Oleic acid anhydride

Figure 11.8 Replication of RNA in self-reproducing vesicles. The initial vesicles contained the enzyme Q(3 replicase and the four ribonucleotides in excess, as well as the RNA template (the MDV-1 template). The division of vesicles is induced by the addition of oleic acid anhydride and the duplication of the figure is idealized, as in reality division occurs on a statistical basis. (Adapted from Oberholzer etal, 1995b.)...

HOOC-[CHa]8-COOH, CioH.aO. Colourless leaflets m.p. 134°C. Manufactured by heating castor oil with alkalis or by distillation of oleic acid. Forms an anhydride, m.p. 78 C. The esters of sebacic acid are used as plasticizers, especially for vinyl resins. 

Figure 12.12 THM GC/MS curves of a Winsor Newton lemon alkyd paint (a) and of an alkyd sample taken from Fontana s work Concetto spaziale (1961) (b). Peak assignments 1, 1,3 dimethoxy 2 propanol 2, 1,2,3 trimethoxy propane 3, 3 methoxy 1,2 propandiol 4, 4 chloro benzenamine 5, 3 methoxy 2,2 bis(methoxymethyl) 1 propanol 6, 3 chloro N methyl benzenamine 7, 3 methoxy 2 methoxymethyl 1 propanol 8, 4 chloro N methyl benzenamine 9, phthalic anhydride 10, 3 chloro 4 methoxy benzenamine 11, suberic acid dimethyl ester 12, dimethyl phthalate 13, azelaic acid dimethyl ester 14, sebacic acid dimethyl ester 15, palmitic acid methyl ester 16, oleic acid methyl ester 17, stearic acid methyl ester 18, 12 hydroxy stearic acid methyl ester 19, 12 methoxy stearic acid methyl ester 20, styrene 21, 2 (2 methoxyethoxy) ethanol 22, 1,1 oxybis(2 methoxy ethane) 23, benzoic acid methyl ester 24, adipic acid dimethyl ester 25, hexadecenoic acid methyl ester 26, dihydroisopimaric acid methyl ester 27, dehydroabietic acid methyl ester 28, 4 epidehydroabietol...

Fatty acids have also been converted to difunctional monomers for polyanhydride synthesis by dimerizing the unsaturated erucic or oleic acid to form branched monomers. These monomers are collectively referred to as fatty acid dimers and the polymers are referred to as poly(fatty acid dimer) (PFAD). PFAD (erucic acid dimer) was synthesized by Domb and Maniar (1993) via melt polycondensation and was a liquid at room temperature. Desiring to increase the hydrophobicity of aliphatic polyanhydrides such as PSA without adding aromaticity to the monomers (and thereby increasing the melting point), Teomim and Domb (1999) and Krasko et al. (2002) have synthesized fatty acid terminated PSA. Octanoic, lauric, myristic, stearic, ricinoleic, oleic, linoleic, and lithocholic acid acetate anhydrides were added to the melt polycondensation reactions to obtain the desired terminations. As desired, a dramatic reduction in the erosion rate was obtained (Krasko et al., 2002 Teomim and Domb, 1999). 

Reaction with acetic anhydride and oleic acid gives bismuth trioleate, Bi(C 13143302)3. 

Figure 7.17 Hydrolysis of oleic anhydride catalyzed by spontaneously formed oleic acid vesicles at 40 °C, (a) during the first 3 h, and (b) during a long observation time. A vesicle suspension (10 ml in 0.2 M bicine buffer (pH 8.5)) was overlaid with 0.25 mmol oleic anhydride and 0.025 mmol oleic acid. The increase of the concentration of oleic acid/oleate is plotted as a function of reaction time. Initial concentration of oleic acid/oleate 0 mM ( ), 5 mM ( ), 10 mM (o), 20 mM ( ). For an initial oleic acid/oleate concentration of 20 mM, the concentration of oleic anhydride (A) present in the vesicles during the reaction is also plotted (b, right axis). (From Walde et al, 1994b.)...

All the models mentioned thus far are based on autopoietic self-reproduction experiments. The experimental implementation of a homeostatic mode of the autopoietic minimal system, which is also illustrated in Figure 8.3, proved to be much more difficult, and was realized only in 2001 (Zepik et al., 2001). It is based on the oleic acid surfactant system and is schematized in Figure 8.5 (respecting the theoretical scheme of Figure 8.3) there are two competitive reactions, the reaction Up forms oleate surfactant from the hydrolysis of the anhydride and the other reaction destroys oleate via oxidation of the double bond. 

Giant vesicles have been the subject of several international meetings and specialized literature (Luisi and Walde, 2000 Fischer et al., 2000). There are several reasons for this interest. One is that, because of their size, they can be observed by normal optical microscopy, without using the much more expensive and indirect electron microscopy. Figure 10.7 shows, as an example, the transformations brought about by the addition of a water-insoluble precursor (oleic anhydride) to oleic acid giant vesicles (Wick et al., 1995). 

Oleic acid/oleate vesicles containing the enzyme Q(3 replicase, the RNA template and the ribonucleotides. The water-insoluble oleic anhydride was added externally. 

As with inorganic solid catalysts, the most extensively studied system was acetic acid—ethanol [428,432,434,444—448]. Other alcohols used in kinetic studies were methanol [430,449,450], 2-propanol [438], 1-bu-tanol [429,431,433,451—458], allyl alcohol [459], 1-pentanol [434] and ethyleneglycol [460] besides acetic acid, the reactions of formic [450], propionic [443,461], salicylic [430,449], benzoic [453—457] and oleic acids [430,451—453] and of phthalic anhydride [462] have been reported. Investigation of a greater variety of reactants is reported in only one paper [463] six alcohols (C4, Cs and C8) and five acids (mainly dicarboxylic were studied. Transesterification kinetic studies were performed with ethyl formate [437,439,441], isobutyrate [437,439—441] acetate [402, 435—437,439—442], methoxyacetate [441] and acrylate [403,404,464, 465] the alcohols used were methanol [402,435,437,439—442,450],... 

Earlier reports [50] showed that vesicles composed of oleic acid can grow and reproduce as oleoyl anhydride spontaneously hydrolyzed in the reaction mixture, thereby adding additional amphiphilic components (oleic acid) to the vesicle membranes. This approach has recently been extended by Hanczyc et al. [51], who prepared myristoleic acid membranes under defined conditions of pH, temperature, and ionic strength. The process by which the vesicles formed from micellar solutions required several hours, apparently with a rate-limiting step related to the assembly of nuclei of bilayer structures. However, if a mineral surface in the form of clay particles was present, the surface in some way catalyzed vesicle formation, reducing the time required from hours to a few minutes. The clay particles were spontaneously encapsulated in the vesicles. The authors further found that RNA bound to the clay was encapsulated as well. 

Growing membrane systems have been used to obtain artificial infrabiological systems. Walde et al. [47] have carried out the synthesis of polyadenylic acid in self-reproducing vesicles [48], in which the enzyme polynucleotide phosphorylase carried out the synthesis of poly-A, and membrane vesicle multiplication was due to the hydrolysis of externally provided oleic anhydride to oleic acid. The snag is that the enzyme component is not auto-catalytic. Enzymatic RNA replication in vesicles [49] suffers from the same problem. It is also not known whether redistribution of the entrapped enzymes into newly formed vesicles occurs or not. An affirmative answer would be evidence for vesicle reproduction by fission. 

For the esterification of terephthalic acid with ethylene glycol at 473 K, SO /TiCh calcined at 773 K is much more active than SiC -A Ch as shown in Fig. 6 [60]. The SO /TiCh showed a maximum activity when calcined at 573 K for the esterification of oleic acid with glycerol and of propionic acid with butanol at 403 K [61], where the active sites were attributed to Bronsted acid sites from a correlation between the activity and the Bronsted acidity. The esterification of phthalic anhydride with 2-ethylhexanol to form dioctyl phthalate is also efficiently catalyzed by solid super-acids, the selectivity being more than 90% [62]. The... 

Figure 25.3. Ion trap mass spectrum of ESI-MS3 of [ROR + Li - ROOH]+ at m/z 625.5. For abbreviations, see Figure 25.2. 0 CH=CHC00H is a,p-unsaturated oleic acid from the sn-2 position. R CH=CHCOOH is a,p-unsaturated ricinoleic acid from the sn-2 position. C7H14O is the loss from the cleavage between C-ll and C-12 of ricinole-ate chain. C3H40 is the loss of glycerol backbone to form acid anhydride of two fatty acids. R"CH=C=0 is a ketene from ricinoleate at the sn-1,3 position.

On an industrial scale, the traditional method for cleavage of carbon-carbon double bonds is ozonolysis, used for the manufacture of azelaic acid and nonanoic acids from oleic acid, and of butane tetracarboxylic acid from tetrahydrophthalic anhydride. The process is effectively a quantitative and mild process.178 However, it is capital and energy intensive. The intermediate ozonide is worked up either reductively or oxidatively to produce the aldehyde, ketone or carboxylic acid. Hydrogen peroxide is the common oxidizing agent used in the second step.179-181 Oxygen can also be used either alone182 or in combination with zeolites.183 Reviews on ozonolysis are available and the reader is directed to reference 184 for further information. 

Alkenes may also be transformed into vicinal dicarbonyl compounds. The treatment of alkenes with selenium dioxide, although possible, does not give satisfactory yields [509]. Better results are obtained when unsaturated compounds such as oleic acid are oxidized with potassium permanganate buffered with acetic anhydride [861],... 

In the presence of acetic anhydride, potassium permanganate oxidizes oleic acid at -5 to 10 °C over a period of 2.5 h to 9,10-diketostearic acid... 

Hydrogenation. Carboxylic acids are reduced to aldehydes by hydrogen in the presence of (PhjPl Pd and pivalic anhydride. Alkenoic acids (oleic acid, erucic acid) give unsaturated aldehydes. Diacids are similarly reduced. 

Figure 3. Freeze-fracture electron microscopy analysis of the vesicle size distribution in the case of the spontaneous vesiculation of oleic acid/oleate. (A) Vesicles formed from the hydrolysis of 25 mM oleic anhydride (overall concentration) at 30 °C, yielding 50 mM oleic acid/oleate. (B) Vesicles extruded throughout 50 nm diameter filters. (C) Vesicles formed upon hydrolyzing 20 mM oleic anhydride (same conditions as in A) in the presence of pre-added extruded vesicles B—all in 0.2 M bicine buffer pH 8.5. For details see ref. 8.

Figure 8. (A) Autocatalytic hydrolysis of oleic anhydride in the presence of 1.9 mM Carbobenzoxy-Phe-His-Leu-OH and Ci e-ONp in 0.02 mM borate buffer pH 8.5. Here the progress of the concentration of formed oleate/oleic acid is reported as a function of time. (B) The simultaneous initial velocity of the hydrolysis of Cl 6-0 Np is measured.

Enzymes can also be used in sc carbon dioxide.185 A Pseudomonas lipase immobilized on silica gel gave better conversions and enantioselectivity in the acetylation of racemic alcohols with acetic anhydride than when used in organic solvents.186 The lipase-catalyzed esterification of glycidol gave 83% enantioselectivity, which is as favorable as when the reaction is run in organic solvents.187 An immobilized lipase has been used in the ethanolysis of cod liver oil.188 Another immobilized lipase has been used to convert oleic acid to various esters.189 The use of a lipase in sc carbon dioxide for analyses of fats in foods cuts solvent use by 98%.190 Polyesters have been made enzymatically in carbon dioxide.191... 

OLEIC ACID, SODIUM SALT (143-19-1) CjjHjgOjNa Combustible solid (flash point unknown). Contact with strong oxidizers may cause fires or explosions. Hydrolyzed in water, forming an alkaline solution. Aqueous solution is incompatible with acids, organic anhydrides, acrylates, alcohols, aldehydes, alkylene oxides, substituted allyls, cresols, caprolactam solution, epichlorohydrin, ethylene dichloride, glycols, isocyanates, ketones, maleic anhydride, nitrates. 

Bismuth Oleate, Oleic acid bismuth salt bismuth trioleate. CMHwBiOe mol wt 1053.36. C 61-57%. H 9-477°. Bi 19.84%. O 9.11%. [CHj(CH, CH=CH(CHj)7COO]3Bi Prepd from Bi203, acetic anhydride, and oleic acid Consi-dine, Brit. pat. 947,749 (1964 to Metal Thermit). 

Oleic acid undergoes an interesting transformation when treated with a small quantity of nitrous anhydride. In a few minutes it is converted into a solid substance, which appears from its reactions to have a structure identical with that given above for oleic acid. The compound formed, called elaidic acid, is considered to be a stereoisomer of oleic acid, the relation between the two being similar to that between crotonic and... 

Vorlander described unsaturated polyesters which were produced from ethylene glycol and maleic anhydride in 1894,- but commercial unsaturated polyesters were not Introduced until the 1920 s. The first commercial free radical-curable unsaturated polyesters were produced by Klenle and Hovey, who condensed dlfunctlonal glycols, such as ethylene glycol with phthalic anhydride and an unsaturated aliphatic acid such as oleic acid.- — - The name alkyd, which was derived from the prefix in alcohol and the suffix in incorrectly spelled "akyd" was used to describe these important polyesters. 

The paths to the production of compounds containing an oxadiazole ring from isatoic anhydrides are more varied. For example, the synthesis of 5-(2-aminophenyl)-3-phenyl-l,2,4-diazole in two stages was patented a mixture of phenylacetonitrile, hydroxylamine sulfate, and the salt of the dibutylamide of sulfonated oleic acid was kept with an aqueous solution of sodium carbonate at 90°C for 5 h, the anhydride 1 was added, and the reaction mixture was kept at the same temperature with 50% aqueous sodium hydroxide for 1 h [12],... 

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