Fatty acids petroselinic

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... 

Petroselinic acid, an isomer of oleic acid, is found in many seed oils of the Um-belliferae family (ranging from 50-90% of oil composition). It can be oxidised to adipic and lauric acids, and may have pharmaceutical and cosmetic applications. Coriander is being evaluated as a potential source of this fatty acid in Europe. 

The saponifiable portion of the fatty oil accounts for about 90% of the total fixed oil and is characterized by a very high content of octadecenoic acids. Petroselinic and oleic acid occur at similar levels and jointly comprise 74-85%, linoleic 7-16% and palmitic 4-8%, of the constituent fatty acids. During prolonged storage of the spice, the free fatty acid content gradually increases and this is a good indicator of the age of the material. The contents of fatty acids, sterols and total tocopherols in a deodorized oil derived from coriander seeds (yield up to 28%) are compared with those in sunflower oil and tests on the biological effects of coriander oil are reported by Mironova et al. (1991). Of the fatty acids present, total C18 1 acids (petroselinic acid + oleinic acids) constituted 80—82% and petroselinic acid alone 50—60%, and the food value was lower than that of sunflower oif. Kim et al. (1996) found the production of petroselinic acid from cell suspension cultures of C. Sativum. 

Of the fatty acid in the fixed oil, most of which is contained in the polygonal cells in the seed endosperm, total monounsaturated acids account for 10% and total polyunsaturated fatty acids 2%. The main components of an expressed oil are petroselinic acid (up to 75%), oleic acid (up to 25%), linoleic acid (up to 15%) and palmitic acid (up to 5%) (Weiss, 2002). 

Guiet et al. (2003) demonstrated that deuterium (2H) distribution in fatty acids was non-statistical and could be related to isotopic discrimination during chain extension and desaturation. Petroselinic acid (C18 1A6) (Fig. 21.4), a fatty acid characteristic of the seeds of the Apiaceae, has been shown to be biosynthesized from palmitoyl-ACP (C16 0) by two steps, catalysed by a dedicated A4-desaturase and an elongase. The isotopic profile resulting from this pathway is similar to the classical plant fatty acid pathway, but the isotopic fingerprint from both the desaturase and elongase steps shows important differences relative to oleic and linoleic acid biosynthesis. 

The list of natural fatty acids exceeds 1000, but commercial interest is limited to a smaller number— perhaps around 20. Ignoring the lipid membrane, rich in ot-lino-lenic acid and present in all green tissue, the three dominant acids in the plant kingdom are palmitic, oleic, and linoleic, sometimes accompanied by stearic acid and by linolenic acid. Others, occuring in specialty oils, include myristic, lauric, erucic, hexadecenoic, petroselinic, y-linolenic acid, eleostearic and isomers, ricinoleic, and vemolic (Table 1). 

Petroselinic add (Z)-6-octadecenoic acid]. H3C-(CH2),o-CH=CH-(CH2)4-COOH, C,gH3402, Mr 282.47, mp. 32-33°C, bp. 215-217°C (0.2-0.3 kPa) soluble in organic solvents. P. was first found as the glycerol ester in the seed oil of parsley (Petro-selinum crispum), it is a characteristic component of the seed oils of umbelliferous and ivy plants. The fatty acids of these seed oils contain up to 87% P. (e.g. fat coriander oil, 75-80%). P. is also used as a starting material in oleochemistry. For nutritional-physiological aspects, see Lit.. ... 

Figure 22.2 [A] General triglyceride structure and fatty acid percentage composition of common plant oil. [B] Fatty acids commonly used in polymer chemistry [a] oleic acid, [b] linoleic acid, (c) linolenic acid, [d] erucic acid, [e] petroselinic acid, [f] ricinoleic acid, [g] vernolic acid, [h] 10-undecenoic acid (reprinted with permission of Montero de Espinosa et al., 2011, Elsevier [10]].

For example, fatty acids containing hydroxy groups, e.g. ricinoleic acid (fZJ-9, 12-OH 18 1) in seeds of Ricinus communis [38], or certain positional and geometrical isomers of unsaturated fatty acids, e.g. petroselinic acid (fZ)-6 18 1) in seed lipids of Pimpinella anisum [17,19], Petroselinum crispum [29] andD. carota [39], and eleostearic acid (Z)-9, (E, E)-, 13 18 3) in the seed lipids of M. charantia [36], are not detected in the lipids of cell cultures of these plants. Vaccenicacid (fZ)-ll 18 1), however, is a constituent fatty acid of triacylglycerols and other lipids of P. crispum callus as well as various tissues of the intact plant, except seeds (Table 2) [29]. 

Various positional isomers exist in nature and c/s-6-octadecenoic acid (petroselinic acid) is found in seed oils of the Umbelliferae, for example, while c/s-11-octadecenoic acid is the major unsaturated fatty acid... 

As isomers differing in ECL value by about 0.04 should be separable on most WCOT column, it would be expected that those fatty acids with central double bonds (about 4-18 1 to 9-18 1) will not be easily resolved petroselinic (6-18 1) and oleic acids occur together in some seed oils and are not readily resolved by GC (although this is possible with reversed-phase HPLC [168]). In the monoenoic fatty acids from animal tissues, there tend to be isomers in which the double bond positions are two carbon atoms apart, because they are formed... 

Major components of the oil are d- mo-nene (ca. 60%) and other limonene-type terpenes4selinene (ca. 10%), and about 3% phthalides. Other constituents include santa-lol, a- and P-eudesmol, dihydrocarvone, and fatty acids (linoleic, palmitic, petroselinic, stearic, oleic acids, etc.), among others (jiangsu ... 

Parsley seed oil contains mainly apiole, myristicin, tetrametboxyallybenzene, and a-pinene. It also contains petroselinic acid and other volatile fatty acids (see also celery seed oil) ... 

We can expect that the increasing usage of renewable feedstocks will also enlarge agricultural biodiversity. Petroselinic acid from Coriandrum sativum was already mentioned as a possible feedstock for adipic acid. Calendula officinalis offers a most interesting Cl8 fatty acid with a conjugated triene... 

Unsaturated fatty compounds such as oleic acid, petroselinic acid, erucic acid, ricinoleic acid, linoleic and linolenic acid, andlO-undecenoic acid and also the respective esters, alcohols and native oils are alkenes, and contain an electron-rich C—C double bond that can be functionalized in many different ways by reactions with electrophilic reagents [287]. 

The dried fruits are an important ingredient of spices, such as curry powder, seasonings, confectionery and flavoring spirits. The fruits contain a volatile oil, which is used for flavoring and also in pharmacy. Besides the - essential oil, c. seeds also contain a fatty oil at about 20% of the - seed weight, where the major fatty acid component is - petroselinic acid at about 80%. 

Unsaturated fatty compounds are of interest as renewable raw materials (1). These compounds can be functionalized at the C,C-double bond by electrophilic addition reactions to give new oleochemicals with potentially new and interesting properties. The alkylaluminum chloride-induced Friedel-Crafts acylation of unsaturated fatty compounds (Fig. 1), such as oleic acid [la], 10-undecenoic acid [2a], petroselinic acid [3a], and erucic acid [4a], and the respective esters and alcohols yield the corresponding P,y-unsaturated ketones (2,3). 

Fig. 1. Unsaturated fatty compounds oleic acid [1a], 10-undecenoic acid [2a], petroselinic acid [3a], erucic acid [4a], and the respective esters [1b]-[4b] and alcohols [1c]-[4c]...

Intramolecular acylations are also possible with unsaturated fatty compounds (2). The intramolecular reaction of petroselinic acid chloride and EtAlCl2 gave the cyclic product [20] with an exocyclic double bond (Scheme 9). The ring closure took place regioselectively at C-6. The pure ( )-adduct was isolated in a yield of 58%. The unsaturated ketone [20] could be easily hydrogenated to give 2-dodecylcyclohexanone [21]. 

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