Synthesis of Sebacic Acid

CH302C(CH2)4C02H Monomethyl ester of adipic acid 

CH302C(CH2)8C02CH3 Dimethyl ester of sebacic acid 

In the above process, anodic coupling of the monomethyl ester of adipic acid takes place. The electrolyte is a 20% aqueous solution of monomethyl adipate, neutralised with sodium hydroxide. The anode is platinum-plated with titanium and the cathode is of steel. 

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An excellent synthesis of myristic acid is thus achieved from readily accessible starting materials. An alternative synthesis of myristic acid utilises hexanoic acid (M-caproic acid n-hexoic acid) (X) (2 mols) and methyl hydrogen sebacate (XI) (1 mol) the products, after hydrolysis, are Ji-decane (XII), myristic acid (XIII) and hexadecane-1 16-dlcarboxylic acid (XIV) ... 

Synthesis. Functionalized monomers (and oligomers) of sebacic acid (SA-Me2) and 1,6 -bis(/ -carboxyphenoxy)hexane (CPH-Me2) were synthesized and subsequently photopolymerized as illustrated in Figure 1. First, the dicarboxylic acid was converted to an anhydride by heating at reflux in methacrylic anhydride for several hours. The dimethacrylated anhydride monomer was subsequently isolated and purified by dissolving in methylene chloride and precipitation with hexane. Infrared spectroscopy (IR), nuclear magnetic resonance (NMR) spectroscopy, and elemental analysis results indicated that both acid groups were converted to the anhydride, and the double bond of the methacrylate group was clearly evident. 

Ethyl and 2-fluoroethyl 9-bromononanecarboxylate and ethyl and 2-fluoroethyl 9-fluorononanecarboxylate were all prepared from 9-bromononanecarboxylic acid, made by the action of hydrogen bromide and sulphuric acid on 9-acetoxynonane-carboxylic acid, which in turn was obtained by a four-stage synthesis from sebacic acid. 

The process starts from the potassium salt of the adipic acid half ester (about 10 to 30 mol % neutralized). It has successfully been scaled up to the experimental production scale by Asahi. A simplified process scheme for the entire synthesis is shown in 225). While Asahi was predominantly concerned with the anodic oxidation of monomethyl adipate, BASF mainly worked on the synthesis of sebacates of higher alcohols. 

Brown-Walker reaction — Important generalization and extension of the Kolbe reaction (1891) (- Kolbe synthesis) leading to the synthesis of a variety of long-chain dicarboxylic acids and esters using monoesters of dicar-boxylic precursors. Among the most used application belongs the production of sebacic acid diethylester from hydrogen ethyladipate... 

The second approach was applied in the synthesis of fatty acid terminated polyanhydrides. Polyanhydrides based on sebacic acid, and terminated with oleic, stearic, linoleic or lithocholic acid, or combinations of several fatty acids were synthesized 21). The general structure of fatty acid terminated polyanhydrides is shown in Figure 1. 

Asahi Chemical is said to have been using the Kolbe synthesis for the production of sebacic acid for 20 years now. The electrolysis itself is one of three chemical steps (Scheme 7). In the first step, the monoester of adipic acid is produced. This is anodically dimerized to dimethyl sebacate. This ester is hydrolyzed to give crude sebacic acid. 

Other modifications of vegetable oils in polymer chemistry include the introduction of alkenyl functions, the study of novel polyesters and polyethers and the synthesis of semi-interpenetrating networks based on castor oil (the triglyceride of ricinoleic acid) [42], and also the production of sebacic acid and 10-undecenoic acid from castor oil [44]. Additionally, the recent application of metathesis reactions to unsaturated fatty acids has opened a novel avenue of exploitation leading to a variety of interesting monomers and polymers, including aliphatic polyesters and polyamides previously derived from petrochemical sources [42, 45]. 

Lipase-catalyzed synthesis of poly(l,4-butyl sebacate) from reactions of 1,4-butanediol and sebacic acid or activated derivatives of sebacic acid were studied by Linko et al. [51]. Reactions between 1,4-butanediol with sebacic acid,... 

Armenia) and, from 1959, at the Severodonetsk branch of GIAP (Gosudarstvennyy Institut Azotnoy Promyshlennosti, Azot Association, Ukraine). In 1967, Freydlin came into VNIPIM and began with a team of coworkers to develop the world s first industrial-scale electrosynthesis of sebacic acid [96, 97]. The process includes condensation of methyl adipate according to Brown-Walker synthesis (-edai schema), with subsequent hydrolysis ... 

The synthesis of terpoly(ester-6-ether-6-amide)s is a four-step process (Scheme 2) [12,17-20]. The second, third and fourth step take place in the presence of a magnesium titanate organometallic complex as a catalyst (10 wt% solution in n-butanol). The first step involves a hydroljdic condensation polymerization (the pressure decreases from 0.8-1.5 MPa to 0.1 MPa, at 280-320°C for 6-10 h) in the presence of sebacic acid as a stabilizer of the molecular weight. 

Oxides of Platinum Metals Anodes of platinum (and more rarely of other platinum metals) are used in the laboratory for studies of oxygen and chlorine evolution and in industry for the synthesis of peroxo compounds (such as persulfuric acid, H2S2O8) and organic additive dimerization products (such as sebacic acid see Section 15.6). The selectivity of the catalyst is important for all these reactions. It governs the fraction of the current consumed for chlorine evolution relative to that consumed in oxygen evolution as a possible parallel reaction it also governs the current yields and chemical yields in synthetic electrochemical reactions. 

Poly(lactic acid) (PLA) has also been added to poly(SA) via melt polycondensation to produce the triblock copolymers poly(lactic acid-Wock-sebacic acid-Wock-lactic acid) (P(LA-block-SA-block-LA)) by Slivniak and Domb (2002). The PLA (d-, l-, and dl-) was incorporated by acetylation and addition to the PSA synthesis. They showed the formation of stable stereocomplexed particles with increased melting points and reduced solubility, and studied the degradation and drug release characteristics of the same (Slivniak and Domb, 2002). The stereocomplexes self-assemble as a consequence of the chirality in the PLA portions of the chains (Slivniak and Domb, 2002). 

A 100% natural polymer based entirely on agricultural products, the polyester elastomer obtained by reacting castor oil with a castor oil derivative, sebacic acid, was the basis for the synthesis of SIN s. 

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