl ester

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Transformation of Methyl Linoleate to its Conjugated Derivatives with Simple Pd(OAc)₂/Lewis Acid Catalyst