Oleic acid epoxidation

P6-25c Oleic acid epoxide (E) is produced by the catalytic epoxidation of oleic acid (OA) [J. Fotopoulos, C. Georgakis, and H. Stenger, Chem. Eng. Sci, 51, 1899 (1996)]. The raw materials are pure benzaldehyde (B) and oleic acid (OA). Unfortunately, undesired products are also formed, including benzoic (BA) and perbenzoic acids (PBA). The reaction sequence is... 

Typically, soHd stabilizers utilize natural saturated fatty acid ligands with chain lengths of Cg—C g. Ziac stearate [557-05-1/, ziac neodecanoate [27253-29-8] calcium stearate [1592-23-0] barium stearate [6865-35-6] and cadmium laurate [2605-44-9] are some examples. To complete the package, the soHd products also contain other soHd additives such as polyols, antioxidants, and lubricants. Liquid stabilizers can make use of metal soaps of oleic acid, tall oil acids, 2-ethyl-hexanoic acid, octylphenol, and nonylphenol. Barium bis(nonylphenate) [41157-58-8] ziac 2-ethyIhexanoate [136-53-8], cadmium 2-ethyIhexanoate [2420-98-6], and overbased barium tallate [68855-79-8] are normally used ia the Hquid formulations along with solubilizers such as plasticizers, phosphites, and/or epoxidized oils. The majority of the Hquid barium—cadmium formulations rely on barium nonylphenate as the source of that metal. There are even some mixed metal stabilizers suppHed as pastes. The U.S. FDA approved calcium—zinc stabilizers are good examples because they contain a mixture of calcium stearate and ziac stearate suspended ia epoxidized soya oil. Table 4 shows examples of typical mixed metal stabilizers. 

Based on the composition of the C18 family of cutin monomers we postulated that oleic acid would be > hydroxy la ted first, followed by epoxidation of the double bond at C-9 followed by the hydrolytic cleavage of the oxirane to yield 9,10,18-trihydroxy acid. This postulate was experimentally verified by the demonstration of specific incorporation of exogenous 18-hydroxyoleic acid into 18-hydroxy-9,10-epoxy C18 acid in grape berry skin slices and apple fruit skin disks, and incorporation of exogenous labeled 18-hydroxy-9,10-epoxy C18 acid into 9,10,18-trihydroxy C18 acid of cutin in apple fruit skin slices [61]. 

The lower activity of Ti-beta(OH) in the epoxidation of an alkene containing a polar head (oleic acid, Table XI) was attributed by Blasco et al. (13) to the different adsorption properties of the two catalysts. A strong adsorption of oleic acid through the polar head on the relatively more hydrophilic Ti-beta(OH)... 

Epoxidation of oleic acid over Ti-beta prepared in fluoride (F) and alkali (OH) medium... 

Intramolecular epoxidation is also possible with this system.2 Thus treatment of the ortho ester (1) of oleic acid with H202 in CH2C12 leads to the epoxide 2 in 40% yield, probably via the intermediate a. 

In the mid-sixties, Atlas Chemical Industries investigated the reaction of epoxides with isohexides. Transformation of isosorbide (3) by ethylene oxide affords polyoxyethylene isosorbide (62), which was treated with oleic acid to afford the corresponding diesters (63), and these were further transformed into epoxidized products167 (64) (see Scheme 12). On treating all three iso-... 

An interesting system that is applied in the epoxidation of soybean oil is MTO immobilized on niobia combined with UHP as oxidant. The different components of soybean oil have been studied separately, and it was found that oleic acid can be epoxidized completely with 1 mol% MT0/Nb205 in 2 h at room temperature. When raising the temperature to 50°C and lowering the catalyst amount to 0.2 mol%, complete epoxidation is reached in as little as 10 min. In applying the same procedure to linoleic and linolenic acid, excellent yields of epoxidized product are obtained within 30 min. In attempts to reuse the catalyst in this reaction, it was found that the catalyst remains active for three runs, although no numerical data is provided to underline this [39, 76]. 

Another oil used for epoxidation with MT0/H202 is the oil from Jatropha curcas L. also known as Barbados or Physic nut. As with palm oil, it mostly consists of oleic acid (50%) and linoleic acid (29%) and various saturated fatty acids (20%). With 0.5 mol% of MTO and 12 mol% of pyridine in biphasic conditions, it was found that Jatropha oil can be completely epoxidized within 1.5 h [78]. 

Some insects use hydrocarbons as sex pheromones. For example, the housefly, Musca domestica, uses a mixture including (Z) -9-tricosene, the corresponding epoxide and ketone, and several methyl alkanes (2iI). The tricosene is derived by chain elongation of oleic acid, and the epoxide and ketone are made from it. The methyl alkanes are made de novo from acetate and propionate, with one propionate unit per molecule supplying the branch carbon. Propionate can arise from the degradation of valine or isoleucine, but not from succinate, although succinate may serve as an acetate precursor. 

The peracid methods invariably open the epoxide with reversion of configuration, i.e. trans-diol formation. Aryl substituents, however, are converted to the cw-diols with retention of configuration.118-120 Olefins which have been hydroxylated by means of in situ percarboxylic acid techniques include cyclohexene (65-73%),121 dodecane (91 %)122 and oleic acid (99%).123 Chlorestrol has been frans-hydroxylated with performic acid in high yield (91%).124... 

Figure 1339 Surface ligand oxidation strategy for synthesis of functionalized oleic acid-capped UCNPs. (a) Direct oxidization with the Lemieux-von Rudloff reagent and (b) epoxidation and further coupling with mPEG-OH.

In Sec. 17.10 a mechanism is proposed for the conversion of ethylene bromo-hydrin into ethylene oxide in the presence of base, (a) To what general class does this reaction belong (b) Using models, show the likely steric course of this reaction, (c) Can you suggest a reason why sodium hydroxide readily converts /r<7/i5-2-chlorocyclohexanol into cyclohexene oxide, but converts the c/5-isomer into entirely different products (d) Account for the fact that addition of chlorine and water to oleic acid (c(5-9-octadece-noic acid) followed by treatment with base gives the same epoxide (same stereoisomer) as does treatment of oleic acid with a peroxy acid. 

Recently, Bouh and Espenson reported that MTO supported on niobia catalyzed tlie epoxidation of various fatty oils using UHP as the terminal oxidant (Scheme 12). Oleic acid, linoleic acid and linolenic acid were all epoxidized in high yields (80-100%) within less than 2 h. Moreover, the catalyst could be recycled and reused without any loss of activity. 

Fatty acid epoxides have numerous uses. In particular, oils and fats of vegetable and animal origin represent the greatest proportion of current consumption of renewable raw materials in the chemical industry, providing applications that cannot be met by petrochemicals [64]. Polyether polyols produced from methyl oleate by the Prileshajev epoxidation (using peracetic acid) are an example. Epoxidized soybean oil (ESBO) is a mixture of the glycerol esters of epoxidized linoleic, linolenic, and oleic acids. It is used as a plasticizer and stabilizer for poly (vinyl chloride) (PVC) [1] and as a stabilizer for PVC resins to improve flexibility, elasticity, and toughness [65]. The ESBO market is second to that of epoxy resins and its world wide production... 

Isomerization, epoxide Perchloric acid (oleic acid y-stearolactone). 

Another early discovery was that CALB accepts H202 as nucleophile to produce peroxycarboxylic acids from esters or carboxylic acids (perhydrolysis activity can also be found in other serine hydrolases) [46, 47]. The in situ formed peracid can subsequently be used to epoxidize an alkene by (non-enzymatic) Prileshajev epoxidation. Hence, oleic acid incubated with CALB and H202 will produce 9,10-epoxyoctadecanoic acid [48]. Other alkenes can be epoxidized by H202 and a catalytic amount of carboxylic acid (and CALB) (Scheme 13.2) [49],... 

The epoxidation of petrochemical alkenes is an intensely investigated oxidation reaction and in recent years numerous homogeneous catalysts have been developed for this reaction. However, so far the catalytic epoxidation of fatty compounds has been investigated only marginally. Sobczak and Ziolkowski reported on the epoxidation of oleic acid with organic hydroperoxides catalyzed by molybdenum complexes [37]. Typical homogeneous catalysts include Mo(CO)6 and Mo02(acac)2. 

The methatesis of vegetable oils with ethylene is a very interesting way to obtain new unsaturated structures to be transformed into new polyols via the epoxidation - alcoholysis route. Trioleine was used as a model compound (the triester of glycerol with oleic acid), the methatesis reaction with ethylene being catalysed by a special ruthenium catalyst [72]. The resulting triglyceride, with terminal double bonds, after removal of the 1-decene formed, is transformed into polyols by epoxidation, followed by alcoholysis with methanol (reactions 17.27 and 17.28). 

Taking DOP as the reference standard of performance for low-temperature flex efficiency, other commercial plasticizers that are significantly better performers include linear dialkyl phthalates and alkyl esters of sebacic, azelaic, adipic, phosphoric, and epoxidized oleic acids. Significantly poorer performers are tricresyl phosphate, diphenyl phthalate, butyl benzyl phthalate, and branched dialkyl phthalates. 

There are three major types of epoxy resins cycloaliphatic epoxy resins (R and R are part of a six-membered ring), epoxidized oils (R and R are fragments of an unsaturated fatty acid, such as oleic acid in soybean oil), and glycidated resins (R is hydrogen and R can be a polyhydroxyphenol or a polybasic acid). The first two types of epoxy resins are obtained by the direct oxidation of the corresponding olefin with a peracid as illustrated by the following ... 

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