Synthesis of fatty acid‐based 3,6‐disubstituted‐1,2,3,6‐tetrahydro‐phthalic acid anhydride derivatives

Abstract

Fatty acid based 3,6-disubstituted-1,2,3,6-tetrahydro-phthalic acid anhydride derivatives were synthesized by Rhodium catalysed addition of maleic anhydride to linoleic and oleic acid. The maleinisation of linoleic acid leads to cyclohexenoic anhydrides having an allylic double bond. The cis-configuration of this double bond was confirmed by synthesis of the corresponding anhydrides via Diels-Alder reaction of calendic acid, alpha-eleostearic acid and beta-eleostearic acid with maleic anhydride, which was reported to be highly regio- and stereoselective. These compounds were co-injected with the products of the Rh-catalysed maleinated linoleic acid into HPLC column so that the peaks of the resulting chromatogram could be allocated to the corresponding cyclohexenoic anhydrides. Besides the activity of the used catalysts RhCl₃(H₂O)₃ and Rh(OAc)₂, their selectivity towards the cyclohexenoic anhydrides was investigated. Furthermore the influence of reaction temperature, equivalents of maleic anhydride and reaction time was analysed to determine the optimum reaction conditions for the highest overall yields of the resulting 3,6-disubstituted-1,2,3,6-tetrahydro-phthalic acid anhydride derivatives

Maleinisation of monounsaturated fatty acids by Rh‐catalysis

“…, 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].…”

Highly Water‐Soluble Amphiphilic Cyclodextrins Bearing Branched and Cyclic Oleic Grafts

“…The BSA products are a mixture of 4 regioisomers (represented as a single compound for simplification) whereas CSA product corresponds to 1 regioisomer (Scheme ). This mixture of branched and cyclic products was originated from two catalytic mechanisms as described by Behr and Eschig . The mechanisms of thermic and rhodium‐catalyzed maleinisations are presented in supporting information (see supporting information; Schemes S1 and S2, respectively).…”

“…Behr et al were the first to describe the rhodium catalyzed maleinisation of oleic acid derivative followed by Eschig and al. (Scheme b) . This catalytic way mainly produced cyclic succinic anhydrides (CSA) but also BSA which are similar to the products formed by thermic way.…”

Stepwise catalytic transformations of renewable feedstock arising from plant oils

“…From these trienes featuring ( E ) and ( Z ) double bonds, a highly regio‐ and stereoselective [4 + 2]‐cycloaddition was found involving preferentially the ( E )‐configured conjugated double bonds. Metal‐catalyzed Diels–Alder cycloadditions from dienic fatty esters have also been carried out in the presence of Lewis acid and transition metal catalysts .…”