Vinyl linoleate

The synthesis of monomers derived from fatty acids incorporating end-functions susceptible to classical poly addition reactions has been revived recently and yielded interesting results. Vinyl oleate (VO) and vinyl linoleate (VL) were synthesised by a transvinylation reaction of the corresponding fatty acids with an excess of vinyl acetate (VAc) in bulk using a safe iridium-based catalyst instead of previously used mercury-based counterparts (which are not acceptable today because of safety concerns) [91]. Scheme 4.21 summarises this synthesis in the case of OA. 

N.A. Alliin, iodine, diallyl trisulfide, 2-vinyl-4h-l,3-dithin, ajoene, linoleic acid, diallyl disulfide, scordinins, selenium.98 99 107 511 Reduce serum cholesterol, lower blood pressure, and platelet aggregation. It is anticancer, antimicrobial, antithrombotic. 

Phenanthroline in the presence of heavy metals acts as an activator of the polymerization of vinyl compounds558,559 and other olefins.560-564 It also assists the dimerization of olefins in the presence of titanium catalysts.565,566 It enhances the metal catalyzed oxidation of ascorbic acid567 and dimethyl sulfoxide.568 On the other hand, on its own it can inhibit several polymerization processes.545,569 It also stabilizes butadiene and isoprene and prevents their dimerization.570 It prevents peroxide formation in ether,571 inhibits the vinylation of alcohol572 and stabilizes cumyl chloride.573 It accelerates the vulcanization of diene rubbers574 and copolymers.575 1,10-Phenanthroline catalyzes the autooxidation of linoleic and ascorbic acids in the absence of metals.567... 

Bis(acetylacetonato)manganese shows smoke-retarding properties in poly(vinyl chloride) but Mn203 and MnC03 seem to be superior in this respect.5 The so-called manganese soaps having as anions octanoate, stearate, linoleate, naphthenate and others are used as driers (see Section 66.6.1) for printing inks, varnishes and paints.45... 

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... 

Five-membered heterocyclic amines have been attracting attention for a long time. Their antioxidant effect was confirmed in model experiments. Derivatives of indole and carbazole are HS for PVC and copolymers of vinyl chloride [92], Some indoles are medical or biological AO protecting against chemical carcinogenesis or chemically induced hepatoxicity [93]. 6-Hydroxycarbazole suppresses oxidation of methyl linoleate, its sacrificial transformation yields a QI. 2,2-Disubstituted l,2-dihydro-3-oxo(or phenylimino)-3//-indoles (15a, b, R = Me, Et) have a potential importance as HS for PO [36]. 

Functionalized olefins can be classified in two groups the <5-fimctionalized olefins in which the functional group is not directly branched on the double bond but on an alkyl chain of the olefin as in the case of oct-7-en-l-al or linoleic alcohol, and the a-functionalized olefins in which the functional group is directly branched on the double bond as in the case of methyl acrylate or phenyl vinyl ether. The results described for these two groups will be discussed separately. Hydroformylation of water-soluble olefins in two-phase system with water-insoluble catalysts is far beyond the scope of this chapter and will not be discussed here (1, 2]. 

Chemical reactions with alkyd resins can take place via their hydroxyl or carboxyl groups as well as via the double bonds of the unsaturated fatty acids. Isocyanates, epoxy resins, or colophony, for example, may be reacted with the hydroxyl groups. The carboxyl groups can be reacted with polyamidoamines (reaction products formed from dimerized linoleic acid and ethylenediamine) to form thixotropic resins, or can react with hydroxy-functional silicone precondensates. The double bonds of the unsaturated fatty acids permit copolymerization with vinyl compounds [e.g., styrene or (meth)acrylic acid derivatives]. 

Chloro-1 -nitropropane Ethylbenzene intermediate, stabilizer prep. o-s-Butylphenol intermediate, stabilizer PVC Isooctyl 3-mercaptopropionate intermediate, stabilizer vinyl Thioglycolic acid intermediate, stabilizers Benzoyl chloride Methyl caprate Methyl caproate Methyl caprylate Methyl laurate Methyl linoleate Methyl myristate Methyl oleate Methyl palmitate Methyl palmitate oleate... 

Bis (4-vinyl oxy butyl) hexanediyibiscarbamate C20H36O2 Ethyl linoleate C20H36O4... 

Figure 5. Polymerization mechanism and VAc/linseed oil copolymer structure (in the example, the triglyceride contains one linoleic and two linolenic chains). The poly(vinyl acetate) radical intermediate (I) reacts with a double bond of the triglyceride (II) and produces the radical intermediate (III), which after other reaction steps is transformed into the product (IV).

The hydroperoxy epidioxides formed from photosensitized oxidized methyl linoleate are important precursors of volatile compounds, which are similar to those formed from the corresponding monohydroperoxides. Thus, 13-hydroperoxy-10,12-epidioxy-tra 5 -8-enoic acid produces hexanal and methyl lO-oxo-8-decenoate as major volatiles (Figure 4.24). The 9-hydroperoxy-10,12-epidioxy-rrans-13-enoic acid produces 2-heptenal and methyl 9-oxononanoate. Other minor volatile products include two volatiles common to those formed from the monohydroperoxides, pentane and methyl octanoate, and two that are unique, 2-heptanone and 3-octene-2-one. The hydroperoxy epidioxides formed from autoxidized methyl linolenate produce the volatiles expected from the cleavage reactions of linolenate hydroperoxides, and significant amounts of the unique compound 3,5-octadiene-2-one. This vinyl ketone has a low threshold value or minimum detectable level, and may contribute to the flavor impact of fats containing oxidized linolenate (Chapter 5). 

The reaction of an alcohol with a vinyl ester proceeds much faster than with an alkyl ester or a haloalkyl ester to form the desired product in higher yields Kobayashi and co-workers [36-41] studied the polymerisation of the divinyl esters of dicarboxylic acids with diols, triols and sorbitol. The polymerisation behaviour was strongly dependent on the monomer structure, enzyme origin and reaction conditions. Under appropriate conditions, an aliphatic polyester with a MW higher than 2 x lO Da was obtained. The polymerisation of divinyl adipate with 1,4-BDO by PFL, in isopropyl ether at 45 °C for 48 h, produced a polyester with a MW of 6,700 Da and a yield of 50% (Scheme 12.8, [1]), whereas the use of CAL was also employed to produce crosslinkable polyesters [40]. Divinyl sebacate and glycerol were polymerised in the presence of the unsaturated fatty acids, oleic acid, linoleic acid and linoleinic acid. NMR analysis revealed that the reaction proceeded with regioselectivity during the... 

Proline and proline derivatives have been utilized extensively as chiral catalysts for a wide range of asymmetric transformations [40, 132]. Gelman has documented a remarkable case in which enolizable aldehydes undergo selective Michael additions to enone acceptors (Equation 28) [133]. Diphenylpro-linol methyl ether (165) proved superior to other prolinol derivatives in terms of enantioselectivity and reactivity. As an example, the addition of oc-tanal (163) to ethyl vinyl ketone (164) in the presence of 5 mol% of 165 was carried out without solvent to furnish 166 in 87% yield and >95% ee. 

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